The Condensation of the Methyl Dipropyl Carbinols with Phenol in the Presence of Aluminum Chloride

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DOCTORAL DISSERTATION SERIES t i t l e The Q q n d e m s a 7/o n Of The Mefhvl diprojov) Ctrbrnoh

U M Fhfbol Ih The Presence Of /Uumimtn Chloride





M k h i& ih J7*i c Q /k & e




m i


i i i i i i i










"by CA RL R I D G E K E L O Y

A THESIS ■ Submitted, to the G r a d ua te School of M i c h i g a n State College of A g r i c u lt u re and A p p l i e d Science in partial fulfilment of the requirements for the degree of D O C T O R OF P HI L O S O P H Y

D e p a r t m e n t of C he mi st ry 1942

ACKNOWLEDC-EMSNT The writer wishes to express his

sincere s r a titude to

Dr. R. C. Huston for the kindly interest and helpful


gestions which have made possible the c om pletion of this work.

T AB LE OF CONTENTS I n t r o d u c t i o n ............................... page 1 Hi storical


Th eo re ti ca l ................................ E x p er im e nt al Pr oc edures


2 9 17

M a t e r i a l s ............................


P r e p a r a t i o n of Carblnols






C o n d e n s a t i o n s ..................... Derivatives Proof of Struc tu re


................. 25 .






T a b l e s ................................

27 32

D i s c u s s i o n ...................................... 35 Summary B ib li o g r a p h y

..................... ................................

38 39

1 INTRODUCTION In previous papers from this laboratory (1) the con­ densations of tertiary butyl,

tertiary amyl,

tertiary hex-

y l , and tertiary heptyl alcohols wi th phenol in the p r e ­ sence of anhydrous aluminum chloride have bee n described. Of the seventeen possible tertiary octyl alcohols,

all (2)

but the methyl dipropyl carbinols have been condensed with phenol by us ing aluminum chloride as the condensing agent. The purpose of this paper is to describe the condensation of these remaining tertiary octyl alcohols.


2 HI b i On I oA h G 0 nd.ens9.ti0 n may be d ef ined as the u n i o n of two or more organic molecules or parts of the same molecule without the elimination of component atoms)

(with or

in w hich the new

c om bi na ti on is effected b e tw ee n c a r b o n ‘'atoms.

It is a p r o ­

cess closely associated wit h the history of synthetic o r g a n ­ ic chemistry.

Internal condensation,

atoms within a molecule, compounds,

the linking of carbon

leads to the f o r m a t i o n of cyclic

whereas external condensation is the u n io n of two

or more differ en t molecriles to p ro duce a molecule of greater com pl ex it y and, generally,

of greater m ol ec ul ar weight.

The u n io n b e tw ee n molecules or parts of the same m o l e ­ cule is usually promoted by u ns at u r a t i o n and by the tendency exhibited by unsaturated atoms to saturate themselves. W h e t h e r the combining molecules are already u n s a t u r at ed or are rendered unsaturated by the withdrawal of ce rtain e l e m ­ ents,

a catalyst is re quired to b ri ng about the condensation,

s erving/either as a d e h y d r at in g agent,

as an activator,


both. Condensations

involving d e h y d r a t i o n are very numerous.

A mo ng the d eh yd ra ti on catalysts that have b e e n used may be menti on ed the following: phosphorus pentoxide,

sulfuric acid, phosphoric acid,

m ag ne si um chloride,

zinc chloride,

phosphorus p e n t a c h l o r i d e , aluminum chloride,

ferric c h l o r ­

ide, (both the anhydrous salt and in the form of the hexahydrate),

stannic chloride,

ac'etic acid,

sulfuric and acet-

3 ic acid mixture, b o r o n trifluoride, h y d r o g e n chloride, h y d r o ­ gen fluoride, ide.

