Polymerization Studies of
Unsaturated Derivatives of Beta-Nitrostyrene
JAMES L. NASH, JR.
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
TABLE OF CONTENTS
LIST OF TA.BLES ..................... .. ... ...... iii
I. II iTRODUCTION AND HISTORICAL NOTES ...... I
A. Literature Review.......................... I
3. Statement of the Problem ................ 11
C. Source and Parification of Reactants ......., 3
II. PREPARATION OF ALDEHYDEE INTERMAEDL4TES 14
A. General Discussion ................ ...... 14
E, Experimental .......................... 19
III. PREPARATION OFS NITROSTYRENES.......... 28
A. General Discussion ...................... 28
B. Experimental ........ .. . . . . . .... 31
IV. LYMEIZ.TIC STUDIES .................. 43
A. General Discuin ......................... 43
B. Experimental ......................... 45
V. DISCUSSION OCF RESULTS ..................... 69
VI. ZUMMARY................................... 78
BIBLIOGRAC PHY....................... ................. 80
ACKNCWLEDGEMENTS ................................ 85
BIOGRAPHICAL ITEMS ................................ 86
COMMITTEE REPORT ................................... 87
LIST OF TABLES
Table P age
L .Phyzical Con rants of New Aldehydes... ............. 17
II. Analyses of New Aldehyde.......... . ......... ... 18
IIL Phyical Constants and AnalyseL. of TNewv
-Nitrostyrenes..... .... .. ........ ... 30
INTRODUCTION AND HISTORICAL NOTES
A. Literature Review
1. Preparation of Aldehyde Intermediates
The methods which have most generally been used in the prepara-
tion of allyl aryl ethers, namely, refluxing of the phenol with allyl
bromide and anhydrous potassium carbonate in acetone and higher boil-
ing ketones such as methyl ethyl ketone, have been unsatisfactory for
phenolic aldehydes, especially those which condense with ketones in
the presence of potassium carbonate. Consequently, absolute ethanol
has been substituted for the ketones with excellent results (13).
The rearrangement of allyl ethers of enols and phenols to
C-allyl derivatives when heated to high temperatures was first observ-
ed by L. Claisen (14, 15) when he attempted to distill 0-allylaceto-
acetate at atmospheric pressure in the presence of ammonium chlo-
ride and beta-naphthol allyl iether under twelve millimrieters pressure.
This rearrangement has been extended to include several -ubstituents
in the aromatic nucleus as well as a great number of heterocyclic
nuclei (56). None of the substituents in the aromatic nucleus affect the
rearrangement to any appreciable extent. The meta directing groups,
do not hinder the reaction, and correspondingly, strong ortho-para
directing groups do not favor it. Ester groups do not interfere with the
rearrangement, but, if a free carboxyl or aldehyde group is ortho or
para to the allyloxy group, it may be replaced by the allyl radical
with evolution of carbon dioxide and carbon monoxide respectively
With the exception of a very few cases such as derivatives of
polyhydrobenzenes (3, 33, 43, 54), the migration of the allyl group
has always been to the ortho position, when available, and has pro-
duced good yields. In the exceptions, thiz migration has been to the
para position. If the ortho positions have been occupied, the migrating
allyl group has occupied the para position. In the case where the two
ortho and the para positions have been occupied, the compound under-
goes decomposition or as mentioned above, replaces groups such as
the carboxyl and aldehyde, but, never enters the meta position (13, 16).
The mechanism of the rearrangement is represented by the
following illustration (17, 18, 19, 30, 59):
CH --- HZCH=CHZ (5. G Hz
A study of several allyl ethers has shown that in no case where
the rearrangemnent takes place to the ortho positions is the substituted
allyl group attached to the nucleus after rearrangement by the same
carbon atom which was attached to the oxygen. The attachment has
usually been by the gamma-carbon which involves inversion with a
subsequent shift of the double bond of the allyl group from the beta,
gamma-position to the alpha, beta-position. Exceptions are gan-ima-
ethylallyl phenyl ether (30, 37) and gamrnma-propylallyl phenyl ether
(38) where the delta-carbon attaches itself to the nucleus.
The rearrangement to the ortho-position has been classified as
a first-order reaction (34, 35) and as was expected required neither
acid nor base to catalyze it. The breaking of the carbon-ox:ygen bond
and the attachment of the gamma-carbon to the ortho-position must be
simultaneous. This step, rather than enolization of the hydrogen,
must be the rate-determining step. The rearrangei-ent has been shown
to be intramolecular, since mixtures of allyl ethers yield none of the
cross products which would result in an intermolecular reaction (31).
2. Preparation of 4-Nitrostyrenes
Simon (5Z), in 1839, prepared and identified the first of many
nitrostyrene derivatives when he nitrated the steam distillate of storaxx
oil," which was predominantly cinnamic acid, and obtained -nitro-
Until the later part of the nineteenth century, when Henry (27)
prepared -nitrostyrenes by condensation of the appropriate aromatic
alde hyde with nitromethane in the presence of zinc chloride at elevated
temperatures, nitration of acids similar in structure to cinnamic acid
was the only method used in preparingy-nitro-tyrenes.
Priebs (46) and Posner (45) studied the method of Henry by pre-
paring various /_-nitrostyr anes. Priebs also studied the effect of
alkali on the compounds he obtained and reported that amorphous
products resulted which could not be identified. We assume on the basis
of work done today that these unidentifiable materials are the polymners
of the originaly-nitrostyrenes. MeiSenheimer (41) reported that
sodium rnethylate when added to/-nitrostyrene entered the 1, 4-posi-
tions, forming a salt, but, fifty to eighty per cent of the!-nitro-
styrene formed an amorphous: solid. No further study of this was re-
ported until Butler and Carter (10) polymerized severa1y-nitro-
styrene z by the use of ;odium methylate.
Thiele (57, 58) made additional Studies on the condensation of
aromatic aldehydes with nitromethane and found that an excess of
alcoholic potassium hydroxide served exceptionally well as a condensing
agent at a temperature of 0C. In this condensation an intermediate
salt is for:ned with the alkali which upon treatment with an excess of
acid, usually hydrochloric, yields the,--nitrostyrene. Bouveault and
Wahl (5) reported that the method of Thiele was not satisfactory in
every case for the preparation ofX-nitrostyrene-z and used sodium
n.ethoKide as the ccndenring agent, in place of alcoholic potassium
hydroxide. The reaction equations involving a base are as follows:
D= KaGH I C-=NO 2
S+ CH+NO, -. + HC1 ----
CH=CHNC)O 4- KC1 +H2O
In 1911, Rernfry (49) became concerned with the condensaton of
aromatic aldehydes with nitromethane in the presence of alkali and,
from reports of previous investigators, concluded that the character
of the -ubstituent groups on the aromatic nucleus had an effect on the
subsequent condensation of the aldehydes. Even though he was unable
to admit any generalization with regard to the condensation, his study
gave some indication of the effect that certain groups exhibited in the
various positions on the aromatic nucleus. He found that the hydroxyl
group substituted in the para position, alone or in conjunction with
other group,&, inhibits this condensation. The free carboxyl groups
also prevent condensation, but, upon esterification will not interfere.
Knoevenagel and Walter (36) and Hahn and Stiehl (26) observed
that 4-hydrioxy-3-methoxyben:aldehyde did not condense with nitro-
methane under Thiele's procedure, but, the condensation did take
place in good yields with methylamine as the catalyst. Burton and
Duffield (9) stated that the condensation of 4-hydroxybenzaldehyde with
nitromethane was best effected v':th methylarnine or aniline as the
catalyst, according to unpubiizhed data obtained in 1934 by C. W.
Shoppee, but gave no details. Hahn and Stiehl report no condensation of
4-hydrcxybenzaldehyde wvth nitromethane by Thiele's n-ethod or by
use of methylamine as catalyst, whereas, Schales and Graefe (51)
using aniline as catalyst and beat obtained the desired product in good
In the previously mentioned case of Knoevenagel and Walter,
the time r-,uired for the reaction to go to completion was approxi-
mately one week. Worrall and Cohen (61) described a faster -rIodifi-
cation which also used a primary amine as a catalyst, but required a
short heating period. Other methods are: addition of N204 to styrene
(60), nitration of various phenyl ethylenes- (I, Z, 32), use of ammonium
acetate anl glacial acetic acid as a catalyst (41), addition of nitrosyl
chloride to styrenes (44), addition of nitryl chloride to styrenes (55),
and use of nitro alcohols heated with phthalic anhydride (8).
The preparation oftZ-nitrostyrenes has continued for the pa;t
twenty years not only for thei-nmelves alone, but, as interrnediate- in
the preparation of various amines and oximes either by electrolytic
reduction (53), or catalytic hydrogenation (47, 48, 64). Worrall has
studied the 1, 4 addition of various basic organic compounds partic-
ularly amino and hydroazino bases (62, 63, 64, 65, 66). /7-Nitro-
styrenes have i recently been checked and found in many instances to be
effect:vs in coa-Tbating insects (6, 40), fungi (4, 6, 4%), mold (.C) and
bacteria (4,20, 4C, 51).
3. Alkali Polymerization of--n-Nitrostyrenes
The effect of alkali onu-.nitrostyrenes wa. noted by Priebs when
he reported that amorphous products resulted which could not be
identified (46). Iveisenheimer (41) also reported that when sodium
methylate was added to -nitrostyreneL, fifty to eighty per cent :-rned
an amorphous solid. Nof-L-ther study of this was reported until Butler
and Carter (10) reported that eleven-6-nitro/tyrenes were polymerized
by using catalytic amounts of ;O1.:Lium ethylate in absolute ethanol. All of
the polymers were either amorphous solids or very viscous gurn-.
Only the viscous gums were .oluble to varying extents in acetone and
alcohol. On the basis of this latter work it is reasonable that the
unidentifiable materials of Prisbs and Meisenheimer were the polymers
of the original ---nitrostyrene-.
4. Polymerization of Vinyl Substituted Ethers
The earliest polymerization of ethers containing a vinyl group
or groups was carried out in the presence of inorganic polymnerizing
agent.3 such as SnCI 2, SnC], AC13, Al(-OG4)3, FeCl.3, and ZnCI,
(ZI). The ethers used included several alkyl vinyl ethers, aryl vinyl
ethers, and the mono- and di-vinyl ethers of di- and tri-ethylene
glycc!s and polyglycols.
Vinyl ethers of formula R'R"CR "OP., in which R was aliphatic,
aromatic, or hydroaromatic radical and R', Ri, and R'1 were hydro-
gen atom- or aliphatic re.-idueE, were polym-erized by bringing them,
singly or in a mixture, into contact with the inorganic agents listed
above and in addition B-3, HBF4, SiCl4, KHSO4, alum, or practi-
cally anhydrous HSO4, H PIC4, HCI, or HF (22). The products may
be employed in coating and adhesive purposes, as substitutes for oils
in oil-filled sub-cil or, submarine cables, as substitutes for polishing
waxes, as intermediate layers in laminated giasz and as softening
and -lastifying agents for India rubber and rubber-like polymerization
product,: of diolefins or for masses from polymerized styrene. Ethers
of the general formula R I2C:C(COP R)R3 in which R denotes an aliphatic,
aromatic or hydroaromatic hydrocarbon :radical or a radical of the
glycols or polyglycols or their monovinyl, monovinyl alkyl, mono-
alkyl, -nonocycloalkyl or monoaryl ethers, and R., R2 and R denote
hydrogen atoms or alkyl radicals, gave, when palymerized in the
presence c.f the above agent, products with shinilar properties and
Alkyl and aryl vinyl ethers have been found to undergo violent
polymerization upon addition of iodine (12). Considerable differences.
in polymerizability were discuzsed, and the aryl ether was found to be
the least sensitive to its action. A closed ring chain structure with
the structural units arranged in regular order and joined by normal
single bonds was proposed for the polymer.
Rubber-like product-L: were obtained when vinyl isobui-yl ether was
polymnerized below 100C. in the presence of 'a small portion of volatile
halide such as BF3 (23),
Sulfur dioxide was used as a polymerizing agent (with or without
conjoint use of other polynmerizing agents such as AICI or BiF3) at a
temperature of -10C. or lower with ethers such as vinyl butyl ether,
vinyl ethyl ether, the vinyl sther of N-hydrox-yethyl-m-toluidine or
glycerol formaldehyde acetal vinyl father (24).
Vinyl butyl ether, vinyl ethyl ether, and vinyl ether:, of N-hyd-oxy-
ethyl-m-toluidine, N-hydroxyethyl aniline, N-hydroxyethyl-rn-chloro-
aniline, 8-hydrosy-quinoline, ethanolan-,ine, glycerol formaldehyde
acetal, and the corres:ponding acetals from acetaldehyde, benzaldehyde
and acetone, or mixtures of these ethers were polynmerized by treatment
with SO., with or without solvents (25). The polymer of N-hydroxy-
ethyl-rnm-toluidine may be coupled with diazo Iolution3 to give dyes of
high molecular weight.
E.hers containing both vinyl and allyl groups have been prepared
and polyrnerized. It was found that ethers of this type possessed a
combination of properties of particular value in coating compounds (28).
