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A STUDY OF THE REDUCTION AND FRAGMENTATION OF SOME TERTIARY
CARBINOLS WHEN CONDENSED WITH BENZENE IN THE PRESENCE
OF ALUMINUM CHLORIDE

by
ROBERT V. SMITH

A THESIS
S u b m i t t e d t o t h e G r a d u a t e Scho ol o f M ic higan
S t a t e C o l l e g e o f A g r i c u l t u r e an d A p p l i e d
S cien ce in o a r t i a l f u l f i l l m e n t o f the
req u irem en ts f o r the degrep o f
DOCTOR OF PHILOSOPHY

D e p a rtm e n t o f C h e m i s t r y
19^9

ACKNOWLEDGMENT
The a u t h o r w i s h e s t o e x p r e s s h i s s i n c e r e ^ g r a t i t u d e
f o r t h e h e l p f u l g u i d a n c e a n d i n s p i r a t i o n g i v e n by Dean
R a l p h C. H u s to n d u r i n g t h e c o u r s e o f t h i s p r o b l e m .

234490

TABLE OF CONTENTS

Introd u ctio n
H isto rical

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

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

T h e o r e t i c a l ................................................ .....................................
E xperim ental - P a r t I
P re p a ra tio n of A lcohols . . .

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

Condensation A pparatus

. . . .

C ondensation P ro c ed u re

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

F r a c t i o n a t i o n and I d e n t i f i c a t i o n

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

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

E xperim ental - P a r t I I
P re p aratio n of D eriv ativ es

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

I d e n t i f i c a t i o n o f F r a c t i o n IV, P a r t 0 . . . .
D i s c u s s i o n ...........................................................................................
Summary

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

B ibliography

INTRODUCTION
E x t e n s i v e s t u d y h a s b e e n made i n t h e p a s t on t h e
a l k y l a t i o n o f a ro m a tic n u c l e i , p a r t i c u l a r l y benzene and
p h en o l, w ith t e r t i a r y a lc o h o ls in the presen ce of
a n h y d r o u s aluminum c h l o r i d e .

The g r e a t e r s h a r e o f t h e s e

i n v e s t i g a t i o n s must b e c r e d i t e d t o D r. R. C. Huston a n d
coworkerc o f t h i s l a b o r a t o r y .

D u rin g t h e s e i n v e s t i g a t i o n s

i t was o b s e r v e d ( 1 ) t h a t t h e r e was a m arked d e p r e s s i v e
i n f l u e n c e on t h e c o n d e n s i n g c a p a b i l i t y o f a l c o h o l s i n
w hich t h e r e was an a c c u m u l a t i o n o f a l k y l g r o u p s on t h e
c a r b o n atom a d j a c e n t t o t h e h y d r o x y l c a r b o n .

Subsequent

s t u d i e s by H u sto n a n d Awuapara ( 2 ) , H u s to n and B a r r e t t
( 3 ) . Huston a n d Van Dyke ( •

a n d H u s to n and K r a n t z ( 5 ) ,

h a v e r e s u l t e d i n t h e i s o l a t i o n o f compounds w hich c o u l d
be a c c o u n t e d f o r o n l y b y an a p p a r e n t f r a g m e n t a t i o n o r
re a rra n g e m e n t and f r a g m e n ta tio n o f th e a lc o h o l d u rin g the
reactio n .

T h e se more r e c e n t I n v e s t i g a t i o n s h a v e l e d t o

the b e l i e f t h a t f ra g m e n ta tio n , r a t h e r th an d ep ressiv e
in f lu e n c e o f h ig h ly b ran ch ed a l c o h o ls , accounts f o r the
decreased y ie ld s o f the expected a lk y l benzenes.
I n t h e work o f H u s to n a n d F rie d e m a n n ( 6 ) , H u sto n a n d
J a c k s o n ( 7 )» a n d H u sto n and Hughes ( 8 ) , a s a t u r a t e d h y d r o ­
c a r b o n f r a c t i o n was i s o l a t e d a n d I d e n t i f i e d a s t h a t
co rresponding to the a lc o h o l condensed.

No s a t i s f a c t o r y

e x p l a n a t i o n was o f f e r e d f o r t h i s a p p a r e n t r e d u c t i o n o r
“p u l l i n g o u t " o f t h e oxygen o f t h e a l c o h o l .
I t was t h e p u r p o s e o f t h i s i n v e s t i g a t i o n t o s t u d y
t h e f:g a g m e n t a t i o n and r e d u c t i o n o f a l l p o s s i b l e t e r t i a r y
o c t a n e I s , h e p t a n o l s , h e x a n o l s , t e r t i a r y amyl a n d t e r t i a r y
b u t y l a l c o h o l , i n w h ic h t h e r e a r e o n l y p r i m a r y a l k y l
g r o u p I n g s a t t a c h e d t o t h e h y d r o x y l c a r b o n , i . e . , no a l k y l
s u b s t i t u e n t s a t t a c h e d to carbon a d j a c e n t to th e h y d ro x y l
carbon

HISTORICAL
The f i r s t a t t e m p t a t u s i n g a l c o h o l s a s a g e n t s f o r
t h e a l k y l a t i o n o f a r o m a t i c n u c l e i was r e p o r t e d b y N e f
(9) i n I S 9 7 .

He p r e p a r e d d i p h e n y l m e t h a n e b y c o n d e n s i n g

benzyl a lc o h o l w ith benzene i n th e p re se n ce o f anhydrous
aluminum c h l o r i d e .

R e p e a t i n g t h i s work i n 1 9 1 6 , H u s t o n

and F riederaann (10) r e p o r t e d o t h e r p r o d u c t s f o r m e d d u r i n g
the r e a c t i o n .

These i n v e s t i g a t o r s (6) a l s o c o n d e n s e d

m e th y lp h e n y lo a rb in o l and e t h y l p h e n y l c a r b i n o l w ith benzene
i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e a n d o b t a i n e d
i n a d d i t i o n t o t h e e x p e c t e d c o n d e n s a t e , e t h y l b e n z e n e and
propylbenzene r e s p e c t i v e l y , in approxim ately te n p e r c e n t
y ield s.

The f o r m a t i o n o f t h e s e p h e n y l a l k a n e s , a p p a r e n t l y

t h r o u g h r e d u c t i o n o f t h e c a r b i n o l , was n o t s a t i s f a c t o r i l y
ex plained.

The optimum mole r a t i o o f a l c o h o l , b e n z e n e and

aluminum c h l o r i d e f o r t h e p r o d u c t i o n o f t h e main c o n d e n s ­
a t i o n p r o d u c t was a l s o e s t a b l i s h e d by t h e s e i n v e s t i g a t o r s
as o n e, f i v e and o n e - h a l f moles r e s p e c t i v e l y .

In creasin g

t h e am ounts o f aluminum c h l o r i d e d i d n o t i n c r e a s e t h e
y ield s.

L e s s b e n z e n e and h i g h e r t e m p e r a t u r e s g a v e more

b y-products.

H u sto n a n d S a g e r ( 1 1 ) showed t h a t p r i m a r y

a l c o h o l s w o u ld n o t c o n d e n s e w i t h b e n z e n e i n t h e p r e s e n c e
o f a n h y d r o u s aluminum c h l o r i d e u s i n g o n e - h a l f mole o f t h e
c o n d e n s i n g a g e n t t o one mole o f t h e a l c o h o l .

N o r r i s and

S tu rg is

(12)

showed t h a t o n l y p o o r y i e l d s w e r e o b t a i n e d

u s i n g l a r g e amounts o f a lu m in u m c h l o r i d e a t e l e v a t e d
tem peratures.

The l a t t e r a l s o e s t a b l i s h e d t h a t t h e

r e a c t i o n o f a l c o h o l s a n d a r o m a t i c n u c l e i was a f u n c t i o n
o f t h e q u a n t i t y o f aluminum c h l o r i d e a n d t e m p e r a t u r e a s
T z u k e r v a n i k a n d N az aro v a ( 1 3 ) h a d p r e v i o u s l y d e t e r m i n e d
in r e g a r d to t h e c o n d e n sa tio n o f secondary a l c o h o l s .
I n 1933 H u sto n and D a v i s ( lU-) f o u n d t h a t from t h e
c o n d e n s a t i o n o f t r i p h e n y l c a r b i n o l , t r i p h e n y l m e t h a n e was
o b t a i n e d , r a t h e r th a n t h e e x p e c t e d t e t r a p h e n y l m e t h a n e .
T his i s a n o t h e r example o f t h e a p p a r e n t r e d u c t i o n o f t h e
c a r b i n o l t o f o rm t h e c o r r e s p o n d i n g h y d r o c a r b o n .

H u sto n

and G-oodemoot ( 1 5 ) hav e shown t h a t , i n g e n e r a l , a l c o h o l s
a l k y l a t e arom atic n u c le i i n

th e presen ce o f anhydrous

aluminum c h l o r i d e o n l y when t h e r e i s a s t r a i n e d c a r b o n
a t t a c h e d to th e hydroxyl g r o u p .

H u s to n , Pox a n d B i n d e r

(1 ) found t h a t s t r a i g h t - c h a i n c a rb in o ls , such as dim ethyln - b u t y l c a r b i n o l , m e th y l e t h y l - n - p r o p y l c a r b i n o l a n d t r i ­
e t h y l c a r b i n o l con d e n se m ore r e a d i l y t h a n b r a n c h e d - c h a l n
carb in o ls.

They e x p l a i n e d t h a t t h e l a t t e r h a v e a l a r g e r

t e n d e n c y t o f o r m u n s a t u r a t e d compounds a n d t e r t i a r y a l k y l
ch lo rid es.
I t was f i r s t o b s e r v e d by G u sta v so n ( 1 6 ) o n l y a y e a r
a f t e r t h e announc em e nt o f t h e F r l e d e l - C r a f t s r e a c t i o n
t h a t th e tendency f o r r e a r r a n g e m e n t o f a l c o h o l s in t h i s
r e a c tio n i s prim ary >

secondary >

te rtia ry .

He f o u n d

t h a t i s o p r o p y l b e n z e n e ( cu m e n e) was fo u n d b y c o n d e n s i n g

e i t h e r n - p r o p y l o r i s o p r o p y l b r o m i d e s w i t h benzen e i n th e
p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .

T h is r e a r r a n g e -

m ent phenomena was l a t e r c o r r o b o r a t e d by o t h e r wq:r k e r s
( 1 7 , I S , 19)*

This is o m e r iz a tio n o f a lc o h o ls in the

p r e s e n c e o f aluminum c h l o r i d e t o t h e more s t a b l e s e c o n d a r y
a n d t e r t i a r y a l k y l g r o u p s i s more p r o n o u n c e d w i t h t h e lo w e r
m olecular w eight a lc o h o ls .

H owever, a s t h e c a r b i in o l

i n c r e a s e s i n m o l e c u l a r w e i g h t a n d becomes h i g h l y b r a n c h e d ,
it

t e n d s t o d e g r a d e o r f r a g m e n t i n t o l o w e r molecu:l a r w e ig h t

compounds w h i c h c a n e i t h e r c o n d e n s e w i t h b e n z e n e , a d d h y d r o gen c h l o r i d e o r c h l o r i d e a n i o n , p o l y m e r i z e o r b e r e d u c e d .
T h i s was o b s e r v e d b y H u s t o n , G u i l e , S o u l a t i and Wasson (20)
i n 19*4-1 •

I t w as o b s e r v e d t h a t when 2 , *4-, *4--t r i m e t h y l - 2 -

p e n t a n o l a n d 2 , 3 »3 “ 't r i me t h y l - 2- p e n t a n o l w ere c o n d e n s e d w i t h
b e n z e n e low y i e l d s o f t h e e x p e c t e d c o n d e n s a t e w ere o b t a i n e d .
T hese i n v e s t i g a t o r s a l s o showed t h a t f r a g m e n t a t i o n was d im in ­
ish e d a t reduced tem peratures.

The y i e l d o f a l k y l b e n z e n e

a n d d e g r a d a t i o n i s a l s o a f u n c t i o n o f t h e amount o f aluminum
c h lo rid e used ( 1 ) .
More r e c e n t l y o t h e r I n v e s t i g a t o r s ( 3 » *4-, 5) h a v e shown
d e m e t h y l a t i o n a n d m e t h y l m i g r a t i o n t o t a k e p l a c e d u r i n g th e
condensation of h ig h ly branched c a r b i n o ls .

F o r e x a m p le ,

H u s to n and B a r r e t t ( 3 ) h a v e shown t h a t t h e c o n d e n s a t i o n o f
d i m e t h y l - t - b u t y l c a r b i n o l p r o d u c e d t - a m y l b e n z e n e an d t r i m e t h y l s t y r e n e i n a d d i t i o n t o t - b u t y l b e n z e n e and t h e

expected h e p ty lb e n z e n e .

The f o r m a t i o n o f t h e f i r s t two

p r o d u c t s c o u l d o n ly b e e x p l a i n e d b y d e m e t h y l a t i o n , t h e
f o r m a t i o n o f t - b u t y l b e n z e n e by f r a g m e n t a t i o n .

Huston

and Van Dyke (k-) o b t a i n e d m e thyl c h l o r i d e , t - b u t y l and
t - a m y l b e n z e n e from t h e c o n d e n s a t i o n o f 2 , 2 , 3- t r i m e t h y l 3- p e n t a n o l w h ich c o u l d o n l y be e x p l a i n e d b y d e m e t h y l a t i o n ,
m e th y l m i g r a t i o n and f r a g m e n t a t i o n .

H uston and K r a n t z ( 5 )

have shown t h a t m e t h y l g r o u p m i g r a t i o n a n d f r a g m e n t a t i o n
t a k e s p l a c e i n t h e c o n d e n s a t i o n o f 2 , 3 , ^ - t r l m e t h y l - 2p e n tan o l w ith benzene.

They r e p o r t t h e i s o l a t i o n o f i s o ­

b u t a n e , t - b u t y l and t - a m y l benzene w i t h o n l y a s m a l l am ount
of the octylbenzene form ed.

A l t h o u g h Awuapara (2) o b t a i n e d

n e a r l y f i f t y p e r c e n t y i e l d o f t - b u t y l b e n z e n e from t h e
c o n d e n s a t i o n o f 2 ,3 , ^ - t r i m e t h y l - 3- p e n t a n o l i n which a
m e th y l r a d i c a l must m i g r a t e , he o b t a i n e d o n ly v e r y s m a l l
y i e l d s o f t - b u t y l a n d t - a m y l b e n z e n e s from t h e c o n d e n s a t i o n
o f 2 ,^4—d i m e t h y l - 3- e t h y l - 3 - p e n t a n o l s i n c e t h e i r f o r m a t i o n
n e c e s s i t a t e s t h e m i g r a t i o n o f an e t h y l g r o u p .
H u s to n and Hughes (&) r e p o r t e d t h e i s o l a t i o n o f s e c b u t y l b e n z e n e from t h e c o n d e n s a t i o n o f 3 - p h e n y l - 3 - b u t a n o l
w ith benzene.

A lso J a c k s o n (7 ) I s o l a t e d i s o p r o p y l b e n z e n e

and s e c - b u t y l b en z en e f ro m t h e c o n d e n s a t i o n s o f d l p h e n y l i s o p r o p y l c a r b i n o l and d i p h e n y l s e c - b u t y l c a r b i n o l r e s p e c t i v e l y
with p h e n o l .

They w ere f i r s t t h o u g h t t o r e s u l t from t h e

breakdow n ( w i t h h y d r o g e n a t i o n ) o f t h e c o n d e n s a t i o n p r o d u c t s
u n d e r t h e i n f l u e n c e o f aluminum c h l o r i d e .

However, when

p - h y d r o x y t r i p h e n y l i s o p r o p y l m e t h a n e w as d i s s o l v e d i n l i g r o i n

a n d t r e a t e d w i t h aluminum c h l o r i d e , no i s o p r o p y l b e n z e n e
c o u l d be I s o l a t e d .

I n s te a d 1 ,l-d ip h en y l-2 ~ m eth y l-l-p ro p en e

was fo u n d a l o n g w i t h p h e n o l .

They c o n c l u d e d from t h i s t h a t

t h e s e c - a l k y l b e n z e n e was form ed d u r i n g t h e p r o c e s s o f
c o n d e n s a t i o n a n d n o t by d e c o m p o s i t i o n o f t h e c o n d e n s a t i o n
product.

The h y d r o g e n d o n o r was n o t d e t e r m i n e d .

THEORETICAL
The I s o l a t i o n o f a l k y l h a l i d e a n d a l k e n e from t h e
co n d en satio n o f a lc o h o l and benzene u s in g anhydrous
aluminum c h l o r i d e a s a c a t a l y s t s t r o n g l y i n d i c a t e s t h a t
t h e r e i s a c l o s e r e l a t i o n s h i p between t h e s e t h r e e a l k y l ­
a tin g agents in the a l k y l a t i o n r e a c t i o n .
I t has been p ro p o sed t h a t a l l o f the th r e e a l k y l ­
a t i n g a g e n t s h a v e a common i o n i c i n t e r m e d i a t e i n t h e
a lk y la tio n r e a c t i o n , t h a t th e r e a c tio n w ith a lc o h o ls
in v o lv es the fo rm atio n o f a lk en es a n d /o r a lk y l h a l i d e s
as i n t e r m e d i a t e s .

O t h e r i n t e r m e d i a t e s w hich h a v e b e e n

p r o p o s e d a r e c o m p le x e s o f aluminum c h l o r i d e w i t h t h e
a l c o h o l and a r o m a t i c n u c l e i .

A lkyl h a l i d e s and a l k e n e s

r e q u i r e o n l y c a t a l y t i c a m o u n ts o f aluminum c h l o r i d e
w h i l e a l c o h o l s r e q u i r e a l a r g e r amount due t o t h e complex
form ed ( 1 2 ) .
As t o t h e r e a c t i v i t y o f a l c o h o l s i n t h e a l k y l a t i o n
r e a c tio n the o rd e r i s b en zy l > t e r t i a r y > secondary >
prim ary.

T h i s i s shown by t h e f a c t t h a t b e n z y l a l c o h o l

r e q u i r e s o n l y t r a c e s o f a weak c a t a l y s t su c h a s z i n c
c h l o r i d e w h ile m ethyl a l c o h o l r e q u i r e s a c o n s i d e r a b l e
q u a n t i t y o f a p o w e r f u l c a t a l y s t suc h a s aluminum c h l o r i d e .
The a s s u m p t i o n t h a t t h e a l k y l a t i o n r e a c t i o n b e t w e e n
a l c o h o l and b e n z e n e , u s i n g a d e h y d r a t i n g a g e n t s u c h a s
aluminum c h l o r i d e , t a k e s p l a c e by d i r e c t rem o v a l o f w a t e r

d o e s n o t e x p l a i n t h e r e a r r a n g e d and l o w e r m o l e c u l a r
w eight p r o d u c ts o b ta in e d .

