Group Title: study of electronic interactions in certain vinyl ethers
Title: A study of electronic interactions in certain vinyl ethers
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Permanent Link: http://ufdc.ufl.edu/UF00097975/00001
 Material Information
Title: A study of electronic interactions in certain vinyl ethers
Alternate Title: Electronic interactions in certain vinyl ethers, A study of
Physical Description: v, 86 l. : illus. ; 28. cm.
Language: English
Creator: Thompson, Ronald Earl, 1931-
Publisher: s.n.
Place of Publication: Gainesville
Publication Date: 1962
Copyright Date: 1962
 Subjects
Subject: Vinyl ethers   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
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Thesis: Thesis--University of Florida.
Bibliography: Bibliography: 83-85.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Bibliographic ID: UF00097975
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000423907
oclc - 11025639
notis - ACH2312

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A STUDY OF ELECTRONIC INTERACTIONS

IN CERTAIN VINYL ETHERS












By
RONALD EARL THOMPSON


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY










UNIVERSITY OF FLORIDA


August, 1962
























































UNIVERSITY OF FLORIDA


3 1262 08552 2653












ACKNoULEDGIENTS


The author wishes to express his deep appreciation to

Dr. G. B. Butler whose guidance, counsel, assistance, and

encouragement during the execution of this work were of

inestimable value.

The author also wishes to express his gratitude to

Dr. W. S. Brey, Mrs. K. N. Scott, and coworkers, without whose

assistance the physical property deterr.inations could not have

been trade; to Dr. A. H. Gropp and his coworkers for their

advice and counsel in the interpretation of the infrared spectra,

to L. S. Pijanowski and H. W. Latz for the infrared spectra,

and to the members of his advisory committee and his fellow

graduate students whose advice and criticism were a constant

source of inspiration and encouragement.

Finally, the author wishes to express his great appreciation

and his sense of deep indebtedness to his wife, Roslyn, whose

forbearance, longsuffering, and understanding during months of

neglect made this work possible.

The financial support of this research by the National

Science Foundation is also gratefully acknowledged.


- ii-













TABIE OF CONTENTS


Page
ACKiO-JLEDG1 IETS ii

LIST OF TABLES iv

LIST OF FIGURES v

Chapter

I. IHTRODUCTIO; 1

Background 1

Statement and Development of the Problem 3

Delineation of Objectives and Methodology 9

Source and Purification of Frcacnts 13

II. EXPERI!INTAL 14

Preparation of the CorDounds 14

Physical IMeasurements 33

III. DISCUSSION OF RESULTS 64

Preparation of the Compounds 64

Physical Ieasurements 67

IV. SU?: ARY 82

BIBLIOGRAPHY 83

BIOGRAPHICAL SKETCH 86


-iii-













LIST OF TAPES


TADULATIOI OF

TABULATION OF
SPECTPA

TAiULATIO:I OF(
COIIPOUNDS

TABULATION OF
COMPOUNDS

COT-I;APSro:I


DIPOLE :i0:,iT DATA

MAXIMA IN ULTRA-VIOLET ABSORPTION


OTLAR PEFPACTIOHI DATA FOR VEYLOXY


E:OLAT. REFRACTION DATA FOR ETHYLOXY


YIELDS OF SYNTHETIC ETHIODS


-iV-


Table

1.

2.


3.


4.


5.


Page

35


39


62


63

65












LIST OF FIG-ULS


Figure Page

1. ULTRfA-VIOLET ABSOFPTIOI SPECTPA OF 2-VINYLOXY-
ETHOX1JIuZEiE AND 2-ETHYLOXYE'THOXYEENZEE 0O

2. ULTPA-VIOLET ABSORPTION SPECTRA OF 2-(2-VI YLOXY)-
ETHO:zI;ENZAL~iYI AND 2- (2-ETIIYLOXY)ETHOXY-
BENZALDEhIDE 41

3. ULTPA-VIOLST ABSORPTIONJ SPECTRA OF 3-(2-VhiYLOXY)-
ETHOm;Y~EiIZALDEHYIE AND 3- (2-ETHYLOXY)ETHOXY-
EElIZALDEHYTE 42

4. ULTRA-VIOLET ABSORPTION SPECTRA OF 4-(2-VINYLOXY)-
ETHOXYBENZALPElYIDE AN1D 4-(2-ETHYLOXY)ETHOXY-
BENZALnEa-YIE 43

5. ULTRA-VIOLET AESORPTIOI SPECTRA OF 2-(2-VITYLOXY)-
ETHOXYSTYRENE AND 2-(2-ETOHYrLIO)ETHOXYSTY'iEE 44

6. ULTRA-VIOLET ABSORPTION SPECTRUM OF 3-(2-VVIYLOXY)-
ETH OXYSTYVEIE 45

7. ULTRA-VIOLET AESOFPTIT; SPEC7TA OF 4-(2-VI]flLOXY)-
ETIIOXYSiTTE;iE AID 4-(2-ETHYLO: C)ETiIOX'YSTYfREIE 46

8. ULTRA-VIOLET ABSORPTION SPECTRA OF 2-(2-VINYLOXY)-
ETHO:Y- P-I!ITROSTYFXEiE AND 2-(2-ETHYLO:XY)ETHOXY-
B-NITROSTYWELfl 47

9. ULTRA-VIOLET ABSOPTIO: SPECTRaUI! OF 3-(2-ETHYLOXY)-
ETiHO:CY-B-lIITOSTYF:EITE 48

10. ULTRA-VIOLET AESORPTION SFE 'iA OF 4-(2-VI YLCY)-
ETaH- B-IJITEOSiFTZFIEi AIND 4-(2-ETILTOXY)EITHO\rY-
3P-NITTOSTYPEIE 49













CHAPTER I

INTRODUCTION


Background


In an attempt to develop a model cross-linking monomer,

Butler and Nash (1) first studied ethers containing both vinyl

and allyl groups, which were found to undergo polymerization by

a sequence of two steps. The first step, giving rise to linear

polymers from ethylene glycol vinyl allyl ether and ethylene

glycol vinyl crotyl ether, used boron trifluoride etherate as

the initiator with toluene as the solvent at -700C. These

investigators then used benzoyl peroxide as the initiator at

65oC. to cross-link the original polymer, obtaining solid

polymers, which softened at high temperatures, and which were

insoluble in the usual organic solvents. Thus the boron

trifluoride etherate initiated polymerization of the vinyl

group in the monomer; benzoyl peroxide initiated polymerization

of the unreacted allyl groups in the linear polymer.

Next they turned their attention to monomers containing

two sites of unsaturation differing very markedly in their

reactivity. Such model compounds would be the 2-vinyloxyethoxy-

B-nitrostyrenes. In as much as one of the vinyl groups was

highly electron deficient (with respect to the vinyl group in

ethylene), being directly attached to a nitro group and a

-L-




-2-


phenyl group, while the other was electron rich (with respect to

the same standard), being directly attached to an oxygen atom,

it seemed logical that compounds of this type would be ideal

for such a study.

Thus the electron deficient double bond should be polymerized

by the use of an anionic initiator, such as sodium methoxide, to

give a linear, soluble polymer, containing the unreacted vinyloxy

groups in the sidechains. Boron trifluoride etherate, which was

so successfully employed in past vinyl polymerizations of this

same group, would then be used to polynerize these residual

vinyloxy groups, producing a cross-linked, insoluble polymer.

Nash (2) reported the preparation of certain of these

compounds and found that the electron deficient beta-nitrostyrene

group was readily polymerized with sodium methoxide as initiator.

However, he also reported that the monomeric 2-vinyloxyethoxy-

B-nitrostyrcnes were unreactive towards boron trifluoride

etherate, under conditions which lead to the facile polynerization

of the Standard monomer, vinyl 2-ethylhexyl ether.

In a separate investigation, Butler (3) showed that a series

of vinyl ethers all possessed an infrared absorption peak at

8.32 nicrons (1202 cn-1) and two other carbon-carbon double bond

peaks at 6.08 and 6.18 microns (1645 and 1618 cm-1). These

compounds were readily polyncrized with boron trifluoride

etherate to give linear, soluble polymers in which the 8.32 micron

peak had disappeared and the 6.08 and 6.18 micron peaks were

considerably diminished.





-3-


Nash investigated the various isomeric 2-vinyloxyethoxy-

benzaldehydes and 2-vinyloxyethoxy-B-nitrostyrenes, and found

that all three isomers of this aldehyde possessed these infrared

absorption bands, while the 8,32 micron peak was absent in the

spectra of the 3- and 4-isomers of the reported beta-nitrostyrenes.

As can be anticipated, the three aldehydes could be polymerized

with boron trifluoride etherate. In as much as it was not

known whether the 8.32 micron peak was attributable to the

benzaldehyde moiety (as benzaldehyde also displayed a peak at

the same place) or the vinyloxy moiety, no definite conclusions

were reached on this point at that time.



Statement and Develomnent of the Problem


In as much as Nash reported that the vinyl double bond in

the vinyloxy group of the beta-nitrostyrenes was not subject to

boron trifluoride etherate polymerization, and that the infrared

spectra of these compounds did not possess the 8.32 micron peak,

the problem immediately suggested itself: are these two facts

related to a common cause? If so, what features in the structure

of these compounds are responsible for these observations? How

can these features, when and if found, be definitely shown to

be so responsible?

Taking 4-(2-vinyloxy)ethoxy-P-nitrostyrene as an example,

the classical structure of which would be I, one of the most

important contributing structures would be II. This would place

a fairly strong oxoniu ion two (saturated) carbon atoms removed




-'4-


from the oxygen atom of the vinyloxy group. Thus the tendency

of one of the unshared pairs of electrons of this oxygen aton,

to give rise, via a delocalization process, to a contributing

structure such as III would be somewhat diminished by the

induction on the part of said oxonium ion across the intervening

saturated hydrocarbon bridge.


f=CII-(


-CH2-CI2-- CH-CH2


III


To the extent to which a form such as III does not contribute

to the structure of the compound, the electron density on the

terminal carbon atom of the vinyloxy group would not be augmented

by such a delocalization process. Ibreover, this resonance

effect (+R), to use the terminology of Could (4), no longer

being considered, electrons would be attracted from the double









bond of the vinyloxy group by the inductive effect (-I) of the

oxygen atom, and the combination of these two effects would

be that the pair of electrons, constituting the pi bond of

the vinyloxy group would not be free to coordinate with the

empty orbital of the boron atom in the initiator. Since the

polymerization proceeds by this form of initiation, this would

account for the lack of reactivity of the beta-nitrostyrenes

towards boron trifluoride etherate, and hence, their lack of

Lewis acid polymerizability. Therefore, since a form such

as II does contribute strongly to the structure of the compound,

this would seem to explain the experimental data.

Gould (5) states that the pK of chloroacetic acid (chlorine

atom inducing across one methylene group) is 2.86, of beta-

chloropropionic acid (chlorine atom inducing across a two

carbon saturated hydrocarbon bridge) is 4.00, and that of

acetic acid is 4.80. Thus it is seen that, while still present,

the induction by the chlorine atom in the beta position is

quite minor as compared to that in the alpha position. Thus

it was felt that the above explanation, relying on the induction

of the oxonium ion across a two carbon saturated hydrocarbon

bridge, left something to be desired.

Another explanation was devised, wherein the contributing

forms, such as II and III are both considered to have important

and simultaneous contributions to the structure of the compound,

as in IV:




-6-


0 e
=C H-C CH-~H0



IV


Here, one of the unshared pairs of electrons of the oxygen atom

of the vinyloxy group is free to be delocalized and contribute

to the extreme form as depicted in III and IV, essentially

unhindered by the beta-oxonium ion's weak induction. However,

being highly polarized by the nearly positive charge on the

phenolic oxoniun ion, located ji atoms away, it is not free to

be donated to the empty orbital of the boron atom in the

initiator (or, at least, not as free as is one of the electron

pairs on the ethyl ether oxygen atom in the original boron

trifluoride otherate complex). To the extent to which this

polarization-favored quasi-six-nonbe red ring contributes to

the structure of the coLpound, it could as rwll explain the

experimental observations.

The construction of a model, representative of a form such

as IV, shows that such a structure is feasible. Moreover,

nanipulation of this model lead to the observation that co-planarity

between the 0-C-C system of the vinyloxy group and the 021!-C-C

phenyl-0 system of the beta-nitrostyryloxy group could be

established at the expense of having the two oxygen atoms in

the -0-CH2-CH2-O- group in the Eaughe conformation. The slight

increase in the energy of the system due to this unfavored

conformation would probably be more than overcome by the energy




-7-


lowering of a -o cloud overlap (even though across an area

between two atoms not joined by a signa bond) which could also

extend the D cloud delocalization.

Shostakovskii (6) postulated a resonance structure for

vinyl ethers, for which the rotation of the alkyl group about

the C-0 bond would be hindered, giving rise to the two rotational

isomers:



1H2C=C ,R and H2C=C



V VI


The work of Brey (7,8) and Tarrant (8) gave excellent support

for this type of isomerism. However, the formation of a ring,

as described above, would not allow the existence of both of

these isomers. The isomer, similar to the second one depicted (VI),

would correspond to IV; the other isomer, similar to the first

one depicted (V), would not allow the ring to form. Thus the

predictions would be that, based on the above explanation,

compounds of the type herein discussed, in whose infrared

absorption spectra the 8.32 micron peak is absent, or at least

significantly shifted from this value, should not be susceptible

to boron trifluoride etherate polymerization and should exhibit

only one peak of the two at (about) 6.08 and 6.18 microns.

The method of choice to investigate the above mentioned

postulation would be to obtain the infrared spectra of the

compounds to be studied. The ultra-violet spectra of those




-8-


vinyloxy compounds having a spectral shift in the 8.32 micron

peak and only one peak (the 6.18 micron peak) in the 6.08-6.18

micron region should then be compared to the ultra-violet spectra

of the corresponding ethyloxy compounds. If such an extension

of the 2j cloud deloalization does not exist, that is, if

there is no interaction between the vinyloxy ji cloud system

and the A cloud system of the beta-nitrostyryloxy portion of

the molecule, then substitution of the ethyloxy group for the

vinyloxy group should lead to the disappearance of only one

peak in the ultra-violet spectrum (and then only if the vinyloxy

group has an ultra-violet absorption maxima in the range available)

and have no change on any others present. On the other hand,

if there is an electronic interaction of the type postulated

in these vinyl ethers, the substitution of the vinyloxy group

by an ethyloxy group should produce a shift in the wavelength

and a change in the extinction coefficient of at least one of

the maxima present in the spectrum of the vinyloxy compound,

and such a shift should be toward shorter wavelength (toward

higher energy).

Another method used to investigate the polarization-favored

ring would be the determination of the dipole moment and the

molar refraction of the various cornounds. Structure IV would

be expected to have a different dipole moment than either II or

III, with III probably having the lowest value, II being

intermediate, and IV having the highest value.

If the ring is forced and a for such as IV contributes

strongly to the actual structure of the compounds, either by




-9-


the polarization-favored nech=nisa, the extension of P2 cloud

delocalization, or both, the electronic environment of the

beta-hydrogens on the vinyloxy group should be sufficiently

altered as to be detectable as a change in the chemical shift

of these hydrogen atoms in the nuclear magnetic resonance

spectra of these compounds. These determinations are being

made by Dr. W. S. Brey and coworkers, and will be reported

independently.