These ethers were easily ..lyz- ed in solution in an orga-nic -.olvent
in contact w;i. a catalyst ;.uch as FeCl3 or 2nCI. au*l, Roy,
Fluchaire and Collardeau (42) and Butler aind Na-h (11) accomrnplished
polyr.erization cef ethers of tha typ descri-bed in two ztepz. In the case
of Paul, .2,y, Flucha-ire aniL Collardeau, Qolyrm-erization of the vinyl
grr-uyp in vinyl allyl ether was carried out at temperatures less than
Z5C. sing toluene as the solvent and BF3(CGH3)?C- as the cataly %.
Butler anc. Nas.h reported that vinyl allyl or -ubstituted allyl ethers of
ethylene glycol in toluene at -7 ?C. was poly-merl'zd u-;in EF3(C2Hs)O
as the catalyst. In both cases linear polymers were obtained. In the
second Lte_, of this p? ,rTerizatlon, Paul, Roy, Fluchaire and
Colla-deau used benzcyl percx-ide, below 10CC. in the absence of air,
to catalyze the reaction lhan praducinLj a hard and breakable substance,
insoluble in organic solventt, and dilute acid, bui, Loluble in concen-
trated HN,3 and HT.-.25. 3itler and Nash u -.n- benroyl -peroxide at
650C., co-,nplet.d the polyrn,-rzation of the linear p:.olymers they ob-
tainaed from ethylene glycol ,inyl allyl ether and ethylene glycol vinyl
crotyi sher. The polyrr.er obtained in this second step were insolu-
ble in organic solvents and showed no signs of _oftening when heated
thus sugge.--:tng cross-linked polymers.
B. ':.a.e en of the Problem
For many pu.po4e6 it is important to -.art to. a polymer in its
final state, as film, coaL.in. or moulded article, a high resistance
again..t solvents and swelling agents and a con: iderable degree o' sur-
face hardness. The presence of two or more functional group pos-
sessing .ha same degree of reactivity toward poly.nerization catalysts
result in the formation of cross-linked or thermoset polymers. I his is
a distincL disadvantage in -.,any cases for the uses outlined above,
The desired situation is to be able to carry out the polymeriza-
tion as a two-step process. Thin would involve a proceiz of conir,:.lled
cro:s -linking, in the sense Lhat in the first -hase of polymerization,
long linear chain molecules are being produced, which are soluble,
pIasticiL;able and thermncplasLic. The cross-lin!.;ing of such molecules
is supposed to set in after Lhe main form-giving prccemj. is co-npleied,
The feazibiiity of such a two-step process ha-- been demonaitrated;
for exarrmple, Butler and Iiah (11) prepared diethe'-c. of ethylene glycol
in which one group was the ',inyl radical, the Dther griup was the
allyl or :sub--tituted allyl radical, and Paul, Roy, Fluchaii-e and
Collardeau (42) prepared vinyl allyl ether. In both cases cited, ;he
linear polymers were I,rmed through the vinyl groiup6 using BF3 as
the catalyst and cross-linkled by a ,eroxide ca-aiysr. through the allyl
As aL ban noten in the previ.u- discussion (i0),76-nitro-
styrene derivatives when treated with alkali such as sodium ethylate,
form amorphous materials, and vinyl and allyl groups show differences
in :-eaciv:I.y toward polymerization catalysts (11, 42), that monorneric
compound, containing any combination of these functional grous-
should be able .heoretically to lend thrae.-.elves under proper conditions
to such a two-tep process. Consequently, the reparation, ident;ifi-
cation, and .olymerization of monomers containing the vinyl arnd
/-nitro.tyrene radicals, the allyloxy and2-nitrostyrene radicai-, and
the allyl andL4-nitrostyrene radicals has been -ur-.uii-.d.
C. Source and --ux i.Lcation of Reactants
Vinyl-A-chloroethyl ether was obtained from Carbide and Carbon
Chemical Corporation and was redistilled and the fraction boiling
between I0U'-I10OC. was recovered for use. 2-Hydroxybenzaldehyde
and 3-hydr-xybenzaldehyde were obtained from Eait-nan Organic
Chemicals and Eastmnan Kodak Company Yrepectively, and were used
without further purification. Allyl bromide and 4-hydro>xybenzaliehyde
were obtained from the .Kathe-.on Company, Incorporated, and used
without further purification. 3-IlIethox.y-4-hydio.-ybenzaldehyde was
obtained from the Monsanto Chemical Company and was used without
further purification. Bensoyl peroxide was obtained from the Lucidoi
Division, I-.ovadel-Agene Corpo ration. Boron trifluoride was obtained
in the form-, of the dieihyi ether complex from General Chenical
PREPARATION OF ALDEHYDE INTERMEDIATES
A. General Discussion
The general mnetho.d found to be the most satisfactory for pre-
paring the aldehydes was as follws: usually one-half mole of the
appropriate phenolic aldehyde- was di&solved in normal sodium hydrox-
ide solution and placed in a fla3k equipped with mechanical stirrer,
condenser, addition funnel, and thermometer. An equal molar
quantity of allyl bromide was then added dropwise while the solution
was heated on a steam bath. Heating was continued from four to eight
hours after the addition of the bromide. The reaction mixture was
cooled and extracted with benzene. The benzene was removed by dis-
tillation, using the steam bath as a source of heat. The residue was
distilled under reduced pressure.
When vinyl 2-chloroethyl ether was to be condensed with the
phenol in question, heat was &pplied for twenty-four hours, otherwise,
the general procedure as above applies.
In order to rearrange the substituted ally phenyl ethers a flask
was connected to an air condenser fitted with a thermometer. Heat
was applied, usually by an electric mantle. The time necessary to
form th? rearr.nged p-.nu.-.: was fifteen :m.n'n,.:t, to five hours and the
tempertu n-'ost g-nerally used was Z2C-Z?I'cC.
The p-henol- f.r-r.e by the ear'angen.ent were di:..olved in
normal -. hdium hydroxide solution and were pIaced in a suitable flask
equipped with mechanical stirrer, adrilioon funnel, thermometer, and
condenser. Dir-ethylsulfate was then added dropvwise while holding
the tern,-erat.iure below 40CC. Heat was aprlikd for four to eight hours
after the addition had been -:' -pleted. Upcn ccOlMng, the -.xture
was e-Ctrac"ed with benzene and -;tilled. The benzene was ze:m->nc.ed
by distillation on a steam bath and the residue e. titled under reduced
T'rrneraturce recorded for the boilin- and ni.eltng points are
uncorrected. Pressures above five millimeters were rnea,:ured vi[h
a Z m-rrer1 gause while those below five millimeters were i-ea ul-ed
with a l..,cl eod gaue.
The refractive indexes were deterriined by means of an Abbe
refractometer at 25C. V hte light was the source of uur-ninai.u.n.
The -pecific gravities were determined at Z5C. -with a ca:ibL-a'-ed
two milliliter specific gravity bottle. Frezhly distilled portions of the
compound2- were used in both the den-ity and refractive index determi-
The carbon-hydrogen content of the aldehyde:, was found by use
of a semi-micro combustion train ff: Miowng the :ex.'l] of ?re-gl.
Cerium oxide on pumice was used as the cataly:.t and Ascarite and
Dehydr-:e as the adsor'-ng agenrL.
The properties analyses, .fnd yields of :hee. new aidehyde are
sumznar.zsd in Tables I an.. IIndiiLdj.al d*aitai.- not covered in this.
general discussion are found in U.e experimental part of h., section.
TA J-E I
PHYSICAL CONSTANTS OF NEW ALDEH1YDES
25 25 MRD
Name n D d Calcd. Found b.p. C/mm m.p. C % Yield
2 -(2 -Vinyloxy)ethoxybenzaldehyde
3 -Methoxy-4-(2 vinyloxv) ethoxy-
ANALYSES OF NEW ALDEHYDES
...Compound ..._ _.....
2 (Z V inyloxy) ethoxybenzaldehyde
C1H10 0 2
12 14 3)
cl IH20 3
c I 2H44
)5 6.21 Z
73 6. 29
13 6.* 29
5 6* 35
B. Ep erimental
1. Preparation of 3 -Allyl -4-maeth:xyben:-aLdehyde
a. Preparation of 4-allyloxybenzaldehyde: _ixty-one and one-
tenth grams (five-tenths mole) of 4-hydroxybonzalcdehyde, -ixty and
five-tenthE gran-ms (five-tnnth.; mole) of allyl bromide, and sixty-nine
and one-tenth gram? (fi.e-tesnth; mole) of potasriuri carbonate were
placed in a five hundred mpili-er flask containing three hundred
milliliters of ninety-five per cent ethanol. The flak was fitted with
a water-cooled reflux condenser, mechanical stirrer, and thern-o.-eter.
The mixture was heated to reflu>; with stirring (or- six hours and then
allowed to cool to room te.nperature. The -alt which formed was
removed by filtration and the ethanol y-emoved by distillation. The
residue which remained after removal of the ethanol was distilled
under reduced pressure. The boiling point was I40-42C. at ten
millimeters. The yield was fifty-five and nine-tenths grams. The
known boiling point was 1-2C. at 10 millimeters.
b. Preparation of 3-allyl-4-methoxybenzaldehyde from
4-allyloxybenzaldehyde: Focrty grams of the 4-allyloxybenzaldehyde
prepared as in (a) was heated, in a three hundred milliliter flask
equipped w.vith an air cooled condenser and theri-mometer, at Z60-0,'GC.
for two hoar... Upon cooling, the dark, viscous material was dissolved
in two hundred and fifty mrniliiliers of normal sodium hydroxide solution
and placed in a five hundred niililiter fiask Luai'pp with mechanical
stirrer, thermometer, acdd:icon funnel, and water-cooled condenser.
Thirty-cne and five-tenths grams of diimethyi sufiate was added drop-
wise while the temperature was maintained below t( C. A1Le the
addition had been completed the resulting mixture was heated for
eight hours on a steam bath. Upon cooling the mixture was made basic
with sodium hydroxide solution and extracted with thf ee if, y-milli-
liter pjortions of benzene. The benzene was removed by distillation
on a steam bath and the residue iiii under j.duccd pressure.
The yield was twelve and eight-Lenth carni.
Physical Constants: 1. 686, nZ5 1. 5648; b.p. 112-15 at
Z-3 millimeters; MRD caicliated 50. 58; MI. .c-".nd 50.37.
Z. .Preparation of 3-Allyloxybenzaldehyde
Thirty grams (twenty-fhve-haundi-edths mole) of 3-hydroxy-
beni:aldehyd.e was dissolved in two hundred and fifty milliliters of
normal aodiurn hydroxide :Alution and placed in a five hundred milli-
liter fla-k equipped with mechanical stirrer, thermometer, and water-
cooled condenser. Thirty gama. of aliyl bromide was added dropwise
with stirring while the solution was heated on a steam bath. The
resulting mixture was reflu:ed for eight hours, and upon cooling was
found to consist of two layers. Tha dark, oily layer was colec'Lcd by
means of a separatory funnel and the remaining solution extracted with
twenty-five milliliters of benzene. The oily material and the benzene
extract were combined and the benzene removed by distillation on a
steam bath. The residue was distillt.Q under reduced pressure. The
yield was forty-eight and nine-tenths grams.
Physical Constant-,; D,5 1. 0777; n25 1. 5497; b.p. 71-4 at
0. 3-0.5 millimeters; MRD calculated 45. 9,'; MR.. found 47. 9Z .
3. 'reparation of 3, 4-Di;nethoxy-5-allylbenzaldehyde
a. Preparation of j-methoxy-4-allyloxybenzaldehyde: One
hundred and fifty-two grams (one mole) of 3-rnethoxy-4-hydroxy-
bensaldehyde and one grani of Santomerse, a product of Monsanto
Chemical Company, were dissolved in a solution of sodium hydroxide
composed of forty grams of -,odium hydroxide in four hundred and
sixty milliliters of water. This solution was placed in a flask
equipped with mechanical stirrer, thermometer, addition funnel and
condenser. One hundred and twenty-two grams (one mole) of allyl
bromide was added dropwise while the soltuion was heated on a steam
bath. The resulting mixture was heated with stirring for six additional
hours upon completion of Lhe addition of the allyl bromide. Upon cooling
the layers were separated and the organic material distilled under re-
duced pressure. The yield was one hundred and sixty-seven grams.
The boiling point was 135-41 at i. 5 to 2 millimeters.
b. Preparation of 5, 4-dirnethoicy-5-allylbenzaldehyde from
3-methoxy-4-allyloxybenzaldehyde: Eighty-two grams (forty-three-
hundredth. mole) of 3-mrnethoxy-4-allyloxybenzaldehyde was divided into
two portions and placed in flasks equipped with air cooled condensers
and thermometers. Each flask was heated at 220-30C. for fifteen
minutes. Upon cooling, the rearranged products were collected and
dissolved in four hundred and thirty milliliters of normal sodium hy*-
droxide solution. This solution was placed in a liter flask equipped
with mechanical stirrer, addition funnel, water-cooled condenser, and
thermometer. Fifty-four and two-tenth5 grams (forty-three-hundredths
mole) of methyl sulfate was added dropwise with stirring while the
temperature was maintained below 40C. Upon completion of the
addition, the mixture was heated on a steam bath for twentyfour houri.
