A QUANTETAT'IVE STUDY OF THE ACIDITY OF CERTAIN HYDROCARBONS

By
R ichard Eben C rocker

A THESIS

S ubm itted to th e Scnool f o r Advanced Graduate S tu d ie s
of M ichigan S ta te U n iv e rs ity o f A g ric u ltu r e and
A pp lied S cience in p a r t i a l f u lf illm e n t of
th e req u irem en ts f o r th e degree of
DOCTOR OF PHILOSOPHY
Department of C hem istry

1999

ProQuest Number: 10008554

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ACKNOWLEDGMENT
The a u th o r w ishes to ex p ress h i s d e e p e st a p p r e c ia tio n
and g r a titu d e to P ro fe s so r H arold H art f o r h is v a lu a b le
guidance and p erso n a l encouragement th roughout th e course
of t h i s s tu d y .
A p p re c ia tio n i s a ls o extended to Mr, S. Meyers on,,
S tan d ard O il Company (In d ia n a ) , W h itin g , In d ia n a , who
a n aly zed a l l 'deliberated hydrocarbons mass s p e c tro m e tr ic a lly
and to th e Petroleum R esearch Fund of th e American Chemical
S o c ie ty whose fe llo w s h ip program provided p erso n al fin a n ­
c ia l. a s s is ta n c e from Jan u ary , 199? th ro u g h Septem ber, 1998-

My W ife

& QUANTITATIVE STUDY OF THE ACIDITY OF CERTA IN HYDROCARBONS

By
R ichard Eben C rocker

AN ABSTRACT

Subm itted to th e School f o r Advanced G raduate S tu d ie s
of M ichigan S ta te U n iv e rs ity o f A g r ic u ltu r e and
A pp lied S eien ce i n p a r t i a l f u lf i l l m e n t of
th e req u ire m en ts f o r th e degree of
DOCTOR OF PHILOSOPHY
Departm ent o f C hem istry
Year 1959

Approved

ABSTRACT
The purpose o f t h i s in v e s ti g a tio n was to stu d y th e e f f e c t o f
s t r u c t u r a l changes on th e a c i d i t y of th e alp h a-h y d ro g en s of c e r t a i n
a lk y la ro m a tic h y d ro carb o n s.

When a lk y la ro m a tic s a r e h e a te d i n th e

p resen ce o f a s u it a b l e c a t a l y s t such a s potassium m e ta l, hydrogens on
th e carbon a lp h a to th e a ro m a tic r in g may exchange.

This r e a c tio n was

i n v e s tig a te d a s a p o s s ib le method f o r d eterm in in g th e r e l a t i v e a c i d i t y
o f h y d ro c a rb o n s.
A.

g e n e ra l pro ced u re f o r th e p r e p a ra tio n o f a lp h a - d e u te ra te d hydro­

carbons was developed which r e s u lte d i n l i t t l e or no deuterium in th e
aro m a tic r in g .

The method in v o lv ed cleav ag e o f th e a p p r o p ria te a r y l -

a lk y l m ethyl e th e r w ith p otassium m etal fo llo w ed by h y d ro ly s is o f th e
o rg a n o m e ta llic w ith deuterium o x id e.
p rep ared i n t h i s manner:

The fo llo w in g hydrocarbons were

cumene-d•Q> , sec-*butylbenzene-d CL , 3-p h e n y l-

p en tan e-d a , 2- p h en y lp en tan e-d ^, 2-ra e th y l-3-p h enylbutane~ da and
2 ,2 -d im e th y l-3 -p h e n y lb u ta n e -d a .

These s ta n d a rd s were analyzed mass

s p e c tr o m e tr ic a lly and th e n used f o r p re p a rin g in f r a r e d c a l i b r a t i o n
cu rv es from which unknown amounts o f deuterium could be d eterm in ed .
S e p a ra tio n o f sm all volum es o f hydrocarbon m ix tu res was accom plish­
ed by a d a p tin g a gas chrom atography a p p a ra tu s so t h a t reco v ery o f th e
in d iv id u a l components was n e a r-q u a n t i t a t iv e .
The e f f e c t s of s e v e ra l c a t a l y s t s , tem p eratu re ra n g e s , r e a c tio n
v e s s e l s and compound ty p es w ere s tu d ie d .

The exchange r a t e s v a r ie d

d i r e c t l y w ith th e amount of c a t a l y s t and a r e a ls o dependent on th e
m olar c o n c e n tra tio n s o f th e h y d ro carb o n s.

C o n d itio n s found most s u i t ­

a b le f o r k i n e t i c experim ents in v o lv ed h e a tin g two hydrocarbons w ith
eth y lb en aen e-d ^ f o r v a ry in g tim es a t 1$0° in se a le d tu b e s u s in g p o t a s s i u m
m eta l a s th e c a t a l y s t .
F i r s t o rd e r r a t e c o n s ta n ts were o b tain ed from p lo ts o f lo g (100/
1C0-^D) v s . t , where %D was th e mole p e rc e n t o f deuterium i n th e hydro­
carbon a t tim e t .
found t o b e :

The o rd e r o f d e c re a sin g r e l a t i v e exchange r a t e s was

cumene, 1 8 .9} s e c -b u ty lb e n z e n e , 8 .1 3 j 2 -ph en y lp en tan e,

6 .915 3 -p h en y lp en tan e , 1,96} 2-m ethyl-3“ p h en y lb u tan e, 1 . 90} 2 , 2 -d im e th y l3 - p h en y lb u tan e, 1 .0 0 .

This o rd e r p a r a l l e l s t h a t o f p r e d ic te d a c i d i t y

o f th e s e compounds.
R e s u lts o b ta in e d a r e c o n s is te n t w ith a mechanism in v o lv in g i n i t i a l
a tta c k by p otassium on th e alpha-hydrogen o f each com peting hydrocarbon
to form th e organopotassium s a l t .

T his i s follow ed by d eu teriu m tr a n s ­

f e r between th e c a rb an io n p o rtio n of th e s a l t aild e th y lb e n z e n e -d ^ .
A tta c k by p o tassiu m i s b e lie v e d to be r a t e d e term in in g in th e case of
most o f th e hydrocarbons s tu d ie d .

Both p ath s a re b e lie v e d to be

d i r e c t l y r e l a t e d to th e a c i d i t y .
D iphenylm ethane d id n o t exchange protium f o r deuterium w ith e th y lbenzene~da u n d er a v a r i e t y o f c o n d itio n s .
o ffe re d ;

An e x p la n a tio n f o r t h i s i s

An a tte m p te d c o m p e titio n r e a c tio n between cumene and p henyl-

cyclopropane u n d er th e exchange c o n d itio n s r e s u lte d in deuterium
t r a n s f e r to cumene b u t p o ly m e riz a tio n of phenylcyc'lopropane.

TABLE OF CONTENTS
Page
INTRODUCTION.......................'................................... . ..................................................

1

EKPERIOTTAX...................................................................

7

£ . S y n th e s e s , ............. *................................................................., ...................
E th y lb en zen e-d ct. ...............................................................................
E th y lb en ® en e"d a,a
- .........*......................................................
(a ) P re p a ra tio n o f ci-phenethyl c h lo r id e - d a ...................
(b ) R eduction o f a -p h e n e th y l c h lo r id e - d ^ .......................
Diphenylmethane~d<i..............................................................................
D iphenylm ethane-d^ .................
C um ene-d^(Procedure A )............................................. - .....................
(a) P re p a ra tio n o f dim ethyl p h e n y lc a rb in o l.....................
(b ) P re p a ra tio n of dim ethylphenylcarbinyl. c h l o r id e ..
(c ) A ttem pted re d u c tio n of d im e th y lp h e n y lc a rb in y l
c h l o r id e ...................................................
Cumene-da (.procedure C ) ...............................................
(a ) P re p a ra tio n o f
2-m eth o x y -2 -p h en y lp ro p an e.....
(b) P re p a ra tio n of
a -p h e n y liso p ro p y l p o tassiu m
(c ) H y d ro ly sis o f cl- phenyl is o p r o pyl p o ta ssiu m ................
Cumene-dp..........................
(a ) P re p a ra tio n o f p-bromocumene..........................................
(b) P re p a ra tio n and h y d ro ly s is o f th e G rignard
re a g e n t from p-bromocumene.......................................
O x id atio n of p~ and a-d eu tero cu m en es.......................................
se c-B u ty lb e n z e n e -d a ............................
(a ) P re p a ra tio n of
2 - p h e n y l-2 -b u ta n o l.....................
(b) P re p a ra tio n o f
2-m ethoxy-2 - p h en y lb u tan e........
(c ) C leavage and h y d ro ly s is o f 2-m ethoxy-2-p h en y l­
butane ................................
2-Phenyl, p e n ta n e ..............................................................................
(a ) P re p a ra tio n o f 2 -p h e n y l-2 -p e n ta n o l...............
(b) D ehydration o f 2 -p h e n y l-2 -p e n ta n o l and hydro­
g e n atio n of r e s u l t i n g o l e f i n s .............................
2-Pheny3.pentane-d<x,....................................
(a) P re p a ra tio n of 2 -m ethoxy-2-phenylpentane................
(b) Cleavage and h y d ro ly s is of 2-m ethoxy-2 - phenylp e n ta n e ...................
3-Phenyl.pentan e ..................................
3 -P h en y l.p en ta n e-d a .
......................................................

v ii

7
7
8
8
9
3.0
10
3.3.
3-1
12
12
13
13
3.3
lit
1$
3.5
16
1?
17
17
3.8
19
3.9
19
20
21
21
22
22
23

TABLE OF CONTENTS - C ontinued

Page
(a ) P re p a ra tio n of .3-p h e n y l-3 -p e n ta n o l.............................
(b) P re p a ra tio n of 3-m ethoxy-3-phenyl p e n ta n e ................
(c) Ci.eavage and h y d ro ly s is of 3'■methoxy-3 - phenylp en t ane ............, ..................................................................
2-M eth y l-3“ p h en y lb u tan e ....................................................................
(a ) P re p a ra tio n o f 3 -m e th y l-2 -p h e n y l-2 -b u ta n o l
(b) P re p a ra tio n o f 2-m ethoxy-3-m ethyl-2rphenyl­
bu tan e ..........
(c) C leavage and h y d ro ly s is of 2-m ethoxy-3-m ethyl2- p h en y lb u tan e
..................................................
3-Methyl=-2-p h e n y lb u ta n e-d e . . . . . . . . . . . . . ........., .....................
2 . 2 -D im eth y l-3 -p h en y lb u tan e .................. . . . . . . ...........................
2 . 2-I)im ethyl-3 - phenylbutane-dcc....................................................
( a ) P re p a ra tio n of 3 ,3 -d im e th y l-2 - p h e n y lb u ta n - 2 -o l..
(b) P re p a ra tio n o f 2 -m e th o x y -3 ,3 -d im eth y l-2 - phenyl­
b u ta n e ....................... ............ . . . . ............................. . . .
(c) Cleavage and h y d r o ly s is of 2-m ethoxy-3, 3d im e th y l-2-p h e n y lb u ta n e ............................... . . . . . . .
High S u rface Sodium..........................................................................

30

B. Exchange S tu d ie s ....................................
A n a ly tic a l P ro c e d u re ...................................................................
S e p a ra tio n P ro c e d u re ...................... ...............................................
Exchange E x p erim en ts.......................
(a ) A p p a ra tu s...............
(b) R e a ctio n C o n d itio n s .................................................
(c ) K in e tic P ro ced u re..................................................................

30
30
37
Lp.
Ip.
Ill;
i|6

RESULTS AND DISCUSSION..........................................................................................

U8

S y n th e tic M ethods..............................................................................................
P roof o f S tr u c tu r e o f Cumene-d^..................................
P re lim in a ry Exchange E x p erim en ts ................. .........................................
K in e tic E x p e rim en ts..........................................................................................
C a lc u la tio n o f R ate C o n s ta n ts ,.................................................................
Mechanism......................................... .....................................................................

1|8
br9
5U
57
6U
65

SUMMARY..........................................................................................................................

78

LITERATURE CITED.......................................................................................................

80

APPENDIX........................................................................................................................

83

v iii

23
2h
2k
25
25
25
26
26
2?
28
28
28

LIST OF TABLES
TABLE
I
II

III

IV

V

Page
A c id ity o f V ario u s Compounds S tu d ied by Conant and
Wheland and by McEwen. , . . . ..................................................................

3

P re p a ra tio n o f sec-B u tylbenzene Samples o f Known, V arying
Deuterium C ontent f o r th e C o n s tru c tio n of th e C a lib r a tio n
C urve, .............................................
3k
C a lc u la tio n o f O p tic a l D en sity from C-D Band a t k .68
M icrons f o r sec-B u ty lb enzene (2 .6 5 M) in Carbon T e tra ­
c h l o r i d e .........................................................................................................

35

Y ie ld s and Deuterium A n aly ses of Hydrocarbons P repared by
E th e r Cleavage w ith P otassium Followed by H y d ro ly sis w ith
50
D euterium O x id e......................................... , ............................................
E f f e c t of C a ta ly s t Q u an tity on th e R ates of Exchange of
Cumene and se c -B u ty lb e n z e n e ,............................

60

VI

E f f e c t o f C o n c e n tra tio n s on R ates o f Exchange.......................

61

V II

C o m p etitio n Between Cumene and sec-B u ty lb e n zen e.....................

62

V III

F i r s t O rder Rate C o n stan ts f o r D euterium T ra n sfe r to
Cumene i n C om petition w ith s e c - B u ty lb e n z e n e ..,......................

66

F i r s t O rder Rate C o n stan ts f o r Deuterium T ra n s fe r to
sec-B u ty lb en zen e in C om petition w ith Cumene
' ..................

6?

R e la tiv e Deuterium Exchange R ates C a lc u la te d from L e a st
S quares S lo p e s ...........................................................................................

69

C om petitio n Between Cumene and s e c - B u ty lb e n z e n e ...

88

X II

C om petition Between sec-B utylbenzene and 3 -P h e n y lp e n ta n e .

89

X III

C o m p etitio n Between sec-B utylbenzene and 2-P h en y lp e n ta n e.

90

C o m p etitio n Between sec-B utylbenzene and 2-M ethyl~3p h e n y lb u ta n e ..........................................................

91

C o m p etitio n Between sec-B utylbenzene and 2 , 2-D im ethyl-3p h e n y lb u ta n e ............................

92

IX.
X
XI

XIV
XV

ix

LIST OF TABLES - C ontinued
TABLE
XVI

Page
F i r s t O rder Rate C o n sta n ts f o r Deuterium T ra n s fe r to
Cumene i n C o m p etitio n w ith s e c -B u ty lb e n z e n e .
..................

93

F i r s t O rder Rate C o n stan ts f o r D euterium T ra n s fe r to s e c B utylbenzene in C om petition w ith Cumene................................

9k

F i r s t O rder Rate C o n stan ts f o r Deuterium T ra n s fe r to s e c B utylbenzene in C o m petition w ith 3 - P h en y lp en tan e

9!?

F i r s t O rder Rate C o n stan ts f o r Deuterium T ra n s fe r to
3-P h en y lp en tan e i n C om petition w ith sec-B u ty lb e n z e n e

96

XX F i r s t O rder Rate C o n stan ts f o r Deuterium T ra n s fe r to s e c B utylbenzene in C om petition w ith 2-P h e n y lp e n ta n e ..................

97

XVII
X V III
XIX

XXI
XXII
X X III

F i r s t O rder Rate C o n stan ts f o r Deuterium T ra n s fe r to
2-P henylpentane i n C om petition w ith s e c -B u ty lb e n z e n e .. . . .

98

F i r s t O rder Rate C o n stan ts f o r D euterium T ra n s fe r to s e c B utylbenzene in C om petition w ith 2 -M eth y l-3 -P h en y lb u tan e.

99

F i r s t O rder Rate C o n stan ts f o r D euterium T ra n s fe r to
2-M etbyl-3 -P h en y lb u tane in C om petition w ith s e c -B u ty lben zen e................................

100

XXIV F i r s t O rder Rate C o n stan ts f o r Deuterium T ra n s fe r to s e c B u tylbenzene in C om petition w ith 2 , 2-D im ethyl-3“ P henylb u ta n e
...................................................................................................101
XXV F i r s t O rder R ate C o n stan ts f o r Deuterium T ra n s fe r to
2 , 2 -D im ethyl-3-P henylbutane i n C om petition w ith s e c B utylbenzene ............................

x.

102

LIST OF FIGURES
FIGURE

Page

1 . P e rc e n t deu teriu m c o n te n t of m ix tu res o f se c-b u ty lb en zen e
and s e c -b u ty lb e n z e n e -d a i n carbon t e t r a c h l o r i d e v s .
o p tic a l d e n s ity a t k *68 m ic ro n s
....................

36

2 . S p i r a l t r a p used w ith Vapor F racto m e te r f o r sample
c o l l e c t i o n ...........................................

3?

3 . Gas chrom atograph showing s e p a ra tio n of eth y lb en zen e,
cumene and se c -b u ty lb e n z e n e ................................

UO

U. Ring exchange over h ig h s u rfa c e sodium on c h a r c o a l . ............

15

5 . In fra re d s p e c tr a showing r e l a t i v e a b s o rp tio n due to a 1:9
and 1 :U r a t i o o f cumene-dp i n cumene-da .............................

5l

6 . N u clear m agnetic reso n an ce s p e c tra o f v a rio u s c u m e n e s .....

£3

7 . I n f r a r e d s p e c tr a i l l u s t r a t i n g th e dependence of exchange
on th e d eu teriu m s o u rc e .........................................................................

56

8 . A lip h a tic C-D s tr e t c h i n g re g io n showing p ro g re s siv e
in c re a s e o f deuterium c o n te n t d u rin g a c o m p e titio n r e ­
a c tio n betw een cumene and sec-b u ty lb e n z e n e u s in g e th y lb enzene-d^ a s deu teriu m so u rc e , potassium m etal as
c a t a l y s t and l 50° a s r e a c tio n te m p e ra tu re ...................................

63

L e a st sq u a re s slo p e s showing r a t e s o f deuterium exchange
c o m p e titio n between cumene and s e c -b u ty lb e n z e n e ......................

68

1 0 . P erc en t deu teriu m c o n te n t o f m ix tu re s o f cumene and
cumene-d^ i n carbon t e t r a c h l o r i d e v s . o p t ic a l d e n s ity a t
I . 65 m ic ro n s
............

83

1 1 . P e rc e n t d eu teriu m c o n te n t of m ix tu re of 3™phenylpentane
and 3-p h e n y lp e n ta n e-d a in carbon t e t r a c h l o r i d e v s . o p tic a l
d e n s ity a t It. 68 m ic ro n s....................................

8i|

12 . P e rc e n t d eu teriu m c o n te n t of m ix tu re s of 2 -phenylpentane
and 2-p h e n y lp e n ta n e-d ^ i n carbon te t r a c h l o r i d e v s . o p t ic a l
d e n s ity a t It - 67 m ic ro n s
..........

85

1 3 . P e rc e n t d eu teriu m c o n te n t of m ix tu re s of 2 -m e th y l-3 -p h en y lb u tan e and 2-m e th v l-3- phenylbutane- da in carbon t e t r a ­
c h lo rid e v s . o p tic a l d e n s ity a t 1 .70 m ic ro n s............................
86
xi

LIST OF FIGURES - C ontinued
FIGURE

Page

l i t . P e rc e n t d eu teriu m c o n te n t o f m ix tu re s o f 2 ,2 -d im e th y l-3 p henylbutane and 2 J2-d im e th y l-3-p h en y lb u ta n e-d a in carbon
t e t r a c h l o r i d e v s . o p t i c a l d e n s ity a t I t.69 m icro n s....................

87

15.

I n f r a r e d spectrum o f ethylbenzene-d^.................................................. 103

16.

I n f r a r e d spectrum o f eth y lb en zen e-d 0 j a ............................................ 10lt

17*

I n f r a r e d spectrum o f diphenylm ethane-d0 .......................................... 105

18 .

I n f r a r e d spectrum of diphenylm ethane-d^ ,a ..................

106

19.

I n f r a r e d spectrum o f cum ene-d^...............

107

20.

I n f r a r e d spectrum o f cum ene-dp.

............................................... 108

2 1 . I n f r a r e d spectrum o f se c -b u ty lb e n z e n e -d a .........................

109

22.

I n f r a r e d spectrum o f 3-p h e n y lp e n ta n e ....................................................110

23-

I n f r a r e d spectrum o f 3 -p h en y lp en tan e-d a .......................................... I l l

2lt.

I n f r a r e d spectrum of 2 -p h e n y lp e n ta n e

.................................. 112

25. I n f r a r e d spectrum o f 2 - phenyl p e n ta n e -d a

........................ ,. 113

26.

I n f r a r e d spectrum o f 2 -m e th y l-3 -p h e n y lb u ta n e

........................... I l l

27.

I n f r a r e d spectrum of 2 -m eth y l-3 -p h en y lb u tan e-d a ............................115

28.

I n f r a r e d spectrum o f 2 , 2 -d im e th y l-3 -p h e n y lb u ta n e ..........................11.6

29 .

I n fr a re d spectrum o f 2, 2-d im e th y l-3-p h e n y lb u ta n e -d a . . . . . . . . 117

INTRODUCTION

1

introduction

This t h e s i s i s concerned w ith a stu d y o f th e a c i d i t y o f a lp h a hydrogens i n s e v e ra l a lk y la ro m a tic h y drocarbons.

B efore d is c u s s in g

th e p re s e n t w ork, however, i t may prove u s e f u l to examine s e v e ra l
p re v io u s, r e l a t e d s tu d ie s which have been re p o rte d , in c lu d in g a l i s t of
hydrocarbons whose a c i d i t y has been in v e s tig a te d .
I t has been g e n e ra lly accep ted t h a t o rg a n o a lk a li compounds e x h ib it
s a l t - l i k e c h a r a c te r (1 ) .

U sing B ronsted*s d e f i n i t i o n of an a c id , th e

hydrocarbon p o r tio n o f such compounds i s d eriv ed from an a c id whose
a c i d i t y must be o f an ex trem ely low o rd e r.

The g e n e ra l method which

h as been u t i l i z e d f o r m easuring th e a c id s tr e n g th of compounds o f t h i s
ty p e i s th e rep lacem en t of a weak a c id by a s tr o n g e r one.

The work of

Conant and Wheland (2) was th e f i r s t attem p t to a s s ig n ,pKa v a lu e s to a
number o f ex trem ely weak o rg an ic a c id s .

This th e y d id by s tu d y in g

m e ta th e ti.c a l r e a c tio n s betw een s a l t s and a c id s , assum ing th e degree
of d i s s o c i a t i o n o f a l l s a l t s to be ap p ro x im a te ly th e same.

I t was only

n e c e s sa ry to determ in e w h eth er th e r e a c tio n
RH * R!K

1.

BK f R.'H

;'l)1

proceeded from r i g h t to l e f t o r v ic e v e rs a w ith each p a ir of a c id and
s a l t (R and R! a r e o rg an ic r e s id u e s ) .

