Citation
An investigation of the relative migratory tendencies of the phenyl and p-tolyl groups in the pinacol rearrangement of the 1,1,2- triarylethylene glycol system

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Title:
An investigation of the relative migratory tendencies of the phenyl and p-tolyl groups in the pinacol rearrangement of the 1,1,2- triarylethylene glycol system
Creator:
Kendrick, Lawrence W., 1925-
Publication Date:
Language:
English
Physical Description:
vii, 88 leaves : illustrations; 29 cm.

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Subjects / Keywords:
Aldehydes ( mesh )
Ketones ( mesh )
Glycols ( mesh )
Pharmaceutical Chemistry thesis Ph. D ( mesh )
Dissertations, Academic -- Pharmaceutical Chemistry -- UF ( mesh )
Ketones. ( fast )
Tracers (Chemistry) ( fast )
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bibliography ( marcgt )
non-fiction ( marcgt )
Academic theses ( lcgft )

Notes

Thesis:
Thesis (Ph.D.)--University of Florida, 1957.
Bibliography:
Includes bibliographical references (leaves 80-86).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Lawrence W. Kendrick.

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Full Text
AN INVESTIGATION OF THE RELATIVE MIGRATORY TEN
DENCIES OF THE PHENYL AND p-TOLYL GROUPS
IN THE PINACOL REARRANGEMENT OF THE
1,1,2-TRIARYLETHYLENE GLYCOL SYSTEM
By
LAWRENCE W. KENDRICK, JR.
A Dissertation Presented to the Graduate Council of
The University of Florida
In Partial Fulfillment of the Requirements for the
Degree of Doctor of Philosophy
UNIVERSITY OF FLORIDA
JUNE, 1957


ACKNOWLEDGMENTS
The author wishes to express his sincere appreciation to
Dr- W. M. Lauter of the University of Florida for his helpful and
timely suggestions, and to Dr. C. J. Collins of the Oak Ridge National
Laboratory for his valuable assistance and guidance in this research.
The author wishes to acknowledge the contribution of each member
of his Graduate Supervisory Committee% Dr. C. H. Becker,
Dr. W. S. Brey, Jr., Dr. L. G. Gramling, Dr. C. B. Pollard, all of the
University of Florida and Dr. L. P. Zill of the Oak Ridge National
Laboratory.
The author also wishes to acknowledge his indebtedness to the
members of the Organic Group, Chemistry Division of the Oak Ridge
National Laboratory for their helpful suggestions and friendly advice.
ii


TABLE OF CONTENTS
ACKNOWLEDGMENTS
LIST OF CHARTS vi
LIST OF TABLES vii
INTRODUCTION 1
HISTORY 10
METHODS AND RESULTS 35
DISCUSSION 42
EXPERIMENTAL 49
Radioactivity Determinations and the Radioactivity
Dilution Method of Yield Determination. 49
Sulfuric Acid Catalyzed Rearrangements. 49
Formic Acid Catalyzed Rearrangements. 50
Aldehyde Stability in Formic Acid. 52
Ketone Cleavage for Carbon-14 Distribution. 53
Ketone Stability in Concentrated Sulfuric Acid. 54
£-Methylbenzhydryl £-Tolyl Ketone (IV). 54
a) Phenyl-£-Tolylcarbinol. 54
b) Phenyl-£-TolyImethyl Chloride. 54
c) Phenyl-£-Tolylacetonitrile 56
d) Phenyl-£-Tolylacetic Acid 56
e) Phenyl-£-Tolylacetyl Chloride 57
f) £-Methylbenzhydryl £-Tolyl Ketone (IV). 57
g) p-Methylbenzhydryl £-Tolyl Ketone-C1^ (iVb). 58
iii


iv
Threo-l,2-di-p-tolyl-l-phenylethylene-2-C"^ Glycol (lb),
Method I. 59
II4.
Threo-l,2-di-p-tolyl-l-phenylethylene-2-C Glycol (lb),
Method II. 60
a) g-Methylbenzyl-a-C1^ Alcohol. 60
b) p-Methylbenzyl-a-C^ Chloride. 60
c) £-Tolylacetonitrile-a=C^. 60
d) £-Tolylacetic Acid (carboxyl-labeled with carbon-l4). 60
e) Preparation of the Glycol (lb). 6l
Threo-l, 2-di-£-tolyl-l-phenylethylene(2-g-^th^l^C^)
Glycol (Ic). 6l
V 14 ,
a) Benzoic Acid-Carboxyl-C 6l
b) Toluene-Methyl-C1^. 6l
c) 4-Methyl-C^-Acetophenone. 62
d) 4-Methyl-Cll+-Mandelie Acid 65
e) 4-Methyl-C^-Phenylacetic Acid 64
f) 4' -Methyl-C^-Desoxybenzoin. 64
g) a-Bromo-4'-methyl-C^-desoxybenzoin. 64
h) 4' -Methyl-C^-benzoin 65
i) Threo-1,2-di1olyl-1-phenylethylene
(2-p-methyl-C1^) Glycol (Ic). 66
Erythro-l,2-di-p-tolyl-l-phenylethylene-2-C1^ Glycol (lb). 66
a) 4,4'-Dimethyldesoxybenzoin. 66
b) 4,4'-Dimethyl-a-bromodesoxybenzoin 67
c) 4,4'-Dimethylbenzoin 67


V
d)Preparation of the Glycol, Erythro-Ib. 67
l,l-Di-£-tolyl-2-phenylethylene-l-Cl14' Glycol (lia). 68
a) Mandelic-carbonyl-C^ Acid. 68
b) Methyl Mandelate-carbonyl-C1^. 68
c) l,l-Di-£-tolyl-2-phenylethylene-l-Cli4' Glycol (Ha). 68
Di-£-tolylphenylacetaldehyde. 69
4,4-' -Dimethylbenzhydryl Phenyl Ketone (V). 70
a) Di-£-tolylcarbinol. 70
b) Di-£~tolylchloromethane. 70
c) Di-£-tolylacetonitrile. 71
d) Di-£-tolylacetic Acid. 71
e) Di-£-tolylacetyl Chloride. 72
f) 4,4'-Dimethylbenzhydryl Phenyl Ketone. 72
Sample Calculations for Ketone Yields, Reaction Path
Yields and Carbon-14 Label Distribution. 73
a)Correction Factor for Ketone Yields from
Threo-Ic and III, and Cleavage Products of
IVcd. 73
b) Ketone Yield Calculations. 75
c) Reaction Path Yields. 75
Derivation of Equation 1 of the Introduction. 76
Analytical Determinations. 78
SUMMARY 79
BIBLIOGRAPHY 80
BIOGRAPHICAL ITEMS 87
88
COMMITTEE REPORT


LIST OF CHARTS
Chart I Rearrangement of Threo- and Erythro-I, and III. 2
II Rearrangement of Ila. 7
III Preparation of Threo-l,2-di-p-tolyl(2-p-methyl-C^) -
1-phenylethylene Glycol (Ic). 36
IV Preparation of Threo-l,2-di-£-tolyl-1-phenyl
ethylene Glycol (lb). 36
V Preparation of Erythro-1,2-di-p-tolyl-l-phenyl-
ethylene-2-C14 Glycol (lb) 37
VI Preparation of l,l-di-p-tolyl-2-phenylethylene-
1-C11+ Glycol (lia) 37
vi


LIST OF TABLES
Table I Comparison of kAr/kH Ratios for Various Systems
in Formic and Sulfuric Acids. L-
IIYields of Ketones IV and V Produced by the Action
of Sulfuric Acid upon I, II, and III. 38
IIIYield of Aldehyde III, Produced by the Action of
Formic Acid upon Glycols I and II. 39
IVFraction of Radioactivity Found in Vc from Cleavage
of IVcd Derived from the Rearrangement of Threo-Ic. 40
V Fraction of Radioactivity in Fragments from Cleavage
of IVab and Vab Resulting from Rearrangement
of Threo-Ib, Erythro-Ib, and Ila. 4l
VISummary of Mole-Fraction Calculations from the
Data of Tables II through V. 4-5
VIISummary of the Ratios Calculated for use in or by
Equation 1. 46
VIIISummary of Yield Determination Experiments for
HgSO^ Rearrangements. 51
IXSummary of Yield Determination Experiments for
Formic Acid Rearrangements. 51
XSummary of Radioactivity Distribution Determinations. 55
vii


INTRODUCTION
A mechanistic correlation of the aldehyde-ketone and the pinacol
rearrangements was reported in 1956 by Benjamin and Collins, (l) In an
earlier paper Collins (2) had evaluated the importance of the conjugate
acid of triphenylacetaldehyde as an intermediate in the pinacol rear
rangement of triphenylethylene glycol and had proposed a mechanism to
explain the observed fates of the carbon-14 labels for different iso
tope position isomers of this glycol when it was subjected to rear
rangement. The extension of these proposals to the rearrangements of
diphenyl-£-tolylacetaldehyde and the two glycols, 1,2-diphenyl-1-
£-tolylethylene glycol and 1,l-diphenyl-2-£-tolylethylene glycol, led
the authors (l) to propose a general mechanism for the rearrangements.
It was found by Benjamin and Collins that through a mathematical
treatment of the mechanism they proposed,, the £-tolyl/phenyl migration
ratio, during the acid-catalyzed rearrangement of the aldehyde to
ketones, was equal to gkT, where the ratio kj/kp was evaluated by means
kp
of equation 1. By a combination of double-labeling techniques and
1)
_ % foroi
^ k0 kH
1 +
1 +
k'
H
^Tol
kH
*The letter, m, with subscript, d, e, etc., represents the mole
fraction of starting material giving product via path, D, E, etc.
Similar usage is employed in the construction of Charts I and II of the
present research. These charts were drawn to represent the rearrange
ment of glycols I and II, and aldehyde III, in a manner predifctable
from the postulations of Benjamin and Collins. (1)
1


o *
CHART I. Rearrangement of Threo- and Erythro~I, and III.


3
radioactivity dilution experiments upon appropriately labeled isotope
position isomers, these authors were able to show that the £-tolyl/
phenyl migration ratio was greater than one, in agreement with other
observations, (3-10) but in contradiction to the conclusion to be drawn
from a simple product ratio of the ketones obtained. It was necessary,
however, for Benjamin and Collins (l) to estimate the kr0iA'jj ratio in
the rearrangement catalyzed by sulfuric acid by means of the proportion,
^oiA'hO^A) ^A'hAcooh) :; Vk^HjAV ; Vk'H(HcooH)
since the value was so large as to preclude an accurate experimental
determination.
The values for the ratios of the specific rate constants found by
Benjamin and Collins can be used to calculate similar ratios in closely
related systems by taking into account what is apparently a decrease
in the values for k$ Ag when the carbonium ion at the migration terminus
is made more stable (Table I), (ll) The values then, for k^ Ag and
k_ ,/k'jj in concentrated sulfuric acid and in formic acid, may be esti-
*
mated for the system in which I, II and III undergo rearrangement
*In this dissertation Roman numerals have been used to designate the
names of the various compounds when repetition of their names would be
cumbersome. In the case of radioactive compounds, a letter has been
appended to the Roman numeral to indicate the position of labeling,
thus la would represent 1,2-di-p-tolyl-l-phenylethylene-l-C1^ glycol,
discretely labeled in the 1-position of the ethylene glycol chain and
lb, the same glycol discretely labeled in the 2-position of the glycol
chain and Ic, this glycol discretely labeled in the ^-methyl group of
the £-tolyl group attached to the 2-position of the chain. More than
one letter (e.g., lab) represents mixtures of the carbon-14 label
between the indicated positions. See page 5-


k
TABLE I
Comparison of k^r/kg Ratios for Various
Systems in Formic and Sulfuric Acids
k/kH
HgSOi).
kTol/k'H
HC00H
k$/kH kTol/k'H
C. J. C. (2)
7.33
1.7a
-
B. M. B. and C. J. C. (l)
6.9
1.15
9-3
Estimated for present
research
6.5c
32d
0.j8e
6.3f
Recalculated value, "based upon the observation that 7$ scrambling
of the chain label occurs in the aldehyde rearrangement. (20)
Midpoint of two extremes, calculated by method of B. M. B. and
C. J. C., using 1.7 for k c6.9/7-35 x 6.9 = 6.5.
d6.3/9.3 = x/48.
el.15/1.7 x 1.15 = O.78
f1.7/l.l5 = 9.3/x.
(Chart I). If the contributions of paths A and B are neglected and the
£-tolyl/phenyl migration ratio is assumed to be ca. 3.0 (l) then by use
of equation 1 the ratio m /m^ may be calculated. From a knowledge of
the me/ma ratio and the k^^/k'g ratio the yield of ketones IV and V in
the ketonic product may then be estimated.


5
2) 2 x £-tolyl/phenyl migration ratio =
_ % ^Tol fe
kP ~ k* k'H md
2x3 = 1 x J2 x
S3
= 1.36
md
3) Now since
. m, + m
^oiA'h = m 32 or md + me = 32 mc
1 +
'H
^Tol
1 +
H
?k
md
i +
52
1 +
S3
*The ratio must be multiplied by 2 since there are two £-tolyl groups
and only one phenyl in the molecule.


6
4) in + m, + m = 1.00
' c d e
5) Substituting 3) in 4)
mc + 32 mc = 1.00
mc = 0.03
md + mg = 0.97
Since the ratio me/md 1-56 or = I.36 m^, then,
+ (1.36 m^) =0.97
md = 0.4l
and me = O.56
The ketones formed from I, through paths C and E, are chemically
identical (IV), thus, mc + mg (0.59) will represent the expected yield
of IV in the ketone product, whereas ketone V is represented by md
(0.4l). Similarly the yields of ketones formed from II (Chart II) and
III may be calculated. These are:
for II mf = 0.13, md = 0.37. = 0.50, V = 50$, IV = 50$;
for III md = IV = 0.43 or 43$, me = V = 0.57 or 57#-
It is possible also to predict from Table I the yield of aldehyde
(III) formed when the glycol (I) is subjected to rearrangement in formic
acid at room temperature. Thus, from Table I, ferol (formic acid)=6.3=
k'g
aldehyde formed < Since the only two products are aldehyde (ill)
moles ketone formed
and ketone (IV), and since the aldehyde itself is stable in formic acid
for short periocfe of time, it follows that the yields of aldehyde and


CHART II. Rearrangement of Ila


8
ketone, respectively, should be 87$ and 13$.
It should be emphasized that although values for the various
ratios discussed are recorded, for example, as 9-3 for k^, ^/k'g in
formic acid, it is not intended that the precision of such values be
interpreted as being better than 10$; for the values of the larger
ratios, the uncertainty may be considerably greater. The reason for
this will be made clear in the treatment of the data for this research.
The ratios are carried through the discussion in this way as an aid to
the reader in identifying them as they occur. Despite these uncertain
ties, it was believed the system involving the rearrangements of I, II
and III should offer near optimum conditions for testing the generality
of the mechanism proposed by Benjamin and Collins because from the
foregoing calculations it appeared the ratio of the two ketones
produced from the glycols (I and II) and the aldehyde (III) should be
near enough to unity to provide a minimum error. It was for this
reason that the rearrangements of compounds I, II and III were chosen
as the subject of the present research.
Examination of equation 1 reveals that because of its magnitude
' is perhaps the most crucial term involved in establishing an
li
accurate kp/kp ratio. A minimum value for this ratio must be
established, then, if we are to test the conclusion of Benjamin and
Collins (l) that the migratory ability of the p-tolyl group is greater
than that of phenyl. Benjamin and Collins (l) were unable to do this
directly, and found it necessary to estimate the value by the indirect
method mentioned in the foregoing discussion.


9
The purposes for which this research were undertaken have been
achieved, in that l) the £-tolyl/phenyl migration ratio in the rear
rangement of aldehyde III in sulfuric acid has been shown to be greater
than unity and 2) the general mechanism (l) for the aldehyde-ketone
rearrangement has been supported for the system of compounds (I, II,
III, IV and V) studied.


HISTORY
The pinacol rearrangement was discovered by Fittig in i860. (12)
Fittig had synthesized pinacol the previous year and found that upon
treatment of the compound with sulfuric acid, the ketone, pinacolone,
was produced. The feature of the reaction which was considered unusual
at the time was the migration of a methyl group from one carbon atom to
an adjacent one:
# OH OH 0
1) CH,-C C-CH, ^CH,C-C(CHj*
5 CH, <3H, 3 ? 5 33
Since the initial work of Fittig, numerous related conversions
have been observed, under a wide variety of acidic conditions. The
reaction is quite general for the 1,2 glycols (commonly called
"pinacols" after the compound of Fittig), as evidenced by the following
discussion, which is concerned with a selected few of the many such
, ?H ?H, N 9
2) (R)2-C C-(R')2 RgR'C-CR* + H20
rearrangements reported in the literature. On treatment of the glycol
with acid, the product formed may be an aldehyde or a ketone, depending
upon the nature of the groups, R, and the acid strength of the reaction
medium. The reaction takes place when R is alkyl, aryl, part of an
*The equations in this, and other sections are numbered independently;
that is, the first equation in each section is numbered l).
10


11
alicyclic structure, or hydrogen.
Examples of the generality of the rearrangement may he seen from
the following examples:
3)
5)
6)
7)
8)
9)
PH pH .,.
CH5-C jjH g-A ^ (CH3)2CHCHO (13)
OH OH
o66-ch^
k k 5
A
CH2C-CH5 (14)
OH
d
OH
fcEt
Et
cone
H2S04'
Cr^V0 + nr (i
xEt M~~Et
'Et
o=? S,-, Q-;"
(15)
OH OH
t>-C C- IPn + xo-s-c^ <*.*>
'v 2
pH 9H ft
2C 9-CH5 h2S0U> 2CHC-CH3 (l8)
H
4>2pC-4> > d>5CCHO + ?-
OH OH H+
CH02 (2)
cone. ,9
> OC-CHO,
HoS0
2&ul|.


12
OH (¡)H ,., 9 Q A
10) -ToleC-0 > pC-CHO + 0-CH^ + £-ToC-Ch( (1)
H i ^ £-Tol ]d-To1 4>
i
conc.
h2so4
OH OH
11) op-c-
H -Tol
dil *
H+
Vt
(1)
t
conc.
h2so4
1f
t
OH OH
12) OC 6-0
CH*
conc.- > CHC
H2S04 CH
5
9 ,
+ 42CHC-CH3 (19)
"small amount"
The products of the rearrangement of glycols which are incompletely
substituted may be aldehydes and/or ketones. Aldehydes are often
produced when the reaction is catalyzed by weak acids or by dilute
mineral acids and ketones alone are usually produced under strongly
acid conditions or at high temperatures. In much of the early work the
yields of the ketones produced were not accurately determined. In some
reactions in which two ketones were produced, only one was isolated;
often, because of its insolubility, that ketone formed in lesser yield
was the only product identified, (l, 21) The aldehydes formed during
these rearrangements are themselves convertible to ketones under the
influence of strong acids, or of dilute or weak acids at elevated


13
temperatures, (1, 22-25) and thus the aldehyde-ketone rearrangement is
known to he intimately related to that of the pinacols. Examples of
the production of aldehydes (or aldehydes and ketones) in the presence
of dilute or weak acids are seen in equations 3, 9, 10 and 11 and in
the following cases:
13)
dil
HgSO^
CHCHO
(26)
d
optically active
9H 9H
Ik) 2CCH2 > 15)
9H 9H
0_C C(CH,)p
dil
(ch3)2-L
H 52
HgSO^
OH OH
16)
I 1
-> och2cho
(29)
H H
17)
OH 9H
-G-4)
o2chcho
(30)
H H
ia)
, 9H 9H
(ch5)2c-ch2
- HpO
180-200
(CH5)2CHCH0
(28)
(3D
The conversion of aldehydes to ketones in the presence of strong
acids may he illustrated hy the following examples:
ih
19) (ch,)2-9-cho
J
(CH )9Hfi-CH (32)
J

14
fl
20) OpC-CHO 2?P4_^ -CHC- (32)
CH* CH*
21) 5CCHO
22) 02C-CHO
£-To1
cone
^2^0^
1^ CH2 (2)
cone. 9 9 .
jr qn,"^ OC-CH + £-TolB-CHO (1)
*2S0k \£-Tol 2
, i, ___ cone.
23) O-C-CHO ^
6-
CHj H2S1^
CHx
fi 0 A
1 CHO>2 + 08-CHf (33)
\Q
CH*
0 0
24) 4>2C-CH0 S2§P4^ 4>2CHC-Et + 4>-CH-8- (32)
kt t
33^
Et p
25) 4>-p-CH0 222?4_^ EtCHC-Et (32)
Et *
HoSOk 9
26) CH5C-CHO > CH^CHC-Et (34)
-Anisyl -Anisyl
67^
cone. ft
27)O-CH-CHO ~ Qn > CHoC-
CH5 H2S04
:2c/-ch3 (25)
Although discovered first, the pinacol rearrangement is in reality
a Wagner-Meerwin type transformation. Wagner's (35) first example
involved the transformation of isobprneol'into camphene (equation 30).
Wagner's correct interpretation of the course of the dehydration
furnished the basis for the explanation of a variety of "1,2 shifts,"


15
as they are commonly named. (24) These reactions, historically classi
fied under such names as Wagner, Meerwein, Nametkin, Demjanow, Finacol
and Tiffeneau, have recently been discussed by Ingold, Bartlett, Eliel
and Cram. (23, 36-38) The Wagner-Meerwein type reaction may be
formulated as:
R i
28) t
-f
or
>C 6-
+ XY
where Y is the entering group or causative agent, X is the leaving
group and R the group migrating during rearrangement. The relation of
the pinacol rearrangement may be seen by a like formulation:
29)
H H
R
-6C
H
H ^
In order to understand the mechanism of this reaction, the effects of
solvent, and of changing Y" and X must be established. The stereo
chemistry about carbon-1, carbon-2 and R must also be known, as well as
the electrical effects within the molecule. These factors will be
considered at a later point in this discussion.
In the transformation of isoborneol to camphene, Wagner correctly
interpreted the course of the dehydration to involve the breaking of
the 1-6 carbon bond (equation 30) and the subsequent formation of a new
bond between the 2 and 6 positions. Such a transformation requires that
the 2-carbon position undergo a Walden inversion.(39)


16
Further light was thrown on the problem some years after Wagners
observations by Meerwein, who observed that ring expansion (40) or
51)
52)
ring expansion
methyl migration
ring contraction could occur during such dehydrations. (4l)
55)
CH5-CH-CH3
* +
25#
ch5
75#
Nametkin, in a series of papers in 1915, (42-44) reported his


17
observations of a reaction quite similar to that reported by Wagner.
For example, fenchyl alcohol, upon dehydration, was converted into
a-fenchane, with bond migration analogous to that observed by Wagner.
Demjanow, in the years 1902 to 1907; published a series of papers
describing the results of his studies upon deamination reactions
involving ring expansions. Thus cyclobutylmethylamine, when treated
with nitrous acid, was observed to produce, in addition to the expected
cyclobutylcarbinol, a considerable amount of the ring expansion
product, cyclopentylalcohol. (45) Cyclohexylmethylamine gave cyclo-
heptyl alcohol (46) and cyclopropylmethylamine gave a jnixture of cyclo
butyl alcohol and cyclopropylcarbinol (47) under similar conditions.
Of the other variations of the Wagner-Meerwein and pinacol trans
formations, the dehydrohalogenation reaction and the "semipinacol
deamination," have been most studied. The dehydrohalogenation reaction
may be illustrated by a transformation observed by Tiffeneau. (48) As
can be seen in equation 55; the reaction proceeds through the elimi
nation of the elements of hydrogen iodide and the migration of the


18
p-tolyl group.
OH
55) 4>--CH2I
The "semipinacol deamination" may be characterized by the reaction
of l,2-diphenyl-l-p-tolyl-2-aminoethanol when treated with nitrous
acid. McKenzie (49) treated the optically active amine with nitrous
acid and obtained two products, one of which (B) was optically active,
indicating that the reaction, in part at least, followed a stereo
specific course.
The mechanism of the pinacol rearrangement has been studied for
many years. Erlenmeyer (50) suggested a cyclopropane intermediate,
which required loss of a hydrogen atom from the migrating group. This
mechanism was shown not to be possible in the case of aryl migration,
by the work of Montagne, (51, 52) since loss of hydrogen from the
ortho-position in a group with a para-substituent would yield a meta
substituent as the result of the shift. It was found that the para-
substituent remained intact. In a more general way, Meerwein and
van Emster (55) were able to disprove the cyclopropane intermediate
idea in the Wagner-Meerwein rearrangement of isobornyl esters to


19
camphenea case in which Erlenmeyer's proposition appeared to have a
better chance of success. It was found that tricyclene, which is a
cyclopropane derivative corresponding to the presumed cyclopropane
intermediate for this reaction, could not be converted into camphene
under conditions which isoborneol yields camphene smoothly.
Breuer and Zincke in 1879 (30) proposed ethylene oxides as inter
mediates in the rearrangement. This mechanism has been disproved for
the most part by Tiffeneau (5^) and McKenzie (55) and their co-workers
who found, in the dehydration of glycols, deamination of 2-amino-
alcohols and dehydrohalogenation of 2-iodo-alcohols, that the oxide
could not be isolated from an incomplete reaction, and yet the oxide
was found to be sufficiently stable under the same conditions to have
permitted its recovery, had it been formed. Moreover, Lane and
Walters (56) observed that triphenylethylene oxide is easily convertible
to the glycol under mildly acidic conditions. Gebhart and Adams (57)
support this view but found that tetraphenylethylene glycol, in acetic
acid catalyzed by perchloric acid, underwent rearrangement to the oxide
to the extent of about 80This oxide, however, is not converted to
the glycol under conditions which readily cause formation of triphenyl
ethylene glycol from its oxide.
The free-radical hypothesis, as introduced by Tiffeneau (58) and
used by McKenzie in the 1920's, (25) was proposed prior to the accumu
lation of much knowledge as to the properties of free radicals. Subse
quently the theory has fallen into disuse, largely for two reasons.
The first is the absence of chain reaction and polymerization products


