Jan. 20, 19.

55 SYNTHESIS
CONVENIENT OF a- AND P-ALKYLSTYRENES 369
1.0 g. (95.%) of Y crystallized (the yield using IV was 43%); Anal. Calcd. for CnH2:O: C, 89.31; H , 6.03. Found:
recrystallized from 60-90" ligroin, m .p. 93". C, 89.28; H, 6.22; ultraviolet absorption, decreasing from
Anal. Calcd. for C ~ ~ H P OC, O :87.99; H , 6.71. Found: 220-340 mp with pronounced shoulder a t 270 mp, e 9,600.
C, 87.89; H , 6.68; Amax 260 m p , e 15,500; Amin. 242 mM, Dehydration of cis-l,1,2,3-tetraphenyl-2-propen-l-ol (a
e 11,100; breadth of band a t E 12,000, 243-282 mp; no in- trans-cinnamyl alcohol) (XI) by refluxing 88% formic acid
frared bands a t 2.8-3.0 p or a t 5.8-6.1 p . (1 hr.) gave 1,2,3-triphenylindene in 99% yield (identified
a,B-Diphenylchalcone (VIII)lo: m.p. 153". Anal. Calcd. by mixture m a p .with an authentic sample17).
for C27HsO: C, 89.97; H , 5.59. Found: C, 89.74; H , 5.50; Dehvdration of [Link]-tetraohenv1-2-~ro~en-l-o1 f IX)
'

, ,A 242 m r , e 25,000; shoulder a t 285 mu, e 12,000. similarly gave 67% of '1,2,$-triph&yli;denke (kientified)'.
~~

1-Ethoxy-1,Z,3-triphenylindene17 was obtained as a by- 1,2,3-Triphenyli11dene17~18:m.p. 133-134". Anal.

product in one preparation of or$-diphenylchalcone (VIII) Calcd. for C~ZHZO: C , 94.17; H , 5.85. Found: C, 93.70; H ,
where technic21 (lion-dried) bromine was used and the ether 5.79.
solution was dried, evaporated and treated with ethanol; Reaction of phenyllithium with a,@-diphenylchalcone
m.p. 171-172' (Eil7, 172'). I t was characterized by analy- (VIII) , carried out exactly according to the above procedur?
sis and absorption spectra; A,, 245, 322 mp, e 26,200, for 11, gave 67% yield of 1,1,2,3,3-pentaphenyl-2-propene-
10,500; Amin 277 nip, c 3,500; no infrared absorption bands 1-01 (X11)"J; crystallized from chloroform-ligroin mixture,
a t 2.8-3.0 or 5.8-6.1 p . m a p . 164-169' (identified by m.p. analysis and spectral
1,2,3,3-Tetraphenyl-2-propene-l-o1 (IX) .-A slurry of 2 data, and the m.p. 217-218" of its acetate'").
g. of the ketone VI11 in 175 ml. of ether was added to 1g. of Anal. Calcd. for CasHz6O: C, 90.38; H, 5.98. Found:
lithium aluminum hydride in 50 ml. of ether with continued C, 90.00; H , 5.89; ,A, 265-280 mp, 7,500; Amin. 256
stirring for 20 min.; cf;ystallized from 60-90' ligroin; 2.0 mp, e 6,200; infrared band a t 2.86 p; none a t 5.8-6.1 p .
g. (99%), m.p. 93-103 . Slow recrystallization gave large (18) E. P. Kohler and W. E. Mydans, THIS JOURNAL,64, 4667
colorless needles of simi!ar wide melting range. (1932).
(17) E P. Kohler, A m . C h m z . J . , 40, 222 (1910). CHARLOTTESVILLE,
VIRGINIA

[CONTRIDUTION FROM THE DEPARTMENT

O F CHEMISTRY, INSTITUTE OF POLYMER RESEARCH,
POLYTECHNIC INSTITUTE OF
BROOKLYN]

Ionic Po1ymerization.l A Convenient Synthesis of CY- and P-Alkylstyrenes. The

Effect of an a-Alkyl Group on the Ultraviolet Absorption Spectra
BY C. G. OVERBERGERAND DAVIDTANNER^
RECEIVED
MAY28, 1954

A convenient synthesis of a- and 8-alkylstyrenes by the deacetylation of the acetates from carbinols I1 and I11 is reported.
Evidence is presented for the structure of the styrenes based on ozonoiysis and correlation of fractional distillation data and
ultraviolet absorption spectra. Steric inhibition of resonance in the case of or-alkylstyrenes is suggested based on the inter-
pretation of the ultraviolet absorption spectra.

