Title Page
 Table of Contents
 List of Tables
 Preparation of unsaturated secondary...
 Preparation of unsaturated quaternary...
 Resolution of quaternary ammonium...
 Polymerization of quaternary ammonium...
 Discussion of results
 Biographical items

Title: preparation, resolution and polymerization of allyl-type optically active unsaturated quaternary ammonium salts.
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Title: preparation, resolution and polymerization of allyl-type optically active unsaturated quaternary ammonium salts.
Series Title: preparation, resolution and polymerization of allyl-type optically active unsaturated quaternary ammonium salts.
Physical Description: Book
Creator: Squibb, Samuel Dexter,
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Table of Contents
    Title Page
        Page i
        Page ii
    Table of Contents
        Page iii
        Page iv
    List of Tables
        Page v
        Page 1
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    Preparation of unsaturated secondary and tertiary amines
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    Preparation of unsaturated quaternary ammonium salts
        Page 36
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    Resolution of quaternary ammonium salts
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    Polymerization of quaternary ammonium salts
        Page 67
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    Discussion of results
        Page 72
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    Biographical items
        Page 81
        Page 82
Full Text
The Preparation, Resolution, and Polymerization of Allyl-Type Optically Active Unsaturated Quaternary Ammonium Salts

The author wishes to egress his deep appreciation for tho valuable assistance and inspiring direction of Dr# George B Butler who conceived this research project. Hie suggestions and encouragement wore generously contributed in the completion of the research and in the writing of the dissertation*
Special thanks are due Dr. A. H. Gropp, Dr. J, F* Baxter, and Dr. W. 5. Brey for the benefit of many stimulating conferences.
Tho author also wishes to express his gratitude for the assistance and advice so readily given him by his follow graduate students, and for tho patience and encouragement so thoughtfully contributed by his wife.

ACKNOWLEDGMENTS.................... Ii
TABLE OP CONTENTS...................ili
LIST OP TABLES ....... *.......,..,, v
I, INTRODUCTION.................. 1
A. Historical Notes
B. Stat orient of the Problem
C. Source and Purification of Reactants
TERTIARY MINES.............., 9
A. General Discussion
B. Experimental
AMMONIUM SALTS, ....... ......... 36
A. General Discussion
B. Experimental
A. General Discussion
B. Experimental

Seetlon Page
VII. SUI-E1ARY. ................... 76
LIST OP REFERENCES............... 78
BIOGRAPHICAL ITEMS ...............81
COMMITTEE REPORT................. 82

Table Pag
1* Physical Properties of Unsaturated Secondary
Aminos**** 13
2. Analytical Data, Unsaturated Secondary Amines. llj.
3# Physical Properties of Unsaturated Tertiary
Amines* *#* ....*.*. %$
If* Analytical Data, Unsaturated Tertiary Amines 17
$0. Unsaturated Quaternary Ammonium Halides. 1}0
6. Analytical Data, Optically Active Unsaturated
Quaternary Ammonium Salts......... $$
7 Optical Rotation Values for Initial Fractions of d-d-AllylmothallylnethylphonylamoniUEi Camphor-10-sulf onate.............60
8. Optical Rotation Values for Certain Successive Rocrystallizations cf d-d-Allylraothallyl-methylphonylamoxoniua Camphor-10-sulfonate 61

A. Historical Notes
In ammonium salts, the nitrogen atom is covalently bonded to four hydrogen atoms forming the positive ammonium ion, and the electronegative atom or group Is present as an anion with no direct union between the two except for electrostatic attraction (l-l|.).
It was shown that nitrogen in ammonium compounds Is tetrahedral when Mills and Warren (5) succeeded in preparing and resolving li-phenyl-ij-^carbethoxy-bls-plperidinium-1,1*-splrane bromide. This molecule has the nitrogen present as the spirane atom common to the two rings as shown in the apace drawings
With the nitrogen tetrahedron represented in this way, the molecule is asymmetric and should be resolvable* If, however, the nitrogen atom were pyramidal, as many early investigators believed, then this compound would appear as shown below:

This latter aodel possesses a plane of symmetry passing through the nitrogen atom and the groups in th kfk* positions. Those portions of the molecule which lie on either side of the plane of symmetry are mirror Images, and therefore optical isomerism is impossible* Sine Mills and Warren (jj>) succeeded In resolving the compound, it is seen that the first spirane structure Is correct and that the nitrogen is tetrahedral (!)
Realizing that the ammonium Ion is tetrahedral, with only four groups attached directly to the nitrogen atom, It is seen that quaternary ammonium salts with four different groups attached should exhibit optical Isomerisms
Ra R*
R? :
t R,

The negative Ion plays no part in the symmetry of the molecule (1).
In 1891, I>e Bel (6) observed that upon cultivating Penielllum ^laucum in solutions of ethylisobutyl-isopropylmethylammonium chloride, the solution acquired a specific rotation of -7 to 8 indicating that the mold had destroyed some of the dextro isomer. This was th first successful attempt to resolve an optically active quaternary ammonium salt.
In 1899, Pope and co-workers (7, 8) prepared both dextro and levo forms of allylbensylmethylphenylammonium iodide by fractional crystallization of the dextro isomer using d-silver ^-bromo-Tr-camphorsulfonate. The d-d-allyl-benzylmethylphenylammonlum c<-bromo-7T-camphorsulfonate crystallized out of an acetone solution first* The d-al lylbenz ylmethylphenylaramonium iodide was then regenerated by mixing the d-d-diastereoisomer with potassium iodide in water solution. The l-d-allylbenzylmethyl-phenylammonium <^-bromo-7T -camphorsulf onate was contained in the residue, and was recovered by leaching with water, and decomposition with potassium iodide.
Jones and co-workers (9-11) prepared a series of optically active quaternary ammonium salts, and attempted resolution with several different optically active acids. They were successful in a few instances.

Cary, Vitcha, and Shriner (12) have shown that the quaternary ammonium salts which are prepared from sulfonic esters of optically active alcohols are also optically active. They succeeded in preparing the optically active quaternary ammonium salt, d-trimethyl-2-octylammonium p-bromobenzenesulfonate from the reaction of trimethylamlno with d-2-octyl p-bromobensenesulfonate,
B Statement of the Problem
The absence of information in the literature concerning the preparation and resolution of optically active unsaturated quaternary ammonium salts capable of allyl-type polymerization and containing an asymmetric nitrogen atom prompted this study. The preparation of such salts capable of allyl-type polymerization, but with an asymmetric carbon atom rather than a nitrogen atom was also undertaken. Resolution of quaternary ammonium salts of both types was attempted.
It was hoped that certain of the resolved quaternary ammonium salts could be polymerized to give polymers of resin type which retained some optical activity. The effect of these resins on solutions of racemic mixtures of optically active acids was to be determined, If resins were formed, in an effort to find whether any resolution of the racemic acid would take place in a manner similar to

that of Ion exchange reactions,
Ingley (13), who prepared several new unsaturated quaternary ammonium salts and polymerized them, found that unsaturated quaternary ammonium salts containing only on allyl-type group (a functionality equal to two; i.e., on double bond) did not polymerize; that salts with two allyl-type groups (a functionality equal to four; i.e., two double bonds) gave polymers which were water soluble, or non-crosslinked polymers, These polymers were soft and of low molecular weight, and were unsuitable as resins. He also found that three or more allyl-type groups were required to give water insoluble or crosslinked polymers. These polymers were capable of ion exchange reactions.
This phenomenon is unusual in that a functionality of two is usually sufficient to give a water soluble, non-cross linked polymer, while a functionality of three or four usually results in a crosslinked, water insoluble polymer. In an attempt to explain the water soluble property or the apparent lack of crosslinklng of resins containing two allyl-type groups, Angelo (llj.) has proposed a mechanism which could cause a non-crosslinked type of chain growth. This mechanism Involves an alternating intramolecular-intermolecular chain reaction forming a piperidine ring structure. The following scheme illustrates the possible mechanism: (Z Is an initiator,

and R Is a saturated alkyl group.)
1. Initiation; free radical formation:
Z* + R2H HalK
2. Intramolecular growth:
+ /CH2-CH-CHS-Z + .CHs-CH-CHs-Z
R' - RaUT \
3 Intermolecular growths
+ /CH8-CH-CHa-Z +/CHs-CH=CHa

Intramolecular growths
+ /CHs-CH-CHa-Z CHs=CH-0Hs
RsI\ /GHs ^
, .CHg-CH-CHs-Z CH2-CH-CHS etc. 4- R8N ^cilg \^
Thus, an optically active quaternary ammonium salt capable of allyl-type polymerization must contain at least two unsaturated groups. Our interest was limited to salts containing two and three different unsaturated groups. We expected difficulty in finding a solvent in which to determine the optical rotation of the crosslinked polymers

If they formed since Angelo (15) found that most common solvents were unsatisfactory for dissolving the polymers.
Cm Source and Purification of Reactants
Allyl bromide was obtained from Dow Chemical Company and was used as received, Methallyl chloride (2-methyl-3-chloropropene-l) was obtained from Shell Chemical Company, and the fraction boiling between 71.5-72.5 was recovered. Shell Chemical Company also furnished dl-sec-butyl alcohol (dl-2-butanol). Crotyl bromide and IJ-crotylaniline were supplied by Aldrich Chemical Company and were used as received. Aniline and methyl bromide were obtained from Katheson Chemical Company, and the aniline was redistilled before uso. Brothers Chemical Company furnished 11-methyl-aniline and Chlorallyl chloride (2,3-dlchloropropene-l) was prepared by the dehydrohalogenation of 1,2,3-trichloro-propane which was obtained from Peninsular Chem Research, Inc. A 3 1. flask was charged with 295 of 1,2,3-tri-chloropropane and 1600 ml, of 5# sodium hydroxide solution and was heated on a steam bath for one hour. The reaction mixture was then steam distilled, and the lower hallde layer was separated and dried over anhydrous potassium carbonate.

Two hundred and sixty-one grams of product were obtained distilling from 93-95 at 760 mm. for a 55.8$ yield.
Eastman Kodak Company supplied d-tartaric acid, d-camphor-10-sulfonic acid, d-3-bromocamphor, dl-2-octanol, and p-bromobenzenesulfonyl chloride. Silver oxide was dissolved in an aqueous solution of d-camphor-10-sulfonic acid, and upon concentration, yielded d-silver camphor-10-sul-fonate by the method of Pope and Gibson (16),
The tertiary butyl hydroperoxide was obtained as a 60$ solution through the courtesy of Union Bay State Company*
Diallylamine was obtained by the hydrolysis of dlallyl cyanamide, which was obtained from American Cyanamid Corporation. The procedure used was that of Vliet (17) as presented by Gilman (18),
Experimental details for the preparation of other Intermediates used will be found in the various experimental sections which follow.

