Group Title: preparation and reactions of some fluorocarbon acylamino compounds
Title: The Preparation and reactions of some fluorocarbon acylamino compounds
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Title: The Preparation and reactions of some fluorocarbon acylamino compounds
Physical Description: vi, 89, 1 l. : tables. ; 28 cm.
Language: English
Creator: Durrell, William Sandford, 1931-
Publication Date: 1961
Copyright Date: 1961
 Subjects
Subject: Fluorocarbons   ( lcsh )
Organofluorine compounds   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
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Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 85-88.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Bibliographic ID: UF00097981
Volume ID: VID00001
Source Institution: University of Florida
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Resource Identifier: alephbibnum - 000423958
oclc - 11045681
notis - ACH2363

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THE PREPARATION AND REACTIONS

OF SOME FLUOROCARBON

ACYLAMINO COMPOUNDS











By

WILLIAM SANDFORD DURRELL


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, 1961











ACKNOWLEDGMENTS


The author wishes to express his deep appreciation to

Dr. John A. Young, his research director, for his constant

interest and encouragement throughout this investigation.

The members of the entire staff of Reed Laboratory are

also due thanks for their many timely and helpful suggestions.

The success of this work is due in no small part to the

author's wife who was a constant source of inspiration and

encouragement.












TABLE OF CONTENTS


Page

ACKNOWLEDGMENTS ........... ii

LIST OF TABLES ...................................... v

LIST OF FIGURES ...................................... vi

CHAPTER

I. INTRODUCTION ............................... 1

II. DISCUSSION ....... ..... .......... ........... 4

A. Synthesis of Diamides .................. 4

B. Some Reactions of Amides, Diamides,
and Their Derivatives .................. 22

1. The thermal decomposition of
their metal salts .................. 22

2. Reactions with perfluoropropene .... 24

3. Reactions with acyl halides ........ 26

4. Reactions of metal salts of di-
amides with bromine and iodine ....* 29

5. Indirect fluorination with
silver difluoride .................. 31

6. Some reactions of N-bromoper-
fluoroglutarimide .................. 33

C. The Reactions of Dis-(perfluorodi-
methylamino)mercury .................... 40

III. EXPERIMENTAL ............................... 43

A. General .................................. 43

B. Synthesis of Diamides .................. 54


iii







TABLE OF CONTENTS (continued)


Page

1. Reactions of acids and nitriles.... 54

2. Reaction of anhydrides and
amides ............................ 61

C. Some Reactions of Amides, Diamides,
and Their Derivatives .................. 62

1. The thermal decomposition of some
of their metal salts ..o............ 62

2. Reactions with perfluoropropene .... 64

3. Reactions with acyl halides ........ 66

4. Reactions of metal salts of diamides
with bromine and iodine ............ 71

5. Indirect fluorinations of amides
and diamides ....................... 72

6. Some reactions of N-bromoperfluoro-
glutarimide ........................ 74

D. The Reactions of Bis-(perfluero-
dimethylamino)mercury .................. 80

IV. SUMMARY ....... ......................... .... 82

BIBLIOGRAPHY ..................................... 85

BIOGRAPHICAL SKETCH .................................. 89












LIST OF TABLES


Page

TABLE

1. Relative Rates and Equilibria in
the Reaction, RCOOH + R'CN RCONHCOR' ...... 6

2. Nuclear Magnetic Resonance Spectra ........... 46

3. Infrared Spectra Used in this Work ........... 48

4. Reactions of Acids and Nitriles .............. 56












LIST OF FIGURES


Figure Page

1. Yield of diacetamide at 1500. ............ 7

2. Yield of N-acetyltrifluoroacetamide
at 1500. *... *. .... .... .... ......... 8

3. Yield of bis-(trifluoroacet)amide
at 150o ................................ 9

4. Yield of N-acetyltrifluoroacetamide
from the reaction of acetic acid
and trifluoroacetonitrile at 1500. ...... 10












CHAPTER I

INTRODUCTION


Even though Moissan39 first isolated elemental fluorine

in 1886, it is hardly likely that fluorine chemistry could

have developed into a significant area of chemistry had it

not been for the discovery by Swarts of the usefulness of

antimony fluorides in replacing halogens with fluorine.26

The later work of Henne led ultimately to the commercial
26
production of fluorine compounds for the first time, and

still accounts for the greatest proportion of fluorocarbon

derivatives commercially produced.

The discovery of the electrochemical process27 by Simons

has been of great significance in producing classes of fluoro-

carbons generally obtainable only with difficulty, if at all,

from the Swarts process. Indeed, most of the fluorocarbon

derivatives used in this work are derived from products of

this process.

War-time development of nuclear weapons created the need

for materials stable to the volatile, corrosive, highly toxic

uranium hexafluoride used in the gaseous diffusion process in

the separation of the desired uranium235 from the much more

common isotope of mass number 238. The ensuing crash program








developed a tremendous amount of data concerning fluorocar-

bons and their derivatives. Probably most important, the

direct use of elemental fluorine, in conjunction with silver8

or copperl3 as catalysts, gave practical yields of usable

products for the first time. In addition, the indirect method

of fluorination, using a powerful fluorinating agent such as
12
cobaltic fluoride, was found to be useful.

Besides their chemical and oxidative stability, fluoro-

carbons have demonstrated great thermal stability. The

combination of these factors has aroused interest in the

practical applications of these unusual materials. The

theoretical implications of these properties have no less

interest among theorists.

Chemical development of an area requires that the

materials under study undergo convenient chemical reactions.

These properties which arouse great interest in fluorocarbons

therefore hamper development of knowledge concerning them.

In fluorocarbon chemistry a "handle" or functional group

present in the molecule is much more important than in hydro-

carbon chemistry because of the much lesser reactivity of the

C-F bond. Of the various possibilities acyl derivatives are

of great utility and of these fluorocarbon acylamine compounds

seem particularly worthy of study since relatively little

work has been described utilizing these materials. For

instance, almost the only interest in fluorocarbon amides

has been as intermediates in the synthesis of nitriles32








and/or N-bromo amides.31 The N-bromo amides have been of

interest largely in regard to their ability to brominate

or as intermediates in the Ilofmann reaction.3

This study was, therefore, undertaken to elucidate

further the chemistry of these species.

The long-known reaction of acids and nitriles to give

diamides7 was extended to fluorocarbon acids and nitriles

and the reaction studied in considerable detail.

Acylation of fluorocarbon amides is reported only for
4a
the trifluoroacetylation of trifluoroacetamide2 and the

base-catalyzed addition to fluoroolefins is unknown, although

the addition of other amidos to fluoroolefins11 was described

after the work reported herein was complete.

The indirect fluorination of fluorocarbon amides and

their derivatives is not described in the literature

although Bigelow and coworkers192 have carried out the direct

fluorination of several hydrocarbon amides.

The syntheses and several interesting reactions of

fluorocarbon N-bromo amides were studied, and new methods

for preparing amides substituted on the nitrogen by por-

fluoralkyl groups were sought.













CHAPTER II

DISCUSSION


A. Synthesis of Diamides

Reactions of acids and nitriles

In the early stages of this work it was necessary to

prepare bis-(trifluoroacet)amide, (CF3CO)2NH, in quantity.

Earlier work in this laboratory had shown that trifluoro-

acetic acid and trifluoroacetonitrile react quantitatively

at 1500 to give the desired compound in an essentially pure

state. Attempts to scale the reaction up from several gram

quantities to larger amounts, in an autoclave, resulted in

much poorer yields and extensive decomposition. Smith2 had

reported the synthesis of this compound in good yields from

the trifluoroacetylation of trifluoroacetamide with trifluoro-

acetic anhydride. Sufficient quantities were obtained in

this manner to achieve the desired synthetic objectives.

Nevertheless, it seemed desirable to study the acid-nitrile

reaction because of its potential synthetic utility and the

intrinsic value of a more detailed knowledge of its mechanism.

The reaction of nitriles with organic acids was first

studied before the turn of the century37 and, in the case of

acetic acid and acetonitrile at 2000, gave principally the

diamide:
CH COOH + CI3 CN --'CH CONHCOCH








This early study led to the following generalizations:

(1) Fatty nitriles react with fatty acids to give

secondary amides.

(2) Fatty nitriles react with aromatic acids to exchange

their cyano and carboxyl groups to give fatty acids and aro-

matic nitriles.

(3) Aromatic nitriles and fatty acids give mixed

secondary amides.

(4) Aromatic nitriles and aromatic acids give secondary

amides.

There are numerous exceptions to the above as might be

expected from a reaction which is carried out in the 150-200o

temperature range.

No further work was reported until Wiley and Guerrant47

reported that the reactions of phenylacetic acid and nitrile,

and p-nitrophenylacetic acid and nitrile, give an equilibrium

yield of about 40% of the diamides at 175-1900.

In the present work acetic and trifluoroacetic acids

were reacted with aceto- and trifluoroacetonitriles.

Equimolar quantities of the appropriate acid and nitrile

were heated together in glass ampoules at 150 and 2000. The

reactions of acetonitrile were followed by removing the

ampoule after the desired period and evaporating under vacuum

the unreacted acid and nitrile. The nonvolatile residue was

shown to be fairly pure diamide by comparison of its infrared

spectrum with that of a pure sample. However, after reaction








at 2000 and long periods at 1500 decomposition had occurred

to varying extents.

The reactions of trifluoroacetonitrile were followed

by measuring the change in vapor pressure of the volatile

nitrile before and after reaction. The diamide and unre-

acted acid were separated by distillation in large scale

runs and in small scale runs the nonvolatile residue was

examined spectroscopically. It was determined in this manner

that the reaction was basically straightforward since there

were no absorptions of consequence in the infrared spectra

which were not due to the acid or diamide. To test the

reverse reaction pure samples of the appropriate diamide

were treated in the same manner as the acid and nitrile and

the conversions calculated as above.

The experimental results are summarized in Table 1.


TABLE 1

Relative Rates and Equilibria in the Reaction,

RCOOH + R'CN = RCONHCOR'


System: Equil. Hours for rxn. Effect of Catalysis
Conv. to reach 50%
__completion Acid Base

R=CH3,R'=CF3 97%* 2 ++ ++

R=CF3,R'=CH3 72% 3 + 0

R=CF3,R'=CF3 96% 8 +++ +++

R=CH3,R'=C1H3 60% 96 ++ 0

*Apparent equilibrium, see text.




















0
o

o E


\ o




0 o 4-







-OH
S E E E
cI C3 -0.-3 d
4.) Q> u

0000






ITeT J o o
/ 0 0 0D
I I I I1



\o V H
o 0HC




0 00O































\ "0 N P

ep ^ *p Jo (fl



















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4.

(0








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0 0 1-
0 O O r4
<4J 0

0 0 0- (<


















pc)) o
W t l W E





/ O O 0a+


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o co

a*4 -H *c
-H r1 P-4 0






I0

0 0 0




0 C










'.0 00























E




0 00
0 0 c
WtQ 0
I 0 P 0

0 Z
4 .- I4'
0 00
oo C ~





0. 0




N 0




O
i 0 W. 0
o 0 0









o PE
0- 0 -0






U 0


--








110

K 0 PTI-'
S44 N
\PTW~P J PTfl
\ E I ^
\ --i (i -i-

\ (-1 i -: i
\ 4- 4-

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\ __ 0 0 0























































































0 0 0 0


OPTLUITp JO PTOTA


,-4






c,
ai

4.'0

E
00


0
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0 C:


















O 3
*H -i
Sc<






I0 0



0CH





4- 1



-t


bO
*>-(








While Wiley and Guerrant47 had established that the

extent of reaction in the aromatic acid-nitrile systems

are controlled by equilibrium, it remained to be shown that

an equilibrium would obtain in the present cases. In this

work equilibrium was shown by approaching it from either

direction. That is, the pure diamides were heated under

the same conditions as an equimolar solution of the start-

ing acid and nitrile. In the slow reacting acetic acid-

acetonitrile system equilibrium was somewhat difficult to

establish since tar formation and other side reactions

became important after long reaction periods. This problem

was of less consequence in the much faster reacting tri-

fluoroacetic acid-acetonitrile system, and of no consequence

in the trifluoroacetonitrile systems. In the systems where

acetonitrile was present the unroacted, recovered acid-nitrile

mixture was shown by its infrared spectrum to contain a

smaller proportion of nitrile than the starting mixture.
36
This indicates, as is well known, that nitriles undergo

various reactions, in the presence of proton acids, which

would account for the tar formation in these cases. Tri-

fluoroacetonitrile with its lower basicity, due to the

electron withdrawing fluorine substituents, is much less

susceptible to attack by proton acids and, therefore, is

less likely to be destroyed in such side reactions.

The position of equilibrium in the systems studied

presents an interesting situation. Wiley and Guerrant4









noted that electronegative substituents cause greater con-

versions to diamido, but offer no explanation. Our data

substantiate this fact, increasing substitution of fluorine

for hydrogen bringing about increasingly greater equilibrium

conversions, and suggest that these facts might be explained

on the basis of relative resonance stabilization of the

various reactants and products in their ground states.

