D O C T O R A L D I S S E R T A T I O N SERIES

TITLE

4 Sludy of TheFragmentation cf

Same Tertiary Carbtnols When
Condensed \Hith Sensene In The
Preseme o f Aluminum Chloride
a u t h o r Hcnrv Ic\*i t X
jnPyle d a t e / 9 9 Y
UNIVERSITY
PUBLICATION NO.

DEGREE

I 111111111111 11 l | I J I | l | M I | l !

I I 11 I 11 1111 I ! I I I

^

UNIVERSITY MICROFILMS

Hn

ANN

ARBOR

•

MICHIGAN

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o

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i' a.ii _ jJ . j. ir ..--.-i

Or - Jj 0... Xj. Ui.-' '-v.

h e n ry L e r i :
:■r i c.

o f ?.Icohol,

Gaseous, p r o u c r :
^ r o ' 1lie i;r ’ ’e r r

one-:,

I

-l.l

li.

Van b y r e , hd r e i s (PV.. I ;. )
l i . - e e u o l l e p e , 19L'

i r a role.

o:

G.

. i e ioi?

roo t. e r l i r c U a 1.; r t r . r e e..

re

'

;i.-Li. J.--

3 o n i e r a Li c n ,r ■ : e c a r y l r a o u c .■T, -hp-■■'•!.'o'
one r o l e

L'l. .i.

uni y

re

cL'Iorj

<jt.r:!.s.

c ant!

r ,. u i r . I;/ . c ::.i

in

r ,t:Lo

rh1

; i , ;- o l e : : o r . ;r e t ; : e .
_v.

t r a i n or

! :i r i ^

rr .tc u !:rr I ' r - ' o r i o n r t i o n .
JLt 3-»Pi*ir-thyl b u t a r . o l - S

The y i e i r
rood

(

).

o r r , ! - r i i i x t h y l - . d - r L o n y l b u r u n e 1'ro.o 3 , 3 - d i y c Ui. p i ■nr: i . r o l - p v : e

He

chlorid e,

9-c.i Lo r o - i h — io- rot 1 p i y y t y n c one t o e

carbon,

8 , 3- di :yo tl :y lo i. it <?r if e- l , v e r t ' h o m e d

iroioer,

P , 3-d i m t l a y l b u t e n e - h , t o o

8 -me t h y l - ? - oh er>y l p r o r . a n e ( l e e e

in aoout m i n i

not f o u n t ,

mount

uror t i r - r e e
(to... ) .

I s o l a t i o n o f v. r r o l l

t h a n 1 p.) re::

ifc

o n ly ci/irruce

ley. r o -

Tie

or ov.nt o f

o r Trn.yrnen'cation.

P. , 5-11!:.c ti:v l r e n t a n o i - i

T he .c o r . o e n e a t i o n o i
product,

, h - d i r e ;.,nyIpfe:it£.a;aI-8. y i t i r . o e m e r e . y a y e , a a h y e . , ai,ri.. ■.

P , 2 - d i m * t b y I - £ - • n i . e n r l ’*r n i a n e

f'-c h lo ro -P ., 3 - i i r e t h y l r e n t one
ah or eci D b y s i c e l c o r e t e r t e
evidenced

by t h e i s o l a t i o n

whs

(hit).

isolated .

-e er o i l e r

orourt

Tin. urn r Inrmted- h r a c t i c r C y i i ± £ (10- )

r e o r t r o ; < o:" :■, [ - d i u . e . L L p l e - c o m r e - l .
ol

(1 •' ) o r

e r - y / m r t r t i o n , re

8 - r : e t h y T - 8 - p i n . n y l ;'I'or-ine., v :e a b o u t o n e ^ e r c e c t .

8 , 3 , 3 -T rli e t h y lo ut-m ol-S
It
the

v re found uh: l

i n th e eoirdeuaatien o f

ca.ee i n o t h e r a l c o h o l s . ’. ' h e r e a t e r t i a r y

crrlon,

, !.v,. - t i - i r a t hy.'l o n L a n o i - L , r>y vva s
roun ,

n rt i d e a

t o t h e c - -l-.i no]

t h a t d e . n e t l y l ^ t i o n o c c u r e d no r. cdl.i as; f r en pe t n t u n i o ! ' ; o f t h e

foim d i n the

T irol

tv, o a l c o h o l a .

bunt, t y p e

; X.'":.

ia r
oi

'ii-.i'i o

a , f , f - t i d : : a hi y l - f - a h e ioi3.Hv;aae v:as o n l y n i n e

a - v e t h y l - f - : : l ?-nyi:. rcy n a ’.at. :.:ort t h a n :: o u r u e r c e a t .

", 1 , v-triavbhylavannfc;

f ."Ti :U'j ; i co; ol v, etc,

r ah" !'.1r■v or hone

( ‘ ..) an : a , b , a - t r i a u t r - y l -/utt n e - 1

ye r et a t r i l e

£;.■ o v u l e o f f - e a L o r o ( f ) v.cre r e c c v e r t d ,

a e t h e r ’ i t ; . ;v o u t s e v e n p e r c e n t oi' vaci a r, t o :■ , , t - t r i i a i a y i . . ! V t a n o i - f .
r e c o v e r y o i h - c l .Icroy-roy-ane
o rlin a l

ir

la-oyam: ■•.ave e v i d e n c e

a l c o h o l i n t o i n o c u te n e

via. ^o’ooeefc.

i y d 'o e a r f c o m . , r'-a da ,-ly -a t , m e m
of

co.e.i

e to. yi:-i” j. on.

o !' a-i:.e ehy.L-o - a r c a y r .a.oo r t e —
cor:

j ra-o >

:nn a

at r y.d-' - da r/J, avtnnc .

ethylene
eoa'i

::L.:,u c o f i ,. m a no:n.
no

Lie

11.e. f o r a . Li oi. o f a- o a r • t- o . a ,. -an a

o:i d e r e t ' y L - t i o o an.

a ir

to-

o.: lira :. t v t: viar. o f t i e

c-t: m e , bo; t h r e r ■
:i i;i

f u r t h e r c ve i'a rce

that

i a n t i via.

a

....we e v i c t nee

i n the, ii-. o l n t i o n

<■-y ]-'d[.c) vdbici
n itrn lin ,

ra'C ivion

a r t a j o a o t i r a t i o n i;o •:-••• r-1: iy l - 3 - n- h yd r o x y o11e <jv l b u t a n e .
3 , 3 , 5 - n r f c t hy 1 r e n t a i i o l - ?

In the c e l t

oi

3, f., I - i r i n e t h y l p e n t a n o l - S ,

the yi< lei ( I f f )

of toe

o r o nv e t o f

d i r e c t c o n f e n e a t .i o n ,d , ", f - t r i m e b h y l - f - v d - r n y r n n it n n c ,v -a ea.out t h e t a r e at- l o r the
o re ce e i i ' a

-O.oo' o l .

d’he y i e l d

o f f - v e a r 1 - f - / i.a n y l a V ' n n r . e n o .

''■tteT.otf t o i d o l s te- r.-br.tm i or I'-af v l o n x o r i e e

ere

iai

hi

f ccf s t r v l .

3tie

lov e r ( a; ) .

vo m c n e r e c

s l c o h o J •.--a' i c o l a t e . 7 nab ( n i e r e e .or its-, n.rsnsf ormation. i n t o ...-chlo ro-; , 1 , .jtriveoth.ylnt;.ata2ie v.&.£ .iouacb
eonfov.ro,

t o y c - t f t r viib

a t 1 0 0 O-13'b°.

i n . t h e . i s o l a t i o n or norn. hrnrnT i m y n m r e e n V ' of t I'd s ■■■■■■

o r ura v .tui ntea f r a c t i o n

aide i m o t i o n b o iled at

ral.v s i a ana m o l e c u l a r r e f r a c t i o n t::o: tn i t

d e n s i t y and r e f'rc-cti ve index do non c h e e r - i t h
penfceue-3 .

.

I t van t l o u r r t

hydrocarbon f r - c t i o n

cbe c o n a t a n f r t o r b , o , f - t r i c e idy’l -

r,o to a yinturc- con ta i n . i n f

b, !h-ddi,ict]'.yl-‘;' - 0' t h y l ' a i a c r e - l .

a

, -i, a - t r d y eanvi-eaiac r e - 3 arc

ei r u a e r c e r v y i c 3ia' of

i-a cbtainc-'d a i e L

boiled

;o oe a-n o c t e r e t a r i '

aecoaf v a ; t r r - f a a

aa 7 ':0- 7 7 ° ( l ‘t inn).

i n o l e c n l a r re f r a c t i o n si. or eci In e. vole crlv.r fora v i a t o be C p y i i r .
as the n a in product,

. a a j n n i e ana

or: id.-.: td on

vc

air n y l c t h f l h e b o r a , in ' i c v t i ry tiie yia rt ncc o f f-v e cl:yl-d-

Vihenylpentenc-S i n t h e m i x t u r e .

'•

.! re

sxiujrpteb T r a c t i o n v h i c h
p e r c e n t .f • 1. .
i o m u l a.

j :nnj.y,:i

N itration,

by a n a o l p y v o n i a

s an.

t;

inr; or horn Tt.-T"bj. ■;

Ti.no1ol e, etc.

ooj.lc.d a t ot^-B^-0 (IB nun) van o o t H i r e d i n d i v e

r o l c c n l ; . !' r c P m c v i o n rave. C]_2-^18 no ti'.c m o l e c u l a r

rc-duo bio a an i d i r . r o t i '/at ior - ~ nve a v i a t o r r or a h e n o l s wh ic h

contain 1-ver ryel-d-p-hyfroxyphenylpcrtnnc.

A a: nrr u f . l t j ru

d e r i v a t i v e van n o t o o t u i n e u .
g , a , a - T r i n e la.vl

o.; - f

OordcnKotj on or 1 , 1 , b - t r i r n - t b y i v y u T u o I - 2 , v i t h
2 - •••■•hpnylj.H'ntsno or t h e

bn nacre ,

i nr o t - r a b u c t i n y i e l d s 0 r o.hovt t e r a e - c e r t .

c f d - r n c l d y ' l ] ;r n y l r ;,o’' ;:ne ’-nr f n un/i o n e - L c i t p e r c e n t one,
c a n e , vhe re t h e y i e l d o f _t-but y l be;ry ne wan s m i ] ,
IJ o u n c ]

npec

alcohol ro e

p ertane . rvernred
ana

found

65 p e r c e n t .

but

th e

y ield

The u r < s a tu r a te d

the

tic

crlo ri-e

m olecular re f r a c tio n

to

be

, b, 1 - f r i u e t h y l o t n t e n e - l .

in d icated

l i ’uify

d a r ,r f h ” l a t l o : i .

- G0 °

P r o ".vets

moved

0.

ana

ay i o n

fee

Tie.

in

the:

p oin t,

ev alu atio n
of r o tr y l

consisted,

ar

condensation
density
of hydro­
crlo rire

before,

(6

. )

of

73°-ob°

man) . , . a n a l y s i s

and c o la c u la r ,, r e f r u c t i o n , n a v e G ^ h R ^ ^ - s s - th e rro lc c y -la r' ’ "

oxidation

ao eto .h cro n e

pare

a e t h y l p e i j t c n c —? v a c p r e s e n t

in

T h e u n s o t a r e tab* T r a c t i o n

and

and

f o r m u l a and

c o r p ro v . n b s .

ncene-e. binp

f - c h l o r o - P . b , e-+rin.& xryl-

hoilinc

iso latio n

oh' c T u e t h y l a t i o n

a.- i n tne

unsaturafced
(if

saturated

at

sir b it

coyyound fo rc e d

of

not

ras

or

The y i e l d

ju aeren '.ere. not i i. o lo .te O .

by d e c o r a o s i t i o n

c arb o n s vhieli d id

a v e d, b , a-trix eth yl-

as

th e aiain p r o d u c t .

the m i x t u r e .

The

saturated

boiled

at

g - i Jh e n y l - b -

fractio n

Up.)

was,

as cho'j n oy a n a l y s i s ana m o l e c u l a r r e f r a c t i o n a ni ninny o f h e x p l b c hxene ■f i c i
o
o .
a t 95 - 9 9
(la
N itration,

.

.u rn )

aria ''hie}.,

by a n a l o g y ,

s-j.o i J.

r e d u c t i o n and d i a x o l i a a t i o n c a v e a

boiled

" coat., i n ‘ -ve Tlysa-b-pne nr.-lpc- K a n e .
m ix t u r e o f p h e n o l s fror, v - i c l a

sh ar p m e l t i r t y d e r i v a t i v e c o u l c n o t be p r e p a r e d .

There i s

p r e s e n t e d a t h e o r e t i c a l d i s c u s s i o n o f t h e nechania:,;c o f c o n d e n s a t i o n ,

reorrurrfenerrt and f r a y r e n t a t i o n .

"

A THSal o
S u b m i t t e a t o one G r a d u a t e s c h o o l o r S i c h i g a n
S t a t e C o lle g e or A g r i c u l t u r e and A p p lie d
S c i - n c e i n p a r t i a l f u l f i l m e n t o r cue
requirem ents tor tne degree of
SoOruH

Ji1 SHILuoOi?HY

Department

01

1944

Chemistry

-o.i L o i.J'Jr. . i'_. ,T
To ) o c t o r : o i l p h C h a s e H u s t o n t h e
w r i t ~ r v ; i s h e s t o ex 'r<-ss h i s a p p r e c i a t i o n
f o r Lev1 v e r y h e l p f u l c o u n s e l a n d tu 1 l a n c e
■-1v e r h i m I n t h 1 r v; o r k .

CONTENTS

Page
Introduction

1

Hi s t o r i c a l
6

Theoretical.
Experimental
C h e m i c a l s ............................... .... ..............................................

10

P r e p a r a t i o n s o f A l c o h o l s ......................... .

12

Condensation Apparatus.

.

.

.

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

22

.

.

25

I d e n t i f i c a t i o n , and A n a l y s i s .

.

29

General Procedure o f Condensation
Separation,

.

D erivatives

* .

.

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

Proof of S tru c tu re

57

P i g o n .? s i o n

63

Summary

69

B ibliography

.

.

.

.

70

1.
INTRODUCTION
Phe i1- - a c t i o n o r sa t u r a t e d a i l > h a t l c t e r t i a r y
w i t h b e n z e n e ana oha-noi i n t h e
Das b e e n i n v e s t i g a t e d

in

exm eted

by ? r o r e s s o r

octy.L a l c o h o l s .

The y i e l d

c o n d e n s a t i o n n r o a u c t has oeen found t o oe,

al , better

Huston
or the

in gener­

wit.n p n e n o i t n a n w i t n o - n z e n e .

n e g i n n i n x ?;i. Hi t e e
iU.Lt>,, a l l

p r e s e n c e o r aluminum c h l o r i d e

th is laboratory

ana cow orhers thro u g h t n e

a.lconois

vrxc-:: i i

‘. v o m e r s n a v e r e p o r t e d

H u s t o n a n a Hr i edernann { 1 ) i n
1

r a g m e n t a t i o n t o some d e g r e e .

L'his f r a g m e n t a t i o n h a s o ~ e n g r e a t e r wi t h h i g h l y
c o no L a, v/ith a r e s u l t i n g

1

branched a l -

ow y i e I d o r t h e e x 9 e c t e a t e r t i a r y

aixylo-nzene.
i n r e c e n t y eu.r s , an e x t e n s i v e
formed d u r i n g
nwuaoara

12)

fragm entation
studied

study

ox t h e

h a s o e e n ma d e .

products

Huston ana

t e e f o r m a t i o n o i u n s a t u r a t e d c o mp o u n d s

ana or chlori-ae complexes d u rin g

the c o n d e n s a tio n or d i -

i s o p r o p y I m e t h y l and d i - i s o o r o p y l e t h y l c a r b i n o i s w i t h benzene
in

t h e p r e s e n c e oi' a l u m i n u m c t n o r i u e .

iiuston ana b a r r e t t

{3)

c o n s t r u c t e d a f r a c t i o n a t i n g column w i t h s o e c i a i p r o p e r t i e s
in o r d e r t o b e t t e r

s e p a r a t e a nd s t u d y t h e c o mp o u n d s f o r m e d

purine: tne 0o n a e n s a t i o n
with

benzene in

of d i m e t h y l

the frag m en tation

with a v a ry in g degree

In v e s tig a tio n to

u o o u r r i n g when t e r t i a r y

study

fur­

alcohols,

o f b r a n c h i r i g on t h e c a r b o n a t om a d j a ­

c e n t to the hydroxyl carbon,
the

outy < o s r u l n o 1

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

i t was t h e p u r p o s e o f t h i s
ther

tertiary

were c o n d e n s e d w i t h b e n z e n e In

p r e s e n c e o f aluminum c h l o r i d e .

2.
HISTORICAL
A l k y l b e n z o n e s mny be p r e p a r e d
(4) and otrier

workers in

this

laooratory

l e n t r e v lev; o f t h e s e m e t h o d s .
viewed the

1

1r - f i e l d

historically
ticularly

It

and t o

uirit

;>r par-.a c u r i o

bumone was a l s o

prepared

it

(10)

alpha,

(fc)

or e p.areo c u me n e oy t n e c i s t 1 i -

Oy L i e o m a n n

zinc,

wniie

(7)

n c r i ur n o x i c i e .
from o e n z s l a i ~

oabatier

2

a n a co-workers

v a p o r s -or t e r p ^ n e s v r i t n n y -

ppO-poO c e y r - e s c e n t i e r o d e ,

;.r i o x y i a . t i o n i e a c t i o n was u s e d

to prepare

comuounds,

t h e a iono c a r o o n , or u n s a t u r a t e d

oy .p-.r s i n g t n e

cl r ogon ov--r n l c x e i a t

when c o m p o u n d s

such as t e r t i a r y

-icLa wi t n on i c i u m o r

and d i m e t h y l

par­

w i t h sis a r o m a t i c n u c l e u s .

C e r h a r d t -;nd h a h o u r s

t h e de

the purpose of t hi s b r i e f re -

t n o s e c:- _ - s -where w o n d e r s

carbon,

w e r e eoncr-n a n

pr p a r a d

is

out

comoound s w i t h b n n c Vii n g a t

chloride

(5 ) a lso has r e ­

s i d e r eac t i on s , e s p e c i a l l y

with a ’ s t r a i n e d 1 alpha

.Lotion

h a v e g i v e n an e x c e l ­

th-,:‘ g- n ^ r v i m e t h o d s o s t i r - y v/ ere d e v e l o p e d

observed

c sin s o u n d s ,

Calloway

Kaye

o f t h e Kr-iedel and C r a f t s r e a c t i o n

and t h o s e r e l a te d t o i t .
v i D:; t o r e c a l l

oy n u m e r o u s m e t h o d s .

by P u l v e r r n a c h e r

- p h e n y l p e n t a n e by d i s t i l l i n g

alpha diethylhom ophthalic

a m ixture of

acid anhydride,

calcium

o x i d e and s o d i u m h y d r o x i d e .
The

'lurtz r e a c t i o n

secondary b u ty lb e r z e r e
ethyl
to
1

benzene.

prepare

- ororao -

1

3

was u s e d by bchramrn ( 1 1 )
from e t h y l

to

prepare

i o d i d e a n d a l p h a br or n o -

The 3 - r i g n a r d r e a c t i o n wa s u s e d by b p a t h

(12)

- p h e n y l p e n t a n e from e th y l r n a g n e s i u r n b r o m i d e and

- pheny 1

propane;.

