THE A C I D I T I E S OF ARYLAMINES AND ARYLAMMONIUM IONS

by

DOUGLAS DOLMAN

B.Sc, University of British Columbia, 1962

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF

THE REQUIREMENTS FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

in the Department

of Chemistry

We a c c e p t this thesis as conforming to the

required standard

THE UNIVERSITY OF BRITISH COLUMBIA

March, 1966
 In presenting this thesis in partial fulfilment of

the requirements for an advanced degree at the University of

British Columbia, I agree that the Library shall make it freely

available for reference and study. I further agree that per-

mission for extensive copying of this thesis for scholarly

purposes may be granted by the Head of my Department or by

his representatives„ It is understood that copying or publi-

cation of this thesis for financial gain shall not be allowed

without my w r i t t e n permission.

Department of

The U n i v e r s i t y o f B r i t i s h Columb/a
V a n c o u v e r 8, Canada

Date
/
/nOyLcX
 The U n i v e r s i t y of B r i t i s h Columbia

FACULTY OF GRADUATE STUDIES

PROGRAMME OF THE

FINAL ORAL EXAMINATION

FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

of

DOUGLAS DOLMAN

B.Sc, The U n i v e r s i t y of B r i t i s h Columbia, 1962

IN ROOM 261, CHEMISTRY BUILDING

THURSDAY, MARCH 10, 1966, AT 3:30 P.M.

COMMITTEE IN CHARGE

Chairman: I . McT. Cowan

A. V. Bree D. E. McGreer
G. H. Dixon R. E. P i n c o c k
C. A. McDowell . R. Stewart

E x t e r n a l Examiner: J . T. Edward
Department o f Chemistry
McGill University

Research S u p e r v i s o r : R; Stewart
 THE ACIDITIES OF ARYLAMINES AND.ARYLAMMONIUM IONS

ABSTRACT

In order to study quantitatively the a c i d i t y of very

weak acids and at the same time the effect of a polar
aprotic solvent on the b a s i c i t y of hydroxide ion a
Hammett H_ a c i d i t y function based on the i o n i z a t i o n of
24 substituted anilines and diphenylamines has been
established i n the system dimethylsulfoxide-water-
tetramethylammonium hydroxide. The b a s i c i t y of hydro-
xide ion i s increased dramatically as the solvent i s
changed from water to dimethylsulfoxide. The H_ of a
0 , 0 1 1 molar solution of tetramethylammonium. hydroxide
ranges from 12 i n water to 26 i n 9 9 . 6 mole % dimethylsul-
foxide-water, an increase in. b a s i c i t y of fourteen powers
of ten. The increase i n b a s i c i t y i s due to the increased
a c t i v i t y of the hydroxide ion brought about by the reduc-
tion i n i t s solvation i n the poor anion-solvating
solvent, dimethyl sulfoxide and indicates the extensive
solvation enjoyed by the hydroxide ion i n water.

The PKTTA values of the indicator acids vary from

1 3 . 8 4 for 2V4-dinitrodiphenylamine to 2 5 . 6 3 f o r 3 -
chloroaniline. From a plot of log versus Hammett
substituent constants ( cT) f o r six monosubstituted d i - .
phenylamines a rho ( p ) value of 4 . 0 7 i s found. The
magnitude of substituent effects on the a c i d i t y of a n i l i n e
appears to be quite s i m i l a r . The a c i d i t i e s of a l l the
substituted diphenylamines do not follow the above men-
tioned c o r r e l a t i o n with Hammett o" constants; the pKy^
values of 4-amino-, 4-methoxy-, 4-methylsulfonyl-, and
4-nitrodiphenylamine are a l l less than expected from the
Hammett <5 constants for the substituents i n these com-
pounds. The 4 - n i t r o substituent exerts a p a r t i c u l a r l y
large acid-strengthening effect on the a c i d i t i e s of ani-
l i n e and diphenyl amine; the decreases i n pKjj^ being
approximately 8 . 4 and 6 . 8 pK units, respectively.
The pK^values of 17 compounds other than those i n -
dicators used to establish the H_ function have been deter-
mined with the a i d of the H_ function. Most of these com-
pounds are alkyl-substituted 4 - n i t r o a n i l i n e s . A l k y l
groups ortho to the amino group of 4 - n i t r o a n i l i n e cause
a decrease i n the pKy^ (an increase i n a c i d i t y ) . Simi-
l a r l y , N-methyl-, N-ethyl-, and N-isopropyl-4-mitro-
a n i l i n e a r e a l l s t r o n g e r acids' than 4 - n i t r o a n i l i n e i t s e l f .
An e x p l a n a t i o n f o r t h e e f f e c t s of a l k y l s u b s t i t u e n t s on
the a c i d i t y of 4 - n i t r o a n i l i n e i n terms of the s o l v a t i o n
of both t h e i o n i z e d and u n i o n i z e d amines i s advanced.

A Hammett H a c i d i t y f u n c t i o n based on t h e p r o t o n a t i o n
0

of 17 diphenylamines i n 20 volume % ethanol-aqueous sul-

f u r i c a c i d has been e s t a b l i s h e d . The H v a l u e f o r t h e
0

most a c i d i c s o l u t i o n s t u d i e d i s -6.97 f o r 11.2 molar s u l -

furic, acid. T h i s a c i d i t y f u n c t i o n d i f f e r s from t h a t based
on the p r o t o n a t i o n of azobenzenes i n the same s o l v e n t
system; the l a t t e r a c i d i t y f u n c t i o n d i v e r g e s t o more, ne-
g a t i v e H v a l u e s . a s the s u l f u r i c a c i d c o n c e n t r a t i o n i n -
0

creases.

The pKgj^j. v a l u e s f o r the p r o t o n a t i o n of the d i p h e n y l -

amines v a r y from 1.36 f o r 4-methoxydiphenylamine t o -6.21
for 4,4'-dinitrodiphenylamine. A plot, of l o g Kgjj^. v e r s u s
Hammett, <T c o n s t a n t s f o r f i v e mono-substituted d i p h e n y l -
amines y i e l d s a rho ( p ) v a l u e of.3.36. The yKgj^. v a l u e s
f o r 4-methoxy-, 4-m.et.hyl-, 4 - m e t h y l s u l f o n y l - , and 4 - n i t r o -
diphenylamine a r e a l l l e s s (morenegative) than expected
from the Hammett substituent. c o n s t a n t s . S u b s t i t u e n t
e f f e c t s on the b a s i c i t i e s of a n i l i n e and diphenylamine
are the same. T h i s i s e v i d e n t from t h e fact, t h a t a p l o t
of the pKgH-j- v a l u e s of 11 diphenylamines v e r s u s the pKgm-
v a l u e s of the c o r r e s p o n d i n g a n i l i n e s y i e l d s a good
s t r a i g h t l i n e w i t h s l o p e 1.01.

The b a s i c i t i e s of s e v e r a l n i t r o - s u b s t i t u t e d d i p h e n y l -
amines appear t o v a r y r e g u l a r l y and do not r e f l e c t the
presence of a s t r o n g i n t e r a c t i o n between the n i t r o group
and s u l f u r i c a c i d .

A p l o t of the a c i d i t y v e r s u s t h e b a s i c i t y ( p K ^
versus pKgjjj.) f o r n i n e diphenylamines y i e l d s , a s t r a i g h t
l i n e w i t h s l o p e 1.30. In a s i m i l a r p l o t f o r 33 s u b s t i t u t e d
a n i l i n e s and diphenylamines two types of behaviour a r e
observed. Those a n i l i n e s and diphenylamines without an
ortho or para h i t r o group f a l l about t h e l i n e w i t h s l o p e
1.30 w h i l e those amines w i t h a t l e a s t one n i t r o group i n
the ortho or p a r a p o s i t i o n f a l l on a d i f f e r e n t , curved
l i n e w i t h a s l o p e of l e s s than u n i t y .
 GRADUATE STUDIES

F i e l d of Study: Chemistry
Topics i n Physical Chemistry J . A. R; Coope
A. Bree
Topics i n Inorganic Chemistry W. R. Cullen
N. B a r t l e t t
H. C. Clarke
J. T. Kwon
Topics i n Organic Chemistry J. P. Kutney
F. McCapra
A. I . Scott
Spectroscopy and Molecular C. Reid
Structure E. J . Wells
L. W. Reeves
K. B. Harvey
Chemical Kinetics G. B. Porter
D. G. L. James
Physical Organic Chemistry R. Stewart
Organic Reaction Mechanisms R. Pincock
Linear Algebra Ri C. Thompson
 i

ABSTRACT

Supervisor: Professor R. Stewart

In o r d e r to study quantitatively the acidity of

v e r y weak a c i d s and a t the same time the effect of a polar

aprotic solvent on t h e basicity of h y d r o x i d e i o n a Hammett

H_ acidity f u n c t i o n b a s e d on the i o n i z a t i o n of 24 substituted

anilines and d i p h e n y l a m i n e s has been e s t a b l i s h e d in the

system dimethylsulfoxide-water-tetramethylammonium hydroxide.

The b a s i c i t y of h y d r o x i d e ion i s increased dramatically

as the solvent is changed from water to d i m e t h y l s u l f o x i d e .

The H _ o f a 0.011 molar s o l u t i o n of tetramethylammonium

hydroxide ranges f r o m 12 i n water to about 26 in 99.6

mole % d i m e t h y l s u l f o x i d e - w a t e r , an i n c r e a s e in basicity of

fourteen powers of ten. The i n c r e a s e in basicity is due to

the increased activity of the hydroxide ion brought about

by t h e reduction in its solvation i n the poor anion-

solvating solvent d i m e t h y l s u l f o x i d e and i n d i c a t e s the

extensive s o l v a t i o n e n j o y e d by t h e hydroxide ion i n water.

The PKJJA. v a l u e s of the indicator acids vary from

13.84 for 2,4 _ d

i itrodiphenylamine
n
to 25.63 f o r 3-chloro-

aniline. From a p l o t of l o g KJJA. v e r s u s Hammett substituent

constants (CT) for six monosubstituted diphenylamines a rho

( P ) value of 4.07 is found. The m a g n i t u d e of substituent

 ii

effects on the acidity of a n i l i n e appears t o be quite

similar. The a c i d i t i e s of all the s u b s t i t u t e d diphenylamines

do n o t f o l l o w the above mentioned c o r r e l a t i o n w i t h Hammett 0~

constants; the pK H A values of 4-amino-, 4-methoxy-, 4-

methylsulfonyl- and 4 - n i t r o d i p h e n y l a m i n e a r e all less than

expected f r o m the Hammett C Tconstants for the substituents

in these compounds. The 4 - n i t r o substituent exerts a

particularly large acid-strengthening effect on the acidities

of a n i l i n e and d i p h e n y l a m i n e ; the decreases i n pKjj^ b e i n g

approximately 8.4 and 6 . 8 pK u n i t s , respectively.

The pKjj^ v a l u e s of 17 compounds o t h e r than those

indicators used to e s t a b l i s h the H _ f u n c t i o n have been

d e t e r m i n e d w i t h the a i d of the H_ f u n c t i o n . Most o f these

compounds a r e alkyl-substituted 4-nitroanilines. Alkyl

groups ortho to the amino g r o u p o f 4 - n i t r o a n i l i n e cause a

decrease i n the p K ^ (an

H increase i n the acidity).

Similarly, N - m e t h y l - , N - e t h y l - , and N - i s o p r o p y l - 4 - n i t r o a n i l i n e

are all stronger acids than 4 - n i t r o a n i l i n e itself. An

explanation for the effects of alkyl substituents on the

acidity of 4 - n i t r o a n i l i n e i n terms of the s o l v a t i o n of both

the i o n i z e d and u n i o n i z e d amines is advanced.

A Hammett H Q acidity f u n c t i o n b a s e d on the protonation

of 17 d i p h e n y l a m i n e s i n 20 volume % e t h a n o l - a q u e o u s sulfuric

a c i d has been e s t a b l i s h e d . The H n value for the most acidic

 iii

solution studied is -6.97 for 11.2 molar sulfuric acid.

This acidity f u n c t i o n d i f f e r s from that b a s e d on the

protonation of azobenzenes i n the same s o l v e n t system;

the latter acidity function diverges t o more n e g a t i v e H Q

values as the s u l f u r i c acid concentration increases.

The p K j + v a l u e s
BI for the protonation of the

diphenylamines vary f r o m 1.36 for 4-methoxydiphenylamine

to -6.21 for 4,4*-dinitrodiphenylamine. A plot of log

Kgjj+ v e r s u s Hammett 0~ c o n s t a n t s for five mono-substituted

diphenylamines y i e l d s a rho (p) value of 3.36. The

pKgjj+ v a l u e s for 4-methoxy-, 4-methyl-, 4-methylsulfonyl-,

and 4 - n i t r o d i p h e n y l a m i n e a r e a l l less (more negative)

than expected from the Hammett s u b s t i t u e n t constants.

Substituent effects on the basicities of a n i l i n e and

diphenylamine are the same. This i s evident f r o m the fact

that a plot of the PK3JJ+ v a l u e s of 11 d i p h e n y l a m i n e s

versus the pKg + v a l u e s

H of the corresponding a n i l i n e s yields

a good s t r a i g h t l i n e with slope of 1.01.

The b a s i c i t i e s of several nitro-substituted

diphenylamines appear to vary r e g u l a r l y and do n o t reflect

the presence of a strong interaction between the nitro

g r o u p and s u l f u r i c acid.
 iv

A plot of the acidity versus the basicity (pKjj^

versus pKg +) H for nine diphenylamines y i e l d s a straight

line with slope 1.30. In a s i m i l a r plot for 33 substituted

anilines and d i p h e n y l a m i n e s two t y p e s o f behaviour are

observed. Those anilines and d i p h e n y l a m i n e s w i t h o u t an

ortho or para nitro group f a l l about the line with slope

1.30 while those amines w i t h at least one n i t r o group in

the ortho or para position fall on a d i f f e r e n t , curved

line with a slope of less than unity.

 V

TABLE OF CONTENTS

Page

INTRODUCTION 1

A. D e f i n i t i o n s o f A c i d and Base 1
B. The A c i d D i s s o c i a t i o n C o n s t a n t .. .. 2
C. Hammett A c i d i t y F u n c t i o n s 5
D. O t h e r Methods o f M e a s u r i n g A c i d i t i e s .. 19
E. F i r s t and S e c o n d D i s s o c i a t i o n C o n s t a n t s of
Dibasic Acids 21

OBJECTS OF PRESENT RESEARCH 24

METHODS OF APPROACH 26

EXPERIMENTAL 27

A. P r e p a r a t i o n and P u r i f i c a t i o n o f I n d i c a t o r s 27
B. P u r i f i c a t i o n of S o l v e n t s 27
C. P r e p a r a t i o n of S o l u t i o n s 29
D. S p e c t r a l Measurements i n t h e D i m e t h y l s u l f oxide -
Water S y s t e m 31
E. S p e c t r a l Measurements i n 20 Volume % E t h a n o l -
Aqueous S u l f u r i c A c i d .. .. .. .. 34
F. Treatment of the S p e c t r a l Data .. .. 35

RESULTS 39

A. The S y s t e m D M S O - W a t e r - T e t r a m e t h y l a m m o n i u m
Hydroxide .. .. .. .. .. .. 39
B. The S y s t e m "20 % E t h a n o l - A q u e o u s S u l f u r i c
Acid 52
C. P r o b a b l e E r r o r i n H and pK V a l u e s .. .. 55

DISCUSSION 61

A. V a l i d i t y o f the H _ F u n c t i o n 61
B. I n t e r p r e t a t i o n of S o l v e n t B a s i c i t y .. .. 65
C. V a l i d i t y of the H F u n c t i o n
Q 73
D. Comparison of the H F u n c t i o n f o r D i p h e n y l -
Q

amines w i t h o t h e r H F u n c t i o n s
Q .. .. 77
E. C o r r e l a t i o n of S t r u c t u r e w i t h A c i d i t y .. 82
F. A c i d and Base S t r e n g t h s o f N i t r o - s u b s t i t u t e d
A r o m a t i c Amines .. .. .. .. .. 105
G. C o m p a r i s o n of the A c i d i t y and B a s i c i t y o f
A n i l i n e s and D i p h e n y l a m i n e s .. .. .. 118
 vi

SUGGESTIONS FOR FURTHER WORK 127

Appendix A: Preparation and P u r i f i c a t i o n

of Indicators 132

Appendix B: Spectral Data f o r the Indicators 145

A p p e n d i x C: I o n i z a t i o n R a t i o Data .. .. 150

BIBLIOGRAPHY 159
 vii

LIST OF TABLES

Page
I The pKjj Values of the I n d i c a t o r s
A

Used t o E s t a b l i s h the H_ A c i d i t y
Function .. .. .. .. . . . . 41

II H_ Values f o r the System DMSO-Water-

Tetramethylammonium Hydroxide
(0.011 M) 42

III Summary of P K H A Values of V a r i o u s Amine

Acids 49

IV Values of pKgji+ f o r the Diphenylamines

Used t o E s t a b l i s h the H A c i d i t y
Q

Function 54

V H Values f o r the System

D "20 % E t h a n o l " -
Aqueous S u l f u r i c A c i d .. .. .. 56

VI The pKjjA Values of Some A l k y l - s u b s t i t u t e d

A n i l i n e s and Diphenylamines 95

VII The p K A Values of Some

H Nitro-substituted
Diphenylamines .. .. .. .. I l l

VIII Values of pKgji+ a n d

P HA f o r A n i l i n e s
K

and Diphenylamines 122-3

IX A b s o r p t i o n Maxima and Molar A b s o r p t i v i t i e s
of the I n d i c a t o r s i n 95.6 % E t h a n o l 145-6

X A b s o r p t i o n Maxima and Molar A b s o r p t i v i t i e s

of Diphenylamines i n 20% E t h a n o l .. 147

XI A b s o r p t i o n Maxima and Molar A b s o r p t i v i t i e s

of I n d i c a t o r Anions i n DMSO-Water .. 148-9

XII E x p e r i m e n t a l Values of Log [A ] / [HA] f o r the

-

I n d i c a t o r s used t o Determine the H_ Values

i n DMSO-Water-Tetramethylamnionium
Hydroxide (0.011 M) 150-3

XIII Experimental Values of Log [ A ~ ] / [ H A ] f o r

V a r i o u s I n d i c a t o r s i n DMSO-Water-Tetramethyl-
ammonium Hydroxide (0.011 M) .. .. 154-5
 viii

XIV E x p e r i m e n t a l V a l u e s o f L o g [BH+] / [B]

f o r the S u b s t i t u t e d D i p h e n y l a m i n e s U s e d to
D e t e r m i n e the H V a l u e s i n 20 Volume
Q

Percent Ethanol-Aqueous S u l f u r i c A c i d 156-8

 ix

LIST OF FIGURES

Page
1 H_ Acidity Function for the System: DMSO-
Water-Tetramethylammonium Hydroxide
(0.011 M) 44

2 Plot of Log [ A l / M Versus H_ for the

Indicators Used to Establish the H_ Scale 45-47

3 Plot of Log [Ai/flA] Versus H_ for Various

Amines 50,51
4 H Acidity Function for the System: " 2 0 %
Q

Ethanol"-Aqueous Sulfuric Acid .. .. 5 7

5 Plot of Log DBH^/lB] Versus H for the Indicators Q

Used to Establish the H Scale .. .. Q58,59

6 H Acidity Functions in Sulfuric Acid Media 7 8

Q

7 Hammett Correlation of the Acidity of

Substituted Diphenylamines 84
8 Plot of PKHA Anilines and Diphenylamines
o f

Versus pK of Phenols
RA 91
9 Hammett Correlation of the Basicity of
Substituted Diphenylamines .. .. .. 102
10 Plot of PKBH+ o f
Anilines Versus pKg|j+ of
Diphenylamines 104
11 Correlation of the Basicity of Substituted
Diphenylamines and 4 -Nitrodiphenylamines 1 0 8
1

12 Plot of PKHA Versus PKBH+

f o r
Diphenylamines
119

13 Plot of pKjj^ Versus pK + for Anilines and BH

Diphenylamines .. .. .. .. .. 120
 X

ACKNOWLEDGEMENT

I would l i k e to thank P r o f e s s o r R. Stewart for his

guidance and e n c o u r a g e m e n t throughout t h i s work.

I would a l s o l i k e to thank the National Research

Council for generous financial assistance.

 1

INTRODUCTION

A. D e f i n i t i o n s of A c i d and Base

The existence of acids and b a s e s has been recognized

for a long time. The q u e s t i o n of what e x a c t l y is an a c i d or

1:

a base h a s , however, received a variety of answers. Arrhenius

d e f i n e d an a c i d as a substance that ionizes in aqueous

solution to produce a hydrogen i o n and a base as a substance

2 3

that ionizes to produce a hydroxide ion. Bronsted and Lowry

defined an a c i d as a p r o t o n donor and a base as a proton

acceptor. Lewis'* broadened the concept of an a c i d w i t h his

description of an a c i d as a molecule or ion capable of

coordinating w i t h the unshared e l e c t r o n pair of a base.
5

Usanovitch d e f i n e d an a c i d as any s u b s t a n c e capable of

g i v i n g up c a t i o n s or of combining with anions, and a base as

any s u b s t a n c e capable of g i v i n g up a n i o n s or of combining

with cations.

These descriptions vary considerably i n scope. The

definition of A r r h e n i u s r e s t r i c t s acids and b a s e s t o aqueous

solution, while that of U s a n o v i t c h is independent of solvent

and covers a wide v a r i e t y of substances. The l a t t e r definition

has e v e n been e x t e n d e d to o x i d i z i n g and r e d u c i n g a g e n t s by

also d e f i n i n g as acids those substances that combine with

electrons and as bases those substances that give up electrons.

 2

A Bronsted acid i s a special type of Lewis acid

since the p r o t o n f r o m a p r o t o n donor c o o r d i n a t e s with the

la

electron pair of a base . Bronsted acids have r e c e i v e d by

far the greatest attention since it i s possible to describe

these acids in quantitative thermodynamic terms.

B. The A c i d D i s s o c i a t i o n C o n s t a n t

The a c i d i t y of a B r o n s t e d a c i d i n aqueous solution

is expressed i n t e r m s of the equilibrium

HA + nH 0 - A" + H +
(1)
aq ^ 9
aq aq

where " a q " denotes that the species are hydrated. HA i s an

a c i d w i t h any n e t charge and A"~ i s the base conjugate t o HA •

w i t h one u n i t less positive charge. The e q u i l i b r i u m is

expressed by the relation*

(A") (H ) +

K' - _ (2)
(HA)(H 0) 2
n

i n w h i c h the subscript " a q " has been o m i t t e d . In dilute

aqueous s o l u t i o n the quantity (HO) is almost constant and

Q
equal t o u n i t y so t h a t the expression can be rewritten

* The f o l l o w i n g s y m b o l s , [ ] , ( ) , and f w i l l be u s e d t o r e f e r
t o c o n c e n t r a t i o n , a c t i v i t y , and a c t i v i t y c o e f f i c i e n t ,
r e s p e c t i v e l y , on t h e m o l a r s c a l e . As u s u a l , a l l a c t i v i t y
c o e f f i c i e n t s t e n d t o u n i t y as t h e s o l v e n t c o m p o s i t i o n t e n d s
t o w a r d t h a t of the p u r e s o l v e n t ^ * . 3
 ( A " ) (H+)
IC,. = K'(H 0) 9
n
= (3)
m 2
(HA)

7a
The constant K„. i s known as the acid dissociation constant
HA

Because individual activities c a n be determined

for uncharged species only, direct measurement of thermodynamic

dissociation c o n s t a n t s u s u a l l y i n v o l v e s measuring the classical

dissociation constant

[A-] m
K c = (4)
[HA]

as a function of ionic strength and e x t r a p o l a t i n g to infinite

dilution .

Kortum, Vogel and A n d r u s s o w have surveyed methods

of determining acid d i s s o c i a t i o n constants in aqueous

solution.

For the sake of convenience acid dissociation

constants are often expressed i n terms of pK u n i t s , where

P K
HA " - l0g
V (5)

so that one pK u n i t corresponds to a change of one power of

ten i n K. The s m a l l e r the value of pK , the stronger the

acid. It should also be m e n t i o n e d t h a t the basicity of

Bronsted bases i s often expressed i n terms of the pK^ of

their conjugate acids.

 4

S i n c e measurements of acid dissociation constants

require extrapolation of K c to infinite dilution, measurements

must be made i n s o l u t i o n s of low i o n i c s t r e n g t h . If equation

(3) is rewritten as

(HA)
pK„. - log - log G O (6)
H A
(A~)

then i t can be s e e n that there is a limit to the type of

acid for w h i c h pKjj A can be d e t e r m i n e d accurately.

In equation (6) the last quantity is just t h e pH

of the solution (or at least approximates the pH, since

the definition of pH i s now an o p e r a t i o n a l one^ ).c

Now

consider a v e r y weak a c i d w i t h a of 20 in a solution

w i t h pH of 10. If the concentration of HA i s 10 - 3

molar,

then from e q u a t i o n (6) (and n e g l e c t i n g any difference

between activity and c o n c e n t r a t i o n ) the concentration of A~

-13
is 10 molar. This i s much t o o s m a l l t o be m e a s u r e d and
so the direct measurement of pKjj A for this acid is impossible.

There are many a c i d s that do n o t show a p p r e c i a b l e

ionization i n the u s u a l pH r a n g e , and on w h i c h , therefore,

it is i m p o s s i b l e t o make a c c u r a t e measurements in dilute

aqueous s o l u t i o n . Many o f these acids ionize in either

strongly acidic or s t r o n g l y b a s i c media, and i t is of interest

t o use these observations t o make e s t i m a t e s of the dissociation

constants of the acids i n aqueous s o l u t i o n . This also provides

 5

some quantitative knowledge of the acidity of these media.

C. Hammett A c i d i t y Functions

By f a r the most popular approach to this problem

8 9

is that d e v e l o p e d by Hammett and D e y r u p ' . Equation (6)

may be r e w r i t t e n as
[HA] f.-
P K„ A = log — - log (H )-£- +
(7)
H A
[A ] f
HA

and the following d e f i n i t i o n made

f .-
H = - log (H )-^-
+
(8)
f
HA

For two a c i d s , HA^ and HA , i n the same s o l u t i on

2
[HAJ [HA ] 2 f ff --
log ^—^ - log 1
+ log -*- ^
1 2
[ l]
A
M f
A - H A
f
2

(9)

The s u c c e s s of the Hammett treatment depends on t h e last

quantity in equation ( 9 ) being zero or, i n other words, on

the ratio fA-/f„ i n a given s o l u t i o n being independent

A of
A HA
the indicator acid. In t h i s case, the function H is also

independent of the indicator. This has become known as the

10a

Hammett activity coefficient postulate . In t h e event that

this postulate holds, equation ( 9 ) reduces to

P*H A I - PKHA 2 - lo, L J - l o g L _ J (1 0>

and the relative pK's for two a c i d s that are partially ionized

in the same s o l u t i o n c a n be o b t a i n e d by m e a s u r i n g t h e two

quantities on the right side of equation (10). This is

usually done s p e c t r o p h o t o m e t r i c a l l y so t h a t concentrations

-4 -6

of indicator acid, about 10 to 10 molar, that do not

measurably change the medium c a n be u s e d . If the Hammett

postulate holds, then the relative pK's obtained from

equation (10) for two a c i d s s h o u l d be t h e same when

measured in a series of solutions of varying acidity.