20
characteristic of free radical reactions; and the second, the appearance
of a much better theory due to Meerwein and van Emster in 1922.(53> 59)
Dependence upon ionization of the isobornyl chloride to camphene
hydrochloride rearrangement was the key to Meerwein and van Emsters
camphene- isobornyl
hydrochloride chloride
effort. This was strongly supported by these facts: l) the kinetic
rates depended upon the ionizing power of the solvent, 2) the relative
rate orders in a number of solvents were essentially the same as had
been found for the ionizing capacity of triphenylmethyl chloride,
3) the rate increased as the stability of the anion increased, and
k) compounds such as HgClg, SbCl^, SbCl^, FeCl^, and SnCl^, all known
to form additive compounds with the triphenylmethyl chloride, were
powerful catalysts for the rearrangement, whereas halides such as PClj
and SiCl^, which do not yield such additive compounds, had no catalytic
activity. This evidence leaves little doubt that the intermediate is
ionic.
From the foregoing discussion it can be seen that a large number
of the "1,2 shifts" which have been discovered are Wagner-Meerwein or
pinacol rearrangements. Since elucidation of the Wagner-Meerwein


21
rearrangement has met with considerable success in recent years, the
information obtained in these studies will be relied upon heavily in
gaining an insight into the mechanism of the pinacol rearrangement.(6o)
Recent studies of the Wagner-Meerwein rearrangement have been conducted
under conditions in which a specific type of ester interchange occurs.
Although the hydrolysis and solvolysis of the esters of carboxylic
acids generally involve the rupture of the acyl-oxygen bond, (6l, 62)
it has been shown by Cohen and Schneider that esters of the tertiary
alcohol may undergo acid-catalyzed scission of the alkyl-oxygen bond,
while the acyl-oxygen bond remains intact. Also Phillips (63) showed
that the £-toluenesulfonate ester of l-phenylpropanol-2 undergoes
acetolysis to produce acetate which has undergone Walden inversion.(39)
That both carbons 1 and 2 (equation 28) are normally inverted during
rearrangement, was shown by experiments such as the deamination of 1,1-
diphenyl-2-aminopropanol (equation 39). (6k, 65) Examples of similar
39)
behavior in the pinacol rearrangement may be seen in the rearrangement
of levo-l,l-dibenzyl-2-(l1-naphthyl) ethylene glycol to the optically-
active 1,k-diphenyl-3-(1'-naphthyl) butanone-2 (66) in dilute sulfuric


22
acid, (26) and in the formation of optically-active l,2-diphenyl-l,2-
epoxypropane from levo-1,2-diphenyl-l,2-propanediol. (64) In each of
these cases, however, the racemic ketones were obtained when concen
trated sulfuric acid was used as catalyst.
The migrating group itself retains its original configuration.
This has been shown in the case of aryl groups many times, since the
relative positions of substituents on the ring remains unchanged.
Moreover, Lane and Wallis (67) have shown that in the related Wolff
reaction a migrating group such as 2-phenylhexyl retains its original
configuration.
A stereochemical method of investigating the Wagner-Meerwein
reaction was proposed by Roberts and Kimball (68) and illustrated by
Winstein and Lucas (69) in the treatment of racemic erythro-3-bromo-
butanol-2 with hydrogen bromide. Because the product was the erythro
40)
DL
erythro
H*. Sf CH
HBr^
CH,^ 1 2^h
bromonium ion
erythro-meso

identical
5
erythro-meso


23
compound and not the threo racemate, the bromonium ion was postulated.
This ion could then suffer attack by bromide ion on the back side of
either of the two central carbon atoms to yield the erythro compound.
If the planar carbonium ion had been the intermediate, it would have
been expected that some of the threo racemate should be formed. In
like manner, the racemate of threo-3-bromobutanol-2 gave only the DL
dibromide.
Cram (70, 71) applied this principle to the acetolysis of the
tosylates of the isomeric 3-phenyl-2-butanols. Since the threo
D or L
threo


24
tosylate was not converted to any significant amount of the products of
42)
CH3-. f -H
>c
H r OTs^CHj
D or L
CH
QAc ^S|CH,
identical
erythro
the erythro tosylate and the erythro tosylate was not converted to the
products of the threo tosylate, Cram reasoned that rotation about the
two central atoms was restricted, and thus that classical, planar, open
carbonium ions could not be intermediates in these reactions. In order
to account for the results, Cram postulated the bridged phenonium ion
as the configuration-holding intermediate in the reaction sequence.
Similar bridged-type ions had been suggested on theoretical grounds by
Nevell, deSalas and Wilson (72) and others. (73-77)
The electrical effects of the groups within the reactant may
control the course of the reaction and determine which of two groups
will migrate (equations 4-3 and 44). (ll, 78) These effects may also
accelerate the reaction rate. Winstein, et al., (79) has shown that
the exo-p-bromobenzene sulfonate of norborneol undergoes acetolysis at


25
a rate 350 times greater than the rate at which the endo-isomer
acetolyzes. This fact, plus the fact that both exo- and endo-esters
norbornyl-
£-bromobenzene sulfonate
yielded, upon solvolysis, exclusively exo-products, seemed to indicate
that ion G could be an important intermediate in the solvolysis of the
exo-form, since carbon-6 is conveniently situated for participation in
the rate-determining loss of £-bromobenzenesulfonate ion. Such direct


26
participation does not appear possible in the case of the endo isomer,
although it is possible, of course, that ion G could be formed in this
instance subsequent to formation of ion H.
The most striking example of "Neighboring Group Participation," as
this phenomenon is known, is to be seen in the rate enhancement in the
acetolysis of a series of substituted ethanol tosylates. (8o) That the
Ethanol
tosylate Relative k
(ch5)2c-ch2ots
1
OgCHCHgOTs

(CH^g-CHgOTs
05CCH2OTs
53
460
7-7 x 10^
participation of an adjacent group may, at times, control the stereo
chemical course of a reaction is illustrated by the bridged ion
concept, discussed previously.
In an extension of his study of the acetolysis rates of the exo-
and endo-p-bromobenzenesulfonates of norborneol, Winstein (8l) observed
that the optically active exo-ester exhibited a racemization rate which
was faster than the acetolysis rate. This phenomenon was later found
to occur also in the solvolysis of 3-phenyl-2-butyl--toluenesulfonate
(82, 83) and of 2-phenyl-l-propyl--bromobenzenesulfonate. (84, 85)
This phenomenon is called "internal return" and can be illustrated with
the acetolysis 3-phenyl-2-butyl--toluenesulfonate. The ion pair (K),


27
postulated to explain internal return in this system can collapse
reversibly to give the D or L tosylate, or irreversibly tp give ion-
pair (G). If then, internal return is faster than the rate of for
mation of ion-pair (G) and subsequent irreversible collapse to D or L
acetate, then the racemization rate will be greater than the solvolysis
rate.
When 2-phenyl-2-(|>-tolyl)ethylamine is deaminated, the product is


28
found to consist primarily of two carbinols, l-phenyl-2-(j>-tolyl)-
ethanol and 2-phenyl-l-(£-tolyl)ethanol; (86) the former, due to
£-tolyl migration, is present in larger amount. In this case the ratio
of the yields of products is a ratio of the relative abilities of the
two groups to migrate during the rearrangement. Such ratios are termed
variously, "migratory abilities," "migratory tendencies," or "migratory
aptitudes," and imply a ratio of the ability for the group under dis
cussion to migrate, compared to the ability of some reference group to
migrate, given the same environment, the phenyl group being most often
used as the reference group.
An enormous amount of work has been performed in attempts to place
the more commonly observed migrating groups into some relative order,
and to assign some approximate value for the migratory aptitude of
each. Such a compilation would have the obvious utility of allowing
some prediction to be made regarding the relative yields of products,
when several may be anticipated. Among the early investigations
carried out with this object in mind, was that of P. J. Montagne, who
reviewed the work to 1920 that had been performed in the field of
intramolecular migrations. (87) Working with the symmetrical pinacols
of the type RC(0H)C(0H)R, Montagne found the ratio of ketone formed
by phenyl migration to that with R migration, to be, when R was
£-chlorophenyl, 60:k0; when R was £-bromophenyl, 57:^5*
That some progress has been made in this direction can be illus
trated, for example, in the controversy which occurred subsequent to
the publication of the results for the deamination of 2-phenyl-2-


29
(jg-tolyl)ethylamine. (88, 89) It was soon pointed out by Curtin (10)
that the £-tolyl/phenyl migration ratio of approximately 0-9 reported
was probably incorrect. A re-examination of the course of the reaction
(86) showed that this was the case and that the £-tolyl/phenyl
migration ratio was greater than one. This was a result predictable on
the basis of values found previously, for example, for the symmetrical
pinacols, l6; (5, 4) for the acetolysis of 2-phenyl-2-(p-tolyl)ethyl
tosylate, 2.5; (5) for the dehydration of 2-phenyl-2-(£-tolylethanol,
2.0; (6) for the Schmidt reaction, 3.4 to 50; (7-9) for the deami
nation of 2-amino-l-phenyl-l-£-tolylethanol, 1-3- (10)
Assignment of relative migratory aptitudes of a number of migrat
ing groups may be compiled. When steric requirements are not determin
ing, this order always holds for rearrangements other than the pinacol
and aldehyde-ketone. (4, 16, 90)
Evidence for the relegation of the electronic nature of the
migrating group to a position of secondary importance in certain
reactions, has been presented by Curtin and his co-workers, for
reactions involving the deamination of the triarylethanolamines.
(10, 91-95)
In studies (10, 96-99) f the rearrangement during deamination of
aminoalcohols of the type,


30
0
ketones of the type frt-CHgAr were found to be formed. The ratios of
products were qualitatively in the order of the migratory aptitudes for
these groups as found by Bachmann, Moser and Ferguson (k, l6) in their
studies of the tetra-substituted, symmetrical ethylene glycols.
When, however, Curtin deaminated the diasteromers of the amino-
alcohols of the type,
OH NH2
-0 0-
r H
(there are now two asymetric centershence two dl pairs), it was found
that the migratory aptitudes for the groups in different diastereomeric
pairs were not the same. Thus, the erythro pair rearranged to give the
ketone with Ar migration, while the threo pair gave the ketone formed
by phenyl migration. That the electronic nature of the migrating group
was of secondary importance was indicated by the observation that the
aryl group, in the erythro pair always migrated whether it was £-tolyl,
£-anisyl, £-chlorophenyl or a-naphthyl. (100, 101) The threo pair in
all cases gave phenyl migration. Curtin accounts for these obser
vations by suggesting that there is a back-side attack by the migrating
group upon the carbon atom from which the amino group is being removed


31
through a transition state or bridged ion in which the large, bulky,
non-migrating groups are in a trans-configuration.
In a series of papers beginning in 1953> Collins and Bonner, (102,
103) in a study of the Wagner-Meerwein Reaction for the 1,2,2-tri-
phenylethyl system, showed that the bridged phenonium ion could not be
the intermediate in the transformations observed. The data required
the postulation of open-equilibrating carbonium ions, or their equiva
lent, to explain the distribution of the carbon-14 labels that was
observed.
The observations which forced this conclusion may be summarized in
this way:
1) Formic acid, to which a catalytic amount of £-toluenesulfonic
acid had been added, caused statistical distribution in both the
discretely chain- and ring-labeled 1,2,2-triphenylethanol and its
acetate (the bridged ion requires 50:50 distribution of the carbon-14-
in the ring-labeled compounds, whereas statistical, 2/3-l/3 distri
bution was observed).
2) Carbon-14 distribution in the -toluenesulfonate esters of the
alcohol, which was not statistical in either the chain- or ring-labeled
compounds, could be exactly calculated, one from the other, by means of
the rate expressions in a mechanism involving competition between the
initial ion formed and its direct conversion to product on the one hand,
and its equilibration, with subsequent conversion to product on the
other


32
3) Examination of the rates of chain- and ring-label equilibration
and the rate of labeled acetoxyl loss from the 1,2,2-triphenylethyl
acetate, proved that in each instance of acetoxyl loss, a molar
equilvalent amount of chain- and ring-label equilibration occurred.
These observations indicate, a) that no internal return (7^, 8l) occurs
since this would require a slower rate for acetoxyl loss than for
chain- and ring-label equilibration; b) that bridged ions cannot be
intermediates since this would require that the rate of chain-label
equilibration be faster than the rate of ring equilibration; and c) that
completely concerted migration of the phenyl group is excluded since
this would require that the rate of loss of acetoxyl be half the
equilibration rate of the chain-labeled acetate and the rate of equili
bration of the ring-labeled acetate be 3/2 the rate of acetoxyl
exchange, whereas the three rates observed are the same.
As has already been noted, the conversion of substituted acet
aldehydes into ketones through the agency of dilute acids at elevated
temperatures or by means of concentrated mineral acids, has been taken
as evidence of the relationship of this rearrangement to that of the
pinacol rearrangement. The nature of the relationship, however, has
been quite obscure in view of the migratory aptitudes exhibited by the
substituent groups in the related rearrangements, discussed earlier in
this presentation. Some of the anomalous observations may be illus
trated with the following examples:


33
Equation No. 19
20
22
24
25
26
Me
O^Me
4> ^p-Tol
/Et 4/1
Et exclusively
Et ^ £-anisyl
For additional examples of the apparently quite general phenomenon, see
references 23, 24, 32 and 104 through 107*
In an effort to obtain sufficient information to allow correlation
between the pinacol and aldehyde-ketone rearrangements, Collins (2) has
investigated the rearrangements of triphenylethylene glycol and tri-
phenylacetaldehyde, variously labeled with C^. Using the general
mechanism formulated by previous investigators (33> 49, 97, 108, 109)
and applying the idea of open carbonium ions, Collins was led to
propose a mechanism involving 4 reaction paths, which included the
conjugate acid of triphenylacetaldehyde and which adequately explained
the distribution of the C1^ label which was observed. In an extension
of this work, Benjamin and Collins (l) were able to link the pinacol
rearrangements of 1,l-diphenyl-2-j>-tolylethylene glycol, 1,2-diphenyl-
l-£-tolylethylene glycol and the aldehyde-ketone rearrangement of
diphenyl-£-tolylacetaldehyde through the conjugate acid of the aldehyde.
These authors were able to show that the true £-tolyl/phenyl migration
ratio was not given by the ratio of ketonic products (these indicate
phenyl migration in preference to g-tolyl), but rather was given by the


ratio of the specific rate constants as defined in the equation
*T *H *Tol me
kp k, k'R
The significance of this relation is developed in the Discussion
Section of this presentation where these ideas are applied in an
identical manner in the explanation of the results obtained in this
1 +
H
^ol
1+ 3
research.


METHODS AND RESULTS
The syntheses of the carbon-l4 labeled compounds were accomplished
as shown in Charts III, IV, V, and VI. The nonradioactive ketones IV
and V were prepared by adding the diarylcadmium reagent to the
appropriate diarylacetyl chloride; the aldehyde, III, was formed upon
stirring threo-Ic in 90$ formic acid for three days. Each of the
glycols used in this research was subjected to cleavage with lead
tetraacetate and the fragments were examined for radioactivity, in
order to prove the position of the carbon-14 label. All were found to
be discretely labeled in the positions indicated except for erythro-Ib,
which contained 8.1$ of the label in the tertiary carbon. Appropriate
corrections have been made in the tables for this small but significant
percent of carbon-l^ in the number 1 chain position of erythro-Ib.
The aldehyde, III, and the glycols, erythro-Ib, threo-Ib, threo-Ic
and Ila, were subjected to rearrangement in concentrated sulfuric acid
o
at 0 C. Glycols Ic and Ila also were subjected to rearrangement in
formic acid at room temperature. The yields of IV and V, and in the
case of the formic acid rearrangements, III, were determined by the
radioactivity dilution method. The results of these experiments are
given in Tables II and III. The crystalline ketones obtained as a
result of the sulfuric acid rearrangements were cleaved with alkali;
* ft* *
-(j!H-CTol > 4>-CH2-Tol + TolCOOH
Tol
IVab Vb
55


36
CHART III
Preparation of threo-l,2-di-p-tolyl
(2-p-methyl-C1^)-l-phenylethylene Glycol (Ic)
* *
C02 > PhCOOH
PhCHpOH ^Vch*
HC1 W J
AcpO v
AlClj
Cl2
OH
* ?H/P
TolQ-C-OH
H
Hp 8
£_> TolCHpC-OH
Pd-C
1) pci<^
* s
TolCH2C-Ph
AlClj
* H?h
Tolf-C-Tol
OH OH
threo-Ic
CHART IV
Preparation of threo-l,2-di-p-tolyl-l-
phenylethylene-2-C1^ Glycol (lb)
* LlAlHk SOClp *
CHj-fVCQOH % TolCHpOH -%TolCHgCl
KCN
*
> TolCH2C=K
TolCrfgCOOH
continue as per Chart III ^
threo-lb


37
CHART V
Preparation of erythro-l,2-di-p-tolyl-l-
phenylethylene-2-C^ Glycol (lb)
ch2c-oh
* Q Br9
i n > TolCH0C-Tol
1) PC13 2 CST^
2) CH,-^
AlCl-j
0H ) T0I9 8-Tol
2) H+ OH
PhMgBr
CHj
erythro-Ib
CHART VI
Preparation of l,l-di-p-tolyl-2-
ik
phenylethylene-l-C Glycol (lia)
PhCHO
1)KCN* v
2)HC1 *
OH*
Phi-COOH
H
MeOH 9H 8 2TolMgBr
MeUV. PhCC-OMe 1
h2so4 h
1*
5 OH OH
II a


38
TABLE II
Yields of Ketones IV and V Produced by the
Action of Sulfuric Acid Upon I, II, and III
Run Ho.
Reactant
Yield of Ketone ($)
IV V
1
threo-Ib
58.0
42.0
2
threo-Ic
59-6
4o.4
3
threo-Ic
58.3
41.7a
4'
threo-Ic
58.4
41.6
5
threo-Ic
57-3
42.7
Average
58.3
41.7
6
I la
49.6
50.4a
7
I la
47.1
52.9
8
Ila
48.0
52. ob
Average
47.6
52.4
9
III
53-5
46.5
10
III
53-2
46.8
Average
53.4
46.6
11
erythro-Ib
53.4
46.6
aReactions performed at 10 C. Results not included in averages.
IV determined by" dilution technique, total ketone by veight and
V by difference.


39
*9 *
(Tol) -CH-C-0 (Tol)2-CH2 + Vab VIb
*
y i-CHg-Tol +
*
TolCOOH .
IVcd
Vc
The benzoic and £-toluic acid fractions obtained upon cleavage were in
all cases carefully purified by crystallization and sublimation.
TABLE III
Yield of Aldehyde III, Produced by the
Action of Formic Acid Upon Glycols I and II
Run No.
Reactant
Actual Yield (#)
III
Yield of III
Corrected for
94.1$ Recovery
12
threo-Ic
75-9
8O.6
13
Ila
33-9
36.0
14
III
94.1


4o
The neutral, diarylmethane fractions from the cleavages of IVab
and Vab were oxidized with chromic acid:
-CH2-Tol
CrO,
HQAc
ft*
-C-0-COOH
Vila
Tol-CH2-Tol
CrO,
HQAc
L
HOOC--C 0-COOH
Villa
The acidic products Vila and Villa were purified carefully by crystal
lization, The acid degradation products V, VI, VII, and VIII were
assayed for carbon-14 content, the results of these being recorded in
Tables IV and V.
TABLE IV
Fraction of Radioactivity Found in Vc from Cleavage
of IVcd Derived From the Rearrangement of threo-Ic
Run No.
Activity in Vc
2
0.478
2
0.476
3
0.485
4
0.492
5
0.512
5
0.496
Average
0.490


hi
TABLE V
Fraction of Radioactivity in Fragments From Cleavage
of IVab and Vab Resulting from Rearrangements
of Threo-Ib, Erythro-Ib, and Ila
From IVab From Vab
Run No.
Reactant
Vb
Vila
VIb
Villa
1
threo-Ib
0.961
0.039
0.975
0.026
9
Ila
0.018
0.980
0.008
0.955
10
Ila
0.010
-
0.009
-
11
erythro-Ib
-
0.010
-
0.139
16
threo-Ib
O.98O
0.021
O.986
0.014


DISCUSSION
The equation (equation l) given in the Introduction was developed
(l) in an effort to correlate the observed fates of the various
carbon-14 labels during the acid-catalyzed rearrangements of several
triarylsubstituted ethylene glycols and acetaldehydes. The reasons for
extending the investigation to the compounds treated in this research
have been discussed in the Introduction and are concerned with a deter
mination of the generality of equation 1 when applied to closely-
related systems. Accordingly, Charts I and II represent the rearrange
ment mechanism for compounds I, II and III as postulated by Benjamin
and Collins for the system of compounds they studied, (l) Similar
symbols for the various specific rate constants have been used so that
equation 1 retains its original form. The derivation of equation 1, as
applied to this research, is to be found in the Experimental Section.
No steady state assumption (110) is necessary in the derivation.
It should be pointed out that equation 1 is applicable only to
that portion of the pinacol rearrangement which proceeds through
tertiary hydroxyl removal (paths C through E), and the aldehyde-ketone
rearrangement.
The determination of the components for equation 1 may be deduced
from an examination of Charts I and II. For the ratio, ^oiA'g, the
sum of the yields by paths D and E is divided by the yield of path C.
If we now define n^, m^, mc, m, and me, respectively, as the mole
frations of threo- and erythro-Ic which proceed to products through


paths A to E (Chart I), ^oiA'h then is e1ual + me/mc In like
manner, the ratio kg/k^ is obtained by the relation me, + mdtAf
(Chart II). The ratio me/md may be obtained in two ways: 1) From the
double-labeling results in the rearrangement of threo-I, the total
*
mc + me is determined by the yield of TolCOOH from threo-Ib, while the
total m + l/2me is determined from the yield of TolCOOH from threo-Ic.
Solution of the simultaneous equations can give the value for m0.
Since the yield of V gives the total 1% + m, then subtraction of the
*
yield of n^, as determined by the activity in 0=C(C00H)2> gives md;
2) The ratio of the yields IV/V from the rearrangement of aldehyde III,
also gives nig/m^. Both methods should give the same ratio within the
experimental error, if the mechanism of Chart I is to explain the
observed carbon-14 distribution during rearrangement. In order to
obtain the £-tolyl/phenyl migration ratio upon solution of equation 1,
it is necessary to divide kp/kp by 2, since the rearranging system
under study involves two £-tolyl groups and only one phenyl group.
The implications of the pertinent data of the preceding section
may now be considered. Tables II through V reveal the yield of each
ketone produced from the different reactants, as well as the fates of
the various carbon-14 labels. The mechanism given in Charts I and II
accounts for these facts. The consequences of both £-tolyl and of
chain labeling are indicated.
For the threo-I glycol may now be calculated the contributions of
each of the reaction paths. There are several different methods, some
of which are nearly independent one of the other, by which these


calculations may "be made. Since it is the purpose of this research to
determine, by use of equation 1 (see Introduction), whether, in the
rearrangements of I, II, and III the p-tolyl/phenyl migration ratio is
greater than one, we have, for this purpose, treated the data of Tables
II through V in two different ways: l) in the first method the
yields of IV and V from the rearrangement of di-g-tolylphenylacet-
aldehyde (ill) have been ignored, and the averages of the measurements
pertaining to the three glycols have been employed to calculate the
various path yields; 2) in the second method the same data were used as
in the first. We have taken account, however, of the errors probable
in each of the measurements of Tables II through V, and have made the
assumption that all of the errors accumulate in mc, since the determi
nation of a maximum value for mc is crucial in estimating, from
equation 1, a minimum £-tolyl/phenyl migration ratio.*
The results of the foregoing calculations are given in Table VI,
and the values for kg/k^, k^Q^/k'g and the £-tolyl/phenyl migration
ratio (krp/2kp) estimated from each set of calculations are given in
Table VII. Actual sample calculations of the type used in obtaining
the results in the tables are given in the Experimental Section.
It is interesting to observe that the threo- and erythro- configu
rational isomers of I rearrange to give slightly different yields of IV
There is another general method by which the path yields and rate-
constant ratios may be calculated, namely through the use of the ratio
(1.15) of ketones IV:V produced from the rearrangement of aldehyde III
(Table II). This method is much inferior to methods 1 and 2 for it
involves subtraction of large numbers in determining the very small
and is thus extremely sensitive to small changes in the percentages of
ketones produced. This is not true for methods 1 and 2.