A, General Discussion
Because very few unsaturated secondary and tertiary amines containing different groups are commercially available, It was necessary to prepare several of them as Intermediates for the synthesis of the optically active unsaturated quaternary ammonium compounds. It was necessary to reserve certain groups for the fourth group to be added, as only such reactive halides as allyl bromide, methyl bromide, and benzyl bromide will react with these tertiary amines to form quaternary ammonium bromides.
The secondary and tertiary amines in this work were prepared by a further modification of the method described by Gllman (19) and modified by Butler and Bunch (20) and Butler and Ihgley (21), and Involved the addition of the appropriate alkyl or alkenyl halide to a thin paste of the primary or secondary amine and sodium carbonate in water. When preparing a secondary amine from a primary amine, It was necessary to us a largo excess of the primary amine to avoid obtaining an

undeslred symmetrical tertiary amine by-product. In some cases these by-products were useful in other syntheses.
The reactions were carried out in a round-bottomed, three-necked flask of suitable capacity equipped with a mechanical stirrer, cold water reflux condenser, and addition funnel. The reaction mixtures were heated to 100 by means of a Glass-Col heating mantle throughout the reaction time. Vigorous stirring was maintained during and after the dropwise addition of the halide* The reaction time for each reaction was 36 to 1|8 hours* The contents of the flasks were filtered when cool, and the amine layers were separated, dried over sodium hydroxide pallets, and purified by fractional distillation. All the amines prepared in this work were fractionated through a 2 x 60 cm. vacuum-jacketed column supplied through the courtesy of Consolidated Glass Company. The column was packed with corrugated stainless steel protruded packing. Since there was a large difference between the boiling points of the reactants and the products, this column was quite satisfactory. Th distilling pot and head were well Insulated with glass wool to insure good heat exchange between vapor and liquid* The average reflux ratio used was 1/5, with the pot temperature maintained within ight degrees of the head temperature* To reduce decomposition, th distillation was carried out in vacuo when necessary* Much

foaming usually accompanied the distillation and was con* trolled by the addition of a small amount of Dow-Corning Antifoam-A, Ground-glass joint equipment was used both in the preparation and in the purification of the amines. The amines produced were all colorless, mobile liquids, turning yellow slowly upon standing.
Temperatures recorded for the boiling points are uncorrected and are given in degrees Centigrade, Pressures greater than 10 mm, were measured with a Zlmmorli guage, and pressures below 10 ram, were measured with a McLeod guage.
The specific gravities were determined at least in duplicate in a carefully calibrated 10 ml, Cenco specific gravity bottle equipped with a capillary side tube. The refractive indices were determined by means of an Abbe refractometer, Whit light was used as th source of illumination, and constant temperature was maintained throughout the determinations. Freshly distilled samples of the compounds were used in both specific gravity and refractive index determinations to eliminate errors du to decomposition of th amines upon standing.
Many of th intermediate amines prepared were new compounds, or ones which have previously been mentioned in the literature without physical constants. Th

physical constants, analyses, and yields of the secondary and tertiary amines prepared in this work may be f ound in Tables 1, 2, 3, and 1|. Individual details not covered in this general discussion may be found in the experimental part of this section. Micro analyses were run by Drs. 6, Ueiler and F. 5. Strauss of Oxford, England.
B. Experimental
Synthesis of butylmethallylamine. A mixture of 328 g. of n-butylamine and 2l|k g, of sodium carbonate was placed in a two-liter, three-necked flask. To this mixture were added dropwise, over a period of four hours, ij,08 g. of methallyl chloride. The reaction mixture was maintained at 100 throughout the addition and was stirred for 36 additional hours afterwards. A small amount of water was added from time to time during the heating to prevent caking* The reaction mixture was cooled, filtered, and the amine layer separated. The amine layer was dried over sodium hydroxide pellets, and was fractionated. A total of I4I7 of product was collected, boiling in the range 1$0-152 at 760 mm. This quantity represents a yield of 72.9^.
Physical constants:
n8 l.ii-301
*H 77ltf

Compound B.P. 3 0 Yield (jo
t(C) Mm. Calc. Obs.
Butylmethallylamlne 150-152 760 l.k301 0.77^7 72.9 k2*k3
N-Allylanilinea 121-123 31 1.5618 o. 969I1 63.O
b N-Methallylanilln 105-106 10 1.5522 0.9552 56.7 tj.9.002 1+9.18
Allylchlorallylamine 71-72 67 l.i|668 0.9763 60.0 37.591 37.1*7
Previously reported synthesized by a different method (22). Previously reported synthesized by a different method (23).

Compound Empirical Formula Carbon {%) Calcd. Cbs* Hydrogen (#) Calcd. Obs. Nitrogen (#) Calcd* Obs.
Butylmethallylaraine C8H17N 75.6 75.2 13. ij. 13.1 11*0 10*6
MAllylanilinea CHnN * ... a -*
N-Mothallylaniline CxoHt3N 81.6 81.2 8.90 8.88 9.60 10*0
Allylehlorallylamine C0HxoNCl 5k*% 7.60 7.68 10.6 10* Ij.
aN-Allylanlline identified by physical constants given by Carnahan and Hurd (22).

Compoimd B P. D Yield RD
Mm. i%) Calcd. Obs.

Butyldteettellylamine 197-198 760 1.1|456 0.791*8 19.0 59.790 60.73
Butyldicrotylamlne 128-130 56 1.1*531 0.7980 60.5 60.782 61.28
H.H-Diallylanllln 102-101* 7.5 1-5580 0.9575 92.9 58.61*1 58.27
Allyibutylmstaallyl-amlne I8I-I83 760 1.1*1*22 O.7898 88.1* 55.170 55.91*
dl-Diallyl-sec-butylamlnea 90-92 70 1.1*390 0.8075 61.5 51.546 49.95
Butylchlorallyl-methallylasine 86-87 9.5 1.4618 0.9070 69.8 6I.03I 61.06
N,N-Methallylraethyl~ anilin IOI4.-IO6 13 1.5579 0.9395 34.5 54.390 55.21*
H,NChl02?aHyl methallylaniline 136-137 9.0 1.050 21.1 67.226 67.61*

TABLE 3 Continued
t(0) lit. <#>
Calcd. Oba.
tf'enillala,8thallyl" "7-110 2.0 1.SU37 0.9327 73.0 67.777 68.00
dlSn^ShyI^e" 5.7 1-5150 0.9175 W.5 66.1,17 66.1J
A1mSSS!^^a 79-80 30 1.11689 0.9268 55.0 55.9l6 a
The specific gravity and refractive index determinations were made at 27 rather than at 25.

Compound Empirical Carbon (g) Hydrogen (fo Nitrogen ffl
p Formula Calcd.ObsT Calcd. Cba. Calcd.OlosT
Butyldimetfaallylamine HasH 79.6 79.2 12,7 12.5 7.73 8.20
But yldi cr o t ylamino HS3N 79.6 79.9 12.7 12.7 7.73 7.60
N,N-Dlallylanilinoa H1BN . *. .... .... .... ....
Allylbutylmethallyl-amine Gil HsiN 79.0 78.8 12.6 12. 4 8.39 8.45
dl-Diallyl-soc-butyl amine Cio H1SN 78.4 78.1 12.4 12.1 9.15 9.60
Butylchlorallyl-methallylamine HSoNCl 65.7 66.1 9.95 9.72 6.97 6.79
N,N-Methallylmethyl-aniline H1BN 82.0 82.0 9.31 9.21 8.56 8,70
N,N-Chlorallyl-methallylaniline G13 H16NC1 70.5 70.6 7.28 7.15 6. 35 6.34

Empirical. Carbon () Hydrogen (5?) nitrogen Formula Calcd. Gbs. Calcd. Obs. Calcd. Cbs,
II, IT-Crotylmothallyl-aniline
dl-!?,!l-Diallyl-o^ -phonylethylamlne
C14HleH S3.5 O3.9 9.49 9.27 6*93
Cx4H10ir 83.5 83.5 9.49 9.28 6.98
CleHxeIICl 64.9 65.0 8.66 8.60 7.55
Identified by physical constants reported by Carnahan and Hurd (22)

B.P. 150-1520/760 ^
RD (Calculated) l\2.k27
RD (Observed) U2k3
Calculated for CaH1TN: C-75.6& H=l3.l$; N*11.0g
Observed: C=75.2& H13.!$; 2T-10.6^
As a by-product, 76.0 g, of butyldimethallylamlne were obtained boiling from 197-198 at 76 0 mm. for a yield of 19.0^.
Physical constants:
ne l.kk56
&tl 0.791*8
B.P. 197-198/760 mm.
RD (Calculated) 59.790
RD (Observed) 60.73
Calculated for
CisIWT: C=79.6: H=12.7& N=7.73$
Observed: C=79.2& H=12.& N=8.20<
Attempted synthesis of butylcrotylamine.One hundred and eight grams of n-butylamine were mixed with 2l*l* g. of sodium carbonate and enough water to make a thin paste and were added to a one-liter, three-necked flask. After heating to 100, 200 g. of crotyl bromide were added dropwise over a

B.P. 128-130/56 mm.
Ed (Observed) 61.28
Calculated for butylcrotylamine
C6HX71I: C75.6^; B=13.l$; H=il.o$
Calculated for butyldicrotyl-
amlne, C1J3HS3N: C=79.6& B=12.7& N=7.73^
Observed: C=79.9& H=12.7$} N=7.<
The analysis and molar refraction Indicate that butyldlcrotylamlne was produced rather than butylcrotylamine, and on this basis a 6o.5 yield was obtained.
Synthesis of IT-Allylanillne. Two procedures were attempted which varied in the ratio of amounts of starting materials used:
period of three hours. Stirring and heating were continued for three days, and the crude product was separated as described previously, and dried over sodium hydroxide pellets. It was fractionated under reduced pressure, and 81 g. of product were Isolated, boiling in the range 128-130 at 56 mm.
Physical constants: nl* 1.4531

1. Two hundred and thirty-two grams of aniline, 212 g. of sodium carbonate, and 100 ml. of water were placed in a one-liter, three-necked flask fitted with a stirrer, water-cooled reflux condenser, and dropping funnel. Three hundred and two grams of allyl bromide were added through the dropping funnel over a period of six hours, while the mixture was heated to 100 with a mantle* After stirring and heating for three days, the mixture was cooled, filtered, and the amine layer was dried over sodium hydroxide pellets. The amine layer was fractionated, and 201 g. of product were obtained which distilled from 102-101}. at 7.5 Kim An attempt to prepare th p-toluene-sulfonyl chloride derivative by the method of Carnahan and Hurd (22) produced no crystals.
Physical constants;
n|B 1.5580
dtt 0.9575
B.P. 102-10l*/7.5 mm.
Rd (Calculated for
ClsHxeH) 58.61*1
Rjj (Observed) 58.27
Sine Carnahan and Hurd (22) give n^s 1.5556 and the boiling point as 123/l8 mm, for II, H-diallylanl line, this fraction was presumed to be II, ll-dlallylanlllne, and no analysis was obtained. On this basis, a yield of