Consequently, such constancy i n the relative pK's is generally

t a k e n as e x p e r i m e n t a l p r o o f that the quantity log f ^ ^A/

-

f / i ~ «H/Ai
f
actually zero.
i s

A
l 2
Given the thermodynamic for one of the

indicators, then u s i n g the relative p K ' s , the thermodynamic

pK for the second indicator can be o b t a i n e d . The procedure

HA

can be a p p l i e d t o a t h i r d a c i d HA if both HA Q and HA are

partially i o n i z e d i n the same s o l u t i o n . By a choice

of indicator acids with s u i t a b l y spaced p K ' s the ionization

constants of acids w i t h a wide range of p K ' s can be determined

d e p e n d i n g upon t h e range of solvent acidities available.

It s h o u l d be s t r e s s e d that if the Hammett p o s t u l a t e holds

rigorously the P^JJ ' A

s
determined u s i n g t h i s procedure are

the thermodynamic ones for i o n i z a t i o n of the acids in

aqueous solution.
 7

From the same measurements of [HA] / [A"] that are

used to determine the p K ' s of the indicator acids, the Hammett

acidity function, H , can be d e t e r m i n e d for the solutions

in w h i c h the measurements were made. Thus f r o m equations

(7) and (8)

[HA]
H - pK - log (11)
H A
[A~]

For an a c i d t h a t obeys the Hammett postulate it

can be s e e n from e q u a t i o n (11) that the pKjj A of the acid is

equal to the value of H for the solution i n which i t is half

ionized. Also a plot of log [HA] / [A ] -

versus H gives a

straight line with unit slope.

As was m e n t i o n e d e a r l i e r , HA has been u s e d t o refer

to acids of any c h a r g e type. The symbol f o r a Hammett acidity

function is generally written with subscript indicating

the charge on t h e base c o n j u g a t e to the indicator acid

used to determine the H function. Thus H refers to the

o

ionization of acids such as ammonium i o n s w i t h one positive

charge and H _ r e f e r s to the i o n i z a t i o n of neutral acids

s u c h as acetic acid.

Much o f the earlier work on a c i d i t y functions was

9 11
done in strongly acidic media such as aqueous sulfuric acid '
12
Paul and L o n g have r e v i e w e d the work t h a t had been done up
13
to 1956 and Deno has p u b l i s h e d a b i b l i o g r a p h y o f a c i d i t y
 8

functions reported f r o m 1957 t o 1962. Arnett^^ has reviewed

the basicities of organic compounds o b t a i n e d u s i n g acidity

functions and o t h e r methods.

In r e c e n t years it has become quite obvious that

12
the traditional H Q scale , derived largely using primary

amine indicators, does not enjoy widespread quantitative

applicability to the protonation of organic bases. This

is shown by the fact that plots versus H

of log [BH ]/[B]
+

for
..
amides
14,15 _ . . . . „.
a l i p h a t i c ethers
16 .
, pyrroles
17 . , _ 18
, indoles ,
19
and a z u l e n e s do n o t have unit slope as is r e q u i r e d by

equation (11) f o r protonation equilibria g o v e r n e d by H .

Instead, it appears that organic bases f a l l i n t o many

separate classes according to structural differences,

the ionization equilibria of each class describing its own

self-consistent acidity function. Thus, separate H

o
a c i d i t y f u n c t i o n s have been d e r i v e d f o r the p r o t o n a t i o n o f
amides
20 21 22
' ' , p r i m a r y amines
23
, t e r t i a r y amines and
24
i n d o l e s " ^ i n a c i d media.

The d i s p a r i t y between the H functions in sulfuric

23 24
Q

acid for primary and tertiary amines e m p h a s i z e s the

necessity of u s i n g i n d i c a t o r s of o n l y one structural type

in developing a scale. Thus i n 9 0 % s u l f u r i c a c i d , H Q based

23
on the protonation of p r i m a r y amines is -8.93 , while H Q

24
based on t e r t i a r y amines is -11.14 . The d i f f e r e n c e between
 9

the two s c a l e s decreases as t h e c o n c e n t r a t i o n of s u l f u r i c

acid decreases since eventually t h e two s c a l e s must become

identical w i t h pH i n d i l u t e aqueous solution (see e q u a t i o n (8))

The d i f f e r e n c e samong t h e H s c a l e s d e s c r i b e d by
o
the various types o f base stem f r o m c h a n g e s , d e p e n d i n g on

the structure of the base, i n the a c t i v i t y coefficients

22,25,26,27

of b o t h t h e u n c h a r g e d b a s e s and t h e i r positively

charged conjugate acids 1 5

> 2 2
> 2 5
> 2 6
» 2 8
> 2 9
» 3 0
on p a s s i n g f r o m

dilute aqueous solution to strong a c i d media.

In s h o r t , the p r o s p e c t of t h e r e b e i n g o n l y one H Q

function f o r a given solvent system has not m a t e r i a l i z e d

and i n s t e a d several H functions, each d e t e r m i n e d by t h e

o

protonation equilibria o f one n a r r o w f u n c t i o n a l c l a s s of

bases, have e m e r g e d . This does n o t , however, invalidate the

usefulness of a c i d i t y functions i f caution i s exercised in

their use, especially in interpretations of k i n e t i c c o r -

, .. 31,32
relations ' .

One f a c t o r that can c o m p l i c a t e the u s e o f acidity

functions in strongly a c i d media i s t h e b e h a v i o u r o f

unsaturated substituents s u c h as t h e n i t r o and c a r b o x y l groups.

This i s of p a r t i c u l a r importance f o r the H q scales for

23 . ^ .. 24 . .
primary and t e r t i a r y amines i n w h i c h e v e r y indicator
4

possesses at l e a s t one n i t r o substituent. Deno and P e r r -

27
izzolo have shown t h a t the b e h a v i o u r of t h e activity
 10

coefficients of a v a r i e t y of o r g a n i c molecules including

nitrobenzene and b e n z o i c a c i d is similar f r o m 0 t o 60%

sulfuric acid. B e y o n d 60% s u l f u r i c a c i d t h e l a t t e r two

compounds a n d o t h e r s c o n t a i n i n g t h e same g r o u p s show

markedly d i f f e r e n t behaviour from hydrocarbons s u c h as

benzene. The a c t i v i t y coefficients o f compounds containing

the nitro and c a r b o x y l groups decrease r a p i d l y as t h e medium

approaches high (90%) s u l f u r i c acid concentrations, i n contrast

to the b e h a v i o u r o f the a c t i v i t y coefficients o f benzene

and c h l o r o b e n z e n e . In f a c t , nitrobenzene dissolves t o the

27
extent o f 98% i n 96.7% s u l f u r i c a c i d , as compared to
a s o l u b i l i t y o f 0 . 0 0 9 8 m o l e s / 1 0 0 0 grams of s o l u t i o n i n
33
35.8% sulfuric acid . This i s in spite of the f a c t that
34
nitrobenzene i s less than 1% p r o t o n a t e d i n 97% s u l f u r i c acid
27
Deno a n d P e r r i z z o l o have suggested that the
great increase i n s o l u b i l i t y of nitrobenzene at high
33
sulfuric acid concentrations i s due t o f o r m a t i o n o f a

hydrogen bonded s p e c i e s s u c h as (I). Haldna and c o -

35,36

workers have postulated the e x i s t e n c e of a s i m i l a r

species f o r nitromethane i n greater than 85% s u l f u r i c acid.

They a l s o suggest that i n mixtures o f 35 t o 85% s u l f u r i c

a c i d the nitromethane molecule e x i s t s as a h y d r a t e of the

protonated form.
 11

37
Arnett and A n d e r s o n have found that almost all
weak b a s e s b e a r i n g an u n s a t u r a t e d function exhibit behaviour
33

similar to nitrobenzene and b e n z o i c a c i d in sulfuric acid

solutions. Such i n t e r a c t i o n s of s u b s t i t u e n t s with acid

media w o u l d p r e c l u d e accurate estimation of the p K ' s of such

compounds f r o m measurements of their ionization equilibria

24

in these solutions. Arnett and Mach have suggested that

nitroanilines m i g h t be s u c h weak b a s e s because " o f the ability

of the nitro group t o be s t r o n g l y solvated i n medium

strength acid".

Until recently, a c i d i t y f u n c t i o n s i n a c i d i c media

have o c c u p i e d the attentions o f most workers in this field.

In the past five years, however, there has been a considerable

amount o f work done in basic media. T h i s has accompanied

an i n c r e a s e d interest i n the effects of polar aprotic solvents
38
on reactions
 12

Basic s o l u t i o n s have been u s e d t o s t u d y t h e ioni-

zations m a i n l y of n e u t r a l acids. The a p p r o p r i a t e acidity

function for this type of e q u i l i b r i u m

HA - H +
+ A" (12)

is the H_ f u n c t i o n where

IV]
H - pK H A + log — (13)
[HA]

A review of H acidity functions i n basic solutions

39
is t o be p u b l i s h e d i n the near future

There are, in general, t h r e e methods of producing

solvent systems with continuously variable b a s i c i t y , and

H acidity f u n c t i o n s have been d e t e r m i n e d f o r a l l t h r e e

types.

The most obvious, and f i r s t studied, solvent system

type i s that c o n s i s t i n g of a p r o t i c solvent and a s a l t of

its conjugate base. The b a s i c i t y of the system is varied

by c h a n g i n g t h e c o n c e n t r a t i o n of the b a s e . Some systems

40 41,42
of this
t y p e t h a t have been s t u d i e d a r e l i t h i u m , sodium ,
41 40
potassium , and benzyltrimethylammonium hydroxide i n
43 43,44 43,45
water, and l i t h i u m , sodium , and potassium methoxide

in methanol.

At low c o n c e n t r a t i o n s of base (less than 0.1 molar)

42,46
there is a direct relationship between H _ a n d base
 13

concentration of the form

H_ = B + log [OR ]
-
(14)

in which B i s a constant and depends on t h e solvent. As

the concentration of base continues to increase, however,

the H_ i n c r e a s e s beyond t h a t e x p e c t e d from t h i s simple

40 42 44

relationship ' 5
. This results f r o m r e d u c t i o n of the

amount o f free solvent present to solvate an increasing

amount o f b a s e . The t h e r m o d y n a m i c a c t i v i t y of free

hydroxide or alkoxide ions i s p r o b a b l y v e r y much g r e a t e r than

that of the solvated species.

41
The data of S c h w a r z e n b a c h and S u l z b e r g e r f o r H_
in aqueous s o l u t i o n s o f s o d i u m and p o t a s s i u m h y d r o x i d e have
47
been i n t e r p r e t e d by Y a g i l and A n b a r i n terms of the equilibrium

HA + 0 H ( H 0 ) ~ o - A~ + (n + l ) H 0 o (15)
^ n z

They d e r i v e d e q u a t i o n (16) to express H _ as a f u n c t i o n of

the h y d r o x i d e and " f r e e " water concentrations. This is based

on the assumption that the ratio of activity coefficients,

f
A- H20
f 1 > / f
HA OH-f i S z e r 0
"

H pK w + log [OH ] - (n + 1) log [H 0]

2 (16)

In the above e q u a t i o n p K w refers to the ion product of water

and the concentration o f water is th'at n o t bound by the

hydroxide ion ("free" water). Best agreement with the

 14

experimental results was o b t a i n e d f o r n e q u a l to 3 o r ,

in other words, f o r the assumption that hydroxide exists

as a tri-hydrated species.

42
Previously, E d w a r d a n d Wang in a similar

treatment of t h e i r data on H i n solutions o f sodium h y d r o x i d e

had calculated H _ as a f u n c t i o n o f base c o n c e n t r a t i o n and

water activity rather than "free" water concentration.

They p r o p o s e d t h a t the a c t i v i t y coefficient ratio

f T T . f n t i - / f - i s a f u n c t i o n of water activity such that

HA un A

^HA^OH -

log - r l o g (H„0) (17)

f
A"
Thus t h e y u s e d t h e e q u a t i o n

H_ - pKw + l o g [0H~] - (-r+p+1) l o g (H 0)2 (18)

to attempt to calculate H_. In t h i s case the q u a n t i t y p ,

though analogous to n , i s not n e c e s s a r i l y the h y d r a t i o n

number o f t h e h y d r o x i d e i o n but rather the d i f f e r e n c e

in h y d r a t i o n numbers between the l e f t and r i g h t s i d e s of

equation (15). Over the range o f base concentrations

measured (0 t o 4 . 5 m o l a r ) good agreement between calculated

and observed H_ values was o b t a i n e d f o r (-r+p+1) equal to 3.2.

Solutions of c o n t i n u o u s l y v a r i a b l e b a s i c i t y can

also be p r o d u c e d w i t h b i n a r y s o l v e n t systems i n w h i c h one

solvent is itself quite basic. Members o f t h i s type of

 15

system that have been s t u d i e d a r e aqueous solutions of

, , .48,49 ... . . . 50 . 0 . ,51 u

hydrazine , ethylenediamme , and 2-aminoethanol

The t h i r d t y p e of solvent system also uses a

binary solvent system, one of the pair being a hydroxylic

solvent s u c h as water and the other being a polar aprotic

solvent s u c h as dimethylformamide. These solutions themselves

are not particularly basic so that base must be added,

generally as the conjugate base of the hydroxylic member.

A l t h o u g h the basicity c a n be v a r i e d by c h a n g i n g the base

concentration it c a n be v a r i e d j u s t as e f f e c t i v e l y by

changing the composition of the binary solvent pair. At

constant base c o n c e n t r a t i o n , the basicity of this type of

solvent system increases as the p r o p o r t i o n of the polar

aprotic component increases.

Studies of H_ f u n c t i o n s have been made on aqueous

tetramethylenesulfone (sulfolane) solutions containing

40
tetramethylammonium hydroxide and p h e n y l t r i m e t h y l a m m o n i u m
52

hydroxide , aqueous pyridine containing tetramethyl-

ammonium h y d r o x i d e ^ , aqueous d i m e t h y l s u l f oxide (DMSO)

40
c o n t a i n i n g tetramethylammonium hydroxide methanol-,
53
dimethylsulfoxide c o n t a i n i n g sodium methoxide , and e t h a n o l -
54
dimethylsulfoxide c o n t a i n i n g sodium e t h o x i d e

A variety of indicator acids have been u s e d in

s t u d y i n g H_ a c i d i t y functions. These have included acids

 16

i n w h i c h the acidic proton is attached to carbon, nitrogen

41
and o x y g e n . Schwarzenbach and S u l z b e r g e r used indigo
M

derivatives (II) as acids but obtained results suggesting

a greater increase in basicity when s u b s t i t u t e d gluta-

condialdehyde dianils (III) were used.

They s u g g e s t e d that the latter compounds i o n i z e d not by

simple proton loss but rather by a p r o c e s s involving hydroxide

42

addition. Edward and Wang suggested, however, that the

difference i n behaviour is due t o differences in hydration

of the two c o n j u g a t e bases. Using thioacetamide as the

indicator acid, these workers obtained r e s u l t s i n sodium

hydroxide solutions similar to those obtained using the

indigo compounds.
 17

The m a j o r i t y of H _ s t u d i e s have u s e d substituted

anilines (IV) and d i p h e n y l a m i n e s ( V ) 4 0

' 4 4 , 4 8
' 5 1
' 5 2
and
4ft c o CZA

various carbon acids s u c h as fluorene (VI) derivatives

and s u b s t i t u t e d diphenyl- and t r i p h e n y l m e t h a n e s (VII)

as indicators.

// \\ -NH; // \ N

VI VII

Rochester has d e t e r m i n e d an H _ s c a l e in solutions

of sodium methoxide i n methanol u s i n g h i n d e r e d phenols

as acids and h a s found t h a t this scale does n o t rise as

44
rapidly as the scale o b t a i n e d by R i d d and More O ' F e r r a l l
using substituted a n i l i n e s and d i p h e n y l a m i n e s . Similar
56

results have been o b t a i n e d by S t e w a r t and B u c k l e y in

methanol-dimethylsulfoxide solutions c o n t a i n i n g sodium methoxide.

 1 8

Until further work i s done on the dependence of H _

on the structure of the indicators, and in view of the
dependence of H q scales on indicator structures, i t is
advisable to use acids of only one type in determining an
H _ scale.

As an indication of the basicities of the solutions

that have been studied, the H _ values for the most basic
solution in some of the systems will be mentioned. An
aqueous solution of 1 0 molar potassium hydroxide has
41
an H of 1 7 . 3 , 2 . 3 8 molar benzyltrimethylammonium
hydroxide has an H _ of 1 6 . 2 ® , and 4 molar sodium methoxide
4

44
in methanol has an H _ of about 1 7 . 1 . A solution of
40
9 5 mole % hydrazine in water has an H of 1 9 . The effect
of polar aprotic solvents' on hydroxide iOn basicity i s:

very pronounced. The H of a 0 . 0 1 1 molar tetramethylammonium

hydroxide solution i s 1 9 . 2 in 9 5 mole % aqueous tetramethylene-
40

sulfone (VIII) and 1 8 . 6 in 7 0 mole % aqueous dimethyl-

40

sulfoxide (IX) as compared to approximately 1 2 in aqueous

solution. 1

H3C-S-CH3

VIII IX
 19

In a r e c e n t communication 57, Steiner and G i l b e r t

r e p o r t e d measurements made i n d i m e t h y l s u l f o x i d e c o n t a i n i n g

small amounts o f w a t e r or m e t h a n o l . The base was added

in the form of the potassium s a l t of the conjugate base of

dimethylsulfoxide. The p K ^ v a l u e s of a series of h y d r o -

carbon a c i d s , the weakest being triphenylmethane with a

pK^ of 2 7 . 2 , were d e t e r m i n e d b a s e d on the value of 18.4

for the pK H A o f 4 - n i t r o a n i l i n e o b t a i n e d by S t e w a r t and

40
O'Donnell . It would appear that s o l u t i o n s with H_ of

about 30 c a n be o b t a i n e d i n t h i s system.
D. O t h e r Methods o f M e a s u r i n g A c i d i t i e s

Some of the earliest measurements of the

acidities of v e r y weak a c i d s were made by C o n a n t and

Wheland
58 and by McEwen
5Q . T h e y s t u d i e d the equilibrium

e s t a b l i s h e d between one weak a c i d and t h e potassium salt

of another i n ether solution. The p o s i t i o n o f the equilibrium

was d e t e r m i n e d

HA-L + K+Ag - K % + HAg (19)

colorimetrically. This technique has been u s e d w i t h modern

60
spectrophotometers by S t r e i t w i e s e r and c o - w o r k e r s and by
57
Steiner and G i l b e r t
K i n e t i c measurements of hydrogen i s o t o p e exchange

have been u s e d t o compare the strengths o f weak a c i d s . For

 20

this approach to be v a l i d it is essential that the rate of

attainment of e q u i l i b r i u m is directly related to the

position o f e q u i l i b r i u m and t h a t ionization is the rate-

determining process i n hydrogen exchange reactions^.

62
Shatenshtein and c o - w o r k e r s have s t u d i e d hydrogen isotope
e x c h a n g e o f weak h y d r o c a r b o n a c i d s in liquid ammonia w i t h
60,61,63
potassium amide. Streitwieser and h i s s t u d e n t s have
made s i m i l a r s t u d i e s i n cyclohexylamine with lithium
60
cyclohexylamide as base. T h e y have shown that the
equilibrium acidities of, a s e r i e s of fluorene derivatives (VI)

d e t e r m i n e d i n t h i s s y s t e m by the method o f C o n a n t and

58
Wheland g i v e a f a i r c o r r e l a t i o n w i t h the r e l a t i v e r a t e s
of h y d r o g e n - t r i t i u m exchange i n methanol c o n t a i n i n g sodium
64
methoxide

It is necessary to be c e r t a i n in interpreting

isotope exchange rates that i o n i z a t i o n of the proton

actually determines the rate of its exchange. For the

e x c h a n g e of the methyl hydrogens of toluene i n the cyclo-

hexylamine solvent system there is a kinetic isotope

, 63b
effect, k / k , greater than 10 >. . Hydrogen exchange in
H D

this system o b v i o u s l y i n v o l v e s b r e a k i n g of the carbon-

h y d r o g e n bond i n the rate-determining step. On the other

hand, i n dimethylsulfoxide with potassium t-butoxide as

base the kinetic isotope effect, k

D / k
T » i s
approximately

unity and t h e r e f o r e , presumably, k /k is also approximately

H D
 21

65
unity . It appears that in this system the breaking of

the carbon-hydrogen bond i s not, or is only p a r t i a l l y , rate-

determining i n exchange r e a c t i o n s . Consequently, relative

rates of hydrogen exchange in this medium c a n n o t readily

"be t a k e n as a measure of acidity.

E. First and S e c o n d D i s s o c i a t i o n C o n s t a n t s of D i b a s i c A c i d s

The present knowledge o f first and s e c o n d dissociation

constants for acids of the type H-Z-H, i n which both acidic

protons are attached to one central atom, is limited.

Some v a l u e s that are known i n c l u d e pK-^ and pK^ f o r E^S, 7.1

and 13.1 respectively, and f o r I ^ S e , 3.9 and 10.0

66

respectively . There is a difference of about 6 pK

units between the pK's for the first and s e c o n d dissociations

of t h e s e two a c i d s . The f o l l o w i n g processes

NH* - H +
+ NH_
4 3
(20)

NH - H • + NH~
+

>J 2

must also be c o n s i d e r e d as the first and s e c o n d ionizations

of an a c i d o f the type H-Z-H. The pK, and pK of the ammonium

67 68
ion are 9.25 and an e s t i m a t e d 35 respectively. The

difference here is about 25 pK u n i t s .

40

Stewart and O ' D o n n e l l have d e t e r m i n e d the acid

dissociation constants for a series of nitro-substituted

 22

anilines and d i p h e n y l a m i n e s u s i n g Hammett H _ a c i d i t y functions

in a variety of m e d i a . The d i s s o c i a t i o n constants for the

corresponding ammonium i o n s o f many o f these compounds

had been d e t e r m i n e d p r e v i o u s l y u s i n g the H Q scale. A plot

o f pK (as ordinate) versus pK Q (as abscissa) for the

1 ^
69

ammonium i o n s gave a l i n e w i t h s l o p e of about 0.6

T h i s means that substituents have a larger effect on the

acidity of ammonium i o n s t h a n on the acidity of the

corresponding neutral amines. Such an e f f e c t is surprising

since the opposite might have been p r e d i c t e d . Ionization

of the neutral amine p r o d u c e s an a n i o n c a p a b l e of dispersing

its negative charge over an a r o m a t i c ring; this is not possible

for the positive charge of the anilinium ion. It w o u l d be

expected that substituents on the r i n g s h o u l d have a

considerable effect on the charge delocalization and

consequently on t h e energy of the anion. One w o u l d e x p e c t

this to be r e f l e c t e d in a greater effect of substituents

on t h e equilibrium (21) than on e q u i l i b r i u m (22).

 23

-NH, H+
+ VNH; (22)
 24

OBJECTS OF THE PRESENT RESEARCH

This work was u n d e r t a k e n to study s o l u t i o n s of

greater basicity t h a n had been p r e v i o u s l y s t u d i e d u s i n g the

method o f Hammett. The b i n a r y s o l v e n t system water-dimethyl-

sulfoxide c o n t a i n i n g tetramethylammonium h y d r o x i d e appeared

to hold considerable promise for great b a s i c i t y since it

had been shown t h a t a s o l u t i o n o f 70 mole % d i m e t h y l -

40

sulfoxide has an H _ o f 18.6 . As t h e r e m a i n i n g 30 mole

% of the water is removed the basicity w o u l d be e x p e c t e d to

continue to rise. It had a l s o been f o u n d t h a t the rate of

racemization of (+)-2-methyl-3-phenylpropionitrile (X) as

catalysed by m e t h o x i d e i o n i s a c c e l e r a t e d by a f a c t o r o f
g
a p p r o x i m a t e l y 10 upon c h a n g i n g t h e s o l v e n t f r o m m e t h a n o l
70
to dimethylsulfoxide . Its high d i e l e c t r i c constant,
71
48.9 at 20°, and i t s a b i l i t y to dissolve a wide variety
72

of compounds also commend dimethylsulfoxide for such a

study.

CH 3

Furthermore, the dissociation constants of the

anilines and d i p h e n y l a m i n e s u s e d as indicators w o u l d be

o b t a i n e d from t h i s study. It was hoped t h a t this would

 25

provide some i n f o r m a t i o n on s u b s t i t u e n t effects on the

acidity of amines.

The d e t e r m i n a t i o n of the dissociation constants

of the conjugate acids of a series of diphenylamines as

well as of the diphenylamines themselves was a l s o under-

taken to examine further the linear relationship between

pK and pK of anilinium and diphenylammonium i o n s observed

1 2
69
by S t e w a r t and O ' D o n n e l l for the nitrated analogs
 /

26

METHODS OF APPROACH

The i o n i z a t i o n of a n i l i n e s and d i p h e n y l a m i n e s is

a c c o m p a n i e d by a marked change in electronic absorption spectra.

The anions e x h i b i t strong light absorption i n the visible

or near ultraviolet regions w i t h maxima at wavelengths at

which the u n i o n i z e d compounds t r a n s m i t all, or almost all,

the incident l i g h t . This provides a convenient means for

following the ionization equilibria of these amines.

The i o n i z a t i o n of these amines i n strong acid

media can a l s o be s t u d i e d t h i s way, since, on p r o t o n a t i o n ,

the l o n g wavelength absorption of these amines disappears.

All indicators used i n t h i s work showed v i r t u a l l y

instantaneous spectral changes upon a d d i t i o n o f base to

their solutions in dimethylsulfoxide-water mixtures. The

spectra of the u n i o n i z e d amines c o u l d be r e g a i n e d by

neutralizing the base w i t h a c e t i c acid. These two observations,

instantaneous and r e v e r s i b l e spectral changes, were used

as criteria of i o n i z a t i o n by p r o t o n l o s s for all acids.

 27

EXPERIMENTAL

A. Preparation and P u r i f i c a t i o n o f Indicators

Some of the compounds were o b t a i n e d from commercial

sources; the others were p r e p a r e d by known m e t h o d s . Infor-

mation on t h e i r preparation and p u r i f i c a t i o n i s to be found

in the appendix A .

M e l t i n g p o i n t s were determined i n c a p i l l a r i e s using

a Buchi m e l t i n g point apparatus and are uncorrected.

Sublimation proved to be a most u s e f u l technique

both i n p u r i f y i n g compounds and i n r e c o v e r i n g products

from r e a c t i o n mixtures. In s e v e r a l cases it was the only

practicable method o f p r o d u c t recovery since reaction

conditions were so d r a s t i c as to produce large amounts of

tarry materials. S u b l i m a t i o n s were carried out at temperatures

near the m e l t i n g p o i n t s of the compounds and u n d e r o i l pump

pressure.