O b serv atio n of th e c o lo r o f th e

s o lu tio n , which i s v e ry c h a r a c t e r i s t i c f o r a number of m e ta llic com­
pounds, and c a rb o n a tio n of th e r e a c tio n m ix tu re fo llo w ed by i s o l a t i o n
of th e r e s u l t i n g c a rb o x y lic a c id s were th e two methods used f o r

2

d e te rm in in g on which s id e of th e e q u a tio n e q u ilib riu m l a y .

T his s tu d y

was l a t e r extended by McEwen (3) who used a s p e c tro s c o p ic method (u sin g
e tio p o rp h y rin I a s an i n d ic a to r and sodium trip h e n y lm e th y l as th e b ase
u sed to t i t r a t e th e a c id ) and a p o la r im e tr ic method ( in which an
o p t i c a l l y a c tiv e a c id was u se d , e q u ilib riu m b ein g determ ined w ith th e
a id o f a p o la r im e te r ) .

Both o f th e s e s tu d ie s a ssig n e d approxim ate

v a lu e s o f s tr e n g th on th e b a s is of th e eq u a tio n
pKx - pK2 = lo g [(R j” )/(R-xH)] - lo g [(R 2" ) / ( R 2H)]
w here pKx and pK2 a re th e r e s p e c tiv e a c id s tr e n g th s , (R1 ) and (R2 )
a r e th e c o n c e n tra tio n s o f th e r e s p e c tiv e an io n s and ; RXH) and (R2H)
a r e th e c o n c e n tra tio n s o f th e co rresp o n d in g a c id s .

Conant and Wheland

e s tim a te d t h a t m e ta th e sis would proceed to 90% com pletion i f th e a c id s
d i f f e r e d by two pK u n i t s .

However, in th e case of th e c o lo r im e tr ic

m easurem ents, a f i v e '“f o ld ex cess of one re a g e n t was u se d , r e s u l t i n g in
a d if f e r e n c e o f O.lt pK u n i t s co rresp o n d in g to 90% com pletion.

As a

re fe re n c e s ta n d a rd , Conant and Wheland chose th e pK v a lu e of 20 fo r
acetophenone w h ile McEwen u sed th e known v a lu e of 16 f o r m ethanol.
Table I l i s t s some of th e r e s u l t s o f th e s e i n v e s tig a t o r s .
K leene and Wheland (I4.) extended t h i s s e r i e s to phenylcyclohexane
and p h e n y lc y c lo p e n ta n e ,

The o rd e r of d e c re a sin g a c id s tr e n g th was found

to be diphenylm ethane v p h en y lcyclopentane > cumene v p h en y lcy clo h ex an e.
Bryce--Smith (5) has s tu d ie d th e a c i d i t y o f s e v e ra l hydrocarbons
by i n v e s t i g a t i n g th e m e ta la tlo n of alk v lb e n z e n e s by alk y l-so d iu m and
-p o ta ssiu m compounds.

He found t h a t th e tendency f o r r e a c tio n a t th e

3

TABLE I
ACIDITY OF .VARIOUS COMPOUNDS STUDIED BY CONANT AND
WHELAND (2) AND BY McEWEN (3)

A cid

Acid

pK

M ethanol

16

Iso p ro p y l a lc o h o l
E th y l a lc o h o l
B enzyl a lc o h o l

18

t e r t - B u t y l a lc o h o l
A cetophenone
Tr ip h e n y lc a rb in o l

19

9- P h en y lflu o re n e
Indene
P h en y lacety len e

21

M phenylam ine

23

pK

F lu o ren e

25>

A n ilin e

27

Di phenylb en zylm ethane

31

Triphenylm ethane

33

Diphenylmethane

3o

1 , 1- D iphenylpro pene

36

Cumene

37

E thane

a lp h a - p o s itio n of th e s id e ch ain d ecreased in th e o rd e r, to lu e n e >
ethylbenzerie

cumene.

He a ls o determ ined isom er r a t i o s f o r th e

m e ta la tio n o f cumene by e th y l p otassium , n- pro p y l potassium , n-am ylpotassium and n-airylsodium , d is c o v e rin g t h a t th e m eta-isom er always
predom inated.

From th e d a ta o b tain ed i n th e c o m p e titiv e m e ta la tio n of

benzene and cumene by e th y lp o ta ssiu m , p a r t i a l r a t e f a c to r s were c a lc u ­
l a t e d from w hich i t was c o n c lu d e d .th a t, q u a l i t a t i v e l y , each hydrogen
atom i n cumene was l e s s a c id ic th a n a hydrogen atom i n benzene, th e
o rd e r o f d e c re a s in g a c i d i t y b ein g p a ra - meta - a lp h a - o rth o - - b e ta .

h

C o n sid e ra b le work has been a p p e a rin g i n th e S o v ie t l i t e r a t u r e
s in c e 19^0 d e a lin g w ith d eu teriu m exchange a s a method f o r com paring
th e s tr e n g th o f v e ry weak a c i d s .

The b u lk of t h i s work has been done

by S h a te n s h te in ( 6 , 7 ) , who determ ined th e amount o f exchange f o r a
number o f hydrocarbons i n D20 , ND3 and NJJ3 c o n ta in in g potassium amide
a t v a rio u s te m p e ra tu re s .

In clu d ed i n th e l i s t o f compounds s tu d ie d

w ere benzene, to lu e n e , in d en e . .flu o ren e, trip h e n y lm e th a n e , d ip h e n y lm ethane, acenaphthene and n a p h th a le n e .

S h a te n s h te in p o in te d out th e

p a r a lle lis m betw een th e f i r s t o rd e r r a t e c o n s ta n ts which he o b ta in e d
and th e i o n iz a tio n c o n s ta n ts o f Conant and Wheland ( 2 ) .

A somewhat

s im i l a r pro ced u re was fo llo w ed by R oberts ( 8 ) who determ ined th e exchange
r a t e s o f v a rio u s o - , m- and p -d e u te ra te d benzene d e r iv a tiv e s w ith
potassiu m amide i n l i q u i d ammonia.

The r e s u l t s were in te r p r e te d on th e

b a s is o f th e r e l a t i v e a c i d i t y of th e v a rio u s aro m atic h y d ro g en s.
W hile th e method o f d eu teriu m -p ro tiu m exchange in hydrocarbons i n
b a s ic media h as been l i t t l e used u n t i l r e c e n t y e a r s , exchange in acid
media h a s been e x te n s iv e ly s tu d ie d .

A l a r g e volume of work concerned

w ith d eu teriu m exchange of a l i p h a t i c and a ro m atic hydrocarbons in
d e u te r o s u lf u r ic a c id h as appeared i n th e l i t e r a t u r e , much b ein g done by
Ingold and W ilson ( 9 ) , Stevenson (1 0 ), B urw ell (11) and Gold (1 2 ,1 3 ).
S h a te n s h te in ( l l t , l ^ ) has a ls o s tu d ie d th e deuterium exchange of a number
o f a ro m a tic hydrocarbons in l i q u i d hydrobrom ic a c id c o n ta in in g deu teriu m
bromide and determ ined f i r s t o rd e r r a t e c o n s ta n ts f o r th e v a rio u s
hydrogen atoms on th e aro m atic r in g .

Some compounds in c lu d e d i n t h i s

work were b enzene, to lu e n e , e th y lb e n z e n e , cumene, te r t- b u ty lb e n z e n e ,

5

n -b u ty lb e n z e n e , n -p ro p y lb e n ze n e, 3“ p h en y lp en tan e, diphenylm ethane,
trip h e n y lm e th a n e , n a p h th alen e and f lu o r e n e .

I t was found in th e c a se

of th e a lk y lb e n z e n e s t h a t a l l r in g - and alp h a-h y d ro g en s w ere exchanged
f o r d e u teriu m , a lth o u g i hydrogens f u r t h e r removed from th e aro m atic
rin g w ere n o t.
R e c e n tly , R apoport and Sm olinsky (16) r e p o rte d th e s y n th e s is of
flu o ra d e n e

w hich c o n ta in s an u n u s u a lly a c id ic hydrogen.

T his compound could be

removed from benzene by w ashing w ith d i l u t e aqueous a l k a l i and exchanged
hydrogen f o r deu teriu m i n b o ilin g deu teriu m e th o x id e .

I t has a pKa

v a lu e o f 11 ± 0 . 5 *
A nother example o f th e a c id ic p r o p e r tie s of alp h a-h y d ro g en s in
a lk y la ro m a tic compounds i s th e work of de P o s tis (U l) who r e p o rte d t h a t
cesium m etal l i b e r a t e s hydrogen from to lu e n e .
I t i s a p p a re n t from th e fo re g o in g d is c u s s io n t h a t , a lth o u g h th e
r e l a t i v e a c i d i t y o f a w ide v a r i e t y o£ hydrocarbons has been d eterm in e d ,
th e b u lk o f th e work i s q u a l i t a t i v e .

A lso , p re v io u s i n v e s tig a to r s have

lim ite d th em selv es m ainly to compounds w ith r e l a t i v e l y la r g e d if f e r e n c e s
in a c i d i t y , due, in. p a r t , to th e la c k o f a s e n s i t i v e method f o r d eterm in ­
in g sm all v a r i a t i o n s .
The p re s e n t s tu d y was prompted by th e d isc o v e ry t h a t a lp h a-h y d ro g en s
o f a lk y la ro m a tic s exchange a t m easurable r a t e s in th e presence of
r e a c t i v e a l k a l i m e ta ls , m etal h y d rid e s and o th e r b a se s ( 1 7 ) .

6

For exam ple, e th y lb e n z e n e -d a , when r e flu x e d over potassium m e ta l, d i s p ro p o rtio n a te d to e th y lb e n z e n e - d ^ a and o rd in a ry e th y lb e n z e n e .
CHDCH3

—^

<

>-CD2CH3 +

O'
(v

> C H 2CH3

(2)

Presum ably an o rg a n o m e ta llic compound i s produced i n sm all q u a n tity

0 ° - — —-- — •—
>C H 0

V

>

&

CH3

( o r d e u te ro n ) from th e a lp h a carbon atom o f a n o th e r hydrocarbon m olecule.
In t h i s way exchange o c c u rs.
I f th e a n io n ic s p e c ie s could s e l e c t betw een two so u rces o f a lp h a
p ro to n s , presum ably i t would o b ta in th e p ro to n from th e more a c id ic
so u rc e .

The r e l a t i v e r a t e s o f deu teriu m exchange of two hydrocarbons

m ight f u r n i s h , th e n , a method f o r m easuring t h e i r a c i d i t i e s .
The purpose o f t h i s i n v e s t ig a tio n was to d eterm in e by t h i s method
th e e f f e c t of s t r u c t u r a l changes on th e a c i d i t y o f th e alp h a-h y d ro g en
o f c e r t a i n a lk y la r o m a tic s .

B r i e f ly , t h i s in v o lv ed th e sy n th e se s o f

v a rio u s a lk y la r o m a tic s , a llo w in g two n o n -d e u te ra te d hydrocarbons to
compete f o r th e d eu teriu m o f a d e u te r a te d s p e c ie s i n th e p resen ce o f an
a p p r o p ria te c a t a l y s t , ■s e p a r a tio n o f th e components and a n a ly s e s f o r
d eu teriu m c o n te n t from which exchange r a t e s were c a lc u la te d .

The

ex p erim e n ta l s e c tio n which fo llo w s c o n ta in s d e t a i l s o f th e s y n th e s e s
and exchange p ro ce d u re, in c lu d in g th e a n a l y t i c a l and s e p a r a tio n te c h ­
n iq u e s .

Examples o f th e r a t e s o b ta in e d and a d is c u s s io n concerned w ith

an i n t e r p r e t a t i o n of th e s e d a ta a re g iven jn th e s e c tio n on r e s u l t s and
d is c u s s io n .

I n th e appendix c a l i b r a t i o n cu rv es and exchange r e s u l t s

and r a t e s a r e g iv e n .

EXPERIMENTAL

7

EXPERIMENTAL
A. S yntheses
The d e u te r a te d hydrocarbons were sy n th e siz e d by th r e e g e n e ra l
m ethods:

(A) r e d u c tio n of s u it a b l e compounds with, lith iu m aluminum

d e u te r id e and lith iu m d e u te r id e , (B) r e a c tio n of th e a p p ro p ria te
G rignard re a g e n t w ith d eu teriu m oxide and (C) cleav ag e o f a -p h e n y la lk y l
m ethyl e th e r s w ith m e ta llic potassium fo llo w e d by h y d ro ly s is w ith
d eu teriu m o x id e .
In in s ta n c e s where th e n o n -d e u te ra te d hydrocarbons were n o t a v a i l ­
a b le com m ercially, th e y were s y n th e s iz e d , u s u a lly by methods d i f f e r e n t
from th o s e re q u ire d to make th e co rresp o n d in g a - d e u te r a te d compound.
The p r e p a ra tio n of each o rd in a ry hydrocarbon i s im m ediately follow ed
by th e s y n th e s is o f i t s d e u te ra te d c o u n te r p a rt.
E thylbenz ene-d^ (P ro ced u re A)

E th y lb en ze n e-d a was

p rep ared acco rd in g to th e method of E l i e l (1 8 ).

A 2f>0-m l. round-bottom ed f l a s k was equipped w ith a r e f lu x condenser
p r o te c te d w ith a d ry in g tu b e , a 125>-ml. a d d itio n f u n n e l, a d ry argon
i n l e t and a T ru -b o re s t i r r e r w ith a T eflo n b la d e .
p ip e tte d

In to t h i s v e s s e l was

m l. o f te tra h y d ro f u ra n ( d i s t i l l e d from potassium h y droxide

8

and th e n f r e s h l y d i s t i l l e d from lith iu m aluminum h y d rid e ) follow ed by
1 .1 g. (0 .0 2 6 mole) o f lith iu m aluminum d e u te r id e (M etal H ydrides Inc..,
9&\% p u r ity ) and 3»2 g. (O.38 mole) of lith iu m d e u te rid e (M etal H ydrides
I n c ., 98$ p u r i t y ) .

Then, w ith o u t w a itin g f o r th e s lu r r y to d is s o lv e ,

3U.5 g* (0 . 21+5 mole) o f a lp h a -p h e n e th y l c h lo r id e ( 19) was added w ith
s tirrin g .

No marked exotherm ic r e a c tio n was n o te d .

The r e a c ta n ts were

s t i r r e d a t g e n tle r e f lu x f o r tw e n ty -fo u r h o u rs, a f t e r which th e r e a c tio n
m ix tu re was allow ed to co o l to room te m p e ra tu re .

The excess h y d rid e s

were removed by th e dropw ise a d d itio n of a s o lu tio n o f 20 ml. o f w ater
i n 30 m l, o f te tr a h y d r o f u r a n .

The m ixture was poured onto 100 g. of

i c e and 20 m l. o f s u l f u r i c a c id .

The bottom aqueous la y e r was s e p a ra te d

and e x tr a c te d w ith 100 m l. o f pentane which was combined w ith th e
o r ig i n a l o rg an ic l a y e r .

These were washed s u c c e s s iv e ly tw ice w ith 100

ml., o f w a te r, fo u r tim e s w ith 100 ml. o f 85$ o rth o phosphoric a c id ,
tw ice w ith 100 m l. o f w a te r, once each w ith 100 ml. of 10$ potassium
ca rb o n ate s o lu tio n and 100 ml, o f w a te r.

The o rg an ic l a y e r was d rie d

o v e rn ig h t over 10 g. o f anhydrous calcium c h lo r id e , th e n f r a c t i o n a l l y
d i s t i l l e d th ro u g h a sm a ll g la s s h e lic e s -p a c k e d column.

There was

o b tain ed 2 1 . k g* ( 82$) o f eth y lb e n z e n e -d ^ , b . p . 132.5° \ (31 mm.),
n ^° = 1 . 1+9 5 0 .

k k ss s p e c tro m e tric a n a ly s is in d ic a te d d L = 98*5 - 0 . 1$,

d0 = 1 .5 ± 0 .1$ and no d eu teriu m atoms in th e b e ta p o s itio n s .
E thylbenz ene- S t ^

fvProcedure A)

(a ) P r e p a ra tio n o f a -p h e n e th y l c h lo r id e -d a

9

The r e a c tio n v e s s e l d e s c rib e d i n th e p r e p a ra tio n o f e th y lb en zen e-d a
was u s e d .

To an ic e -c o o le d m ix tu re o f 0 .8 g. ( 0. 02 mole) of lith iu m

aluminum d e u te r id e i n 25 m l. o f d ry te tra h y d ro f u ra n was added dropw ise
w ith s t i r r i n g 8 .0 g. (0 .0 6 ? mole) o f aceto p h en o n e.

The m ixture was

th e n h e a te d a t r e f l u x f o r tw enty m in u tes, a f t e r which th e m ix tu re was
cooled and 20 ml. o f w a te r slo w ly added dro p w ise.

L ayers were s e p a ra te d ,

th e aqueous la y e r e x tr a c te d tw ice w ith 50 ml. of e th e r and th e combined
o rg an ic l a y e r s washed s u c c e s s iv e ly w ith 30 m l. each o f w a te r, 10$
sodium c a rb o n a te s o lu tio n and w a te r.

A f te r d ry in g o v e rn ig h t over 6 g.

o f anhydrous magnesium s u l f a t e , th e e th e r was removed by d i s t i l l a t i o n
and th e a -p h e n e th y l a lc o h o l-d a w hich rem ained, w ith o u t f u r t h e r p u r i f i ­
c a tio n , was added dropw ise to 16 g. (O.lU mole) o f th io n y l c h lo r id e .
The m ix tu re was allo w ed to stan d f o r f o u r h o u rs, then f r a c t i o n a l l y
d i s t i l l e d u s in g a sm all g la s s h e lic e s -p a c k e d column.

The a-phenethyl.

c h lo r id e -d a th u s o b ta in e d w eighed 6 .9 g- ( 73$ ) , b . p . 93~6°/Uo mm.,

ng5*3 = 1.5212.
(b ) R eduction of a -p h e n e th y l c h lo rid e -d ^
The p ro ced u re d e s c rib e d i n th e p r e p a ra tio n of eth y lb en zen e-d a
was fo llo w e d .

From 6 .9 g-

mole) o f a -p h e n e th y l c h lo r id e -d a ,

0 .8 g. (0.09 mole) o f lith iu m d e u te r id e and 0 .2 g, (0.005 mcle) o f
lith iu m aluminum d e u te r id e , th e r e was o b ta in e d 3*1 g» (59$) of e th y lb en zen e, b . p . 133“ ^ °(7 h6 mm.), ng5 - l.ij95U*

Mass s p e c tro m e tric

a n a l y s is showed d 2 *= 9 6 .6 t 0 , 1$, d x = 3 .U ± 0 .1$; d0 < 0 . 1$; no b e ta d eu teriu m atom s.

10

Di ph enylm ethan e-dq (P ro ced u re A)

U sing th e pro ced u re d e s c rib e d in th e p re p a ra tio n of eth y lb en zen e-d a,
20.3 g « (0 .1 0 mole) o f ben zh y d ryl c h lo rid e (p rep ared i n 86% y ie ld from
b en zh y d ro l and th io n y l c h lo r id e ) , 1 .3 g, (0 .1 6 mole) o f lith iu m d e u te rid e
and 0.U g. (0 .0 1 mole) o f lith iu m aluminum d e u te rid e a f t e r r e a c tio n
y ie ld e d [| .0 g . (2k%) o f sy m -te tra p h e n y le th a n e , m.p. 208° ( r e c r y s t a l l i z e d
from c h lo ro fo rm ), and 8.3 g. \%0%) o f diphenylm ethane, b . p . 100°/3 mm.,
n^° = 1 . 5 / 6 / .

The i n f r a r e d spectrum of th e sy m -tetra p h en y leth an e

in d ic a te d th e ab sen ce o f any deuterium atom s.

Mass s p e c tro m e tric

a n a ly s is showed th e diphenylm ethane-dc to c o n ta in d x = 9 5 . 8/S, dQ = h *2/S.
D iphenylm ethane-dq a

(P ro ced u re A)

The f i r s t a tte m p t to p re p a re d ip h e n y lm e th a n e -d ^ a was by th e
r e d u c tio n of benzophenone d ic h lo r id e w ith lith iu m aluminum d e u te rid e
and lith iu m d e u te r id e .

Benzophenone d ic h lo r id e was o b tain ed in Q0%

y i e l d from th e r e a c tio n o f benzophenone and phosphorous p en tach lo ri.d e
(20).

The g e n e ra l pro ced u re c i t e d in th e p re p a ra tio n of eth y lb en zen e-d a

was fo llo w e d .

A sm all amount o f l i q u i d b o ilin g from 95>-125°/3 nun. was

c o lle c te d w hich was n o t f u r t h e r i d e n t i f i e d a lth o u g h th e in f r a r e d spectrum

11

was re c o rd e d .

C o n sid e ra b le s o lid m a te r ia l rem ained w hich, upon s e v e ra l

r e c r y s t a l l i z a t i o n s from benzene, produced a 20$ y ie ld of w h ite s o lid ,
m.p. 219- 20° and b e lie v e d - to be te tra p h e n y le th y le n e ( l i t . m.p. 220- 1°
( 21 ) ) .

D ip h e n y lm e th an e -d ^ a was s u c c e s s f u lly p rep ared u s in g a procedure
s im ila r to t h a t o f e th y lb en zen e-d a a by re d u c tio n o f benzophenone w ith
lith iu m aluminum d e u te r id e to form benzhydrol-d<x fo llo w ed by co n v ersio n
w ith th io n y l c h lo r id e to benzhydryl c h lo r id e i n 81$ y ie ld from benzo­
phenone.

The b en zh y d ry l c h l o r i d e - ^ was reduced w ith lith iu m d e u te rid e

and lith iu m aluminum d e u te r id e to diphenylm ethane b . p . l i b 0/ 10 mm.,
n|; 0 *= 1 .5 7 7 1 , i n 59$ y i e l d , mass s p e c tro m e tric a n a ly s is :
d-j. = 6 .7 $ , d0 *= 1 .6 $ .

d 2 = 9 1 *7$,

A lso , a f t e r r e c r y s t a l l i z a t i o n from chloroform ,

a 9$ y i e l d o f s y m -te tra phenyl e th a n e , m.p. 206. 5°-*207.0 ° , was o b tain ed
whose in f r a r e d spectrum in d ic a te d th e presen ce o f a C-D a b s o rp tio n peak.
Cumene-dq (P ro ced u re A)

(a) P r e p a ra tio n o f d im e th y lp h e n y lc a rb in o l

To th e G rignard re a g e n t p rep ared from 9 .0 g. (0..37 mole) of
magnesium tu r n in g s and 5 6 .2 g. , 0.325 mole) of m ethyl io d id e in anhydrous

12

e t h e r was added dropw ise lj.2 .0 g. (0.350 mole) of acetophenone i n J4O ml.
o f a b s o lu te e t h e r .

A f te r deco m position w ith a s o lu tio n of JO g. c f

ammonium c h lo r id e in 2.00 m l. o f w ater and work-up w ith k% sodium
b i s u l f i t e s o lu t i o n , th e r e was o b tain ed 35*3 g. ( 80$) o f th e w h ite , lowm e ltin g s o li d c a r b in o l, b . p . 53“?5° / l .5 mm.
(b) P re p a ra tio n o f d im e th y lp h e n y lc a rb in y l c h lo rid e

O

CH3
L

; C1

D im eth y lp h en y lcarb in y l c h lo r id e (22.) was p repared by th e a d d itio n
o f hydrogen c h lo rid e a t 0° to d im eth y lp h en y lcarb in o l in 6f% y ie ld and
a ls o to a lp h a -m e th y ls ty re n e ( 23) in 63% y i e l d , b . p . 53- 6° A ‘2 mm.,

ngo = 1.5212.
(c ) A ttem pted r e d u c tio n o f d im e th y lp h e n y lc a rb in y l c h lo rid e
S e v e ra l ro u te s f o r p re p a rin g cumene-d^ were in v e s tig a te d .