On t h e b a s i s o f a l k y l a t i o n

t a k i n g p l a c e from t h e f o r m a t i o n o f t h e a l k y l h a l i d e a s
an i n t e r m e d i a t e . T z u k e r v a n l k ( 1 3 ) h a s p r o p o s e d t h e
f o l l o w i n g m echanism f o r t e r t i a r y a l c o h o l s .
t - c 5Hn ° H

+

A lC lj

t - C H 0A1C1
5 11
2
C5H10

t

» t-C ^H 1]LOA1012

------>

+

HC1

t - 0 5 H1:LC6 H5 +

HOI

C H
+
5 10

A1C1 OH
2

HC1 ------ » t - C ^ C l

t - C 5Hu 01

+

CgHg

-" S 3 ,

The i s o l a t i o n o f a l k e n e s and a l k y l h a l i d e s h a s been
o f f e r e d a s e x p e r i m e n t a l e v i d e n c e o f t h e above t y p e
reactio n s.

E v o l u t i o n o f HC1 g a s d u r i n g t h e r e a c t i o n

was e x p l a i n e d b y t h e f o r m a t i o n o f t h e aluminum c h l o r i d e - - a l c o h o l c o m p le x w i t h s u b s e q u e n t e l i m i n a t i o n o f t h e g a s .
He a l s o p r o p o s e d t h i s t y p e o f mechanism f o r s e c o n d a r y
a l c o h o l s , a l t h o u g h h e f o u n d no c h l o r i d e s o r a l k e n e s a s
by-products.

N o r r i s a n d S t u r g i s (12) h a v e p r o p o s e d a

s i m i l a r m e c h a n ism .

T h i s mechanism, h o w e v e r , d o e s n o t

e x p l a i n t h e r e a r r a n g e d p r o d u c t s fo u n d by Kaye (22) from
h i s work on t h e c o n d e n s a t i o n o f some s e c o n d a r y a l c o h o l s
w i t h b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r ­
id e.

Complex f o r m a t i o n o f a l c o h o l s a n d aluminum c h l o r i d e

h a s been i n v e s t i g a t e d by s e v e r a l w o r k e r s ( 2 3 , 2 k ) .
The f o r m a t i o n o f a l k e n e s d u r i n g t h e r e a c t i o n h a s
b e e n u s e d t o p r o p o s e a mechanism w hereby r e a r r a n g e m e n t
o f t h e a l k y l g r o u p s o f c e r t a i n p r i m a r y and s e c o n d a r y

alcohols takes p la ce.

I n c o n n e c t i o n w i t h t h i s , McKenna

a n d Sowa (25) p r o p o s e d a mechanism i n v o l v i n g o l e f i n s as
in te rm e d ia te s in ord er to h e lp expl a in rearrangem ents
during a lk y la tio n .

U sin g b o r o n t r i f l u o r i d e a s a c a t a l y s t

t h e y h a v e i s o l a t e d s m a l l a m o u n ts o f a l k e n e s a n d t h e i r
p o l y m e r s from t h e p r o d u c t s o f t h e r e a c t i o n .
R -C H 2 -C H 2 0H
r - ch=ch2

R -C H = CH,

+ C6 H £ .

R C H (C gH ) CH.
5

Thus t h e c o n d e n s a t i o n o f a p r i mary a l c o h o l w i t h
benzene le a d s to a secondary a l k y l benzene.

A l th o u g h

t h i s mechanism may a c c o u n t f o r t h e f o r m a t i o n o f a l k e n e s ,
a l k y l h a l i d e 8 a n d r e a r r a n g e d p r o d u c t s , i t must be
n e c e s s a r i l y ex clu d ed in th e c a se o f b o th b enzyl a lc o h o l
( 6 ) a n d b e n z h y d r o l ( 1 0 ) i n w h ic h i n t e r r a e d i a t e o l e f i n
form ation i s im possible.

Both o f t hese a lc o h o ls are

e ffe c tiv e a lk y la tin g ag en ts.
S e v e r a l i o n i c m echanisms h a v e been p r o p o s e d by
v a r io u s w orkers in t h i s f i e l d ,
a t t a c k on t h e a r o m a t i c n u c l e i .

a l l in v o lv in g a catanoid
Howe v e r , o n l y t h e t h e o r y

o f P r i c e (2 6 ) w i l l b e m e n t i o n e d h e r e .

This th e o ry

i n v o l v e s an e l e c t r o p h i l l c a t t a c k on t h e a l k y l a t i n g a g e n t ,
w i t h s u b s e q u e n t f o r m a t i o n o f a c a rb o n lu m i o n .

W e rty p o ro c h

an d F i r l a ( 2 7 ) hav e d e m o n s t r a t e d by c o n d u c t a n c e s t u d i e s
t h e f o r m a t i o n o f an i o n i c com p lex b e t w e e n aluminum
c h l o r i d e and a l k y l h a l i d e .

U l i c h a n d Heyne (23) h a v e m e a s u r e d t h e e q u i l i b r i u m
fo r th e fo rm a tio n o f c e r t a i n o f the c a t a l y s t - a l k y l h a lid e
com plexes p o s t u l a t e d by W e rt y p o r o c h a n d i n a d d i t i o n , f o u n d
t h a t t h e r a t e o f a l k y l a t i o n was d i r e c t l y p r o p o r t i o n a l t o
t h e c o n c e n t r a t i o n o f t h i s c a t a l y s t - a l k y l h a l i d e complex*
T h is t y p e o f com plex can a l s o be shown u s i n g oxygen
c o n t a i n i n g compounds s u c h a s a l c o h o l s , e t h e r s , e s t e r s , e t c .
c*
h ci
R : 0 :H + A1:C1 ; = * R : 0 :A1:C1
R+ + ( 0 H A 1 C 1 J Cl
Cl
'
T h is a g a i n shows t h e f o r m a t i o n o f t h e e l e c t r o n
d e f i c i e n t carbonlum i o n .

The a t t a c k on t h e b e n z e n e r i n g

t h e n p r o c e e d s a n a l o g o u s t o h a l o g e n a t i o n w hereby t h e c a r bonium i o n c o m p l e t e s i t s o c t e t by a s s o c i a t i o n w i t h a p a i r
o f e l e c t r o n s f ro m a d o u b l e bond o f t h e a r o m a t i c n u c l e u s .
I p a t i e f f a n d C orson (2 9 ) h a v e shown t h a t t h e above
i

e q u a t i o n i s r e v e r s i b l e by c o n v e r t i n g p - d i - t - b u t y l b e n z e n e
in benzene s o l u t i o n to t- b u ty lb e n z e n e i n th e p r e s e n c e o f
a cataly st*

A l t h o u g h t h e ab o v e r e a c t i o n i s r e v e r s i b l e ,

several in v e stig a to rs

( 3 0 , 3 1 , 3 2 ) h a v e shown t h a t

c a t a l y s t s w i l l remove o n l y t e r t i a r y a l k y l g r o u p s u n l e s s
v i g o r o u s c a t a l y s i s w i t h aluminum c h l o r i d e i s e f f e c t e d .
T his f a c t and th e g r e a t e r ease of a l k y l a t i o n w ith t e r t i a r y
a l k y l a t i n g a g e n t s i s u n d o u b t e d l y due t o t h e t e n a c i t y w i t h
w h ich t h e R g r o u p w i l l r e t a i n e l e c t r o n s i t s h a r e s w i t h t h e
s u b s titu e n t group, h a l i d e , hydroxyl, e t c .

The o r d e r o f

e l e c t r o n e g a ti v ity being prim ary ) se co n d ary ) t e r t i a r y .
Y/here t h e R g r o u p o f t h e a l k y l a t i n g a g e n t i s h i g h l y

b r a n c h e d t h e r e a c t i o n becomes a l i t t l e more com plex a s
e v i d e n c e d by t h e i s o l a t i o n o f b y - p r o d u c t s suc h a s l o w e r
m olecular w eight c h l o r id e s , iso b u ta n e , t - b u t y l benzene,
etc.

T his, o f c o u rse , s tr o n g ly i n d i c a t e s a fragm entation

and r e a r r a n g e m e n t r e a c t i o n a s i n d i c a t e d by t h e f o l l o w i n g
exam ple:
CH, ™

f

* CH^-C^

+ CH2=CH2

ch 3

The s h i f t o f t h e m e t h y l g r o u p t o t h e p o s i t i v e c a r b o n
w i t h s u b s e q u e n t s c i s s i o n o f t h e c a r b o n t o c a r b o n bond to
form a low e n e r g y l e v e l t e r t i a r y g r o u p i n g a c c o u n t s f o r
t h e i s o l a t i o n o f t e r t i a r y b u t y l b e n z e n e and l o w e r m o l e c u l a r
w eight c h l o r i d e s .

I n some c a s e s (k-) t h e m e th y l g r o u p h a s

become p e r m a n e n t l y d e t a c h e d w i t h t h e f o r m a t i o n o f m e th y l
chloride.

The i s o l a t i o n o f l s o b u t a n e ( 5 . 21) and n o t

i s o b u t e n e shows t h a t r e d u c t i o n h a s t a k e n p l a c e d u r i n g th e
reactio n .
The r e a r r a n g e m e n t s e n c o u n t e r e d i n t h e s e a l k y l a t i o n
r e a c t i o n s , p a r t i c u l a r l y where t h e r e i s b r a n c h i n g on t h e
carbon a d j a c e n t to th e h y d ro x y l carbon i s , o f c o u r s e , in
agreem ent w i t h W hitm ore's
rearrangem ent s •

(33)

v ie w s on m o l e c u l a r

EXPERIMENTAL - PART I
I .

P r e p a r a tio n o f A lcohols
A ll of th e p o s s i b l e t e r t i a r y o c t a n o l s , h e p t a n o ls ,

and h ex a n o ls h a v in g o n ly p r im a r y a l k y l groups a t t a c h e d
t o h y d r o x y l c a r b o n were s e l e c t e d f o r t h i s s t u d y w i t h
t h e e x c e p t i o n o f 4—E t h y l - 4 —h e p t a n o l , 4—M e t h y l - * ! - - h e p t a n o l ,
a n d 2 , iJ-,iJ ~ T r i m e t h y l - 2 - p e n t a n o l w hich w ere p r e v i o u s l y
stu d ied .

T e r t i a r y amyl a n d t e r t i a r y b u t y l a l c o h o l s , w h ic h

were a l s o c o n d e n s e d i n t h i s w o rk , w ere o b t a i n e d d i r e c t l y from
t h e s to c k r o o m .

The a l c o h o l s p r e p a r e d w ere p r o p e r l y i d e n t i ­

f i e d by p h y s i c a l c o n s t a n t s a n d , as a m a t t e r o f i n t e r e s t ,
3 , 5 - D i n l t r o b e n z o a t e s were a l s o s u c c e s s f u l l y p r e p a r e d and
analyzed for n itr o g e n .

Micro-Dumas m e th o d was u s e d .

A.

2-M ethyl-2-heptanol

B.

3-M ethyl-3-heptanol

G.

3-E thyl-3-hexanol

D.

2 ,*}—D i m e t h y l - 2 - h e x a n o l

E.

2 ,5-D im et h y l - 2 - h e x a n o l

F.

2, ^-D im ethyl-if-hexanol

a.

2-Me t h y l - 2 - h e x a n o l

H.

3-M ethyl-3-hexanol

J.

3-E thyl-3-pentanol

K.

2 ,4—D i m e t h y l - 2- p e n t a n o l

L.

2-M ethyl-2-pentanol

M.

3 - M e t h y l - 3- p e n t a n o l

N.

2-M ethyl-2-butanol

0.

2-M ethyl-2-propanol
P a r t A.

2-M ethyl-2-heptanol

OH,
i 3
CH5 -C-CH2-CH2-CH2-CH2 -CH;5
OH
As a l l o f t h e a l c o h o l s were p r e p a r e d by t h e a d d i tio ji o f e s t e r , k e to n e o r a c i d to a G rig n a rd r e a g e n t , only
t h e d e t a i l e d p r o c e d u r e f o r t h e p r e p a r a t i o n o f t h e above
a l c o h o l w i l l be g i v e n ,
2 - M e t h y l - 2 - h e p t a n o l was p r e p a r e d by t h e a d d i t i o n o f
a c e t o n e t o n - a m y l magnesium b r o m i d e , f o l l o w e d ky t h e
h y d r o l y s i s o f t h e r e s u l t i n g a d d i t i o n compound.

The

G r i g n a r d was p r e p a r e d b y p l a c i n g £>5 grams ( 3 . 5 m o le s ) o f
magnesium t u r n i n g s i n a t h r e e l i t e r ,

t h r e e n e c k e d , round

bottom f l a s k equipped w ith a g l y c e r i n e s e a le d m echanical
s t i r r e r , r e f l u x c o n d e n s e r, and d r o p p in g f u n n e l.

The

c o n d e n s e r a n d d r o p p i n g f u n n e l were c l o s e d w i t h c a l c i u m
c h lo rid e f i l l e d drying tu b e s .

The r e a c t i o n was s t a r t e d

by r u n n i n g i n t o t h e f l a s k , on t o p o f t h e magnesium, a b o u t
5 ml o f a 1 : 1 m i x t u r e o f a n h y d r o u s e t h e r and n - a m y l brom­
ide ,

The e t h e r was d r i e d o v e r f r e s h l y c u t sodium and t h e

n - a m y l b r o m id e d r i e d o v e r a n h y d r o u s c a l c i u m c h l o r i d e to
remove w a t e r , and a l c o h o l , a n d d i s t i l l e d c o l l e c t i n g t h a t
p o r t i o n b o i l i n g b e tw e e n 1 2 7 - 131°C» a n d h a v i n g a i n d e x o f
r e f r a c t i o n o f 1 J l M -4 a t 20°C .
from 3 -5

m inu tes,

A f t e r allo w in g to s ta n d

s i x h u n d r e d ml o f a n h y d r o u s e t h e r was

added t h r o u g h t h e t o p o f t h e c o n d e n s e r , t h e m e c h a n i c a l
s t i r r e r s t a r t e d , a n d t h e r e m a i n d e r o f t h e n -am y l b r o m i d e e t h e r s o l u t i o n ( 5 2 2 .5 g b r o m i d e ; 3 - 5 m o le s )

(600 ml e t h e r )

a d d e d a t su c h a r a t e a s to k e e p t h e r e a c t i o n u n d e r c o n t r o l .
E x t e r n a l c o o l i n g w i t h i c e was u s e d i n o r d e r t o I n c r e a s e
the r a t e of a d d i tio n .

A t o t a l o f 1200 ml o f e t h e r was

u s e d f o r t h e 3*5 mole r u n o r 3^2 ml p e r mole o f G r i g n a r d .
A f t e r t h e a d d i t i o n o f t h e b ro m id e was c o m p l e t e d t h e
r e a c t i o n m i x t u r e was s t i r r e d f o r two h o u r s and t h e n
a l l o w e d to s t a n d o v e r n i g h t .

The G r i g n a r d r e a g e n t was

t h e n t i t r a t e d a c c o r d i n g t o t h e m ethod d e s c r i b e d by G ilm an,
W i l k e n s o n , F i s c h e l , and M eyers ( 3 ^ ) «

The c a l c u l a t e d

amount o f G r i g n a r d f o r an a v e r a g e r u n was 3*2 m o le s o r
an a c t u a l y i e l d o f

On t h i s b a s i s 126 grams ( 3 . 2

m oles) o f a c e t o n e i n a n h y d r o u s e t h e r (*K)0 ml p e r mole)
was a d d e d a t a r a t e o f one d r o p p e r s e c o n d .

The a c e t o n e

was d r i e d o v e r a n h y d r o u s p o t a s s i u m c a r b o n a t e a n d d i s t i l l e d
c o l l e c t i n g t h a t p o r t i o n b o i l i n g b e tw e e n 5 5 " 57°C a n d h a v i n g
an i n d e x o f r e f r a c t i o n o f 1 . 3 5 9 1 a t 20°C.
A f t e r t h e a d d i t i o n o f t h e a c e t o n e was c o m p le t e t h e
m i x t u r e was s t i r r e d f o r two h o u r s a n d t h e n a l l o w e d to
Hr

stand o v e rn ig h t.

The a d d i t i o n p r o d u c t was th e n h y d r o l i z e d

w i t h i c e and enough 1 :1 s u l f u r i c a c i d a d d e d to d i s s o l v e t h e

A lthough t h e a u t h o r , i n m ost o a s e s , d i d n o t add b e n z e n e a t
th is p o in t,

B a ile y ( 35) found t h a t by

addingbenzene, d i s t i l l ­

i n g o f f th e

e t h e r , and r e f l u x i n g a t a h i g h e r t e m p e r a t u r e

was a b l e to

i n c r e a s e t h e y i e l d o f t h e a l c o h o l a s much a s IJfZ

i n th e case

o f 2- M e t h y l - 3- e t h y l - 3 - p e n t a n o l .

he

b a s i c magnesium s a l t s .

The e t h e r a l c o h o l l a y e r was

s e p a r a t e d f ro m t h e w a t e r l a y e r and t h e l a t t e r e x t r a c t e d
w ith e t h e r .

The com bined o r g a n i c l a y e r s were washed w i t h

10 p e r c e n t sodium c a r b o n a t e u n t i l b a s i c t o l i t m u s , and
t h e n w i t h d i s t i l l e d w a t e r , and d r i e d o v e r a n h y d r o u s
sodium s u l f a t e f o r t w e n t y f o u r h o u r s .

The e t h e r was

removed t h r o u g h a 60 x 1 cm Fenske t y p e column p a c k e d
w ith l / l 6 in c h g la s s h e l i c e s .

The a l c o h o l was c o l l e c t e d

o v e r a two d e g r e e r a n g e a t r e d u c e d p r e s s u r e .
Y ield :

5I #

BP17

: 63- 65° C

ng°

: 1 .4 2 3 5

d |°

: 0 .8 1 5 6

3 ,5-D initrobenzoate:

M.P. ^3-l|H.°C
% N

C a l c , g .63
Obs. £ . 4 0

T h i s a l c o h o l was p r e p a r e d by Whitm ore and W i l l i a m s
( 3 6 ) and t h e p h y s i c a l c o n s t a n t s a g r e e w i t h t h e i r work i n
w hich t h e y p r e p a r e d t h e a l c o h o l by t h e same m e th o d .
P a r t B.

3-M ethyl-3-heptanol

CH1 ■>
CH^-CHg-C -CHg-CHp-CHg-CH^
OH
T h is a l c o h o l was p r e p a r e d b y t h e a d d i t i o n o f m e th y l
e t h y l k e t o n e t o n - b u t y l magnesium b r o m i d e .
Y ield :

68#

BP15 :

6l-63°C

n§°

1 . 1^270

:

D{j°

:

0.325g

3 .5 -D in itrob en zoate'

M.P.

5 3 - 5 iJ-°C

^ N

C alc.
S . 63
Obs. S.B25

T h is a l c o h o l was p r e p a r e d by Whitmore and B a d e r t s c h e r
( 3 7 ) a n d S nyder ( 3S) by t h e same m e th o d .
1

P a r t C.

3 ” E‘t ^ y l - ' 3 “h e x a n o l
CH,
•

P

9H2
c H j - c h 2 - c - c h 2- c h 2- c h 3
OH
T h is a l c o h o l was p r e p a r e d by two d i f f e r e n t m e th o d s ,
b o t h h o w e v e r, i n v o l v i n g u s e o f t h e G r i g n a r d r e a g e n t .

The

f i r s t method u s e d was t h a t o f Huston and B a i l e y (35 ) i n
w h ich one mole o f n - b u t y r i c a c i d was a d d e d t o t h r e e moles
o f e t h y l magnesium b r o m i d e .