The mixture was then cooled and made basic by adding an excess of
sodium hydroxide solution and extracted with two fifty-milliliter portions
of benzene. The benzene was removed by distillation on a steam bath
and the residue distilled under reduced pressure. The yield was
fifty-three and two-tenths grams.
Physical Constants: D1.5 1.1134; n25 1. 5-577; b.p. 112-16 at
1. 5 millimeters; MRD calculated 56. 85; MRD found 59.49.
4. Preparation of 2-(2-Vinyloxy)ethoxcybenzaldehyde
Sixty-one and one-tenth giamrns (five-tenths mole) of
2-hydroxybenzaldehyde was dissolved in five hundred milliliters of
normal sodium hydroxide solution and placed in a liter flask equipped
with mechanical stirrer, water-cooled condenser, addition funnel and
thermometer. Fifty-three gramnr (five-tenths mole) of vinyl 2-chloro-
ethyl ether was added dropwise with stirring while the mixture heated
on a steam bath. The heating was continued for twenty-four hours
after the addition had been completed and upon cooling the mixture was
extracted with three fifty-milliliter portions of benzene. The benzene
was removed by distillation when heated on a steam bath and the residue
distilled under reduced pressure. The yield was thirty and three-
tenths gra ns.
25 5 i o.
Physical Constants: D2 1.1195; n25 1.5448; b.p. 120-4 at
0.5 millioneters; MRiD calculated 52.23; MRID found 54.41.
5. Preparation of 3-(2-Vinyloxy)ethoxybenzaldehyde
Thirty grams (twenty-five-hundredths mole) of 3-hydroxy-
benzaldehyde was dissolved in two hundred and fifty milliliters of
normal sodium hydroxide solution and placed in a five hundred milli-
liter flask equipped with mechanical stirrer, water cooled condenser,
addition funnel, and thermometer. Twenty-six and five-tenths grams
(twenty-five-hundredths mole) of vinyl 2-chloroethyl ether was added
dropwise with stirring while heated on a steam bath. Heating of the
mixture was continued for .enr.y-four hours after the addition had
been completed and upon cooling was extracted with three fifty-milli-
liter portions of benzene. The benzene was removed by distillation
when heated on a steam bath and the residue distilled under reduced
pressure. The yield was twenty and four-tenths grams.
Physical Constants: D51. 1178; n25 1.545Z; b.p. 106-9
at 0. 3 millimeters; MR.D calculated 52. 23; MR found 54. 25.
6. Preparation of 4-(2-Vinyloxy)ethoxybenzaldehyde
Sixty-one and one-tenth grarns (five-tenths mole) of 4-hydroxy-
benzaldehyde was dissolved in five hundred milliliters of normal
sodium hydroxide solution and placed in a liter fla.sk equipped with
mechanical stirrer, water-cooled condenser, addition funnel and
thermometer. Fifty-three grams (five-tenths mole) of vinyl 2-chloro-
ethyl ether was added dropwise with stirring while the mixture was
heated on a steam bath. The heating of the mixture was continued for
twenty-four hours after the addition had been completed, and upon
cooling the mixture was extracted with two fifty-milliliter portions of
benzene. The benzene was removed by distillation when heated on a
steam bah and the residue distilled under reduced pressure. The
yield was eijiteen grams. The liquid solidified upon standing at room
Physical Constants: D25 1.1195; n25 1.5608;b.p. 120-5 at
1. 5 millimeters; MRD calculated 52.23; MRD found 55.58; n. p.
7. Preparation of 3-Methoxy-4-(2-Vinyloxy)ethoxy-
One hundred fifty-two and two-tenths grams (one mole) of
3-methoxy-4-hydroxybenzaldehyde was di. solved in five hundred
milliliters of two normal sodium hydroxide solution and placed in a
liter flask equipped with mechanical stirrer, water-cooled condenser,
addition funnel and thermometer. One hundred and six grams- (one
mole) of vinyl 2-chloroethyi ether was added dropv"ise with stirring
while the mixture was heated on a steam bath. The heating was contin-
ued for twanty-four hours after the addition had been completed and
upon cooling was found to contain solid material. The solid was col-
lected by filtration and recrystallized from ethanol. The yield was
forty-eight and tv.-o-tWunths gp'am-s.
Fhyical Constant: m.p. 77-80C.
8. Preparation of 2-Methoxy-3-allylbenzaldehyde
a. ,Preparation of Z-allyloxybenzaldehyde: Two hundred and
forty-four grams (two moles) of Z-hydroxybenzaldehyde and two grams
of Santomerse D were dissolved in a solution of sodium hydroxide
composed of eighty gram.3 of sodium hydroxide in nine hundred and
twenty milliliters of water. This solution was placed in a flask
equipped with mechanical stirrer. thermometer, additi'.n funnel, and
condenser. Two hundred and forty-four grams (two moles) of allyl
bromide was added dropwise while the solution was heated on a steam
bath. The resulting mixture was heated with stirring for six additional
hours xpon completion of the addition of the allyl bromide. Upon
cooling, the layers were zeiparated and the material distilled under
reduced pressure. The yield was two hundred forty-four grams. The
boiling point was 97- I0Z at 2-3 millimeters.
b. Preparation of 2-methoxy-3-allylbenzaldehyde from 2-allyl-
oxybenzaldehyde: Eighty-one and one-te.Ih -ramrs (five-tenths mole)
of 2-allyloxybenzaldehyde was placed in a three hundred milliliter
flask equipped with an air cooled condenser and thermometer. The
contents of the flaskwere heated to 220-230C. for five hours. A sharp
increase in the rate of rise of the temperature was noted at 210-20.
The rearranged material was dissolved in five hundred milliliters of
normal sodium hydroxide solution and placed in a liter flask equipped
with mechanical stirrer, addition funnel, water-cooled condenser, and
thermometer. Sixty-three and one-tenth grams (five-it6nths mole) of
dimethyl suIfate was added droprwise with stirring while the temperature
was maintained below 40C. Upon completion of the addition, the
mixture was heated on a steam bath for four hours. The mixture was
then cooled and made basic by adding an excess of sodium hydroxide
solution and ext-ract., with three fifty-rnilflit.teL' portionn- of benzene.
The benzene was remnoved by -lictillation on a steam bath and the
residue distilled- under reduced pressure. The yield was twenty-fc i.
grams. The boiling point was 121-5 at 7-8 m-illineters. The known
boiling point was 12o at 9 millimeters.
CHA- T E III
PREPARATION OF /-NITROSTYRENES
A, C'znl-3rall DiScul-.F^Loa
The general method found to be the most satisfactory for the
preparation of the -nitrostyrenes was as follows: usually five-
hundredths mole of the appropriate aldehyde and an equal molar
quantity of nitromethane were dissolved in ethanoll and placed in a
flask equipped with mechanical stirrer, therm-no-'eter, and addition
funnel. The flask was immersed in an ice :,ath and the contents cooled
to 100C. :5odiumn hydroxide equal in molar quantity to the aldehyde
used was dissolved in water, cooled to 10C., and added drop%%-wise to
the solution of aldehyde and nitromethane. The period of reaction after
the addition of the base varied from fifteen minutes to six hours. The
reaction mixturee was then poured into ice water and added at a fast
drop-rate to an excess of hydrochloric acid solution. Usually, a yellow,
bulky precipitate formed which was recrystallized from methanol or
ethanm.l. In two cases an oil Feparated when the reaction mixture was
added to the excess acid, The oil was -ubjected to dietillation under
reduced 'e. sure.
Temperatures recorded for the boiling and melting points are
uncorrected. Pressures were measured by a McLeod gauge.
The refractive indexes were dULeriinecd by means of an A.bbe
refractometer at 250 C. Whice light was the sou-rce of illumination.
The specific gravitieo were determined at Z5C. with a calib ated
two milliliter specific gravity bottle. Freshly distilled portions of the
compound were used in boLh the denrsities and refractive index
The carbon, hydrogen and nitrogen content of the.'-nitrostyrenes
were determined by the Rowland Chemical Laboratories with the ex-
ception of four carbon-hydrogen determinations done by the investigator.
The method of Pregl was used and lead peroxide was the agent
employed to trap out the oxides of nitrogen.
The properties, analyses, and yields of these ne9id-nitro-
styrene. are summarized in Table III. Individual details not covered
in the general discussion can be found in the experimental part of
PHYSICAL CONSTANTS AND ANALYSES OF NEW NITROSTYRENES
4-Allyl c :,xy -/-nitro styrene
3 Mvlethoxy-4-allyloxy- nitro stryene
3-(2-V i nyloxy)ethoxy- nitro styrene
Gi iH ilO5N
G I H I10 3 N
c I 11 34N
C12 13 104N
C11 Hl10 3N
c 12H i 304 N
C13 H15 05N
Mn. p. C
Yield % N %*C
45. 53 6. 80 64. 1 3
19.01 6.39 65.74
67.48 6.80 64.13
18.71 5.95 61.Z7
52.00 5.62 62.64
48,55 6.80 64.13
62.0? 5.95 61.27
66.98 5.95 61,27
36.94 5.24 58.81
% H % N
5. 38 6. 77
5.98 6. 39
5. 38 6, 66
B. Lc x ips.rinenal
1. Preparation of 4-Allyloxy- )-natroztyrene
Nine and seven-tenths grams (six-hundredths mole) of 4-allyloxy-
benzaldehyde and three and seven-tenths grams (six-hundredths mole)
of nitromethane were dissolved in thirty milliliters of methanol and
placed in a three hundred milliliter flask equipped with mechanical
stirrer, thermometer, and addition funnel. The laz2 was immersed
in an ice bath and the contents cooled to iG0C. Two and four-tenth,
grams of sodium hydroxide was dissolved in four :rniililiter: of xater,
cooled tcj iOC, and was added d.opwise to the solution in the flask.
Zui ring the addition of the ,odiHmn hydrox-ide a. -.hite bulky precipitate
formed. The reaction was continued for an additional fifteen minutes
upon con-ipletion of the addition of the base. The reaction mixture was
then poured into ice water and filtered while cold into an excess of
hydrochlo-ric acid solution at a fast drop-rate with vigorous stirring.
A yellow .olid &eparated -L-sn!ediatecly which upon recrystadllization gave
a yield of eight and three-tenth-7 grans.
P-hysical Constant: M. .. was 90-iC.
2. Preparation of 3-Allyl-4-i-nethoxy-9-nitrootyrene
Twvo attempts were made to isolate this compound according to
the following methods:
a. aght and ight- -nth._ r-m, (five-hunr-.lred -- mole) of
S3-allylr6--r''acdehyd and threce -an one-Lenth grams (five-
1nuiredzth- mole) of nit-ro-eotha-ne were diss.alved in thi-:ty "-lli;Liric.s
of nethanci and placed in a :e hundred milliliter flask e a'pped ith
mechanical stirrer, Lhem-rcncter, and addition funnl. The flask was
inmanrersed in an ice bath and the solution cooled to IC,C. Two grams
(five-hundredths mole) of sodium hydroxide was diss.olved infour mnilli-
liters of water, cooled to 1GC., and added dropwise to the contents of
the flaS.-:. No precipitate foln -ed during the addition of the base or
during the additional two hours allowed for the reaction to continue. The
reaction mixture was poured into ice water. A small amount of oil
separated which was removed by extracting the cold solution with three
twenty-mifliliter portion; of ether. The extracted basic solution was
then added at a fast drop-rate to an excess of hydrochloric acid solution.
An oil separated which was removed from the acid mixture by extracting
with three twenty-milliliter portions of ether. The ether was removed
under reduced pressure leaving a residue of three grams. This residue
would not crystallize from several common laboratory solvents even
when cooled to exceptionally low temperatures by lowering into a
mixture of dry ice and acetone, nor wauld it freeze in the absence of
zolvent;L, thus indicating a probable freezing point well below room
b. ihe same :-oced.re as in (a) was followed xccpt that lo-zy-
five and three-tendhi grain= (twenty-fiv-hundret.., mole) of 3-allylr
*4-n rethlioxybenialdehyde, f'i.-Lccn and nine-tenths g::aiyr (twenty-five-
hundredcLha mole) of nfILrInIeALade, and ten and four-,.enthc grams
(twenty-iive-hundredths niolt) of zodiunm hydroxide in ten milliliters
of water were used. One hundred inilliliters of n-athanol was used as
The residue, which : ernained after extracting the acid solution
with four fifiy-mnillil iter portions of ether and removal of the ether
by redacin, the presouire, was diCtilled. under reduced pressure
giving a yield of 6. 0 gr amns. It was noted that a brown gas was given
off during the distillation and the pressure of the system could not be
lowered below three n-Ailinecters which indicated decorapo .ition.
With tse evidence of decomposition in mind, the physical contents
were taken and the compound checked for nitrogen by sodium fusion,
The oubf-,,uenL formation of the blue precipitate oi Fruscian Blue
indicated tie presence of nitrogen. Five-tenths grams of the material
was dic.olved in eLhaniol and treated with three drops of 20% sodium
mnethoxide in absolute ethanol. An insoluble polyrmer separated
irn irediately, thus indicating the pre-,ence of !they/-nitruzityrene. It
became evident that the preparation of this -ni.ro-tyrene Lnvolve,
the problems of purification.