Delineation of Objectives and Methodolog~


The primary objectives of this investigation were the

preparation of the compounds and the determination of certain

of their physical properties. The secondary objectives were

to discover the correlation between these physical properties

and the structure of the compounds and to determine if these

correlations could be successfully employed in the explanation

of the previously reported, experimentally observed behavior

of these compounds towards polymerization.

The compounds to be prepared in this investigation were

grouped into two series: (a) ethylene glycol substituted-

phenyl vinyl ethers, and (b) ethylene glycol substituted-phenyl

ethyl ethers. Since the compounds in the second (ethyloxy)

series were somewhat similar to those in the first (vinyloxy)

series, it was decided, when applicable, to utilize the same

methods in their preparation as were employed in the preparation

of the compounds of the vinyloxy series,




-10-


The compounds to be prepared were: (a) 2-vinyloxycthoxy-

benzene, 2-, 3-, and L2.(2-vinylo:y)cthojbcnznaldehyde, 2-, 3-,

and h:-(2-vinyloxy)-ethoxystyrcne, and 2-, 3-, and h-(2-vinylory)-

ctho:y-P-nitrostyrene, and (b) 2-ethylo.yetlhoxlbcnzene, 2-, 3-,

and 4-(2-ethyloxy)ctho:ybcnzaldchyde, 2-, 3-, and 4-(2-ethyloxy)-

cthoxystyrenc, and 2-, 3-, and 4-(2-ethylo;:y)etho:cy-B-nitrostyrene.

The sinllarity of the two series is apparent.

Butler (3), in the preparation of 2-vinyloxyethoxrybcnenc,

and Nash (2), in the preparation of 2-, 3-, and 4-(2-vinyloxy)-

ethoVybenzaldehyde, used essentially the same synthetic procedure:

a basic aqueous solution of phenol or the appropriate hydroxy-

benzaldehyde, prepared in situ by dissolving the phenol in an

aqueous potassium hydroxide solution, was treated with 2-chloro-

ethyl vinyl ether. The resulting mixture was heated for some

tine (usually twenty-four hours), then cooled to room temperature,

and extracted with benzene. The benzne solution was then dried

and the bulk of the solvent removed by distillation. Fractional

distillation of the residual oil gave the desired product.

In the preliminary stages of this investigation these

methods of preparation were recheckd with excellent agreement.

However, it was felt that the relatively low yield (2-vinyloxy-

ethoxybcnzene: 21.0 per cent; 2-(2-vinyloxy)cthoxybenzaldehyde:

31.53 per cent; 3-(2-vinyloxy)ethoxybenzaldchyde: 42.46 per cent;

and 4-(2-vinyloxy)ethoxybenzaldehyde: 18.70 per cent) was at

least partially due to the hydrolysis of the 2-chloroethyl vinyl

ether by either water, present in overwhelming excess, or by an





-11-


equilibrium concentration of hydroxide ions. It was thus

decided to investigate the feasability of the isolation of the

anhydrous potassium salt of these phenols, then allowing this

potassium salt to react with 2-chloroethyl vinyl ether in some

non-hydroxylic, inert medium in which they were mutually soluble.

The solvent of choice was N,N-dinethylforramide. The results of

this phase of the investigation will be discussed under "Discussion

of Results."

Nash (2) also reported the preparation of 3. and 4-(2-vinyloxy)-

ethoxy-P-nitrostyrene. His reported method of synthesis was

rechecked and, indeed, the compounds which were thus obtained

showed excellent agrcccnt in melting point with those reported.

However, the nuclear magnetic resonance spectra of these compounds,

in failing to show the presence of any vinyloxy hydrogen atoms

in these compounds, began to cast a serious doubt on the validity

of the assignment of the reported structure of these compounds.

This doubt lead to the resubnission of these compounds for

analysis, in an even purer state on the basis of melting point

than that reported: "3-(2-vinylox)ethoxy-.-nitrostyrene,"

m.p.: 113.5-114.0oC. as compared to 112-1130C. and "4-(2-vinyloxy)-

ethoxy-0-nitrostyrene," m.p.: 123.5-124.00C. as compared to

121-1220C. The carbon, hydrogen, and nitrogen analyses of these

compounds were in good agreement with the analyses that would

be calculated for 3-(2-hydroxy)ethoxy-Bq nitrostyrene and 4-(2-hydroxy)-

ethoxy-B-nitrostyrene. Thus the final stage in the preparation of

these compounds, treatment of the basic condensation reaction





-12-


mixture of the appropriate 2-vinyloxyothoxybenzaldehyde,

nitroncthano, methanol, and aqueous potassium hydroxide solution

rith excess hydrochloric acid solution lead to tho hydrolysis

of the vinyl ether. This facile hydrolysis of vinyl others is

reported in the literature (9-13).

Thus, to the best klno~lcdgo of the author, the only compounds

included in this investigation that are nowin to have been

previously reported in the chemical literature are 2-vinyloxy-

othoxybcnzcnc and the 2-, 3-, and 4-(2-vinyloxy)cthoxybenzaldehydec,

and these compounds have been prepared by a conewhat different

method and in significantly better yields to justify their

inclusion in this series of otherwise nw, unreported corounds,

over and above the fact that they are the intermediates for

the corresponding styrenes and beta-nitrostyrenes.

Finally, in as much as these aldehyde intermediates were

synthetically available, and since benzaldehyde Ias knoim to

undergo the Wittig (14) reaction with ease, it was decided to

investigate this synthetic route to a ne series of potentially

interesting monomrs. These compounds, being 2-vinyloxyethoxy-

styrenes, would possess tWo double bonds of somewhat differing

reactivities towards polymerization, and thus my well be

ideally constituted for a polyncrization study, similar to that

conducted by Dutler and Hash (cf. Pef. 1). The synthesis of the

2-ethylo:zyethoxystyrenes was also investigated, not only due to

the fact that they would be interesting mnonomers for polymerization

studies, but also since their physical properties should be







compared to the physical properties of the vinyloxy compounds.

Since polymerization studies were outside the scope of this

investigation, no such studies were conducted.



Source and Purification of Pcarents


Phenol (U. S. P. grade, fused) was obtained from J. T. Baker
Chemical Company, Phillipsburg, Pennsylvania, and was used without
purification.

2-Hydroxybenzalcehyde (salicylaldehyde, Fisher Reagent
Chemical) was obtained from Fisher Scientific Company, Fairlawn,
New Jersey, and was used without further purification.

3-Hydroxvbenzaldehyde (practical) was obtained from L. Light
and Company, Limited, Colnbrook, England, and was used without
purification.

4-Hvdroxybenzaldehyde (practical) was obtained from Eastman
Organic Chemicals Division, Distillation Products Industries,
Rochester, New York, and was used without further purification.

Vinyl 2-chloroethyl ether was obtained from Carbide and
Carbon Chemicals Company, Union Carbide and Carbon Corporation,
New York, New York, and was used without further purification.

2-Bromoethyl ethyl ether (Reagent grade) was obtained from
Penninsular Cheresearch, Incorporated, Gainesville, Florida,
and was used without any further purification.

Butyl lithium in hexaie solution was obtained from Foote
Iinernl Company, hWest Chester, Pcnnsylvania, and was used
without purification,

lIethvltroihenylphosnhonium bronide was obtained from this
laboratory and was used without further purification.













CHAPTER II

EXPERIZEIITAL


Preparation of the Compounds


A. 2-Vinyloxyethoxybenzene.--This diether was prepared

(a) according to the method of Butler (3) and (b) by the method

described below.

1. Preparation of the potassium salt.--A solution of

47.06 g. (0.5000 mole) of phenol in 50 rl. of absolute ethanol

was added to a solution of 32.74 g. (0.5000 mole) of 85.7 per

cent potassium hydroxide in 350 nl. of absolute ethanol. The

solvent was removed by distillation; residual misture was

removed by the use of the benzene azeotrope. The lavender,

crystalline solid was washed with anhydrous ethyl ether to

remove any unreacted phenol, filtered, and dried over calcium

sulfate at reduced pressure. Due to the extremely hygroscopic

nature of this salt, it was used immediately.

2. Preparation of the diether.--The above potassium

salt was dissolved in a solution of 58.60 g. (0.5000 mole plus

10 per cent excess) of 2-ch oroothyl vinyl ether in 200 ml.

of redistilled dinethylformanide, by stirring on a steam bath.

Stirring and heating were continued for ten hours. Upon being

cooled to room temperature, the reaction mixture was diluted


-14.




-15-


with one liter of distilled water and then repeatedly extracted

with ethyl ether. The ethereal extracts were dried over anhydrous

magnesium sulfate and the bulk of the solvent removed by atmospheric

distillation. The residual oil was fractionally distilled under

vacuum to give 51.57 g. (6P.81 per cent yield) of a clear,

colorless liquid, b.p.: 103-105oC./7.5 mr. of mercury. Redistil-

lation of a 46.20 g. sample of this material gave 44.57 g.

(96.47 per cent recovery; 60.00 per cent relative over all yield)

of a clear, colorless liquid, b.p.: 102-103oC./10 mmi of mercury,
30
nD: 1.5152.
Analysis: Calculated for C10H1202, per cent: C, 73.20;

H, 7.32. Found, per cent: C, 73.10; H, 7.hl.

B. 2-(2-Vinylocy )ethoxvbenzaldehyde.--This diether was

prepared in a manner entirely analogous to that described above.

1. Preparation of the potassium salt.--The potassium

salt was prepared on a 1.0000 mole scale by the substitution of

salicylaldehyde for the phenol in the previous procedure. The

yield of yellow, crystalline solid, after drying to constant

weight, was quantitative.

2. Preparation of the diether.-This diether was

prepared on a 0.7500 mole scale from 120.0 g. of the potassium

salt, 87.9 g. of 2-chloroethyl vinyl ether, and 500 ml. of

redistilled dimethylformamide, by the procedure cited above.

Fractional distillation of this product gave 106.61 g. (73.95 per

cent yield) of a clear, colorless liquid, b.p.: 101-103oC./0.1 mm.

of mercury; n30: 1.5427.
D .




-16-


Anaysis: Calculated for C11H1203, per cent: C, 68.73;
II, 6.29. Found, per cent: C, 68.43; H, 6.25.

C. 3-(2-Vinvloxy)ethoxybenzaldehyde.--With the exception

of a slight modification in the preparation of the potassium

salt, this diether was prepared in the same manner as cited above.

1. Preparation of the potassium salt--This potassium

salt was prepared on a 0.3000 mole scale by adding 19.65 g. of

85.75 potassium hydroxide dissolved in 150 ml. of absolute

ethanol to a solution of 36.64 g. of n-hydroxybenzaldehyde in

150 ml. of absolute ethanol cooled to the vicinity of 50C.

Heat was not supplied during the vacuum distillation used to

remove the solvent. After being washed with anhydrous ethyl

ether to remove any unreacted m-hydroxybenzaldehyde, filtered,

and dried, the yield of greenish yellow, crystalline solid was

47.00 g. (97.77 per cent yield).

2. Preparation of the diether.-This diether was

prepared in the same manner as described above from 47.00 g.

(0.2934 mole) of the potassium salt, 42.63 g. (0.2934 mole

plus 36.4 per cent excess) of 2-chloroothyl vinyl ether, and

250 ml, of redistilled dinethylfornanide. Fractional distillation

of the crude product gave 46.31 g. (82.11 per cent yield) of a

clear, colorless liquid, b.p.: 106-107oc./0.50 nm. of mercury;
19
nD : 1.5470. This is the material referred to as the "liquid

notification."

Analysis: Calculated for C11H1203, per cent: C, 68.73;

I, 6.29. Found, per cent: C, 68.57; H, 6.47.




-17-


By the low temperature removal of solvent by reduced pressure
distillation of a small amount of a benzene solution of the "liquid

modification," a solid was produced. This solid was used to seed

a 15.98 g. sample of the "liquid modification," resulting in the

crystallization of a total of 13.48 e. (84.36 per cent yield) of

a white, crystalline solid, n.p.. 39.0-40.5oC. Fecrystallization

of a 10.00 g. sample of this solid from pentane gave 7.75 g.

(77.5 per cent recovery) of a white, crystalline solid, m.p.:

41.0-42.00C. This is the material referred to as the "solid

modification."

Analysis: Calculated for C11H1203, per cent: C, 68.73;

H, 6.29. Found, per cent: C, 68.89; H, 6.27.

D. 4-(2-Vinylox )ethoxybenzaldehyde.--This diether was

prepared in the same manner as 2-(2-Vinyloxy)ethoxybenzaldehyde,

described above.

1. Preparation of the potassium salt.--The potassium

salt was prepared in quantitative yield on a 0.5000 mole scale

from 61.06 g. of j-hydroxybenzaldehyde and 32.75 g. of 85.7 per

cent potassium hydroxide.

2. Preparation of the diether.--This diether was

prepared on 0.5000 mole scale from 80.11 g. of the potassium

salt, 53.28 g. of 2-chloroethyl vinyl ether, and 200 ml. of

redistilled dimethylformamide. Distillation of the crude product

gave 79.28 g. (82.49 per cent yield) of clear, light tan liquid,

b.p.: 133-1400C./lI. rn. of mercury. As the liquid crystallized

on the refractoieter platform, the index of refraction could not




-18-


be determined; however, this solid material was used to seed

the liquid. In this manner a total of 77.59 g. (97.87 per cent

recovery; 80.74 per cent over all yield) of a light tan,

crystalline solid, m.p.: 39.540.50C., was obtained. Pecrystal-

lization failed to change the melting point, but did give a white,

crystalline solid.

Analysis: Calculated for CI1H1203, per cent: C, 68.73;

H, 6.29. Found, per cent: C, 68.95; H. 6.38.

E. 2-(2-Vinvloxy )ethoxystyrene.--This styrene was prepared

by the 'ittig (14) reaction from the ethylene ylid (prepared

i ~jtu) and the previously prepared 2-(2-vinyloxy)ethoxybenzaldehyde.

1. Preparation of the methylene ylid.--Dry nitrogen gas

was passed over a vigorously stirred slurry of 89.31 g. (0.2500 mole)

of nethyltriphenylphosphonium bromide in one liter of anhydrous

ethyl ether for one hour at room temperature. Then 188 ml. of

a 14.90 per cent solution of butyl lithium in hexane was slowly

added by neans of a hypodermic syringe. After an additional

30 minutes of stirring, the yellow reaction mixture was nearly

clear.

2. Preparation of the styrene.--A solution of 48.06 g.

(0.2500 nole) of 2-(2-vinyloxy)ethoxybenzaldehyde in 250 ml. of

anhydrous ethyl ether was slowly added with constant stirring to

the above reaction mixture. The white slurry was then stirred

overnight. After the addition of one liter of distilled water

to the reaction mixture and stirring for a short time, the

two phases were separated. The aqueous phase was repeatedly




-19-


extracted with ethyl ether. These ethereal extracts were

combined with the original ethereal phase and the whole was

extracted with water, then dried over anhydrous magnesium sulfate.