antimony trichloride,

and titanium t e t r a c h l o r ­

Of these condensation cataijrsts the ones listed below

have be en shown to be more efficient and of greater a p p l i c a ­ bility,

so an example of each is listed: Zinc chloride was the catalyst used by Fi scher

and Roser

(3) in the preparation of aminotriphenylmethane

by condensing benzhydrol with aniline hydrochloride. Sulfuric acid was employed as a catalyst by Be ck e r (4) in 1882 when he condensed m-nitrobenzyl alcohol and benzene to yield m - n i t r o d i p h e n y l m e t h a n e . Mixtures of acetic and sulfuric acids were used by Meyer and Munster (5)

in condensing benzyl alcohol and b e n ­

zene to give d i p h e n y l m e t h a n e . Stannic chloride was the condensing agent used by Michael and Jeanprstre


in preparing phenyltrirnethylphen-

y lacetonitrile from mesitylene and p h e n y l h y d r o x y a c e t o n i t r i l e . Phosphorus pentoxide was employed by He mi l ia n (7) as a catalyst in the condensation of benzhydrol with p-xylenje to forrn diphenyl-p-xylylrnethane. Magnesium chloride was the catalyst used by M a zz ar a (8 ) in condensing propyl alcohol with m-cresol to give propylm-cresol. Hydrogen chloride was employed by Noelting (9)

in p r e ­

p ar in g p-nitrodimethyldiaminod iphenyltolylmethane from pnirtodimethylaminobenzhydrol and m-toluidine. Zincke (10) announced the reaction of aromatic h y d r o ­

carbons with h a l o g e n compounds

in the pre se nc e of zinc dust:


V -


C 6 H 5H + C 1 C H 2 .06H5


C 6 H 5 C H 2 C 5H 5 +JHC1

S ince aluminum chloride catalyzes the same reaction,


chloride may be formed as an intermediate. Because of its po we rf ul d e h y d r a t i n g ac t i o n al uminum chloride has engaged the a tt e nt io n of workers

in this l a b o r ­

atory, both in studies of its uses and in attempts

to d e t e r ­

mine the possible me chanisms by w h ic h it acts. Friedel and Grafts


first introduced aluminum

chloride as a catalyst in c on de n s a t i o n reactions among a l i ­ phatic compounds.

They at first observed that alum i nu m

chloride acts in the cold on amyl chloride to pr o duce h y d r o ­ gen chloride, hydrocarbons

of the c o m p o s it io n CnH 2 n + o* an{3-

h i g h l y condensed hydrocarbons.

L a te r they found that t r e a t ­

ment of mixtures of organic chlorides and aromatic h y d r o c a r ­ bons w it h . a l u m i n u m chloride led to the format io n of such alk y l a t i o n products as toluene,

etliylbenzene, or amylbenzene,

and acylation products like benzophenone.

A possible m e c h ­

anism for the Fried sl -C r af ts rea ct io n would be the c o m b i n a ­ tion of the catalyst with the benzene derivative: II

CgR^H t A I C I 3 this intermediate would then react with the halide:

- R ’ci --- * ■lerz and W e it h

a i c i 3 - R ' c 6r 5 .


(1 2 ) condensed two molecules of phenol

to produce diphenyl ether b y u s i n g a l u mi nu m chloride, while \Jass

(1 3 ) used this catalyst in cond en si n g d i c hl or oe th yl en e

oxide with benzene to give triphenylethane.

These reactions

indicated that the a l u m i n u m chloride may 3 erve as a d e h y ­ d ra ting agent as v/ell as a catalyst. shown when draebe (l4)

This was still further

succeeded in pr od u c i n g small amounts

of aniline b y treating benz e ne w i t h h yd ro xy l am in e in the presence of aluminum chloride. The con de ns at io n of chloral,

chloral hydrate, bromal,

and trioxymethylene w i t h various organic compounds

in which

an el imination of w at er occurred was reported b y Fr ankforter and co-workers

(15) who showed that,

did not b ring about the same reactions

since sulfuric acid in some cases,


aluminum chloride was acting not only as a d e h y d ra ti ng agent but also as a catalyst. The first reported c o n d e n s a t i o n of alcohols wi th a r o ­ matic compounds was the work of A u e r

(16) w ho ,' in 1884,

condensed ethyl alcohol with phenol u sing zinc c hloride as a catalyst. resulted..

A mixture of ethylphenol and e thylphenetole Anisole was obtained w h e n methyl alcohol was

substituted for ethyl alcohol. In 1897 Nef (17)

obtained di ph en y l m e t h a n e by the r e ­

a ction b et w e e n benzene and benzyl alcohol in the presence of aluminum chloride. F r i e d e m a n n (18) cent.

In r ep ea t i n g this work Hu s t o n and

found that this r e a c t i o n gave a thirty p e r ­

yield of d i p h en y lm et ha ne as well as smaller amounts of

o- and p-d.ibenzylbenzene, a h y d r o c a r b o n h av i n g the f or mula

C 2 7 H 2 4 ' an