TABLE VI
1+5
Summary of Mole-Fraction Calculations From
the Data of Tables II Through V
Mole
Fraction
threo-I
Method of Calculation
1
erythro-I threo-I
2
erythro-I
%
0.008
0.065
0.011
O.O65
b
0.018
0.005
0.023
0.005
mc
0.005
(-) value
0.046
0.020
md
0.1+09
0.1+01
0.4o6
0.401
e
O.560
0.541
0.514
0.509
For Glycol II
m_p
0.177
0.169
ffl,d
0.347
0.355
m'
e
0.476
0.476


46
TABLE VII
Summary of the Ratios Calculated for use in or by Equation 1
Ratio
Method
1
of Calculation
2
me/md
1.37
1.27
k0)/kH
4.7
4-9
km ,/k'TT from threo-I
190
20
k,p/2kp from threo-I
25
2.25
km ,/k' from erythro-I
Tol H -
00
45
k,p/2kp from erythro-I
00
5
and V. That this result is due mostly, if not entirely, to different
contributions of paths A and B in the two cases may be demonstrated by
comparing the ratios of (mc + me)/m, for the rearrangements of three-
and erythro-Ib, in which the total (mc + m0), is determined by the
yield of TolCOOH (Vb) in each case. From the threo isomer this is
0566/0o408 = 1.385* whereas for the erythro isomer it is 0.529/0.401 =
1.32. These ratios are the same within experimental error. Additional
support for this explanation is the reversal in relative contributions
of paths A and B in the threo and erythro isomers. These values are
sufficiently large to preclude their reversal by experimental error


alone. It then is apparent that the aryl group added by means of the
Grignard reagent to the appropriate benzoin is not the predominantly
migrating group when the rearrangement proceeds through secondary
hydroxyl removal, i.e., insofar as the reaction proceeds through paths
A and B, it is stereospecific. (91-95) Benjamin and Collins (l) were
not able to observe this phenomenon because with the isomers of 1,2-di-
phenyl-l-^-tolylethylene glycol, there was too little secondary
hydroxyl removal to allow them to differentiate paths A and B.
Examination of the p-tolyl/phenyl migration ratios listed in Table
VII makes it clear that an exact value for the ratio cannot be given
for the reactions under study. The significant point is, however, that
when even extreme values, deliberately chosen, are used as the com
ponents of equation 1, the minimum value for the £-tolyl/phenyl
migration ratio is found to be greater than one, and the most probable
value, based upon average values for the components is in the range of
three to five.
Additional support for a somewhat higher value for kp0i/k'jj, than
the minimum of 20, is found in the rearrangement of tri-£-tolylethylene
glycol, (ill) where it is found, if the assumption is made that the
contribution to the product through secondary hydroxyl removal is of
the same order of magnitude as found for the erythro-Ib above, that the
kp0-^/k'jj must be at least 25* Moreover in the rearrangements of
threo-Ic and Ila in formic acid, when the ^toiA'a and k$Ag values are
treated in the same way as previously reported, (l) it is found that
kroiA'n in concentrated sulfuric acid is 57*5*


48
In view of the experimental errors that have been discussed, the
values for the ratios and the yields of ketones produced in both
sulfuric and formic acids agree with those predicted in the Intro
duction better than expected. In addition, even though the simple
ratio of ketones obtained from aldehyde III indicates the p-tolyl/
phenyl migration ratio to be less than one, solution of equation 1 for
this system shows that the most probable value is significantly
greater than one, in agreement with previous observations. (3-10) It
is important also to note that the variations in the relative amounts
of ketones from the glycols and aldehyde are successfully predicted by
equation 1. The results of this research, therefore, provide strong
evidence in support of the mechanism for the pinacol rearrangement
proposed by Benjamin and Collins, (l) and in addition provide a
possible explanation for the occasionally observed, partially stereo
specific course of the rearrangement. (26, 49, 100, 101, 66)


EXPERIMENTAL
Radioactivity Determinations and the Radioactivity Dilution Method of
Yield Determinations.
The radioactivity assays reported in this dissertation -were per
formed 'on a vibrating reed electrometer, using the wet combustion
procedure which was described by Neville (112) and modified by Bonner
and Collins. (113) This method has also been described by Raaen and
Ropp. (ll4)
The calculation of the yields of the reaction products by the
carbon-14 dilution method was performed by means of the equation:
Al (l + X) = A0X: where
Aq = molar activity of the starting material = molar activity of
undiluted product for which calculation is to be made.
A.^ = measured molar activity of purified, diluted product.
= weight of nonradioactive analog added.
X = weight of radioactive product with molar radioactivity equal
to Aq.
This technique was discussed by Mayor and Collins. (115) The mechanics
of the actual dilutions were performed in the manner described in the
section next below.
Sulfuric Acid Catalyzed Rearrangements.
In a typical experiment 3.082 gm. of glycol or aldehyde was added
to 70 ml. of concentrated sulfuric acid, previously cooled to 0 C. in
an ice-salt bath. Stirring was continued while the temperature was
49


50
maintained between -2 to 0 C. At the end of 30 minutes, the reaction
mixture was poured into TOO ml. of ice-water mixture with vigorous
stirring. The mixture was extracted five times with 100 ml. portions of
ether in a separatory funnel and the combined ether extracts were
washed twice with 100 ml. portions of water, once with 50 ml. of satu
rated aqueous sodium bicarbonate and again with 100 ml. of water. The
ether solution was then evaporated to dryness on the steam bath, the
residue dissolved in chloroform, transferred quantitatively to a 100
ml. volumetric flask and dilution to 100 ml. made with chloroform. One
50 ml. aliquot was transferred to a flask containing 2.000 gm. of
nonradioactive ketone IV and the remaining 50 ml. aliquot was trans
ferred to a flask containing 2.000 gm. of nonradioactive ketone V. The
contents of each flask were stirred until complete solution was
effected, and the solvent was removed in an air stream on the steam
bath. The residue in each case was dissolved in 95$ ethanol, treated
with Norit and filtered through a talc pad. On seeding the solutions
with the appropriate ketones and cooling with an ice bath, the ketones
crystallized. After crystallizing each sample five times from ethanol,
50 mg. of the nonradioactive ketone corresponding to the contaminating
ketone was added and each sample was again crystallized five times from
ethanol. Melting points of ketone V were always 56.5-575> while
those of ketone IV were in the range 65-67 and were considered to be
sufficiently pure for C-lk assay. See Table VIII.
Formic Acid Rearrangements.
In a typical experiment, 2.000 gm. of the glycol was stirred with


TABLE VIII
SUMMARY OF YIELD DETERMINATION EXPERIMENTS FOR HgSO^ REARRANGEMENTS
Run Start ing8.
Wt. of
Starting
Ketone
Yield
Aliquot
Theory of
Ketone in
Wt. of IV
Added to
Assay of
Recovered
Wt. of V
Added to
Assay of
Recovered
No. Compound
Compound
Theory
Taken
Aliquot
Aliquot
IV
Aliquot
V
1
Threo-Ib
3.0815
2.908
1/2
1.454
2.000
0.5995
2.000
0.4705
2
Threo-Ic
10.610
10.000
i/4
2.500
2.500
1.758
2.500
1.279
3
Threo-Ic
1.049
0.988
1/2
0.495
1.000
0-937
1.000
O.669
4
Threo-Ic
2.000
1.885
1/2
0.943
2.000
1.069
2.000
O.766
5
Threo-Ic
5-225
4.930
l/lO
0.493
1.450
0.786
0-955
0.8313
6
Ila
1.059
1.000
1/2
0.500
1.000
0.3915
1.000
0.3975
7
Ila
5-100
4.811
1/2
2.405
2.500
0.6523
2.500
0.7077
8
Ila
I.O606
1.000
1
1.000
1.500
0.5055
See Table
II
9
III
2.0592
2.0592
1/2
1.0296
2.000
0.954
2.000
0.807
10
III
3-090
3.090
2/5
1.236
2.000
1.2185
2.000
1.050
11
Erythro-Ib
4.6586
4.420
1/2
2.210
3-000
0.4793
3.000
0.4505
aMolar activities in millicuries per mole of starting compounds: Threo-Ib, 2.124;
Threo-Ic, 5-221; Ila, 2.155; III, 5-221; Erythro-Ib, 2.112.
TABLE IX
SUMMARY OF YIELD DETERMINATION EXPERIMENTS FOR FORMIC ACID REARRANGEMENTS
Run
No.
Starting
Compound
Wt. of
Starting
Material
Ketone-
Aldehyde
Yield
Thpnry
Aliquot
Taken
Theory of
Aid. and
Ketone in
A1iqunt
Wt. of III
Added to
Aliqunt
Assay
of 2,4-
DNPH
Actual
Yield of
Cald Yield of III
on 94.1#
Recovery Basis
12
Threo-Ic
2.000
1.886
l/lO
0.1886
0.150
2-553
75-9
80.6
13
Ila
2.000
1.886
i/5
0.3772
0.200
0.839
33-9
36.0
14
III
1.000
1.000
0.200
0.200
2.531
94.1
- "


52
100 ml. of 90# formic acid for three days. The mixture was then poured
into 500 ml. of water and extracted five times with chloroform. The
combined chloroform extracts were washed twice with water, once with
saturated aqueous sodium bicarbonate and again with water. The chloro
form solution, after concentration on the steam bath, was transferred
quantatively to a 200 ml. volumetric flask. A 20 ml. aliquot was taken
and added to 150 mg. of nonradioactive aldehyde, III, stirred until the
solution was homogeneous, and evaporated to dryness. The residue was
dissolved in 95# ethanol, treated with Norit and filtered through a
talc pad. The ethanolic solution was then treated while boiling, with
a mixture consisting of 300 mg. of 2,4-dinitrophenylhydrazine, 2 ml. of
concentrated sulfuric acid, and sufficient water to make a clear
solution. The mixture was boiled for 15 minutes (during which time the
oily globules which first separate, solidify), then cooled in an ice
bath and the product removed by filtration. The product was purified
by crystallization from 95# ethanol (large volume, ca. 300 ml.
required). The product had a melting point of 190 and was bright
yellow in color. See Table IX.
Aldehyde Stability in Formic Acid.
In order to determine the recovery of the aldehyde under the
reaction conditions, the foregoing procedure was repeated with puri
fied, radioactive III. At the end of the three-day reaction time, the
formic acid-aldehyde mixture was cooled in ice and the crystalline
aldehyde was removed by filtration, to yield 93# of the aldehyde,
m. p. 93-4 The mother liquor (formic acid) was poured into 500 ml.


53
of water, extracted with chloroform as in the above procedure, and
the aldehyde, obtained by filtration, was added to the chloroform
extract. The extract was transferred to a volumetric flask and the
yield was determined by the radioactivity dilution method. In this way
the yield was determined to be 94. 1$ (Table IX).
Ketone Cleavage for Carbon-14 Distribution.
In a typical experiment 0.5 gm. of the ketone was heated under
reflux in an atmosphere of nitrogen with 30 ml. of 2% methanolic
potassium hydroxide for 24 hours, (l) The methanol was removed by
distillation under nitrogen and the residue was dissolved in 200 ml. of
water. The aqueous solution was extracted five times with ether and
acidified. The liberated acid was then extracted with ether and the
solvent was removed by distillation. The acid was purified by crystal
lization from water, followed by sublimation.
The ether extract, containing the diaryImethane fragment, was
evaporated to dryness and the residue was heated under reflux with a
mixture of 20 ml. of glacial acetic acid, 2.0 gm. of chromium trioxide
in 2 ml. of water, and 3 ml. of concentrated sulfuric acid. After 45
minutes, the reaction mixture was poured into 100 ml. of ice water and
the precipitated acid was filtered from the mixture, washed with water
and dissolved in aqueous sodium bicarbonate. The aqueous solution was
treated with Norit, filtered through a talc pad and acidified to
recover the acid. When the acid was 4,4'-dicarboxybenzophenone the
product was crystallized from boiling glacial acetic acid; when
£-benzoyl benzoic acid, purification was accomplished either by


5^
sublimation of the acid or conversion to the methyl ester by means of
diazomethane and subsequent crystallization from methanol. See Table X.
Ketone Stability in Concentrated Sulfuric Acid.
In separate experiments, 1.000 gm. of each of the product ketones
was stirred with 20 ml. of concentrated sulfuric acid while the temper-
o
ature was maintained at 4 C. After 50 minutes the mixture was poured
into ice water and extracted in a manner identical with that employed in
t
the glycol and aldehyde rearrangements. In the case of 4,4-dimethyl-
benzhydrylphenyl ketone (V), the recovery of ketone with m. p. 58 C.,
was 9Q.&¡o, and in the case of 4-methylbenzhydryl-£-tolyl ketone (IV),
the recovery of ketone with m. p. 68 C. was 99*1- The fluorescent
green coloration and ether insoluble material which was always observed
in the sulfuric acid rearrangements, was entirely absent in the ketone
stability tests.
p-Methylbenzhydryl p-Tolyl Ketone (IV).
a) Phenyl-p-Tolylcarbinol.
An ether solution of 100 gm. of phenyl-j>-tolyl ketone was treated
with 14 gm. of lithium aluminum hydride in dry ether in the usual
manner. After hydrolysis with water and dilute hydrochloric acid, the
ether layer was separated and the aqueous layer was extracted twice
with ether. The combined ether extracts were washed with water and
dried over anhydrous sodium sulfate, then evaporated to dryness. There
resulted 97*1 gm. of the desired carbinol; m. p. 54. (ll6)
b) Phenyl-p-Tolylmethyl Chloride.
A hexane solution of 97-1 gm. of the carbinol was treated with


TABLE X
SUMMARY OF RADIOACTIVITY DISTRIBUTION DETERMINATIONS
Fragments
from IV
Fragments
from V
Assay of
Assay of
Run
No.a V
VII
VI
VIII
IV Used
V Used
Remarks
1
0.5727
0.0255
0.4695
0.0125
0.5995
0.4705
ma and computed from VII
and VIII.
2
0.7918
-
-
-
1.758
-
2
0.4749
-
-
-
1.059
-
3
0.4256
-
-
-
0.937
-
4
0.4959
-
-
-
1.069
-
5
0.3785
-
-
-
O.7865
**
5
2.575
-
-
-
5-221
-
6
0.007
-
0.005
-
0.5915
0.3975
7
0.007
-
O.OO65
-
0.6525
0.7077
9
0.4507
-
-
-
0.954
-
10
0.5955
-
-
-
1.2185
-
Correct for 8.1# scramble
11
-
0.0451
-
0.0997
0.4793
0.4505
for Table V.
15
2.640
-
-
-
5-221
-
From rearrangement of III.
16
2.094
0.0456
2.045
0.0289
2.124
2.124
From rearrangement of
threo-Ia.
^un numbers correspond to those used in Table VIII.


56
80 ml. of thionyl chloride dissolved in 200 ml. of hexane. After the
initial vigorous reaction has subsided, the mixture was heated on the
steam hath under reflux for l-l/2 hours. After the reaction was
complete, the hexane and excess thionyl chloride were removed under
reduced pressure and the product was distilled, to yield 104 gm. (98$)
of water-white oil; b. p. 158-163 /l mm. (116)
c) Phenyl-p-Tolylacetonitrile.
A mixture of 104 gm. of phenyl |>-tolylmethyl chloride and 50 gm.
of cuprous cyanide were placed in a round-bottomed flask and a short
air condenser was attached. The flask was immersed in a Wood's metal
bath and heated to 215 After 4 hours the flask was removed, cooled
and the contents extracted with acetone. The acetone solution was
allowed to stand overnight and filtered through a Celite pad. The
acetone was removed by distillation and the product was distilled under
reduced pressure. There was obtained 85 gm. (85-5$) of the nitrile.
On crystallization from hexane the product separated as white crystals;
m. p. 61-62. (117)
d) Phenyl-p-Tolylacetic Acid.
A mixture of 85 gm. of the nitrile, 600 ml. of 50$ aqueous
sulfuric acid and 200 ml. of glacial acetic acid was refluxed overnight.
The reaction mixture was cooled, poured into one 1. of ice-water
mixture and stirred until the acid solidified. The product was
filtered and washed with water. The solid was digested with saturated
sodium bicarbonate solution on the steam bath for 50 minutes, treated
with Norit and filtered. On acidification there was obtained 84.5 gm.


57
(91-5$) of the acid; m. p. II6-II6.50. (107)
e) Phenyl-p-Tolylacetyl Chloride.
To a solution of 84 gm. of phenyl £-tolylacetic acid in 100 ml. of
benzene was added 5^ ml. of thionyl chloride. After the addition was
completed, the solution was allowed to reflux on the steam bath for 1
hour. The benzene and excess thionyl chloride was removed by distil
lation under reduced pressure. An additional 50 ml. of benzene was
added and distilled to remove the last traces of thionyl chloride.
The residue was then dissolved in 100 ml. of dry benzene and used
directly for the following preparation. (102a)
f) p-Methylbenzhydryl p-Tolyl Ketone (IV).
£-Tolyl magnesium bromide was prepared from 151 gm. of g-bromo-
toluene and 21.5 gm. of magnesium turnings. The ether solution was
cooled and then treated with 85 gm. of anhydrous cadmium chloride,
while being stirred vigorously. After the cadmium chloride had been
added, the reaction mixture was heated under reflux for 1 hour. Most
of the ether was removed by distillation, 600 ml. of dry benzene was
added and the distillation continued until the distillate temperature
reached 65. Dry benzene (150 ml.) was added and the reaction mixture
cooled with ice water. While the mixture was being stirred vigorously,
the acid chloride solution, as described above, was added slowly.
After the acid chloride solution had been added, the reaction mixture
was stirred for 1 hour at room temperature, then 50 minutes under
gentle reflux. The reaction mixture was decomposed with ice, followed
by addition of sufficient concentrated hydrochloric acid to dissolve


58
the metal salts, and the benzene layer was separated. The aqueous
layer was extracted twice with an ether-benzene mixture (2:1). The
combined extracts were washed with water, 5$ aqueous sodium hydroxide
and again with water, dried with anhydrous sodium sulfate and the
solvents distilled. The brown, oily residue was steam distilled to
remove di-£-tolyl, and the dried oil was distilled under reduced
pressure. The fraction boiling 215-240 at 0.5 mm was collected,
dissolved in hexane and allowed to crystallize. There was obtained
53.6 gm. (48$) of the ketone; m. p. 67.5-68.5-
Anal. Calc'd for C22H200; C, 88.00; H, 6.71; Found: C, 88.09,
88.01; H, 6.69, 6.80.
The oxime was prepared by treating 1 gm. of the ketone in 5 ml. of
pyridine and 5 ml. of 95$ ethanol with 1.4 gm. of hydroxylamine hydro
chloride. The mixture was heated under reflux for 4-l/2 hours and the
alcohol and pyridine removed under reduced pressure. The residue was
stirred with 120 ml. of water and extracted with ether. Upon evapo
ration of the ether solution and crystallization twice from 95$
ethanol, there resulted 0.2 gm. of the oxime; m. p. 210-210.5 C.
Anal. Calc'd for C22H21N0; C, 83.8$; H, 6.67$; Found: C, 83.96;
H, 6.78.
g) p-Methylbenzhydryl p-Tolyl Ketone-C^ (iVb).
This ketone was prepared in the same manner as that above, radio-
*
active cuprous cyanide (CuCN was prepared by a modification of the
method of Barber) (ll8) being used in the preparation of the phenyl
£-tolylacetonitrile. The phenyl j>-tolylacetic acid had a radioactivity


59
assay of 2.195 0.009 me/mole. The pure ketone melted at 67-68, and
had a radioactivity assay of 2.205 0.011. Structure and radio
chemical label position determinations were accomplished by subjecting
a sample of the ketone to cleavage with 25$ potassium hydroxide in
methanol in an atmosphere of nitrogen, (l) On oxidation of the neutral
fraction with chromic acid in acetic acid, £-benzoylbenzoic acid was
obtained in 87$ yield, m. p. 198-199; and was nonradioactive. The
£-toluic acid was obtained by acidification of the aqueous solution
from the cleavage reaction, yielding 100$ of air-dried crude product;
m. p. 174-176. One crystallization from water sufficed to yield the
pure acid, m. p. 178-179; with a radioactivity assay of 2.167 0.001
me/mole.
l4
Threo-l,2-di-p-tolyl-l-phenylethylene-2-C Glycol (lb), Method I.
£-Methylbenzhydryl £-tolyl ketone-C1^ (8 gm.) was dissolved in 120
ml. of glacial acetic acid was treated with 20 ml. of concentrated
nitric acid (119) and allowed to reflux for 25 minutes. The mixture
was then poured into ice water, and extracted with ether, which was, in
turn, washed with water, saturated aqueous sodium bicarbonate solution,
and again with water. After being dried over anhydrous sodium sulfate,
the solution was used directly for the reduction without further
treatment.
A slurry was prepared with 4.5 gm. of lithium aluminum hydride in
dry ether and the solution of the ketol was added slowly. The mixture
was stirred for an additional hour, water added to decompose the excess
hydride and to completely hydrate the metal hydroxides. The ether


6o
solution was removed by filtration and evaporated to dryness. The
slightly oily, brown residue was washed with petroleum ether and
crystallized from ethanol. Repeated crystallization from ethanol gave
1 gm. of glycol; m. p. 147-150, radioactivity assay 2.179 mc/mole.
The remaining material had am. p. of 150-135; identical with the
behavior of an approximately equal mixture of the two diasteriomers,
prepared as described below.
Threo-l^-di-p-tolyl-l-phenylethylene-g-C1^ Glycol (lb), Method II.
l4
a) p-Methylbenzyl-a-C Alcohol.
Carboxyl-labeled jj-toluic acid (55*5 gm.) was treated with 25 gm.
of lithium aluminum hydride in ether solution in the usual way. After
the excess hydride was destroyed by the cautious addition of water and
separation of the ether solution, there was obtained 48.8 gm. (98$) of
the carbinol.
14
b) p-Methylbenzyl-a-C Chloride.
The above carbinol was treated with 100 gm. of thionyl chloride
in 150 ml. of hexane. Upon removal of the excess thionyl chloride and
hexane under reduced pressure, there was obtained 55*1 gm. (98$) of the
chloride.
c) p-Tolylacetonitrile-a-C^.
The g-methylbenzyl-a-C1^ chloride was treated with sodium cyanide
according to the method of Vogel. (120) Upon distillation of the
product there was obtained 43-9 gm- of the nitrile (85.5$)
d) p-Tolylacetic Acid (Carboxyl-labeled with carbon-14).
-Tolylacetonitrile-a-C1^ (43.9 gm.) was treated with 100 ml. of


6i
50$ aqueous sulfuric acid, to which had been added 50 ml. of glacial
acetic acid. (120) After heating at reflux for one hour, the mixture
was poured over 500 gm. of ice and the precipitated acid was removed by-
filtration. The crude acid was melted under water, with stirring, the
flask was then cooled in an ice bath and the acid was removed by
filtration. The acid was then dissolved in dilute sodium hydroxide and
the solution was filtered through a pad of Celite. Upon acidification
of the filtrate and cooling, there was obtained 59 4 gm. (78$) of the
pure acid; m. p. 90-91 (121)
e) Preparation of the Glycol (lb).
The glycol was prepared by identical methods as indicated for the
tolyl-labeled glycol discussed below, 194 gm. of the above a-labeled
£-tolyl acetic acid being employed. There was obtained 5*7 gm. of the
, o
glycol; m. p. I56-157 The melting point was undepressed when mixed
with an authentic sample of the tolyl-labeled glycol. Depression in
melting point to 150-155 was observed when mixed with approximately
equal amounts of the threo-isomer prepared as described below. Radio-
chamical assay, 2.121 0.001 mc/mole.
Threo-l,2-di-p-tolyl(2-p-methyl-C1^)-l-phenylethylene Glycol (Ic).
a) Benzoic Acid-carboxyl-C-1-^.
This compound was prepared by the carbonation of phenyl magnesium
bromide with radioactive carbon dioxide, using standard vacuum line
technique. (122)
14
b) Toluene-methyl-C
The carboxyl-labeled benzoic acid was esterified by the method of


62
Aeree (123) and then treated with lithium aluminum hydride in dry
14
ether. The resulting benzyl-a-C alcohol was purified by distil
lation. Zinc amalgam was prepared as directed in "Organic Synthesis."
(124) Zinc (120 gm.) was treated with 12 gm. of mercurous chloride,
and then washed with water. The amalgam, 200 ml. of water, 25 ml. of
concentrated hydrochloric acid, and 25 gm. of radioactive benzyl
alcohol, were heated under reflux for 30 hours. Additional 25 ml.
portions of hydrochloric acid were added at 8-hour intervals. The
mixture was then steam distilled and the toluene was separated, washed
with water and dried over anhydrous calcium chloride. Upon filtration
and distillation there was obtained 9-22 gm. (44$) of toluene;
b. p. 111-115, refractive index 1.4945, compared with 1.4935 for an
authentic sample. Products from several such preparations were diluted
with nonradioactive toluene to yield 43 gm. of toluene-C^ with a
radioactivity assay of 22.55 mc/mole.
14
c) 4-Methyl-C -acetophenone.
In a modification of the method reported in "Organic Synthesis,"
(139) 42 gm. of methyl-labeled toluene in 200 ml. of carbon disulfide
was first treated with 150 gm. of anhydrous aluminum chloride and
then, while being refluxed gently over a period of 45 minutes, with
4l gm. of acetic anhydride. Refluxing was continued for l-l/2 hours
after which the carbon disulfide was removed by distillation and the
residue was poured onto ice to which had been added sufficient concen
trated hydrochloric acid to dissolve the aluminum salts. This mixture
was extracted with ether, the ether was washed twice with water, once