B. P u r i f i c a t i o n of Solvents

Dimethylsulfoxide (DMSO) was s t i r r e d in a closed

vessel over powdered c a l c i u m h y d r i d e f o r at least two

days and t h e n d i s t i l l e d u n d e r r e d u c e d p r e s s u r e . Fractions

containing the first 15 to 20% and t h e last 10 to 15%

of the distillate were discarded. N i t r o g e n gas was u s e d i n

 28

the leak. A Perkin triangle was u s e d t o cut fractions

allowing nitrogen to be i n t r o d u c e d d i r e c t l y on t o p of the

distilled DMSO i n the collection vessels. These flasks

were s e a l e d w i t h ground g l a s s stoppers w h i c h were further

sealed w i t h masking tape and t h e n t r a n s f e r r e d to a dry box

with n i t r o g e n atmosphere. In t h i s way the DMSO was protected

from atmospheric moisture and o x y g e n .

The DMSO o b t a i n e d i n t h i s manner was shown t o contain

less t h a n 0.01% w a t e r by t i t r a t i o n with Karl Fischer reagent.

When t h e DMSO was t o be u s e d t o make solutions

c o n t a i n i n g more than 90 mole % DMSO i t was f u r t h e r purified

73

by a s i m p l i f i e d zone f r e e z i n g method . This consisted of

c o o l i n g the vessel i n an i c e - w a t e r bath u n t i l 75

to 85% o f the DMSO had f r o z e n and t h e n d e c a n t i n g the

remaining l i q u i d . The s o l i d was m e l t e d and the procedure

repeated. D e c a n t i n g of the liquid was done i n the dry box

under nitrogen atmosphere.

Water that was u s e d f o r p r e p a r i n g DMSO-water

mixtures was d i s t i l l e d , boiled and t h e n c o o l e d w i t h nitrogen

bubbling through it.

T e t r a m e t h y l a m m o n i u m h y d r o x i d e was o b t a i n e d f r o m

Eastman O r g a n i c C h e m i c a l s e i t h e r as a 10% aqueous solution

or as the crystalline pentahydrate and was u s e d w i t h o u t further

purification.
 29

Sulfuric a c i d was B a k e r and Adamson R e a g e n t

grade material.

Constant b o i l i n g ethanol (95.6% e t h a n o l ) was

prepared from commercial 100% e t h a n o l by a d d i t i o n o f the

amount of water c a l c u l a t e d to give the azeotropic composition

f o l l o w e d by d i s t i l l a t i o n . After a f i r s t fraction of

approximately 5%, the n e x t 60% was c o l l e c t e d and u s e d for

measurements with s u l f u r i c acid.

C. Preparation of Solutions

Stock solutions of DMSO-water were p r e p a r e d and

stored in ordinary l i q u i d reagent b o t t l e s stoppered with

rubber serum s t o p p e r s with a f l a p that c o u l d be b e n t down

over the l i p and n e c k of the bottle f o r m i n g an a i r t i g h t seal.

The membrane o f the serum s t o p p e r c o u l d be penetrated

many t i m e s without losing its seal. C a r e was t a k e n that

the solutions d i d not splash against the rubber stoppers.

The b o t t l e and s t o p p e r were w e i g h e d , transferred

to the d r y box and t h e n a calculated amount of DMSO i n t -

roduced i n t o the bottle with a large syringe. The stoppered

bottle was t h e n removed f r o m t h e d r y box and w e i g h e d

again. Finally, the r e q u i r e d amount o f water was added -

a g a i n by s y r i n g e - ahd-a t h i r d w e i g h i n g made. From the three

w e i g h i n g s the exact c o m p o s i t i o n of the solvent c o u l d be

calculated.
 30

Solutions c o n t a i n i n g more t h a n 9 7 . 5 mole % DMSO

were p r e p a r e d i n a s i m i l a r manner f r o m DMSO and a s o l u t i o n

of about 50 mole % DMSO.

Indicator measurements i n the DMSO-water system

were done u s i n g a c o n s t a n t concentration of b a s e , 0.011

molar tetramethylammonium h y d r o x i d e . Introduction of the

base i n a 10% aqueous s o l u t i o n a l s o introduces water into

the system and t h u s produces an u p p e r l i m i t of approximately

97 mole % on t h e amount o f DMSO p r e s e n t i n the system.

This upper l i m i t can be e x t e n d e d to about 99.5 mole %

DMSO by u s i n g t e t r a m e t h y l a m m o n i u m h y d r o x i d e pentahydrate

and in this c a s e base was i n t r o d u c e d i n t o the DMSO-water

mixtures by way o f a stock s o l u t i o n of the latter compound

in DMSO.

A sample of the tetramethylammonium h y d r o x i d e

pentahydrate was g r o u n d i n a m o r t a r , weighed i n t o a stoppered

flask and an a p p r o p r i a t e amount of DMSO a d d e d . The

mixture was s h a k e n and warmed t o cause dissolution. There

was a l w a y s a small amount of u n d i s s o l v e d m a t e r i a l (possibly

carbonate) and t h i s was removed by f i l t r a t i o n t h r o u g h a

sintered-glass funnel. The c l e a r s o l u t i o n was transferred

to a glass reagent bottle and s t o p p e r e d w i t h a serum stopper.

All the above operations, except the w a r m i n g , were carried

out i n the d r y box u n d e r n i t r o g e n atmosphere.

 31

Samples of the base s o l u t i o n were t i t r a t e d with

standardized hydrochloric acid using phenolphthalein

indicator. A s o l u t i o n of about 0.12 molar base c o u l d be

prepared in this way. The w a t e r content of the solution

was d e t e r m i n e d by K a r l Fischer titration i n methanol - acetic

acid. C o r r e c t i o n was made f o r the water formed from neutra-

lization of the base.

Solutions prepared in this manner were initially

colorless but turned yellow after one or two w e e k s . After

t h r e e weeks there was a s l i g h t drop of about 4% i n base

concentration, p r e s u m a b l y due t o decomposition caused by

74 75

a t t a c k by h y d r o x i d e i o n on the tetramethylammonium ion j'

Consequently, measurements u s i n g the s o l u t i o n were made

within two weeks of its preparation. It is interesting

that no e t c h i n g of glass containers, syringes or absorption

cells by s o l u t i o n s of hydroxide i o n i n DMSO was e v e r noticed

during this work d e s p i t e their great basicity.

D. Spectral Measurements i n the Dimethylsulfoxide-Water

System

All measurements of spectra were made i n 1 cm

silica cells u s i n g a Bausch and Lomb Model 502 recording

spectrophotometer. The i n s t r u m e n t was e q u i p p e d w i t h constant-

temperature cell holder having a l i q u i d capacity of 300 ml.

 32

Water from a bath t h e r m o s t a t e d at 2 5 ° C was pumped t h r o u g h

the cell holder.

Since many o f the anions used in this work,

especially the more basic ones, reacted readily with

76

oxygen, the procedure d e v e l o p e d p r e v i o u s l y by O ' D o n n e l l

was u s e d t o protect them f r o m oxygen.

The solutions were p r e p a r e d i n 1 cm s i l i c a

absorption cells fitted with a s i l i c o n e rubber disc in the

ground g l a s s neck. The d i s c s were o f the type used as

injection septums i n gas chromatography. They c o u l d be

pierced many t i m e s with small gauge s y r i n g e needles without

leaking and were i n e r t t o DMSO. In p r e p a r i n g a solution,

the cell was f i r s t fitted with a s i l i c o n e disc and then

two s y r i n g e needles inserted through this. Nitrogen was

passed i n through one of the needles so t h a t the cell was

flushed continuously with nitrogen. Next, 30 microliters

of a solution of indicator acid (2 -25 x 10 molar) in

DMSO was added f r o m a 50 microliter syringe fitted with a

Chaney a d a p t e r . The c o n c e n t r a t i o n of stock solution was so

chosen as to produce an a b s o r b a n c e near 0.7 to 0.8 in the

final solution when the indicator was completely ionized.

A p p r o x i m a t e l y 2 ml o f DMSO-water s o l u t i o n was then added w i t h

a 5 ml s y r i n g e also fitted w i t h a Chaney adapter.

 33

In the case of anions reactive w i t h oxygen it proved

profitable t o bubble n i t r o g e n t h r o u g h the solution for

about two m i n u t e s a t this point. T h i s was s i m p l y accomplished

by l o w e r i n g the t i p of the nitrogen i n l e t syringe needle

b e l o w the liquid level.

The syringe needles were t h e n removed f r o m the

silicone disc, the cell transferred to the cell compartment

of the spectrophotometer and a l l o w e d t o e q u i l i b r a t e f o r at

least 10 m i n u t e s . Finally the base was a d d e d w i t h a t h i r d

syringe either as a 10% aqueous s o l u t i o n or as a 0.12

molar s o l u t i o n i n DMSO; the amount a d d e d b e i n g s u f f i c i e n t

to bring the concentration of tetramethylammonium h y d r o x i d e

in the cell to 0.011 molar. The s p e c t r u m o f the solution

was t a k e n i m m e d i a t e l y and r e t a k e n at least once after an

interval of 3 or 4 minutes to insure that the indicator

solution was s t a b l e . In t h e few c a s e s where the anion

appeared to react i n some manner, the absorbance of the

solution was o b t a i n e d by e x t r a p o l a t i o n of the readings

o b t a i n e d at appropriate time intervals to the time of a d d i t i o n

of the base. In g e n e r a l , however, the s p e c t r u m showed no

change for at least 10 to 15 minutes.

Except for the a d d i t i o n of 30 m i c r o l i t e r s of

indicator s o l u t i o n i n DMSO, a b l a n k s o l u t i o n was prepared

in the same manner as d e s c r i b e d above u s i n g t h e same

 34

DMSO-water stock solution. This s o l u t i o n was u s e d i n the

reference beam of t h e spectrophotometer.

The f i n a l c o m p o s i t i o n of the s o l u t i o n was calcu-

l a t e d from the volumes of a d d e d components and their

densities. The d e n s i t y d a t a for the DMSO-water m i x t u r e s at

77

2 5 ° C were those of Cowie and T o p o r o w s k i

E. Spectral Measurements i n 20% E t h a n o l - a q u e o u s S u l f u r i c Acid

An a t t e m p t was made t o determine the dissociation

constants of the ammonium i o n s of s u b s t i t u t e d diphenylamines

in aqueous s u l f u r i c a c i d . Diphenylamine itself proved

sufficiently s o l u b l e i n water for spectral measurements in

1 cm c e l l s . However s e v e r a l other diphenylamines,

including the chloro-, trifluoromethyl, methylsulfonyl-

and 3 , 4 ' - d i n i t r o - s u b s t i t u t e d compounds, were so i n s o l u b l e

as to p r e c l u d e measurements i n 1 cm c e l l s and, in several

cases, i n 10 cm c e l l s . It was d e c i d e d , therefore, to

78 79

adopt the procedure of J a f f e and c o - w o r k e r s ' who s t u d i e d

the basicities of azobenzenes i n "20% ethanol"-aqueous

sulfuric acid solutions. The amines p o s s e s s e d sufficient

solubility in this medium c o n t a i n i n g a p p r o x i m a t e l y 19

volume % e t h a n o l .

The s o l u t i o n s were p r e p a r e d i n the following way.

Two ml o f a s o l u t i o n of an amine (1 - 3 x 10 - 4
molar) in

constant b o i l i n g ethanol (95.6%) was p i p e t t e d i n t o a 10 ml

 35

volumetric f l a s k w h i c h was t h e n filled to the mark w i t h

aqueous s u l p h u r i c a c i d of the appropriate strength. The

stoppered f l a s k was t h e n s u s p e n d e d i n a water b a t h thermos-

t a t e d at 25°C for at least 10 minutes. At high acid

concentrations h e a t was e v o l v e d on a d d i t i o n o f the acid

to the ethanol and the thermostated solutions had t o be

topped o f f w i t h more a c i d due t o the contraction of the

volume o f the s o l u t i o n on c o o l i n g . The s o l u t i o n was then

transferred to a 1 cm s i l i c a cell and the spectrum of the

solution taken after further e q u i l i b r a t i o n i n the cell

holder. A l l spectra were invariant with time. A blank

solution prepared i n the same manner (except for the

absence of amine i n the ethanol) u s i n g the same a c i d stock

solution was u s e d i n t h e reference beam.

The concentration of the a c i d i n each solution

was d e t e r m i n e d v o l u m e t r i c a l l y by t i t r a t i o n of a blank

solution w i t h 0.1 molar sodium h y d r o x i d e .

F. Treatment of the Spectral Data

In the DMSO-water s y s t e m the longest wavelength

absorption maxima f o r most of the a n i o n s showed solvent

dependence; these generally s h i f t e d to longer wavelength

as the fraction o f DMSO i n c r e a s e d . The s h i f t for most of

the anions of the a n i l i n e s and d i p h e n y l a m i n e s was about 5mu

on p a s s i n g f r o m 10% t o 90% i o n i z a t i o n .
 36

In the sulfuric a c i d media the position of the

absorption maxima of the neutral diphenylamines shifted

about 3 or 4 nyjk on p a s s i n g f r o m 10% t o 90% ionization for

the nitrodiphenylamines and n o t at all for the others. The

shift was t o longer wavelength as the acid concentration

increased.

The e q u a t i o n s for H Q and H_ can be w r i t t e n as

H D = pK BH + - log (23)

and H_ = pK^ + log — - (24)

H A
[HA]

respectively. Since there are such large changes in

absorption spectra for anilines and d i p h e n y l a m i n e s on

80

ionization the following expressions can be u s e d to

calculate the ratios [BH*] / [B] and [A ] / [HA] f rom

-
the

spectral data

[BH+] 6 B -e (25)
L>] £ " £BH +

= (26)
[HA] e-- € A

where £ B i s the m o l a r a b s o r p t i v i t y o f the n e u t r a l amine at

i t s w a v e l e n g t h of maximum a b s o r p t i o n

^BH + i s t h e m
^ o a r
absorptivity of its conjugate base
at the same wavelength
 37

£ i s the m o l a r a b s o r p t i v i t y , at the same w a v e l e n g t h ,

o f a s o l u t i o n i n w h i c h the indicator is partially
ionized,

and £ ~ i s the m o l a r a b s o r p t i v i t y o f the

A a n i o n at its
w a v e l e n g t h o f maximum a b s o r p t i o n

£ H A i s the molar a b s o r p t i v i t y of the neutral amine at

t h e same w a v e l e n g t h

£ i s the m o l a r a b s o r p t i v i t y , a t the same w a v e l e n g t h ,

of a s o l u t i o n i n w h i c h the indicator is partially
ionized.

Since, as was n o t e d p r e v i o u s l y , the absorption

maxima s h i f t e d w i t h change in solvent c o m p o s i t i o n £ g , EA~>

and £ were m e a s u r e d at the a b s o r p t i o n maximum f o r e a c h solution.

23

T h i s method has been u s e d by J o r g e n s o n and H a r t t e r to

correct for medium s h i f t s . It was f e l t that this method would

best correct for these shifts. Also, since for any g i v e n

indicator all the measurements were made u s i n g the same

concentration of indicator the absorbance (A) rather than

the molar absorptivity (Q was used.

The molar absorptivity (GA - ) °f a n a n i o n w a s

obtained

in a s o l u t i o n the H_ of w h i c h was a l e a s t 2 units higher than

the pK of the indicator. In the case of 3-chloro-, 3-

HA

trifluoromethyl- and 3 - c y a n o a n i l i n e it was n e c e s s a r y to use

a s o l u t i o n of potassium t-butoxide i n DMSO t o obtain £ - for

the anions. The t - b u t o x i d e ion is known t o be an extremely

strong base i n DMSO, since it appears to be in equilibrium with

81 82
the conjugate base o f DMSO i t s e l f 5
 38

For 3,4'-dinitro-, 4-nitro-3'-trifluoromethyl- and

4-nitrodiphenylamine the molar absorptivities of the anions

v a r i e d w i t h the solvent c o m p o s i t i o n so t h a t the extent

of i o n i z a t i o n was d e t e r m i n e d by m e a s u r i n g the disappearance

of the peak due t o the neutral amine r a t h e r than the appearance

of the peak due t o the anion. T h i s was p o s s i b l e since the

anions absorbed little at the wavelength of maximum absorption

of the neutral amines.

Similarly, i n the work i n a c i d s o l u t i o n s , the

molar absorptivity of a neutral amine (Eg) was obtained

in a s o l u t i o n the H Q of w h i c h was a t least 2 units above the

pKg + H of the indicator. In t h e case of 4,4 -dinitrodiphenyl-

f

amine t h e molar absorptivity (Eg) c h a n g e d s l i g h t l y with

acid concentration so t h a t it was n e c e s s a r y t o measure Eg

over a range of solutions of from 0 t o 6.5 molar sulfuric

acid and e x t r a p o l a t e to the region of ionization.

Appendix B c o n t a i n s spectral data for the amines

in constant b o i l i n g ethanol and f o r their anions i n DMSO-

water mixtures.

Appendix C contains the ionization ratio data for

the amines i n the DMSO-water and 20% ethanol-water-sulfuric

acid systems.
 39

RESULTS

A. The S y s t e m D M S O - W a t e r - T e t r a m e t h y l a m m o n i u m H y d r o x i d e

From s p e c t r a l measurements on s o l u t i o n s of amine

indicators i n the mixtures o f DMSO-water c o n t a i n i n g 0.011

molar tetramethylammonium hydroxide the ratios of the

concentrations of i o n i z e d to unionized indicator (I

[A "3 / [HA] ) are obtained as described i n the previous section.

From t h e s e ratios are then obtained the relative pK v a l u e s

of the amine indicators and the H values for the solutions

in w h i c h the measurements were made.

The r e l a t i v e pK v a l u e s were o b t a i n e d by Hammett's

9

method of comparing i o n i z a t i o n r a t i o s of overlapping

indicators i n the same s o l u t i o n . The q u a n t i t y log I

was p l o t t e d against solvent composition f o r each indicator

and a smooth c u r v e drawn t h r o u g h the points for each plot.

Values of log I between -1 and 1 c o r r e s p o n d i n g t o 10% and

90% ionization, respectively, were u s e d i n the plots.

Where successive curves overlapped, differences were taken

at regular intervals and the results averaged. These

a v e r a g e s gave the differences between the pK v a l u e s of the

indicators.

The r e f e r e n c e acid, the indicator for which the

acid dissociation is known, was 2,4-dinitrodiphenylamine.

 40

40
Stewart and O ' D o n n e l l have determined values of 13.83,

13.83 and 1 3 . 8 5 i n three solvent systems for its pK H A . The

value 13.84 for the pK of this compound was t h e n used

HA

with the relative pK v a l u e s of the rest of the indicators

to calculate their t h e r m o d y n a m i c PKjj A values. Table I

contains a list of the indicators used to e s t a b l i s h the H _

scale along with t h e i r pK values obtained in t h i s work.

HA

Literature values o f pKjj^ a r e also presented for those

compounds t h a t have been u s e d p r e v i o u s l y .

The H _ v a l u e s for the DMSO-water m i x t u r e s were then

calculated from the pKjj A values of the indicators listed

in T a b l e I and the values of l o g I o b t a i n e d from the

smoothed c u r v e s mentioned above. T h i s was a c c o m p l i s h e d u s i n g

equation (13).
[ A l [A"]
H_ = PK + log — - (I - — ) (13)
H A
[HA] [ H A ]

For a given s o l u t i o n , H_ i s generally an a v e r a g e of values

o b t a i n e d f r o m two or more indicators.

Table II lists the average H values for the

DMSO-water m i x t u r e s a l o n g w i t h the average d e v i a t i o n of the

individual values f r o m the mean. Also, the indicators that

were used to determine the H_ f o r a particular solution are

given i n the last column. The numbers i n t h i s column refer

to the numbers of the indicators l i s t e d i n Table I.

 41

TABLE

The pK V a l u e s of the I n d i c a t o r s Used

HA
t o E s t a b l i s h the H _ A c i d i t y F u n c t i o n

Indicator pK reported
PjblA H A

Diphenylamines

1 2,4-dinitro ( 1 3 . 84) (13.84) 1

2 3,4'-dinitro 14. 66
3 4-nitro-3'-trifluoro-
methyl 14. 96
4 4-nitro 15. 67 15.90* 15.68
5 2-nitro 17. 91 17 57 a

6 4-methylsulfonyl 18. 80
7 3-nitro 19. 53
8 3,4'-dichloro 19. 73
9 3 - t r i fluoromethyl 20. 48
10 3-chloro 20. 73
11 4-chloro 21. 33
12 3-methoxy 2 2 . 22
13 H 2 2 . 44
14 4-methyl 2 2 . 95
15 4-methoxy 23. 22

Anilines

16 4-chloro-2-nitro 17. 08 17.22' 17.13

17 2,3,5,6-tetrachloro 19. 22
18 4-cyano 22.,68
19 3 ,4,5-trichloro 22.,86
20 3,5-dichloro 23. 59
21 3,4-dichloro 24.,60
22 3-cyano 24.,64
23 3-trifluoromethyl 25. ,40
24 3-chloro 25. ,63

a Stewart and O ' D o n n e l l , ref. 40

b L a n g f o r d and B u r w e l l , ref. 52, as corrected i n r e f . 40

 42

TABLE II

H_ V a l u e s f o r the System

DMSO-Water-Tetramethylammonium Hydroxide ( 0 . 0 1 1 M)

Mole % DMSO H _ Value A v e . D e v . f r o m Mean Indicators

10.32 13.17 - 1
15.20 13.88 0.04 1,2
20.18 14.49 .02 1,2,3
2 3 . 57 14.86 .01 2-4
26.95 15.22 .005 2-4
30.11 15.54 .005 2-4
33.42 15.87 .02 3,4
36.79 16.17 .005 4,16
39.86 16.48 .01 4,16
43.27 16.83 - 16
46.54 17.12 .02 5,16
49.59 17 .42 .005 5,16
52. 55 17.73 .01 5,16
55.95 18.08 .02 5,6,16
58.56 18.34 .02 5,6,17
62.27 18.72 .01 5,6,17
64.20 18.92 .005 6-8,17
69.09 19.41 .01 6-8,17
71.35 19.65 .01 6-9,17
73.69 19.90 .02 7-9,17
76.12 20.14 .005 7-9
78.36 20.38 .01 7-11
80.78 20.68 .005 9-11
83.14 20.97 .005 9-11
85.46 21.27 .01 9-11
88.79 21.61 .02 10-13
90.07 21.98 .005 12-14,18,19
92.47 22.45 .01 12-15,18,19
94.74 23.01 .01 13-15,18-20
95.77 23.32 .005 13-15,18-20
96.21 23.48 .01 14,15,18-20
97 .13 23.88 .02 20-22
97.89 24.25 .005 20-22
98.29 24.50 .01 20-23
98.71 24.84 .01 21-24
99.14 25.30 .01 21-24
99.59 26.19 .05 23,24

a Numbers r e f e r to those i n table I

 43

Figure 1 is a plot of H_ v e r s u s composition of the

DMSO-water-tetramethylammonium hydroxide system. The value

of H_ f o r 0.011 m o l a r tetramethylammonium hydroxide in

w a t e r was c a l c u l a t e d f r o m the equation

H_ - pK w + log [OH"] (27)

This relationship was f o u n d t o hold for solutions of

sodium h y d r o x i d e of f r o m 0.01 t o 1 molar concentration by

42
Edward and Wang . If this relationship is assumed t o hold
go

for tetramethylammonium hydroxide and t h e value 14.00

used f o r pK w then the H for 0.011 m o l a r hydroxide ion is

12.04.
It i s evident from e q u a t i o n (13) t h a t a plot of

log I versus H_ should give a straight l i n e with u n i t slope

and intercept equal to the pK R A of the indicator. Figure 2

is such a p l o t of log I (log [A"[| / [HA] ) v e r s u s H_ for the

indicators i n Table I. L i n e s of u n i t slope with intercepts

equal to the p K ^ values of the indicators have also been

drawn. The f i t of the experimental values of log I to

these lines is a measure of the precision of the results

and of the v a l i d i t y of the whole procedure.

The pKjj^ v a l u e s of a number of compounds were

determined f r o m the H_ s c a l e using equation (13). These

were a c i d s that were not u s e d i n the establishment of the

FIGURE I H_ ACIDITY FUNCTION FOR THE SYSTEM: D M S O - W A T E R -
TETRAMETHYLAMMONIUM HYDROXIDE (O.OI I M)
FIGURE 2 PLOT OF LOG [A~]/[HA] VERSUS H_ FOR THE INDICATORS
USED TO ESTABLISH THE H_ SCALE

THE NUMBERS REFER TO THE COMPOUNDS IN TABLE I

H_
13 14 15 '16 17
J I I 1 . L
FIGURE 2 (CONT.)

18
 48

H_ s c a l e and c o n s i s t e d m a i n l y of alkyl-substituted 4-

nitroanilines. The pKjj A of an a c i d was t a k e n as the

intercept of a plot of log I versus H _ , that is, the H _

of the s o l u t i o n i n w h i c h the indicator is half ionized.

These p l o t s are not all of u n i t slope, especially for the

substituted nitroanilines. However, for four d i c h l o r o a n i l i n e s

the slopes are, within experimental error, unity.

The acids, their pK H A values and the slopes of the

plots of log I (log [A"|] / [HA] ) versus H are listed in

Table III and the above mentioned p l o t s are shown i n F i g u r e 3.

The plot for 2,6-di-t-butyl-4-nitroaniline is not a

straight line although it appears the points approach a

line of u n i t s l o p e for values of log I less than zero.

An e s t i m a t e was made o f the pK H A of 4 - a m i n o d i p h e n y l -

amine. An a c c u r a t e measurement c o u l d not be made because

of the difficulty in purifying this compound and its

readiness to react w i t h the slightest trace of oxygen in

the basic media. A value of 24.2 was o b t a i n e d f r o m a

comparison of its ionization ratios i n three solutions with

those of 4-methoxydiphenylamine.
 49

TABLE III

Summary of pR™. V a l u e s of V a r i o u s Amine A c i d s

Compound p K
HA Slope of p l o t
of l o g I v s H _

1. 4-nitroaniline 18. 91 0 .92

2. 4-nitro-2-methylaniline 18. 83 0 .91
3. 4-nitro-2,6-dimethylaniline 18. 71 0 .89
4. 4-nitro-2,6-di-t-butylaniline 17. 4
5. 4-nitro-3,5-dimethylaniline 21. 16 1 .05
6. 4-nitro-2,3,5,6-tetramethyl-
aniline 22. 66 1 .18
7. 4-nitro-N,2-dimethylaniline 18. 58 0 .96
8. 4-nitro-N-methy1aniline 18.49 0 .99
9. 4-nitro-N-ethylaniline 1 8 . 58 0 .95
10. 4-nitro-N-isopropylaniline 1 8 . 66 0 .95
11. 4-nitro-N-t-butylaniline 1 9 . 64 1 .02
12. 4-nitro-N-triphenylmethyl-
aniline 1 7 . 98 0 .99

13. 2,3-dichloroaniline 23. 14 1 .00

14. 2,4-dichloroaniline 23. 46 1 .00
15. 2,5-dichloroaniline 22. 71 1 .04
16. 2,6-dichloroaniline 22. 40 1 .02

17. 2,2'-dipyridylamine 1 9 . 91 0 .85

a
pKjjA t a k e n as the H _ a t half ionization
FIGURE 3 PLOT OF LOGM/NA1 VERSUS H_ FOR VARIOUS AMINES

o
51
 52

B. The System "20% Ethanol"-Aqueous S u l f u r i c A c i d

The P R , ™ * v a l u e s for the i o n i z a t i o n of the diphenyl-

DH
ammonium i o n s in this medium were o b t a i n e d i n the same way

(28)

as the values for the i o n i z a t i o n of the neutral amines

in the basic medium. The r e f e r e n c e base was d i p h e n y l a m i n e .