?hy"cl Constants: D2. 1 7 5152; b. p. -75 IC.
at 3 r-;iliU-.eters; .R.. calc...!later! 61. 47; M1'.f:,r un? 6E 56.
3. Preparation of 3-Allyloxy- 9nitrostyrene
Ten and three-tenths grams (seven-hundredths mole) of 3-allyl-
oxybenzaldehyde and four and three-tenths grams (seven-hundredths
mole) of nitromethane were dissolved in thirty milliliters of methanol
and placed in a three hundred milliliter flask a quipped with mechanical
stirrer, thermometer, and addition funnel. The flask was immersed
in an ice bath and the contents cooled to 10OC. Two and eight-tenths
grams of sodium hydroxide was dissolved in five milliliters of water,
cooled to 100C., and was added dropwise to the solution in the flaskr.
No precipitate formed during the addition of the
solution or in the hour following the completion of the addition. The
reaction mixture was poured into ice water and the resulting solution
added at a iazt drop-rate to an excess of hydrochloric acid solution.
A yellow pDecipitate formed immediately which upon recrystallization
from methanol gave a yield of six and seven-tenths ramrns.
Phyc.ical Constant: M, p. 59-6C0.
4. Preparation of 3-?Methoxy-4-allyloy- nItro-tyrene
Nine and six-tenths grai-s (five-hundredthr mole) of 3-mnethoxy-
4-allyloxybenzaldehyde and three and one-tenth grams (five-hundredths
mole) of n-tro-oanthasen were ,'.rr.lved in thir-ty 7-1,. ? of methanol
and tlacea in a three hundred r!ile-z-r 1a'.- uipej with n mechanical
stirrer, rher-nmncter and adrftion ,.u-, The flh..,. was immersed
in an ice bath and the contents cooled to 1C0C, Twc ':ram z (five-
hundredths mole) of sodium hydroxide was ..isFov.ed in five niiili.iter
of water, cooled to 10C., and was added dropwis, to the solution
in the flask. A white, bulky precipitate formed during the addition.
Fifteen minutes were allowed for the reaction to continue upon comple-
tion of the addition of the bas-. The reaction mixture was then pou:-ed
into ice water. A white solid which separated from the aqueous solution
was coilectod by filtration and dried. Claisen (13) reported that
3- rneithoxy- 4-allyloxybenzaldehyde could not be di tilled v,-ithout
effecting a small amount of rearrangemrent to the phenol. Recrystalli-
zation of th,' solid yielded a compound melting at 85-6C. The res;-::-ted
melting point of 3-mnethcx.yr-4-hydroxy-5-allylben-al[dehyde was 85-60C.
The fltrate obtained when the solid was removed froen the aqueous
mixture, was added at a fast drrcp-rate to an excess of hyd:ochloric acid
solution. A yellow, bulky precipitate formed invz-iedi4ately. Upon re-
crystalli'ation from nethano), ihis precipitate gave a yield of two and
Physical Constant: M.p. 110-iliOC.
5, Preparation .- f 3, p-ntr o t ene
'Tenr and two-'.ntr g.-ar.-.. (f.:'-'.hunv'.rith. imole) of 3, --'-- ethoxy-
5-allylben :ald'ehlyde and three and one-tcnth g';.- (Civz-h&alr" edth:
mnole) of n'.rc'-neth:Lne were ".- -olved i Thirty-five miiliters of
m.ethan. -.nd placed in a f..:.h :.iil,;.i2c with r-echanical stirrer,
thermometer and additon funnc2i. The flask was irnmersed in an ice
bath and the contents cooled to 10C., Two grains (five-hundredths
mole) of sodium hydroxide was diczoh'ed in five milliliters of water,
cooled to 'C1C., and was added dropwviise into the flask with stirring.
A fine pred.i2itate formed di-nring the additi:n-. of the base. An addi-
tional fifteen minutes was allowed a-fter- the addition of the base for
the reaction to proceed to completion. At this time the reaction mix-
ture was poured into ice water and the re.zultning solution was added
at a fast s,-.-rate to an excess of hydrochloric acid solution. A.
yellow, bulky r precipitate began to form immediately which upon re-
crystallization from mnethanol gave a yield of six and five-tenths
Dhy.:ical Constant: M. n. 71-2C.
6. Preparation of 2-(2-Vinyloxy) ethoxy-Jnitrostyrene
Two attempts were made to isolate this compound according to
the following, methods:
a. Nine and six-tenth: Framns (five-hundredth; mole) of
2-(2-v'-yL::y)e1-h. :;:bur'-l.':.',3hy and three and one-tenth g:'-:.:
(five-h.'2.eidth.: mole) of nitrz-:- :har-e were dissolved in thirty .ni'li-
liters _:f :-.ethanol and Fl !..'c in a e'-:::i:' -'h -.1 h ncc
stirrer, 1tL; h'.c --r, and .:'.Jiior_ f'i_"n -". TI. l -.' was immersed
in an ice bath and the contents cooled to I.C. T ,:c* gri--n-. (five-
huindredth' mole)of sodium r-.-',.o:-ide was di.isolved in fi`- milliliters
of water, c oed to 10 C., and added 'dropvise to the contents of
the flask. No precipitate formed during the addition of the base or
during the following hour alv:ere for the reaction to continue. The
reaction mixture was pou.ired into ice water and 1h. re :ulthig solution
added at a fast dro --'-ate to,4an excess of hydrochlori-c acid solution.
An oil ..eparated from the acid solution which was collected by ex-
tracting the solution with three tvsenty-milliliter portions of -Lher.
The ether was remTr ved by reducing the pressure, leaving a residue
of four and six-tenths graTr.e. The residue vould not crystallize
from several common laboratory solvents, nor would it freeze in the
absence of solvents when imr. e-r.3ed in a mixture of dry ice and acetone,
thus in.icatilrg a probable freeing point well below room te-rrperature.
b. The same procedure as in (a) was followed except that forty-
eight grai--.. (twenty-five-hInidr edth : mole) of 2- (2-vinyloxy)ethoxy-
benzaldehydo, fi.ften and nine-tenths grams (twenty-fiv,O--hundredth;
mole) of n'tromethane, and ten and four-tenths grama; (twenty-five-
nuu-ndr-.-..... .; mole) of sodium hi..- .::. in ten mnilliliters of water were
used. One hu--'. -. e : -;.-lit_ I -.. of methanol war 1. --e-.1 as the solvent.
The residue, which .r-. .nr-.1 after .t,-. ct'.n the acid solution
with four flfty-rnilliliter portions of .at: .r and removal of the ether,
by r-du.icl, the -3---.2sure, was -cc.-lect,-d. The ": idue was subjected to
distillation under 'ed:ced zccJ:'Lu-e. The :,\-s nire of the system could
not be maintained below 1. 5-2 nTillinret.rs ani a brown 7a-; was g've-n
off vwhen the pot temperature reached 150C. The zb-:e.'uent formation
of a Pu-.i.n Blue p.ecipitat- from a ?olution zAh'-ained by a sodium
fusion, 'ndicate@- the presence of nitrogen.
7. Preparation zf "-(2-Vinyloxy)ethocy---nttrostyrcena
,W.n: a.nd six-'tenLs grar-mu (five-hundredth,., mole) of 3-(2-vinyl-
o;.ry)-thos:ybanzalc.,ehyde and three and one-tenth" grams (fiv.-.I.undredths
mole) of ni.to:..nchthan.e were :: ;.cmlve.d in thiity miilliters of '.ethanol
andpl;ccc' in a flask c.i;.e wi-,"- mechanical stirrer, thermometer
and additi.cn funnel. The fLast. was -"Aaced in an ice bath and its contents
loweredy to 010C. Two ;rarn- o.f sodium hydroxide was dissolved in
four ?r..llliters of water, cooked, to 10CQ., and added dropwise to the
coluLion in Lhe flask. The reaction was allowed to continue for fifteen
.ninatez, following the addition of the base, and then poured into ice
water. The re.aulting solutionon was added at a l'ast drop-rate to an excess
of hydrochloric acid solution. A yellow precipitate formed immediately
which .Fin recrystalLization -'a;n mothancl ^-. a yield of seven Zn
thr --ee-1; t,. .i-.., g;a. c:: ...
"-.'hy.-L; Constant: -..p. li2-i3C.
3. Preparation of .,.-(2-Vinylory)ethoxy-iinitrostyrene
Eight and six-tenth0 g-arns (fouri--hundred.hL. mole) of 4-(2-vinyl-
oxy)cthaoxybenzaldehyde and two and five-tenth. grams (four-hundredths
mole) of nitromethane were di 1sj.lved in tv/mn. y- fve milliliters uf
metha. nol and: placed in a flask ;ilped with mechanical stirrer,
the-i-nL.'t--, and addition ILaiaa-i. The flask was immersed in an
ice bath and the contents cc.-lced to 10i0C. One and six-tenths g'aini
(fou:'-h-,undi cdth, mole) of sodium hydroxide was di.;.l-o.'1d in four .-.ailli-
liters of water, cooled to 10C.7., and added dopwie to the solution
in the flac-1. A wvhie, bulky i 'ecipitatc formed. during the addition of
the base. The reaction was J.:-.wzd to continue for fift-cn minutes
after ao'.-Lion of the addition of the base. The reaction mixture was
poured into ice water and the r,:djtnin solution was added at a fL- .t
d,.:-prate towan excess of hyd,--ochlor'ic acid solution. yellow, buI.ly
preciptate formed rhich u1..1. recrystallization from methanol gave a
yield of seven and one-terith grams.
Phy.cal Constant: M.p. iZl -.c,.
9. Preparation of 3- eth.y-4- (2-vinylosy)ethoxy..
1]even nnd one-tenth *-- ., (f.ve-hundr'-tb. mole) of 3-.'-#.c;;yy-
4-(2-vinylo:y:)eth.o::yben:;-al '5h) ;tudi three and one-tenth grams
(five-hundredthT mole) of nitromethane were diz--.oel' e in hir-y mrnilli-
liters of methanol and -lace'! in a flaT- ,u";pf.1 vith mechanical
stirrer, thermometer, -and addition funnel. The flask was immersed
in an ice bath and the contents cooled to 10C. Two grams (five-
hundredths m.ole) of fodiurn hydroxide was di sol-',- in four milliliter-
of water, cooled to 10C., and added dropwise to the solution in the
flask. No precipitate formed during the addition of the base or during
the following fifteen minutes allowed for the reaction to continue. The
reaction mixture was poured into ice water and the -'olid se paratinL
was removed by filtration. This solid was the starting aldehyde. The
filtrate was added at a fast drop-rate to an excess of hydrochloric acid
solution. A yellow solid separated immediately which upon recrystal-
lization fronn methanol gave a yield of four an'i nine-tenths gram s.
Physical Constant: M. ,. 164-5oC.
10. Preparation of Z-Allyloxy-, litrostyrene
Nine and six-tenths grams (six-hundredth. mole) of 2-allylixy-
benzaldehyde and three and seven-tenths grams (six-hundredths mole)
of nitromnethane were dissolved in thirty-five n.illiliterc. of methanol
and placed in a flask equipped with mechanical stirrer, thernmomrneter,
and addition funnel. The flask was immersed in an ice bath and the
contents cooled to 1OC. Two and four-tenths grams (six-hundredths
mole) of sodium hydroxide was dissolved in five milliliters of water,
cooled to .10C., and added dropwi-,e to the contents of the flask. No
bulky precipitate formed during the addition of the base. The reaction
was continued for two hour s. The mixture was poured into ice water
and the resulting solution was added at a fast drop-rate to an excess
of hydrochloric acid solution. An oil -eparated which was collected
by extracting with three twenty-milliliter portions of ether and the
ether removed by evaporation at reduced pressures. This oil was
recrystallized first from methanol and then from ethanol by immersing
the recrystallizing solution into a mixture of dry ice and acetone.
The yield was five and five-tenths grams.
Physical Constant: M.p. 43-4C.
11. Preparation of 2-Methoxy- 3-ally- "nitr-ostyrene
Ten and five-tenths grains (six-hundredths mole) of Z-methoxy-
3-allylben,.aldehyde and three and seven-tenths grams (six-hundredtha
mole) of nitromethane were dissolved in thirty milliliters of methanol
and placed in a flask equipped with mechanical stirrer, thermometer,
and addition funnel. The flask was immersed in an ice bath and the
contents cooled to 100C. Two and four-tenths grams of sodium
hydroxide was dissolved in five milliliters of water cooled to 10C.
and added dropwise to the contents of the flask. No precipitate formed
during the addition of the base or in the following hour allowed for the
reaction to continue. The reaction mixture was poured into ice water
and the resulting solution added to an excess of hydrochloric acid
solution. A yellow, bulky precipitate formed which when recrystal-
lized first from methanol and then ethanol gave a yield of two and
Physical Constant: M.p. 54-50C.
A. General Discussion
The polymerization studies are classified into three general
groups, namely: (I) acid catalyzed polymerization, (2) base cata-
lyzed polymnerization, and (3) peroxide catalyzed polymerization.