An organic acid is a hybrid of the following structures:

0 0o 0-
II I I +
RC-OH RC-OH -- RC=OH
+
IA IB IC


For a nitrile we may write:

+
RC;N .- RC=N-

IIA IIB


And for a secondary amide:


0 HO O0H 0 O-H 0
II I II I I I 1 I I II
RC-N-CR' *-- RC-N-CR' *-- RC=N-CR' 9- etc.
+ +
IIIA IIIB IIIC


If R is an alkyl group, the energies of the B structures

may be lowered by either inductive or hyperconjugative effects,

while if it were a trifluoromethyl group the B structures

would be of higher energy relative to A or C structures, in

which there is no positive charge adjacent to the trifluoro-

methyl group. Since a nitrile has no available form of the








C type, it should follow that electronegative substituents

destabilize a nitrile to greater extent than either an acid

or a diamide, assuming resonance structures of the C type

make a real contribution.

A concise illustration of the situation just described:


CF COOH-CF3CN

CH3 COOH-CF CN __
Average
Energy (CFCO)2NH
Reactants
CF COOH-CrCN ,. CH CONHCOCF Energy
IProduct
CH3COOH-CH 3_CN _- (CH 3CO)2NH


The difference in energies of products and reactants is

a rough estimate for the value of H for the reaction, and

since entropy change should be about constant for any of the

acid-nitrile systems, we may use the familiar relationship:


AH A &F = -RTInK

Thus, the greater the value of -aH, the greater should be

the conversion to diamide. The order of increasing conver-

sions can be estimated from the preceding discussion to be

in the order:

CH COOH-CH CN CF COOH-CH CN < F COOH=CFCN CH COOH-CF3CN

This corresponds approximately to the order of increasing con-

version found experimentally.

Care must be taken to differentiate between apparent

equilibrium and actual equilibrium in the CH COOI-CF CN system.








The equation involved in this case is:

CH3COOH + CF3CN -CF3COCNHCOCH3' CF3COOH + CH3CN

The reaction proceeds rapidly to give an apparent equilibrium

mixture composed of 97 of the mixed diamide. As time passes

the actual equilibrium mixture consisting of mixed diamide,

acetonitrile, trifluoroacetic acid, and small but unknown

amounts of acetic acid and trifluoroacetonitrile will obtain.

In one experiment the CF COOH CH CN mixture was

allowed to react at 2000 for eight hours. Fractionation of

the product gave a small amount of bis-(trifluoroacet)amide

in the most volatile fraction of the diamide cut, and because

of its considerably higher boiling point, diacetamide was

easily isolated from the high boiling residue. Finding these

diamides is to be expected from the total equilibrium in this

system:

CF COOH+CH3CN = CF CONBCOCH3-- CH COOH+CF CN

CF 3CN JICH, CN

(CF3CO) 2NH (CH3CO) 2NH


There is another reaction which can occur but which is

only of consequence in hydrocarbon systems. That is the

reaction of the diamide with acid:

RCONHCOR + RCOOH -= (RCO)20 + RCON}I2


Davidson showed10 that an equilibrium of this type exists in

the case of dipropionamide and propionic acid and the reaction









of diacetamide and acetic acid was reported19 even earlier.

Even if this reaction were important in the CH COOH-CH CN

system, it would not change any of the conclusions reached

but would only serve to emphasize them since the correction

of the results for the formation of any acetamide, boiling

point 2220, would decrease the yield of nonvolatile materials

and therefore decrease the equilibrium conversion even more.

In none of the fluorocarbon systems was any of the amide

found except as discussed later in the thermal decomposition

of the sodium salt of the mixed diamide, CH3CONHCOCF3.

To explain the results of the earlier workers37 in the

same manner is tempting. Thus, in a typical fatty acid-

aromatic nitrile system the following equilibrium would exist:

ArCOOH + RCN --ArCONHCOR. RCOOH + ArCN

Since the equilibrium lies to the right, it is obvious that

the fatty acid-aromatic nitrile pair are the more stable.

If it is assumed that, as in the previous cases, the relative

stabilities of the nitriles are the most important single

factor, then the obvious rationalization is that the aromatic

ring's pi electrons are more available for lowering the energy

of the resonance structure IIB than these of an alkyl group,

which is wholly expected on the basis of modern electronic

theory.

An explanation for the relative rates of reaction of

the various systems studied is less obvious. At first sight

the most obvious sequence of steps is:









0 0-
11 I
RC;N + R'C-OHI R =N-CR' (1)

OH


0 -OH- 0 +OH- OH 0

R=tN-CR =R=N-CR' -- RC=K-CR' (2)

OH

Tautomerization would then give the product.

If the first step were slow and the subsequent steps

fast, the most important factor should be the nucleophili-

city of the nitrile and the eleetophilicity of the acid or,

in other words, the ability of the pair of unshared electrons

on the nitrogen to attack the carbonyl carbon of the acid.

Thus, the fastest reaction might be expected to be that

between the nitrile with the most available electrons and

the acid with the most electron deficient carbonyl carbon.

Using these criteria, the relative rates of the systems

studied should be:

CF3COOH- C-CHC CN CH COOH-CHC CCOH-CFCN> CH COOII-CF3CN

Instead it was found that the reaction between acetic acid

and trifluoroacotonitrile is the most rapid and that between

acetic acid and acetonitrile the slowest. Therefore, either

the simple mechanism given is not followed, or an alternative

pathway is available.

It should also be noted that acids should catalyze the

reaction by enhancing the reactivity of the carbonyl group








of the acid unless the unshared nitrile electrons effectively

scavenge the system of acid.

The major requirements of an alternative mechanism are

that it must explain:

(1) The higher than anticipated reactivity of tri-

fluoroacetonitrile.

(2) The enhancement of rate in all cases by the addition

of small amounts of acid.

(3) The enhancement in rate, in systems containing tri-

fluoroacetonitrile, by addition of small amounts of base.

The above requirements are met if it is assumed that the

oxygen atom of the carbonyl group might participate by simul-

taneously attacking the nitrile carbon in the following manner:

R R R

C C C

0 N = 0 0 N -- product

C C C

R' OH R' OH R' OH

Using this mechanism as an alternative pathway in systems

containing trifluoroacetonitrile, all of the experimental

results may be rationalized. Considering only these systems,

it can be seen that acetic acid would react more rapidly than

trifluoroacetic acid because of the greater availability of

the carbonyl oxygen for participation, overcoming the lower

reactivity of its carbonyl carbon in comparison with tri-

fluoroacetic acid. In view of this it is not surprising that









these systems are catalyzed by base. The carboxylate anion

is less electrophilic than the unionized species but, more

important, has an increased capability for attack on the

nitrile carbon, thus resulting in a higher reaction rate in

the presence of base:


R R R
I I I


0 N, 0 N product
/ \ //
C c C

R' 0 R' 0- R' 0"

This mechanism might be expected to be followed only

in systems in which the nitrile has an abnormally electron

deficient carbon atom and is particularly susceptible to

nucleophilic attack such as in trifluoroacetonitrile, as

shown above. It is, therefore, likely that in the systems

containing acetonitrile the simple mechanism given originally

is followed. There is no catalysis by base in these systems

and trifluoroacetic acid reacts much more rapidly than acetic

acid by virtue of its more electron deficient carbonyl carbon.

All the systems studied are catalyzed to varying degrees

by sulfuric acid. Apparently, then in both mechanisms the

rate is increased as the concentration of the protonated,

highly electrephilic species increases:

0 H+ +OH
II I +
R'C-OH = R'C-OH *-- R'C-(OH)2







This result is compatible with the simple mechanism but is

not wholly expected in the participation mechanism since the

effect here should be to lower the availability of the elec-

trons on the oxygens adjacent to a formal charge. Apparently

the effect of increasing the olectrophilicity of the carbonyl

carbon more than makes up for the former effect. When acetoni-

trile was the nitrile constituent acid catalysis was less

effective. In these cases the nitrile probably competes with

acid for protons. As mentioned previously, acetonitrile is

known to react with proton acids.

A third possible mechanism, which Davidson10 assumes,

is the preliminary formation of the isoimide, IV, which then

decomposes to the imide or diamide in the following manner:

N N N

R-C H R-C H R-C H
I I II
0 0 0 0 0 0
\\ / (1) \ // (2) //
c C c
I I I
R' R' R'


IV

Using this mechanism it is difficult to account for the

experimental results. First, since the reactions involving

acetonitrile are not base catalyzed, (2) must be the rate-

determining step in these cases. Conversely, (1) must be

the rate-dteermining step in systems containing trifluoro-

acetonitrile since they are base catalyzed. Since the over-

all rates are about the same in the reactions of these two








nitriles with trifluoroacetic acid, we are saying, in effect,

that acetonitrile is more olectrophilic than trifluoroaceto-

nitrile in their reactions with trifluoroacotic acid. This

is obviously false; trifluoroacetonitrile is well known to

be more susceptible to reactions with nucleophiles, as has

been previously discussed.

There is some possibility that the isoimido mechanism

is a special case, such as postulated for the participation

mechanism. There is a resemblance in these two mechanisms,

particularly in the decomposition of the isoimide to diamide.

The important difference is that in the isoimide case the

attack of oxygen on carbon occurs prior to, rather than

simultaneously with, attack of nitrogen on carbon. Thus, in

the trifluoroacetonitrile systems the fact that they are base

catalyzed might be explained but a rationalization of the

enhancement of rate by acid becomes more difficult.

The case for any of the mechanisms is certainly neither

proved nor disproved, but on the basis of present information

a combination of the simple and participation mechanisms seems

most reasonable.

Reactions of anhydrides and amides

Smith's"' method of synthesis was used to prepare suffi-

cient quantities of bis-(trifluoroacet)amide for use as an

intermediate. This reaction may be written

CF CONH2 + (CF CO) 0 t (CF CO) NH
3 2 2' (cF300)2N







Attempted trifluoroacetylation of N-methyltrifluoroacet-

amide in the same manner gave the desired N-methyl-bis-(tri-

fluoroacet)amide only in low yield. It was found that the

N-methyl diamide reacted with trifluoroacetic acid to give

trifluoroacetic anhydride and the starting amide. Again we

have an equilibrium situation:

(CF3CO)20 + CF3CONIICH3 C (CFCO) 2NCH3 + CF3COOH

In this case the equilibrium lies to the left, whereas in the

trifluoroacetamide-trifluoroacetic anhydride reaction it lay

far to the right (since it was not detectable under the con-

ditions used). It seems doubtful that any arguments on an

electronic basis can be brought forward which would explain

the large effect of substituting a methyl group for hydrogen.

A methyl group in place of the hydrogen in structure IIIC on

page 12 would, if anything, lower its energy due to the

greater electron donating capacity of methyl over hydrogen.

The actual explanation would seem, therefore, to be involved

with steric or entropic considerations.

It is interesting to contrast the absence of any forma-

tion of nitrile in the trifluoroacetamide-trifluoroacetic

anhydride system with results reported by Davidson10 in the

benzamide-benzoic anhydride system in which an equilibrium

mixture containing 90% benzonitrile and only 2.7% dibenz-

amide is reached by refluxing at 224-243 for an hour. The

reason for the difference in ease of formation of nitrile in

the two systems may be related to the relative thermodynamic








stabilities of the nitriles (in this case trifluoroacetonit-

rile and benzonitrile) or may be strictly kinetic since we

have no good evidence that the fluorocarbon system is at

equilibrium with respect to the formation of nitrile.


B. Some Reactions of Amides, Diamides,

and Their Derivatives

1. The thermal decomposition of their metal salts

The thermal decomposition of the sodium salt of bis-

(trifluoroacet)amide gave a fair yield of 2,4,6-tris-(tri-

fluoromethyl)-1,3,5-triazine, presumably by the reaction:

CF3 N CF3
C C
I I1
3 (CF3 O)2N -- N N + 3 cF3co00

c
C

CF3


Although the mechanism for this transformation was not

studied, it is certain that it is not due to the base cata-

lyzed trimerization of trifluoroacetonitrile,5 because none

of the highly volatile trifluoroacetonitrile was evolved

into a cold trap, which certainly would be expected if it

were an intermediate. It might seem possible that an "acti-

vated" form trimerizes before it can proceed to nitrile.

N 0 N O" N 0 triazine
// \ // 1 \ / . /. .
CF3-C C CF3-C C CF3-C C
3-\ C3\ 3\ 0 c .z- \c
0 CF3 0 CFJ O CF CF CN+CF COO-
3- 3F 3








This mechanism demands that in the base catalyzed

reaction of acid and nitrile, which seems to go through

the same intermediate, the trimer should be formed to the

exclusion of diamide. Since this was shown earlier not to

be the case, the mechanism must involve either a series of

additions or some other form of simultaneous reaction of

two or more imide anions.