92.9$ was obtained.
2. Aniline (1|65 g), sodium carbonate (212 g.), and water (150 ml,) were placed in a two-liter, three-necked flask, and 2l|2 g, of allyl bromide were added dropwise. The isolation procedure, as employed before, was used after heating and stirring for 36 hours. Upon fractionation under reduced pressure, 167,5 S ? product distilled from 121-123 at 31 mm. This represents a yield of 63.0$ based on IT-allylanlllne Physical constants; nge 1.5618
d6 0.9694
B.P. 121-123/31 mm,
Rr, (Calculated for
CeHiaH) 44*384
Hp (Observed) 4448
The p-toluenesulfonyl chloride derivative was prepared by the method of Carnahan and Kurd (22), and melted from 66-67 without recrystallization, Carnahan and Hurd (22) report the melting point of N-allyl p-toluene-sulfonanillde as 69, and the boiling point of N-allyl-aniline as 115 at 23 mm. Therefore the fraction was presumed to be N-allylanlllne, and no analysis was run. Synthesis of H-methallylanillne, To synthesize H-methallylanlllne, 279 g. of aniline were added to a

watery paste of 212 g. of sodium carbonate, and to this solution, 272 g. of methallyl chloride were added drop-wise with stirring* The reaction mixture was maintained at 100 for 21* hours, The amine layer was isolated in the usual way, and was fractionated under reduced pressure. Two hundred and fifty grams of product were obtained boiling from 105-106 at 10 mm. for a yield of 6*7$*
Physical constants;
nlB 1.5522
di 0.9552
B.P, 105-106/l0 urn,
RD (Calculated) 1*9,002
RD (Observed) ii.9,18
Calculated for
CX6HlaH: C=8l,6& E8.90& H=9.60
Observed; C=8l.2& H=8,88& N=10,0^
Synthesis of allylchlorallylamine, A 500 ml. flask was charged with 57 g. of allylamine, 80 g, of sodium carbonate, and approximately $0 ml, of water. One hundred and eleven grams of chlorallyl chloride wore added dropwlse with stirring over a period of three hours while the flask was heated to 100 with a mantle* Heating and stirring were continued for 1*8 hours, and the amine layer was Isolated as described previously, Upon fractionation, 79 g. of product

wore obtained boiling from 71-72 at 67 mm* for a yield of 60*0^*
Physical constants?
48 1.2(668
dse 0*9763
B.P. 71-72%7 mm.
RD (Calculated) 37.591
Rj) (Observed) 37.47
Calculated for
CaH10ITCl: C-54-8^; H=7.60ft N=10,6
Observed; C=4.5& H=7.68& 11=10,
Synthesis of allylbutylmethallylamine.In a two-liter, three-necked flask, fitted with a water reflux condenser, stirrer, and addition funnel were placed 381 g. of butylmethallylamine, 170 g, of sodium carbonate, and enough water to make a thin paste. To this mixture were addod dropwise 363 g. of allyl bromide while being stirred and heated to 100 with a mantle* After heating and stirring for 30 hours, the mixture was cooled, filtered, and the amine layer separated. After drying over sodium hydroxide pellets and fractionating, 434 S* of product were obtained boiling from 181-183 at 760 mm, for a yield of 88*4$,
Physical constants;
ng6 1,4422

SB 28
Rj) (Calculated) Hp (Observed)
55.170 55.94
C=79*0& B=12.6& 17=8.39# C=78.8& 11=12.4ft !T=8,!5<
Synthesis of dl-diallyi-sec-butylamlne, Two methods were used for the synthesis of this amine:
1, Diallylamine (48.5 g.), sodium carbonate (53.0 g,), and enough water to make a paste were placed in a 500 ml, flask, and 68,5 g, of dl-sec-butyl bromide were added dropwise over a period of one hour, while th reaction mixture was stirred and maintained at 100, Stirring and heating were continued for four days, and th amine layer was Isolated as usual. When fractionated under reduced pressure, 11*3 S. product were obtained distilling from 90-92 at 70 mm. for a yield of 16*1$,
90-92/70 mm.
RD (Calculated) RD (Observed)
5L546 49.95

Analysis ?
Calculated for Ci Hi lis
C78.^l H12,l$J 1?9.15$ C=?8.l: E-12.1fr H9.6o
2* This route of synthesis was suggested by Butler (2k) who successfully obtained the amine using the same reactants; A one-liter flask was charged with 1!jj6 g, of dl-sec-butylamine, 225 S* of sodium carbonate, and 100 ml, of water, Then kk S* of allyl bromide were added dropwiso while heating to 100, Heating and stirring were continued for 36 hours, and the reaction mixture was cooled. Isolation and fractionation in the usual way produced 188 g, of product distilling from 90-93 at 71 mm, for a yield of 61,5$,
A comparison of the physical constants of this product with the one previously prepared shows them to be identical, and no analysis was determined*
or of l-dlallyl-sc-butylamino,Three attempts were made to isolate an optical antipode of dl-dlallyl-sec-butylamine to use in th synthesis of optically active quaternary
Physical constants;
I.4387 0,8069
90-93/71 mm.
Attempted synthesis of d-dlallyl-soc-butylamine

ammonium salts;
1. Th resolution of dl-soc-butyl alcohol to give d-sec-butyl alcohol was carried out by the method of Pickard and Konyon (25) as modified by Kantor and Hauser (26) Phthalic anhydride (592 g,) and dl-sec-butyl alcohol (296 g.) were placed in a two-liter, on@-neckod flask fitted with a reflux condenser. After refluxing for eight hours on a steam bath, th mixture was poured into 12 1, of 1 M sodium carbonate and was allowed to stand overnight, Th alkaline solution was extracted three times with 200 ml, portions of ether to remove unestorified alcohol and phthalic esters, and the dl-sec-butyl hydrogen phthalate was then precipitated with 5 M hydrochloric acid, Th stor was extracted with chloroform and was dried over anhydrous sodium sulfate, Upon removal of tho chloroform with a water aspirator, the viscous ester slowly formed a crystalline mass which had a melting point of 53-56 Two hundred and sixty-five grams of product (29,9$) wore obtained and were used without further purification, A second run produced 232 g, of product (29.8$) which were combined with the first run, Kantor and Hauser (26) give the molting point of dl-soc-butyl hydrogen phthalate as 58,5-59,5 after recrystalllzation,
Th 1-brucine salt of dl-sec-butyl hydrogen phthalate was formed by refluxing 497 g# of th str,

856 g* of 1-brucine, and 1350 ml. of acetone overnight. Four hundred and fifty-five grama of crystals were obtained upon cooling, and after six reorystallizations from 500 ml. portions of methanol. 314 g. of brucine salt remained with
MS* ~ ~2,96 *c 88 3.9i{26, ethanol) for a yield of 1*6.8$. Kantor and Hauser (26) report [k Jg -2.75 to -2.94 (c 4* ethanol),
The brucine salt was hydrolyzed back to the active alcohol by the method of Sprung and Mallis (27), Upon steam distillation of 314 g. of the brucine salt with 500 ml, of 6 H sodium hydroxide solution, and consequent saturation of the distillate with potassium carbonate, the d-sec-butyl alcohol separated. It was dried over anhydrous potassium carbonate and was distilled. Twenty-seven grams of product wore obtained boiling from 98-99 at 760 mm, and with [^J = + 11,89. This represents an overall yield of 4*7$. Kantor and Hauser (26) report the boiling point as 98,0-99.5 and [<<]gT + 13.78.
The method of Lovene and Marker (28) was employed to convert d-sec-butyl alcohol into 1-sec-butyl bromide* Twenty-seven grams of d-soc-butyl alcohol were saturated with dry hydrogen bromide gas at 0. After standing for an hour, the mixture was warmed on a steam bath for one-half hour, and water was added to separate the bromide.

The bromide was washed with cold concentrated sulfuric acid, then with 1 H sodium carbonate, and extracted with ether. After drying over anhydrous sodium sulfate, 13,0 g, of 1-sec-butyl bromide were obtained distilling from 88-91 at 760 mm, for a yield of 26.1$, The 1-sec-butyl bromide exhibited [oC]f, 10,51*, Levone and Marker (28) give the boiling point as 91 and fpC]^B ~ 13.79. Some racemlzation has probably occurred as was pointed out by Sprung and Wallis (27).
Thirteen grams of 1-sec-butyl bromide were added dropwise with stirring to a thin paste of 10,6 g, of dlallylamine, 10,0 g, of sodium carbonate, and 5*0 ml, of water* After heating and stirring for 36 hours, the amine was Isolated in the usual way. Six grams of product were obtained distilling from 89-91 at 70 mm, for a yield of 1*1*4$ based on diallyl-sec-butylamine. The pure liquid exhibited [o(]g = + 0.0l* and + 0.01 which indicated (within experimental error) that racemlzation had occurred.
Physical constants:
89-91/70 mm.
+ 0.04 and + 0.01 (pure liquid; identical samples)

The physical constants indicate that the product was dl-diallyl-sec~butylaminej therefore, no analysis was made*
2, Ten grams of 1-mallc acid, 15*3 g of dl-dlallyl-sec-butylamine, and 50 ml. of water were warmed on a steam bath for one-half hour and were cooled slowly. This method is similar to that of Loven (29) as presented by Blatt (30) for the resolution of dl-o(-phenylethylamlne, Ho crystals were deposited after one week, so the mixture was concentrated to approximately 25 ml, and was again allowed to cool, A viscous oil was formed which could not b induced to crystallise,
3, A procedure similar to that above utilizing d-eamphor-10-sulfonic acid also resulted in a viscous oil which could not bo induced to crystallize*
Synthesis of butylchlorallylmethallylamine*--A one-liter flask was charged with 127 g. of butylmethallylamine, 106 g* of sodium carbonate, and approximately 150 ml* of water. The reaction mixture was heated to gentle reflux, and 111 g, of chlorallyl chloride were added over a period of two hours* Stirring and heating were maintained for four days, Th amine layer was isolated and dried as usual, and was fractionated. On hundred and forty grams of butyl-chlorallytaethallylarain were obtained distilling from 86-87 at 9*5 ram, for a 69,8$ yield*