In order to determine quantitatively the steric hydration3 or dehydr~halogenation~ of the appro-

effect of alkyl groups on the rate of addition of an priate alcohol or alkyl halide, respectively, for the
ion pair to a vinyl group by use of the copolymeri- preparation of a-alkylstyrenes usually gave mix-
zation technique, a series of pure CY- and P-alkylsty- tures of products, either due to double bond isom-
renes have been prepared. This paper reports the erization or rearrangement of the carbon skeleton.
preparation and characterization of I, R = CzHb, Reported decarboxylations of P-alkylcinnamic acids
R' = H; R = n-C3H7, R' = H ; R = iso- were unsatisfactory for large scale preparation due
C3H7, R = H ; R = H, R' = CHr: R = H, R' = to small yields5 Since deacetylation is known to
CzHs and R = H,R' = n-C3H7. Copolymerization proceed through a cyclic mechanism without rear-
data will be reported separately. rangement,6 this method seemed preferable for the
R preparation of pure a-alkylstyrenes.
0
I/
0 0-C-CHs
It I
CsHj-CH-CH2-O-C-CH3 CsHs-CH-CH2-R
1
Although these styrenes have previously been R
prepared in a variety of ways, we wish to report a I1 I11
convenient preparation for the pure monomers by
deacetylation of I1 to obtain the a-alkylstyrenes The synthesis of the P-alkylstyrenes was eEected
and 111 t o obtain the P-alkylstyrenes. Furthermore, by a similar procedure, although many other use-
the preparation of the pure monomers by one in- ful procedures are recorded in the literature (Table
vestigator has made i t possible to compare their 111).
physical properties. (3) (a) Footnote a, ref. 1 , Table 111; (b) Mme. Ramart-Lucas and
Examination of the literature revealed that de- Mlle. Amagat, Comfit. rend., 184, 30 (1927): (c) P . Ramart and P.
Amagat, A n n . chim., 8, 263 (1927); (d) Mme. Ramart-Lucss and P.
(1) This is the fourth in a series of papers concerned with ionic Amagat, Bull. SOC. chim., 16. 108 (1932).
catalyzed polymerization; for the third, see C. G. Overherger, R . J. (4) (a) Footnote c, ref. 1, Table 111; (b) C. R. Hauser, P. S. Skell,
Ehrig and D. Tanner, THISJOURNAL, 7 6 , 7 7 2 (1954). R . D. Bright and W. B . Renfrow, THISJOURNAL, 69, 589 (1947).
(2) A portion of a thesis submitted by D . Tanner in partial fulfill- (5) Footnote a , ref. 2, Table 111; footnote b , ref. 1, Table 111.
ment of the requirements for the degreeof Doctorof Philosophyin the (0) E. R. Alexander and A. Mudrak, THISJOURNAL, 78,1810 (1980);
Graduate School of the Polytechnic Institute of Brooklyn. see also reference 18 lor discussion and earlier references.
370 C. G. OVERBERGER
AND DAVIDTANNER 1'01. 77

TABLE I
C~H~-CHCHZO-AC, CsH5-CHCHz-R
SUBSTITUTED
PHENYLETHYL
ACETATES I I
R OAc
B.P., Yield,' Carbon, % Hydrogen, %
'
R group 'C. Mm. ?25D
I d254 % Formula Calcd. Found Calcd. Found
a-CzHs 91 2 1.4915 0.9932 82 C12H1802 74.96' 75.13 8.38 8.46
a-n-CaH7 112 4 1.4882 1.0082 80 Ci3Hi802 75.69' 75.88 8.79 8.70
a-i-CsH7= 105 4 1.4903 0.9973 78 C13H1802 75.69' i5.41 8.79 8.71
B-CHP 82 4 1.4893 ,9891 83 CllH1,02 74.12' i4.23 8.19 5.36
P-CzH; 92 4 1.4866 ,9936 83 CIZHI~OV 74.96' 74.77 8.38 8.26
P-n-CaHtd 96 2 1.4852 ,9862 80 ClaH180:! 75.69' 75.69 [Link] 8.89
E. E. Blaise and A. Courtot, Bull. SOC. chim., [3] 35, 595 (1906), reported b.p. 135" (15 mm.), prepared from the alcohol
and acetic anhydride. Errera, Gam. chim. ital., 16, 323 (1886), b.p. 227-228", from 1-phenyl-1-chloropropaneand silver
acetate; P. A. Levene and R . E. Marker, J . Biol. Chem., 97, 379 (1932), b.p. 130' (35 mm.), d24, 1.006. V. Grignard,
Ann. chim. phys., [7] 24,467 (1901), b.p. 117-11S0 (8 mm.) ; P. H . Levine and R. E. Marker, footnote b, b.p. 134' (30 rnm.),
dzz4 1.0000; J. Kenyon and S. M. Partridge, J . Chem. Soc., 128 (1936), b.p. 125' (16 mm.), nZ0.5~ 1.4889, by heating the
carbinol with acetic anhydride in pyridine. P. A. Levene and R . E. Marker, b.p. 140' (20 mm.), Pa 0.988. e After
fractionation. 'Analyqis by Schwartzkopf Microanalvtical Laboratory, Elmhurst, N.Y. fl Analysis by Dr. K. Ritter,
Zurich, Switzerland.

