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CONDENSATION GP SOME ALK‘Y‘L
PHENYL CARBINOLS WITH PHENGL
IN THE PRESENCE 8F
ALUWNUM Ci-iLORVDE

Thesis for the Dogma 6% M. S.
?\*3§CH§GAN STATE COLLEGE
Henry Roger Ceur'i'ney

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CORDENSATION 0F SOLE ALKYL PHENIL CARBINOLS WITH PHENGL

IN THE PRESENCE OF ALUEINUH CHLUKIOE

By
Henry Roger Com-they

A IHESIS
Submitted to the School of Oraduntc Studies of Richigan
State College of Agriculture Ind Applied Sciencu
in patina. fulfillmnt of the mutant:
tar tho degreo of

MASH}? OF SCIENCE

Department of Chemistry
19h?

 

 

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Introductionoooo...............o..............oo
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EXperimental..................o.........o.o.....

I Preparation of Aromatic Aliphatic

carbiHOIBOOOQOQQQOOooooo-ooooooocntouoooo

II Aluminum Chloride Condensations..........
III Claisen Rearrangement....................
IV Derivatives..............................
Theoretical.....................................
Discussion......................................

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IETRODUCTIOH

Although previm workers in thie laboretory here condeneod
elkyl phenyl cerbinole with phenol, the study of then condoned-
tine ne etill incaplote.

The «tho ellgrlphenol one reported only in the condeneetia:
of propyl phoxvl eel-bind with phonol. Ite for-etial new be ex-
pected in ell condoneetione of this type. For thie roe-on it
no considered desireble to continue the :5to of the condensa-
tion of mm phony]. oerbinole with phenol. liethyl through emyl
phonyl oerbinola me propered, end omdanaed with phenol in the
promo of amnion chloride.

HISTORICAL

A canpleto review of the litereturo dueling with the elkyle-
tion of caustic empounde would be needlou repetition. hay
previous pepere heve furnished brief end teirly complete surveys
(1), (2), end (3). An may. survey on the role or llunimn
mmncmommmwwmm (h).

Sincethieworkieeetudyotthe Wtionofelkyl
phenyl curbinole with phenol in the presence of elmimn chloride,
mly those reseerchee dealing with this subject will be own-rind.

Eerlier workers in this lebweta'y who condensed elcohols
with phenol, used tee methods. Huston end Hsieh (20) devised e
procedure where the elcohol end phenol were diesolwed in petroleum
other, end the ole-imam chloride wee edded in portions. Eeterdehl
(2].)Ioditiedtheprooedm'ootauetenendfleiehby ueingnoeolvent
to cadence some secondary elcohde with phenol. Breiter (22) need
this method to condense octyl "elcohole with phenol. The second pro-
cedure develwed by Burton end Rodrick (23) mined of Impending
the eluimn chloride in petrolom other end edding e eolution of
phenol end oerbinol in petrolom other dropwiee tron e dropping
funnel.

irattic alcohols had not been condensed with ermtic com-
pounds in the presence of elminun chloride until Boston and
mm (21:) began their investigetime in 1916. Leter, they
extended their experiment (25) to eecondery elcohols with benzene
end elmimn chla'ido using netlwl phony]. oerbinol, ethyl phervl
carbinol end benelvdrol, obtaining diphenylmothene, diphenylpropeno

.2-

and triphem'lmetheno respectively. The temperature end amounts

of reegents were varied to find conditions for the greatest yield.
In preparing 1,1-diphenylethene they obtained the best yield (65)?)
by keeping the tempereture below 10°C and using one half of e
molecular equivalent of nethyl pherwl cerbinol end five moles of
beam. Under these conditions they eleo obteinod a box yield of
l,l-diphonylpropane. fiesta md I-‘riednann (Loc.cit.) repa't that
enexoeeeoteluinmehla'idetendstoelinineteephmyloren
tum radioel m- th. product «potion: if the tnperature is
not kept low.

Alkylatim of phenol by moons of methyl end ettwlphenyl car-
binols no reported by Huston, Lewis, end Grotunut (5) in 1927.

They obtained 33-351 p-Wdrcnq—l,l-diphenylethane, and 27-30;
I p-lvdroxy-l,l-diphenylpropeno from the two carbinols. Proof thet
the. entering group tekes the pare position on phenol was obtained
by oxidising the methyl ether to p-eethoxybeneophenone.

In 1926 Bartlett (6), working in this laboretosy condensed
butyl phetwl carbine). with phenol. a. obteined a 335‘ Yield of
p-twdrdxy-lfi-diphenylpontane, but it was not pure enough to re—
crysteuise or for. e derivative. He node no Mott!” ortho
isomer.

Huston and Strickler (7) oondmsed propyl phony]. eerbinol
with phenol in 1927 to obtein 20% p-Ivdroxy-lJ-diphenylbutane end
6% o-bydrouyql,l-diphenylbutene. Up to this tine the properetion
of the ortho alkylphenol hed not been reported. They also

-3-

prepared the ortho ieoeer by Cleieen'e (8) method or ring alkyle-
tion, ee additional evidence of its (motion.

Thu, a etudy of the eltylatim of phenol Iith alkyl phenyl
carbinole, initiated by m 81d co-Iem‘kere included the tint
four alkyl phony]. carbinole with the publication of Hutu: end
Strickler in 1933.

WWW“.
I Preparation of Aromatic- Aliphatic Carbinols

Amyl phenyl carbinol can be conveniently prepared by the
addition of a Grignard reagent to benealdehyde the best results
are obtained when heat is not applied (9) and particularly by
controlling the relative proportion of the reactants. In study-
ing ethyl phony]. carbinol, Keisenheiner (10) found that the best
results could be obtained when the Grignard reagent and the ban-
aaldehyde were in the propel-tin 3:2, otherwise large quantities
of bensyl alcohol and high boiling by—products are obtained.

The preparation or anal pheml carbinol will be described
indetail, the other whinolswerepreparedbythe s-aeethod.
See table I fa- data.

