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CONDENSATIQNS OF ORTHO— REL PARA-CHLOROFHEKOLS
WITH ERTIARY ALYL AND BUTYL ALCOHOLS

IN THE PRESZJCE OF A1013

COKDFKSATIOSS OF ORTHO- AND PARA-CELOHQPHFHOLS
WITH TVRTIARY AmYL ALL BUTYL ALCOHOLS

IN THE PRESJNCE OF AICIS

A THESIS

Submitted to the Faculty of Michigan State
College of Agriculture and Applied Science as
partial fulfillment of the requirements for the

degree of Master of Science.

William R. Coleman

September 1937

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A C K N O W L E D G E m'E L T

The author wishes to take this opportunity to
sincerely thank Dr. R. C. Huston for his kind
assistance and counsel which made the completion

of this work possible.

331.622

 

Historical
Experimental

(1) Condensation of tertiary amyl
alcohol with o-chlorophenol

(2) Condensation of tertiary butyl
alcohol with o-chlorOphenol

(3) Condensations of the tertiary
alcohols with p-chlorophenol
Summary

Bibliography

HISH‘OI‘11CAL

Sul‘uric acid, Thosyhorcus rentoride, 7inc
chl ride, ttfitrochltric scii, Frflfuric rryizscetic
acids, also.ute almosol, stannic c“loride, and
acetic acid are the reasents cannon}? used to
Enrinzj el‘oni: ttv= c nudeulsa*3iori 077 sthnz‘;ic zilccfléolss
with aromatic comyounds to form deri'htives of
di- or trithenylmethane.

Anhydrous aluminum chloride fiFS been used in
organic chemistry as a dehydrating agent by merz
end Wieth (l); Wass (u); Frankforter and
Kritchensky (3); Frankforter and Kolcetinur (4);
and others.

The type of condensation described in this
paper is a modification of the well known Friedel-
Crafts reaction. By this reaction the introduction

of an alkyl or acyl group by means of the corres-

ponding halide and aluminum chloride is accomplished:

A1015

 

C6H6 + CQHbBI‘

NJ,
O
C
:1;
_+
:2
[u
"1

In this reaction the hydrogen halide is .plit off.
Although anhydrous aluminum chloride had been
used as a dehydrating agent to quite some extent in

organic chemistry the work of Huston and co-workers

was the tirst concerning the dehydrating action on

J V

0" . I , .(‘I' ,- \ ‘IJ ‘ ' -‘-
aromatic alone 15 an} arenatic courounds in the

L)

presence of that agent. In 1915 Huston and Friedmann
(R) Ingwrted.€;Tfldfi yiel i of dividenyl m Hiene fixin the
reaction of Ven7Vl alcohol and benzene in the pre-
sence o” alunnnum chloride. Chev rercrtei later \3)
innit secenvtary QTWMTDtic efl<3ohols EfllCh arigfiienyl—

,nethyl and phenylethyl cexlflznfljs react with benzene

in the presence of aluminum chloride to give the ;
correSponding hydrocarlons in good yield. I
Huston (7) reported that ben7y1 alcohol reacts
with phenol in the fresence of aluminum chloride to
give a good yield of p-benzylphenol according to
the equation:
AIC13
CBHSCHgoHFFCGHSOH -——————+ CUHSCH200H4OH-+H2O
Later Huston and co-workers (8) reported that aromatb
secondary alcohols such as benshydrol, phenylmethyl,
phenylethyl and phenyl n-proDyl carbinols react with '

phenol inthe presence of aluminum chloride to give
the corresponding para substituted phenols.

In 1924 Huston and Goodemoot (9) reported the
condensations of some cyclo alkyl carbinols with
ben7ene in the presence of aluminum chloride.

In 1926 Huston and Sager (10) reported that

saturated aliphatic alcohols do not condense with
benzene. They found that unsaturated alcohols,
such as allyl alcohol, willcondense with benzene.
However, in 1936 Huston and Hsieh (11) reported
that aliphatic primary d.cohols do not condense
with phenol or benzene inthe presence of aluminum
chloride. Alphatic secondary and tertiary alcohols
condense with benzene to give the correSponding
alkylbenzenes. Aliphatic tertiary alcohols condense
with phenol to give good yields of p-tertiary-alkyl
phenols.