3.
The a 1 lev1 b en z en e r- h a v e b e e n p r e p a r e d by t h e r e d u c t i o n
t.e - h r h a l o - a n
by

substituted

t ' v ;- r e d u c t i o n

o f k-* t o n e s ,

-••-n i n t h ‘-> o r ° ,::,n c o f
It

acids,

n 1 ckel

i e i n t ^ r ° s t i n ••••t o n o t e

r- n o t i o n s d u r i n g t h G rafts

d e riv a tiv e s with

initial

m a i n e d urrlcvulop-r-e i'or

in

pas si "g,

r O'1"- ‘ i c a . l 1 y p o u n d
Of t h e v a r i o u s
e ofion

to

of long chain

alkyl h slid es

concept p re­

r eno t i u n was c o n f i n e d

met . e ^

stared

to

aoove, th e Grianard r e -

f ~w m e t h o d s t h a t

elv es a cure a lk y l—

t h i s m e t h o d he s b e - n u s e d by h i n g e s

p r e o a r e many o f t h •- a 1 k y l b •'n z e n a s

-with, . o p t i c a l

a nd

t r ea-t ed w1 t h t h i n

y :: a r s whl ie- f i r

on cl G r a f t s

good y l e i i ? .

e l s e made u s e

one o f t h e

- y d r u. g^n.

i s o n ,;' o f t h e

b---nz '-n--- i n

that

r - • A c t i o n v.n-- a l l '-'Viatic arid r e ­

fifty

v a i l " ! t h a f In-:- r ’r i n d e l

) j and

(Id) »

q a o r ac -<r b on s wiv'ti arnvl c h 1 o r i d e wo.
?'■ I • f i r s t

3

a nd k e t o a c i d s w i t h h y d r o -

observations of t r ie d e l

( 1 5 ) was t h e f o r m a t i o n

■l u m i n u : h s t r i p s .

sodium ( 1

of

(16).

o f ths- l r i g r : a r G r e a c t i o n
activity

(17).,

Levene and b a r k e r

to o b t a i n

compounds

.........

. . . . . . ...

p e r h a p s t h e m o s t w i d e l y u s e d and mor e d i r e c t m e t h o d I s
th"

c o n d - n s a t i. on r u c t i o n

t'-T'-r, s s t - r , o l e f i n ,
matic nucleus
condensation
hydrogen

wherein

a,cents i n c l u d e

aluminum c h l o r i d e .

tine

some

cataly tic apart.

chloride,

boron f l u o r i d e , hydrogen
Although t h i s

often has the disadvantage

sulphuric

The

acid,

c h l o r i d e , and

method h a s t h e a d v a n t a g e

o f b-'ing r a p i d and in m o st c a s e s w i l l

form m i x t u r e s d i f f i c u l t

alcohol,

o r n n p h t h e n e i s c o m b i n e d w i t h an a . r o -

i n t h e pres-poo-- o f

fluoride,

on a l k y l h a l i d e ,

g i v e a good y i e l d ,

of giv in g other

to se p a ra te

it

p r o d u c t s which

from t h e main p r o d u c t .

4.
Professor

H u s t o n and c o w o r h e r 3 oi' t o i s

f o e u s c d th'-'ir a t t e n t i o n

on t h e c o n d e n s a t i o n

h o ls with arom atic n u c le i
ide,

o,nd t h e

in t h e

of v a rio u s

alco­

rr<: ?;■ n e e o f a l u m i n u m c h l o r ­

This r e a c t i o n

field

in 1916.

was u s e d f i r s t

f r i ~ s u. 0 s 111 u t e

other

products

benzene- s a s r a i l ,

as

provess.

t r ip h e n y l c i r o i n - 1 , rave

: - n - ° d w i t s h-'-nzen■=■ m :, b - r

t h a n t h rj e x p e c t e d t e t r a p h o n y

and some t e r t i a r y

with t e r t i a r y

(21)

a l c o h o l s c o r a e n s - - d w i t h b e n z e n e and t o l u e n e
both

1

-

butyl,

hexyl a lc o h o ls condensed

w i t h b - n z - r n e , a nd t h e wor k o f I r u. cer v a n i k

aareed

the t e r t i a r y

t r i phe ny lm e t h a r e when c o n -

The work o f H u s t o n and Fox ( 2 0 )

wMeh

and

an any 1 a l k a n e . s p r o b a o l y

I n 1933 Huston and Ja.vis ( 1 9 ) n o t e d t h a t

amyl,

formed

i i - i - l g r r - a c t i o n s Ss v - a i v e n d i -

for med by a s o l i t t i n y

tertiary

by

oy H u s t o n ar,d F r i e d e m a n r .

These w o rk -rs r e s o r t e d

d a r i n y the- r~: a c t i . a .

a l e oh.il,

has

i n 1 3 9 7 t o p r e p a r e d i oh e n y 1 ir. e t h a n o f r o m o e n z y l a l ­

c o h o l and b e n z e n e , and v i e r e p e a t e d
(1)

have

are-, t e r p a r t o f t h t:* wo r k i n t h i s

b'?--n a c c o m p l i s h e d by t h e m .
Mef ( 1 8 )

laboratory

--s. t o t h - mai n r e a c t i o n

with

tertiary

y e v e r c- su 1. t s

and t h e

s i d e r---ac-

t i an s ,
The wo r k o f H u s t o n and

!ulie

(22) w i t h t e r t i a r y

a s w e l l a <? t h e wor k o f H u s t o n a n d l e s s o n
f r a yment a t i on t o >k p i a 0 a wh-n h i g h l y
condensed.

The

indicated

that

or ar. 0 h ed member s w e r e

work o f Aw u a o a r a ( 2 ) and t h a t

h a s been m e n t i o n e d .

of barret.t

(3)

These w o ro e rs found t h a t c o n d e n s a t i o n s

a t hlmher t e m p e r a t u r e s
lower y i e l d s

(23)

alcohols

mr.ve e r - g f e r

yields

o f b y - p r o d u c t s and

o f t n e e x p e c t e d compound o f t h e c o n d e n s a t i o n .

They m.L' 0

not d th at

n y -n t did not

follow

olurn inurn c h l o r i d e a s » ' c o n d e n s a t i o n
t h - • maos a c t i o n

.Law a o o v e a c e r t a i n

conc-ntraoion.
I t wo .• t h e o u r o o s e o f t h i s
•work

0

--nun by t Vr-se w o r k e r s ,

t h e t h a v e an i n c r ' e p l m

in o r l - r

usLnp; s e l e c t e d

tertiary

alcohols

m e t h y l rrr o s p i n o on t h e a l p h a o a r s o n ,

•-•n-3 t o c o n dens'-'- th-on v / i t h
num c h i o r i d ' - ,

inv--Btieatlon to co n tin u e the

o-m zr-no i n

t h e oreo' - - nce o f a l u m i ­

t o coon oar--' tn-'- or sp--r t l o;’ o f

to e

re-

o

i 3 Hi y

1 su y'-in: b"d f o r

o r -i n a I i o h " *’■: o A l c o h o l and b e n z e n e

t h e corn t e n o a t I on r e a c t i o n
s e ems c o m p l e t e l y

satls-

fa c t try .

y,

Any bh ’

h ov/ ev *r ,

must be r - l a t ed

to

-d a lly I halides , si nc t h e y

v1 1 h
yHLss

It

t h e s i Ay l a s i on

also

I v e pood

allrylbenz-nes.

of th

nr o n

1- o

heve to

t h e e v i . 1 —s e e H a t

- ”•11

to

i s l a ■.>or a t o r y vvh •■r-- m o s t o f t h e v;orh h a s D's-n

d on e

facto

orou-bt

.
' ;

H uston

■rouo o f trr-

<3

hav"

and a r o m a t i c

nvdro narhons,

the

conhydroxyl

carbon of

~ :i n n e r s t r a i n *

Ai r i t ,

1

e catiroid

theory as revl-v;e:

i':r -n-i,tion o f a. p o s i t i v e

mi

curia y the

nhov.n t h a t ,

I c o h o l vr s a c f i v e t ;::-d an:! t h e a l o n e

alcohol

plains

rl cov; o r H r
leohols

d ‘~n no t I o n of

th ~

a nd s u a o r ‘a- s e e

roirts

t. o t o r- ?no b "•
I l y n t by

.■ ' i h a n i s n

list

ion.

i.OhiC- '.-G.OrnplnX o.elwee.n - a l u m i n u m c h l o r i d e

in

cy P r i c e
tils

(?4 ) ex-

t - i eor y an

a n d ..the a l c o h o l

is

formed f i r - t ,
G H-t C ti-f

^ H-j

i

i

GH x-C
H

i

J

T

-C
C.Iy

' whi c h d i s s o c i - '

OfT

0 .H3
\

G H-,-

0
rl

rl'T

1

v

\

on5

t -s i n t o

AlGl-3

#

C H -G
* H

GHy

sn e l e c t r o n - d e f i c i e n t

01

G1
.

-» A1*01
Cl

c a r b o n i c in i o n .

OH3 CH

V

•

-»AlOl
1
Cl

-G
GH3

Th e c a r b o n l u m

+

l>H_ a
i
i
~y - 0

CH-,-C
J 1
' H

'

-G+
1
CH.,

+

( H0 - A 1 C 1 .-S'J

i o n t h e n may r e a c t w i t h b e n z e n e d u e t o

a r o m a t i c prop : r

11

es

of

0

enzene.

the

7.
OH,
1
O d y

1

6

1 J

A

-C +

H

J rL,

+

[

CH3

1J

— >

r

-CJ

V

-O r

H

*i

OH, OH,
i
i
' \ r

0
I ince t e r t i a r y
the conO"aratlon
in t n e

o r ? - - - n o-

oi do r ' o c l L - m

bon s u l a c e n t

to

jrouo

the c r i m i n a l

positive

positive

scission

ch3

h

l

CHV C
h„, , H

to too

from

a l c o h o l s with oenzene
Laboratory,

so t h a t

a

..oat

caroori w ith

a r r a n g e m e n t of t h e m o le cu le

ch3

isolated

t,o t b ^ a o o v e m e c h a n i s m .

v o m i t i v e r, 1t h a r e s u l t i n g
O
l

H+

^

ot a l u m i n u m c o l o r id--; ir. t o i s

mo ot lr-

to:- e l e c t r o n

+

H

o ften has beer

pr oduct ; - . o f t e r t i a r y

■: s h i f t o f j n a l k y l
in

buty Ib -n z-n e

0 ri p

is,

a sol f t

the

car­

c a r b o n now o e c o m e s

o f tin- c h a i n :

H C h ;5
1 »

*, ‘

- C * f —» CH^- 9 fC
- C H p - ? H-C- G+ +
CH3
H shHp

T h i s r e - . r r sn^erc-'-nt a nd c l e a v e m*- a l l o y /
n u c l e u s t o r - - ' a c t t o for r r t e r t i a r y

ooty

CH2 =CH2

tne
1

fictlvated benzene

benzene in the

ft

♦; C O

selected.
0 H3

- 3 - h
IHb

u rl 3

+

0-

” *

O ' v
X/ - . 1 3

The t h - ' O r y o f s p l i t t i n g

and re c o m b in a tio n

s u e p o r t f r o m t h e wo r k o f ko d z i ew an ov/ s k i
wo r k o f H u s t o n e nd k r i e d e m a n
,of t h e

products

in

the

formation

H u s t o n a n d boo.demoot
chloride

alkylates

(1)

(26)

(25)

of croups has

and from t h e

who f o u n d a n t h r a c e n e a s o ne
of d i phery l r n e th a n e .

als.

h a v e shown t h a t

by n i t o n s o f a n a l c o h o l

aluminum

o n ly where t h e r e

is

'o) •

■'f r ' "'-d -*nroon o tt-Wiv-p.
:.’hv. v/ o r k o f

to t o -

: ni t z - s c u ,

-l y dr oxy

Ls-s c c-scu , and I o n e sou

PoYoi ne - ' t h a t ,

f ;i - e I k y Ui f i on by me t o

on o c t i v - t i o n

r'-otijn

nuclear

trn-

In

their

by

co r -

d r oo« an

a s o-s: ]

is

and

th-

| r

f.-

( :?3)

I
- Av

in

follow !'

1:j .. ^t; ..
1

sllpnatic

ern-

is e s s e n tia lly

-

of

o a l o ~en o r e r e n l l z e d ,
,vi t h o u t a c a t a l y s t .

fir.-' m-o non

aosrsnovs
fore-s'

(2?)

o c c u r r i n / mien su i t o o Le a c t i v i t y

sue> 'Or t t o

T iis.-a v n u l
0

halides

1

o.r; elf-vo t'-ei t e m p e r a t u r e

1’hLs

- a ' oup.

1

srn s u "'pee t e d

ve t o n

i. b a

ay

chloride

of

the

ooos-r :

.,h 3 ^ n 3
J ri

+

•OCXs Al

AIG1-

aov, n

^ ri^
I
ft r T ST
Oil"?-"’-/
ysCH2

GCloAl

i"to

+

an

■+*

HGl

o lefin

A1 G1 o

JH

GHa

H

oil.

p
I
C

HGl

*• a; .
>
hi ■ o n y

->

To- c h l s r i ;s t h o n mry r - u c t

• h -z ~ y
■
■■-j A"

: v .. ■G1
G Ha,
.

.vita: t o - a c t i v o t e d n u c l e u s
GH-j GH^
«

Wti -

LA.

Cl
l- n

0 ~

3

addition
hol,

+•

Products

toe

nCl

tne

oy r e s . r r a n . y e t n e n t may w e l l b e

c o n d e n s a t i on r e a c t i o n

v?l t b a l u m i n u m e h l o r i d -

-• Gt i ^ +

oetween aluminum c h l o r i d e ,

snd b e n z e n e f o l l o w e d

bo s i s f o r

*

G -C
Sh3 h

since

have oeen r e p o r t e d

alco­
the

add 1 1 i or p r o d u c t s
(29) •

1

I , f.

LL

14,
500 m l . w ide
The

first

three

m outh b o t t l e s

b o ttle

b o ttles

was

h a lf

connected

of

ieliv ery

tubes.

s e r v i n r a s a t r a p , f o l l o w e d by

em pty,

fu ll

w ith

40 p e r

f o l l o w e d by a n o t h e r t r a p b o t t l e ,

cent

sodlam h y d r o x id e ,

and t h i s f o l l o w e d by t h r e e

bo t i l c s n a i f f u l l o f c o n c e n t r a t e d s u l p h u r i c a c i d ,

final­

and

l y a n o t h e r e m n t y i m p h.;> id 1 e w 1 ! h a Ic 1 i v > e y tube l e a d ! up to
Hie

iwao t i o n f l a s k .

T h is

t ube w a s f i t t e d v/i t h a

d eliv ery

th r c i' - o u y s t o n - e o c k to b e t t e r contro.1
m s

Lrifo

the

rea ctio n

tfne r e a o r i o n ,

sin ce

fla sk

eltrm

esn ecia lly

■..o' a

l'.vo

fit

a nd

m s was s d m ii-t e d ,

■■■>[' "i.. \i o f

p.

at

me

a b s o r b - u i a e-p n c

befo re the r e a c t i o n s t a r t e d
bn i ' o i ' e mo re

rin-

bcrLuitLut o f

ueal

of

.ms

t h e n wo '-.Id n e e d c o o l i. nr.
The

r e a ctio n . flar.k

co n sisted .

l i t e r t h r e e - n e c k f l a s k ( f o r one : e .'wo m o l e s ) ,

ecv wit;'; e m e c h a n i c s l yip;ce r l oe s t i r r e r arm u r e f l u x onn-

ccnser.

The c o n d e n s e r was c l o s e d wi t h a c a l c i u m c h l o r i d e

Lube^''.

v/'aen

t he li.aynesiuin had u l s a i s . e a r a i ,

was s t i r r e d , at. l e a s t one hb’i r is-n.z;
a l ; it a h o u r , and t i t r a t e d

for

t h e lm-upont

a tovnto

stand an­

m r e o n t a p c o f d : ,iyno.ru r e a p t a t

\ • ' *• ; *

e c u a.l v o l u m e o f

eth er at

w ith

.Ill, w

stirrb w .

tl.rm t h e

a d d ition

l y s m . v, 1 u
(u su a lly

is.;

100 m l.

the

rate

u'd.rrlur

at

of

one

leas

Isid b o o n c o m p l e t e d ,

o r on p e r
one hour

second
from

the

the-; o r o d u c t war; ip..sUro-

. 1 m io u r l ! c o n c e n t r e t e a

hydrochloric a c id

p e r m ole)

the i s .s i c

to

d issolve:

( f ) A l l m a t e r i a l s end a p r a r a t u s were d r i e d
t h e m o i s t u r e and c a r b o n d i o x i d e o f th e

pa.; ;

arm p r o t e c t e a
a ir.

from

15.

e

l a y e r v/i-s sep&ivited and t h e vvat-'r l a y e r e x t r a c t e d a t

l e a s t t h r e e t i n e s wi Ih e t h e r .

The combi ned e t h e r l a y e r s

v/ere v/a rr.ed will' 5 p e r c u n t sodi um c a r t o n a to 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 ] I ed w a t e r .

Tie p r o d u c t was 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 f o u r h o u r s o r l o n y e r .

The

VS- a/TJ p
Dhu

:

0.8115

nf'u

:

1.4141

T h i s a l c o h o l h a s b e e n p r e p a r e d by Henry (35) and i ' d r a r
(56).

hex

( 80)

alcohol.

i”o r ’d u

in h is

lab oratory

a lso

prism r

•

.,he

The above c o n s t a n t s checks h v1 t h t h o s e o f 1:a.-m

01 v Clip
I

i

H;yC-Cih> -C -C -OH
" II
v Oil3
t,T
T h i s a l c o h o l was y t e r n ais. b,
r c ; . , ' ,.,lvn b
bromllo.
;

'•bo:;.i v o r to* t

v

iec-

t: a ■. .a: :h too Grl yoo r a
' '

b u t y l mai ;ne simii

The a r i c o d u r c t o r t nc iiri.’c i r ' - i t r m ■<’- ' I s
a' 1■“•

s

1 h> -i r a to cy

■
~ ■s ;
(21).

.sn.s'sn'i

:: e mo
1 lay
1/ e r byt' D o c t o r K.L. G u i l e

,».u.
p r e p a r a t i o n o f t h i s a l c o h o l -was t he same as t he r e a c t i o n i n
P a r t A.

T h i s a l c o h o l was p r e p a r e d by B i n d e r (37) w o r k i n g

in t h I s l a b o r a t o r y .

The f o l l o w i n g c o n s t a n t s c hec ked c l o s e l y

w i t h t h o s e o b t a i n e d b \ him:
Yield:

55-601') *■ '

*25

56- 57°C.

3

:

7bO :

129-131°C

d| °

.

0.8055

fiO
' "! i

•

1. 4 2 7 5

P a r t C.

2,o,o-Trimethylbutarioi-2
CH,O CH.,
I

H,C-C
PIT

I

“ C -OH
*
3 CH.o

Thi s a l c o h o l was p r e p a r e d by a d d i n g p i n a c o l o n e t o
methylmagneaimnbrojvdde a c c o r d i n g to t he above met hods o f a d d ­
i n g k e t o n e s to G r i g u a r d r e a g e n t s .
P i n a c o l o n e was p r e p a r e d a c c o r d i n g to t he met hod g i v e n i n
' r g a n i e S y n t h e s e s (38) as f o l l o w s :

A five l i t e r three-neck

f l a s k was f i t t e d w i t h a s e p a r a t e C'j f u n n e l -md a l o n g r e f l u x
c o n d e n s e r ( w i t h a 18- 15 mm. i n n e r t u b e ) c l o s e d a t t he ton
wi th a c a . c i u m c h l o r i d e

tube.

E i g h t y grams o f magnesium and

800 ; 1. o f <-•r y be n z e n e were p l a c e d i n t h e f l a s k .