63
with 10$ NaOH and. again with water. The ether solution was then dried
over anhydrous calcium chloride, filtered, and the ether was removed by
distillation. The residue was fractionated, the fraction b. p. 80-85
at 5 mm. (Feist, F. (125) gives b. p. 111-114/13 mm.) being retained
(yield, 51 gm., 83$).
d) 4-Methyl-C-^-mandelic Acid.
This compound was prepared by dissolving 56.47 gm. of £-methyl-
acetophenone in 250 ml. of methanol and adding 500 ml. of 20$ aqueous
sodium hydroxide. Chlorine gas was bubbled through the solution slowly
while it was vigorously stirred. The solution gradually became almost
clear while the temperature rose to 60. From time to time additional
sodium hydroxide solution was added until a total of one 1. was present.
Stirring was continued for an additional 20 minutes, and a small
quantity of acetone was added to remove the excess chlorine. The
mixture was treated with Norit and filtered. Upon acidification of the
filtrate with concentrated hydrochloric acid, the precipitate was
removed. The yield of £-toluic acid, methyl labeled, was 7 gm. The
aqueous solution was then extracted with ether in a continuous
extraction apparatus and the ether was removed by distillation. The
yield of 4-methylmandelic acid was 45 gm. (64.5$); m. p. 145-146 (this
is the method of VanArendouk and Cupery for the preparation of j)-toluic
acid, except that the chlorine is added slowly and the temperature does
not rise as high);(126, 127) The product was further characterized by
preparation of the ethyl ester, m. p. 77 ; (121) and reduction with
lithium aluminum hydride to £-tolylethylene glycol, m. p. 76, (107)


64
in agreement with the literature.
e) 4-Methyl-C1*<-phenylacetic Acid.
To a solution of 21 gm. of the 4-methylmandelic acid in 185 ml. of
glacial acetic acid was added 20 ml. of concentrated sulfuric acid and
3.2 gm. of 30$> palladium on charcoal catalyst. The mixture was hydro
genated at atmospheric pressure, while being stirred vigorously. After
20 hours, the theoretical quantity of hydrogen had been adsorbed. The
catalyst was then removed by filtration. The filtrate was diluted with
water and extracted with chloroform. The chloroform solution was washed
with water and evaporated to dryness, to yield 16 gm. (84.4$) of the
acid; m. p. 88-90 (128)
f) 4'-Methyl-C1^-desoxybenzoin.
To 35-6 gm. of £-tolylacetic acid was added 50 gm. of phosphorous
pentachloride. After the vigorous reaction ceased, the mixture was
wanned on a water bath for 30 minutes, cooled, and 150 ml. of dry
benzene was added. The mixture was then treated with 65 gm. of
anhydrous aluminum chloride, and, after the initial vigorous reaction
ceased, the mixture was heated under reflux for 1-1/2 hours and was
poured onto an ice-hydrochloric acid mixture. The product was
extracted three times with a benzene-ether mixture (1:4), the combined
extracts washed with water and evaporated to dryness. There was
obtained 31*3 gm. (62.6$) of the desoxybenzoin; m. p. 98-99. (129)
g) a-Bromo-4' -methyl-C^-desoxybenzoin.
A solution of 28.3 gm. of 4'-methyl-Cll+-desoxybenzoin was prepared
in 100 ml. of carbon disulfide and was placed in a flask fitted with an


65
efficient reflux condenser and an inlet tube for nitrogen. 21.8 gm. of
bromine, dissolved in 50 ml. of carbon disulfide, was then added slowly
while a rapid stream of nitrogen was passed through the solution
(adapted from method of Ward). (130) After all of the bromine had been
added and the evolution of hydrobromic acid gas slackened, the solvent
was removed by distillation under reduced pressure, in an atmosphere of
nitrogen. When the carbon disulfide ceased to distill, 30 ml. of
hexane was added and distilled. The product was again treated with
hexane in the same fashion and then warmed on the steam bath under
reduced pressure in order to remove the last traces of the carbon
disulfide solvent. The residue was used directly for the preparation
. Ik
of 4'-methyl-C -benzoin, described below.
h) 4' -Methyl-C^-benzoin.
The a-bromo-4'-methyl-C^-desoxybenzoin from the above preparation
was dissolved in one 1. of 95$ ethanol and an equivalent amount of 10$
ethanolic sodium hydroxide was added. The solution was stirred for
10 minutes and poured into two 1. of water. Aqueous hydrochloric acid
(20$) was added until the solution was just acid. The mixture was
allowed to stand for 10 minutes, the precipitate was filtered, yielding
29 gm. (95$) of the crude product, from which 26 gm. of the pure
material was obtained on crystallization from ethanol, m. p. Il8.(l3l)
This material was found to have a radioactivity assay of 20.3 mc/mole
and was diluted with nonradioactive 4'-methylbenzoin to a tracer level
of approximately 5 mc/mole.


66
l4
i) Threo-l,2-di-p-tolyl-l-phenylethylene(2-p-methyl-C )
Glycol (Ic).
A Grignard reagent was prepared from 189 gm. of £-bromo toluene and
26.5 gm. of magnesium turnings. To it 100 gm. of the above V-methyl-
benzoin was added slowly over a 30-minute period, and the mixture was
heated under gentle reflux for 1 hour. The mixture was hydrolyzed with
an aqueous ammonium chloride solution and the ether: layer separated.
The aqueous layer was extracted three times with ether, the ether
extracts were combined and washed with water, dried over anhydrous
sodium sulfate and concentrated to approximately 150 ml. Then 500 ml.
of hexane was added and the mixture allowed to stand overnight. The
solid was filtered and crystallized from 85$ ethanol. Yield of pure
glycol, m. p. 156.5-157, was 45 gm. (32$).
Anal. Calc'd for C!22H22(-)2: 3*0; H, 6.97; Found: C, 82-92,
83.06; H, 6.99} 7-00. Radioactivity assay, 5-221 mc/mole.
Erythro-l,2-di-p-tolyl-l-phenylethylene-2-C^-Glycol (lb).
a) 4,4'-Dimethyldesoxybenzoin.
To 20 gm. of the -tolylacetic acid, prepared as for the threo-
glycol (lb) above, was added 11 ml. of phosphorous trichloride and
(132) 60 ml. of toluene. The toluene solution was decanted onto 30 gm.
of anhydrous aluminum chloride and after the initial vigorous reaction
subsided, the mixture was heated on a steam bath for 1 hour. The
reaction mixture was poured over an ice-concentrated hydrochloric acid
mixture and the toluene layer separated. The aqueous layer was
extracted three times with a benzene-ether mixture (4:1) and the


67
combined organic extracts were washed twice with water. On evaporation
of the solvents there resulted a yellow oily solid which was washed once
with a little cold hexane and then dissolved in hot 95$ ethanol.
Following treatment of the ethanolic solution with Norit and filtration,
19*9 gm. (67$) of the desoxybenzoin was obtained; m. p. 101-102. (133)
b) 4,41-Dimethyl-a-bromodesoxybenzoin.
The a-bromodesoxybenzoin was prepared as described previously for
4'-methyl-a-bromodesoxybenzoin, using 19-9 gm. of the desoxybenzoin
above, and 14.8 gm. of bromine in 75 ml. of carbon disulfide. Upon
evaporation of the solvents, a solid compound separates, which upon
crystallization from hexane has am. p. of 96, and a radioactivity
assay of 2.037 mc/mole (calculation based on molecular weight of 303)*
c) 4,4'-Dimethylbenzoin.
The bromodesoxybenzoin from above was treated with base in
alcoholic solution, followed by acidification in a manner described
previously for the preparation of V-methylbenzoin. 9*9 gm. (46$) of
pure benzoin was obtained; m. p. 87-88. (134)
d) Preparation of the Glycol, Erythro-Ib.
To a Grignard solution prepared from 2.74 gm. of magnesium turn
ings and 157 gm. of bromobenzene in ether, was added 9-9 gm. of
4,4'-dimethylbenzoin. After the addition was complete, the mixture was
allowed to reflux gently for 4 hours. The reaction mixture was poured
into ice water and ammonium chloride was then added to dissolve the
magnesium hydroxide. The ether layer was separated and the reaction
mixture was extracted three times with 100 ml. portions of ether. The


68
combined ether solutions were washed with water and evaporated to dry
ness. Crystallization from 95$ ethanol gave 7*4 gms. of the glycol;
m. p. l60-l6l. Radiochemical assay, 2.102 mc/mole.
Anal. Calc'd for C22H222> C> 83-0; H, 6.97. Found: C, 82.72;
H, 7.08.
14
l,l-Di-p-tolyl-2-phenylethylene-l-C Glycol (lia).
a) Mandelic-carbonyl-C^ Acid.
This compound was prepared by the method of Vogel (135) from
benzaldehyde, radioactive sodium cyanide, and sodium bisulfite, with
subsequent hydrolysis of the nitrile with concentrated hydrochloric
acid.
. 1 k
b) Methyl Mandelate-carbonyl-C .
This compound was prepared by the method of Aeree (123) by reflux
ing the acid in anhydrous methanol in the presence of concentrated
sulfuric acid, followed by distillation of the product.
c) l,l-Di-p-tolyl-2-phenylethylene-l-Cllt' Glycol (lia).
A Grignard reagent was prepared in ether solution with 84 gm. of
£-bromotoluene and 14 gm. of magnesium turnings. To this solution was
14
added 22.5 gm. of methyl mandelate-carbonyl-C and the mixture
refluxed for 4 hours. The reaction mixture was decomposed with a
solution of ammonium chloride, the ether layer was separated, washed
with water, dried over anhydrous sodium sulfate and evaporated to dry
ness. The semisolid residue which remained was dissolved in a small
ft
amount of benzene and hexane was added. 22 gm. (51*5$) of glycol
separated; m. p. 155-157. Crystallization from 95$ ethanol produced


69
the pure glycol; m. p. 158-158.5; radioactivity assay 2.153 0.015
me/mole. (21) On oxidation of the glycol with chronium trioxide in 50#
aqueous acetic acid, the neutral fraction yielded di-j>-tolyl ketone
with radioactivity assay of 2.140 mc/mole. The benzoic acid fraction
was nonradioactive.
Anal. Calcd for C22H222: C> ^-0; 6.97; Found: C; 83.27;
H, 7-11.
Di-p-tolylphenylacetaldehyde.
A 5-000 gm. sample of l,2-di-£-tolyl(22£^ijtethyl-C^)-1-phenyl-
ethylene glycol (Ic) was stirred at room temperature with 350 ml. of
90$ formic acid for 98 hours. On cooling the reaction mixture in an
ice bath and subsequent filtration, 3-764 gm. (79-8^) of the nearly
pure aldehyde was obtained; m. p. 93-94. On crystallization from 95^>
ethanol gave the pure compound; m. p. 94.5-95- Radiochemical assay,
5-235 0.025 mc/mole.
Anal. Calcd for C2gH2oO; C, 88.10; H, 6.73; Found: C, 88.10;
87.83; H = 6.59, 6.52.
The 2,4-dinitrophenylhydrazone was prepared by treating 20 ml. of
a hot ethanolic solution of 500 mg. of the aldehyde with a solution of
500 mg. of 2,4-dinitrophenylhydrazine, 1 ml. of concentrated sulfuric
acid and 5 ml. of water. After boiling the solution for 20 minutes, it
was cooled and the precipitate was removed by filtration. In several
preparations the crude 2,4-dinitrophenylhydrazone had a low and broad
melting point. Boiling for 10 minutes with a large volume of hexane or
crystallization from a large volume of ethanol gave the bright yellow


70
product with sharp melting point; 190.5-191* Radioactivity assay,
5.205 mc/mole. Further proof of the identity of the aldehyde was
obtained by comparison of its ultraviolet spectrum with that of the
known aldehyde, diphenyl-£-tolylacetaldehyde. Both curves have
identical characteristics.
Anal. Calc d for CggH^O^; C, 69.85; H, 5*24; Found: C, 70.66;
H, 5*07*
4,4*-Dimethylbenzhydrylphenyl Ketone (V).
a) Di-p-tolylcarbinol.
An ether solution of 40 gm. of di-£-tolyl ketone was added slowly
to a stirred slurry of 7*3 gm. of lithium aluminum hydride in 500 ml.
of ether. After the addition was completed the solution was allowed to
stir for an additional 15 minutes, after which 50$ ethyl acetate in
ether was added slowly in sufficient quantity to destroy the excess
hydride. Water was then added, followed by sufficient concentrated
hydrochloric acid to dissolve the metal hydroxides. The ether layer
was separated and the aqueous layer was extracted with ether. The
combined ether extracts were washed once with water and evaporated to
dryness. The product crystallized on cooling and several different
runs gave yields of 98$ or better of the theory. Crystallization from
hexane yields the pure carbinol; m. p. 70. (136)
b) Di-p-tolylchloromethane
A solution of 40 gm. of di-£-tolyl carbinol in 100 ml. hexane was
heated under gentle reflux while 38 ml. of thionyl chloride was added
dropwise. Reflux was continued for l-l/2 hours, after which the hexane


71
and the excess thionyl chloride was removed under reduced pressure.
The slightly colored product, which on distillation (b. p. 163-I680/
0.6 mm.) gave 108 gm. (95-7$) of a water white oil, crystallized
spontaneously on standing. Crystallization from hexane gave the pure
compound; m. p. 44-45. (136)
c) Di-p-tolylacetonitrile.
A mixture of 100 gm. of di-j>-tolylchloromethane and 45-5 gm. of
cuprous cyanide (20$ excess) were placed in a flask with an air
condenser attached and immersed in a Wood's metal bath, preheated to
l80. The mixture was heated for 5-l/2 hrs. with occasional mixing,
while the temperature was slowly increased to 220. The product was
removed from the bath, cooled and 250 ml. of acetone was added. The
acetone solution was filtered to remove the copper halide cake, which
was washed on the filter with an additional 100 ml. of acetone. The
acetone solution was allowed to stand overnight in the refrigerator
after which it was again filtered to remove the fine sediment of copper
halide which had settled out. The acetone was removed under reduced
pressure and the product was distilled (b. p. l65-175/7 mm.) to yield
69 gm. (72$) of a slighly yellow oil which spontaneously crystallized
on standing. Crystallization from hexane yields pure white crystals;
m. p. 46.5-47. Hoch (117) gives b. p. 212/l8 mm. and does not record
the melting point of the compound.
d) Di-p-tolylacetic Acid.
A mixture of 65 gm. of di-£-tolylacetonitrile, 120 ml. of glacial
acetic acid and 600 ml. of 50$ aqueous sulfuric acid were heated under


72
reflux with vigorous stirring for 3-1/2 hours. The mixture was then
cooled and poured into one 1. of ice water and stirred for 1 hour,
during which time the acid, which first separated as an oil, solidi
fied. The product was removed hy filtration and washed with cold
water. The air-dried product weighed 60 gm. (85$); m. P- 1^3 (157)
e) Di-p-tolylacetyl Chloride.
This compound was prepared from 67.1 gm. of di-£-tolylacetic acid
in 250 ml. of hexane, by treatment with 100 ml. of thionyl chloride.
After the reaction had almost ceased at room temperature, the mixture
1 o
was warmed to not more than 40 under reduced pressure to remove the
hexane and excess thionyl chloride. After distillation ceased, 50 ml.
of dry benzene was added and distillation continued. This process was
repeated to remove the last traces of thionyl chloride. After the
thionyl chloride was removed the residue was dissolved in 100 ml. of
dry benzene and used without further purification in the preparation of
the ketone below.
f) 4,4*-Dimethylbenzhydryl Phenyl Ketone.
A Grignard reagent was prepared in the usual way from 131 gm. of
bromobenzene and 20.3 gm- of magnesium turnings. To the cooled
solution was added, in small portions, 80 gm. of anhydrous cadmium
chloride, vigorous stirring being maintained. After the addition was
complete, the mixture was stirred at room temperature for 30 minutes,
then under gentle reflux for an additional 30 minutes. Almost all of
the ether was removed by distillation, 100 ml. of dry benzene was added
and distillation continued. When 100 ml. of distillate had been


73
collected, an additional 200 ml. of benzene was added and the distil
lation was continued until the condensing vapor had a temperature of
68. Then 500 ml. of dry benzene was added and the mixture was cooled
to 10-15. While vigorous stirring was maintained, the solution of
di-£-tolylacetyl chloride was added slowly. Stirring was continued at
room temperature for 30 minutes and then under gentle reflux for 1
hour. The reaction mixture was poured into water, sufficient concen
trated hydrochloric acid was added to dissolve the magnesium and
cadmium salts, and the benzene layer was separated. The aqueous layer
was extracted with 200 ml. of an ether-benzene mixture (4:1) and the
combined organic layers were washed three times with water. The
solutions were dried over anhydrous sodium sulfate and the solvents
removed by distillation. The brown oily residue was then steam dis
tilled to remove di-phenyl, dried and distilled under reduced pressure.
The fraction, b. p. 236-242 at 0.5 mm., was a slightly yellow oil
weighing 77 gm. After three crystallizations from ether-hexane (l:20)
at dry ice temperature, 66 gm. (79$) of the pure ketone was obtained;
m. p. 57-58. (21)
Anal. Calc'd for C22H200: C, 88.00; H, 6.71: Found: C, 88.06;
H, 6.71.
Sample Calculations for Ketone Yields, Reaction Path Yields and
Carbon-Ik Label Distribution.
a) Correction Factor for Ketone Yields from Threo-Ic and III, and
Cleavage Products of IVcd.
It may be seen from Table X for Runs 2-5 and 9, 10, 15, that


74
cleavage of the ketone IV from the dilution yield determinations gives
a slightly lower value for £-tolyl label scrambling than does the
cleavage of the undiluted ketone. Since in the case of the aldehyde
50:50 distribution is demanded (and observed for the undiluted ketone)
it is apparent that a correction is necessary for this observation.
Since this behavior is probably due to a minute quantity of highly
radioactive contaminate in the glycol, threo-Ic, because of the method
of synthesis, we have applied the correction factor 47/50 in the
following manner: 47/50 X uncorrected ketone yield = corrected ketone
yield and, since the £-tolyl scrambling recorded in Table IV is also
affected, 50/47 X uncorrected £-tolyl scrambling = corrected £-tolyl
scrambling. This correction factor is, of course, only approximate.,
being derived from the average of the two values for Vc (47$; Table X,
Runs 9 and 10) and the fact that 50$ is required and observed (Table X,
Run 15). Since, however, the factor is close to unity, rather wide
limits are allowable in its accuracy without introducing significant
error by its use. Substantially the same correction is arrived at by
plotting the observed percentages of £-tolyl scrambling against the
ratio by which the ketone was diluted, and extrapolating to zero
dilution. This correction is required only in the calculations of data
derived from the rearrangements conducted with threo-Ic or the aldehyde
III. Moreover, no correction was needed for the ketone V because these
dilutions were consistently more readily purified, and upon cleavage,
in control experiments, the ketone fragments did not indicate any
contamination, as was found for ketone IV.


75
b) Ketone Yield Calculations.
Application of the equation A^ (D]_ + X) = A0 X, mentioned earlier
in this section, gives, for Run 2 (Table VIII), the uncorrected values
of 51<1$ for the yield of IV and 32.6$ for the yield of V. The
corrected yield of IV (47/50 x 51l) is 48$. The yields of IV and V
were then normalized to show the relative yields of IV and V in the
ketonic product, giving values of 59 6$ and 40.4$ for IV and V,
respectively (Table II).
c) Reaction Path Yields.
Consideration of Chart I and the degradation schemes on pages 35>
36 and 40, shows that when threo-Ib undergoes rearrangement only path B
yields £-benzoylbenzoic acid which contains the carbon-14 label. There
fore the molar activity (Table V) of this compound (Vila), together with
the yield of IV (Table II) is a measure of the yield by path B. Thus
m^j = 0.039 x O.583 = 0.023 as one value (Table VI). Calculation of
is performed in like manner using the yield of Vab and Villa.
The total contribution to product via paths A and D is given by
the yield of V (Table II), hence ma + md = 0.417 and from Table VI the
average value for is 0.008, giving a value for m of 0.409
Methods for calculating the ratio me/W have been given previously
(page 43). From a knowledge of this ratio, e. g., 1.37 (Table VII,
Method l), and m, the value for mg may be calculated, thus 1.37 x
0.409 = O.56O (Table VI).
Calculations for mc may be performed in several ways-', one of which
is described here. The yield of IV (Table II) gives mb + mg + mg which


76
is O.583. From this is subtracted the sum 1^+1% calculated as
described above, thus O.583 (0.018 + O.560) = 0.005 (Table VI).
Derivation of Equation 1 of the Introduction.
In the following scheme, X1, Xg, and X^ represent three ionic
species in a dynamic equilibrium. If then this scheme is correct, the
specific rate-constant ratio bp/kp, rather than the product ratio IV/V,
Aldehyde III
@ k* > (Tol)2-9-CHOH (Tol)2C-C-4>
kp H
kp
(Tol)2CHC-4
/
^ol
^T
V
Tor
9H
-Cp-Tol
H
l
CHC-Tol
Tor
IV
represents the relative migratory abilities of the one phenyl and the
two £-tolyl groups of aldehyde III, when this aldehyde is subjected to
acid catalysis. Now if x^, x2, and x^ are the instantaneous, time-
variable concentrations of the ions X^, Xg, and Xy respectively, then
from the above scheme
2) dXg(t)/dt = kp x-jUJ-kj, XgitJ-kp xg(t)
3) dx5(t)/dt = bp x^iO-k^ x5(t)-k'H x^it).


77
Since all reactions were allowed to go to completion, equations 2 and 3
are now integrated between the limits zero and infinity.
oo oo rco ran
4) xg =1^1 xx(t)dt kj xg(t)dt xgit)
oo o o
dt
5) x,
03 rco rco rco
= fcpj xx(t)dt krjioiJ x5(t)dt kHJ x5(t)
dt.
Joo roo roo
x^tJdtjJ x2(t)dt, and J x,(t)dt
are now
replaced with the "integration areas" S^, Sg, and S^,and then since at
t = 0 and t = oo, the concentration of all intermediates are zero,
equations 4 and 5 become:
6) kps1 k0s2 kjjSg = 0
7)
k S
T 1
k S
Tol 3
k' S = 0
H 3
or:
6) s Vi
k4> + kH
7) S* = ^1
3
H


78
and at complete reaction, since S^, S2 and S3 represent the total moles
of X^, X2, and X3 formed during period t = 0 and t = 00, and m and nig
represent the moles of product formed through paths D and E (Chart I),
respectively;
8) = kHS2 .
me k'jjSj
Substitution of equation 6 and 7 for S2 and S3, respectively, in
equation 8 and simplifying gives equation 1.
The derivation of equation 1 is made possible by use of the "area
theorem" of Hearon, (138) who pointed out the utility of this theorem
in chemical kinetics.
Analytical Determinations.
The carbon and hydrogen analyses for this dissertation were
performed by the Huffman Microanalytical Laboratories, Wheatridge,
Colorado.


SUMMARY
Phenyl-di-£-tolylacetaldehyde and the related system of glycols;
threo-1,2-di-p-tolyl(2-p-methyl C1^)-1-phenylethylene glycol, threo-
l,2-di-j3-tolyl-l-phenylethylene-2-Cx glycol and 1,l-di-jD-tolyl-2-
phenylethylene glycol, have been subjected to rearrangement in cold,
concentrated sulfuric acid. The yields of the ketones (4-methyl-
benzhydryl jD-tolyl ketone and 4,4'-dimethylbenzhydryl phenyl ketone)
produced were obtained in each case by the radioactivity dilution
method. The fates of the carbon-14 labels of suitably labeled reactants
were determined by appropriate degradation methods, followed by radio
activity assay of the degradation products. By means of the equation,
= ^ol ^e
kp k0 k'H md
1 +
k'H
^ol
1 +
and a mechanism involving open, equilibrating carbonium ions, it has
been established that the p-tolyl/phenyl migration ratio in the
rearrangement of the aldehyde is not reversed, but is almost certainly
greater than unity. The mechanism correlating the aldehyde-ketone and
pinacol rearrangements, proposed by B. M. Benjamin and C. J. Collins
(l) in 1956, is thus supported.
79


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80


81
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t
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\
33* Roger, R. and McKay, W. B., J. Chem. Soc., 332 (1933)*
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82
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85
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(1943).


86
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428(1925).
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(1953).
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(1928).
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Vol. I, pp. 109-111.