The s e c o n d method was t h a t

u s e d by C l a r k and R i e g e l (39 ) i n w hich d i e t h y l k e t o n e was
ad d e d t o p r o p y l magnesium b r o m i d e .

A lt h o u g h t h e se co n d

method p r o d u c e d s l i g h t l y b e t t e r y i e l d s t h e f i r s t method
i s more f e a s i b l e c o s t w i s e .

The p h y s i c a l c o n s t a n t s ch ecked

f o r each p r e p a r a t i o n .
Y ield:

50^ ( u s i n g b u t y r i c a c i d )
(u s in g d ie th y l ketone)

BPi 2 :

57-59°C

nj*0

:

i . i j .316

D^°

:

0 .B370

3 .5-D in itro b e n z o a te :

M. P.
f* N

62-63°C
C a l c , g .63
Obs. B .7 ^

P a r t D.

2D lm ethyl-2-hexanol

9H3

?H3

CH^-C -CH0-CH-CH0-CH-,
J \
2
2
3
OH
T h i s a l c o h o l was p r e p a r e d by two d i f f e r e n t m e t h o d s .
The f i r s t m e th o d u s e d was t h a t o f H u s to n and G u i l e (20)
i n w h i c h a c e t o n e was a d d e d t o a c t i v e - a m y l magnesiuni
brom ide.

The s e c o n d method i n v o l v e d t h e a d d i t i o n o f

c a r b o n d i o x i d e t o a c t i v e - a m y l magnesium b r o m id e anc. t h e n
t h e a d d i t i o n o f m e t h y l magnesium b r o m i d e t o t h e a c i d
c o m p le x .

I n t h e l a t t e r m e th o d t h e c a r b o n a t i o n o f t h e

a c t i v e - a m y l magnesium b r o m i d e was a c c o m p l i s h e d a c c o r d i n g
t o t h e p r o c e d u r e g i v e n i n O r g a n i c S y n t h e s i s (1+0) w i t h
s lig h t m o d ification s.

The a c t i v e - a m y l magnesium b r o m id e

was p r e p a r e d i n a 5 - H ‘t e r , t h r e e - n e c l c f l a s k e q u i p p e d w i t h
s t i r r i n g m otor, condenser and dropping f u n n e l.

For t h e

c a r b o n a t i o n t h e d r o p p i n g f u n n e l was r e p l a c e d w i t h a g l a s s
t u b e w h ic h e x t e n d e d 2 cm a b o v e t h e s u r f a c e o f t h e
G rignard.

To t h i s t u b e was a t t a c h e d f o u r s a f e t y b o t t l e s ,

two o f w hich c o n t a i n e d s u l f u r i c a c i d .
was c o n n e c t e d a t a n k o f C02 g a s .

To t h e s e b o t t l e s

The r e a c t i o n f l a s k was

c o o l e d e x t e r n a l l y by s o l i d c a r b o n d l o x l d e - e t h e r to
a p p ro x im a te ly -12°C.

The t e m p e r a t u r e r o s e t o 0°G d u r i n g

t h e a d d i t i o n o f t h e c a r b o n d i o x i d e , w h ich to o k a p p r o x i ­
m a t e l y 5-g- h o u r s f o r a t h r e e mole r u n .

The a d d i t i o n was

c o m p l e t e when t h e t e m p e r a t u r e d r o p p e d and t h e s o l u t i o n
o f t h e a c i d com plex became d a r k and s y r u p y .

The me i h y l

magnesium b r o m i d e was a d d e d d i r e c t l y to t h e a c i d complex
w ith s t i r r i n g .

A f t e r t h i s a d d i t i o n was c o m p l e t e t h e

f l a s k was f i t t e d w i t h a g o o s e - n e c k t u b e a n d c o n d e n s e r ,
and t h e e t h e r s l o w l y d i s t i l l e d o f f u n t i l t h e t e m p e r a t u r e
r o s e to 50-55°C .

Then 1 l i t e r o f a n h y d r o u s b e n z e n e was

added and th e r e a c t i o n m ix tu re r e f l u x e d f o r f o u r h o u rs
before h y d ro ly sis.

A c c o r d i n g t o t h e work o f H u s to n and

B a i l e y (3 5 ) t h i s p r o c e d u r e i n c r e a s e d t h e y i e l d o f a l c o h o l
a s much a s I J f i i n one p a r t i c u l a r c a s e a l r e a d y m e n t i o n e d .
The p h y s i c a l c o n s t a n t s o f t h e a l c o h o l a r e i n a g r e e ­
ment f o r b o t h m ethods o f p r e p a r a t i o n .
Y ield:

2.k-% ( u s i n g a c e t o n e )

(using carbonation)
BP20 :
:

62-6^°C
1 .^ 250
0 .S 2 1 3

3 ,5 -D in itro b en zo ate:

M .P .

4g.5-lj-9°C

% N

C alc,
Obs.

g .6 3
g .6 9

T h is a l c o h o l was a l s o p r e p a r e d by Levene a n d Marker
(4-1) u s i n g t h e e t h y l e s t e r o f 3- m e t h y l p e n t a n o i c a c i d
a n d m e th y l magnesium i o d i d e .
P a r t E.

2 , 5 -Dimet h y l - 2 - h e x a n o l

CH-jj
OH^
CH -C CH_-CH»-CH-CH_
3 T
2
2
3
OH
T h i s a l c o h o l was p r e p a r e d by D r. G u i l e o f t h i s
l a b o r a t o r y by t h e a d d i t i o n o f a c e t o n e t o is o a m y l magnesium
b rom ide.

BPy^g:

1 5 1 . 6°C

ngO

;

1 .4210

Dj-°

:

0 .315^

3 ,5-D in itr o b e n z o a te :

M. P.

6l-62°C

% N

C alc,
O b s.

g.6'3
<3.95

I t was a l s o p r e p a r e d by L eve ne a n d M arker (40) ,
u s in g the e t h y l e s t e r o f 4-m ethyl p e n ta n o ic a c i d and
m e t h y l magnesium i o d i d e .
P a r t F.

2,4-D lm ethyl-4-hexanol

?H3
?H3
CH.,-CH-CH_-C -CH -CH_
j
d 1
2 3
OH
T h is a l c o h o l was p r e p a r e d b y two d i f f e r e n t m e t h o d s .
The f i r s t m e th o d em ployed by Levene a n d M arker ( 4 l ) was
t h e a d d i t i o n o f a c e t o n e t o i s o b u t y l magnesium b r o m i d e .
The s e c o n d m e th o d was t h a t employed b y C l a r k e (42) i n which
m e t h y l l s o b u t y l k e t o n e was added t o e t h y l magnesium b r o m i d e .
T h is method gave much b e t t e r y i e l d s a n d a p u r e r p r o d u c t .
A p p a r e n t l y when t h e r e i s a c h o i c e o f G r i g n a r d r e a g e n t s , su c h
as in th e p r e p a r a t i o n o f t h e above a l c o h o l and o t h e r s p r e ­
p a re d f o r t h i s problem ,

t h e more com plex t h e G r i g n a r d

re a g e n t used, the po o rer th e y i e l d of alcohol o b ta in e d .
The t h e o r e t i c a l a s p e c t o f t h i s phenomena w i l l be t a k e n up
u n d e r th e d i s c u s s i o n p a r t o f t h i s t h e s i s .
Y ield :

21^ ( u s i n g a c e t o n e )
56j£ ( u s i n g m e t h y l e t h y l k e t o n e )

BP15

: 5 1 .5 -5 2 C

n*°

: 1A275

D^°

: 0 . g 260

3 , 5-D in itr o b e n z o a te :

M .P.
% N

P a r t G.

52-53°C
C a lc ,
O b s.

g .6 3
g .9 3

2 -M e th y l-2 -h e x a n o l

CH3
CH-.-C -CH -CH -CH -CH
s i
2
2
2
3
OH
T h is a l c o h o l was p r e p a r e d a c c o r d i n g t o t h e m ethod
u s e d b y W hitm ore a n d Church ( ^ 3 ) and W hitm ore and
B a d ertsch er

(37)

i n w h ic h a c e t o n e was a d d e d t o n - b u t y l

m agnesium b r o m i d e .
Y ie ld

67^

BP

5 9 -6 l°C

25
20
n
D

20

1 .^ 1 7 9
0 .g l2 2

3 ,5 -D in itr o b e n z o a te :

M .P .
% N

P art H .

5 3 -5 ^ °C
C a lc .
9*02
O b s. g . 6 g

3-Me-th y l - 3 - h e x a n o l

ch3
C H - t - C H Q- C - C H - C H - C H
y
I
2
2
3
OH
T h is a l c o h o l was p r e p a r e d a c c o r d i n g t o t h e m ethod
u s e d b y W hitm ore a n d B a d e r t s c h e r ( 3 7 ) i n w h ic h m e t h y l
e t h y l k e t o n e was a d d ed t o e t h y l m agnesium b r o m i d e .

Y ield
BP

53-5^°c

12
20
n
D

1 . 11-231

20

0.2219

3 ,5 -D in itro b en zo ate:

Part J.

M .P .

^3-^°C

% N

C alc. 9 .02
Obs. 9 . 5*1-

3 -E thyl-3-pentanol
CH7
4h 2
CHa -CH_-C -C H -C H
2
2 1
2
3
OH

T h i s a l c o h o l was p r e p a r e d a c c o r d i n g t o t h e m ethods
u s e d b y Moyer and M a rv e l (4-4-) a n d Whitmore a n d
B a d e r t s c h e r ( 3 7 ) i n w h ic h d i e t h y l c a r b o n a t e was a d d e d t o
e t h y l magnesium b r o m i d e .
Y ield

10 %

BP

72-73°c

52

n

f

i , h 29 k

Di

0.2395

>f

3 , 5- D i n i t r o b e n z o a t e :

P a r t K.

M.P .

11 2-119°C

% N

C alc. 9.02
Obs. 9 . 1 7

2,*1—D i m e t h y l - 2 - p e n t a n o l
ch3
CH,
CH-.-C -CH0-CH-CH_
j l
2
3
OH

T h i s a l c o h o l was p r e p a r e d b y t h e a d d i t i o n o f m e th y l
i s o b u t y l k e t o n e t o m e t h y l magnesium b r o m i d e .

Edgar,

C a l i n g a e r t a n d M a rk e r ( ^ 5 ) p r e p a r e d t h e same a l c o h o l b y
t h e a d d i t i o n o f a c e t o n e t o i s o b u t y l magnesium b r o m id e
and o b ta in e d only a 3° p e r c e n t y i e l d .

This i s a n o th e r

exam ple i n w h ic h t h e c h o i c e o f G r i g n a r d r e a g e n t h a s a
g r e a t b e a r i n g on t h e y i e l d and p u r i t y o f t h e p r o d u c t
o b tain ed .
Y ield:

59#

b? 1 7

lf3°C

:

l . H -172
0 .5 1 0 6
3 ,5 -D in ltro b en zo ate:

M.P.
# N

69-70°C
Calc. 9 .0 2
Obs. 9 . 0 7

T h is a l c o h o l was a l s o p r e p a r e d by de G r a e f ( ^ ) .
P a r t L.

2-M ethyl~2-pentanol
?H3

CH,-C -CH -CH0-CH,
3 «
2 2 3
OH
T h i s a l c o h o l was p r e p a r e d by t h e method u s e d by
H u sto n and H s i e h ( ^ 7 ) an*3- Fox (lJ-5) , i n w h ic h a c e t o n e was
a d d e d t o n - p r o p y l magnesium b r o m i d e .
Y ield:

70.2#

BP63

: 65 -66°C

ng°

: 1.1J-1Q8S

Dj*0

: o.&lkG

3 , 5- D i n i t r o b e n z o a t e :

M.P.

Obs.
L it.

71-72°C
71-72°C

P a r t M.

3**M eth yl-3-p en tanol
CH
ch 3 - ch 2 - c

-CH^-CH^

OH
T h is a l c o h o l was p r e p a r e d by t h e m ethod u s e d b y
H u s to n a n d H s l e h (^7) i n w h i c h m e t h y l e t h y l k e t o n e was
a d d e d t o e t h y l magnesium b r o m i d e .
Y ield:

70.1#

BP 7

: 6 5 - 66°C

n^O

: l A l 71

Djj°

: 0.3222

3 ,5-D in itro b e n z o a te :

P a r t N.

M.P.

O bs.
L it.

95*5-96.5°C
9 5 * 5 - 9 6 . 5°C

2-M ethyl-2-butanol

T h is was o b t a i n e d d i r e c t l y from t h e s to c k r o o m o f a
CP g r a d e h a v i n g p h y s i c a l c o n s t a n t s w h i c h a g r e e d w i t h
lite r a tu r e values.
Part 0.

2-M ethyl-2-propanol

T h is was a l s o o b t a i n e d d i r e c t l y from t h e s to c k r o o m
o f a CP g r a d e h a v i n g p h y s i c a l c o n s t a n t s w hich a g r e e d w i t h
lit e r a t u r e values.

11•

The C o n d e n s a t i o n A p p a r a t u s
The a p p a r a t u s u s e d f o r t h e c o n d e n s a t i o n o f t h e

v a r i o u s a l c o h o l s was e s s e n t i a l l y t h e same a s t h a t
d e v i s e d b y Van Dyke ( ^ ) i n t h i s l a b o r a t o r y w i t h t h e
e x c e p t i o n o f a few m in o r m o d i f i c a t i o n s .

Figure 1

shows a d i a g r a m o f t h e c o n d e n s a t i o n , a p p a r a t u s w i t h t h e
im p o rta n t p a r t s i n d i c a t e d by l e t t e r and l i s t e d below .
A.

A t h r e e - n e c k , round bottom f l a s k , th e s i z e v a r y in g

w i t h t h e amount o f a l c o h o l c o n d e n s e d .
B.

D ro p p in g f u n n e l w i t h i n n e r s e a l e d t u b e f o r e q u a l ­

i z i n g t h e p r e s s u r e i n o r d e r t o kee p o u t m o i s t u r e a n d
f o r m i n g an a i r t i g h t s y s t e m .
C.

M e c h a n i c a l s t i r r e r c o n s i s t i n g o f an e l e c t r i c m o t o r

and a g l y c e r i n e - r u b b e r s e a l e d g l a s s r o d s t i r r e r .
D.

Carbon d i o x i d e g e n e r a t o r s y s t e m c o n s i s t i n g o f a

vaouum b o t t l e o f c o n c e n t r a t e d s u l f u r i c a c i d and a
mercury s a f e t y v a lv e to r e l e a s e gas p r e s s u r e .
E.

A s i d e a r m d e l i v e r y t u b e t o which i s a t t a c h e d a

therm om eter and r e f l u x c o n d e n s e r .
F.

Two way s t o p cock i n o r d e r t o b y p a s s t h e i c e - s a l t

w ater cooled t r a p .
G.

I c e - s a l t w ater cooled t r a p f o r condensing the vapors

o f t h e l o w e r v o l a t i l e l i q u i d s s u c h a s b e n z e n e and t h e
alco h o l.
H.

Two way s t o p cock i n o r d e r t o b y p a s s t h e s o l i d

carbon d io x id e - a c e to n e c o o led t r a p l e a d i n g to th e n i t r o ­
m eter.

I.

S o lid carbon d io x id e -a c e to n e co o led t r a p to condense

t h e h i g h l y v o l a t i l e l i q u i d s n o t b o i l i n g l o w e r t h a n -SO°C.
J.

One way s t o p cock o p e r a t e d i n c o n j u n c t i o n w i t h s t o p

c o c k s F a n d H.

T h i s was c l o s e d when L was a d j u s t e d t o

bypass the t r a p .
K.

M erc u ry t r a p t o p r e v e n t b a c k p r e s s u r e due t o t h e

c o o l i n g down o f t h e s y s t e m to w a r d s t h e end o f t h e r e a c t i o n
L.

S afety b o t t l e .

M.

Gas n i t r o m e t e r c o n t a i n i n g 5 ° p e r c e n t CP p o t a s s i u m

h ydroxide f o r a b s o rb in g t h e carbon d io x id e and hydrogen
ch lorid e.

The n i t r o m e t e r was o f J 0 0 m l . c a p a c i t y w i t h a

d i a m e t e r o f 25 mm i n t h e v e r t i c a l s e c t i o n s a n d 10 mm i n
the curved s e c t i o n .

M e r c u r y was p l a c e d i n t h e b a s e t o

s e a l t h e p o t a s s i u m h y d r o x i d e s o l u t i o n from t r a p L .
N.

N i t r o m e t e r l e v e l i n g b u l b c o n s i s t i n g o f a 250 m l.

dropping f u n n e l .

FIGURE 1
3

III.

C o n d e n satio n and F r a c t i o n a t i o n
The a l c o h o l s p r e p a r e d a s d e s c r i b e d w ere c o n d e n s e d

w i t h b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r ­
ide.

The p r o c e d u r e u s e d i n r e g a r d t o c o n t r o l o f t e m p e r a ­

t u r e , mole p r o p o r t i o n a n d r a t e o f a d d i t i o n o f r e a c t a n t s
was s i m i l a r t o t h a t em p lo y ed by s e v e r a l w o r k e r s i n t h i s
la b o ra to ry , studying t h i s p a r t i c u l a r a lk y la tio n r e a c t i o n .
I t was e s t a b l i s h e d by H u s to n a n d F rie d m an n ( 6 ) t h a t t h e
p r o p o r t i o n o f b e n z e n e t o a l c o h o l f o r o b t a i n i n g maximum
y i e l d s o f a l k y l b e n z e n e was a p p r o x i m a t e l y 5 m o le s t o 1
resp ectiv ely .

The e x c e s s b e n z e n e n o t o n l y a c t s a s a

d i l u e n t in t h i s case b u t a l s o m inim izes d i s u b s t i t u t i o n .
The above m o l a r r a t i o o f b e n z e n e - a l c o h o l was m a i n t a i n e d
t f o r e a c h c o n d e n s a t i o n w i t h t h e e x c e p t i o n o f 3 - e t h y l - 3p e n t a n o l i n w h ic h a 1 : 1 mole r a t i o was u s e d .

The r e a s o n

f o r t h i s e x c e p tio n w i l l be e x p la in e d u n d er P a r t J .

It

was a l s o d e t e r m i n e d by t h e a u t h o r ( 2 1 ) t h a t t h e mole
r a t i o o f a l c o h o l - a l u m l n u m c h l o r i d e f o r o b t a i n i n g m axi­
mum y i e l d s o f a l k y l b e n z e n e was 1 : 0 . 5 r e s p e c t i v e l y .

As

t h e p r o c e d u r e f o r a l l c o n d e n s a t i o n s and f r a c t i o n a t i o n s
was t h e same o n l y one w i l l b e d e s c r i b e d i n d e t a i l .
One h u n d r e d s e v e n t y n i n e a n d o n e - h a l f grams ( 1 . 3 5
m oles) o f CP a n h y d r o u s aluminum c h l o r i d e was p l a c e d i n
t h e r e a c t i o n f l a s k a l o n g w i t h IO53 grams (13*5 m o le s ) o f
anhydrous th io p h e n e - f r e e b en zen e.