A mixture

o f 90 grams o f m e r c u r i c c h l o r i d e and 505 ml. o f a c e t o n e were
p l a c e d i n t he s e p a r a t e ry f u n n e l ,

About o n o - t a l f o f t h i s

(1) Ba s e d m on t he G r i g u a r d r e - ' . r e n t .

rea ctio n

v/us

of

anoed,

benzene

furth er

V/*•.

v/ell

u<

i.n :

wu s c o o l e d

with

of

251 m l.

of

acetone

v/as a '.lie a b e f o r e t h e r e no c i o n s t o :r
v;n s v i s i b l e
qy

• j r ■.1 rac i

rmjC^v:; u: ,

con tin u ed

t ■:e, f l a s k

a .M ixture

rea ctio n

I'--.-

ana

A f t e r a l l o f t h e a c e t o no •■-•.rd - a r o c r i c

w ater b a th .
had b een

vigorou s

one
i -1

■niu,' c:a-1r h o u r .

i.he f l a s k

hour.
the

c h i o r L ,e

and nod m l.
.

,7hen no

vnn:, Vr-a fc;b o:, ■■

r^.-ic t i or. t o o k r l u o e ,

r u :. - o on e r . n v

at. i c e

vie a in:,,

v i. (.acra-vi

anu :r... •) ’ ■i,

Tr.en two h u n d r e d m l . o f wn iu.r went,

;:uiv' i re u. .'v

T1 ie m i x t u r e

t i.'CUiUe HI id l i t t e r e d .

u.iol

vn.c
The

and

;die m i x t u r e

then. '"v ' i o v

uc.utt.d

ur- no ae'U'U/ 0 3

30.1.10. '.VeO l ' l t u

I'liev

to

tllu

f l a s k and h e a t e d 1 0 m i n u t e s w i t h a f r e s h 5 0 0 m l . p o r t i o n o f
benzene.

T h i s se c o n d m ix t u r e was f i l t e r e d ,

f i l t r a t e s were d i s t i l l e d

to

o n e-h a lf

arid t h e c o m b i n e d

t h e i r o r i g i n a l volum e.

The r e m a i n i n g b e n z e n e s o l u t i o n v/as t r e e . f e d w i t h 5 0 0 m l . o f
w a t e r and c o o l e d t o 10 d e g r e e s c e n t i g r a d e .
h y d r a t e was f i l t e r e d uit<~ r

The p i n a c o l

> rni a n t e s by s u c t i o n , washed wi t !

be n z e i i ' ■, and a i r d r i e d a t room t e m p e r a t u r e .
h y d r a t e was t r e a t e d w i t h 750 grams o f

6

This p in ac o l

N sulphuric acid for

e v e r y 250 grama o f t h e h y d r a t e and d i s t i l l e d u n t i l no more
p i n a c o l o n e came o v e r w i t h t h e w a t e r ,

The d:: s t i ] i a to was

s e p a r a t e d f r om t he w a t e r and d r i e d o v e r c a l c i u m c h l o r i d e ,
filtered,

and f r a c t i o n a l l y d i s t i l l e d .

The f r a c t i o n b o i l i n g

(2) A 30 m i n u t e i n d u c t i o n p e r i o d was r e q u i r e d u n l e s s h e a t e d ,
H e a t i n g was n o t d e s i r a b l e b e c a u s e o f t h e r a p i d r e a c t i o n
once s t a r t e d .

18,
f rom 10 3 - 1 0 5 d e g r e e s c e n t i g r a d e a t 749 ram. was u s e d .

The

y i e l d was u s u a l l y 2 5 - 3 0 p e r c e n t b a s e d on the magnesium*
The G r i g n a r d r e a g e n t was p r e p a r e d a s i n P a r t A.
a l c o h o l f or me d a s o l i d h y d r a t e i f s p e c i a l cr

The

v/aa r.ot u s e d .

The a d d i t i o n p r o d u c t , for med d u r i n g t h e p r e p a r a t i o n o f Hie
a l c o h o l , v/y.;; h y d r o l y s e d ,

t he o

1

7a y e r

-.3 p a r a

.vater l a y 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 e t h e r .

t e d , and t he
Then t h e

combi ned e t h e r l a ye r r -./are washed w.lil, C p e r c e n t sodium
e: .rtunat-.- I - •.;

:>t f o l l o w e d by w a t e r w a s h i n g .

The e t h e r

s o l u t i o n was d r i e d o v e r sodi um, t h e e t h e r removed t h r o u g h
a col umn, a n d t h e a l c o h o l d i s t i l l e d o v e r sodium a t r e d u c e d
pressure.

A s h o r t column and a s h o r t c o n d e n s e r , c a r e f u l l y

d r i e d , wer e u s e d .
tillatio n , wen

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

sealed a i r tig h t.

after dis­

The a l c o h o l was d i s ­

t i l l e d t h e r e a f t e r a t a t m o s p h e r i c o a e u u n ; cverr red ‘ .i.h - ) •
Yield:

75-80^ 2)

b 744 :

12 9 - 1 3 1 ° C.

B2 q

49-52°C.

;

The a l c o h o l was p r e p a r e d i n t h i s l a b o r a t o r y by B i n d e r
(37) and by B a r r e t t ( 3 ) «
(39) I n 1 875.

I t was p r e p a r e d f i r s t by B u t i e r o w

E d g a r (36) a l s o h a s p r e p a r e d i t .

P a r t D.

2,2,3-Trimethylpentanol-3
? H3 ?H3
H C-C -C -OH
3
CH„ 6 Ho
° CH,
O

I ) ’Then u s e d f o r c o n d e n s a t i o n s , b e n z e n e was a dde d i m m e d i a t e ­
l y upon b r e a k i n g the s e a l o f the c o n t a i n e r s .
(2) Based u p o n t h e G r i g n a r d r e a g e n t .

19 .

T h i s a l c o h o l was p r e p a r e d by t he u s e o f t h e G r i g n a r d
reaction,

a d d i n g p i n a c o l o n e t o e t h y l ma g n e s i u x n b r o ml d e .

The

p i n a c o l o n e and t h e G r i g n a r d r e a g e n t we r e p r e p a r e d a c c o r d i n g
to the above p r o c e d u r e s , and t h e r e a c t i o n f o r the a l c o h o l
c a r r i e d out as b e f o r e .

Fart E.

B1 7 4 9 • l e e - l o r

0

.

rit-ld:

. (

0

;>

1)

2 , 3 , 5 - T r i me t h y I p e n t a no 1 - f:
7rl~ CPU
1

1

ILC-OIi.C - 9 -OK
' r^ui
o
o
i

The b e s t met hod f o r the p r e p a r a t i o n o f t h i s a l c o h o l was
f ound to be ti c a d d i i . i >u < f i,-.* bbvl t e r t i a r y amyl k e t o n e to
m e t h y l ma g n e s i u m b r o m i d e .

The k e t c . i e was p r e p a r e d by a d o i n g

t e r t i a r y amyl magnesium br omi de d r o p - w i s e t o a c e t y l c h l o r i d e
a c c o r d i n g t o t h e Whitmore p r o c e d u r e ( 4 0 ) .

Then t h e a l c o h 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 she k e t o n e to m e t h y l m a g n e s i umbromide a c c o r d i n g t o t h e E dga r p r o c e d u r e ( 4 1 ) , and was
s i m i l a r to t h e . r e a c t i o n s f o r the a l c o h o l s p r e p a r e d above.
The p r o d u c t was h y d r o l y z e d and d r i e d a-, u s u a l .
G r i g n a r d wat p r e p a r e d as i n F a r t A.

t h e me t h y l

The Whitmore and Edgar

p r o c e d u r e s were u s e d by D o c t o r R. L. G u i l e (22) o f t h i s l a b ­
o r a t o r y and d e s c r i b e d by him i n d e t a i l .
Due t o t h e d i f f i c u l t y o f p r e p a r i n g t e r t i a r y G r i g n a r d s
i n good y i e l d s ,

t he p r o c e d u r e f o r t e r t i a r y amyl mat me s l u m

b r o mi d e i s d e s c r i b e d h e r e i n d e t a i l .
P h o s p h o r o u s t r i b r o m i d e was p r e p a r e d by t h e f o l l o w i n g
met hod;

t h i s i s a m o d i f i c a t i o n o f t he p r o c e d u r e found i n

O r g a n i c S y n t h e s e s ( 4 2 ) : T h i r t y - s e v e n grams ( 1 , 2 gram atoms)
71,' Tit liUC ~oEGri :: r <_niur e u uy Oi arko a no j rx s (; 7 ; .

JO.
o f d r i e d r e d p h o s p h o r o u s were s u s p e n d e d i n 250 ml . o f r e d i s ­
t i l l e d c a r b o n t e t r a c h l o r i d e i n a d r y one l i t e r t h r e e - n e c k
f l a s k equipped with a condenser sealed with a calcium c h lo r ­
ide tube, a gly ce rin e s t i r r e r ,

and a d r o p p i n g f u n n e l .

f l a s k was c o o l e d w i t h a m i x t u r e o f i c e and s a l t ,

The

and 342

grams ( 4 . 2 mol e s ) o f br omi ne were a dded d r o p - w i s e w i t h s t i r ­
ring.

The c a r b o n t e t r a c h l o r i d e and e x c e s s br omi ne were d i s ­

t i l l e d from t h e m i x t u r e w i t h t h e a i d o f a s h o r t a i r c on­
denser.

The t r i b r o m i d e was d i s t i l l e d from t he r e m a i n i n g

mixture in to a C laisen d i s t i l l i n g f l a s k .
p h o s p h o r o u s t r i b r o m i d e was r e d i s t i l l e d ,

The c r u d e
and t h e f r a c t i o n d i s ­

t i l l i n g f r om 168- 172 d e g r e e s c e n t i g r a d e a 750 mm. was u s e d .
The y i e l d was from 6 0 - 7 0 p e r c e n t .

Du r i n g e a c h o f t h e s t e p s ,

t h e s y s t e m was p r o t e c t e d from t h e m o i s t u r e o f t h e a i r w i t h a
calcium c h lo rid e tube.
Then, t e r t i a r y amyl br omi de was p r e p a r e d by p l a c i n g 232
grams ( 0 . 8 7 mol e s ) o f t h e p h o s p h o r o u s

t r l b r o i .Ode i n a d r y

one l i t e r t h r e e - n e c k f l a s k e q u i p p e d as i n t h e p r e p a r a t i o n o f
t h e t r i b r o m i d e and c o o l e d w i t h a m i x t u r e o f i c e and s a l t .
Then, 250 grams ( 2 . 6 1 mol e s ) o f r e d i s t i l l e d t e r t i a r y amyl
a l c o h o l ( b o i l i n g from 101-102 de gre e r c e n t i g r a d e a t 750 mm.)
wen a dde d d r o p - w i s e o v e r a p e r i o d o f t h r e e h o u r s .

The mi x­

t u r e was washed w i t h f i v e m l , o f s a t u r a t e d sodium b i s u l f i t e
solution,

t he w a t e r l a y e r s e p a r a t e d , and t h e p r o d u c t was

washed tv/ice w i t h c o l d c o n c e n t r a t e d s u l p h u r i c a c i d .

The

l a y e r s were s e p a r a t e d and V'O c - n d e br omi de washed w i t h
w a t e r , and t h e n w i t h 25 ml . o f s a t u r a t e d sodium b i c a r b o n a t e
solution.

The l a y e r s were s e p a r a t e d a g a i n and t he br omi de

washed v / it h w a t e r , 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 , and
d istilled .

The f r a c t i o n b o i l i n g from 106 -1 0 9 d e g r e e s c e n t i ­

g r a d e a t 7 4 6 . 2 mm, was u s e d .

The y i e l d was u s u a l l y from

00-80 p e r c e n t .
The t e r t i a r y amyl b ro m id e t h u s p r e p a r e d was u s e d im­
m e d i a t e l y to p r e p a r e t h e G r i g n a r d r e a g e n t ,

s i n c e i t was

n e c e s s a r y t h a t t h e b ro m ide be p u r e and f r e e from decom­
p o s i t i o n . p r o d u c t s t h a t form ed

a

„G.i ig.

The b ro m ide was d i l u t e d w i t h an e q u a l volume o f e t h e r
and a d d e d d r o p - w i s e to one mole o f p u r e d ry m a g n e s i u m ^ )
s u s p e n d e d i n 400 m l . o f a n h y d r o u s e t h e r .
ru n s were made v / it h s a t i s f a c t o r y r e s u l t s .

Larger or sm aller
The e t h e r and

t e r t i a r y amyl b r o m id e m i x t u r e was a d d e d v e r y s l o w l y , one
dro p p e r two t o t h r e e s e c o n d s , d u r i n g t h e e n t i r e r e a c t i o n ,
and a l a r g e e x c e s s o f t h e b r o m id e was a v o i d e d a t f i r s t
b e fo re the r e a c t i o n s t a r t e d .

The y i e l d was 5 0 -6 0 p e r c e n t .

The a l c o h o l h a s b e e n p r e p a r e d b y N o r t o n (43) and a l s o
by G u i l e ( 2 2 ) .

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

th o se d e te rm in e d by th es e w orkers f o r th e a l c o h o l .
Y ield:

4 5 -6 0 %

b 745 :

155-157°c.

Brio

:

59-61°C .

ng°

:

1 .4 3 9 7

d| °

:

0 .8 5 2 0

(1) A l l o y magnesium was f o u n d to be u n s a t i s f a c t o r y , , f i n e l y
d i v id e d , magnesium gave im p r o v e d y i e l d s , b u t i t was
n e c e s s a r y to add t h e b r o m id e more s l o w l y .

III.

The Con d........e n s a t i o-- -n- A,Ao>.o a------rat.us
The f o l l o w i n g p h o t o g r a p h a n d f i g u r e 1 show t h e c o n ­

d e n s a t i o n a p p a r a t u s a s i t was d e v e l o p e d a n d u s e d i n t h e l a s t
o f t h e c o n d e n s a t i o n s a n d a s i t was e m p l o y e d i n r<-p<~.Hting
some o f t h e e a r l i e r c o n d e n s a t i o n s .
The p u r p o s e a n d s i z e o f e a c h p a r t w i l l h e d e s c r i b e d
h e re w h ile th e g e n e ra l u se i n c o n d e n sa tio n s w i l l he g iv en
i n t h e S e c t i o n IV u n d e r t h e g e n e r a l p r o c e d u r e s f o r t h e
c o n d e n s a tio n o f th e a l c o h o l s v/ith b e n z e n e .
A--A t h r e e - n e c k r e a c t i o n f l a s k ,

the

s i z e o f which

v a r i e d a c c o r d i n g to th e number o f m oles o f a l c o h o l
condensed.
B--An e l e c t r i c m o to r f o r s t i r r i n g .
C-~ The g l a s s

s t i r r e r and g l y c e r in e

seal,

(A m e r c u r y

s e a l was n o t u s e d b e c a u s e o f t h e b a c k p r e s s u r e
created ).
D--The a l c o h o l a d d i t i o n tu b e w i t h i n n e r s e a l e d tu b e
and c o n n e c t i o n s f o r th e p u rp o s e o f e q u a l i z a t i o n o f
pressure.

The s i z e o f t h i s

tube a ls o v a r i e d a c c o rd ­

in g to th e number o f m oles o f a l c o h o l c o n d e n s e d .
E— The c a r b o n d i o x i d e g e n e r a t o r ( f o r s o l i d c a r b o n d i ­
oxide)

o f 125 m l . c a p a c i t y .

p— D rying tr a p f o r the carbon d io x id e c o n ta in in g con­
centrated
it

s u lp h u r ic a c i d , w ith a T -tube c o n n e c tin g

to th e a d d i t i o n

to th e a i r .
G— S a f e t y v a l v e

tube i n orcter to a llo w an o p e n in g

T h i s t r a p was o f 100 m l . c a p a c i t y .
to

the a i r .

25.

H--The th e rm o m e te r su sp en d e d i n s i d e

the co nd en ser.

I--W ater co n d en ser.
J--Ice

s a l t c o o le d t r a p u s e d to co n d en se and h o ld

benzene and a lc o h o l v a p o rs .

T h i s t u b e was 3 x 1 . 5

inche s .
F.--C arbon d i o x i d e - a c e t o n e c o o le d t r a p u s e d to condense
and h o l d any s u b s t a n c e t h a t d i d n o t b o i l lo w e r th a n
-80°C.

T h i s t u b e was t h e

same s i z e

as tra p

(J).

L— Two-way s t o p - c o c k u s e d t o d i r e c t t h e g a s e s t h r o u g h
trap

(K) o r d i r e c t l y

to the n i t r o m e t e r from t r a p

(J).

M— One-way s t o p - c o c k o p e r a t e d i n c o n j u n c t i o n v / i t h s t o p ­
c o c k (L) f r o m t r a p

T h i s s t o p - c o c k was c l o s e d

when s t o p - c o c k

(I,) was o p e n e d t o a l l o w g a s e s t o go

p a st trap

a n d o p e n e d when s t o p - c o c k

; K) ,

gases through tra p
b

( K) .

(L) f o r c e d

( K) .

— M ercury w e l l c o n n e c te d to s t o p - c o c k s

(L)

and

(Ivi)

by

m ea n s o f t h e Y - c o n n e c t i n g t u b e a n d 90 m l . o f v e r t i c a l
1 mm. c a p i l l a r y

tubing.

The w e l l was o f 100 m l .

ca­

p a c i t y a n d c o n t a i n e d m e r c u r y t o a h e i g h t o f 4 mm.
The c a p i l l a r y

d i p p e d 3 mm. i n t o

the m ercury.

This

c a p i l l a r y h a d t h e e q u i v a l e n c e o f 7 0 0 mm. o f m e r o u r y •
0 - - I m p t y t r a p o f 100 m l . c a p a c i t y t o h o l d l i q u i d s f r o m
c o n t a i n e r (P) i n c a s e th e m e rc u ry f a i l e d

to h o l d .

P - - C o n t a i n e r f o r a 5 p e r c e n t s o l u t i o n o f brom ine i n
carbon t e t r a c h l o r i d e .

T his c o n t a i n e r was t a p e r e d a t

th e end i n o r d e r to c o n c e n t r a t e

t h e amount o f l i q u i d

havin g gases p a sse d through i t .

I t euun a l r . e d 1 0 m l .

when h a l f f u l l .
R - ~ D r o p p i n g f u n n e l o f 25 m l .

c a p a c i t y , u s e d to h o ld p u re

“b r o m i n e u n t i l .n e ed e d .
' " - - T h e n i t r o m e t e r was o f 300 m l .

c a p a c i t y v/ith a

d i a m e t e r o f 25 mm. iri t h e v e r t i c a l
10 mm. i n t h e c u r v e d s e c t i o n ,
the le v e l o f the tr a p s
p l a c e d i n th e bottom o f
from t r a p
fille d

s e c t i o n s and

and had i t s

(K) a n d ( J ) .

h e a d above

K e r c u r y was

t h e n i t r o m o !.■>c- to s e e l

i t

( 0 ) a n d 50 p e r c e n t p o i a i n n . h y d r o x i d e

t h e r e m a i n i n g s p a c e o f t h e tii t r o r u e t e r ,

U--F3. t r o m e t e r l e v e l i n g b u l b o f 2 5 0 m l . c a p a c i t y .
The Dewar f l a s k s u s e d t o h o l d t h e b a t h so h i t i o n 3 end
m a in ta in the t r a p s

(J)

a n d (K) a t t h e i r d e s i r e d

t e m p e r a t u r e s a r e n o t sho w n .

A .C .