Under each of the general classifications are found one or more sub-
groups which include the polymerizations of the intermediate aldehydes,
J-/-nitro styrenes, and copolymerization of the intermediate aldehydes
and theynitrostyrenes with maleic anhydride,
The acid catalyzed polymerizations were attempted on the
as the catalyst. Solvents which are useful in this reaction must be
able to be lowered to temperatures as low as -10'C. without freezing,
or precipitating the monomer to be polymnerized, and showingg little
tendency to inhibit the polymerization reaction by competing with the
monomer for the catalyst.
The aldehyde& containing the vinyloxy group were polymerized
with BF3- (C2H5)}20 when added to a solution of the catalyst and
toluene at 20C. or lower. The polymer obtained in the case of
3-(2-vinylo.xy)ethoxybenzaldehyde was dissolved in nitromethane and
methanol, cooled to 10C., and treated with sodium hydroxide
solution in an effort to introduce the 1-nitrostyrene grouping into
The jnitrostyrenes were polymnerized by dissolving them in
ethanol tand adding a few drops of a 20% ,solution of sodium mnethoxide
in absolute ethanol. The polymrners formed, with the exception of two,
were insoluble in ethanol. The physical characteristics of the polymers
Each of the intermediate aldehydes and the--tnitrostyrenes
obtained from them were t: a ted with benzoyl peroxide and heated to
100C. for twenty-four hours. The physical properties and character-
istics of the materials obtained were recorded.
Each of the intermediate aldehydes and they^nitrostyrenes
were copolymnerized with an equal molar quantity of maleic anhydride
using benzoyl peroxide as the catalyst. The polymerization reactions
were accomplished at 100C. for twenty-four hours. The physical
properties and characteristic:; of the material obtained were recorded.
B. Zxper inmerntal
I. Acid Catalyzed Polymerizations
a. Polymerization of.---nit-ostyrenes containing the vinyloxy
group using BF." (C.H5)9C as the catalyst: Twenty solvents were
considered for the polymerization of 3-(Z-vinyloxy)ethoxy-- nitro-
styrene, 4-(Z-vinyloxy)ethoxy--'-nitro styrene and 3-methoxy-4-
(2-vinyloxy)ethoxy-7g-nitro-tyrene on the basis of solubility of the
..f-nitrostyrene at temperatures from 250C. to -70OC., freezing point
of the solvent, and reactivity of the solvent toward the catalyst.
No solvent was found for the polymerizatiow which would keep
the monomers in solution when cooled to 200C. or lower unless the
ratio was one to one hundred or greater. Ten of the twenty solvents
tested at room temperature would dissolve the monomers, varying in
extent from very slightly soluble to infinitely soluble. These solvents
were found either not to permit polymerization of a test reagent,
vinyl 2-ethylhexyl ether, because of the reactivity of the BF3 (C2H5)O20
toward them, or to precipitate the monomeric/-nitrostyrene upon
introduction of the BF3(CZH5L)O. Acetone and chloroform were
exceptions, but it was found that the--.nitrostyrenes would not polyrm-
erize even though the vinyl 2-ethylhexyi ether wculd polymerize.
Thi; lack of reactivity exhibited by the /1-nitrostyrenes was
further inveAiigated because it has been shown, according to
unpublished reports by G. B. Butler, University of Florida, that
vinyl phenyl ether and vinyl substituted-phenyl ethers of ethylene
glycol would polymerize when treated with BF3 (CZ H 5) 0 under similar
conditions as outlined above. Butler showed from the infrared spectra
that, in the case of vinyl Z-methallylphenyl ether of ethylene glycol,
vinyl 2-allylphenyl ether of ethylene glycol, vinyl 2-allyl-4-chloro-
phenyl ether of ethylene glycol, vinyl Z-c rotylphenyl ether of ethylene
glycol, and vinyl phenyl ether of ethylene glycol, a peak was exhib-
ited by all of the ethers at approximately 8. 34 microns. In the case
of the first four named ether6, this peak disappeared completely when
the polymer of each was obtained by treating the monomer with
BF3' (C2H5)ZC as outlined above. The vinyl phenyl ether of ethylene
glycol was not polymerized and checked. In the case of the vinyl
3-(Z-nitrovinyl)phenyl ether of ethylene glycol, vinyl 4-(Z-nitrovinyl)-
phenyl ether of ethylene glycol, and vinyl 3-methoxy-4-(Z-nitrovinyl)-
phenyl ether of ethylene glycol, prepared by the investigator, this
peak at 8. 34 microns did not appear in the infrared spectra of the
Infrared spectra of the intermediate aldehydes used in pre-
paring the-J-nitrostyrenes were made. Each of the curves exhibited
a peak at 8. 34 microns but a check of the infrared spectra curve of
bensaldehyde shows a peak at the same place. Consequently, no
definite conclusions regardin the ef-fect of the 2-nitrovinyl group on
the phenyl radical can be made on the basis of the information collect-
ed, but all known vinyl phenyl and substituted phenyl ethers of ethylene
glycol have shown a tendency, to polymrnerize under the outlined condi-
tions with tlie exception of th,? 2-ni-trovinyl ..ub-tizLuted ones.
The solvents tested in the ; olymerization attsmpti on the
nitrostyrenes were: Uiethyl ether, ethanol, rnethanol, ethylene
dichloride, methyl chloride, carbon zetrachlo:'ide, chloroform,
trichloroethylene, toluene, benzene, amyl acetate, acetone, ,,
triflucro toluene, for-rnamnide, petroleum ether, b.p. ?'O0C., 2-propanol,
I-p ropancl, cliorobenzene, nitromethare: and Tnethylene chloride.
b. Polyni-erization of aldehydes containing the vinyloxy group
using BF.-(C>H})?.C as the catalyst:
(1) :olymerization of S-(2-vinyloxy)ethoxybanzaldehyde: A two
hundred m'.iliiter flask was fitted with a mechanical stirrer, addition
funnel, cal _iu-n chloride tube filled with potas;-iuna carbonate and a
low temperature thermometer. Two milliliters of dry toluene and four
milliliter, of B3F 3 (CZHS)O were placed in the flask and cooled to
-35C. by immersion of the fiask in a mixture of dry ice and acetone.
Five and fEvea-tenths grams (three-hundredths mole) of 3-(2-vinyloxy)-
ethoxybenzaldehyde was added dropwise over a period of one-half
hour. A s-lig.ht increase in temperature was noted upon the introduction
of each diop. After the addition had been co.-npleted, the reaction was
allowed to continue for one hour. At the end of the reaction peri-od,
ten rmilliiite 's of mnethanol was introduced to inactivate the catalyst.
During the polymerization reaction, solid material separated and
showed little tendency to di.:solve when the methanol was added. After
the reaction mixture had war "aed to room temrnpecature, ,he insoluble
material was removed by filtration. This material was white, .Alightly
elastic, soluble in acetone, slightly soluble in methanol and softened
The toluene-methanol filtrate was distilled under reduzad pres-
sure and the residue, along with the insoluble portion collected above
by filtration, was dissolved in a minimum amount of 50% methanol and
nitromethane. The resulting solution was placed in a two-hundred
milliliter flask equipped with mechanical stirred., thermometer, and
addition funnel. One and two-tenths grams (three-hundredths mole) of
sod'iumrn hydroxide dissolved in two milliliters of water and cooled to
10C. was added dropwise to the solution in the flask. A precipitate
did not form during this addition or in the following hour allowed for
the reaction to continue. Solid material precipitated upon pouring the
reaction mixture into ice water. This solid material was collected by
filtration and the filtrate added at a fast drop-rate with vigorous
stirring to an excess of hydrochloric acid solution. The small amount
of oil present in the acid *;oiution was extracted with two, twenty illi-
liter portions of ether. The volatile solvents were removed under re-
duced pressure and the residue, ,v.eighing two-tenths gram, was dis-
.olved in ethanol. This ethanol solution when treated with two drop.- of
20% sodium -nethoxide in absolute ethanol showed no sign.-, upon
heating for one hour, of poiyr.er formation such as the formation of
insoluble materials. The insoluble material obtained, when the reaction
mixture was poured into ice water, was dissolved in hot ethanol and
treated with two drops of a 20% solution of sodium methoxide in
absolute ethanol. A precipitate did not form after heating as above.
Under these experimental conditions., it became eviLnt that
the aldehyde group in the polymer did not condense with' the nitro-
methane in the presence of alkali, since no insoluble, amorphous
materials were formed upo. the introduction of .odium methoxide to
solutions thought to contain -nitrostyrene groups.
(2) Polymerization of 2-(2-vinyloxy)ethoxybenzaldehyde: One
gramn of 2-(Z-vinyloxy)etho.xybenc:aldehyde was dissolved in toluene
and cooled to -30C. One-half milliliter of BF, (C2H5)20 was added
dropwise. A sharp increase in temperature was n ti.ed upon the intro-
duction of each drop of the catalyst and the solution became very
viscous. The reaction was allowed to continue for one hour. Two
milliliter. of methanol was added the reaction mixture to inactivate
the cataly-t. The solvent was removed by di-tilLation under -'educed
pressure. The residue was very viscous, yellow in color, slightly
soluble in ethanol, incthanol and benzene, and zoiuble in acetone.
(3) ?oiyymerizatizon of j -n Ltho02y- 4-(2 -vlayloyy)ethoiybenz-
aldehyd&.: One gcain of 3-nmethcxy-4-(Z-vinyIoxy)thc:y'enzaldehyde
was dis.ol-ed in toluene and treated as in (2), except that the temper-
ature could not be lowered belowv 200C. without cau- ing the aldehyde
to crystalliLe. The product of the polymerization reaction was a
black Zolic, fusing with decon-pc.ition at 115-ZCC., insoluble in
ethanol, nethanil and benzene, and soluble in acetone.
2. Base Catalyzed Polyermizationo
a. Polymerization of 4-allyloxy-_ nitrostyrene with sodium
rnethoxide: Three-tenths gram.- of 4-allyloxy- -nitrostyrene was
dissolved in fifteen milliliters of absolute ethanol by heating. Upon
cooling, three drops of Z70 sodium methoxide in absolute ethanol was
added to the solution. The solution became cloudy immediately,
followed by rapid precipitation of an insoluble material. The mixture
was heated for one hour on a steam bath, to insure complete reaction,
cooled, and filtered to collect the solid material. After drying, the
material vveighed three-tenths gram, was light tan in color, fused
with deco-Tiposition at 245-5GC., and was insoluble in ethanol, benzene,
acetone, chloroform and rnethanol. The melting point of the monomer
was 50- C.
b. P-'olyi':erization 3-al lyloxy--- io -ene ..ith .dur
mnithoxide: Three-tenth gara-n- of 3-alily3:-y nitrostyrene was
diiL.olved in ten milliliters of absolute ethanol and three dropc '3of
2C.G' sodium methoxide in absolute cL:ihaol was added to the Lolution.
The -clution became cloudy imnnediately and was heated for one hour
on a steam bati. to insure c mI- "let 2 reaction. Uion cooling, the
mixture gave a yield, when filtered and dried, of two-tenths g:arn..
The r-ater'ai was tan in Color, fused with decoinpo3.ition at Z35-;0,C.,
and insoluble in ethanol, benzene, acetone, chloroform, and mre.hanol.
The melting point of the monomer was 59-600C.