The P JJ+
K
B value of its conjugate a c i d was f o u n d t o be 0.78
from a comparison of its i o n i z a t i o n with that of the

conjugate acid of 4-nitroaniline i n aqueous solutions of

hydrochloric acid. The f o l l o w i n g e q u a t i o n was used

B
F

pK BH + - PK BR + = log I A - l o g 1^ + log'
A D

(29)
where the letters " A " and ' ' D " r e f e r to 4-nitroaniline and

diphenylamine respectively, and I ' r e f e r s to the ratio

(BH 3/[B].
+
Experimentally it was f o u n d t h a t l o g 1^ -

log 1 ^ had a v a l u e o f 0.217 - .004 f o r seven solutions of

hydrochloric acid varying in strength f r o m 0.03 t o 0.5

molar. There appeared no t e n d e n c y of this quantity to

vary, within experimental error, with a c i d concentration.

 53

Since the last term in equation (29) must, by definition,

be z e r o in dilute aqueous solution it is very probably

zero i n the hydrochloric acid solutions because of the

constancy of the l o g I' - l o g I' term. Thus the number

A D

0.217 is the difference i n pK DlJ + values for 4-nitroaniline

and d i p h e n y l a m i n e .

This difference c o m b i n e d w i t h the pKgjj+ value

84 85
of 1.00 for 4-nitroaniline ' gives a value of 0.78 for
the pK + of diphenylamine. A value of 0.79 has been
B H
85
f o u n d by P a u l , although i t is recorded as 0.78 in the
12

r e v i e w o f P a u l and L o n g . The pKg + v a l u e s H of all the

substituted d i p h e n y l a m i n e s are b a s e d on a pKgjj+ value

of 0.78 for diphenylamine.

Equation (23) was u s e d t o calculate H Q values for

the various acid solutions. As b e f o r e , two or more

indicators were g e n e r a l l y u s e d t o calculate H Q for

H
° - PK
BH +
" l 0 g 1
' "(' 1
" T^J I ( 2 3 )

each solution.

Table IV l i s t s the d i p h e n y l a m i n e s and t h e i r pkg + H

values used to calculate the H Q f u n c t i o n i n "20% ethanol"-

aqueous sulfuric acid.

 54

TABLE IV

Values of p K _ „ + for the Diphenylamines

on
u s e d t o E s t a b l i s h the H Q Acidity Function

Substituents PKBH+

1 4-methoxy 1.36
2 4-methyl 1.20
3 none (0.78)
4 3-methoxy 0.40
5 4-chloro 0.01
6 3-chloro -0.45
7 3-trifluoromethyl -0.78
8 3,4'-dichloro -1.19
9 3-nitro -1.61
10 4-methylsulfonyl -2.54
11 4-nitro-3'-methyl -2.93
12 4-nitro -3.13
13 2-nitro -4.12
14 4-nitro-3'-chioro -4.15
15 4-nitro-3'-trifluoromethyl -4.47
16 3,4'-dinitro -5.19
17 4,4'-dinitro -6 . 21

a
This value d e t e r m i n e d i n aqueous s o l u t i o n s o f HC1
 55

Table V l i s t s the mean H D values determined for

these solutions a l o n g w i t h the average d e v i a t i o n of the

individual values f r o m the mean and a l s o the identity of

the indicators used to calculate H 0 f o r each solution.

Figure 4 is a plot of the data in Table V.

Figure 5 is a plot of the experimental values of

log I' ( [ B H +
] / [ B ] ) versus H . Q As b e f o r e , lines of unit

slope with intercepts equal to the pK BH + values of the

indicators have also been drawn f o r comparison. The fit

of the experimental points to the lines is a measure of

the v a l i d i t y of the results.

C. Probable E r r o r i n H and pK V a l u e s

With all acidity functions it is difficult to

estimate the uncertainty in H values and i n the pK v a l u e s

of the indicators used to determine them. The further

an acidity function is f r o m the u s u a l pH range the greater

likelihood of e r r o r s because of the stepwise procedure used

to e s t a b l i s h it. For example, in strongly basic solutions

any e r r o r encountered i n d e t e r m i n i n g the difference in

PK-HA v a l u e s between two o v e r l a p p i n g i n d i c a t o r s is

incorporated i n the pK H A value of the less acidic one and

also i n the H_ values determined from i t s ionization ratios.

Errors can be m i n i m i z e d by u s i n g a l a r g e number o f overlapping

 56

TABLE V

H Q Values f o r t h e S y s t e m "20% Ethanol"-Aqueous

Sulfuric Acid

M o l a r i t y of H G Value A v e . D e v . from Indicators 3

H2SO4 Mean

0.0163 1. 86 0.01 1,2

0.0339 1.56 .01 1,2
0.0567 1 .34 .00 1-4
0.0808 1.18 .005 1-4
0.163 0.87 .00 1-4
0.245 0.67 .01 1-4
0.406 0.41 .00 1-5
0.611 0.17 .01 3-6
0.763 0.03 .00 3-7
0.914 -0.10 .00 3-7
1.26 - 0 . 35 .005 4-8
1.47 -0.48 .005 4-8
1.72 -0.63 .00 5-8
1.98 -0.78 .00 5-9
2. 25 -0.93 .01 5-9
2.49 -1.07 .00 6-9
2.73 -1.20 .005 6-9
3.07 -1.40 .005 7,8
3.29 - 1 . 53 .00 7-9
3. 58 -1 .70 .01 7-10
3.76 -1.81 .01 8-10
4.14 -2.03 .01 8-11
4.38 -2.17 .005 9-12
4.62 -2.32 1005 9-12
4.90 - 2 . 51 .01 9-12
5.15 -2.65 .01 10-12
5.41 -2.81 .005 10-12
5.66 -2.97 .00 10-12
5.95 - 3 .18 .03 10-14
6.47 - 3 . 52 .02 10-15
6.81 -3.. 75 .01 11-15
7.16 -3.99 .005 12-15
7.64 -4.33 .005 13^-16
8.14 -4.69 .02 13-16
8.44 -4.91 .03 13-16
8.87 -5.20 .005 15-17
9.31 -5.54 .00 16,17
9.81 -5.91 .005 16,17
10.18 -6.19 .005 16,17
10.65 -6.54
- 17
11.22 -6 .97
- 17
a
Numbers r e f e r t o those i n T a b l e IV
FIGURE 5 PLOT OF LOG[BH + ]/[B] VERSUS H POP, THE INDICATORS
G

USED TO ESTABLISH THE H SCALE 0

(i) (a

THE NUMBERS REFER TJ THE COMPOUNDS IN TABLE TV

0 -2
59
 60

indicators so t h a t the H value for a given s o l u t i o n i s not

dependent on t h e data for one indicator and by u s i n g

indicators of the same s t r u c t u r a l type to ensure that the

Hammett a c t i v i t y coefficient postulate is obeyed as

closely as possible.

The pK v a l u e s in this work a r e recorded to two

decimal places. This is valid for the relative pK v a l u e s

of indicators that are n o t more than one or two pK u n i t s

apart. The u n c e r t a i n t y in this case is probably - .03 to

- .05 pK u n i t s . The u n c e r t a i n t y i n the t h e r m o d y n a m i c pK

values, however, is likely greater than this and the

figure i n the second decimal place is of little significance

This is particularly true of v e r y h i g h p K j ^ v a l u e s and o f

large negative values of pKg +. H

 61

DISCUSSION

A. Validity of the H_ Function

The use of the Hammett p r o c e d u r e to e s t a b l i s h an

H_ f u n c t i o n f o r the i o n i z a t i o n of aromatic amines in the

DMSO-water s y s t e m seems j u s t i f i e d . This i s evident in the

fact that the plots of l o g I versus solvent c o m p o s i t i o n gave

parallel curves for overlapping indicators. It can also

be s e e n i n the good agreement i n H_ v a l u e s calculated using

different indicators (Table II) and i n t h e fit of the

experimental points for l o g I to the lines of u n i t slope

(Figure 2) .

A s shown i n T a b l e I I and F i g u r e 2, a number of

indicators have in general been u s e d t o determine H_ f o r each

solution. This procedure ensures that the H _ s c a l e is not

too dependent on any one indicator.

B o t h p r i m a r y and s e c o n d a r y amines have been used

in constructing the H_ s c a l e and i t appears that the ionization

behaviour i n the DMSO-water system of b o t h t y p e s of amines

is d e s c r i b e d by one acidity function. This fact is

p a r t i c u l a r l y evident in Figure 2 for the indicators

ionizing i n the r e g i o n of H_ from 21.5 to 24.0. In this

range there are seven closely spaced indicators of w h i c h

three are p r i m a r y amines and f o u r are secondary amines.

 62

The p l o t s of log I versus H_ f o r both types of indicator

are parallel to one another i n d i c a t i n g that the ionization

of p r i m a r y and s e c o n d a r y amines is g o v e r n e d by one H _ f u n c t i o n .

The e x i s t e n c e of o n l y one H _ s c a l e for both

p r i m a r y and s e c o n d a r y amines c o n t r a s t s w i t h the fact that

there are separate H Q scales to describe the protonation

of p r i m a r y and t e r t i a r y 2 3 > 2 4 a n d also, quite probably,

28

secondary amines in s u l f u r i c acid mixtures. The different

behaviour in acidic and b a s i c media is not unreasonable in

view of current ideas on the solvation of ammonium i o n s .

The f a c t that ionizations of the ammonium i o n s

resulting from p r i m a r y , secondary and t e r t i a r y amines

are d e s c r i b e d by d i f f e r e n t H Q functions is believed to

stem, to a great extent, from d i f f e r e n c e s i n the solvation

of these ammonium i o n s 2 4 > 2 5 , 2 8 ^ w hich is reflected in the

activity coefficient term fgjj+ ° ^ ^ n e

expression
f B

H 0 - -log (H+) (30)

f
BH +

The d i f f e r e n c e s i n the solvation of the ammonium i o n s is

in turn b e l i e v e d to be a r e s u l t of specific solvation of

these ions involving formation of strong hydrogen bonds

between the h y d r o g e n atoms on the nitrogen atom of an

QQ Ort ftfi

amine and the oxygen atom o f a water molecule » ' . The

number o f such interactions and hence the solvation of

 63

FH\[

the ammonium i o n w i l l depend on whether the amine is primary,

secondary or tertiary.

H y d r o g e n b o n d i n g of this type i n amine a n i o n s should

be o f little importance because of the negative charge

on the n i t r o g e n atom. For these i o n s h y d r o g e n bonds

FHM—H

involving the electron pairs on t h e nitrogen atom w o u l d be

more important, Since there are two p a i r s of unshared

electrons on an amine a n i o n r e g a r d l e s s o f whether it is

p r i m a r y or secondary it w o u l d be e x p e c t e d (neglecting

steric effects) that the s o l v a t i o n of these i o n s w o u l d be

quite similar. In v i e w of this, the use of j u s t one H _ f u n c t i o n

to describe the i o n i z a t i o n of p r i m a r y and s e c o n d a r y amines

in basic solution is reasonable.

 64

A test of the v a l i d i t y of H _ f u n c t i o n s i s the

agreement among p K j j A v a l u e s measured in different solvent

systems. In T a b l e I i t c a n be s e e n that the agreement

between the pKjj A values determined i n t h i s work a n d t h o s e

determined i n aqueous s u l f o l a n e by L a n g f o r d a n d B u r w e l l 4 0

for 4 - n i t r o d i p h e n y l a m i n e and 4 - c h l o r o - 2 - n i t r o a n a i l i n e is

very good (differences of .•'Ol a n d .05 r e s p e c t i v e l y ) . The

40

agreement with the v a l u e s of Stewart and O ' D o n n e l l

measured i n t h e same s o l v e n t i s not quite as g o o d . A

large discrepancy exists f o r the pKjj A value of 4-nitroaniline

as observed in this work, 18.91, a n d by S t e w a r t a n d

O'Donnell 4 0
, 18.37, and by L a n g f o r d and B u r w e l l 4 0
' 5 2
, 18.39.

It s h o u l d be n o t e d t h a t 4-nitroaniline was n o t u s e d i n

determining the H _ s c a l e in this work and t h a t the slope

of the p l o t of l o g I versus H _ i s 0.92 for this compound..

4-Nitroaniline was n o t u s e d i n d e t e r m i n i n g t h e H _

scale since the p l o t of l o g I v e r s u s solvent composition

for i t was n o t p a r a l l e l to similar plots f o r the indicators

4-methylsulfonyldiphenylamine and 2,3,5,6-tetrachloroaniline

that ionize i n t h e same range of solvent composition.

Because of the b e h a v i o u r of 4 - n i t r o a n i l i n e , the a l k y l der-

ivatives of t h i s compound were also not used t o determine

H_. The s l o p e s of t h e p l o t s of l o g I versus H _ f o r most

of these compounds (Table III) l i e between 0.95 and 1 . 0 5

 65

and it appears that the i o n i z a t i o n of these compounds is

governed at l e a s t approximately by H _ . However, f o r some

others, s u c h as 4 - n i t r o - 2 , 3 , 5 , 6 - t e t r a m e t h y l a n i l i n e (slope

= 1.18), the s l o p e s of the p l o t s vary considerably from

unity i n d i c a t i n g that the i o n i z a t i o n of these compounds

is n o t g o v e r n e d by H _ . The c a u s e of t h i s variance i n the

behaviour of t h e 4 - n i t r o a n i , l i n e derivatives i s n o t known.

The i o n i z a t i o n o f one n o n - n i t r o aromatic amine, 2,2'-

dipyridylamine (slope = 0.85), i s also n o t g o v e r n e d by H _ .

B. Interpretation of Solvent Basicity

The a d d i t i o n of d i m e t h y l s u l f o x i d e t o aqueous

solutions of hydroxide i o n has a g r e a t e f f e c t on t h e

basicity of these solutions. Thus t h e H _ o f 0 . 0 1 1 molar

tetramethylammonium hydroxide rises f r o m 12 i n w a t e r to

26 i n 9 9 . 5 mole % DMSO, an i n c r e a s e o f 14 powers of t e n

in basicity (as measured by i t s e f f e c t on a r y l a m i n e ionization).

In F i g u r e 1 i t c a n be s e e n that the b a s i c i t y increases

steadily as t h e s o l v e n t composition proceeds from aqueous

to 85 mole % DMSO. In t h i s region the p l o t of H _ versus

mole % DMSO i s n e a r l y linear with slope, d(H_)/d(mole %

DMSO), of about 0.10. Above 85 mole % DMSO the slope

increases and t h e b a s i c i t y rises very quickly as the water

concentration approaches zero. From 95 t o 9 7 . 5 mole %

 66

DMSO, H _ i n c r e a s e s by a l m o s t one u n i t and f r o m 9 7 . 5 to

99.0 mole % H _ i n c r e a s e s again by one unit.

What are the causes for the g r e a t enhancement in

basicity of hydroxide i o n i n DMSO solutions?

One approach to answering t h i s question is to

consider the e q u i l i b r i u m between hydroxide i o n and

indicator a c i d , HA,

(0H~) a q + HA A" + (n+l)H20 (31)

in which the hydroxide ion i s considered to be intimately

solvated by a number o f w a t e r m o l e c u l e s . The number n

can be c o n s i d e r e d e i t h e r as the h y d r a t i o n number o f the

47
hydroxide ion or, if the indicator or its anion are
also intimately solvated, as the difference in solvation
42

numbers between the left and r i g h t sides of e q u a t i o n (31).

The effect of a d d i n g DMSO t o the system is to drive this

equilibrium to the right, an e f f e c t that is interpreted as

an i n c r e a s e in basicity of the hydroxide ion.

It is possible to derive the following expression

for H_ i n terms of the equilibrium in equation (31).

(OH")
H = log (n + 1) log (H 0)2 - log (32)
K
w
 67

On t h i s basis the change i n H_ with i n c r e a s i n g concentration

o f DMSO c a n be a t t r i b u t e d to changes i n hydroxide ion

acitivity, i n water activity and i n t h e , activity coefficient

ratio f A -/f H A .

It is difficult to predict the effect upon the

last term i n e q u a t i o n (32) of c h a n g i n g the solvent from

water to DMSO. Since such p o l a r aprotic solvents as

38

DMSO a r e poor at s o l v a t i n g anions the activity coefficient

f -
A of an amine a n i o n p r o b a b l y i n c r e a s e s i n the change from

water t o DMSO. This increase is not as large as that suffered

by the hydroxide ion since anions larger t h a n the chloride

87 88

ion are not considered to be i n t i m a t e l y h y d r a t e d ' in

aqueous s o l u t i o n . A t any r a t e , the term l o g f ~ / f H A A probably

increases as the amount o f DMSO i n t h e system increases and

consequently w i l l tend to decrease H _ -

The large increases i n H _ upon the a d d i t i o n of

DMSO t o the s y s t e m must be due t o increases i n the activity

of the hydroxide i o n and t o decreases i n the water activity.

The decrease i n water activity is not due j u s t to a dilution

e f f e c t but a l s o t o t h e a b i l i t y o f DMSO t o complex w i t h water
by f o r m a t i o n o f s t r o n g hydrogen b o n d s ' 8 9 9 0
. This fact is

also evident from the large heats o f m i x i n g of DMSO and

77

water . Data f o r the activity of water i n DMSO-water

mixtures at 2 5 ° are not available, however data are available

 68

n 91
for 70 . They show t h a t as the water content decreases

and the DMSO c o n t e n t i n c r e a s e s not o n l y does t h e activity

of the water decrease but also the activity coefficient,

f
water' steadily decreases.

The increase i n H _ due t o decrease of the water

activity will depend on t h e state of hydration of the hydroxide

ion and t o a much l e s s e r extent on the hydration of the

indicator and i t s anion. As was m e n t i o n e d above, large

anions s u c h as those of aniline and d i p h e n y l a m i n e a r e not

considered to be e x t e n s i v e l y hydrated. On t h e other hand,

such s m a l l anions as the fluoride and h y d r o x i d e ions are

87 8R
strongly hydrated i n aqueous solution 5
. Estimates of
the number of w a t e r m o l e c u l e s i n the hydration shell of
( 47
the hydroxide i o n have been made. Y a g i l and A n b a r

found that the H_ values for aqueous s o d i u m and potassium

hydroxides c o u l d be c a l c u l a t e d assuming a hydration number

of 3. Other estimates of the hydration number vary from

4 8 8
to 6 9 2
> 9 3
„ if the number n i n e q u i l i b r i u m (31) and

in equation (32) is i d e n t i f i e d w i t h the hydration number

of the hydroxide ion then the position of the equilibrium

and therefore the basicity of the solution depend on a t least

the fourth power of the water activity.

This dependence o f H _ on w a t e r activity must

account for a part of the increase i n H_ w i t h i n c r e a s e in

 69

DMSO c o n t e n t especially i n the linear p o r t i o n of the curve

in Figure 1. However, it cannot account for all the

increase in this region. For example, if the H_ i s assumed

to depend on t h e f o u r t h power of the water activity and

91

the activity data f o r DMSO-water at 70° is assumed to

approximate that at 2 5 ° then the change of H _ f o r 0,011

molar h y d r o x i d e on p a s s i n g f r o m w a t e r to 50 mole % DMSO

s h o u l d be a b o u t 2 units. (This i s the change due to the

mass action effect and not due t o the change i n hydroxide

activity.) F i g u r e 1 shows t h a t the actual change i n H_

is 5.5 units. Thus, the increase i n b a s i c i t y upon a d d i n g

DMSO t o aqueous s o l u t i o n s of hydroxide ion i s due partly

to the reduction i n water activity and i t s subsequent

mass action effect on t h e e q u i l i b r i u m between hydroxide

ion and a c i d and p a r t l y to the increased activity of the

hydroxide ion.

The activity coefficient of the h y d r o x i d e must

show l a r g e increases even at low DMSO c o n c e n t r a t i o n s since

reasonable assumptions about water activity and h y d r a t i o n

numbers do n o t account for the large increase i n H_ i n this

region of solvent composition. It s h o u l d be p o i n t e d out

that o n l y at compositions greater t h a n 99 mole % DMSO

does the water concentration become s o l o w as to approach

that of the hydroxide i o n . In f a c t , i n the most, basic

 70

solution studied, 9 9 . 5 9 mole % DMSO, the ratio of concentrations

of water t o hydroxide ion is s l i g h t l y greater than 5.

An e x p l a n a t i o n of the increase i n hydroxide ion

activity at low DMSO c o n c e n t r a t i o n s may l i e i n the effect

o f DMSO on the structure of water. L i q u i d water is

considered to retain much o f the open s t r u c t u r e of ice in

w h i c h the water m o l e c u l e s are h y d r o g e n bonded t o four other

94a

water m o l e c u l e s in a tetrahedral array . Small ions and

multivalent ions increase the viscosity o f water and are

believed to promote f o r m a t i o n of an i c e - l i k e s t r u c t u r e in

the water m o l e c u l e s b e y o n d the nearest neighbour molecules.

Such a n i o n s as F ~ and O H b e l o n g t o -
this class and are said
* w , . • 9 4 b

to be s t r u c t u r e - m a k i n g ions . Larger ions decrease

the viscosity o f w a t e r and a r e b e l i e v e d to b r e a k down the

ice-like structure of water b e y o n d the nearest neighbour

molecules. This class is

s a i d t o be s t r u c t u r e - b r e a k i n g and
- - 94b
contains s u c h a n i o n s as C l , B r , I and NOg . Some
i o n s are i n t e r m e d i a t e i n c h a r a c t e r and have l i t t l e effect
on the structure of liquid water.

Q 5

Frank has p o i n t e d out that ions of opposite

character i n the same s o l u t i o n b r i n g about an i n c r e a s e in

their activity coefficients over that to be e x p e c t e d if they

were not structure-altering. Consider, f o r example, a

structure-making cation and a s t r u c t u r e - b r e a k i n g anion. The

 71

cation tends to p r o d u c e more structure i n the water and

consequently creates a hostile environment f o r the anion,

which i n t u r n "wants" to break down the structured

environment. The r e v e r s e argument also applies. The net

result is that the ions tend to salt each other out of

solution and t h u s produce an i n c r e a s e in their activity

coefficients. These e f f e c t s can be s u r p r i s i n g l y large.

95

Frank has interpreted some e . m . f . measurements as

indicating that the activity coefficient of the iodide ion

in 0.03 molar tetrabutylammonium i o d i d e i s 8.65 times

as large as the activity coefficient of the iodide ion in

0.03 molar potassium iodide. The i o d i d e i o n i s structure-

breaking, the tetrabutylammonium ion i s strongly structure-

m a k i n g and the potassium ion i s weakly s t r u c t u r e altering.

The increased activity of the i o d i d e i o n i n the first

solution is a result of the strongly opposed c h a r a c t e r s of

the te"trabutylammonium and i o d i d e ions.

As was m e n t i o n e d a b o v e , the hydroxide ion i s a

structure-making ion. Consequently, anything that breaks

down the structure of water w i l l increase the activity

coefficient of the hydroxide ion and, therefore, the

basicity of the solution. The a d d i t i o n o f DMSO t o the solution

may have this effect. The a b i l i t y o f DMSO to form strong

89 90

h y d r o g e n bonds w i t h water m o l e c u l e s ' may p e r m i t it to

break down the partial ice structure of w a t e r . This is

 72

s u p p o r t e d by t h e fact that the d e n s i t y o f DMSO-water

77
mixtures is greater than that expected from a d d i t i v i t y

This would n o t be e x p e c t e d if the open, ice-like

structure of w a t e r persisted. Further, the addition of

DMSO t o w a t e r causes the water proton magnetic resonance

96
signal to shift t o higher magnetic field , an e f f e c t that
97

is g e n e r a l l y i n t e r p r e t e d as a r e d u c t i o n i n hydrogen bonding ,

This is also consistent with a b r e a k - d o w n of the water

structure. A l l the evidence, however, i s not consistent

with this picture. The v i s c o s i t y o f DMSO-water mixtures

is greater t h a n w o u l d be e x p e c t e d f r o m a d d i t i v i t y whereas

break-down of the hydrogen-bonded i c e - l i k e s t r u c t u r e of

water s h o u l d be a c c o m p a n i e d by an i n c r e a s e d fluidity 9 4
* .
3

It is possible, then,that the b a s i c i t y of h y d r o x i d e

ion solutions is i n c r e a s e d at low DMSO c o n c e n t r a t i o n s due

t o b r e a k i n g down o f t h e water structure. This argument,

however, has n e g l e c t e d the effects of t h e s e changes on the

activities of the indicator and i t s anion. It is possible

that the effects w o u l d be s i m i l a r f o r b o t h s p e c i e s because

of the relatively small structural changes of the amines

on ionization and the charge d i s p e r s a l over one or two

aromatic rings i n the anion. In t h i s case the effects on

the equilibrium in equation (31) would cancel.

 73

The cause of the r a p i d u p - s w i n g i n H _ as the solvent

c h a n g e s f r o m 80 to 100 mole % DMSO i s most probably the

break-down of the hydration s h e l l of the hydroxide ion

brought about by the efficiency w i t h which the DMSO competes

with the hydroxide ion for the water m o l e c u l e s . A decrease

in the number of w a t e r m o l e c u l e s s o l v a t i n g the hydroxide

ion brings about a great increase in its activity and

therefore i n the basicity of the solution. This is

s u p p o r t e d by the very low s o l u b i l i t y o f sodium h y d r o x i d e

in DMSO (upper l i m i t of 7.6 x 10" 4

molar) 9 8
.

It m i g h t be p o i n t e d o u t t h a t DMSO p o s s e s s e s the

ability not only to produce large changes i n equilibrium

processes, as observed in this work, but also in kinetic

processes. The base c a t a l y z e d racemization of certain

hydrocarbons 7 0
, the saponification of e s t e r s 9 0
' 9 9
and

nucleophilic aromatic substitution 1 0 0

all show dramatic

increases in rate when the solvent is changed from water

or alcohol t o DMSO or m i x t u r e s of these solvents w i t h DMSO.

C. Validity of the H 0 Function

The H Q scale i n ethanol-aqueous sulfuric acid has

been d e t e r m i n e d u s i n g i n d i c a t o r s of one structural type,

substituted diphenylamines. This is an i m p o r t a n t point,

considering the sensitivity of H Q functions to the

 74

structure of the basic center. Unfortunately, the measure-

ments c o u l d not be made i n completely aqueous sulfuric acid

because of i n s u f f i c i e n t s o l u b i l i t y of the diphenylamines.

The introduction of e t h a n o l into the solvent precludes any

direct comparison of the results obtained in this work

0*3 04
with the results obtained using primary and tertiary

aromatic amines.