For the preparation of the alcohols corresponding TABIE I1

to IT, the appropriate acids were reduced to the al- Pmor YSIS OF PHEYYLETHYL
ACETATES
cohols in high yield by means of lithium aluminum U't of
Wt un
hydride.' The secondary alcohols similar to struc- of cracked Sty-
ture I11 were prepared by reduction of the appro- R Drops/ Tub;
ace ace- rene,
tates, tates, yield,
priate ketone with the same reagent. With one ex- Group sec temp, C g g lllrU

ception (Experimental section) these alcohols (I1 CY-C~HS 1 3 492-506 35 3 76" 1.51383"
and 111) are known and described in the literature CY-CZH, 1 0 486-526 34 3 71" 1 5270"
prepared by other methods. The yields for these a-CnH5 1 . 0 540-562 25 0 79" 1 5272"
reductions are high (R = CzHh, R' = H, 89%; ay-CZH5 1 0 517-560 130 18 F i b I 5264*
R = n-CaHT,R' = H, 91%; R = iso-C3H,; R' = C Y - ~ - C ~1H0 ~ 520-550 83 0 60b 1 519Sb
H, 80%; R = H, R' = CHa, 87%; R = H, R' = a-~-C3Hj 0 i 550-560 101 0 60b 1 514C,b
n-C3H7, 83%) and this method is a preferred pro- 8-CH3 1 5 516-572 53 0 81" 1 5454"'c
cedure. Complete experimental details and com- P-CH3 I 0 539-588 46 0 85" 1 5449"'"
parison of physical data with other reported values P-CHI 0 7 520-550 806 0 83" 1 5461"'
are omitted for brevity and can be obtained from P-CIH, 0 7 420-468 26 5 59" 1 535f1"'~
the senior author on request. The acids used in the P-CzH5 10 540-660 70 0 60" 1 5425"d
reduction for the a-alkyl sequence were prepared B-CaHs 1 0 530-566 100 0 72" 1 5367"'d
by hydrolysis of the corresponding nitriles. I n one P-CzH5 1 0 508-520 100 0 74" 1 5359a'd
case ( a-isopropyl) hydrolysis of a-phenylisovalero- !3-CpH, 10 510-554 195 0 70" 1 534Vd
nitrile gave exclusively the amide under conditions P-n-CzH, 1 0 526-554 140 0 50' 1 5455*
in which a-phenyl-n-valeroni trile (a-n-propyl) gave a After distillation hut before fractionation. After
only acid indicating a considerable steric effect. fractionation. c After fractionation, n% 1.6487. After
The amide was then reduced directly to the alcohol fractionation, n% 1.5401
with sodium and ethanoL4b The properties of the isomers from the fractionation data strongly indi-
acetates are described in Table I. Pyrolysis ex- cate the proposed structures.
periments are described in Table I1 and the sty- For the /3-alkylstyrenes, careful fractional distill
renes are described in Table 111. All of the sty- ation gave a homogeneous product, but initial frac
renes we prepared were purified carefully by tions indicated the presence of an isomeric material
fractional distillation. For the a-alkylstyrenes, There was a steady increase in refractive index
the fractionations indicated only one product and from n Z 5 D1.5402 to 1.5498 for @-methyland 1.5380
it therefore is very unlikely that isomerization to 1.5439 for P-ethylstyrene in the initial fractions
of the double bond or rearrangement of the carbon It appeared a t first that pyrolysis had resulted in
skeleton had occurred. Further confirmation of the isomerization of the double bond. This view
the structure of the a-alkylstyrenes was afforded by was supported by ultraviolet absorption spectra of
ozonolysis. Formaldehyde and ethyl phenyl, pro- lower boiling fractions (Table V) which gave lower
pyl phenyl and isopropyl phenyl ketones were the extinction coefficients. Any migration of the
only products found on ozonolysis of a-ethyl, a-n- double bond out of conjugation with the ring would
propyl and a-isopropylstyrenes, respectively. decrease absorption. However, reaction with po-
Formaldehyde dimethone and the 2,4-dinitrophen- tassium hydroxide a t high temperatures of frac-
ylhydrazones of the above ketones were isolated in tions having the lower intensity resulted in no
greater than 50% yields. hlthough this evidence change in the boiling point or refractive index of
does not exclude the possibility of small amounts of the starting materials indicating that the double
isomeric products, these degradative products bond already had been conjugated with the ben-
along with the absence of any indication of other zene ring. This suggested that the lower boiling
(7) (a) R. F. Nystrom and W. G. Brown, THISJ O U R N A I , 69, 1197 product was a cis isomer and we will report on
(1947); (b) R. F . Nystrom and W. G. Brown, i b i d . , 69, 2548 (1947). this problem in the future.
Jan. 20, 19ij5 CONVENIENT OF a- AND p-ALKYLSTYRENES
SYNTHESIS 371