C. P:clymerization of 31- nethoxy- 4-allylo:.yj--nitro3 styrene
with sodium methoxide: Three-tenths gram of 3-nrnctho..-y-4-allyloxy-
_?-nitr.3tyrene was dissolved in fifteen -nilliliters of ethanol and
three drops of 20Q sodium methoxide in absolute ethanol was added
to the solution. The solutionn first became red and then cloudy. The
resulting mixture was heated for one hour on a steam bath, cooled,
the solid removed by filtration and dried. The dried material weighed
two-tenths gram,, was tan in color, insoluble in ethanol, benzene,
acetone, chloroform and rnethanol but showed .signs of softening in
all of them. The fusion point of the material was 215-20C. with
decormapos-iion. The mrnelting point of the monomer was 1lO-11C.
d. olym.erlrzat.on -) ,4- .inioth::y-5-ally-_J-n5trostyc-ene
with sodium methoxide: Three-tenths grams 'f 3, 4-diriethoxy-5-allyl-
nitro'zy:.:end was dis,-,lved in fifteen milliliters of absolute ethanol
by heating, and upon cooling three drop of Z'C% -diur) methoxide in
absolute ethancl- was added to the solution. The solution immediately
became cl.-. idy aid was hsated fo" one hour on a steam bath to insure
co-plete reaction. Upon co-lAin, the mixture was filtered to remove
the insolu.bie material, which w-;,hen dried gave a yrieid of fifteen-
handredth. grand. The material was cream in color, showed no
sign of fusing, but charred when heated to ,C60OC., was insoluble in
ethanol, benzene, acetone, chloroform and methanol. The melting
point of the monomer was 71-2.C.
e. Polymerization of 3- (Z- vinylo })ethoxy----nitrostyrene with
sodium nrethoxidd Three-tenth.5 of a gramT of L--(2-vinyloxy)ethoxy-
/nitro;tyirene upon war ring was dissolved in twenty n illilite'rs of
ethanol and upon cooling three drops of 20% sodium methoxide in abso-
lute ethanol were added to the solution. The solution became cloudy im-
mediately and was heated on a steam bath for one hour to insure complete
reaction. The mixture was cooled, filtered and the solid material
dried. The material was brown in color, fused with decomposition at
215-20C. and was insoluble in ethanol, benzene, acetone, chloroform
and methanol. The melting point of the monomer was 112-13 30C.
f. .:.lyin-e. lzatid, c. -2 Lylo.y),;.h^,x/ i niiic -.lrcne
with i..ud.mn.iethoxide: Thre.-tenths ..... of 4-(2-vinyl:..y)'ihog-r
=it-.:L !tyrene was dissol-..r2 in fLfe.an milliliters ^ ethanol by
heatLn; on a steam !aih. U? .....ig three drops of 2C ;.-dii-
methoxide in _bc.iL- eLhan-.l was a.dl.2 to the -clutcn, prcdiing a
red solution followed J-v-r.n.edaeey by cloudiness. The mixture was
heated "oi- one hour on a steam ,ath, cooled, and filtered to remove
the cli:. material which upon drying weigh-ed two-tenths a:- .. The
material was tan in color, fu--ecd with "Icoarpojri:i at Z..5--CC. and
was in.oluble with cign- of oCftrning in ethanol, benzene, acetone,
chloroform and rnethanol. Thc nimelting point of the monomer was
g. .', y-nerizati.on of &-mfethuxy-4-(2-vjnyloxy )et.hoxy-
-ni.istz" ayj.gine with sodium ..etho;idc: Three-tenths gramn of
3-' z- zthoxy-4-(Z-v inyloxy)ethoxy -nitrostyrene upon heating was
dissolve-" in forty-five milliliters of ethanol. Three drops of 20%
sodium rne:'hoxide in absolute ethanol was added to the solution when
cool, produ.cing an nii-nediat. cioudinezs.. The mrnixt-ure was heated
for one hour on a steam bath, cooled, and fiterad in order to remove
the solid material. The dried material -*rcighed twenty-five-hand redths
gra-n, was light tan in color, fused with decon..osition at -0C-O5C.,
and was insoluble in ethanol, benzene, acetone, chloroform, and
.--ethaa.:.L. Th7 melting poI.t the monomer was 154-5C.
r .. a ... th 4onoe 1 as 15-5C.
h.- 7 y':'y-. r-attocn .'f 2-s" y--- nf.tro.. ty:era \;'ith ..du-
;.eth.:-,?de: Thr.oe-b-nth: ^ -of 2-allyjo: y -itrostyrene was
dissolve. in ten milliliters :,f ethanol. The solution turned '-< -Vpon
aditon ofth.re .rp oftr- 2(7.1 -.diu-. inthcxU.! n absolute cthanol,
but showed no 'n: of b-c-:.;-ing cloudy even afsr-. having been heated
for om hour on a steam .bhh. Th- ethanol was r 2 nov,:;' by evapora-
tion -nc redhcer pressure I ..-i. a residue ahlcl- f-aiied to cry- tal-
lize. Thi- -. residue was ;'..htly viscous, dal'-: red in color, and
soluble in thangl, benzene, acetone, chloroform, and methanol.
The In.eltinb point of the monomner was 43-4C.
i. Polyr, eie-ization o;- 2-n,.thoxy--aliyl-_-nitro-tyrene with
sodium nnethoxid.e: Three-t-enth:. gram.. of 2--.-a tho.-y-3-allyl- -nitro-
styrene was dissolved in ten milliliters of ethanol and treated with
three dr..p-L of 20o s,-diu:z- :-etho-:de in ab--olut2 ethanol. The solu-
tion i-n-.ed'.tely beca-ne red but showed no *;;.gn-7 of cl..uine-s. The
solution was heated on a steam bath for one hour ;-ithout producing
any insoluble material. The ethanol was evaporated under- reduced
pressure, leaving a dark red residue v/hich failed to crystallize. The
residue was slightly viscous, and soluble in ethanol, benzene, acetone,
chloroform and rethanol. VTie melting point of the monomer was
3-. ... C l.:? .Polymerizations
a. ._-^cyn-r --:.-:at-:n of -t!i '-ernmediate a-ehy-.- ,-.,ith b .:-n :..vl
p .-_ .: The following ex::,:Fer--.ental p_-,-,c? .ur, a-lpps to each of the
eleven .-- lehy'ec-; subjected to polymerization v-t' 'bcnr.-,yl peroxide:
fi.-2-t-.'n. . g.-.-a-. of the a -'- _.-_r to be F-.Ay-....-.i:. -d -ong with fivN e-
7hnl-e.,h gram of b 1nzel p:.:-.. ::; were ,1.d in a three Inch t.. t
tube and t.-L:O- Z .....-.hly. A .h--.-no...t..- was inserted in the test
tube to 'e te.-pen-at ;... The test tube was fitLe-d vi-h a
to,'pe and inserted in the '.p of a common '.1granic laboratory, six
inch ditit-ng column '.;-i"h side armn. The .:.i.-le arm was attached to
a steamn line by means of r-'.. .. tubing and the bottom of the column
used to drain the c,=nden2:e i steam. The contents of the test tube were
then heated with steam at 0. for twenty-four hours. TJion cooling,
the phy!ic character. ZIc-. of the material were recorded. The
reaction was observed ca'.-f..IlIy at the start of the heating period for
any rapn.1 rise in t :-pe-ature and any temperat.-re increase above
GO0C. vhizch "ndicated l,.....
The 2hy.-.ical :haracte-i,:tics of the material obtained from each
aldehyde- are listed below under the name of :he -:idehyde .u. d.
(1) A-lyhrly-,ben-_-za- ,,y..: The 'L -p.erature rose to IIZC.
during the initial hating. Upon cooling, the r-aterial was very
viscous and tacky, --oluble in acetone and chloroform, and insoluble in
benzene, tc-luen., c ihanol, and mnethanoi. The color of the final
material was :ed as cor:.pared to pE.le yellow for i-le mnonomer.
(Z) d-,iyt-4-c rLhocybj l .idehy: A t7.L x -n ature increase was
not. noted 6di.izng iih initial Upon cLo-alig, the material was
silghciy viscous, soluble in benzene, toluene, .ciL-X.'m, and acetone,
and insoluble in ethanol and hnol. Ihe color of the final material
was rt;L as compared to yellow for the monomer.
(3) -Allyloxybenzaldehyde: A e.ipvature increase was not
noted daLXg the initial heatlaig. U., n cooling, the material was
viscous, oLabi& in acetone, benzene, toluene, and chloroform, 4.nd
insoluble in ethanol anc methanol, The colzr of the final material
was red as coirpared to white 11 the monomer.
(4) A..- Aetjy4-a.lylo:ybenzalce-hyda: A :en--eature increase
was not noted JiX ing the initial hat-i. Upon co"ciln-, the .-ateraial
was not viscous and soluble in acetone, benzene, toluene, chlo-'ofoi n,
ethanol, and methanol. TLie color of the final material was ..el as
com-ared to pale yellow for chie monomer.
(5) ....D--metho --ai1 yl bjenz .iehydie: A temperature increase
was not noted during the initial heating. Upon o.l: n the material
was very lightly viscous, ..labie in benzene, toluene, chloroform,
acetone, and insoluble in ethaxcLard methanoL The color of t-ihI. final
material was rc. as compared to yellow for the monomer.
(6) 2-(Z -Vinmyloxy)ethoxybenzaldehyde: The temperature in-
creased to I IGC during the initial heating. Upon cooling, the
material was very viscous, soluble in benzene, toluene, chloroform,
acetone, nitromethane, and insoluble in ethanol and methanol. The
final material was pale yellow in color.
(7) 3-(.-Vinyloxy)ethoxcybenzaldehyde: The temperature in-
creased to IC10C. during the initial heating. Upon cooling, the
material was viscous, soluble in benzene, toluene, chloroform,
acetone, and nitromethane and insoluble in ethanol and methanol.
The final material was yellow in color.
(8) ..-(2-Vinyloxy)ethoxybenzaldehyde: The temperature in-
creased to 145C. during the initial heating. Upon cooling, the
material was very viscous, Alightly soluble in benzene, and toluene,
soluble in chloroform, acetone and nitromethane, and insoluble in
ethanol and methanol. The color of the final material was yellow.
(9) 3-Methoxy-4-(2.-vinyloxy) ethoxybenzaldehyde: The
temperature increased to 125C. during the initial heating. Upon
cooling, the material became glassy. The material was soluble in
benzene, toluene, chloroform, acetone, and nitromethane, insoluble
in ethanol and methanol and fused at 60-5C. The color of the final
material was red.
(<1) Z-Allyloxybenzaldehyde: A temperature increase was not
noted during the initial heating. Upon cooling, the material was not
viscous, was soluble in benzene, toluene, chloroform, acetone, and
slightly soluble in ethanol and methanol. The final material was red
in color as compared to yellow for the original monomer.
(il) 2 -Me thoxy- 3-allylbenzaldehyde: A temperature increase
was not noted during the initial heating. Upon cooling, the material
was not viscous and was soluble in benzene, toluene, chloroform,
acetone, methanol, and eLhanol. The color of the final material was
red as compared to yellow for the monomer.
b. Copolymerization of the intermediate aldehydes and maaleic
anhydride with benzoyl peroxide: The following experimental proce-
dure applies to the copolymerization of each aldehyde and maleic
anhydride with benzoyl peroxide: five-tenths gram of the aldehyde,
twenty-fiva-hundredths gramn of maleic anhydride, and five-hundredth.
gram of ben-oyl peroxide were placed in a three inch test tube and
mixed thoroughly. A thermometer was inserted in the test tube to
observe temperature changes. The test tube was fitted with a stopper
and inserted in the top of a common organic laboratory, six inch dis-
tilling column with side arm. The side arm was attached to a steam
line by means of Ixubber tubing and the bottom of the column used to
drain the condensed steam. The contents of the test tube were then
heated with steam at 100C. for twenty-four hoars. Upon cooling, the
physical characteristics af the material were recorded. The
-eac-J.on was observed carefully at the start of the heating period for
any rapid rise in temrnperature and any temperature increase above
IG0C'. which would indicate polymerization.
The physical characteristics of the material obtained from each
aldehyde are listed below under the name of the aldehyde used.
(1) 4-,kAliyloxybenzaldehyde: The temperature increased to
1580C, luri-ng the initial heating. Upon cooling, the material was
very viscous, almost a glakj, red in color, slightly soluble in acetone,
and dilute base, and insoluble in benzene, toluene, methanol, ethanol,
(2) 3-Allyl-4-rmethoybenzaldehyde: The temperature increased
to 125C. during the initial heating. Upon cooling, the material was a
gla&s, red in color, fused at 45-50C., was soluble in acetone, slightly
soluble in benzene, toluene, chloroform, and insoluble in ethanol and
(3) 3-Alyloxybenzaldehyde: The temperature increased to 1i35'C.
during the initial heating. Upon cooling, the material was a gla. red
in color, fused at 60-65C., was soluble in acetone, base, slightly
soluble in chloroform, and insoluble in benzene, toluene, methanol,
(4) j-Methoxy-4-allylc.xybenzaldehyde: A temperature increase
was not noted during the in itial heating. Upon cooling, the material
showed no 3igns of polymerization but had changed irom yellow to red
in color. The final material was soluble in benzene, toluene, chloro-
form, acetone, ethanol, and methanol.
(5) 3, 4-Dirnethoxy-5-ally3ben aldehyde: The temperature in-
creased to 10GC. during the initial heating. Upon cooling, the
material was viscous, red in color, .oluble in acetone, base, and
chloroform, slightly -soluble in benzene and toluene, and very slightly
soluble in ethanol and methanol.
(6) Z-(2-Vinyloxy)ethoxybenzaldehyde: The temperature in-
creased to 13C0C. during the initial heating. Upon cooling, the
material was a glass., softening at 110-15G., red in color, =oluble in
base, insoluble in benzene, toluene, chloroform, methanol, ethanol,
(7) $-(2-Vinyloxy) ethoxybenzaldehyde: The temperature in-
creased to i z36C. during the initial heating. Upon cooling, the mate-
rial was a glass, yellow in color, softening at oC-65GC., was soluble
in base and insoluble in benzene, toluene, chloroform, acetone, ethanol,
(8) 3-Methoxy-4-(Z-vinyloxy)ethoxybenzaldehyde: The temper-
ature increased to 149'C. during the initial heating. Upon cooling,
the material was a glass, dark brown in color, -oftened at 115-2CC.
v.'ith decomposition, was soluble in base and acetone, slightly soluble
in chloroformn, and insoluble in benze-ne, toluene, methanol, and
(9) Z-Allylcxybenzaldehyde: The temperature increased to
131C. during the initial heating.. Upon cooling, the material was very
viscous, red in color, Zoluble in acetone and bare, very slightly
soluble in benzene and toluene, and insoluble in inethanol and ethanol.