The i n t r o d u c t i o n of e t h a n o l into the solvent

also makes it particularly important that indicators of

one type be u s e d . This c a n be illustrated by a result

obtained with 4 - n i t r o a n i l i n e and d i p h e n y l a m i n e . First,

equation (29) may be r e a r r a n g e d as follows:

log I A - log I D = P K B H + - P K B H g - log

VBH'/ \ -B D

(33)

where " A " and " D " r e f e r to 4-nitroaniline and d i p h e n y l a m i n e ,

respectively, and I ' refers to the ratio of the concentrations

of ammonium i o n t o amine. It will be r e c a l l e d that the

quantity on the left side of e q u a t i o n (33) i s equal to 0.22

and the last term is zero i n aqueous solutions of hydrochloric

acid. In s o l u t i o n s of sulfuric acid of 0.03 to 0.9 molar

in 20 volume % e t h a n o l - w a t e r the quantity on the left side

of e q u a t i o n (33) is 0.07 - .01. Since the difference between

 75

the PKgjj+ v a l u e s for the two amines is 0.22 the last term

in the equation cannot be z e r o , that is, the Hammett

activity coefficient postulate 1 0

is not obeyed. Consequently,

4-nitroaniline cannot be u s e d t o anchor an H Q scale for

secondary amines i n 20 volume % e t h a n o l - w a t e r .

The Hammett p o s t u l a t e appears t o be o b e y e d i n

this solvent when amines of the same t y p e are used. From

p r e l i m i n a r y measurements i n aqueous dilute sulfuric acid

the difference i n the pKgjj+ v a l u e s for 4-methoxydiphenylamine

and d i p h e n y l a m i n e was f o u n d to be 0 . 5 9 . In 20 volume %

ethanol the difference was f o u n d t o be 0 . 5 8 (Table IV).

The f a c t that the Hammett p o s t u l a t e is not o b e y e d when

c o m p a r i n g the protonation of a primary with a secondary

amine i n 20 volume % e t h a n o l - w a t e r is probably a result of

the importance o f h y d r o g e n b o n d i n g i n the solvation of their

26 28 86

ammonium i o n s 5 5
and the sensitivity of the solvation

to solvent changes

In T a b l e V , i t can be s e e n that the agreement

among the H Q values calculated for a given s o l u t i o n using

different, indicators is generally very good. Figure V

shows t h a t for the most part closely spaced indicators with

accurately parallel ionization slopes have been u s e d .

 76

The pK jj+ v a l u e s
B f o r almost a l l the diphenylamines

used i n t h i s work have n o t been h i t h e r t o determined. Hammett

g

and D e y r u p , i n t h e i r o r i g i n a l work i n s u l f u r i c acid,

obtained a value o f - 2 . 5 0 f o r t h e pKgjj+ o f 4 - n i t r o d i p h e n y l -

amine. This had been d e t e r m i n e d w i t h r e f e r e n c e t o an H Q

28

scale constructed using aniline indicators. Taft has

shown t h a t the i o n i z a t i o n behaviour of t h i s compound i n

sulfuric acid i s anomalous when compared t o t h e b e h a v i o u r

of the primary amines u s e d b y Hammett and D e y r u p .

The H Q value o f 5.5 molar sulfuric acid i s
12
-2.50 determined u s i n g primary amines, and 4 - n i t r o d i p h e n y l -
amine i s half ionized in this solution. U s i n g the t e r t i a r y
24

amine scale , the H Q of 5.5 molar sulfuric acid i s

-3.58. Consequently, i f the " p K B H +" value for this compound

had been d e t e r m i n e d w i t h r e f e r e n c e t o the second H Q scale

a value o f - 3 . 5 8 w o u l d have been o b t a i n e d . Of c o u r s e , the

true pKgjj+ v a l u e f o r 4-nitrodiphenylamine cannot, be o b t a i n e d

from e i t h e r of these scales b u t must be d e t e r m i n e d with

reference t o an H Q f u n c t i o n f o r secondary amines.

There i s no r e a s o n to believe that the H Q of 5.5

molar s u l f u r i c a c i d f o r secondary amines w o u l d n o t l i e between

the values f o r primary (-2.50) and t e r t i a r y (-3.58) amines.

This also means that the pK ti+ value

R f o r 4-nitrodiphenylamine
 77

should also lie between the same l i m i t s . The pKgjj+ f o u n d

in this work i s -3.13 and l i e s near the middle of these

extremes.

D. C o m p a r i s o n of the H Q Function f o r Diphenylamines with

Other H 0 Functions

As was m e n t i o n e d b e f o r e , the H Q scale obtained in

this work i s not directly comparable with those determined

for p r i m a r y and t e r t i a r y amines b e c a u s e of the use of

ethanol i n the solvent. Jaffe and c o - w o r k e r s ' ' ' ° 0

have

determined an H 0 scale for the protonation of azobenzenes (XI)

in the same s o l v e n t system that has been u s e d i n t h i s work.

Figure 6 is a plot of H Q versus molarity of sulfuric acid

for: (i) azobenzenes i n 20 volume % e t h a n o l - a q u e o u s sulfuric

78 79
acid ' , (ii) d i p h e n y l a m i n e s i n 20 volume % e t h a n o l -
aqueous sulfuric acid, (iii) anilines i n aqueous sulfuric
12
acid , and (iv) tertiary aromatic amines i n aqueous sulfuric
. ,24
acid

X I
FIGURE 6 Ho ACIDITY FUNCTIONS IN SULFURIC ACID MEDIA

-si
oo

DIPHENYLAMINES) IN 20 VOL % ETHANOL-AQUEOUS

• • AZOBENZENES J SULFURIC ACID

PRIMARY AROMATIC AMINES 1 IN AQUEOUS

TERTIARY AROMATIC AMINESJ SULFURIC ACID

CONCENTRATION OF H S0 (MOLARITY)
2 4
 79

For purposes of d i s c u s s i o n the scale for primary

amines i n aqueous sulfuric acid will be c a l l e d H Q ' , the

scale for d i p h e n y l a m i n e s i n 20 volume % e t h a n o l - a q u e o u s

su l f u r i c acid will be c a l l e d H Q ' ' , the scale for tertiary

aromatic amines i n aqueous sulfuric acid will be called

H ''',
0 and the scale for azobenzenes i n 20 volume % e t h a n o l -

aqueous sulfuric acid will be c a l l e d H ^ ^.Q

=

First, it s h o u l d be p o i n t e d o u t that it is possible

that the H 0
N = N
scale o f Yeh and J a f f £ 7 9
s h o u l d be shifted

t o more negative H Q values. This arises because of the

manner i n which t h e i r scale was a n c h o r e d to the region of

dilute acid. Azobenzenes of sufficient basicity to protonate

in this region were n o t available and so 4- and 2-nitroaniline

were u s e d as indicators. It has just been shown t h a t the

Hammett p o s t u l a t e is not o b e y e d i n 20 volume % e t h a n o l -

w a t e r when c o m p a r i n g the protonation of a primary and

secondary amine. There is no r e a s o n to b e l i e v e that it

would be o b e y e d on c o m p a r i n g the protonation of a primary

amine and an a z o b e n z e n e . Azobenzene b e a r s c l o s e s t resemblance

to a tertiary amine because of the lack.of hydrogens attached

to the nitrogen atoms. This would cause the discrepancy in

the apparent pK v a l u e s obtained i n the comparison of an

azobenzene w i t h an a n i l i n e t o be greater than that observed

in the case of 4-nitroaniIine and d i p h e n y l a m i n e . The

N=N
direction of this discrepancy is such t h a t the H Q scale
 80

w o u l d be s h i f t e d t o more n e g a t i v e v a l u e s had i t been based

in the d i l u t e a c i d r e g i o n on the i o n i z a t i o n of an azobenzene

w i t h known pKgjj+. It is not p o s s i b l e to estimate the

magnitude of this shift.

Figure 6 shows t h a t at concentrations of a c i d less

than 4 molar the H Q

N = N
scale is s l i g h t l y more p o s i t i v e than

the H Q ' ' scale but at greater concentrations the H 0 ^ =

^

scale becomes p r o g r e s s i v e l y more n e g a t i v e than the H 0 ' '

scale. Considering the d i s c u s s i o n above, the relative

positions of the two s c a l e s might a c t u a l l y be reversed

in the low c o n c e n t r a t i o n range. A t any r a t e , the divergence

of the two s c a l e s at high acid concentration i s not unexpected,

It can be s e e n that the H Q ' and H Q ' ' ' scales diverge as

the acid concentration increases. If the cause of this

divergence is the specific interaction of the ammonium i o n s

25 28
of the p r i m a r y and t e r t i a r y amines w i t h s o l v e n t molecules '
then a divergence would a l s o be e x p e c t e d for the H 0 ' ' and
N=N

H Q scales. Azobenzenes resemble tertiary amines and

consequently a difference i n the H 0 scales for azobenzenes

and f o r diphenylamines (secondary amines) w o u l d be expected.

At acid concentrations of less than 3 molar both

the H ' and H

Q Q ' ' ' scales i n aqueous a c i d are more negative

than the H 0 ' 1

scale i n 20 volume % e t h a n o l - a q u e o u s acid.

At h i g h e r c o n c e n t r a t i o n s of acid, however, the scale in 20

 81

volume % e t h a n o l d e c r e a s e s at a greater rate than e i t h e r of

the aqueous scales. The f i r s t observation is consistent with

the fact that the a d d i t i o n of e t h a n o l to aqueous solutions

tends to increase the pH 7 9

' 1 0 1
. A l s o Braude and Stern 1 0 2

have shown t h a t H Q i n 0.1 molar hydrochloric acid increases

on p r o c e e d i n g f r o m aqueous to 55 mole % e t h a n o l - w a t e r

solutions and t h e n d e c r e a s e s u n t i l in ethanol H Q is less

(more a c i d i c ) than i n water.

The s e c o n d o b s e r v a t i o n , that the H Q ' ' function in

the ethanol-aqueous s u l f u r i c a c i d mixtures decreases (becomes

more acidic) at a greater rate than e i t h e r the H * or H

0 0 ' ' '

functions i n aqueous a c i d at the higher acid concentrations,

can be e x p l a i n e d , as p o i n t e d out by Yeh and J a f f e , on the

basis of two effects. The f i r s t is that at a constant

molarity of a c i d the mole f r a c t i o n of H2SO4 i n 20 volume %

ethanol-aqueous acid is greater than it is i n aqueous solution

due t o the greater molecular weight and m o l a r volume of the

ethanol as compared t o the water. At high acid concentrations

this becomes important since there is less hydroxylic

solvent present to solvate the protons i n the ethanolic

solutions than there is i n the aqueous solutions. The

second e f f e c t stems f r o m the fact that ethanol is a weaker

102

base t h a n w a t e r . T h i s means that EtOH* is a stronger acid

than H 3 0 . +
As t h e molarity of sulfuric acid increases,

the concentration of water d e c r e a s e s w h i l e the concentration

 82

of e t h a n o l remains constant i n the ethanol-water-sulfuric

acid system. This leads to an i n c r e a s i n g amount of EtOHg

as compared t o the amount o f I ^ O * and c o n s e q u e n t l y to a

greater acidity for the s o l u t i o n because of the greater

inherent acidity of EtOHrj.

E. C o r r e l a t i o n of S t r u c t u r e with Acidity

One o f the important consequences of the great

basicity of solutions of h y d r o x i d e i o n i n DMSO-water mixtures

is that it has a l l o w e d the pKjj A values of aromatic amines

that do n o t possess the nitro g r o u p as a substituent to

be d e t e r m i n e d . Hammett a c i d i t y scales, i n both strong

acid and base m e d i a , u s i n g amine indicators, have all made

exclusive use of n i t r o - s u b s t i t u t e d aromatic amines. This

has resulted from n e c e s s i t y rather than choice. However,

the extension of the H_ s c a l e to values b e y o n d 19 has

a l l o w e d the s t u d y of the acidity of a s e r i e s of d i p h e n y l a m i n e s

w i t h a wide v a r i e t y of s u b s t i t u e n t s whose e f f e c t s on the

acidity of d i p h e n y l a m i n e are not d o m i n a t e d by the presence

of a n i t r o substituent.

Inspection of T a b l e I w i l l show t h a t the pKjj A of

diphenylamine i s very sensitive to substituent effects.

The p K j j A values of a l l the monosubstituted diphenylamines

do n o t correlate w i t h the Hammett C P v a l u e s n o r w i t h any one

modification of them. However, if only diphenylamines with

 83

well-behaved substituents are considered, a good correlation

is o b t a i n e d between pK H A and CT. From a p l o t of log K H A

versus ,j-l 3a
0
^ Q J , ^ e unsubstituted, 4-methyl, 3-methoxy,

4-chloro, 3-chloro, and 3 - n i t r o d i p h e n y l a m i n e s a p value

104

of 4.07 is found*. The c o r r e l a t i o n coefficient, r, for

this plot is 0.991. The p l o t is shown i n F i g u r e 7.

The m a g n i t u d e of the p value is a measure of the

sensitivity of the acid strength of diphenylamine to

substituents. It s h o u l d be compared t o p values of 1.00

for benzoic a c i d s 1 0 4
, 2.23 for phenols 1 0 5
, and 2 . 8 9 for

anilinium ions 1 0 5
for aqueous systems at 25°. Thus the

acidity of diphenylamine i s more sensitive to substituent

effects than are the acidities of benzoic a c i d , phenol or

the anilinium ion.

The p K j j A values for 3,4'dichloro and 3-trifluoro-

methyldiphenylamine were n o t u s e d i n the correlation in Figure

7; the first because the compound h a s two s u b s t i t u e n t s in

different rings and the second because the <j~ v a l u e of the

substituent is not well established. If, however, the

* In t h i s and s u b s e q u e n t c o r r e l a t i o n s the method o f

l e a s t mean s q u a r e s has been u s e d t o c a l c u l a t e the best,
straight line. The e q u a t i o n s g i v e n by J a f f e ^ ° 4 have
been u s e d f o r t h i s p u r p o s e .
 8 4

FIGURE 7 HAMMETT CORRELATION OF THE ACIDITY

OF GUSBSTITUTED DIPHENYLAMINES
a 4-NH 2

\ f J 4- O C H 3
- 23 o \ 4 -- C H 3

\ G 3-OCH3 \
- 22 \ r=.99i

ON4-CI
- 21
©\3-CI
\)< 3-CF3

- 20
X 3 4'-diCI
(

3-NO2
P HAK

- 19
\. A 4-S0 CH
2 3

- 13
\.
- 17 ° - - cr VALUES U^ED IN CORRELATION
\/
/\ --cr VALUES 'NOT USED IN CORRELATION

•- S° VALUES

- 1 6
A- --6~ VALUES
4-N0 L 2

SIGMA
.3 -.2 -.1 0 .1 .2 .3 .4 .5 .6 .7 .8 .9 10 II 1.2
l 1 i 1 1 i 1 1 > 1 1 1 1 1 1 1
 85

sum of the CH v a l u e s for the two c h l o r o groups and the

1 Ofi

value of 0.49 for the 3-trifluoromethyl group, obtained

f r o m the i o n i z a t i o n of anilinium ions, are used then the

points for these two compounds f a l l near the line.

There are four compounds, 4-amino-, 4-methoxy,

4-methylsulfonyl, and 4 - n i t r o d i p h e n y l a m i n e , for which the

P HA
K v a l u e s d o n
°t correlate w i t h 0~. This is not altogether

surprising since the substituents i n these compounds

display variable resonance e f f e c t s d e p e n d i n g on the nature

of the reaction site ' ' 1 3 1 0 4

, The a c i d i c site in diphenyl-

amines is attached d i r e c t l y to the aromatic r i n g while it

is not in benzoic acids (whose i o n i z a t i o n s are used to

determine c r v a l u e s ^ ) . . 1 3
It m i g h t be e x p e c t e d , then, that

the four substituents m e n t i o n e d above w o u l d behave differently

in the i o n i z a t i o n of diphenylamines.

Thus f o r the 4-amino and 4 - m e t h o x y g r o u p s resonance

interaction of the type, (XII), that i s very probably of

some importance i n the benzoic acids ' 1 3

is of little importance

in the diphenylamines. This is s u p p o r t e d by the fact that

HpN-

XII
 86

the pK H A values for these two compounds are f a i r l y well

correlated (figure 7) w i t h CT° v a l u e s (determined from

reactions i n which resonance effects are minimal *^* ) .

10 3

On the other hand, resonance interaction of the

f o l l o w i n g type is of greater importance for the anion of

OpN-

XIII

diphenylamine than for the a n i o n of b e n z o i c acid. The

0~"value for the 4-nitro group i s 0 . 7 7 8 i n the ionization

of b e n z o i c acids 1 0
^ ,
3
1.27 i n the i o n i z a t i o n of p h e n o l s and

anilinium ions 1 0 3 c
and must be a s s i g n e d a value of 1.65

in the i o n i z a t i o n of d i p h e n y l a m i n e s .

C o m p a r i s o n of substituent effects on the acidity

of p h e n o l s and d i p h e n y l a m i n e s s h o u l d be i n t e r e s t i n g since

these compounds a r e quite similar. ( A n i l i n e s w o u l d be

better nitrogen analogs of phenols than are diphenylamines,

however there is i n s u f f i c i e n t data for a good comparison.)

The p value for i o n i z a t i o n of diphenylamines i s 1.8 times

as large as the p for i o n i z a t i o n of p h e n o l s ; that is, the

effects of substituents on t h e acidity of d i p h e n y l a m i n e are 1.8

times as great as they are on t h e acidity of p h e n o l . This is

 87

probably a result of the greater importance of charge

delocalization i n the aromatic ring i n the anion of

diphenylamine than of p h e n o l .

In t e r m s o f the resonance viewpoint, structures

s u c h as (XIV) and (XV) s h o u l d c o n t r i b u t e more to the

fi <—> < > • f i

XIV xv
resonance h y b r i d of the diphenylamine anion than the

corresponding structures, (XVI) and (XVII), to the

C r <- >=0

XVI XVII

resonance hybrid of the phenoxide ion. This is because

of the smaller difference in electronegativity between

carbon (2.5) and n i t r o g e n (3.0) t h a n between carbon and

oxygen (3.5) ' l c 1 0 7

. Substituents on the ring should

perturb the charge delocalization. This perturbation will

therefore be g r e a t e r for the a n i o n of diphenylamine than

the phenoxide ion. This i n ' t u r n suggests that the acidity

 88

of d i p h e n y l a m i n e s h o u l d be a l t e r e d more by s u b s t i t u e n t s in

the aromatic ring than the a c i d i t y of phenol.

From t h e s e same arguments it w o u l d be expected

that the a c i d i t y of toluene i s e v e n more sensitive to

substituent effects t h a n the a c i d i t y of d i p h e n y l a m i n e or

phenol. Although the equilibrium acidities of substituted

(34)
toluenes have n o t been d e t e r m i n e d , there is indirect

evidence that the a c i d i t y of toluene is affected to a

greater extent by substituents.

Streitwieser and K o c h ^ 0 8
have m e a s u r e d t h e relative

rates of d e u t e r i u m exchange of a series of substituted

toluenes i n cyclohexylamine with l i t h i u m and c e s i u m

cyclohexylamide as catalysts. A plot of log (relative

exchange rate) versus Hammett CT v a l u e s yields a line with

p (slope) of 4. If the r e l a t i o n s h i p between the relative

rate of h y d r o g e n - d e u t e r i u m exchange and t h e equilibrium

acidities of substituted toluenes were known t h e n t h e p

value for i o n i z a t i o n of toluenes c o u l d be calculated. This

relationship is not known; however, it is known f o r another

series of carbon acids.

 89

Andreades® 4
has d e t e r m i n e d the relative rates of

t r i t i u m exchange for a series of carbon a c i d s w i t h the

fluorene structure (XVIII) i n sodium methoxide-methanol.

Streitwieser and c o - w o r k e r s have d e t e r m i n e d the

equilibrium acidities for these same acids i n the cyclo-

hexylamine system. A plot of log (relative exchange rate)

versus pK f o r this series of acids gives a fairly good

' 60

plot with slope of -0.4 . If a similar relationship

were to hold for the toluene series t h e n the p value for

toluene i o n i z a t i o n w o u l d be a p p r o x i m a t e l y 10. There is

a great deal of u n c e r t a i n t y in^ s u c h an e s t i m a t i o n ;

XVIII

however, it does indicate that the p> f o r i o n i z a t i o n of

toluenes is greater than f o r the i o n i z a t i o n of p h e n o l or

diphenylamine. This is i n agreement w i t h the prediction

that the magnitude of substituent effects on acidities

should increase i n the series phenol, diphenylamine ( a n i l i n e ) ,

toluene.
 90

The data on the ionization of anilines is

insufficient to attempt a Hammett plot or e v e n to make a

direct comparison w i t h the data for diphenylamines.

However, it is possible to make a comparison of the

acidities of anilines and d i p h e n y l a m i n e s indirectly by

comparing them b o t h to a common q u a n t i t y , the acidity of

phenols. Thus, Figure 8 contains a plot of the pKjj A values

of anilines and d i p h e n y l a m i n e s versus those of phenols.

The pKjj A values of the monosubstituted phenols are from

the data of Biggs and R o b i n s o n 1 0

^ and t h o s e for the dichloro-
109
phenols are from the data of Robinson

The best straight line through the points for the

diphenylamines is drawn. It was calculated omitting the

points for the 4-nitro and 4 - m e t h y l - s u l f o n y l substituents

and has slope 1.95 - .13 and c o r r e l a t i o n coefficient,

r, of 0.988. This slope is slightly higher than the p

values for the ionization of diphenylamines and phenols

would l e a d one to expect.

A line w i t h the same s l o p e is drawn t h r o u g h the

points for the anilines. It can be s e e n t o accomodate

most o f the points, suggesting that substituent effects

in,the ionization of anilines are the same as in diphenylamines.

The difference along the ordinate between the two lines,

4.9 pK u n i t s , represents the difference i n pKjj A values

 91

FIGURE 8 PLOT OF P K H A OF ANILINES AND DIPHENYL-

70 Q 75 8.0 8.5 9.0 9.5 10.0

 92

caused by r e p l a c i n g an amino h y d r o g e n o f a n i l i n e with a

phenyl group. This can be u s e d t o calculate a pKjj^ value

of 27.3 for aniline f r o m the value 22.44 of d i p h e n y l a m i n e .

This is in excellent agreement w i t h the PKJJA value of 27

59
o b t a i n e d by McEwen thirty years ago. The agreement,

however, must be c o n s i d e r e d largely fortuitous since his

values were b a s e d on s e m i - q u a n t i t a t i v e measurements in a

solvent of low d i e l e c t r i c and on an a r b i t r a r y value of

16 f o r the pKjj^ o f methanol.

It m i g h t be n o t e d i n Figure 8 that the points for

the 4-nitro substituent for b o t h the aniline and the

diphenylamine fall w e l l b e l o w the lines that correlate

most of the data. This substituent, then, has a much

greater effect on the acidity of aromatic amines than would

be e x p e c t e d f r o m i t s effect on the acidity of phenol. This

was m e n t i o n e d e a r l i e r in a different way when i t was

stated that the 4-nitro substituent has an a p p a r e n t sigma

value of 1.65 i n the i o n i z a t i o n of diphenylamines as

compared to 1.27 i n the i o n i z a t i o n of phenol. On the other

hand, the 3-nitro substituent behaves as w o u l d be expected

since the point for it lies on the line correlating the

P HA
K v a l u e s o f
phenols and d i p h e n y l a m i n e s .

The d i f f e r e n c e i n behaviour of the nitro group

at the 3 (meta) and 4 ( p a r a ) positions is no doubt due to

 93

the large c o n t r i b u t i o n made i n the latter c a s e by the

structure (XIX) to the resonance h y b r i d o f the anion of

4-nitroaniline and o f 4 - n i t r o d i p h e n y l a m i n e .

0 N-
2 H <—> ~0pKt=<)-=NH

XIX

The s t u d y o f a series of alkyl-substituted

4-nitroanilines p r o d u c e d some interesting results. The

effect of alkyl substituents ortho to the amino g r o u p

is to increase the acid strength (decrease the pKjj )A of

4-nitroaniline. T h u s one o r t h o m e t h y l group decreases

the pK|j A
o f
4-nitroaniline by 0 . 0 8 units, two o r t h o methyl

g r o u p s by 0 . 2 0 units and two t - b u t y l g r o u p s by more than

1.0 units. The e f f e c t of these groups is i n the opposite

direction to t h a t w h i c h w o u l d be e x p e c t e d on the basis of

simple inductive effects.

It is encouraging, at least with regard to the

validity of the results, that s i m i l a r trends are observed

in the acidities of ortho-alkyl-4-nitro-phenols. The p K ^

values of these compounds have been m e a s u r e d in aqueous

solution where it is not necessary to resort to the Hammett

 94

technique to determine acid dissociation constants. The

pKjj^ v a l u e s for these anilines and p h e n o l s are listed in

Table V I .

The e f f e c t of alkyl substituents is better

illustrated by t h e data i n T a b l e VI f o r phenols since

they are more complete than for anilines. The p K ^ of

2,6-dimethylphenol is approximately 0.6 units greater than

the pKjj^ o f phenol; that is, phenol i s the stronger acid.

It m i g h t be e x p e c t e d t h e n that 4-nitrophenol w o u l d be

about 0.6 pK u n i t s stronger as an a c i d t h a n 2,6-dimethyl-

4-nitrophenol. In f a c t it is not; the pKjj^ v a l u e s of the

two compounds a r e r o u g h l y the same. With b u l k i e r ortho

groups the effect i s even greater since 2,6-di-t-butyl-4-

nitrophenol is 0.5 pK u n i t s stronger as an a c i d t h a n 4-

nitrophenol rather than b e i n g an e x p e c t e d 1 . 7 units weaker.

The d a t a for 4-nitroanilines, though l i m i t e d , i s similar

in trend.

The e x p l a n a t i o n for the acid strengthening

effects of ortho alkyl groups on the acidity of 4-nitro-

aniline and 4 - n i t r o p h e n o l is not at all obvious. Steric

inhibition to solvation of the a n i o n s w o u l d be e x p e c t e d to

bring about the opposite effect. That solvation is probably

restricted for the anions with bulky ortho groups is evidenced

by the fact that 2,6-di-t-butylphenol is too insoluble in

 95

TABLE VI

The P K J J A V a l u e s of some Alkyl-Substituted

Anilines and P h e n o l s

Substituents P^HA ^v
°f
a u e p K
HA v a l u e o f Lit
substituted substituted ref
aniline phenol

none 10.00 105

2-methyl 10.29 113
4-methyl 10.26 113
4-t-butyl 10.23 110
2,6-dimethyl 10. 59 114
3,5-dimethyl 10.14 114
2,6-di-t-butyl 11.70b 110
4-nitro 18.91 7.15 105
2-methyl-4-nitro 18.83
2,6-dimethyl-4-nitro 18.71 7.19 114
2,6-di-t-butyl~4-nitro 17 . 4 a
6.65 110
3,5-dimethyl-4-nitro 21.16 8.25 114
2,3,5,6-tetramethyl-4-
nitro 22.66

a
approximate value

e s t i m a t e d f r o m a Hammett p l o t for 4-substituted-

2,6-di-t-butylphenols
 96

water at h i g h pH t o allow spectral measurements t o be made

on i t s ionization 1 1 0
. In f a c t it has been r e p o r t e d that

2,6-di-t-butyl—4-methyiphenol is insoluble in aqueous

alkali of any strength 1 1 1

.