The benz ene -a lura inura

c h l o r i d e m i x t u r e was h e a t e d t o r e f l u x w i t h s t i r r i n g f o r
a c t i v a t i o n p u r p o s e s a n d was t h e n a l l o w e d t o c o o l t o room

tem perature*

T h ere was no n o t i c e a b l e c o l o r c h a n g e a t

t h i s p o i n t , how ever s m a l l amounts o f g a s e o u s h y d r o g e n
c h l o r i d e w ere p r o d u c e d .

A f t e r r e a c h i n g room t e m p e r a t u r e

t h e s y s t e m was swept o u t w i t h o a r b o n d i o x i d e u n t i l m i c r o ­
bubbles appeared in th e n itr o m e te r .

The c a r b o n d i o x i d e

g e n e r a t o r was t h e n t u r n e d o f f a n d t h e a l c o h o l ( 2 , ^ - D i m e t h y l - 2- p e n t a n o l i n t h i s c a s e )

( 31^ g ra m s; 2 . 7 m o le s )

a d d e d a t s u c h a r a t e a s t o kee p t h e t e m p e r a t u r e o f t h e
r e a c t i o n b e l o w 35°^«

G aseou s e v o l u t i o n u s u a l l y t o o k

p la c e d u rin g th e a d d itio n o f the f i r s t o n e - th ir d o f th e
a l c o h o l an d b a c k p r e s s u r e was n o t i c e d a f t e r a p p r o x i m a t e l y
one h a l f o f t h e a l c o h o l was a d d e d .

This back p r e s s u r e

was a p p a r e n t l y due t o t h e h e a t o f t h e r e a c t i o n s u b s i d i n g
and th e c e s s a t i o n o f th e fo rm a tio n o f any gaseous p r o ­
ducts.

At t h e end o f t h e a d d i t i o n o f t h e a l c o h o l t h e

t e m p e r a t u r e d r o p p e d t o a r o u n d t h i r t y d e g r e e s i n m ost
condensations.

S t i r r i n g was c o n t i n u e d f o r .a p e r i o d o f

two h o u r s and t h e n t h e r e a c t i o n mix was a l l o w e d t o s t a n d
f o r tw e n ty -fo u r hours b e f o r e h y d r o ly s is .

At t h i s t i m e

a n y g a s c o l l e c t e d i n t h e n i t r o m e t e r was t r a n s f e r r e d t o
g a s b u r e t t e s a n d t e s t e d f o r c o n d e n s i b i l i t y , b u r n i n g and
th e s u p p o rtin g o f com bustion.

The o n l y g a s w h ich form ed

d u r i n g any o f t h e c o n d e n s a t i o n s was i d e n t i f i e d a s i s o ­
b u t a n e a n d t h e n o n l y when s u c h was fo rm e d by t h e f r a g m e n ­
t a t i o n of the a lc o h o l.

The o n l y v o l a t i l e l i q u i d c o n d e n s e d

i n t h e d r y - l c e a c e t o n e c o o l e d t r a p was I s o b u t a n e and t h i s
o n l y when t h e c o n f i g u r a t i o n o f t h e a l c o h o l c o n d e n s e d

p erm itted frag m en tatio n .

The a l c o h o l d e s c r i b e d i n t h i s

c o n d e n s a t i o n (2 • ^4—D i m e t h y l - 2 - p e n t a n o l ) d i d f r a g m e n t and
i s o b u t a n e was fo u n d i n t h e above m e n t i o n e d t r a p .

I t was

i n t e r e s t i n g t o n o t e t h a t i n e a c h c a s e 7/here l s o b u t a n e was
p r o d u c e d i t d i d so d u r i n g t h e f i r s t one t h i r d a d d i t i o n o f
the a lc o h o l.

The l s o b u t a n e was t h e n f r a c t i o n a t e d many

tim es by a llo w in g i t

to come s l o w l y t o room t e m p e r a t u r e

and p a s s i n t o a n o t h e r r e c e i v e r c o o l e d by d r y - i c e a c e t o n e
where i t v/as r e c o n d e n s e d .

T h is p r o c e d u r e f r e e d i t from

h y d r o g e n c h l o r i d e and a n y b e n z e n e w h ich e s c a p e d t h e i c e s a l t w ater co o led t r a p .
The h y d r o l y s i s o f t h e r e a c t i o n com plex was
a c c o m p l i s h e d by t h e a d d i t i o n o f s m a l l p i e c e s o f i c e i n t o
the r e a c t i o n f l a s k , w ith s t i r r i n g .

The t e m p e r a t u r e u s u a l l y

r o s e s h a r p ly a t t h i s p o i n t and th e n s u b s i d e d .

Then 200

m l. o f d i s t i l l e d w a t e r was added i n 5° nil* p o r t i o n s .

No

a c i d was u s e d i n t h e h y d r o l y s i s , a s t h e w a t e r was
s u f f ic ie n t to d isso lv e th e b a s ic s a l t s a f t e r considerable
stirrin g .

The o r g a n i c l a y e r was t h e n s e p a r a t e d f ro m t h e

a q u e o u s l a y e r , t h e l a t t e r e x t r a c t e d t h r e e t i m e s w i t h 50
m l. p o r t i o n s o f b e n z e n e , a n d t h e com bined e x t r a c t s p l u s
t h e o r i g i n a l o r g a n i c l a y e r w ere w a sh e d w i t h 10$ sodium
c a r b o n a t e a n d t h e n d i s t i l l e d w a t e r , and t h e n d r i e d o v e r
a n h y d r o u s sodium s u l f a t e .

The c o l o r o f t h e s o l u t i o n s o f

t h e v a r i o u s c o n d e n s a t i o n s , a t t h i s p o i n t , v a r i e d from
l i g h t o r a n g e t o d a r k g r e e n i s h y e l l o w , a l l h a v i n g an
opalescent tin g e .
A l l i n i t i a l d i s t i l l a t i o n s were c a r r i e d o u t by a

60 x 1 . 0 cm column p a c k e d w i t h 1 / 1 6 i n c h g l a s s h e l i c e s .
The h e a d on t h e column was d e s i g n e d f o r d i s t i l l a t i o n
under reduced p r e s s u r e w ith a take o f f f o r p e r m it tin g
reflu x .

Thus i t was p o s s i b l e t o a l l o w t h e v a p o r s t o

come t o e q u i l i b r i u m b e f o r e a c u t was made.

The s o l v e n t

i n e a c h c a s e was d i s t i l l e d o f f a t a t m o s p h e r i c p r e s s u r e .
D uring t h i s p e r i o d o f th e d i s t i l l a t i o n a carbon d i o x i d e a c e t o n e c o o l e d t r a p was c o n n e c t e d b e t w e e n t h e h e a d o f t h e
column and t h e vacuum s a f e t y f l a s k .

T h i s was f o r t h e

p u r p o s e o f c o n d e n s i n g any lo w b o i l i n g l i q u i d s w h ic h m ig h t
h a v e bee n d i s s o l v e d i n t h e s o l v e n t .
I t was f o u n d i n many c a s e s by w o r k e r s i n t h i s
l a b o r a t o r y (4-, 5 ) , p a r t i c u l a r l y w i t h t h e h i g h l y b r a n c h e d
c a r b i n o l s , t h a t i t was n e c e s s a r y t o rem ove t h e c h l o r i d e
f r a c t i o n s b e f o r e d i s t i l l a t i o n o f th e a l k y l benzene
fractio n .

The a u t h o r h a d , i n most o a s e s , no a p p a r e n t

d i f f i c u l t y in t h i s r e s p e c t , i . e . c h lo rid e contam ination,
p r o b a b l y due t o t h e n a t u r e o f t h e a l c o h o l s c o n d e n s e d .
I n t h e one o r two c a s e s w h e r e i t was n e c e s s a r y t o remove
t h e c h l o r i d e c o n t a m i n a t i o n , t h i s was a c c o m p l i s h e d by
r e f l u x i n g t h e a l k y l b e n z e n e o b t a i n e d from t h e i n i t i a l
f r a c t i o n a t i o n w i t h an e q u a l volume o f f i f t y p e r c e n t
a l c o h o l i c p o ta ssiu m h y d ro x id e fo r a p e r i o d o f fo u r to
six hours.

The o r g a n i c l a y e r was t h e n s e p a r a t e d from

t h e w a t e r l a y e r , washed s e v e r a l t i m e s w i t h d i s t i l l e d
w a t e r u n t i l n e u t r a l t o l i t m u s and t h e n d r i e d o v e r a n h y ­
drous potassium c a rb o n a te .

Upon d i s t i l l a t i o n t h e a l k y l

b e n z e n e was f o u n d f r e e from c h l o r i d e .

O c c a s s lo n a lly the

h i g h e r f r a c t i o n s were a l s o c o n t a m i n a t e d w i t h u n s a t u r a t e d
compounds.

T h i s u n s a t u r a t i o n was rem ove d by t h e a d d i t i o n

o f f i v e p e r c e n t b r o m in e i n c a r b o n t e t r a c h l o r i d e u n t i l
c o l o r p e r s i s t e d , re m o v a l o f e x c e s s b r o m i n e w i t h t e n p e r ­
c e n t sodium b i s u l f i t e , t h e n w a s h in g w i t h d i s t i l l e d w a t e r ,
and d ry in g over anhydrous p o ta ssiu m c a r b o n a te .
O th e r colum ns u s e d f o r f u r t h e r p u r i f i c a t i o n w ere o f
t h e same t y p e e x c e p t s h o r t e r i n l e n g t h o r s m a l l e r i n b o r e .
T h ese were o f t h e s i z e s 20 x 1 . 0 cm p a c k e d w i t h 1 / 3 2 i n c h
g l a s s h e l i c e s ; 30 x 1 . 8> cm p a c k e d w i t h l / l 6 i n c h g l a s s
h e l i c e s ; $2 x O.S cm p a c k e d w i t h I / 3 2 i n c h g l a s s h e l i c e s .

P a r t A.

The c o n d e n s a t i o n o f 2 - M e t h y l - 2 - h e p t a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F ractio n I .

2-M ethylheptane

E i g h t t o t w e l v e grams o f t h e s a t u r a t e d h y d r o c a r b o n
p e r mole o f a l c o h o l c o n d e n s e d was i s o l a t e d .

I t was

c o n t a m i n a t e d to a s m a l l d e g r e e w i t h t h e c o r r e s p o n d i n g
u n s a t u r a t e d h y d r o c a r b o n , a s was t o b e e x p e c t e d .

T his

was e a s i l y rem oved by s h a k i n g s e v e r a l t i m e s w i t h s m a l l
p o rtio n s o f cold c o n c e n tra te d s u l f u r i c a c id .

As no

d e r i v a t i v e c o u l d b e p r e p a r e d i t was i d e n t i f i e d by i t s
p h y s i c a l c o n s t a n t s , w h ic h a r e i n c l o s e a g r e e m e n t w i t h
th o se r e p o r te d in the l i t e r a t u r e (^ 9 ) .
A verage Y i e l d ;

g .g#

B P^;

115-ll6°C

n§°

1.J962

:

Dg°

:

0 .7 0 0 1

M * : C a l c . 3 9 . 1 6 Obs. 3 9 . 1 2
R
T h i s h y d r o c a r b o n was a l s o i d e n t i f i e d by means o f i t s
i n f r a - r e d s p e c t r a w hich i s
F ractio n I I .

shown i n F i g . 2 .
C hloride-A lcohol

S i x t o e i g h t grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f o c t y l
c h l o r i d e a n d u n c o n d e n s e d a l c o h o l and was n o t s e p a r a t e d
or p u rified .

The o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c

o f t e r t i a r y a l c o h o l s , and g a v e a h e a v y c h l o r i d e t e s t w i t h
5 percent alco h o lic s ilv e r n itr a t e .
F raction I I I .

2-M ethyl-2-phenylheptane

T h i s f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
The p h y s i c a l c o n s t a n t s do n o t a g r e e w i t h t h o s e r e p o r t e d
in the l i t e r a t u r e

(20).

A v erag e Y i e l d :

2J.k-fe

BP.

69-70oC

4°

1 .^ 9 10

D2p

0 . 8S702

MR

C alc.

6 3 .2 7

O bs. 6 3 .1 6

D a t a f o r t h e c a l c u l a t i o n o f m o l e c u l a r r e f r a c t i o n was
t a k e n from S h r i n e r and F u s o n , " I d e n t i f i c a t i o n o f O r g a n ic
Compounds".

F ra c tio n IV .

Dark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e and am o u n ted t o 37 grams p e r mole o f a l c o h o l
condensed.

P a r t B.

The c o n d e n s a t i o n o f 3 - M e ^ y l - 3 - h e p t a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F raction I .

3“M e t h y l h e p t a n e

Ten t o t w e l v e grams o f t h e s a t u r a t e d h y d r o c a r b o n
p e r mole o f a l c o h o l c o n d e n s e d were i s o l a t e d .

The same

t r e a t m e n t f o r r e m o v a l o f t r a c e s o f u n s a t u r a t i o n was
employed a s w i t h F r a c t i o n I , P a r t A.

The p h y s i c a l

c o n s ta n ts were i n c lo s e agreem ent w ith th o s e r e p o r t e d
i n t h e l i t e r a t u r e ( ^ 9 )»
A verage Y i e l d :

9*5$

BP^9 :

1 1 7 . 5 °C

n^°

1 . 39 BO

:

O .7 055

C alc.

3 9 .1 6

Obs. 3 9 . 1 ^

T h i s h y d r o c a r b o n was a l s o i d e n t i f i e d by means o f i t s
i n f r a - r e d s p e c t r a w h ich i s shown i n F i g . 3 .
F raction I I .

C h l o r i d e - A lc o h o l

E i g h t t o t e n grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f o c t y l
c h l o r i d e and u n c o n d e n s e d a l c o h o l a n d was n o t s e p a r a t e d
or p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c

o f t e r t i a r y a l c o h o l s , a n d i t gav e a h e a v y c h l o r i d e t e s t
w ith 5 p e r c e n t a l c o h o l i c s i l v e r n i t r a t e .
F ractio n I I I .

3-M ethyl-3-phenylheptane

T h i s f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s i c a l c o n s t a n t s do n o t a g r e e w i t h t h o s e r e p o r t e d
in the l i t e r a t u r e . ( 50).
A verage Y i e l d
BP

111°C

D
.20
D

1 .4 9 5 5

Ik
t20
n

O.B77B
C alc. 63.27

F r a c tio n IV .

Obs. 6 3 . 1 2

D ark v i s c o u s r e s i d u e

T h i s f r a c t i o n was t h a t c o l l e c t e d a b o v e t h e a l k y l
b e n z e n e and a m o u n te d t o 27 grams p e r mole o f a l c o h o l
condensed.

P a r t C.

The c o n d e n s a t i o n o f 3 - E-fch y l “ 3-*l e x &nol w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
T h i s a l c o h o l was c o n d e n s e d i n p r e v i o u s work (21)
a n d t h e h y d r o c a r b o n f r a c t i o n was s e p a r a t e d b u t n o t
p o s i t i v e l y i d e n t i f i e d as 3- E t h y l h ep tan e a s i t s p h y s i c a l
c o n s ta n ts d id n o t ag ree w ith th o se r e p o r t e d in th e l i t ­
e r a t u r e (^9 ) .
F ractlo n I .

3 " E‘t ^1y l h e x a n e

Ten t o t w e l v e grams o f t h i s h y d r o c a r b o n p e r mole o f

a l c o h o l c o n d e n s e d w ere I s o l a t e d .

As i t s p h y s i c a l c o n s t a n t s

from s e v e r a l c o n d e n s a t i o n s a g r e e d w i t h e a c h o t h e r b u t n o t
w ith th o s e r e p o r t e d in t h e l i t e r a t u r e , a s m entioned ab o v e,
a s p e c i a l column was b u i l t w i t h t h e t h o u g h t t h a t F r a c t i o n
I m i g h t p o s s i b l y b e composed o f two o r more I s o m e r s .

T h is

column was 93 x 0.S5 cm i n s i z e and p a c k e d w i t h I / 3 2 i n c h
g lass h e lic e s .

Two s e p a r a t e f r a c t i o n s were c o l l e c t e d upon

d i s t i l l a t i o n b o i l i n g two d e g r e e s a p a r t .

In fra -re d sp ectra,

F i g . 4 , o f t h e two f r a c t i o n s compared f a v o r a b l y w i t h t h e
s p e c t r a f o r 3 - E t h y l h e x a n e sh o w in g them t o be composed
m ainly o f t h i s hydrocarbon w ith a p p a re n tly d i f f e r e n t
degrees of im p u rity .

The p h y s i c a l c o n s t a n t s f o r t h e o r i g ­

i n a l f r a c t i o n s a p p e a r below.
A v erage Y i e l d
BP.

74 6

P a r t D.

10- 12#
H 5 -i i 6°o

120

1.3930

)20
Df

0.7052

M.R

C a l o . 3 9 .1 6

Obs. 39.0 2

The c o n d e n s a t i o n o f 2 ,4-D im et h y l - 2 - h e x a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F r a c t i o n _I.

lsobutane

This f r a c t i o n w as. condensed in th e carbon d io x id e

acetone cooled tr a p d u rin g th e co n d en satio n .

Repeated

d i s t i l l a t i o n s f r e e d th e hyd ro carb o n o f hydrogen c h l o r i d e
and b e n z e n e i m p u r i t i e s a n d g av e a c o n s t a n t b o i l i n g r a n g e .
An A u s c h u t z t h e r m o m e te r was u s e d f o r r e c o r d i n g i t s b o i l ­
ing te m p e ra tu re .

The r e f r a c t i v e i n d e x o f t h e i s o b u t a n e

was t a k e n on an o r d i n a r y Abbe t y p e r e f r a c t o m e t e r .

A cetone

c o o l e d by s o l i d c a r b o n d i o x i d e was f o r c e d b a c k a n d f o r t h
t h r o u g h t h e p r i s m s i n s u c h a manner a s t o k e e p t h e te m p e r ­
a t u r e as s te a d y as p o s s i b l e a t -25°C.

M o i s t u r e was k e p t

from t h e t o p a n d b o t t o m p r i s m s u r f a c e s by s e a l i n g i n a
p i e c e o f anhydrous ca lciu m c h l o r i d e w ith sm all p l a t e s o f
g l a s s and o r d i n a r y s t o p c o c k g r e a s e .

Several readings

w ere t a k e n a n d a v e r a g e d .
A v erag e Y i e l d

F raction I I .

3 . 1*

BP

-10.2°C

S 25

1 .3 5 1 A

2 ,^-D lm ethylhexane

F i v e t o s e v e n grams o f t h e s a t u r a t e d h y d r o c a r b o n p e r
mole o f a l c o h o l c o n d e n s e d w ere i s o l a t e d .

S im ilar t r e a t ­

ment f o r r e m o v a l o f t r a c e s o f u n s a t u r a t i o n was em ployed
a s w i t h F r a c t i o n I , P a r t A.

The p h y s i c a l c o n s t a n t s a r e

in c lo s e agreem ent w ith th o se r e p o r te d in th e l i t e r a t u r e
(W Average Y ie l d :

3.8$

Dif

:

0.7012

:

C alc.

3 9 .1 6

O bs.

3 9 .Og

T h i s h y d r o c a r b o n was a l s o i d e n t i f i e d by means o f i t s
i n f r a - r e d s p e c t r a w hich i s shown by F i g . 5 .
F ractio n I I I .