Reroval of the bulk of the solvent by a reduced pressure distil-

lation gave a thick, semi-solid oil, which was repeatedly

extracted with petroleum ether. Again, the bulk of the solvent

was removed by reduced pressure distillation. The residual oil

was fractionally distilled under vacuum to give 22.26 g.

(46.80 per cent yield) of a clear, colorless liquid, b.p.:

85-890C./0.50 mm. of mercury; n9,: 1.5480-1.5485. Redistil-

lation of 20.00 g. of this material gave 15.53 g. (77.65 per cent

recovery; 36.34 per cent relative over all yield) of a clear,

colorless liquid, b.p.: 90-91C./0.70 mn. of mercury; n7.5: 1.5441.

Analysis: Calculated for C12H1402, per cent: C, 75.76;

H, 7.42. Found, per cent: C, 75.68; H, 7.20.

F. 3- (2-Vinylox)ethoxystyrene .--This styrene was prepared

in exactly the same manner as described above.

1. Preparation of the methylene ylid.--The methylene

ylid was prepared in exactly the same manner as described above,

but on a 0.1000 mole scale, from 35,73 g. of nethyltriphenyl-

phosphonium bromide, 90 ml. of a 15.04 per cent solution of

butyl lithium in hexane, and 350 nl. of anhydrous ethyl ether.

2. Preparation of the styrene.--This styrene was

prepared as described above, but on a 0.1000 mole scale.

Distillation of the crude production gave 8.46 g. (44.48 per cent

yield) of a clear, colorless liquid, 89-114C./0.08 mm. of mercury;




-20-


30
nD : 1.5325-1.5410. Combination of this material and that
produced by a subsequent synthesis to give a starting charge

of 17.00 g. and redistillation gave a total of 12.10 g. (71.18 per

cent recovery; 31.80 per cent relative over all yield) of a

clear, colorless liquid, b.p.: 79-84oC./0.06 nv. of mercury;

n3O: 1.5435.

Analysis: Calculated for C12i1402, per cent: C, 75.76;

H, 7.42. Found, per cent: C, 75.85; H. 7.47.

G. 4-(2-Viryvloyy)ethoxystyrene.--This styrene was prepared

in an analogous manner to that described above, but was purified

differently.

1. Preparation of the methylene ylid.--The ethylene

ylid was prepared exactly as described above on a 0.2000 mole

scale from 71.45 g. of methyltriphenylphosphoniun bromide,

150 nl. of a 15.04 per cent solution of butyl lithium in hexane,

and 750 ml. of anhydrous ethyl ether.

2. Preparation of the styrene.--The same procedure,

as described above, was followed up to the point of the reduced

pressure distillation of the petroleum ether solvent. At this

point, instead of a residual oil, 28.00 g. (72.82 per cent yield)

of a waxy, white solid was obtained. This material melted

(m.p.: 54-560C.) to give a cloudy melt, suggesting the presence

of triphenylphosphine oxide as an impurity, Chronatographic

purification over an activated alumina column, followed by

recrystallization of the product, gave a total of 19.14 g.

(68.35 per cent recovery; 49.77 per cent over all yield) of







lustrous, white flakes, m.p.: 59.5-60.5oC.

Analysis: Calculated for C12H1402, per cent: C, 75.76;

H, 7.42. Found, per cent: C. 75.59: H. 7.19.

H. 2-(2-Vinyvlo~e-)ethoxy- -nitrostyrene.--Fundanentally these

compounds were made according to the method of Thiele (15), with

slight modifications, as described below. A solution of 48.05 g.

(0.2500 mole) of 2-(2-vinyloxy)ethoxybenzaldehyde, 15.26 g.

(0.2500 mole) of redistilled nitromethane, and 250 ml. of

ethanol was cooled in an ice bath to the vicinity of 50C.

with constant stirring. A solution of 16.37 g. (0.2500 mole)

of 85.7 per cent potassium hydroxide in 50 rl. of distilled

water and 100 ml. of methanol was added dropwise, at such a

rate that the temperature of the reaction mixture did not rise

above 50C. The clear, greenish yellow solution was then poured

over 250 g. of ice in a separatory funnel and the resulting

white mixture was slowly poured into a vigorously stirred

mixture of 22.5 ml. of concentrated hydrochloric acid solution,

250 g. of ice, and 250 nl. of cold, distilled water. The yellow

precipitate was filtered under suction, immediately washed with

two liters of cold, distilled water, and then with one liter

of distilled water at room temperature, and then sucked air dry.

A total of 53.23 g. (90.51 per cent yield) of yellow powder,

m.p.: 56-580C., was obtained.

Eccrystallization of a 25.00 g. sample of this material from

ethanol gave a total of 15.00 g. (60.00 per cent recovery;

54.31 per cent relative over all yield) of a fine, yellow,




-22-


crystalline solid, m.p.: 62.0-62.5oC. Subsequent recrystallizations

failed to change the nelting point.

Analysis: Calculated for C12I13i04, per cent: C, 61.27; 1

N, 5.95. Found, per cent: C. 61.44; H, 5.71. N. 5.91

I. 3- (2-Vinyloxy)ethox-B-nitrostvrene .--Despite repeated

attempts to synthesize this compound, either using e-."t'l" the

procedure developed for the successful synthesis of 2-(2-vinyloxy)-

ethoxy-~-nitrostyrene, or modifications in addition rate,

addition time, or addition order, no successful synthesis for

this compound has as yet been developed.

J. l- (2-Vinyloxy)ethoxy-8-nitrostrene .--The procedure

developed for the above synthesis was successful for the synthesis

of this compound from 19.23 g. (0.1000 mole) of 4-2-vinyloxy)-

ethoxybcnzaldehyde, 6.11 g. (0.1000 mole) of redistilled nitro-

methane, and 125 ml. of ethanol, with a basic solution of

6.55 g. (0.1000 mole) of 85.7 per cent potassium hydroxide

dissolved in 20 ml. of water and 40 ml. of methanol, and an

acidic solution of 9.0 ml. of concentrated hydrochloric acid

solution, 100 g. of ice, and 100 ml. of cold distilled water.

The product obtained was a yellow powder, m.p.: 107-1080C.,

with a yield of 12.70 g. (53.97 per cent). Recrystallization

fron absolute ethanol gave 9.50 g. (74.85 per cent recovery;

40.40 per cent over all yield) of bright yellow crystals,

m.p.: 108.0-108.50C.

Anarysis: Calculated for C121 3104, per cent: C, 61.27;

H, 5.57; H, 5.95. Found, per cent: C, 61.21; H, 5.51; !I, 5.95.




-23-


K. 2-Ethyloxyethoxybenzene.--This diether was prepared in

the same manner as 2-vinyloxyethoxybenzene.

1. Preparation of the potassium salt.--A solution of

13.53 g. (0.2500 mole) of phenol in 50 ml. of absolute ethanol

was added to a solution of 16.37 g. (0.2500 mole) of 85.7 per

cent potassium hydroxide in 100 ml. of absolute ethanol. The

solvent was removed by distillation at reduced pressure; residual

moisture was removed by the use of the benzene azeotrope. The

lavender, crystalline solid was washed with ethyl ether, then

dried over calcium sulfate under reduced pressure. The yield

of dry salt was 30.45 g. (99.67 per cent).

2. Preparation of the diether.--The above potassium

salt was dissolved in a solution of 42.10 g. (0.2500 mole plus

10 per cent excess) of 2-bromoethyl ethyl ether in 150 ml. of

redistilled direthylfornamide by stirring on a steam bath.

Stirring and heating were continued for ten hours. Upon being

cooled to room temperature, the reaction mixture was diluted

with one liter of distilled water and repeatedly extracted with

ethyl ether. The ethereal extracts were dried over anhydrous

magnesium sulfate and the bulk of the solvent removed by

atmospheric distillation. The residual oil was fractionally

distilled under vacuum to give 18.81 g. (45.26 per cent yield)

of a clear, colorless liquid, b.p.: 101-102oC./7.0 mm. of mercury;

n3 1.4958-1.4967. Redistillation gave 12.45 g. (66.19 per

cent recovery; 29.96 per cent over all yield) of a clear, colorless

liquid, b.p.: 101-1020C./7.5 nm. of mercury; n0: 1.4960; d30:

0.9971 g./ml.




-24-


Analysis: Calculated for C10H1402, per cent: C, 72.26;

H, 8.49. Found, ner cent: C, 72.07; H, 8.42.

L. 2- (2-Ethyloxy )ethoxyben.zaldeh.yd .--This diether was

prepared in a manner analogous to that used in the preparation

of 2-(2-vinyloxy)ethoxybenzaldchyde.

1. Preparation of the potassium salt.-A solution of

122.12 g. (1.0000 mole) of salicylaldchyde in 50 ml. of 95 per

cent ethanol was slowly added to a solution of 65.48 g.

(1.0000 mole) of 85.7 per cent potassium hydroxide in 350 ml.

of 95 per cent ethanol, with stirring in an ice bath. The

yellow potassium salt was removed by filtration, washed with

pentane, and then ethyl ether. A large amount of ethyl ether

was added to the filtrate and the resulting mixture was filtered

and washed with ethyl ether. The crops of potassium salt were

combined and dried at reduced pressure. The yield (160.2 g.)

was quantitative.

2. Preparation of the diether.-A solution of 40.05 g.

(0.2500 mole) of the potassium salt in 42.09 g. (0.2500 mole

plus 10 per cent excess) of 2-bromethyl ethyl ether and 150 nl.

of redistilled diethylformanide was heated on the steam bath

for ten hours with constant stirring. Upon being cooled to

room terperaturc, the reaction mixture was diluted with 600 nl.

of distilled water, then repeatedly extracted with ethyl ether.

The ethereal extracts were dried over anhydrous magnesium sulfate

and were then reduced to a small volume of residual oil by the

atmospheric distillation of the solvent. Fractional distillation




-25-


of the residual oil under vacuum gave 40.26 g. (82.91 per cent

yield) of a clear, light yellow liquid, b.p.: 94-980C/0.08 am.

of mercury; n : 1.5225. Combination of this material and that

from a subsequent run and redistillation gave a total of 69.50 g.

of a clear, colorless liquid (from a starting charge of 104.80 g.),

a recovery of 66.32 per cent and a relative over all yield of

54.99 per cent; b.p.: l15-l160C./I.0 mr. of mercury; n0: 1.5250;
d3.0 1.0785 g./ml.

Analysis: Calculated for CllH1403, per cent: C, 68.02;

H, 7.27. Found, per cent: C, 67.93; H, 7.23.

M. 3-(2-Ethyloxy)ethoxybenzaldehyde.--This diether was

prepared in a manner analogous to that used for 3-(2-vinyloxy)-

ethoxybenzaldehyde.

1. Preparation of the potassium salt.--A solution of

16.37 g. (0.2500 mole) of 85.7 per cent potassium hydroxide in

100 ml. of 95 per cent ethanol was added to a solution of

30.53 g. (0.2500 mole) of j-hydroxybenzaldehyde in 100 ml. of

95 per cent ethanol and the resulting solution was evaporated
to dryness under vacuum without the application of heat. The

light brown, crystalline solid was not isolated, but was

immediately used for the next step.

2. Preparation of the diether.--The potassium salt

was dissolved in a solution of 38.26 g. (0.2500 mole) of 2-bromoethyl

ethyl ether in 200 ml. of redistilled dimethylformanide. This

solution was heated on the steam bath with constant stirring for

five hours. The reaction mixture was cooled to room temperature




-26-


and diluted with one liter of distilled water. This mixture

was repeatedly extracted with ethyl ether. The ethereal extracts

wore dried over anhydrous magnesium sulfate, then were reduced

in volume to a residual oil by the atmospheric distillation of

the solvent. Fractional distillation of this oil under vacuum

gave 31.42 g. (64.72 per cent yield) of a clear, colorless

liquid, b.p.: 114-118oC./0.80 am. of mercury; n30: 1.5182-1.5228.

Redistillation of 50.00 g. of a combination of this material

and that from a subsequent run gave 48.06 g. (96.12 per cent

recovery; 62.21 per cent relative over all yield) of a clear,

colorless liquid, b.p.: 104-105.C./0.5 m. of mercury; 30: 1.5234;

d30: 1.0799 g./ml.

"Analsir: Calculated for C11H1403, per cent: C, 68.02;

H, 7.27. Found, per cent: C, 67.86; H, 7.48.

N. 4- (2-Ethyloxy)ethoxybenzaleydhde.--This diether was

also prepared in a manner similar to that used for the corresponding

vinyloxy compound, but was purified by distillation.

1. Preparation of the potassium salt.-A solution of

65.48 g. (1.000 mole) of 85.7 per cent potassium hydroxide in

250 ml. of 95 per cent ethanol was added to a solution of

122.12 g. (1.000 mole) of n-hydroxybenzaldehyde in 250 ml. of

95 per cent ethanol. The solvent was removed on the steam bath

under reduced pressure. The lavender solid was ground to a

powder, washed with anhydrous ethyl ether, filtered, and dried.

The yield was quantitative.

2. Preparation of the diether.--The potassium salt was
dissolved in a solution of 153.03 g. (1.000 mole) of 2-bromoethyl




-27-


ethyl ether in 500 ml. of redistilled dimethylformamide. The

solution was heated on the steam bath with constant stirring

for ten hours. After cooling to room temperature, the reaction

mixture was diluted with 3 liters of distilled water, and then

repeatedly extracted with ethyl ether. The ethereal extracts

were dried over anhydrous nagnesiun sulfate and then reduced

in volume to a residual oil by the atmospheric distillation of

the solvent. Fractional distillation of this residual oil under

vacuum gave 153.17 g. (78.86 per cent yield) of a clear, pink

liquid, b.p.: 128-1300C./1.4 .am. of mercury; 30: 1.5389-1.5409.

Redistillation of a 152.00 g. sample of this material gave 128.38 g.

(82.48 per cent recovery; 64.56 per cent relative over all yield)

of a clear, colorless liquid, b.p.: 127-128oC./1.2 mm. of mercury;

n0: 1.5401; d30: 1.0866 g./ml.

Analysis: Calculated for C1H1403, per cent: C, 68.02;

H, 7.27. Found, per cent: C, 67.86; H, 7.27.

0. 2-(2-Ethyloyy)ethoxystyrene.--This styrene was prepared

in the same manner as the corresponding vinyloxy compound.

1. Preparation of the methylene ylid.--Dry nitrogen

gas was passed over a vigorously stirred slurry of 71.45 g.

(0.2000 mole) of methyltriphenylphosphonium bromide in 500 ml.

of anhydrous ethyl ether for 30 minutes. With the system still

under nitrogen sweep, 180 ml. (0.2000 mole plus 44 per cent excess)

of a solution of 14.95 per cent butyl lithium in hexane was slowly

added by means of a hypodermic syringe. After an additional

30 minutes of stirring under nitrogen sweep, the solution was

nearly clear.