A possible explanation of these phenomena m i g h t

lie in solvation effects on b o t h the ionized and u n i o n i z e d

species. In t h e a n i o n o f p h e n o l the negative charge must

reside p r i m a r i l y on t h e oxygen atom where it c a n be s t a b i l i z e d

by s o l v a t i o n . The i n t r o d u c t i o n o f b u l k y alkyl groups ortho

to the oxygen h i n d e r s s o l v a t i o n and c o n s e q u e n t l y increases

the energy of the anion. However, if a substituent such as

the nitro group i s p l a c e d at the 4 - p o s i t i o n of phenol a

large p o r t i o n of the ions negative charge w i l l reside on this

s u b s t i t u e n t . w h i c h h a s no h i n d r a n c e to solvation. Thus, the

effect of substituents i n the para p o s i t i o n capable of

supporting part of the negative charge i n the phenoxide ion

(or a n i l i n e anion) is to lessen the a c i d weakening effect

of ortho alkyl groups.

The f i n d i n g s of Cohen and J o n e s 1 1 0

support such

and e x p l a n a t i o n . They m e a s u r e d t h e pKjj A values of two

series of p h e n o l s of the type (XX) and (XXI) and f o u n d that

the difference between the pK values f o r members o f the

 97

F W / V - O H

= t-BUTYL

XX X X I
two s e r i e s with a given substituent R decreases as the

substituent becomes more electron withdrawing (as measured

by the Hammett 0 parameter).

This explanation can account for a lessening of

the a c i d weakening e f f e c t of ortho alkyl groups; however

it cannot account for the apparent acid strengthening

effect of these groups in 2,6-di-t-butyl-4-nitroaniline and

the corresponding phenol. A further process is required

to explain this and i t is possible that it involves solvation

of the amino and h y d r o x y l functions of the unionized anilines

and phenols.

In a recent attempt to explain the basicities of

aliphatic amines and o f N - a l k y l a n i l i n e s i n t e r m s o f the

hydration of the neutral amines and t h e i r ammonium ions,

26 86

Condon ' was drawn t o the conclusion that hydration of

the free aniline or N-alkylaniline is base w e a k e n i n g by 1.6

pK u n i t s as compared to aliphatic amines. This increased

 98

importance of h y d r a t i o n i n the a n i l i n e b a s e s as compared

to the aliphatic amines was a t t r i b u t e d to the greater

importance o f h y d r o g e n b o n d i n g of the type (XXII) in aniline

than in aliphatic amines (XXIII). This is reasonable since

XXII XXIII

the nitrogen atom i s at the positive e n d of the dipole in

X 07 to
aniline whereas i t is p r o b a b l y at the negative end i n
aliphatic amines^. H y d r o g e n b o n d i n g s h o u l d be o f similar
112
or greater importance in phenols

The p r e s e n c e of large groups ortho to the hydroxyl

or amino f u n c t i o n may weaken or e l i m i n a t e h y d r o g e n bond

solvation and c o n s e q u e n t l y raise the energy of the phenol

or aniline. T h i s w o u l d be an a c i d s t r e n g t h e n i n g effect

which i n c o n j u n c t i o n w i t h the first explanation might result

in 2,6-di-t-butyl-4-nitrophenol being a stronger acid than

4-nitro p h e n o l and 2 , 6 - d i - t - b u t y l - 4 - n i t r o a n i l i n e being a

stronger a c i d than 4-nitroaniline.

 99

The i m p o r t a n c e of the nitro group i n d e l o c a l i z i n g

the charge on the anions of 4-nitrophenol and 4-nitroaniline

c a n be s e e n f r o m the effect of putting alkyl groups ortho

to the nitro group. Two m e t h y l groups ortho to the nitro

group t w i s t it out of planarity w i t h the ring, reducing the

resonance interaction w i t h the ring 1 1

^. The r e s u l t is

a decrease of 1.1 pK u n i t s i n the acidity of 4-nitrophenol

and 2 . 2 pK u n i t s i n the acidity of 4-nitroaniline. With

methyl groups ortho to b o t h the nitro and amino functions

the pKjj A of 4-nitroaniline increases by 3 . 7 units; that is,

it becomes a considerably weaker acid.

The pKjj^ v a l u e s of some 4 - n i t r o a n i l i n e s with alkyl

substituents on the nitrogen, as w i t h the other alkyl

substituted 4-nitroanilines, showed some u n e x p e c t e d effects.

The d a t a are listed i n Table III. The s t r i k i n g feature

is that the pKjj A values of N - m e t h y l , N - e t h y l , and N -

isopropyl-4-nitroaniline are less than that of 4-nitroaniline

itself. As b e f o r e , it w o u l d be e x p e c t e d on the basis of

the usual inductive effects that the substitution of methyl

for the h y d r o g e n of the amino g r o u p w o u l d i n c r e a s e the

P HA
K OJ
" 4-nitroaniline. The a c i d i t i e s of the N-alkyl-

4-nitroanilines do f a l l i n the order expected from their

inductive effects as m e a s u r e d by T a f t ' s CP* p a r a m e t e r s 1 0 3

^;

however, they do n o t show a l i n e a r correlation.

 100

An e x p l a n a t i o n for the fact that N-methyl-4-

nitroaniline is a stronger a c i d than 4-nitroaniline might

lie i n the solvation of the u n i o n i z e d amines. If, as

26

suggested by Condon , these amines are solvated by formation

of h y d r o g e n bonds as shown, (XXIV) and (XXV), the substitution

of methyl for one of the h y d r o g e n atoms on the nitrogen

destroys the site of one of the hydrogen bonds. Since the

measurements were made i n DMSO-water m i x t u r e s it is

possible t h a t DMSO r e p l a c e s water in this type of hydrogen

bonding, particularly since DMSO f o r m s s t r o n g hydrogen bonds

QQ I "I C

with proton donors ' . The l o s s of solvation destabilizes

N-methyl-4-nitroaniline with respect to 4-nitroaniline.

It m i g h t be p o s s i b l e that this decrease in solvation energy

is large enough t o overcome the inductive effect of the

methyl group c a u s i n g N - m e t h y l - 4 - n i t r o a n i l i n e to be a stronger

acid than 4-nitroaniline.

 101

The e f f e c t of substituents on the acidity of

the diphenylammonium i o n (the basicity of diphenylamine) is

similar in trend to their effect on the acidity of d i p h e n y l a m i n e

Again, no one s e t o f Hammett s u b s t i t u e n t constants correlates

the acidities of all the ammonium* i o n s . Figure 9 contains

a plot o f pKg + v e r s u s
H C~^^^ a
for the following diphenylamine

3-methoxy, 4-chloro, 3-chloro and 3 - n i t r o d i p h e n y l a m i n e and

diphenylamine itself. The r e a c t i o n constant p is 3.36 - .04

with c o r r e l a t i o n coefficient r of 0 . 9 9 9 . The p o i n t s for

3-trifluoromethyldiphenylamine ( 0 ~ •» .49 ) and for

3,4'-dichlorodiphenylamine ( ^ O = .600)
-
fall very close to

the line. As b e f o r e , the pK j+ v a l u e s

BI for the compounds

w i t h the 4-methoxy, 4-methyl, 4 - m e t h y l s u l f o n y l , and 4-nitro

w

substituents do n o t correlate w i t h o~. The p o i n t s for the

electron-releasing substituents, 4-methoxy and 4 - m e t h y l , can

be b r o u g h t near the line by u s i n g CT ^^

0
instead of <J~.

For the strongly electron withdrawing s u b s t i t u e n t s , 4-

methylsulfonyl and 4 — n i t r o , the use of 0 1 0 3 c

rather than

G -
brings the points closer to the line.

There is c o n s i d e r a b l y more data on the basicities

of a n i l i n e s than of diphenylamines since the protonation

of the monosubstituted a n i l i n e s takes place within the pH

105

range. Biggs and R o b i n s o n found that for twelve anilines

with s u b s t i t u e n t s r a n g i n g from 4 - m e t h y l «T" = - . 1 7 0 1 0 3 a

) to
 1 0 2

4 - 0 C H \ •
FIGURE 9 HAMMETT CORRELATION OF THE
BASICITY OF SUBSTITUTED DIPHENYLAMINES
- 1.0

6) H

- 0 . 5

CD 3 - 0 C H 3

- 0 . 0
\ ) 4-CI p = 3-36
\ r = . 9 9 9

\> 3—Cl
- - 0 . 5

\x 3 - C F 3

- -1.0

V 3,4-diCI
P^BH + \

- -1.5

C3 3 - N 0 2

0 — 0 " VALUES USED IN CORRELATION \

- - 2 . 0 X---0" VALUES NOT USED IN CORRELATION \
0 ~ ° VALUES \

A--CT" VALUES \
- - 2 . 5 \ A 4 - S O 2 C H 3

- - 3 . 0 SIGMA V-NO 2

- . 2 0 0 . 2 .4 .6 ,8 1.0 \l.2 A
i 1 1 1 J 1 ^ " 1
 103

3-nitro (CT" •= .710 1 0 3 a

) there is a good c o r r e l a t i o n of

pK BH + w i t h 0~. The r e a c t i o n constant p is 2.89, although

a value of 3.00 is obtained for p u s i n g the pKgjj* values

for the five a n i l i n e s corresponding to the five diphenyl-

amines u s e d above in calculating p for the protonation of

117

diphenylamines. Fickling and c o - w o r k e r s have found

that the reaction constant p for the protonation of

substituted N,N-dimethylanilines is 3.43. On t h i s basis,

substituent effects on t h e basicity of secondary and

tertiary aromatic amines are s l i g h t l y larger i n magnitude

than on p r i m a r y a r o m a t i c amines.

A plot of the pK BH + values of d i p h e n y l a m i n e s

versus the pKg + v a l u e s

H of the corresponding a n i l i n e s ,

using a wider v a r i e t y of substituents than those used to

calculate p , gives a f a i r l y good s t r a i g h t l i n e with slope

near unity. For eleven compounds whose b a s i c i t i e s range

over 5 pK u n i t s , the equation r e l a t i n g the pKg + H of a

diphenylamine (DPA) t o the pKg + H of the corresponding aniline

(An) is

<? BH DPA
K +) =
"3.98 + 1 .01 (pKg H + ) A n (35)

F i g u r e 10 is a plot of the data for this l i n e w h i c h has

correlation coefficient, r, of 0 . 9 9 8 . The pKg + v a l u e s H of

1 OS
the a n i l i n e s are taken f r o m the data of B i g g s and R o b i n s o n
 104

F I G U R E 10 PLOT OF P K B H + OF ANILINES VERSUS

PK +
B H OF DIPHENYLAMINES

P I W (ANILINE)
0 1 2 3 4 5 6
 105

except for the values for 3-trifluoromethylaniline, g i v e n by

106
Shephard , and 4 - m e t h y l s u l . f o n y l a n i l i n e , f r o m the
118
compilation of P e r r i n .

On the basis of the r e l a t i o n s h i p expressed in

equation (35) the magnitude of substituent effects on the

basicities of a n i l i n e and d i p h e n y l a m i n e a r e , on the

average, the same. For the hypothetical aniline with

pKgjj+ o f zero the pKgy+ o f the corresponding diphenylamine

is -4.0; that is, the replacement of a proton of the amino

group of the aniline by a p h e n y l g r o u p d e c r e a s e s the

basicity by 4.0 units. It will be r e c a l l e d that the

same r e p l a c e m e n t increases the acidity of aniline by 4.9

pK u n i t s . The d i f f e r e n c e i n the basicities of an aniline

and the corresponding diphenylamine i s due n o t only to

the different electronic effects of p h e n y l as compared to

hydrogen but also to differences i n the solvation energies

of the primary and s e c o n d a r y amines and t h e i r conjugate

J 26,86
acids

F. Acid and Base S t r e n g t h s of N i t r o - s u b s t i t u t e d Aromatic

Amines

It was m e n t i o n e d i n the Introduction that there is

a body o f e v i d e n c e to suggest that the nitro group takes

part i n some specific interaction w i t h a component of

concentrated acid solutions. The e x a c t nature of this

 106

interaction is not known. H o g f e l d t and L e i f e r 1 1 9

have

interpreted the solubility data 3 3

for nitrobenzene in

aqueous sulfuric acid i n terms of complex formation between

the nitro g r o u p and mono- and t r i h y d r a t e d protons. Deno and

27

Perrizzolo have suggested the existence of a hydrogen

bonded complex between a molecule of nitrobenzene and

another of sulfuric acid. The q u e s t i o n then arises of how

the basicities of n i t r o - s u b s t i t u t e d aromatic amines are

affected in solutions of high acid concentration. It

37

has been s u g g e s t e d that nitroanilines are weak bases

partly because of such i n t e r a c t i o n s between the nitro

g r o u p and t h e acidic media.

It was f e l t that some i n f o r m a t i o n m i g h t be gained

about the effect of strongly acidic media on the basicity

of nitro aromatic amines f r o m measurement of the basicities

of a series of substituted diphenylamines. Any p e c u l i a r i t y

of the nitro substituent might show up i n a Hammett 0~jO plot

or in a correlation of the basicities of substituted anilines

with the corresponding diphenylamines. The p r o t o n a t i o n of

4-nitroaniline occurs in r e l a t i v e l y dilute acid (approximately

0.1 N HC1) i n w h i c h the nitro g r o u p s h o u l d not be affected

by the acid. On the other hand, 4-nitrodiphenylamine and

2-nitrodiphenylamine are half i o n i z e d i n 5.9 and 7 . 3 molar

aqueous-ethanolic sulfuric acid respectively.

 107

It is obvious from F i g u r e s 9 and 1 0 that the

behaviour of the nitro g r o u p as a substituent in sulfuric

acid is very similar to its behaviour i n aqueous solutions

within the pH r a n g e . In t e r m s o f the Hammett substituent

constant, the 4-nitro g r o u p has sigma v a l u e of 1 . 1 6 in the

protonation of d i p h e n y l a m i n e s as compared t o 1 . 2 7 for the

protonation of anilines 1 0
^ .
0
In v i e w of the limited data

(5 pKgjj+ v a l u e s ) used to calculate p for the protonation

of d i p h e n y l a m i n e s and t h e change in structure between

diphenylamine and a n i l i n e , the discrepancy i n the signma

values for the 4-nitro substituent is not significant.

In t h e correlation of the PK BH + values of anilines with

those of the d i p h e n y l a m i n e s ( F i g u r e 1 0 ) the fit of the points

for the 2 - and 4 - n i t r o substituents is as good as for the

other substituents.

The b a s i c i t i e s of the following two s e r i e s of

diphenylamines also correlate quite well w i t h one another.

XXVI XXVII

Figure 1 1 is a plot of the P K B H + values of the mono-

substituted d i p h e n y l a m i n e s (XXVI) versus the PK TT+R values

 108

FIGURE II CORRELATION OF THE BASICITY OF SUBSTITUTED

DIPHENYLAMINES AND 4'-NITR0DIPHENYLAMINES
h "7

0 -I -2 -3 -4
J I I I L
 109

of the correspondingly substituted 4-nitrodiphenylamines

(XXVII). The s l o p e of the line is 0.86 i n d i c a t i n g that the

effect of substituents on b a s i c i t y is smaller in the

second s e r i e s than i n the first. This is probably a

result of the interaction of the amino g r o u p w i t h the

nitro g r o u p i n one r i n g causing a decrease in its inter-

action with substituents i n the other ring. The point

for Z equal to 3-nitro falls on the plot with three non-

nitro substituents w h i l e the point for Z equal to 4-nitro

falls a little b e l o w the line.

It can be s e e n that the effect of the nitro group

on the basicity of d i p h e n y l a m i n e s does not e x h i b i t any

observable change on p r o c e e d i n g from d i l u t e to concentrated

acid. This is not to say that the nitro g r o u p does not

f o r m a complex w i t h some component of strongly acidic media

since it may do so at higher acid concentrations than were

used here (approximately 11 molar s u l f u r i c acid) or it may

be t h a t the presence of such an i n t e r a c t i o n is not

observable i n s u c h an i n d i r e c t , f a s h i o n as this.
 1 1 0

It is interesting to consider the effect of the

nitro g r o u p on the acidity of aromatic amines. The 4-nitro

substituent increases the acidity of a n i l i n e and d i p h e n y l a m i n e

by a p p r o x i m a t e l y 8 . 4 and 6 . 8 pK u n i t s respectively. On

the other hand t h e 3-nitro substituent increases the

acidity of d i p h e n y l a m i n e by o n l y 2 . 9 pK u n i t s . The

exalted acidity of 4-nitroaniline and 4-nitrodiphenylamine,

in w h i c h the substituent is conjugated w i t h the amino

group, must s u r e l y be a r e s u l t of the extensive delocalization

of the charge i n the anions of these acids.

The e f f e c t of two n i t r o groups on the acidity of

an a r o m a t i c amine is not additive; the second n i t r o group

causes a smaller increase than e x p e c t e d . This is illustrated

in Table VII for d i p h e n y l a m i n e s where the calculated pK H A

values refer to the values expected f r o m a d d i t i o n of the

increments for the individual substituents. It is obvious

that the substituent effects are not additive. In t h e case

of phenols, the d e v i a t i o n from a d d i t i v i t y i s i n the opposite

direction. Thus, 2,4,6-trinitrophenol is a stronger

acid (PKHA of 0 . 2 2 ) by more than 1 pK u n i t t h a n w o u l d be

expected f r o m the pK H A values of phenol ( 1 0 . 0 0 ) , 2-nitro-

phenol (7.21) and 4 - n i t r o p h e n o l ( 7 . 1 5 ) 1 0 5

.

In T a b l e V I I the largest deviations from a d d i t i v i t y

occur i n the compounds w i t h n i t r o groups i n both r i n g s , as

 Ill

TABLE VII

The pKjj^ V a l u e s o f Some Nitro-substituted

Diphenylamines

Substituents Observed p K ^ Calculated pK ^ H

none 22.44
2- n i t r o 17.91
3- n i t r o 19.53
4- n i t r o 15.67
2,4-dinitro 13.84 11.14
3,4'-dinitro 14.66 12.76
4,4'-dinitro 14.08 a
8.90
2,4,6-trinitro 10.38 a
6.61
2,4,4'-trinitro 12.35 a
4.37

a
r e f . 40

a result, no d o u b t , of the i n a b i l i t y of b o t h r i n g s to attain,

simultaneously, maximum o v e r l a p w i t h the n i t r o g e n atom.

Not o n l y does the n i t r o substituent produce large

increases i n the a c i d i t y of aromatic amines b u t i t also

produces large rate accelerations i n the a t t a c k of n u c l e o p h i l e s

1 on 121
on a r o m a t i c substrates . Farr, B a r d and Wheland have

observed that the d i s s o l u t i o n of m - d i n i t r o b e n z e n e (XXVIII)

in liquid ammonia y i e l d s a purple s o l u t i o n capable of

c o n d u c t i n g an e l e c t r i c a l current p r o b a b l y due t o t h e formation

of the i o n (XXIX). Similarly, Bolton, Miller and P a r k e r 1 2 2

found that 4-nitrofluorobenzene (XXX) r e a c t s in dimethyl-

formamide w i t h a z i d e ion without liberation of f l u o r i d e i o n

 112

H NH
2

0;
+ 2NH 3
NHl-
N0 2 N0 2

XXVIII XXIX

to give a c o l o r e d s o l u t i o n b e l i e v e d t o be a r e s u l t of the

formation of the ion (XXXI).

XXX XXXI

Such a d d i t i o n r e a c t i o n s are also possible with

hydroxide or alkoxide ions. T h i s means that addition of

these ions to nitro aromatic amines may be a competing

p r o c e s s w i t h i o n i z a t i o n by p r o t o n loss, particularly in

the case of amines w i t h more than two n i t r o substituents in

123

one r i n g . Thus, Crampton and G o l d have shown, u s i n g nuclear

magnetic resonance spectroscopy, that 2,4,6-trinitroaniline

(XXXII) i n DMSO r e a c t s w i t h s o d i u m m e t h o x i d e predominantly

by m e t h o x i d e ion addition rather than by p r o t o n dissociation.

 113

On the other hand, 2,4-dinitroaniline (XXXIII) and 2,4-

dinitrodiphenylamine i o n i z e by p r o t o n loss.

XXXIII

Hydroxide i o n a d d i t i o n can compete with dissociation

even in mono-nitroanilines. The n i t r o group i s most

effective at increasing acid strength when s i t u a t e d at

the 2 or 4 p o s i t i o n of aniline. S i m i l a r l y the nitro group

facilitates a d d i t i o n to aromatic compounds i n the ortho and

para positions.
 114

In 4 - n i t r o a n i l i n e (XXXIV) the nitro group exhibits

a great acid strengthening effect so that this compound

reacts with hydroxide i o n by p r o t o n loss rather than hydroxide

addition.

NH 2 NH

OH" H 0
2

N0 2 NO;

XXXIV

In 3 - n i t r o a n i l i n e (XXXV) the nitro group d i s p l a y s its

weakest acid strengthening effect whereas the compound

is still susceptible to hydroxide i o n a d d i t i o n at a position

ortho or para to the nitro group.

XXXV

Thus, i n 97 mole % DMSO c o n t a i n i n g 0.011 molar

hydroxide ion 3 - n i t r o a n i l i n e does not u n d e r g o , as does

 115

4-nitroaniline, a rapid spectral change characteristic

of i o n i z a t i o n by p r o t o n loss but rather produces a broad

absorption i n the region f r o m 300 to 550 mjj that increases

in intensity with time. In the same s o l u t i o n a similar

spectral change o c c u r s w i t h n i t r o b e n z e n e for which proton

124

abstraction f r o m the aromatic r i n g i s improbable . It

appears then that these two compounds r e a c t by hydroxide

ion addition in strongly basic solutions. It is interesting

that 3 - n i t r o d i p h e n y l a m i n e (XXXVI) r e a c t s by dissociation

XXXVI
rather than addition. This is due t o the fact that the

addition of the p h e n y l group t o the amino g r o u p o f 3-

nitroaniline increases the acidity of the amino h y d r o g e n by

nearly 5 pK u n i t s whereas i t produces only a secondary

effect on the susceptibility of the aromatic r i n g to

hydroxide ion addition.

125

Rochester , from a study of the ultraviolet

absorption spectrum of 4-nitroaniline i n aqueous sodium

hydroxide (0 to 17 molar) has concluded that 4-nitroaniline

takes part i n two e q u i l i b r i a d e p e n d i n g on the concentration

 116

of the base. The f i r s t e q u i l i b r i u m predominates in the

region from 0 to 8 molar sodium h y d r o x i d e , and i s charac-

terized by a s h i f t i n the l o n g wavelength absorption

maximum f r o m 381 to 400 mju ; the second equilibrium

predominates from 8 to 17 molar base and i s characterized

by a f u r t h e r shift of the absorption maximum t o 433 mjj, .

Rochester has suggested that the first equilibrium is

hydroxide ion a d d i t i o n to the 4-nitroaniline and the second

is proton abstraction from t h i s complex.

Others ^'^ 4
who have used 4 - n i t r o a n i l i n e as an

indicator i n aqueous sulfolane w i t h added base have not

reported that it i o n i z e s by o t h e r than simple proton loss.

Similarly, the spectral changes observed in this work suggest

o n l y one e q u i l i b r i u m . It seems q u i t e possible that the

shift of absorption maximum o b s e r v e d by R o c h e s t e r in 0 to

8 molar base is not the result of hydroxide ion addition

to 4-nitroaniline but r a t h e r is a result of a change in

the character of the medium. T h e r e must be a considerable

change i n the nature of the solvent i n g o i n g from water

to 8 molar sodium h y d r o x i d e since the concentration of

free water (water not bound t o the hydroxide ion) in 8

molar sodium h y d r o x i d e is reduced to one h a l f of its value

47

in water . The e f f e c t s of change in solvent on the position

of the l o n g wavelength a b s o r p t i o n maximum o f 4-nitroaniline

 117

are large. Pearson 1 2

6 h a s observed s h i f t s f r o m 320 mjj in

n-hexane to 380 mjj i n d i m e t h y l f ormamide .

The p o s s i b i l i t y o f the spectrum change being the

result of a medium e f f e c t was t e s t e d by m e a s u r i n g the absorption

spectrum of 4-nitroaniline i n approximately 7 molar potassium

fluoride solution. This showed t h a t the long wavelength

absorption maximum i s s h i f t e d 8 to 10 mp. to the red with

an i n c r e a s e of about 10 % i n the molar absorptivity, £ , as

compared t o i n water. A smaller shift of 4 t o 6 mjj^ was

observed i n 8 molar sodium p e r c h l o r a t e . Rochester

observed a shift of about 19 mjj i n 8 molar sodium hydroxide

with a small increase i n molar absorptivity (the actual

increase is not reported) 1 2

5 o

It seems q u i t e reasonable, then, to conclude that

the absorption maximum o f 4 - n i t r o a n i l i n e is s h i f t e d to the

r e d on p a s s i n g f r o m w a t e r to 8 molar sodium h y d r o x i d e due

to a change i n the solvent and i t s interaction with the

4-nitroaniline. The s i z e of the shift depends on t h e added

salt- p r o b a b l y on i t s a b i l i t y to complex the water. This

means that 4-nitroaniline does not react by h y d r o x i d e

ion a d d i t i o n i n 0 to 8 molar sodium h y d r o x i d e as suggested

125
by Rochester
 118

G. C o m p a r i s o n o f the Acidity and B a s i c i t y of Anilines

and D i p h e n y l a m i n e s

69

Stewart and O ' D o n n e l l have found that a plot

of p K H A (as ordinate) versus pK j+BJ (as abscissa) for a

series of a n i l i n e s and d i p h e n y l a m i n e s w i t h n i t r o group

substituents y i e l d s a l i n e with slope of 0 . 6 . Using some

of the data obtained in t h i s work, a similar plot for a

series of seven m o n o s u b s t i t u t e d d i p h e n y l a m i n e s , a d i c h l o r o -

diphenylamine and d i p h e n y l a m i n e i t s e l f also gives a straight

line but w i t h s l o p e 1.30 - .05 and w i t h correlation

coefficient r of 0 . 9 9 5 . The p l o t is shown i n F i g u r e 12.

The p o i n t s for three mono-substituted d e r i v a t i v e s -

4-methylsulfonyl, 2-nitro, and 4 - n i t r o d i p h e n y l a m i n e - do

not fall on t h i s line.

The v a l u e of 0 . 6 for the slope f o u n d by Stewart

69

and O ' D o n n e l l indicates that substituents have a greater

effect on b a s i c i t y t h a n on a c i d i t y for nitrated anilines

and d i p h e n y l a m i n e s whereas the slope of 1 . 3 0 for the compounds

in Figure 12 indicates that the opposite is true for diphenyl-

amines w i t h most other substituents, i n c l u d i n g the nitro

g r o u p i n the meta position.

Figure 13 is a p l o t s i m i l a r to Figure 12 with

most of the data at present available for a n i l i n e s and

diphenylamines. This i n c l u d e s the data in Figure 12 and

 119

-24 F I G U R E 12 PLOT OF P K H A VERSUS PKBH+ FOR

DIPHENYLAMINES 7

p 4 - 0 C H 3
- 23 / 4 - C H 3

p H
©/ 3 - 0 C H 3

- 2 2

SLOPE =1.30 /
r= -995 / 4-c|
- 21

A 3-CI
/ 3
P HA
3 _ C F

- 20
/© 34-"-diCI
y

© / 3 - N 0 2

- 19
\*
s \ / 4-S0 CH 2 3

~ 18
X 2-N02
P KHA=2I.44-HI.30PKBH+

-17 /

-16 /
4-N02

PKBH+
- 15 -4 -3
1 1 1 1
- 2 - 1 0 1 2

1 1 1
 120

FIGURE 13 PLOT OF pK H A VERSUS P K B H + FOR

ANILINES AND DIPHENYLAMINES
h 26

2 4 <•>,• ANILINES
B,X DIPHENYLAMINES

A'
22

P^HA
h 20

- 16
^>/^ o a n d p-NITRO AMINES

r 14

2
P^BHf
-10 -8 -6 -4 -2 0 4
__L_
 121

also that of Stewart and 0 ' D o n n e l l D y

except that dissociation

constants determined in this work were u s e d where applicable.