Preparation of A1131 Phergl Carbinol ‘

The reaction was carried out in a 5 liter three-neck flask
fitted with a mechanical stirrer, reflux condenser, and chopping
funnel. The condenser and dropping tunnel were fitted with cal-
ciun chloride tubes filled with a calcite: chloride-soda line nix-
turetoprotectthe reactioneixturetroenoistm'esndcarbmdi-
oxide.

Into the dry flask was placed 6.]; atoll! (153.6 3.) magnesium
turnings with 500 el. anhydrous other. To start the reaction
25 al. of en emyl bromide (B.P. 128-129 fibm,Ҥol.m) was
added. The remainder of the 6 moles (9hlg.) o! and bromide mixed
with one liter of anhydrous ether, was added dropwise when it was
evident thatthereactimhad started. hedxturewas stirred

.5...

for two hours after addition of the bromide then allowed to’ stand
overnight. -

Il'he Grignard reagent was analysed by Gilmsn'e (ll) method
in which an aliquot was hydrolysed with standard acid, and back
titrated with standard base. Starting with 6 moles amyl braids,
5.? moles (9535) Grignard reagent was obtained.

The Grignard reagent eas packed in ice and 3.8 moles 0402.83.)
freshly redistilled bonsaldelvde (B.P. 17h-l78°c./7h3 mm.) in one
liter anhydrous other was added dropwise. After addition was com--
plete thenixturewas stirredfortwohmrsandallowedtostand
overnight. Arter- mdrolysis with ice and dilute lurdrochloric acid,
the organic layer was separated. The water layer was extracted
four times with 150 nl. ether. The ether extracts were canbined,
washed with 10% soditm bicarbonate then water and dried over anrvo
drous sodium sulphate. The other was removed (distilled) at atmos-
pherio memo and the residue fractionated at reduced pressure.

After three distillatials, h73.5g. 70% m1 pheml carbinol
was obtained, boiling at 128431°c./6m.

 

 

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EXPERIEEHTAL
II Aluminum Chloride Condensations

To ascertain which.nethod‘weuld give better yields in condens-
ing secondary aliphatic-eroaatic alcohols with phenol, two condense-
tions were carried out.‘ One mole of butyl phenyl csrbinel‘sas con-
densed‘with phenol according to the.method of Huston and Hsieh (20).
The carbinol and phenol were dissolved.in anhydrous petroleum ether,
and the aluminum chloride added in portions. The result‘was (86.183.)
36% crude alkylphenol, boiling at 155-166°c. Am. A second conden-
sation was carried out using the method of Huston and Hedrick (23).
The aluminum chloride was suspended in anhydrous petroleum ether and
a.nixture of phenol and carbinol in petroleum ether added dropiise.
One mole of butyl phenyl carbinol by this.aethnd.preduced.only
(56.965?) m crude allqlphenol, boiling at 155-466°c./l sin. The
temperature during the condensations'was not allowed to rise above
30°C.

To determine the effect of taperature on the yield at “kyl-
phenol, two condensatiens‘eere carried out. One-fourth sole or
methyl phenyl oarbinol‘ees condensed with one-fourth sole phenol
using one-eighth.nole aluainun chloride according to the procedure
of Huston, Lewis and Grotenut (S) modified.by using anhydrous
petroleum other as a solvent. When the telperature was kept below
ho° c. during addition of the alumina: chloride (20.16 g.) In;
p-hydroxy-l,l-diphenylethane was produced. a second condensation

was carried out under similar conditions but the temperature during

-8-

addition of to. allmimm chloride was not allowed to exceed 10°C.,
the yield of p-hydroay-lJ-diphenylethane increased to (22.58g.)
héz.

* To determine the effect of low temperature on the condensa-
tim of longer chain carbinols, one—half mole butyl phenyl car-
binol was condensed with .6 I010 phenol using .25 mole aluminum
chloride and pets-elem ether. The temperature was held under 10°C.
Under these conditius phenol crystallised on the side of the flask
and the reaction aixture retained yellow. After eight hours at
10°C. the reaction aixture was allaed to were up to roan tempera-
ture and stirred fa' four hours. The characteristic deep red addi-
tion product was formed and a 36% yield of alkylphenol resulted.
This is evidence that a longer carbon chain alcohol, requires a
higher temperature for condensation.

A - Condensation of Methyl Ml Carbinol With Phenol

a as liter three—neck flask was fitted with a mercury sealed
mechanical stirrer, condenser containing a thermaneter and an addi-
tion tube for introduction of the anhydrous alminue chloride fro.
a shaker. The follaing reagents were introduced into the flask:
.hl mole (50 g.) methyl phewl cubinol, .50 aole “7.50 z.) phenol
and 1‘00 .1. anlvdrous petroleu other. The anlwdroue alminua
chloride was added in snall partials over a period of he hours
while the teaperature nae held belw 10° C. using an ice bath.
A pink color was first produced, then as the color deepened to an

orange, gaseous hydrogen chloride was given off and a gummy addition

-9...

product formed. The mixture was stirred for eight hours and then
allowed to stand twelve hours before hydrolysis with ice and dilute
hydrochloric acid. The organic layer was separated, and the water
layer extracted three times with SW. of other. The ether extracts
were combined and washed with 10% sodium bicarbonate to remove the
acid and than water to remove the base.