U1
£
□
13

25.
•

-Ufa6 .- G e n e r a l P r o c e d u r e f o r t h e C o n d e n s a t i o n o f t h e
A l c o h o l s w i t h Benzene

The a l c o h o l s p r e p a r e d w e 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 a n h y d ro u s aluminum c h l o r i d e a c c o r d i n g to the
g e n e r a l m e t h o d s by Kaye ( 4 ) ,
o rato ry ,

and o t h e r w o rk e rs i n t h i s l a b ­

f o r t h e f i r s t few c o n d e n s a t i o n s ,

arid f o r t h e m o s t

p a r t a t a te m p e ra tu re betw een 40-45 d e g re e s c e n t ig r a d e i n
o r d e r to o b t a i n

t h e maximum a m o u n t o f f r a g m e n t a t i o n a s d e ­

term ined by B a r r e t t

(3)•

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

i n the study of the c o n d ensation

n I!0 du. 0 t a . t . h a t f s Rfts and Inw I v t ] i r r 119. to vi *- ’ s va"- r < i >b !.:• !. :icd
■— 1 1. i '5 t h e r e a c t i o n .

T h i s was n o t i c e d ^ e s p e c i a l l y when t h e

p r o d u c t s w e r e h y d r o l y z e d w i t h o u t s t a n d i n g by t h e s o l u b i l i t y
o f t h e s e g a s e s a n d low b o i l i n g p r o d u c t s i n t h e
I t was n e c e s s a r y
dens a tio n

solvents.

to modify t h e o r i g i n a l p r o c o d a r c s o f eon-

i n o r d e r t o de t e r m I tie i f

ra te d or u n sa tu ra te d o r both,
F o r com parison p u rp o s e s

t h e s e go. s e s w e r e s a t u ­

a nd t h e i r a m o u n t s .
t h e o r i g i n s 1 arid, m o d i f i e d

.

m e t h o d s a r e d e s c r i b e d ix. d e t a i l .
The f i r s t
n e ok f l a s k

f ew c o n d e n s a t i o n s w e r e c a r r i o n

fitted

with a g ly c e rin e

n e l w ith a calcium c h lo rid e

stirrer,

ir. a u n i n c -

a dropping fun­

t u b e , and a w a t e r c o n d e n s e r

f i t t e d w ith a calcium c h lo rid e

tube.

were c a r r i e d o u t I n a m o l e c u l a r r a t i o
o n e - t h i r d m o l e o f a lu m i n u m c h l o r i d e ,
zene.

out

A ll o f the r e a c tio n s
o f one m o le o f a l c o h o l ,
and f i v e m oles o f b e n ­

The b e n z e n e a n d t h e a l u m i n u m c h l o r i d e w e r e s u s p e n d e d

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

26.
betw een 40-45 d e g re es c e n t ig r a d e .
a lc o h o ls , b u t a f t e r the i n i t i a l
n e c e s s a r y to c o n t r o l
a ll

The r a t e v a r i e d w i t h t h e

reactio n ,

i t u s u a l l y was

t h e r a t e a t one d r o p p e r s e c o n d .

A fter

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

on e h o u r o r l o n g e r a n d h y d r o l y z e d on i c e w i t h s t i r r i n g .
C o n c e n t r a t e d h y d r o c h l o r i c a c i d ( 2 0 0 m l . p e r m o l e ) was a d d e d
to d i s s o l v e

the b a s ic

salts

o f alum inum .

I t was l a t e r d i s ­

c o v e r e d t h a t t h e a c i d was n o t n e c e s s a r y f o r t h e a l c o h o l s
used.

The b e n z e n e l a y e r was s e p a r a t e d a n a t h e w a t e r l a y e r

e x tra c te d a t l e a s t three

tim es w ith b e n ze n e, e t h e r , o r

h e x a n e d e p e n d i n g u p o n t h e b o i l i n g p o i n t o f s u s p e c t e d low
b o i l i n g f r a c t i o n s in the c o n d e n sa tio n p ro d u c t.

Both l a y e r s

w ere t h e n d r i e d o v e r a n h y d ro u s sodium s u l f a t e .
The m a j o r i t y o f t h e c o n d e n s a t i o n s w e re r u n w i t h t h e
m o d ifie d equipm ent (se e f i g u r e 1 ) ( 1 ) .

The f o l l o w i n g d e ­

s c r i p t i o n o f t h e c o n d e n s a t i o n p r o c e d u r e was g e n e r a l f o r a l l
th e a l c o h o l s d i s c u s s e d and v a r i e d o n ly s l i g h t l y i n d e t a i l
w hich w i l l be d i s c u s s e d u n d e r th e s e p a r a t i o n ,

an aly sis,

and

i d e n t i f i c a t i o n o f the f r a c t i o n s .
The a lu m i n u m c h l o r i d e was s u s p e n d e d i n t h e b e n z e n e a n d
h e a t e d t o r e f l u x t e m p e r a t u r e f o r one h o u r t o d r i v e o f f l a r g e
amounts o f a i r d i s s o l v e d i n th e b e n z e n e .

Hydrogen c h l o r i d e

w a s e v o l v e d i n l a r g e a m o u n t s a n d t h e a lu m i n u m c h l o r i d e f i n a l ­
l y went in to

s o l u t i o n w i t h a change i n c o l o r s i m i l a r to t h a t

found i n c o n d e n s a tio n s .

When t h e a lu m in u m c h l o r i d e was a d d e d

a f t e r t h e b e n z e n e was h e a t e d a n d c o o l e d ,
(1)

there

se em e d t o h a v e

The I m p r o v e m e n t s a n d g l a s s b l o w i n g f o r 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 e r e made b y D o c t o r G . L . G-oerner o f t h i s l a b ­
o rato ry .

b e e n no c h a n g e i n t h e c o n d e n s a t i o n p r o d u c t s .

During t h i s

t i m e t h e n i t r o m e t e r was n o t c o n n e c t e d t o t h e s y s t e m ,
t a i n e r (P) f i g u r e

1 c o n t a i n e d no b r o m i n e ,

con­

and th e t r a p s

(K)

a n d ( J ) w e r e n o t c o o l e d , b u t t h e s y s t e m was w a s h e d o u t w i t h
carbon d io x id e by p la c in g
e ra to r (E).

s o l i d carbon d io x id e in the gen­

The c a r b o n d i o x i d e was a l l o w e d t o p a s s u n t i l

t h e b e n z e n e w a s c o o l e d t o room t e m p e r a t u r e ,
h o l was m e a s u r e d i n t o

th e dropping fu n n el

each o n e -th ir d p o r tio n .

then the a lc o ­

(D) a n d m a r k e d a t

The c o n t a i n e r (P) was h a l f f i l l e d

w i t h a 5 p e r c e n t s o l u t i o n o f brom ine i n c a rb o n t e t r a c h l o r ­
i d e a n d t h e n p u r e b r o m i n e was l e f t i n t h e f u n n e l (R) i n
c a s e t h a t m o r e b r o m i n e was n e e d e d .

The n i t r o m e t e r was c o n ­

n e c t e d and g a s e s a llo w e d to flow th ro u g h th e system u n t i l
t h e b u b b l e s i n t h e n i t r o m e t e r b ecam e m i c r o - b u b b l e s .
( J ) was c o o l e d w i t h a s a l t - i c e m i x t u r e a n d t r a p
s o lid carbon d io x id e-aceto n e m ix tu re.

Trap

(K) w i t h

mh c s t o p - c o c k s

(L)

a n d (M) w e r e a d j u s t e d so t h a t t h e g a s e s p a s s e d i n t o t h e
( K) ,

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

trap

The r e ­

a c t i o n b eg an w i t h th e f i r s t drop w ith a change i n c o l o r o f
the r e a c t i o n m ix t u r e and a r i s e i n t e m p e r a t u r e .
t u r e o f 45°C.

was r e a c h e d i n a b o u t f i f t e e n m i n u t e s a n d r e ­

m ained a t a b o u t t h a t
d itio n

A tem pera­

te m p e ra tu re f o r the r a t e o f a lc o h o l

( a b o u t one d r o p p e r s e c o n d ) .

ad­

H y d r o g e n c h l o r i d e was

ev o lv e d d u rin g th e f i r s t o n e - t h i r d a d d i t i o n of the a lc oh ol*
Vlhon o n e - h a l f o f t h e a l c o h o l was a d d e d , b a c k p r e s s u r e was
c re a te d in the

s j s t e m a nd m e r c u r y f r o m t h e t r a p

much a s 2 0 0 - 3 0 0 mm. i n t h e c a p i l l a r y .

( H) r o s e a s

The e v o l u t i o n o f g a s e s

b e g a n t o d e c r e a s e when o n e - t h i r d o f t h e a l c o h o l was a d a e d .

k f t e x'* t w o - t n i r d s o f t h e a l c o h o l wa s a d d e d ,
me

rem aining one- th ir d

me

reaction,

and bo th

decreased u n til

the

did not increase
she

tem perature

re a c tio n m ixture

the

tem perature of

and t h e b ack p r e s s u r e

readied

r oom t e m p e r a ­

r|,h e n t h e s y s t e m wt . . w a s h e d o u t w i t h c a r b o n u i o x i d e

ture.

:; n i, LI m i c r o - b u b b l e s w o r e o b t a i n e d ,
t . r ao

rap id a d d itio n of

( K) wa s t r a n s f e r r e d

warm u p f r o m
mi:; m r e

the

or

was

a n / o t h e r low b o i i L n r

through tills
ic e ' were

tection,

co o lin g

r e ; >t

c n b e. in : t o ] . y n . ' a

substances

v.nf

the ' n i t r o m e t e r .

Dewar f l a s k s ,

traps

sr. p u r a n ; f m m

gums

Three pounds o f

fractions

’ dry

twenty - f o u r n o u r s and

O ne-half

t o one

the con­

p a c k e d on t h e o u t s i d e

for pro­

(K) a n d ( J ) .

t h e l ow t e m o e n a t u r e b a t h s f o r
H em p el's gas a n a l y s i s ap p a ­

r a t u s wa s u s e d f o r t h e a n a l y s i s o f t h e g a s e s e x c e p t
purified

to

the m a j o r i t y o f

were used to m a i n t a i n
the

oscutmu as

t h e n e e d s o f one con d en s e t i o n .

t h e a l c o h o l was u s e d f o r

nexion i r o n s ,

In

Li >o c a r b o n a L o t h m - a c e t o n e

s u f f i.c join I; t o wor d wi i n i'o r

took c a re o f
mo l e o f

trap in to

condensed

to t i . e n i t r o m e t e r by a l l o w ! up; i t

tumoerafuro of

(-T 0 o C.) ,

The l i q u i d

the

i s o l a t e d which w i l l be d e s c r i b e d u n d e r

a n aly sis of f r a c t i o n s .

29 .
'/«

The S e p a r a t i o n ,

Id en tific atio n ,

The g e n e r a l p r o c e d u r e

for

the c o n d e n s a t i o n o f the a l c o ­

h o l s was d i s c u s s e d i n S e c t i o n IV .
in a l l

a nd A n a ] y s i s o f P r o d u c t s

The p r o d u c t s w e r e s t i r r e d

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

shown Dy t h e d e c r e a s e o f t e m p e r a t u r e t o room t e m p e r a t u r e .
I n some c a s e s

t h e s t i r r i n g was c o n t i n u e d s e v e r a l h o u r s arid

th e r e a c t i o n p r o d u c t s a ll o w e d to s t a n d o v e r n i g h t b e f o r e
t h e y were h y d r o l y z e d .

B oth p r o c e d u r e s were u s e d s e v e r a l

tim es w ith eac h a lc o h o l.

No d i f f e r e n c e

in the p ro d u c ts i s o ­

l a t e d was o b s e r v e d e x c e p t i n t h e am o u n t o f g a s d i s s o l v e d i n
the

so lv e n t.

S e v e r a l m oles o f e a c h o f t h e a l c o h o l s were con­

densed u n t i l

th e amounts o f th e h i g h b o i l i n g f r a c t i o n s o f th e

c o n d e n s a t i o n p r o d u c t s were l a r g e enough f o r f r a c t i o n a t i o n .
T h i s was e s p e c i a l l y t r u e

in the case of 2 ,2 ,3 - tr im e th y l-

p e n ta n o l- 3 and 2 , 3 , 3 - t r i m e t h y l p e n t a n o l - 2 b ecause o f the
sm all y i e l d o f the h i g h e r f r a c t i o n s .
p r o d u c t s were d r y i n g ,

W hile th e c o n d e n s a t i o n

the g a ses c o l l e c t e d i n the n i t r o m e t e r

( f i g u r e 1) a n d I n t h e t r a p s

(K) a n d ( J } w e r e a n a l y z e d .

g a s e s w h ich c o u l d n o t be l i q u i f i e d by th e t r a p
a n a l y z e d w i t h Hempel’ s gas a n a l y s i s a p p a r a t u s .

The

(K) w e r e
The g a s e s

g a v e a n a v e r a g e v a l u e o f 1 3 - 1 9 p e r c e n t o x y g e n when o n e - h a l f
to t h r e e - f o u r t h s o f a m o le o f a l c o h o l was c o n d e n s e d .

T his

was I n t e r p r e t e d t o mean t h a t a i r e n t e r e d t h e s y s t e m t h r o u g h
the g ly c e rin e

s t i r r e r a f t e r th e back p r e s s u r e from th e r e a c ­

tio n had su b sid ed .
M ethane, h y d r o g e n , and e th a n e were s u s p e c t e d as b e i n g
p r e s e n t in the gases sin ce
flam e. But i f p r e s e n t ,

they burned w ith a f a i n t blue

th e y were I n to o s m a ll c o n c e n t r a t i o n s

30.
to be d e t e c t e d and s e p a r a t e d w i t h the a p p a r a t u s .

However,

the g a ses p a r t l y reduced c u p ric oxide i n the case o f 2 ,3 ,3 t r im e th y lb u ta n o 1-2 c o n d e n sa tio n .

In an o th er c ase,

c u p r i c o x i d e was c h a r r e d t o a c a r b o n - l i k e m a s s .

the

Since th e s e

g a s e s w ere s m a ll i n amount and c o u ld n o t be l i q u i f i e d u n d e r
the c o n d i t i o n s '^ ,

no f u r t h e r w ork was a t t e m p t e d w i t h t h e m .

One t o two g r a m s o f b e n z e n e a n d s m a l l a m o u n t s o f a l c o h o l
were c o l l e c t e d i n t r a p

(J)

in each con den sation .

c h l o r i d e was l i q u i f i e d i n t r a p

M ethyl

(K) when 2 , 2 , 3 - t r i m e t h y l -

p e n t a n o l - 3 a n d 2 , 3 , 3 - t r i m e t h y l p e n t a n o l - 2 were c o n d e n s e d .

In

the case o f 2 , 3 -d im e th y lb u ta n o l-2 ? 2 ,3 -d im eth y lp en tan o l-2 ,
a n d 2 , 3 , 3 - t r i m e t h y l b u t a n o l - 2 no l i q u i d was d e t e c t e d i n t r a p
(K) b u t t h e g a s e s f r o m t h e n i t r o m e t e r b u r n e d w e a k l y w i t h a
b lu e flam e and a y e llo w to g r e e n is h f r i n g e .
A fter drying,

the s o lv e n ts f o r the l i q u i d f r a c t i o n s 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 were d i s t i l l e d a t a t m o s p h e r ic
p r e s s u r e w ith a m o d ifie d C la is e n f l a s k h aving a f o u r te e n
i n c h c o lu m n ( 4 4 ) .

The d i s t i l l a t i o n s w e re c o n t i n u e d f o r m o s t

o f t h e c o n d e n s a t i o n s f r o m t h i s p o i n t w i t h t h e s p e c i a l c o lu m n
b u i l t by B a r r e tt

( 3 ) u n t i l i t was n e c e s s a r y f o r d i s t i l l a t i o n

a t r e d u c e d p r e s s u r e f o r an e x te n d e d p e r i o d w i t h sm a ll amounts
of m a t e r i a l .

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

p e r i o d s and th e

s p i r a l gave too l a r g e a h o l d - u p .

t i o n s were d i s t i l l e d

The f r a c ­

from t h i s p o i n t w i t h sm a ll m o d if ie d

C l a i s e n f l a s k s w i t h colum ns o f v a r i o u s l e n g t h s a c c o r d i n g to
(1)

The c o n c e n t r a t i o n o f g a s e s was s m a l l b e c a u s e o f t h e e n ­
tra n c e of a i r a f t e r the back p r e s s u r e .
T his m ix tu re o f
s i r a n d h y d r o c a r b o n s c o u l d n o t be s a t i s f a c t o r i l y a n a ­
l y z e d w i t h t h e Hempel a p p a r a t u s .

the

size of fra c tio n s .

F a i r l y g o o d s e p a r a t i o n s w e r e made

w i t h f l a s k s h o l d i n g 5 m l. o f s o l u t i o n w ith s i x i n c h co lu m n s.
D i s t i l l a t i o n d i f f i c u l t i e s were g r e a t l y r e d u c e d by r e ­
m o v i n g t h e a l k y l c h l o r i d e b e f o r e d i s t i l l a t i o n was c o n t i n u e d
b e y o n d t h e low b o i l i n g f r a c t i o n s .
re flu x in g w ith s t i r r i n g ,

T h i s was a c c o m p l i s h e d b y

t h e combined h i g h f r a c t i o n s

b o i l i n g above 115-130 d e g re e s c e n t i g r a d e )
h o u r s w i t h an e q u a l volume o f f i f t y
tassium hyd roxi de ( .

(those

f r o m two t o f o u r

p e r cent a lc o h o lic po­

The l a y e r s w e re s e p a r a t e d w i t h o u t

a d d i n g w a t e r a n d t h e o r g a n i c l a y e r was w a s h e d s e v e r a l t i m e s
w ith w ater-

The r e m a i n i n g e m u l s i o n was w a s h e d w i t h w a t e r ,

th e o r g a n i c l a y e r s e p a r a t e d and washed s e v e r a l tim e s w i t h
w ater.

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

drous p o tassiu m c a rb o n a te .

Upon d i s t i l l a t i o n

was f o u n d f r e e f r o m c h l o r i d e a s a r u l e .
n e c e s s a r y to r e p e a t the p ro c e d u re .

the m a te ria l

S o m e t i m e s i t was

Even a s m a ll amount o f

t h e a l k y l c h l o r i d e made s e p a r a t i o n d i f f i c u l t w i t h r e s u l t i n g
h ig h v alu es f o r the c o n sta n ts o f each f r a c t io n .

The a b o v e

t r e a tm e n t and c a r e f u l d i s t i l l a t i o n f o r f r a c t i o n s l e s s
t w e n t y grams gave f r a c t i o n s

than

s u f f i c i e n t l y pure f o r the p r e p ­

a r a t i o n o f d e r i v a t i v e s a f t e r c o n s t a n t s and q u a l i t a t i v e
h a d i n d i c a t e d t h e c l a s s o f compound i n v o l v e d ,

tests

a l t h o u g h some

f r a c t i o n s w e r e m ore o r l e s s m i x t u r e s a f t e r f i n a l d i s t i l l a ­
tio n .

(1)

A sm all t a r r y

residue

rem ained i n each c o n d e n s a t io n .

The a l c o h o l i c p o t a s s i u m h y d r o x i d e was made b y a d d i n g d i ­
r e c t l y t o t h e r e a c t i o n f l a s k 50 g r a m s o f p o t a s s i u m h y ­
d r o x i d e a n d 50 g ram s o f a l c o h o l f o r e a c h 100 g r a m s o f
o rganic m a te r ia l.
No w a t e r was u s e d a t t h i s p o i n t .

o <3•

bom etim es f r a c t i o n s b o i l i n g h i g h e r th a n th e e x p e c te d p r o d u c t
were o b t a i n e d i n a p p r e c i a b l e

q u a n t i t i e s an d were s u s p e c t e d

o f b e i n g d i - and t r i - s u b s t i t u t e d a l k y l b e n z e n e s .