C h l o r i d e - A lc o h o l

S i x to e i g h t grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f o c t y l
c h l o r i d e a n d u n c o n d e n s e d a l c o h o l a n d was n o t s e p a r a t e d o r
p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c o f

t e r t i a r y a l c o h o l s , and i t g a v e a h e a v y c h l o r i d e t e s t w i t h
5 percent alco h o lic s ilv e r n itr a t e .
F ra c tio n IV.

2-M ethyl-2-ph enylprop ane

T h is f r a c t i o n , l i k e i s o b u t a n e , r e s u l t e d from t h e
frag m en tatio n o f th e a lc o h o l during con d en satio n .

Its

p h y s ic a l c o n s ta n ts ag reed w ith those r e p o r te d in the l i t ­
e r a t u r e ( 5 )*

I t was a l s o I d e n t i f i e d by i t s a c e t a m l n o

d e r i v a t i v e p r e p a r e d a c c o r d i n g t o t h e work o f I p a t i e f f and
S c h r a e r lin g ( 5 2 ) .

Two m l . o f t h e t - b u t y l b e n z e n e were

p l a c e d i n a t e s t t u b e a n d 5 m l . o f m ixe d a c i d ( 50^ c o n c .
HNO^ - 50$ c o n c . H^SO^) were s l o w l y a d d e d t o t h e a l k y l
benzene w ith shaking.

A f t e r allo w in g to c o o l, the n i t r a

t i o n p r o d u c t was p o u r e d on c r a c k e d i c e , e x t r a c t e d w i t h
e t h e r s e v e r a l t i m e s , w ashed w i t h w a t e r a n d t h e n t h e e t h e r
evaporated o f f .

The r e s i d u e was a l l o w e d to c o o l a n d t h e n

a few m l. o f a l c o h o l w ere a d d e d , 5 S ° f g r a n u l a t e d t i n
a n d 5 m l. o f c o n c . HC1, a few d r o p s a t a tim e w i t h s t i r r i n g .

T h is was a llo w e d to sta n d f o r 30 m in u te s to in s u r e com­
p l e t e r e d u c t i o n o f t h e n i t r o compound.

The a m i n e - S n C l g -

HC1 complex was t h e n d e c a n t e d from t h e e x c e s s t i n and
t h e amine r e l e a s e d from t h e complex w i t h
hydroxide.

ko% sodium

The amine was t h e n e x t r a c t e d w i t h e t h e r , t h e

e t h e r washed w i t h 10% KgCO-^.

The e t h e r was t h e n e v a p o ­

r a t e d from t h e a m in e , a l l o w e d t o c o o l a n d t h e n 2 m l . o f
a c e t i c an h ydride added.

The a c e t a m i n o d e r i v a t i v e

c r y s t a l l i z e d a l n o s t im m ediately.
s e v e ra l tim es w ith

Ho% a l c o h o l .

I t was r e c r y s t a l l i z e d
W h i te p e a r l y p l a t e s ,

M.P. l 6 9 ° C .
A verage Y i e l d
BP

73S

BP

12
ni20
D
>20
D

M
R
F r a c t i o n V.

l.'p/o

l 69- i 7o ° c
56.5-57°C
1 .11-918
0 .8 6 5 6
C alc.

^ .7 9

Obs.

*l4.9lJ-

2 ,*1—D i m e t h y l - 2 - p h e n y l h e x a n e

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t ,
I t s p h y s i c a l c o n s t a n t s a g r e e w ith t h o s e r e p o r t e d i n the
literatu re

(1).
A v erag e Y i e l d
BP3
n 20
D
D20

1 9 . 6^

6 9-7l°c
l . H - s 20

0 .2 7 1 2
C alc.

63.27

Obs. 6 3 .5 0

F r a c t i o n V I.

Dark v i s c o u s r e s i d u e

T h i s f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e a n d am o u n ted t o 3 S . 3 grams p e r mole o f a l c o h o l
condensed.

P a r t E.

The c o n d e n s a t i o n o f 2 , 5 -Dimet h y l - 2 - h e x a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e *
F ractio n I .

2 , 5-D im ethylhexane

S i x t o e i g h t grams o f t h e s a t u r a t e d h y d r o c a r b o n p e r
mole o f a l c o h o l c o n d e n s e d w ere i s o l a t e d .

S im ilar t r e a t ­

ment f o r r e m o v a l o f t r a c e s o f u n s a t u r a t l o n was em ployed
a s w i t h F r a c t i o n I , P a r t A.

The p h y s i c a l c o n s t a n t s a r e

in d o s e agreem ent w ith th o s e r e p o r t e d in the l i t e r a t u r e
(^9).
A v erage Y i e l d
BP

736

5.7#
io 7 -io g ° c

n

1 .3 9 3 0

»r

0.6952

M
C alc.
3 9 .1 6 Obs. 3 9 . 1 ^
R
T h i s h y d r o o a r b o n was a l s o i d e n t i f i e d by means o f i t s
i n f r a - r e d s p e c t r a w hich i s shown i n F i g . 6 .
F raction I I .

C h l o r i d e - A lc o h o l

Seven t o n i n e grams o f t h i s f r a c t i o n c o l l e c t e d p e r
m ole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f o c t y l
c h l o r i d e a n d u n c o n d e n s e d a l c o h o l and was n o t s e p a r a t e d o r
p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c o f

t e r t i a r y a l c o h o l s , and i t gave a heavy c h l o r i d e t e s t w ith
5 percent alco h o lic s ilv e r n itr a t e .
F ractio n I I I .

2 ,5-D im ethyl-2-phenylhexane

T h is f r a c t i o n Was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s i c a l c o n s t a n t s do n o t a g r e e w i t h t h o s e r e p o r t e d i n
the l i t e r a t u r e

(20).
A v e ra g e Y i e l d

F ra c tio n IV .

2 1 . 5$

io 6 -io g °c

B? l 6
2°
niD
20
d!

0.6697

M.
R

C alc.

1.4-910

63.27

O bs. 6 3 . 1 9

Dark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d ab o v e t h e a l k y l
b e n z e n e and am ounted to 24-.6 grams p e r mole o f a l c o h o l
condensed.

P a r t F.

The c o n d e n s a t i o n o f 2 , 4 —D i m e t h y l -4—h e x a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F ractio n I .

lsobutane

T h is f r a c t i o n r e s u l t e d from t h e f r a g m e n t a t i o n o f
the a l c o h o l .

I t was o o l l e c t e d and p u r i f i e d i n t h e same

manner a s F r a c t i o n I , P a r t D.
A v erage Y i e l d
b p 737
% 25

4-. 6v°
%
-10.1°C
1.3517

F raction I I .

2 , —D lm e t h y l h e x a n e

T hree t o f i v e grams o f t h e s a t u r a t e d h y d r o c a r b o n
p e r mole o f a l c o h o l c o n d e n s e d w ere I s o l a t e d .

S im ilar

t r e a t m e n t f o r r e m o v a l o f t r a c e s o f u n s a t u r a t i o n was
em ployed a s w i t h F r a c t i o n I , P a r t A.

The p h y s i c a l con­

s t a n t s a re i n c lo s e agreem ent w ith th o s e r e p o r t e d in
the l i t e r a t u r e

(^9)•
A v erag e Y i e l d :

3*9$

BP™ :

1 0 S .5 -1 0 9 ° C

nD
D20

1.3962

h

0.7012

C a l c . 3 9 . 1 6 O b s . 3 9 .1 0
MR
T h i s h y d r o c a r b o n was a l s o i d e n t i f i e d by means o f
i t s i n f r a - r e d s p e c t r a w h ic h i s shown i n F i g . J .
F ractio n I I I .

C h lo rid e - A lcohol

E i g h t t o t e n grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f o c t y l
c h l o r i d e a n d u n c o n d e n s e d a l c o h o l and was n o t s e p a r a t e d
or p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c

o f t e r t i a r y a l c o h o l s , a n d i t gav e a h e a v y c h l o r i d e t e s t
w ith 5 p e rc e n t a lc o h o lic s i l v e r n i t r a t e .
F r a c tio n IV.

2-M ethyl-2-phenylpropane

T h is f r a c t i o n , l i k e i s o b u t a n e , r e s u l t e d from t h e
frag m entation o f the a lc o h o l d u rin g co n d e n satio n .

Its

p h y s i c a l c o n s ta n ts a g re e d w ith those r e p o r t e d in the
lite ra tu re (5).

I t was a l s o I d e n t i f i e d b y i t s a c e t a m i n o

d e r i v a t i v e p r e p a r e d a c c o r d i n g t o t h e work o f I p a t i e f f

a n d S c h m e r l i n g ( 5 2 ) a n d g i v e n u n d e r F r a c t i o n IV , P a r t D,
W hite p e a r l y p l a t e s , M.P. l 6 9 ° C .
A verage Y i e l d
BP 7I14

l6 B .5 -l6 9 °C

BP

5 2 . 5- 53°°

15

n
.20
D
M.
R
F r a c t i o n V.

.*

2 2

1.4-918
o . 866o
C alc.

44.79

Obs. ^ . 9 4 -

2 , 4 —D i m e t h y l -4—p h e n y l h e x a n e

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s ic a l c o n s ta n ts a g re e w ith those r e p o r te d in the
literatu re

( 5° ) •
A verage Y i e l d
BP

1
20
n
D
D20
4-

“r
F ractio n V I.

1 9.17*
6 9 .5 -7 0 °c
1.4-920
0.8731
C alc.

63.27

Obs. 6 3 . 4-7

Dark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e a n d am ounted t o 77*2 grams p e r mole o f a l c o h o l
condensed.

P a r t G.

The c o n d e n s a t i o n o f 2 - M e t h y l - 2 - h e x a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F ractio n I .

2 - M e th y l h e x a n e

The a b o v e h y d r o c a r b o n was n o t i s o l a t e d i n q u a n t i t a t i v e

am ounts due t o t h e f a c t t h a t i t was p r e s e n t i n s u c h a
s m a l l amount as com pared t o t h e l a r g e e x c e s s o f b e n z e n e *
A lthough i t b o l l s a p p r o x im a te ly ten d e g r e e s above benzene
i t was n o t p o s s i b l e , w i t h t h e s t i l l u s e d , t o s e p a r a t e
enough f o r p u r i f i c a t i o n p u r p o s e s .

I t was t h e r e f o r e n e c ­

e s s a r y t o f r a c t i o n a l l y f r e e z e t h e h y d r o c a r b o n o u t by
p la c in g in th e r e f r i g e r a t o r in a beaker f o r o n e -h a lf hour
p e r i o d s , d e c a n tin g the l i q u i d o f f each tim e u n t i l th e
c o n c e n t r a t e w ould n o t f r e e z e when p l a c e d i n t h e f r e e z i n g
com partm ent.

I t was t h e n t r e a t e d w i t h c o l d c o n c e n t r a t e d

HgSO^ t o remove t r a c e s o f u n s a t u r a t i o n , w ashed w i t h t e n
p e r c e n t Na^CO^, d i s t i l l e d w a t e r and t h e n d r i e d o v e r
a n h y d r o u s KgCO^.

F r a c t i o n a l d i s t i l l a t i o n gave f o u r grams

o f t h e p u r e h y d r o c a r b o n from 2 . 3 m o le s o f a l c o h o l o o n densed.

I t s p h y s i c a l c o n s t a n t s were i n c l o s e a g r e e m e n t

w ith those r e p o r te d in th e l i t e r a t u r e

(4-9).

859.5 C
1 .3 * 5 5

0.6790
Calc.

3^*53

Obs.

35*26

The h y d r o c a r b o n was a l s o I d e n t i f i e d by means o f i t s
i n f r a - r e d s p e c t r a w h ich i s shown i n F i g . 0 .
F ractio n I I .

C h l o r i d e - A lc o h o l

F o u r t o f i v e grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f h e p t y l
c h l o r i d e and u n c o n d e n s e d a l c o h o l a n d was n o t s e p a r a t e d o r
pu rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c o f

t e r t i a r y a l c o h o l s , and i t g a v e a h e a v y c h l o r i d e t e s t w i t h
5 percent alco h o lic s ilv e r n itr a t e .
F ractio n I I I .

2-M ethyl-2-phenylhexane

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s ic a l c o n s ta n ts ag re e w ith th o se r e p o r te d in the
lite ra tu re

(1 ).
A verage Y i e l d :

F ra c tio n IV.

31•3%

BP I S

96-97°0

n

4°

1.1*925

D f

0 . 871 k

Mr

C alc.

5 ^ .6 5

O bs. ^ 8 . 8 0

Dark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d a b o v e t h e a l k y l
b e n z e n e a n d am ounted t o 35*5 grams p e r mole o f a l c o h o l
condensed.

P a r t H.

The c o n d e n s a t i o n o f 3 - M e t h y l - 3 - h e x a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F ractio n I .

3-M ethylhexane

Four gram s o f t h e a b o v e h y d r o c a r b o n were i s o l a t e d
i n t h e same m anner a s F r a c t i o n I , P a r t G-, from 2 . 2 2
m oles o f a l c o h o l c o n d e n s e d .

I t s p h y s i c a l c o n s t a n t s w ere

in c lo s e agreement w ith th o se r e p o r t e d in the l i t e r a t u r e
U 9).

BP733 !

g9 -5 -9 0 °0

n 20

1.3*595

:

The h y d ro c a rb o n
in fra -re d

sp ectra

D^°

:

0.6390

Mr

:

C alc.

was

w hich

a lso

is

F ractio n I I .

3 4 -.53 O b s . 34 - . 3 6

I d e n t i f i e d bym eans

shown b y

F ig .

of

its

9»

C h l o r i d e - A lc o h o l

S i x to e i g h t grams o f t h i s f r a c t i o n c o l l e c t e d p e r
m ole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f h e p t y l
c h l o r i d e and u n c o n d e n s e d a l c o h o l a n d was n o t s e p a r a t e d o r
p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c o f

t e r t i a r y a l c o h o l s , a n d i t gave a h e a v y c h l o r i d e t e s t w i t h
5 percent alco h o lic s ilv e r n i t r a t e .
F ractio n I I I .

3-M ethyl-3-phenylhexane

T h i s f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s i c a l c o n s ta n ts a g r e e w ith th o s e r e p o r t e d i n the
lite ra tu re

(1 ).
A v erage Y i e l d
BP

14-

n

£

d5 °
mr

F ra o tio n IV.

3 0 .0 $
9 9 -l0 i° c

1.4-960
0.3736
C alc.

5 2 .6 5

Obs.

53.72

Dark v i s c o u s r e s i d u e

T h i s f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e and am ounted to 3^*7 grams p e r mole o f a l o o h o l
condensed.

P art J.

The c o n d e n s a t i o n o f 3 ~ S t h y l - 3 - p e n t a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F raction I .

3-Ethylpentane

T hree a n d o n e - h a l f grams o f t h e above h y d r o c a r b o n
w ere i s o l a t e d i n t h e same manner a s F r a c t i o n I , P a r t Gfrom I .6 3 m o le s o f a l c o h o l c o n d e n s e d .

I t s ph ysical

c o n s t a n t s were i n c l o s e agreem ent w ith th o s e r e p o r t e d
in the l i t e r a t u r e

( ^ 9 )•

bp7ih

92.5-93°C

n 20
D
n20
%

1 .39*10
0.6995

M
C a l c . 3 ^ .5 3
Obs. 3^ .73
R
The h y d r o c a r b o n was a l s o i d e n t i f i e d by means o f i t s
i n f r a - r e d s p e c t r a which i s
F raction I I .

shown by F i g . 1 0 .
C h lo rid e - A lcohol

Three t o f o u r grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f h e p t y l
c h l o r i d e a n d u n c o n d e n s e d a l c o h o l a n d was n o t s e p a r a t e d
or p u rifie d .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c

o f t e r t i a r y a l c o h o l s , a n d i t gave a h e a v y c h l o r i d e t e s t
w ith 5 p e r c e n t a lc o h o lic s i l v e r n i t r a t e .
F raction I I I .

3-E thyl-3-phenylpentane

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s ic a l c o n s ta n ts a g re e w ith th o se r e p o r t e d i n the
literatu re

(1 ).
Average Y i e l d :

33*2#

«p°

:

X. <4-970

D^0

0 .0 7 9 9

mh

C alc.

F r a c t i o n IV.

5 0 .6 5

O b s. 5 0 . 7 7

D a rk v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d a b o v e t h e a l k y l
b e n z e n e and am ounted t o 2 $ .k - grams p e r mole o f a l c o h o l
condensed.

P a r t K.

The c o n d e n s a t i o n o f 2 , ^ - D i m e t h y l - 2 - p e n t a n o l

w i t h b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e
F raction I .

Isobutane

T h is f r a c t i o n r e s u l t e d from t h e f r a g m e n t a t i o n o f t h e
alco h o l.

I t was c o l l e c t e d a n d p u r i f i e d i n t h e same manner

a s F r a c t i o n I , P a r t D.
A v e ra g e Y i e l d
BP733

2 . 2$
-10.^°C
1.3516

F ractio n I I .

2 ,4-D im ethylpentane

The h y d r o c a r b o n c o u l d n o t b e I s o l a t e d a s i t b o i l s
a t t h e same t e m p e r a t u r e a s b e n z e n e .
F raction I I I .
Five t o

C h lo rid e - A lcohol

s i x grams o f t h i s f r a c t i o n c o l l e c t e d c o n ­

t a i n e d a m i x t u r e o f h e p t y l c h l o r i d e and u n c o n d e n s e d
a l c o h o l a n d was n o t s e p a r a t e d o r p u r i f i e d .

I t s o d o r was

c a m p h o r -lik e , c h a r a c t e r i s t i c of t e r t i a r y a l c o h o l s , and i t
gave a heavy c h l o r i d e t e s t w ith 5 p e r c e n t a l c o h o l i c s i l v e r
n itrate.

F ra ctio n IV ,

2-M ethyl-2-phenylpropane

T h i s f r a c t i o n l i k e l s o b u t a n e , r e s u l t e d from t h e
f ra g m e n ta tio n o f th e a lc o h o l during co n d e n sa tio n .

Its

p h y s ic a l c o n s ta n ts ag reed w ith those re p o r te d in th e
literatu re

( 5 )»

I t was a l s o i d e n t i f i e d by i t s a c e t a m i n o

d e r i v a t i v e p r e p a r e d a c c o r d i n g to t h e work o f I p a t i e f f
a n d S c h m e r l i n g ( 5 2 ) and g i v e n u n d e r F r a c t i o n IV, P a r t D.
W hite p e a r l y p l a t e s , M.P. l 6 2 . 5 ° C .
A verage Y i e l d
BP

73^

BP

F r a c t i o n V.

2 . 8$
1 6 2 - 1 6 2 . 5°C
5 6.5-57°c

12
ni20
D
2°
D

0 .2 6 5 6

M.R

Calc.

l.i^ lg

W-.79

Obs. ^ . 9 6

2 , iJ - D i m e t h y l - 2 - p h e n y l p e n t a n e

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t
I t s p h y s i c a l c o n s t a n t s do n o t a g r e e w i t h t h o s e r e p o r t e d
in the l i t e r a t u r e

(1 ) .

A v erage Y i e l d
BP,12

22.5-23°C

n!‘f

l.il- 9 1 2

M.R
F r a c t i o n V I.

2 2 . 2$

0 .2 7 0 6
C alc.