In model

ex p erim en ts o rd in a ry cumene was p rep ared i n 30% y ie ld from th e r e a c tio n
o f p h e n y llith iu m w ith is o p ro p y l brom ide, 61% y ie ld from benzene, is o ­
p ro p y l brom ide and aluminum c h lo rid e {2k) and k3% y ie ld from th e
r e d a c tio n o f d im e th y lp h e n y lc a rb in y l c h lo rid e w ith lith iu m h y d rid e and
lith iu m aluminum h y d rid e .
Cumene-dQ was p rep ared by two m ethods, th e f i r s t b eing th e r e ­
d u c tio n o f d im e th y lp h e n y lc a rb in y l c h lo rid e wi.th lith iu m d e u te rid e and
lith iu m aluminum d e u te r id e fo llo w in g th e procedure o u tlin e d in th e
p r e p a r a tio n o f eth y lb e n z e n e -d a .

This r e s u lte d in a m ixture o f

cumene-dQ and a -m e th y ls ty re n e , w hich, a f t e r in v e s tig a tin g s e p a ra tio n
methods in c lu d in g chrom atography w ith s i l i c a g e l and. o x id a tio n by cold
potassium perm anganate, was s e p a ra te d by b ro m in a tio n o f th e a-m eth y ls ty re n e i n th e dark u s in g carbon t e t r a c h l o r i d e a s solvent..

S in ce only

a 12% y i e l d o f cumene-da* b .p . 58°/27 mm., n£° - I .I 4918, was r e a liz e d
a f t e r t h i s p u r i f i c a t i o n p ro c ed u re, th e fo llo w in g , more g e n e ra l method
was employed w hich i s s im ila r to t h a t o f Brown's ( 2p ) .
Cumene-dc (P ro ced u re C)
(a ) P r e p a ra tio n o f 2-m ethoxy-2 - phenylpro pane
CH.
i 3
c -

t

och3

3

ch3

The g e n e ra l pro ced u re of Z ie g le r (26) was follow ed w herein a-m eth y ls ty re n e and m ethyl a lc o h o l i n a 1 :2 m olar r a t i o were allow ed to stan d
with- s e v e r a l d rops o f 10% p e r c h lo ric a c id a t £0° f o r i|8 h o u rs.

A d ilu te

s o lu tio n o f sodium h y d ro x id e was th e n added and th e o rg an ic la y e r
s e p a ra te d , washed w ith w a te r, d r ie d over anhydrous sodium s u lf a t e and
d is tille d .

A 62% y i e l d o f 2-m ethoxy~2-phenylpropane, b .p . 7 8 °/i3 mm.,

was o b ta in e d .
(b) P r e p a ra tio n o f a -p h e n y lis o p ro p y l potassium

The method of Z ie g le r (26) was fo llo w e d .

A 5>00-ml. th re e -n e c k e d

round-bottom ed f la s k equipped w ith a r e f lu x condenser p ro te c te d w ith a
d ry in g tu b e , a therm om eter, a d d itio n f u n n e l, d ry argon i n l e t and a
h ig h -sp e e d s t i r r e r was swept o v e rn ig h t w ith d ry argon and a ls o h eated
w ith a f r e e flam e to a s s u re rid d a n ce o f w a te r.

U sing a p i p e t t e , 200 ml.

o f h ep tan e ( f r e e d from o l e f in s and w a te r by tre a tm e n t w ith potassium
perm anganate, c o n c e n tra te d s u l f u r ic a c id , d ry in g , d i s t i l l a t i o n and
s to r a g e over sodium m etal) and II4.8 g. (0.38 mole) of potassium m etal
( f r e s h l y c u t u n d e r h ep tan e) were added to th e r e a c tio n f l a s k .
t u r e was h e a te d w ith an e l e c t r i c m antle to 65°.

The mix­

When most o f th e

po tassiu m m etal had m elted , th e s t i r r e r was tu rn e d on and 30.0 g. ( 0.20
m ole) o f 2-m ethoxy-2- phenyl pro pane was added dropw ise over a n in e ty m inute p e rio d .

The c o lo r o f th e m ix tu re changed from th e i n i t i a l grey-

m e ta llic th ro u g h cinnamon to a deep maroon.

The tem p eratu re o f th e

r e a c tio n m ix tu re was m a in tain e d between 614- 72° th ro u g h o u t t h i s p e rio d .
The m ix tu re was s t i r r e d a t 70° f o r s ix h o u rs, th e n allow ed to co o l to
room te m p e ra tu re .

When th e s t i r r i n g was stopped, th e f in e ly - d iv id e d

w in e -c o lo re d o rg a n o m e ta llic began to s e t t l e o u t.

The a -p h e n y liso p ro p y l

po tassiu m was n o t f u r t h e r i s o l a t e d b u t used in s i t u f o r th e p r e p a ra tio n
o f cumene-do,.
( c ) H y d ro ly sis o f a -p h e n y liso p ro p y l potassium
To th e f l a s k c o n ta in in g a -p h e n y liso p ro p y l potassium was added dro p w ise o v er t h i r t y m inutes a s o lu tio n of 8.2 g. (0.U5> mcle) of deuterium
oxide (■> 9 9 .5 # Ds0 , o b ta in e d from th e S tu a r t Oxygen C o., San F ra n c isc o )

15

i n 75 m l. o f te tra h y d ro f u ra n ( f r e s h l y d i s t i l l e d from lith iu m aluminum
h y d rid e ) w ith s t i r r i n g .

The w h ite m ix tu re was allow ed to stan d over­

n ig h t u n d er a b la n k e t o f d ry a rg o n .

The fo llo w in g m orning th e m ix tu re

was h e a te d a t g e n tle r e f lu x and s t i r r e d f o r t h i r t y m in u tes.

Then 20

ml. o f w a te r was added and th e w h ite , s o lid potassium d e u te ro x id e
d is s o lv e d .

The bottom aqueous la y e r was e x tr a c te d w ith 50 ml. of

pentane and th e combined o rg a n ic la y e r s d r ie d o v e rn ig h t over 1$ g. of
anhydrous calcium c h lo r id e .

The c o lo r le s s s o lu tio n was th e n d i s t i l l e d ,

th e f r a c t i o n b o ilin g a t 1 5 0 .5 ° (738 mm.) b ein g c o lle c te d .
1 3 .1 g. ( 57/0 o f cumene, n^° = 1.U903, was o b ta in e d .

A y ie ld of

Mass sp e c tro m e tric

a n a ly s is showed i t to c o n ta in d x = 8 2 .6$, d0 = 1 7 - i$ , no b e ta -d e u te riu m .
Cumene-d£ (P ro ced u re B)

(a ) P re p a ra tio n of p-bromocumene

The pro ced u re o f Brace and Todd (27) was fo llo w e d .

To an i c e -

co o led m ix tu re o f 1±5.0 g . (0.3.3.7 mole) of bromobenzene and 2 .2 g.
(0 .0 1 6 mole) o f powdered anhydrous aluminum c h lo r id e was slow ly ( t h i r t y
m in u tes) added w ith s t i r r i n g 15 g. (0 .1 9 mole) of iso p ro p y l c h lo r id e .
The orange r e a c t i o n m ix tu re was h e a te d on a steam b a th f o r tw enty

16

minutes. The deep-red mixture was poured onto J4O g. of ice and the
lower milky layer separated and washed with concentrated sulfuric acid
eight times (until the acid layer became only slightly colored). The
organic layer was then washed successively with water., dilute sodium
bicarbonate solution and water. After drying overnight over 5 g. of
anhydrous calcium chloride, the mixture was distilled and

29.7

g.

{19%)

of p-bromocumene was collected, boiling at 95”30/9 mm,, nj~c = 1.5V /0
(literature values: b.p.

89 °/lO

mm., ng° = 1.5362 ( 28 ); b.p.

97 - 8 °/ 5

mm.,

ng° = 1.5569 (56)).
(b) P re p a ra tio n and h y d ro ly s is o f th e G rignard re a g e n t from p-bromocumene.
This pro ced u re was p a tte rn e d a f t e r th e method d e sc rib e d by H art (1 7 ).
In a d ry 250-m l. th re e -n e c k e d f la s k equipped w ith a d ry n itro g e n i n l e t ,
a d d itio n f u n n e l, s t i r r e r and r e f lu x condenser f i t t e d w ith a d ry in g tu b e
was p laced 2.1). g, (.0.10 mole) o f magnesium tu rn in g s and 20 ml. of d ry
e th e r.

Then a s o lu tio n o f 30 ml. o f e th e r and 20 g. (0 .1 0 mcle) of

p-bromocumene was added dropw ise so a s to keep th e r e a c tio n m ix tu re a t
g e n tle r e f l u x .

A f te r t h i s a d d itio n th e m ixture was re flu x e d f o r one

ho u r and th e n co o led w ith an ic e b a th .

A s o lu tio n o f 6 .0 g. (0.33 mole)

o f deuterium oxide (9-3+$ D20 , S tu a r t Oxygen C o., San F ra n c isc o ) in 50
m l. o f te tr a h y d r o f u r a n ( f r e s h l y d i s t i l l e d from lith iu m aluminum h y d rid e )
was added dropw ise over a th ir ty - m in u te p e rio d .

The r e a c tio n m ixture

was r e flu x e d two h o u rs, allow ed to s ta n d o v e rn ig h t and r e flu x e d a g a in
one h o u r.

A f te r c o o lin g , th e bottom aqueous la y e r was s e p a ra te d and.

e x tr a c te d w ith two 50-m l. p o rtio n s o f e th e r .

The combined o rg an ic

17

la y e r s .w e re d rie d o v e rn ig h t (anhydrous calcium c h lo r id e ) and d i s t i l l e d
th ro u g h a s h o r t V igreaux column.

The f r a c t i o n which b o ile d from I n ­

l35>° was r e d i s t i l l e d th ro u g h a sm all g la s s h e lic e s -p a c k e d column: th e
f r a c t i o n b o ilin g a t llj.8- 1510 w eighed 11.7 g. {91%), n^° = I.J 4892, and
th e mass s p e c tro m e tric a n a ly s is showed:

d t = 8 2 .1%, d0 = 17*3$, no

be b a-d eu teriu m .
O x id a tio n o f p- and a-deuterocum enes
In o rd e r to e s ta b li s h u n e q u iv o c a lly th e s id e c h a in and r in g
d e u te r a tio n o f th e s e cumenes, th e y were o x id ized to benzoic a c id .

The

pro ced u re g iv en in O rganic S yntheses (29) was fo llo w ed u s in g 10 ml. of
c o n c e n tra te d n i t r i c a c id , 30 m l. of w a te r and 2 .0 g. (0.016 mole) o f
cumene (p - o r a - d e u te r o ) .

The b en zo ic a c id was produced i n a p p ro x i­

m ate ly £0% y i e l d , w h ite n e e d le s r e c r y s t a l l i z e d from w a te r, m .p. 122°.
O x id atio n s o f cumene u s in g a lk a lin e potassium perm anganate o r s u lf u r ic
acid -so d iu m d ichrom ate r e s u l t e d i n v e ry low y ie ld s of benzoic a c id j
th e l a t t e r method was b e lie v e d p a r t i c u l a r l y poor due to th e known a b i l i t y
o f s u l f u r i c a c id to cause deuterium exchange ( 9 ) .
sac-B u ty lb en zen e-d q (P ro ced u re C)

(a ) P re p a ra tio n o f 2 -p h e n y l-2 -b iita n o l

18

T his was p re p are d u s in g a procedure s im ila r to t h a t d e s c rib e d in
th e p r e p a ra tio n o f 2 -p h e n y l-2 -p e n ta n o l.

To th e G rignard re a g e n t p re ­

p ared from 25*0 g . (,1.03 m oles) o f magnesium tu rn in g s and l^O g. (0 .9 6
mole) o f e th y l io d id e was added 60 g. (0 .5 0 mole) o f acetophenone.
The 2-phenyl~2-bubanol th u s produced was f r a c t i o n a l l y d i s t i l l e d and
5 6 .0 g. (?5$) c o lle c te d , b .p . 65-*6°/2.0 mm,, n 20 = I .5187 ( l i t e r a t u r e
v a lu e n 22 = l,5 lf> 8 ) (2 2 ).
(b ) P re p a ra tio n o f 2-methoxy- 2- phenylbutane

The procedure u sed was s im ila r to t h a t employed by W a llis (30)
and Oonant (3 1 ).

In a 500-m l. round-bottom ed f la s k was p laced 60.0 g.

(0.1+0 mole) o f 2 - p h e n y l-2 -b u ta n o l, 100 ml.. (2*5 m oles) o f m ethanol and
3 .6 m l. o f c o n c e n tra te d s u l f u r i c a c id .
stan d o v e rn ig h t a t room te m p e ra tu re .

The m ixture was allow ed to
E th e r (100 m l.) was added t o th e

m ix tu re , fo llo w ed by 100 m l. of s a tu r a te d sodium c arb o n ate s o lu tio n .
The l i q u i d was d ecan ted from th e sodium carb o n ate which p r e c ip ita te d ,
and th e e th e r and some m ethanol removed on a steam b a th .

The bottom

aqueous l a y e r th u s formed was s e p a ra te d and e x tra c te d u s in g two 100-m l.
p o r tio n s o f e t h e r .

The combined o rg an ic la y e r s were f i l t e r e d th ro u g h

anhydrous magnesium s u l f a t e and d rie d o v e rn ig h t over 20 g . of anhydrous
magnesium s u l f a t e .

The m ix tu re was d i s t i l l e d i n v acu o . I4I4.I4. g. ( 68$)

o f 2-m eth cx y -2 -p h en y lb u tan e b e in g o b ta in e d , b .p . 66-7°/5*0 mm..

19

n^ 5 * 1 .1#68 ( l i t e r a t u r e v a lu e s :

b ,p . 6 3 "5°/2-3 mm. (3 0 ), n^ 5 = 1.1+981,

1.1+991 ( 3 2 ) ) .
( c ) C leavage and h y d ro ly s is of 2-m ethoxy-2 - p h enylbutane.
F o llow ing th e pro ced u re o u tlin e d in th e p re p a ra tio n o f cumene-da ,
ll+ *8 g. (O.38 mole) o f potassium m etal and 32.9 g» ( 0 .2 0 mole) of
2-m ethoxy-2-p h en y lb u ta n e were allow ed to r e a c t f o r seven hours a t 68°
fo llo w ed by th e a d d itio n o f 8 .2 g. of deuterium o x id e.

The s e c - b u ty l-

benzene th u s produced was d i s t i l l e d , f r a c ti o n s bein g c o lle c te d b o ilin g
a t ?U°/27 mm., n^° * I.I+89I+.
m e tric a n a ly s is showed:

The y ie ld was 16.5> g. (61+$)j mass spect-ro-

d x = 1+6.6$, d0 = 53*k%, no b e ta - or gamma-

d eu teriu m ato m s,
2 - Phenyl pentane

( a ) P re p a ra tio n of 2 -p h e n y l-2 -p e n ta n o l

o

The pro ced u re was s im ila r to t h a t d e sc rib e d f o r d im eth y lp h en y lc a r b in o l.

The G rig n ard re a g e n t p rep ared from 7£.0 g. (0 .9 6 mole) of

n -p ro p y l c h lo r id e and 2 ^ .0 g. (1 .0 3 mole) o f magnesium tu rn in g s in
e th e r was t r e a t e d a t 0 ° w ith 60.0 g. (0.5*0 mole) of acetophenone in

20

d iy e t h e r .

A f te r s t i r r i n g a t g e n tle r e f lu x f o r fo u r hours and w ork-up

w ith w a te r (n o t a c i d ) , th e r e was o b tain ed 6 6 .6 g. (81$) of 2-phenyl2 -p e n ta n o l, b .p , 7 ^ ~ 6 °/2 .1 ran.,, n®° = l .£ l3 3 ( l i t e r a t u r e v a lu e :
112-3° /lU ram.) (2 2 ),
(b ) D eh y d ratio n o f 2 -p h e n y l-2 -p e n ta n o l and h y d ro g en atio n of r e s u lti n g
o le fin s ,
A ra o d ifica ti.o n o f th e method of Huston and Kaye (33) 'was u se d .
2 - P h en y l-2 - p e n ta n o l was d eh y d rated by h e a tin g a t r e f lu x and c o ll e c t in g
th e w a te r formed i n a d i s t i l l i n g r e c e iv e r .

A f te r rem oval of th e w ater

l a y e r and d ry in g over anhydrous calcium c h lo rid e o v e rn ig h t, th e
r e a c t i o n m ix tu re was d i s t i l l e d .

2-P h e n y l-2 - pentene (and iso m e rs),

b .p ; IQ6-110°/U0 mm., was o b ta in ed in '(b% y ie ld (based on acetophenonej
th e 2 - p h e n y l-2 -p e n ta n o l was n o t p u r if ie d in t h i s p r e p a r a tio n ) .
T his o l e f i n was th e n p a r t i a l l y reduced by adding L.0 g. (1 .7 mole)
o f sodium m e tal to a s o lu tio n o f 37 g* (9 .2 £ mole) o f o le f in i n 37!? ml.
o f a b s o lu te e th a n o l„ A f te r th e sodium had r e a c t e d 300 ml. o f w ater
was added, th e r e s u l t i n g la y e r s s e p a ra te d , th e bottom aqueous la y e r
e x tr a c te d w ith th r e e 100-m l, p o r tio n s o f e th e r and th e combined o rg an ic
la y e r s washed w ith 100 m l. of s a tu r a te d sodium c h lo rid e s o lu tio n .

The

r e s u l t i n g l i g h t y ello w s o lu tio n was shaken w ith 200 ml. of co ld s a tu r a te d
potassiu m perm anganate f o r t h i r t y seco n d s, 20 g. o f sodium b i s u l f i t e
added and. th e la y e r s s e p a ra te d .

The w ater la y e r was e x tr a c te d tw ice

w ith e th e r and th e combined o rg an ic la y e r s d rie d over lf> g* o f anhydrous
sodium s u l f a t e .

The d r ie d m ix tu re was f r a c t i o n a l l y d i s t i l l e d through

a monel h e lic e s -p a c k e d column, 31 g. (81|$) b ein g c o lle c te d a t

21

6y.£-68.0°/9 mm,, nj^0 = 1.U92Y, However, when a sample of this product
was p u t th ro u g h gas chrom atography a p p a ra tu s , th e p resence of a sm all
amount o f s l i g h t l y h ig h e r b o il i n g im p u rity was a p p a re n t.

T his was

p ro b ab ly 2 -p h e n y l-2 -p e n te n e , an a u th e n tic sample of w hich, when putth ro u g h th e gas chrom atography a p p a ra tu s under th e same c o n d itio n s ,
caused a peak to be reco rd e d a t th e same tim e i n t e r v a l as th e im p u rity .
To remove t h i s o l e f i n , th e m ix tu re was placed in a 500-m l. h y d ro g en atio n
b o t t l e and 123 m l. o f a b s o lu te e th a n o l w ith 0.118 g. o f platinum d io x id e
was added.

A f te r th r e e and o n e -h a lf hours of h y d ro g en atio n , th e

p re s s u re had dropped from $1.1 to

>0 p . s . i . and ceased to d e c re a se .

Work-up gave 2i+.2g., b .p . l87~8°(YUU mm.), n~° « I .I 4879 ( l i t e r a t u r e
v a lu e :

n~° = 1 . U876) ( 2 8 ) , o f c h ro m a to g ra p h ic a ily -p u re 2-p h e n y lp e n ta n e .

2 - P henylpentane-dq (P ro ced u re C)

( a ) P re p a ra tio n o f 2-m ethoxy-2-phenylpentane

This was p rep ared in $6% y ie ld from $0 .0 g. (0 .3 0 mole) of
2 -p h en y l-2 ~ p en tan o 'l, 123 m l, ('3*0 m oles) o f m ethanol and 2 .6 m l. of
s u l f u r i c a c id a s d e s c rib e d i n th e p r e p a ra tio n o f 2 -m ethoxy-2-phenylbutane.

22

P ro d u ct b o i l i n g from 66-9°/2.1+ mm., n^° = 1.1+959-1.1+982, was c o lle c te d .
(b ) C leavage and h y d ro ly s is o f 2 -m ethoxy-2-phenylpentane.
The same p ro ced u re as t h a t u sed f o r p re p a rin g cumene-da was
employed.

A f te r 8 .2 g. (0 .2 1 mole) of potassium m etal and 1 9 .6 g.

(0 .1 1 mole) o f 2 -meth oxy- 2- ph eny 1 pen ta n e had been p e rm itte d to r e a c t a t
68° f o r tw elv e ho+irs, 5»0 g. (0 .2 5 mole) o f deuterium oxide was added.
The 2 - p h enylpentane th u s produced was d i s t i l l e d , th e f r a c t i o n c o lle c te d
b o ilin g a t 7 3 ° /l2 mm., n^° *= 1 . 1+880, n*5 = 1.1+857, weighed 1 0 .0 g. (6 1 $ ).
Mass s p e c tro m e tric a n a ly s is showed:

d 2 = 61+. 1%, d0 *= 3 5 -9%, no b e ta - ,

gamma- o r d e lta -d e u te riu m atom s.

3-Phenylpentane

V
r
7
C
\

c h 2c h 3

//

CHj.CHj

A pro ced u re s im ila r to t h a t o f P in e s, V esely and I p a t i e f f (3l+) was
fo llo w e d .

In a t y p i c a l ru n , a 200-m l. s t a i n l e s s - s t e e l Magne-Dash

a u to c la v e was charged w ith 1+6 g. (0 .5 0 mole) of to lu e n e , 0.89 g. (0.023
m ole) o f potassiu m m etal and 1+.1+ g. ( 0 .1 8 mole) o f sodium h y d rid e .
The a u to c la v e was flu s h e d s e v e ra l tim es w ith dry n itr o g e n .

E th y len e

was th e n added to a p re s s u re o f 810 p . s . i . (by th e lo s s in w eig h t of
th e e th y le n e ta n k , i t was determ ined t h a t 31 g. (1*1 m oles) of e th y le n e
was ad d ed ), th e m agnetic s t i r r e r a d ju s te d to o p e ra te a t m oderate speed
and th e a u to c la v e h e ated e l e c t r i c a l l y to 190°.

A f te r e ig h t h o u rs, th e

23

p re s s u re had dropped to 61+0 p . s . i .

The a u to c la v e was v en ted and a

stream o f n itro g e n passed th ro u g h f o r s e v e ra l h o u rs.

A f te r th e m ixture

i n th e bomb was f i l t e r e d th ro u g h g la s s wool and 100 ml. of benzene
used t o r i n s e th e a u to c la v e and g la s s woo]., th e f i l t r a t e and benzene
w ashings w ere washed w ith 100 m l. o f w a te r, d rie d overnight, over 10 g.
o f anhydrous calcium, c h lo r id e and d i s t i l l e d a t reduced p re s s u re th ro u g h
a g la s s h e lic e s -p a c k e d column.