P a r t A --T h e c o n d e n s a tio n o f 2 , 3 - d im e th y lb u ta n o 1-2
w ith benzene i n th e p re se n c e o f anhydrous
a lu m i n u m c h l o r i d e .
F raction I
Three

2 , 3-D im ethylbutene-1

t o f i v e g r a m s o f t h i s m a t e r i a l 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 when t h e s o l v e n t was r e m o v e d .
I t gave an u n s a t u r a t e d

Lest w ith a 5 p e r c e n t s o l u t i o n o f

b r o m i n e i n c a r b o n t e t r a c h l o r i d e a n d was f r e e f r o m c h l o r i d e .
L a r g e r amounts were i s o l a t e d a f t e r th e a l c o h o l i c
hydroxide

treatm en t,

potassium

and b o t h p o r t i o n s were i d e n t i f i e d as

2 ,3 - d i m e th y l b u t e n e - l by p r e p a r in g 2 - c h l o r o - 2 ,3 - d i m e th y lb u ta n e from the a l c o h o l ^ ^
S h r i n e r a n d Puson (45)

and t r e a t i n g

h o lic potassium hydroxide.
c a l w ith

1)
(2)

t h e m e t h o d g i v e n by

t h i s c h lo rid e w ith a lc o ­

' T h e p r o d u c t o b t a i n e d was i d e n t i ­

t h a t o b t a i n e d from th e c o n d e n s a tio n .

checked w ith

vreld^)

a c c o r d in g to

those

r e p o r te d i n the l i t e r a t u r e

The c o n s t a n t s
(51).

The

a n d c o n s t a n t s 7/ere d e t e r m i n e d , a s f o l l o w s :

See P a r t d on p r o o f o f s t r u c t u r e .

A l l y i e l d s f o r th e c o n d e n s a t i o n s were b a s o u u i r c c f l y
u :on' t h e a l c o h o l u n l e s s o t h e r w i s e i n d i c a t e d .
Iden­
t i f i e d f r a c t i o n s were c a l c u l a t e d i n terms o f ' or can:,,
w h ile u n i d e n t i f i e d f r a c t i o n s and r e s i d u e s were r e p o r u e a
i n or-am s .

Y ield:

is

B7 4 5 :

55-59°C.

v f

^ 1)

.

1.5915

:

0.6874

M*
:
C alc.
29.53
Obs.
29.33
R
F ractio n II
2 -C hloro-2,3-dim ethvlbutane
T his f r a c t i o n d i s t i l l e d w ith o u t d i f f i c u l t y a f t e r the
s o l v e n t was r e m o v e d .
alco h o lic

I t gave a heavy c h l o r i d e

silv er n itra te ,

t e s t w ith

a n d t h e same c o n s t a n t s a s t h e co 111-

pound p r e p a r e d from the a l c o h o l f o r the p u rp o s e s o f F r a c t i o n
I-

The c o n s t a n t s c h e c k e d w i t h t h o s e r e p o r t e d i n

atu re

(59).

I t gave th e f o l l o w i n g y i e l d and c o n s t a n t s :

Y ield:

18%

B7 4 1 :

106-109°C.

n 20

.

1.4298

d 20
4

.

0.8772

mr

the l i t e r -

C alc.
34.67
Obs.
35.40
!
F ractio n I I I
2 - M e th y 1 - 2 - p h e n y l p r o p a n e

T h i s f r a c t i o n was i s o l a t e d i n s m a l l a m o u n t s when one
m o le o r m ore o f t h e a l c o h o l was c o n d e n s e d .

I t was i d e n ­

t i f i e d b y means o f th e a c e ta m in o d e r i v a t i v e ( ( 4 6 )
(1)

which

T w o - t h i r d s o f t h i s y i e l d came f r o m t h e d e c o m p o s i t i o n o f
th e chloro-com pound by a l c o h o l i c p o ta s s iu m h y d r o x id e .
M o le cu lar r e f r a c t i o n d a ta f o r a l l the c a l c u l a t i o n s
were t a k e n from S w ie t o s l a w s k i ( 5 8 ) .

(2)See P a r t F f o r the p r e p a r a tio n o f d e r i v a t i v e s .

34.
r e q u i r e d , many r e c r y s t a l l i z a t i o n s

for p u rificatio n .

p h y s ic a l c o n s ta n ts ag reed w ith those
and Auspos ( 5 2 ) .

The

r e p o r t e d by H ennion

Tne f o l l o w i n g c o n s t a n t s ,

e x ce p t the de­

riv ativ e ,

were o b t a i n e d a f t e r com bining s e v e r a l o f th e s e

frac tio n s

from s e v e r a l c o n d e n s a t i o n s i n o r d e r to p u r i f y th e

fractio n :
Y ield

0 .9 %

B,741

165-168°C.

B510

5 2 - 5 4 C.

n.i20
D
D.2A0

1.4910

M.
R
M P t.

0.8632
C alc.

44 .8 5

Obs.

43.95

2-M et h y l - 2 - p - a c e t a m i n o p h e n y l p r o p a n e
168-171°C.

F r a c t i o n IV

2 , 3-Dim et h y l - 2 - p h e n y l b u t a n e

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 a n d
w as o b t a i n e d i n g o o d y i e l d s .

I t was d i s t i l l e d w i t h t h e

s p e c i a l colum n u s i n g th e s p i r a l c o i l

(3).

v e r i f i e d b y th e a c e ta m in o d e r i v a t i v e (1)

Its

i d e n t i t y was

and the c o n s t a n t s

checked c l o s e l y w ith th o se found by o t h e r w orkers in t h i s
lab o ra to ry (47).
The f o l l o w i n g y i e l d a n d c o n s t a n t s w e r e d e t e r m i n e d :

(1)

See P a r t F f o r t h e p r e p a r a t i o n o f d e r i v a t i v e s .

*5£>

*

Y ield;

40%

B741 :

2 0 3 - 2 0 5 ° G.

B2 5

:

99-101°c.

nD

:

1.4988

D^°

:

0. 8 8 1 4 -

20

:
M .Pt.:

C alc.
54.05
Obs.
54.07
2 , 3 - D i m e t h y l - 2 - p - a c e t a m i u e p h e n y l b u t a n e 11B-119 C.

mr

F r a c t i on V
Y ield :

1

T arry residue
gram

*1 ■

P a r t B — The c o n d e n s a t i o n o f 2 , 3 - d i m e t h y l p e n t a n o l - 2
wl uu b e n z e n e i n

^,-U,T,1
t h e p r e s e n c e o> 4xfT> cenViTrrr
tx u .i^ y v j.x
.

alum inum c h l o r i d e .
F ractio n I

2 , 3-D im eth ylp en ten e-1

T h i s f r a c t i o n was s e p a r a t e d f r o m t h e b e n z e n e i n s m a l l
amounts w i t h d i f f i c u l t y .

I t was d i f f i c u l t t o d e t e r m i n e

the

t o t a l a m o u n t t h a t was f o r m e d d u r i n g t h e c o n d e n s a t i o n f o r
th is

reason.

I t was i d e n t i f i e d b y c o m p a r i s o n w i t h t h e com­

pound p r e p a r e d from 2 - c h l o r o - 2 , 3 - d i m e t h y l p e n t a n e
t o t h e p r o c e d u r e s u s e d i n P a r t A, F r a c t i o n 1 .

according

The p h y s i c a l

c o n s t a n t s checked w ith th o se r e p o r t e d i n tho l i t e r a t u r e

(53).

The f o l l o w i n g y i e l d a n d c o n s t a n t s w e r e d e t e r m i n e d :
Y ield:

io%'( 1 )

B7 4 4 :
20
nD
:

82-84°C

D
?0
4

Mr

:
:

1.4025
0.7055
C alc.

34.98

Obs.

34.28

( 1 ) F o u r - f i f t h s o f t h i s y i e l d was o b t a i n e d f r o m F r a c t i o n I I
o f t h i s c o n d e n s a tio n by the a l c o h o l i c p o ta s s iu m h y d ro x id e
treatm en t.

36.
F ractio n I I

2 -C h lo ro -2 , 3-dim ethylpentane

T h is f r a c t i o n decomposed on a t t e m p t s to d i s t i l l i t
atm o sp h eric p r e s s u r e .

I t gave a h eav y c h l o r i d e

at

t e s t a n d was

com pared w i t h th e c h l o r i d e p r e p a r e d from the a l c o h o l a s i n
P a r t A, F r a c t i o n I .

The c o n s t a n t s p r o v e d t h a t t h e compounds

w e r e i d e n t i c a l a n d t h e y a g r e e d w i t h c o n s t a n t s d e t e r m i n e d "by
B inder ( 37) .
Y ield :

The f o l l o w i n g c o n s t a n t s w e r e d e t e r m i n e d :
14 $

>

39-42°C

Hd

:

1.4355

D f

:

0.8783

mr

:

Cl

:

Bi s

20

C alc.

39.27

Obs.

C alc.

26.37$

Found 2 6 . 9 9 $ ^1 ^

F ractio n I I I

39.95

2-M ethyl-2-phenylpropane

T h i s f r a c t i o n was n o t s e p a r a t e d e a s i l y u n t i l one o r
more m o l e s o f t h e a l c o h o l was c o n d e n s e d .
riv ativ e (
c u lty .

The a c e t a m i n o d e ­

f o r one c o n d e n s a t i o n was p u r i f i e d w i t h d i f f i ­

I t g a v e t h e same c o n s t a n t s a s F r a c t i o n I I I ,

P a r t A.

F r a c t i o n s from s e v e r a l c o n d e n s a t i o n s were s a v e d and p u r i ­
f i e d In o r d e r to determ ine th e fo llo w in g c o n s ta n ts :

(1)

The a n a l y s i s f o r t h e c h l o r i n e was b y P r e g l ' s m i c r o
tech n iq u e.

(2)

See P a r t F f o r t h e p r e p a r a t i o n o f d e r i v a t i v e s .

37.
Y ield

1%

B740

165-168°C *
57-59°C
1.4912
0.8631
C alc.

M. P t

44.85

Obs. 4 3 .9 5

2-Met h y l - 2 - p - a c e t a m i n o p h e n y l p r o p a n e
168-171°C•

F r a c t i o n . IV

2 , 3-Dim et h y l - 2 - p h e n y l p e n t a n e

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

I t was v e r ­

i f i e d by th e ace ta m in o d e r i v a t i v e , and th e c o n s t a n t s checked
w i t h t h o s e p r e v i o u s l y d e t e r m i n e d f o r t h i s compound i n t h i s
l a b o r a t o r y (47)*

The f o l l o w i n g y i e l d a n d c o n s t a n t s w e r e d e ­

term ined:
Y ield :

22%

B740 :

219-221°C.

B

105-IOT *C,-

U

'

:

1.4966
0.8801

4

C alc.
M. P t

58.65

58.43

2,3-D im et h y l - 2 - p - a cetam in o p h en y l p en tan e
85-86°C .

F ractio n V
Y ield :

Obs.

Tarry resid u e

2 grams

38.
PartC

--The co n d en satio n o f 2 ,3 ,3 - tr im e th y lb u ta n o l- 2
w ith benzene i n the p re s e n c e o f anhydrous
alum inum c h l o r i d e ( 1 ) .

F ractio n I

2 - O hioro-propane

T h i s f r a c t i o n was v e r y s m a l l a n d s m a l l a m o u n t s o f t h e
d e r i v a t i v e wsre i s o l a t e d .

The a n i l i d e was p r e p a r e d i n t h e

m anner d e s c r i b e d by S h r i n e r and Fuson ( 4 5 ) ,
o f t h e p u r i f i e d d e r i v a t i v e were o b t a i n e d .
l u t i o n gave a s t r o n g c h l o r i d e

Sm all amounts
The e t h e r s o ­

t e s t a f t e r c a r e f u l w ashing

w i t h 10 p e r c e n t s o d i u m c a r b o n a t e s o l u t i o n .

T his i n d i c a t e d

t h a t t h e c h l o r i d e was n o t due t o d i s s o l v e d h y d r o g e n c h l o r ­
id e.

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

frac tio n a tin g

th e e t h e r s o l u t i o n from th e c o n d e n s a t io n ex­

t r a c t i o n w ith the

s p e c i a l c o lu m n ( 3 ) .

The f r a c t i o n could n o t

be c o m p l e t e ly s e p a r a t e d from th e e t h e r b e c a u se o f the c l o s e
r a n g e o f t h e b o i l i n g p o i n t s o f t h e two c o m p o u n d s .

The e t h e r

m i x t u r e b o i l i n g f r o m 3 5 - 3 6 d e g r e e s c e n t i g r a d e a t 750 mm. was
u s e d f o r t h e p r e p a r a t i o n o f t h e d e r i v a t i v e ",

Since the

i s o p r o p y l c h l o r i d e was n o t c o m p l e t e l y s e p a r a t e d a n d t h e p u r e
a n i l i d e o b t a i n e d i n sm a ll am ounts,

no y i e l d was c a l c u l a t e d .

"(1) T h i s a l c o h o l was i n v e s t i g a t e d i n d e t a i l b y B a r r e t t (3)
a n d was s e l e c t e d h e r e i n o r d e r t o c o m p a r e t h e g a s e s a n d
u n s a t u r a t e d com pounds w i t h t h e a l c o h o l s i n t h i s s e r i e s
u n d e r t h e same c o n d i t i o n s a n d w i t h t h e same t e c h n i q u e s .
T h i s a l c o h o l was p a r t i c u l a r l y d i f f i c u l t t o h a n d l e a n d
condense.
The a l c o h o l f o r m e d a s o l i d h y d r a t e a n d a
so lide c h lo rid e .
They d i s t i l l e d t o g e t h e r a n d w e re
s e p a r a te d by f r a c t i o n a l c r y s t a l l i z a t i o n .

59.
M. P t . r

2 -M eth y l-p ro p io n an ilid e^)
105-108°C.
F ractio n I I

1 , 2 - D ibrom o-ethane

T h l a f r a c t i o n was o b t a i n e d
by means o f

the bromine

trap

i n one

(P)

to

figure

two g r a m y i e l d s

1 , wh e n t h r e e - f o u r t h s

o f a m o l e o r m o r e o f t h e a l c o h o l was c o n d e n s e d .
b r o m i n e was d e s t r o y e d

w ith aqueous

m i x t u r e wa s e x t r a c t e d w i t h e t h e r ,
sodium s u l p h a t e ,

filtered,

fie d Claisen fla s k .
oc i'6 co
tiiose
';!< ■ :

re

listed

sodium b i s u l p h i t e .

and d i s t i l l e d

camcl

The

d rie d over anhydrous

The c o mp o u n d was

cl b y j>t>,h od o r

The e x c e s s

i n a sm a ll modi­

sufficiently

pure

to

j.. l>s c o n s t.;iu p S corrcijva.^tr.icu^

in chem istry handbooks•

cg

The f o l l o w i n g c o n s t a n t s

do t o m l. rad :
Y ield:

0,87y

B
:
7 4- a

1 3 0 - 1 5 2 ° C.

P
hi « aj - j u- * .*

p • *p->. O n \_t

'J

9

1.5401
F r a c t i on I I I
This
o f

the

f r a c t i o n was o b t a i n e d i n

a l e oho ?_ was c o n d e n s e d •

distillation

of fra c tio n II

;,e r u i n e d a t

that

for h alogen

bp

ci t s t . a

(1)

1 , B-Dibrorno-rropano

we m

oo tai

Lime.

s m a l l y i e l d when one mole

I t was c o l l e c t ' d du

above and i t s

r in g

b o ilin g p o u r

oe-

The p u r i f i e d p u t ' o n was a n a l y z e d

the C ac tu s p r o c e d u r e

(if),

aeci :

phis derivative
Calc ( 6 0 ) .

the

has been re p o rte d

oy

U nnerv/ood

arid

Y ield

0.5%

B74 4

138-145°C.

Br

C alc.
F r a c t i o n IV

79.15%

Found 7 8 . 3 7 %

2 ,3 ,3 -T rim eth y lb u te n e-l

Sm all am ounts o f t h i s

f r a c t i o n wore o b t a i n e d when t h e

s o l v e n t was r e m o v e d , b u t t h e g r e a t e r p o r t i o n came f r o m t h e
d e c o m p o s i t i o n o f t h e c h l o r o - c o m p o u n d w i t h 50 p e r c e n t a l c o ­
h o lic potassium hydroxide.

I t was i d e n t i f i e d b y i t s

prepa­

r a t i o n f r o m 2 - c h l o r o - o , 3 , 3 - t r i m e t h y l b u t a n e w h i c h was p r e ­
p a r e d f r o m t h e a l c o h o l a s I n P a r t A, F r a c t i o n I .
c o n s t a n t s c o rre s p o n d e d to
(54).

The

those r e p o r t e d i n the l i t e r a t u r e

The f o l l o w i n g y i e l d a n d c o n s t a n t s w e r e o b t a i n e d :
Y ield :

5%( 1 )

B743

74-76°C.
1.4023

D
f

0.7029

M.R

C alc.

F ractio n V

35.93

Obs.

33.48

2 -C h lo ro -2 , 3 , 3 - 1rim ethylbutane

T h i s f r a c t i o n was a s o l i d c h l o r i d e a n d d i s t i l l e d o v e r
w i t h th e s o l i d h y d r a te o f the a l c o h o l .
separate

I t was n e c e s s a r y t o

th e m f r o m t h e h i g h e r f r a c t i o n s a n d t h e n d e t e r m i n e

th e amount o f c h l o r i n e (

from a m ix tu re o f the tw o.

c h l o r i n e c o n t e n t was 8 . 3 8 % .
f i e d b y m ea n s o f i t s

The

The a l k y l c h l o r i d e was i d e n t i ­

p r e p a r a t i o n from th e a lc o h o l as s t a t e d

(1) B ased~on th e " a l k y l c h l o r i d e from th e c o n d e n s a t i o n , w hich
i n t u r n was c a l c u l a t e d f r o m a m i x t u r e o f t h e h y d r a t e o f
the a lc o h o l by a C arius a n a ly s is ( 49) .

41.
i n F r a c t i o n IV a b o v e .

The f r e e z i n g p o i n t a n d b o i l i n g p o i n t

c h eck ed w i t h th o se o b t a i n e d by B a r r e t t ( 3 ) .

The f o l l o w i n g

c o n s t a n t s were d e te r m i n e d :
Y ield :

2% ^

B7 45 :

129-131°C.

M.Pt.:

123°c.

F r a c t i o n VI

H y d r a t e o f 2 , 3 >3 - t r i m e t h y l b u t a n o l - 2

T h i s compound was t h e a l c o h o l w i t h one m o l e c u l e o f
w a t e r w h i c h f o r m e d a s o l i d a s d i s c u s s e d i n F r a c t i o n IV .
was i d e n t i f i e d b y e x p o s i n g t h e a l c o h o l
bu tan o i-2
d ried .

to m o is t a i r .

It

(2 ,3 ,3 -trim eth y l-

'The c r y s t a l s w e r e s e p a r a t e d a n d

T h i s com pound was i d e n t i f i e d by B i n d e r ( 5 7 ) .

The

y i e l d and t h e c o n s t a n t s were d e te r m i n e d as f o l l o w s :
Y ield:

1% ^

B7 4 q :

120-124°C•

M.Pt.:

80-82°C.

F r a c t i o n VII

2-Met h y l - 2 - p h e n y l p r o p a n e

T h i s compo und was o b t a i n e d a f t e r t h e s o l i d s were c l e a r e d
from th e c o n d e n s a t io n p r o d u c t s and I d e n t i f i e d as i n P a r t A
a n d B.

The f o l l o w i n g y i e l d a n d c o n s t a n t s w ere o b t a i n e d :

(1) B a sed u pon th e m i x t u r e from th e c o n d e n s a t i o n .
no te page 40).