TABLE
I11
SIDECHAINALKYLSUBSTITUTED
STYRENES
Percentage compositionf
B.P., Carbon Hydrogen
R group "C. (atm.) n25~ d% Formula Calcd. Found Calcd. Found
a-CzHSO 181 1.5264 0.8868 CioHiz
cy-n-CsH? 201 1.5195 .9042 C11H14 90.35 90.50 9.65 9.59
a-i-CaH? 192 1.5146 .8954 CiiHi4 90.35 90.30 9.65 9.64
&CH$ 176 1.5487 .9155 CpHio 91.46 91.27 8.56 8.57
P-CzHj" 200 1.5401 ,9070 CioHi2 90.84 90.90 9.15 9.16
(I S. Sabetay, Bull. soc. chim., 141 47,614 (1930), reported b.p. 177-180' (742 mm.), T Z ~ 1.5262,
~ D prepared by the action of
anhydrous potassium hydroxide on 2-phenylbutanol-1; J. D. A. Johnson and G. A . R. Kon, J. Chem. SOC.,2748 (1926),
b.p. 81-82' (20mm.), [Link] boiling @-ethylcinnamicacid with 50% sulfuric acid; oxidation with potassium permanganate
gave propiophenone. M. Tiffeneau, Ann. chim. phys., [8] 10, 322 (1907), b.p. 198-202", do 0.9138, by decarboxylation of
B-propylcinnamic acid dibromide; Johnson and Kon, footnote a, b.p. 86' (14 mm.), 3 3 4 7 % , by boiling P-propylcinnamic
acid with 50% sulfuric acid, oxidn. with potassium permanganate gave butyrophenone. A . Klages, Ber., 36,3688 (1903),
b.p. 82' (12 mm.), 191-192" (753 mrn.), d13.840.8991, %13D 1.5181, by heating l-chloro-l-phenyl-l,2-dimethylpropane with
pyridine a t 125'. oxidation with chromic acid yielded isobutyrophenone; Johnson and Kon, footnote'a, b.p. 89' (15 mm.),
31-38%, by boiling P-isopropylcinnamic acid with 50% sulfuric acid, oxidation with potassium permanganate gave isobutyro-
phenone. A. Klages, Ber., 36,2572 (1903), b.p. 177" (756 mm.), dZo40.9141, POD 1.5492, by warming l-chloro-l-phenyl-2-
bromopropene-1, with sodium and alcohol; A. Bruylants, Bull. sot. chim. Belges, 59, 421 (1950), b.p. 64" (10 mm.), d16r
1.5524, by dehydration of the corresponding alkylphenylcarbinol with a trace of H2SO4, side reactions led to
0.9158, n 1 5 ~
ketones and to cyclic trimers of the corresponding ketones; L. Bateman and J. I. Cunneen, J. Chem. Soc., 2283 (1951),
b.p. 65' (14 mm)., nl'D 1.5490, by isomerization of allylbenzene. A. Klages, Bet-.,37,2312 (1904), b.p. 89-90' (15 mm.),
dl64 0.9124, +D 1.5414, from 1-chloro-1-phenylbutane and pyridine a t 125", A. Bruylants, footnote d, b.p. 76' (10 mm.),
d% 1.5467, by dehydration of the corresponding alkylphenylcarbinol with a trace of sulfuric acid, side reaction led to ketones
and tocyclic trimers; R. Ya. Levinaand N. A. Shcheglova, J . Gen. Chem. (U.S.S.R.),11,527(1941), b.p. 65.5-66' (4 mm.),
n2O~1.5378, d204 0.9006, obtained by isomerization of 4-phenyl-1-butene over A1201 a t 250°, dibromide. f Analyses by
Schwarzkopf Microanalytical Laboratory, Elmhurst, N. Y.
The marked difference in absorption between a- TABLE IV
alkylstyrenes, styrene and @-alkylstyrenes (Table ULTRAVIOLET
ABSORPTION
SPECTRAOF NUCLEAR
AND SIDE
IV)&is of interest. The extinction coefficient of CHAINALKYLSTYRENES
styrene is greatly reduced when an alkyl group is Absorption peaks
substituted in the a-position. The extinction co- Alkyl I I1 I11 IV
styrenes Xmax emax Xmax emsx Xmsx emax Xmsx emax
efficient maxima decreases progressively from @-C;Hs 251 17,640 .. .. 284 1125 293 725
14,620 for styrene to 11,400, 10,100, 9,390 and 7,800 P-CHs 251 17,300 .. .. 284 956 293 621
(hyperchromic shift) for a-CHs, CY-CZH~, a-n-C3H7 Styrene 248 14,620 273 768 282 759 291 534
and a-iso-C3H, styrene, respectively. There is a-CHs 243 11,400 .. .. .. .. .. ..
ct-C~H8 240 10,100 .. .. .. .. .. , .
also a small but significant hypsochromic effect. u-n-CzHr 239 9,390 ,. .. .. ,. .. .