In 1933 Klarmcinn, Shternow and Gates (13)
reported the preparation of para tertiary amyl
o-chlorophenol by the ether rearrangement. The

boiling point was reported as lOS-llooat 2mm.

EXPERIMEMTAL

Tertiary amyl and tertiary butyl alcohols and
p-chlorophenol were obtained from the Eastman Joisk
Co. The o-chlorophenol was prepared according to
the method of Huston and Keeley (1?). The anhydrous
aluminum chloride was of good grade.

(1) COiiDl—ZIQSATICN or n:-1:1‘1.2.:cr mm. ALCOUOL WITH
0- CHLOROPE-Twli‘. OI.

e'rams (.2 mole) of o-chlorOphenol and

L)

Twenty-six
eighteen grams (.2 mole) of tert-amyl alcohol were
suSpended in lOOcc. of petroleum ether in a 50000.
three neck flask fitted with a mercury-sealed stirrer,
a reflux condenser and a thermometer. Twenty-six
grams (.2 mole) of anhydrous aluminum chloride were
added slowly to the mixture so that the temperature
did not rise above 30°C. Stirring was continued three
to four hours after all the aluminum chloride had
been added. After standing over night the mixture,
dark red in color, was treated with 100g. of ice and
lOOcc. conc. HCl to effect hydrolysis. The ether-water
mixture was separated and the water layer was washed
three times with ethyl ether. The ether extracts were
combined and dried over anhydrous sodium sulfate.

The ether was removed by distillation and the residue

was fractionated. All fractionations were carried
out at 5mm. pressure. The first fraction 50-800 was
discarded since it contained ether and unreacted
reagents. The second fraction was colk>cted from
80-1000. The residue was a dark gummy mass. The
fraction was purified by repeated fractionation
until the boiling point was constant at 91-920C.

The second fraction was then subjected to distil-
lation at atmOSpheric pressure in a distilling flask.
The final product boiled at BEE-286.50 at 736mm.

The equation of the reaction is as follows:

A1C1KL

HOC©+ H08: 3CH? I-zcn '7 HochH- 320 +320
rs

CH52

 

The mole equivalents of the alcohol, chloro-
phenol and aluminum chloride were varied, however,
the best yields were obtained when equal mole
equivalents of the three substances were used.

PROOF OF STRUCTURE OF P-TERT.AmYL O-CHLOROPHENOL

Five tenths mole of p-tert. amyl phenol, prepared
by the method of Huston and Hsieh (11), was suSpended
in chloroform in a 5000c three necx flask and
chlorinated at room temperature until the theoretical
amount of chlorine had been taken up. The contents
of the flask were stirred mechanically during the

chlorination. The chloroform was evaporated

off and tho rasultiny oil was TUTifiPd by fiisfiil-
lotion at atmos-hnric prossurp. Th” rnrificd oil
a - fir. fizro 1.4 .,
oo17nd at c-4-”~Q at 7.Tmm.

.As ?nrthpr proof'cH753tructnro both :roducts,
ohtainpd ty condnnsation and chlorination, wovo

1

trnatnd Tito diphenyl carquin¢ chloridn to form
the djp‘qnnvl an-thsnp f1F'T‘i‘f"+i‘I“S. }.~«‘)T.r". of Hip

rasulting nrefhanoq h94 2 melfiing foint of 312-11”

both mercen31V2fid for chlorino Cuntpnt. the

czivnl"wnw1 ”anCfiflnwfo is 0.91. 'man actual axwwvii
ES flotnrminnd by th? T9?* Vomh mpfhod was 9.05L

in the case of the product and 9.0 % for tho proof.

0:

(9) CONDRESATION OF LLHTIARY bUTYL ALCOHOL WITH
O-CHLOROPRfiNOL
The condensation was carried out using the
same procedure as that outlined for #1. The method
of purification was also the same. The resulting
oil boiled at 2”l-2£2.5° at 743mm pressure.

The equation of the reaction is as follows:

pH A1013 9H3
HOQ+ HOOJCH3 —————+ HOO-O—CHK + H20
Cl CH3 ‘ Cl CH '

PROOF OF STRUCTIRH OF P-TERT.BUTYL O-CHLOROPHFKOL
18 grams of p-tert.amyl phenol were chlorinated
in the same manner as #1. The resulting oil boiled

940-241.5° under 742mm pressure.