The ether extract was dried over anhydrous sodium sulphate.
The ether was distilled off at atmospheric pressure and the residue
fractionated at reduced pressure using a 10 in. heated Vigreux
column. d

_ The following fractions were obtained:

up to 83°c./18mn. 7.10 g. phenol discarded

(l) 75 - 93°C./lmm. 20.22 g. phenol and carbinol

(2) 131 .- 150°C./lm. 113.30 3. alkyl phenol

(3) 11.8 - lSo°c./lmm. 5.16 8. alkyl phenol

(h) Residue 11.1.2 3.
Fraction'(2) partially solidified, fraction (3) solidified imme-
diately. Fraction (2) on redistillation crystallised giving 1.1.22 g.
boiling at lhB-lSO°C./lm. This gives a total yield of (1.6.1.5 g.)
57% p-mdroxy-ln-dlpnanrlotme. The solid as recrystallised tron
petrolem ether to a constant halting point, foo-ling needles aelt-
lng at S?-57.S°c. Human, Lewis and Grotemut (5) prepared
WW-lfi-diphenylethane, obtained 33-351 yield and report a
melting point or 57-58%. and a boiling point of 168-170°C./5nn.
he ortho substitution product was eomected but not formed in

~10-

quantities sufficient for isolation.
B - Condensation of Ethyl Phenyl Csrbinol With Phenol

The condensation was carried out using the same procedure as
in the condensation of methyl phenyl carbinol with phenol, except
that the temperature of the reaction aixture was held under 15°C.

when the aluminu- chloride was added. The reagents were as follows:

.75 nole (102 g.) etlvl phenyl carbinol
.875 mole (82.3 g.) phenol

.750 ml. anlwdrous petroleum ether

.375 mole (50.0 g.) aluminum chloride

The first addition of aluminum chloride produced a yellow
color which changed to orange then to blue. Gaseous hydrogen
chloride was given off and the calm renained purple, after two-
thirds of the almimss chloride had been added. The folla'ing frac—
tions were obtained from the first distillation:

(1) up to 83°C.],l8m. 17.36 3- phenol

(2) 65-90°c./hm. 10.81. g. phenol and carbinol
(3) 133-170°C./6m. 12.77 g.

(h) l70—l7S°C./6nn. 66.21. g.

(5) mm. ‘ 53.75 g.

7 hactiens (3) and (h) were redistilled giving the following
fractions:

(1) 1h5-1h7°C./lnm. 2.82 g. {301.5828
(2) 1&7-15h°c./1m. 2.1.8 g. n§°l.sasa
(3) lSli-lS7°C./lmn. 36.83 g. n§°1.586h
(14) 157°C./1mn. 25.118 g.
(S) Residue 12.53 g.

Fraction (1) was undoubtedly the ortho substituted phenol but
it is formed in such a small amount it is impractical to work with.
Fraction (2) was a nixture of ortho and para substituted phenol.
Fractions (3) and (h) solidified, they were the main product,
p-hydrory-l,1-diphstwlpropane. The overall yield of ctho and para
substituted phenol was (67.61 g.) 113$ with (2.82 g.) 2% o—hydroxy—l,
l-diphenylpropane and (62.31 g.) 39% P‘WM~1,l-diphenylpropane.

The solid was recrystallised from ligroin to a constant neit-
ing point of 66-67°c., forming very fine crystals having a powdery
appearance. The bensoyl derivative formed rectangular crystals
melting at 67°C. .

Huston, Lewis and Grotonut (5) prepared p-hydreo-l,l-dipnony1-
prepane, obtained a 27-30; yield and repa't a boiling point of
175-177°C./6nn. and a aclting point of 61.5%. The bensoyl deriva-
tive melted at 67°C.

C - Condensation of Propyl Phetgl Carbinol With Phenol

The condensation was carried out using a procedure siailar to
previous condensations, but the temperature of the reaction Iiature
was not allowed to rise above 25°C. The following reagents were used:

.12..

.60 mole (81.2 g.) propyl phenyl carbincl
.72 mole (67.68 g.) phenol

500 nl. anhydrous petroleum ether

.30 mole “0.00 g.) aluminm chloride

The first addition of alminm chloride produced a pink
color which turned to purple on addition. of more aminum chloride.
Gaseous hydrogen chloride was given off and the usual gunmw red-
purple addition product was formed.

The folluing fractims were obtained Iran the first distilla-

tiom

' (1) up to 83°C./18ms. (75.72 3.) other a phenol
(2) 60~89°C./lle. (25.0h g.) phenol & carbinel
(3) 97-1h8°c./1mm. (15.57 g.)
(h) 1h8-151°c./1In. (22A? 3.)
(5) 151-159°c./1m. (32.12 g.)
(6) Residue (28.67 g.)

Fractions (3) (h) and (S) were refractionated several times.
The ortho and para substituted phenols were difficult to separate
by distilletion because of the ease with which they superheat.
The following tractims were finally obtained:
(1) m9-131°c./1m (13.75 3.) £01.58”
(2) 151-151°c./1-. ( M38 5.) n§°1.saoo
(3) 157-159°c./1n. ._ (32.88 g.) $1.5m
Fractiu (l) was e-lxydroxy-l,l-dipherw1butane, tractim (2)
a nixture of the wtho and para substituted phenol and traction
~13—

(3) p-‘hydroxy-l,l-diphemr1butane. This last fraction solidified
on cooling. The overall yield of alkyleted phenol was (50.61 g.)
37:: with (13.75 g.) 101 o-lvdroxy-l,l-diphenylbutane and (22.h8 g.)
2M! p-mdroxy-lJ-diphenylbutane.

The solid para substituted phone]. was recrystallised from
petroleum ether to a cmstant melting point of h6-h7°C. The ban--
sqirl derivative forms long rectangular crystals melting at 70-71%.

' Huston and Strickler (7) Prepared o—hydrm-lA-dephenyl-
butane by two hethods. They obtained a 6;: yield using alminun
chloride and a 12-13% yield by the Claisen rearrangsnent of the
other. They report a boiling point of mauve/em. button and
Strickler (Loo. cit.) also prepared p—hydroxy-lfi-diphenylbutme.
TheyobtainedayieldefMandreporttheboilingpointas
Bis-156° ./6m. and the ulting point as b9-50°c. The bonsoyl de-

rivative melted at 70—71%.

D - Condensation of Butyl Phemrl Carbinol With Phenol
The first condensation was carried out in the usml Jenner,
the temperature being held under 30°C. during additim of elmimn
chloride. The following reagents were used:
1.0 male (161; g.) butyl pheqyl carbinol
1.2 mole (112.8 g.) phenol
1000 ml. anhydrous petroleum ether
.5 mole (66.6 g.) alminun chloride
The first addition of aluninun chla'ide produced a violet
color which deepened on addition of we aluninm chloride to a
".11"

red-violet. Gaseous hydrogen chlcide was liberated and the usual
puny-red addition product formed. The following fractions were

obtained for the first fractionation:

(1) 60—85°c./18nn. 311.58 3. phenol

(2) 7h-86°c./1m. 17.75 g. phenol n carbinol
(3) 125—133°c./1m. 8.15 g.