Similar treatment of the mixed diamide resulted in

the following transformation:

CF CO

N- CF3CONHCOCH3I CF CONH2 + tars

C3 CO


A 70% yield of trifluoroacetamide was obtained based on

diamide, and 140% based on sodium. The exact nature of

this reaction remains unknown, however, in particular the

relationship with the related reaction of bis-(trifluoro-

acet)amide.

Sodium perfluoroglutarimide decomposed to a carbon-

aceous mass from which no identifiable products could be

isolated.

The thermal decomposition of the mercury salt of bis-

(trifluoroacet)amide did not give any identifiable products

except metallic mercury, and traces of expected pyrolysis

products, trifluoroacetic acid, trifluoroacetonitrile, and

fluoroform. The mercury salt of perfluoroglutarimide was









considerably more thermally stable than that of bis-(tri-

fluoroacet)amide, a portion subliming at 4700 rather than

entirely decomposing.


2. Reactions with perfluoropropene

Additions of nucleophiles to fluoroolefins have been

known since 1946 when Hanford and Rigby15 reported the re-

action of alcoholates with several fluoroolefins. The re-

action has been of considerable synthetic utility. Among
29
the nucleophiles used, as well as various alcohols,29 have

been amines,30 mercaptans,33 organometallic compounds29

and, while this work was in progress, amides.1

Addition has not been reported, however, of fluorine

substituted amides or diamides to fluoroolefins. Additions

of four of these materials to perfluoropropene were attempted,

trifluoroacetamide, N-methyltrifluoroacotamide, perfluoro-

glutarimide, and bis-(trifluoroacet)amide. Of these only

N-methyltrifluoroacetamide gave the desired addition product:

Na CF2=CFCF
CF3CONHCH3 CF3CON(CH3)


CF3CON(CH3) CF2CFHCF3


The anion of the amide was made by adding sodium to the

molten amide and heating gently until evolution of hydrogen

was complete. The addition was carried out in an autoclave

and gave a 75% yield after 40 hours at 800. The distilled

product was shown to be 98-990 pure by vapor phase








chromatography. The structure of the adduct was shown une-

quivocally by means of the proton magnetic resonance spectrum

which showed, besides an absorption associated with the

N-methyl protons, a proton peak which exhibited a complicated

fine structure, a complete interpretation of which is incom-

plete but which is undoubtedly due to a proton in the

position, X-CF2CFHCF3. The product slowly evolved HF, but

an attempt to isolate the dibromide of the olefinic product

was unsuccessful.

Attempted additions using identical conditions were

totally unsuccessful with the other amides mentioned pre-

viously. The sodium salts of all these materials were rather

unstable compared to the sodium salt of N-methyltrifluoro-

acetamide. The sodium salt of perfluoroglutarimide was most

readily prepared by an exchange reaction with sodium methyl-

ate, methanol being removed under vacuum until the dry imide

salt remained. The sodium salt prepared in this manner was

totally inert to perfluoropropene at 100o and decomposed at

slightly higher temperatures. When sodamids was added to

perfluoroglutarimide the mixture sparked and burned. The

attempted reaction of the sodium salt of bis-(trifluoroacet)

amide with perfluoropropene resulted only in decomposition to

give the triazine discussed previously.


*A complete description of the nuclear magnetic resonance

spectra of this compound will be reported on by Dr. W. S.

Brey and coworkers.








3. Reactions of acyl halides

As with perfluoropropene, only N-methyltrifluoroacet-

amide underwent reaction with acyl halides. Attempted

reactions of the sodium, mercury, and silver salts of per-

fluoroglutarimide; and of the sodium and mercury salts of

bis-(trifluoroacet)amide with trifluoreacetyl and/or per-

fluoroglutaryl chloride were unsuccessful. With perfluoro-

glutaryl chloride and the mercury salt of perfluoroglutar-

imide the desired reaction was:


[CF2 (CF2CO)22NHg + CF2(CF2COCl)2-- CF2 (CF2CO)2NCOCF2CF2CF2-

CON(COCF2)2CF2 + HgC12


While none of the desired N,N,N',N'-bis(perfluoroglut-

aryl) perfluoroglutardiamide was formed in this reaction, a

successful and interesting synthesis was eventually found

which is described later*

The sodium salt of N-trifluoromethylacetamide, prepared

from sodium sand in ether or tetrahydrofuran, reacted with

trifluoroacetyl chloride to give the desired N-methyl-bis-

(trifluoroacet)amide. This compound could also be prepared

from the amide and acyl chloride in the presence of pyridine,

as described by Thompson. 4

The sodium salts of both the imide and the diamide gave

precipitates with trifluoreacetyl chloride but no triacyl

nitrogen compounds were obtained. The only volatile products

were the diethyl etherate (when diethyl ether was used as the









solvent) and the tetrahydrofuranate (when tetrahydrofuran

was used as the solvent) of trifluoroacetic acid. Addition

compounds of this type were originally reported by
16
Hauptschein and Grosse. The diethyl etherate had the same

physical constants given by these workers and measurement of

the relative intensities of the proton absorptions in the

proton resonance spectrum confirmed the formula proposed

originally for the etherate, 3 CF3COOI2 (C2H5)20. The

formula of the unreported tetrahydrofuranate was shown by

the same means to be 2 CF COOH*C4Hg0.

Trifluoroacetyl chloride must have been the source of

the acid found in the product since it was the common re-

actant in both systems. Since neither of the etherates were

found in the reaction with the N-methyl amide, the imide and

the diamide must play a role in the formation of acid, but

there is insufficient information to draw any conclusions.

It was thought that the mercury salts of the imide and

the diamide might be more likely to react with acyl chlorides

in the desired manner since the mercury salt of N,N'-bis-

(trifluoroacetyl)hydrazine reacts fairly readily with tri-
48
fluoroacetyl and perfluoroglutaryl chlorides.

The mercury salts of the imide and the diamide were

synthesized by means of their exchange reaction with mer-

curic acetate in anhydrous media. The mercury salts were

completely unreactive toward the acyl halides in any system









tried at temperatures up to 1000. Use of trifluoroacetic

acid or FC 102 (an inert fluorocarbon ether mixture) as

solvents was also ineffective.

It is well known41 that the silver salt of perfluoro-

glutarimide is reactive toward bromine in trifluoroacetic

acid. Trifluoroacetyl chloride was reacted with silver salt

under identical conditions but instead of N-trifluoroacetyl-

perfluoroglutarimide, trifluoroacetic anhydride was formed,

evidently from the reaction of the acyl halide with the

silver salt of trifluoroacetic acid. It is to be expected

that the trifluoroacetate and perflueroglutarimide anions

exist in an equilibrium:

CF3COO- + CF2(CF2CO)2NH CF3COOH + CF2(CF2CO)2N-


but whether either would actually exist as the free, uncem-

plexed anion is difficult to say. It is likely that silver

plays a more important role than the above equilibrium would

suggest. At any rate, trifluoroacetyl chloride reacts

preferentially with trifluoroacetate anion (or a complex

silver salt), and bromine reacts preferentially with the

anion of perfluoroglutarimide (or its complex silver salt).

The silver salt of perfluoroglutarimide was prepared free

of trifluoreacetic acid but, using excess imide as solvent,

no reaction occurred with the acyl chloride.

The nonreactivity of the imide and diamide anions toward

electrophiles, such as acyl halides and fluoroolefins, is








probably due to resonance stabilization of the anion by the

electronegative substituents. Thus, the anion of N-methyl-

trifluoroacetamide, being less stabilized by the electron

donating methyl group, undergoes reactions with both tri-

fluoroacetyl chloride and perfluoropropene.


4. Reactions of metal salts of diamides with bromine and

iodine
18
Either the silver 8 or the mercury salts of perfluoro-

glutarimide could be.brominated readily in trifluoroacetic

acid to give N-bromoperfluoroglutarimide. Iodine reacted

slowly with the silver salt of perfluoroglutarimide but the

product was too unstable to isolate.

Bis-(trifluoroacet)amide did not react with bromine

under the above conditions, however. The bromine which was

absorbed when added to the silver salt of the diamide in

trifluoroacetic acid reacted according to the equations

below to give N-brometrifluoroacetamide.41


Ag20 + 2 CF COOH --2 Ag + CF COO" + H20


H20 + (CF3CO)2NH CF3CONH2+ CF CO011

Ag+,Br2
CF3CONH2 CF CONHBr


When the residue which remained after evaporating the tri-

fluoroacetic acid from the brominated mixture was treated

with dry HBr the immediate formation of bromine was noted.








Both trifluoroacetamide and bis-(trifluoroacet)amide were

present in this product. Under anhydrous conditions,

achieved by adding a slight excess of trifluoroacetic

anhydride to the reaction mixture, neither the silver,

sodium, nor the mercury salts reacted with bromine. It

may be concluded, therefore, that any reaction in the

original bromination was due to trifluoroacetamide being

present.

The difference in reactivities of perfluoroglutarimide

and bis-(trifluoroacet)amide toward bromine is remarkable.

Since both compounds should have similar electronic environ-

ments about their nitrogen atoms, the reason for this great

difference must lie elsewhere. This might be attributed to

the stabilities of the metal complexes. It could well be

that perfluoroglutarimide forms a stable silver complex in

solution and that the first step in bromination is complex-

ing of bromine with silver followed by intramolecular trans-

fer of bromine. Such sequences for complex ion reactions
25
have been demonstrated in numerous cases, This conject-

ural mechanism might be written:


CF2CO CF2CO CF2CO
/ Br2
CF2 N-Ag ---- CF2 N-AgBr2-- CF2 NBr + AgBr
\ /\ / \ /
CF2CO CF2CO CF2CO


In the bis-(trifluoroacet)amide case a lower stability

of the complex, compared to the free anion and silver ion,









would explain its lesser reactivity toward bromine. Further

evidence for this point will be given in the next section.


5. Indirect fluorination with silver difluoride

Bis-(trifluoroacet)amide reacts with silver difluoride

at 600 and atmospheric pressure to give trifluoroacetyl

chloride and trifluoromethyl isocyanate. A plausible mech-

anism is3
AgF2 AgF2
(CF CO)2NH- Ag2 CF3CO)2N A--- CFCOF + CF CON: -- CF NCO


The parenthesized radical may or may not have an independent

existence; that is, it may actually be a complex of divalent

silver which is rapidly attacked by nascent fluorine or de-

composes to give the transitory radical which is then attacked.

In either case the attack occurs to break the carbon-nitrogen

bond to form trifluoroacetyl fluoride and the electron defi-

cient nitrogen compound which rearranges, as in the Hofmann

reaction, to the isocyanate. Both the acyl fluoride and

isocyanate volatilize as formed out of the reaction vessel

into a cold trap.

Perfluoroglutarimide might be expected to react similar-

ly but under the same conditions gives no volatile products

after an initial evolution of HF. Even at much higher temper-

atures in an inert diluent only a silver salt can be isolated.

Formation of a complex is indicated in both cases, in

the diamide case as an intermediate and in the imide reaction

as a stable product. Earlier work49 has shown that silver










difluoride gives more specific reactions with compounds

containing carbon-nitrogen unsaturation than other strong

fluorinating agents. This specificity might well be attri-

buted to preliminary formation of a complex, thus lowering

the activation energy and allowing the fluorination to be

carried out under relatively mild conditions:


AgF2 \
NH ---- N AgF + HF (1)




N AgF = N- + AgF (2)


In the case of bis-(trifluoroacet)amide the equilibrium

in (2) lies far to the right and further fluorination occurs

rapidly. With perfluoroglutarimide the equilibrium lies to

the left and further fluorination does not occur under the

conditions used. As in the attempted bromination, the

relative stabilities of the complexes allow a reasonable

mechanism to be offered and rationalizes seemingly anomalous

behavior. Further, it was previously noted that the mercury

salt of the diamide is considerably less stable thermally

than that of the imide.

Attempted fluorination of perfluoroglutarimide with

iodine pentafluoride failed to give any fluorinated product,

only perfluoroglutarimide being identifiable in the product.








Bis-(trifluoromethyl)carbamyl fluoride and perfluoro-

N,N -dimethylacetamide react similarly to one another with

silver difluoride:


AgF2
(CF3)2NCOX Ag2 (CF3)2N. + COFX

S(CF3)2NN(CF3)2

AgF2

a (CF ) 2NF


X = F,CF3


In both cases the products were the same but the pro-

portions of each varied. When X = F, the yield of the

nitrogen fluoride was 60% and hydrazine only 13%, whereas

when X = CF3 the yield of the nitrogen fluoride was only

30% and the yield of hydrazine up to 45%. The reason for

this difference may be due to the replacement of fluorine

with the trifluoromethyl group, or may be due to differences

in the condition of the silver difluoride used. In the

heterogeneous reactions of silver difluoride the effect of

the surface area on yields can be tremendous.