-28-


2. Preparation of the styrone.--A solution of 38.48 g.

(0.1981 mole) of 2-(2-ethyloxy)ethoxybenzaldehyde in 100 ml.

of anhydrous ethyl ether was added dropwise. After an additional

30 minutes of stirring, 250 ml. of water was added and stirring

was continued until two definite phases were detected and no

more gas was evolved. The ethereal layer was separated and the

aqueous layer was extracted with ethyl ether. The ethereal

solutions were combined, back-extracted with water, and then

dried over anhydrous magnesium sulfate. Evaporation of the

solvent by reduced pressure distillation gave a residual oil,

which was fractionally distilled under vacuum to give 12.45 g.

(32.69 per cent yield) of a clear, colorless liquid, b.p.:

69-72oC./0.03 in. of mercury; n30: 1.5245.

Salys Calculated for C12H1602, per cent: C, 74.97;

H, 8.39. Found, per cent: C, 74.89; H, 8.56.

P. (2-Ethyloxy)ethoxystyrene.--This styrene was prepared

in the sam manner as the corresponding vinyloxy corpourd.

1. Preparation of the methylene ylid.--Dry nitrogen

gas was passed over a vigorously stirred slurry of 26.87 g.

(75.2 millinoles) of methyltriphenylphosphonium bromide in

300 al. of anhydrous ethyl ether for 15 minutes. With the

system still under nitrogen sweep, 50 ml. (80.0 millimoles;

75.2 millimoles plus 6.38 per cent excess) of a 14.95 per cent

solution of butyl lithium in hexane was slowly added by means

of a hypodermic syringe. After an additional 15 minutes of

stirring under nitrogen sweep, the reaction mixture was nearly

clear.




-29-


2. Preparation of the styrene.--A solution of 14.60 g.

(75.2 millimoles) of 3-(2-ethyloxy)ethoxybenzaldehyde in 100 ml.

of anhydrous ethyl ether was then added dropwise to the above

reaction mixture. After two hours of additional stirring, 200 ml.

of distilled water was added and stirring was continued until

two definite phases were detected and no more gas was evolved.

The aqueous phase was separated from the ethereal phase and was

repeatedly extracted with ethyl ether. These ethereal extracts

were combined with the original ethereal phase. This ethereal

solution was extracted with water, dried over anhydrous magnesium

sulfate, and reduced in volume to a residual oil by the reduced

pressure distillation of the solvent. Fractional distillaticn

of this residual oil under vacuum gave 9.65 g. (66.74 per cent

yield) of a clear, colorless liquid, b.p.: 90-92OC./0.10 lm. of

mercury; rn0: 1.5240.

The infrared absorption spectrum and the nuclear magnetic

resonance spectrum of this material indicated the presence of

the unreacted starting aldehyde. Up to the time of this writing,

no satisfactory method for the separation of the styrene from

the aldehyde, for the destruction of the aldehyde, or for the

complete conversion of the unreacted aldehyde into product

styrene has been developed. This problem is under active

investigation at the present time.

Analysis: Calculated for C12H1602, per cent: C, 74.97;

H, 8.29. Found, per cent: C, ; H,




-30-


Q. Il(2-Ethyloxv)etho styrene.--This styrene as prepared

in a manner similar to that used for the synthesis of the

vinyloxy compound.

1. Preparation of the rethylene ylid.--This non-isolated

intermediate was prepared on a 0.1000 mole scale in the manner

previously used front 35.72 g. of methyltriphenylphosphoniun

bromide, 400 ml. of anhydrous ethyl ether, and 90 ml. of a

14.95 per cent solution of butyl lithium in hexane.

2. Preparation of the styrene.--The procedure, used

for the successful synthesis of 2-(2-ethylox,) ethoxystyrene,

was followed, using the above methylene ylid solution and a

solution of 19.42 g. (0.1000 mole) of 4-(2-ethyloxy)ethoxy-

benzaldehyde in 100 ml. of anhydrous ethyl ether, followed

by three liters of distilled water. Fractional distillation

of the residual oil under vac-uu gave 8.19 g. (42.59 per cent

yield) of a clear, colorless liquid, b.p.: 103-1050C/l.l mn.

of mercury; n 0 1.5315. An infrared absorption spectrum and

a nuclear magnetic resonance spectrum of this material showed

that there was no detectable amount of contamination with

unreacted aldehyde.

Analysis: Calculated for C12H1602, per cent: C, 74.97;

H, 8.39. Found, per cent: C. 74.92; H, 8.49.

R. 2- (2-Ethyloxy)ethoxy-t-nitrostyrene .--A solution of

19.42 g. (0.1000 mole) of 2-(2-ethyloxy)ethoxybenzaldehyde,

6.10 g. (0.1000 mole) of redistilled nitromethane, and 100 ml.

of nethanol was cooled in an ice bath with constant stirring





-31-


to the vicinity of 50C. Then 100 ml. of a 1.00 N aqueous

solution of potassium hydroxide was added at such a rate that

the temperature of the reaction mixture did not exceed 10OC.

Poured over 100 g. of ice in a separatory funnel, this cloudy

mixture was slowly added to a constantly stirred mixture of 100 ml.

of a 1.00 N aqueous hydrochloric acid solution and 200 g. of ice.

Filtration of the resulting thick, yellow suspension, followed by

washing with cold distilled water, and suction drying, gave

16.32 g. (68.77 per cent yield) of a yellow powder, m.p.: 35-35OC.

Recrystallization from methanol gave 11.22 g. (68.75 per cent

recovery; 47.28 per cent over all yield) of yellow crystals,

m.p.: 37.0-38.OOC. A final recrystallization of this material

gave a total of 11.00 g, (98.04 per cent recovery; 46.35 per cent

over all yield) of yellow crystals, m.p.: 38.0-38.5C.

Analysis: Calculated for C12H15N0, per cent: C, 60.75;

H, 6.37: N. 5.90. Found, per cent: C, 60.63; H, 6.50; N, 5.92.

S. 3-(2-Ethyloxy)ethoxy---nitrostyrene.-After cooling a

solution of 19.42 g. (0.1000 mole) of 3-(2-ethyloxy)ethoxybenzaldehyde,

6.10 g. (0.1000 mole) of nitromethane, and 100 ml. of methanol to

the vicinity of 50C. in ice with constant stirring, 100 ml. of a

1.00 N aqueous solution of potassium hydroxide was added at such

a rate that the temperature of the reaction mixture did not

exceed 100C. The yellow solution was poured over 100 g. of ice

in a separatory funnel, then added drop by drop to a mixture of

100 ml. of a 1.00 N aqueous hydrochloric acid solution and 100 g.

of ice, vigorous manual stirring being employed throughout the





-32-


addition. The thick, yellow slurry was then filtered, washed

with cold water, and dried by suction. After drying over

anhydrous calcium sulfate under vacuum overnight, the yield of

dry, yellow powder was 19.00 g. (83.59 per cent yield), n.p.:

36-390C. Recrystallization from rnethanol gave a total of

13.35 g. (70.26 per cent recovery; 56.26 per cent over all

yield) of yellow flakes, m.p.: 43.0-C4.OOC. A final recrystal-

lization from a 50-50 mixture of ethyl ether and pentane gave

12.00 g. (96.78 per cent recovery; 50.57 per cent over all yield)

of yellow, crystalline material, m.p.: 44.5-45.00C.

Analyi? : Calculated for C12H5N 04, per cent: C, 60.75;

H, 6.37; N, 5.90. Found, per cent: C, 60.64: H, 6.24; N, 5.91.

T. 4- (2-Fthyloxv)ethoxv-B-nitrost.rene. -After a solution

of 19.42 g. (0.1000 mole) of 4-(2-ethyloxy)ethoxybenzaldehyde,

6.10 g. (0.1000 mole) of nitromethane, and 100 ml. of methanol

was cooled in an ice bath with constant stirring to the vicinity

of 50C., 100 ml. of a 1.00 N aqueous solution of potassium

hydroxide was added at such a rate that the temperature of the

reaction .ixture did not exceed 100C. The reaction mixture was

then poured over 100 g. of ice in a separatory funnel, then

added with vigorous manual stirring to a mixture of 100 ml. of

a 1.00 aqueous hydrochloric acid solution and 100 g. of ice.

The resulting yellow slurry was filtered, washed with cold water,

and sucked air dry. A total of 16.35 g. (68.82 per cent yield)

of yellow powder, m.p.: 55-650C., was thus obtained. Recrystal-

lization of this material from methanol gave a total of 9.71 g.




-33-


(59.46 per cent recovery; 41.21 per cent over all yield) of
fine, yellow needles, m.p.: 74.0-74.5Oc.
Analysis: Calculated for C12H15N04, per cent: C, 60.75;

H, 6.37; N, 5.90. Found, per cent: C, 60.82; H, 6.45; N, 5.89.


PhFysic-. rncsure-ents

A. Dinole fob-ent Measurerent.--The method of Popov and
Holm (16) was used exclusively. Briefly, this consisted of
making up solutions of varying concentrations on a weight/weight
basis for each of the desired compounds in benzene (or dioxane)
and determining the dielectric constant, the specific volume,
and the square of the index of refraction for each of the
solutions. These values were then plotted against the weight
fraction of solute, W2, for each solution. The best straight
line was then drawn through these experimental points and
extrapolated to infinite dilution (W2 = 0). Determination of
the intercept and the slope of the line for each of the three
above-mentioned determinations gave, respectively, the values

el and a, 1/ and 8, [(n0)12 and y. These quantities were
used to determine the quantities P2, and PM, the polarization
of the solute at infinite dilution and the molar refraction,
respectively, by the relations:


=( +) + (21 + LT)(e2-

2 32) 2) + (111 + 0)(n)1 1)
. .M 1 ) ;? -d + 2 ( nq ) ) 2 )







These quantities, in turn, were used in the determination of ,

the dipole moment, by the expression:


,4= (0.2230)(P2 )1/2

A rigorously purified sample of anisole was used to determine

the accuracy of the method. The experi-ntal data are tabulated

in Table 1.

1. Purification of the solvents:

a. Benzen.--The benzene used was Phillips "Pure

Grade, 99 mole per cent minimum." This was dried and fractionally

distilled over sodium ribbon. The distillate boiling at ambient

pressure between 80-81oC. was collected, and cooled three-fourths

of the sample was frozen. The crystals were isolated by decan-

tation, and were allowed to melt. The nelt was stored over

sodium ribbon and redistilled immediately before use.

b. 1,4-Dioxane.--The dioxane used was ~ atheson,

Coleman, and Bell's "Spectroquality Reagent" grade. This was

dried over calcium hydride, filtered, and distilled at ambient

pressure over anhydrous calcium sulfate. The distillate boiling

between 100.5-101.50C. was collected, and cooled until three-

fourths of the sample was frozen. Front this point on, it

received the same treatment as described above.

2. Apparatus used:

a. Capacitance cell.--The capacitance cell was

supplied by Balsbaugh Laboratories and was a modified type 2TN25,

having a determined caoacitance at 30.0aC. of 24.53 micromicrofarads,

at a frequency of 10 kc.


-34-





-35-


C' '.0 N 0 O H H C




S\ Uo oo\ ON c


H 0 0 r.0 0
1-4 4. * * *











S o o o o a O


o uo -- o H
H 4 N H H H mc
"3 C' 0 N \ C C) O 0
., , * * * *



nH --' l m C r-. a
N N oN N N N N N 0




E 0O p


Hl rl \ rN r H 0
S08 0 0 0 c o "0





SC C CO C C 0
|
0 0N C 0 H 0 c




ci O O O O O O


4 l C N 0 N H N
E- x\ ll l o o l









U O O 0 0C
U' 0C 0 \ 0 0o 0

So cN No N N N l Ni A


4 C4 4 4 4 4 4 4 .

0 o




0 1 I




A C^ c1 -4^ -4! A





-36-


V, CO mN 41 C8




Q U CO N 0
S C' C \ \ C-




",p N N N dN CA O


S O 0 r C o-
H 4 0 O N D
H. H NO 4 I H O

c co o o N o 0
H N C> NN N 0 C0

O 0 0 0 Hr 0 H






O O'O O O O
V O CO CO Oi O i O
0 0 0 0 0 0 0 0




0 P O\ \0







* o *O cO o o
0 ( 0 N 0 0 o
C4 4 C4 C4 C C4 C4
o o o o o o- o ,0










t o o o oO o1
C N N N N H H
C\ O \ C S (m S S









0 co 0 o0
C) cn 0 c- *n
9 Cl P\ < C CM N C- N
\ N H N tN 0
0 N W ii Wi r-I N
0 H r-H H -I H 4 0

















S0 o0 o o C o\
0 C 0 S
O cH H

C0 C0 0 C0 C0 C0 0 0






0 9 0 0 0 0 N 4

S N H H N N 'V.
00 0 "t



a' i C- C, o
0 2 p ri o" A H
N cN N N- 0 N





-37-


S\30 Lt


cO rc



$ o


No o










o o C.
*
Co













o O C-
CO H NCO





0 0
g


C> 0
\0














c or o o0
o o S
o0 0









0 N
H*







o ,- 0
8 ON
00
0 0











oH, C-
H 0














*0 I & ^
2 2 f g
8 -4
I o o r
$ ~5 o







b. Capacitance bridge.-The capacitance bridge

was GCneral Radio Company Type 716-C, operated by the substitutional

method, at a frequency (fo) of 10 kc. and a factor (M) of 1.

c. Oscillator.-The oscillator was General Radio

Company Type 1302-A, operated at a frequency of 10 kc.

d. Substitutional capacitor.--This was General Radio

Company Type 722-N, using 400 4D icromicrofarads as the zero base.

B. Ultra-violet Absorotion Snectra.-The ultra-violet

absorption spectrum of each compound was obtained for various

concentrations of the compound in abo Tlnt ethanol solution.

A Bausch and Lomb Spectronic 505 double-beam recording spectro-

photometer .as used with a matched pair of 1.000 ca. quartz

cells, using a latched set of 9.90 im. quartz spacers. The

absorbance values for the various solutions were corrected for

solvent absorbance, by recording solvent against solvent on the

same paper used for the spectra of the compound used as solute,

and subtracting these values from the observed absorbance values.

These corrected absorbance values were then plotted against the

concentration of the solutions, thus giving a check of the

applicability of Beer's law. Only values which showed good or

better applicability of Beer's law were used in the determination

of the extinction coefficient. The results of these studies

are briefly sunnarized in Table 2, and are given in detail in

Figures 1-10.

C. Infrared Absorption Spectra.--The infrared absorption

spectrum of each compound was obtained using (a) plates or thin




-39-


TABLE 2

TABULATION OF IAXI A DI ULTRA-VIOLET ABSORPTION SPECTRA


Alkyloxy Substituent


Cozoound


Vinylo:y


y(ne)


2- Alkyloxvethoxy-
benzene



2-(2-Alkyloxy)ethoxy-
benzaldehyde


3- (2-Alkyloxv)ethoxy-
benzaldehyde


- (2-Alkyloy )ethoxy-
benzaldehyde


2- (2-Alkyloxy)ethoxy-
styrene


3- (2-Allvloxy)cthoxy-
styrene


4- (2-Alkyloxy)ethoxy-
styrene



2-(2-AIkyloxy)ethoxy-
--nitrostyrene



3- (2-Alkyvloxy)cthoxy-
0-nitrostyrene


4-(2-Alkyloyy)ethoxy-
B-nitrostyrene


218.5
265.0
270.0
276.5

213.0
252.0
317.0

217.0
251.0
310.0

205.5
218.0
274.5

207.0
247.5
299.0

214.0
249.0
294.0

208.0
261.5
280.0
288.0

199.0
240.0
300.0
346.0


0 0
. .