BIOGRAPHICAL ITEMS
The author, Lawrence "W" Kendrick, Jr., was born in Underwood,
Alabama, on September l6, 1925* He completed his elementary and
secondary education in the Shelby County schools, and was graduated
from Thompson High School in 19^3* He attended Howard College,
Birmingham, Alabama, for one term prior to entering the United States
Navy in 19^3* During his Naval Service, he was commissioned a Naval
Aviator and served in that capacity until his release from active duty
in 1949. While on active service in the Navy he attended Carson-Newman
College, Jefferson City, Tennessee, for one year.
In January 1950, Mr. Kendrick entered the School of Pharmacy at
Howard College and received the degree of Bachelor of Science in
Pharmacy in June, 1953* After having completed the requirements for
his degree from Howard College, Mr. Kendrick transferred to the
College of Pharmacy at the University of Florida in September, 1952,
where he is still in attendance.
While he pursued the degree of Doctor of Philosophy, Mr. Kendrick
was a Fellow of the Oak Ridge Institute of Nuclear Studies. His
research was done at the Oak Ridge National Laboratory under the joint
sponsorship of that Laboratory, the Oak Ridge Institute of Nuclear
Studies, and the University of Florida.
The author is a member of the American Chemical Society, American
Pharmaceutical Association, Research Society of America (RESA), Gamma
Sigma Epsilon, honorary chemical society, and of Rho Chi, honorary
pharmaceutical society.
87


This dissertation was prepared under the direction of the chairman
of the candidate's supervisory committee and has been approved by all
members of the committee. It was submitted to the Dean of the College
of Pharmacy and to the Graduate Council and was approved as partial
fulfillment of the requirements for the degree of Doctor of
Philosophy.
June 3, 1957
p £.
i -
Dean, College of Pharmacy
Dean, Graduate School
SUPERVISORY COMMITTEE:
88


Full Text
AN INVESTIGATION OF THE RELATIVE MIGRATORY TEN¬
DENCIES OF THE PHENYL AND p-TOLYL GROUPS
IN THE PINACOL REARRANGEMENT OF THE
1,1,2-TRIARYLETHYLENE GLYCOL SYSTEM
By
LAWRENCE W. KENDRICK, JR.
A Dissertation Presented to the Graduate Council of
The University of Florida
In Partial Fulfillment of the Requirements for the
Degree of Doctor of Philosophy
UNIVERSITY OF FLORIDA
JUNE, 1957

ACKNOWLEDGMENTS
The author wishes to express his sincere appreciation to
Dr» W» M. Lauter of the University of Florida for his helpful and
timely suggestions, and to Dr» C» J. Collins of the Oak Ridge National
Laboratory for his valuable assistance and guidance in this research.
The author wishes to acknowledge the contribution of each member
of his Graduate Supervisory Committees Dr» C. H» Becker,
Dr. W. S. Brey, Jr., Dr. L. G. Gramling, Dr. C» B. Pollard, all of the
University of Florida and Dr. L. P. Zili of the Oak Ridge National
Laboratory.
The author also wishes to acknowledge his indebtedness to the
members of the Organic Group, Chemistry Division of the Oak Ridge
National Laboratory for their helpful suggestions and friendly advice.
ii

TABLE OF CONTENTS
ACKNOWLEDGMENTS ii
LIST OF CHARTS vi
LIST OF TABLES vii
INTRODUCTION 1
HISTORY 10
METHODS AND RESULTS 35
DISCUSSION 42
EXPERIMENTAL 49
Radioactivity Determinations and the Radioactivity
Dilution Method of Yield Determination. 49
Sulfuric Acid Catalyzed Rearrangements. 49
Formic Acid Catalyzed Rearrangements. 50
Aldehyde Stability in Formic Acid. 52
Ketone Cleavage for Carbon-14 Distribution. 53
Ketone Stability in Concentrated Sulfuric Acid. 54
£-Methylbenzhydryl £-Tolyl Ketone (IV). 54
a) Phenyl-£-Tolylcarbinol. 54
b) Phenyl-£-TolyImethyl Chloride. 54
c) Phenyl-j>-Tolylacetonitrile 56
d) Phenyl-£-Tolylacetic Acid 56
e) Phenyl-p-Tolylacetyl Chloride 57
f) £-Methylbenzhydryl £-Tolyl Ketone (IV). 57
g) p-Methylbenzhydryl £-Tolyl Ketone-C1^ (iVb). 58
iii

Iv
Threo-l,2-di-p-tolyl-l-phenylethylene-2-C~^ Glycol (lb),
Method I. 59
l4
Threo-l,2-di-p-tolyl-l-phenylethylene-2-C Glycol (lb),
Method II. 60
a) g-Methylbenzyl-a-C1^ Alcohol. 6o
b) p-Methylbenzyl-a-C^ Chloride. 6o
c) £-Tolylacetonitrile-a~C^. 6o
d) £-Tolylacetic Acid (carboxyl-labeled with carbon-l4). 6o
e) Preparation of the Glycol (lb). 6l
Threo-1,2-di-£-tolyl-l-phenylethylene (
Glycol (ic). 6l
a) Benzoic Acid-Carboxyl-C . 61
b) Toluene-Methyl-C1^. 6l
c) 4-Methyl-C^-Acetophenone. 62
d) 4-Methyl-C^-Mandelic Acid • 65
e) 4-Methyl-C-^-Phenylacetic Acid . 64
f) 4' -Methyl-C^-Desoxybenzoin. 64
g) a-Bromo-4’-methyl-C^-desoxybenzoin. 64
h) 4' -Methyl-C^-benzoin . 65
i) Threo-1,2-di-j>-tolyl-l-phenylethylene
(2-p-methyl-C1^) Glycol (Ic). 66
Erythro-l,2-di-p-tolyl-l-phenyIethylene-2-C1^ Glycol (lb). 66
a) 4,4'-Dimethyldesoxybenzoin. 66
b) 4,4'-Dimethyl-a-bromodesoxybenzoin . 67
c) 4,4'-Dimethylbenzoin • 67

V
d)Preparation of the Glycol, Erythro-Ib. 67
l,l-Di-£-tolyl-2-phenylethylene-l-Clit' Glycol (lia). 68
a) Mandelic-carbonyl-C-^ Acid. 68
b) Methyl Mandelate-carbonyl-C1^. 68
c) 1,1-Di-j>-t olyl-2 -phenyle thylene- 1-C ^ Glycol (lia). 68
Di-£-tolylphenylacetaldehyde. 69
k,V-Dimethylbenzhydryl Phenyl Ketone (V). 70
a) Di-£-tolylcarbinol. 70
b) Di-£~tolylchloromethane. 70
c) Di-£-tolylacetonitrile. 71
d) Di-|>-tolylacetic Acid. 71
e) Di-jji-tolylacetyl Chloride. 72
f) 4,4'-Dimethylbenzhydryl Phenyl Ketone. 72
Sample Calculations for Ketone Yields, Reaction Path
Yields and Carbon-1^ Label Distribution. 73
a) Correction Factor for Ketone Yields from
Threo-Ic and III, and Cleavage Products of
IVcd. 73
b) Ketone Yield Calculations. 75
c) Reaction Path Yields. 75
Derivation of Equation 1 of the Introduction. 76
Analytical Determinations. 78
SUMMARY 79
BIBLIOGRAPHY 80
BIOGRAPHICAL ITEMS 87
88
COMMITTEE REPORT

LIST OF CHARTS
Chart I Rearrangement of Threo- and Erythro-I, and III. 2
II Rearrangement of Ila. 7
III Preparation of Threo-l,2-di-p-tolyl( 2-£-methjrl-C^) -
1-phenylethylene Glycol (Ic). 36
IV Preparation of Threo-l,2-di-p-tolyl-l-phenyl-
ethylene Glycol (lb). 36
V Preparation of Erythro-1,2-di-p-tolyl-l-phenyl-
ethylene-2-C1^ Glycol (Ih) 37
VI Preparation of l,l-di-p-tolyl-2-phenylethylene-
1-Cll+ Glycol (Ila) 37
vi

LIST OF TABLES
Table I Comparison of k^r/kg Ratios for Various Systems
in Formic and Sulfuric Acids. li¬
li Yields of Ketones IV and V Produced by the Action
of Sulfuric Acid upon I, II, and III. 38
III Yield of Aldehyde III, Produced by the Action of
Formic Acid upon Glycols I and II. 39
IV Fraction of Radioactivity Found in Vc from Cleavage
of IVcd Derived from the Rearrangement of Threo-Ic. 40
V Fraction of Radioactivity in Fragments from Cleavage
of IVab and Vab Resulting from Rearrangement
of Threo-Ib, Erythro-Ib, and Ila. 4l
VISummary of Mole-Fraction Calculations from the
Data of Tables II through V. I5
VIISummary of the Ratios Calculated for use in or by
Equation 1. k6
VIIISummary of Yield Determination Experiments for
HgSO^ Rearrangements. 51
IXSummary of Yield Determination Experiments for
Formic Acid Rearrangements. 51
XSummary of Radioactivity Distribution Determinations. 55
vii

INTRODUCTION
A mechanistic correlation of the aldehyde-ketone and the pinacol
rearrangements was reported in 1956 by Benjamin and Collins, (l) In an
earlier paper Collins (2) had evaluated the importance of the conjugate
acid of triphenylacetaldehyde as an intermediate in the pinacol rear¬
rangement of triphenylethylene glycol and had proposed a mechanism to
explain the observed fates of the carbon-lk labels for different iso¬
tope position isomers of this glycol when it was subjected to rear¬
rangement. The extension of these proposals to the rearrangements of
diphenyl-£-tolylacetaldehyde and the two glycols, 1,2-diphenyl-1-
£-tolylethylene glycol and 1,l-diphenyl-2-j>-tolylethylene glycol, led
the authors (l) to propose a general mechanism for the rearrangements.
It was found by Benjamin and Collins that through a mathematical
treatment of the mechanism they proposed,, the £-tolyl/phenyl migration
ratio, during the acid-catalyzed rearrangement of the aldehyde to
ketones, was equal to ^T, where the ratio kj,/kp was evaluated by means
kp
of equation 1. By a combination of double-labeling techniques and
r kR
1) Íí , % ^-Tol ¡V* kfol
*P k« ' k'H ’ "d 1 + \
k(j>
*The letter, m, with subscript, d, e, etc., represents the mole
fraction of starting material giving product via path, D, E, etc.
Similar usage is employed in the construction of Charts I and II of the
present research. These charts were drawn to represent the rearrange¬
ment of glycols I and II, and aldehyde III, in a manner predifctable
from the postulations of Benjamin and Collins, (l)
1

* o
CHART I. Rearrangement of Threo- and Erythro-I, and III.

3
radioactivity dilution experiments upon appropriately labeled isotope
position isomers, these authors were able to show that the ¿-tolyl/
phenyl migration ratio was greater than one, in agreement with other
observations, (3-10) but in contradiction to the conclusion to be drawn
from a simple product ratio of the ketones obtained. It was necessary,
however, for Benjamin and Collins (l) to estimate the kr0iA'jj ratio in
the rearrangement catalyzed by sulfuric acid by means of the proportion,
kTol/k'H(H2S0i|-) :kTol/k'H(HC00H) i sk^/k^H^) ;k0/k'H(HCOOH)
since the value was so large as to preclude an accurate experimental
determination.
The values for the ratios of the specific rate constants found by
Benjamin and Collins can be used to calculate similar ratios in closely
related systems by taking into account what is apparently a decrease
in the values for k^/kg when the carbonium ion at the migration terminus
is made more stable (Table I), (ll) The values then, for k^/k^ and
in concentrated sulfuric acid and in formic acid, may be esti-
*
mated for the system in which I, II and III undergo rearrangement
*In this dissertation Roman numerals have been used to designate the
names of the various compounds when repetition of their names would be
cumbersome. In the case of radioactive compounds, a letter has been
appended to the Roman numeral to indicate the position of labeling,
thus la would represent 1,2-di-¿-tolyl-1-phenylethylene- 1-C ^ glycol,
discretely labeled in the 1-position of the ethylene glycol chain and
lb, the same glycol discretely labeled in the 2-position of the glycol
chain and Ic, this glycol discretely labeled in the ¿-methyl group of
the ¿-tolyl group attached to the 2-position of the chain. More than
one letter (e.g., lab) represents mixtures of the carbon-14 label
between the indicated positions. See page 5-

k
TABLE I
Comparison of k^/kg Ratios for Various
Systems in Formic and Sulfuric Acids
WkH
H2SO4
kTol/k'H
HCOOH
WkH kTol/k 'h
C. J. C. (2)
7-33
1.7a
»
B. M. B. and C. J. C. (l)
6.9
1.15
9-3
Estimated for present
research
6.5c
32d
0-78e
6.3f
Recalculated value, "based upon the observation that 7$ scrambling
of the chain label occurs in the aldehyde rearrangement. (20)
“Midpoint of two extremes, calculated by method of B. M. B. and
C. J. C., using 1.7 for k^/kjj in HCOOH.
c6.9/7-33 x 6.9 = 6.5.
d6.3/9.3 = x/48.
el.15/1.7 x 1.15 = O.78
f1.7/l.l5 = 9-3/x.
(Chart I). If the contributions of paths A and B are neglected and the
j>-tolyl/phenyl migration ratio is assumed to be ca. 3.0 (l) then by use
of equation 1 the ratio nig/m^ may be calculated. From a knowledge of
the me/ma ratio and the bj^/k'jj ratio the yield of ketones IV and V in
the ketonic product may then be estimated.

5
2) 2 x £-tolyl/phenyl migration ratio =
_ % ^Tol p fe
kP k4> k*H md
2x3= 1 x 32 x
S3
ÍS = 1.36
md
3) Now since
^olA'H = " 32 or md + me = 32 mc
1 +
H
^Tol
1 +
H
m
e
md
1 +
32
1 +
S3
*The ratio must be multiplied by 2 since there are two £-tolyl groups
and only one phenyl in the molecule.

6
4) m + m, + m = 1.00
' c d e
5) Substituting 3) in 4)
mc + 32 mc = 1.00
m = 0.03
c
md + mg = 0.97
Since the ratio me/°id = 1-36 or me = I.36 md, then,
md + (I.36 md) = 0.97
md = 0.4l
and me = O.56
The ketones formed from I, through paths C and E, are chemically
identical (IV), thus, mc + mg (0.59) will represent the expected yield
of IV in the ketone product, whereas ketone V is represented by md
(0.4l). Similarly the yields of ketones formed from II (Chart II) and
III may be calculated. These are:
for II - mf « 0.13, md« = 0.37, = 0.50, V = 50$, IV = 5C$J
for III - md = IV = 0.43 or 43$, mg = V = 0.57 or 57$.
It is possible also to predict from Table I the yield of aldehyde
(III) formed when the glycol (i) is subjected to rearrangement in formic
acid at room temperature. Thus, from Table I, (formic acid)=6.3=
k'g
^9, aldehyde _ formed # Since the only two products are aldehyde (ill)
moles ketone formed
and ketone (IV), and since the aldehyde itself is stable in formic acid
for short periocb of time, it follows that the yields of aldehyde and

CHART II. Rearrangement of Ila

8
ketone, respectively, should be 87$ and 13$.
It should be emphasized that although values for the various
ratios discussed are recorded, for example, as 9-3 for in
formic acid, it is not intended that the precision of such values be
interpreted as being better than - 10$; for the values of the larger
ratios, the uncertainty may be considerably greater. The reason for
this will be made clear in the treatment of the data for this research.
The ratios are carried through the discussion in this way as an aid to
the reader in identifying them as they occur. Despite these uncertain¬
ties, it was believed the system involving the rearrangements of I, II
and III should offer near optimum conditions for testing the generality
of the mechanism proposed by Benjamin and Collins because from the
foregoing calculations it appeared the ratio of the two ketones
produced from the glycols (I and II) and the aldehyde (ill) should be
near enough to unity to provide a minimum error. It was for this
reason that the rearrangements of compounds I, II and III were chosen
as the subject of the present research.
Examination of equation 1 reveals that because of its magnitude
' is perhaps the most crucial term involved in establishing an
II
accurate k^/kp ratio. A minimum value for this ratio must be
established, then, if we are to test the conclusion of Benjamin and
Collins (l) that the migratory ability of the p-tolyl group is greater
than that of phenyl. Benjamin and Collins (l) were unable to do this
directly, and found it necessary to estimate the value by the indirect
method mentioned in the foregoing discussion.

9
The purposes for which this research were undertaken have been
achieved, in that l) the £-tolyl/phenyl migration ratio in the rear¬
rangement of aldehyde III in sulfuric acid has been shown to be greater
than unity and 2) the general mechanism (l) for the aldehyde-ketone
rearrangement has been supported for the system of compounds (I, II,
III, IV and V) studied.

HISTORY
The pinacol rearrangement was discovered by Fittig in i860. (12)
Fittig had synthesized pinacol the previous year and found that upon
treatment of the compound with sulfuric acid, the ketone, pinacolone,
was produced. The feature of the reaction which was considered unusual
at the time was the migration of a methyl group from one carbon atom to
an adjacent one:
# OH OH 0
1) CH,-C C-CH, ^CH,C-C(CH,K
3 CH, fcH 3 ? 3 3 3
Since the initial work of Fittig, numerous related conversions
have been observed, under a wide variety of acidic conditions. The
reaction is quite general for the 1,2 glycols (commonly called
"pinacols" after the compound of Fittig), as evidenced by the following
discussion, which is concerned with a selected few of the many such
, , , 9® 9® 9
2) (R)2-C C-(R')2 ^ R^'C-CR» + H20
rearrangements reported in the literature. On treatment of the glycol
with acid, the product formed may be an aldehyde or a ketone, depending
upon the nature of the groups, R, and the acid strength of the reaction
medium. The reaction takes place when R is alkyl, aryl, part of an
*The equations in this, and other sections are numbered independently;
that is, the first equation in each section is numbered 1).
10

11
alicyclic structure, or hydrogen.
Examples of the generality of the rearrangement may he seen from
the following examples:
3)
5)
6)
7)
8)
9)
PH pH ...
CHv-C CH ^ (CH.)pCHCHO (13)
5 6h5 k h+ 5 ¿
OH OH
0Ó— fc-CH,
k k -
R
CH2C-CH5 (14)
OH
d
OH
—fc—Et
Et
cone â– 
H2S04'
cdV° + nr ° a?)
xEt t
Et
Q=?Z CK"
(15)
OH OH
♦-C C-D
cone. _ .9
H2S04
DC
+ x-TUL
- w - (16,17)
3d
pH 9H ft
02C —p-CH5 h2S0U> D2CHC-CHj (18)
H
D2p—C-D ——- > O.CCHO + D?-CHDP (2)
OH OH H+ J
cone. ,9
> OC-CHD,
HoS0

12
. 9H 9H dll
10) p-To±C—C-0 -Sii
H ¿ H+
«6
9
(1)
If
cone.
h2so4
It
OH pH
11) 0p-C-
H ¿-Tol
dil >
H+
(1)
ft
cone.
-9
^2^4
It
It
OH OH
12) C C-'t
á ch5
££2£^ «CHO»
H2S04 CH
5
+ ♦gCHC-CHj (19)
"small amount"
The products of the rearrangement of glycols which are incompletely
substituted may be aldehydes and/or ketones. Aldehydes are often
produced when the reaction is catalyzed by weak acids or by dilute
mineral acids and ketones alone are usually produced under strongly
acid conditions or at high temperatures. In much of the early work the
yields of the ketones produced were not accurately determined. In some
reactions in which two ketones were produced, only one was isolated;
often, because of its insolubility, that ketone formed in lesser yield
was the only product identified, (l, 21) The aldehydes formed during
these rearrangements are themselves convertible to ketones under the
influence of strong acids, or of dilute or weak acids at elevated

13
temperatures, (1, 22-25) and thus the aldehyde-ketone rearrangement is
known to he intimately related to that of the pinacols. Examples of
the production of aldehydes (or aldehydes and ketones) in the presence
of dilute or weak acids are seen in equations 3, 9, 10 and 11 and in
the following cases:
13)
dil
HgSO^
CHCHO
(26)
d
optically active
9H 9H
14) $2C—CH2 » 9H 9H ,,n f
15) -C C(CH_)0 — » (CH^)o-C-CHO (28)
H 52 H2S04 0 ¿
OH OH
16) 0-C—¿H » 4>CH2CHO (29)
H H
OH 9H
17) ♦-$—9-0» ► 4>2CHCHO (30)
H H
9H 9H
IS) (CH,)pC—CHP §2° y (CH.)pCHCHO (31)
0 ¿ ¿ 180-200 5
The conversion of aldehydes to ketones in the presence of strong
acids may he illustrated hy the following examples:
19) (ch5)2-9-cho > (CH5)9H§-CH (32)
0 0

Ik
20)
21)
p
OpC-CHO — 2^P4-^ O-CHC-O (32)
ch5 ¿h3
0>,CCHO C°nC,„> 4>§-CH»p (2)
3 Z2S0k
22)
23)
2k)
25)
26)
27)
cone. „ „
02f-CHO HpSO^ ^“CH\
¿-Tol ¿ 4
?-CH^ + £-To1?-CH4>2 (1)
£-Tol
a cone.
O-C-CHO —-_I—^
¿r1
CHj H2S°1^
€^c-
CH*
fi 0 y*
J CH0o + OC-CH: (33)
\Q
CH*
0 0
02C-CH0 Et Ét
33^
Et _ __ p
4>-p-CHO 52§?4_^ EtpHC-Et (32)
Et
67^
;t H2S04 g
——CHjCHC-Et (34)
¿-Anisyl ¿-Anisyl
ch3c-cho
cone. p.
0-CH-CHO ~ gn—* OCHoC-
CH5 H2S04
:2c/-ch3 (25)
Although discovered first, the pinacol rearrangement is in reality
a Wagner-Meerwin type transformation. Wagner's (35) first example
involved the transformation of isobprneol-into camphene (equation 30).
Wagner's correct interpretation of the course of the dehydration
furnished the basis for the explanation of a variety of "1,2 shifts,"

15
as they are commonly named. (24) These reactions, historically classi¬
fied under such names as Wagner, Meerwein, Nametkin, Demjanow, Pinacol
and Tiffeneau, have recently been discussed by Ingold, Bartlett, Eliel
and Cram. (23, 36-38) The Wagner-Meerwein type reaction may be
formulated as:
R t
28)
-f—
or
>C - t-
+ XY
where Y is the entering group or causative agent, X is the leaving
group and R the group migrating during rearrangement. The relation of
the pinacol rearrangement may be seen by a like formulation:
R | R |
29) —6 C —C_
ÓH ÓH 6h ®
©
.c_
¿H
-<—>
0 R
-a-fc<
In order to understand the mechanism of this reaction, the effects of
solvent, and of changing Y“ and X must be established. The stereo¬
chemistry about carbon-1, carbon-2 and R must also be known, as well as
the electrical effects within the molecule. These factors will be
considered at a later point in this discussion.
In the transformation of isoborneol to camphene, Wagner correctly
interpreted the course of the dehydration to involve the breaking of
the 1-6 carbon bond (equation 30) and the subsequent formation of a new
bond between the 2 and 6 positions. Such a transformation requires that
the 2-carbon position undergo a Walden inversion.(39)

16
Further light was thrown on the problem some years after Wagner's
observations by Meerwein, who observed that ring expansion (40) or
31)
32)
ring expansion methyl migration
ring contraction could occur during such dehydrations. (4l)
33)
CH5-CH-CH3
* ó 4-
25#
ch5
75#
Nametkin, in a series of papers in 1915, (42-44) reported his

17
observations of a reaction quite similar to that reported by Wagner.
For example, fenchyl alcohol, upon dehydration, was converted into
a-fenchane, with bond migration analogous to that observed by Wagner.
Demjanow, in the years 1902 to 1907; published a series of papers
describing the results of his studies upon deamination reactions
involving ring expansions. Thus cyclobutylmethylamine, when treated
with nitrous acid, was observed to produce, in addition to the expected
cyclobutylcarbinol, a considerable amount of the ring expansion
product, cyclopentylalcohol. (45) Cyclohexylmethylamine gave cyclo-
heptyl alcohol (46) and cyclopropylmethylamine gave a fixture of cyclo¬
butyl alcohol and cyclopropylcarbinol (47) under similar conditions.
Of the other variations of the Wagner-Meerwein and pinacol trans¬
formations, the dehydrohalogenation reaction and the "semipinacol
deamination," have been most studied. The dehydrohalogenation reaction
may be illustrated by a transformation observed by Tiffeneau. (48) As
can be seen in equation 55; the reaction proceeds through the elimi¬
nation of the elements of hydrogen iodide and the migration of the

18
p-tolyl group.
OH
55) <0-4-CH2I
AgN05 > 0C-CH2-^^-CH3
The "semipinacol deamination" may he characterized by the reaction
of l,2-diphenyl-l-p-tolyl-2-aminoethanol when treated with nitrous
acid. McKenzie (49) treated the optically active amine with nitrous
acid and obtained two products, one of which (B) was optically active,
indicating that the reaction, in part at least, followed a stereo¬
specific course.
The mechanism of the pinacol rearrangement has been studied for
many years. Erlenmeyer (50) suggested a cyclopropane intermediate,
which required loss of a hydrogen atom from the migrating group. This
mechanism was shown not to be possible in the case of aryl migration,
by the work of Montagne, (51, 52) since loss of hydrogen from the
ortho-position in a group with a para-substituent would yield a meta¬
substituent as the result of the shift. It was found that the para-
substituent remained intact. In a more general way, Meerwein and
van Emster (55) were able to disprove the cyclopropane intermediate
idea in the Wagner-Meerwein rearrangement of isobornyl esters to

19
camphene—a case in which Erlenmeyer's proposition appeared to have a
better chance of success. It was found that tricyclene, which is a
cyclopropane derivative corresponding to the presumed cyclopropane
intermediate for this reaction, could not be converted into canrphene
under conditions which isoborneol yields canrphene smoothly.
Breuer and Zincke in 1879 (30) proposed ethylene oxides as inter¬
mediates in the rearrangement. This mechanism has been disproved for
the most part by Tiffeneau (5^) and McKenzie (55) and their co-workers
who found, in the dehydration of glycols, deamination of 2-amino-
alcohols and dehydrohalogenation of 2-iodo-alcohols, that the oxide
could not be isolated from an incomplete reaction, and yet the oxide
was found to be sufficiently stable under the same conditions to have
permitted its recovery, had it been formed. Moreover, Lane and
Walters (56) observed that triphenylethylene oxide is easily convertible
to the glycol under mildly acidic conditions. Gebhart and Adams (57)
support this view but found that tetraphenylethylene glycol, in acetic
acid catalyzed by perchloric acid, underwent rearrangement to the oxide
to the extent of about 80$. This oxide, however, is not converted to
the glycol under conditions which readily cause formation of triphenyl¬
ethylene glycol from its oxide.
The free-radical hypothesis, as introduced by Tiffeneau (58) and
used by McKenzie in the 1920's, (25) was proposed prior to the accumu¬
lation of much knowledge as to the properties of free radicals. Subse¬
quently the theory has fallen into disuse, largely for two reasons.
The first is the absence of chain reaction and polymerization products