(h) 150—180°c./1nn. 96.08 g.
8 (S) 180—200°C./1m1. 13.58 g.

(6) Residue 68.33 8.

Fractions (1) end (2) were discarded after several distilla-
tions the following fractions were obtained.
(1) 155-157°c./1m. 16.65 g.
(2) 158-162°C./lm. 12.06 g.
(3) 163-165°C./1m. I 20.32 g.
(h) 165-166°c./1m. 37.15 g.

Fraction: (1) was o—twdrm-l,l-dipheny1pentene, fractiais (2)
end (3) n nixture of ortho and “para substituted phenol, and frac-
tion (h) Wdrory-lJ-diphenylpontene. The para alkylphenol sol-
idified on standing. The overall yield of alkylphenol was (86.18 g.)
361, with (16.65 g.) 7% pure o—hydrooq-l,l-diphenylpentane and
(37.15 g.) 15% pure p-hydroxy-l,l-diphexmlpentane.

A second condensation was carried out using the method of
Huston and Rodrick (23). The apparatus was the same as in previous
condensations except that a drapping funnel was substituted for the

aluminum chloride addition tube. One—half nole (66.6 g.) alueimn
.15.

chloride was suspended in 700 ml. anhydrous petroleum ether in a
[twoéliter three-neck flask. 'A mixture of 1.2 mole (112.8 g.)
phenol, 1 mole (16h g.) butyl phenyl carbinol and 200 ml. anhy-
drous petroleum.ether was added dropwiee over a period of 6 hours.
ifter one hour e.yellow solid adhered to the sides of the flask,
and gaseous hydrogen chloride was evolved. Twenty minutes later
the color deepened to a reddwiolet. The Iixture was stirred h
hours after the addition was complete, and allowed to stand 10
hours before hydrolysis. Fractions Obtained from the first distil-

lation are as follows:

(1) 60-85°C./18 um. 29.56 g. phenol

(2) 80—9o°c./1mn. 17.30 g. phenol & cerbinol
(3) 1h5-175°c./1mm. 6h.5h g.

(h) 180a230°C./lmm. 12.86 g.

(S) Residue 53.60 g.

Fractions (1) and (2) were discarded and the others redis-
tilled several times. The following fractions were isolated:

(1) 155-158°c./1-. 11.82 g.
(2) 159-162° ./1nn. 3.67 g.
(3) 161-163°C./1m. 28.27 g.
a.) 163-166°c./1m. 7.97 8.

Fraction (1) was o—hydroxy-l,l-diphenylpentene, Fraction (2)
a mixture of ortho and para substituted.phenols, and fraction (3)
and (h) p-hydrony-i,1-dipbony1pentono. Fractions (3) and (t)
-16-

solidified on standing. The overall yield of alkylphenol was
(56.96 3.) 2b,: with (11.82 g.) 5;: pure o-hydroxy—Ll-diphenyl-
pentane and (36.21; g.) 15,! pure para iemner.

The corresponding fractions of allquphenol firm the two
condensations of butyl phenyl eerbinol and phenol were combined and
redistilled in an attmpt to separate the ortho and para elkyl-
phenols more completely. The remain; fractions were obtained
from two moles of carbinol:

(1) 155-157°c./1m. 52.25 g. ,n§°1.5685
(2) 157-16h°c./1-n. 5.12 g. n§°1.5665
(3) 16h-166°c./1-. 86.16 3. (solid)

Fru two moles of the carbinol, the two methods of prepara—
tion gave an overall yield of alkyl phenol of (11311.13 3.) 301
with fraction (1) (52.25 g.) 10% e-m'droxy-lfl-diphenylpentane
and fraction (3) (86.16 g.) 20% p—hydroxy-l,l-diphenylpentme.
The solid para isomer was recrystallised frm petroleum ether
fuming fine needles melting at 35-36%.

Bartlett (6) condensed butyl phmyl earbinol with phenol in
this laboratcry in 1926. He reported a boiling point of 17o-171°c.
/sm. to:- p—hydroxy—lJ—diphenylpentme but no ulting point, and
did not identify the ortho ism.

Since o-kwdroxy-lA-diphexwlpentane has not been reported in
the literature, a carbon hydrogen analysis was carried out with

the following results:

.11.

Sample I .OObTBBg

Sample 11 .009276g
Calculated for 017 H20 0

Sample I found

Sample II found

002,.01h79h H20, .003510
002..016hlh H20, .003916
c, 8h.9hz H. 8.398
c. 8h.75£ H, 8.21%
c, 8h.85% H, 8.31%

E - Condensation of m1 Phenyl Carbinol‘ with Phenol

This condensation see carried out under conditions identical

with the first condensation of hutyl phenyl carbinol, the tempera-

ture was held under 30°C. while the aluminun.chloride was added

over a.peried of two hours. The reagents used were as follows:

1 sole (1783.) In]. phewl carbine).

1.2 3010 (112.8 to)

phenol

1000 ml. anhydrous petroleua.ether

.5 mole (66.63.) aluminum chloride.

The fractions isolated from the first distillation were as

follows:

(1) up to 85°C./18mm. 56.733. some other & phenol

(2) 7h-105°c./1nm.

(3) 106-172°c./1mm.
(h) 172-173°c./1-u.
(5) 173-175°c./1m.

(6) 175-230°C./lln.-

(7) Residue

11.20 g. carbinol
35.7h g.
21.82 g.
61.20 g.
66.9h g.
2.30 g.

Fractions (1) and (2) were discarded, the others were redistilled

several times resulting in the following fractions:

.13-

(1) 115.16600e/IMe 5038ge

‘(2) 166-171°c./1mm. 9.05g.
(3) 171-173°c./1m. 39.23g. .30 1.5600
(1.) 178-178°c./1m. 611.38g. .30 1.5601.
(5) 178-183°c./1mm. 9.8hg.
(6) Residue 52.3g.