The pK B H + and p K f l A values are listed in Table VIII.

Statistical corrections for the number o f ionizable

86 127

protons ' were a p p l i e d t o the pK v a l u e s i n Table VIII

before p l o t t i n g them i n F i g u r e 13. The c o r r e c t i o n s are:

for the pKgjj+ o f anilinium ions, add l o g 3; for the pKjj^

of anilines and the pKgjj+ of diphenylammonium i o n s , add

log 2; for the pK H A of d i p h e n y l a m i n e s , no correction..

In F i g u r e 13 it can be s e e n that the amines

appear to fall i n t o two c l a s s e s . The a n i l i n e s and

diphenylamines without n i t r o groups f o r m one class.

The points for the anilines in this group f a l l slightly

b e l o w the projection of the line for the diphenylamines

b u t show a s i m i l a r trend. The o t h e r class of amines is

comprised of those a n i l i n e s and d i p h e n y l a m i n e s containing

at least one n i t r o group o r t h o or para to the acidic

amino g r o u p . These amines fall on a s l i g h t l y c u r v e d line

of smaller slope.

The different behaviour of the nitrated anilines

and d i p h e n y l a m i n e s as compared t o the other substituted

amines must be a r e s u l t of the peculiar effect that the nitro

group has on t h e acidity of aromatic amines. The effect

of the nitro g r o u p on the basicity of aniline is quite

 122

TABLE V I I I

V a l u e s o f p K g ^ and p K H A for

Anilines and Diphenylamines

Substituents PK + Lit. Lit.

P^A
BH

ref . a
Ref.

Anilines

3-chloro 3.52 105 25.63

3-trifluoromethyl 3.20 106 25.40
3-cyano 2.75 105 24.64
4-cyano 1.74 118 22.68
3,4-dichloro 2.97 109 24.60
3,5-dichloro 2.38 109 23.59
2,3-dichloro 1.76 109 23.14
2,4-dichloro 2.02 109 23.46
2,5-dichloro 1.53 109 22.71
2,6-dichloro 0.42 109 22.40
4-nitro 1.00 105 18.91
2-nitro - 0.26 105 17.88 40
2-nitro-4-chloro - 1.07 128 17.08
4-nitro-2,5-dichloro - 1.78 23 16.05 40
4-nitro-2,6-dichloro - 3.27 23 15.55 40
2,4-dinitro - 4.26 128 15.00 40
2,4-dinitro-6-bromo - 6.68 23 13.63 40
2,4,6-trinitro -10.10 23 12.20 40

Diphenylamines

4-methoxy 1.36 23.22

4-methyl 1.20 22.95
none 0.78 22.44
3-methoxy 0.40 22.22
4-chloro 0.01 21 .33
3-chloro - 0.45 20.73
3-trifluoromethyl - 0.78 20.48
3,4'-dichloro - 1.19 19.73
3-nitro - 1.61 19.53
4-methylsulfonyl - 2.54 18.80

Continued.
 123

Table VIII - Continued..

Substituents P BHK +
Lit. P HA
K
Lit.
Ref. a
Ref. a

Diphenylamines

2-nitro - 4.12 17.91

4-nitro - 3.13 15.67
4-nitro-3'-
trifluoromethyl - 4,47 14.96
3,4'-dinitro - 5.19 14.66
4,4'-dinitro - 6.21 14.08 40

a values without reference were d e t e r m i n e d i n this

work
 125

regular. The pKgjj+ o f 2 , 4 , 6 - t r i n i t r o a n i 1 i n e w o u l d be

e x p e c t e d t o be - 9 . 7 2 b a s e d on the p K _ „ + v a l u e s of a n i l i n e
bn
(4.60), 2-nitroaniline (-0.26), and 4 - n i t r o a n i l i n e (1.00) 1 0 5
.
23

It h a s been d e t e r m i n e d t o be - 1 0 . 1 0 . On the o t h e r hand,

the effect of the n i t r o g r o u p on t h e a c i d i t y of a n i l i n e is

quite irregular. The p K H A value of 2,4,6-trinitroaniline

w o u l d be e x p e c t e d t o be 0 . 1 b a s e d on the p K y A of a n i l i n e

( e s t i m a t e d t o be 2 7 . 3 ) , 2-nitroaniline (17.88) 4 0
, and 4 -

nitroaniline (18.91). It h a s been f o u n d 4 0

t o be 1 2 . 2 0 .

Thus t h e f i r s t nitro group i n the o r t h o or para p o s i t i o n of

aniline produces a g r e a t enhancement in acidity, however

the effect on a c i d i t y of the s e c o n d a n d s u b s e q u e n t

substituents i s dampened. On t h e o t h e r hand the basicities

of a n i l i n e s vary r e g u l a r l y with m u l t i p l e substitution.

The e q u a t i o n f o r the l i n e i n Figure 12 relating

the acidities t o the b a s i c i t i e s of d i p h e n y l a m i n e s i s

P HA
K =
21.44 + 1 . 3 0 ( p K BR +) (36)

It is interesting t o use t h i s equation to estimate a value

for the p K H A o f ammonia f r o m i t s p K g + . H The P K

B H
+
° f ammonia
67

is 9.25 but since there are f o u r i o n i z a b l e protons on t h e

ammonium i o n a s compared t o two on t h e diphenylammonium i o n

the factor l o g 2 must be added t o t h e p K g + . H U s i n g the

value 9.55 f o r t h e P gjj+ ° f ammonia a v a l u e

K
of 33.8 is
 126

obtained for the pK R A from e q u a t i o n (36). This in turn

must be c o r r e c t e d f o r the fact that ammonia has three

ionizable protons whereas d i p h e n y l a m i n e has one so that

the dissociation constant for the former compound s h o u l d

be t h r e e times as large as that given i n equation (36).

Thus the factor l o g 3 must be s u b t r a c t e d from 33.8 to give

68

a value of 33.3 for the p K j ^ of ammonia. Bell has

estimated that the p K „ . of ammonia i s 35.

 127

SUGGESTIONS FOR FURTHER WORK

One o f the potential applications of Hammett

acidity functions is the elucidation of reaction mechanisms

through the quantitative treatment of a c i d and base

catalysis. Procedures have been o u t l i n e d f o r use of

31 32 129
correlations of reaction rates with H Q ' or H_ as

a criterion of mechanism. Most c o r r e l a t i o n s that have

been made involved reactions of acids or b a s e s o f structural

types different from those of the indicators that were used

to determine H _ or H . Q In o r d e r to draw v a l i d conclusions

about the reaction mechanism it is necessary that the

ionization of the substrate involved i n the reaction be

g o v e r n e d by the acidity f u n c t i o n u s e d i n the correlation.

This has p r o b a b l y not been so i n many cases.

Since aromatic amines were u s e d t o e s t a b l i s h the

H_ s c a l e i n DMSO-water it would be p r e f e r a b l e , in any

investigation of correlations of rate with H_ i n this

system, to study the reaction of an a r o m a t i c amine substrate

One s u c h r e a c t i o n is the f o l l o w i n g base c a t a l y z e d intra-

130 131
molecular condensation of 2-amino-2'-nitrobiphenyl '
 128

This reaction proceeds almost quantitatively in refluxing

131

methanol c o n t a i n i n g sodium h y d r o x i d e , p r o b a b l y by

an a l d o l - t y p e mechanism i n v o l v i n g i o n i z a t i o n of the amino

g r o u p f o l l o w e d by a t t a c k of the a n i o n on t h e nitrogen

atom o f the nitro group 1 3 2

. The i o n i z a t i o n o f the

amino g r o u p s h o u l d be g o v e r n e d by t h e H_ scale established

in this work f o r DMSO-water m i x t u r e s .

It s h o u l d be p o s s i b l e to m o d i f y the rate of the

reaction by p l a c i n g s u b s t i t u e n t s in either ring. The

kinetics c o u l d be f o l l o w e d c o n v e n i e n t l y by m e a s u r i n g the

increase in light absorption due t o the azoxy chromophore

of the product.

An i n t e r e s t i n g companion s t u d y w o u l d be the

reaction 1 3 0
' 1 3 1
i n w h i c h the n u c l e o p h i l i c atom i s carbon

rather than nitrogen.

 129

It w o u l d be interesting to study the basicity in

polar aprotic solvents of s u c h weak b a s e s as phenoxide,

benzoatej acetate, and f l u o r i d e ions since it is quite

possible that some of these ions, when s t r i p p e d o f their

s o l v a t i n g water m o l e c u l e s , w o u l d become quite basic. For

example, the fluoride i o n appears to be a s t r o n g base in

aprotic solvents since tetraethylammonium f l u o r i d e when

warmed i n t h e s e solvents y i e l d s ethylene and t r i e t h y l a m m o n i u m

fluoride ^^ 1
Such a s t u d y s h o u l d p r o v i d e information about

the solvation of these ions i n aqueous solution.

C C H C H - ) N F " — ^ — * CCH CH -) NHF +• C H = C H

3 2 4
+
3 2 3 2 2

134

A solvent, that has proven to be u s e f u l in

carrying out a great number o f organic reactions involving

anions is hexamethylphosphoramide (XXXVII).

 130

[(CH )2N-] P=0

3 3

XXXVII

It has a wide l i q u i d range (4-232°) and a f a i r l y large

135
dielectric constant (D = 30 at 25°) . Because of the
135

extremely weak a c i d i t y of its h y d r o g e n atoms hexamethyl-

phosphoramide does not react with such s t r o n g b a s e s as the

anion of cyclohexylamine, unlike DMSO. Since potassium

hydroxide and t - b u t o x i d e appear to be v e r y s t r o n g bases in

hexamethylphosphoramide 1 3 5
it m i g h t be p o s s i b l e t o extend

the H_ scale in this solvent.

Recently, Gordon has made s t u d i e s i n molten

quaternary ammonium s a l t s and h i s r e s u l t s should stimulate

interest in this field. The r e l a t i v e l y low m e l t i n g p o i n t s

of some of these salts s h o u l d a l l o w them t o be studied

136a

using standard instrumentation. Gordon s u g g e s t s that

the nucleophilic reactivity of anions i s e n h a n c e d as the

medium p r o g r e s s e s from p r o t i c solvent to polar aprotic

solvent to fused s a l t . The b a s i c i t y of anions should also

be e n h a n c e d i n fused s a l t s and d e s e r v e s some study.

Solubility s h o u l d be no p r o b l e m s i n c e nearly all types of

organic compounds, w i t h the exception of saturated hydrocarbons,

 131

are miscible w i t h the fused salts near their melting

. 136c
points
 132

APPENDIX A : P r e p a r a t i o n and P u r i f i c a t i o n o f Indicators

4-Methoxydiphenylamine: prepared by r e a c t i o n of 4-hydroxy-

diphenylamine (Eastman Organic Chemicals) with d i -

m e t h y l s u l f ate in basic solution. The p r o d u c t melted

at 104.5 - 105° after recrystallization three times

f r o m aqueous ethanol and once from petroleum ether

(65-110°) f o l l o w e d by s u b l i m a t i o n . Lit. m.p. 105° .

4-Methyldiphenylamine: prepared f r o m p - t o l u i d i n e and b r o m o -

benzene by the same method u s e d by S c a r d i g l i a and

Roberts 1 3 8
to prepare 3-methyldiphenylamine. After

several recrystallizations from petroleum e t h e r (65 -

110°) f o l l o w e d by s u b l i m a t i o n the product melted at

87.5 - 88°. Lit. m.p. 89° 1 3 7

.

Diphenylamine: obtained f r o m Eastman O r g a n i c C h e m i c a l s was

recrystallized from petroleum e t h e r (30-60°) and

o 0
137
sublimed, m.p. 53-53.5 . Lit. m.p. 54

3 - M e t . h o x y d i p h e n y l amine : 3 - h y d r o x y d i p h e n y l amine prepared from

139

aniline and r e s o r c i n o l by the method o f Calm was

methylated in basic s o l u t i o n with d i m e t h y l s u l f a t e . After

sublimation f o l l o w e d by two r e c r y s t a l l i z a t i o n s from

petroleum ether (65-110°) the product melted at 68.5-69°.

Lit. m.p. 72° 1 4

° .
 133

3- C h l o r o d i p h e n y l a m i n e : prepared from 3-chloroacetanilide

141
and iodobenzene by G o l d b e r g ' s method of preparing
20

diphenylamines, b.p. 335°/739 mm, n ^ 1.6507. Lit. b.p.

340°/766 mm 1 4 2
.
4- C h l o r o d i p h e n y l a m i n e : p r e p a r e d by t h e general method of
143 144
Chapman ' . N-Phenylbenzimino-4-chlorophenyl
ether (XXXVIII), prepared from 4 - c h l o r o p h e n o l and
i 43a

benzanilide by the same method u s e d by Chapman for

the preparation of N - p h e n y l b e n z i m i n o - 3 - h y d r o x y - p h e n y l

ether, was h e a t e d for two h o u r s at 280-300° i n a Woods'

metal bath to yield a dark, viscous material that was

hydrolyzed and the resulting 4-chlorodiphenylamine

(XXXIX) isolated according to the method o f C h a p m a n ^ ^ .1

After several recrystailizations from petroleum ether

(65-110°) f o l l o w e d by s u b l i m a t i o n , the product melted

at 68.5-69°. Lit. m.p. 70.6° 1 4 5

.
 134

3,4'-Dichlorodiphenylamine: prepared by the same method u s e d

in the p r e p a r a t i o n of 4 - c h l o r o d i p h e n y l a m i n e . N-3-
143a

Chlorophenylbenzimino-4-chloro-phenyl ether, prepared

from 4 - c h l o r o p h e n o l and b e n z - 3 - c h l o r o a n i l i d e , was h e a t e d

for two h o u r s at 2 9 0 - 3 0 0 ° and the r e s u l t i n g material

refluxed in alcoholic potassium hydroxide f o r two

hours 1 4 3 <
*. After several recrystallizations from

petroleum ether (65-110°) f o l l o w e d by s u b l i m a t i o n t h e

product, 3,4'-dichlorodiphenylamine, melted at 61-62°.

Lit. m.p. 6 3 - 6 4 ° 1 4 6
.

3-Trifluoromethyldiphenylamine: obtained from A l d r i c h

Chemical C o . was d i s t i l l e d u n d e r r e d u c e d p r e s s u r e , the

middle cut d i s s o l v e d i n dry ether and hydrogen

chloride gas b u b b l e d t h r o u g h the s o l u t i o n . The p r e c i p i t a t e

was f i l t e r e d o f f , washed w i t h e t h e r and r e c r y s t a l l i z e d

from d r y benzene. It was t h e n d i s s o l v e d i n aqueous

sodium c a r b o n a t e , extracted with ether, the e t h e r

solution dried, the e t h e r removed and t h e amine

distilled again, n 2 0
1.5675. Lit. n 2 5
1.5655 1 4 7
.

3-Nitrodiphenylamine: prepared from 3-nitrobromobenzene and

1 48

acetanilide by t h e method u s e d by Hodgson and Dodgson

for the p r e p a r a t i o n of 3,3'-dinitrodiphenylamine.

After three recrystallizations f r o m aqueous ethanol,

sublimation and a n o t h e r recrystallization from aqueous

 135

ethanol the p r o d u c t melted at 1 1 0 - 1 1 1 ° . L i t . m.p.

o 137
112°

4-Methylsulfonyldiphenylamine: prepared from 4 - b r o m o p h e n y l -

149

methylsulfone and a c e t a n i l i d e by the method u s e d by

Nodiff and c o - w o r k e r s f o r the p r e p a r a t i o n of

3-methylsulfonyldiphenylamine. The p r o d u c t was r e -

crystallized from benzene, ethanol and e t h y l a c e t a t e ,

sublimed, p a s s e d down an a l u m i n a column w i t h benzene-

acetone (3:1) mixture and f i n a l l y recrystallized

from benzene-petroleum e t h e r (65-110°), m.p. 1 6 8 - 1 6 8 . 5 ° .

Analysis; C H N S
calc. 63.13% 5.30% 5.66% 12.96%
found 63.20% 5.80% 5.45% 12.80%
4-Nitrodiphenylamine: h a d been p r e p a r e d and p u r i f i e d previously
76 d

in this laboratory, m . p . 131-133 . L i t . m.p.

133° 1 4 1
.

2- N i t r o d i p h e n y l a m i n e : o b t a i n e d f r o m Eastman Organic

Chemicals was r e c r y s t a l l i z e d twice from a c e t i c acid,

m.p. 73-74°. L i t . m.p. 7 5 ° 1 4 1

.

3- 4 ' - D i n i t r o d i p h e n y l a m i n e : p r e p a r e d f r o m the s o d i u m s a l t of

2-chloro-5-nitrobenzenesulfonic acid (Eastman O r g a n i c

Chemicals) and 3 - n i t r o a n i l i n e by t h e g e n e r a l method

1 51

o f U l l m a n n a n d Dahmen . The p r o d u c t was r e c r y s t a l l i z e d

f r o m aqueous acetic acid, passed down an a l u m i n a column

 136

with benzene-acetone (1:1) mixture and r e c r y s t a l l i z e d

from b e n z e n e - p e t r o l e u m ether (65-110°) pair, m . p . 215-

216°. L i t . m.p. 2 1 7 ° 1 5 2
.

4-Nitro-3'-methyldiphenylamine: prepared and p u r i f i e d by

Dr. A. Buckley in this laboratory, m.p. 1 2 7 - 1 2 8 ° .

4-Nitro-3'-chlorodiphenylamine: prepared and p u r i f i e d by Dr

A. Buckley in this laboratory, m.p. 1 2 9 - 1 3 0 ° .

Lit. m.p. 1 2 9 ° 1 5 3
.

4-Nitro-3'-trifluoromethyldiphenylamine: p r e p a r e d and

purified by D r . A . B u c k l e y i n t h i s laboratory, m.p.

137.5-138.5°.

2,4-Dinitrodiphenylamine: h a d been p r e p a r e d and p u r i f i e d

previously ^ 7
in this laboratory m.p. 1 5 5 - 1 5 6 ° .
o 154
Lit. m . p . 155
T . 1 c c

4,4'-Dinitrodiphenylamine: h a d been p r e p a r e d and p u r i f i e d

76 o
previously in this laboratory, m . p . 213-216 .

Lit. m.p. 2 1 6 ° 1 5 5
.

3-Chloroaniline: obtained f r o m Eastman Organic Chemicals

was d i s t i l l e d f r o m z i n c dust and r e d i s t i l l e d before

use, n 2 0
1.5933. L i t . n ° 1.5931
2 1 5 3
.

3-Trifluoromethylaniline: obtained from Matheson, Coleman

and B e l l was d i s t i l l e d t w i c e , n ^ ° 1.4795. Lit. n 2 5

 137

1.4775 1 5 6

3- C y a n o a n i l i n e : prepared from 3 - b r o m o a n i l i n e and cuprous

cyanide by t h e g e n e r a l method o f F r i e d m a n and S c h e c t e r

157

The p r o d u c t was s u b l i m e d , recrystallized

from c h l o r o f o r m - p e t r o l e u m ether (30-60°) pair, sublimed,

recrystallized from c y c l o h e x a n e - c h l o r o f o r m p a i r , and

1 I n

sublimed again, m . p . 52-53 . L i t . m.p. 5 2 °

4- C y a n o a n i l i n e : o b t a i n e d f r o m Eastman Organic Chemicals

was s u b l i m e d , r e c r y s t a l l i z e d three times from aqueous

ethanol, sublimed, r e c r y s t a l l i z e d from cyclohexane-

c h l o r o f orm p a i r and s u b l i m e d a g a i n , m.p. 8 5 - 8 6 ° .

o 117
Lit. m . p . 86

2.3- D i c h l o r o a n i l i n e : obtained from A l d r i c h Chemical Co.

was d i s t i l l e d and r e c r y s t a l l i z e d once from cyclohexane

and t w i c e from hexane, m . p . 26 - 2 6 . 5 ° . L i t . m.p.

23.5 - 24° 1 0 9
.

2.4- Dichloroaniline: obtained f r o m Eastman Organic Chemicals

was r e c r y s t a l l i z e d twice from methanol and s u b l i m e d ,

m.p. 61.5 - 62.5°. L i t . m.p. 6 3 ° 1 0 9

.

2.5- Dichloroaniline: o b t a i n e d from A l d r i c h Chemical Co.

was r e c r y s t a l l i z e d twice from cyclohexane and s u b l i m e d

m.p. 49 - 50°. L i t . m . p . 50 - 50.5° 1 0 9

.
 138

2,6-Dichloroaniline: obtained from A l d r i c h Chemical Co. was

recrystallized from c y c l o h e x a n e , distilled, and recry-

stallized from hexane, m.p. 37.5-38°. Lit. m.p. 38.5-

o 109
39

3,4-Dichloroaniline: prepared by the reduction of 3,4-

dichloronitrobenzene (Columbia O r g a n i c Chemicals Co.)

with stannous c h l o r i d e by t h e method o f F e r r y and

co-workers 1 5 8
used f o r the reduction of 4-nitro-4'-

acetylaminodiphenylsulfone. After sublimation and two

recrystallizations from cyclohexane the product

melted at 71-72°. Lit. m.p. 72° 1 0 9

.

3,5-Dichloroaniline: prepared by f i r s t deaminating 2,6-

dichloro-4-nitroaniline (Eastman O r g a n i c Chemicals)

159a
using the procedure of Vogel for the deamination
of 2,4,6-tribromoaniline and t h e n reducing the

resulting 3,5-dichloronitrobenzene i n the same manner

158

used for 3,4-dichloronitrobenzene. After sublimation

two r e c r y s t a l l i z a t i o n s from c y c l o h e x a n e , and sublimation

again the product melted at 49.5 - 51°. Lit, m.p.

50 - 50.5° 1 0 9
.
3,4,5-Trichloroaniline: prepared by the reduction of 3,4,5-

trichloronitrobenzene (Columbia O r g a n i c Chemicals Co.)

with stannous c h l o r i d e by the same m e t h o d 1 5 8

used in

the reduction of 3,4-dichloronitrobenzene. After

 139

recrystallization from e t h a n o l and cyclohexane

f o l l o w e d by s u b l i m a t i o n the product melted at 9 7 -

9 7 . 5 ° . Lit. m.p. 8 9 ° 1 6 0
; 9 4 - 9 5 ° 1 6 1
; 1 0 0 ° 1 6 2
;

1 0 1 ° 1 6 3
.

2,3,5,6-Tetrachloroaniline: prepared by r e d u c t i o n of the

corresponding nitro compound. 2,3,5,6-Tetrachloronitro-

benzene (Columbia O r g a n i c Chemicals C o . ) (0.05 mole),

50 gram of zinc amalgam I^JJD a n c j 59 \ m Q ± concentrated

hydrochloric a c i d were r e f l u x e d i n 1 5 0 ml o f ethanol

for three hours. On c o o l i n g t h e reaction mixture

the product crystallized out and was collected. After

recrystallization twice from petroleum e t h e r ( 6 5 - 1 1 0 ° ) ,

once from e t h a n o l , and t w i c e f r o m aqueous acetic acid

followed by s u b l i m a t i o n the product melted at 106.5 -

1 0 7 . 5 ° . Lit. m.p. 1 0 7 - 1 0 8 ° 1 6 4
.

4-Nitroaniline: obtained f r o m Eastman Organic Chemicals

was r e c r y s t a l l i z e d twice f r o m aqueous ethanol, m.p.

1 4 7 - 1 4 8 ° . Lit. m.p. 1 4 8 . 5 - 1 4 9 . 5 ° 1 6 5
.

2-Methyi-4-nitroaniline: prepared by the method o f Page

166
and Heasman . After two r e c r y s t a i l i z a t i o n s from
methanol the product melted at 1 2 9 . 5 - 1 3 0 . 5 ° . Lit.
o 1 6 6
n 1 6 7
m.p. 1 3 4 - 1 3 4 . 5 ° ; 1 3 1 . 5 - 1 3 2 . 5 ° .
 140

2,6-Dimethyl-4-nitroaniline: p r e p a r e d by t h e method of
• I C Q

Wepster . A f t e r two r e c r y s t a l l i z a t i o n s from

aqueous e t h a n o l the product m e l t e d at 161-162°.

Lit. m.p. 163.5 - 164.5° 1 6 8

.

2,6-Di-t-butyl-4-nitroaniline: 1,3,5-tri-t-butylbenzene was

prepared from 1 , 4 - d i - t - b u t y l b e n z e n e (Eastman Organic

Chemicals) and t - b u t y l c h i o r i d e by the method of Ross

and c o - w o r k e r s * * . 1 9
This compound was t h e n nitrated

and t h e nitro group reduced t o yield 2,4,6-tri-t-

170
butylaniline by t h e method o f B u r g e r s and co-workers
The l a t t e r compound was n i t r a t e d by the method of
171

Burgers and c o - w o r k e r s to give the desired 2,6-

di-t-butyl-4-nitroaniline, which, after recrystallization

once f r o m aqueous e t h a n o l and t w i c e from e t h y l acetate-

petroleum ether (65-110°) pair, m e l t e d at 259-260°.

Lit. m.p. 257-258° 1 7 1

.

3,5-Dimethyl-4-nitroaniline: p r e p a r e d by t h e method of
172

Wepster and V e r k a d e . After two recrystallizations

from e t h a n o l f o l l o w e d by s u b l i m a t i o n the compound

m e l t e d at 130.5 - 131°. Lit. m.p. 131-132° 1 7 2

.

2,3,5,6-Tetramethyl-4-nitroaniline: 1,2,4,5-tetramethyl-

benzene (Eastman Organic Chemicals) was n i t r a t e d to

give the dinitro derivative by the method of S m i t h

and D o b r o v o l n y 1 7 3
which, i n turn, was p a r t i a l l y reduced.
 141

by t h e method of Hampson and c o - w o r k e r s 5

to give

the desired product. After two s u b l i m a t i o n s and

three recrystailizations from e t h a n o l the compound

melted at 160.5 - 161°. Lit. m.p. 161-162° 1 7 5

.

N-Methyl-4-nitroaniline: prepared from 4-nitroacetanilide

and m e t h y l i o d i d e by the method of Pachter and K l o e t z e l

176

After two r e c r y s t a i l i z a t i o n s from ethanol

f o l l o w e d by s u b l i m a t i o n the product melted at 150.5 -

151.5°. Lit. m.p. 153-154° 1 7 6

.
N-Ethyl-4-nitroaniline: prepared from 4-nitroacetanilide
-1 rvsy

and e t h y l i o d i d e by the same method used f o r the

N-methyl compound. After two r e c r y s t a i l i z a t i o n s from

ethanol f o l l o w e d by s u b l i m a t i o n the product melted

at 94.5-95.5°. Lit. m.p. 95°

N,2-Dimethyl-4-mitroaniline: prepared from 2-methyl-4-nitro-

aniline and m e t h y l i o d i d e by the same p r o c e d u r e used

in the preparation of N - m e t h y l - 4 - n i t r o a n i l i n e . After

recrystallization f r o m aqueous ethanol, sublimation

and two more recrystailizations f r o m aqueous ethanol

the product melted at 135.5 - 136.5°. Lit. m.p. 137° 1 7 8

.