(See f o o t ­

42.
Y ield
B
7 40

166-169°C.

BJ11

5 3° C .

nt20
D
}
D20
4
Mr

1.4910
0 .8 6 3 2

M .P t.

2-Me t h y l - 2 - p - a c e t a m i n o p h e n y l p r o p a n e

C alc.

44.85

Obs.

43.95

168-170°C.
F ra c tio n V III

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

T h i s c om pound was i d e n t i f i e d b y i t s

acetam ino d e -

r i v a t l v e v-*• > a n d t h e c o n s t a n t s g i v e n b y Fox ( 2 0 ) .
c o n stan ts also

The

c o rre s p o n d e d to th o se g iv e n f o r th e f r a c t i o n

i s o l a t e d by B a r r e t t

(3).

The f o l l o w i n g y i e l d a n d c o n s t a n t s

were d e t e r m i n e d :
Y ield:

*7°

Br

189-192°C•

B
]
11
.20
nD
I
.20
4

69-70°C.

7 41

1.4931
0.8735
C alc.

R
M .P t.

49.45

Obs. 4 9 .1 1

2-Met h y l - 2 - p - a c e t a m i n o p h e n y l b u t a n e
139-142°C .

F r a c t i o n IX

2 -M eth y l-3-phenylbutene-2

T h is f r a c t i o n c o rr e s p o n d e d to the f r a c t i o n i s o l a t e d and
id e n tif ie d by B a rre tt

(1)

(3)

a s t r i m e t h y l s t y r e n e a n d was o b -

Se e P a r t F f o r t h e p r e p a r a t i o n o f d e r i v a t i v e s .

45,
t a i n e d . i n on e t o two g r a m y i e l d s p e r m o le o f a l c o h o l c o n ­
densed.

The f o l l o w i n g c o n s t a n t s w e r e d e t e r m i n e d :

Y ield :

1.3#

B727

:

188-193°C

B11

;

8 8 - 9 3 C.

" i°

=

1.5185

o f

:

0.8921

Mr

:

C alc.

F raction X
T h i s was
V ,

\J y

i~, r , s r \ 4 - ,-y

4- ot

-LOO

,

v ,

,.-3 ,—i -v-,

VAOxa- VCXO- i - V w

te rm in e d asfo llo w s

Obs.

49.60

2 ,3 ,3 -

thee x p e c te d

Ct V- »00 CUUO. i 1.0*

B arrett

49

a l k y l b e n z e n e a n d was i d e n t i f i e d
^

^

m v »
U l ^

andco rre sp o n d e d

rt A p
O
WO iiO

f

‘1 n f
n
o . J. A >_/ 1_4

W C*
t * V. a

& mm
s-

to t h o s e o b t a i n e d by

(3):

Y ield

9%

B

1 0 0 -1 0 3 °C.

11

n 20
‘D
D,20
4

1.5014

M.R

C alc.

M .P t.

2 , 3 ,3 -T rim e th y l-2 -p -a c e ta m in o p h e n y l butane

0.8665
58.65

Obs.

59.77

142-143°c.
F r a c t i o n XI
Y ield :

T arry resid u e

3 grams

P a r t D — The 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 p e n t a n o l - 3
w ith benzene i n the p re s e n c e o f anhydrous
a lu m i n u m c h l o r i d e .
(1)

See P a r t F f o r t h e p r e p a r a t i o n o f d e r i v a t i v e s

F ractio n I

M ethyl c h l o r i d e

T h i s f r a c t i o n was i s o l a t e d a s a l i q u i d i n t r a p
figure 1,

I t was i d e n t i f i e s by d i s t i l l i n g

( K) ,

from the con­

t a i n e r i n w h i c h i t was c o l l e c t e d i n t o a n o t h e r t u b e t h e
same s i z e .
liv ery

The two c o n t a i n e r s w e r e c o n n e c t e d w i t h a d e ­

tube,

A low t e m p e r a t u r e t o l u e n e

p la c e d in the d i s t i l l i n g
sto p p er.

t h e r m o m e t e r was

t u b e b y means o f a two h o l e r u b b e r

The o t h e r h o l e was u s e d f o r t h e d e l i v e r y t u b e .

The r e c e i v i n g t u b e was l e f t f r e e

to th e a i r .

Both tu b e s

were p l a c e d i n b a t h s o f s o l i d c a r b o n d i o x id e and a c e t o n e .
The t e m p e r a t u r e was c o n t r o l l e d b y g r a d u a l l y l i f t i n g
low erin g the d i s t i l l i n g

tube i n the b a t h .

and

The l i q u i d was

d i s t i l l e d and s e p a r a t e d from sm a ll amounts o f b enzene t h a t
form ed a s o l i d i n t h i s

trap(^).

Then t h e m e t h y l c h l o r i d e

was c o l l e c t e d i n a s m a l l s a m p l e t u b e h a v i n g two s i d e arms
w i t h s t o p - c o c k s a n d o n e o f t h e s i d e arms was a n i n n e r s e a l e d
t u b e r u n n i n g t o t h e b o t t o m o f t h e s a m p le t u b e .

This a llo w e d

f o r t h e m e t h y l c h l o r i d e t o be r e t a i n e d a s a g a s a n d t o be
f o r c e d o u t s lo w ly by l i q u i d s

i n o r d e r to b u rn i t .

The g a s

b u rn e d w i t h a deep y e llo w flam e w ith a g re e n f r i n g e .

Known

m e t h y l c h l o r i d e was t r e a t e d i n t h e same m a n n e r a n d g a v e t h e
same p r o p e r t i e s a n d c o n s t a n t s .

T h i s l e f t no d o u b t a s t o i t s

id en tity .

(1)

T h is s m a ll amount o f m a t e r i a l r e s u l t e d from th e v a p o r
l e f t o n t h e t u b e when t h e b e n z e n e was h e a t e d t o d r i v e
o u t a l l a i r , a n d was n o t t h e r e s u l t o f t h e i n e f f i c i e n c y
o f th e tr a p (J) f i g u r e 1, .

45.
Y ield :

4#

B7 4 5

~24 t o - 2 2 ° C .

:

F ractio n II

3 ,4 ,4 -T rim eth y lp en ten e-2

T his f r a c t i o n c o rre sp o n d e d to 3 , 4 , 4 - t r i m e t h y l p e n t e n e - 2
as r e p o r t e d i n th e l i t e r a t u r e

(55-56).

However,

the p r e s ­

e n c e o f 2 - e t h y l - 3 , 3 - d i m e t h y l b u t e n e - l was n o t e x c l u d e d ,
th e c o n s t a n t s r e p o r t e d (57)

since

f o r the l a t t e r a ls o c lo s e ly

a g re ed w ith the c o n s ta n ts o f t h i s f r a c t i o n .

- T h i s compound

was c o m p a r e d w i t h t h a t o b t a i n e d f r o m t h e a l c o h o l i c p o t a s ­
sium h y d r o x i d e t r e a t m e n t o f th e c h l o r i d e p r e p a r e d from th e
a l c o h o l a s i n P a r t A, F r a c t i o n I .

The c o n s t a n t s o b t a i n e d

f r o m t h e two com pounds w e r e i n c l o s e a g r e e m e n t .

The c a r b o n

and h y d r o g e n were d e te r m i n e d by P r e g l ’ s m i c r o - t e c h n i q u e .
The y i e l d a n d f o l l o w i n g c o n s t a n t s w e r e d e t e r m i n e d :
Y ield:

45$(1 )

B745 :

106-108 °C.

n§°

:

1.4211

D20
4

:

0.7282

mr

:

G
H

C alc.

3 9.24

Obs.

:

C alc.

85.61#

Found 8 5 . 5 5 %

:

C alc.

14.38%

F o un d 1 3 . 9 1 #

F raction I I I

39.58

3 -C h lo ro -2 ,2 ,3 -trim eth y ip en tan e

T h i s compound was i d e n t i f i e d b y I t s p r e p a r a t i o n f r o m
the a l c o h o l as s t a t e d above f o r F r a c t i o n I and by the a n a l y ­
s i s o f th e c h lo r i n e c o n te n t by P r e g l ' s m icro-m ethod.
(l)

T his

B a s e d e n t i r e l y u p o n t h e c h l o r o —compound i n F r a c t i o n I I I .

46.
ch lo rid e

was v e r y s t a b l e .

pheric pressu re

I t c o u ld be d i s t i l l e d a t atm os­

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

t r e a t m e n t i n o r d e r t o c o m p l e t e l y c o n v e r t t h e compound i n t o
the u n s a t u r a t e d com ponent.

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

were n o t fo u n d i n th e l i t e r a t u r e .

The f o l l o w i n g y i e l d a n d

c o n s t a n t s were d e te r m i n e d :
Y ield

50$

B745

158-160°C.

B16

5 7 - 5 8 C.

20

n
"D
D20

1.4609
0.8 8 4 0

M
R

C alc.

43.87

Obs.

Cl

C alc.

23.86$

Pound 2 3 . 6 3 $

F r a c t i o n IV

44.09

2-M et h y l - 2 - p h e n y l p r o p a n e

T h is f r a c t i o n which a p p e a re d i n a l l
was i d e n t i f i e d ,
d eriv ativ e.

a s i n P a r t A, F r a c t i o n I I I ,

3$

B 14

57-59°C.

B'750

1 6 6 - 1 6 9 C.

n 20
D

1.4910

“r
M .P t.

by i t s

acetam ino

The c o n s t a n t s w e r e d e t e r m i n e d a s f o l l o w s :

Y ield

4°

the c o n d e n s a tio n s ,

0.8632
C alc.
2 - M e

44.85

Obs.

43.95

t h y l - 2 - p - a c e tam inophenyl propane

168-170°C.

F ractio n V

2-M et h y l - 3 - p h e n y l p e n t e n e - 2

T h i s compound was a r o m a t i c i n n a t u r e a n d h i g h l y u n s a t u ­
rated .

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

s ta n ts w ith the l i t e r a t u r e
styrene d e riv a tiv e .

(61)

i n d i c a t e d t h a t i t was a

O x id a tio n w ith p o ta s s iu m perm angnate

gave d e g r a d a t i o n p r o d u c t s w h i c h
ev id ence

th at th is

f u r t h e r su p p o rte d the

compound was 2- m e t h y l - 3 - p h e n y l - p e n t e n e - 2 .

The f o l l o w i n g y i e l d a n d c o n s t a n t s w e r e o b t a i n e d :
Y ield:

8$

B15

:

74-77°C.

ng0

:

1.4980

I> f°

:

0.8738

Mr

:

C alc.

53.66

Obs.

C

:

C alc.

89.92$

Found 8 8 . 9 9 $

H

:

C alc.

10.07$

F o un d 1 0 . 5 4 $

F r a c t i o n VI

3 -Me t h y 1 - 3 - p h e n y l p e n t a n e

An a t t e m p t was made t o p r o v e
pound by i t s
the

53.86

conversion in to

the s t r u c t u r e o f t h i s

t h e b e n z o y l e s t e r , ( 1 ) b u t du e t o

s m a l l y i e l d o f m a t e r i a l w h i c h was d i f f i c u l t

s a t i s f a c t o r y d e r i v a t i v e was o b t a i n e d .

on th e b a s i s o f the p h y s i c a l c o n s t a n t s

t o p u r i f y , no

However, on t h e b a s i s

of the d e m e th y la tio n t h a t o c c u rre d i n t h i s

tain ed ,

com­

con den sation ,

(47) and a n a l y s i s ob­

t h e e v i d e n c e was s t r o n g l y i n f a v o r o f 3 - m e t h y l - 3 -

phenylpentane f o r t h i s f r a c t i o n .

The f o l l o w i n g y i e l d a n d

c o n s t a n t s were o b t a i n e d :
("l)" See " p a r t G o n p r o o f o f s t r u c t u r e .

and

48,
Y ield

5%

B.15
n. 20
'D
D20

85-88°C.

M
R

C alc.

54.05

Obs.

C

C alc.

88.81%

Pound 88 .75%

H

C alc.

11.19%

Pound 11 .64%

1.5015
0.8875

F r a c t i o n VII

53.77

2 , 2 ,3 -T rim eth y l-3 -p h en y lp en tan e

T h i s f r a c t i o n was t h e e x p e c t e d a l k y l b e n z e n e a n d was
a n a l y z e d f o r c a r b o n and h y d ro g e n by th e P r e g l m i c r o - t e c h n i q u e ,
The c o n s t a n t s d e t e r m i n e d a g r e e d w i t h t h o s e d e t e r m i n e d b y
o th e r w orkers in t h i s

lab o rato ry

(48).

The y i e l d a n d c o n ­

s t a n t s were d e te rm in e d as f o l lo w s :
Y ield

10%

B

107-110°C.

15
n 20
"D

1.5031

20

d4

0.8901

M
R
I
C

C alc.

H

63.516

Obs.

-Calc ,.

88.34%

Found 88 .2 9%

C alc.

11.66%

Found 11.73%

F ra c tio n V III
Y ield :

6 3 . JO

Tarry resid u e

4 grains

P a r t E — The 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 p e n t a n o l - 2 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 ro u s aluminum c h l o r ­
ide .

49.
F raction I

M ethyl C h lo rid e

T h i s f r a c t i o n was i s o l a t e d , i n t r a p

(K) , f i g u r e

a l i q u i d a s d e s c r i b e d i n P a r t D, F r a c t i o n I ,
in the

1, as

and i d e n t i f i e d

same w a y .

Y ield :

5%

B7 4 q :

-24 to - 2 2 ° c .

F ractio n II

2 , 3 ,3 -T rim eth y lp en ten e -1

T h i s f r a c t i o n was i d e n t i f i e d i n t h e same way a s t h e
s i m i l a r f r a c t i o n i n P a r t D, F r a c t i o n I I .
a g re e d w i t h th o s e g iv e n by E g l o f f

(61).

The c o n s t a n t s
The f o l l o w i n g y i e l d

and c o n s t a n t s were o b t a i n e d :
Y ield:

50$(1 )

B7 4 4

:

106-109

n§°

:

1.4205

D^°

:

0.7366

:

C alc.

F raction I I I

C.

38.53

Obs.

38.11

2 -C h lo ro -2 , 2 ,3 -trim eth y lp en tan e

T h i s com pound was i d e n t i f i e d b y i t s

p r e p a r a t i o n from the

a l c o h o l b y t h e p r o c e d u r e d e s c r i b e d i n P a r t A, F r a c t i o n I

(45).

The c h l o r i d e f o r m e d i n t h e c o n d e n s a t i o n was a n a l y z e d f o r
c h lo r i n e by P r e g l ’ s m ic r o - a n a ly s i s .

The c h l o r i d e was f o u n d

to be j u s t a s s t a b l e as 3 - c h l o r o - 2 , 3 , 3- t r i m e t h y l p e n t a n e .
fo llo w in g y ie ld ,

(1)

an aly sis,

and c o n s t a n t s were o b t a i n e d :

B ased e n t i r e l y upon th e chloro-com pound from F r a c t i o n
III.
"
?

The

50.

Y ield:

5 5#

B
7 40 *

156-159°c .

B15
n 2°

5 5 - 5 7 C.

=
:

1.4629
0.8845

“r

:

C alc.

43.87

Obs.

Cl

:

C alc.

23.86%

F o un d

F r a c t i o n IV

2-M ethyl-2-phenylpropane

T his f r a c t i o n ,

a s i n t h e c a s e o f P a r t D, F r a c t i o n IV,

was f o r m e d i n t h e c o n d e n s a t i o n i n s u f f i c i e n t q u a n t i t y t o be
e a sily p u rifie d .
tiv e

I t was I d e n t i f i e d b y t h e a c e t a m i n o d e r i v a ­

a n d th e f o l l o w i n g y i e l d and c o n s t a n t s were d e t e r m i n e d :
Y ield

2.5%

B,
740

166-168°C.

B

6 0 - 6 3 G.

n

15
20

20
L
J4
M
R
M .P t.

1.4909
0.8587
C alc.

44.85

Obs.

44.05

2-Met h y l - 2- p - a c e t a m i n o p h e n y l p r o p a n e
168-169°C.

F ractio n V

2-P h en y l-5 -m eth y lp en ten e-2

T h i s compo und w a s a r o m a t i c i n n a t u r e a n d g a v e a p o s i t i v e
t e s t f o r u n s a t u r a t i o n w ith 5 p e r c e n t brom ine I n c a rb o n
tetrach lo rid e.

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

s u s p e c t e d com pound a n d o x i d a t i o n w i t h p o t a s s i u m p e r m a n g n a t e
gave a d e g r a d a tio n p r o d u c t ^ ^

(1)

which s u p p o r te d th e e v id e n c e

See P a r t G on p r o o f o f s t r u c t u r e .

for tn is

compound a s b e i n g 2 - p h e n y l - 3 - m e t h y l p e n t e n e - 2 .

compound h a s b e e n r e p o r t e d b y Doss ( 6 0 ) .

T his

The f o l l o w i n g y i e l d

and c o n s t a n t s were d e te r m i n e d :
Y ield:

2 . 8%

B15
20
nD
T 20
d4

:

78-83°C

:

1.4921

:

0.8723

M
R

:

C alc.

F r a c fclon VI

53. 6b

Obs. 5 3 .2 5

2-Met h y l - 2 - p h e n y l p e n t a n e

T h i s com pound was s a t u r a t e d a nd a r o m a t i c i n n a t u r e .
S in c e d e m e t h y l a t i o n a l s o o c c u r r e d i n th e c o n d e n s a t i o n from
w h i c h t h i s f r a c t i o n was i s o l a t e d a n d since- t h e p h y s i c a l c o n ­
sta n ts

(62)

in d icated

th at

t h i s compound was 2- m e t h y l -

2 - p h e n y l p e n t a n e , a n a t t e m p t was made t o c o n v e r t i t
alp h a n a p h th y lu reth a n e d e riv a tiv e

in to

the

The d e r i v a t i v e was o b ­

t a i n e d i n s m a l l a m o u n t s , v e r y i m p u r e , a n d no a b s o l x i t e p r o o f
o f t h e s t r u c t u r e was o f f e r e d .
to th e f a c t t h a t t h is

However, a l l e v id e n c e p o i n t e d

f r a c t i o n was a m i x t u r e c o n t a i n i n g

m ostly 2 -m eth y l-2 -p h en y lp en tan e.

The f o l l o w i n g y i e l d a n d c o n ­

s t a n t s were d e t e r m i n e d :
Y ield

3 . 1%

B.
15

95-99°C.

20

D
20
4
R
(1)

1.4989
0.8825
C alc.

54.07

Obs.

See P a r t G o n p r o o f o f s t r u c t u r e .

54.01

52.
Bp&otion. V I I

2 , 3 , 3-Trim e t h y l- 2 - p h e n y lp e n t a n e

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 a n d
its

c o n s t a n t s c o r r e s p o n d e d t o t h e p r o d u c t a s p r e p a r e d by

workers i n t h i s la b o r a to r y

(50).

was p r e p a r e d f o r v e r i f i c a t i o n .

The a c e t a m i n o d e r i v a t i v e
The f o l l o w i n g c o n s t a n t s an d

y i e l d were o b t a i n e d :
Y ield:

10#

B7 4 q :

230-233°C .

B1

:

109-111

20
nD

:

n
,
1.5011

20
D4

:

0.8868

;

C alc.

M .P t.:

G.

63.26

O b s.

6B .JX

2 , 3 , 3 - tr im e t h y l - 2 - p - acetam inophenyl pen tan e
90-92°C.