This indicates that steric inhibition of resonance a-i-C3H7 234 7,800 .. ,. .. .. .. .,
may exist here and markedly effects the absorp-
tion spectra. The ultraviolet absorption spectra reason for this hypochromic effect then the higher
of P-methylstyrene and a-methylstyrene have been boiling fraction may be the trans form and the
reported previously. Kochghas discussed the spec- small amount of lower boiling fraction, the cis
tra of the @-methylcompound in detail.3c In the form.
case of P-alkyl groups there are two effects operat- Experimental lo
ing. The extinction coefficient (e) increases from Preparation of Carbinols .-A typical example is illus-
14,620 for styrene to 17,300 and 17,640 for @-CH3 trated. 2-Phenylbutanol-1 was prepared in 89% yield from
16.42 g. (0.1 mole) of a-phenylbutyric acid (Eastman Kodak
and P-CzHb, respectively, for the large absorption Co.) and 4.75 g. (0.125 mole) of lithium aluminum hydride,
maxima (Amax. 2510 A.) with corresponding in- b.p. 81" (2 mm.), n Z 41.5178.
~ In a typical experiment, the
creases in the second, 2840 A., and third peaks, product was obtained sufficiently pure to use directly with-
2930 A., as well. Here there is a small increase out distillation: b.p. 120-121" (15 rnm.), prepared by re-
duction of the amide with sodium and alcohol3b; b.p. 120;
toward longer wave lengths. In addition to a 121' (18 mm.), by reduction of the amidesa; b.p. 95-96
steric effect there may be additional resonance (4 mm.), by treating (2-~henylethyl)-ethyl amide with
contributions resulting from hypercon jugation. nitrous acid"; b.p. 122-123 (18 mm.), 75% by reduction of
A lower boiling fraction (n% 1.5446) of p-meth- the amide.4b
a-Phenylvaleronitrile was prepared from benzyl cyanide
ylstyrene had an extinction coefficient maxima for by alkylation with sodium amide and n-propyl iodide ac-
three peaks of 16,200 (Amax. 2510), 750 (Amax 2840) cording to the procedure described by Hancock and Cope12
and 455 (Amax. 2930), while a higher boiling fraction who prepared a-cyclohexylphenylacetonitrile. From 82 g.
(n% 1.5471) had 16,700, 970 and 620. A lower (0.70 mole) of benzyl cyanide and 128 g. (0.80 mole) of n-
propyl iodide there was obtained 88 g. (70%) of a-phenyl-
boiling fraction (n2'D 1.5372) of (3-ethylstyrene had valeronitrile, b.p. 96-98' (2 mm.), T Z ~ 1.5025
D (b.p. 255-
extinction coefficient maxima of 16,000, 1,030 and 261°, no yield given's).
640 while a higher boiling fraction (d5D 1.5392) AnaZ.I4 Calcd. for C11H13N: C, 82.97; H , 8.23; N,
had 17,700, 1,190 and 755. If steric effects are the 8.80. Found: C, 83.01; H, 8.37; N, 8.78.
( 8 ) The spectra have been deposited as Document number 4330 (10) All melting points are uncorrected.
with the AD1 Auxiliary Publications Project, Photoduplication Serv- (11) P. A. Levene, L. A. Mikeska and K . Passoth, J . Biol. Chcm., 88,
ice, Library of Congress, Washingtrn 25, D. C. A copy may be se- 27 (1930).
cured by citing the Document number and by remitting in advance (12) E. M. Hancock and A. C. Cope, O i g . Synlheacs, 26, 25 (1945).
$1.25 for photoprints or $1.25 Ior 35 mm. microfilm payable to: Chief, (la) R. H . Pickard and J. Yates, J . Ckcm. Soc., 96, 1017 (1909).
Photoduplication Service, Library of Congress. (14) Analyses by Dr. K. Ritter, Zurich, Switzerland; Dr. F .
(9) H P . Koch,J. Chcm. Soc., 1123 (1948). Schwarzkopf, Elmhurst, N. Y.
372 C . G. OVERBERGER
AND DAVID
TANNER VOl. 77