Rj) (Calculated) Hp (Observed)
8687/9. mm,
Calculated for CxoHgoHCl:
0-65.7$; H=9.95$; N6.97# C=66,l$; H9.72$J H=6,79$
Synthesis of IT,N-methallylmethylanlline, --A one-liter, three-necked flask was charged with 214 g, of N-methylaniline, 200 g. of sodium carbonate, and 100 ml. of water. The reaction mixture was heated to gentle reflux while 181 g, of methallyl chloride were added dropwise with stirring over a period of four hours. The amine was then Isolated as usual, and was fractionated under reduced pressure. One hundred and eleven grams of product were obtained distilling from 104-106 at 13 mm. for a yiold of 34.5$.
Physical constants;
1.5579 0,9395 104-106A3
3 8
3 0

RD (Calculated) 54.390
RD (Observed) 55.24
Calculated for
OnHX6If: 0=82.0$; B*9*31$5 N*8*56$
Observed: 0=82.0$; K=9.21$; H8*?0$
When M,H~methallylmthylanilin was distilled, 12 g of solid matter wore carried over with the distillate. Th solid material was filtered from the distillate, dried on a porous plat, and stored in a vacuum desiccator. It gave a sharp molting point at 123, Th chloride analysis corresponds to dimothallylmothylphenylammonium ohlorido, Th yield was 3.6$.
Calculated for
CieH2SKCl: 0il4.08$
Observed: Cl=13.82$; 13.85$
Synthesis of IT, U-chlorallylmethallylanillne, A one-liter, three-necked flask was charged with 220*5 of N-methallylanilin, 106 g* of sodium carbonate, and 150 ml, of water* Over a period of four hours at gentl reflux, 166*5 g of chlorallyl chloride wore added dropwise* Heating and stirring were continued for 24 hours, and th amine layer was separated and dried In th usual way. The amount of distillate boiling between 136-137 at 9,0 mm. was 70,0 g* for a yild of 21,1$.

1.5545 1,050
136-13?/9*G mm.
2 7
Rjq (Calculated) Rj) (Observed)
Calculated for ClaHleITCl;
C~70,5$> H=7.28$$ 11=6,35$ C=70.6$j E=7.15$; H6*34$
Synthesis of H.H-crotylmethallylanlllne, H-Crot yl-anilino (100 g,), 42 g, of sodium carbonate, and 50 *il. of water were placed in a 500 ml,, three-necked flask. To this mixture were added dropwise over a period of four hours 62 g, of methallyl chloride while the temperature was maintained at 100, Heating and stirring were continued for 48 hours, and the product was separated and dried over sodium hydroxide pellets, Tho amount of distillate obtained from 107-110 at 2,8 mm, was 33,3 g. for a yield of 73*0$,
Physical constants:
nD7 1.5437
RD (Calculated) Rj) (Observed)
107-110/2,8 mm*

Calculated for
C14Hiel5 C83.5ft'B*9.1*9ft I6.98$
Observed! C=83.9ft B=9.2?ft 1J=6,80$
Synthesis of dl-tTiH-diallyl-^-pheuyletfaylaraine,
33a a one-liter, three-necked flask were placed 121 g. of dl-c*l-phnylethylamine, 132.5 6* of sodium carbonate, and 50 ml. of water. To this mixture were added with stirring, at gentle reflux, 21*2 g. of allyl bromide. The addition required four hours, and the reaction mixture was heated and stirred for an additional four hours. Isolation of th product in the usual way produced 95*5 upon fractionation for a yield of 1*7*5$* Tho product distilled from IO3-IOI*0 at 5*7 m*
Physical constants}
RD (Calculated) RD (Observed)
103-10l|.o/5*7 mm. 66.1*17
Analysis; Calculated for
083.5ft H*9*t*9ft. 2^6.98$ C83.5ft H*9.28ft 1*6,80$

Synthesis of allylcbaorallylmethallylamine.Allyl-chlorallylamino (65 g.) and sodium carbonate (53 g.) were placed in a 500 ml. flask, and 1*5 of methallyl chloride were added dropwise through the dropping funnel over a period of 3 hours while hosting to 100 with a mantle. Stirring and heating were maintained for 1*8 nours, and th amine layer was isolated in the usual way. Upon fractionation, 50.5 B* of product wore obtained distilling over from 79-80 at 30 mm. for a yield of 55.0$,
Physical constants:
87 87
79-80/30 mm.
RD (Calculated) Hp (Observed)
55.91*6 55.71*
Calculated for CioHigNCl:
C=61*.9ft R=8.66$; U=7.55$ C=65.0$; H8,60$; N7.58$

A, General Discussion
The general method used for the preparation of most of the unsaturated quaternary ammonium halides was that of Angelo (31), and involved tho addition of allyl bromide or methyl bromide to the appropriate tortlary amine, either with or without a solvent. Suitable solvents were acetone, methylothyl ketone, and acetophenone. If th reaction was not exothermic, the reaction mixture was hold at reflux temperature for some tlm# It was necessary to maintain anhydrous conditions at all times.
Tertiary aminos also form quaternary ammonium salts with alkyl sulfonates, and an attempt was mad to prepare dl-trIallyl-2-octylammonium p-bromobenzenasulfonat by the method of Cary, Vitcha, and Shriner (12), which Involved th refluxlng of dl-2-octyl p-bromobenzenosulfonat, triallylamin, and dry other under anhydrous conditions for a short time.

A small amount of crystalline product waa obtained.
During the isolation of N, H-methallylmethylanillne, a few crystals of dimetnallylmothylphenylaBMonium chloride were contained in the distillate. Their purification and analysis may be found in the previous section.
Because of their hygroscopic nature, several of the quaternary ammonium halides were isolated as oils rather than as crystalline solids. It was not possible to crystallise these oils by any of the usual methods of crystallization such as cross-seeding, freesing, scratching, mixed solvents, and so on, The crude products were subjected to rather strenuous methods of dehydration, such as maintaining them under a pressure of G, mm, at 100 for several days; however, no crystallization occurred. Certain of these oils were too impure to give accurate halide analyses,
Where crystals were obtained, it was usually necessary to use speed in filtration and handling of the products

since most of them were very hygroscopic in the impure state. Ether which had been dried over sodium was used to precipitate and wash the products. Certain of the products could be recrystallized by dissolving them in hot absolute ethyl alcohol and adding dry ethyl ether or dry isopropyl ether until cloudiness appeared. They were then allowed to cool slowly in a vacuum desiccator,
Most of the crystalline unsaturated quaternary ammonium salts obtained in this work were white, deliquescent solids, very soluble in water and alcohol, and insoluble in dry ether. 10 products were stored under anhydrous conditions and usually decomposed slowly, turning yellow,
One quaternary ammonium salt, dl-triallyl-sec-butylammonium bromide, could be crystallized from a very concentrated water solution and could be stored in a beaker exposed to the air without noticeable decomposition.
The halogen content of the quaternary ammonium salts was determined by the method described by Plerc and Haenisch (32), which involved direct titration with 0,1 JF silver nitrate solution and back-titration with 0,1 H potassium thlocyanate solution using ferric alum indicator for the back-titratlon.
Melting points were determined by the open-capillary tube method with the aid of a copper melting point block,

and they ar uncorrected.
The melting points, analyses, and yields of those quaternary ammonium salts are summarised in Table 5, Individual details of preparation are discussed in the experimental section*
B Experimental
Synthosis of dl-allylbutylmethallylmethylammonium bromide.In a throe-nocked, one-liter flask, fitted with a gas inlet tube, a stirrer, and a Dry Ico condenser, were placed lj2 g. of allylbutylmethallylamlne and 0 ml, of acetone. Methyl bromide was then bubbled through th reaction mixture until it was saturated, Th mixture was gently refluxed for six hours, and allowed to stand for three days during which time a few crystals separated. The flask was cooled in an lee-salt bath, and a larg amount of crystallization took place. Th contents wore filtered and wore washed repeatedly with dry ethyl other* A further crop of crystals was obtained by adding dry ether to the filtrate. Thirty-eight grams of product was obtained for a yield of 58,0$, The crystals wore extremely hygroscopic and wore stored in a. vacuum desiccator over anhydrous calcium chloride at on millimeter pressure, A portion of th crystals was dissolved In hot acetone and re crystallized three times*. A small amount of

" Ammonltici Bromide Pornula M.P. (c) Analyses Calcd. Cf, Br) Obs# Yield <$)
dl-Allylbutylmethallylmethyl ll|2 30.1*6 30.43 30.47 58.0
dl-Allylbntylchlorallyl-methallyl C14H30ITClBr a 2^,81 b 13*0
dl-Allylmethalljlmethyl-phonyl CisHsoIJBr 119 28.32 28.63 28.52 65.ii-
DiHothallylKothylphenyl Ci0H3aHCl 123 li>.08 13.82 13.85 3.6
dl-Allylchlorallylmethallyl-phenyl CieHsiMClBJ? a 23*33 22.07 22.64 78.9
dl~Allylcroty3methallyl phenyl Ci6HS2liBr a 27.03 b 90.3
dl-Triallyl- oC -phenylethyl Oi7Ha*ITBr a 2U.81 2if*58 24#71 75.2,