F r a c tio n s were c o lle c te d which c o r r e s ­

ponded to to lu e n e , n -p ro p y lb en zen e, 3 "phenylpsntane and 3 - e th y l- 3 p h e n y lp e n ta n e .

A f r a c t i o n b o ilin g a t 53“ 8 °/6 mm., w eighing 9*1 g* (1 2 $ ),

n^° = 1.1+881+ ( l i t e r a t u r e v a lu e :

n^° = 1,1+877) (2 8 ), was c o lle c te d as

3 - phenyl p entane and a f r a c t i o n b o ilin g a t 78- 8l ° /6 mm. w eighing '13-0 g.
(15/6) was c o lle c te d a s 3 ~ e th y l-3 ~ p h en y lp en tan e.
3 - phenylpentane-dQ (P ro ced u re C)

(a ) P r e p a ra tio n o f 3 ~ p h e n y l-3 -p e n tan o l

F ollow ing th e pro ced u re d e s c rib e d i n th e p re p a ra tio n of 2 -p h en y l2 -p e n ta n o l, e th y l magnesium bromide (p re p a re d from 25 g. (1.01+ m oles)
of magnesium tu rn in g s and 105 g* (0 .9 6 mole) of e th y l bromide) was

2k

t r e a t e d w ith 67 g. (0 .5 0 mole) o f propiophenone.
p e n ta n o l produced was c o lle c te d a t
1 .^1 2 6 ( l i t e r a t u r e v a lu e :

7U°/2 . U ram.,

The 3 - p h e n y l-3-

nj~5 =

n^° = 1 .5152,

b .p . 8 5 - 8 ° /l mm., n^5 = 1.5128) (35) and

w eighed 5 6 .8 g. (70%).
(b ) P r e p a ra tio n o f 3~m ethoxy-3-phenylpentane.

/

CH.,CH3
“

C-OCH3
\
3
c h 2c h 3

In a manner s im i l a r to t h a t d e sc rib e d in th e p re p a ra tio n of 2-methoxy2 -p h en y lb u ta n e , 5 9 .0

g.

(9 .3 1 mole) o f 3~phenyl-3- pent.anol, 120 m l.

(3 .0 m oles) of m ethanol and 2 .6 ml. of s u lf u r i c a c id were allow ed to
sta n d f o r th re e d ay s.

Upon d i s t i l l a t i o n , 22.0

g.

(hl%) o f 3~methoxy-3-

p h en y lp en tan e, b .p . 7L-5°/3«5 mm., n^° = 1.5030 was c o lle c te d .
(c) C leavage and h y d ro ly s is o f 3-m ethoxy-3-phenyl p e n ta n e .
U sing th e procedure d e s c rib e d u n d er th e p re p a ra tio n of cumene-da,

18. k g- (0.103 mole) of 3"methoxy-3-phenylpentane and

(.(

g. (0.20 mole)

of potassium metal were permitted to react at 68° for eleven hours,
after which 6.2 g. (0 . 3 1 mole) of deuterium oxide was added and the
resulting 3“phenylpentane distilled.

The fractions boiling at

6/.5-68.5°/19 mm., nj~° = l.lj.876 , weighed

8.3

g. (56$). Mass spectro-

metric analysis indicated: dx «= 53*3$, d.0 = 1*6.7$, no betadeuterium atoms.

or

gamma-

25

2-M e th y l-3 - phenylbutane
A ttem pts to p rep a re t h i s compound, by re d u c tio n o f 2 -m eth y l-3 p h e n y l-2 -b u ten e r e s u lte d i n m ix tu res o f th e o l e f in and s a tu r a te d hydro­
carb o n .

The hydrocarbon was p rep ared u s in g P rocedure C, o rd in a ry

w a te r b e in g used in s te a d of deu terium oxide in th e h y d ro ly s is s te p .
(a )

P r e p a ra tio n o f 3 -m e th y l-2 -p h e n y l-2 -b u ta n o l.

C-CH(CH3 )

.■ T his a lc o h o l was p rep ared i n a s im ila r manner to t h a t d e s c rib e d
f o r 2 -p h e n y l-2 -p e n ta n o l.
75,0

To iso p ro p y l magnesium c h lo r id e ; formed from

g. ( 0 .9 6 mole) o f iso p ro p y l c h lo rid e and 25-0 g. (1.03 m oles) of

magnesium tu rn in g s ) was added 60 g. (0*50 mole) of acetophenone.
a lc o h o l was o b ta in e d i n

The

y i e l d (UU-3 g.)> b .p . 76- 7 ° / 2 .5 mm.,

n^° = 1 .5 l8 9 ( l i t e r a t u r e v a lu e s :

7 7 ,0 -7 7 . 5 ° / 2 .6 -2 .9 mm., n£5 = 1.5137)

(3 6 ).
(b)

P re p a ra tio n o f 2 -m eth o x y -3 -m ethyl-2-phenylbutane.

c- c h ( c h 3 )

OCHo

F o llo w in g th e pro ced u re o u tlin e d in th e p r e p a ra tio n of 2-methoxy2 - p h en y lb u tan e, 3 9 .6 g. (0 .2 i| mole) of 3 -m e th y l-2 -p h e n y lb u ta n -2 -o l,
100 m l. ( 2 .5 m oles) of m ethanol and 2 .5 ml. of s u l f u r i c a c id a f t e r

26

s ta n d in g th r e e days y ie ld e d 22.3 g. {$2%) of 2-m ethexy-3 -m eth y l-2phenylfcutan.e, b .p . 72-5°/l+.0 mm., ng° = 1.1+992.
( c ) C leavage and h y d ro ly s is o f 2 -m ethcxy-3 -m eth y l-2 -p h en y lb u tan e.
To 1 1 .8 g. (0 .3 0 mole) o f potassium m etal and 27.0 g. (0 .1 5 mole)
o f 2-methoxy-3** m e th y l-2 - phenylbutane in dry h ep tan e (which had been
allo w ed to r e a c t a t 68° f o r s ix h o u rs) was added 10 ml. of w a te r in
75 m l. o f te tr a h y d r o f u r a n .

Work-up gave 1 $ .6 g. {'(1%) of 2-m ethvl-3-

p h en y lb u tan e, b .p , 63°/8«8 mm.j n£° = 1.1+912 ( l i t e r a t u r e v a lu e s :

b .p .

6 6 .2 ° /l0 mm.? n ^ 0 = 1.1+86) ( 28) .
3-M e th y l-2 - p h en y lb u tan e-d a (P rocedure C)

C-CH(CH3 ) 2
D
U sing th e pro ced u re d e s c rib e d i n th e p re p a ra tio n of cumene-da,
20.8 g. (0 .1 2 mole) of 2-m ethoxy-3“m ethyl-2~ phenylbutane and 8.3 g.
(0 .2 1 mole) o f p otassium m etal w ere allow ed to r e a c t f o r e ig h t hours
a t 6 8 °.

Then

g* (0 .2 6 m ole) o f deuterium oxide was added and th e

r e s u l t i n g 3-m e th y l-2 - phenylbutane c o lle c te d as th o se f r a c t i o n s b o ilin g
from 69 .5 "7 0 .0 ° /1 2 ram., nj~° ~ 1.1+903Mass s p e c tro m e tric a n a ly s is showed:
o r gamma-deuterium atom s.

The y ie ld was 1 2 .1 g. ( 83$ ) .
d x * (0.1%, d0 «= 29.1$, no b e ta -

27

2 , 2 -D im eth y l-3 -p h en y lb u tan e

C-C(CH3 ) 3

This procedure i s s im ila r to t h a t employed by Schm erling and West
(3 7 ).

A o n e - l i t e r round-bottom ed th re e -n e c k e d f la s k equipped w ith a

s t i r r e r , co n d en ser, a d d itio n fu n n e l and a dry argon i n l e t was th o ro u g h ly
d r ie d u s in g a f r e e fla m e .

To th e G rignard re a g e n t from th e io d in e -

i n i t i a t e d r e a c tio n o f 20 g. (0 .8 2 mole) o f c le a n magnesium tu rn in g s
w ith 92 g. ( 1 .0 m ole) o f t e r t - b u t y l c h lo r id e i n anhydrous e th e r was
added dropw ise a t 0 ° a s o lu tio n o f 90 g. ( 0 .50 mole) o f a -p h e n e th y l
brom ide (p re p a re d i n 8l$S y ie ld from a-m eth y lb en zy l a lc o h o l and phosphor­
ous trib ro m id e ) i n $0 ml. of d ry e th e r .

Work-up a s u s u a l, u s in g d i l u t e

h y d ro c h lo ric a c id f o r h y d r o ly s is , gave 20 g. o f p ro d u c t, b .p . y 6 -8 °/9 mm.,
n^° *= 1.1*973•

A h ig h e r b o il i n g f r a c t i o n ( b .p . 130-160° /5 mm.) was a ls o

c o lle c te d which c r y s t a l l i z e d upon c o o lin g .
m ethanol gave w h ite n e e d le s , m .p. 123-1*° •
be 2 ,3 -d ip h e n y lb u ta n e ( l i t e r a t u r e v a lu e :

R e c r y s ta lliz a ti o n from
T his s o lid was b e lie v e d to
m .p. 1 2 6 ') (3 8 ).

The li q u i d

f r a c t i o n was r e flu x e d over sodium m etal f o r one h o u r, th e n f r a c t i o n a l l y
d is tille d .

P roduct b o i lin g from 63-lt°/5 mm., d| 5 = O .892, n~° = 1.1*951

( l i t e r a t u r e v a lu e s :

5 0 - l ° / l mm.,

= 1.1*950) ( 3 /) , w eighing 1 0 .5 g-

(13$) was c o lle c te d a s 2 , 2 -d im eth y l~ 3 -p h en y lb u tan e.

28

2 , 2-D im ethyl-3™ phenylbutane-da (P rocedure C)

CH.
c- cvch3 ) 3

D
(a ) P re p a ra tio n o f 3 , 3™ dim ethyl-2-phenylbutan-2-ol
CHl3
a

C-C(CH3 ) 3
I
OH

The g e n e ra l method o u tlin e d f o r th e p re p a ra tio n of 2-p h e n y l-2p en tan o l was fo llo w e d .

To t e r t - b u t y l magnesium c h lo rid e (p rep ared from

180 g . (1 .9 5 m oles) o f t e r t - b u t y l c h lo r id e and $0 g. ( 2.06 mole) of
magnesium tu rn in g s ) was added 125 g. (l.o U mole) of acetophenone.
D i s t i l l a t i o n th ro u g h a V igreaux column gave 9 1 -h g- o f p ro d u ct b o ilin g
a t 53”"9 0 °/1 .2 mm.

R e d i s t i l l a t i o n th ro u g h a packed column gave k l . 2 g.

(23$) o f a p ro d u c t, b .p . l l ° / l . 2 mm., n^° = 1.516U.
(b ) P re p a ra tio n o f 2-m ethoxy™ 3j3™ dim 3thyl-2-phenylbutane.
CH.
C-C(CH3 ) 3
och3

An a tte m p t to p re p a re t h i s compound from 3 ,3 “d im eth y l-2 -p h e n y lb u ta n - 2 -o l an.d m ethanol r e s u lte d on ly in reco v ery o f s t a r t i n g m a te r ia l.
The e th e r was p re p a re d , however, em ploying a method s im ila r to t h a t of
Z e is s (3 2 ).

In a dry o n e - l i t e r th re e -n e c k e d round-bottom ed f la s k

29

equipped w ith an a d d itio n fu n n e l, condenser, d ry argon i n l e t and h ig h ­
speed s t i r r e r was p laced UOO m l. of anhydrous benzene and 3 6 . h g.
(0.20U mole) of 3 ,3 -d im e th y l-2 -p h e n y lb u ta n -2 -o l.

F r e s h ly - c u t potassium

m etal ^8.1 g .j 0.21 mole) was th e n added to th e w a te r-w h ite s o lu tio n .
R eflux f o r th re e days was n e c e ssa ry f o r th e red potassium s a l t to be
produced.

A f te r t h i s p erio d 85*0 g. (0 .6 0 mole) o f m ethyl io d id e was

added and th e m ixture re flu x e d w ith s t i r r i n g f o r tw enty h o u rs .

A f te r

th e sodium io d id e was allow ed to s e t t l e , th e s o lu tio n appeared alm ost
c o l o r le s s .

W ater (120 m l.) was added to th e s t i r r e d m ix tu re , th e

bottom aqueous 3.ayer s e p a ra te d and e x tra c te d w ith 200 ml. of e th e r ,
and th e combined o rg a n ic la y e r s d rie d over 20 g. of anhydrous magnesium
s u lf a te .

S olvent was removed u s in g a steam b a th and th e y e llo w re sid u e

f r a c tio n a te d , y ie ld in g 2£.£ g. {'{&%) of 2 -m eth o x y -3 ,3 -d im eth y l-2 -p h en y lb u tan e , b .p . 79“ 8U°/3 *3 mm., n^° = 1 . ^ 0 i |l - l .5065.
,c) C leavage and h y d ro ly s is of 2 -m eth o x y -3 ,3 -d im eth y l-2 - p h en y lb u tan e.
Follow ing th e procedure d e sc rib e d in th e p r e p a ra tio n of cumene-da,
25.5 g- (.0.133 mole) o f 2-m ethoxy-3,3“ d im e th y l-2 -phenylbutane and 10.3
g. ^0.26 mole) o f potassium m etal were allow ed to r e a c t f o r t h i r t e e n
h ours a t 68°.

Then y .£ g. (0 .3 8 mole) o f deuterium oxide was added

and th e r e s u l t i n g 3 , 3 -d im ethyl~ 2-phenylbatane d i s t i l l e d .

The f r a c t io n s

b o ilin g from 6U -6°A -b mm., n*° *= l . l t f 5 2 , and w eighing 11.8 g. ($$%)
were combined.

Mass s p e c tro m e tric a n a ly s is gave d x = £ l.L $ , d0 * U8.6#,

no b e ta - o r gamma-deuterium ato m s.

30

Hig h S u rface Sodium (HSS)
F ollow ing th e g e n e ra l procedure d e sc rib e d i n th e b u l l e t i n ’-High
S u rfa c e Sodium on I n e r t S o lid s" ( 3 ? ), 2£ g. of dry N o rite and 2 .5 g*
o f f r e s h l y - c u t sodium m etal were s t i r r e d to g e th e r a t 160° f o r f o r t y
m inutes and th e n allo w ed to co o l to room te m p e ra tu re .

The HSS was

removed th ro u g h a "goose-neck" w ith a 2I4./I4.O sta n d a rd ta p e re d j o i n t at.
one end and a 1U/35 j o i n t a t th e o th e r .

The sm a lle r j o i n t was tap ed to

sm a ll, p re v io u s ly wei.ghed, sample v i a l s and th e la r g e r j o i n t was f i t t e d
to th e r e a c tio n f l a s k .

By t i l t i n g th e com plete a p p a ra tu s , th e IBS

could be made to e n te r th e v i a l s , ap p ro x im ately one gram b ein g placed
in each v i a l .
High S u rfac e Potassium (HSP) was s im ila r ly p rep ared .

B. Exchange S tu d ie s
In p r in c ip l e , th e procedure c o n s is te d in h e a tin g a m ixture of an
a - d e u te r a te d a lk y la ro m a tic and two n o n -d e u te ra te d a'lk y laro m atics in
th e p resen ce o f an a p p ro p ria te c a t a l y s t , w ithdraw ing samples p e r io d ic ­
a l l y , s e p a ra tin g th e s t r u c t u r a l l y pare components and a n a ly z in g each
f o r i t s deuterium c o n te n t.

A v a r i e t y of c o n d itio n s was s tu d ie d b e fo re

a s u it a b l e pro ced u re was developed which gave s a ti s f a c t o r y k in e t ic
re s u lts .
A n a ly tic a l P rocedure
Because a mass sp ec tro m e te r was n o t a v a ila b le f o r r o u tin e a n a ly s e s ,
th e d eu teriu m c o n te n t of th e v a r io u s hydrocarbons, a f t e r being s u b je c te d

31

to exchange c o n d itio n s , was d eterm ined u s in g th e C-D s tr e tc h in g freq u en cy
in th e i n f r a r e d .

Samples o f a l l d e u te ra te d hydrocarbons were analyzed

mass s p e c tr o m e tr ic a lly by Mr. S , Meyerson, S tan d ard O il Company (In d ia n a ) ,
W h itin g , In d ia n a.

The in f r a r e d s p e c tra o f s o lu tio n s o f th e s e d e u te ra te d

hydrocarbons i n carbon t e t r a c h l o r i d e were reco rd ed u sin g a Perkin-E lm er
Model 21 double-beam in f r a r e d sp ectro p h o to m eter w ith sodium c h lo rid e
c e l l s o f 0.£l5> mm. w id th .
I t was o r i g i n a l l y in te n d e d to u se ethylbenzene-dcc as th e deuterium
so u rce and to compare th e r a t e o f se lf-ex ch an g e o f eth y lb en zen e w ith
th e r a t e o f exchange w ith a n o th e r hydrocarbon.

A lthough th e r e a re

a p p r e c ia b le d if f e r e n c e s i n th e in f r a r e d s p e c tra of th e pure o rd in a ry ,
mono-a, and d i - a , a d e u te ra te d eth y lb en zen es (se e F ig u re s 1$ and 1 6 ), a
s u it a b l e a n a l y t i c a l method could n o t be worked out f o r m ix tu res of th e se
th r e e due to th e o v erla p p in g o f t h e i r C-D a b s o rp tio n peaks.

A s im ila r

s i t u a t i o n was encountered i n th e case of o rd in a ry , mono-a and d i - a ,a
diphenylm ethane.

Hence, i t was d ecided to u se eth y lb en zen e-d a m erely

a s a source o f deuterium and to a llo w two d i f f e r e n t hydrocarbons to
compete f o r th e deuterium i n th e e th y lb e n z e n e -d ^ .
C a lib r a tio n c u rv es were p rep ared c o r r e la ti n g th e deuterium c o n te n t
o f th e v a rio u s hydrocarbons w ith th e i n t e n s i t y of th e C-D s tr e tc h in g
fre q u e n c y in th e in f r a r e d re g io n n e a r U.'/ m icrons.

Samples of known

deu teriu m c o n te n t were p rep ared by d i l u t i n g th e mass s p e c tra n a liz e d
d e u te ra te d sam ples w ith o rd in a ry hydrocarbon.

The s o lv e n t was carbon

t e t r a c h l o r i d e (M a llin c k ro d t " A n a ly tic a l R eagent") p u r if ie d (Uo) by
r e f lu x in g over m ercury m e tal f o r th re e hours and under a s o lu tio n of

32

100 g. o f sodium hydroxide in 350 ml. o f w ater and 100 m l. of 9$%
e th a n o l f o r two h o u rs, w ashing th r e e tim es w ith w a te r, once w ith d i l u t e
s u l f u r i c a c id and th re e tim es w ith w a te r, d ry in g over anhydrous calcium
c h lo r id e and c a r e f u l l y d i s t i l l i n g from phosphorus pentoxide th rough a
tw e n ty -fo u r in c h g la s s h e lic e s -p a c k e d column (th e f i r s t 1$% b ein g d is ­
ca rd ed ).

U su a lly th e volume r a t i o o f hydrocarbon to carbon t e t r a ­

c h lo r id e was 1 :1 .1 ;,

Under th e exchange c o n d itio n s employed, seldom d id

a hydrocarbon g a in more th a n 1%% deuterium .

Thus, most c a l i b r a t io n

cu rv es were p re p a re d u s in g sam ples c o n ta in in g from 0-1$% deuterium .
The g e a rs o f th e in f r a r e d in stru m e n t were s e t to sp read th e re g io n
o f i n t e r e s t (3 * 0 -6 .0 m icrons) over a 30 cm. ran g e.

A t 3.000 m icrons,

w ith b o th c e l l s f i l l e d w ith s o lv e n t and in p la c e , th e in stru m e n t was
a d ju s te d to th e fo llo w in g s p e c if ic a tio n s :
S l i t w idth

990

Response

1

Per c e n t T ransm ission
Gain
S u p p ressio n
F ilte r
Speed
S l i t c o n tr o ls
Scanning c o n tr o l

95
5
2

Auto
U
Auto
For

The spectrum o f s o lv e n t v e rs u s s o lv e n t was reco rd e d .

The 0%

tra n s m is s io n l i n e was o b tain ed by c lo s in g th e sample beam window and
re c o rd in g th e spectrum o f s o lv e n t in only th e re fe re n c e beam ( t h i s a ls o

33

c o in c id e d w ith th e maximum a b s o rp tio n of th e C-H peak a t 3 -2 -3 -5 >0 •
The s p e c tra o f s o lu tio n s c o n ta in in g known and v a ry in g amounts of
d e u te ra te d hydrocarbon w ere re co rd ed and th e r a t i o of th e p e rc e n t
tra n s m itta n c e of th e s o lv e n t to th e p e rc e n t tra n s m itta n c e o f th e
sample ( I q/ i ) was d eterm in e d .

The lo g a rith m o f t h i s r a t i o ( o p tic a l

d e n s ity ) was p lo tte d a g a in s t p e rc e n t deuterium c o n te n t to o b ta in a
l i n e a r r e l a t io n s h i p from which th e p e rc e n t deuterium in unknown samples
was d eterm in ed .

Table I I g iv es a t y p i c a l example showing q u a n titie s

o f hydrocarbons used i n th e p r e p a ra tio n of a c a l i b r a t io n c u rv e.
The volume r a t i o o f h y d ro carb on/carbon te tr a c h lo r id e o f Is 1.1+ was
u sed f o r th e c a l i b r a t i o n c u rv es o f a l l d e u te ra te d hydrocarbons except
2 , 2 -d im e th y l-3“ p h enylbutane, f o r which a r a t i o of 1 . 80:0 .0 6 was u se d .
S e v e ra l f a c t o r s e n te re d in to t h i s ch o ice of 1 : 1 .It.

Forem ost, when a

m ix tu re was s e p a ra te d u s in g th e Vapor F ra c to m e te r, volumes of only
s l i g h t l y over 0 .1 m l. w ere c o lle c te d ( e s p e c ia lly when only a sm all
c e n te r " c u t” was made to in s u r e u l t r a - c l e a n s e p a r a tio n ) .

S ince a volume

o f 0 .2 0 m l. was re q u ire d to f i l l th e in f r a r e d c e l l s , a volume of 0.100
m l. o f hydrocarbon and O.li+0 m l. o f carbon t e tr a c h lo r id e ( t o t a l volume
0 .2 U0 m l.) r e s u l t e d i n s u f f i c i e n t q u a n tity to f i l l th e c e l l s and a ls o
produced in te n s e s p e c tra ca p ab le of d is c e rn in g sm all p e rcen tag es o f
d eu teriu m .

Table I I I g iv es th e a n a l y t i c a l d a ta used i n th e p r e p a ra tio n

o f th e c a l i b r a t i o n curve (F ig u re 1) f o r sec-b u ty lb en zen e-d G,

O ther

c a l i b r a t i o n cu rv es were s im i l a r l y p rep ared and a re reco rd ed i n th e
appen d ix o f th e t h e s i s (F ig u re s 1 0 - lli) .