20
characteristic of free radical reactions; and the second, the appearance
of a much better theory due to Meerwein and van Emster in 1922. (53> 59)
Dependence upon ionization of the isobornyl chloride to camphene
hydrochloride rearrangement was the key to Meerwein and van Emster*s
camphene- isobornyl
hydrochloride chloride
effort. This was strongly supported by these facts; 1) the kinetic
rates depended upon the ionizing power of the solvent, 2) the relative
rate orders in a number of solvents were essentially the same as had
been found for the ionizing capacity of triphenylmethyl chloride,
3) the rate increased as the stability of the anion increased, and
4) compounds such as HgClg, SbCl^, SbClj, FeCl^, and SnCl^, all known
to form additive compounds with the triphenylmethyl chloride, were
powerful catalysts for the rearrangement, whereas halides such as PClj
and SiCl^, which do not yield such additive compounds, had no catalytic
activity. This evidence leaves little doubt that the intermediate is
ionic.
From the foregoing discussion it can be seen that a large number
of the "1,2 shifts" which have been discovered are Wagner-Meerwein or
pinacol rearrangements. Since elucidation of the Wagner-Meerwein

21
rearrangement lias met with considerable success in recent years, the
information obtained in these studies will be relied upon heavily in
gaining an insight into the mechanism of the pinacol rearrangement.(6o)
Recent studies of the Wagner-Meerwein rearrangement have been conducted
under conditions in which a specific type of ester interchange occurs.
Although the hydrolysis and solvolysis of the esters of carboxylic
acids generally involve the rupture of the acyl-oxygen bond, (6l, 62)
it has been shown by Cohen and Schneider that esters of the tertiary
alcohol may undergo acid-catalyzed scission of the alkyl-oxygen bond,
while the acyl-oxygen bond remains intact. Also Phillips (65) showed
that the £-toluenesulfonate ester of l-phenylpropanol-2 undergoes
acetolysis to produce acetate which has undergone Walden inversion.(39)
That both carbons 1 and 2 (equation 28) are normally inverted during
rearrangement, was shown by experiments such as the deamination of 1,1-
diphenyl-2-aminopropanol (equation 39). (64, 65) Examples of similar
39)
behavior in the pinacol rearrangement may be seen in the rearrangement
of levo-1,l-dibenzyl-2-(1'-naphthyl) ethylene glycol to the optically-
active 1,4-diphenyl-3-(l’-naphthyl) butanone-2 (66) in dilute sulfuric

22
acid, (26) and in the formation of optically-active l,2-diphenyl-l,2-
epoxypropane from levo-1,2-diphenyl-l,2-propanediol. (64) In each of
these cases, however, the racemic ketones were obtained when concen¬
trated sulfuric acid was used as catalyst.
The migrating group itself retains its original configuration.
This has been shown in the case of aryl groups many times, since the
relative positions of substituents on the ring remains unchanged.
Moreover, Lane and Wallis (67) have shown that in the related Wolff
reaction a migrating group such as 2-phenylhexyl retains its original
configuration.
A stereochemical method of investigating the Wagner-Meerwein
reaction was proposed by Roberts and Kimball (68) and illustrated by
Winstein and Lucas (69) in the treatment of racemic erythro-3-fcromo-
butanol-2 with hydrogen bromide. Because the product was the erythro
erythro-meso
Í
40)
identical
CH
erythro
bromonium ion
erythro-meso

23
compound and not the threo racemate, the bromonium ion was postulated.
This ion could then suffer attack by bromide ion on the back side of
either of the two central carbon atoms to yield the erythro compound.
If the planar carbonium ion had been the intermediate, it would have
been expected that some of the threo racemate should be formed. In
like manner, the racemate of threo-3-bromobutanol-g gave only the DL
dibromide.
Cram (70, 71) applied this principle to the acetolysis of the
tosylates of the isomeric 3-phenyl-2-butanols. Since the threo
D or L
DL pair
threo

24
tosylate was not converted to any significant amount of the products of
42)
CH3~. f , -H
>c—
H ~ OTs^CHj
D or L
CH
QA.C
identical
erythro
the erythro tosylate and the erythro tosylate was not converted to the
products of the threo tosylate, Cram reasoned that rotation about the
two central atoms was restricted, and thus that classical, planar, open
carbonium ions could not be intermediates in these reactions. In order
to account for the results, Cram postulated the bridged phenonium ion
as the configuration-holding intermediate in the reaction sequence.
Similar bridged-type ions had been suggested on theoretical grounds by
Nevell, deSalas and Wilson (72) and others. (73-77)
The electrical effects of the groups within the reactant may
control the course of the reaction and determine which of two groups
will migrate (equations 43 and 44). (ll, 78) These effects may also
accelerate the reaction rate. Winstein, et al., (79) has shown that
the exo-p-bromobenzene sulfonate of norborneol undergoes acetolysis at

25
a rate 350 times greater than the rate at which the endo-isomer
acetolyzes. This fact, plus the fact that both exo- and endo-esters
norbornyl-
£-bromobenzene sulfonate
yielded, upon solvolysis, exclusively exo-products, seemed to indicate
that ion G could be an important intermediate in the solvolysis of the
exo-form, since carbon-6 is conveniently situated for participation in
the rate-determining loss of £-bromobenzenesulfonate ion. Such direct

26
participation does not appear possible in the case of the endo isomer,
although it is possible, of course, that ion G could be formed in this
instance subsequent to formation of ion H.
The most striking example of "Neighboring Group Participation," as
this phenomenon is known, is to be seen in the rate enhancement in the
acetolysis of a series of substituted ethanol tosylates. (8o) That the
Ethanol
tosylate Relative k
(ch5)2c-ch2ots
1
»2CHCH2OTs

(CH^gÓ-CHgOTs
4>5CCH2OTs
53
460
7.7 x 10^
participation of an adjacent group may, at times, control the stereo¬
chemical course of a reaction is illustrated by the bridged ion
concept, discussed previously.
In an extension of his study of the acetolysis rates of the exo-
and endo-p-bromobenzenesulfonates of norborneol, Winstein (8l) observed
that the optically active exo-ester exhibited a racemization rate which
was faster than the acetolysis rate. This phenomenon was later found
to occur also in the solvolysis of 3-phenyl-2-butyl-¿-toluenesulfonate
(82, 83) and of 2-phenyl-l-propyl-¿-bromobenzenesulfonate. (84, 85)
This phenomenon is called "internal return" and can be illustrated with
the acetolysis 3-phenyl-2-butyl-j> -1 o luenesulfonate. The ion pair (K),

27
postulated to explain internal return in this system can collapse
reversibly to give the D or L tosylate, or irreversibly tp give ion-
pair (G). If then, internal return is faster than the rate of for¬
mation of ion-pair (G) and subsequent irreversible collapse to D or L
acetate, then the racemization rate will be greater than the solvolysis
rate.
When 2-phenyl-2-(j>-tolyl)ethylamine is deaminated, the product is

28
found to consist primarily of two carbinols, l-phenyl-2-(|)-tolyl)-
ethanol and 2-phenyl-l-(£-tolyl)ethanol; (86) the former, due to
£-tolyl migration, is present in larger amount. In this case the ratio
of the yields of products is a ratio of the relative abilities of the
two groups to migrate during the rearrangement. Such ratios are termed
variously, "migratory abilities," "migratory tendencies," or "migratory
aptitudes," and imply a ratio of the ability for the group under dis¬
cussion to migrate, compared to the ability of some reference group to
migrate, given the same environment, the phenyl group being most often
used as the reference group.
An enormous amount of work has been performed in attempts to place
the more commonly observed migrating groups into some relative order,
and to assign some approximate value for the migratory aptitude of
each. Such a compilation would have the obvious utility of allowing
some prediction to be made regarding the relative yields of products,
when several may be anticipated. Among the early investigations
carried out with this object in mind, was that of P. J. Montagne, who
reviewed the work to 1920 that had been performed in the field of
intramolecular migrations. (87) Working with the symmetrical pinacols
of the type RC(0H)C(0H)R, Montagne found the ratio of ketone formed
by phenyl migration to that with R migration, to be, when R was
£-chlorophenyl, 60:k0; when R was £-bromophenyl, 57:^5*
That some progress has been made in this direction can be illus¬
trated, for example, in the controversy which occurred subsequent to
the publication of the results for the deamination of 2-phenyl-2-

29
(jg-tolyl)ethylamine. (88, 89) It was soon pointed out by Curtin (10)
that the £-tolyl/phenyl migration ratio of approximately 0.9 reported
was probably incorrect. A re-examination of the course of the reaction
(86) showed that this was the case and that the £-tolyl/phenyl
migration ratio was greater than one. This was a result predictable on
the basis of values found previously, for example, for the symmetrical
pinacols, l6; (5, 4) for the acetolysis of 2-phenyl-2-(p-tolyl)ethyl
tosylate, 2.5; (5) for the dehydration of 2-phenyl-2-(£-tolylethanol,
2.0; (6) for the Schmidt reaction, J.K to 5*0; (7-9) for the deami¬
nation of 2-amino-l-phenyl-l-£-tolylethanol, 1.3. (10)
Assignment of relative migratory aptitudes of a number of migrat¬
ing groups may be compiled. When steric requirements are not determin¬
ing, this order always holds for rearrangements other than the pinacol
and aldehyde-ketone. (4, 16, 90)
Evidence for the relegation of the electronic nature of the
migrating group to a position of secondary importance in certain
reactions, has been presented by Curtin and his co-workers, for
reactions involving the deamination of the triarylethanolamines.
(10, 91-95)
In studies (10, 96-99) of the rearrangement during deamination of
aminoalcohols of the type,

30
0
ketones of the type «fctí-CHgAr were found to be formed. The ratios of
products were qualitatively in the order of the migratory aptitudes for
these groups as found by Bachmann, Moser and Ferguson (k, l6) in their
studies of the tetra-substituted, symmetrical ethylene glycols.
When, however, Curtin deaminated the diasteromers of the amino-
alcohols of the type,
OH NH2
_¿_ ¿_
i i
At H
(there are now two asymetric centers—hence two dl pairs), it was found
that the migratory aptitudes for the groups in different diastereomeric
pairs were not the same. Thus, the erythro pair rearranged to give the
ketone with Ar migration, while the threo pair gave the ketone formed
by phenyl migration. That the electronic nature of the migrating group
was of secondary importance was indicated by the observation that the
aryl group, in the erythro pair always migrated whether it was £-tolyl,
£-anisyl, £-chlorophenyl or a-naphthyl. (100, 101) The threo pair in
all cases gave phenyl migration. Curtin accounts for these obser¬
vations by suggesting that there is a back-side attack by the migrating
group upon the carbon atom from which the amino group is being removed

31
through a transition state or bridged ion in which the large, bulky,
non-migrating groups are in a trans-configuration.
In a series of papers beginning in 1953> Collins and Bonner, (102,
103) in a study of the Wagner-Meerwein Reaction for the 1,2,2-tri-
phenylethyl system, showed that the bridged phenonium ion could not be
the intermediate in the transformations observed. The data required
the postulation of open-equilibrating carbonium ions, or their equiva¬
lent, to explain the distribution of the carbon-14 labels that was
observed.
The observations which forced this conclusion may be summarized in
this way:
1) Formic acid, to which a catalytic amount of £-toluenesulfonic
acid had been added, caused statistical distribution in both the
discretely chain- and ring-labeled 1,2,2-triphenylethanol and its
acetate (the bridged ion requires 50:50 distribution of the carbon-14-
in the ring-labeled compounds, whereas statistical, 2/3-l/3 distri¬
bution was observed).
2) Carbon-14 distribution in the £-toluenesulfonate esters of the
alcohol, which was not statistical in either the chain- or ring-labeled
compounds, could be exactly calculated, one from the other, by means of
the rate expressions in a mechanism involving competition between the
initial ion formed and its direct conversion to product on the one hand,
and its equilibration, with subsequent conversion to product on the
other•

32
3) Examination of the rates of chain- and ring-label equilibration
and the rate of labeled acetoxyl loss from the 1,2,2-triphenylethyl
acetate, proved that in each instance of acetoxyl loss, a molar
equilvalent amount of chain- and ring-label equilibration occurred.
These observations indicate, a) that no internal return (7^, 8l) occurs
since this would require a slower rate for acetoxyl loss than for
chain- and ring-label equilibration; b) that bridged ions cannot be
intermediates since this would require that the rate of chain-label
equilibration be faster than the rate of ring equilibration; and c) that
completely concerted migration of the phenyl group is excluded since
this would require that the rate of loss of acetoxyl be half the
equilibration rate of the chain-labeled acetate and the rate of equili¬
bration of the ring-labeled acetate be 3/2 the rate of acetoxyl
exchange, whereas the three rates observed are the same.
As has already been noted, the conversion of substituted acet¬
aldehydes into ketones through the agency of dilute acids at elevated
temperatures or by means of concentrated mineral acids, has been taken
as evidence of the relationship of this rearrangement to that of the
pinacol rearrangement. The nature of the relationship, however, has
been quite obscure in view of the migratory aptitudes exhibited by the
substituent groups in the related rearrangements, discussed earlier in
this presentation. Some of the anomalous observations may be illus¬
trated with the following examples:

33
Equation No.
19 Me
20 0^>Me
22 0> -Tol
24 o/Et = 4/1
25 Et exclusively
2 6 Et ^ £-anisyl
For additional examples of the apparently quite general phenomenon, see
references 25, 24, 52 and 104 through 107*
In an effort to obtain sufficient information to allow correlation
between the pinacol and aldehyde-ketone rearrangements, Collins (2) has
investigated the rearrangements of triphenylethylene glycol and tri-
phenylacetaldehyde, variously labeled with C^. Using the general
mechanism formulated by previous investigators (53> 49, 97, 108, 109)
and applying the idea of open carbonium ions, Collins was led to
propose a mechanism involving 4 reaction paths, which included the
conjugate acid of triphenylacetaldehyde and which adequately explained
the distribution of the C1^ label which was observed. In an extension
of this work, Benjamin and Collins (l) were able to link the pinacol
rearrangements of 1,l-diphenyl-2-j>-tolylethylene glycol, 1,2-diphenyl-
l-£-tolylethylene glycol and the aldehyde-ketone rearrangement of
diphenyl-£-tolylacetaldehyde through the conjugate acid of the aldehyde.
These authors were able to show that the true £-tolyl/phenyl migration
ratio was not given by the ratio of ketonic products (these indicate
phenyl migration in preference to £-tolyl), but rather was given by the

ratio of the specific rate constants as defined in the equation
*1 - *H *Tol me
kp k, k'H
The significance of this relation is developed in the Discussion
Section of this presentation where these ideas are applied in an
identical manner in the explanation of the results obtained in this
1 +
H
^ol
1+ 3
research.

METHODS AND RESULTS
The syntheses of the carbon-l4 labeled compounds were accomplished
as shown in Charts III, IV, V, and VI. The nonradioactive ketones IV
and V were prepared by adding the diarylcadmium reagent to the
appropriate diarylacetyl chloride; the aldehyde, III, was formed upon
stirring threo-Ic in 90$ formic acid for three days. Each of the
glycols used in this research was subjected to cleavage with lead
tetraacetate and the fragments were examined for radioactivity, in
order to prove the position of the carbon-14 label. All-were found to
be discretely labeled in the positions indicated except for erythro-Ib,
which contained 8.1$ of the label in the tertiary carbon. Appropriate
corrections have been made in the tables for this small but significant
percent of carbon-l^ in the number 1 chain position of erythro-Ib.
The aldehyde, III, and the glycols, erythro-Ib, threo-Ib, threo-Ic
and Ila, were subjected to rearrangement in concentrated sulfuric acid
o
at 0 C. Glycols Ic and Ila also were subjected to rearrangement in
formic acid at room temperature. The yields of IV and V, and in the
case of the formic acid rearrangements, III, were determined by the
radioactivity dilution method. The results of these experiments are
given in Tables II and III. The crystalline ketones obtained as a
result of the sulfuric acid rearrangements were cleaved with alkali;
* fi* * *
0-CHg-Tol + TolCOOH
Tol
IVab Vb
35

36
CHART III
Preparation of threo-l,2-di-p-tolyl
(2-p-methyl-C^)-1-phenylethylene Glycol (ic)
* *
C02 —» PhCOOH
PhCHpOH ^"^-CH*
¿ HC1 W J
AcpO .
AlClj
* ?H/P
Toig-C-OH
H
Hp * 8
—£_* TolCHpC-OH
Pd-C ¿
1) PCI5 * §
-L 4 TolCHpC -Ph
o^ r jn ' d
2) c6h6
A1C1
* Hfh
T0I9-C-T0I
OH OH
threo-Ic
CHART IV
Preparation of threo-l,2-di-p-tolyl-l-
phenylethylene-2-C1^ Glycol (lb)
*
COOH
LiAlHk *
4 TolCHpOH
SOCL
a *
TolCHpC1
KCN
*
> TolCHpCSN
TolCrfgCOOH
continue as per Chart III ^
threo-Ib

37
CHART V
Preparation of erythro-l,2-di-p-tolyl-l-
phenylethylene-2-C~*~^ Glycol (lb)
ch2c-oh
* Q Br0
—< k TolCH^C-Tol
1) PC157 2 CS0
2) CH,-^ 2
A1C1X
0H ^ T0I9— fi-Tol
2) H+ OH
PhMgJBr
ch5
erythro-Ib
CHART VI
Preparation of l,l-di-p-tolyl-2-
l4
phenylethylene-l-C Glycol (lla)
PhCHO
1)KCN* v
2)HC1 *
OH*
Ph¿-COOH
H
MeOH 9H 8 2TolMgBr
MeUV. ■» PhC—C-OMe *
h2so4 h
5 OH OH
II a

38
TABLE II
Yields of Ketones IV and V Produced by the
Action of Sulfuric Acid Upon I, II, and III
Run Ro.
Reactant
Yield of Ketone ($)
IV V
1
threo-Ib
58.0
42.0
2
threo-Ic
59-6
4o.4
3
threo-Ic
58.3
41.7a
4'
threo-Ic
58.4
41.6
5
threo-Ic
57-3
42.7
Average
58.3
41.7
6
I la
49.6
50.4a
7
I la
47.1
52.9
8
Ila
48.0
52. ob
Average
47.6
52.4
9
III
53-5
46.5
10
III
53-2
46.8
Average
53.4
46.6
11
erythro-Ib
53.4
46.6
Reactions performed at 10° C. Results not included in averages.
1^
IV determined by'dilution technique, total ketone by veight and
V by difference.

59
(Tol) -CH-C-* » (Tol)2-CH2 + COOH
Vab VIb
*
* $-CH2-Tol +
*
TolCOOH .
IVcd
Ve
The benzoic and £-toluic acid fractions obtained upon cleavage were in
all cases carefully purified by crystallization and sublimation.
TABLE III
Yield of Aldehyde III, Produced by the
Action of Formic Acid Upon Glycols I and II
Run No.
Reactant
Actual Yield ($)
III
Yield of III
Corrected for
94.1$ Recovery
12
threo-Ic
75-9
8O.6
15
Ila
55-9
36.0
14
III
94.1

4o
The neutral, dlarylmethane fractions from the cleavages of IVab
and Vab were oxidized with chromic acid:
4>-CH2-Tol
CrO,
HQAc
♦ -C--COOH
Vila
Tol-CH2-Tol
CrO*
p >
HOAc
L
HOOC--C — 0-COOH
Villa
The acidic products Vila and Villa were purified carefully by crystal¬
lization, The acid degradation products V, VI, VII, and VIII were
assayed for carbon-14 content, the results of these being recorded in
Tables IV and V.
TABLE IV
Fraction of Radioactivity Found in Vc from Cleavage
of IVcd Derived From the Rearrangement of threo-Ic
Run No.
Activity in Vc
2
0.478
2
0.476
5
0.483
4
0.492
5
0.512
5
0.496
Average
0.490

hi
TABLE V
Fraction of Radioactivity in Fragments From Cleavage
of IVab and Vab Resulting from Rearrangements
of Threo-Ib, Erythro-Ib, and Ila
From IVab From Vab
Run No.
Reactant
Vb
Vila
VIb
Villa
1
threo-Ib
0.961
0.039
0.975
0.026
9
Ila
0.018
0.980
0.008
0.955
10
Ila
0.010
-
0.009
-
11
erythro-Ib
-
0.010
-
0.139
16
threo-Ib
O.98O
0.021
O.986
0.014

DISCUSSION
The equation (equation l) given in the Introduction was developed
(l) in an effort to correlate the observed fates of the various
carbon-14 labels during the acid-catalyzed rearrangements of several
triarylsubstituted ethylene glycols and acetaldehydes. The reasons for
extending the investigation to the compounds treated in this research
have been discussed in the Introduction and are concerned with a deter¬
mination of the generality of equation 1 when applied to closely-
related systems. Accordingly, Charts I and II represent the rearrange¬
ment mechanism for compounds I, II and III as postulated by Benjamin
and Collins for the system of compounds they studied, (l) Similar
symbols for the various specific rate constants have been used so that
equation 1 retains its original form. The derivation of equation 1, as
applied to this research, is to be found in the Experimental Section.
No steady state assumption (110) is necessary in the derivation.
It should be pointed out that equation 1 is applicable only to
that portion of the pinacol rearrangement which proceeds through
tertiary hydroxyl removal (paths C through E), and the aldehyde-ketone
rearrangement.
The determination of the components for equation 1 may be deduced
from an examination of Charts I and II. For the ratio, ^ToiA'g, the
sum of the yields by paths D and E is divided by the yield of path C.
If we now define ir^, m^, mc, m¿, and mg, respectively, as the mole
frations of threo- and erythro-Ic which proceed to products through

43
paths A to E (Chart I), ^olA'ii then is equal to md + me/mc* In like
manner, the ratio kjj/k^ is obtained by the relation me, + md,/mf
(Chart II). The ratio me/md may be obtained in two ways: 1) From the
double-labeling results in the rearrangement of threo-I, the total
*
mQ + mg is determined by the yield of TolCOOH from threo-Ib, while the
total m + l/2me is determined from the yield of TolCOOH from threo-Ic.
Solution of the simultaneous equations can give the value for mg.
Since the yield of V gives the total 1% + m¿, then subtraction of the
*
yield of n^, as determined by the activity in 0=C(C00H)2> gives md;
2) The ratio of the yields IV/V from the rearrangement of aldehyde III,
also gives nig/m^. Both methods should give the same ratio within the
experimental error, if the mechanism of Chart I is to explain the
observed carbon-14 distribution during rearrangement. In order to
obtain the £-tolyl/phenyl migration ratio upon solution of equation 1,
it is necessary to divide kp/kp by 2, since the rearranging system
under study involves two £-tolyl groups and only one phenyl group.
The implications of the pertinent data of the preceding section
may now be considered. Tables II through V reveal the yield of each
ketone produced from the different reactants, as well as the fates of
the various carbon-l4 labels. The mechanism given in Charts I and II
accounts for these facts. The consequences of both £-tolyl and of
chain labeling are indicated.
For the threo-I glycol may now be calculated the contributions of
each of the reaction paths. There are several different methods, some
of which are nearly independent one of the other, by which these

44
calculations may "be made. Since it is the purpose of this research to
determine, by use of equation 1 (see Introduction), whether, in the
rearrangements of I, II, and III the £-tolyl/phenyl migration ratio is
greater than one, we have, for this purpose, treated the data of Tables
II through V in two different ways: l) in the first method the
yields of IV and V from the rearrangement of di-£-tolylphenylacet-
aldehyde (ill) have been ignored, and the averages of the measurements
pertaining to the three glycols have been employed to calculate the
various path yields; 2) in the second method the same data were used as
in the first. We have taken account, however, of the errors probable
in each of the measurements of Tables II through V, and have made the
assumption that all of the errors accumulate in mc, since the determi¬
nation of a maximum value for mc is crucial in estimating, from
equation 1, a minimum £-tolyl/phenyl migration ratio.*
The results of the foregoing calculations are given in Table VI,
and the values for kg/k^, krpol/k'H and the £-tolyl/phenyl migration
ratio (bp/2kp) estimated from each set of calculations are given in
Table VII. Actual sample calculations of the type used in obtaining
the results in the tables are given in the Experimental Section.
It is interesting to observe that the threo- and erythro- configu¬
rational isomers of I rearrange to give slightly different yields of IV
♦There is another general method by which the path yields and rate-
constant ratios may be calculated, namely through the use of the ratio
(1.15) of ketones IV:V produced from the rearrangement of aldehyde III
(Table II). This method is much inferior to methods 1 and 2 for it
involves subtraction of large numbers in determining the very small
and is thus extremely sensitive to small changes in the percentages of
ketones produced. This is not true for methods 1 and 2.