5 2 .6 5

Obs. 5 2 .7 7

D a rk 'v isc o u s re s id u e

T h is f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e a n d am ounted t o
condensed.

grams p e r mole o f a l c o h o l

P a r t L.

The c o n d e n s a t i o n o f 2 - M e t h y l - 2 - p e n t a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F raction I .
Five t o

2-M ethylpentane

s e v en grams o f t h e s a t u r a t e d h y d r o c a r b o n

p e r mole o f a l c o h o l c o n d e n s e d were i s o l a t e d .

S im ilar

t r e a t m e n t f o r r e m o v a l o f t r a c e s o f u n s a t u r a t i o n was
employed a s w i t h F r a c t i o n I , P a r t A.

The p h y s i c a l c o n ­

s t a n t s a r e in c lo s e agreem ent w ith th o s e r e p o r t e d i n the
literatu re

(*4-9) •
Average Y i e l d :
B P ^:

1*0%

6 0 - 6 0 . 5° C

n§°

: 1 .3 7 2 0

D^°

: 0 .6 5 5 8

M

: C alc.

29*91

o b s . 3 0 . IS

T h is h y d r o c a r b o n was a l s o i d e n t i f i e d by means o f
i t s i n f r a - r e d s p e c t r a w h i c h i s shown by F i g . 1 1 .
F ractio n I I .

C h l o r i d e - A lc o h o l

T hree t o f o u r grams o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f h e x y l
c h l o r i d e and u n c o n d e n s e d a l c o h o l and was n o t s e p a r a t e d
or p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c

o f t e r t i a r y a l c o h o l s , a n d i t gav e a h e a v y c h l o r i d e t e s t
w ith 5 p e rc e n t a lc o h o lic s i l v e r n i t r a t e .
F ractio n I I I .

2-M ethyl-2-phenylpentane

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s ic a l c o n s ta n ts a g re e w ith th o se r e p o r te d in th e

lite r a tu r e ( l ) .
A verage Y i e l d
BP

11120
n
D
20

Mr
F ra c tio n IV .

32.7^
3iJ~35°c
l.iJ-9^5
0.3725
C a l c . 5 ^ .0 3

Obs. 5 ^ .0 5

D ark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e and am o u n ted t o 2 1 . 2 grams p e r mole o f a l c o h o l
condensed.

P a r t M.

The c o n d e n s a t i o n o f 3 - M e t h y l - 3 - p e n t a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F ractio n I .

3-M ethylpentane

E i g h t t o n i n e gram s o f t h e s a t u r a t e d h y d r o c a r b o n
p e r mole o f a l c o h o l c o n d e n s e d w ere i s o l a t e d .

S im ilar

t r e a t m e n t f o r r e m o v a l o f t r a c e s o f u n s a t u r a t i o n was
em ployed a s w i t h F r a c t i o n I , P a r t A.

The p h y s i c a l con­

s t a n t s a re in c lo s e agreem ent w ith th o s e r e p o r te d in the
literatu re

(^9).
A v erage Y i e l d
BP
13
20
n
D
D20

1 0 . 2$

33-3^°C
1.37^0
O.66 5 5

M
C a l c . 2 9 .9 1
Obs. 3 0 .OO
R
T h is h y d r o c a r b o n was a l s o i d e n t i f i e d b y means o f i t s
i n f r a - r e d s p e c t r a w h ich i s shown by F i g . 1 2 .

F ractio n I I .

C h lo rid e - A lcohol

T h r e e t o f o u r grama o f t h i s f r a c t i o n c o l l e c t e d p e r
mole o f a l c o h o l c o n d e n s e d c o n t a i n e d a m i x t u r e o f h e x y l
c h l o r i d e a n d u n c o n d e n s e d a l c o h o l a n d was n o t s e p a r a t e d o r
p u rified .

I t s o d o r was c a m p h o r - l i k e , c h a r a c t e r i s t i c o f

t e r t i a r y a l c o h o l s , and i t gave a h e a v y c h l o r i d e t e s t w i t h
5 percent alco h o lic s ilv e r n i t r a t e .
F ractio n I I I .

3-M ethyl-3-phenylpentane

T h is f r a c t i o n was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .
I t s p h y s ic a l c o n s ta n ts agree w ith th o se r e p o r te d in the
literatu re

(1 ) .
A v erage Y i e l d

F ra ctio n IV .

35 *9^

BP
IS
20
n
lD
D,20

O.S7S5

M.

C alc.

63-g4-°C
1.4-960

54-.03

O bs.

53*91

Dark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d above t h e a l k y l
b e n z e n e a n d a m o u n te d t o 19*5 grams p e r mole o f a l c o h o l
condensed.

P a r t N.

The c o n d e n s a t i o n o f 2 - M e t h y l - 2 - b u t a n o l w i t h

b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s aluminum c h l o r i d e .
F r a c t i o n I_.

2-M ethylbutane ( is o p e n ta n e )

Three a n d o n e - h a l f grams o f t h i s h y d r o c a r b o n w ere
i s o l a t e d from t h r e e m oles o f t e r t i a r y amyl a l c o h o l .

It

was p u r i f i e d by d i s t i l l a t i o n d u r i n g w h ich i t was p a s s e d
t h r o u g h c o l d c o n c e n t r a t e d s u l f u r i c a c i d t o remove any
u n satu ratio n p resen t.

I t s p h y s ic a l c o n s ta n ts agreed w ith

th o se r e p o r t e d in the l i t e r a t u r e (5 3) .
A verage Y i e l d
BP

7^-2
.20
n
D
.20

26 .5-2B °C
1.3552
0.6197

M.
R

C alc.

F raction I I .

2 5 .2 9 Obs.

2 5 .3 2

C h lo rid e - A loohol

Two t o t h r e e grams o f t h i s were i s o l a t e d p e r mole
o f a lc o h o l condensed.

I t was n o t s e p a r a t e d o r p u r i f i e d .

I t gav e a h e a v y c h l o r i d e t e s t w i t h 5 p e r c e n t a l c o h o l i c
c i l v e r n i t r a t e , and i t s o d o r was c h a r a c t e r i s t i c o f t h a t
o f the o r i g i n a l a lc o h o l.
F raction I I I .

2- M e t h y l - 2 - p h e n y l b u t a n e

T h is was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .

Its

p h y s ic a l c o n s ta n ts ag ree w ith th o se r e p o r t e d in the
literatu re

( 5 )*
A v erage Y i e l d
BP
BP

7^2
185

1 B9- 1 90° c
6 6 . 5- 6 7 ° c

n

l.^ to

d £°

0 .B735

M
R

Calc,

■?

Obs. ^ 9 . ^ 0

F r a c t i o n IV .

Dark v i s c o u s r e s i d u e

T h is f r a c t i o n was t h a t c o l l e c t e d ab ove t h e a l k y l
b e n z e n e and am ounted t o 27 grams from a t h r e e mole r u n .
I t u n d o u b t e d l y c o n s i s t s o f some d i - t e r t - a m y b e n z e n e an d
u n s a t u r a t e d p o ly m eric m a t e r i a l as I t gave a p o s i t i v e
te s t for u n satu ratio n .

Part 0.

The c o n d e n s a t i o n o f 2 - M e t h y l - 2 - p r o p a n o l w i t h

b e n z e n e In t h e p r e s e n c e o f an h y d r o u s aluminum c h l o r i d e .
F r a c t i o n I_.

2-M ethylpropane ( is o b u ta n e )

Four grams o f t h i s h y d r o c a r b o n w e re i s o l a t e d a n d
p u r i f i e d i n t h e same m anner a s F r a c t i o n I , P a r t D.
A v erage Y i e l d :
B

2 .2 2 %

P

- 1 0 .5°C

n - 25 :
F raction I I .

1.35x6

C h lo rid e - A lcohol

One t o two grams o f t h i s f r a c t i o n w ere i s o l a t e d p e r
mole o f a l c o h o l c o n d e n s e d .
p u rified .

I t was n o t s e p a r a t e d o r

I t gav e a h e a v y o h l o r i d e t e s t w i t h 5 p e r c e n t

a l c o h o l i c s i l v e r n i t r a t e , a n d i t s o d o r was c h a r a c t e r i s t i c
of th a t of th e o rig in a l a lc o h o l.
F raction I I I .

2-M ethyl-2-phenylpropane

T h is was t h e e x p e c t e d c o n d e n s a t i o n p r o d u c t .

Its

p h y s ic a l c o n s ta n ts agree w ith those r e p o r te d in the
l i t e r a t u r e ( 5 ).
A v erage Y i e l d :

55$

6S .5°C

BP7 ^

i

BPl S

56-57°C

nD°

I.i|-91S

d| °

0 . S 656

Mr

C alc.

F r a c t i o n IV.

*14.79

3 . 5 grams

Bp7 3 g :

2 1 9 . S°C

ng°

8

1 . *1-928

D |°

:

O .S 691
ISO

D lnitro d e riv a tiv e :

M.P.
fo N

O xidation:

l|4.94-

Not I d e n t i f i e d

Y ield:

M.W. :

O b s.

l 6 k —l 6 ^ ° 0

C alc.
Obs.

I O .37
1 0 . Si

neg ativ e

F r a c t i o n V.

1 ,*1—D i - t e r t - b u t y l b e n z e n e

Seven gram s o f t h e w h i t e c r y s t a l l i n e s o l i d w ere
i s o l a t e d from t h r e e m o le s o f a l c o h o l c o n d e n s e d .

The

h y d r o c a r b o n was r e c r y s t a l l i z e d from 95# e t h y l a l c o h o l .
W hite rh o m b ic n e e d l e s .
Y ield:

1 .2 #

BP20 :

1 1 5 -1 1 6 °C

M.P.

76°C

:

2 ,6 -D in itro -d i-te rt-b u ty lb e n z e n e :
R esidue:

6 gram s

M.P.

191-192°C

EXPERIMENTAL - PART I I
P re p aratio n o f D eriv ativ es
0

3 ,5-D i n ltr o b e n z o a te s of th e A lcohols
The a b o v e d e r i v a t i v e s w ere p r e p a r e d a c c o r d i n g t o t h e
p r o c e d u r e a s o u t l i n e d i n C h e r o n i s and E n t r l k e n on t h e
p re p a ra tio n of t e r t i a r y alcohol d e riv a tiv e s , except fo r
s lig h t m o d ificatio n .

O n e - h a l f gram o f a l c o h o l was p l a c e d

i n an e i g h t i n c h t e s t t u b e a l o n g w i t h a l a r g e e x c e s s o f
3 , 5- D i n itr o b e n z o y l c h l o r i d e and dry p y r i d i n e .

T h is was

t h e n p l a c e d on t h e ste am b a t h f o r f o u r t o s i x h o u r s ,
c o o l e d to room t e m p e r a t u r e , t h e n c o o l e d i n an i c e b a t h .
F i v e p e r c e n t s u l f u r i c a c i d was t h e n a d d e d u n t i l t h e o d o r
o f p y r i d i n e was d i s c h a r g e d and a f a i n t o d o r o f a l o o h o l
c o u l d be d e t e c t e d .

The v o l u m i n o u s p r e c i p i t a t e was t h e n

f i l t e r e d , w ashed w i t h w a t e r s e v e r a l t i m e s and t h e n p l a c e d
in a b eak er.

T h is p r e c i p i t a t e was t h e n t r e a t e d w i t h t e n

p e r c e n t sodium c a r b o n a t e t o r e l e a s e t h e p y r i d i n e from i t s
sa lt,

f i l t e r e d and t h e r e m a i n i n g p r e c i p i t a t e r e c r y s t a l l ­

i z e d s e v e r a l tim e s from l i g r o l n .
A cetam ln o d e r i v a t i v e o f t e r t - B u t y l b e n z e n e
The p r o c e d u r e f o r t h e p r e p a r a t i o n o f t h e above
d e r i v a t i v e i s o u t l i n e d on p . 3 7 .
D in ltr o A lkylbenzenes
The a b o v e d e r i v a t i v e s were p r e p a r e d b o t h w i t h mixed

a c i d a n d fum ing n i t r i c a c i d Sp. G-r. 1 . 5 a p p r o x .

The

p r o c e d u r e u s i n g mixed a c i d was c a r r i e d o u t a t room te m p e r ­
a t u r e b jr a l l o w i n g t h e r e a c t a n t s t o s t a n d f o r s e v e r a l h o u r s .
O n e - h a l f gram o f a l k y l b e n z e n e was s l o w l y ad d e d t o a mix­
t u r e o f f o u r c . c . o f c o n c . s u l f u r i c a c i d Sp. G-r. l.gij- and
f o u r c . c . o f c o n c . n i t r i c a c i d 70 %, w i t h s h a k i n g and c o o l ­
ing.

T h i s m i x t u r e was t h e n a l l o w e d t o s t a n d f o r s e v e r a l

h o u r s , p o u r e d on i c e , f i l t e r e d , w ashed w i t h d i s t i l l e d w a t e r
a n d r e c r y s t a l l i z e d s e v e r a l t i m e s from 95$ e t h y l a l c o h o l .
The p r o c e d u r e u s i n g f u m in g n i t r i c a c i d was c a r r i e d
o u t a t 0 °C.

T w e n t y - f i v e c . c . o f f um ing n i t r i c a c i d were

p l a c e d i n a s m a l l E r l e n m e y e r f l a s k a n d c o o l e d t o 0°C i n
an i c e b a t h .

The a l k y l b e n z e n e was t h e n added d r o p by d r o p

w ith shaking.

A f t e r a d d i t i o n was c o m p l e t e t h e r e a c t i o n

m ix was t h e n p l a c e d i n t h e r e f r i g e r a t o r f o r 2 k - h o u r s
a t w hich ti m e c r y s t a l s were w i l l f o r m e d .

These c r y s t a l s

w e r e t h e n f i l t e r e d a f t e r f i r s t p o u r i n g on c r a c k e d i c e ,
w ashed w i t h d i s t i l l e d w a t e r and r e c r y s t a l l i z e d s e v e r a l
t i i h e s from 95$ e t h y l a l c o h o l .
I d e n tif ic a tio n of F ractio n IV , P a rt 0 .
The p h y s i c a l c o n s t a n t s f o r t h i s f r a c t i o n , p . 5^ ,
ag ree f a i r l y w ell w ith th o s e r e p o r te d fo r p - t - b u t y l - i s o propylbenzene ( 50) .
its

An a t t e m p t was t h u s made t o p r o v e

I d e n t i t y by means o f i t s

b y B a r b i e r ( 5 ^)*

d in itro d e riv a tiv e as reported

The d i n i t r o d e r i v a t i v e o f F r a c t i o n IV

was p r e p a r e d u s i n g b o t h m ix e d a c i d a n d fuming n i t r i c a s
o u tlin e d above.

L i g h t y e l l o w p l a t e s were formed w hich

m e l t e d a t l 6 H—l 65 °G from b o t h m ethods o f p r e p a r a t i o n .
N i t r o g e n a n a l y s i s by m ic ro Dumas m ethod showed t h e p r e s ­
ence o f two n l t r o g r o u p s .

T h is m e l t i n g p o i n t d o es n o t

agree w ith t h a t r e p o r te d in the l i t e r a t u r e

( 5^ ) , t h u s i t

was n e c e s s a r y t o p r e p a r e p - t e r t - b u t y l - l s o p r o p y l b e n z e n e ,
n i t r a t e i t a n d c h e ck t h e m e l t i n g p o i n t o f t h e d i n i t r o
d eriv ativ e.

The h y d r o c a r b o n was p r e p a r e d a c c o r d i n g t o t h e

p r o c e d u r e a s o u t l i n e d by B a r b l e r ( 5^) u s i n g i s o p r o p y l b e n zene (cumene) , t e r t - b u t y l a l c o h o l a n d c o n c e n t r a t e d s u l f u r i c
acid.

T his was t h e n n i t r a t e d a n d i t s m e l t i n g p o i n t d e t e r ­

mined a s 2 1 2 - 2 1 ^°C.

In o r d e r to p ro v e t h a t th e p r o d u c t

was t h e p a r a i s o m e r , i t was o x i d i z e d w i t h b o i l i n g 20$
n i t r i c a c id and th e t e r t - b u t y l b e n z o i c a c i d i s o l a t e d .

T h is

a c i d m e l t e d a t l 6 ^ ° C , w h ic h c o r r e s p o n d s t o t h a t r e p o r t e d
f o r p - t e r t - b u t y l b e n z o i c a c id (55)•
From t h e c a l c u l a t i o n o f F r a c t i o n I V 1s m o l e c u l a r w e ig h t
by n i t r o g e n a n a l y s i s o f i t s d i n i t r o d e r i v a t i v e i t was
t h o u g h t t h a t i t m ig h t be t h e t e r t - b u t y l - e t h y l b e n z e n e i s o ­
mer.

p - t e r t - B u t y l - e t h y l b e n z e n e was t h u s p r e p a r e d and

n itrated .
9^-95°C.

I t s d i n i t r o d e r i v a t i v e had a m e ltin g p o i n t of
O x i d a t i o n gave p - t e r t - b u t y l b e n z o i c a c i d .

The n e x t s t e p i n t h e i d e n t i f i c a t i o n o f F r a c t i o n IV
was i t s o x i d a t i o n i n o r d e r t o d e t e r m i n e t h e p o s i t i o n o f
i t s a l k y l g r o u p s on t h e r i n g .
n i t r i c acid f a i l e d .

O x i d a t i o n u s i n g 20$ b o i l i n g

T his m ight I n d i c a t e t h a t e i t h e r

F r a c t i o n IV was a m i x t u r e , o f which a d i - t e r t - b u t y l b e n z e n e
i s o m e r was p r e d o m i n a n t , o r t h a t i t i s

an i n d a n I s o m e r formed

by c y c l i z a t i o n o f an o r t h o d i a l k y l b e n z e n e t h r o u g h t h e

a c t i o n o f aluminum c h l o r i d e .

To e l i m i n a t e t h e f o r m e r

t h o u g h t , p - d i - t e r t - b u t y l b e n z e n e was n i t r a t e d t o c h e c k i t s
m e ltin g p o in t w ith th a t r e p o r te d in the l i t e r a t u r e .

The

d e r i v a t i v e m e l t e d a t 1 9 0 - 1 9 1 °C , w h ic h a g r e e d w i t h t h a t
r e p o r t e d by B o e d t k e r ( 5 6 ) .
From t h e f o r e g o i n g r e s u l t s one i s a b l e t o c o n c l u d e
t h a t F r a c t i o n I V , P a r t 0 i s an i s o m e r whose m o l e c u l a r
w e i g h t c o r r e s p o n d s t o C ^ H i g * as c a l c u l a t e d from i t s p u r e
d i n i t r o d e r i v a t i v e , c o n t a i n s an a r o m a t i c n u c l e u s w h ich
can b e n i t r a t e d and p o s s i b l y a c a r b o c y o l l c r i n g w h ich
cannot be o x i d i z e d .

T h i s t y p e o f s t r u c t u r e c o u l d b e formed

by e l i m i n a t i o n o f m e t h y l g r o u p s from t h e d i - t e r t - b u t y l b e n z e n e i s o m e r t o form e i t h e r e t h y l o r i s o p r o p y l - t e r t b u t y l b e n z e n e o r / a n d an i n d a n is o m e r b y c y c l l z a t i o n .