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PREPARATION

OF

sec-BUTYLBENZENE SAMPLES OF KNOWN, VARYING DEUTERIUM
FOR THE CONSTRUCTION OF THE CALIBRATION CURVE

CONTENT

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35

TABLE I I I

CALCULATION OF OPTICAL DENSITY FROM C-D BAND AT U.68 MICRONS FOR
sec-BUTYLBENZENE (2 .6 5 M) EN CARBON TETRACHLORIDE

Sample

■

P e rcen t D

I q/'I

D[log ( I 0/ l ) ]

1

0 .0

1.105

0.0U3li

2

2.3

1.180

0 . 0/19

3

U.7

1.267

0.1028

h

9 .3

1 . J4I4.2

0.1590

5

1 8 .6

1.885

0 .2 /5 3

6

28,0

2 -I4J4O

O.3 8 /U

F ig u re 1 . P e rc e n t deu teriu m c o n te n t of m ix tu res o f s e c -b u ty lbenzene and se c -b u ty lb e n z e n e -d n i n “carbon t e t r a c h l o r i d e v s .
o p t i c a l d e n s ity a t U ,68 m icro n s. (C o n c e n tra tio n o f hydrocarbon =
2 . 6 5 Mv)
o.Uo

Optical

D en sity

0 .3 0

0.20

0 .10

P ercen t Deuterium

36

37

S e p a ra tio n P rocedure
Because o f th e expense of th e d e u te ra te d compounds and u n a v a il­
a b i l i t y o f some o f th e o rd in a ry hydrocarbons, only sm all q u a n titie s
w ere u sed i n th e exchange r e a c tio n .

Thus, i t became n e c e ssa ry to

dev elo p a procedure f o r s e p a ra tin g a three-com ponent hydrocarbon mix­
tu r e whose t o t a l volume was abo u t one m i l l i l i t e r .
The f i r s t hydrocarbon chosen f o r exchange w ith ethylbenzene was
d iph en y lm eth an e.

I t was f e l t t h a t th e s e m ight be se p a ra te d u s in g a

chrom atographic column.

A lthough a c tiv a te d alum ina proved u n s u c c e s s fu l,

80 mesh s i l i c a g e l r e a d ily se p a ra te d th e two u s in g carbon t e t r a c h l o r i d e
a s th e e lu e n t.

The p ro g re ss of th e hydrocarbons through th e column

was follow ed by ta k in g th e in f r a r e d spectrum of bach 2-3 m i l l i l i t e r
f r a c t i o n a s i t was c o lle c te d .

However, t h i s tech n iq u e d id n o t e a s ily

le n d i t s e l f t o th e s e p a ra tio n of hydrocarbons more c lo s e ly r e l a t e d in
s t r u c t u r e , e s p e c ia lly a three-com ponent hydrocarbon m ix tu re, so a n o th e r
method was sought f o r accom plishing t h i s .
t t appeared t h a t gas chrom atography was p a r t i c u l a r l y a t t r a c t i v e
f o r s e p a ra tin g such m ix tu res an d , a c c o rd in g ly , a Perkin-E lm er Model
Vapor F rac to m e te r was remodeled and adapted f o r t h i s purpose.

A f te r

c o n s id e ra b le e x p e rim e n ta tio n , b e s t r e s u l t s were o b tain ed u s in g an
asb esto s-w rap p ed e l e c t r i c a l l y - h e a t e d s e c tio n o f o n e -e ig h th in ch copper
tu b in g which Extended s ix in c h e s from th e e x it s id e o f th e in stru m e n t
and to w hich was s e a le d a 10/30 sta n d a rd ta p e re d male j o i n t .

Only

s e v e ra l seconds e la p se d between th e tim e a s ig n a l was reco rd ed and th e
tim e th e sam ple g iv in g r i s e to t h a t s ig n a l appeared a t th e e x i t .

38

The sam ples w ere c o lle c te d in s p i r a l tr a p s whose dim ensions a r e shown
in F ig u re 2 ,

The e x i t end o f th e s p i r a l t r a p was p ro te c te d w ith a

d ry in g tu b e c o n ta in in g D r i e r i t e .

These t r a p s , which were cooled in

l i q u i d a i r d u rin g th e c o l l e c t i o n , proved q u ite e f f i c i e n t f o r g a th e rin g
n e a r - q u a n t i t a t i v e y ie ld s o f th e sam ples.

A lso , t h i s method a ffo rd e d a

c le a n s e p a ra tio n f o r th e hydrocarbons u se d .

The most d i f f i c u l t com­

pounds to s e p a ra te from each o th e r were ethylbenzene and cumene,
a lth o u g h even t h i s was done w ith l i t t l e d i f f i c u l t y as shown in F ig u re 3*
O r ig in a lly , a tw o-m eter o n e -fo u rth in ch a n a l y tic a l column was used
c o n ta in in g P erkin-E lm er packing ty pe ’’A" (d id e c y l p h th a la te on f i r e b r i c k ) .
However, s in c e t h i s column was r e s t r i c t e d to samples of about 0.05 m l.,
o f te n f i v e to s ix ru n s were n e c e s sa ry in o rd e r to c o l l e c t a s u f f i c i e n t
volume f o r q u a n tita tiv e in f r a r e d .

This s i t u a t i o n was rem edied w ith th e

a c q u i s it i o n of a th re e -m e te r o n e-in ch p r e p a ra tiv e column w ith packing
of type ,;A'? and a s im ila r column of type "0" ( s ilic o n e p ac k in g ).

These

p r e p a ra tiv e columns p e rm itte d th e c le a n s e p a ra tio n of s e v e ra l m i l l i ­
l i t e r s of hydrocarbon m ix tu re in from two to th r e e h o u rs.

The c a r r i e r

gas used w ith th e s e l a r g e r columns was oil-pum ped n itro g e n and was
u s u a lly re g u la te d from 5-10 p . s . i . th rough th e column.
The column te m p era tu re was o p erated n e a r 100° u n t i l th e ethylbenzene
was c o lle c te d , th e n o fte n r a is e d to 110-130° to h a s te n th e passage of
th e rem aining com ponents.

To in s u re a c le a n s e p a ra tio n , from two to

s ix m inutes w ere allow ed to e la p se from th e tim e a peak began to appear
on th e re c o rd e r u n t i l a t r a p was put in p lace to s t a r t th e c o lle c t io n
of t h a t component.

L ik ew ise, th e t r a p was removed s e v e ra l m inutes

39
10/30 Standard. Tapered j o i n t s

13 cm.

8 ram. P yrex tu b in g

6 cm.

lli mm. Pyrex tu b in g

F ig u re ?..

S p ir a l t r a p used w ith Vapor F rac tc m e te r f o r
sample c o l l e c t io n .

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b e fo re th e l a s t o f t h a t hydrocarbon had passed th rough th e d e te c to r .
F u rth er^ th e e x i t tu b e was r in s e d w ith aceto n e and wiped c le a n b e fo re
each t r a p was secu red in p la c e .

As a t r a p was removed, a 10/30 male

s ta n d a rd ta p e re d plug was q u ic k ly in s e r te d in th e e n tra n c e end o f th e
t r a p an d , w ith th e d ry in g tu b e s t i l l on th e e x i t end, th e tr a p was
allow ed to reach room tem p eratu re (h asten ed by warming in a stream of
w a te r ) ,

Then tfye d ry in g tube was removed and an o th er plug in s e r te d in

i t s p la c e .
.A f te r th e l iq u id had d ra in e d to th e bottom of th e tr a p , th e d e s ire d
volume ( u s u a lly 0.100 m l.) of compound was withdraw n u sin g a 0 .2 ml.
p ip e tte g rad u a te d to 0.0 0 5 m l., th e a p p ro p ria te amount (u s u a lly 0 . 11*0
m l.) o f p u r if ie d carbon t e t r a c h l o r id e added, th e in f r a r e d spectrum of
th e m ix tu re reco rd ed and th e p ercen t deuterium determ ined u s in g th e
c a l i b r a t i o n curve p rep ared f o r t h a t hydrocarbon.
Exchange Experim ents
(a ) A pparatus
An a u to c la v e o f th e ty p e used in p rev io u s exchange r e a c tio n s ( 17)
d id n o t r e a d i l y le n d i t s e l f to th e sam pling n e c e ssa ry f o r k in e tic
m easurem ents n o r d id th e tem p eratu re c o n tr o l seem ad e q u a te .

A ccordingly,

s e v e ra l c a t a l y s t s , te m p e ra tu re s and a p p a ra tu s d esig n s were s tu d ie d w ith
th e hope o f f in d in g n o t only a more s u it a b le r e a c tio n v e s s e l, b u t
optimum r e a c tio n c o n d itio n s .
The v e s s e l f i r s t used c o n s is te d of a 50-ml. Erylenm eyer f la s k w ith
a 20-cm, West condenser se a le d to th e to p of th e f l a s k .

The c a t a l y s t

and hydrocarbon components were added th ro u g h th e to p of th e condenser

which was f i t t e d w ith a 19/38 fem ale sta n d a rd ta p e re d j o i n t .

A f te r th e

a d d itio n of th e r e a c t a n t s , a male 19/38 sta n d a rd ta p e re d j o i n t to which
a stopcock was a tta c h e d was p laced in th e to p o f th e condenser.
P e r io d ic a lly , sam ples were removed from th e f la s k th rough a heavy
w alled c a p i l l a r y tu b in g which e n te re d th e s id e of th e Erylenm eyer
th ro u g h a r in g s e a l .

One end o f th e tu b in g extended to w ith in an

e ig h th in c h of th e bottom of th e f l a s k , w h ile th e o th e r end le d to a
th re e -w ay sto p co c k .

By th e p ro p er m an ip u latio n of t h i s stopcock, th e

v e s s e l could be flu s h e d w ith a stream of dry argon b e fo re or d u rin g a
ru n , th e f la s k co u ld be ev acu ated , or a sample could be withdrawn..
Tem perature was re g u la te d by p la c in g th e f l a s k in a c o n s ta n t tem p eratu re
b a th th r e e in ch es deep, u n d ern eath which was a Mag-Mix m agnetic s t i r r e r
fo r a g ita tio n .
In th e co u rse o f t h i s work, one hundred and n in e exchange r e a c tio n s
w ere a tte m p te d , th e f i r s t t h i r t y b ein g done in th e a p p a ra tu s d e sc rib e d
abov e.

A p p ro p ria te c a t a l y s t s , tem p eratu re ranges and hydrocarbons

s u it a b l e f o r k i n e t i c experim ents were determ ined in t h i s a p p a ra tu s .
U n fo rtu n a te ly , t h i s r e a c tio n v e s s e l s u ffe re d from s e v e ra l d isad v a n ta g es
f o r a c c u ra te k i n e t i c m easurem ents.

These in clu d ed fre q u e n t plugging

o f th e c a p i l l a r y tu b in g w ith c a t a l y s t and th e l i m i t a t i o n t h a t tem pera­
tu r e s above th e b o ilin g p o in t of any of th e components o fte n r e s u lte d
in th e co n d en satio n c f t h a t compound in th e condenser th u s red u cin g
th e p o s s i b i l i t y of exchange w ith t h a t hydrocarbon.
Because of th e s e d i f f i c u l t i e s , i t was n e c e ssa ry to r e s o r t to se a le d
tu b e s f o r th e k i n e t i c ex p erim en ts.

A cco rd in g ly , segments o f 1$ mm.

h3

Pyrex tu b in g e ig h t in c h e s lo n g se a le d a t one end and w ith a neck ap p ro x i­
m ately 8 nun. O.D. f iv e in c h e s from th e se a le d end were p rep ared .
tu b e s were d r ie d a t 110° f o r s e v e ra l hours b e fo re u s e .

The

They were th en

a tta c h e d to th e end of a t r a i n which could supply d ry argon (concen­
t r a t e d s u l f u r i c a c id , potassium hydroxide p e lle ts ) o r a vacuum, w ith
s u it a b l e sto p co ck s and m ercury s a f e ty v a lv e .

The tube was s u c c e s s iv e ly

ev acu ated and f i l l e d w ith argon ap p ro x im ately tw enty tim es to in s u re
removal o f w a te r vapor and oxygen.

A f te r a f i n a l f i l l i n g w ith dry

a rg o n , th e tu b e was removed and te m p o ra rily s to p p e re d .

The a p p ro p ria te

amount o f hydrocarbon m ix tu re was p ip e tte d in to th e tu b e follow ed by
th e a d d itio n o f a p re v io u sly weighed q u a n tity of c a t a l y s t .

U su ally

i t was n e c e s sa ry to c u t th e c a t a l y s t in to s e v e ra l p ie c e s sc t h a t i t
cou ld e a s i ly pass through th e c o n s tr ic tio n in th e tu b e .

For th e

o c c a s io n a l p ie c e t h a t d id g e t stu ck i n th e neck, a b ra s s rod was used
t o push th e c a t a l y s t in to th e main body of th e tu b e .

The tu b e was

r e tu rn e d to th e argon t r a i n , a s l i g h t vacuum a p p lie d and th e tu b e se a le d
o f f a t th e c o n s tr i c t i o n .
Tem perature was c o n tr o lle d w ith in ± 0 . ^ J using an in s u la te d m in era l
o i l b a th one f o o t i n d iam eter and one fo o t deep equipped w ith two 2^0w a tt k n if e h e a te r s and a b im e ta llic s p i r a l r e g u la to r .

Thorough, co n tin u ­

ous m ixing was accom plished by mounting th e tu b es on e x te n s io n clamps
which w ere a tta c h e d to one arm o f a Model BB, B u r r e ll ,rW rist-A c tio n ”
S haker ( B u r r e ll C o rp o ra tio n , P itts b u r g h , P e n n sy lv an ia).

The tu b e s were

f ix e d a t r i g h t a n g le s to th e arms of th e sh ak er and th e c e n te r of each
tu b e moved i n an a rc ap p ro x im ately th re e in ch es long and a lte r n a te d

hh

d i r e c t io n o v er one hundred tim es every tw enty seconds.

The u se o f th e s e

s e a le d tu b e s proved v ery s u c c e s s fu l and a l l q u a n tita tiv e r e s u l t s were
o b ta in e d u s in g th e s e a s r e a c tio n v e s s e l s .
(b) R eactio n C o n d itio n s
S e v e ra l c a t a l y s t s were in v e s tig a te d .

A v ery r e a c tiv e c a t a l y s t was

d e s ir a b le f o r a llo w in g k i n e t i c s to be measured a t low te m p e ra tu re s.
High s u rfa c e sodium (IKS) on charcoal, and h ig h s u rfa c e potassium (H3P)
on th e sarnie su p p o rt were t r i e d .

I t was found t h a t exchange occu rred

w ith HSP a s low a s 65° , b u t u n f o rtu n a te ly n e it h e r of th e s e c a t a l y s ts
was v e ry d isc rim in a tin g ,, a p p re c ia b le deuterium o c c u rrin g on th e arom atic
r in g a s w e ll a s th e s id e ch a in a s shown by th e appearance of in f r a r e d
bands a t U-UO m icrons (th e a l i p h a t i c C-D band appears n e a r U.68 m icrons)
(See F ig u re 1;).

The c a t a l y s t which was b e s t s u ite d f o r s id e -e h a in

exchange proved to be potassium m etal w hich, a s id e from being more
e a s i l y handled th a n HSS o r HSP, i s a l i q u i d above 63°, allo w in g a f r e s h
s u rfa c e o f c a t a l y s t to be c o n tin u a lly exposed to hydrocarbon d u rin g
exchange.

So t h a t re p ro d u c ib le r e s u l t s could be o b ta in e d , samples o f

p otassium had to be used which d id n o t d i f f e r from one a n o th e r in w eig h t.
I t was found co n v en ien t to weigh th e samples on a m agnetically-dam ped
ch ain cm atic a n a l y t i c a l b a la n c e .

A w eighing b o t t l e tw o -th ird s f u l l of

potassiu m m e ta l-d rie d m in era l o i l was weighed to th e n e a r e s t m illig ra m .
Then a p ie c e o f potassium ro u g h ly th e w eig h t d e s ire d was f r e s h l y c u t
u nd er d ry h e p ta n e , picked up w ith fo rc e p s , d rie d w ith ab so rb an t p ap er,
p laced i n th e m in e ra l o i l i n th e w eighing b o t t l e and th e b o t t l e rew eighed.

Percent

T ransm ission

100

U.o

5-0
M icrons

F ig u re

1.0

6.0
Microns

5-0
M icrons

Ring exchange over h ig h su rfa c e sodium ;,HSS) on
c h a r c o a l.
A = E th y lb enz eneB = E th y lb enz ene-d^ a f t e r exchange w ith cumene a t 100°
f o r 6 hours over HSS.
C = Cumene a f t e r exchange w ith eth y lb en zen e-d a a t 100°
f o r 6 h ours over HSS.
Note th e appearance of two C-D bonds:
U.UO^l and a l i p h a t i c C-D a t U.6 8 >u.

aro m atic C-D a t

6.0

T h is p ro ce ss o f c u ttin g and rew eighing was re p e a te d u n t i l th e d e s ire d
w eig h t o f c a t a l y s t was o b ta in e d .

When i t became n e c e ssa ry to c u t th e

potassium i n t o s e v e ra l p ie c e s to make a d d itio n to th e r e a c tio n tube
e a s i e r , t h i s c u t t i n g was lik e w is e done under d ry h ep tan e, th e m etal
b ein g touched d ry w ith a b so rb a n t paper b e fo re b ein g p laced in th e tu b e .
A nother f a c t o r which was s tu d ie d was th e e f f e c t of te m p e ra tu re .
E xperim ents were run u s in g th e v a rio u s c a ta ly s ts from 6£ - l? £ ° .

In a l l

cases h ig h e r te m p e ra tu re s r e s u lte d in an in c re a se d r a t e of deuterium
exchange, b u t, u n f o rtu n a te ly , th e r a te o f arom atic r in g exchange
in c re a s e d more r a p id ly th a n th e r a t e of s id e ch ain exchange.

The

tem p eratu re o f l £ 0° was f i n a l l y s e le c te d as a s u ita b le tem p eratu re f o r
con d u ctin g th e k i n e t i c s u sin g potassium m etal as a c a t a l y s t because
th e s id e c h a in exchange o ccu rred a t a d e s ir a b le r a t e w h ile th e aro m atic
r in g exchange was sm a ll.
(c) K in e tic Procedure
For each k i n e t i c run a sto ck s o lu tio n c o n ta in in g th e p ro p er r a t i o
o f hydrocarbon components was p re p a re d .

W ith th e a id of a 1 ml. p ip e tte

grad u ated t o 0 .0 1 m l., i d e n t i c a l volumes were placed in each tu b e from
t h i s sto ck s o lu tio n .

Most o f th e k i n e t i c s were done by p re p a rin g te n

tu b e s and a llo w in g two tu b e s each to r e a c t a t 1^0° f o r two, f o u r, s ix ,
e ig h t and te n h o u rs.

A t th e d e sig n a te d tim e, each tube was q u ic k ly

removed from th e b a th , cooled f o r a m inute in a b eak er of m in era l o i l
a t room te m p e ra tu re , th e n cooled i n an ic e b a th .

A f te r s e v e ra l m inutes

th e tu b e , which was u s u a lly covered in s id e w ith th e deep-red c o lo r
c h a r a c t e r i s t i c o f th e o rg a n o m e ta llic formed, was opened and th e d eep -red

l i q u i d removed u s in g a m edicine dropper p u lle d bo a c a p i lla r y and added
to 1 m l. o f d i s t i l l e d w a ter in a 30-m l. s e p a ra to ry fu n n e l.

There was

some r e a c tio n when t h i s was done, alth o u g h u s u a lly no more th an a
g e n tle e v o lu tio n o f hydrogen.

When t h i s e v o lu tio n had subsided (h asten ed

by s w irlin g th e f u n n e l), th e bottom y ello w , aqueous la y e r was withdrawn
and th e w h ite hydrocarbon la y e r washed w ith a n o th er ml. of w a te r.
A f te r rem oval o f t h i s aqueous phase, th e rem aining c l e a r , c o lo r le s s
o rg an ic l a y e r was w ithdraw n th ro u g h th e to p o f th e fu n n e l w ith a c a p il­
l a r y m edicine d ropper and p la c e d , to g e th e r w ith s e v e ra l p ie c e s of
D r i e r i t e , i n a t e s t - t u b e th r e e in ch es lo n g c o n s tru c te d from 8 mm. Pyrex
tu b in g .
la b e lle d .

The tu b e was sto p p ered w ith a ru b b er serum b o t t l e cap and
The purpose o f th e serum b o t t l e cap was th e ease w ith which

one could w ithdraw th e sample in to a hypodermic sy rin g e and i n j e c t i t
in to th e Vapor F racto m e te r f o r s e p a ra tio n .

RESULTS AND DISCUSSION

U8

RESULTS AMD DISCUSSION
S y n th e tic Methods
O rd in ary hydrocarbons which were needed f o r th e exchange e x p e ri­
ments w ere e i t h e r o b ta in e d com m ercially or sy n th e siz e d by methods
r e p o rte d in th e l i t e r a t u r e .

Samples of a lp h a -d e u te ra te d hydrocarbons

of known deu teriu m c o n te n t were a ls o n e c e s sa iy f o r p re p a rin g c a l i b r a t io n
cu rv es ( c o r r e l a t i n g p e rc e n t deuterium w ith th e i n t e n s i t y o f th e C-D peak
i n th e I n f r a r e d ) so t h a t th e amount of deuterium exchanged could be
d e te rm in e d ,
When i t became a p p a re n t t h a t .synthesis by re d u c tio n of th e appro­
p r i a t e t e r t i a r y c h lo rid e w ith lith iu m aluminum d e u te rid e and lith iu m
d e u te rid e

LiAlD.

(3)

r e s u lte d i n poor y ie ld s o f th e d e s ire d compound, a n o th e r ro u te was
so u g h t.

A method which appeared to be s u ite d f o r t h i s purpose was

cleav ag e o f th e co rresp o n d in g a-m eth y l e th e rs w ith an a l k a l i m etal
( to form th e o rg a n o m e ta llic compound) follow ed by h y d ro ly s is w ith
deu teriu m o x id e .

C©K© - 5 4

O

c -d
L

:k)

k9

T his procedure proved to be a p p lic a b le f o r a l l th e re q u ire d compounds
( s e e Table IV ).
D uring th e p r e p a ra tio n of cumene-*

by t h i s p ro ced u re, a paper

app eared by R u s se ll (1+2) who, claim ed t h a t cumene p repared in a s im ila r
manner (m ajor d if f e r e n c e s were sodium -potassium a ll o y in s te a d of
potassium o n ly ,

e th e r

s o lv e n t r a th e r th a n heptane and deuterium c h lo rid e

in s te a d o f deu teriu m oxide to in tro d u c e th e deuterium ) co n tain ed O .2I4
aro m atic d eu teriu m atoms p er m o lecule.