6. Some reactions of N-bromoperfluoroglutarimide

It has been reported that both N-bromotrifluoroacet-

amide40o21 and N-bromosuccinimide52 form addition compounds

with cyclohexene, of the type :NHHCHBr(CIH2)4, and Young50








reported the facile addition of bis-(trifluoromethyl)nitro-

gen bromide to perfluoropropene:


(CF3)2NBr + CF3CF=CF2--- (CF3)2NCF2CFBrCF3


It seemed feasible to carry out the analogous addition of

X-bromoperfluoroglutarimide to perfluoropropene. When these

two were allowed to stand together in the dark no reaction

occurred, but if exposed to sunlight er heated in the presence

of peroxide a rearrangement of the X-bromo compound occurred

rather than bromination of, or addition to, olefin. It was

shown that the reaction occurred in the presence of perfluoro-

propene or chlorotriflueroethylene, but not in the presence

of trifluoroaceticanhydride or in the compound by itself.

The product was found to be o-bromoperfluorobutyryl

isocyanate, Br(CF2)3CONCO. The following evidence is offered:

(a) The product gave a band in the infrared spectrum

at 4.39 microns, indicating either nitrile or isocyanate, and

a negatively substituted carbonyl band at 5.5 microns. It

reacted violently with water, but gave no precipitate with

AgNO3 and did not oxidize iodide ion.

(b) It had a nuclear magnetic resonance spectrum, as

did its hydrolysis product, which conclusively showed an open

chain structure of the type X-CF2CF2CF2-Y.

(c) Hydrolysis gave '-bromoperfluorobutyramide, which

was identified by its infrared and nuclear magnetic resonance







spectra, as well as elemental analyses. Unfortunately, as

noted in the experimental section, the analytical result

for bromine on the amide was slightly low.

(d) The reaction with benzyl alcohol gave a product

which, according to the infrared spectrum and elemental

analyses, was Br(CF2)3 CONHCOOCH2C6H5.


Because of the cleanness of the rearrangement reaction,

good yields of a relatively pure product were obtained. Per-

fluoroglutarimide, present as a contaminant in the N-bromo

compound, was the only detectable impurity, along with the

unreacted olefin. It was immediately obvious that all the

elements of the starting material were present in the product

and that it actually was a rearrangement that was being dealt

with. There are only three possible products which contain

the -(CF2)3- chain:

BrCO(CF2) 3NCO,

CF2(CF2CO)2NBr --- BrCOO(CF2)3CN, or

Br(CF ) 3CONCO


The first product may be eliminated since its hydrolysis

should give a succinic acid derivative and bromide ion. The

second possible product should give a glutaric acid deriva-

tive and positive bromine which would oxidize iodide to free

iodine. It did neither of these. The third possibility

must, therefore, be the actual product.








Also important, a similar rearrangement has been re-

ported for N-bromosuccinimide34*22923 to give 9-bromoprop-

ionyl isocyanate.
34
Martin and Bartlett propose a mechanism which simply

involves rearrangement of the succinimide radical:

0 0

CH2CO CH2C CH2* C
2\ 2\ Br*
I NBr -- N -- --- BrCH2CH2CONCO
/ / /
CII2CO CH2C CH}2C
0 0
23
Johnson and Bublitz,2 in a systematic study, showed that

the mechanism was more complex. In addition to chloroform

or bromoform as solvent, a terminal olefin containing a 20

or 30 allylic hydrogen was required to be present. Under

these conditions addition rather than abstraction of allylic

hydrogen, the usual reaction of the succinimide radical,14,46

might be expected to be favored. Since the rearrangement of

N-bromoperfluoroglutarimide occurs under somewhat similar

conditions, it might be surmised that the first step is

addition, but rearrangement of either the adduct radical

or a subsequent intermediate occurs to give the observed

product. Unfortunately, no reactions of this type have been

reported to this writer's knowledge. The rearrangement bears

a formal resemblance to the reactions of trifluoroacetamide34

and c-nitroacetamide7 with aqueous hypobromite which Barr

and Haszeldine3'P formulate as follows:









CF3 C= CF3 + NCO-

Br-N- Br


In anhydrous media the sodium salt of N-bromotrifluoro-

acetamide decomposes in a normal Hofmann fashion to give

sodium bromide and trifluoromethyl isocyanate. The analogy

is almost certainly only formal since in the trifluoromethyl-

acetamide case an ionic mechanism is followed, whereas the

light and peroxide catalyzed decomposition of N-bromoper-

fluoroglatarimide is certainly free radical in nature.

The exact mechanism must remain in doubt until a more

thorough study of both systems is possible.

The most unusual finding in this study was that N-bromo-

perfluoroglutarimide reacts, with increasing difficulty, with

hydrogen bromide, benzoyl bromide, and perfluoroglutaryl

chloride to give bromine and the corresponding N-H or N-acyl

compound:


CF2(CF2CO)2NBr + HBr----CF2(CF2CO)2NH + Br2


CF2(CF2CO)2NBr + C6H5COBr ---CF2(CF2CO)2NCOC6H5 + Br2


CF2(CF2CO)2NBr + C1CO(CF2)3COC1 --CF2(CF2CO)2NCOCF2CF2CF2CON-

(COCF2)2CF2


The reactions of hydrogen and benzoyl bromides were

rapid and essentially quantitative. The N-benzoyl compound

was identified by its infrared and nuclear magnetic resonance









spectra which agreed with the proposed structure in every

detail. The nuclear magnetic resonance spectrum was partic-

ularly useful, showing absorptions similar to those of the

imide itself, but slightly shifted, and since only two types

of fluorine were present the benzoyl group must be substi-

tuted on the nitrogen, instead of on the carbonyl oxygen,

which could be considered a possibility.

It was noted that the N-benzoyl compound picked up

moisture from the atmosphere extremely rapidly.

The reaction with perfluoroglutaryl chloride gave a

25% yield of N,N,N ,N'-bis-(perfluoroglutaryl)perfluoro-

glutardiamide. It appeared that bromine was formed but the

fate of the chlorine is not known. About half the N-bromo

compound was recovered. Once again nuclear magnetic reson-

ance was important in the proof of structure, showing four

types of fluorine in the area ratios of4:2:8:4, as expected

from the structure:

CF2CO. COCF2
/ 2 / \
CF2(c) NCOCF2CF2CF2CON (c) CF2
\ / \ /
(d) CF2CO (a)(b)(a) COCF2(d)

(c) (c)


In addition, the fine structures of the assigned peaks

were identical to those in the parent systems, perfluoro-

glutarimide and perfluoroglutaryl chloride, and the chemical









shifts wore similar but, as expected, not identical. Al-

though this compound is probably sensitive to water, it

was not tested because of the small amount on hand.

The reaction failed with trifluoroacetyl bromide and

perfluorooctanoyl bromide, perhaps due to the impossibility

of removing bromine from the reaction mixture in the first

case and the difficulty of separating perfluorooctanoic

acid from any of the expected product which might have been

formed in the second case. In both reactions an initial,

rapid formation of bromine occurred which was undoubtedly

due to reaction of the N-bromo compound with dissolved HBr.

As mentioned before, this is a very rapid reaction. After

this initial surge, evolution of bromine was very slow,

evidently slower than the inevitable picking up of moisture,

which occurred even though every normal precaution was taken.

In less unusual reactions, the N-bromo compound oxidized

mercury to mercuric bromide and formed the mercuric salt of

the imide; it also reacted with bis-(1,2,2,2-tetrafluoro-

ethyl)mercury to give the previously unknown 1,1,1,2-tetra-

fluoro-2-bromoethane in 50% yield.

It appears that all of the reactions of the N-bromo

compound which were studied, with the possible exception

of its rearrangement to w-bromoperfluorobutyryl isocyanate,

depend in some way on the highly positive nature of the

bromine and its oxidizing power.









The driving force behind the reaction with acyl halides

is not clear unless the positive bromine functions as a

Lewis acid, similarly to a Friedel-Crafts catalyst, to form

an acylium ion which may then react with the weakly nucleo-

philic imide anion:


CF2(CF2CO)2NBr = CF2(CF2CO)2N- + Br+


Br+ + RCOBr -- RCO + Br2


CF2(CF2CO)2N- + RCO+ -- CF2(CF2CO)2NCOR


The fact that hydrogen and benzoyl bromides react much

more rapidly than triflueroacetyl and perfluorooctanoyl

bromides favors this mechanism since the positively charged

ions formed in the first and second cases should be much

more stable.

Thermodynamically speaking, there is a net gain of

stability of about 20 kcal due almost wholly to the very

weak N-Br bond.45


C4 The Reactions of Bis-(per-

fluorodimethylamino)mercury

Bis-(perfluorodimethylamino)mercury has been found to

react readily with several acyl halides to give the fluoro-

carbon amides. This is the first reported general synthesis

of compounds of the type: RCON(CF3)2. The compounds where







R = CF CH and CH5 were made from the respective acyl

chloride in essentially quantitative yields:


(CF3)2N-Hg-N(CF3)2 + RCOC1 --- RCON(CF3)2 + HgC12


The trifluoromethyl derivative had already been prepared

in low yield from the electrochemical process.51

While the properties of these materials were not studied

in detail, except for the previously described indirect

fluorination of perfluoro-N,N-dimethylacetamide, the benzoyl

compound appeared to be quite stable to water while the per-

fluoro derivative seemed to be very easily hydrolyzed.

The mercurial, surprisingly, failed to react with phos-

gene, except slowly to form perfluoro-2-azapropene. Although

the other reactions occurred at or below room temperature,

this one had not proceeded to a substantial extent even after

five days at 1000.

The mercurial reacted readily with trimethylchlorosilane

to form, not the expected silazane, but the azomethine, as

above, and trimethylfluorosilane. It would seem likely that

the silazane is formed as an intermediate:


(CF )N-Hg-N(CF )2 + (CH ) SiCl --- CF )2NSi(CH )3


CF N=CF2 + (CH3)3SiF

The decomposition of the silazane is analogous to the

following pyrolysis, used to synthesize the azomethine:51




42


6000
(CF3)2NCOF CF N=CF2 + COF2


Mao33a observed the formation of azomethine in an

attempted reaction of the mercurial with phosphonitrilic

chloride trimer.













CHAPTER III

EXPERIMENTAL


A. General

All temperatures are given in degrees centigrade and

are uncorrected. The elemental analyses are by Schwarzkopf

Microanalytical Laboratory, Woodside, New York.

The fractionations described herein were carried out

on standard columns, the size and type of packing depending

upon the degree of difficulty of the desired separation and

the amount of material available.

The vapor phase chromatography was carried out on a

Perkin-Elmer Vapor Fractometer, Model 154-B. The column

was packed with the ethyl ester of Kel-F Acid 8114 supported

on Celite. The infrared spectra were taken on a Perkin-

Elmer Model 137B double beam "Infracord" Spectrophotometer,

equipped with sodium chloride optics. Nuclear magnetic

resonance spectra were obtained with a 60 mc Varian NMR

Spectrophotometer, using CF3COOH as a reference standard.

The following chemicals were commercial products and

were used as received without further purification:








Chemical Source

Ethyl trifluoroacetate Peninsular ChemRosearch

Perfluoropropene Peninsular ChemResearch

Trifluoroacetonitrile Peninsular ChomResearch

Trimethylchlorosilane Peninsular ChemResearch

Perfluoroglutaryl chloride Hooker Electrochemical Co.


The fluorocarbon solvents, FC 102 (a mixture of fluoro-

carbon ether) and FCN-43,(C4F )3N, are products of the Minne-

sota Mining and Manufacturing Company.

The following compounds were synthesized for this work

by the literature method given:

CF3COC1 This compound was prepared by the method of

Henne17 from CF3COOH and benzoyl chloride.

CF COBr As above, this compound was prepared from the
44
appropriate benzoyl halide, as described by Tinker.

(CF3CO) 0 This compound was prepared in the manner of
3 2-
Clark and Simons,9 from CF3COOH and P205.

(CF-) N-Hg-N(CF2 This mercurial was prepared by the

method described by Young50 from the reaction of HgF2 and

perfluoro-2-azapropcne, CF3N-CF2.

CF2(CF2CO)2NH Perfluoroglutarimide was synthesized

by the method of McBee35 from perfluoroglutardiamide.

The following compounds were commercial products that

were further purified prior to use by the means given:







Acetonitrile was dried over calcium chloride and frac-

tionated, the fraction boiling from 81.6-82.00 was used.

Acetic acid was fractionated, the cut boiling from

118-118.50 was taken.

Trifluoroacetic acid was fractionated from a small

amount of P205, the cut boiling from 72-72.5o was used.

Most of the materials used and made in this work dis-

played varying degrees of ease of hydrolysis by atmospheric

moisture. In general, all the materials were protected

from moisture by carrying out the appropriate manipulations

in a dry-box, or rapidly in the open room. Some of the

materials were so hygroscopic, or reactive toward moisture,

that extreme care had to be taken to insure good results.