TABLE V
SPECTRA O F FRACTIONS
ULTRAVIOLET ABSORPTION O F @-METHYL
AND &ETHYLSTYRENE
Absorption peaks
I I1 I11
Alkplot yrene Fraction n% Wt.. g. X ~ S X( m d emax Xmax (me) emax Xmex (ma) einnx

@-CHI 1 1.5446 22 246 16,200 283 750 292 5 455

8-CHt 2 1.5456 22 247 16,200 283.5 934 292 5 GOO
8-CH: 3 1.5471 10 248 16,700 283 5 9i0 292 5 620
8-C2H6 1 1,5372 10 248 16,000 283 5 1030 292 5 640
8GHs 2 1 5387 10 249 17,700 283.5 1200 ,092 5 io0
8-CZH6 3 1.5392 3 250 17,700 283 5 1190 292.5 I?-
i50

a-Phenylvaleric acid was prepared by hydrolysis of a- a- and 8-Alkyl Substituted Styrenes h e p a r e d by Pyroly-
phenylvaleronitrile. The method of hydrolysis recom- sis of the Acetates.-A procedure similar t o the one
mended by Rossalymo16 is to heat the nitrile with hydro- for the pyrolysis of 2-alkyl-1,4-butanediol diacetatess was
chloric acid a t 180-190'; the procedure of Pickard and used with several experimental modifications. The a- and
Yates recommended boiling for 8-9 hours with dilute sulfuric ,&substituted acetates were added dropwise through a Pyrex
acid (3:2). Combining these procedures, 88 g. of the ni- glass tube (17 mm. i.d., 19 mm. 0.d.) mounted vertically
trile was refluxed with 75% of sulfuric acid and 10 g. of so- in an electric furnace, and packed with 6 X 6 mm. Raschig
dium chloride with mechanical stirring for 22 hours and the rings for 13 in., of which 12 in. were heated. The tempera-
product isolated in the usual way, b.p. 132' (3 mm.), m.p. ture of the "cracking oven" was obtained with the use of an
51-52', recrystallized from an alcohol-water mixture iron-constant and thermocouple junction contained within a
(b.p. 161-163' (10 mm.), m.p. 52Ol4)). piece of glass tubing, and placed outside and halfway down
2-Phenylpentanol-1, not previously reported, was pre- the length of the column. The thermocouple was placed
pared by reduction of 120 g. (0.67 mole) of a-phenylvaleric in this fashion since the pyrolysis was carried out a t atmos-
acid with 32 g. (0.84 mole) of lithium aluminum hydride, pheric pressure and it was necessary to have a closed sys-
b.p. 110' (6 mm.), n S 4 1.5123,91%.
~ tem at the top of the column in order to force the vapors
Anal. Calcd. for CllHlsO: C, 80.44; H , 9.82. Found: down into the receiving flask. Also, this eliminated any
C, 80.43; H , 9.98. possibility of channeling which might occur if the thermo-
a-Phenylisovaleronitrilewas prepared from benzyl cyan- couple were placed inside the tube as described in reference
18. The receiving flask contained a side arm leading to the
ide by alkylation with sodium amide and isopropyl iodide atmosphere and was cooled to Dry Ice temperatures. The
according to the procedure described by Hancock and Cope.12 drop time, oven temperature and yields are listed for various
From 246 g. (2.1 moles) of benzyl cyanide and 384 g. (2.26 pyrolysis experiments in Table 11.
moles) of isopropyl iodide there was obtained 263 g. (72%) After pyrolysis of the corresponding acetate, each mono-
of a-phenylisovaleronitrile, b.p. 106' (6 mm.), n 2 4 . 6 ~mer was distilled under reduced pressure through a Fenske
1.5032 (b.p. 245249" (765 mm.)le). type19 total condensation-partial take off fractionating
Anal. Calcd. for CIIHlqN: C, 82.97; H, 8.23; N, 8.80. column, 53 cm. in height, 12 mm. i d . , packed with '78 in.
Found: C, 83.07; H , 8.38; N, 8.95. class helices and surrounded bv an electricallv heated iacket.
2-Phenylisopentanol-1 was prepared by pouring a solu- ?he physical constants and analyses for thepure monomers
tion of 85 g. (0.48 mole) of phenylisopropylacetamide dis- are listed in Table 111.
solved in one liter of absolute ethanol into 132 g. (5.7 moles) Ultraviolet Absorption Spectra.-Ultraviolet absorption
of clean sodium according to the procedure described for spectra were determined with a Beckman quartz ultraviolet
the preparation of 2-phenylbutanol-1 .ab Originally the spectrophotometer using absolute ethanol as solvent. The
carbinol was t o be prepared by lithium aluminum hydride data for the ultraviolet absorption spectra of styrene and
reduction of the corresponding acid ; however, hydrolysis of the a- and &alkyl substituted styrenes are given in Table
a-phenylisovaleronitrile, instead of going directly t o the IV. and the data for various fractions of 8-methvl and B-
acid, yielded a product consisting almoqt entirely of the ethyl styrene in Table V.
amide. This was of interest since the hydrolysis was Attempted Isomerization of p-Alky1styrenes.-A proce-
carried out under conditions identical to those of the n- dure similar to the one described for the isomerization of
propyl compound in which the acid was obtained as the ma- eugenol to isoeugenol" was attempted with p-methyl and
jor product. The alcohol boiled a t 93" (4 mm.), Z * ~ D P-ethyl styrene. The monomers (20 g.) were each weighed
1.5160, 80% (b.p. 130' (15 mm.), no yield or refractive into a nickel crucible immersed in an nil-bath and powdered
index,8b b.p. 130-132" (15 mm.), 66%, no refractive index,3c potassium hydroxide was added until it rose above the solu-
b.p. 127' (15 mm.) by reduction of the ethyl ester of di- tion. The mixture was heated a t 160" for 3.5 hours and
methylatropic acid with sodium and alcohol17). then allowed to stand overnight. The solid "cake" which
Anal. Calcd. for C11H160: C, 80.44; H, 9.82. Found: formed was ground in a mortar, extracted with ether, aiui
C, 80.14; H , 9.75. distilled. There was no change in the boiling point or re-
fractive index of either monomer indicating that the double
Acetylation of the Carbinols.-In a typical experiment, bond was conjugated with the benzene ring.
95 g. (0.64 mole) of 2-phenyl-n-propylcarbinol, 153 g. (1.5 A second procedure was used in which p-methylstyrene
moles) or 142 ml. of acetic anhydride and 25 g. of so- ( n Z 41.5460) ~ was dropped into a copper container contain-
dium acetate was heated to boiling and allowed to re- ing solid potassium hydroxide pellets and heated in an oil-
flux for 10 to 20 hours. The excess anhydride was de- bath a t 231)'.
composed carefully by the dropwise addition of water while per tube which The dropping funnel was connected to a cop-
extended several inches below the potassium
the mixture was refluxing. An excess of water was then hydroxide so that the 8-methylstyrene might bubble through
added, the solution was allowed to cool, and poured into a
2-liter separatory funnel. The solution was then washed the liquid alkali. The pressure of the system was sustained
several times with portions of 20% sodium carbonate, cx- a t 80 mm. and the p-methylstyrene removed a t a rate of 30
tracting with ether each time until carbon dioxide evolution drops per minute. The distillate was redistilled through a
stops, and then washed with water until the solution was Vigreux-type column and the liquid showed no change in
neutral to litmus. The ether solution of the acetate was refractive index.
dried over anhydrous sodium sulfate, the ether removed, Ozonolysis of a-Alkyl Substituted Styrene Monomers.-
and the acetate distilled under reduced pressure through a The same procedure of ozonolysis was used for a-ethyl,
22-cm. Vigreux column. a-n-propyl and a-isopropylstyrene. About 3% ozone was
The physical contents, yields arid analyses of the acetates
are listed in Table I. (18) C. G. Overberger, A. Fischman, C. W. Roberts, L. 13. Arond
and J. Lal, THIS JOURNAL, 7 8 , 2540 (1951).
(15) A. Rossalymo, Ber., 22, 12.15 (1889). (19) T. P. Carney, "Laboratory Fractional Distillation." The Mac-
(16) F. Bodroux and F. Taboury, C o m p f . rend., 160, 531 (1910); millan Company, N e w York, N. Y., I W Q , p p . 111-115.
Bull. SOC. chim., [ 2 ] 7, 666 (1910). (20) S. J. Gokhole, J. J. S:tdborough a n d I T E . Watson, J . Indinw
( 1 7 ) E E. BIaisesnd A. Cwrt?!. i b i d . El 81. ,505 (1QM). l a s f . Sci., 6, 241 (1923).
Jan. 20, 1955 POLYENES
CONJUGATED AND ~POLYPHENYLS 373