TABLE 5 Continued
Ammonium Bromide Formula M.P. Cc) Analyses ($ Br) Yield <$>
Calcd. Obs.
dl-Diallylmothyl- cL -phenyl-ethyl C18H3SHBr a 27.03 26.86 26.83 83.O
dl-MalW-a-octjl3 OjjgHgolTSOgBr 89-90 * .. *. # 23.0
dl-Triallyl-soe-butyl CX3Hs4IfBr 96-97 29.17 29.22 29.06 81.8
dl-Diallylmethyl-sec-butyl 108-110 32.26 32.01 32.17 68.1
was not determined because compound was not obtained in crystalline
Compound was not obtained In pur enough form for analysis.
clsolated as the ammonium chlorido, and th analyses are given as $ CI.
dIsolated as the ammonium p-bromobonzonesulfonato with tho following analysis Calculated for CsaH36HS03Br. C 56.9$; H = 7.ip-$ Observed % C = 56.3$> K = 7.01$

dry ether was added to the hot acetone to initiate the crystallization. The melting point became constant at lll2.
Calculated for ClsHs4IBr: Br30.lj.S$ Observed: Br30.1j.3; 30,ltff0
Synthesis of dl-allylbutylchlorallylmothallyl-ammonium bromide--Butylchlorallylmethallylamine (101 g.), ally! bromide (60,5 g. )? and acetophenone (80 g,) were mixed together in a beaker, placed in a desiccator, and allowed to stand. After standing for four days there was no evidence of reaction, so the reaction mixture was warmed to 100 under anhydrous conditions, Upon standing for two months no crystals were obtained* After washing the solution well with dry ethyl ether, the oily liquid was dried in a vacuum desiccator at one millimeter pressure for two days over anhydrous calcium chloride, Twenty-one grams of viscous liquid was obtained for a yield of 13,05?, The compound was not obtained in a form pure enough for an analysis which would correspond to the calculated value.
Synthesis of dl-allylmethallylmethylphenylammonlum bromide. IT, Il-I-fethallylme thylaniline (161 g.) and allyl bromide (121 g,) were thoroughly mixed together and ware placed in a desiccator over anhydrous calcium chloride. The mixture was stirred occasionally, and crystals began

to form in approximately one hour. The completely solidified mass of crystals was filtered and washed with acetone until th crystals wore perfectly whit. After recrystal-lizatlon from an ethyl alcohol-acetone mixed solvent, they gave a sharp molting point at 119 On hundred and eighty-four grams of product wer obtained for a yield of 65.4$. Analysis;
Calculated for CiaHBoITBr: Br=28.32$ Observed: Br=28.63$5 28.52$
Synthesis of dl-allylchlorallylmethallylphenyl-ammonium bromide.Sixty grams of H,N-ehlorallylmethallyl-aniline and 32.8 g. of allyl bromide were allowed to stand in a desiccator over anhydrous calcium chloride for four days. Ho crystals separated, so the mixture was maintained at 100 on a hot plate for two hours under anhydrous conditions, but upon cooling slowly, no crystals were deposited. However, a water soluble, viscous layer separated. Upon standing in a desiccator for two months, no crystals wer deposited. Th lower viscous layer was separated, washed repeatedly with dry ether, and stored in a vacuum desiccator which was pumped overnight at on millimeter. Sevonty-three grams of viscous product was obtained for a yield of 78.9$.

Calculated for CleH21HClBr: Br23.33$ Observedj Br22.07^; 22,61^
The low bromide percentage indicated that the product was still contaminated.
Synthesis of dl-allylcrotylmethallylphenylammonium bromide,In a beaker were placed 18,9 g, of II,IT-erotyl-methallylaniline and 12.1 g, of allyl bromide* After stirring and allowing to stand in a desiccator over anhydrous calcium chloride for four hours, a viscous layer began to form, After approximately three months, no crystallisation had occurred. The viscous, oily layer was separated, washed several times with dry ethyl ether, stored in a vacuum desiccator, and pumped at one millimeter pressure overnight. Twenty-eight grams of viscous product was obtained for a yield of 90. 3^. The product was very impure, and no bromide analysis corresponding to the calculated value could bo obtained.
Synthesis of dl-triallyl- oC -phenylethylammonium bromide.A 2$0 ml., three-necked flask, fitted with a stirrer, water reflux condenser, and dropping funnel, was charged with 20*1 g, of II, H-diallyl- o(. -phenylethylamine and 20 ml, of dry methylethyl ketone. While the temperature was maintained at 50, 12.1 g* of allyl bromide were added dropwise, and stirring and heating were continued for three

hours. On cooling, two layors wore obtained, tho lower being very viscous and water soluble. Ho crystals wero formed after standing for one month, The viscous layor was separated, washed four times with anhydrous ethyl other, and stored at one millimeter pressure overnight, Twenty-four and two-tenths grams of product were obtained for a yield of 75.2$.
Calculated for Q% 7H34HBr; Br=2l|.8l$ Observed; Br24.58$ 24,71$
Synthesis of dl-dlallylmethyl- -phenylethyl-ammonium bromide, H, IT- Dlallyl- oi -phonylethylamine (20.1 g.) and methylethyl ketone (35 ml) were placed in a 250 ml., three-necked flask fitted with a stirrer, Dry Ice condenser, and a gas inlet tube. Methyl bromide was bubbled through the solution until an excess had been added as observed by a rapid Increase in the reflux rate, and tho mixture was allowed to stand overnight. Ho crystals were observed, so the reaction mixture was warmed at a gentle reflux for two hours, and was cooled, A small amount of methyl bromide was introduced at this time to guarantee an excess. A gummy, viscous layer bogan to form, and was allowed to stand In a vacuum desiccator. After standing for two months at one millimeter pressure, a gummy layer was still present, but no crystals wer

observed. The gummy layer was separated, washed four times with dry ethyl ether, and pumped at a pressure of one millimeter overnight, A viscous oil was still present* The yield was 83.0.
Calculated for ClcH2SHBr: Br=2703$ Observed? Br26,86$f 26*83$
Synthesis of dl-trlallyl-2-oetylammonium p-bromo-bonseneaulfonate,The preparation of dl-2-octyl p-bromo-bensenesulfonato was carried out by the method of Gary, ?iteha, and Shrlner {12). Thirteen grams of dl-2-octanol were placed in a dry 200 ml. flask, and 31,2 g. of p-bromo-bensonesulf onyl chloride were added* An ice-salt bath was applied, and when the temperature had fallen to 0, the stirrer was started, Dropwise, 31*6 g, of pyridine were added over a period of throe hours. Stirring was continued for three hours at 0. The reaction mixture was:made acid to litmus with approximately 90 ml* of 4 N hydrochloric acid, and the ester was extracted with ether* After drying the extract over anhydrous sodium sulfate, the ether was removed with a water aspirator* The ester was recrystal-lized by dissolving the residue in three times its volume of dry methanol, and by cooling it in a Dry Ice-acetone bath. The crystals were filtered while cold, and 22 g, were obtained melting from 38-390 for a 63.1$ yield.

Gary, Vitcha, and Shrinor (12) report the melting point of dl-2~cctyl p-bromobenzcnesulfonate an 1*0-41 after re-crystalllzation. The ester hydrolyzed very rapidly in air* Triallylamine (3 ml,), dl-2-oetyl p-bromobns en sulfonate (35 g5* and dry ethyl other (10 ml,) wer r fluxed undr anhydrous conditions for three hours. Upon cooling and adding 25 ml, of dry ether, crystallization took plac, Th crystals were filtered and wore dried on a porous clay plat in a desiccator, Th product melted at 89-90, and 1,1 g, were obtained for a yield of 23.0$, Analysisj
Calculated for C20HaoOalJSBrt C5&9$: H74l$ Observed: C=56.3$j H=7.01$
Synthesis of dl-trlallyl-soc -butylammoniura bromide. This compound was preparod by two methods;
1, Tho first method is rather unusual in that water was employed as a solvent. Usually unsaturated quaternary ammonium salts of allyl-type are much too hygroscopic to be crystallized from water, Butler (23*) obtained the compound in a similar manner. Allyl bromide (24,2 g,), dl-diallyl-soc-butylamin (30.6 g,), and water (25 ml,) wer placed in a 200 ml. flask and ware heatod to 70 for two hours. Upon cooling and allowing to stand, crystals began to separate in clusters. Those wore filtered and were re-crystallized by dissolving them in tho least amount of hot

methylethyl ketone, and by adding dry isopropyl ether until cloudiness appeared. Upon cooling, I4.O.2 g, of product were obtained melting from 96-98 for a yield of 71}-. 3$. Analysis;
Calculated for ClaH34HBr: 8^29.17$ Observed* Br=29.22$: 29.06$
2. In a test tube were placed 3. 06 g. of dl-diallyl-sec-butylamine and 2.1|2 g* of allyl bromide. The test tube was corked tightly and was allowed to stand while crystallization took place. Pour and one-half grams of product were obtained melting from 93-9l| for a yield of 81.8$, Upon recrystallization as above, the product melted from 96-97, and no analysis was made.
Synthesis of dl-diallyl-sec-butylmethylammonium bromide, Excess methyl bromide was bubbled Into 3,0 g, of dl-diallyl-sec-butylamine in a test tube. The teat tube was stoppered tightly and was allowed to stand, Crystals formed after two or three days. They were recrystalllzed by dissolving them in the least amount of hot methylethyl ketone, adding dry isopropyl ether until the solution became cloudy, and cooling slowly. Two such recrystallizations produced 3,2 g. of hygroscopic crystals melting from 108-110 for a yield of 671$.

Calculated for ClaLH22HBr: Br=32#26$ Observed: Br=32*Ql$j 32*17$

A, General Discussion
An attempt was made to resolve two crystalline unsaturated quaternary ammonium bromides containing an asymmetric nitrogen atom into optical antipodes* Only two such quaternary ammonium halides were obtained in crystalline form, namely, dl-allylbutylmothallylmethyl-ammonlum bromide and dlallylme t hallylm thylphenylammonium bromide.
Resolution of dl-triallyl-soc-butylammonlum bromide and of dl-triallyl-2-octylammonium p-bromobenz enesulfonate was also attempted. Those quaternary ammonium salts contain an asymmetric earbon atom and were obtained in crystalline form.
The general scheme employed for tho resolution of
th bromides was that of Pop and Peachoy (?). The racemic
quaternary ammonium salt, Q Br", was reacted with d-silver camphor-10-sulf onat, Ag*** C", by boiling th two together for an hour or so in acetone. The d-sllver camphor-10* sulfonate was prepared either directly in the reaction

mixture by using equimolar amounts of silver oxide and d-camphor-10-sulfonic acid, or by the previous conversion of the active acid to the salt with silver oxide* The reactions which take place may be represented schematically:
d- q* Br" d-d- Q+ C~
. + d- Ag C * + AgBr
1- 07 Br" 1-d- Q+ C"
Racemic Diastereo-
mixturo isomers
The diastereoisomers possess different physical and chemical properties, and after filtering from silver bromide, they may be separated by fractional crystallisation from acetone,
The difficulties encountered in this type of separation include the following:
1* The diastereoisomers may form an isomorphous solution which cannot be separated,
2* They may separate as oils which do not crystal-
3, The diastereoisomers may have only alight differences in solubilities*
The second difficulty was encountered when d-silver camphor-10-sulfonate was reacted with dl-allylbutylraethallyl-
methylammonium bromide, and the diastereoisomers separated as oils which could not be induced to crystallize from several different solvents employed* The resolution of this

salt was also attempted with d-silver 3-bromocamphorsulfonate, and by converting it into the hydroxide form with silver oxide in alcoholic solution, and consequent reaction with d-tartaric acid. All attempts produced viscous oils which could not be crystallized.
Upon reaction of dl-allylmethallyimethylphenyl-ammonium bromide with equimolar amounts of silver oxide and dcamphor-10-sulfonic acid by boiling the three together in acetone for an hour, silver bromide was precipitated. It was removed by filtration, and upon cooling the resultant solution in an ice bath, a white solid precipitated and was filtered off. It was washed well with acetone, and the specific and molecular rotations were determined In water solution. The molecular rotation of this sample averaged +6*?,l}ij. at 22 using the sodium D line as the light source. Since d-siIvor camphor-10-sulfonate had a molecular rotation of +50*59 under similar conditions, it is seen that the increase in molecular rotation can be ascribed to the ammonium ion, and that some resolution of the quaternary ammonium salt has been affected. Upon concentrating the acetone solution further, three other crops of crystals were obtained showing increases in molecular rotation of +11^,25, +ll,l}5# and +0,35, respectively, over that expected of the original d-silver camphor-10-sulfonate. This progressive decrease in molecular rotation indicates that less