Among these were: (CF3)2N-Hg-(CF3)2, (CF3CO)2NH,

BrCF2CF2CF2CONC0, CF2(CF2CO)2NCOC6H5, and probably

[CF2(CF2CO) 2N]2 (COCF2)2CF2.
Volatile materials were handled as a matter of course

in a glass vacuum system, using standard techniques.










Nuclear

Compound


CF2CO
/ \
1. CF2(a) NH
\ /
(b) CF2CO

(a)


2. CF2(CF2COC1)2

(b) (a)


3. CF2(CF2CO)2NCOC6H5

(b)(a)


4. BrCF2CF2CF2CONH2

(a)(b)(c)




5. BrCF2CF2CF2CONCO

(a)(b)(c)




CF2CO

6. CF2(c) NCOCF2 CF2

L(d)CF2CO (a) 2(b)


TABLE 2

magnetic Resonance Spectra

Nuclei Peak Area Chemical Fine
Shift Structure

a 4 47.0 ppm triplet

F b 2 60.6 pentet


35.7

45.9


42.1

57.1


-15.1

42.1

42.2


-14.2

4o0.

38.7


41.7

46.7

49.0

55.6


singlet

singlet


triplet

pentet


triple triplet

triplet

triplet


triple triplet

triplet

triplet


singlet

singlet

triplet

pentet








TABLE 2 (continued)


Compound


Nuclei Peak Area Chemical Fine
Shift Structure


5.57 ppm


7. (CF CO)2NCH3


8. CII3CON(CF3)2


9. C6H5CON(CF3)2


10. CF3CON(CH3)FCF HCF3


11. 2 CF3COOH-C4Hg0

(a) (b)


12. 3 CF COOH*2

(a)


3.44



-21.3


-21.5


heptet
(barely
resolved)

singlet


singlet


**

**


a 1

b 4


a 1

b 3.3


(C2H 5)20

(b)


* Two slightly nonequivalent quartets.

** Complex spectrum; a full interpretation is not yet complete but
all evidence presently available fits structure given.







TABLE 3
Infrared Spectra Used in this Work

Principal Absorptions (Microns)


(Phase)

1. (CF3C0)2NH

(CC14 soln.)


2. CF3CONHCOCH3*

(relt)





3. (CH3CO)2NH
(melt)



4. CF3CONIICH3*

(melt)





5. (CF3C0)2 CH3*

(plates)


2.86(m), 3.1-3.2(m), 4.28(w),

5.64(s), 5.74(s), 6.25(m), 6.75(w),

8.15(s), 8.25(s), 10.-10.l(w),

14.30(m).


3.0-3.1(m), 3.33(w), 5.60(s),

5.79(s), 6.6(m), 7.05(w), 7.27(m),

7.60(m), 8.22(s), 8.65(s), 9.79(m),

10.85(w), 11.16(w), 13.62(m).


3.00(s), 3.38(m), 5.79(s), 5.95(s),

6.7(s), 7.05(m), 7.30(s), 8.38(s),

9.70(s), 10.90(w).


3.02(s), 3.22(w), 3.40(w), 5.78(s),

6.35(m), 7.05(m), 7.40(w), 7.60(w),

8.50(s), 11.36(w), 13.33(w),

13.82(m).

3.4-3.5(w), 5.68(s), 5.74(s),

6.83(m), 7.30(s), 7.55(m), 8.60(s),

9.38(s), 9.92(m), 11.80(w),

13.05(m), 13.29(w), 13.93(s).


Compound









Compound
(Phase)

6. CF3CON(CH3)CF2-

CFHCF3*

(plates)


TABLE 3 (continued)

Principal Absorptions (Microns)


3.35(w),

7.27(s),

8.25(s),

11.30(m)

13.10(w)


5.73(s), 6.73(w), 7.18(m),
7.41(m), 7.72(s), 7.93(s),

8.60(s), 8.93(m), 9.28(s),

, 11.72(m), 12.60(w),

, 13.90(s), 14.35(s).


7. CF2(CF2C0)2NH

(melt)





8. [CF2(cF2o)2N] 2 Hg*

(plates)







9. CF2(CF2CO) 2NAg*

(plates)


3.02(m), 3.50(w), 5.59(m), 5.70(s),

7.07(w), 7.50(m), 8.00(s), 8.13(s),

8.60(s), 8.95(s), 9.55(s), 10.l1(m),

12.5-13.0(w).

6.0(s), 6.38(w), 7.20(m), 7.30(w),

7.55(w), 7.75(m), 8.05(w), 8.30(m),

8.70(s), 9.18(w), 9.54(s), 10.22(s),

10.58(w), 10.00(w), 10.23(w),

13.30(m).

5.90(s), 6.20(s), 6.55(m), 7.50(m),

7.80(s), 8.2-8.7(s), 9.1(s),

9.65(s), 10.2(s), 11.13(w),

12.20(m), 13.20(m).









Compound
(Phase)

10. [(CF3co)2N]2-Hg*

(Nujol mull)



11. 2 CF3COOH'C4H80*

(plates)







12. 3 CF3COOH.

2 (C2H5)20

(plates)





13. (cF3cN)3
(gas)



14. (CF3)2NF

(gas)

15. (CF3)2NN(CF3)2

(gas)


rABLE 3 (continued)

Principal Absorptions (Microns)

4.80(m), 5.8(m), 6.00(s), 6.87(m),

7.29(m), 8.3-8.7(s), 11.8(w),
12.47(w).

2.8o(w), 3.35-3.45(s), 3.7(m),

4.0(s), 5.1(m), 5.64(s), 6.89(w),

7.35(m), 7.55(m), 8.25-8.6(s),
9.62(s), 10.90(w), 11.40(m),

12.3(m), 12.82(m), 14.30(s).


3.4(m), 3.72(w), 4.0(m), 5.1-

5.2(w), 5.60(s), 6.92(w), 7.21(w),

7.7(w), 8.22(s), 8.58(s), 9.14(m),
9.4(m), 10.3-10.4(w), 12.0(w),

12.3(w), 12.7(w), 14.32(m).

6.35(s), 7.06(s), 7.55(m), 7.70(m),

7.80(m), 8.00(s), 8.39(s),
11.60(s), 14.15(s).


7.60(s), 7.87(s), 8.02(s), 8.15(s),

10.25(m), 14.05(m).


7.46(m), 7.70(s), 8.10(s), 8.40(s),

11.26(m), 13.45(m), 13.85(s).










Compound
(Phase)

16. (CF3)2NH

(gas)



17. (CF3)2NCOF

(gas)



18. (CF3)2NCOCF3

(gas)



19. CF3N=CF2

(gas)


20. CF3NCO

(gas)

21. CF2(CF2C0)2NBr

(plates)





22. Br(CF2)3CONCO *

(plates)


TABLE 3 (continued)

Principal Absorptions (Microns)


2.85(m), 6.63(s), 7.40(s), 7.90(s),

8.30(s), 8.72(s), 10.5(m),

11.32(w), 13.50(w), 14.7(m).


5.30(s), 7.27(s), 7.60(s), 8.10(s),

8.20(m), 9.68(m), 10.05(s),

13.5-14.0 (m).


5.55(m), 7.35(s), 7.65(s), 7.90(s),

8.10(s), 8.35(m), 8.55(m), 8.80(m),

9.96(m), 11.25(m), 13.6(m).


5.51(m), 7.50(s), 7.71(s), 7.90(s),

8.31(s), 9.9-10.0(s), 13.9(m).


4.39(m), 6.89(m), 8.30(s), 8.70(s),

9.7(m), 13.9(m).


5.90(s), 6.09(s), 7.19(m), 7.53(m),

7.78(s), 8.16(m), 8.27(m), 8.65(s),

9.6(m), 10.13(s), 12.11(m),

13.20(m), 13.71(w).


4.39(s), 5.50(s), 6.5-6.6(m),

6.98(m), 8.35(s), 8.85(m), 9.35(m),

10.1(m), 12.4-12.6(m), 14.25(m).







TABL]

Compound
(Phase)

23. Br (CF2) 3CONHC00-

-CH2C6H5 *

(molt)









24. Br(CF2)3CONH2*

(Nujol mull)





25. CF2(CF2CO)2NCOC6H5*

(melt)







26. CF2(CF2CO)2NCOCF2 -

CFCF2CCON(COCF2)2-

CF2 *


E 3 (continued)

Principal Absorptions (Microns)


2.85(w), 2.96(m), 3.23(w), 3.32(w),

5.50(s), 5.69(s), 6.28(w), 6.05(s),

6.33(m), 6.71(m), 7.6-9.0(s),

9.55(m), 9.70(m), 9.92(m), 10.3(m),

10.8(w), 11.2(m), 11.73(m),

12.01(m), 12.43(s), 12.93(m),

13.3-13.5(m), 14.32(s).

2.97(m), 3.12(m), 5.90(s), 6.20(w),

7.87(m), 8.5(s), 8.75(s), 9.03(s),

9.86(w), 12.21(w), 13.08(w),

14.55(w).


3.22(w), 5.56(s), 5.83(s), 6.25(m),
6.70(m), 6.90(m), 7.5(s), 7.9-

8.8(s), 9.6(s), 10.05(s), 10.5(s),

11.67(m), 12.1(m), 12.95(S),

13.4(m), 14.2(m), 14.6-14.8(s).

5.45(s), 5.78(s), 7.5(s), 8.1-

9.0(s), 9.5-9.6(s), 10.0(s),

10.44(m), 9.4-9.6(m), 12.9-14.0(m).


(plates)









Compound
(Phase)

27. CF3CHFBr*

(gas)



28. I3c CON(CF3)2*

(gas)



29. C6H5CON(CF3)2*

(plates)









30. (CH3)3SiF

(gas)24


TABLE 3 (continued)

Principal Absorptions (Microns)


7.32(m), 7.79(s), 8.30(s), 8.70(s),

9.10(s), 11.5(m), 13.2(m), 14.4-

14.6(m).


3.22(w), 5.60(s), 7.3-7.7(s),

8.0-8.7(s), 9.9-10.0(s), 9.67(m),

13.9(m).


3.23(w), 5.50(s), 5.77(s), 6.25(m),

6.90(m), 7.5-7.7(s), 7.93(s),

8.3-8.5(s), 9.33(w), 9.64(m),

9.86(m), 10.03(s), 10.7(w),

11.32(s), 12.53(m), 12.99(m),

13.70(m), 14.2-14.5(s).


3.34(w), 7.70(w), 7.90(s), 10.92(s),

11.70(m), 13.1-13.2(m).


*Compound previously unknown.







B. Synthesis of Diamides

1. Reactions of acids and nitriles

Both CH COOH and CF COOH were reacted with CH CN and

CF CN at 150 and 2000. The reactions involving the higher

boiling CH3CN were carried out in ordinary glass ampoules,

while heavy-walled ampoules were used for the low-boiling

(-64) CF3CN. The volume of the ampoules was 7-10 ml.

For the reactions with CH CN a solution of equimolar

quantities of the nitrile and the appropriate acid was

prepared. One gram (+ 0.02) quantities of this solution

were weighed into the ampoule, the ampoule frozen in liquid

air, evacuated, degassed, and sealed. The ampoule was

allowed to come to room temperature and then completely

immersed in a constant temperature bath maintained at

150+0.50 for the desired period. Upon removal the tubes

were cooled to room temperature, the tip of the tube broken

open, and the tube weighed. The volatile unreacted starting

materials were removed at 1 mm. Hg and the contents reweighed.

The method was checked by repeating one run using 19 g. of

the CF3COOH-CH3CN solution. The conversion of the small

scale run was 68% and that obtained by distillation of the

19 g. run was 69%.

CF3CONHCOCH3, b.p. 900 at 60 mm. Hg

Anal. calcd. for C4H4F3NO: C, 31.0%; H, 2.58%;

N, 9.03%. Found: C, 31.25; H, 2.76%; N, 8.58%









In the reactions involving CF CN care was taken that

the ampoules used were strain free. Whether this precaution

was important is not known, although there were no losses of

samples due to failure of the ampoules. The acid, or a solu-

tion of catalyst in the acid, was weighed into the ampoule

and then a known amount of nitrile condensed into the ampoule.

The ampoule was degassed, evacuated, and sealed. While still

cold the ampoule was placed in a wire screen cage and after

warming to room temperature the ampoule, in its caGe, was

placed in a furnace maintained at 150+10 for the desired

reaction period. Upon removal the ampoule was frozen in

liquid air, removed from its cage, and opened into the

vacuum system. The change in pressure from the starting

amount of nitrile was used to calculate conversion.

The measurements of the reversion of diamide to nitrile

and acid in experiments starting with pure diamide were made

in similar fashion.