The

fo rm atio n of a gas c o l l e c t e d in the n itr o m e te r d u rin g the
c o u r s e o f t h e r e a c t i o n w h ic h would n o t c o n d e n s e b u t b u r n e d
w i t h a b l u e f l a m e was e v i d e n c e o f t h e f o r m a t i o n o f m e th a n e .

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3 ,5-D ln itr o -

Moles

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Moles

A lC lj

Cond­

per

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Mole

A lcohol
Condensed
% N

% N

C alc.

Obs.

il.3-.i4-M-

g .6 3

g . l *0

l.lJO

0.5

None

53- 5^

g .63

g.gg

2.17

0 .5

None

62-6 3

g .6 3

g .7 ^

0.73

0 .5

None

g .6 3

g .69

1 . 9 1*-

0.5

3.1*

61 -6 2

g .63

S . 95

1.22

0 .5

None

52-53

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S . 93

l.g g

0 .5

53-5^

9.02

2.9S

2 .3

0 .5

M.P.

°c.
2 -Me t h y l -

Isobutane

A lcohol

2- h e p ta n o l

3-M ethyl3- h e p t a n o l

3-E thyl3- h e x a n o l

2,^-D lm ethylkv

2- h e x a n o l

^9.5

f

2 , 5-D im ethyl2- h e x a n o l

2 ,lt—D im e th y l hexanol

2-M ethyl2- h e x a n o l

None

A lk a n e

tert-B u ty l-

A lkyl

R esidue

Y ield

benzene

Benzene

Y ield

Y ield

(above a l k y l
benzene)
Y ield

g.gjj

None

2 7 .4 $

52g

9 . 5*

None

2 k . 2%

6o g

None

25.1#

23-5?

1 . 3^

1 9 . 6#

7 5 -5e

3.8*

„

1

5 .7 /5

None

2 1 . 3%

3°g

3-9*

2 . 2%

1 3 . 2%

7 7 . £g

Not
q u an titativ e

None

3 1 . 3*

3 1 .5 s

Moles

3 ,5 -D in itro Moles

benzoate
A lcohol

Cond­

Condensed

ensed

A1C1

3

per ,

Isobutane

Mole

M.P.

$ N

$ N

°C.

C alc.

Obs.

U-3-W-.

9.02

9 . 514-

2.22

0 .5

None

l i g -119

9 .02

9.17

I .63

0 .5

None

69 -7 0

9.02

9*07

2 .7 0

0.5

2 . 2$

2.0

0 .5

None

2.0

0.5

None

3.0

0 .5

None

3.0

0.5

2 . 22 $

3-M ethyl-

A lcohol

3-hexanol

3-E thyl3-pentanol

2 , ^-D im ethyl2 -pentanol

In

2- M e t h y l ^ 2-pentanol

71-72

literatu re

3- M e t h y l 3-pentanol

2- M e t h y l 2- b u t a n o l

2-M ethyl2-propanol

In
95*596.5

lite ra tu re

-

No
d e r i v a t i v e made

No
d e r i v a t i v e made

Alkane

tert-B u ty l-

A lkyl

R esidue

Y ield

benzene

Benzene

(above a lk y l
benzene)

Y ield

Y ield
Y ield

Not
None

3 0 . 0#

77g

None

33-2JS

4 -1 .5 g

2.J3#

2 2 . 2#

120g

None

3 2 . 7^

4 - 2 . 5g

1 0 .2 #

None

35-9^

39g

l.g #

None

40#

27g

•

•

Q u an titative

Not
Q u an titative

Not i s o l a t e d

7$

1 .1 4 # p - D i- t e r t -

2 .2 2 #

55#

55/S
bu tylbenzen e

DISCUSSION
I n 19^5» D r . G. L . G o e r n e r o f t h i s l a b o r a t o r y
condensed 3 -E th y l-3 -h e x a n o l w ith benzene In th e p rese n c e
o f a n h y d r o u s aluminum c h l o r i d e and I s o l a t e d a f r a c t i o n
w h ic h h e t e n t a t i v e l y i d e n t i f i e d as b e i n g a s a t u r a t e d a l i ­
p h a t i c h y d r o c a r b o n fo rm e d a p p a r e n t l y t h r o u g h t h e r e d u c t i o n
o f the a lc o h o l.

As t h e p h y s i c a l c o n s t a n t s o f t h i s f r a c t i o n

d id n o t agree w ith those r e p o r te d in th e l i t e r a t u r e
i t was n o t d e f i n i t e l y I d e n t i f i e d .

(4-9)

T his f i n d i n g l e d to th e

problem o f t h i s t h e s i s , and th e a u t h o r found th ro u g h
s p e c tro s c o p ic s tu d ie s t h a t th e hydrocarbon f r a c t i o n
i s o l a t e d from t h e above c o n d e n s a t i o n c o n s i s t e d m a i n l y o f
3 - E t h y l h e x a n e a p p a r e n t l y c o n t a m i n a t e d w i t h a n o t h e r is o m e r
fo rm e d b y a c t i o n o f t h e aluminum c h l o r i d e .
D u rin g t h e p r e p a r a t i o n o f t h e a l c o h o l s u s e d i n t h e
c o n d e n s a t i o n s , t h e i m p o r t a n c e o f s e l e c t i n g s im p le G r i g n a r d
r e a g e n t s , where more t h a n one p o s s i b i l i t y e x i s t s , was
brought o u t.

F o r e x a m p le , t h e p r e p a r a t i o n o f 2 ,k ~ D im e th y l-

h e x a n o l may r e q u i r e e i t h e r e t h y l magnesium b r o m id e o r
l s o b u t y l magnesium b r o m id e t o r e a c t w i t h m e t h y l l s o b u t y l
k e t o n e and m e t h y l e t h j ' l k e t o n e r e s p e c t i v e l y .

When t h e

f o r m e r i s u s e d a y i e l d o f JOfe i s o b t a i n e d w h e re a s o n l y a
y i e l d o f 21^ i s o b t a i n e d u s i n g t h e l a t t e r p r o c e d u r e .
A n o t h e r exam ple i s t h e p r e p a r a t i o n o f 2 ,4—D i m e t h y l - 2 p e n t a n o l from i s o b u t y l magnesium b r o m id e and a c e t o n e ( ^ 5 )
g i v i n g a y i e l d o f 30^ , w h e r e a s t h e a u t h o r o b t a i n e d an

y i e l d o f t h e c a r b l n o l u s i n g m e t h y l magnesium b r o m id e
and m e t h y l i s o b u t y l k e t o n e .

A pparently th e strtffcturefof

the ketone used i s o f l i t t l e

s ig n ific a n c e as to y ie ld ,

a s a c e t o n e was u s e d i n a l l o f t h e f o l l o w i n g p r e p a r a t i o n s .
2, D im ethyl-2-hexanol
2-M ethyl-2-heptanol
2
D im ethyl-2-pentanol
2-M ethyl-2-pentanol

a c t - a m y l MgBr - A c e to n e
n - a m y l MgBr - A c e to n e
i s o - b u t y l MgBr - A c e to n e
n - b u t y l MgBr - A c e to n e

2k%

5^$
30$
§7$

A lso e x a m p le s i n w h ic h m e t h y l e t h y l k e t o n e was employed
a r e shown b e l o w .
2 t k~ D i m e t h y l - 4 - h e x a n o l
3-M ethyl-3-heptanol

i s o - b u t y l M gBr-methyl e t h y l k e t o n e
21 f0
n - b u t y l M gB r-m ethyl e t h y l k e t o n e

The t h e o r e t i c a l s i g n i f i c a n c e o f f t h e above phenomena
h a s b e e n s t u d i e d b y s e v e r a l i n v e s t i g a t o r s among whom
N o l l e r ( 3 7 ) h a s shown t h a t s o l u t i o n s o f d i - i s o b u t y l mag­
n e s i u m , w h i c h w ere p r a c t i c a l l y h a l o g e n f r e e , r e d u c e d
b e n z o p h e n o n e to b e n z h y d r o l a s w e l l a s t h e o r i g i n a l G r i g n a r d
reag en t co n tain in g halogen.

I n c o n n e c t i o n w i t h t h i s , he

h a s a l s o shown t h a t t h e G r i g n a r d r e a g e n t p r e p a r e d from i s o ­
b u t y l b r o m id e a t a c o n c e n t r a t i o n o f a b o u t 1 . 3 m o l a r , e x i s t s
t o t h e e x t e n t o f 75$ i n t h e form o f d l i s o b u t y l magnesium.
N o l l e r a n d H i l m e r ( 5 8 ) h a v e a l s o shown t h a t t h e amount o f
t h i s r e d u c t i o n i n c r e a s e s w i t h t h e I n c r e a s i n g d l a l k y l mag­
n e s iu m c o n t e n t o f t h e s o l u t i o n b u t i s n o t p r o p o r t i o n a l to
t h e amount o f d i a l k y l magnesium p r e s e n t .

The d l a l k y l

magnesium p r e s e n t i n G r i g n a r d s o l u t i o n s a p p e a r s t o b e
i n f l u e n c e d more by t h e s t r u c t u r e t h a n t h e m o l e c u l a r w e ig h t
of the a lk y l r a d i c a l .

O th e r com peting s id e r e a c t i o n s a re

p i n a c o l f o r m a t io n , e n o l i z a t i o n , c o n d e n sa tio n and c o u p l­
in g , a l l a p p a re n tly concerned w ith th e s t r u c t u r e of th e
a l k y l group o f th e G rig n a rd r e a g e n t .
Whitmore (33) ^ a s o b s e r v e d t h a t c a t a l y s t s s u c h a s
aluminum c h l o r i d e c a u s e m o l e c u l e s t o r e a r r a n g e by m e t h y l
g r o u p m i g r a t i o n s a n d i n 1916 B o e d t k e r a n d H a l s e ( 3 0 )
n o t i c e d r u p t u r e o f t h e m o l e c u l e w i t h aluminum c h l o r i d e
as c a ta ly s ts .

S i n c e t h i s t i m e Huston a n d c o - w o r k e r s

h a v e shown t h a t w henev er t e r t i a r y a l c o h o l s e x h i b i t i n g
m e t h y l g r o u p s on t h e a l p h a c a r b o n atom a r e c o n d e n s e d
w i t h b e n z e n e i n t h e p r e s e n c e o f aluminum c h l o r i d e , m e th y l
g r o u p m i g r a t i o n t a k e s p l a c e f o l l o w e d by f r a g m e n t a t i o n .
A lso i n a l l h i g h l y b r a n c h e d a l c o h o l s one o f t h e p r o d u c t s
o f c o n d e n s a t i o n i s t h e low e n e r g y t e r t i a r y b u t y l b e n z e n e
a n d more r e c e n t l y fo u n d ( 5 ) i s o b u t a n e .

In view o f the

a bove phenomena i t was t h o u g h t t h a t a l c o h o l s s e l e c t e d
f o r t h i s problem should be a l l p o s s i b l e s t r u c t u r e s in
w h ich a l l a l k y l g r o u p s a t t a c h e d t o c a r b i n o l c a r b o n a r e
prim ary.

T h i s would m in i m i z e f r a g m e n t a t i o n a l l o w i n g a

b e t t e r s t u d y o f t h e r e d u c i n g phenom ena.

A lso i t would

show i f b r a n c h i n g on t h e a l p h a c a r b o n atom was a p r e ­
r e q u i s i t e f o r fra g m e n ta tio n o r i f a lc o h o ls w ith bran ch in g
on t h e / ^ - c a r b o n atom w ould f r a g m e n t a n d i f s o , w h e r e , i n
r e l a t i o n t o t h e p o s i t i v e c a r b o n , f o rm e d by t h e e l e c t r o p h i l i c a t t a c k o f t h e aluminum c h l o r i d e on t h e a l c o h o l .

In

c o n s id e r a tio n o f th e m o le cu lar s t r u c t u r e o f th e non-branched
a lc o h o ls condensed i . e . ,

2 - M e t h y l - 2 - h e p t a n o l , i t w o uld

h a r d l y be e x p e c te d t h a t any f ra g m e n ta tio n o r re a rra n g e m e n t
w ould t a k e p l a c e a s t h e y a r e a l l o f a r e l a t i v e l y lo w e n e r g y
l e v e l , a n d t h e c h a n c e o f w e a k e n in g a n y b ond b y e l e c t r o n
c o n c e n t r a t i o n would n o t be v e r y g r e a t , a s would b e t h e c a s e
w here b r a n c h i n g e x i s t s on e i t h e r o r b o t h t h e
carbon atom s.

- and / 3

-

I t was shown t h a t b r a n c h i n g on t h e JT - c a r b o n

atom i s a p p a r e n t l y t o o f a r rem oved from t h e e l e c t r o n
d e f i c i e n t carbon to cause f ra g m e n ta tio n .
The i o n i c mechanism o f P r i c e ( 2 6 ) , a s a l r e a d y d i s ­
c u s s e d i n t h e t h e o r e t i c a l p o r t i o n , h a s g a i n e d t h e m ost
f a v o r a s a means whereby d i r e c t a l k y l a t l o n , m e t h y l grou p
m i g r a t i o n a n d f r a g m e n t a t i o n can b e s a t i s f a c t o r i l y e x p l a i n e d .
On t h e b a s i s o f h i s t h e o r y , t h e c a r b o n i u m i o n i s f o rm e d by
a t t a c k o f t h e e l e c t r o p h i l i c a g e n t , aluminum c h l o r i d e , on
a lc o h o l, a lk y l h a lid e , o l e f i n , or a lk y l benzene.

The

e l e c t r o n d e f i c i e n t c a t i o n t h e n r e c e i v e s i t s p a i r from t h e
d o u b l e bond o f t h e b e n z e n e r i n g , a n a l o g o u s t o h a l o g e n a t i o n i n w h ic h t h e h a l o g e n c a t i o n c o m p l e t e s i t s o c t e t by
a s s o c i a t i o n w i t h a p a i r o f e l e c t r o n s from t h e d o u b l e bond
o f the arom atic n u c le u s.

Showing t h e f o r m a t i o n o f t h e

c a r b o n i u m i o n from t h e a l c o h o l , t h e r e a c t i o n p r o c e e d s i n
the fo llo w in g s t e p s .
1.

( R ) , C :0 ;H
*

2.

“

*

Cl
A1:C1

ci

H Cl
( R ) ^ C :0 :A 1 :C 1 ------ > (R)^C+
Cl
• •

+

Al(OH)ClJ

The c a rb o n iu m i o n i s t h e n a b l e t o s t a b i l i z e i t s e l f i n
one o f two w ay s:

E ith e r by a s s o c ia tio n w ith a p a i r of

e l e c t r o n s from t h e b e n z e n e r i n g w i t h f o r m a t i o n o f a l k y l
b e n z e n e a s shown i n s t e p 3 *
H
J.

( R ) 3C+

♦

( 0

-------,

( R ) 30 : P

— *

+H*

H
o r by l o s s o f a p r o t o n w i t h f o r m a t i o n o f o l e f i n w hich i n
t u r n may c o n d e n s e w i t h b e n z e n e o r a d d h y d r o g e n c h l o r i d e
w h ic h i n t u r n may c o n d e n s e .

A ll of th e se apparent i n t e r ­

m e d i a t e s , ex o e p t o f c o u rs e th e c a t i o n , have been i s o l a t e d
from t h e r e a c t i o n .
I n t h e c a s e o f a l c o h o l s i n w hich t h e r e i s b r a n c h i n g
on t h e - c a r b o n

atom t h e mechanism i s a l i t t l e more com­

p l e x a n d compounds o f l o w e r m o l e c u l a r w e i g h t a r e i s o l a t e d .
The r e a c t i o n may p r o c e e d i n t h e f o l l o w i n g m a nner.
CH -CH -C -CH2 -C -CH

+ A id

! -CH

j

+

Al(OH)Cl

ch lo rid e
CH-z

The c a rb o n iu m i o n i n t e r m e d i a t e may t a k e an a l t e r n a t i v e
c o u r s e i n w h ic h a c i s s i o n o f c a r b o n - c a r b o n bond o c c u r s .

H
cn3
OH, - 6 — C-f-

—

■>

CH -CHzCH-CH

9h3

CH_-C -CH_ -f2

—>

(polym erize)
3

•>

ch 3

CH - 6 -CH
3

+

(condense o r red u ce)

3

The t e r t i a r y b u t y l c a t i o n may c o n d e n s e w i t h b e n z e n e
t o form t e r t - B u t y l b e n z e n e o r b e r e d u c e d t o I s o b u t a n e .
The s e c o n d a r y c a t i o n u n d o u b t e d l y s t a b i l i z e s i t s e l f , by
o l e f i n f o r m a t i o n w hich i n t u r n may p o l y m e r i z e t o h i g h e r
m olecular w eig ht u n s a t u r a t e s .

E v i d e n c e o f t h i s was

shown by H u s to n and K r a n t z ( 5 ) »
I t m i g h t b e s u s p e c t e d t h a t f r a g m e n t a t i o n would t a k e
p l a c e n e x t to th e c a t i o n i n a l l c a s e s , how ever, i t has
b e e n shown i n t h i s work t h a t c i s s i o n t a k e s p l a c e a t t h a t
p o i n t w h ich f a v o r s t h e d i r e c t f o r m a t i o n o f t h e t e r t i a r y
b u ty l group.

F o r e x a m p le , t h e c o n d e n s a t i o n o f 2 , k - D i-

m e t h y l - 2- h e x a n o l r e s u l t e d i n t h e i s o l a t i o n o f i s o b u t a n e
a n d t e r t - b u t y l b e n z e n e a n d no i s o p e n t a n e and t e r t - a m y l
b e n z e n e w h io h w o u ld be e x p e c t e d i f t h e f r a g m e n t a t i o n t o o k
p la c e a d j a c e n t to the c a t i o n .

One m i g h t draw from t h i s

c o m p a r i s o n t h a t t h e r e l a t i v e e n e r g y d i f f e r e n c e s betv/een
i s o b u t a n e a n d I s o p e n t a n e a r e l a r g e e nough so a s t o f a v o r
t h e f o r m a t i o n o f t h e f o r m e r where t h e s t r u c t u r e o f t h e
alcohol i s

s u c h t h a t e i t h e r c o u l d b e form ed t h r o u g h f r a g ­

m entation.
I n t h e a u t h o r s p r e v i o u s work ( 2 1 ) i t was d e t e r m i n e d
th at a ra tio

o f 1 mole o f a l c o h o l t o 0 . 5 m oles o f aluminum

c h l o r i d e g a v e t h e maximum y i e l d o f t h e a l k y l b e n z e n e .