J

ct-

a
The diphenyl urethane derivatives were prerared
from both the products of condensation and chlorination.

Each of the resulting derivatives melted at 142-1430.

The calculated chlorine percentage is 9.35. The
percentage found was 9.34 for the derivative of the
product obtained Ly candensation, and 9.4? for the
promvct obtained by chlorination.

The halogen percentage of the products of con-

densation was detEraned by the Carius method.

.. I
The p-tertiary-alkyl products are hveroscooic

and take up water very rapidly.

G)

(3) CONDENSATION OF TEXTIARY AMYL AND BUTYL
ALCOHOLS WITH P-CHLOROPHENOL

These condensations were carried out using the
same procedure as given under §l. After the final
fractions were purified by fractionation and distil-
lation they solidified and were recrystallized from
petroleum ether. The crystals obtained from all of g
these condensations melted at 57°. The melting
point of p-chlorophenol given in the literature is
37°. The Parr Bomb determination of the halogen
content of the crystals showed that they were

p-chlorophenol.

Table l.

CONDVNSATIONS OF TERTIARY ALCOHOLS WITH O-CHLOROPHENOL

Reactants in holes

 

 

 

Alcohol Phenol AlClz Product B.P.°C Yield
Tert-amyl .6 .6 .6 p-tert-amvl 255-256.5° 37%
alcohol o-chlorophenol 736mm
Tert-butyl 0
alcohol .6 .6 .6 p-tert—butyl 24l-242.5 24%

o-chlorophenol 743mm

 

CONDFNSATIONS OF TERTIARY ALCOHOLS WITH P-CHLOROPHENOL

Tertiary alcohols do not condense with p-chlorophalol.

CONSTANTS

Chlorine%
Compound B.P.°C Calc. Found

P-tertiary-amyl 956-266.5°/736mm 17.85 17.43
o-chlorOphenol

P-tertiary-butyl 24l-P42.5O/743mm 19.23 18.61
o-chlorophenol

Table 2.

IO

DERIVATIVES OF P-TFRTIARY-ALRYL (LCHLOROTHFNOLS

Diphenyl Urethanes

Compound L.P.OC
P-tertiary-amyl 116.1170
o-chlorophenol

. 4 o
P-tertlary-butyl 1/2-143
o-chlororhenol

Nitro Derivatives

P-tertiary-amyl 108.109o
o-chlorophenol

o
P—tertiary-butyl 114-115
o-chlorophenol

Chlorinefi

Calc. Found
9.01 9.03 E
9.35 9.31

14.58 15.20

15.45 15.70

1. Tertiary amyl and butyl alcohols condense

with o—chlorophenol in the fresence of aluminum

chloride to eive good yields of p-tertiary-alhyl

o-chlorophenols.

|
2. Tertiary alkyl alcohols do not condense
with r-chlororhenols i”

n tflle } resrulce (Df 311LnlYPNn

. DiphenYl Urethane end nitro derivatives of

the p-tertiary-alkyl o-chlororhenols were prerered.

ll

 

 

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BILLIOGRAFHY

Lerz and Keith, Err., 14, 169, (1681).
Wass, Ler., 15, lb28,(1882).

Frankforter and Kritchensky, J.Am.Chem.Soc.,

36, 1511, (1 :‘14).

37, 385, (1915).
Frankforter and Kolcatinur, 1316., 36, 1f. H9,(191 ).
Huston and Friedmann, I:id., 38, 2597, (1916).
Huston and Friedmann, 1212., 40, 785, (l 18).

Huston, Ibid., 46, 2776, (1994).

Huston and others, lfiig., 49, 1365, (1927);'
“5, 4317, (less).

Huston and Goodemoot, Ibid., 56, 2432, (1934).

Huston and Sager, Ibid., 48, 1965, (1926).

Huston and Hsieh, Ibid., 58, 439, (1936).

Huston and Neeley, 1212-: 57, 2176, (1936).

Shternow, Gates and Klarmcinn, Ibid., 55,2576, (19..

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