TABLE 4

Reactions of Acids and Nitriles


Reaction of acetic acid and acetonitrilea at 150+0.50

time(hrs.) conversionb catalyst

48 17.5

108 27

156 45

204 50

318 60

24 30 5% H2S04 by

54 45 5% H2SO4 by

70.5 52 5% H2SO4 by

54 22 5% NaOAc by

132 38 5% NaOAc by


Reaction of diacetamide at 150+0.5o

time (hrs.) % unreactedb

48 96

108 90

156 89c

204 87c

54 84

132 d

54 94

132 90


catalyst









5% H2S04 by wt.

5% H2S04 by wt.

5% XaOAc by wt.

5% NaOAc by wt.


wt.

wt.
ft.
Ot.

wt.

it*








TABLE 4 (continued)

Reaction of trifluoroacetic acid and acetonitrile at 150+0.50

time (hrs.) conversionb catalyst

2 43

6 59

8 69

24 43c

30.5 44ce

0.92 33 5% H2SO4 by wt.

3.2 60 5% H2SO4 by wt.

0.92 30 5% KOOCCF3 by wt.

3.2 48 5% KOOCCF3 by wt.


Reaction of N-acetyltrifluoroacetamide at

time (hrs.) % unreactedb

2 80.5

6 76

8.2 76

24 53c

30.5 49ce

1 87c

3.25 77c

1 94


150+0.50

catalyst
-









5% I-HSO4 by wt.

5% H2SO4 by wt.

5% KOOCCF3 by wt.







TABLE 4 (continued)

Reaction of trifluoroacetio acid and trifluoroacetonitrile

at 150+0.50


time (hrs.)

1.5

7.92

20

0.75

3

2

4.25


% conversionf

16

51

84

77

93

79

91


catalyst






5% H2SO4 by wt.

5% H2S04 by wt.

5% KOOCCF3 by wt.

5% KOOCCF3 by wt.


Reaction of bis-(trifluoroacet)amide at 150+0.50

time(hrs.) % unreactedf catalyst

14 98


5% 2S04 by wt.

5% H2SO4 by wt.








TABLE 4 (continued)

Reaction of acetic acid and trifluoroacetonitrile at 150+0.50

time (hrs.) % conversionf catalyst

1.25 37

3 64

6 97

1 73 10% H2SO4 by wt.

2 87c 10% H2S04 by wt.

1 71 10% NaOAc by wt.

2 85 10% NaOAc by wt.



Acid:nitrile reactions at 2000

system time (hrs.) % conversionO

CH COOH:CH CN 24 45

CF3COOII:CHI3CN 8 50h

CF COOH:CF3CN 8 50





a. The isolated diacetamide fractions were combined and re-
crystallized from hexane to give fluffy white crystals,
m.p. 69.5-70.50 (lit. m.p. 590).38

b. Corresponds to per cent nonvolatile at 1 mm. Hg.

c. Product partially decomposed and insoluble in acetone.

d. Product largely decomposed and insoluble in acetone.

e. Infrared spectrum of recovered, unreacted starting mater-
ial showed greater concentration of acid than in starting
mixture.




60


TABLE 4 (continued)


f. Based on unrecovered trifluoroacetonitrile.

g. Conversions are only approximate as decomposition was
extensive at this temperature.

h. Fractionation of the product obtained by reacting 38 g.
of an equimolar mixture under these conditions gave 16
g. of recovered starting materials, 18 g. of a cut boil-
ing from 80-90o at 60 mm. Hg, which, from its infrared
spectrum, was shown to contain some (CF CO) 2H boiling
at about 1000 at 1-2 mm. Hg; and several grams of tarry
residue.








2. Reaction of anhydrides and amides

Reaction of (CF3CO)20 and CF3COINJ2. Essentially the
42
method described by Smith 2 was used. Careful fractionation

of the mixture of CF3COOH and (CF3CO)2NH gave a 76% yield of

the diamide boiling at 1450 and having a malting point of

around 700. The imide when pure was a very hygroscopic

solid melting at 84.5-85.50.

Reaction of (CF3CO)20 and CF3CONHCH3. Using the method
42
of Smith,2 as above, 25 g. (0.2 moles) of CF3CONHCH3 and 42

g. (0.2 moles) of anhydride were heated together under a

fractionation column on total reflux. After several days

the pot temperature had risen only from 51 to 75. The

contents were cooled and sealed together in a glass ampoule.

After heating at 1200 for two days the ampoule was cooled

and opened. Careful fractionation gave largely recovered

starting materials, but 8 g. of impure material boiling

around 1000 was obtained which was shown to be largely the

desired product, (CF3CO)2NCH13, by comparison with an authen-

tic sample prepared by a different method described later.

Two grams (0.009 moles) of the pure material and one gram

(0.009 moles) of CF3COOH were sealed together in a glass

ampoule. After heating at 1500 for 36 hours the ampoule was

cooled and opened into the vacuum system. An infrared

spectrum showed almost complete reversion to anhydride and

N-methyl amide.







C. Some Reactions of Amides, Diamides,

and their Derivatives

1. The thermal decomposition of some of their metal salts

Thermal decomposition of salts of (CF3CO)gNH. The salts

were made and decomposed in the following manner:

(a) A slurry of sodium sand was prepared by shaking

molten sodium vigorously in xylene in a stoppered Erlen-

meyer flask. When the finely divided sodium had cooled it

was washed repeatedly with dry tetrahydrofuran. To such a

mixture, containing 2.3 g. (0.1 g. atom) of sodium in 300

ml. of tetrahydrofuran, was added 21 g. (0.1 moles) of

(CH3CO)2NH in 50 ml. of tetrahydrofuran. Evaporation of

the solvent left a clear, yellowish-brown syrup. This

material was gradually heated at 1500 over a 12-hour period.

Charring began at 800. After three days at 1300 there was

obtained 2 g. of CF3H condensed in a cold trap. Distillation

of the charred, partially solid residue gave 5 g. of the

triazine, (CF3CN)3. b.p. 950, nD25 1.3195. Known values20

for (CF3CN)3are b.p. 950, nD25 1.3161. Comparison of the

infrared spectrum with that of a known sample confirmed the

identification.

(b) The Hg salt of (CF3CO)2NI was prepared by reflux-

ing under a fractionation column a mixti:..~ of 166 g. (0.88

moles) of mercuric acetate at 120 mm.Hg. The CH COOH was

slowly taken off, eventually 27 g. (theory, 24 g.) including








an intercut being removed. After taking off the excess

(CF3CO)2NH and finally drying at 1000 at 0.5 mm.Hgl the

pure salt remained.

Anal. Calcd. for C F12HgN204: Hg, 32.4. Found: Hg,31.4

The dry Hg salt was heated at 200-3400. The only volatile

materials were small amounts of CF3COOH, CF3CN, and some

CF H. The residue consisted of metallic Hg and carbonaceous

material.

Thermal decomposition of salts of perfluoroglutarimide.

(a) The sodium salt of perfluoroglutarimide was pre-

pared by mixing, with cooling, equimolar quantities of the

imide and sodium methylate, in methanol solution, then re-

moving the methanol by evaporation under reduced pressure.

It was stable at 1200 but decomposed rapidly at 140o to a

carbonaceous mass.

(b) The Hg salt of perfluoroglutarimide was prepared

in the same manner as described for the synthesis of the

mercury salt of (CF3CO)2NH.

Anal. Calcd. for C10F12HgN204: Hg, 31.2. Found: Hg,31.06

The dry mercury salt was heated for six days at 4700. Of 5 g.,

3 g. remained as residue, a portion of which was metallic Hg,

the remainder a charred mass. One g. of imide had distilled

into a receiver and 1 g. of the Hg salt had sublimed out of

the heated portion of the apparatus.







Thermal decomposition of the sodium salt of CF3CON-

HCOCH 3 A solution of 1.2 g. (0.05 g. atom) of Na in 15.5

g. (0.1 moles) of the diamide was heated at 130-1350 for 72

hours with little effect. After 36 hours at 1600 the solu-

tion had darkened considerably and a small amount of CF 31

evolved into a cold trap. Distillation gave 8 g. of

CF3CONH2. This represents a 70% yield based on diamide,

or 140% based on sodium. The residue was an intractable

material having the consistency of asphalt.


2. Reactions with perfluoropropene

CF3CONH(CH3). An excess of CH3NH2 was bubbled into

CF3CO2C2H5 at room temperature. The C2HO5H which was formed

was fractionated off and the product distilled over at 157-

160. Yields in the neighborhood of 80% were easily obtained.

The product solidified in the flask as it distilled, m.p.

60.5-62.0.

Anal. Calcd. for C3H4F3NO: C, 28.4%; H, 3.15%;

N, 11.03%. Found: C, 28.6%; H, 3.38%; N, 10.86%.

C3CON(CH3)CF2CFHCF One hundred and sixty-eight grams

(1.3 moles) of CF3CONH(CH3) was heated with 4 g. (0.17 g.atom)

of metallic sodium until it had dissolved. The solution of

sodium salt was reacted with 40 g. (0.25 moles) of CF3CF=CF2

in a rocking autoclave at 800 for 40 hours. Upon cooling

and opening the bomb into the vacuum system essentially no

olefin was recovered. Fractionation gave 52 g. (75%) of







adduct boiling at 115-1160, n 28 1.3170, 98-99% pure by

vapor phase chromatography. Upon standing HF was evolved

and both the infrared and nuclear magnetic resonance spectra

indicated the formation of an unsaturated material. The

adduct was allowed to stand six months, then a small amount

of Br2 in CC14 was added but no decolorization occurred.

Attempted reaction with CF CONH2. Twenty-eight grams

(0.25 moles) of CF3CONHg, 1.2 g. (0.05 g. atom) of sodium

were heated and rocked at 800 in an autoclave overnight.

After cooling, 25 g. (0.16 moles) of CF3C=CF2 was added

and the mixture rocked and heated at 800 for 18 hours.

Upon cooling and opening the autoclave into the vacuum

system, all the olefin was recovered unchanged. The residue

in the autoclave was considerably decomposed. Repeating the

reaction using 6 g. (0.25 g. atom) of sodium made no differ-

ence in the results.

Attempted reaction with perfluoroglutarimide. Forty

grams (0.18 moles) of perfluoroglutarimide and 2 g. (0.09

g. atom) of sodium were heated together at 1200 but before

solution was complete extensive decomposition and carbonation

occurred. When.a gram or so of sodamide was added to the

imide the mixture sparked and burned. The sodium salt was

best prepared by reacting the imide with sodium methylate

and removing methyl alcohol until only the dry salt remained.

In this way 8.8 g. (0.04 moles) of imide was mixed with 0.01







moles of methylate in 2.5 cc of methyl alcohol. After re-

moval of the alcohol by evaporating under reduced pressure

the sodium salt was sealed in a glass ampoule with 3 e.

(0.02 moles) of CF CF=CF2. The ampoule was heated and

rocked at 85-1000 for 12 hours. On cooling and opening

the ampoule into the vacuum system the olefin was recovered

unchanged. The clear, syrupy residue in the ampoule was

soluble in water#

Attempted reaction with (CF CO)2NH. Thirty grams

(0414 moles) of (CF3CO)2NH, 1.5 g. (0.06 g. atom) of sodium,

and 6 g. (0.04 moles) of CF3CF=CF2 were reacted in an auto-

clave in the same manner as in the synthesis of CF3CON(CH3)

CF2CFHCF3 The CF2CF=CF2 was recovered unchanged and frac-

tionation of the residue gave 7 g. of the triazine, (CF3CN)3.

3. Reactions with acyl halides

(CF3CO) NCH3

(a) In tetrahydrofuran- A slurry of sodium sand was

prepared by shaking molten sodium vigorously in xylene in

a stoppered Erlenmeyer flask. When the finely divided sodium

had cooled it was washed repeatedly with dry tetrahydrofuran.

To such a mixture, containing 2.3 g. (0.1 g. atom) of sodium

in 300 ml& of tetrahydrofuran, was added, with stirring and

cooling, 13.7 g. (0~1 moles) of CF3CONII(CH3) dissolved in

a small amount of tetrahydrofuran. Then 13*2 g. of CF3COC1

(0.1 moles) was condensed into the cooled solution which was







stirred overnight and then brought to reflux. Filtration

and fractionation gave, after the solvent was removed, 5 g.

(25%) of (CF3CO)2NCI3, b.p. 118.

Anal. Calcd. for C511'F6NO2: C, 26.90; H, 1.34%;

N, 6.28%. Found: C, 27.2%; H, 1.52%; N, 5.99%.

(b) In excess CF3CONH(CH3) -

Sixty-eight grams (0.5 moles) of CF3CONH(CH3), 2.3 g.

(0.1 g.atom) of sodium, and 15 g. (0.11 moles) of CF3COCI

were reacted in an autoclave in the same manner as in the

synthesis of CF3CON(CH3)CF2CFHCF3 except that CF3COC1 re-

placed the CF CF=CF2, Fractionation of the semi-solid

product gave 7 g. (25%) of (CF3CO)2NCH3, b.p. 116-1180.