It

was i n t e r e s t i n g t o n o t e t h a t i n u s i n g a 1 : 1 m ole r a t i o
o f a l c o h o l - c a t a l y s t , t h e r e d u c t i o n seemed t o b e e n h a n c e d
a s was f o u n d i n t h e c a s e o f 3“Me‘t ^ y l “ 3- ^ eP ‘l:ano l «

A 1 3 .g $

y i e l d o f t h e c o r r e s p o n d i n g h y d r o c a r b o n was o b t a i n e d a s
compared w i t h 9 »5$ y i e l d u s i n g a 1 :0*5 mole r a t i o .
However, i n t h e f o r m e r c o n d e n s a t i o n , no s e p a r a t a b l e
f r a c t i o n o f a l k y l benzene could be o b t a in e d .
o f 2 ,*1~ D i m e t h y l - 4 —h e x a n o l , an

In th e case

y i e l d o f i s o b u t a n e and

a 3 *5^ y i e l d o f t h e c o r r e s p o n d i n g h y d r o c a r b o n were i s o ­
l a t e d when a 1 : 1 mole r a t i o o f a l c o h o l - c a t a l y s t was u s e d
a s compared t o

i s o b u t a n e a n d 3 *9^ o f t h e c o r r e s p o n d ­

i n g h y d r o c a r b o n were o b t a i n e d u s i n g a 1 : 0*5 mole r a t i o .
A gain no s e p a r a t a b l e f r a c t i o n o f a l k y l b e n z e n e c o u l d b e
o b t a i n e d i n t h e form er c a s e .
Many ex a m p le s a p p e a r i n t h e l i t e r a t u r e on t h e r e d u c ­
t i o n o f h y d r o g e n a c c e p t o r s i n r e a c t i o n s w hich aluminum
c h lo rid e i s used as c a t a l y s t .

U n fo rtu n a tely these

r e a c t i o n s o c c u r ov er: a w i d e ‘.r a n g e 6f c o n d i t i o n s making
i t d ifficu lt

to e v a lu a te t h e i r r e s u l t s in o r d e r t h a t they

m ight be o f h e l p in e x p la in in g the r e d u c t io n i n the
a u t h o r s work.

As was m e n t i o n e d i n t h e h i s t o r i c a l p o r t i o n ,

evidence of re d u c tio n of a lc o h o ls d u rin g condensation
w i t h b e n z e n e a n d p h e n o l h a s b e e n r e p o r t e d by H uston a n d
Hughes ( 8>) , H u s to n and F r le d e m a n n ( 6 ) , H uston and J a c k s o n
(7).

No e x p l a n a t i o n a s t o t h e s o u r c e o f h y d r o g e n was

advanced.
V a r i o u s exam ples o f r e d u c t i o n o f compounds c o n t a i n i n g
hydrogen a c c e p t o r s co nfirm th e e v o l u t i o n of hydrogen

e f f e c t e d by t h e a c t i o n o f aluminum c h l o r i d e on a r o m a t i c
compounds.

The f a t e o f t h e h y d r o g e n e v o l v e d i s d e f i n i t ­

e l y shown.

F r e u n d ( 5,9 ) f o u n d t h a t when n i t r o b e n z e n e i s

b o i l e d w i t h b e n z e n e a n d aluminum c h l o r i d e t h e r e i s f o rm e d ,
i n a d d i t i o n t o much r e s i n o u s m a t t e r , a n
p-am inobiphenyl.

y ie ld of

Here t h e h y d r o g e n i s e v o l v e d by c o n d e n ­

s a t i o n o f t h e b e n z e n o i d compound t o a b i p h e n y l d e r i v ­
a t i v e as w e ll as th e hydrogen produced d uring form ation
o f t h e r e s i n o u s mass.
Pummerer and B i n o p f l ( 6 0 ) d e m o n s t r a t e d t h e d e h y d r o g e n a t i n g e f f e c t o f aluminum c h l o r i d e i n b e n z e n e b y
conv ersion o f azobenzene i n t o p-am inobiphenyl in
yield s.

Pummerer a n d P r e l l ( 6l ) a l s o showed t h a t d i a r y l -

hydroqulnones a re r e a d i l y o b ta in e d by tre a tm e n t o f p-benzoquinone w ith a ro m a tic h y d ro c a rb o n s , p h e n o ls o r p h en o l e t h e r s
i n t h e p r e s e n c e o f aluminum c h l o r i d e .
V o rla n d e r and P r i t z s c h e r ( 62) d e m o n s tra te d t h a t r i n g
c l o s u r e o f b e n z i l l c a c i d o c c u r s upon t r e a t m e n t w i t h alum ­
inum c h l o r i d e .
A1C1
*
OH

COOH

/ \

H

COOH

A l e x a n d e r , J a c o b y a n d Fuson ( 6 3 ) f o u n d t h a t r e d u c t i o n
o c c u r r e d i n a t t e m p t e d r e a c t i o n o f 1 , l - d i a r y l - 2- a c y l e t h y l e n e s w i t h b e n z e n e and alum inum c h l o r i d e .

I n s t e a d o f con­

d e n s a tio n o n ly h y d ro g e n a tio n to th e co rresp o n d in g s a t u r ­
ated d ia ry l-k eto n es occurred:

( A r ) pC:CHCOR
d

■- C5 H£------^
AlCl^

( A r ) ? CH-CH? COR

A l t h o u g h I t was f o u n d t h a t t h e r e a c t i o n i n v o l v e d
a l s o r e p la c e m e n t o f th e a r y l g ro u p , th e o r i g i n o f the
h y d r o g e n was unknown,
N e n i t z e s c u a n d I s a c e s c u (6*0 h a v e n o t e d t h e h y d r o ­
g e n a t i o n phenom ena i n t h e r e a c t i o n o f a l l y l c h l o r i d e
w i t h b e n z e n e i n t h e p r e s e n c e o f aluminum c h l o r i d e .

The

f o r m a t i o n o f an a n t h r a c e n e d e r i v a t i v e i n t h e c o n d e n s a t i o n
w i t h e v o l u t i o n o f h y d r o g e n r e s u l t s i n an anomolous c o u r s e .
W lspek a n d Z u b e r ( 6 5 ) c l a i m t h a t by v a r y i n g t h e c o n d i t i o n s ,
a f r a c t i o n may b e o b t a i n e d , w hich c o n s i s t s p r i m a r i l y o f
n-propylbenzene.

H owever, N e n i t z e s c u and I s a c e s c u s t a t e

t h a t t h e f o r m a t i o n o f n - p r o p y l b e n z e n e i s due t o t h e u s e
o f aluminum c h l o r i d e w hich h a s been " p o i s o n e d " by a d d i t i o n
of w ater.

H ere t h e . c a t a l y s t i s so w eakened t h a t i t e f f e c t s

d e h y d ro g e n a tio n o f a s im u lta n e o u s ly formed d ih y d r o a n t h r a ­
c e n e , a n d a s u b s e q u e n t r e d u c t i o n o f t h e p r i m a r i l y form ed
-chloropropylbenzene i s th ereb y o b ta in e d .
I t i s n o t e w o r t h y t h a t i n many ex a m p le s o f aluminum
c h l o r i d e c o n d e n s a t i o n s i n w h ich r e d u c t i o n h a s b e e n o b s e r v e d
t h e r e h a s a l s o b e e n i s o l a t e d a b i p h e n y l t y p e compound,
a n t h r a c e n e d e r i v a t i v e a n d / o r much r e s i n o u s m a ss.

The form ­

a t i o n o f t h e s e compounds i s a c c o m p a n ie d by t h e f o r m a t i o n o f
hydrogen.

In a d d i tio n to t h i s , N enitzescu ( 66) p o in ts out

t h a t i n t h e a c t i o n o f aluminum c h l o r i d e on s a t u r a t e d h y d r o ­
c a r b o n s , t h e e l e c t r o n s a r e bound so f a s t t o c a r b o n t h a t t h e
f o r m a t i o n o f a s t a b l e com plex c a n n o t b e c o n s i d e r e d .

I t may,

h o w e v e r , c a u s e an a t t r a c t i o n o f t h e e l e c t r o n s o f c a r b o n
atom s w hereb y a r e v e r s i b l e d e f o r m a t i o n o f t h e e l e c t r o n
sh e lls occurs.

T h is l o o s e n s one o r more bonds so i s o m e r ­

i z a t i o n can o c c u r .

I f a c c e p to r s f o r hydrogen a r e p r e s e n t

re d u c tio n takes p la c e .

H a lo g e n compounds h a v e b e e n shown

to a c t as a c c e p to r s f o r t h e hydrogen ev o lv ed .

F u r t h e r , the

s a t u r a t e d carbon c h a in s them selves can a lso a c t as
a c c e p t o r s f o r t h e h y d r o g e n by b reakdow n i n t o l o w e r m o l e c u l a r
w e i g h t compounds.

In a d d itio n to t h i s , N enitzescu p o in ts

o u t t h a t th e hydrogen in th e s a t u r a t e d h y d ro carb o n s i s
s t r o n g l y a c t i v a t e d f o r w hich re a s o n i t
p o s s i b l e r e d u c t io n s o f halogen .

i s capable o f a l l

The a r o m a t i c h y d r o c a r b o n s

a r e i n a m i d d l e p o s i t i o n b e t w e e n s a t u r a t e d h y d r o c a r b o n s and
o lefin s.

T h a t i s , t h e y f o rm no s t a b l e compounds, a s do

o l e f i n s , b u t t h e i r e l e c t r o n s h e l l s a r e c o n s i d e r a b l y more
d e f o r m e d t h a n t h o s e o f s a t u r a t e d h y d r o c a r b o n s , so t h a t t h e y
a r e c a p a b l e o f t h e known r e a c t i o n s .
I n t h e a u t h o r s work i t was h o p e d t h a t a compound c o u l d
b e i s o l a t e d from one o f t h e r e a c t i o n s whose f o r m a t i o n would
n e c e s s a r i l y r e s u l t in the fo rm a tio n o f hydrogen.

T h is

would a c c o u n t f o r one o f t h e u n d o u b t e d l y many s o u r c e s o f
hydrogen d u r in g the c o n d e n s a tio n .

S i n c e i t was s u s p e c t e d

t h a t m ethane was g i v e n o f f d u r i n g a l l c o n d e n s a t i o n s i t may
b e s a f e t o assume t h a t d e m e t h y l a t i o n h a d t a k e n p l a c e ( 6 7 ) •
I t h a s b e e n shown ( 6 ) t h a t a l k y l g r o u p s t e n d t o s p l i t from
th e a lp h a carbon o f a l k y lb e n z e n e s and t h a t t h i s carbon has
a t e n d e n c y to w a r d f r e e r a d i c a l f o r m a t i o n ( 6& ) .

As a l r e a d y

d e s c r i b e d I n P a r t I I o f t h e e x p e r i m e n t a l a f r a c t i o n was
i s o l a t e d between t e r t - b u t y l b e n z e n e and p - d i - t e r t - b u t y l benzene in th e t e r t - b u t y l a lc o h o l co n d e n satio n .
as su m e d t h a t

I f i t is

t h i s compound was e i t h e r p - t e r t - b u t y l - i s o -

p r o p y l b e n z e n e o r p - t e r t - b u t y l - e t h y l b e n z e n e t h e s e compounds
c o u l d e a s i l y r e a c t , u n d e r t h e i n f l u e n c e o f aluminum c h l o r ­
i d e , w ith benzene o r a n o th e r m olecule o f t e r t - b u t y l b e n z e n e
i n t h e f o l l o w i n g m a n n er.

CH,
f-t.r - c - CH\

The f a i l u r e o f F r a c t i o n IV , P a r t 0 t o o x i d i z e to a
b e n z o ic a c i d d e r i v a t i v e cannot be e x p la in e d .
I f the a l k y l p o r t i o n i s l a r g e r , th en c y c l l z a t i o n could
take p la o e .
C#s

C "CH,

H

I
CH,

T h i s t y p e o f r e a c t i o n was shown by P i n e s , u n p u b l i s h e d
w ork, t o t a k e p l a c e when p - i s o b u t y l t o l u e n e o r p - s e c - b u t y l
t o l u e n e was r e a c t e d w i t h

m ethylcyolohexene in th e p r e s ­

e n c e o f e i t h e r s u l f u r i c a c i d o r h y d r o g e n f l u o r i d e a t 0°C.

The 4—m e t h y l c y c l o h e x e n e was r e d u c e d t o m e t h y l c y c l o h e x a n e
t o t h e e x t e n t o f 60$ o r m o r e .

The f a c t t h a t f r a c t i o n s

i s o l a t e d above t h e p - d i - t e r . t - b u t y l b e n z e n e c o n t a i n e d p r e ­
d o m i n a n t l y a r o m a t i c g r o u p s , a s shown by t h e r e f r a c t i v e
i n d e x and n i t r a t i o n , m ig h t f u r t h e r s u p p o r t t h e above
th eo ry .
I f a c y c l i c l n d a n s t r u c t u r e i s assu m ed f o r F r a c t i o n
IV , P a r t 0 , t h i s c o u l d o n l y form by c y c l i z a t i o n o f an
o rth o d lalk y lb en zen e.
A n o t h e r main s o u r c e o f h y d r o g e n i s u n d o u b t e d l y t h e
l a r g e amount o f r e s i n o u s m a t e r i a l f o r m e d , p a r t i c u l a r l y w i t h
t h e c o n d e n s a t i o n o f t h e more h i g h l y b r a n c h e d a n d h i g h e r
m o le cu lar w eight a l c o h o l s .

More r e d u c t i o n was fo u n d i n

th ese ca ses.
The f o r m a t i o n o f i s o b u t a n e may be a c c o u n t e d f o r b y t h e
re d u c tio n of is o b u ty l c a tio n , iso b u ten e a n d /o r t e r t - b u t y l
ch lo rid e.

I t c o u l d a l s o r e s u l t from t h e d i r e c t c r a c k i n g

o f t h e o o t y l b e n z e n e i n t h e f o l l o w i n g m anner:
CH
CH-jr
CHj-CH-CHg-C -CgH^

CH^
CH^-CH-CH^

+

CH^
CH^-CHsC -CgH^

CHo
1 eTo s u p p o r t t h e above a s s u m p t i o n H u sto n a n d B a r r e t t ( 3 )
f o u n d , i n a d d i t i o n t o i s o b u t a n e , 2 - m e t h y l - 3- p h e n y l - 2 - b u t e n e ,
3 , 3- d i m e t h y l - 2 - p h e n y l - l - b u t e n e , i n t h e c o n d e n s a t i o n o f 2 , 3 »3 - t r i m e t h y l - 2 - b u t a n o l w i t h b e n z e n e and aluminum c h l o r i d e .
I n p r e v i o u s work (21) , t h e a u t h o r h a s shown t h a t th e
p r e s e n c e o f an a r o m a t i c n u c l e u s i s a p p a r e n t l y n e c e s s a r y i f

red u ctio n i s r e a liz e d .

n -H e x an e was s u b s t i t u t e d f o r b e n z e n e

i n t h e r e a c t i o n o f 3 - E t h y l - 3 - h e x a n o l and aluminum c h l o r i d e .
Compounds i s o l a t e d were t h e d e h y d r a t i o n p r o d u c t s o f t h e
a l c o h o l and u n r e a c t e d a l c o h o l .
One i s a b l e o n l y t o p o s t u l a t e i n what form t h e h y d r o ­
gen a c c e p t o r i s i n d u r i n g r e d u c t i o n .

I f one assum es t h a t

t h e f o r m a t i o n o f t h e o l e f i n i s n e c e s s a r y t h i s would n o t
e x p l a i n t h e f o r m a t i o n o f t r i p h e n y l m e t h a n e when t r i p h e n y l c a r b i n o l i s condensed w ith benzene in the p rese n ce of
aluminum c h l o r i d e .

I f one a ssu m es t h a t t h e ca rb o n iu m i o n

o r complex i s r e d u c e d , one must th e n p o s t u l a t e t h e f o rm ­
a tio n of a h y d rid io n .
I t i s more l o g i c a l t o assume t h a t a n e c e s s a r y p r e ­
r e q u i s i t e in t h i s r e a c t i o n i s th e fo rm atio n of th e c h lo rid e
w h ic h i s i n t u r n r e d u c e d by a t o m i c h y d r o g e n w i t h t h e form ­
a t i o n o f t h e s a t u r a t e d h y d r o c a r b o n and h y d r o g e n c h l o r i d e .
In connection w ith t h i s ,

t w e l v e grams o f i s o b u t a n e w ere

i s o l a t e d from a t h r e e mole c o n d e n s a t i o n o f t e r t - b u t y l
c h l o r i d e , b e n z e n e a n d aluminum c h l o r i d e i n c o m p a r is o n w i t h
o n l y f o u r a n d o n e - h a l f grams i s o l a t e d d u r i n g t h e conden­
s a t i o n of a s i m i l a r run u s i n g t e r t - b u t y l a l c o h o l.

T h is

o b s e r v a t i o n would a l s o t e n d t o e l i m i n a t e t h e p r o b a b i l i t y
t h a t t h e r e d u c t i o n t a k e s p l a c e t h r o u g h t h e f o r m a t i o n , o f an
aluminum t e r t - a l k o x i d e .

41
SUMMARY
1.

Fourteen t e r t i a r y a lc o h o ls having only prim ary a lk y l

g r o u p i n g s a t t a c h e d t o c a r b l n o l c a r b o n w ere p r e p a r e d an d
c o n d e n s e d w i t h b e n z e n e i n t h e p r e s e n c e o f a n h y d r o u s alum ­
inum c h l o r i d e .
2.

F r a g m e n t a t i o n was shown t o t a k e p l a c e o n l y w i t h t h o s e

a l c o h o l s h a v i n g b r a n c h i n g on t h e b e t a c a r b o n ato m .

C ission

o f t h e a l k y l r a d i c a l a l w a y s t o o k p l a c e a t suc h a p o i n t a s
to f a v o r d i r e c t f o r m a t i o n o f t h e i s o b u t y l c a t i o n w h ic h was
i s o l a t e d i n t h e form o f i s o b u t a n e and t e r t - b u t y l b e n z e n e .
B r a n c h i n g on t h e gamma c a r b o n i s a p p a r e n t l y to o f a r removed
from t h e p o s i t i v e c a r b o n t o e f f e c t f r a g m e n t a t i o n .
3.

R e d u c t i o n was shown t o t a k e p l a c e d u r i n g c o n d e n s a t i o n

a s e v i d e n c e d by t h e i s o l a t i o n o f t h e p a r a f f i n h y d r o c a r b o n
c o rre sp o n d in g to th e s t r u c t u r e o f the a lc o h o l condensed.
I s o b u t a n e was a l s o i s o l a t e d i n t h o s e c a s e s where f r a g m e n t ­
a tio n of the alco h o l o cc u rred .
The p a r a f f i n h y d r o c a r b o n s were i d e n t i f i e d by t h e i r
p h y s i c a l c o n s t a n t s and i n f r a - r e d s p e c t r o g r a m s .

T ert-b u ty l­

b e n z e n e was i d e n t i f i e d by i t s a c e t a m i n o d e r i v a t i v e , i s o ­
b u t a n e by i t s b o i l i n g p o i n t and r e f r a c t i v e i n d e x a t -2 5 °C ,
and p - d i - t e r t - b u t y l b e n z e n e by i t s 2 , 6 - d i n i t r o d e r i v a t i v e .
3 , 5 - D i n i t r o b e n z o a t e s o f t h e a l c o h o l s c o n d e n s e d w ere a l s o
prepared.
5.

P o s s i b l e mechanisms h a v e b e e n p r o p o s e d f o r t h e f r a g ­

m e n t a t i o n a n d r e d u c t i o n phenom ena.

I t was shown i n p r e v i o u s

w ork t h a t t h e p r e s e n c e o f an a r o m a t i c n u c l e u s i s n e c e s s a r y
f o r re d u c tio n to tak e p la c e under th e c o n d itio n s of the
reactio n .

R e d u c t i o n seemed t o be e n h a n c e d c o n s i d e r a b l y

when t e r t - b u t y l c h l o r i d e was s u b s t i t u t e d f o r t e r t - b u t y l
alcohol.

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