One mole of carbinol gave an overall yield of (103.61g.) 111% sub-
stituted phenol (fraction 3 and h), with fraction ( 3) representing
(39.233.) 15% o-kwdrmq-l,l-diphenylheme and fraction (1;) repre-
senting (611.383.) 25% P-lvdroxy-l , 1-diphezvlhexane. The para
isomer solidified in the ice box but raisins an oil at roan towers-
ture. It would not crystallize from petroleum ether or hexane
like similar eupounds, but formed a crystalline 04- naphthylure-
thane like other para substituted phenols.

Neither ortho nor para hydroxy-l,l-diphenylhexane has been
reported in the literature, carbon-hydrogen analysis were carried
out as follows: I

o-hydromy-l , 1-dipheny1hexane

Sample I .ooh736g. 002, .01h693 H20, .003595

Sample II .ooh332g. 002, .013h5 8,0, .003303

Sample I found c, 8h.61% _ H, 8.56%

Samplo II found c, 8h.58% H, 8.52%
p-hydroxy-l , l-diphenylhexane

Sample I .003h783. 002, .010830g. H20, .002778

Sample II .0033933. 00,, .0105863. 320, .002666

.19..

W. I found C, 8he92.‘ B, 8e92f’

Saple 11 found c, 85.09% H, 8.79";-
Calculated for 0153.220 oaths-8,: u, 6.72%

40-

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~21-

EXPEREENTAL
III Claieen Rearrangement

A. Preparation of o-Hydroxy-l,1-diphenylpentane

In order to determine the characteristic difference between
the ortho and para substituted phenols, the ortho canpound was
prepared by Claisen's method of ring alkylation. (8) He shows
that ortho alkylation of phenols result when sodium phenolate is
heated with certain allq'l halides in a non-dissociating medium.
Praparation of :- Chloroamylbensene

This compound was prepared by the method of Kharash and
Kleiman (26). Dry hydrogen chloride was bubbled thru .5 mole
(82g.) of butyl phenyl carbinol, a water layer formed after the
secmd hour, mdrogen chloride was bubbled thru fa' one hour we
and the mixture was allowed to stand overnight at -lO°C. The
water layer was separated, and the 4' ehloroamylbensene washed with
water and dried over a anhydrous calciun chloride to remove water
and unreaeted carbinol. The 4-chloroamylbensene was used in the
following condumation without further purification.
Condensation of d-Chloroamylbensene and Sodim Phenolate

In a 500 ml. three-neck flask fitted with a condenser and
thermometer, .112 mole (9.70g.) finely chopped sodim was suspended
in 150 ml. of anhydrous toluene. Then .15 aole (112.33.) phenol
was added, after a few minutes a vigorous reaction took place
which gradually diminished. The mixture was refluxed at 120°C.
for 3 hours until all the sodim reacted, then cooled and the

-22-

chloromylbensene added. The resulting mixture was refluxed
for thirty-two hours. Then it was cooled and washed with water.
The mixture was distilled to 120°C. to remove water and toluene.
The residue was dissolved in 250 ml. or Claisen's (27) alcoholic
potassium lwdroxide solution and extracted four times with so al.
petroleum ether. Vavon and Zakaria (28) root-mend that petroleum
ether be used for the extractim a: the ether and that excess
alkali be uployed. The remainder was acidified with dilute
hydrochloric acid and extracted {our tiles with 50 ll. of diethyl
ether. Both ether extracts were washed with water, dried over
anhydrous sodium sulphate and the solvent reaoved by distillatim.
Isolation of o-hydray-l,l-dipherwlpentane
The diethyl ether extract was distilled using a 10 inch
Vigreux column, resulting in the following fractions:
(1) up to 70°C./1m. (3.85g.) phenol

(2) 70-llO°C./lmm. (6.303.) sane phenol
(3) lfi’fimem (Moéflfie)
(h) ROIidu. (MeBBQe)

Most of fraction (3) distilled at lSh-lSS°C./lm., it was redis-
tilled giving (10.823.) 9% o—hydroxy-l,l—diphenylpentane boiling
at 155-157°C./lm., up20 1.5682, Sp. G.£°l.037. These constants
check with those obtained when the suns coupound was prepared using
aluminum chloride.

A carbon—hydrogen determination was carried out on this
sample of o-hydroxy-Ll-diphenylpentane with the following results:

-23-

Sample II .00159723. 002, 4051476 H20, .003662

Sample 1 round c, 8h.69% a, 8.1h%
Sample II totmd C, 8h.87% H, 8.21%
CllcU1.t.d for 017H220 C, 85.98% H) 8e39%

Isolation of l-Phervl-l-pentene and Pherfil Ann'lphegl Ether
The petroleum ether extract of the alcoholic KOH solution
was distilled giving the fencing fractions:

(1) 70-86°c./‘1m. 7.86g.
(2) 90-1309c./lm. 6.1332.
(3) 137-1h2°c./1m.- among.
(14) Residue 8.583.

Fractions (1) and (2) gave a positive Baeyer test for mature--
tion, they were redietilled several tines giving 10.023. l-phenyl-
l—pentene boiling dt 85-66°c./5m., n30 1.5310, 3p.o.fi° .8901.
Prevost and Kaujat (29) report 13317 1.5313: 513.0. to .8921“

1 Fraction (3) m redistilled several times giving (15,673.)
13.51 MI asnylphenyl other. boiling l)2-l3h°C./lm, 1:920
1.51M. Sp.d. 2}: .9983.