F ra c tio n V III
T h i s f r a c t i o n was n o t i d e n t i f i e d b u t was s u s p e c t e d o f
b e in g a m ixture o f d i -

It d istille d

and t r i - 3 u b s t i t u t e d a l k y l b e n z e n e s .

a b o v e 129 d e g r e e s c e n t i g r a d e a t 13 mm. b u t

o v e r a wide r a n g e .
Y ield :

3 grams

F r a c t i o n IX
Y ield

:

Tarry resid u e

2 g ram s

Part F

The P r e p a r a t i o n o f D e r i v a t i v e s

1.

Acetam ino d e r i v a t i v e s

T h e s e compounds w e r e p r e p a r e d a c c o r d i n g t o t h e m e t h o d
o f I p a t i e f f and S c h m e rlin g (46)

i n the f o l lo w in g m anner: A

m i x t u r e o f o n e t o two m l . o f t h e a r o m a t i c h y d r o c a r b o n a n d
5 r a l • o f a n i t r a t i n g m i x t u r e was s h a k e n u n t i l

the r e a c t i o n

no l o n g e r e v o l v e d h e a t a n d h a d c o o l e d n e a r l y t o room t e m ­
p eratu re,

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

of co n cen trated n i t r i c

and c o n c e n tr a te d s u l f u r i c a c i d s .

The r e s u l t i n g m o n o n i t r o - c o m p o u n d was p o u r e d u p o n c r a c k e d i c e
and e x t r a c t e d t h r e e

tim es w ith e t h e r .

was w a s h e d t w i c e w i t h w a t e r ,
steam b a t h .

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

and th e e t h e r e v a p o r a t e d on a

The o i l was d i s s o l v e d i n a l c o h o l a n d 5 gr a m s o f

g r a n u l a r t i n and 5 m l. o f c o n c e n t r a t e d h y d r o c h l o r i c a c i d
added.

The m i x t u r e was s h a k e n u n t i l no t u r b i d i t y was o b ­

s e r v e d when a few d r o p s w e r e a d d e d to w a t e r .

Then t h e m i x ­

t u r e was a l l o w e d t o s t a n d t h i r t y m i n u t e s i n o r d e r t o a s s u r e
com plete r e d u c tio n .
the
in to

steam b a t h .

S o m e ti m e s i t was n e c e s s a r y t o h e a t on

The l i q u i d was d e c a n t e d fr o m t h e e x c e s s t i n

20 m l . o f w a t e r ,

e x tra c te d w ith e th e r ,

sodium h y d r o x i d e added i n o r d e r to f r e e
k a l i was a d d e d u n t i l
w hich f i r s t

the am ine.

The a l ­

the p r e c i p i t a t e of t i n h y d ro x id e ,

f o r m e d , was r e d i s s o l v e d .

t r a c t e d w i t h e t h e r , washed w i t h w a t e r ,
drous potassium c arb o n ate .
from th e d r y i n g a g e n t ,
m l. o f a c e t i c

a n d 40 p e r c e n t

The m i x t u r e was e x ­
and d r i e d w i t h a n h y ­

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

t h e e t h e r e v a p o r a t e d , a n d one t o two

a n h y d r i d e added to th e r e s i d u e .

Som etim es, a t

54.
th is p o in t

the d e r i v a t i v e c r y s t a l l i s e d .

The e x c e s s a n h y ­

d r i d e was h y d r o l y z e d b y w a r m i n g w i t h 5 m l . o f w a t e r ,
s o l u t i o n e v a p o r a t e d n e a r l y to d r y n e s s ,

co o led ,

The i m p u r e d e r i v a t i v e was w a s h e d f r e e o f a c e t i c
r e c r y s t a l l i z e d f r o m 50 p e r c e n t a l c o h o l .

the

and f i l t e r e d .
a c i d and

Hexane o r i s o p r o p y l

a l c o h o l d i l u t e d w i t h w a t e r was u s e d s a t i s f a c t o r i l y

for re­

c ry stalliz atio n .
2.

A.lpha n a p h t h y l u r e t h a n e s

T h e s e co m po u nd s w e r e p r e p a r e d a c c o r d i n g t o Ivialnerbe ' s
procedure
uu ile

( 6 3 ) w h i c h was u s e d w i t h some m o d i f i c a t i o n s by

( 6 4 ) a n d a l s o by Kaye { 4 ) •
(a) P r e p a r a t i o n of the m o n o n itro -a lk y lb e n z e n e s :
T w e n ty - f o u r m l.

n itric

and s u l f u r i c

acids

of a m ixture of c o n c e n tra te d
i n e q u a l p a r t s b y v o lu m e w e re a d d e d

drop-w ise

t o o n e - t e n t h o f a mole o f t h e a l k y l b e n z e n e w i t h

shaking.

The t e m p e r a t u r e was n o t a l l o w e d t o e x c e e d 50

degrees c e n tig ra d e .
t u r e was c o m p l e t e ,
water

b ath

'/Tien t h e a d d i t i o n o f

th e n i t r a t i n g m ix­

t h e r e a c t i o n m i x t u r e - was h e a t e d o n a

f o r two h o u r s .

Then i t was p o u r e d u p o n i c e a n d

e x tra c te d w ith e th e r.

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

tim es w ith a s a tu r a te d

salt

on

a steam b ath .

The

s o l u t i o n a n d t h e e t r i e r rem oved

residue

was d i s t i i I e d u r u l e r r e u u e e d

pressure.
(b)

The R e d u c t i o n o f t h e n l t r o - c o m p o u n d :
The n i t r a t e d , a l k y l b e n z e n e

amine
the

by

catalytic

catalyst,

was

converted I n to

i-re

h y d ro g en a tio n , u s i n g p la t in u m oxxu e as

according

to

i.he p r o c e d u r e

given

in

hitm an

(6b) .

I h e a p p a r a t u s was c a l i b r a t e d w i t h a known compound a t room
tem p eratu re.

The c o m po u nd t o b e r e d u c e d was p l a c e d i n t h e

s h a k i n g b o t t l e w i t h 100 m l . o f a l c o h o l a n d 0 . 1 g ram o f
c a t a l y s t t o r e a c h 15 g r a m s o f t h e n i t r o - c o m p o u n d .
c o n t a i n i n g t h e m i x t u r e was e x h a u s t e d o f a i r ,

The b o t t l e

and hy d ro g en

u n d e r 5 - 1 0 a t m o s p h e r e s o f p r e s s u r e was a d m i t t e d u n t i l
pressure

c e a s e d to f a l l .

The m i x t u r e was f i l t e r e d f r o m t h e

p l a t i n u m compound, t h e a l c o h o l d i s t i l l e d
th e amine d i s t i l l e d
p rep ared by B ailey

the

from th e am ine, and

a t 1 - 2 mm. o f p r e s s u r e .

The c a t a l y s t was

( 6 6 ) a c c o r d i n g to th e m ethod g i v e n by

V o o r h e e s a n d Adams ( 6 7 ) :

C h l o r o p l a t i n i c a c i d was f u s e d w i t h

an e x c e s s o f sodium n i t r a t e
m e l t was a l l o w e d t o c o o l ,

a t 550 d e g r e e s c e n t i g r a d e .

The

d i s s o l v e d i n w a t e r , and the h y ­

d r a t e d p l a t i n u m d i o x i d e was r e m o v e d b y s u c t i o n .

I t was

w a sh e d w i t h a s o l u t i o n o f 1 p e r c e n t sodium n i t r a t e ,

dried,

and u s e d i n t h a t form .
(c)

C o n v e r s i o n o f th e amine i n t o

the p h en o l:

A h o t s o l u t i o n o f 11 m l . 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 d i s s o l v e d i n 50 m l . o f w a t e r was a d d e d t o e a c h o n e t e n t h mole o f am ine i n a b e a k e r .

The s o l u t i o n was s t i r r e d

and p la c e d i n an i c e - s a l t b a t h .

The m i x t u r e was m a i n t a i n e d

a t zero d e g re e s c e n tig r a d e w hile a s a t u r a t e d aqueous s o lu tio n
o f e i g h t grams o f sodium n i t r i t e
stirrin g .
all

the

urea,

was a d d e d s l o w l y w i t h

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

s u s p e n d e d amine s u l f a t e

d isso lv ed .

d i s s o l v e d i n a minimum o f w a t e r , was a d d e d s l o w l y f o r

e a c h o n e - t e n t h mole o f t h e a m in e.
to

Then two g r a m s o f

The s o l u t i o n was a l l o w e d

s t a n d f o r t e n to f i f t e e n m in u te s and th e n p o u re d i n t o a

56.
fo u r l i t e r beaker co n tain in g
on th e

s t e a m b a t h two h o u r s .

two l i t e r s

o f w a t e r and. h e a t e d

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

w ith e t h e r and p la c e d in a G la ise n f l a s k .
removed and w a t e r added to
was s t e a m d i s t i l l e d ,

the r e s i d u e .

the d i s t i l l a t e

Then t h e m i x t u r e

e x tr a c te d w ith e th e r ,

d r i e d o v e r a n hy d ro u s sodium s u l f a t e .
filtere d ,

The e t h e r was

and

The e t h e r s o l u t i o n was

t h e e t h e r rem oved, and th e p h e n o l d i s t i l l e d

at

reduced p re s s u re .
(d) P r e p a r a t i o n o f th e a lp h a n a p h t h y l u r e t h a n e :
The p h e n o l was t r e a t e d w i t h h a l f i t s

volum e o f

a lp h a n a p h t h y l i s o c y a n a t e , and c a t a l y z e d by the a d d i t i o n o f a
few d r o p s o f a n a n h y d r o u s e t h e r s o l u t i o n o f t r i m e t h y l amine
The m i x t u r e was s h a k e n ,

sto pped w ith a cork having a c a l ­

c i u m c h l o r i d e d r y i n g t u b e a n d warmed f i v e t o f i f t e e n m i n u t e s
on a steam b a t h .

The d e r i v a t i v e

c r y s t a l l i z e d on c o o l i n g and

was r e c r y s t a l l i z e d f r o m l i g r o i n .
3.

2 , 4-D in itro p h en y lh y d razo n es

T h e s e co m po u nd s w e r e 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 x i r e
g i v e n b y S h r i n e r and Fuson ( 6 8 ) i n th e f o l l o w i n g m anner:
(2)
The u n s a t u r a t e d h y d r o c a r b o n s w e r e o x i d i z e d t o a k e t o n e '
a n d two m l . o f t h e k e t o n e m i x e d w i t h 1 . 5 g r a m s o f 2 , 4 - d i n i t r o p h e n y l h y d r a z i n e a n d 100 m l . o f a l c o h o l .

T h i s m i x t u r e was

b r o u g h t to b o i l i n g on a steam b a t h and 2 m l. o f c o n c e n ­
t r a t e d h y d ro c h lo ric a c id added.

The m i x t u r e was h e a t e d

(1) K ep t a n h y d ro u s o v e r a n h y d ro u s sodium s u l f a t e .
(2)

See P a r t G on p r o o f o f s t r u c t u r e .

57.
u n til

a l l m a t e r i a l was i n s o l u t i o n

m in u tes),

and a llo w e d to c o o l.

and washed w ith c o ld a l c o h o l.
l i z e d from h o t a lc o h o l ,
4.

(u su ally

two, t o f i v e

The p r e c i p i t a t e

was f i l t e r e d

The d e r i v a t i v e was r e c r y s t a l ­

eth y l a c e ta te ,

o r chloroform .

O xim es

T h e s e c o m p o un d s w e r e 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 o f S h r i n e r and P uson (69)

I n th e f o l l o w i n g m anner:

The u n s a t u r a t e d h y d r o c a r b o n s w e r e o x i d i z e d t o k e t o n e s ^ ) ,
a n d 0 . 2 g r a m o f t h e k e t o n e m i x e d w i t h 2 m l . o f 10 p e r c e n t
sodium h y d r o x i d e .
c le a r so lu tio n .

S o m e t i m e s a l c o h o l was a d d e d t o g i v e a
T hen 0 . 5 g r a m o f h y d r o x y l a m i n e h y d r o c h l o r ­

i d e i n 3 m l . o f w a t e r was a d d e d t o t h e k e t o n e m i x t u r e ,
warmed 10 m i n u t e s o n a s t e a m b a t h ,

and c o o le d i n i c e .

C r y s t a l l i z a t i o n was i n d u c e d b y s c r a t c h i n g t h e w a l l s o f t h e
c o n t a i n e r o r a d d in g a s m a ll amount o f w a t e r .

The oxime was

r e c r y s t a l l i z e d from w a te r o r d i l u t e a l c o h o l .

I t was n e c e s ­

s a r y t o a d d a minimum o f s o l v e n t b e c a u s e o f t h e

so lu b ility

o f the oxim es.
P art G

Proof of S tru c tu re

1.

2 , 3-D im et h y l b u t e n e - 1 and 2 - c h l o r o - 2 , 3 - d im e t h y l b u t a n e ^^

(a)
bu ten e-1

In o r d e r to prove
the

stru ctu re

the

stru ctu re

of 2 , 3 -d im eth y l-

o f 2 - c h l o r o - 2 - 3 - d i m e t h y l b u t a n e was

(1)

See P a r t G o n p r o o f o f s t r u c t u r e .

(2)

S i m i l a r c o m p ou n ds w e r e f o r m e d i n e a c h c o m d e n s a t i o n a n d
t h e i r s t r u c t u r e p ro v e d as w ith t h e s e compounus.
A ll
c o n s t a n t s were l i s t e d u n d e r each f r a c t i o n .

58.

p r o v e n f i r s t by i t 3 p r e p a r a t i o n fr o m 2 , 3 - d i m e t h y l b u t a n o l -2
•according to S h r i n e r and Fuson (45) as f o l l o w s :
m l. o f a l c o h o l ,
c h lo ric acid ,
stirrin g .
(1 m o l e )

10 m l . o f a r e a g e n t c o n s i s t i n g o f h y d r o ­

a n d z i n c c h l o r i d e , was a d d e d d r o p - w i s e w i t h

The r e a g e n t was p r e p a r e d b y d i s s o l v i n g 136 g ram s
o f anhydrous z in c c h lo r id e

co n cen trated h y d ro ch lo ric a cid .
during

the a d d i t i o n .

u sed w ith the t e r t i a r y

i n 105 g ram s (1 m o le ) o f

The m i x t u r e was c o o l e d

C o n c e n t r a t e d h y d r o c h l o r i c a c i d may be
a lc o h o ls w ithout th is

w ith re d u c e d y i e l d s o f the c h l o r i d e .
a fter

For each 1

th is

a d d i t i o n w e r e s^ T>ar°ted

The l a y e r s f o r m e d
the c h l o r i d e l a v e r

d r i e d w i t h a n h y d r o u s sodium s u l f a t e .
f i l t e r e d and d i s t i l l e d

reagent, b u t

The c h l o r i d e was

a t reduced p r e s s u r e .

The c o n s t a n t s

we r e c o m p a r e d w i t h t h o s e f o u n d i n t h e l i i e r a t u r t .

•and.

w ith

t h o s e o b t a i n e d f r o m t h e compound c o m in g fr o m t h e c o n o e n s a L ion.

If

the l i t e r a t u r e

did not riv e

all

the c o n s t a n t s

no s i r e d , t h e n t h e c o w r o a n a was c o n v e r t e d i n t o

the unsa tu ra ted

compo und ( b ) a n d t h e c o n s t a n t s o f t h e l a t t e r c o m p a r e d w i t h
the l i t e r a t u r e .

C h l o r i n e a n a l y s i s was made a l s o o n t h e com­

p o u n d c o m i n g f r o m t h e c o n d e n s a t i o n when s u f f i c i e n t c o n s t a n t s
were n o t g i v e n .
(b)

The s t r u c t u r e

o f t h e compound 2 , 3 - d i m e t h y l b u t e n e - l

w a3 p r o v e d by r e f l u x i n g 2- c h l o r o - 2 , 3- d im e th y lb u ta n e w ith i t s
v o l u m e o f 50 p e r c e n t a l c o h o l i c p o t a s s i u m h y d r o x i d e f o r a
p e r i o d o f two h o u r s .

Then t h e compound was i s o l a t e d a nd

m i n i f i e d as d e s c r i b e d on page 31.

The p r o c e d u r e was r e ­

p e a t e d u n t i l a c o m p l e t e c o n v e r s i o n was o b t a i n e d .

U sually

59.
one t r e a t m e n t f o r t h e l e a s t b r a n c h e d compounds an d two t r e a t ­
m e n t s f o r t h e m ore h i g h l y b r a n c h e d compounds s u f f i c e d .

If

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

a s w e l l as v /ith the

ch lo ro -co m p o u n d from th e c o n d e n s a tio n ,

then the

stru ctu re

o f t h e u n s a t u r a t e d compound was c o n s i d e r e d t o be p r o v e n .
any s u b s t a n c e rem a in e d a f t e r th e a l k a l i

treatm en t,

If

the un­

s a t u r a t e d compound was t r e a t e d w i t h d r y h y d r o g e n c h l o r i d e an d
t h e r e s u l t i n g compound c o m p a r e d w i t h t h e p r e p a r e d c h l o r o compound a s t o c o n s t a n t s .
2.

2-M et h y l - 3 - p h e n y l p e n t e n e on p a g e 47
T h i s compound was s y n t h e s i z e d b y B a i l e y

K lages' procedure

(70).

(66) usin g

P o ta s s iu m d ic h ro m a te and a c e t i c

a c i d were t r i e d f i r s t as an o x i d i z i n g m ix tu re In o x i d i z i n g
t h i s compound t o t h e k e t o n e .

T h i r t e e n g r a m s o f t h e com­

p o u n d w e r e r e f l u x e d two h o u r s w i t h 36 g r a m s o f p o t a s s i u m
d i c h r o m a t e a n d 30 gram s o f a c e t i c a c i d .

The r e a c t i o n m i x ­

t u r e was p o u r e d u p o n i c e a n d -water a n d e x t r a c t e d v / i t h e t h e r .
The e t h e r s o l u t i o n was w a s h e d v / i t h w a t e r a n d d r i e d v / i t h a n h y ­
d r o u s sodium s u l f a t e .
tered

The e t h e r was rem ov e d f r o m t h e f i l ­

s o l u t i o n and the r e s id u e d i s t i l l e d u n d er reduced

pressure.

Most o f t h e o r i g i n a l 2 - m e t h y l - 3 - p h e n y l p e n t e n e - 2

was r e c o v e r e d a n d t h e r e s i d u e g a v e no s a t i s f a c t o r y
tiv e.
B arrett
(71).

deriv a­

The o x i d a t i o n was r e p e a t e d u s i n g t h e m e t h o d o f
( 3 ) w h i c h was a m o d i f i c a t i o n f r o m S h r i n e r a n d P u 3on
Ten g r a m s o f t h e known 2 - m e t h y l - 3 - p h e n y l p e n t e n e - 2

w e r e r e f l u x e d w i t h 22 g r a m s o f p o t a s s i u m p e r m a n g n a t e and o3

60.
grams o f c o n c e n t r a t e d s u l f u r i c

acid d ilu te d in w ater.

r e a c t i o n was c o o l e d i n a n i c e b a t h u n t i l

the

The

r e a c tio n sub­

s i d e d a n d t h e n was g e n t l y r e f l u x e d o n a w a t e r b a t h o ne h o u r .
The r e f l u x e d m i x t u r e was t r e a t e d a s a b o v e i n t h e c a s e o f
t h e d i c h r o m a t e o x i d a t i o n a n d t h e d i s t i l l a t i o n p r o d u c t s were
u s e d to p r e p a r e th e 2 , 4 - d i n i t r o p h e n y l h y d r a z o n e d e r i v a t i v e .
P r o p i o p h e n o n e was o n e o f t h e e x p e c t e d , d e g r a d a t i o n p r o d u c t s .
I t was s y n t h e s i z e d f r o m p r o p i o n y l c h l o r i d e
th e F r i e d e l and C r a f t s " r e a c t i o n
the

(72).

and b e n z e n e u s i n g

Then s e v e n gram s o f

s u s p e c te d 2 -m e th y l-3 -p h e n y lp e n te n e - 2 from thn condensa­

t i o n was t r e a t e d w i t h 16 g r a m s o f p o t a s s i u m p e r m a n g n a t e a n d
24 g r a m s o f c o n c e n t r a t e d s u l f u r i c

a c id d ilu te d w ith w ater

a n d t h e p r o d u c t p u r i f i e d a s i n t h e c a s e w i t h t h e known com­
pounds above.