He analyzed th e cumene by hig h

r e s o lu tio n n u c le a r m agnetic re so n an ce, in f r a r e d and mass sp ectro sco p y .
I t th e r e f o r e became n e c e s sa ry to e s ta b li s h th e p o s itio n o f th e deuterium
i n th e d e u te r a te d cumene prepared by th e method d e sc rib e d in t h i s
t h e s i s (Mass sp e c tro m e tric a n a ly s is o f fra g m e n ta tio n peaJcs u n f o rtu n a te ly
does n o t a llo w one to d is tin g u is h r in g - from a lp h a-d eu teriu m (1+3 )) P roof o f S tr u c tu r e o f Cumene-d^
The in f r a r e d spectrum of our product showed e s s e n t i a l l y no aro m atic
C-D band ( U.U m ic ro n s), b u t th e spectrum o f R u sse ll* s p ro d u ct a ls o
showed o n ly s l i g h t aro m atic C-D a b s o rp tio n .

In o rd er to examine t h i s

band more c a r e f u l l y , cumene-dp was prepared by th e fo llo w in g scheme:
Br

Br

D

i- p r o p y l bromide
A.1C1,
CH(CH3 )
This p ro d u ct showed a s tro n g aro m atic C-D band a t U.liO m icrons (se e
F ig u re 2 0 ).

The p ercen tag e o f deuterium in th e cumene-d^. and cumene-dp

50

TABLE IV
HELDS P D DEUTERIUM ANALYSES OF HYDROCARBONS PREPARED BY ETHER
CLEAVAGE WITH POTASSIUM FOLLOWED BY HYDROLYSIS
WITH DEUTERIUM OXIDE

Y ield
From E th er
( P ercen t)

Hydrocarbon

Mass S p ectro m e tric A n a ly sis
P e rc e n t d^
P ercen t dd

Cumene

£7

82.6

17 .u

sec-B u ty lb enzene

6k

U6 .6

£3-U

2-P henylpentane

6k

6U.1

35.9

3 -P h en y lp en tan e

$6

53.3

I46.7

2-M ethyl-3"phenylbutane

83

70.1

29.9

£L.U

U8 .6

2 , 2 -d im e th y l-3 - phenjdLbutane

Note: Mass- s p e c tro m e tric a n a ly se s a re w ith in 1% of a b s o lu te v a lu e and
show no b e t a , gamma o r d e l t a deuterium atom s.
were e s s e n t i a l l y i d e n t i c a l (8 2 ,6$ and 82,7$ r e s p e c tiv e l y ) .

A rom atic

deu teriu m was e a s i ly d is c e m a b le in m ix tu res c o n ta in in g a 1:9 and 1 : 1;
r a t i o o f cumene-dp to cumene-dg. (se e F ig u re $ ) .

I t i s s a fe to conclude,

th e r e f o r e , t h a t a c c o rd in g to i n f r a r e d a n a ly s is , cumene-da prep ared by e th e r
cleav ag e a s d e s c rib e d i n t h i s t h e s i s co n tain ed < 5$ aro m atic deuterium .
F u rth erm o re, a sample of cumene-da prep ared by th e fo llo w in g scheme
0
II

CH3-C-CH3

D
T t A

111

■■ '

I
CH3-C-CH3

OH

D
PRr 1

■

I
CH3-C -C H 3

Br

(6)

51

100

100

80

80

Percent

T ransm ission

ao
W
m
•rl
g
•H

Ui

E-i

60

60
<D
O
f-.
0)

Oh

J4O

Uo

I4.0

5 .0
1 p a r t cumene-dp
9 p a r ts cumene-da

ii.o

5 .0
1 p a r t cumene-dp
h p a r ts cumene-da

F ig u re
In fra re d s p e c tra showing re ].a tiv e a b s o rp tio n due to a
1 :9 and 1:1* r a t i o o f cumene-dp in cumene-da- The aro m atic C-D
band (U.I4.O m icrons) ro u g h ly doubles in i n t e n s i t y , in d ic a tin g th e
absence o f r in g - d e u te r a te d m a te r ia l in th e cumene-da prep ared by
e th e r c leav ag e-

52

(and k in d ly s u p p lie d by A. S t r e itw ie s e r , J r . ) had an in f r a r e d spectrum
e s s e n t i a l l y i d e n t i c a l w ith t h a t of th e cumene-da p repared i n t h i s
la b o r a to r y .
The n u c le a r m agnetic resonance s p e c tra (se e F ig u re 6) a re a ls o
c o n s is te n t w ith th e s t r u c t u r a l assignm ents based on in f r a r e d .

The C

band (due to m ethyl p ro to n s on th e s id e ch ain ) i s s p l i t in o rd in a ry ,
r in g - d e u te r a te d and p-bromo cumene, b u t n o t i n th e product from e th e r
c le a v a g e .

This s p l i t t i n g i s due to th e a - p ro to n in th e f i r s t th re e

compounds and, t h e r e f o r e , only a low (< 20%) p ercen tag e o f th e ct-hydrogens
in th e p ro d u ct from e th e r cleav ag e can be p ro to n s; th e r e s t must be
d e u te ro n s .

F u rth erm o re, a B band, due to th e t e r t i a r y p ro to n o f th e

s id e c h a in , i s t o t a l l y ab se n t from t h i s m a te r ia l, w hereas i t appears in
th e o th e r th r e e s p e c tr a .
F i n a l l y , cumene-da (from e th e r cleavage) and cumene-dp were o x id ized
to ben zo ic a c id .

U n fo rtu n a te ly , th e re g io n in th e benzoic a c id spectrum

from I4..U—ii -8 m icrons i s n o t f r e e from in te r f e r e n c e s .

A s tro n g band a t

J4.J4O m icrons a t t r i b u t a b l e to aro m atic C-D was observed, however, i n th e
ben zo ic a c id o b tain ed from cumene-dp.

From th e s p e c tra of m ix tu re s,

one can conclude t h a t th e r e i s l e s s th a n e ig h t p e rc e n t r in g d e u te r a tio n
in th e cumene-da.
A sample o f cumene-da (p re p ared by e th e r cleavage and a d d itio n o f
deu teriu m oxide) was s e n t to R u sse ll who agreed t h a t i t co n tain ed l i t t l e
o r no aro m a tic d eu teriu m .

(F o r an e x p la n a tio n of th e d iff e r e n c e in

b e h a v io r o f deu teriu m c h lo rid e in e th e r v s . deuterium o xide, see
re fe r e n c e 5 7 0

53

cumene

p-bromocumene

cumene-d

F ig u re 6 . N u clear m agnetic resonance s p e c tra o f v a rio u s cumenes.
The la c k o f s p l i t t i n g of th e C band and th e t o t a l absence o f a B
band i n th e spectrum of cumene-da a re r e s u l t s e n t i r e l y c o n s is te n t
w ith th e s t r u c t u r a l assig n m en t. The A band i s due to pro to n s on
th e aro m atic r in g .

Preliminary Exchange Experiments

I n i t i a l experim ents were w ith ethylbenzene-d^ and diphenylm ethane,
i t b e in g th o u g h t b e s t to look f o r la r g e d iff e r e n c e s in a c i d i t y f i r s t .
No exchange o ccu rred u n d er th e c o n d itio n s employed, which in clu d ed
te m p e ra tu re s from 80-175°, r e a c tio n tim es from 2-67 hours and th e u se
o f po tassiu m m e ta l, h ig h s u rfa c e potassium (HSP) and high s u rfa c e
sodium (HSS) a s c a t a l y s t s .

This u n a n tic ip a te d r e s u l t was a p p a re n tly

caused by to o g re a t a d iff e r e n c e in a c i d i t y .

The diphenylm ethyl an io n ,

reso n an ce s t a b i l i z e d by two aro m atic r in g s , presum ably was n o t s u f-

-

f i c i e n t l y b a s ic to remove a d eu tero n from eth y lb en zen e.

0 * 0 ~ 0 - 0 *et°The n e x t exchange a tte m p ts were betw een ethylbenzene-da and cumene
whose a c i d i t i e s were expected to be more com parable.

Here a ls o ,

p otassium m e ta l, HSP and HSS were used a s c a t a l y s ts .

A p p reciab le

exchange o c cu rre d in each c a se , b o th i n th e s t i r r e d r e a c to r and in
s e a le d tu b e s . U n fo rtu n a te ly , th e s e l f exchange of e th y lb enz ene-da i s
d i f f i c u l t to a n a ly s e q u a n t i t a t i v e ly w ith in f r a r e d .

I t was decided

th e r e f o r e to r e s t r i c t th e stu d y to hydrocarbons c o n ta in in g only one
b e n z y lic (a lp h a ) hydrogen and to allo w two n o n -d e u te ra te d hydrocarbons
to compete f o r th e deuterium i n a t h i r d .

Because of th e e x te n siv e

d eu teriu m exchange w ith th e aro m atic r in g when HSS and HSP were used
( s e e F ig u re 1 0 , potassium m etal was u sed a s th e exchange c a t a l y s t in
a l l a d d it i o n a l e x p erim en ts.

F u r th e r , because o f th e reaso n s l i s t e d in

55

th e E x p erim en tal s e c tio n , u se of th e r e a c tio n f l a s k was d is c o n tin u e d
and s e a le d tu b e s used i n a l l subsequent r e a c tio n s .
The c o m p e titio n between cumene and sec-b u ty lb en zen e f o r th e
d eu teriu m i n e th y lb enz ene-da , u sin g potassium m etal as c a t a l y s t , was
e x te n s iv e ly s tu d ie d .

I t was found t h a t w h ile r in g exchange a t 130-1^0°

was o n ly s l i g h t , th e r a t e o f s id e ch ain d e u te r a tio n was a ls o r e ta rd e d
compared to h ig h e r te m p e ra tu re s .

Most k in e tic s were th e r e f o r e c a r r ie d

o u t a t 150° , a tem p e ra tu re which ,gave m easurable exchange r a t e s i n
re a so n a b le tim es ( te n h o u rs) b u t s t i l l was s u f f i c i e n t l y low to make
r in g d e u te r a tio n a minor s id e r e a c tio n .
The e f f e c t o f u s in g e th y lb enz ene-d^ compared w ith cumene-da a s a
so u rc e o f deu teriu m was s tu d ie d .

R eactio n s in which sec-b u ty lb en zen e

competed w ith 2-m eth y l-3 -p h en y lb u tan e u s in g e th y lb enz ene-da i n one case
and cumene-da i n th e o th e r were run u s in g i d e n t i c a l tem p e ra tu re s and
amounts o f c a t a l y s t .

I t was found t h a t more r in g d e u te r a tio n o ccurred

w ith cumene-da th a n w ith ethylbenzene-da*

A lso , s id e -c h a in d e u te r a tio n

proceeded 30-50$ f a r t h e r w ith e th y lb enz ene-da ^ a n w ith cumene-da (se e
F ig u re 7 ) .

These r e s u l t s m ight have been a n tic ip a te d because th e

in d u c tiv e e f f e c t o f th e a d d itio n a l m ethyl group i n cumene would make
i t s a lp h a hydrogen l e s s a c id ic th a n th o se in e th y lb en zen e.

This means

t h a t an a lp h a -d e u te riu m atom i n eth y lb en zen e, b eing more l a b i l e , would
be more r e a d i l y exchanged th a n one i n cumene.
u s in g cumene-

The f a c t t h a t exchanges

r e s u l t i n more r in g d e u te r a tio n i n th e com peting

h ydro carb on s i s p ro b ab ly lik e w is e r e l a t e d to th e d ecreased a c i d i t y .
B ryce-S m ith (5)» who s tu d ie d th e m e ta lla tio n r e a c tio n between cumene

56
2 -M eth y l-3 - phenylbutane

s ec-Bu ty lb enz ene

100

100

90

80
o

•H

to
to

•H

e

CO

70

Jh

E-f

(D
O
S
h
CD
cu

60

50

Uo

I4.6

M icrons

5-0

J4.6
Microns

F ig u re 7* I n f r a r e d s p e c tr a i l l u s t r a t i n g th e dependence of
exchange on th e deuterium so u rce. sec-B utylbenzene and
2-m e th y l-3 -p h e n y lb u ta n e were allow ed to compete f o r th e
d eu teriu m i n eth y lb en zen e-d a ( s o lid l i n e ) and cumene-da
( d o tte d l i n e ) . Exchanges w ith cumene-da r e s u lte d i n more
d eu teriu m i n th e r in g ( U-U0 m icrons) and l e s s i n th e s id e
.c h a in (U.68 m icro n s) .

5 .0

57

and e th y l p o tassiu m , found th e p a ra and meta hydrogens in cumene tc be
more e a s i l y removed th a n th e a lp h a .

He in te r p r e te d t h i s a s meaning

t h a t th e s e r in g p o s itio n s were more a c i d i c .

C orresp o n d in g ly , th e

dim eth y l phenyl c a rb a n io n formed from cumene, b ein g more b a s ic th a n th e
co rresp o n d in g io n from e th y lb e n zen e, m ight e a s i l y e x tr a c t an aro m atic
hydrogen from sec-b u ty lb en zen e or 2-m ethyl~ 3-phenylbutane.

The r e s u l t ­

in g c arb a n io n could a tta c k a n o th e r m olecule of cumene-da to form th e
p ro d u ct w ith r in g d eu teriu m .

T his sequence of r e a c tio n s i s shown below .

ch3

db 0
CH3

For th e k i n e t i c ' ex p erim en ts, th e n , e th y lb enz ene-da was used a s th e
so u rce of exchangeable d eu terium .
K in e tic Experim ents
K in e tic s were fo llo w ed by a llo w in g exchange r e a c tio n s to ru n in
se a le d tu b e s f o r v a r io u s p e rio d s o f tim e , th e n a n a ly z in g f o r th e per­
c e n t d eu teriu m i n th e o r ig i n a l l y n o n -d e u te ra te d components u s in g
q u a n t i t a t iv e i n f r a r e d .

(10)

58

The hydrocarbons s tu d ie d corresponded to
R
/
CH
\

w here th e a lk y l groups w ere:
R
CH3

ch3

ch3
ch3

^2^5
n -C a ^

ch3

i-C a ^

ch3

t-C 4HQ

c 2h5

c 2h5

In one ex p erim en t,' phenyl cyclopropane was examined in co m p etitio n
w ith cumene f o r th e deuterium in e th y lb enz ene-d^.

A f te r 8-10 hours

o v er p otassium a t 150°, th e cumene had exchanged as expected (1 2 .9 # -d a
a f t e r 10 h o u rs ), b u t th e phenylcyclopropane could n o t be reco v ere d j i t
a p p a re n tly polym erized a s evidenced by a lo s s i n liq u id volume and th e
p ro d u c tio n o f c o n s id e ra b le b la c k , t a r r y r e s id u e .

A lthough phenylcyclo­

propane does n o t a p p ea r amenable to stu d y by t h i s method, i t i s p o s s ib le
t h a t p h en y lcy c lo a lk a n es w ith l a r g e r rin g s could be so s tu d ie d .
I t was d e s ir a b le to d em o nstrate t h a t no rearran g em en ts o r o th e r
s id e r e a c tio n s o ccu rred d u rin g an exchange ru n .

A f te r th e q u a n tita tiv e

i n f r a r e d s p e c tr a o f th e r e a c ta n ts from th e sample o f maximum r e a c tio n
tim e were re c o rd e d , th e s e s o lu tio n s were d ilu te d from th e 1:1.1* volume
r a t i o to a 1:20 r a t i o o f hydrocarbon to carbon t e t r a c h l o r i d e and th e
in f r a r e d s p e c tr a examined from 2.0-11*.5 m icrons.

These were compared

59

■with th e s p e c tr a of th e o rd in a ry hydrocarbons.

In no case was any

change n o te d o th e r th a n th o se caused by th e s u b s t i t u t i o n o f deuterium
i n th e m o lecu le .

A lso , a ub la n k ” ru n was c a r r ie d out betw een s e c -

b u ty lb en ze n e and 2 ,2 -d im e th y l-3~ phenylbutane u s in g potassium m etal and
o rd in a ry eth y lb e n z e n e .

The in f r a r e d s p e c tra of b o th th e sec-b u ty lb en zen e

and th e 2 , 2-d im eth y l-3 '-p h enylbutane a f t e r exchange were i d e n t i c a l w ith
th o s e b e fo re exchange.
The amount o f c a t a l y s t and th e c o n c e n tra tio n of th e r e a c ta n ts
P
a f f e c te d th e a b s o lu te r a t e s o f exchange.
each s e a le d tu b e w ere:

The u s u a l q u a n ti tie s used in

0.0051 mole (0.20 g .) of potassium m etal,

0.00286 mole o f each o rd in a ry hydrocarbon and from 0.350 ml. (0.00285
mole) to 0.600 m l. (O.OOU93 mole) of eth y lb en zen e-d a.

As m ight be

a n t i c i p a t e d , th e r a t e o f exchange was n ot a s g re a t when a sm a lle r m olar
r a t i o o f c a t a l y s t was u sed , a lth o u g h th e r e l a t i v e r a t e s were s t i l l
s im ila r (se e Table V ).

F u rth e r, i t was d isco v e re d t h a t a l t e r i n g th e

m olar r a t i o o f th e two com peting hydrocarbons r e s u lte d in a d ecrease
i n th e p e rc e n t d eu teriu m exchanged, a lth o u g h th e t o t a l number of moles
o f-d e u te riu m exchanged rem ained ap p ro x im ately c o n s ta n t

see Table V I).

W ith in a given exchange ru n , th e w eight o f potassium m etal in each
sample v a r ie d no more th a n 2-3# and th e volumes of hydrocarbon were
w ith in 1 -2 # o f each o th e r .

The p r e c is io n to which th e q u a n tita tiv e

i n f r a r e d co u ld be i n t e r p r e t e d was ± 0 .2 # d euterium .
Table V II l i s t s t h e . r e s u l t s of a k i n e ti c run in v o lv in g c o m p e titio n
betw een cumene and se c -b u ty lb e n z e n e .
g iv en i n th e A ppendix.

The rem aining k i n e t i c ru n s a r e

F ig u re 8 shows th e p ro g re s siv e appearance of

th e C-D peak d u rin g t h i s exchange.

60

EFFECT OF CATALYST QUANTITY ON THE RATES OF EXCHANGE OF CUMENE AND seo-BUTYLBENZENE
(Ethylbenzene-d^ is deuterium source, T = lf>0 )

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EFFECT OF CONCENTRATIONS ON PATES OF EXCHANGE
(T = lf?0°, time = k hours)

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63
Cuinene

sec-B u ty lb enz ene
100

80

100

o

•H

03
03

8

80
. 6 hr

•r!

03
03

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10 h r
Uo

5-0
M icrons

Uo

U.6

5 .o

Microns

F ig u re 8 . A lip h a tic C-D s tr e tc h in g r eg io n showing p r o g r e ssiv e
in c r e a s e o f deuterium c o n te n t du rin g a co m p etitio n r e a c tio n
betw een cumene and sec -b u ty lb en ze n e u s in g eth y lb en zen e-d a as
deuterium s o u r c e , potassium m etal a s c a t a ly s t and 15>0 as
r e a c tio n tem p eratu re. (These data are ta b u la te d in Table V I I . )

6U

C a lc u la tio n o f R ate C o n stan ts
The r a t e c o n s ta n ts were c a lc u la te d u s in g th e v a lu e s f o r deuterium
exchange found i n T ables VII and XI-XV.

The o v e r - a ll e q u a tio n f o r

i n i t i a l , exchange of equim olar q u a n titie s of two hydrocarbons (RH and
R*H) w ith a t h i r d c o n ta in in g deuterium (R”D) may be w r itte n :
RH
(100 - x.)
+ R"D

+

R"H

R*H
(100 - y)
where
x = p e rc e n t o f RD a t tim e t
y = p e rc e n t of R* D a t tim e t
100

- x = p e rc e n t o f RH a t tim e t

100

- y = p e rc e n t o f R*H a t tim e t

The f i r s t o rd e r k i n e t i c e q u a tio n (I4I4.) ,
2.303
k “ " t

-i

100
g 100 - %l

where %D i s e it h e r x or y was used f o r th e c a lc u la t io n o f th e r e a c tio n
r a te c o n s ta n t, k , f o r each exchange.
T ables VI I I and IX l i s t th e v a lu es' obtained from t h i s eq u a tio n ,
to g e th e r w ith th e v a lu e o f each run a s determ ined by th e l e a s t squares
s lo p e (Uj?) o f lo g jlOO/lOO-$D) v e rsu s tim e f o r cumene and s e c -b u ty l­
b en zen e.

C orresponding t a b le s fo r th e oth er exchanges may be found

65

i n th e A ppendix.

F ig u re 9 shows a t y p i c a l l e a s t sq u ares p l o t.

In most c a s e s , samples f o r d u p lic a te p o in ts were ru n a t th e same
tim e to be a s su re d o f eq u al exchange c o n d itio n s .

In one in s ta n c e ,

how ever, two s e p a ra te runs were made s e v e ra l weeks a p a r t, each c o n s is t­
in g o f f iv e sam ples (2 , U, 6, 8 and 10 h o u rs ).
T ables T i l , V III and DC.
.

-

e

.

5-27 x 10

and 5*39 x 10

These d a ta a r e in

The average r a t e c o n s ta n ts f o r cumene were
_ 6

and f o r se c -b u ty lb en zen e, 2.1$ x 10

_ 6

and

-6

2.39 x 10

.

I t i s a p p a re n t t h a t th e r a te c o n s ta n ts were f a i r l y

re p ro d u c ib le .
Table X l i s t s th e r e l a t i v e r a t e s of exchange f o r a l l hydrocarbons
s tu d ie d , a v a lu e of 1 .0 0 b ein g a s sig n e d to th e hydrocarbon w ith th e
slo w e st exchange r a t e (2 ,2 -d im e th y l-3 -p h e n y lb u ta n e ).
Mechanism
Any ad eq u ate i n t e r p r e t a t i o n o f th e d a ta assem bled in th e p re s e n t
in v e s t i g a t i o n would be supplem ented by a knowledge o f th e r e a c tio n
mechanism (I4.6 ) .

S ev e ral d i f f e r e n t mechanisms of m e ta la tio n have been

advanced in r e c e n t y e a r s , th e main d if f e r e n c e b ein g th e r e l a t i v e
im portance o f th e r o le p lay ed by th e a l k a l i m e ta l.

From t h e i r p h y s ic a l

p r o p e r tie s i t a p p e a rs t h a t a l k y l - and a ry l-p o ta s siu m compounds a r e
p o la r and behave as u n d is s o c ia te d io n - p a ir s ( 1 ) .

Morton ,'h7” 5 l) has

v i s u a l i z e d s id e - c h a in m e ta la tio n of a lk y la ro m a tic s as an e l e c t r o p h i li c
p ro c e ss where th e le a d in g r o l e was t h a t o f th e a lk a li- m e ta l c a tio n ,
th e a n io n a id in g b u t r e le g a te d to a m inor p a r t.

In t h i s i n t e r p r e t a t i o n

th e r e s i d u a l p o l a r i t y o f th e m etal c a tio n a t t r a c t s th e e le c tr o n s of
th e carbon-hydro gen c o v a le n t bond in th e s id e c h a in , th u s lo o se n in g th e

66

TABLE V III
FIRST ORDER. RATE CONSTANTS FOR DEUTERIUM TRANSFER TO CUMENE
IN COMPETITION WITH see-BUTYLBEN?ENE
(D euterium so u rc e : eth y lb en zen e-d ^ ; c a t a l y s t: potassium
m e ta l; te m p e ra tu re : l 5 0 ° l r e a c tio n v e s s e l: se a le d tu b e s .
Data c a lc u la te d from Table V II.)