195.5
.236.0
346.0
2Z,-,


loglo

3.92
3.11
3.24
3.17

4.27
3.95
3.60

4.36
3.92
3.44

4.09
4.14
4.26

4.44
4.10
3.59

4.47
4.06
3.36

4.24
4.18
3.89
3.80

4.50
3.92
4.03
4.03

. .
. .


4.53
4.02
4.32


Ethoxy


(-,a An )


195.0
220.5
271.0
277.5

214.0
251.0
318.0

218.5
251.5
310.0

197.0
219.0
275.0

210.0
246.0
300.0

. @



205.0
258.5
290.0
303.0

201.0
242.5
302.5
350.0

202.5
222.0
248.0
307.0
197.0
239.0
350.0


loglOC

4.53
3.94
3.26
3.18

4.36
4.06
3.71

4.41
4.00
3.50

4.24
4.15
4.30

4.40
4.12
3.65




4.34
4.37
3.49
3.23

4.45
3.97
4.08
4.03

4.39
3.94
3.88
4.19
4.37
4.01
4.32





-40-


*1
O














H1


.......







I





o o1 0 0 0 u1 C0
NC 0 O CJ C (N4 0
4 4t- 4d- C^ (NI fN (4 C


3010011





- 41-


V) 0 iV 0 Vn o 0 ip
C 0o c- Vn C-
-4 4 CA (S c, c4


O3lori


0
CO



















0


cv























C)
0,M










14





































































v" o C ,
a r\
CM o c
*


-42-


0


















,,
A














I



CA
^- ^-


1f |






en


30T010





-43-


o U 0 0 N o0
o C- c- 0 C CA


II









H'-















.r1
c'

^H o




-44-


0\ O g
4 4 cv- l
cl C l


V0) 0 0ry
('4 N N
CC (
CJ du d


o














8-




v






S
Cl.




I
c
.1






-45-


o 4 o v o cu- o
'c C^ 0c (C ) C\J 00


OOOO'I1


v o
(N 0
* *
-3- -3





















































0
~F. N (4


cuc
(V
(V


C,

0~

(3







































































* *
4^-^


0
0


301301


-.7-


CO



























00
8 I
E







co









co


*foE
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Fn





-48-


o /

















o



8i -
o III





'c ,

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S\.I
/ *











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C\Z


I iI I I I
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-49-


* 0
C4 C


30Soyi


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mu~a


Cr

00e

01


Hc\





-50-


cells with the neat liquid, in the case of liquid compounds,

and (b) carbon tetrachloride solution, Nujol or a similar oil

mull, potassium bromide pellet, or liquid melt, as appropriate,

for solid compounds. Both sodiun chloride and calcium fluoride

prisms were used. Using all of these variables, the spectrum

of each cornound reported represented the best of the obtained

spectra. A Perkin-Elmer Corporation IMdel 21 double-beam

recording spectrophotometer was used for all spectra. In the

following description of the spectra, the following order is

used: frequency, in wavenumbers (em-1), relative intensity of

the peak (strong, s.; medium, m.; and weak, w.), its shape

(sharp, s.; moderate, m.; and broad, b.), and the assignment

of the peak.

1. 2-Vinyloxyethoxybenzene.--3125 w., m., C-H stretch

of the alpha hydrogen of vinyloxy group; 3067, m., b., asymmetric

C-H stretch of beta hydrogens of vinyloxy group; 3049, m., s.,

symmetric C-H stretch of beta hydrogens of vinyloxy group;

2924, s., s., assymetric C-H stretch in ethylene group; 2882, s.,

s., symmetric C-H stretch in ethylene group; 1639, 1621. s., s.,

C-C stretch in vinyloxy group; 1600, 1587, 1495, all s., s.,

C-C stretch in phenyl group; 1435, s, s., C-H bend in ethylene

group; 1366, m., s., C-C stretch in ethylene group; 1321, s., s.,

asymmetric C-C stretch in vinyloxy group; 1302, 1294, m., s.,

symnetric C-C stretch in vinyloxy group; 1245, s., s., phenyl

C-0 stretch in phenyl ether; 1199, s., s., vinyl C-0 stretch

in vinyloxy group; 1175, m., s., aliphatic C-0 stretch in ethoxy

group.




-51-


2. 2-(2-Vinyloxy)ethoxybenzaldehyde.--3067, w., m.,

C-H stretch of beta hydrogens in vinyloxy group; 2924, w., s.,

asymmetric C-H stretch in ethylene group; 2874, w., s., symmetric

C-H stretch in ethylene group; 1689, s., s., C-0 stretch in

aldehyde group; 1639, 1621, m., s., C-C stretch in vinyloxy

group; 1600, 1484, s., s., C-C stretch in phenyl group; 1453,

m., s., C-H bend in ethylene group; 1397, m., s., C-C stretch

in phenyl-aldehyde group; 1366, s., s., C-C stretch in ethylene

group; 1322, s., s., asymmetric C-C stretch in vinyloxy group;

1289, s., s., symmetric C-C stretch in vinyloxy group; 1244,

s., s., phenyl C-0 stretch in phenyl ether; 1198, s., s.,

vinyl C-0 stretch in vinyloxy group; 1155, m., s., aliphatic

C-0 stretch in ethoxy group.

3. 3-(2-Vinyloxy)ethoxybenzaldehyde.--3067, w., s.,

asymmetric C-H stretch of beta hydrogens in vinyloxy group;

2941, m., s., symmetric C-H stretch of beta hydrogen in vinyloxy

group; 2882, w., s., asymmetric C-H stretch in ethylene group;

2849, w., s., symmetric C-H stretch in ethylene group; 2825,

2740, w., s., C-H stretch in aldehyde group; 1695, s., s.,

C-0 stretch in aldehyde group; 1639, 1621, m., m., C-C stretch

in vinyloxy group; 1597, 1585, 1484, s., s., C-C stretch in

phenyl group; 1449 s., s., C-H bend in ethylene group; 1389,

m., s., C-C stretch in phenyl-aldehyde group; 1362, w., s.,

C-C stretch in ethylene group; 1323, s., s., asymmetric C-C

stretch in vinyloxy group; 1282, s., s.. symmetric C-C stretch

in vinyloxy group; 1264, s., m., phenyl C-0 stretch in phenyl




- 2-


ether; 1199, s., s., vinyl C-0 stretch in vinyloxy group;

1164, m., s., aliphatic C-0 stretch in ethoxy group.

4. 4-(2-Vinyloxy)ethoxybenzaldehyde.-- 3125, w., s.,

C-H stretch of alpha hydrogen in vinyloxy group; 3077, w., s.,

asymmetric C-H stretch of beta hydrogens in vinyloxy group;

2941, w., m., synetric C-H stretch of beta hydrogens in vinyloxy

group; 2882, w., m., asymetric C-H stretch in ethylene group;

2874, w., s., symxetric C-H stretch in ethylene group; 2817,

2732, w., s., C-H stretch in aldehyde group; 1704, s., s.,

C-0 stretch in aldehyde group; 1639, 1618, s., s., C-C stretch

in vinyloxy group; 1603, 1582, 1508, 1481, m., s., C-C stretch

in phenyl group; 1453, w., s., C-H bend in ethylene grouo;

1429, w., s., para-substituted benzene; 1389, w., s., C-C

stretch in phenyl-aldehyde group; 1368, w.,., ., C-C stretch in

ethylene group; 1324, m., s., asymmetric C-C stretch in vinyloxy

group; 1261, s., s., symmetric C-C stretch in vinyloxy group;

1230, w., s., phenyl C-0 stretch in phenyl ether; 1202, s., s.,

vinyl C-0 stretch in vinyloxy group; 1163, m., m., aliphatic

C-0 stretch in ethoxy group.

5. 2-(2-Vinyloxy)ethoxystyrene.--3067, m., m., asymmetric

C-H stretch of beta hydrogens in vinyloxy group; 3030, m., m.,

symmetric C-H stretch of beta hydrogens in vinyloxy group; 2924,

s., s., asymmetric C-H stretch in ethylene group; 2874, s., s.,

synmetric C-H stretch in ethylene group; 1639, 1618, m., m.,

C-C stretch in vinyloxy group; 1597, 1577, 1484, s., s., C-C

stretch in phenyl group; 1449, s., s., C-H bend in ethylene group;




-53-


1412, m., s., C-H stretch in vinyl of styrene group; 1366,

m., s., C-C stretch in ethylene group; 1322, s., s., asymmetric

C-C stretch in vinyloxy group; 1290, s., s., asymmetric C-C

stretch in vinyloxy group; 1241, s., m., phenyl C-C stretch

in phenyl ether; 1199, s., s., vinyl C-0 stretch in vinyloxy

group; 1133, m., m., aliphatic C-0 stretch in ethoxy group.
6. 3-(2-Vinyloxy)ethoxystyrene.--3125, w., s., C-H

stretch of alpha hydrogen in vinyloxy group; 3077, m., s.,

asymmetric C-H stretch of beta hydrogens in vinyloxy group;

2933, s., s., symmetric C-H stretch of beta hydrogens in vinyloxy

group; 2874, w., m., asymmetric C-H stretch in ethylene group;

2817, w., m., symmetric C-H stretch in ethylene group; 1637,

1617, s., s., C-C stretch in vinyloxy group; 1605, 1597, 1582,

1575, 1511, 1484, all s. to m., s., C-C stretch in phenylgroup;
1445, s., s., C-H bend in ethylene group; 1414, w., m., C-H

stretch in vinyl of styrene group; 1366, w., m., C-C stretch

in ethylene group; 1323, s., s., asymmetric C-C stretch in

vinyloxy group; 1287, s., s., symmetric C-C stretch in vinyloxy

group; 1264, 1244, s., s., phenyl C-0 stretch in phenyl ether;
1199, s., s., vinyl C-0 stretch in vinyloxy group; 1172, m., m.,

aliphatic C-0 stretch in ethoxy group.

7. 4-(2-Vinyloxy)ethoxystyrene.--3058, w., s., asymmetric

C-H stretch of beta hydrogens in vinyloxy group; 2924, w., s.,

symmetric C-H stretch of beta hydrogens in vinyloxy group; 1639,

1618, m., s., C-C stretch in vinyloxy group; 1605, 1577, 1511,

w., m., C-C stretch in phenyl group; 1451, m., s., C-H bend in





-54-


ethlene group; 1410, m., m., stretch in vinyl of styrene group;

1370, m., s., C-C stretch in ethylene group; 1325, s., S.,

asynnotric C-C stretch in vinyloxy group; 1285, s., s., symmetric

C-C stretch in vinyloxy group; 1250, 1241, s., s., phenyl C-0

stretch in phenyl ether; 1202, s., s., vinyl C-0 stretch in

vinyloxy group; 1163, m., m., aliphatic C-0 stretch in ethoxy

group.

8. 2-(2-Vinyloxy)ethoxy-8-nitrostyrene.--3125, w., m.,

C-H stretch of alpha hydrogen in vinyloxy group; 3077, w., m.,

asymmetric C-H stretch of beta hydrogens in vinyloxy group;

2985, m., s., syr-etric C-H stretch of beta hydrogens in vinyloxy

group; 2924, s., s., asymmetric C-H stretch in ethylene group;

2865, w., m., symmetric C-H stretch in ethylene group; 1631,

1605, s., s., C-C stretch in vinyloxy group; 1575, 1506, 1493,

s., s., C-C stretch in phenyl group; 1449, m., s., C-H bend

in ethylene group; 1366, s., s., C-C stretch in ethylene group;

1321, m., s., asynmetric C-C stretch in vinyloxy group; 1299,

w., s., symetric C-C stretch in vinyloxy group; 1250, m., s.,

phenyl C-0 stretch in phenyl ether; 1198, s., s., vinyl C-0

stretch in vinyloxy group; 1161, m., s., aliphatic C-0 stretch

in ethoxy grouo.

9. 4-(2-Vinyloxy)ethoxy---nitrostyrene.--3106, m., m.,

asymmetric C-H stretch of beta hydrogens in vinyloxy group; 2924,

m., m., symnetric C-H stretch of beta hydrogens in vinyloxy

group; 2899, s., m., asynnetric C-H stretch in ethylene group;

2857, s.. n.. symmetric C-H stretch in ethylene group; 1621,

m., s., C-C stretch in vinyloxy group; 1600, 1570, 1508, 1490,




-55-


m., s., C-C stretch in phenyl group; 1451, s., s., C-H bend

in ethylene group; 1425, m., m., para-substituted benzene;

1374, s., s., C-C stretch in ethylene group; 1332, m., m.,

asymmetric C-C stretch in vinyloxy group; 1307, s., s., symmetric '

C-C stretch in vinyloxy group; 1248, s., s., phenyl C-0 stretch

in phenyl C-0 stretch in phenyl ether; 1193, s., s., vinyl

C-0 stretch in vinyloxy group; 1171, s., m., aliphatic C-0

stretch in ethoxy group.

10. 2-Ethyloxyethoxybenzene.--3067, w., m., asymmetric

C-H stretch in ethyloxy group; 2985, n., s., symmetrical C-H

stretch in ethyloxy group; 2924, n., s., asymmetric C-H stretch

in ethoxy group; 2874, m., s., symmetrical C-H stretch in

ethoxy group; 1603, s., s., C-C stretch in phenyl group; 1590,

s., s., C-C stretch in phenyl group; 1497, s., s., C-H

deformation in CH2 units; 1453, n., s., asymrretrical CH3 deformation

in ethyloxy group; 1389, w., m., C-C stretch in phenyl group; 1374,

m., s., symmetrical CH3 deformation in ethyloxy group; 1355, m.,

s., unassignedd); 1333, w., b., C-C stretch in phenyl group;

1304, m., n., C-C stretch in phenyl group; 1292, 1274, phenyl-

C-0 stretch in phenyl ether; 1174, m., s., aliphatic C-0 stretch

in ethoxy and ethyloxy groups.

11. 2-(2-Ethyloxy)ethoxybenzaldehyde.--3067, w., m.,

asymmetrical C-H stretch in ethyloxy group; 2976, m., s.,

symietrical C-H stretch in ethyloxy group; 2924, m., s.,

asymmetrical C-H stretch in ethoxy group; 2865, m., s., symmetrical

C-H stretch in ethoxy group; 2762, w., n., C-H stretch in aldehyde

group; 1689, s., s., C-0 stretch in aldehyde group; 1597, 1582,







s., s., C-C stretch in phenyl group; 1484, s., s., C-H deformation

in CH2 units; 1458, s., m., asymmetrical CH3 deformation in

ethyloxy group; 1397, m., s., C-C stretch in phenyl group; 1372,

m., m., symnetrical CH deformation in ethyloxy group; 1353,

w., n., unassignedd); 1302, w., m., C-C stretch in phenyl group;

1287, 1244, s., m., phenyl-C-0 stretch in phenyl ether; 1189,

s., m., bending the ortho-disubstituted benzene; 1163, s., s.,

aliphatic C-0 stretch in ethyloxy and ethoxy groups.