The h y d r a z o n e was p r e p a r e d a s b e f o r e .

T h ese

p r o d u c t s gave th e f o l l o w i n g d a t a :
M .P t. o f the d e r i v a t i v e
M. P t .

f r o m known p r o p i o p h e n o n e :

195-197°C.

o f d e r i v a t i v e from o x i d a t i o n p r o d u c ts o f
s y n t h e s i z e d 2- m e t h y l - 3 - p h e n y l p e n t e n e - 2

M .P t. o f d e r i v a t i v e
the

: 196-197°c.

from o x i d a t i o n p r o d u c ts of

su sp ected 2 -m ethyl-3-phenylpentene-2

196-198°C.

M .P t. o f m ixed d e r i v a t i v e s from s y n t h e s i z e d
p ro p io p h e n o n e and th e d e r i v a t i v e from the
o x id a tio n o f the

s u s p e c t e d 2 -me t h y 1 -

3 - p h e ny l p i . n t e n a - 2

195-198°C .

M .P t. o f m ix tu re o f 2 , 4-d in itr o p h e n y lh y d r a z in e
a n d t h e h y d r a z o n e o f t h e known p r o p i o ohenone

17 2 - 1 8 0 ° C .

61.
Iv!»P t « o.i. t h e ox.Lme o f t h e known p r o p l o o h e n o n e
ihe d e r i v a t i v e s

:

52-54°C *

f r o m t h e o x i d a t i o n p r o d u c t c o m in g f r o m t h e

c o n d e n s a t i o n were p u r i f i e d w i t h d i f f i c u l t y by u s i n g mixed
s o l v e n ts o f a l c o h o l , b e n ze n e, and e t h e r .

An u n i d e n t i f i e d

d e r i v a t i v e was i s o l a t e d w h i c h r n e l t e d f r o m 2 0 2 - 2 0 4 ° C .

Ihe

a b o v e d a t a c o m b i n e d w i t h t h e c o n s t a n t s o n p a g e 4V gave
good a s s u r a n c e

t h a t t h e compound was 2- m e t h y l - 3p h e n y l -

p en ten e-2 .
3.

3-M et h y l - 3 - p h e n y l p e n t a n e on p a g e 47

T h i s f r a c t i o n was c o n v e r t e d i n t o
s c r i b e d i n P a r t F, 2 .

the phenol as de­

The y i e l d o f t h e p h e n o l w?? t o o

s m a l l t o p u r i f y by f r a c t i o n a t i o n .

An a t t e m p t t o p r e p a i ' e t h e

b e n z o y l e s t e r r e s u l t e d i n a n o i l y m as s t h a t w o u l d n o t c r y s t a l ­
liz e .

A few i m p u r e c r y s t a l s w e r e i s o l a t e d t h a t m e l t e d f r o m

110-115°C.
given;

A l t h o u g h no a b s o l u t e p r o o f f o r t h i s f r a c t i o n was

f r o m t h e c o n s t a n t s d e t e r m i n e d f o r t h e f r a c t i o n and

f r o m t h e f a c t t h a t a p h e n o l i c compound was o b t a i n e d ,
w r i t e r was c e r t a i n t h a t

the

t h e compound was 3- m e t h y l ~ 3 p h e n y l -

ren tan e.
4.

2 - P h e n y l - 3 - m e t h y l p e n t e n e - 2 o n p a g e 50

T h i s f r a c t i o n was o x i d i z e d b y t r e a t i n g 2 . 7 g r a m s o f t h e
s u b s t a n c e w i t h 6 . 2 g r a m s o f p o t a s s i u m p e r m a n g n a t e and 9 . 3
\
grams 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 d i l u t e d w i t h w a t e r i n th e
same m a n n e r a s w i t h 2 - m e t h y l - 3 - p h e n y l p o n t e n e - 2 .
was o ne o f t h e

s u s te c te d degrade t i o n p r o d u c ts .

Ace Lophenone
' h o <,,A-

d i n i t r o p h e n y I h y d r a z o n e o f known a c e t o p h e n o n e vr-s r r e p a r e a .
The f o i l ' s w i n g d a t a wei c o o t s i n e d :

M . P t . o f d e r i v a t i v e f r o m known

acetophenone

:

249-250°C.

;

248-251°C.

:

25i-253°0.

M .P t. o f d e r i v a t i v e from o x i d a t i o n p ro d u c ts
o f s u s p e c t e d 2- p h e n y 1- o - m e t h y 1pen ten e-2
M .P t. o f m ixed d e r i v a t i v e s
Tae a t o v e d a t a c o m b i n e d w i t h t h e f a c t s
proved th a t

the

from the c o n s t a n t s

f r a c t i o n was 2- p h e n y l - o - m e t h y l p e n t e n e - 2 .

5 . 2 - M e t h y l - 2 - p h e n y l p e n t a n e o n p a g e 51
T h i s f r a c t i o n a l s o was c o n v e r t e d i n t o
s c r i b e d i n P a r t F,

2.

The y i e l d was v e r y s m a l l a n d a p u r e

f r a c t i o n was n o t o b i s i n o d .

An a t t e m p t to form, t h e a l p h a

n a p h t h y l u r e t h a n e p o r d u c e d an o i l

t h a t would n o t c r y s t a l l i z e .

No r i g o r o u s p r o o f o f s t r u c t u r e was o f f e r e d .
p h en o lic

compound was f o r m e d f r o m t h i s

tio n occurred in

the phenol as de­

However, a

fractio n .

th e c o n d e n s a t io n from which t h i s

D em ethylafrac tio n

wa., i s o l a t e d a n d t h e p h y s i c a l c o n s t a n t s c o r r e s p o n d e d t o t h e
s u s p e c t e d compound i n
known t o b e a m i x t u r e .

s p i t e o f t h e f a c t t h a t t h e f r a c t i o n was
I t was e e r t a i n ,

th erefo re,

t h a t the

m a j o r i t y o f t h i s f r a c t i o n c o n t a i n e d 2- m e t h y l - 2- p h e n y l p e n t a n e .

6
D ISCU SSIO N

The a m o u n t o f f r a g m e n t a t i o n ,

r e s u l t i n g from th e a c t i o n

o f alum inum c h l o r i d e u s e d i n t h i s i n v e s t i g a t i o n ,
a cc o rd w ith o t h e r w orkers

was i n

( 5 ) who f o u n d t h a t c o n d e n s a t i o n a t

h i g h e r t e m p e r a t u r e s p r o d u c e d more f r a g m e n t a t i o n t h a n a t lo w ­
e r tem p eratu res,

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

g r e a t e r a t the h ig h e r te m p e ra tu re s .
s e le c te d carb in o ls

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

show ed f u r t h e r t h a t more o f t h e s e f r a g ­

m e n t s f o r m e d a n d i n t h e g r e a t e r y i e l d a s t h e b r a n c h i n g on
t h e h y d r o x y l c a r b o n was I n c r e a s e d .
p e c te d alk v lb en ren e
fragm ents in c re a s e d .

wa^

decr*eo.sed

The y i e l d o f t h e e x ­
ms

th e

number

and

T h ere fo re the co n d en sa tio n s a t

h i g h e r t e m p e r a t u r e s gave th e b e s t o p p o r t u n i t y to
m echanism f o r th e c o n d e n s a t io n o f t e r t i a r y

vi.eld o f
the

study a

c a r b i n o l s i n the

p r e s e n c e o f a n h y d ro u s aluminum c h l o r i d e .
Other* w o r k e r s h a v e o b s e r v e d t h a t c a t a l y s t s o f t h e t y p e
o f alum inum c h l o r i d e h a v e c a u s e d p r o d u c t s to r e a r r a n g e
and - t o b r e a k t h e m o l e c u l e s
cleaved.,

(31).

(7 3 )

W h e t h e r t h e m o le cu le : was

r e a r r a n g e d , o r d e m e th y l a te d by v a r i o u s c a t a l y s t s

s e em e d t o b e d e p e n d e n t l a r g e l y u p o n t h e v a r y i n g c o n d i t i o n s
of tem perature, p re ssu re ,
w e ll as the c a t a l y s t
In
of

th is

catalytic

b u tan o l-2 ,
o en tan o l- 2 .

and e l e c t r o n i c

c o n fig u r a tio n as

itse lf.

i n v o s t i g a t i o n one wo uld e r r e . c t
a c t i o n o f aluminum c h l o r i n e

2 , 2 , 3 - 1 r i m e th y 1: e n l a n o l - 3 ,

For the most p o r t

a t

the

s a t y n e

on 1 , 3 , n - t r l r . c t r y 1 r , 3 , - : - t r >nc t.i y l -

t h i s was t r u e .

uowo<n —,

the c a s e o f 2 , 3 , 3 - t i ' i m e t h y l b u t a n o l - 2 , s m a ll amounts o f

*u

64.
ethylene

a n d p r o p y l e n e w e r e o b t a i n e d a n d d e m e t h y l a t i o n was

d etected .

W h il e i n

the case o f 2 , 2 , 3 - t r im e th y l p e n ta n o l- 3

and 2 , 3 , 3 - t r i m e t h y l p e n t a n o l - 2 , r e l a t i v e l y l a r g e amounts o f
m e t h y l c h l o r i d e w e r e o b t a i n e d a n d no u n s a t u r a t e d compounds
c o m p a r a b le to e t h y l e n e o r p r o p y l e n e were i s o l a t e d .
Common t o a l l

t h e c o n d e n s a t i o n s , h o w e v e r , was t h e

re a rra n g e d p ro d u c t 2-m eth y l-2 -p h en y lp ro p an e.

The y i e l d o f

t h i s p r o d u c t b e ca m e l a r g e r a s t h e b r a n c h i n g o f t h e a l c o h o l
was i n c r e a s e d .
also

The f o r m a t i o n o f t h e a l k y l c h l o r i d e was

common t o a l l

to b e more s t a b l e

the c o n d e n s a tio n s .

The c h l o r i d e p r o v e d

i n the case o f the h ig h ly branched

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

H ere,

the

s p e e d o f r e a c t i o n se e m e d g r e a t e r b e t w e e n t h e c a t i o n o f t h e
c a r b i n o l and th e c h l o r i d e io n th a n betw een th e c a r b i n o l
c a t i o n and th e a c t i v a t e d benzene n u c l e u s .

The s t a b i l i t y

o f t h e a l k y l c h l o r i d e was shown i n t h e c a s e o f t h e more
b r a n c h e d c a r b i n o l s w h e r e t h e c o r r e s p o n d i n g a l k e n e was n o t
i s o l a t e d f r o m t h e r e a c t i o n p r o d u c t s , b u t was i s o l a t e d i n t h e
le s s branched c a rb in o l condensations.
I n t h e c a s e o f t h e more h i g h l y b r a n c h e d c a r b i n o l s ,
d e m e t h y l a t i o n was d e f i n i t e , w i t h m e t h y l c h l o r i d e i s o l a t e d i n
two c a s e s ,
o th er case.

a n d w i t h e t h y l e n e a n d p r o p y l e n e i s o l a t e d i n one
The low b o i l i n g h y d r o c a r b o n s t h a t came o v e r a s

g a s e s below -80°C . i n d i c a t e d i n a l l c a s e s a l o s s o f a l k y l
groups.

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

c a r b i n o l s as would be e x p e c te d .

It

se em e d i m p o r t a n t to

n o te t h a t th e g r e a t e r the y i e l d o f m ethyl c h l o r i d e ,

the

s m a l l e r th e y ie ld , o f e t h y l e n e and r e l a t e d p r o d u c t s ,

and the

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

the

s m a ll e r th e y i e l d o f m ethyl c h l o r i d e .

Where t h e a m o u n t s o f

p r o d u c t s r e s u l t i n g fro m th e l o s s o f a l k y l g r o u p s were l a r g e ,
t h e h i g h e r f r a c t i o n s 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 g a v e two
t y p e s o f compounds t h a t v e r i f i e d
One t y p e was t h e
cases.

t h i s lo s s o f a lk y l groups.

s t y r e n e d e r i v a t i v e w h i c h was f o u n d i n t h r e e

The t y p e was t h e l o w e r b o i l i n g

saturated a lk y l-

b e n z e n e f o u n d i n t h e same t h r e e c a s e s .
I n l i g h t o f th e th e o r y upon which t h i s
was b a s e d ,

In v estig atio n

a lo w b o i l i n g a l k y l c h l o r i d e was e x p e c t e d .

2 ,3 ,3 -trim eth y lp en tan o l-2 ,

For

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

p e c t e d a s one o f th e p r o d u c t s a f t e r th e r e a r r a n g e m e n t i n
w h i c h t h e t e r t i a r y b u t y l c a t i o n was f o r m e d .

A l t h o u g h some

o f t h e c o n d e n s a t i o n s w e r e r u n a t low t e m p e r a t u r e s I n o r d e r
to I n v e s t i g a t e

th is

fractio n ,

i t was n o t f o u n d .

p e c t e d f r a c t i o n was f o u n d i n one c a s e

T his ex­

( 2 , 3 , 3 - 1 r i m e t h y 1-

b u t a n o l - 2 ) i n th e form o f i s o p r o p y l c h l o r i d e i n sm a ll
am ounts.

The f o l l o w i n g e q u a t i o n s i l l u s t r a t e

mechanism f o r a l l

the p roposed

th e c o n d e n s a t io n s , u s i n g 2 , 3 , 3- t r i r n e t h y l -

p e n ta n o l -2 as the i l l u s t r a t i v e

exam ple:

The c a r b o n i u m i o n was b e l i e v e d t o h a v e b e e n f o r m e d a c ­
c o rd in g to P r ic e

(2-1) i n

th e f o i l wing m anner:

oo
ch 3 ch 3
CH,-CHP-C - 6
-OH
"
2 &H, OH,

(H0A1C13 ) "

This c a t io n
a ch lo rid e

A1C1 O
*

*

CH-2
o CHs
i o ht
-0
- Ci
ch3 ch3

H H
HCHHCH
CH,-CHo-{ : C-t
" hchhch
H II

+

i o n f r o m t h e HC1

fo rm ed in th e r e a c t i o n o r from
t h e alum inum com plex to g iv e

t I

+. HC1

l o s t HC1 t o

t h e AlCl* com plex
3
to form the A lk e n e , o r
t h e a l c o h o l l o s t HOH b e c a u s e

o f the d e h y d ra tin g a c tio n o f
AICI3

2

)

Cl

H
H
HCH HCH ..
CH~-CK0-C -C : C l :
°HCH HCH *’
H
H"

she a l k y l c h l o r i d e .
then

(

1

then re a c te d w ith

The a l k v l c h l o r i d e

Cl
Ai: c l
Cl
(1 )

CH-7 - C H iO
o - Ci

(b)

-HC1

H
HCH
H
CH^-CHQ-C : C ' - CH
5
mCH HCH
H
H
-HOH

(4 )

H
H
HCH HCH
CH -CH - C : c : OH :
HCH HCH
H
H”

(5)

The b e n z e n e was a c t i v a t e d b y
t h e AICI3 ,
H
. *C .
H C **
C H
«•
C
H
H C

+

H
. C
H C *

c :

H C

C H

AlCl--/O
C
H

* C
H
and th e c arb o n iu m io n from
sten

two r e a c t e d .

H
HCH
+C
HCH
H

H
HCH
-c - c h 2ch3
HCH
H

(

6)

67.
H
HG
..
'
HC

H
HCH
VC -C
i HCH
H
CH
G*
H

H
H£H
-G -CHgCH-z
h 6h
H

(7 )

P a r a l l e l w i t h t h e s e r e a c t i o n s was t h e r e a r r a n g e m e n t o f t h e
carbonium io n .
H
H
H
H
HCH HCH
HCH i H? H
CHg-CHr2 -G-,
—>
--4—
- 9C. +* r —
'> cCH,-CHo
h kJ, - c h 2cL ------C
C
J - CC'CH
-CHS
-f; HCH) HCH c
! HCH
VH/
H
H
• •

ch

CH3
-qV
CH^

----- ;>

H
-f-

ch ,

-

chp : c

:

gh

H

io;

The r e a r r a n g e d f r a g m e n t s r e a c t e d w i t h t h e a c t i v a t e d b e n z e n e
n u c le u s and th e l i b e r a t e d c h lo r id e io n o f the r e a c t i o n o r
one p r o d u c t fo rm e d an a l k e n e .
H
HG

CH3

° ■’ c :

HC ,

+ c ; GH3

CH

H
___ }

CH„

HC
it
HC

• c H
H H H
C H . - 6 :C::C.'H
6 k

G -6H-C H 3
I CH3
CH

(9)

c '
H

+

hci

— ?>

or

H
c h 3- c h 2 - c - c h 3
Cl
H
ch 3 c

■>
When d e m e t h y l a t i o n t o o k p l a c e ,

H
:

c

(10)

H
::

c

:

h

(n )

H
t h e r e a c t i o n may h a v e f o l l o w e d

two p a t h s , o n e i n w h i c h t h e e l e c t r o n s f o r m e d a d o u b l e b o n d ,

68 •

y

?.H3 CH3
C .* CHg CH3
ch3 ch3

— ;>

/N
V
V

_G — c
6h3
ch3
fcH, CH3

CH,p-CH,

>C ! s C -CH2-CH3
c h 3 oJHW

0

o r one I n w hich a p r o to n from th e
H5C1
reacted, w ith

+

th e

^GH3 : ~ >

reactio n

ch3ci

-b

H

d e m e t h y l a t e d compound

gh3 gh3

^j c : c : ch2ch3

(12)

ch3

— •>

1^)"c ’

-

[

ch4
c h 2--c h 2

* CH2 " CH3 +
c h 3ci

ch3 ch3

or

ch3

CH^-CH'z,

I

2 H

ch3

jl^ j -c : c -ch2-ch3

CEU

(14)

SUMMARY
1*

The method, o f c o n d e n s a t i o n o f c a r b i n 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 alum inum c h l o r i d e h a s b e e n m o d if i e d i n such
a manner t h a t the n a tu r e o f a l l

r e a c t i o n p r o d u c t s c o u l d be

in v estig ated .
2.

Five

tertia ry

c a r b i n o l s w i t h i n c r e a s e d b r a n c h i n g on t h e

h y d r o x y l c a r b o n have b e e n c o ndensed w i t h benzene i n the
p r e s e n c e o f a n h y d r o u s a lu m in u m c h l o r i d e a n d t h e r e a c t i o n
products
3.

stu d ied .

D e m e t h y l a t i o n was f o u n d t o be p r o n o u n c e d i n t h e more

h ig h ly branched a lc o h o ls ,
4.

F r a g m e n t a r y p r o d u c t s w e re i s o l a t e d a nd i d e n t i f i e d

w hich v e r i f i e d
5.

a n d was e v i d e n t i n o t h e r c a s e s .

the d e m e th y la tio n p ro c e s s .

A p r o c e d u r e h a s b e e n s u g g e s t e d f o r th e removal o f a l k y l

c h l o r i d e s w hich have p r e v e n te d the
6.

sep aratio n of fra c tio n s .

A mechanism f o r th e c o n d e n s a tio n o f t e r t i a r y c a r b i n 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 alu m in u m c h l o r i d e
a t e le v a t e d te m p e ra tu re s has been proposed.

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