Phenyl edylphenyl ether has not been reported in the litera-
ture. A carboli'F-hydrogen amlysis was carried out with the follow-
in; result:

Salple I .00h291g. 002, .013356g. 1120, .003616

Sample II .003659g. 002, .0113693. 3,0, .00303h

Sample I found C. 8h.891 H, 8.1;261
Sample 11 found C, 8h.7h% H. 8.29%
Calculated for C17H200 C, 8he9hz H, 8.39;

4h-

B. Preparation of o-Hydroq-lA-diphern-lhexafi
This compound was prepared by. the same method as o—hydroxy-l,
l-diphenylpentane. The mounts otreagents used were as follows:
.51: sole (97.113.) alwl pherwl carbinel
.5 I010 (11.53.) sodiua
.6 nole (56.13.) phenol
150 I1. anhydrous toluene
The following fractins were obtained from the diethyl ether
extract:
' (1) 55-61°c./.5m.. (1.533.):5031; phenol
(2) 157-169°c./1m. (2.313.)
(3) l6?-l?2°0./lm. (11.88 g.)
(h‘) Residue 19.393.
Fraction (2) and (3) were redistilled several times giving
(9.7hg.) 7.5% o-hydroay—l,lsdiphsnylhelans boiling at.l7l-173°c.
/lm., 20 1.5607. The index of refraction of the same compound .
prepared using aluinun chla'ide was 520 1.5600.
A combustion was carried out on this fractiu with the follow-
ing results: ‘ -
Seaple I , .005137s. 002, .015910 1120, .003935
Salple n .0012803. 002» 4101.003 3,0, .001008

Sample I found 0. 81.x“ 3., 8.57%
Sample II found c, 85.29% H, 8.81%
Calculated rod- 0183220 0. 88.98% H, 8.72%

.25-

lgolation of l-Phenyl-l-hexene and Phenyl Hexlphenyl Ether
The petroleum ether extract of the alcoholic potassium
hydroxide solution on distillation gave the following fractions:
(1) 81-96%./1m. (23.1%.)
(2) 77-122°C./lm. (5.20g.)
(3) lhh-lh7°c./hn. (20.228-)
(1;) Residue 13.933.
Fraction (1) was redistilled several times giving 9.85 g- of
1 phenyl-l-haxene boiling at 97-98°C./hm. The index of to.
fraction was carefully determined a. an” 1.525h. snaffle .887h.
Harvel (30) and co—workers report 111235 1.5377, Dis .9h55.

I To obtain further evidence of the formation of l-phenyl-l-
hexene, the compound was oxidised-with permanganate by the method
of Shriner and Fuson. Bensoic acid, with a melting point of .121—
122°C. was isolated. The aqueous residue was extracted with other
to remove the valeric acid. The ether: extract was dried over anlv-i
drous sodium sulphate and the ether reacted. The aside of "lei-1c
acid was formed by refluxing the acid with thionyl chla-ide, and
then pouring the reaction nirture on cold cmoentrated a-onia.

The solid formed was filtered off and the mania solution extracted
with chloroform The chlorofora solution was concentrated and the
snide of valeric acid crystallised. After recrystallisation frm
chla'ofora it aelted at 106° . Shrinerand M (31) report the
melting point of the amide of valeric acid as 106° .

Fraction (3) free above was redistilled giving (115.83g.) 10;

~26-

phenyl hen'lphemrl ether boiling at lSh-lSS°C./2mm. 111320 1.5388,

Sp.G. 23 e9866e

A carbon-daydrogen determination was carried out on the ether

with the following results:

Sample I .00h30hgo
eupl. II .0032573.
Sample I found

Sample 11 found
Calculated for 0183220

002: 4313353:
coz. .010119
c, 8h.62%
0, 8h.73%
c, 8h.981

.27-

H20 3 0003276
H20, .00252),
H , 8.517%
B , 8.673%
H , 8.722%

33.
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~28-

EXPERIh-E ENTAL
IV DERIVATIVES

The d-naphtmrlurethan. 3:5 dinitrobensoate (32) end bensoate
(33) were prepared from o-hydromy-l ,1—diphenylpentene in an attempt
to obtain a crystalline drrivetive for the ortho eubetituted phenols,
but all three derivativee rentined ea oila.

The ofvnaphtlwmrethm derintivee were prepared from the part
substituted phenole according to the method of French and Wirtel
(3b) and analysed for nitrogen.

Te eeegr. or elkylphenol m added one milliliter off—naph-
tlvl ieecyannte. A few drope of an ether eolution of trimetl'wlanine
were Added to catalyze the reaction. The reaction nixture wae pro-
tected from moisture by a calcium chloride tube, and warned on e.
steam both for an hour, then two milliliters of water tore added to
rmave the excess ‘fonaphtlwl ieocyanate. On cooling, it solidified.
The solid was extracted several times with boiling ligroin, in
twenty milliliter portions, and the insoluble material filtered off.
The inaphthylurethen crystallised as mall white plates, and was
recrystallized from 11min to constant melting point.

eie

Th0 of-naphtlvlurethene were analysed for nitrogen by the semi-
micro Kjeldahl lethod (35). Ten to thirty milligrln eI-plee were
used and the-anemic evolved wee absorbed in excess .01 N hydro-
chloric acid, the excess acid was beck titrated with .01 N sodium
hydroxide.

-29-

afimmmmnmyws

 

 

 

TABLE IV
p-Hydroxy-l,1- uniting Celculeted Experimental
diphenyl- ‘zgggg__ % H 3 H
Ethane llhpllh.5°c. 3.77 . 3.76
3.60
Prop-n. 1h2-lh2.5°C. 3.6h 3.63
3.61
Butane 13h~135°c. 3.51 3.58
3.57
Pentane 108-109°c. 3.39 3-h2
3.37
Hexane 10h-10h.5°c. 3.28 3.21
3.19

rm'rr-a
T‘t:b§-.s A 4:14

 

I C1e2s en Hearrar: m2enfs

 

in 15223 Cleisen (36) published work on the carbon alkyletion
of phenole in the ring. He found that both oxygen and carbon
all: lation of phenols took place, when elkyl halides and eociun
derivetivee of mohqdric phenols were reacted. when a dissociat-
in; media such an methyl or .2131 alcohol was used 01122312 elkyln-
tion of phenol wee forared,*while in a,non~dieeocietinz medium
such ee beneene or toluene nore of the carbon alkylntion 1. pro-
duced. Claieen further noted flat the nneetmted alkyla affect
the carbon elkylation to e greater extent than do saturated alkyle.
The tendency toward carbon nlkyletion ie etill further increased
if alkyl phenols ere need.