12. 3-(2-Ethyloxy)ethoxybenzaldehyde.--3067, w., m.,

asymmetrical C-H stretch in ethyloxy group; 2985, m., s.,

symmetrical C-H stretch in ethyloxy group; 2933, m., a.,

asyrretrical C-H stretch in ethoxy group; 2874, m., m., syinetrical

C-H stretch in ethoxy group; 2740, w., m., C-H stretch in aldehyde

group; 1704, 1701, s., s., C-0 stretch in aldehyde group; 1597,

1585, s., s., C-C stretch in phenyl group; 1484, s., s., C-H

deformation in CH2 units; 1449, s., m., asymmetrical CH0 deformation

in ethyloxy group; 1389, m., n., C-C stretch in phenyl group;

1376, m., m., syneitrical CH deformation in ethyloxy group;

1355, w., m., unassignedd); 1325, m., n., C-C stretch in phenyl

group; 1290, 1266, s., a., phenyl-C-0 stretch in phenyl ether;

1171, m., m., aliohatic C-0 stretch in ethoxy and ethyloxy groups.

13. 4-(2-Ethyloxy)ethoxybenzaldehyde.--3067, w., m.,

asymmetrical C-H stretch in ethyloxy group; 2976, m., s., symmetrical

C-H stretch in ethyloxy group; 2933, n., s., asymmetrical C-H

stretch in ethoxy group; 2874, m., s., symmetrical C-H stretch in

ethoxy group; 2740. m., m., C-H stretch in aldehyde group; 1692,

1686, s., s., C-0 stretch in aldehyde group; 1603, 1577, s., s.,


-56-




-57-


C-C stretch in phenyl group; 1508, s., s., C-H deformation in

CH2 units; 1451, m., m., asymmetrical CH3 deformation in ethyloxy

group; 1422, m., m., para-disubstituted benzene; 1393, w., m.,

C-C stretch in phenyl group; 1374, w., m., symmetrical CH3

deformation in ethyloxy group; 1355, w., m., unassignedd);

1312, n., s., C-C stretch in phenyl group; 1261, 1235, 1217,

s., m., phenyl-C-0 stretch in phenyl ether; 1163, s., s.,

aliphatic C-0 stretch in ethoxy and ethyloxy groups.

14. 2-(2-Ethyloxy)ethoxystyrene.--3067, w., m.,

asymmetrical C-H stretch in ethyloxy group; 3021, w., m.,

C-H stretch of alpha hydrogens in styrene group; 2976, m., s.,

symmetrical C-H stretch in ethyloxy group; 2933, m., s., asymmetrical

C-H stretch in ethoxy group; 2874, m., s., symmetrical C-H stretch

in ethoxy group; 1629, s., s., C-C stretch in vinyl of styrene

group; 1603, 1577, s., s., C-C stretch in phenyl group; 1486,

s., s., C-H deformation in CH2 units; 1451, s., s., asymmetrical

CH- deformation in ethyloxy group; 1418, n., m., CH2 deformation

in vinyl of styrene group; 1385, w., m., C-C stretch in phenyl

group; 1374, m., m., symmetrical CH3 deformation in ethyloxy

group; 1355, w., m. unassignedd); 1316, m., m., C-C stretch in

phenyl group; 1294, s., n., C-H deformation of alpha hydrogen

in vinyl of styrene group; 1247, s., a., phenyl-C-0 stretch in

phenyl ether; 1190, w., n., bending in ortho-disubstituted

benzene; 1163, m., m., aliphatic C-0 stretch in ethyloxy and

ethoxy groups.

21. 4-(2-Ethyloxy)ethoxystyrene.-3096, w., m.,

asymmetric C-H stretch in ethyloxy group; 3049, w., n., C-H





-58-

'stretch of altha hydrogen in styrene group; 2994, m., s.,

symnetric C-H stretch in ethyloxy group; 2941, m., s., asymmetrical

C-H stretch in ethoxy group; 2882, m., s., syTmetrical C-H

stretch in ethoxy group; 1631, M., m., C-C stretch in vinyl of

styrene group; 1610, s., s., C-C stretch in phenyl group; 1577,

w., m., C-C stretch in phenyl group; 1511, s., s., C-H deformation

in C 2 units; 1456, w., s., asymmetrical CH3 defornation in

ethyloxy group; 1422, w., m., para-disubstituted benzene; 1412,

w., m., CH2 deformation in vinyl of styrene group; 1385, w., m.,

C-C stretch in phenyl group; 1374, w., s., syr-etrical CH3

deformation in ethyloxy group; 1355, w., m. unassignedd); 1304,

w., m., C-C stretch in phenyl group; 1294, C-H deformation of

alpha hydrogen in vinyl of styrene group; 1238, s., s., phenyl-

C-0 stretch in phenyl ether; 1178, s., s., aliphatic C-0 stretch

in ethyloxy and ethoxy groups.

16. 2-(Ethyloxy)ethoxy-0-nitrostyre.--3115, w., s.,

C-H stretch in vinyl of beta-nitrostyrene group; 3086, w., m.,

asynnetrical C-H stretch in ethyloxy group; 2994, m., s.,

synnetilcal C-H stretch in ethyloxy group; 2941, m., s.,

asymmetrical C-H stretch in ethoxy group; 2890, a., s., symmetrical

C-H stretch in ethoxy group; 1637, s., s., C-C stretch of vinyl

in beta-nitrostyrene group; 1605, 1580, s., s., C-C stretch in

phenyl group; 1550, m., b., C-N stretch in beta-nitrostyrene

group; 1524, 1520, 1515, s., s., C-C1 stretch in CC4 (solvent);

1495, m., s., C-H deformation in CH2 units; 1451, s., s.,
asy-retrical Ci3 deformation in ethyloxy group; 1389, w., m.,

C-C stretch in phonyl group; 1377, w, m., symmetrical CH




-59-


deforration in ethyloxy group; 1344, s., Ir., C-N stretch in

beta-nitrostyrene; 1304, m., m., C-C stretch in phenyl group;

1294, m., m., C-H deformation of alpha hydrogen in vinyl of

beta-nitrostyrene; 1258, s., s., heanvl-C-O stretch in phenyl

ether; 1196, m., m., bending in ortho-disubstituted benzene;

1166, n., m., alinhatic C-0 stretch in ethoxy andethyloxy groups.

17. 3-(2-Ethyloxy)ethoxy-3-nitrostyrene.--3125, w., s.,

C-H stretch in vinyl of beta-nitrostyrene group; 3077, w., m.,

asymmetrical C-H stretch in ethyloxy group; 2994, m., s.,

symmetrical C-H stretch in ethyloxy group; 2941, m., s.,

asymmetrical C-H stretch in ethoxy group; 2882, m., s.,

symmetrical C-H stretch in ethoxy group; 1642, s., s., C-C

stretch in vinyl of beta-nitrostyrene group; 1603, 1580, m., m.,

C-C stretch in phenyl group; 1563, 1550, w., m., C-N stretch

in beta-nitrostyrene; 1527, s., s., C-Cl stretch in CC14 (solvent);

1486, m., m., C-H deformation in CH2 units; 1445, i., m.,

asymmetrical CH3 deformation in ethyloxy group; 1391, w., m.,

C-C stretch in phenyl group; 1376, w., n., symmetrical CH

deformtion in ethyloxy group; 1348, s., s., C-N stretch in

beta-nitrostyrene; 1318, w., m., C-C stretch in phenyl group;

1299, m., s., C-H deformation of alpha hydrogen in vinyl of

beta-nitrostyrene; 1274, s., s., phenyl-C-0 stretch in phenyl

ether; 1232, m., m., C-C1 stretch in CC14 (solvent); 1178,

m., m., aliphatic C-0 stretch in ethoxy and ethyloxy groups.

18. 4- (2-Ethyloxy)ethoxy-8-nitrostyrene.--3115, w., m.,

C-H stretch in vinyl of beta-nitrostyrene group; 3040, w., m.,




-60-


asynietrical C-H stretch in cthyloxy group; 2976, n., s.,

syzetrical C-H stretch in othyloxy group; 2924, m., s.,

asymmetrical C-H stretch in ethoxy group; 2874, m., s.,

syTnetrical C-H stretch in ethoxy group; 1634, s., a., C-C

stretch in vinyl of beta-nitrostyrene grouo: 1605, 1572, s., a.,

C-C stretch in phenyl group; 1546. m., b., C-N stretch in

beta-nitrostyrene; 1522, s.,., ., C-Cl stretch in CC14 (solvent);

1508, C-H deformation in CH2 units; 1453, m., s, asymmetrical

CH3 deformation in ethyloxy groip; 1425, m., s., para-disubstituted

b-enzen; 1385, w., m., C-C stretch in phenyl group; 1374, w., m.,

syretrical CH deformation in ethyloxy group; 1350, s., s.,

C-N stretch in beta-nitrostyrene; 1309, m., s., C-C stretch in

phenyl group; 1294, w., s., C-H defornation of aloha hydrogen

in vinyl of beta-nitrostyrene; 1255, s., m., phenyl-C-0 stretch

in phenyl ether; 1238, m., m., C-C1 stretch in CC14 (solvent);

1174, s., s., aliphatic C-0 stretch in ethoxy and ethyloxy

groups.

D. Iblar Fcfraction and Exaltation of -blar Pefraction.--The

values for the experimentally determined molar refractions were

a by-product in the dipole moment determination. As such, both

for solids and liquids, all of the experimental determinations

were made at the san terperaturc, 30.0oC. The calculations

were executed according to the methods of Vogel (17) and

Eisenlohr (18). The values of the atomic and group parameters

used in these calculations were as follows:








Quantity



Carbon atom

IHydrogen atom

Oxygen atom carbonyll)

Cxygen aton (other)

Carbon-carbon double bond

Nitro group (aromatic)


The results of these determinations are

and 4.


Value of Parameter

Vogel Eisenlohr

2.591 2.418

1.028 1.100

2.211 2.211

1.764 1.643

1.575 1.733

7.30 7.30


tabulated in Tables 3


-61-





-62-


TABLE 3

TABULATION OF MOLAR rEFRACTION DATA
FOR VINYLOXY COMPOUNDS


Compound


Calculated


Found


Vogel Eisenlohr


2-Vinyloxyethoxy-
banzene

2- (2-Vinyloxy)ethoxy-
1-nzaldehyde

3- (2-Vinyloxy)ethoxy-
benzaldehyde

4- (2-Vinyloxy)ethoxy-
benzaldehyde

2-(2-Vinyloxy)ethoxy-
styrene

3- (2-Vinyloxy)ethoxy-
styrene

4-(2-Vinyloxy)ethoxy-
styrene

2- (2-Vinyloxy)e thoxy-t
P-nitrostyrene

4- (2-Vinyloxy)ethoxy-
P-nitrostyrene


48.07


52.88

52.88


52.88

56.89


56.89


56.89

63.16


63.16


47.60


52.23

52.23


52.23


56.37


56.37


56.37


62.57


62.57


48.33

55.08

54.26


56.22


59.14


58.37

58.66


66.35

71.40


Exaltation

Vogel Eisenlohr

0.26 0.73


2.20 2.85

1.38 2.03


3.34 3.99

2.25 2.77

1.48 2.00


1.77 2.29


3.19 3.78

8.24 8.83




-63-

TABLE 4
TABULATION OF MOLAR REFRACTION DATA
FOR ETHYLOXY COMPOUNDS


Compound


Calculated


Found


Vogel Eisenlohr


2-Ethyloxyethoxy-
benzene

2- (2-Ethyloxy)ethoxy-
benzaldehyde

3-(2-Ethyloxy)ethoxy-
benzaldehyde

4- (2-Ethyloxy)ethoxy-
bcnzaldehyde

2- (2-Ethyloxy)ethoxy-
styrene

4- (2-Ethyloxy)ethoxy-
styrene

2- ( 2-Ethyloxy)ethoxy-
B-nitrostyrene

3- (2-Ethyloxy)ethoxy-
0-nitrostyrene

4-(2-Ethyloxy)ethoxy-
3-nitro styrene


48.56


53.36


53.36


53.36

57.37

57.37

63.64

63.64

63.64


48.0?


52.69

52.69

52.69


56.83

56.83

63.03


63.03

63.03


49.95

54.99


54.71

55.97

59.63

60.34


73.88

73.98

77.58


Exaltation

Vogel Eisenlohr

1.39 1.88

1.63 2.30


1.35 2.02

2.61 3.28

2.26 2.80


2.97 3.51

10.24 10.85

10.34 10.95

13.94 14.55












CHAPTER III

DISCUSSION OF PESULTS


Preparation of the Co rounds


For the nost part, the primary objectives of this investigation

have been successfully realized. With the exception of 3-(2-vinyloxy)-

ethoxy-B-nitrostyrone (which has not as yet been successfully

prepared) and 3-(2-ethyloxy)etho:ystyrcnc (which was prepared, but

not in a pure state),' the nuclear magnetic resonance spectra, the

infrared spectra, and the elemental analyses of the confounds were

in agreement with the structures proposed. The yields of the

various compounds, which will be discussed in nore detail below,

are quite respectable, and are the yields of the conmounds in a

state of hiLg purity. De to the relatively high boiling points

of these compounds, no assay of their purity by the techniques

of vapor phase chromatography was attennted.

A. Previously Prepared Cornounds.--A comparison in the

yields reported for those compounds prepared by the old "wt"

method with the yields obtained for the same compounds prepared

by the new "dry" nrthod is presented in tabular form in Table 5,

where the quantity "Per Cent Increase" has been calculated by

the expression:

Per Cent Increase
=, er cEat viold (new method) ner cent yield (old method) 100.
per cent yield (old nethod)
-64-







TABLE 5

COMPARISON MI YIELDS
OF SYNTHETIC ITIIODS


Compound Per Cent Yield Per Cent Increase

(Old lethod) (New Method)

2-Vinyloxyethoxy- 21.00 60.00 185.7
benzene

2-(2-Vinyloxy)ethoxy. 31.53 73.95 134.6
benzaldehyde

3-(2-Vinyloxy)ethoxy- 42.46 82.11 93.38
benzaldehyde 63.64* . .*

4-(2-Vinyloxy)ethoxy- 18.70 80.74** 331.8
benzaldehyde


Solid modification, not previously reported, no comparison possible.

This yield is of crystalline solid; the reported yeild from the old
method was based on liquid, although it was reported that the liquid
crystallized on standing.-


-65-





-66-


The advantage of thn nr method seems quite apparent.

B. Styrenes.-The yields of these compounds are as follows:

2-(2-vinyloxy)ethoxystyrene: 36.34 oer cent; 3-(2-vinyloxy)-

ethoxystyrene: 31.80 per cent; 4-(2-vinyloxy)ethoxystyrene:

49.77 Der cent; 2-(2-ethyloxy)ethoxystyrene: 32.69 per cent;

and 4-(2-ethyloxy)ethoxystyrene: 42.59 per cent. These are

not particularly high yields. There are probably two reasons

for these coaparitively low yields: first, it has been shown

in this laboratory (19, 20) that the Wittig (14) reaction does

not go to completion; and second, styrenes are known to undergo

a facile therral polynerization (21-27). A distillation,

conducted at a temperature sufficiently elevated to allow

separation of the styrene and the parent aldehyde, resulted

in a large amount of polymeric residue in the distillation

flask. The higher the temperature and pressure (the lower

the vacuum), the more efficient the separation and the more

polymeric residue. This fact, coupled with a close similarity

in boiling points, is the main reason that 3-(2-ethyloxy)-

ethoxystyrene was not prepared in a pure state. Various

chroratographic techniques for the purification of this compound

are under investigation at the Dresent time.