and less of the d~d-diasterooisomer was precipitated, and that more and more of tho 1-d-diastereoiaomer was present in the precipitate.
The first crop of crystals obtained was recrystallized, and tho increase In rotation gradually became constant at +27.24, +26,i|l|., and +27*36 on thro successive rocrystal-lizations, Thus, almost puro d-d-allylmethallylmethyl-phonylammonlum eamphor-10-sulfonat was obtained, and resolution was effected,
Upon mixing water solutions of th d-d-allyl-methallylmethylphonylammonium camphor-10sulfonat and potassium Iodide, the quaternary ammonium Iodide was finally isolated, but when mixed with aqueous potassium bromide, no quaternary ammonium salt was regenerated In crystalline form, Upon allowing the aqueous solution to evaporate slowly in a vacuum desiccator, th potassium bromide crystallized out of solution before th quaternary ammonium bromide. This was due to the great tenacity with which.th original quaternary ammonium bromide was.'holding water*.
'Th resolution of dl-triallyl-sc-butylammonium bromide was also attempted with silver salts of d-camphor-10-oulfonic acid, d-3-bromocamphorsulfonic acid, and d-tartaric acid without success,. An attempt was mad to resolve th tertiary amine, dl-diallyl-sec-butylamine,

before Its conversion into the quaternary ammonium salt, but without success. Details for the attempted resolution may be found In Section II,
For the resolution of dl-triallyl-2-octylammonium p-br omobenzenesulfonato into optical isomers, it was first necessary to resolve dl-2-octanol. This was accomplished by converting the alcohol into the hydrogen phthalate ester by the method of Levene and Mike ska (33), and consequent resolution by the method described by Adams (3U), The procedure of Gary, Vitcha, and Shriner (12) was used to convert d-2-octanol into d-2-octyl p-bromobenzonesulfonate by reaction tfith p-bromobenzenesulfonyl chloride. The ester was 6o2# as optically pure as the product obtained by Gary, Vitcha, and Shriner (12), It hydrolyzed very rapidly in air, and was reacted..as quickly as possible with triallyl amine. An optically active product, d-triallyl-2-oetyl-ammonium pbromobenz ene sulfonate, was obtained with
M | = + 1.3.
Analytical data for the optically active unsaturated quaternary ammonium salts prepared in this work is summarized in Table 6,
B, Experimental Optical rotation measurements throughout this work were made on a Rudolph Model So High-Precision Polarimeter

Compound M.P. (c) c Cg/lOO ml.) Solvent Mr Mr Yield
d-d-Allylmothallylmethyl-phonylammonium Camphor-10-Sulfonat 130-131 0.7264 0.7540 0. 7li20 0.5i|20 water water water water +17.96 +17.86 +17.99 +17.85 +77.83 +77.03 +77.95 +76.95 2.7
d-Allylmethallylmothyl-phonylamonlum Iodide lllf.-ll5 0.5956 water + 8.06 +26.6 79.8
d-Triallyl-2-oetyl~ 89-90 2.7000 othanol + 1.30a +4.54 73.9
ammonium p-Bromobsn-zonesulfonat
Constanta are determined at 20, and tho product is believed to b 60.2$ optically pur.

having as its smallest scale division 0.002. Samples were allowed to come to equilibrium with the temperature in the air-conditioned room in which the instrument was housed, and the temperatures recorded are those of the room at the time the readings were made* A sodium vapor lamp served as a light source* Observed angles of rotation were determined on duplicate samples* and at least five readings were taken approaching the endpoint from each side, the average value being used*
For pure liquids specific rotations were calculated according to the formula (35)*
where [<*]p is the specific rotation at temperature t referred
to the D line of sodium (5893 A), a is the observed angular rotation, 1 is the length of the column of liquid in decimeters, and d is the density of the liquid in grams per milliliter*
For solutions specific rotations were calculated according to the formulas
r/lt 100 a
where a is the observed angular rotation, 1 is the length of the column of liquid in decimeters, and c is the concentration of solute expressed in grams per 100 ml. of solution.

The molecular rotations were calculated according to the equations
, [0(1% x molecular weight
MD= -153-
This value is useful in comparing different salts of the same acid or base. All salts of optically active acids or bases should have very nearly the same molecular rotation per gram equivalent (36),
The specific rotations of solutions were compared in the same solvent and at similar concentrations if possible. This was necessary because specific rotation varies with the concentration and with the solvent (37)
Attempted resolution of dl-allylbutylmethallyl-methylammonium bromide, Three procedures were attempted:
1, dl-Allylbutylmethallylraethylammonium bromide (26,2 g) was added to approximately 100 ml, of dry redistilled ethyl acetate which contained approximately 33*8 g, of d-sliver camphor-10-sulfonate* The reaction mixture was boiled for one hour on a steam bath, and the precipitated silver bromide was filtered off* The solution was placed in a vacuum desiccator, and the acetone was removed by vacuum distillation, A viscous oil was formed which did not crystallize after standing for four months*
The prooedure was repeated using different solvents, namely, acetone, methyl alcohol, methyl alcohol-ethyl

acetate, ethyl acetate-acetone, water, and cyclohexanone, and In all cases oils were obtained* Several of the ordinary methods of crystallization, such as cooling slowly, freezing, mixed solvents, seeding with other crystalline substances, and scratching, failed to produce a crystalline product*
2* dl-Allylbutylmethallylmethylamaonium bromide (26*2 g) was treated with 12*0 g of silver oxide In an ethyl alcohol solution, and the reaction mixture was warmed and stirred on a hot plate* The precipitated silver bromide and excess silver oxide were filtered off, and the filtrate was allowed to run into an alcoholic solution of 15*0 g* of d-tartaric acid* The solution was warmed for one hour on a steam bath, then concentrated by vacuum distillation* A very viscous oil was obtained which could not be induced to crystallize*
3* dl-Allylbutylmethallylmethylainmonium bromide (29 g*) silver oxide (12*8 g*), and d-3-brcmocamphorsul-f onic acid were warmed in 150 ml* of acetone for one hour, and, after filtering from silver bromide, were allowed to cool slowly In an ice room* After one month a viscous oil remained, but no crystallization had occurred*
Resolution of dl-allylmethallylmethylphenylammonium bromide.Silver oxide (76 g.), d-camphor-10-sulf onic acid (151 g*), and dlally2jaethallylmethylphenylammoniura bromide

(181*. g*) were placed in an 800 ml. beaker which was filled to approximately 700 ml. with acetone* The mixture was placed on & steam bath, boiled for two hours, cooled, and allowed to stand for two hours* The mixture was then heated to boiling, and the precipitated silver bromide was filtered from the hot solution* By cooling the filtrate to room temperature, and allowing the acetone to evaporate slowly, different fractions of powdery crystals were obtained. These fractions were washed well with acetone, and the wash solution was combined with the filtrate to be further evaporated* The filtrate possessed a dark color at this point* The succeeding crops of crystals melted from I30-I3I0, and a total of four crops was obtained before the filtrate became too gummy to work with. The specif ic rotation and the molecular rotation were determined in water solution at 22 for each of these four fractions, and the molecular rotation was based on the molecular weight of l|33*3 expected from d-d-allylmethallyl-methylphenylammonium camphor-10-sulfonate The molecular, rotation of d-silver camphor-10-sulfonate is reported as
at 25 by Pope and Peaehey (38), and as +49*4 at 16 by Pope and Gibson (39). The molecular rotation of three separate preparations of d-silver camphor-10-sulfonate was determined at 22, and an average value of -B>0*$9 was ob-
tained* This value was chosen as the reference molecular

Fraction wr e Hr A (Mr)
(1) +15.10 1.0396 +65*44 +14#85
(2) +14.96 i.584o +64,84 +14.25
(3) +13.32 1*7392 +62.04 +11.45
(4) +11*76 1,8800 +50*94 + 0,35
rotation valuo of the d-camplior-lO-culf onate Ion, and should be nearly constant for all salts of d-camphor-10-sulfonlc acid. The value, A ( [h] g*}, ^ calculated, and is tho difference between the molecular rotation obtained for tho d-d-allylmethallylrnDthylphonylammonlura camphor-lO^sulfonate fractions, and the molecular rotation, +50*59, espectod from the camphor-10-sulfonato ion. The wlue Al [H] Is) represents the contribution of the positive d-allylmothallylmethylphenylammonium Ion to th molecular rotation, and should b essentially constant for all salts containing It, regardless of tho negative ion present. If tho salt is completely resolved. The values for the specific rotation, molecular rotation, and A([m] |s) obtained for the four fractions of d-d-allylmethallylmethyl-phenylammonium camphor-10-sulfonate ar summarised in Tabl 7.
mTMZLimm?m!L?mimMmomwL camphor-io-sulfonate ,