The formation or ortho eubetituted phenols has been explained
according to the mechanism proposed by Claieen end co—workere (8)
for the formation of e bonzyl phenol.

H E;
O 0 - CO

0, mm... 0 0‘66)"
\

g—EQ ©2120; (j—go

fhe eimpleet course of the reaction would result in the formation

of the other. But when the reaction in carried out in e non-die-

sociating medium (toluene) the «the substituted phenol is also

formed, this may be accounted for by assuming that the benayl
chloride adds to the phenol in the manor ehoen, aodiue chloride

then aplita of! leaving a empexmd of quinoid atructure ehioh
choline toning the ortho eubstituted phenol.

In 1926, Val Awe, Wagner, and Bahr (37) attempted to ex-
plain the ring alkylatim noted in connection Iith the Claisen
rearranguent. they advanced three hypotheesas

(1) The {creation at addition products and subsequent aplit—
tingetfofealtaeindicatedhyClaim.

(2) Initial oxygen alkylation, followed by rearranguent of
the molecule to carbon alhdatin.

(3) The separation of the natal and halogen as a metalic
halide, leaving a free alkyl radical and a free end
radical, the tee radicals then canbine to ton the
alkylated phenol.

The first Methods agrees with Glaieen. Tarbell (38) in more
recent work agrees with the second theory of initial mgen

alkylation. The third theory acme not reasonable. the fore--
ation of the free anal radical would require a pretax ahitt, as

ehoum in the {alluring eeriee of reactions.

©:o a: Q ".02. ' :63;

ea —___—-’ ‘3 “—fi "

 

:5: (3.1: h; :é+ +— 1C“
R " R
H
©: C.“ + 503H -——-> ICQ
'4 R oH

Thin mechanic: will be used no tho booio to uploin the
mechanism of CIRioen'o hotbed of ring ablation.

urban (38) otudiod tho thonnd roorranguont a: 01:1
phenyl othoro. Bo ouppcrto the cyclic oloctrcnic nachoniu pro-
posed by Kurd, and Pollock (12). The: loom thot tho mun
effect of hoot on tho oyst- oltoro tho pooitim of tho doctrm
pair which bindo tho ollyl group to tho aygon, oo thot o om-

ioniootion occurs.

 

I” 1

.9 "" +
c:c-—c-—o-—-—c:c -—;c :c--o ; 0—020
o9 ‘
Thio effect canbined with tho apotm proximity of tho otano at

tho and of tho systou, brings obout o tamporory ring doom and

readjustment of tho oloctrmo/C
0.06.! __ 110! CEC -

<1 :3 © *6” 0“

 

Li w

‘I‘his mechanism is only satisfactory for compounds where the olkyl
group is unsaturated. The send-ionic positive carbon seeks to
satisfy its electron deficiency by appropriating electrons from
the neigl'l‘ooring double bond.

Claisen showed tho effect of the medium in which the resc-
tion occurred by reacting ollyl branide with oodim phenolote in
alcohol, obtaining 90% of the ether, whilo o non-dissociating
medium like become or toluene gave only 301 other end 70% ollyl-
phenol.

host of tho work concerning ollwl phenyl others end elkyl-
phenols hos been o. studyr of the reorrongement of the other, no
effort hoo been made to onelyoo the effect of o non-dissociating
median on the rooction. The most generolly occepted views con-
sider ether fox-motion es the first step with subsequent reerronge-
ment to on olkyl phenol in o dissocioting median. Also direct
carbon alkylotion is considered to toko place in o. non—dissociot-
ing medium. These theories ore not completely ootiefoctory be-
cause they foil to uplein the effect of tho medium on corbon
end m’gen Alkyhtion.

A more plousible reaction mechanism involves the formotion
of o corbonim ion from the holido end o corbonion from the
sodium phenolote. The cofibenion exists in equilibrium of two
forms due to o proton shift.

80:. i 510:0: H

oo o. '. oo

3 .—

A dissociating medium (alcohol) favors ether formation by union
of the carbonium ion with the ether form of the carbanion. The

proton shift of the carbanion is inhibited by the polarity of its

environment.
Om mQ ——+©'§*E Q

A non-dissociating;nediun (toluene or benzene) fevers phenol
formation by union of the carboniun ion with the phenol forn.of
the corbanion. A proton shift of the oerbenion activates the

ortho position of the aromatic nucleus.
H

.0

z 0 1

Q5» + £0 ["35 Q

This mechanism explains the fact of other and phenol formation
in both media. It also explains why phenol formation is favored
in e nonpdissociating medium, and ether formation is favored.in
a dissociating medium.

The thermal rearrangement of the ether with or without sol-
vent as reported by ”I'm-bell can be manned by a shift of the
equilibrium of the carbonion from the other form to the phenol
form under the influence of heat. Since the rearrangement is _
exothermic (38}, a conversion to the lower energy level would be

expected.

II Aluminum Chloride Condensations

Several theories have been proposed in attempting to explain
the mechanism of alkylation of’aromatic nuclei with alcohols in
the presence of a dehydrating catalyst as aluminum chloride. No
one theory seems to be completely satisfactory. These theories
have been thoroughly discussed by previous workers in this labora-
tory and sill be only mentioned here.

Hustm and co-workers had observed in their early investiga—
tions that aluminum chloride favored condensation only when the
alpha carbon atom of the alcohol was double bonded or the member
of a benseno ring. Further evidence of this theory is presented
in the condensations under consideration in this paper. 'lelsh
and Drake (39) in condensing dimethyl phenol carbinol, and methyl
diphenyl carbinol with phenol at 100°C. using .5 mole phenol per
mole carbinol, report the formation of an olefin fro-Ltho carbinol.
They propose a mechanism whereby the aromatic compound is added to

the define
c 5 H 3”,; CH2+ r105 shoe _.. 05H; CH3
OH

This type mechanism could not be postulated‘lhero the alcohol is
incapable of dehydration to on olefin (bensyl alcohol). No olefins
were isolated in the condensation of secondary alkyl phenyl car-
binols with phenol, it is doubtful that the condensation proceeds

by this mechanism.