C. Beta-Nitrostyre-es.--As far as the 2-vinyloxyethoxy-

8-nitrostyrenos are concerned, the synthetic procedure used

was extremely bad; that these compounds were formed at all is

surprising, that they were isolated in as high yields as reported

is even nore so. The use of low temperature in the final stage




-67-


of this method undoubtedly diminished the rate of vinyl ether

hydrolysis. The use of an inverted addition order (adding the

neutralizing hydrochloric acid solution to the basic reaction

mixture, so that there would be no excess of acid solution to

catalyze the hydrolysis) was investigated. However, under these

more ideal conditions, the desired compounds could not be

isolated. For this practical reason the reported preparative

methods, with their disadvantages, were used. In the

2-ethyloxyethoxy-B-nitrostyrenes, since there is little danger

of a similar hydrolysis of the ethyl group, under the same

reaction conditions, this method is satisfactory. The reason

that the yields were no higher in these compounds is probably

due to the reactivity of the polar beta-nitrostyrene group,

especially towards polymerization. The mother liquors from

the recrystallizations of these compounds always contained

dark, viscous oils or gucry amorphous solids, indicating the

presence of polymeric material.



Physical Measurenents

In order to obtain a check on the accuracy of the method

used to determine the dipole moments, the dipole moment of a

rigorously purified sample of anisole was determined. The

experimentally determined value of 1.25 D (in benzene at 30C.)

was in excellent agreement with the value of anisole quoted

by Weissberger (28) of 1.25 D and in good agreement with

Lumbroso's value (29) (in benzene at 200C.) of 1.28 D. Thus




-68-


it was judCgd that this nothod is satisfactory for the desired

decree of accuracy.

No definite quantitative conclusions can be drawn front

these data until nodol compounds can be synthesized and their

dipolo nozents determined in a syster.atic manner, so as to arrive

at theoretical values for the dipole moments of these compounds.

However, so-e qualitative comparisons with analogous cornounds,

the dipole nonents of which are reported in the literature,

can be made.

1. cDnzeno.--Lunbroso (29) determined the dipole

moment of phenol (in benzene solution at 200C.) to be 1.47 D

and that of anisole (benzene, 200C,) to be 1.28 D. The value

of the dipole moment of phenetole, according to Li (30)

(benzene, 25oC.) was stated as 1.0 D. The dipole moments of

2-vinylo:ycthorybenzene and 2-otiylo::yethoxybenzene, determined

in this investigation (benzene, 300C.) were found to be 1.78 D

and 1.91 D, respectively. They are of the sam order of

nagnitude as the other values for unsubstituted phenyl alkyl

ethers. The lower value for the vinyloxy coemound could be

due to a contribution of the ring form, similar to IV (p. 6)

or to a contribution of the linear form, similar to III (p. 4).

The infrared absorption spectrum of 2-vinyloxyetho:xybenaene

exhibits both of the two peaks at 1639 cm1 and 1621 cnml, as

well as chowing no appreciable shift of the 8.32 micron (1199 cn-l)

peak, indicating that the ring form (IV) does not contribute

to the structure of the compound; it is compatable with the linear

form (III). On the other hand, a comparison of the ultra-violet





-69-


absorption spectra of the vinyloxy and ethoxy corapounds shows

a considerable shift in the short wavelength region, suggesting

that there is a contribution of the ring form. That this shift

is not due to a linear form contribution, and that the spectral

shift is not due to the difference in the position of the

absorption maxima of the vinyloxy group and the ethyloxy group,

will be discussed in the following section. The interpretations

of the various physical properties seem to give conflicting

indications as to the structure of these compounds, and therefore

no conclusions can be reached concerning an interaction of the

type proposed in these compounds.

2. Aldehydes.--In 2-(2-vinyloxy)ethoxybenzaldehyde the

ring is effectively prevented from being formed by the large

amount of steric hinderance afforded by the ortao-aldehyde

groW. Thus only linear forms should contribute, and the

physical properties of this compound and the physical properties

of 2-(2-ethyloxy)ethoxybenzaldehyde should be somewhat similar.

This prediction is borne out quite well by the physical properties

that have been determined for these compounds. The dioole

moments of 2-(2-vinyloxy)ethoxybenzaldehyde and 2-(2-ethyloxy)-

ethoxybenzaldehyde are 4.69 D and 4.49 D, respectively, which

represents a difference of only 0.20 Debye units and are somewhat

similar to the values cf the dipole moment of 2-rothoxybenzaldehyde,

reported by Curran (31) as 4.21 D (benzene, 250C.) and by

LuDbroso (32, 33) as 4.19 D (benzene, 200C.).

The similarity in the physical properties of 2-(2-vinyloxy)-

ethoxybenzaldehyde and 2-(2-,ethyloxy)ethoxybenzaldehyde is also





-70-


displayed in their infrared absorption spectra. Thus the

carbon-oxygen stretching absorption peak occurs at the same

wavenunber in both the vinyloxy compound (1689 cm-1) and the

ethyloxy compound (1689 cn"l). Also the infrared spectrum of

the vinyloxy compound exhibits the two peaks at 1639 cr-1 and

1621 em" attesting to the fact that the ring form does not

contribute to the structure of this compound. Thus the ultra-

violet spectra of these two compounds would be expected to be

quite similar. Inspection of Figure 2 (p. 41) show this to

be the case. Also the difference between the molar exaltation

of 2-(2-vinyloxy)ethoxybenzaldehyde (2.20; Table 3, p. 62)

and 2-(2-ethyloxy)ethoxybonzaldehyde (1.63; Table 4, p. 63)

is only 0.57.

In 3-(2-vinylory)ethoxybenzaldehyde, while there is no

steric hindcrance to the formation of the ring, the contribution

of a phenolic oxonium ion form, analogous to II (p. 4) is

relatively minor, for the phenolic oxygen atom and the aldehyde

group are not suitably located on the benzene ring as to be in

mutual conjugation. The dipole amments of 3-(2-vinyloxy)-

ethoxybenzaldehyde (3.13 D) and 3-(2-ethyloxy)ethoxybenzaldehyde

(3.45 D), while not as similar as the previous compounds, differ
by only 0.32 Debye units. Thus the other physical properties

would be expected to be somewhat similar, as in the previous case.

The difference in the position of the carbon-oxygen

stretching absorption peak of the.aldehyde group in the infrared

spectra of 3-(2-vinyloxy)othoxybenzaldehyde (1695 cmrl) and





-71-


3-(2-ethyloxy)etho:ybenzaldehyde (1701 clm1), 6 cr-1, is close

to the accuracy with which the spectral positions can be determined

on the chart paper (plus or minus 0.01 microns; plus or minus

3 cm"1 in this range of :avonu:ibers). The infrared spectrum of

the vinyloxy compound exhibits both of the absorption peaks

at 1639 cm1 and 1621 cml1 and shows no appreciable shift in

the peak at 1199 cn"1 (8.34 microns).

Inspection of the ultra-violet spectra of these compounds

shows that, while there is a great deal of similarity in the

spectra, a slight difference is becoming apparent in the short

wavelength end of the spectra. The molar exaltations of these

two compounds are nearly identical (1.38 and 1.35, for the

vinyloxy and the ethyloxy compounds, respectively). In

conclusion, it may be stated that the physical properties of

3- (2-vinyloxy)ethoxybenzaldehyde and 3-(2-ethyloxy)ethoxy-

benzaldehyde indicate that these two compounds probably have

the same type of structure, with respect to the type of

interaction postulated, and that the ring form of the type

postulated could, at the most, have only a slight contribution

in the structure of 3-(2-vinyloxy)ethoxybenzaldehyde.

In 4-(2-vinyloxy)ethoxybencaldehyde, since the two

substituents on the benzene ring are in a position arn to

each other, there is no steric hinderance to the formation of

the ring, and the two groups are in conjugation. Thus, if the

ring is formed as postulated, a considerable difference in the

physical properties of -(2-vinyloxy)ethoxybenzaldehyde and




-72-


4-(2-ethyloxy)othoxybenzaldehyde would be predicted. In considering

the dipole moments of those two compounds, it is found that the

dipole norent of the vinyloxy compound (4.08 D) is smaller than

that of the ethyloxy compound (4.48D) by 0.40 Debye units. This

is a reversal of the situation in the 2-(2-alkyloxy)cthoxy-

benzaldehyde series, where the nonent of the vinyloxy compound

was larger than that of the ethyloxy compound. This difference

of 0.40 Debye units is greater than that in the preceding

3-(2-allyloxy)ethoxybenzaldehyde series, and is certainly

greater than the experimental error in the determination of

these properties.

This apparently anomolous difference in the dipole noments

of these two compounds may indicate that the postulated ring

form has a significant contribution to the structure of

4-(2-vinyloxy)ethoxybenzaldchyde. If this is the case, a

considerable difference would be expected in the position of

the aldehyde carbon-oxygen stretching absorption peak in the

infrared spectra of these compounds. The observed positions

of this peak in the saectra of 4-(2.viLiyloxy)etho:ybcnzaldehyde

(1704 cm1 ).and 442-ethyloxy)ethorybenzaldehydo (1692 cn-1

and 1686 cn-1 split from a central value of 1689 or 1 -- which,

incidently, is the position in both of the 2-isomers) differ by

15 cn" a value which is greater than the error in the deter-

iination of the position of the peak.

Since both of the peaks at 1639 cn-1 and 1618 cm-1 are

present in the infrared spectrum of 4-(2-vinyloxy)ethoxy-

benzaldehyde, the ring is obviously not formed to the exclusion




-73-


of the linear form. A semi-quantitative study was undertaken

on the amplitude of these peaks. Since the spectra obtained were

in per cent transmittance, the reciprocal of the transmittance

values of the maxima were subtracted from the reciprocal of the

transmittance values of an extrapolated base line. The ratio

of the peak height in absorbance units of the 6.08 micron peak

(1639 cml-) to that of the 6.18 micron peak (1621 cml) in the

same units was then calculated. This order was chosen for, to

the extent that the ring would be formed, the 6.08 micron peak

would diminish. This ratio was calculated for each of the three

isomeric 2-vinyloxyethoxybenzaldehydes, and was found to be:

2-isorer; 0.553; 3-isomer: 0.512; 4-isomer: 0.394. Since it

was concluded that in the case of the 2-isomer only the linear

form was present, the fraction of the contribution of this form

would be 1.00. Normalizing these ratios so that the ratio of

the 2-isomer is 1.00, the following new ratios are obtained:

2-isomer: 1.00; 3-isomer: 0.942: 4-isomer: 0.713, which, when

converted into per cent, become: 2-isomer: 100 per cent (linear

form); 3-isomer: 94 per cent (linear form); and 4-isomer: 71

per cent (linear form).

The above study was admittedly only semi-quantitative;

however, it indicates that, in the case of the 3-isomer, only

about 6 per cent of the actual structure of this compound could

be contributed by the postulated ring form. Thus it is not

difficult to explain why the study of the physical properties

of this compound failed to do more than indicate a possibility







of a small contribution of the postulated ring form. The

prediction of this study of about a 29 per cent contribution

by the postulated ring fonrm to the structure of 4-(2-vinylo:y)-

cthoxybcnzaldchyde should be capable of verification (or at

least support) by a study of the reminder of the physical

properties of this compound.

A comparison of the ultra-violet absorotion spectra of

4-(2-vinyloxy)ethoxybenzaldehyde and 4-(2-ethyloxy)ethoxy-

benzaldehyde (Figure 4, p. 43) chows a considerable shift in

the position of the short wavelength peak. The position of

the raxiia in the ethyloxy compound is 197.0 nillimicrons and

that of the vinyloxy compound is 205.5 nillinicrons, a shift

of 8.5 millimicrons, a value considerably greater than the

experimental error in the determination of the position of

these naxina. 1breover, the shift is in the predicted (cf. p. 8)

direction, indicating that, as far as this neak is concerned,

at least, the vinyloxy coeaound is the low r-energy compound

of the two. Finally, the nolar exaltation of the vinylo:x

compound (3.34) is about 28 per cent greater than that of the

cthyloxy compound (2.61). It is interesting to note that the

value of this increase in molar exaltation (28 per cent) is

quite close to the per cent contribution of the ring form

predicted in the "semi-quantitative study" (29 per cent).

In conclusion it may be 'stated that the study of the

physical properties of 4-(2-vinyloxy)ethoxybcnzaldehyde and

4-(2-ethyloxy)ethoxybenzaldehydo indicated that, for the most




-75-


part, these two compounds have the same type of structure, but

that there probably is a significant contribution of the postulated

ring form to the actual structure of 4-(2-vinyloxy)ethoxybenzaldehyde.

3. Styrenes.--The dipole moments of 4-methylstyrene

(0.38 D) and 3-methylstyrene (0.36 D), determined by Evarard

and Sutton (34), are so close to the value quoted for toluene

(0.37 D) by Gould (35) that some authors (34) feel that the

dipole noment of styrene, itself, within the limits of experimental

accuracy, in indistinguishable from zero. Con~aring this with

the dipole rmoent reported (36) for benzaldehyde (2.75 D), it

would be predicted that, if-there were any contribution at all

of an interaction of the type postulated, it would be of such

ninor importance as to cause differences in the physical properties

of these compounds so small that they would approach the

experimental error of these determinations. In as much as the

physical properties of 4-(2-vinyloxy)ethoxybenzaldehyde gave

the most indicative evidence for the existence of the postulated

interaction, it would be expected that the greatest difference

in the 2-alkyloxyethoxystyrenes in this investigation would

occur in the 4-isomers..

The difference in the dipole moment of 4-(2-vinyloxy) -

ethoxystyrene (2.15 D) and 4-(2-ethyloxy)ethoxystyrene (2.08 D)

is 0.07 Debye units. This value is approaching the experimental

error of the determination and is too small a difference to

use for even a qualitative study of an interaction of the type

postulated. An inspection of the ultra-violet spectra of these




-76-


two compounds (Figure 7, p. 46) shows a small shift in the

short wavelongth end of the spectra. Althourh'the shift is

in the predicted direction (vinyloxy compound absorption maxima

at longer wavelength), its value, 3.0 millinicrons, is approaching

the accuracy with which the position of the maxina, especially

somewhat "rounded" maxima, can be determined from the chart

paper (plus or minus 0.5 millinicrons) and the accuracy of the

instrLent (same value). Thus it nay be stated that, while only

very qualitative conclusions may be reached concerning inter-

actions in these compounds of the type postulated, the strongest

contribution to the actual structure of any of these styrenes

would probably occur in 4-(2-vinyloxy)ethoxystyrene, and even

in this comound such a contribution would probably be

extremely minor, if detectable.