Fifty grams of CF3CONH(CH3) were recovered. Since no CF3COC1

was recovered, it is likely that it had leaked from the auto-

clave during the reaction period.

(c) In pyridine- Six and six-tenths grams (Oi05 moles)

of CF3CONH(CH3), 4.0 g. (0.05 moles) of pyridine, and 6.6 g.

(0.05 moles) of CF3COC1 in 25 ml. of tetrahydrofuran were

sealed in a glass ampoule. Upon warming to room temperature

a precipitate formed* After standing overnight the ampoule

was cooled and opened, then filtered and fractionated. After

the solvent was removed 3 g. (30%) b.p. 115-125o was obtained

which was largely (CF3CO)2NCH3, as shown by comparison of the

infrared spectrum with that of an authentic sample.








Attempted reactions of CF3COC1 with metal salts of

(CF3CO) NH.

(a) Using the procedure that was successful previously

in the synthesis of (CF3CO)2NCH3, 4.6 g. (0.2 g.atom) of

sodium sand, 500 ml. of tetrahydrofuran, 42 g. (0.2 moles)

of (CF3CO)2NH, and 26.4 g. (0.2 moles) of CF3COC1 were re-

acted. Subsequent filtration and fractionation gave 30 g.

b.p. 123.5-124.5. As shown by infrared and nuclear magnetic

resonance, this was the tetrahydrofuranoate of CF3COOH. The

empirical formula is 2 CF3COOH.C4HgO, according to relative

absorption of the protons in the nuclear magnetic resonance

spectrum.

(b) The mercury salt was finely powdered and 30 g.

(0.05 moles) was heated with 6.6 g. (0.05 meles) of CF3COC1

along with 75 g. of (CF3CO)20 in a rocking autoclave at 800

for 24 hours. After cooling the autoclave and opening it

into the vacuum system, the volatile product was removed.

The bomb was evacuated for 12 hours, any additional volatile

material being trapped in a liquid air-cooled trap. Distil-

lation of the combined volatiles gave only recovered starting

materials.

Attempted reactions of CF3COC1 with perfluoroglutarimide

and several of its metal salts.

(a) Forty-four grams (0.2 moles) of the sodium salt of

perfluoroglutarimide, prepared by evaporation of methyl









alcohol under vacuum from a solution of equimolar amounts

of the imide and sodium methylatewas taken up in dry ether.

This solution was cooled while reacted with 26.4 g. (0.2

moles) of CF3COC1. A gelatinous precipitate of NaCl formed

rapidly. Stirring was continued for three hours and after

filtration the solution was fractionated. A product boiling

at 105-1080, 6 g., was obtained and after 10 g. of an inter-

cut 30 g. of recovered imide was taken over at 900 mm. Hg.

The 105-1080 product was subsequently shown to be the ether-

ate of CF3COOH, reported b. p. 102. The empirical formula,

also previously reported, 3 CF COOH'2 (C2H5)20 was confirmed

according to the relative proton absorption in the nuclear

magnetic resonance spectrum.

(b) Repetition of the above reaction using tetrahydro-

furan as solvent resulted in the formation of the previously

described tetrahydrofuranate of CF3COOH.

(c) Eleven grams (0.05 moles) of perfluoroglutarimide

was dissolved in a solution of 5.8 g. of Ag20 in 100 cc of

CF COOH. After condensing 6.6 g. (0.05 moles) of CF3 COC

into the above solution it was allowed to stand for several

days at 10-200. The solution was filtered from the voluminous

precipitate which had formed and distilled to give only

several grams of (CF3CO)20, CF COOH, and most of the starting

perfluoroglutarimide.

The above quantities of Ag20, CF3COOH, and imide were

mixed as above and then the CF3COOH fractionated off, the









last traces under reduced pressure. Twenty-two grams of

additional imide were added to its dry silver salt to form

a thick slurry which was reacted with 6.6 g. (0.05 moles)

of CF3COC1 in a rocking autoclave for two days at 500.

Distillation of the product gave only starting materials

in addition to some CF3COOH.

Attempted reactions of perfluoroglutaryl chloride with

the mercury salt of perfluoroglutarimide.

(a) Twenty-five and six-tenths grams (0.04 moles) of

the mercury salt, 9.1 g. (0.04 moles) of perfluoroglutaryl

chloride, and 50 ml. of FC 102 were stirred together vigor-

ously in a creased flask at reflux (ca. 1000). After three

days the solvent was fractionated off, along with unreacted

chloride from which separation was impractical, and the

residue sublimed onto a cold finger at 1 mm. HIg. This sub-

limate consisted only of the mercury salt and some perfluoro-

glutarimide.

(b) In trifluoroacetic acid- Sixteen grams (0.025 moles)

of the mercury salt and 6 g. (0.025.moles) of perfluoroglut-

aryl chloride were heated at reflux temperature in 75 g. of

CF3COOH. The mercury salt was slightly soluble at this

temperature and, upon cooling, the salt recrystallized.

After three days of refluxing the mixture was cooled and

filtered. Fractionation gave recovered CF3COOH, 5 g. of per-

fluoroglutarimide and 1 g. of dark residue which was discarded.








4. Reactions of metal salts of diamides with bromine and

iodine

N-bromoperfluoroglutarimide. Bromination of the silver

salt of perfluoroglutarimide in CF3COOU7 by the method of

Henne,.8 gave yields of 70% when carried out in the cold.

The product could be distilled at 500 at 2 mm. Hg into a

cooled receiver in which it would solidify. The purity was

determined by titrating with thiosulfate the 12 formed from

addition of the N-bromo compound to aqueous KI. The purity

varied from 85-95%, the only identifiable impurity being

unreacted perfluoroglutarimide. The mercury salt could be

added to CF3COOH and brominated to give comparable results.

Attempted brominations of metal salts of(CF3CO)2NH.

Using the procedure of IIenne, two volatile products were

obtained. The first was an easily sublimed solid and the

second, secured in much lesser amounts, was a liquid boil-

ing at 50-600 at 2 mm. Hg. Titration of the iodine liberated

from iodide gave the following results for positive Br:

Calod. for (CF3CO)2NBr: 27.8%

Calcd. for CF CONHBr: 42.1%

Found: solid, 33.1%; liquid, 22.8%

The solid product gave CF3CONH2, along with a small amount

of (CF3CO)2NH, on reaction with anhydrous HBr. A slurry of

the dry Hg salt of (CF3CO)2NH in CF3COOH did not absorb Br2,

nor was any absorbed in the above method if sufficient








(CF3CO)20 was added to insure that no water was present.

Substitution of metallic sodium for Ag20 had no effect either.

Attempted synthesis of N-iodoporfluoroglutarimido. Sub-

stitution of I2 for Br2 in the above reaction resulted in a

much slower reaction, as evidenced by the lesser rate of

formation of silver halide as the reaction proceeded. Even

after four days of stirring in the dark only 50o of the

theoretical amount of AgI had formed. Filtration and evapor-

ation under vacuum resulted in the removal of CF3COOH and 12,

which seemed to be constantly formed. Finally, 10% of theory

of material which boiled at 80-90O at 2 mm. Hg was obtained.

Even in the dark this material rapidly decomposed, 12 being

formed. The only identifiable substance left after removal

of the 12 was perfluoroglutarimide.

5. Indirect fluorinations of amides and diarnides

Fluorination of (CF3CO)2NH. Thirty grams (0.21 moles)

of AgF2 was suspended in 60 ml. of FC 102 and stirred while

10 g. (0.05 moles) of (CF3CO)2NH was added slowly, out of

contact with the atmosphere, gaseous products being collected

in a liquid air-cooled trap. The reaction temperature was

maintained at 600 by adjusting the rate of addition, then

raised to reflux (ca. 1000) for a short period of time.

The condensate in the trap amounted to 5 g. and had a mol.

wt. of 103-122. Its infrared spectrum showed all the lines

for CF COF and CF3 CO, plus traces of unidentified products.








Attempted fluorination of perfluoroglutarimide. Sixty-

five grams (0.45 moles) of AgF2 was suspended in 100 ml. of

(C4F9)3N and stirred while 35 g. (0.15 moles) of imide was

added at reflux (ca. 1600). Extensive etching of the glass

vessel indicated the formation of HF. The reaction of the

black AgF2 to form a tan product was also evident, as was

the evolution of heat. No volatile products were obtained.

Since there was excess AgF2 present, no attempt was made to

isolate the solid product except for enough to obtain an

infrared spectrum. Two grams (0.009 moles) of perfluoro-

glutarimide and 1 g. (0.0045 moles) of IF5 were heated at

reflux for six hours. Iodine was formed on the walls of the

vessel but no volatiles were obtained. The rather viscous

residue was quite clear and only slightly colored. An infra-

red spectrum showed no bands not attributable to the starting

materials.

Fluorination of tF3)2NCOF. Thirty grams (0.2 moles) of

AgF2 and 20 grams (0.1 moles) of (CF3)2NCOF were rocked in

an autoclave at 100o for 18 hours. The volatile contents

were then fractionated to give 7.5 g. of overhead at Dry Ice

temperature, mol. wt. 68.5-81.6, largely COF2, mel. wt.

66;10 g. (60%) of (CF3)2NF, b.p. -370; and 4 g. of column

holdup which was shown from its infrared spectrum to be a

mixture of (CF3)2NCOF and (CF3)2NN(CF3)2. Passing through

aqueous alkali gave 2 g. of relatively pure hydrazine.








Fluorination of (CF3)2NCOCF3. Fifteen grams (0.1 moles)

of AgF2 and 10 g. (0.04 moles) of (CF3)2NCOCF3 were rocked

in an autoclave at 1000 for 24 hours. Fractionation of the

volatile product was only partially successful because of

the small amount, but the following amounts of products

were estimated from the infrared spectra of the various

cuts: 3.5 g. of CF3COF, 2 g. (30%) of (CF3)2NF, 3 g. (45%)

of (CF3)2NN(CF )2, and 1.5 g. of (CF3)2NH which was probably

present as an impurity in the starting material.

6. Some reactions of N-bromoperfluoroglutarimide

The free-radical rearrangement of N-bromoperfluoro-

glutarimide. Fifteen grams (0.05 moles) of N-bromo com-

pound and 5 g. (0.033 moles) of CF3CF=CF2 were sealed to-

gether in a heavy-walled ampoule and left in direct sunlight

for four days. The original yellowish color disappeared

after the first day and there was no further change. Dis-

tillation of the product resulted in recovery of all the

olefin and a quantitative yield of BrCF2CF2CF2CONCO, b.p.

420 at 30 mm. Hg. This material reacted almost explosively

with water and a drop placed on a watchglass exposed to the

atmosphere turned solid in just a few seconds. The aqueous

solution gave no precipitate with AgNO3.

The above quantities were reacted in the presence of

1 g. of benzoyl peroxide in an autoclave at 1000 to give

comparable results.







When 5 g. (0.011 moles) of the N-bromo compound and

2.5 g. (0.02 moles) of CF2=CFCl were sealed in a heavy-walled

ampoule and placed in direct sunlight for several hours the

yellow color disappeared. The ampoule was cooled and opened

into the vacuum system to recover the olefin quantitatively

and give 5 g. of the acyl isocyanate obtained previously.

When (CF3CO)20 was substituted for the CF2=CFC1 in the

above experiment no reaction occurred even after two days in

direct sunlight except for the formation of some Br2. The

only other identifiable material was the unchanged N-bromo

compound.

Fifteen grams of the N-bromo compound was sealed by

itself in an ampoule and left in direct sunlight for three

days, after which time what seemed a considerable amount of

Br2 had formed, but fractionation after removal of the Br2

gave only the N-bromo compound, 80% being recovered along

with some of the perfluoroglutarimide.

BrCF CF2CF CONHCOCH C 2p The isocyanato from above was

allowed to stand two weeks in an ether solution of benzyl

alcohol. Evaporation of the solvent left a solid residue

which gave, upon recrystallization from cyclohexane, fluffy

crystals, m.p. 76.5-78.50.

Anal. Calcd. for C12HgBrF6NO3: C, 35.2%; H, 2.0%;

N, 3.-4. Found: C, 35.7%; H, 2.3%; N, 3.0%.








BrCF2CF CF2CONH2. The isocyanate, 3 g., was added

dropwise to an excess of water with which it reacted vio-

lently. The white solid which formed was filtered, washed

thoroughly with dilute NaHC03, then water. After drying

and recrystallizing from benzene, 1.5 g. of solid melting

at 98-1000 was obtained.

Anal. Calcd. for C4H2BrF6NO: N, 5.11%; Br, 29.2%.

Found: N, 5.00%; Br, 26.90, 26.78%.*

Reaction with HBr. Two grams of the N-bromo compound

and 1 g. of HBr were sealed together in a glass ampoule and

allowed to warm to room temperature. Bromine was formed

immediately and after an hour the ampoule was opened into

the vacuum system. Perfluoroglutarimide remained after the

volatiles were removed.