(10) 2-Methoxy~3 -a lylbenzaldehyde: The teamperaturB increased
to 134:C. during the initial heating. Upon codcing, the material was
viscous, dark brown in color, soluble in base, acetone, and chloroform,
slightly soluble in benzene and toluene, and very slightly soluble in
ethanol and methanol.
c. golymrerization of the -nitrostyrenet with benzoyl peroxide:
The following experimental procedure applies to each of the nine
-nitrotAyrenes subjected to polymerization with benzoyl peroxide: five-
Eenths grand of the 1-nitro:-;tyrene and five-hundredths gram of benzoyl
peroxide were placed in a three inch test tube and mixed thoroughly.
A thermometer was inserted in the test tube to observe temperature
changes. The test tube was fitted with a stopper and inserted in the top
of a common organic laboratory, six-inch distilling column with side
arm. The side arm was attached to a steam line by means of rubber
tubing and the bottom of the column used to drain the condensed steam.
The contents of the test tube were then heated wLh steam at IC0'C. for
twenty-four hours. Upon calling, the physical characteristics of the
material were recorded. The reaction was observed carefully at the
start of the heating period for any rapid ri3e in ten-perature and any
temperature increase above ltO3C. which indicated polymerization.
The physical characteristics of the material obtained frora each
/-nitro;.tyrene are listed below under the name '.f the-/-nitrostyrene
(1) 4-A!iyloxy://-nitrostyrene: A termperatiire increase was not
noted during the initial heating. The material upon cooling was viscous,
dark brown in color, would not crystallize from methanol, was soluble
in acetone, and very slightly soluble in benzene, chloroform and
toluene. The melting point, of the original monomer was 9G- 10C.
(2) 3-Allyloy-,-j.nit:otyrene: A temperature increase was not
noted during the initial heating. The material upon cooling was viscous,
dark red in color, v,'oulil not crystallize from methanol, was soluble
in acetone, anJ insoluble in benzene, toluene and chlorofo:rm. The
m-nelting point of the original monomer was 59-600C.
(3) 3-A ethoxy-4-allylo0. ---nitrostyrene: A temperature in-
crease was not noted during the initial heating. Upon cooling, the
material was recrystallized from methanol. The melting point of the
material recovered was 10-09C0. The melting point of the original
monomner was 110-11C. No change was obier-s in a mixed rrm oing
(4) 3, -l-Dimethoxy-5-allyl-. '-nitroEtyrene: A temperature in-
crease was not noted during the initial heating. Upon recrystallization
from mrnethanol, a co-nmpound r-- citing at 68- 'o0C, was recovered. The
melting pil:-nt of the or:ginail monomer was 71- C. A n.ixe.d mn2lting
point cThowved no deflection.
(5) 3-2-V lnyixy)ethoxy-.-jnitrostyree: A temperature in-
crease was not noted during the initial heating. The material upon
cooling was viscous, da.-r' brown in color, would not recryatallize
from rm.ethanol, was Ioluble in acetone, slightly z-oluble in chloroform
and very :-lightly soluble in benzene and toluene. The melting point of
the original monomer was 112 I13C.
(6) 4-(2-Vinyloxy)ethoxr-j- -nitrostyrene: A temperature in-
crease was not noted during the initial heating. The material upon
cooling was viscous, black in color, would not recrytallise from
methanol, was soluble in acetone, and slightly soluble in chloroforCm,
benzene, and toluene. The melting point of the original monomer was
(7) 3:-Methoxy-4-(2-vnylox-y)ethoxy-5 -nitrostyrane: A temrpera-
ture increase was not noted during the initial he-.ting. The material
upon cooling was viscous, dark red in color, wou.dd not recrystallize
from methanol, was olable in acetone, and insoluble in chloroform,
benzene, and toluene. The melting point of the original! monomer was
(8) 2-Allyloxy- -nitro styrene: A temperature increase was not
noted during the initial heating,. The material upon cooling was viscous,
brown in color, would not recry.itallize from rm-ethanol, was soluble in
acetone, and insoluble in benzene, chloroform, and toluene, The
melting point of the original monomer was 43-40C.
(9) 2-Meth cxy- -all- ty-nitrostyrene: A temperature increase
was not noted. The material xpon cooling was slightly viscous, dark
red in color, would not recrystallize from methanol, was soluble in
acetone, and slightly soluble in benzene, chloroform and toluene.
The melting point of the original monomer was 54-5C.
d. Gopolymerization of the J-nitrosty.enes and :naleic anhydride
with benzoyl peroxide: The flowing experimental procedure applied
to the copolymerization of each -nitrostyrene and maleic anhydride
with benzoyl peroxide: five-tenths gram of thef-nitrostyrene,
twenty-five-hundredths grama of maleic anhydride, and five-hundredths
gram of benzoyl peroxide were placed in a three inch test tube and
mixed thoroughly. A thermometer was inserted in the test tube to
observe temperature changes. The test tube was fitted with a stopper
and inserted in the top of a common organic laboratory six inch distilling
cc,1urnn wv.i side arm. The :;de arm was attached to a steam line by
mzans of r:abbcr rubing and the bottom of the col".n-n used to drain the
condensed steam. The content-: of the test tube were then heated at
100C. fPo twenty-four hours. Upon c.)oling, the pnlyrnerization
mixture was extracted with benzene to remove any maleic anhydrid,:,
which ranar-ined unreacted. The benzene insoluble material was
checked to dter._ine if it were the oriainAl -nitr tyrene or a polymer.
The insoluble material, xv;.'hich did not correipcnd to the original
-nit-rotyrene, was eramnin-d and its physical characteristics re-
c-rded. The polymerization reaction was ob-eerved carefully at the
start of the heating period for any rapid rise in temperature and any
temperature increase above 1CCoO. which would indicate polymerization.
(1) 4-Allyloxy ny-nitrostyrene: A temperature increase was not
noted during the initial heating. Extraction of the cooled material with
benzene, yielded three-tenthZ gramn of product, fusing with deco_.po-
sition at 110-15C., brown in color, soluble in base, very slightly
-oluble in acetone and insoluble in benzene, toluene, methanol, ethanol,
and chlorofor'mr. The nmelting point of the original monomer was 90-1C,
(2) 3-Allyloxy- -nitrostyrene: A temperature increase was not
noted during the initial heating. Extraction of the cooled material with
benzene, yielded three-tenth, gram of product fusing with decomposition
at 90-110C., brown in color, soluble in acetone and base, and
in.czluble in ethanol, "-'.eta.c-l, calcroform anC t lu-. The -nl'"ing
point of he .-ig, n.il l monomer was 59-07C.
(3) --Meth-xy- a llylx--2-nit--.oztyr-ne: A temperature in-
crease was n.: noted CUrlrin the Lritil heating. _.ec y.tallization of
the ?olynmerizatlon reaction rm.ixcture )c duced three-tenths gramn of
materii anutiag at 1--1 iG0'-. The n-.elin- pa hn of the original
monomer was liO-110C. W'.: ca-nge in a .iixed :..-lting '.-Lat was
(4) :., -i-.&.ctho:y-_ -- Ilyl .-nit rty,:en : A temperature in-
crease was not notod eucig the initial hat:rg. Extraction of the
cooled material with benzene, yielded four-tent.h. grarn of material
fusing v;'ith deco npoeition at iC5-lIlCC,. dark red in color, --&LIble
in acetone and base, insoluble in ethanol, rnethanol, chloroform, and
toluene. The melting point of the o'ig-nal monomer was 71-2 C.
(5) 3(- Vinylci:y)etho.-Anitrostyrene: A temperature in-
crease was not noted 'Luring the initial heating. The dark brown,
viscous material obtained upzrn cooling, was j:iuble in base and acetone,
.lightly soluble in methanol, and insoluble in ethanol, benzene. toluene,
and chloroform. The melting point of the oi-xlal monomer was
(E) 4- (2--Vinyloxy)e~hoxy-'nitros .tyrenc: A temperature in-
crease was not noted during the initial heating. .Extraction of the
viscous brown material b.enth ben: nre did not y: :-:! a solid. .',a.. :a:.-
tion .-.f the benzene extract c'-'l not produce a trace of maleic =-uhydr.de.
The viscous material was .:.o!.a.le in base, acetone, slightly olublec in
ehlorcforr-i, and insoluble in *icthn'-nl, cehnol, br.:n.ene, and toluene.
The mne.tCr.; i:nt of the o: :Crv..l monomer was Zl.I-2C.
(7) 3-Metho'r--.- (2-v-ny \::y).hc.::y --ni.:osty: ne: A L.zrp,-r-
atnue increase was not no't during the initial heating. E:.xrraction of
the co.,oled material wvith ben;-ene yield-d a dark brown material,
fus.n. a:. 205- 10C., soluble 'n ba:-e and acetone, and insoluble in
toluene, clcroforn-, ethanol, an,' methanol. The- nricItIng poent of -he
orc.ina.! Smonomer was 164-5-C.
(8) 2-Aly:ylcxy-_-n ro ty'cnane: A te ir.2aIut'' increase was not
noted during the initial heat:ng. E-.t'action of thle ccledC material
with benzene yielked three-I:fcnth, gramn of darl brown material,
fu;ing at 60-5C., sclubic-le in base and acetc.ne, very Ai.'htly soluble
in toluene and chloroforrin, z.ndr inlcluble in Tnethanol and ethanol. The
melting noint of the original nonomer was 4 -1C.
(9) -MAethoxy- 3f-all y.-_ nitiro- n tyrenz : A te-ni-;erature increase
was not noCd during the initial heating. Extraction of the cooled
mnate i !, with benzene, yielded four-tenths g.-a of a light tan 3olid,
fusing at I55-6eC., ..oluble in base and acetone, slightly soluble in
chlorofocrm, and insoluble in Pthanol, methanol, ..nd toluene. T-he
mrr.,eltig p'.Kn.- of the or--inai m-onomrer was .!-S0.
C 7'-'.""1. V
DISCUSSION OF RESULTS
c.Vnnc-na;io.n of :heun.'il ccnt-nin the aldhde hd- .rp with
allyl bromide and'-vinyl 2-chlorot.'hy! ether was accomplished in the
:najo"ity .'f ths. cases vi-.th ease and in .':?. yie':;. Instead of re-
flu'--nj; the mixture composed -;f t-ie pheii.l, the h:1.o-natcd ccnr.'-ound,
nota: -iu-n carbonate, and th? solvent, absolute .ethanol, the ha!ogen-
ated c.3wap :,.t:ix was adc-l to a solution of the ph ?ncl in sodium hy .:ox-
ide and then r-flu--!d. Th,- time necessary for the c-nden.-ation to
take [zla.ce varied. The less reactive vinyl 2-c'il-:o- othyl ether re-
-.uired tr:nty-four hours of he!tirn as co-i-ared to approxim.:rnataly five
hours i C the condemn ; Ft.on of allyl bromide.
The rearranged ally1! ethers were not is-olated but were dissolved
in a solution of sodium y.-.-i...de and condensez; i with dirr.ethyl sulfate
under condition- very similar to the previously outlined conden-ation
of allyl brornide with the phenol,
rdt.-..gether, eleven aldehydes were prepared by the methods li.?ted
above. S-.'2n of the aldehydes have not b!en reported previously in
the !'Lter-a.ture. No attern;it was made to prepare derivatizesof the new
aldehyde. other than ths -nt:.'.o.-tyr-yne. phy. ial constants were
determ-irned and analyses rn-i-J on the new aldehyde-.
The method of Worrall (61) was uzed to convert nine of the
eleven aldehydes pr.- "int: the- /nii -, o.;t yrc..- Th. yiel:I`.
obtained vr-i L from 18.7 to 6f. 9 .2- cent. Tw'o of the Sehyd^S,
namely -- ..yl-4-~nethoxyb.r. .. hy de ar. 2- e ihoxy-
enrzaid:Thy condensed H. "nitromnethane, but their-nitrostyrenes
were not o3i.;'nc.-- in a a j.:..-;- .ncui to zh.'-'. in.l their y.cal
constants or for analyses. .. .... L ere made
to cry -tl. :I2 the :.-.puJ- ii. -t-'renes i:rc-u. various solvents.
Dec'-,:p-j tin of the /-nitr.:. ty:n resulted ia they were jecmed
to di.t'.llat'ci. It was evident that ?1.*-ification and not the mctho.d of
,.iar-ation of the two -nl .,.yrenes was fli- facir to overcome.
The two stage polymerization of the /-ittcr: tyrenes, as ,-uLLincd
in the -tat=aernt of the ?wobl.-;., was studied a.nd found under the
condition. used in thi- in.-;.tUiaotion to be -; az2-'c'al if not iapCc-3ible.
_"'ciy.r -rization of t.h .-nitrostyrenez in e ..i v.ith sodium
n-;eth3o:2 -e 'ducsd insoluble polymers in all cases with the exception
of th-z two -nitr=: -/r:'v. 3- which were ort'..3 substituted. Even though
it was Inown that -il:- ;tyj wa: itself and it'1t5d --it-rc-te2
produce,' hi-uble polymers, it w-as desirable i-o determine v-',hcth-r or
not the same was true for the -nitrostyrenes cp-p- 1 during th:-
ve*e;ti-.t4:'.tn. Since the .oly.-nesa obtained are n.::oubl, or fuse at
te:Trpera tu ias of 2CC0 or higher, it became I rnpi ?, to cross-link
the polymners by using other catalysts such as peroxides for the polymers
of $-nitrostyrenes containing allyl or allyloxy groups and BF3* (CH5),0
for the polymers of/-nitrostyrenez containing the vinyloxy group.