4. Beta-ilitrostyrenes.--If a comparison, similar to

that nade between styrene and benzaldehydo, is iade between

the dipole moment of beta-nitrostyreno (4.51 D, benzene, 25C,.;

4.50 D, benzene, 250C., 4.27 D, dioxane, 250C.; reported by

Vasil/eva et J. (37), Sutton et1a. (38), and Gaebel and Wenzke (39),

respectively) and that reported for benzaldehyde (2.75 D) by

Sryth (36), it would be predicted that the contribution of an

interaction of the type postulated would be stronger in the

more polar be9t-nitrostyrenes than in the aldehydes.

Since the bet-nitrovinyl group would be expected to have

even greater steric requirements than the aldehyde group, and

since it was postulated that the steric requirements of the




-77-


ortho-aldehyde group in 2-(2-vinyloxy)ethoxybenzaldehyde

prevented the formation of the ring and thus any contribution

from an interaction of the type postulated, then it would be

expected that there would be no contribution of this type in

the structure of 2-(2-vinyloxy)ethoxy-B-nitrostyrene. Thus

only the linear form should contribute to the structure of this

co ounr ,nd the physical properties of this compound and those

of 2-(2-ethyloxy)ethoxy-B-nitrostyrene should be quite similar.

The dipole moments of-the vinyloxy compound (5.81 D) and

the ethyloxy compound (5.65 D) are actually quite similar,

differing by only 0.16 Debye units, a difference even smaller

than that encountered in the corresponding aldehydes. No

reported values for the dipole moment of 2-alkyloxy-5-nitrosytrenes

were found in the literature.

The infrared absorption spectrum of 2-(2-vinyloxy)ethoxy-

D-nitrostyrene shows two peaks at 1631 c- and 1605 cm1, as

would be expected. Although those peaks are slightly shifted

with respect to the positions of the corresponding peaks in

2-(2-vinyloxy)ethoxybenzaldehyde, this could well be due to

the solvent effect. 2-(2-Vinyloxy)ethoxybenzaldehyde, being a

liquid, had its infrared spectrum determined as a pure liquid;

2-(2-vinyloxy)ethoxy-P-nitrostyrene, on the other hand, being

a solid had its infrared spectrum determined in carbon

tetrachloride solution. Also, the position of the strong peak

at 1198 cm"1 (8.35 microns) in the infrared spectrum of the

beta-nitrostyrene is not.signific antly shifted from the "normal"

position of 1202 cm-1 (8.32 microns).




-78-


On this basis it would be expected that the ultra-violet

spectra of 2-(2-vinyloxy)ethoxy-P-nitrostyrene and 2- (2ethyloxy)-

B-nitrostyrene would be quite similar. An inspection of

Figure 8, p. 47, show that these two spectra are quite similar.

The only physical property that was determined for these compounds

that showed an anomolous discrepancy was the molar exaltation.

The molar exaltation values for all three isomers of 2-ethyloxy-

ethoxy- -nitrostyreno were very hich; therefore these values

can only be used with great reserve. Thus it may be stated that

2-.-vinyloxy)ethoxy-0-nitrostyree and 2-(2-ethyloxy)ethoxy-0-

nitrostyrenc probably have the same type of structure and that

an interaction of the type proposed does not have any significant

contribution to the structure of 2-(2-vinyloxy)ethoxy--O-

nitrostyrene.

3-(2-Vinyloxy)ethoxy-3-nitrostyrene has not been prepared

as yet and thus no further discussion of this isomer is possible.

So far in this investigation, within any series of

positional isomers, if the physical properties of any isomer

have shown a deviation from those of the remainder of the series,

suggesting the intervention of, and some degree of structural

contribution from, an interaction of the type that has been

postulated, this isomer has been the 4-isomer. This trend would

not only be expected to be continued by 4-(2-vinyloxy)ethoxy-B-

nitrostyrene, but also to be intensified. Thus it would be

predicted that the postulated ring form, IV (p. 6), would show

a stronger contribution to the structure of this compound than

it has shown to th structure of any other.




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The difference between the dipole moment of 4-(2-vinyloxy)-

ethoxy-0-nitrostyrene (5.43 D) and that of -(2-ethyloxy)ethoxy--

nitrostyrene (6.14 D) is 0.71 Debye units. This difference is

even more significant than its value would indicate, for, as

can be seen, the moment of the vinyloxy compound is the lesser,

the reverse of the situation encountered in the 2-isomers

(where the ring did not have a contribution). If this difference

in the dipole moments of these two compounds signifies the

contribution of the ring form to the actual structure of

4-(2-vinyloxy)ethoxy-'-nitarstyrene, as it suggests, the other

physical properties should also show a difference between these

two compounds.

The infrared spectrum of the linyloxy compound exhibits

only one peak in the range 1639-1618 cm-1, and this peak occurs

at 1621 cm"1 (6.17 microns). The "normal" 8.32 micron peak

has been shifted to 1193 ca- (8.38 microns), a shift of 9 cm".

A consideration of the physical properties of 4-(2-vinyloxy)-

ethoxy-&-nitrostyrene that have been discussed up to this point

would certainly suggest not only that the ring form has a

significant contribution to the structure of this compound, but

also that the contribution of the linear form is so small as to

escape detection (no peak was present in the infrared spectrum

of this compound at or near 1639 cm- ). Final, confirmatory

evidence would be expected from the remainder of the physical

properties.

An inspection of the ultra-violet spectra of these two

compounds shows that such is not the case, for the two spectra





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are quite similar. Thus, independently considered, the ultra-

violet spectra would indicate that the structures of the two

compounds would be the sane. The only explanation offered for

the lack of confirnatory evidence in the ultra-violet spectra

is that the change in the electronic structure of the vinyloxy

compound by the proposed interaction produces a change in the

position of a maximum that was outside of the region investigated.

Finally, a consideration of the values of the molar

exaltation of these cormounds shows that, even though the

ethyloxy cormound still has a much larger exaltation than the

vinyloxy compound (13.94 to 8.24, a difference of 5.60), it

was not as Iuch larger than the vinyloxy compound as was the

case in the 2-isomers (ethyloxy: 10.24; vinyloxy: 3.19, a

difference of 7.05). In conclusion it may be stated that the

dipole -oment data suggest that there nay be a contribution by

the ring form preacnt, the infrared data indicates that this is

the only form present, and the ultra-violet data indicates that

this form is probably not present, and the molar exaltation data

indicates almost nothing. Thus, until further investigations

can be carried out on these and related compounds, no definite

conclusions can be reached concerning the structure of

4-(2-vinyloxy)ethoxy-p-nitrostyrene.

5. Other Co.wounds.-An investigation, very similar to

this investigation, is presently underway, the objectives of which

are the preparation and the determination of the physical properties

of a third series of compounds. These compounds include:




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4- (2-vinyloxy)-ethoxyacetophenone, 4- (2-vinyloxy)othoxy-a-

methylstyrene, 4- (2-vinyloxy)ethoxy-a-methyl- -nitrostyrene,

4-(2-ethyloxy)ethoxyacetophenone, 4- (2-ethyloxy)ethoxy-c-

methylstyrene, and 4- (2-ethyloxy)ethoxy-c- nethyl-_-nitrostyrene.

It is hoped that this investigation will finally give the

conclusive evidence for the proposed interaction.

In conclusion one final note should be made concerning the

8.32 micron peak in the infrared absorption spectra of the

2-vinyloxyetho;zbenzaldehydes (cf. p. 3). Since the infrared

spectrum of 4-(2-ethyloxy)ethoxybenzaldehyde did not contain

this peak, the 8.32 0.02 micron peak can be unambiguously

assigned to the (linear) vinyloxy group.












CHAPTER IV

SUI.5'.Ar.Y

2-Vinyloxyethoxybenzene, 2-, 3-, and 4-(2-vinyloxy)-

ethoxybenzaldehyde, 2-, 3-, and 4.(2-vinyloxy)ethoxystyrene,

2- and 4-(2-vinyloxy)ethoxy-P-nitrostyrene, 2-ethyloxyethoxy-

benzene, 2-, 3-, and 4-(2-ethyloxy) ethoxybenzaldehvde,

2- and 4-(2-ethyloxy)ethoxystyrene, and 2-, 3-, and 4-(2-ethyloxy)-

B-nitrostyrene have been prepared. The dipole moment of these

conmounds has been determined. The infrared and the ultra-

violet absorption spectra of these compounds have been obtained.

The molar refraction and the molar exaltation of these compounds

have been determined.

A study of the experimentally determined physical properties

of these compounds has lead to the postulation of an electronic

interaction, in the form of a non-bonded six-membered ring,

similar to that proposed by Butler (40-42) and supported by

Jones (43), Marvel (44), Field (45), and Schuller (46), anong

others. Cram and Kopecky (47) have also proposed an analogous

type of interaction. Evidence for the contribution of this

type of interaction to the structure of 4-(2-vinyloxy)ethoxy-

benzaldehydc has beon gained.


-E2.











BIBLIOGRAPHY


1. G. B. Butler and J. L. Nash, J. AM. Chen. Sec., 72, 2538 (1951).

2. J. L. Nash, "Polymerization Studies of Unsaturated Derivatives
of Beta-Iitrostyrenes," Ph. D. Dissertation, University of
Florida, 1953.

3. G. B. Butler, _. An. Chem. Soc., 27, 482 (1955).
4. E. S. Gould, mechanism m and Structure in Organic Chemistry,"
Henry Holt and Co:apany, New York, New York, 1959, p. 217.

5. E. S. Could ib., p. 201.
6. M. I. Eatuev, E. N. Prilezhaeva, and M. F. Shostakovskii,
BM. aa. sci. U...S., Clsse sci. chg., 1947, 123.
7. M. L. V. Brey, "The Preparation and Properties of Vinyl and
Glycidyl Fluoroethers," Ph. D. Dissertation, University of
Florida, 1956.
8. M. L. Brey and P. Tarrant, J. k,. Chen. Soc., 79, 6533 (1957).

9. C. McKinley, U. S. Pat. 2,533,172, Dec. 5, 1950 to General
Aniline and FilM Corporation (C. J., A5, 3407 [19513).
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Pat. 630,926, Oct. 24, 1949 (C. A., t4, 4021 [19503).
11. A. Zahorka and K. Weimann, Ibnatsh, L9, 229 (1938) (C. A.,
92, 4415 [19383).
12. R. Paul, s. ch m. Franc (), 1, 971 (1934) (C. A.,
_22, 786 [1935]).
13. A. Kailan and S. Schwebel, oFnajth., 3, 55 (1933) (C. A.,
2L8, 2982 [19341).
14. (a) J. Levisalles, Bull. g. S=. France, 1958, 1021.

(b) U. Schollkopf, An Chem., 7, 260 (1959).

(c) S. Trippett, "Advances in Organic Chemistry," Vol. I,
Intersiience Publishers, Ine., New York, New York, 1960,
pp. 83-102.


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-84-


(d) R. C. Slagel, Illinois Se'innr, Nov. 17, 1961, pp. 92-101.
15. (a) J. Thiele, ar., _a, 1294 (1899).
(b) J. Thiele and 3. Haeckel, Ann., .2, 7 (1902).
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17. A. I. Vogel, J. r Soc., 1i~8, 1842.
18. F. Eisenlohr, Chen. Zentr. (;), ., 625 (1911).

19. C. F. Hauser, T. W. Brooks, 1M. A. Praynond, and G. B. Butler,
J. rg. (in press).
20. C. F. Hauser, M. L. Miles, and G. B. Butler, J. C e. r,
(in press).
21. K. Kirchner and F. Patat, hkromo. C~m. 251 (1960).

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American Cyanamid Company (_. A., .5, 17967 [1960]).

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(_. _A., ~ 14299 [19593).
24. F. Patat and K. Kirchner Naturwissenschaften, 45, 129
(A. _A., ., 14299 [1958]).
25. J. A. ~alchore, U. S. Pat. 2,745,824, ay 15 1956 to
American Cyananid Company (C. ,A, 5O, 12537 [1956]).
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5052 (1953).
27. J. W. Breitenbach and W. Thury, Anz. Akad. li ss. iJn.
'Moth. -natrw. Klasse, 83, 4 (19467 (_. ., !, 8735 [19493).
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"Physical Methods of Organic Cheristry," Part II, 2nd Ed.,
Interscience Publishers, Inc., New York, New York, 1949,
p. 1614.

29. H. Lunbroso, L)1. soA. S=. Franc, 1955, 643 (9. A., 49,
11340 [1955]).

30. N. C. C. Li, J. a=.* PILa., 2, 1068 (1939) L(. A., Z4, 297 [1940]).

31. C. Curran, J. An. Chen. Soc., 67, 1835 (1945).
32. H. Lumbroso and P. Rfupf, Bull. ,ac. chim. Fr-ane, 1950,
371 (C. A., 44, 7106 [19591TT




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33. H. Luwbroso, A. fac. ~ i. Toulouse, ci. nath,
et sci. hys., 14, 9 (1950) (L. A., Z8, 5783 1195j47.
34. K. B. Everard and L. E. Sutton, Nature, 1,62 104 (1948)
(C. A., 42, 8037 [1948]).
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36. C. P. Smyth, "Dielectric Constant and ;blecular Structure,"
The Chemical Catalog Corpany, Inc., New York, lieu York,
1931, p. 196.
37. V N. Vasileva, V. V. Perskalin, and V. G. Vasil^ev,
8)~" a. SSj SS, 14, 620 (1960) C. A. 12780

38. K. B. Everard, L. Kumar, and L. E. Sutton, J. Chem. SOc.
1951, 2807.
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(1938).
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3615 (1958).
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2748 (1959).













BIOGRAPHICAL SKETCH


Ronald E. Tho-pson was born on December 11, 1931, in

St. Augustine, Florida. He graduated from Ketterlinus High

School, St. Augustine, Florida, in 1949. He spent three years,

eleven months, and ten days in the defense of the country during

the Korean Conflict, being stationed in Texas and the Philippine

Islands. He attended the University of Florida, from which he

graduated in 1958 with the degree of Bachelor of Science in

Chemistry. He attended Wayne State University, Detroit, Michigan,

as a Parke, Davis, and Company Research Fellow, from which he

graduated in 1960 with the degree of Master of Science. He

returned to the University of Florida as a graduate research

assistant under Dr. G. B. Butler.

The author is a member of Gamma Sigma Epsilon, National

Chemistry Honorary Fraternity, and served as President of the

Beta Alpha Chapter, University of Florida, from 1961 to 1962.

He is a past Vice-President of the University of Florida Section,

Student Affiliates of the the American Chemical Society. He

is a omeber of the American Chemical Society and The National

Rifle Association.

The author is married to the former Roslyn Berman and is

the father of one child, David Earl. His hobbies are photography,

architecture, music, stanp collecting and money collecting.

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This dissertation was prepared under the direction of the

chairman of the candidate's supervisory committee and has been

approved by all members of that committee. It was submitted

to the Dean of the College of Arts and Sciences and to the

Graduate Council, and was approved as partial fulfillment of

the requirements for the degree of Doctor of Philosophy.



August 11, 1962




Dean, CHo-lge of Artsand Sciences




Dean, Graduate School

Sueyisory Comittee:


Chairman






































33 409




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