passed through a solution of 2 g. of the monomer dissolved methone derivative, m.p. 0189°, 59%; 2,4-dinitrophenyl-
in 50 ml. of ethyl acetate until the reaction was complete. hydrazone, m.p. 190-191 , 45% (formaldehyde dimeth-
The reaction mixture was kept a t Dry Ice temperatures t o one, m.p. 189’; ethyl phenyl ketone 2,4-dinitrophenyl-
prevent the loss of any formaldehyde which might be liber- hydrazone, 191O)**; a-n-propylstyrene, methone derivative
ated during the course of the reaction. The reaction time of m.p. 188.5-189’, 52%; 2,4dinitrophenylhydrazone, m.p.
each experiment was approximately 45 minutes. Decom- 189-190°, 57% (n-propyl phenyl ketone, 2,4dinitrophenyl-
position of the ozonide was carried out by a procedure simi- hydrazone, m.p. 188 or 190°)en; a-isopropylstyrene, meth-
lar to that of Hurd and BlanchardZ1in which the ozonide one derivative, m.p. 189’. 53%; 2,4-dinitrophenylhydra-
was poured into 50 ml. of water and 10 g. of zinc dust and zone, m.p. 157-158’, 62% (isopropylphenyl ketone, 2 , 4
the mixture mechanically shaken for 20 minutes. The zinc dinitrophenylhydrazone, m .p. 163O. zx
dust was collected on a filter and the water layer separated A mixture of methone derivatives from the ozonide de-
from the organic layer in a separatory funnel. To the composition products of the a-ethyl, a-propyl and a-iso-
former there was added a solution of 36.4 g. (0.026 mole) of propylstyrenes were mixed together with formaldehyde di-
methone dissolved in 25 ml. of 50% ethanol and to the latter methone, m.p. 189’, with no depression of the melting
there was added a solution of 2.57 g. (0.13 mole) of 2,4-
dinitrophenylhydrazine dissolved in 20 ml. of concentrated point.
sulfuric acid t o which was added 20 ml. of water. Crystals Acknowledgment.--We wish to thank the Office
separated almost immediately in all experiments. The of Naval Research, Contract No. NR-343 (00)
methone derivatives were recrystallized from 95% ethanol
and ethyl acetate mixtures. The melting points and yields for their generous support of this work.
of the derivatives of the ozonide decomposition products (22) E. H. Huntress and S. P. Mulliken, “IdentiBcation of Pure
for the three monomers were as follows: a-ethylstyrene, Organic Compounds,” John Wiley and Sons, Inc., New York, N. Y.,
1941.
(21) C. D. Hurd and C. A. Blancbard, TRISJOURNAL., 71, 1461
(1950). N.
BROOKLYN, Y.