TABLE VI
45
Summary of Mole-Fraction Calculations From
the Data of Tables II Through V
Mole
Fraction
threo-I
Method of Calculation
1
erythro-I threo-I
2
erythro-I
%
0.008
0.065
0.011
O.O65
“b
0.018
0.005
0.023
0.005
mc
0.005
(-) value
0.046
0.020
md
0.409
0.401
0.4o6
0.401
“e
O.560
0.541
0.514
0.509
For Glycol II
0.177
0.169
m'd
0.347
0.355
m'
e
0.476
0.476

46
TABLE VII
Summary of the Ratios Calculated for use in or by Equation 1
Ratio
Method
1
of Calculation
2
me/md
1.37
1.27
k$/kH
4.7
4-9
km ,/k'TT from threo-I
190
20
kp/2kp from threo-I
25
2.25
km ,/k* from erythro-I
Tol H •——-
00
45
kp/2kp from erythro-I
00
5
and V. That this result is due mostly, if not entirely, to different
contributions of paths A. and B in the two cases may be demonstrated by
comparing the ratios of (mc + me)/m¿, for the rearrangements of threo-
and erythro-Ib, in which the total (mc + me), is determined by the
# .
yield of TolCOOH (Vb) in each case. From the threo isomer this is
0.566/o.4o8 = 1.385, whereas for the erythro isomer it is 0.529/0.401 =
1.32. These ratios are the same within experimental error. Additional
support for this explanation is the reversal in relative contributions
of paths A and B in the threo and erythro isomers. These values are
sufficiently large to preclude their reversal by experimental error

alone. It then is apparent that the aryl group added by means of the
Grignard reagent to the appropriate benzoin is not the predominantly
migrating group when the rearrangement proceeds through secondary
hydroxyl removal, i.e., insofar as the reaction proceeds through paths
A and B, it is stereospecific. (91-95) Benjamin and Collins (l) were
not able to observe this phenomenon because with the isomers of 1,2-di-
phenyl-l-jj-tolylethylene glycol, there was too little secondary
hydroxyl removal to allow them to differentiate paths A and B.
Examination of the p-tolyl/phenyl migration ratios listed in Table
VII makes it clear that an exact value for the ratio cannot be given
for the reactions under study. The significant point is, however, that
when even extreme values, deliberately chosen, are used as the com¬
ponents of equation 1, the minimum value for the £-tolyl/phenyl
migration ratio is found to be greater than one, and the most probable
value, based upon average values for the components is in the range of
three to five.
Additional support for a somewhat higher value for ^TolA 'h> than
the minimum of 20, is found in the rearrangement of tri-p-tolylethylene
glycol, (ill) where it is found, if the assumption is made that the
contribution to the product through secondary hydroxyl removal is of
the same order of magnitude as found for the erythro-Ib above, that the
kp^/k'jj must be at least 25* Moreover in the rearrangements of
threo-Ic and Ila in formic acid, when the ^toiA'a and- values are
treated in the same way as previously reported, (l) it is found that
kroi/k'n in concentrated sulfuric acid is 37*5*

kQ
In view of the experimental errors that have been discussed, the
values for the ratios and the yields of ketones produced in both
sulfuric and formic acids agree with those predicted in the Intro¬
duction better than expected. In addition, even though the simple
ratio of ketones obtained from aldehyde III indicates the £-tolyl/
phenyl migration ratio to be less than one, solution of equation 1 for
this system shows that the most probable value is significantly
greater than one, in agreement with previous observations. (3-10) It
is important also to note that the variations in the relative amounts
of ketones from the glycols and aldehyde are successfully predicted by
equation 1. The results of this research, therefore, provide strong
evidence in support of the mechanism for the pinacol rearrangement
proposed by Benjamin and Collins, (l) and in addition provide a
possible explanation for the occasionally observed, partially stereo¬
specific course of the rearrangement. (26, k9, 100, 101, 66)

EXPERIMENTAL
Radioactivity Determinations and the Radioactivity Dilution Method of
Yield Determinations.
The radioactivity assays reported in this dissertation -were per¬
formed 'on a vibrating reed electrometer, using the wet combustion
procedure which was described by Neville (112) and modified by Bonner
and Collins. (113) This method has also been described by Raaen and
Ropp..(ll4)
The calculation of the yields of the reaction products by the
carbon-14 dilution method was performed by means of the equation:
Ai (Di + X) = AqX: where
Aq = molar activity of the starting material = molar activity of
undiluted product for which calculation is to be made.
A.^ = measured molar activity of purified, diluted product.
= weight of nonradioactive analog added.
X = weight of radioactive product with molar radioactivity equal
to Aq.
This technique was discussed by Mayor and Collins. (115) The mechanics
of the actual dilutions were performed in the manner described in the
section next below.
Sulfuric Acid Catalyzed Rearrangements.
In a typical experiment 3.082 gm. of glycol or aldehyde was added
to 70 ml. of concentrated sulfuric acid, previously cooled to 0° C. in
an ice-salt bath. Stirring was continued while the temperature was
49

50
maintained between -2° to 0° C. At the end of 30 minutes, the reaction
mixture was poured into 700 ml. of ice-water mixture with vigorous
stirring. The mixture was extracted five times with 100 ml. portions of
ether in a separatory funnel and the combined ether extracts were
washed twice with 100 ml. portions of water, once with 50 ml. of satu¬
rated aqueous sodium bicarbonate and again with 100 ml. of water. The
ether solution was then evaporated to dryness on the steam bath, the
residue dissolved in chloroform, transferred quantitatively to a 100
ml. volumetric flask and dilution to 100 ml. made with chloroform. One
50 ml. aliquot was transferred to a flask containing 2.000 gm. of
nonradioactive ketone IV and the remaining 50 ml. aliquot was trans¬
ferred to a flask containing 2.000 gm. of nonradioactive ketone V. The
contents of each flask were stirred until complete solution was
effected, and the solvent was removed in an air stream on the steam
bath. The residue in each case was dissolved in 95$ ethanol, treated
with Norit and filtered through a talc pad. On seeding the solutions
with the appropriate ketones and cooling with an ice bath, the ketones
crystallized. After crystallizing each sample five times from ethanol,
50 mg. of the nonradioactive ketone corresponding to the contaminating
ketone was added and each sample was again crystallized five times from
ethanol. Melting points of ketone V were always 56.5-57*5°> while
those of ketone IV were in the range 65-67 , and were considered to be
sufficiently pure for C-lk assay. See Table VIII.
Formic Acid Rearrangements.
In a typical experiment, 2.000 gm. of the glycol was stirred with

TABLE VIII
SUMMARY OF YIELD DETERMINATION EXPERIMENTS FOR HgSOj*. REARRANGEMENTS
Run
No.
Start ing8.
Compound
Wt. of
Starting
Compound
Ketone
Yield
Theory
Aliquot
Taken
Theory of
Ketone in
Aliquot
Wt. of IV
Added to
Aliquot
Assay of
Recovered
IV
Wt. of V
Added to
Aliquot
Assay of
Recovered
V
1
Threo-Ib
5.0815
2.908
1/2
1.454
2.000
0.5995
2.000
0.4705
2
Threo-Ic
10.610
10.000
i/4
2.500
2.500
1.758
2.500
1.279
5
Threo-Ic
1.049
O.988
1/2
0.495
1.000
0-957
1.000
O.669
4
Threo-Ic
2.000
1.885
1/2
0.945
2.000
1.069
2.000
O.766
5
Threo-Ic
5-225
4.950
l/lO
0.495
1.450
0.786
0-955
0.8515
6
Ila
1.059
1.000
1/2
0.500
1.000
0.5915
1.000
0.5975
7
Ila
5-100
4.811
1/2
2.405
2.500
0.6525
2.500
0.7077
8
Ila
I.O606
1.000
1
1.000
1.500
0.5055
See Table
II
9
III
2.0592
2.0592
1/2
1.0296
2.000
0.954
2.000
0.807
10
III
5-090
5.090
2/5
1.256
2.000
1.2185
2.000
1.050
11
Erythro-Ib
4.6586
4.420
1/2
2.210
5-000
0.4795
5-000
0.4505
aMolar activities in millicuries per mole of starting compounds: Threo-Ib, 2.124;
Threo-Ic, 5-221; Ila, 2.155; III, 5-221; Erythro-Ib, 2.112.
TABLE IX
SUMMARY OF YIELD DETERMINATION EXPERIMENTS FOR FORMIC ACID REARRANGEMENTS
Run
No.
Starting
Compound
Wt. of
Starting
Material
Ketone-
Aldehyde
Yield
Th perry
Aliquot
Taken
Theory of
Aid. and
Ketone in
AHqunt
Wt. of III
Added to
Aliqunt
Assay
of 2,4-
DNPH
Actual
Yield of
Cal'd Yield of III
on 94.1$
Recovery Basis
12
Threo-Ic
2.000
1.886
l/lO
0.1886
0.150
2-555
75-9
80.6
15
Ila
2.000
1.886
l/5
0.5772
0.200
0.859
55-9
56.0
14
III
1.000
1.000
0.200
0.200
2.551
94.1

52
100 ml. of 90# formic acid for three days. The mixture was then poured
into 500 ml. of water and extracted five times with chloroform. The
combined chloroform extracts were washed twice with water, once with
saturated aqueous sodium bicarbonate and again with water. The chloro¬
form solution, after concentration on the steam bath, was transferred
quantatively to a 200 ml. volumetric flask. A 20 ml. aliquot was taken
and added to 150 mg. of nonradioactive aldehyde, III, stirred until the
solution was homogeneous, and evaporated to dryness. The residue was
dissolved in 95# ethanol, treated with Norit and filtered through a
talc pad. The ethanolic solution was then treated while boiling, with
a mixture consisting of 500 mg. of 2,4-dinitrophenylhydrazine, 2 ml. of
concentrated sulfuric acid, and sufficient water to make a clear
solution. The mixture was boiled for 15 minutes (during which time the
oily globules which first separate, solidify), then cooled in an ice
bath and the product removed by filtration. The product was purified
by crystallization from 95# ethanol (large volume, ca. 300 ml.
required). The product had a melting point of 190° and was bright
yellow in color. See Table IX.
Aldehyde Stability in Formic Acid.
In order to determine the recovery of the aldehyde under the
reaction conditions, the foregoing procedure was repeated with puri¬
fied, radioactive III. At the end of the three-day reaction time, the
formic acid-aldehyde mixture was cooled in ice and the crystalline
aldehyde was removed by filtration, to yield 93# of the aldehyde,
m. p. 93-1+°• The mother liquor (formic acid) was poured into 500 ml.

53
of water, extracted with chloroform as in the above procedure, and
the aldehyde, obtained by filtration, was added to the chloroform
extract. The extract was transferred to a volumetric flask and the
yield was determined by the radioactivity dilution method. In this way
the yield was determined to be 94. 1$ (Table IX).
Ketone Cleavage for Carbon-14 Distribution.
In a typical experiment 0.5 gnu of the ketone was heated under
reflux in an atmosphere of nitrogen with 30 ml. of 25$ methanolic
potassium hydroxide for 24 hours, (l) The methanol was removed by
distillation under nitrogen and the residue was dissolved in 200 ml. of
water. The aqueous solution was extracted five times with ether and
acidified. The liberated acid was then extracted with ether and the
solvent was removed by distillation. The acid was purified by crystal¬
lization from water, followed by sublimation.
The ether extract, containing the diaryImethane fragment, was
evaporated to dryness and the residue was heated under reflux with a
mixture of 20 ml. of glacial acetic acid, 2.0 gm. of chromium trioxide
in 2 ml. of water, and 3 ml. of concentrated sulfuric acid. After 45
minutes, the reaction mixture was poured into 100 ml. of ice water and
the precipitated acid was filtered from the mixture, washed with water
and dissolved in aqueous sodium bicarbonate. The aqueous solution was
treated with Norit, filtered through a talc pad and acidified to
recover the acid. When the acid was 4,4'-dicarboxybenzophenone the
product was crystallized from boiling glacial acetic acid; when
£-benzoyl benzoic acid, purification was accomplished either by

54
sublimation of the acid or conversion to the methyl ester by means of
diazomethane and subsequent crystallization from methanol. See Table X.
Ketone Stability in Concentrated Sulfuric Acid.
In separate experiments, 1.000 gm. of each of the product ketones
was stirred with 20 ml. of concentrated sulfuric acid while the temper-
o
ature was maintained at 4 C. After 50 minutes the mixture was poured
into ice water and extracted in a manner identical with that employed in
t
the glycol and aldehyde rearrangements. In the case of 4,4-dimethyl-
benzhydrylphenyl ketone (V), the recovery of ketone with m. p. 58° C.,
was 98.8°¡o, and in the case of 4-methylbenzhydryl-|)-tolyl ketone (IV),
the recovery of ketone with m. p. 68° C. was 99*1$* The fluorescent
green coloration and ether insoluble material which was always observed
in the sulfuric acid rearrangements, was entirely absent in the ketone
stability tests.
p-Methylbenzhydryl p-Tolyl Ketone (IV).
a) Phenyl-p-Tolylearbinol.
An ether solution of 100 gm. of phenyl-£-tolyl ketone was treated
with 14 gm. of lithium aluminum hydride in dry ether in the usual
manner. After hydrolysis with water and dilute hydrochloric acid, the
ether layer was separated and the aqueous layer was extracted twice
with ether. The combined ether extracts were washed with water and
dried over anhydrous sodium sulfate, then evaporated to dryness. There
resulted 97*1 gm* of the desired carbinol; m. p. 54°. (ll6)
b) Phenyl-p-Tolylmethyl Chloride.
A hexane solution of 97*1 gm. of the carbinol was treated with

TABLE X
SUMMARY OF RADIOACTIVITY DISTRIBUTION DETERMINATIONS
Fragments
from IV
Fragments
from V
Assay of
Assay of
Run
No.a V
VII
VI
VIII
IV Used
V Used
Remarks
1
0.5727
0.0255
0.4695
0.0125
0.5995
0.4705
% and m^ computed from VII
and VIII.
2
0.7918
-
-
-
1.758
-
2
0.4749
-
-
-
1.059
-
3
0.4256
-
-
-
0.937
-
4
0.4959
-
-
-
I.O69
-
5
0.3785
-
-
-
O.7865
-
5
2.575
-
-
-
5-221
-
6
0.007
-
0.005
-
0.5915
0.3975
7
0.007
-
O.OO65
-
0.6525
0.7077
9
0.4507
-
-
-
0.954
-
10
0.5955
-
-
-
1.2185
-
Correct for 8.1# scramble
11
-
0.0451
-
0.0997
0.4793
0.4505
for Table V.
15
2.64o
-
-
-
5-221
-
From rearrangement of III.
16
2.094
0.0456
2.045
0.0289
2.124
2.124
From rearrangement of
threo-Ia.
^un numbers correspond to those used in Table VIII.

56
80 ml. of thionyl chloride dissolved in 200 ml. of hexane. After the
initial vigorous reaction has subsided, the mixture was heated on the
steam bath under reflux for l-l/2 hours. After the reaction was
complete, the hexane and excess thionyl chloride were removed under
reduced pressure and the product was distilled, to yield 104 gm. (98#)
of water-white oil; b. p. 158-l63°/l mm. (116)
c) Phenyl-p-Tolylacetonitrile.
A mixture of 104 gm. of phenyl j>-tolylmethyl chloride and 50 gm.
of cuprous cyanide were placed in a round-bottomed flask and a short
air condenser was attached. The flask was immersed in a Wood's metal
bath and heated to 215°• After 4 hours the flask was removed, cooled
and the contents extracted with acetone. The acetone solution was
allowed to stand overnight and filtered through a Celite pad. The
acetone was removed by distillation and the product was distilled under
reduced pressure. There was obtained 85 gm. (85•5%) of the nitrile.
On crystallization from hexane the product separated as white crystals;
m. p. 61-62°. (117)
d) Phenyl-p-Tolylacetic Acid.
A mixture of 85 gm. of the nitrile, 600 ml. of 50# aqueous
sulfuric acid and 200 ml. of glacial acetic acid was refluxed overnight.
The reaction mixture was cooled, poured into one 1. of ice-water
mixture and stirred until the acid solidified. The product was
filtered and washed with water. The solid was digested with saturated
sodium bicarbonate solution on the steam bath for 50 minutes, treated
with Norit and filtered. On acidification there was obtained 84.5 gm*

57
(91-5#) of the acid; m. p. II6-II6.50. (107)
e) Phenyl-p-Tolylacetyl Chloride.
To a solution of 84 gm. of phenyl £-tolylacetic acid in 100 ml. of
benzene was added 5^ ml. of thionyl chloride. After the addition was
completed, the solution was allowed to reflux on the steam bath for 1
hour. The benzene and excess thionyl chloride was removed by distil¬
lation under reduced pressure. An additional 50 ml. of benzene was
added and distilled to remove the last traces of thionyl chloride.
The residue was then dissolved in 100 ml. of dry benzene and used
directly for the following preparation. (102a)
f) p-Methylbenzhydryl p-Tolyl Ketone (IV).
£-Tolyl magnesium bromide was prepared from 151 gm. of £-bromo-
toluene and 21.5 gm. of magnesium turnings. The ether solution was
cooled and then treated with 83 gm. of anhydrous cadmium chloride,
while being stirred vigorously. After the cadmium chloride had been
added, the reaction mixture was heated under reflux for 1 hour. Most
of the ether was removed by distillation, 600 ml. of dry benzene was
added and the distillation continued until the distillate temperature
reached 65°. Dry benzene (150 ml.) was added and the reaction mixture
cooled with ice water. While the mixture was being stirred vigorously,
the acid chloride solution, as described above, was added slowly.
After the acid chloride solution had been added, the reaction mixture
was stirred for 1 hour at room temperature, then 30 minutes under
gentle reflux. The reaction mixture was decomposed with ice, followed
by addition of sufficient concentrated hydrochloric acid to dissolve

58
the metal salts, and the benzene layer was separated. The aqueous
layer was extracted twice with an ether-benzene mixture (2:1). The
combined extracts were washed with water, 5$ aqueous sodium hydroxide
and again with water, dried with anhydrous sodium sulfate and the
solvents distilled. The brown, oily residue was steam distilled to
remove di-£-tolyl, and the dried oil was distilled under reduced
pressure. The fraction boiling 215-240° at 0.5 mm was collected,
dissolved in hexane and allowed to crystallize. There was obtained
53.6 gm. (48$) of the ketone; m. p. 67*5-68.5°*
Anal. Calc'd for C22H200; C, 88.00; H, 6.71; Found: C, 88.09,
88.01; H, 6.69, 6.80.
The oxime was prepared by treating 1 gm. of the ketone in 5 ml. of
pyridine and 5 ml. of 95$ ethanol with 1.4 gm. of hydroxylamine hydro¬
chloride. The mixture was heated under reflux for 4-l/2 hours and the
alcohol and pyridine removed under reduced pressure. The residue was
stirred with 120 ml. of water and extracted with ether. Upon evapo¬
ration of the ether solution and crystallization twice from 95$
ethanol, there resulted 0.2 gm. of the oxime; m. p. 210-210.5° C.
Anal. Calc'd for C22H21N0; C, 83.8$; H, 6.67$; Found: C, 83.96;
H, 6.78.
g) p-Methylbenzhydryl p-Tolyl Ketone-C^ (iVb).
This ketone was prepared in the same manner as that above, radio-
*
active cuprous cyanide (CuCN was prepared by a modification of the
method of Barber) (ll8) being used in the preparation of the phenyl
£-tolylacetonitrile. The phenyl £-tolylacetic acid had a radioactivity

59
assay of 2.195 - 0.009 mc/mole. The pure ketone melted at 67-68°, and
had a radioactivity assay of 2.205 - 0.011. Structure and radio¬
chemical label position determinations were accomplished by subjecting
a sample of the ketone to cleavage with 25# potassium hydroxide in
methanol in an atmosphere of nitrogen, (l) On oxidation of the neutral
fraction with chromic acid in acetic acid, £-benzoylbenzoic acid was
obtained in 87# yield, m. p. 198-199°; and was nonradioactive. The
£-toluic acid was obtained by acidification of the aqueous solution
from the cleavage reaction, yielding 100# of air-dried crude product;
m. p. 174-176°. One crystallization from water sufficed to yield the
pure acid, m. p. 178-179°; with a radioactivity assay of 2.167 * 0.001
mc/mole.
l4
Threo-l,2-di-p-tolyl-l-phenylethylene-2-C Glycol (lb), Method I.
£-Methylbenzhydryl £-tolyl ketone-C1^ (8 gm.) was dissolved in 120
ml. of glacial acetic acid was treated with 20 ml. of concentrated
nitric acid (119) and allowed to reflux for 25 minutes. The mixture
was then poured into ice water, and extracted with ether, which was, in
turn, washed with water, saturated aqueous sodium bicarbonate solution,
and again with water. After being dried over anhydrous sodium sulfate,
the solution was used directly for the reduction without further
treatment.
A slurry was prepared with 4.5 gm. of lithium aluminum hydride in
dry ether and the solution of the ketol was added slowly. The mixture
was stirred for an additional hour, water added to decompose the excess
hydride and to completely hydrate the metal hydroxides. The ether

6o
solution was removed by filtration and evaporated to dryness. The
slightly oily, brown residue was washed with petroleum ether and
crystallized from ethanol. Repeated crystallization from ethanol gave
1 gm. of glycol; m. p. 147-150°, radioactivity assay 2.179 mc/mole.
The remaining material had am. p. of 130-135°; identical with the
behavior of an approximately equal mixture of the two diasteriomers,
prepared as described below.
Threo-l^-di-p-tolyl-l-phenylethylene-g-C1^ Glycol (lb), Method II.
l4
a) p-Methylbenzyl-a-C Alcohol.
Carboxyl-labeled £-toluic acid (55*5 gm.) was treated with 25 gm.
of lithium aluminum hydride in ether solution in the usual way. After
the excess hydride was destroyed by the cautious addition of water and
separation of the ether solution, there was obtained 48.8 gm. (98$) of
the carbinol.
14
b) p-Methylbenzyl-a-C Chloride.
The above carbinol was treated with 100 gm. of thionyl chloride
in 150 ml. of hexane. Upon removal of the excess thionyl chloride and
hexane under reduced pressure, there was obtained 55*1 gm. (98$) of the
chloride.
c) p-Tolylacetonitrile-a-C^.
The £-methylbenzyl-a-Cli|' chloride was treated with sodium cyanide
according to the method of Vogel. (120) Upon distillation of the
product there was obtained 43-9 gm- of the nitrile (85.5$)•
d) p-Tolylacetic Acid (Carboxyl-labeled with carbon-14).
¿-Tolylacetonitrile-a-C1^ (43.9 gm.) was treated with 100 ml. of

6i
50$ aqueous sulfuric acid, to which had been added 50 ml. of glacial
acetic acid. (120) After heating at reflux for one hour, the mixture
was poured over 500 gm. of ice and the precipitated acid was removed by-
filtration. The crude acid was melted under water, with stirring, the
flask was then cooled in an ice bath and the acid was removed by
filtration. The acid was then dissolved in dilute sodium hydroxide and
the solution was filtered through a pad of Celite. Upon acidification
of the filtrate and cooling, there was obtained 59» 4 gm. (78$) of the
pure acid; m. p. 90-91°• (121)
e) Preparation of the Glycol (lb).
The glycol was prepared by identical methods as indicated for the
tolyl-labeled glycol discussed below, 19-4 gm. of the above a-labeled
£-tolyl acetic acid being employed. There was obtained 5*7 gm» of the
, o
glycol; m. p. I56-157 . The melting point was undepressed when mixed
with an authentic sample of the tolyl-labeled glycol. Depression in
melting point to 150-155° was observed when mixed with approximately
equal amounts of the threo-isomer prepared as described below. Radio-
chamical assay, 2.121 - 0.001 mc/mole.
Threo-1,2-di-p-tolyl(2-p-methyl-C1^)-1-phenylethylene Glycol (Ic).
a) Benzoic Acid-carboxyl-C-1-^.
This compound was prepared by the carbonation of phenyl magnesium
bromide with radioactive carbon dioxide, using standard vacuum line
technique. (122)
14
b) Toluene-methyl-C
The carboxyl-labeled benzoic acid was esterified by the method of

62
Aeree (123) and then treated with lithium aluminum hydride in dry
14
ether. The resulting benzyl-a-C alcohol was purified by distil¬
lation. Zinc amalgam was prepared as directed in "Organic Synthesis."
(124) Zinc (120 gm.) was treated with 12 gm. of mercurous chloride,
and then washed with water. The amalgam, 200 ml. of water, 25 ml. of
concentrated hydrochloric acid, and 25 gm. of radioactive benzyl
alcohol, were heated under reflux for 30 hours. Additional 25 ml.
portions of hydrochloric acid were added at 8-hour intervals. The
mixture was then steam distilled and the toluene was separated, washed
with water and dried over anhydrous calcium chloride. Upon filtration
and distillation there was obtained 9-22 gm. (44$) of toluene;
b. p. 111-115°, refractive index 1.4945, compared with 1.4935 for an
authentic sample. Products from several such preparations were diluted
with nonradioactive toluene to yield 43 gm. of toluene-C"^ with a
radioactivity assay of 22.55 mc/mole.
14
c) 4-Methyl-C -acetophenone.
In a modification of the method reported in "Organic Synthesis,"
(139) 42 gm. of methyl-labeled toluene in 200 ml. of carbon disulfide
was first treated with 150 gm. of anhydrous aluminum chloride and
then, while being refluxed gently over a period of 45 minutes, with
4l gm. of acetic anhydride. Refluxing was continued for l-l/2 hours
after which the carbon disulfide was removed by distillation and the
residue was poured onto ice to which had been added sufficient concen¬
trated hydrochloric acid to dissolve the aluminum salts. This mixture
was extracted with ether, the ether was washed twice with water, once