It is possible in the case of the two ortho substitutedd -nitro-
styrenes, namely, 2 -allyloxy -7nitrostyrene and Z-methoxy-3-allyl-
-nitrostyrene, which, when treated with sodium rnethoxide, did not
produce insoluble polymers, that sterically the polymerization was
inhibited, thu,- producing very low molecular weight polymers which
would show considerable differences in solubility. None of the original
monomer could be recovered from the material obtained in the case of
the ortho substituted -nitrooctyrenes.
Polymerization of the/y-nitrostyrenes containing the vinylcxy
group, namely 3-(2-vinyloxy)ethoxy- -nitrostyrene, 4-(Z2-vinyloxy)-
ethoxy--nitrostyrene, and 3-3nethoxy-4-(2-vinyloxy)ethoxy- -nitro-
styrene, with BF3. (C2H5)2C in an effort to produce linear polymers,
which would lend themselves to cross-linking through the 2-nitrovinyl
group, was not only complicated by the fact that solvents could not
easily be found to :support tha reaction, but, when they were found, no
evidence of polymerization was obtained. A test reagent, vinyl
2-ethylhexyl ether, polymerized under the same conditions.
According to unpublished information obtained from G. B. Butler,
University of Florida, vinyl phenyl ether and vinyl substituted-phenyl
-ether. of --thylene glyco! h.&-. been *--717r:-ierized when treated with
BF3- (CZH )ZO under the conditions en-.-.:oyed in the case of the
.-nitr:-;'v-.ene rleriva~t:.ve.:. Qtule- also ahoxwed by inlf-ared s;ect-a
that, in ti- case of vinyl Z--ncth.llyl'phenyl ether of ethylene giyc:-.l,
vinyl Z-allylphenyl ethe" of 2t.hyiene glyc -.!, v 2nyl Z-allyl-4-chloro-
phenyl ether of ethylene gly:._.!, vinyl 2-cr-tylhen.yl ether of ethylene
glycol, and vinyl I-hSnyl etheZ- of ethylene glycol, a peak was exhibited
by all of the ethers at app--oxirnztly 8. 34 microns. Thi-. peak, in the
case of the first four na-.-ed etherz, di sappeared completely when the
polye-.er of each obtained by treating the monomer with BF3" (G zH5)zO
as previc.u ly described, was checked by infrared. Vinyl phenyl ether
of ethylene glycol was not polyr.srized and checked. In the case of
the three previously mentioned 9-nitrostyrenes, thi.. peak at 8. 34
microns did not ppea" in the infrared :-ect -a of the monomer.
Since vinyl phenyl and all known vinyl iL-.btuted-phenyl ethc'- i
of ethylene glycol, including the ones prepared in this, investigation
have shown a tendency to p-lyn erize under the outlined condition.- with
the exception of the discus!sc, -"' -nitrostyrenes, it oeco:nies apparent
that the Z-nitrovinyl group pl.ay-, a definite role in preventing the
polymneriz.-tion of the--nitro-.-ityrenes containing the vinyloxy group.
Poly:.aeriization of any vir-yi or vinyl sub;tituted-phenyl ether
with B3" (CH5)20 would involve the attaching of the BF3 to the
terminal carbon atom of the vinyloxy group. This would be accomplished
when ,a pair of the electrons making up part of the double bond shifts to
the terminal carbon atom, thuin producing one of its possible resonance
structureL. The attachment of the BF3 to this negative carbon atom
would destroy the resonance, thu3 leaving a positive carbon atom.
This positive carbon atom would attach itself to a negative carbon atom
in the same manner as BFy3. Such a process would eventually produce
a long chain molecule. The mechanism of the reaction is illustrated
by the following equation:
-OCH2CH2OCH-CHZ --- 0.OCHOCH2OCH-CHBF3
Q C CH0"OCH0CHFOCH-CH0
^sGCH zCH20CH-CHZBF3 ---------------------
GH-CH2-CH-CGH ,BF 3
H 2 H 2-
It is apparent that anything preventing or inhibiting the initial
shift of the pair of electrons making up the double bond also prevents
the possibility of the polymerization of the compound with acid type
catalysts such as BF3" (C2H5),O. On the basis of the absence of a
peak of 8. 34 microns, which was considered to be due to the actual
shifting of the electrons in the vinyloxy group, this preventing or in-
hibiting of the electron shift appears to be the reason why polymers
were not obtained from the '-nitrosty -ene- under consideration.
An examination of the structure of the nitrostyrenes showed that
the resonance and inductive effects could inhibit, if not completely
prevent, any shift of electrons necessary to promote polymerization,
The following structure illustrates the discussed effect :
.CH=CH -N -t-
The lack of reactivity of the vinyloxy group toward polyrmeriza-
tion with .3F" (CzH5)aO in the.>nitrostyrenes prevented the formation
of linear ?olymers capable of being cross-linked through the 2-n itro-
vinyl group with sodium methoxide. This lack of reactivity would be
expected in the intermediate aldehydes, but to a lesser degree than
would be found in the 7- nitrcstyreneG. Since the aldehydes were
polyrnerized with BF3 (CH5)20O, it became evident that the aldehyde
group dees not have as great an inhibiting effect as the 2-nitrovinyl
group, even though the same type of resonance and inductive effect is
The linear polymer of 3-(2-vinylo.xy)ethoxybenzaldehyde obtained
by using BFi" (CzHQ5)O as the catalyst t, was dissolved in nitrotrethane
and n methanol, followed by the addition of sodium hydroxidq In an effort
to introduce the 2-nitrovinyl group into the polymer. Under the condi-
tions of -he experiment, no evidence cof condensation of Athe nitro-
methane and aldehyde group was found.
Polymerization reactions of the aldehyde- and7--nitro styrenes
singly, and copolynierization of each aldehyde and S-nitrostyrene
individually, with maleic anhydride using benzoyl peroxide as the
catalyst, were studied. The aldehydes in all cases showed a greater
tendency to polymrnerize than did their analogous /,-nitrostyrenes.
The failure of 3-methoxy-4-allyloxybenzaldehyde and 3-methoxy-
4-allyloxy-n-mitrostyrene to copolyrnerize individually with maleic
anhydride, using benzoyl peroxide as the catalyst, can possibly be
attributed to the presence of a trace of 3-rnetho:cy-4-hydroxy-5-ally!-
benzaldehyde, which formed in the preparation of 3-methoxy-4-allyloxy-
benzaldehyde. Phenols are known to inhibit peroxide catalyzed
The normally ready responv.'e of monovinyl ethers to electrophilic
catalysts and their comparatively low reactivity in free radi-cal
polyrnerization- have been attributed to their electron-rich double
bond -.nd to a low degree of resonance. Due to thi. low reactivity, it
has been incorrectly stated th.-,t vinyl alkyl ethers do not homo-
polymerize in arueou:: emulsion because they are so readily hy,' -,
lyzed. .-.ctually, vinyl all.yl ether' :, such as th- isobutyl monomer,
very slowly yield viscous Y-If-_d low polymers under the action of
lauroyl peo:xide in bulk at 60 C. by all;ane er.ulfate emulsion,
as well as by the action of ultraviolet light. Cnly by ionic polymeri-
zation have high-Ti-rlecular, solid homopoly2necs been obtained fror.
the lower alh-yl vinyl ether ; (52).
It is theoretically possible that the tendency of the aldehyde6
andK-nitr3ztyrenes containing the vinyloxy group to polymerize
ingly and copolymerize individually with maleic anhydride, when
treated v..ith benzoyl peroxide, was accomrpli hed because of the
possible resonance and inductive effect--. The tendency of free-iadi-
cal formation, based on the electrophilic nature of the ring substitution,
wv:uld be greater in the case of the aldehyde. The electrons rna!:ing
up the double bond in the vinyloxy group would not shift to the terminal
carbon atom as readily when electrophilic group-_ were ring-substituted
thus n-.ak.ing it pos.-ible for the electrons to :hift and form free radicals,
which would lend ther)-elves to a greater extent to polymerization under
the influence of peroxide catalysts. The follbwIng structures illustrate
the di.cuL.ed effects:
CH'CH N^ C--H
(OCH.,CHOCH-CH--c. -C CH C OCH-CI
Experimental evidence showed that, in all cases, the aldehydei
containing the vinyloxy group polymerized singly and copolyrnerized
individually with maleic anhydride, using benzoyl peroxide as the
catalyst. The polymers,: obtained were very viscous with the exception
of one which was a glass.
None of the -nitrootyrenes containing the vinyloxy group :showed
the tendency to polymerize as readily as their analogous aldehydes
under the same conditions.
Ele'vin aldehydes were prepare.-1, seven of which were not re-
-.crted prc-;ou.-ly in the !it.. nature. Thy-ical con.-tant.- were deter-
mined and analysis m-ade &:. each new aldehyde. The aldehylde- were
prepared by reacting the -pi.'ate hydroxybenzaldehy.-l- in a solu-
tion of sodium hydroxide v.th allyl bromide, ":eart'anernment of '-he
product ,Ltah.id, and conda i-.-.aton of the re.-.uli.g hydroxy-allyl-
.sub.ititutel benzaldehyde in a solution of s-cd'ur, hydroxide with di-
Nine new- nltro tyrenes were obtained from th,- aldehyde.
prepared. Two of the al.Iehjrde-- apparently formed the nitrostyrene:
but could not be purified ,uffici:nritly to permit .Thar-acterization.
Physical constants were determined and ah-lysis :niae for each new
/-nitroj.tyrene. The. ynitrostyrenes were pre-pared by conden-ing
the app .p:-iate ald. hyde .i.h nit-:omethane in th3 presence of ;odium
hydroxide. The salt ferr.-ie.. during this conden:atio.n was converted
to 'the_-nitrostyrene by adding it as an aqueou.s solution to an excess
of hydrochl,- oric acid olutin.
The7,-nitrostyrenes were /subjected to polymerization with
sodium methoxide. Only the.-nitrostyrenes ,,h".ch were orth.
uzub'tjtutei with regards to the 2-nitrovinyl group failed to p-roduce
Thb--nitrostyrenes .nnQ ,ciehyde.- containing the vinylc-ry group
were ,:ubj-e,. to poliyrne-ization unsng BFr' CaN5Vz? as the ...C.."y.
The aldehfie-e polymerized but the--nit:-o vyreiie2 were recover-ed
as the monomer from the reaction solution. Ir-Ir.'_.ed evidence
pointed to an inhibition or prevention of the electron *h.ft in the vinyl-
oxy group which was necesar..-y to pe-rnilt poly-.-rne-ration.
The aldehydes andcA-nitrostyrenes were polymeri_-zed L-ingly,
and copolyrnrerized individually, with mnaleic anhydride u-:ing ben:.--yi
peroxide as the catalyst. The aldehyde in all cases showed a gr-eater
tendency to p-lymerize than did its analo- gousa-n. _rostyrene der'vative.
The two-stage polyn-.er-zati.sn which were proposed originally,
were not p-.7ac tical becau.e *: '_f t lac'- cof s.olubility of the polymers
obtaine! ';,ith c.,diuni rs-etho:._e, .he lack .)f reactivity of the vinyl-
oxy group; in thc- n!tro.a.s-yrene: t--:'wa, rd BF3 an-', the slight tendency
of the 7nitrostyrenes to po1.ycr''ze with benn.oyf peroxide.
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AC iN 01V LEDGEMENTS
The author wishes to express his sincere appre-
ciation to Dr. George B. Butler who conceived this
research project and under whose direction this work
was performed. His suggestions and encouragement,
both in carrying out the research described and in
the writing of the dissertation, were generously
The author also wishes to express his sincere
thanks to the other members of his committee for
their valuable advice and suggestions,
Grateful acknowledgement is made to Dr. A. H.
Gropp and Miss Mary L. Van Natta for the time and
information contributed in the study of the infrared
James L. Nash, Jr. was born in Muhlenberg County, Kentucky,
on September 24, 1926. He pursued his undergraduate studies at
Western Kentucky State College, Bowling Green, Kentucky, and was
awarded the degree of Bachelor of Science in August, 1948.
He enlisted in the United States Air Corps in August, 1944,
and was called to active duty in March,1945. He was discharged in
September, 1946, after nineteen months of active service.
In September, 1948, he entered the graduate school of the
University of Florida and was awarded the degree Master of Science
in February, 1950.
He was awarded a Graduate Assiiatantship in September, 1948,
a University Graduate Fellowship in September, 1949, and appointed
to the full-time position of Interim Assistant in Research in May, 1951.
Mr. Nash is a member of the American Chemical Society.
This dissertation was prepared under the direction of the chair-
man of the candidate's .-upervi:.ory committee and has been approved
by all members of the committee.. It was submitted to the Dean of
the College of Arts and Sciences and to the Graduate Council and was
approved as partial falfilment of the requirements for the degree of
Doctor of Philosophy.
January 31, 1953
Dean, College of Arts and Sciences
Dean, Graduate School