The decreasing values of A([m]^8) for succeeding precipitating fractions indicate that less and less of the d-d-allylmethallylmethylphonylaiTraoniuri camphor-10 sulfonate is being deposited.
Fraction (1) was rocrystallised from acetone until the specific and molecular rotations became constant on three successive crystallizations, The results are summarized In Table 8,
Crystallization [o (4) +17*96 0.7264 +77.83 +27.24
($) +17.86 0*75^0 +77.03 +26.44
(6) +17*99 0*7il20 +77-95 +27.46
The value* A([h]Jb), Is essentially constant, and indicates that the positive d-allylmothailylmothylphenyl-ammonium ion should have a molecular rotation of approximately +27.
Four and one-half grams of product remained after crystallization (6) and melted from I3O-I3I0, Fractions (2) and {3} were combined and were recrystallized from acetone eight times to give an additional 3*2 g* of product

melting from 130-131 with [k]s +17.85 (0*0.5420} and [mJ J s= +76.95* These combined products represent a yield of 2.7$*
Analysis s
Calculated for
C8*K38H04S: C=66,7$i H8,l5$J N=3,23$
Observed: C=66.5$J H=3,09$; H-2.89$
Attempted regeneration of d-allylmethallylmethyl-fhenylammonlum bromide. One gram of d-d-allylmethallyl~ methylphenylammonium camphor-10-sulfonate in one milliliter of water was poured into 0.5 g of potassium bromide contained in one milliliter of water, No crystallization occurred in the solution so the mixture was stored in a desiccator, and the water was allowed to evaporate slowly. Crystals formed after some time, and were dried on a porous clay plate; however, their high melting point (greater than 300) indicated that the product was potassium bromide rather than d-allylmethallylmethylphenylammonium bromide. The quaternary ammonium salt appeared to be too hygroscopic to be crystallized from a water solution.
Regeneration of d-allylmethallylmethylphenylammonium iodide,Two grams of d-d-allylmethallylmethylphenylammonium camphor-10-sulfonate and 2.0 g# of potassium iodide were mixed together in 3 ml, of water, A white precipitate was formed, and was immediately filtered. It was dried on a porous clay plate in a vacuum desiccator at one millimeter

pressure overnight, and had a sharp molting point at 114-115 A total of 1*2 g, of product was obtained for a yield of 79.8$.
Physical constants; M.P. 114-115
MS* +806 (0=0.5956, water)
[nj|s +26.6
The value of +26,6 for tho molecular rotation of d-allylmethallylmethylphenylammonium iodide Is another Indication that the positive ammonium ion contributes the same amount to the molecular rotation regardless of the negative ion present.
Calculated for C14HS0NI: 1=38.60$ Observed: 1=38.21$} 38,07$
Attempted resolution of dl-triallyl-sec-butyl-ammonium bromide.Three procedures were employed;
1, In a one.liter boaker were placed 273 g. of dl-triallyl-sec-butylammonlum bromide, 23.2 g, of d-caaphor-10-sulfonlc acid, 11,5 g. of silver oxide, and approximately 500 ml, of acetono, 1 Tho mixture was stirred and heatod on a steam bath for two hours, and the silver bromide which formed was filtered off, Upon allowing the acetone to evaporate slowly, a thick, viscous oil was deposited which could not be induced to crystallize.

2* The above procedure was repeated using 15*0 g* of d-tartaric acid rather than d-camphor-10-sulfonic acid, A viscous oil was deposited,
3* The above procedure was repeated using 31*1 g* of d-3-bromocamphorsulfonie acid rather than d-camphor-10-sulfonic acid* A viscous oil was deposited.
Resolution of dl-trlallyl-2-octylammonlum pbromo-benzenesulfonate, In 700 ml* of acetone were dissolved 508 g. of dl-2-octyl hydrogen phthalate and 682 g* of brucine* The solution was filtered and cooled in an ice room where crystallization occurred. The crystals were filtered, pressed, and washed with 100 ml. of acetone* They were dissolved in 500 ml* of hot methanol and were poured into 600 ml* of 5 H hydrochloric acid. The ester layer was separated and was steam distills d from f>00 mx# of 30$ sodium hydroxide solution. The d-2-octanol was insoluble in water and was separated and dried over anhydrous potassium carbonate. The product distilled from 85-86 at 20 mm., and l3 g* were obtained for a 36*0$ yield. The specific rotation of the pure liquid was + 6*50, Since Gary, Vitcha, and Shriner {12} report
D^Jl)6 88 + l0* for d-2-octanol, the product was approximately 65$ optically pure.
In a 250 ml,, three-necked flask were placed 73*3 g. of p-bromobenzenesulfonyl chloride and 30,2 g, of d-2-octanol.

The mixture was cooled to 0 in an ico-salt hath, and
73.3 g* of pyridine was added over a period of two hours
with stirring. Stirring was continued for an additional
five hours at 0. The reaction mixture was made acid to
litmus by th addition of 5 If hydrochloric acid, and tho
ster was extracted with other. After washing with cold
water, tho extract was dried over anhydrous sodium sulfate,
and the other was removed with an aspirator, Tho ster
solidified in an ice-room and molted at 38, The specific
rotation was + 1|.26 (c=1.1757 ethanol) at 20. Cary,
Vitcha, and Shrlner (12) report [WJg8 + 7*06 (c=l|81|.)
and the melting point as 31. Th product was 60.2$
optically pur based on +706 as a reference specific
rotation valu if ho racemlzation occurred. The ster
hydrolyzed very rapidly in air.
Calculated for
Ci4HsiOsSBrs 0*1*8.1$; H=6.C2$
Observed! 0-1*8.6$; H=5.92$
Triallylamine {6.85 g.) and d-2-octyl p-bromobenzone-
sulfonat (17*5 G) were mixed and heated under anhydrous
conditions on a steam bath for 2l* hours. Upon cooling, a
thick oil remained. It was repeatedly washed with dry
ethor and was re crystallized by dissolving it in the
least amount of hot absolut ethanol, adding dry other
until the first cloudiness appeared, and then allowing

it to cool slowly. The product molted from 89-90, and 18 g. were obtained for a yield of 73*9$. The specific rotation, [p(]g, was + I.30 (c=2.7000, ethanol). Theoretically, the product was 60.2$ optically pure if no racemlzation occurred, and [^f]| would bo + 2.15 for an optically pure sample under similar conditions. Attempts to convert th quaternary ammonium p-bromcbnzensulf onate into th quaternary ammonium iodide and bromide by mixing with aqueous solutions of potassium bromide and potassium iodid failed to givo a crystalline product. Analysis:
Calculated for
CsaH36NS03Br: C~56.9$J B=7.1jl$
Observed; C=56.1j.$j E~6.99$

A* General Discussion
Bunch (kO) found that quaternary ammonium salts containing at least two allyl or two methallyl groups could he polymerized using tertiary butyl hydroperoxide as an initiator. Tngley (1|1) also reported that quaternary ammonium salts with an allyl and a chlorallyl group could be polymerized in like manner. Usually when two unsaturated groups were present* the polymers were soft, gummy, and non-crystalline. Three or more unsaturated groups were needed to give a polymer which was water insoluble, and one which would undergo ion exchange reactions*
It was expected that the quaternary ammonium salts prepared in this work should also polymerize. Soft, gummy, dark brown polymers were obtained in all cases except that of dl-trlallyl-sec-butyl ammonium bromide* It would not polymerize nor co-polymerize with acrylonitrile or bis(di-allylmethyljethylenediammonium dibromide. The other polymers were similar to some of the polymers prepared by Ingley (1*1) and Bunch (40), and it is now believed that they are of very low molecular weight, possibly diraers.

A certain amount of decomposition usually accompanied tho polymerizations, probably because of impurities in th monomer* .
Polymerizations wer attempted by dissolving on gram of th monomer in approximately two drops of water, adding approximately 0.02 g* of tertiary butyl hydroperoxide in a beaker, and allowing the mixture to stand at 70 for. approximately 2k hours*. Upon cooling at th end of this time, the solubility of th polymer in water was determined* Reruns for certain of the samples were made in sealed bottles which were first swept with nitrogen, sine Angolo (k2) observed that oxygen could exhibit some inhibiting factor in the polymerization. Ho noticeable alteration In th appearance of th polymers was brought about by this change in procedure.
Ho polymer in any case was obtained which was suitable for an ion'exchange resin.
B. Experimental
Poller of dl-allylbutylmethallylmethylammonlum bromld*A .mixture of 10 g. of tho monomer, 10 drops of. water, and 0.17 g. of tertiary butyl hydroperoxide was placed in a beaker in an electric oven and was held at 60 for two days. A light brown, rather soft, viscous polymer was obtained which was.completely water soluble.

Because of its water-solubility, the polymer was unsuitable for an ion exchange resin*
Polymer of dl-allylmethallylmethylphenylammonlum bromide*A mixture of 1.0 g* of the monomer, two drops of water, and 0*02 g. of tertiary butyl hydroperoxide was placed in a beaker in an electric oven and held at 60 for three days. A dark brown, gummy polymer was obtained which was water-soluble and was unsuitable for ion exchange reactions.
Polymer of dl-allylchlorallylmethallylphenyl-ammonlum bromide.A mixture of one gram of monomer, in the form of a viscous liquid, and 0.02 g. of tertiary butyl hydroperoxide was placed in a beaker, and held at 60 for two days In an oven, A dark brown, viscous polymer was obtained which was water-insoluble. However, because of its viscous nature, it was unsuitable for an ion exchange resin.
Polymer of dl-triallyl- oC -phenylethylammonium bromide*A mixture of one gram of monomer, in the form of a viscous oil, 0,02 g, of tertiary butyl hydroperoxide, and two drops of water were placed in a beaker, and held at 60 for two days in an oven, A dark brown viscous polymer was obtained which was water-insoluble. However, because it was not obtained in a solid form, it was unsuitable for a resin.

Polymer of dl-diallylmethyl- oC -phenylethylammonium bromide*A mixture of one gram of monomer, in, the form of a viscous liquid, 0,02 g* of tertiary butyl hydroperoxide, and two drops of water were placed in a beaker and hold at 60 for two days in an electric oven. A dark brown, vlscouf polymer was obtained which was water-miscible. It was unsuitable for a resin.
Polymer of d-d-allylmothallylmothylphenylammonium camphor-10-sulfonate. A mixture of one gram of monomer* 0*02 g. of tertiary butyl hydroperoxide, and two drops of water was placed in a beaker, and allowed to stand in an oven for 2lj. hours at 70. A viscous, brown-black oil was formed which was unsuitable for an ion exchange resin* Decomposition was extensive*
Attempted polymerization of dl*trlallyl-sec-butyl-ammonium bromide.Two procedures were employed:
1. A Mixture of one gram of monomer, 0.02 g. of tertiary butyl hydroperoxide, and two drops of water was placed in a beaker and was allowed to stand for 21+ hours at 70. A solid, crystalline substance was formed which molted from 95*96 V This corresponds to the melting point of the monomer.
2 Tho procedure above was repeated in a sealod glass bottle which was first swept with nitrogen. After 2k hours a black liquid remained, and no rosin was obtained.

Attempted copolymerlzation of dl-trlallyl-sec-butyl-ammonium bromide with bis (diallylmethyl) ethylenedlammonium dlbromide*A mixture of one gram of each of the monomers, 0.02 g# of tertiary butyl hydroperoxide, and two drops of water was placed in a bottle which was swept with nitrogen and sealed. After heating in an oven for 2l| hours at 70, one gram of the spongy polymer was broken up and washed with hot distilled water. Approximately 0.3 g. of the sample was water-insoluble. Since the monomer, bis(dl-allylmethyl) ethylenedlammonium dlbromide readily polymerized by itself, it appeared that no copolymerlzation had occurred, and that the water-insoluble part of the polymer consisted of the quaternary dlammonium dlbromide*
Attempted copolymerlzation of dl-triallyl-sec-butyl-ammonlum bromide with acrylonltrile* The procedure above was repeated using acrylonltrile, and at the end of two weeks at 70, a viscous oil remained* He resin suitable for ion exchange reactions was obtained*
Polymer of d-triallyl-2-octylammonlum p-bromobenzene-sulfonate, One gram of the monomer, 0*02 g. of tertiary butyl hydroperoxide, and two drops of water were placed in a nitrogen swept sealed bottle* After l|S hours in an oven at 70, an extremely viscous polymer remained. It was water-insoluble and had a melting point greater than 200. Because of its viscous nature, the polymer was unsuitable for an ion exchange resin.