63
with 10$ NaOH and again with water. The ether solution was then dried
over anhydrous calcium chloride, filtered, and the ether was removed by
distillation. The residue was fractionated, the fraction b. p. 80-85°
at 5 mm. (Feist, F. (125) gives b. p. 111-114/13 mm.) being retained
(yield, 51 gm., 83$).
d) ¿I-Methyl-C-^-mandelic Acid.
This compound was prepared by dissolving 56.47 gm. of £-methyl-
acetophenone in 250 ml. of methanol and adding 500 ml. of 20$ aqueous
sodium hydroxide. Chlorine gas was bubbled through the solution slowly
while it was vigorously stirred. The solution gradually became almost
clear while the temperature rose to 60°. From time to time additional
sodium hydroxide solution was added until a total of one 1. was present.
Stirring was continued for an additional 20 minutes, and a small
quantity of acetone was added to remove the excess chlorine. The
mixture was treated with Norit and filtered. Upon acidification of the
filtrate with concentrated hydrochloric acid, the precipitate was
removed. The yield of £-toluic acid, methyl labeled, was 7 gm. The
aqueous solution was then extracted with ether in a continuous
extraction apparatus and the ether was removed by distillation. The
yield of 4-methylmandelic acid was 45 gm. (64.5$); m. p. 145-146° (this
is the method of VanArendouk and Cupery for the preparation of £-toluic
acid, except that the chlorine is added slowly and the temperature does
not rise as high);(126, 127) The product was further characterized by
preparation of the ethyl ester, m. p. 77 ; (121) and reduction with
lithium aluminum hydride to £-tolylethylene glycol, m. p. 76°, (107)

64
in agreement with the literature.
e) 4-Methyl-C~Li<-phenylacetic Acid.
To a solution of 21 gm. of the 4-methylmandelic acid in 185 ml. of
glacial acetic acid was added 20 ml. of concentrated sulfuric acid and
3.2 gm. of 30$> palladium on charcoal catalyst. The mixture was hydro¬
genated at atmospheric pressure, while being stirred vigorously. After
20 hours, the theoretical quantity of hydrogen had been adsorbed. The
catalyst was then removed by filtration. The filtrate was diluted with
water and extracted with chloroform. The chloroform solution was washed
with water and evaporated to dryness, to yield 16 gm. (84.4$) of the
acid; m. p. 88-90 . (128)
f) 4'-Methyl-C1^-desoxybenzoin.
To 35-6 gm. of £-tolylacetic acid was added 50 gm. of phosphorous
pentachloride. After the vigorous reaction ceased, the mixture was
warmed on a water bath for 30 minutes, cooled, and 150 ml. of dry
benzene was added. The mixture was then treated with 65 gm. of
anhydrous aluminum chloride, and, after the initial vigorous reaction
ceased, the mixture was heated under reflux for 1-1/2 hours and was
poured onto an ice-hydrochloric acid mixture. The product was
extracted three times with a benzene-ether mixture (1:4), the combined
extracts washed with water and evaporated to dryness. There was
obtained 31*3 gm. (62.6$) of the desoxybenzoin; m. p. 98-99°. (129)
g) a-Bromo-4' -methyl-C^-desoxybenzoin.
A solution of 28.3 gm. of 4'-methyl-C11'1-desoxybenzoin was prepared
in 100 ml. of carbon disulfide and was placed in a flask fitted with an

65
efficient reflux condenser and an inlet tube for nitrogen. 21.8 gm. of
bromine, dissolved in 50 ml. of carbon disulfide, was then added slowly
while a rapid stream of nitrogen was passed through the solution
(adapted from method of Ward). (130) After all of the bromine had been
added and the evolution of hydrobromic acid gas slackened, the solvent
was removed by distillation under reduced pressure, in an atmosphere of
nitrogen. When the carbon disulfide ceased to distill, 50 ml. of
hexane was added and distilled. The product was again treated with
hexane in the same fashion and then warmed on the steam bath under
reduced pressure in order to remove the last traces of the carbon
disulfide solvent. The residue was used directly for the preparation
i ik
of V-methyl-C -benzoin, described below.
h) 4'-Methyl-C^-benzoin.
The a-bromo-4' -methyl-C^-desoxybenzoin from the above preparation
was dissolved in one 1. of 95$ ethanol and an equivalent amount of 10$
ethanolic sodium hydroxide was added. The solution was stirred for
10 minutes and poured into two 1. of water. Aqueous hydrochloric acid
(20$) was added until the solution was just acid. The mixture was
allowed to stand for 10 minutes, the precipitate was filtered, yielding
29 gm. (95$) of the crude product, from which 26 gm. of the pure
material was obtained on crystallization from ethanol, m. p. Il8°.(l31)
This material was found to have a radioactivity assay of 20.3 mc/mole
and was diluted with nonradioactive 4'-methylbenzoin to a tracer level
of approximately 5 mc/mole.

66
l4
i) Threo-1,2-di-p-tolyl-l-phenylethylene(2-p-methyl-C )
Glycol (Ic).
A Grignard reagent was prepared from 189 gm. of £-bromo toluene and
26.5 gm. of magnesium turnings. To it 100 gm. of the above 4'-methyl-
benzoin was added slowly over a 30-minute period, and the mixture was
heated under gentle reflux for 1 hour. The mixture was hydrolyzed with
an aqueous ammonium chloride solution and the ether: layer separated.
The aqueous layer was extracted three times with ether, the ether
extracts were combined and washed with water, dried over anhydrous
sodium sulfate and concentrated to approximately 150 ml. Then 500 ml.
of hexane was added and the mixture allowed to stand overnight. The
solid was filtered and crystallized from 85$ ethanol. Yield of pure
glycol, m. p. 156.5-1570, was 45 gm. (3256).
Anal. Calc'd for C22H22°2: 83.0; H, 6.97; Found: C, 82-92,
83.06; H, 6.99) 7-00. Radioactivity assay, 5*221 mc/mole.
Erythro-l,2-di-p-tolyl-l-phenylethylene-2-G~*~^-Glycol (lb).
a) 4,4'-Dimethyldesoxybenzoin.
To 20 gm. of the ¿-tolylacetic acid, prepared as for the threo-
glycol (lb) above, was added 11 ml. of phosphorous trichloride and
(132) 60 ml. of toluene. The toluene solution was decanted onto 30 gm.
of anhydrous aluminum chloride and after the initial vigorous reaction
subsided, the mixture was heated on a steam bath for 1 hour. The
reaction mixture was poured over an ice-concentrated hydrochloric acid
mixture and the toluene layer separated. The aqueous layer was
extracted three times with a benzene-ether mixture (4:1) and the

67
combined organic extracts were washed twice with water. On evaporation
of the solvents there resulted a yellow oily solid which was washed once
with a little cold hexane and then dissolved in hot 95$ ethanol.
Following treatment of the ethanolic solution with Norit and filtration,
19*9 gm. (67$) of the desoxybenzoin was obtained; m. p. 101-102°. (133)
b) 4,41-Dimethyl-a-bromodesoxybenzoin.
The a-bromodesoxybenzoin was prepared as described previously for
4'-methyl-a-bromodesoxybenzoin, using 19-9 gm. of the desoxybenzoin
above, and 14.8 gm. of bromine in 75 ml. of carbon disulfide. Upon
evaporation of the solvents, a solid compound separates, which upon
crystallization from hexane has am. p. of 96o, and a radioactivity
assay of 2.037 mc/mole (calculation based on molecular weight of 303)*
c) 4,4'-Dimethylbenzoin.
The bromodesoxybenzoin from above was treated with base in
alcoholic solution, followed by acidification in a manner described
previously for the preparation of 4'-methylbenzoin. 9*9 gm- (46$) of
pure benzoin was obtained; m. p. 87-880. (134)
d) Preparation of the Glycol, Erythro-Ib.
To a Grignard solution prepared from 2.74 gm. of magnesium turn¬
ings and 15*7 gm. of bromobenzene in ether, was added 9*9 gm. of
4,4'-dimethylbenzoin. After the addition was complete, the mixture was
allowed to reflux gently for 4 hours. The reaction mixture was poured
into ice water and ammonium chloride was then added to dissolve the
magnesium hydroxide. The ether layer was separated and the reaction
mixture was extracted three times with 100 ml. portions of ether. The

68
combined ether solutions were washed with water and evaporated to dry¬
ness. Crystallization from 95$ ethanol gave 7*4 gms. of the glycol;
m. p. l6o-l6l°. Radiochemical assay, 2.102 mc/mole.
Anal. Calc'd for C22H22°2> 83-0; H, 6.97. Found: C, 82.72;
H, 7.08.
lk
l,l-Di-p-tolyl-2-phenylethylene-l-C Glycol (lia).
a) Mandelic-carbonyl-C^ Acid.
This compound was prepared by the method of Vogel (135) from
benzaldehyde, radioactive sodium cyanide, and sodium bisulfite, with
subsequent hydrolysis of the nitrile with concentrated hydrochloric
acid.
. X k
b) Methyl Mandelate-carbonyl-C .
This compound was prepared by the method of Aeree (123) by reflux¬
ing the acid in anhydrous methanol in the presence of concentrated
sulfuric acid, followed by distillation of the product.
c) l,l-Di-p-tolyl-2-phenylethylene-l-Cllt' Glycol (lia).
A Grignard reagent was prepared in ether solution with 84 gm. of
£-bromotoluene and 14 gm. of magnesium turnings. To this solution was
14
added 22.5 gm. of methyl mandelate-carbonyl-C and the mixture
refluxed for 4 hours. The reaction mixture was decomposed with a
solution of ammonium chloride, the ether layer was separated, washed
with water, dried over anhydrous sodium sulfate and evaporated to dry¬
ness. The semisolid residue which remained was dissolved in a small
amount of benzene and hexane was added. 22 gm. (51*5$) of glycol
separated; m. p. 155-157°» Crystallization from 95$ ethanol produced

69
the pure glycol; m. p. 158-I58.50, radioactivity assay 2.153 - 0.015
mc/mole. (21) On oxidation of the glycol with chronium trioxide in 50$
aqueous acetic acid, the neutral fraction yielded di-£-tolyl ketone
with radioactivity assay of 2.140 mc/mole. The benzoic acid fraction
was nonradioactive.
Anal. Calc'd for C22H22°2: C> 0* ^.97; Found: C, 83.27;
H, 7*11.
Di-p-tolylphenylacetaldehyde.
A 5-000 gm. sample of l,2-di-£-tolyl(22^^th^-C^)-1-phenyl-
ethylene glycol (Ic) was stirred at room temperature with 350 ml. of
90$ formic acid for 96 hours. On cooling the reaction mixture in an
ice bath and subsequent filtration, 3-764 gm. (79-8$) of the nearly
pure aldehyde was obtained; m. p. 93-94°. On crystallization from 95$
ethanol gave the pure compound; m. p. 94.5-95°• Radiochemical assay,
5-235 - 0.025 mc/mole.
Anal. Calc'd for Cgg^gO; C, 88.10; H, 6.73; Found: C, 88.10;
87.83; H = 6.59, 6.52.
The 2,4-dinitrophenyXhydrazooe was prepared by treating 20 ml. of
a hot ethanolic solution of 500 mg. of the aldehyde with a solution of
500 mg. of 2,4-dinitrophenylhydrazine, 1 ml. of concentrated sulfuric
acid and 5 ml. of water. After boiling the solution for 20 minutes, it
was cooled and the precipitate was removed by filtration. In several
preparations the crude 2,4-dinitrophenylhydrazone had a low and broad
melting point. Boiling for 10 minutes with a large volume of hexane or
crystallization from a large volume of ethanol gave the bright yellow

70
product with sharp melting point; 190.5-191°* Radioactivity assay,
5*205 mc/mole. Further proof of the identity of the aldehyde was
obtained by comparison of its ultraviolet spectrum with that of the
known aldehyde, diphenyl-£-tolylacetaldehyde. Both curves have
identical characteristics.
Anal. Calc * d for C, 69.85; H, 5*24; Found: C, 70.66;
H, 5*07*
4,4*-Dimethylbenzhydrylphenyl Ketone (V).
a) Di-p-tolylcarbinol.
An ether solution of 40 gm. of di-£-tolyl ketone was added slowly
to a stirred slurry of 7*5 gm. of lithium aluminum hydride in 300 ml.
of ether. After the addition was completed the solution was allowed to
stir for an additional 15 minutes, after which 50$ ethyl acetate in
ether was added slowly in sufficient quantity to destroy the excess
hydride. Water was then added, followed by sufficient concentrated
hydrochloric acid to dissolve the metal hydroxides. The ether layer
was separated and the aqueous layer was extracted with ether. The
combined ether extracts were washed once with water and evaporated to
dryness. The product crystallized on cooling and several different
runs gave yields of 98$ or better of the theory. Crystallization from
hexane yields the pure carbinol; m. p. 70°. (136)
b) Di-p-tolylchloromethane♦
A solution of 40 gm. of di-£-tolyl carbinol in 100 ml. hexane was
heated under gentle reflux while 38 ml. of thionyl chloride was added
dropwise. Reflux was continued for l-l/2 hours, after which the hexane

71
and the excess thionyl chloride was removed under reduced pressure.
The slightly colored product, which on distillation (b. p. 163-I680/
0.6 mm.) gave 108 gm. (95*7$) of a water white oil, crystallized
spontaneously on standing. Crystallization from hexane gave the pure
compound; m. p. 44-45°. (136)
c) Di-p-tolylacetonitrile.
A mixture of 100 gm. of di-£-tolylchloromethane and 45-5 gm. of
cuprous cyanide (20# excess) were placed in a flask with an air
condenser attached and immersed in a Wood's metal bath, preheated to-
l80°. The mixture was heated for 5-l/2 hrs. with occasional mixing,
while the temperature was slowly increased to 220°. The product was
removed from the bath, cooled and 250 ml. of acetone was added. The
acetone solution was filtered to remove the copper halide cake, which
was washed on the filter with an additional 100 ml. of acetone. The
acetone solution was allowed to stand overnight in the refrigerator
after which it was again filtered to remove the fine sediment of copper
halide which had settled out. The acetone was removed under reduced
pressure and the product was distilled (b. p. l65-175°/7 mm.) to yield
69 gm. (72#) of a slighly yellow oil which spontaneously crystallized
on standing. Crystallization from hexane yields pure white crystals;
m. p. 46.5-47°. Hoch (117) gives b. p. 212°/l8 mm. and does not record
the melting point of the compound.
d) Di-p-tolylacetic Acid.
A mixture of 65 gm. of di-£-tolylacetonitrile, 120 ml. of glacial
acetic acid and 600 ml. of 50# aqueous sulfuric acid were heated under

72
reflux with vigorous stirring for 3-1/2 hours. The mixture was then
cooled and poured into one 1. of ice water and stirred for 1 hour,
during which time the acid, which first separated as an oil, solidi¬
fied. The product was removed by filtration and washed with cold
water. The air-dried product weighed 60 gm. (85#) j m. p. 143°. (137)
e) Di-p-tolylacetyl Chloride.
This compound was prepared from 67.1 gm. of di-£-tolylacetic acid
in 250 ml. of hexane, by treatment with 100 ml. of thionyl chloride.
After the reaction had almost ceased at room temperature, the mixture
. o
was warmed to not more than 40 under reduced pressure to remove the
hexane and excess thionyl chloride. After distillation ceased, 50 ml.
of dry benzene was added and distillation continued. This process was
repeated to remove the last traces of thionyl chloride. After the
thionyl chloride was removed the residue was dissolved in 100 ml. of
dry benzene and used without further purification in the preparation of
the ketone below.
f) 4,4*-Dimethylbenzhydryl Phenyl Ketone.
A Grignard reagent was prepared in the usual way from 131 gm. of
bromobenzene and 20.3 gm. of magnesium turnings. To the cooled
solution was added, in small portions, 80 gm. of anhydrous cadmium
chloride, vigorous stirring being maintained. After the addition was
complete, the mixture was stirred at room temperature for 30 minutes,
then under gentle reflux for an additional 30 minutes. Almost all of
the ether was removed by distillation, 100 ml. of dry benzene was added
and distillation continued. When 100 ml. of distillate had been

75
collected, an additional 200 ml. of benzene was added and the distil¬
lation was continued until the condensing vapor had a temperature of
68°. Then 500 ml. of dry benzene was added and the mixture was cooled
to 10-15°. While vigorous stirring was maintained, the solution of
di-£-tolylacetyl chloride was added slowly. Stirring was continued at
room temperature for 30 minutes and then under gentle reflux for 1
hour. The reaction mixture was poured into water, sufficient concen¬
trated hydrochloric acid was added to dissolve the magnesium and
cadmium salts, and the benzene layer was separated. The aqueous layer
was extracted with 200 ml. of an ether-benzene mixture (4:1) and the
combined organic layers were washed three times with water. The
solutions were dried over anhydrous sodium sulfate and the solvents
removed by distillation. The brown oily residue was then steam dis¬
tilled to remove di-phenyl, dried and distilled under reduced pressure.
The fraction, b. p. 236-242° at 0.5 mm., was a slightly yellow oil
weighing 77 gm. After three crystallizations from ether-hexane (l:20)
at dry ice temperature, 66 gm. (79$) of the pure ketone was obtained;
m. p. 57-58°. (21)
Anal. Calc'd for C22H200: C, 88.00; H, 6.71: Found; C, 88.06;
H, 6.71.
Sample Calculations for Ketone Yields, Reaction Path Yields and
Carbon-14 Label Distribution.
a) Correction Factor for Ketone Yields from Threo-Ic and III, and
Cleavage Products of IVcd.
It may be seen from Table X for Runs 2-5 and 9, 10, 15, that

74
cleavage of the ketone IV from the dilution yield determinations gives
a slightly lower value for £-tolyl label scrambling than does the
cleavage of the undiluted ketone. Since in the case of the aldehyde
50:50 distribution is demanded (and observed for the undiluted ketone)
it is apparent that a correction is necessary for this observation.
Since this behavior is probably due to a minute quantity of highly
radioactive contaminate in the glycol, threo-Ic, because of the method
of synthesis, we have applied the correction factor 47/50 in the
following manner: 47/50 X uncorrected ketone yield = corrected ketone
yield and, since the £-tolyl scrambling recorded in Table IV is also
affected, 50/47 X uncorrected £-tolyl scrambling = corrected £-tolyl
scrambling. This correction factor is, of course, only approximate.,
being derived from the average of the two values for VQ (47$; Table X,
Runs 9 and 10) and the fact that 50$ is required and observed (Table X,
Run 15). Since, however, the factor is close to unity, rather wide
limits are allowable in its accuracy without introducing significant
error by its use. Substantially the same correction is arrived at by
plotting the observed percentages of ¿>-tolyl scrambling against the
ratio by which the ketone was diluted, and extrapolating to zero
dilution. This correction is required only in the calculations of data
derived from the rearrangements conducted with threo-Ic or the aldehyde
III. Moreover, no correction was needed for the ketone V because these
dilutions were consistantly more readily purified, and upon cleavage,
in control experiments, the ketone fragments did not indicate any
contamination, as was found for ketone IV.

75
b) Ketone Yield Calculations.
Application of the equation (D]_ + X) = A0 X, mentioned earlier
in this section, gives, for Run 2 (Table VIII), the uncorrected values
of 51*1# for the yield of IV and 32.6$ for the yield of V. The
corrected yield of IV (47/50 x 51 »l) is 48$. The yields of IV and V
were then normalized to show the relative yields of IV and V in the
ketonic product, giving values of 59-6$ and 40.4$ for IV and V,
respectively (Table II).
c) Reaction Path Yields.
Consideration of Chart I and the degradation schemes on pages 35>
36 and 40, shows that when threo-Ib undergoes rearrangement only path B
yields ¿-benzoylbenzoic acid which contains the carbon-14 label. There¬
fore the molar activity (Table V) of this compound (Vila), together with
the yield of IV (Table II) is a measure of the yield by path B. Thus
m^ = 0.039 x 0.585 = 0.023 as one value (Table VI). Calculation of
is performed in like manner using the yield of Vab and Villa.
The total contribution to product via paths A and D is given by
the yield of V (Table II), hence 1% + md = 0.417 and from Table VI the
average value for nig. is 0.008, giving a value for m¿ of 0.409*
Methods for calculating the ratio me/W have been given previously
(page 43). From a knowledge of this ratio, e. g., 1.37 (Table VII,
Method l), and m^, the value for mg may be calculated, thus 1.37 x
0.409 = O.56O (Table VI).
Calculations for mc may be performed in several ways', one of which
is described here. The yield of IV (Table II) gives mb + mg + mg which

76
is O.583. From this is subtracted the sum m^ + mg calculated as
described above, thus O.583 - (0.018 + O.560) = 0.005 (Table VI).
Derivation of Equation 1 of the Introduction.
In the following scheme, X-^, Xg, and X^ represent three ionic
species in a dynamic equilibrium. If then this scheme is correct, the
specific rate-constant ratio kip/kp, rather than the product ratio IV/V,
Aldehyde III
@ k* <$ ?H
(Tol)2-C-CH0H (Tol)2C-G- ♦ kp H
krr
(Tol)2CHC-0
^ol
^T
V
Tor
© 9H
-c—9-T0I
H
JL
Tor
l
CHC-Tol
IV
represents the relative migratory abilities of the one phenyl and the
two £-tolyl groups of aldehyde III, when this aldehyde is subjected to
acid catalysis. Now if x^, x2, and x^ are the instantaneous, time-
variable concentrations of the ions X^, Xg, and Xy respectively, then
from the above scheme
2) dXg(t)/dt = kp x1(t)-k(j) Xgit)-!^ x2(t)
3) dx5(t)/dt = l&p x^t)-!^^ x5(t)-k'H x5(t).

77
Since all reactions were allowed to go to completion, equations 2 and 3
are now integrated between the limits zero and infinity.
oo r oo roo roo
4) Xg = kpj Xx(t)dt - kJ X2(t)dt - k^J XgCt)
oo o o
dt
5) x,
CD roo roo roo
= fcpj Xx(t)dt - k^-jJ x5(t)dt - k'HJ x5(t)
dt.
Joo roo poo
x^tJdtjJ x2(t)dt, and J x,(t)dt
are now
replaced with the "integration areas" S^, S2, and S^,and then since at
t = 0 and t = oo, the concentration of all intermediates are zero,
equations 4 and 5 become:
6) kps1 - k0s2 - kgS2 = 0
7)
k S
T 1
k S
Tol 3
k' S = 0
H 3
or:
6) s2 =
k4> + kH
7) S, = Vl
3 W+k'H

78
and at complete reaction, since S^, S2 and S3 represent the total moles
of X-]_, X2, and X3 formed during period t = 0 and t = 00, and m¿ and
represent the moles of product formed through paths D and E (Chart I),
respectively;
8) ^d = ^2 .
me k'HS3
Substitution of equation 6 and 7 for S2 and S3, respectively, in
equation 8 and simplifying gives equation 1.
The derivation of equation 1 is made possible by use of the "area
theorem" of Hearon, (138) who pointed out the utility of this theorem
in chemical kinetics.
Analytical Determinations.
The carbon and hydrogen analyses for this dissertation were
performed by the Huffman Microanalytical Laboratories, Wheatridge,
Colorado.

SUMMARY
Phenyl-di-£-tolylacetaldehyde and the related system of glycols;
threo-1,2-di-p-tolyl(2-p-methyl C1^)-1-phenylethylene glycol, threo-
14
l,2-di-£-tolyl-l-phenylethylene-2-C glycol and 1,l-di-jD-tolyl-2-
phenylethylene glycol, have been subjected to rearrangement in cold,
concentrated sulfuric acid. The yields of the ketones (4-methyl-
benzhydryl |>-tolyl ketone and 4,4'-dimethylbenzhydryl phenyl ketone)
produced were obtained in each case by the radioactivity dilution
method. The fates of the carbon-14 labels of suitably labeled reactants
were determined by appropriate degradation methods, followed by radio¬
activity assay of the degradation products. By means of the equation,
^T _ ^ol ^e
kp " H * k'H • md
1 +
k'H
^ol
K
i + _S
and a mechanism involving open, equilibrating carbonium ions, it has
been established that the p-tolyl/phenyl migration ratio in the
rearrangement of the aldehyde is not reversed, but is almost certainly
greater than unity. The mechanism correlating the aldehyde-ketone and
pinacol rearrangements, proposed by B. M. Benjamin and C. J. Collins
(l) in 1956, is thus supported.
79

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BIOGRAPHICAL ITEMS
The author, Lawrence "W" Kendrick, Jr., was born in Underwood,
Alabama, on September l6, 1925* He completed his elementary and
secondary education in the Shelby County schools, and was graduated
from Thompson High School in 19^3» He attended Howard College,
Birmingham, Alabama, for one term prior to entering the United States
Navy in 19^3* During his Naval Service, he was commissioned a Naval
Aviator and served in that capacity until his release from active duty
in 1949. While on active service in the Navy he attended Carson-Newman
College, Jefferson City, Tennessee, for one year.
In January 1950, Mr. Kendrick entered the School of Pharmacy at
Howard College and received the degree of Bachelor of Science in
Pharmacy in June, 1953* After having completed the requirements for
his degree from Howard College, Mr. Kendrick transferred to the
College of Pharmacy at the University of Florida in September, 1952,
where he is still in attendance.
While he pursued the degree of Doctor of Philosophy, Mr. Kendrick
was a Fellow of the Oak Ridge Institute of Nuclear Studies. His
research was done at the Oak Ridge National Laboratory under the joint
sponsorship of that Laboratory, the Oak Ridge Institute of Nuclear
Studies, and the University of Florida.
The author is a member of the American Chemical Society, American
Pharmaceutical Association, Research Society of America (RESA), Gamma
Sigma Epsilon, honorary chemical society, and of Rho Chi, honorary
pharmaceutical society.
87

This dissertation was prepared under the direction of the chairman
of the candidate’s supervisory committee and has been approved by all
members of the committee. It was submitted to the Dean of the College
of Pharmacy and to the Graduate Council and was approved as partial
fulfillment of the requirements for the degree of Doctor of
Philosophy.
June 5, 1957
Dean, College of Pharmacy
Dean, Graduate School
SUPERVISORY COMMITTEE:
Chairman
'QjULIa^
88




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