[CONTRIBUTION FROM INSTITUTE O F POLYTECHNICS, OSAKA CITY UNIVERSITY]

Absorption Spectra and Chemical Structures. I. Conjugated Polyenes and

p-Polyphenyls
BY K E N ZHIRAYAMA
~
RECEIVED
JULY 16, 1953

A study is presented of the dependence of spectral absorption on structure in polyene derivatives and p-polyphenyls. In
this paper conjugation of similar chromophoric groups is considered. I t is shown that the wave length of the first absorption
-
maximum may be expressed by (Am.=)* = A B C N ,where N is a proposed index defined by number of conjugated homo-
chromophores, number and type of substituents, and of spectroscopically effective structures.

It has long been known that definite relationships I n spite of the comparative agreement between
exist between the structure of organic molecules the values in column b and those observed, equation
and their visible and ultraviolet absorption spectra; 3 is not valid because the relation between X 2 and n
empirical and theoretical formulas have been ad- is obviously not linear‘ (see Fig. 1).
vanced relating the wave length of the first absorp-
tion maximum with the number of conjugated TABLE I
chromophoric groups. OF DIPHENYLPO POLYENES
ABSORPTIONMAXIMA IN BEN-
But the values calculated by these formulas do not ZENE
Obsd.,‘ Calcd.
always agree satisfactorily with the observed values. n mr a, mr b Bmp c. mr d , mr
However, we have found that the wave lengths 1 306 305 310 311 356
predicted by equation 1,l:in which n is the number 2 334 335 334 357 294
of conjugated groups, agreed well with the observed 3 358 360 358 412 339
wave lengths of the first absorption maximum. 4 384 382.5 380 445 366
(Anlaa)z = u + B ( l - C”) = A - BC“ (1) 5 403 402 400 480 395
(A = a +B) 6 420 420 420 505 416
The adequacy of this functional relationship is 7 435 435.5 438.5 532 438
shown in the following examdes.- K. W. Hawser, R. Kuhn and A. Smakula, Z . p h y s i k .
.
Chem , B29, 384 (1935).
a,o-Diphenylpolyenes : =- C H( = C H-
) . ~
a,a,w,w-Tetraphenylpolyenes:
For benzene solutions, equation 2 holds
(X&:)* = (38.08 - 30.81 X 0.934“) X lo4 mp* (2)
The values in column a of Table I calculated by
equation 2 are more satisfactory than those in col- Equation 4 holds for this series; the agreement be-
umn b calculated by Lewis and Calvin’s formula 32 tween the values for the parameter C in equations 2
(A,)Z = A + Bn (3) (C 0.934) and 4 (C 0.935) should be noted. The
or the values in columns t and d given by Dewar’s (4) Nevertheless, since the numerical disagreement between the
LCAO MO methodss values obtained by equations 2 and 3 are so slight, it m a y be conceded
that the results obtained with the Lewis and Calvin equation are supe-
(1) One possible justification for the functional relation (1) will be rior in the sense that the latter was derived on the basis of a physically
demonstrated in the appendix. signiEcant model. Thus far, our equation has been described merely
(2) G. N. Lewis and M. Calvin, Chem. Reus., 25, 273 (1939). as an empirical relation. In the appendix, however, a justification of
(3) M. J. S. Dewar, J . Chem. SOC.,3544 (1952). the new relation is given.