Sample
1

Tim e'
( s e c .)

P ercen t
D

Log
(100/100-^D)

ki
(xlO 6) ( s e c .

—

—

0

0

7200

2.5

0.01098

3.51

y

7200

3-0

0.01322

U.23

k

llUiOO

8.2

0.03715

5 >9k

f

1U400

7.0

0.03153

5.0U

6

21600

11.2

0,05158

5.50

7*

21600

12.2

0.05652

6.10

8

28800

16. £

0.07831

6.26

r

28800

15. h

0.07262

5.81

10

36000

16.8

0.07986

5-11

11"'

36000

18.7'

0.08991

5.75

2

)

\/

\r

Average
L east Squares Slope

5.33 ± 0.68
5 .$

"These were run two weeks a f t e r th e even-numbered sam ples.

67

TABLE U
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO sec-BUTYLBENZENE
IN COMPET' IT ION WITH CIJMENE
(D euterium so u rc e : ethylbenzene=-da j c a t a l y s t: potassium m etal;
te m p e ra tu re : 150 ; r e a c tio n v e s s e l: se a le d tu b e s . Data c a lc u la te d
from T able V II.)

Sample

Time
( s e c .)

1

0

2

7200

1 .9

O.OO83I4.

2.6 /

3*

7200

1 .6

0.00702

2.25

k

ll^OO

3.9

0.01728

2./6

r

lUUoo

2. 6

0 .0111&

1.83

6

21600

U.3

0.01907

2.03

T

21600

5 .8

0.02596

2.77

8

28800

7.2

0.032L.6

2.60

28800

/•5

0.03387

2.71

10

36000

8.2

0.03715

2.38

11"

36000

8.3

0 .0 3 /6 3

2 .1i l

P ercen t
D
0

Leg
(lOO/lOO-^D)

k1
1
(xlO 6) ( s e c . )
—

—

V/

\t

t./

9"

Average
L e ast Squares Slope

2 .UU ± 0.26
2 .!©

"'"These were run two weeks a f t e r th e even-numbered, sam ples.

F ig u re 9• L e a st sq u ares slo p e s showing r a t e s of deuterium
exchange c o m p e titio n between cumene and sec-b u ty lb en zen e 's e e
.T ables V II, V III arid EX).

0.100

0.080

cumene

100-

100

0.060

bQ
o
H

sec-b u ty lb en zen e
0.02 0

0 .0 0 0

Time ( h r s .)

68

69

TABLE T
RELATIVE DEUTERIUM EXCHANGE PATES CALCULATED FPOM
LEAST SQUARES SLOPES
( 2 , 2 -d im eth y l-3 -p h en y lb u tan e = l.OO)

Number

Hydrocarbon

R e la tiv e Exchange Rate

1

2 ,2 -d im eth y l-3 -p h en y lb u tan e

1.00

2

2-m ethyl-3- phenylbutane

1.90

3

3 - phenylpentane

1.96

k

2 - phenylpentane

6.91

5

sec -b u ty lb e n z ene

8.13

6

cumene

18.9

p ro to n w hich i s th e n re c e iv e d by th e an io n i n a ’’p u s h -p a ll11 ty p e o f
re a c tio n .

This i s i l l u s t r a t e d below u s in g Morton*s n o ta tio n o f a heavy

arrow i n d ic a tin g a m ajor fo rc e (R, R^ and R2 a r e a lk y l gro u p s):

E l e c tr o p h ilic a tta c k by o rg a n o a lk a li re a g e n ts was ex p lain ed by Morton
w ith t h i s mechanism.
B ryce-Sm ith ( 5 ) , on th e o th e r hand, has suggested t h a t th e an io n
i s th e more im p o rta n t s p e c ie s and v is u a l iz e s a t e t r a p o l a r t r a n s i t i o n
s t a t e where th e f u n c tio n o f th e m etal c a tio n i s p u re ly e l e c t r o s t a t i c ,

70

th e d r iv in g f o rc e f o r th e r e a c tio n b ein g th e energy d if f e r e n c e between
c a rb a n io n s « T his concept i s i l l u s t r a t e d below:
R'
*•2
T?

R,

C

Kl^ C - H

(12)
r

X

e

n

+ RH

-

B ryce-S m ith has term ed t h i s ty p e of s u b s tit u ti o n " p r o t o p h i l i c ," in v o lv ­
in g th e rem oval of a p ro to n in th e ra te -d e te rm in in g s te p .

This i s to

be d is tin g u is h e d from a n u c le o p h ilio s u b s t itu tio n in v o lv in g RK which
would in v o lv e a tta c k o n .carbon by R w ith subsequent removal o f a
h y d rid e io n .

As a t e s t o f t h i s mechanism, B ryce-Sm ith (£2) s tu d ie d

th e m e ta la tio n o f deuterobenzene and t o l u e n e - b y e th y l potassium .
He found t h a t protium was re p la c e d by potassium more r a p id ly th a n
d e u te riu m , i n d ic a tin g t h a t , in d eed , th e b re a k in g o f th e carbon-hydro gen
bond i s im p o rtan t in th e ra te -d e te rm in in g s te p .

He f u r t h e r p o in ts out

t h a t th e r a t e o f m e ta la tio n a t a given p o s itio n i s r e la t e d to th e
a c i d i t y o f th e hydrogen which i s re p la c e d .

O b jectio n s r a is e d by B ryce-

Sm ith to Morton® s proposed scheme in c lu d e th e f a c t t h a t th e m etal
c a tio n r e t a i n s th e same e le c tr o n ic c o n fig u ra tio n a f t e r r e a c tio n as
b e fo re and t h a t an e l e c t r o p h i li c a tta c k by th e m etal c a tio n i s n o t in
agreem ent w ith th e e x te n siv e m e ta - s u b s titu tio n o b tain ed in. th e m etal­
a t i o n o f cumene by e th y lp o ta ssiu m n o r w ith th e f a c t t h a t a lk y l groups
ap p ea r to d e a c tiv a te th e r in g to s u b s titu tio n .
In an a tte m p t to do away w ith th e o b je c tio n s of B ryce-Sm ith,
Morton (1*7,53) supplem ented h is p rev io u s mechanism w ith an a l t e r n a t iv e
r o u te , th e r e a c tio n c o n d itio n s d eterm in in g which p ro cess would

71

p re d o m in a te .

T his a d d itio n a l p a th in v o lv e s th e concept of a r a d ic a l-

p a ir a s opposed t o an i o n - p a ir .

H e r e ,.th e f i r s t s te p i s assumed to be

th e d i s s o c i a t i o n of th e o rg a n o a lk a li s a l t (w ith th e hydrocarbon
c o o rd in a te d on th e c a tio n ) in to two r a d i c a l s , follow ed by th e rem oval
o f th e most a c id ic hydrogen in th e hydrocarbon by atom ic a l k a l i m e ta l.
The p ro c e ss i s te rm in a te d by accep tan ce o f t h i s hydrogen atom by th e
a lk y l r a d i c a l .

This sequence i s shown in th e fo llo w in g eq u atio n s:

(13)

R2
R l" C :

r2

H

Ri - c ;0

K©

(iU )

+ H*

H-

+

R-

----->

RH

(15)

Morton p o in te d o u t t h a t t h i s a l t e r n a t i v e p ro cess i s in agreem ent w ith
th e rem oval o f a p ro to n in th e ra te -d e te rm in in g s te p .

This mechanism

i s reg a rd e d by B ryce-Sm ith (5U) a s u n ten ab le s in c e Morton d id n o t supply
d i r e c t ex p erim en tal evidence f o r f r e e r a d ic a ls and because of o th e r
c o n f l ic ti n g ev id en ce.
R eg a rd less o f which mechanism i s c o r r e c t, bo th in v e s tig a to r s ag ree
t h a t th e r e l a t i v e ease o f m e ta la tio n a t any given p o s itio n i s a func­
t i o n o f th e a c i d i t y o f th e hydrogen b e in g d is p la c e d , o r, s ta te d a n o th e r
way, th e s a l t o f th e s tr o n g e s t a c id should be form ed.

W ith t h i s f a c t

i n m ind, th e p re s e n t i n v e s tig a tio n was u n d ertak en i n an attem p t to

72

c o r r e l a t e th e r e l a t i v e a c i d i t y of c e r t a i n hydrocarbo a c id s w ith t h e i r
s tru c tu re .
S e v e r a l p ro c e ss e s a r e e v id e n t i n th e exchange r e a c tio n s s tu d ie d
( 17) :

(1) th e i n i t i a l a tta c k of th e c a t a l y s t on an a lp h a hydrogen to

form th e o rg a n o a lk a li compound, (2) th e exchange r e a c tio n between a
hydrocarbon and a c arb a n io n a n d /o r (3 ) exchange between in o rg a n ic
h y d rid e and. an a lk y la r o m a tic .

Only by th e s e p ath s can th e observed

p ro d u cts be r a t i o n a l i z e d .
The f i r s t s te p , a tta c k by c a t a l y s t , may be v is u a liz e d a s fo llo w s:

( 16 )

The hydrogen (o r deu teriu m ) atom formed can e i th e r u n i t e w ith a second
hydrogen ( o r deuterium ) atom to form hydrogen gas, o r w ith an atom of
potassium to form potassium h y d rid e (o r d e u te r id e ) .

As has been

p re v io u sly m entioned, a tta c k occurs on th e alp h a carbon due to
reso n an ce s t a b i l i z a t i o n o f th e r e s u l t i n g benzyl c a rb an io n .
The n e x t l i k e l y p ro cess i s th e t r a n s f e r o f an alp h a p ro to n (o r
d eu tero n ) from a hydrocarbon to a carb an io n r e s u l t i n g in a new, l e s s
b a s ic c a rb a n io n and l e s s a c id ic hydrocarbon.

This i s i l l u s t r a t e d below:

73

A consequence o f p ath (17) i s t h a t i f equal c o n c e n tra tio n s of carb an io n s
o f d i f f e r e n t b a s i c i t i e s ( i . e . a,a~ d im eth y lb en zy l and a -e th y l-n -m e th y lb e n z y l) w ere to compete f o r a source of deuterium ( i . e . e th y l b enz ene-da ) ,
th e l e s s a c id ic hydrocarbon formed (presum ably, sec-b u ty lb en zen e) should
a c q u ire d eu teriu m more r a p id ly , o th e r f a c to r s b ein g e q u a l.
A n o th er p o s s ib le p a th f o r exchange i s th e d i r e c t a tta c k of a
d e u te rid e io n on th e a lp h a hydrogen of a hydrocarbon, as in d ic a te d :

+ H®

(18)

U n fo rtu n a te ly a t th e p re s e n t tim e , r e a c tio n (18) cannot be d e f i n i t e l y
ru le d o u t a s a p o s s ib le p ro c e ss (alth o u g h th e r e i s l i t t l e precedence
f o r t h i s ty p e o f r e a c t i o n ) .

I t seems p robable t h a t t h i s p ath would

lik e w is e be a m easure o f th e hydrocarbon a c i d i t y , le a d in g to th e same
r e s u l t s a s s te p (17) ( th e l e s s a c id ic hydrocarbon exchanging w ith
deuterium , a t a f a s t e r r a t e ) .

I t w i l l be assumed i n f u r t h e r d is c u s s io n

t h a t exchange o ccu rs predom inantly acco rd in g to ( 1 7 ).

A ll th r e e p ath s

a r e c o n s is te n t w ith f i r s t - o r d e r k i n e t i c s .
From a c o n s id e ra tio n o f th e e l e c t r i c a l e f f e c t s o f th e v a rio u s
a ,a - d ia lk y l. groups on th e hydrocarbons s tu d ie d , q u a l i t a t i v e p r e d ic tio n s
a s to th e o rd e r o f r e l a t i v e a c i d i t y can be made.

The o rd e r o f d e c re a s ­

in g e le c tr o n r e p u ls io n (in d u c tiv e e f f e c t ) i s -C(CH3 ) 3 > -CH(CH3 ) 2 >
-CH2CH3 > -CH3
a c i d i t y a s fo llo w s :

.

T h is le a d s to an o rd e r of d e c re a s in g r e l a t i v e
cumene > sec-b u ty lb en zen e - 2-phenylpentane >

3-p h e n y lp e n ta n e and 2-m eth y l-3 -p h en y lb u t a r e > 2 ,2 -d im e th y l-3 -p h e n y lb u ta n e .

I f s te p (17) xs th e ra te -d e te r m in in g one, th e deuterium exchange r a t e s
sh o u ld in c r e a s e i n th e o rd e r of d e c re a sin g a c i d i t y .

The r e s u l t s o b tain ed

a r e co m p letely re v e rs e d from t h i s o b s e rv a tio n , th e o rd e r o f d e c re a sin g
r a t e s p a r a l l e l i n g t h a t o f p re d ic te d d e c re a sin g a c i d i t y .
The observed r e s u l t s can, how ever, be r a tio n a li z e d by assuming
t h a t s te p (1 6 ) , i n i t i a t i o n of th e exchange by c a t a l y s t , i s r a t e d e te rm in in g .

T his seems e n t i r e ly re a so n a b le from th e f a c t d e c re a sin g

th e amount o f c a t a l y s t d ecreased th e r a t e o f exchange.

F u rth e r, i t i s

f e l t t h a t t h i s s te p i s d i r e c t l y r e l a t e d to th e a c i d i t y of th e hydrogen
d is p la c e d , th e more a c id ic hydrogen b ein g more e a s ily removed ''r e s u ltin g
i n a h ig h e r c o n c e n tra tio n of th e l e s s b a s ic c a rb a n io n ).

This b e l i e f

i s s im ila r to Robert®s (8) assum ption t h a t th e r a t e c o n s ta n ts f o r
rem oval o f p a r t i c u l a r hydrogens in a c id s of s im ila r s tr u c tu r e a re
r e l a t e d to t h e i r e q u ilib riu m i o n iz a tio n c o n s ta n ts , Ha­
l t w i l l be n o te d t h a t th e s t e r i c req u irem en ts o f th e hydrocarbons
s tu d ie d in c r e a s e w ith d e c re a sin g a c i d i t y .

Because of t h i s , i t m ight

be argued t h a t th e d e c re a se in r a t e o f deuterium exchange i s due s o le ly
to a s te r ic f a c to r .

I f s te p (16) ( a tta c k by a potassium atom) i s th e

r a te -d e te r m in in g s te p a s p o s tu la te d , s t e r i c c o n s id e ra tio n s would be
ex p ected to p la y a l e s s dom inant r o le th a n i f p ath (17) ( a tta c k by a
c a rb a n io n ) w ere th e c o n tr o llin g s te p .

I t i s , however, d i f f i c u l t to

d iy o rc e th e s t e r i c f a c t o r s from any of th e p ro c e sse s which may be ta k in g
p la c e .

B ryce-S m ith (5) s tu d ie d th e c o m p etitiv e m e ta la tio n r e a c tio n of

cumene and e th y lp o ta ssiu m and a ssig n e d th e o rd e r of d e c re a sin g r e l a t i v e
a c i d i t y to th e hydrogens on cumene p a ra > meta. > a lp h a > o rth o > -> b e t a .

75

These r e s u l t s a r e n o t co m p atib le w ith th o se o b ta in e d by deuterium
exchange where s u b s t i t u t i o n o ccu rred alm ost e x c lu s iv e ly in th e alp h a
p o s itio n .

B ryce-Sm ith*s r e s u l t s may be due to s e v e ra l f a c t o r s , some

o f w hich a r e n o t d i r e c t l y r e l a t e d to th e a c i d i t y .

One i s t h a t th e

e th y l c a rb a n io n , b ein g v e iy b a s ic , i s n o t a s d is c r im in a tin g a s a
potassiu m atom when d is p la c in g a hydrogen.

T h e refo re , th e lik e lih o o d

of p ro to n rem oval from th e r in g i s g r e a te r .

Secondly, th e s t e r i c

re q u ire m e n t o f th e e th y l carb an io n (p ro b ab ly fu n c tio n in g a s an io n p a i r w ith th e p otassium cati.on) i s c o n s id e ra b ly g r e a te r th a n a
potassiu m atom .

This would te n d to reduce th e p r o b a b ility o f a tta c k

i n th e a lp h a p o s itio n and y e t have l i t t l e e f f e c t on th e meta and p ara
p o s itio n s .
The i n i t i a l a t t a c k , e q u a tio n (1 6 ), need n o t in v o lv e f r e e r a d i c a l s ,
th e p ro c e ss v e ry l i k e l y b ein g co n certed where th e hydrogen atom b ein g
e x p e lle d i s a id e d by a second potassium atom .
shown:

_

T his may be p ic tu re d as

_
R2
T?

*

_^C fH,

Ri q0 K0

f 2K — >

The r e a c tio n m ost p ro b ab ly o ccu rs on th e s u rfa c e of th e l i q u id potassium
m e ta l.
F u r th e r s tu d y on t h i s problem m ight h e lp to e lu c id a te th e mechanism.
A more e x te n s iv e i n v e s t i g a t i o n in to th e e f f e c t v a ry in g amounts of
c a t a l y s t produce on th e r a t e o f exchange would be o f v a lu e i n th e

76

e s ta b lis h m e n t o f s te p (16) a s r a te -d e te r m in in g .

The q u e s tio n of

w h eth er th e hydrogen atom d is p la c e d i n th e i n i t i a l a tta c k forms hydrogen
gas o r potassiu m h y d rid e could be re so lv e d by a n a ly s is f o r hydrogen g as.
A n o th er t e s t f o r th e p o s tu la te d mechanism would be th e a d d itio n of
d e u te r id e io n to th e r e a c tio n m ix tu re .

The r a t e should n o t change

(p ro v id e d th e t o t a l so u rce o f deuterium was c o n s ta n t) i f p ath (16) i s
r a te -d e te r m in in g , w hereas i f (18) were in v o lv e d , a r a t e in c re a s e would
be o b serv e d .
In c o n c lu s io n , i t i s f e l t t h a t th e r e l a t i v e r a t e s ta b u la te d in
T able X r e p r e s e n t th e r e l a t i v e a c i d i t i e s o f th e s e hydrocarbons as
m easured by d eu teriu m exchange over potassium m e ta l.
D suterium exchange a s a method f o r m easuring a c i d i t y can be
extended t o in c lu d e a w ide v a r i e t y o f compounds.

Those p a r t i c u l a r l y

s u ite d a r e hydro carb o n s c o n ta in in g b e n z y lic hydrogens.

An i n t e r e s t i n g

s e r i e s o f compounds to stu d y m ight be a lk y la ro m a tic s , such as cumene,
mono- o r d i - s u b s t i t u t e d i n th e v a r io u s r in g p o s itio n s by groups which
would n o t r e a c t w ith po tassiu m , b u t would be expected to in flu e n c e th e
a c id ity .

The t e r t - b u t y l and phenyl groups a re two such s u b s t itu e n ts .

The s p e c ia l advantage such a system o f f e r s , a t l e a s t when th e o rth o
p o s itio n s a r e u n s u b s titu te d , i s t h a t th e s t e r i c req u irem en ts o f a l l
compounds in t h i s s e r i e s ( i . e . r in g s u b s titu te d cumenes) would be th e
same.
A nother i n t e r e s t i n g c o m p e titiv e exchange r e a c tio n would be t h a t
o f to lu e n e and cumene u s in g e th y lb enz ene-dG a s th e d eu teriu m s o u rc e .
Toluene i s th e m ost a c id ic and cumene th e l e a s t a c id ic of th e th r e e

77

h y d ro c arb o n s.

Because o f t h i s , th e c o n c e n tra tio n o f benzyl c arb an io n s

p r e s e n t i n .t h e r e a c tio n m ix tu re should exceed th o se o f a -p h e n y liso p ro p y l
c a rb a n io n s, im p ly in g t h a t to lu e n e would exchange f a s t e r .

The deuterium

exchange betw een e th y lb en zen e-d a and th e an io n from cumene would be
ex p ected t o proceed n o rm ally , th e d r iv in g fo rc e b ein g th e fo rm atio n
o f th e l e s s b a s ic c a rb a n io n (a-p h e n y l e th y l) and th e l e s s a c id ic hydro­
carbon (cum ene).

E q u ilib riu m should be on th e r i g h t s id e of th e

e q u a tio n below:

■CHCH,

However, i n o rd e r f o r exchange to occur between eth y lb en zen e-d ^ and th e
a n io n from to lu e n e th e exchange in v o lv e s th e p ro d u c tio n o f th e more
b a s ic a n io n ( a - phenyl e t h y l ) and th e more a c id ic hydrocarbon ( to lu e n e ) .
E q u ilib riu m h e re should l i e on th e l e f t o f th e fo llo w in g e q u atio n :

A stu d y o f th e s e r a t e s m ight show t h a t in t h i s r e a c tio n , p ath (17)
(d e u te riu m exchange) becomes ra te -d e te rm in in g f o r to lu e n e w h ile cumene
i s s t i l l dependent upon s te p (16) ( a tta c k by p o ta ssiu m ).

The n e t

r e s u l t may be t h a t cumene would have th e g r e a te r o v e r - a ll exchange r a t e
i n s p i t e o f th e f a c t t h a t i t i s l e s s a c id ic .
i n t e r e s t i n g t e s t o f th e proposed mechanism.

T his would pro v id e an

SUMMARY

78

SUHMA.RX
1 . A g e n e ra l s y n th e tic r o u te to a lp h a -d e u te ra te d a lk y la ro m a tic
h y d ro carb o n s was d ev elo p ed .

T h is Involved cleavage o f th e a p p ro p ria te

a r y l a l k y l m ethyl e th e r w ith potassium m etal and h y d ro ly s is o f th e
r e s u l t i n g o rg a n o m e ta llic w ith deuterium o x id e .

Compounds p rep ared by

t h i s method c o n ta in e d l i t t l e o r no deuterium on th e aro m atic r in g .
fo llo w in g hydrocarbons were s y n th e siz e d u s in g t h i s procedure:

The

cumene-d^,

s e c -b u ty lb e n z e n e -d c , 2- p h en y lp en tan e-d a, 3-p h en y lp en tan e-d a, 2-m e th y l,3-phenylbutane-d<x and 2 ,2 -d im e th y l-3 -p h e n y lb u ta n e -d a .

These s ta n d a rd s

w ere anaJ.yzed mass s p e e tro m e tr ic a lly and th e n used f o r p re p a rin g
c a l i b r a t i o n c u rv es from which unknown amounts o f deuterium could be
d e te rm in e d .
2 . A gas chrom atography a p p a ra tu s was ad ap ted so t h a t sm all volumes
o f hydrocarbon m ix tu res could be se p a ra te d w ith n e a r - q u a n tita tiv e
re c o v e ry o f th e in d iv id u a l components.
3 . A lk y la ro m a tic s , when h e a te d i n th e p resen ce o f a s u ita b le
c a t a l y s t such a s p otassium m e ta l, may exchange hydrogens on th e carbon
a lp h a to th e aro m atic r i n g .