-36-

rankervenik and Euarova (hO) condensed phenols with sec-

oMsry alcohols using excess aluminum chloride and high tempera--
ture. They isolated mall amounts of dialhylphena-l others and
allqlphenyl others, and proposed a nechsnim with others as
intermediates.

ROM 4- 111013 .--,~ H01 + nelzmh)

05.35021 + 1.1013 ——§ 381 + 06230111612

5.161203) +. CéfigcelClz 391a (rinses +5101, + 5.101205
The alkyl other is converted to the dialkyl etha- by alloy-lotion
or rearrange-sent (241).

66:15:25; + hon + $101, 4-4 Rebekah + £18]. on 4. 22:21

2 {535% m3...) Meshes 4- 563503
The sllqlphenol say In under equations of excess cloninun

2

chloride at high temperature by either of the following cathode:
ncéshoa + no]. -——-> acéahoa 4» R61
Céflhm + 66850:! —-—-—‘> 2 1206830!

This aechaniss is questionable as it does not explain the
rearranges-ate obtained man sees secondary alcohols are condensed
with bensene. Also Huston and oer-workers in condensing an).
phenyl carbinols with phenol have not isolated any of the interme-
diate other.

Work carried out in this lobes-stay by Evert (1) in 1935
led to the proposal that addition compounds of aluminum chloride,
the alcohol, and phalol are first formed.

.37-

This complex molecule being unstable, rearranges to a more stable
configuration by splitting out aluminum chloride and water to
yield allq'lphenol.

An ionic type of mechanim has been suggested by Price (142)
for the alkylation of benaene. The formation of an ionic complex
between alaninun chloride and an alkyl halide has been demon-
strated by Wayforoch and Firla (Id). In this complex the carbon-
hologen bond is weakened, and the compound dissociates into an
electron deficient carbonimn ion and a negatively charged alum-

inum cmplex:

 

 

 

 

r 0. - _ a. 1
:01; :01:
+. O. O. 0.. + .0 O. .9.
R :XzAltc -——-—)R and II:A1:C1.
C. .0 O. O. .0 O.
_ =9= 4. _ =9? J

The electron deficient carbonium ion (a) completes its octet
by association with a pair of electrons from a double bond of
the aromatic nucleus. The elkyl benzene is formed by the loss
of a proton. Based on the work of Hustm and Awuapara (hh)
Barrett (1:5) and Van Dyke (3): a mechanism was proposed in which
an initial reaction between aluminum chloride and the alcohol
yielded a complex molecule which decmposed to produce an alkyl
cation or carbonim ion. This mechanism satisfactorily explains
the rearrangement of branched alkyl groups as well as the isola-
tion of low molecular weight alkyl benaenes (22).

Applied to the alcohols under consideration, the mechanism

proposed :1 ave would lead to the following series of reactions.

.35..

H
RCOHRC-OQMC1

B
Q + A1613 "—'—> 0

3

 

H H
RC—0.A101 x 9.0+
H 3 7

0 O + W;

RC+

0 G —-> * GHQ
0
HR

 

.39..

DISCUSSIG

 

Apparently the chain length of the carbinol has sme affect
in detemining the relative amounts of ortho and pus substitution
of phenol. 'In all the condensations under consideration the
total yield of ortho and para alkylphenols varied from 57-30:; yet
the amount of ortho substituted phenol varied inversely fran zero

to 152 (See Table II), as the chain length increased
The melting point or the pun alkylphenols varies with the

carbon chain length. p-hydroxy-l,l—diphenylethane melts at 57°C.
while p-hydroxy-lfl-diphemrlpropane melts at 66°C., a naximm.
The next two hom010gs melt lower, with Hadron-Ll-dipherwl-
hexane twining liquid at roost tauperature. The (naphtrwlure-
thane show the same variation in melting point with the helium
melting point at the sale cmpound.

The two ortho substituted phenols obtained {rm the aluminum
chloride condensation that have not been reported in the litera-
ture were indentii’ied by preparing the same compounds by the
Claissn rearrangement of the ether, and canparing their physical
constants. Carbon—hydrogen analysis were also carried out as
sdditimal proof.

In the preparation of ortho substituted phenols by the
Claisen rearrangement, a phenyl alkene was isolated from the re-
action nixturs. Strickler '(7) reports the formation of l—phenyl-l-
butane true of chlorobutylbensene. The phenyl alkene corresponds
to the chloride and was probably tamed by elimination of HCl
under cmditions of the reaction.

440-

The para imers were identified by comparison of their
p111. sical constants with those obtained by earlier workers in
this laboratory. Additional proof was obtained by preparation
and analysis of the o{ naphtm=lurethans or the para compounds.

The new compound p-deroxy-l,1-diphemlhexane was analyzed for
carbon hydrogen.

1.

2.

3.

h.

SUI-551133

 

Methyl phenyl carbine). thru aml phenyl carbinol were con-
densed with phenol in the presence of alminum chloride.
The expected normal alkyl phenols were isolated from each
condensation.

The yield of para alkyl phenol decreased from 57% for
p-hydroay-l, l—diphenylethane to 38% for p-hydroxy-l, l-di-
phenylpentane, and then increased to gt for p-hydroxy-l,
l-diphenylhexane. The yield of ortho alkylphenol varied
from zero for o-hydroaq-l,l-diphenylethane to 13:5 for
o-m'drony-lfi-diphenylhexane.

The following new compounds were prepared and analyzed;
o-hydroxy-lJ-diphem‘lpentane, phenyl amylphenyl ether,
0-h)’d1‘03Q’-1 ,l-diphenyl hexane, and p-hydroxy-lfl—diphenyl

hexane.

1.

2.

3.

h.

5.

6.

7.

8.
9.
10.

11.

12.

13.

15.

16.

H.

I.

C.

C.

R.

J.

R.

L.
K.

J.

H.

C.

A.

G.

C.

V.

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MICHIGAN STATE UNIVERSITY LIB

II III HIIIIIHII

3 1293 03046 86

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