The procedure used for the preparation of secondary and tertiary amines containing one, two, and three unsaturated groups was found to give good yields. The yields with a few exceptions were above 60$, Unsaturated groups which were employed for the preparation of the amines were allyl, crotyl, methallyl, and ehlorallyl. Sodium carbonate was found to be more satisfactory than sodium bicarbonate for reaction with the hydrogen bromide or hydrogen chloride eliminated in the reaction* All the amines prepared were colorless, mobile liquids when freshly prepared, but slowly turned yellow upon standing.
The attempted preparation of optically active dl-
allyl-sec-butylamine produced the amine with x]* te +0.04
and 0,01. Thus, raeemization (within experimental error)
occurred, and the reaction possibly proceeded by an Sllt type
mechanism as defined by Alexander (43). This mechanism
involves the formation of a carbonium ion, CH3-CHg-CH-CH5, which is stabilized long enough to assume a planar configuration. Subsequent reaction of this species with the free electron pair in diallylamino could lead to raeemization.

More evidence Is needed before a mechanism can be definitely assigned.
Certain of the unsaturated quaternary ammonium salts were obtained In crystalline form. These included dl-allyl-butylmethallylmethylammonium, dl-allylmethallylmethylphenyl-amraoniura, dl-triallylsecbutylaramonium, and dl-dlallyl-methyl-sec-butylammonium bromides and also dl-triallyl-2-octylammonium p-bromobenzenesulf onate. Certain others were obtained in the form of viscous oils, some of which could be dried enough to secure analyses which corresponded to the calculated values. Those for which analyses were secured which corresponded to the calculated values were dl-allylchlorallylmethallylphenylammonium, dl-triallyl- q(. -phenylethylammonium, and dl-dlallylmethyl- oC -phenyl-ethylammonium bromides. The salts, dl-allylbutylchlor-allylmethallylammonium bromide and dl-allylcrotylmethallyl-phenylammonlum bromide, could not be obtained in pure enough state to obtain accurate analyses. There appears to be no correlation between the groups present in the quaternary ammonium salts and the ease of their purification,
Purification was attempted in all cases, but some of the products seemed to resist purification. Hence, these compounds had to be used as obtained. Perhaps the Incomplete polymerization of some of the quaternary ammonium compounds was caused by the impurities contained in these

One unsaturated quaternary ammonium salt, dlallyl~ raothallylmethylphenylammonium bromide, was resolved by th formation of diastoreoisomers with d-camphor-10-sulfonic acid* Th quaternary ammonium iodide could b recovered by treating it with an aqueous solution of potassium iodide; however, th quaternary ammonium bromid could not bs recovered similarly because of Its hygroscopic nature* The method of resolution depends, to a large extent, upon the selective crystallization of one of th dlastreoisomrs from th solvent employed* More often than not, neither dlastereoisomer will crystallize, and th method fails*
Th optically active quaternary ammonium salt, d-triallyl-2octylammonium p-bromobenzenesulfonate, was prepared in approximately 60$ of theoretical optical purity by th method of Cary,Vltcha, and Shrlner (12) Th mechanism for the reaction Is possibly the same as described previously for the reaction of 1-soc-butyl bromid with dlallylamln* In this case, however, the carbonium Ion, C0H13C*H-CH3f la not stabilized long enough for a planar configuration to occur, and some retention of configuration is observed. More evidence Is needod to assign definitely a mechanism.
The allyl-typ quaternary ammonium salts prepared

in this work failed to yield polymers which were suitable for Ion exchange resins. No optically active polymer was prepared, and, consequently, no studies were made of its effect on racemic mixtures of optically active acids. However, it Is felt that progress has been made on the difficult problem of separating racemic mixtures of optically active acids by the use of optically active quaternary ammonium resins in an ion exchange type reaction..

Two now secondary aminos and ton now tertiary aminos, each containing on, two, or throe unsaturated groups, wore prepared and characterized. In addition, two such secondary aminos and one such tertiary amine, previously reported without complete analytical data, wore prepared and characterized. Unsaturated groups which wer employed for the preparation of th amines were allyl, crotyl, methallyl, and chlorallyl. Th majority of th amines had two and three different groups attached to the nitrogen atom;
Eleven new unsaturated quaternary ammonium salts were prepared and characterized, and ten of those contained either an asymmetric nitrogen atom or an asymmetric carbon atom. Certain of the salts wore obtained in crystalline form and included dl-allylbutylmothallylmethylammonlum bromide, di-dialiylmethyi-sec-butylammonlum bromide, and dl-trlallyl-2-octylammonlum p-bromobnzensulfonate. Others, which were obtained as viscous oils and which were obtained in pure enough form to givo accurate halide analyses, included dl-allylchlorallylmothallylphnyl-ammonium bromid, dl-triallyl-

bromide, arid dl-diallylmothyl- ex -phenylethylammonium bromide. One symmetrical unsaturated quaternary ammonium salt, dimethallylmethylphenylammonium chloride, was prepared and characterized.
Attempts were made to resolve dl-allylbutylraethallyl-methylammonium bromide and dl-allylmethallylmethylphenyl-ammonium bromide into optical antipodes. The resolution of dl-allylmethallylraethylphenylammonium bromide was successful; however, only d-allylmethallylmethylphenylammonium iodide was recovered in active form.
Resolution of dl-triallyl-sec-butylammonium bromide and of dl-triallyl-2-octylammonium p-bromobenzenesulfonate was also attempted, and the resolution of the latter was achieved.
Attempts to prepare an optically active allyl-type ion exchange resin from the unsaturated quaternary ammonium salts synthesized in this work wore unsuccessful, In all cases soft, viscous polymers were obtained.

CD H. Gilman, "Organic Chemistry, An Advanced Treatise, Vol* I, John Wiley and Sons, Inc., New York, 11* Y,, 1938, pp. 338-3l|2*
(2) w* Schlenk and J, Holtz, Ber,, 49# 603 (1916).
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(8) . J. Pope and A* W* Harvey, J* Chem, Soc,, 79. 828 (1901).
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(10) 11. B, Thomas and H, 0* Jones, J* Chem, Soc,, 69, 280 (1906), ~-'
(11) H. 0* Jones and J* R, Hill, J. Chem, Soc,* 93* 295 (1908). '""'" '
(12) R. C, Cary, J, F, Vitcha. and R. L. Shriner, J. Orn. Chem., 1, 280 (1936).
(13) F. L* Inftley. Ph.D. Dissertation, University of Florida, 1950, pp. 20-40,
(14) R* J, Angelo, Ph.D, Dissertation, University of Florida, 1955*' PP. 74-75.
(15) Ibid*, p. 81*
(16) W* J. Pope and C* S* Gibson, J* Chem, Soc,, 97, 2216 (1910). ..........

(17) E. B. Vliet, J. Am, Cham. Soc., 1*6, I307 (1921}.).
(18) E, Gilman, "Organic Syntheses," Coll. Vol. I, John
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(19) H, Gilman, "Organic Syntheses," Coll. Vol. I, John
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71, 3120 (1949). ;
(21) G. B. Butler and P. L. Ingley, J. Am. Chem. Soc.,
73,895(1951). ~~ ; -
(22) P. L. Carnahan and C. D. Hurd, J. Chem. Soc,, 52,
1*586 (1930), "~
(23) M. Tamele, C. J, Ott, E, E. Marple, and G. Hearne,
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(2l*) G, B, Butler, Private Communication,
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75, 17ii4 (1953).
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(28) P. A, Levene and R. E. Marker, J. Biol. Chem., 91,
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(30) A. H, Blatt, "Organic Syntheses," Coll. Vol. II,
John Wiley and Sons, Inc., New York, N. Y, 191*3* PP. 506-508.
(31) R. J. Angelo, H. .S, Thesis, University of Florida,
1953 p. 2oT~ ; '
(32) W, C. Pierce and E. L, Haenisch, "Quantitative
Analysis," John Wiley and Sons, Inc., New York, N. Y., 191*8, pp. 300-302.

(33) -P* A* Levone and L. A. Mike ska, J. Biol. Chem.
75, 594 (1927).
(34) R. Adams, "Organic Syntheses," Vol. VI, John Wiley
and Sons, Inc., Now York, II. Y., 1926, p. 68.
(35) T. R. P. Gibb, Jr., "Optical Methods of Chemical
Analysis," McGraw-Hill Book Company, Inc., New York, II* Y. and London, England, 1942, P. 344*
(36) Ibid., p. 358.
(37) Ibid., pp* 356-358.
(38) , J Pope and S, J. Peachey, J. Chem. Soc. 75,
1086 (1899). "-;-~~
(39) W. J. Pope and C* S. Gibson, J. Chem. Soc., 97,
2216 (1910). ~
(40) R. L. Bunch, Ph.D. Dissertation, University of
Florida, 1949, pp. 29-37.
(41) Ingley, op. cit.. pp. 29-40.
(42) R. J. Angolo, Ph.D. Dissertation, University of
Florida, 1955, P* **9
(43) E, R, Alexander, "Principles of Ionic Organic
Reactions," John Wiley and Sons, Inc., New York, II, Y., 1950, pp. 79-85,

Samuel Dexter Squibb was born in Limestone, Tennessee, on June 20, 1931. He pursued his undergraduate studios at East Tennessee State College and was awarded the degree of Bachelor of Science In June, 193>2, graduating with first honors.
In September, 1952, he entered the graduate school of tho University of Florida as a graduate assistant and has been in attendance since that date.
The author has served as a teaching assistant at tho University of Florida for the past three years.
Mr. Squibb Is a member of Gamma Sigma Epsilon and Alpha Chi Sigma fraternities. While an undergraduate, he received the Dean*s Award for scholarship and the American Chemical Society Award for scholarship in Chemistry.

This dissertation was prepared under the direction of tho Chairman of the candidate1s Supervisory Committee and has been approved by all members of the Committee, It was submitted to the Graduate Council and was approved as partial fulfillment of the requirements for the degree of Doctor of Philosophy,
August 11, 1956
Dean, CollegV of Arts and Sciences
Dean, Graduate School

In reference to the following dissertation: AUTHOR: Squibb, Samuel
TITLE: The preparation resolution and polymerization of allyl-type optically
active unsaturated quaternary ammonium salts, (record number: 549783)
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