C6H5CON(COCF21_CF9. Thirteen grams (0.043 moles) of

the N-bromo compound and 7.5 g. (0.043 moles) of C65cCOBr

were mixed together in a distilling flask. The mixture

warmed immediately and Br2 was formed. After heating at

900 under about 45 mm. Hg for four hours, the evolution

of Br2 seemed complete and the resulting clear solution was

fractionated. After 5 g. of forerun there was obtained 8 g.

(60%) of product boiling from 85-86 at 2.5 mm. Hg. This




* While the reason for the low bromine analysis is not known,
sometimes complete decomposition of fluorocarbon bromides
is quite difficult. The NMR evidence, and all else, is so
conclusive that there can be little doubt that the structure
is that given.








material eventually solidified in the receiver and after

recrystallization from n-pentane melted at 39-410. It was

quite hygroscopic and upon solution in water gave no pre-

cipitate with aqueous AgNO3.

Addition of small amounts of AlBr3 had no effect upon

the course of the reaction, nor did the N-bromo compound

react appreciably with AlBr3 alone.

Anal. Calcd. for C12H5F6NNO3 N, 4.30%.

Found: 4.55%.


Reaction with CF3COBr. Fifteen grams (0.05 moles) of

the N-bromo compound and 9 g. (0.052 moles) of CF3COBr were

sealed together in an ampoule and allowed to warm to room

temperature. Even before the contents had completely melted

a considerable amount of Br2 had formed. After standing

overnight the ampoule was opened into the vacuum system and

the volatiles removed. Since an obvious color of Br2 re-

mained, a few ml. of Hg were added but the mixture immediately

became quite hot and additional Br2 was formed which sub-

sequently reacted with the Hg. After several hours the

solid contents were extracted with about 50 ml. of tetra-

hydrofuran. After filtering off the greyish solid and

excess Hg, the solution was evaporated. An infrared spec-

trum of the non-volatile residue showed only the presence

of perfluoroglutarimide and its Hg salt. This residue







weighed 18 g. and appeared to be about 80% Hg salt. .The

volatile product previously obtained was distilled but only

Br2 and recovered CF COBr were obtained.

Reaction with CyF15COBr. The bromide was prepared by

the reaction of C7F15COOH with C6115COBr in 55% yield, b.p.

125.

Anal. Calcd. for C8Fl50Br: Br, 16.8o. Found: 16.39.

Ten grams (0.35 moles) of the N-bromo compound and 17 g.

(0.035 moles) of C7F15COBr were mixed together. Some Br2 .

was formed immediately but even on heating under reduced

pressure little more was formed. Subsequent distillation

gave starting materials, along with some perfluoroglutarimide,

as the only identifiable products.

CF (CF2CO)-NCO(CF2)3CO (COCF2J2CF2, Twenty-one grams

(0.07 moles) of the N-bromo compound and 9 g. (0.033 moles)

of CICO(CF2)3COC1 were heated together at 1000. When the

color of Br2 became noticeable, a slight vacuum was applied

so as to remove that which had formed. After three days Br2

was no longer being formed and the slightly yellow solution

was distilled under vacuum. There was obtained a cut boil-

ing at 35-45P at 60 mm. Hg. which was largely recovered

N-bromo compound. The product was taken at 95-100o at 1.5

mm. Ig, The yield was 6 g., or 28e.

Anal. Calcd. for C15 18i 206: N 4.34%.

Found: 4.74%.









Reaction with Hg. Thirteen grams (0.043 moles) of the

N-bromo compound and 50 g. of Hg were sealed together in

a glass ampoule and allowed to warm to room temperature.

As Br2 was formed initially, considerable heat was evolved.

Eventually the Br2 had all reacted with the Hg and the

ampoule had cooled. It was then opened into the vacuum

system and heated gently. About a half a gram of perfluoro-

glutarimide was obtained. The residue was extracted with

tetrahydrofuran, filtered and evaporated to obtain a nearly

quantitative yield of the Hg salt, identified by means of

its infrared spectrum&

Reaction with Hg(CHFCF3j2. Four grams (0.013 moles)

of the N-bromo compound and 3 g. (0.0075 moles) of the mer-

curial* were heated at 1100 for 24 hours, at which time about

1 g. had collected as overhead in a cold trap. This material

had a mol. wt. of 171 (calcd. for CF CHFBr, 181) and an

infrared spectrum consistent with this structure. Repetition

of the reaction in a sealed tube exposed to sunlight gave

similar results. Sunlight had no effect on the reaction

residue, even after several weeks.




t Furnished by D. E. O'Conner, Department of Chemistry,
University of Florida.








D. The Reactions of Bis-(perfluoro-

dimethylamino)mercury

CF CON(CF 2. Fourteen grams (0.026 moles) of (CF3)2N-HC-

N(CF3)2 were sealed in a glass ampoule with 8 g. (0.06 moles)

of CF COC1 and allowed to warm to room temperature. At this

time a considerable amount of a white precipitate had formed.

Heating the ampoule at 400 for an additional hour caused no

further noticeable change so the ampoule was cooled and

opened into the vacuum system. Approximately 10 g. (80%)

of CF3CON(CF3) was obtained in a relatively pure state out

of 13.5 g. of condensate. The infrared spectrum matched

that of a sample obtained previously from the electrochemical

process.51 The remainder, which was more volatile on dis-

tillation, was mainly unreacted CF3COCI and (CF3)2NH.

CH3CON(CF32 Twelve grams (0.022 moles) of (CF3)2 Ng-

N(CF3)2 and 3.1 g. (0.04 moles) of acetyl chloride were

reacted and distilled as in the synthesis of CF3CON(CF3)2.

There was obtained 5 g. (62%) of product boiling at 66,

mol. wt. 195, found 194.

Anal. Calcd. for C4H3S6NO: N, 7.22%

Found: 7.41%.

C26hCON(CFq2g. Ten grams (0.02 moles) of (CF3)2N-Hg-
N(CF3)2 and 5.4 g. (0.04 moles) of benzoyl chloride were

allowed to warm to room temperature together in a distilling







flask. Subsequent distillation gave 10 g. (95%) of product

boiling at 950 at 90 mm. Hg.

Anal. Calcd. for C9H5F6NO: N, 5.40%.

Found: 5.72%.

Reaction of (CF312N-Hg-N(CF3 1 with COC12. Twelve grams

(0.022 moles) of (CF3)2N-Hg-N(CF3)2 and 2 g. of COC12 were

sealed together in a glass ampoule and allowed to warm to

room temperature. There was no change in appearance of the

contents and after several hours without a precipitate being

formed, the ampoule was heated at 1000. After five days the

ampoule was allowed to cool to room temperature and then

opened into the vacuum system. About 6 g. of volatile prod-

ucts were obtained but these were shown, from the infrared

spectrum, to be a mixture of CF3N=CF2, COC12, and some (CF3)2NH.

The relatively non-volatile residue was unreacted mercurial.

Reaction of (CF3)2N-Hg-N(Crj)p with (CH3g3SiCl. Twenty-

one grams (0.041 moles) of (CF3)2N-Hg-N(CF3)2 and 8.7 g.

(0.08 moles) of (CH3)3SiCl were allowed to warm to room

temperature together in a distilling flask. A solid pre-

cipitate formed, as in previous reactions, but the products

were gaseous, passing through the distilling column and

being condensed in a trap cooled in dry ice-acetone. Eighteen

grams were obtained that were shown by their infrared spectrum

to be a mixture of CF3N=CF2 and (CH3)3SiF.












CHAPTER IV

SUMMARY


The syntheses and reactions of some fluorocarbon acyl-

amino compounds and their derivatives have-been studied.

The reactions of acetic and trifluoroacetic acid with

aceto- and trifluoroacetonitrile to give the diamides,

N-acetyltrifluoroacetarnido and bis-(trifluoroacet)amide,

were carried out and the relative rates of reaction of the

various systems determined at 1500C. Two mechanisms appear

to be followed, the actual choice being dependent upon the

nitrile used. The reactions of the acids with acetonitrile

were catalyzed by acid and these with trifluoroacetonitrile

were both acid and base catalyzed. These reactions were

shown to reach equilibria which were studied by approaching

them from the opposite direction, ie., reversion of the

diamides to the appropriate acid and nitrile. The effect

of substituting methyl for trifluoromethyl groups on the

position of equilibrium is discussed.

The reactions of trifluoroacetamide and N-methyltri-

fluoroacetamide with trifluoroacetic anhydride were studied

but only in the former case were good yields obtained of

the trifluoroacetylated product.









The reactions of metal salts of trifluoroacetamide,

N-methyltrifluoroacetamide, bis-(trifluoroacet)amide, and

perfluoroglutarimide with perfluoropropene were studied;

only N-methyltrifluoroacetamide giving an addition product,

CF3CON(CH3)CF2CFHCF3. The metal salts of bis-(trifluoro-

acet)amide and perfluoroglutarimide failed to react with

acyl chlorides, but again the N-methyl compound reacted in

the desired manner to give N-methyl- bis-(trifluoroacet)-

amide. The sodium salt of bis-(trifluoroacet)amide decom-

posed at 100I C to give 2,4,6-tris(trifluoromethyl)-l,3,5-

triazine.

N-bromo-bis-(trifluoroacet)amide could not be made by

means of the bromination of the silver salt in trifluoro-

acetic acid, although N-bromoperfluoroglutarimide could be

so obtained.

Fluorination of fluorocarbon acylamino compounds with

silver difluoride proceeds in such a manner as to:

(1) Abstract the hydrogen atom(s) from the nitrogen.

(2) Cleave the carbonyl-nitrogen bond to give the acyl

fluoride and a nitrogen species which may either rearrange,

dimerize, or react with fluorine to form an K-F compound.

Thus, bis-(trifluoroacet)amide, p*rfluoro-N,N -dimethyl-

carbamyl fluoride, and perfluoro-N,N -dimethylacetamide

were fluorinated. Attempted fluorination of perfluoroglut-

arimide stopped after evolution of hydrogen fluoride and

the formation of a silver salt.








N-bromoperfluoroglutarimide rearranges under free

radical conditions, in the presence of perfluoropropene

or chlorotrifluoroethylene, to give -bromoperfluorobuty-

ryl isocyanate.

The first fluorocarbon triacyl-nitrogen compound,

NN,N ,N -bis(perfluoreglutaryl)perfluoroglutardiamide,

has been made from the reaction of perfluoroglutaryl

chloride and N-bromoperfluoroglutarimide. The N-bremo

compound reacts readily with benzoyl bromide to give

N-benzoylperfluoroglutarimide, and with hydrogen bromide

to give perfluoroglutarimide. No triacyl compounds were

isolated from the reactions with trifluoroacetyl bromide

or perfluorooctanoyl bromide.

A new synthesis of N,N-bis-(trifluoromethyl) aides

by means of the reaction of bis-(perfluorodimethylamino)-

mercury with acyl chlorides is reported. The acyl chlorides

used were trifluoroacetyl, acetyl, and benzoyl. Neither

phosgene nor trimethylchlorosilane gave the desired amino

derivative.











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49. Young, J. A., Durrell, W. S., and Dresdner, R. D., J.
Am. Chem. Soc., 81, 1587 (1959).

50. Young, J. A., Tsoukalas, S. N., and Dresdner, R. D.,
ibid., 80, 3604 (1958).




88


51. Young, J. A., Simmons, T. C., and Hoffmann, F. W., ibid.,
78, 5637 (1956).

52. Ziegler, K., et al., Ann., 551, 80 (1942).












BIOGRAPHICAL SKETCH


William Sandford Durrell was born October 14, 1931,

in Miami, Florida. He was graduated from Ft. Lauderdale

High School in June, 1949. In August, 1953, he received

the degree of Bachelor of Science in Chemistry from the

University of Florida. From that time until February,

1956, he worked as a research chemist at Peninsular Chem-

Research, Gainesville, Florida, and at the Ethyl Corpor-

ation in Baton Rouge, Louisiana. He was then called into

active duty in the United States Air Force and was stationed

at Wright Air Development Center, Wright-Patterson Air Force

Base, Dayton, Ohio. In January, 1958, he enrolled in the

Graduate School of the University of Florida and has held

the position of Research Assistant until the present time,

while pursuing his work toward the degree Doctor of Phil-

osophy.

William Sandford Durrell is married to the former Mary

Jane Kusbel and is the father of twin daughters. He is a

Captain in the United States Air Force Reserve and is a

member of the American Chemical Society, Alpha Chi Sigma,

Phi Beta Kappa, and Sigma Xi.










This dissertation was prepared under the direction of
the candidate's supervisory committee and has been approved
by all members of that committee. It was submitted to the
Dean of the College of Arts and Sciences and to the Graduate
Council, and was approved as partial fulfillment of the re-
quirements for the degree of Doctor of Philosophy.

June 5, 1961


Dean, College of Arts and Sciences



Dean, Graduate School

Supervisory Committee:



Chairman


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