This r e a c tio n was in v e s tig a te d a s a

p o s s ib le method f o r d e te rm in in g th e r e l a t i v e a c i d i t y of h ydrocarbons.
The te c h n iq u e in v o lv ed m easuring th e r e l a t i v e r a t e s a t which two hydro­
carbons compete f o r th e deuterium i n a t h i r d .
J4. In

p r e lim in a r y

e x p erim en ts, th e e f f e c t s o f s e v e ra l c a t a l y s t s ,

te m p e ra tu re ra n g e s , r e a c tio n v e s s e ls and compound ty p e s were s tu d ie d .
The exchange r a t e s v a rie d d i r e c t l y w ith th e amount o f c a t a l y s t and a ls o

79

depended upon th e molar r a t i o o f th e hydrocarbon r e a c ta n ts .

C o n d itio n s

most s u it a b le f o r k in e t ic experim ents in v o lv e d h e a tin g two hydrocarbons
w ith eth ylb en zen e-d ^ f o r v a r y in g tim es a t l 50 ° i n s e a le d tu b e s u sin g
potassiu m m etal a s th e c a t a l y s t .
5 . F i r s t order r a te c o n s ta n ts were o b ta in ed from, p lo t s o f lo g (1 0 0 /
1 0 0 -^D) v s . t , when %D was th e mole p ercent o f deuterium i n th e hydro­
carbon a t tim e t .
found t o be:

The order o f d e c r e a sin g r e l a t i v e exchange r a te s was

cumene, 1 8 .9 j se c -b u ty lb e n z e n e , 8 .1 3 j 2-p h en y lp en ta n e,

6*91j 3 -p h e n y l p en tan e, 1.96,5 2 -m ethy]-3 - phenylbutane, I . 9 O5 2 ,2 -d im e th y l3 - ph en ylbu tane, 1 .0 0 .

This order p a r a lle ls th a t o f p r e d ic te d a c i d i t y

o f th e s e compounds.

6 . A mechanism i s proposed which accommodates th e r e s u l t s o b ta in ed .
T h is in v o lv e s a r a te -d e te r m in in g a tta c k by potassium on th e most a c id ic
hydrogen o f each compound t o form th e organopotassium s a l t fo llo w e d by
deuterium t r a n s f e r betw een th e carbanion o f an o rg a n o m eta llic and a
d e u ter a te d hydrocarbon m o le c u le .

B oth s te p s a re b e lie v e d t o depend on

th e a c i d i t y o f th e hydrocarbons.

7 . In m isc e lla n e o u s exp erim en ts, diphenylm ethane d id n o t exchange
protium f o r deuterium w ith eth y lb en zen e-d tt under a v a r ie t y o f c o n d it io n s .
An e x p la n a tio n f o r t h i s i s o ff e r e d .

An attem pted c o m p e titio n r e a c tio n

betw een cumene and phenylcyclopropane under th e exchange c o n d itio n s
r e s u lt e d in deuterium t r a n s fe r to cumene but p o ly m eriza tio n o f phenyl­
cyclop rop ane .

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80

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A. R u s s e ll, J . Am. Chem. S o c ., J £ , 3871 (1957).

H3- S.

Meyerson and P. N. I n la n d e r, J , Am. Chem. S o c ., J g .>1058(1957)*

HH. F . D a n ie ls , " O u tlin e s o f P h y sic a i C h em istry ,” John W iley and Sons,
I n c ., Hew York, 1951, p. 3H6.
H5* A. G. W orthing and J . G effn er, "T reatm ent of E xperim ental D a ta ,”
John W iley and Sons, I n c ., New York, 19H3, p. 2H0.
H6. For Review s, see re fe re n c e (1) and H. Gilman an d J . W. M orton, J r . ,
’'O rganic R e a c tio n s ,” V ol. 8. John W iley and Sons, I n c ., New York,
195H, c h a p te r 6 .
H7. A. A. M orton and C. E. C la f f , J r . , J . Org. Chem., 20, 981 (1955).
H8. A. A. M orton and E. L. L i t t l e , J r . and W. 0 . S tro n g , J r . ,
Chem. S o c ,, 6 £ , 1339 (19H3)

J . Am.

H9- A. A. M orton, J . T. M assengale and M. L. Brown, J . Am. Chem. S o c .,
6 7 , 1620 ( 19 H5 ) .
50. A. A.Morton, J .

Am. Chem. Soc., 69, 969 (19H?)*

5 1 . A. A. Morton and E. L. Little, Jr., J. Am. Chem. Soc., J 1 ,H 8 7 (19H9 ) .
5 2 . D. B ry ce-S m ith . V. Gold, D. P. N. S a tc h e ll, J . Chem. S o c ., 27ii3

(195H).
53* A. A. M orton, C. E. C la f f , Jr. and F. W. C o llin s , J. Org. Chen.,
2 0 , H28 (1 9 5 5 ).
5H. D. B ryce-S m ith, J . Chem, S o c ,, 1603 (1956).
55* C. K. In g o ld , " S tr u c tu r e and Mechanism i n O rganic C h e m istry ,”
C o rn e ll U n iv e r s ity P r e s s , I th a c a , New York, 1953, p. 71.
5 6 . J . W. Coperihaver, M. F. Roy and C. S. M arv ell, J . Am. Chem. S o c .,
1311 (1 9 3 5 ).
57* G. A. R u s s e ll, A b s tr a c ts o f P apers P resen ted a t American Chemical
S o c ie ty M eeting, D iv is io n of O rganic C hem istry, Paper 57, Chicago,
Septem ber 7 -1 2 , 1958*

APPENDIX

Optical

D e n sity

F ig u re 1 0 . P e rc e n t d eu teriu m c o n te n t o f m ix tu res o f
cumene and cumene-d^ i n carbon te t r a c h l o r i d e v s .
o p t i c a l d e n s ity a t k.6j? m icrons. (C o n c e n tra tio n o f
hy drocarbon = 2.97 M.)

0.20

10

P e rc e n t Deuterium

83

F ig u re 1 1 . P e rc en t deuterium c o n te n t o f m ixture of
3“ phenylpentane. and 3~phenylpentane~dG in. carbon t e t r a ­
c h lo r id e v s . o p t i c a l d e n s ity a t 1+.68 m icrons.
(C o n c e n tra tio n o f hydrocarbon = 2.1+0 M.)

32

Optical

D e n sity

0 . 21+

0.16

0.08

Percent Deuterium

F ig u re 1 2 , P e rc e n t d e u te riu m 'c o n te n t of m ix tu res of
2 -phen y lp en tan e and 2 -p h en y lp en tan e-d a i n carbon t e t r a ­
c h lo r id e v s . o p tic a l, d e n s ity a t U*67 m icro n s.
(C o n c e n tra tio n o f hydrocarbon = 2.39 M.)

85

0.20

0 .1 2

Optical

D en sity

0.16

0.08

0

2

6

8

Percent Deuterium

10

12

86

F ig u re 1 3 . P e rc e n t deuterium c o n te n t o f m ix tu res of
2 -m e th y l-3 “ p henylbutane and 2-m ethyl-3~ phenylbutane-da
in. carb o n t e t r a c h l o r i d e v s , o p tic a l d e n s ity a t U-70
m ic ro n s, . (Concent r a t io ii of hydrocarbon = 2.1+2 M.)

0.16

~

Optical

D e n sity

0.12

0.08

0.0U

10
Percent Deuterium

F ig u re l l ; . P erc e n t deuterium c o n te n t o f m ix tu re s of
2 ,2 ~ d im eth y l-3 ~ p h en y lbutane and 2 ,2 -d im e th y l“3**phenylb u ta n e -d ^ i n carbon t e t r a c h l o r i d e v s . o p tic a l d e n s ity
a t 1±.69 m icro n s. (C o n c e n tra tio n o f hydrocarbon = U*l6

Optical

D en sity

0 .2 0

0 .1 0

0.05

0

2

6
P e rc e n t Deuterium

8

88

TABLE XI
COMPETITION BETWEEN CUMENE AND sec-BUTYLBENZENE^
(0 .1 0 g . p o tassiu m m e ta l, l£ 0 , 1.200 m3., sto ck s o lu tio n '' p e r ampoule)

Sample

Time
( h r s .)

Potassium
W eight ( g .)

P ercen t Deuterium Exchanged
Cumene
sec-B utylbenzene

1

2

0 . 10U

0 .7

1 .1

2

h

0.103

5 .3

2.2

3

6

0.0 96

1 0 .1

U*9

k

8

0.102

11.0 .

U.6

5

10

O.lOii

1U.2

6.3

■ft
S tock s o lu tio n * I . 8I4.O ml. e th y lb en zen e-d a ^ 2.100 m l. cumene
2 .3I4.O m3.. se c -b u ty lb e n z e n e .

89

TABLE X II
COMPETITION BETWEEN sec-BUTYLBENZENE AND 3 - PHENYLgENTANE
(0 .2 0 g. potassiu m m e ta l, 1$0 , l.I|0 0 m l. sto ck s o lu t i o n ' p er ampoule)

Sample

Time
( h r s .)

Potassium
W eight '( g . )

1

2

0.209

2 .1

0 .7

2

h

0.199

3 .7

0.9

3

b

0 .2 0 $

b .l

0.9

b

6

0 .2 0 k

6.0

1-5

$

6

0.20U

5 .6

l.k

6

8

0.20$

6 .6

1 .7

7

8

0.207

6.7

1 .7

8

10

0.199

8 .6

2.0

9

10

0.207

8.3

2 .1

P e rc e n t Deuterium Exchanged
s ec-B utylb enz ene 3-P henylpentane

"Stock s o lu tio n : $ .0 0 m l. eth y lb en zen e-d c , U.U70 m l. s e c -b u ty l­
ben zen e, )+.9$0 m l. 3 -p h e n y lp e n ta n e .

90

TABLE X III
COMPETITION BETWEEN sec-BUTXLBENZENE AND 2-PHENYLPENTANE
( 0 ,2 0 g. po tassiu m m e ta l, l £0 , 1 .L.00 ml. sto c k s o lu t io n ' p er ampoule)

Sample

Time
( h r s .)

Potassium
W eight ( g .)

P e rc e n t Deuterium Exchanged
&*Butylb enz ene 2-Phenylpentane

1

2

0 .2 0 6

3 ,0

2 .6

2

2

0.208

1 ,9

1 .8

3

h

0.203

1*,0

3 . It

h

k

0.2 0 1

U.3

3 .7

£

6

0.201

6 ,£

6 .1

6

6

0.200

6,2

£ .6

7

8

0.206

8 ,0

6.8

8

8

0.202

8.3

7-0

9

10

0.203

8,7

7 .1

10

10

0.206

7 .8
—

6.7
—

•

^S tock s o lu tio n ; £.000 m l. eth y lb e n z e n e -d a , It.£70 m l. s e c -b u ty l­
b enzene, k ' 9 60 m l. 2 -p h e n y lp e n ta n e .

91

TABLE XIV
COMPETITION BETWEEN sec-BUmBENZENE AND 2-METEYL-3-PgENYLBUTJ\NE
(0 .2 0 g. p o tassiu m m e ta l, 150 , 1 -ljli.0 m l. s to c k s o lu tio n '' p e r ampoule)

Sample

Time
( h rs .)

1

2

0.201;

2.2

0 .8

2

3

0.203

3-5

0 .6

3

k

0.203

3.9

0 .9

It

6

0.201

6.2

1 .5

5

6

0.205

6 .0

1*7

6

8

0.201;

7.2

1*9

7

10

0.205

9*7

2.1*

8

10

0.207

8 .5

1 .9

9

15

0.200

1 2 .1

3-0

10

20

0 .2 0 5

15*2

3 .7

Potassium
W eight ( g .)

P e rc e n t D euterium Exchanged
sec-vBb.tylbenz ene 2-M ethyl~3-phenylbu ta n e

"’'S to ck s o lu tio n : 5*500 m l. e th y lb e n z e n e -d ^ 1;.917 m l. s e c b u ty lb en ze n e j 5*390 m l. 2 -m e th y l-3 "p h en y lb u tan e.

92

TABLE X7
COMPETITION BETWEEN sec-BIJTTLBENZENE AND 2 ,2 -DIMETHYL-3- PHENYLBUTANE
( 0 .2 0 g. potassiu m m e ta l, 1 5 0 ° , 1 .^ 0 0 ml. sto c k s o lu ti o n ' p er ampoule)

Sample

Time
( h r s .)

P otassium
W eight ( g .)

P e rc e n t D euterium Exchanged
se c - Buty lb enz ene 2.,2-D im ethyl-3~phenylb u tan e

].

2

0.299

3 .0

o.h

2

2

0.300

2 .6

0 .3

3

k

0.298

U.7

0 .6

k

h

0.302

J4.8

0 .7

5

6

0.303

6 .6

0 .8

6

6

0.301

6 .6

0 .8

7

8

0.306

7.8

0 .9

8

8

0 .3 0 1

7.8

0 .9

9

10

0.303

9 .1

1.0

10

10

0.302

7.8

1.3

"Stock s o lu tio n ; 6.000 m l. e th y lb e n z e n e -c ^ ; I4,.^470 ml. s e c b u ty lb en ze n e ; 3 .1 8 0 m l. 2 , 2 -d im e th y l- 3 -p h e n y lb u ta n e .

93

TABLE XVI
FIRST ORDER. RATE CONSTANTS FOR DEUTERIUM TRANSFER TO CUMENE
IN COMPETITION WITH sec-BUTYLBENZENE
(D ata c a lc u la te d from Table X I.)

Sample

Time
( s e c .)

P erce n t
. D
0

Log
(100/100-^D)

e ki
_i
(x io " ) {s e c . )

—

—

1

0

2

7200

0.7

0.00303

0.97

3

1UI4OO

£.3

0.02366

3.78

h

21600

10.1

0 .0i|622

b'93

5

28800

11.0

0.05061

U.05

6

36000

1U.2

0.06651

I4.26

.

Average
L e a st Squares Slope

3.60 ± 1.05
1*011

9k

TABLE XVII
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
sec-BUTYLBENZENE IN COMPETITION WITH CUMENE
(D ata c a lc u la te d from Table XI)

Sample

Time
( s e c .)

P e rc e n t
D

Log
(100/100-gD)

0

-----

(xlO 6) ( s e c .

_1

)

-----

1

0

2

7200

1 .1

0.001+79

1.53

3

ll+Uoo

2.2

0.00966

1 .5 5

k

21600

k-9

0.02181

2.33

5

28800

1+.6

0 .0201+1+

1.63

6

36000

6.3

0.02825

1 .8 1
Average

L e a s t S quares Slope

1 .7 7 ± 0.21+
1.82,

95

TABLE XVIII
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
sec-BUTXLBENZENE IN COMPETITION WITH 3 - PHENYLPENTANE
(D ata c a lc u la te d from Table X II)

Sample

Time
( s e c .)

P e rc en t
D

Log
(100/100-#D)

ki
-1
(xlO 6 ) ( s e c . )

0

-----

-----

1

0

2

7200

2 .1

0.0092U

2.96

3

1)|)|00

3 .7

0.01636

2.62

k

HUiOO

I4. I

0.01820

2.91

5

21600

6 .0

0.02686

2.86

6

21600

5 .6

0.02502

2.67

7

28800

6 .6

0.02967

2.37

8

28800

6.7

0.03011

2 .l a

9

36000

8 .6

0.03906

2.50

10

36000

8.3

0.03763

2.U1
Average

L e a st Squares Slope

2.5U ± 0.20
2 -S l

96

TABLE XIX
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
3-PHENXLPENTANE IN COMPETITION WITH sec-BUTYLBENZENE
(D ata c a lc u la te d from TABLE X II)

Time
(sec-)

P e rc e n t
D

Log
(100/100-^D)

1

0

0

----

2

7200

0 .7

0.00303

0.969

3

lUUoo

0 .9

0.00393

0.629

k

U |)|00

0 .9

0.00393

0 .6 29

5

21600

1 .5

0-00655

O.698

6

21600

l.U

0.00612

0.653

7

28800

1 .7

0 . 007U5

0.596

8

28800

1 .7

0.007U5

0.596

9

36000

2.0

0.00877

0.5 6 1

10

36000

2 .1

0 .0092U

0.591

Sample

■

(xlO

e ki
.1
) (sec. )
—

Average
L e a s t Squares Slope

0.658 ± 0.078
0.6*7

97

TABLE XX
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
sec-BUTYLBEN2ENE IN . COMPETITION WITH 2-FHENYLPENTANE
(D ata c a lc u la te d from Table X I I I )

Sample

Time
( s e c ,)

P erc en t
D

Log
(100/100- %D)

(xlO 6) ( s e c .

)

----

----

1

0

2

7200

3.0 .

0.01322.

U.23

3

7200

1.9

0.00877

2.81

k

lUUoo

U-0

0.0177U

2 ,8U

5

lUUoo

J4.3

0.01907

3.05

6

21600

6.5

0.02818

3.01

7

21600

6.2

0.02780

2.96

8

28800

8.0

0.03623

2.90

9

28800

8.3

0.03763

3.01

10

36000

8.7

0.039^3

2.^3

13.

36000

7.8

0.03£27

2.26

0

-1

Average
L e a st Squares Slope

2.96 ± 0.29
2 .J 1

98

TABLE XXI
FIRST ORDER RATE' CONSTANTS FOR DEUTERIUM TRANSFER TO
2 - PHENYLPENTANE IN COMPETITION WITH sec-BUTYLBENZENE
(D ata c a lc u la te d from T able X III)

Sample

Time
( s e c .)

P e rcen t
D

Log
(100/100*#D)

(xlO 6) ( s e c .

)

-----

-----

1

0

2

7200

2 .6

0 . 011HU

3 -66

3

7200

1 .8

0.00788

2.52

h

liUiOO

3.h

0.01502

2 .J4O

5

lUHoo

3 .7

0.01636

2.61

6

21600

5 .6

0.02502

2.67

7

21600

6 .1

0.02735

2.92

8

28800

6.8

0.03060

2.U5

9

28800

7 .0

0.03153

2.52

10

36000

6.7

0.02911

1 .86

11

36000

7 .1

0.03197

2.05

0

„i

Average
L e a st Squares Slope

2,57 ± 0 .32
2.91

99

TABLE XXII
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
sec-BUTYLBEN?,ENE JN COMPETITION WITH 2-METHYL-3- PHENXLBUTANE
(D ata c a lc u la te d from Table XIV)

Sample

Time
( s e c .)

P erc en t
D

Leg
(100/ 100- ^D)

ki
«i
(xlO 6) ( s e c . )

-----

-----

1

0

2

7200

2.2

0.00966

3-09

3

10800

3-5

0.015U9

3.30

h

ihkOO

3 .9

0.01728

2.76

5

21600

6 .2

0.02780

2.96

6

21600

6 .0

0,02686

2.86

7

28800

7.2

0.032L.6

2.60

8

36000

9-7

0.05530

2.83

9

36000

8 .5

0.03858

2.57

10

514000

1 2 .1

0.05603

2.39

11

72000

15-2

0.07159

2.29

0

Average

CM

L e a st Squares Slope

2.76 ± 0 .2 5

100

TABLE XXIII
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
2-METHYL-3- PHENILBUTANE IN COMPETITION WITH sec-BUTYLBENZENE
(D ata C a lc u la te d from Table XIV)

Sample

Time
( s e c .)

P erc en t
D

Bog
(100/100-^D)

kx
(xlO 6) ( s e c .

—

-----

1

0

2

7200

0 .8

0.00350

1.120

3

10800

0 .6

0.00260

0.551+

1+

DillOO

0 ,9

0.00393

0.629

5

21600

1 .5

0.00655

0.698

6

21600

1 .7

0 .0071+5

0.791+

7

28800

■1.9

0 .0083I+

0,667

8

36000

2.1+

0.01055

0.675

9

36000

1.9

0 .0083U

0.531+

10

51+000

3 .0

0.01322

0.561+

11,

72000

3 .7

0.01636

0.523

0

Average
L e a s t Squares Slope

)

0.676 ± 0 . H 8
o .S tf

101

TABLE' IX17
FIRST ORDER RATE CONSTANTS FOR DEDTERHJM TRANSFER TO
sec-BUTYLBENZENE IN COMPETITION WITH 2 , 2-DIMETHYL-3“ PHENYLBUTANE
( Data c a lc u la te d from Table XV)

Sample

Time
( s e c .)

P ercen t
D

LoS
(100/100-^D)

ki
_i
(xlO 6) ( s e c . )

----

-----

1

0

2

7200

2 .6

o.onJjJi

3.6 6

3

7200

3.0

0.01322

U.23

h

1UU00

U.7

0.02090

3.3U

5

1UU00

lw8

0.02135

3.U2

6

21600

6 .6

0.02967

3 .1 6

7

21600

6 .6

0.02967

3 .1 6

8

28800

7.8

0.03527

2.82

9

28800

7-8

0.03527

2.82

10

36000

9 .1

0 .0lpJi3

2.65

11

36000

7.8

0.0352-7

2.26

0

'

Average
L e a st S quares Slope

3 .1 5 ± 0.U3

102

'BIBLE XXV
FIRST ORDER RATE CONSTANTS FOR DEUTERIUM TRANSFER TO
2,2-DIMETHYL-3-PHENYLBUTA.NE IN COMPETITION WITH sec-BUTYLBENZENE
(Data c a lc u la te d from Table XV)

Sample

Time
(sec.)

Percent
D

Log
(i o o /i q o -$d )

_i
(xlO6) (sec.
------

1

0

2

7200

0.1*

0 .00171*

0.557

3

7200

0 .3

0.00131

0.1*17

1*

114*00

0 .6

0.00262

0.1*18

5

114*00

0 .7

0.0030£

0.1*88

6

21600

0 .8

0.0031*9

0-372

7

21600

0 .8

0.0031*9

0.372

8

28800

0 .9

0.00393

0.3H*

9

28800

0 .9

0.00393

0.311*

10

36000

1 .0

0.001*3 6

0.279

11

36000

1.3

0.00568

0.361*

0

)

—

Average
Least Squares Slope

0.390 ± 0P65
0 .3 & )

100

Figure

1$.

Infrared

Spectrum

£o

CO

o

H

d
©
©

I

CO

o

O

uoTscxuistreui q-Tieojad

CM

c

o
(in Carbon

On

of Ethylbenzene-da

T e tr a c h lo r id e ) .

103

100

Figure

16.

Infrared

to

uo

o

CO

$M
d(D

H

CO

I

o

U O T SST U ISirejJj q .U 9 0 J 8 J

of E th y lb en zen e-d a, a (pure l i q u i d ) .

0\

Spectrum

io U

CM

100

Figure

1?.

Infrared

Spectrum

Os

ao

CO

O

Q

uoxss'oustreaj, qAieoued

O
(in Carbon

T e tr a c h lo r id e ) .

O

of Diphenylmethane-da

105

100

Figure

18.

Infrared

Spectrum

CO

o
CO

o

U O T S S T U I S tfB J l,

TJ 3 0 J 8 d

oCM

o

C\i

a (in

On
to

6
o
Sh
O

-P

bO
£u
<
t—
a>I

I

of Diphenylmethane-do

Carbon

T e tr a c h lo r id e ) .

106

100

Figure

19*

Infrared

CO

MD

CO

O

O

UOTBSTUISTTBJCJ, q.U 8O J0J

O
■S
A
tL
§
rH
<D

I

Carbon

w
£o
o
(in

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