N-Isopropyl-4-nitroaniline: 4-nitroaniline (2 gm) was

dissolved i n 10 ml o f DMSO and 1 gm of powdered potassium

hydroxide added c a u s i n g the s o l u t i o n to turn highly

coloured. 2-Bromopropane (2 gm) was a d d e d , the mixture

 142

stirred f o r ten minutes, and t h e n h e a t e d on a s t e a m

bath f o r an h o u r , after w h i c h i t was p o u r e d on t o i c e .

A yellow s o l i d material was s u b l i m e d f r o m the resulting

dark t a r r y product and on r e c r y s t a l l i z a t i o n from benzene-

petroleum ether (65-110°) pair y i e l d e d a high melting

product - probably unreacted 4-nitroaniline. Evaporation

of t h e mother l i q u o r gave about 0.5 gm o f another

yellow s o l i d material that was p a s s e d down a s i l i c a

gel column w i t h b e n z e n e - e t h y l a c e t a t e (5:1) mixture.

The f i r s t band o f f t h e column was c o l l e c t e d and

recrystallized from p e t r o l e u m e t h e r ( 6 5 - 1 1 0 ° ) , m.p.

83-84°.

Analysis:
C H N
Calc. 59.99% 6.71% 15.55%
Found 59.85% 6.41% 15.59%

The NMR s p e c t r u m o f t h e compound i n c a r b o n tetrachloride

with internal TMS s t a n d a r d contains: a doublet centered

at 2.03 X and a n o t h e r at 3 . 5 5 TJ" b o t h w i t h relative

area o f two and s p l i t t i n g o f a b o u t 9.3 c.p.s.; a

broad absorption at about 5.19 X w i t h r e l a t i v e area of

one; a highly structured absorption at about 6 . 3 5 TT

with r e l a t i v e area of one; and a d o u b l e t centered at

8.79 X with r e l a t i v e a r e a o f s i x and s p l i t t i n g o f

about 6.5 c.p.s.

 143

N-t-Butyl-4-nitroaniline: prepared from the r e a c t i o n of

4-nitroaniline and t - b u t y l alcohol i n phosphoric

179

acid by t h e method of Gleim . The p r o d u c t was

passed down a s i l i c a g e l column w i t h benzene-ethyl

acetate (10:1) mixture and the f i r s t band o f f the

column was c o l l e c t e d . T h i s m a t e r i a l was s u b l i m e d and

r e c r y s t a l l i z e d from e t h y l a c e t a t e - p e t r o l e u m e t h e r

( 6 5 - 11 11 0 ° ) pair, m.p. 68.5 - 69.5°. L i t . m.p. 68-

o 180
69.5

Analysis:
C H N
calc. 61.84% 7.27% 14.42%
found 61.95% 7.36% 14.42%

N-Triphenylmethyl-4-nitroaniline: prepared from triphenylmethyl

chloride and 4 - n i t r o a n i l i n e b y t h e method of Verkade

1 81

and c o - w o r k e r s . After three recrystallizations

from e t h a n o l - c h l o r o f o r m pair t h e compound m e l t e d at

223-225°. L i t . m.p. 2 2 3 - 2 2 4 ° 1 8 1
.
2,2 -Dipyridylamine:
s
obtained from Columbia O r g a n i c Chemicals

Co. was r e c r y s t a l l i z e d twice f r o m aqueous ethanol

182
and s u b l i m e d , m.p. 9 3 - 9 4 . L i t . m . p . 94-95

4-Aminodiphenylamine: obtained from Matheson, Coleman and

Bell was d i s t i l l e d , dissolved i n a small amount of

benzene and p r e c i p i t a t e d with petroleum ether (65-110°),

recrystallized from benzene-petroleum ether (65-110°)

 144

pair and t h e n d i s t i l l e d again. The d i s t i l l a t e was

a pale yellow colour and s o l i d i f i e d to give crystals

m e l t i n g at 72.5 - 74.5°. Lit. m.p. 75° 1 5 3

.
 145

APPENDIX B : S p e c t r a l Data f o r the Indicators

TABLE IX

Absorption Maxima a n d M o l a r Absorptivities

of the I n d i c a t o r s i n 95.6% E t h a n o l

Observed Values Repor

Substituent \ <• ref

max. max.

diphenylamines

4-methoxy 284 19,000

4-methyl 286 21,400
none 285 21,300 285 20,250 a
183
3-methoxy 283 18,500
4-chloro 289 24,000
3-chloro 286 21,300
3-trifluoromethyl 286 21,600 285 11.200 184
3,4'-dichloro 290 25,300
3-nitro 27 5 22,300
399 1,180
4-methylsulfonyl 309 26,300
4-nitro 392 21,700 390 21,200 a
183
2-nitro 426 6 ,710 422
423 6,600 d
183
4 - n i t . r o - 3 ' -methyl 394 22,300
4-nitro-3'-chloro 385 22,700
4-nitro-3'-tri fluoro-
methyl 381 19,200
3,4'-dini tro 375 23,200
4,4* - d i n i t . r o 403 34,100 402 37,600 183
2,4-dinitro 352 17 ,700 350
351 17,000 a
183

anilines

3-chloro 242 8,650

293 1 ,970
3-trifluoromethyl 242 9,450
298 2,190
3-cyano 251 7 ,320
320 4,040
 146

TABLE IX (Continued)

Observed Values Reported Values

Substituent ")\ (mu) € A (mu) £ ref

max. / max. '

anilines (Continued)

4-cyano 275 23,600

2,3-dichloro 243 6,670
297 2,830
2 ,4-dichloro 245 11,500
306 2,510
2,5-dichloro 244 8,520
300 3,260
2,6-dichloro 239 6,780
296 3,490
3,4-dichloro 248 ll,600
305 2,040
3,5-dichloro 249 9,360
300 2,320
3,4,5-trichloro 249 12,200
311 2,430
2,3,5,6-tetrachloro 309 4,070
4-ni tro 373 16 ,300 370 16,200 185
4-nitro-2-methyl 375 14,900 379 17,400 185
4-nitro-2,6-dimethyl 377 14,600 374 14,200 185
4-nitro-2,6-di-t.-butyl 379 14,400
4-nitro-3,5-dimethyl 382 4,970 386 5,000 185
4-nitro-2,3,5,6-
tetramethyl 394 1,590 391 1,500 185
4-nitro-N-methyl 386 18,400 391 18,400 185
4-nitro-N-ethyl 388 19,800 386 18,900 a
183
4-nitro-N-isopropyl 389 20,800
4-nitro-N-t-butyl 389 20,100
4-ni tro-N-triphenyl-
methyl 376 19,000
4-nitro-N,2-dimethyl 388 17,900 383 15,300 185

2 , 2 - d i p y r i dylamine
f
264 22,200
312 14,700

a i n absolute ethanol
 147

TABLE X

Absorption Maxima a n d M o l a r A b s o r p t i v i t i e s

of D i p h e n y l a m i n e s i n 20% E t h a n o l

Substituents '\ (ray.) £

max.
4-methoxy 280 14,500
4-methyl 282 15,900
none 282 16,400
3-methoxy 282 14,800
4-chloro 286 18,600
3-chloro 284 16,900
3-trifluoromethyl 284 17,300
3,4'-dichloro 288 20,700
3-nitro 280 22,000
4-methylsulfonyl 309 25,200
4-nitro 409-
410 20,500
2-nitro 444 6,550
4-nitro-3'-methyl 411 20,500
4-nitro-3'-chloro 403 20,600
4-nitro-3'-trifluoro-
methyl 3
400 17,400
3,4'-dinitro 3
396 20,200
4,4'-dinitro b
422 32,300

3
20% e t h a n o l c o n t a i n i n g 2.25 molar sulfuric acid
b
20% e t h a n o l c o n t a i n i n g 2.50 molar sulfuric acid
 148

TABLE XI

A b s o r p t i o n Maxima and M o l a r A b s o r p t i v i t i e s

of Indicator Anions i n DMSO-Water

Observed Values Reported Values

Substituent (ny) £ Mole , c

max DMSO 3

diphenylamines

4-methoxy 370 28,100 99. 8

4-methyl 375 29,700 99. 5
4-amino 372 23,900 99. 8
none 376 28,500 99. 5
3-methoxy 380 25,800 99. 0
4-chloro 374 30,200 97. 1
3-chloro 370 26,900 97. 1
3-trifluoromethyl 368 28,800 97. 1
3-nitro 375 14,800 99. 5
3,4'-dichloro 376 30,600 97. 1
4-methylsulfonyl 383 29,400 83. 1
2-nitro 548 9,220 83. 1 545 9,170 c
76
2,4-dinitro 434 19,000 46. 5 432 21,800 d
76

anilines

3-chloro 386 2,710 loop

3-trifluoromethyl .404 2,500 100 ic

3-cyano 447 2,530 100 ib

4-cyano 337 37,100 99. 5

2,3-dichloro 381 3,550 99. 8
2,4-dichloro 399 3,030 99. 8
2,5-dichloro 385 3,640 99. 5
2 ,6-dichloro 380 4,500 98. 7
3,4-dichloro 400 2,450 99. 8
3,5-dichloro 386 2,820 99. 8
3,4,5-trichloro 397 2,610 99. 5
2,3,5,6-tetrachloro 380 4,480 92. 5
4-nitro 467 30,800 87. 8 467 32,300° 76
4-nitro-2-methyl 471 31,900 92. 3
4-nitro-2,6-dimethyl 474 33,300 92. 3
4-nitro-2,6-di-t-butyl
470 29,300 95. 3
4-nitro-3,5-dimethyl 466 23,600 97. 1
 149

TABLE XI (Continued)

Observed Values Reported Values

Substituent ^ a x . ^ G M o l e
* l a x . ^ C ref
DMSO a

anilines

4-nitro-2,3,5,6-
tetramethyl 507 17,000 99. 5
4-nitro-N-methyl 483 31,200 97. 1
4-nitro-N-ethyl 482 31,300 97. 1
4-nitro-N isopropyl 480 32,000 97. 1
4-nitro-N-t-butyl 480 32,000 97. 1
4-nitro-N-triphenyl-
methyl 490 38,600 92. 5
4-nitro-N,2-dimethyl 485 31,500 97. 1
2-nitro-4-chloro 495 8,440 78. 4
520 8,440 78. 4 516 6,900 c
76

2 ,2'-dipyridylamine 370 16,200 92. 5

a
DMSO-water m i x t u r e s c o n t a i n i n g 0 . 0 1 1 m o l a r t e t r a m e t h y l -
ammonium h y d r o x i d e
b DMSO c o n t a i n i n g p o t a s s i u m t - b u t o x i d e as base
c 95 mole % s u l f o l a n e - w a t e r - 0 . 0 1 1 m o l a r t e t r a m e t h y l a m m o n i u m
hydroxide
d p y r i d i n e c o n t a i n i n g 0.011 molar tetramethylammonium
hydroxide
 150

APPENDIX C : Ionization Ratio Data

TABLE XII

E x p e r i m e n t a l V a l u e s o f L o g [A~] / [HA] f o r the I n d i c a t o r s

U s e d t o D e t e r m i n e the H _ V a l u e s i n DMSO-Water-
Tetramethylammonium H y d r o x i d e (0.011 M.)

< a
< <
H
0
< Q
Q
CO
•p Q CM
< r-i
ra CM /•>
o1 CM
u
o
•H
^ \
CM o
CM
- <
o
!Z5 <
Q
CM 1
T3
C
o
w
CO
1
ft
Q CM
1
Q
o
xn
CD
•*
M
1 -I o
CM
O
CM 1
rH
O
CM
K
CO in

CO
Mole % 1
S5
1 o1 S5
I 1 •»
CM CO CM CM
DMSO

10.32 - .674
15.20 .009 -.741 -1.012
20.18 .683 -.185 - .483
23. 57 1.067 .195 - .117 -.788
26.95 .571 .252 -.452
30.11 .891 .585 -.135
33.42 .933 .183
36.79 .503 -.913
39.86 .757 -.597
43.27 -.253
46.54 .068 -.808
49.59 .356 -.489
52.55 .639 -.170
55.95 .962 .179 -.700
58.56 .447 -.444
59.38 -.8
62.27 .833 -.071
 151

TABLE X I I (Continued)

fl
<
0 /-s P*
-P < r-i a
a o< cj CN
•H CM I < r-l <! ft
C CO - Q ^ Q P< ft O
IH CO lO CM I CO Q Q CO
K O - fer-itHK
O C O S s ^ O O O O
I I I I I I
Mole ' T f t C N C O C O C O C O < t f C O
DMSO

64.20 -.319 -.609 -.805

65.48 .247
68.51 .558
69.09 .182 -.117 -.314
71.12 .833
71.35 .442 .128 -.083 -.838
73.69 .730 .354 .167 -.594
76.12 .609 .428 -.330
78.01 -.397
78.36 .827 .653 -.062 -.918
80.78 .176 -.660
82.75 .207
83.14 .489 -.361
85.17 .496
85.46 .789 -.021
87.51 ..810 -.644
87.79 .294
89.92 -.269
90.07 .658
92.29 .172
 152

TABLE X I I (Continued)

O CO fi c
ca < CM CM
o
<M O
• w <5
CL ft
Q r-l rH

•3 c i a o o o q
e < in n co ^ ^ <§
Mole % 3 4 < C O ~ T J < 4 M " "
DMSO
i'
87.79 -.836
90.07 -.465 -.703 -.882
90.56 -.860
91.48 -.693 -.945
92.47 .012 -.229 -.434
92.52 -.463 -.741
93.47 -.261 -.524
94.34 -.058 -.330
94.74 .562 .310 .156 -.577
95.04 .133 -.133
95.55 .311 .009
95.77 .874 .644 .479 -.280
96.21 .799 .644 -.103
96.64 .650 .407
97 13 .274 -.688 -.740
97.31 .358
97 89 .653 -.345 -.396
 153

TABLE X I I (Continued)

O
+•' o C
a
< <
^> ^

T3 rH _
c
10 J< S
o cj
* oH
Mole % ~ - i t
" C O CO CO CO
DMSO

98.29 .935 -.111 _ . i 4 0 -.906

ll'il " 2 4 4
- 2 0 3
-' 5 5 8
~-777
- 7 3 0
-640 -.105 -.336
a y
' D a
.837 .510

NOTE DPA i s diphenylamine

An i s aniline
 154

TABLE XIII

E x p e r i m e n t a l V a l u e s of Log [ A ] / [ H A ] f o r V a r i o u s
-

I n d i c a t o r s i n DMSO-Water-Tetramethylammonium
H y d r o x i d e (0.011 M)
a
<
CM

r H < c
> » rH <
• P a >> CM

3 < c
SH Xi r H CO < a
0 CO

O 1 >> c a iH
X a
+J P P < o >> a u <
a s - ' • H CO X ! 0 CO

o 1 rH x 1 P CO 1
X
•rl CO P
1
u1 CM CD
1
• H
i
CD
***
o1
T3
C CN r5 rS Jz; CM CM c
r-l 1 1 1 1 I 1 1 1
CM CM CM CM CM CM CM CM CM

O O o o o O O O
r3
o
r3 r5
1 1 1
Mole %
1 1 i 1 i 1
"<#
<f*
DMSO

40.03 -.849
44.97 -.370 -.973
49.82 .069 -.495 -.922
53.96 -.750 -.870
54.63 .461 -.038 -.502 -.588 -.570 -.634 -.849
58.78 -.314 -.434
59.38 .767 .439 -.057 -.145 -.140 -.209 -.437
63.57 .101 .010
64.20 .974 .878 .389 .317 .326 .237 .004
68.41 .534 .430
69.09 .903 . 816 .785 .714 .458
71.35 .940 .704
73.69 .989
 155

TABLE X I I I (Continued)

c
<
cu /->
CM
c c
G •H
<CM O
<
i—i
s
CQ
55

>> rH CO 1
H •H >> W CD
0 XI
3 13 u in•• c c c
-H •rH
a
C8
o
1
•P
rH
>> m
1
<CM CO <CM <CM <CM
•rl 1
a /~\ /-\ /->
n 55 • •H CO rH CM r-l rH rH
a 1 X5 1 CJ 1
u CJ
l-H
O
CM
- 1
O
CM
1
O
CM
1 1
V
1
CM
55
1
1
55
|
CO 55
1 m CO

Mole % TH CM CM CM CM CM

DMSO

64.20 -.714 -.802

69.09 -.240 -.419
71.35 .006 -.228
73.69 .248 -.030
76.12 .519 .188
78.36 .788 .402 -.801
80.78 .652 -.529
83.14 .907 -.218
85.46 .104
87.79 .481
90.07 .913 -.425 -.807 -.721
92.47 -.276 - . 282
94.74 .629 .417 .299 -.122 -.445
95.34 .822 .506 .083 -.264
95.77 .930 .775 .635 -.135
96.21 .969 .798 .323 .012
96 .66 .966 .499 .178

NOTE An i s a n i l i n e
t r i t y l i s triphenylmethyl
 156

TABLE XIV

E x p e r i m e n t a l V a l u e s of L o g [ B H ] / [ B ] f o r
+

the S u b s t i t u t e d D i p h e n y l a m i n e s U s e d t o
D e t e r m i n e t h e H V a l u e s i n 20 Volume P e r c e n t
0

Ethanol-Aqueous S u l f u r i c A c i d

-p
c
CD
3
-P CM
•H <<"\
-
-P r-l
CO i i CJ
£2
3
O I
o
i
CO CO I
CO
O
K CD
C
CO
CJ
rH
CJ CO
CJ K TP
I I O CJ I I
CJ
a TP CO
Molarity TT TP I I CO
H S0 CO
2 4
co

.0163 -.487 -.665

.0339 -.202 -.350 -.792
.0567 .017 -.141 -.555 .937
.0808 .175 .011 -.409 .778
.163 .490 .330 -.098 .467 -.863
.245 .682 .531 .102 .286 -.642
.406 .955 .788 .365 .023 -.397 -.855
.611 .602 . 227 -.151 -.599
.763 .741 . 359 -.028 -.473 -.806
.914 . 869 .494 .105 -.344 -.676
1.26 .741 .356 -.115 -.436 -.855
1.47 .890 .492 .020 -.296 -.715
1.72 .658 .175 -.155 -.572
1.98 .797 .337 .005 -.400
2.25 .932 .470 .152 -.261
2.49 .615 .293 -.120
2.73 .753 .420 .009
 157

TABLE XIV (Continued)

•+->
c
CD I
3 CO
B
CM cj CJ
+5 I I I
CC rH CM
O CO CO
3 i o I CO I I I I
CO CM CO CM CM CM CM
co I
o
55
tc
o
o
55
O
55
o
55 §
Molarity U
i
I I I I I I
CO CO
H S0
2 4
CO CM

1.98 .005 -.400 -.818

2.25 .152 -.261 -.693
2.49 .293 -.120 -.540
2.73 .420 .009 -.385
3.07 .637 .212
3.29 .771 .348 -.072
3.58 .928 .516 .080 -.850
3.76 .632 .192 -.735
4.14 .863 .432 -.500 -.907
4.38 .555 -.357 -.780 -.954
4.62 .722 -.220 -.626 -.789
4.90 .900 -.023 -.435 -.633
5.15 .114 -.280 -.465
5.41 .268 -.122 -.324
5.66 .429 .036 -.165
5.95 .638 .245 .048 -.957 -.914
6.47 .964 .585 .381 -.621 -.602
 158

TABLE XIV (Continued)

co i
-p co I I
c X CM CM
<D
CJ
CJ CO <»-\ /—\
3 I CM CM
l
P CJ O O
•H CO CO 55 55
P I I I I i

o
CO
o
CC CM
o
CN CM CM I I
43 O O
CM
3 55 55 55 55
W I I I I 55 IN OS

TT CM TP I CO TP

Molarity
H S0
2 4

6.47 .585 .381 -.621 -.602 -.888

6.81 .825 .612 -.385 -.385 -.688
7.16 . 858 -.128 -.144 -.455
7.64 .204 .160 -.156 -.857
8.14 .601 . 523 .207 -.516
8.44 . 840 .766 .420 -.306
8.86 .780 .012 -1.026
9. 10 .357 • .662
9, 59 .735 - .298
9, 95 • .017
10.40 .320
10.96 .762
 159

BIBLIOGRAPHY

1. J. Hine " P h y s i c a l Organic C h e m i s t r y " , second e d i t i o n ,

M c G r a w - H i l l Book Company, I n c . , New Y o r k , 1962;
(a) p . 4 3 ; (b) p . 8 8 f f ; (c) p p . 1 - 9 .

2. J. N. Bronsted, Rec. t r a v . chim.,, 42, 718 (1923).

3. T . M. L o w r y , Chem. and I n d . ( L o n d o n ) , 42, 43 (1923).

4. G. N. Lewis, J. Franklin Inst., 226, 293 (1938).

5. W. F . L u d e r a n d S . Z u f f a n t i , " T h e E l e c t r o n i c T h e o r y of
A c i d s and B a s e s " , J o h n W i l e y and S o n s , I n c . , New
Y o r k , 1946, p . 1 4 f f .

6. G . K o r t u m , W. V o g e l and K . A n d r u s s o w , " D i s s o c i a t i o n
C o n s t a n t s o f O r g a n i c A c i d s i n Aqeuous S o l u t i o n " ,
B u t t e r w o r t h s , London, 1961.

7. V . G o l d , " p H Measurements", Methuen and C o . , L t d . ,

L o n d o n , 1956; (a) p . 2 1 ; (b) p . 14; (c) p . 3 4 f f .

8. L . P . Hammett and A . J . Deyrup, J. Am. Chem. S o c , 54,

2721 ( 1 9 3 2 ) .

9. L . P . Hammett, " P h y s i c a l O r g a n i c C h e m i s t r y " , McGraw-

H i l l Book Company, I n c . , New Y o r k , 1940, C h a p . I X .

10. E . M. A r n e t t , i n " P r o g r e s s i n P h y s i c a l O r g a n i c C h e m i s t r y " ,

V o l . 1 , I n t e r s c i e n c e P u b l i s h e r s , New Y o r k , N . Y . ,
1963, p . 234.

11. L . P . Hammett, Chem. R e v . , 1 6 , 67 (1935). '

12. M. A . P a u l and F . A . L o n g , Chem. R e v . , 5 7 , 1 (1957).

13. N . C . Deno, i n "Survey of P r o g r e s s i n Chemistry", V o l . 2,

Academic Press, New Y o r k , 1964, p. 176.

14. A . R. K a t r i t z k y , A. J . W a r i n g and K . Y a t e s , Tetrahedron,

19, 465 (1963).

15. J. T . Edward a n d I . C . Wang, Can. J . Chem., 40, 969 (1962).

16. E . M. A r n e t t and C . Y . Wu, J . Am. Chem. S o c , 84, 1680 (1.962:

17. Y . C h i a n g and E . B . W h i p p l e , J . Am. Chem. S o c , 85
2763 ( 1 9 6 3 ) .
 160

18. R. L . Hinman and J . Lang, J. Am. Chem. S o c , 86,

3796 (1964).

19. F . A . L o n g and J . Schulze, J. Am. Chem. S o c , 86, 327 (1964)

20. K. Yates, J . B . S t e v e n s a n d A . R. K a t r i t z k y , Can. J .

Chem., 42, 1957 (1964).

21. K . Y a t e s and J . B. Stevens, Can. J . Chem., 43, 529 (1965).

22. K. Yates and J . C. Riordan, Can. J . Chem., 43, 2328 (1965).

23. M. J . J o r g e n s o n and D . R. H a r t t e r , J. Am. Chem. S o c ,

85, 878 ( 1 9 6 3 ) .
24. E . M. A r n e t t and G . W. Mach, J. Am. Chem. S o c , 86

2671 (1964).

25. R. H . B o y d , J. Am. Chem. S o c , 85, 1555 (1963).

26. F . E . Condon, J. Am. Chem. S o c , 87, 4485 (1965).

27. N . C . Deno and C . P e r r i z z o l o , J. Am. Chem. S o c , 79,

1345 (1957).

28. R. W. T a f t , Jr., J. Am. Chem. S o c , 82, 2965 (1960).

29. E . M. A r n e t t and R. D . B u s h i c k , J. Am. Chem. S o c ,

86, 1564 (1964).

30. A . F . Trotman-Dickenson, J. Chem. S o c , 1293 (1949).

31. F . A . L o n g and M. A . P a u l , Chem. R e v . , 57, 935 (1957).

32. J. F . Bunnett, J. Am. Chem. S o c , 83, 4956 (1961).

33. L . P . Hammett and R . P„ Chapman, J. Am. Chem. S o c ,

56, 1282 ( 1 9 3 4 ) .
34. R. J . G i l l e s p i e and D . J . M i l l e r , Q u a r t . R e v . , 2, 292
(1948) .
35. U. L . H a l d n a , H . J . K u u r a , H . E . L a a n e s t e and R . K . P u s s ,
R u s s . J . P h y s . C h e m . , 3 8 , 469 ( 1 9 6 4 ) .
36. U. L . H a l d n a and R. K . P u s s , R u s s . J . P h y s . C h e m . , 3 8 ,
1529 ( 1 9 6 4 ) .
37. E. M. A r n e t t a n d J . N . A n d e r s o n , u n p u b l i s h e d r e s u l t s
quoted i n r e f e r e n c e (24).
 161

38. A. J. Parker, Quart. R e v . , 16, 163 (1962).

39. K . Bowden, t o be p u b l i s h e d i n Chem. R e v .

40. R. Stewart and J . P. O ' D o n n e l l , Can. J . Chem., 42, 1681

(1964).

41. G . Schwartzenbach and R. S u l z b e r g e r , Helv. Chim. Acta,

27, 348 ( 1 9 4 4 ) .

42. J. T . Edward a n d I . C . Wang, Can. J . Chem., 40, 399

(1962) .

43. (a) R. S c h a a l and G . L a m b e r t , J. Chim. Phys., 59,

1151 ( 1 9 6 2 ) .

(b) G . L a m b e r t and R . S c h a a l , J. Chim. Phys., 59,

1164 ( 1 9 6 2 ) .

44. R. A . More O ' F e r r a l l and J . H. Ridd, J. Chem. S o c , 5030

(1963) .

45. F„ P e u r e a n d R. S c h a a l , Bull. S o c . Chim. France, 2636

(1963).

46. K . Bowden, Can. J . Chem., 43, 2624 (1965).

47. G . Y a g i l a n d M. A n b a r , J . Am. Chem. S o c , 8 5 , 2376

(1963).

48. N . C . Deno, J . Am. Chem. S o c , 7 4 , 2039 (1952).

49. R. Schaal and P . F a v r i e r , Bull. S o c . Chim. France, 2011

(1959).

50. R. S c h a a l , J. Chim. Phys., 52, 784, 796 (1955).

51. F . Masure and R . S c h a a l , Bull. S o c . Chim. France,

1138, 1141 ( 1 9 5 6 ) .
52. C . H . L a n g f o r d and R. L . B u r w e l l , J r . , J . Am. Chem.
S o c . , 82, 1503 ( 1 9 6 0 ) .
53. R . S t e w a r t , J . P . O ' D o n n e l l , D . J . Cram and R . R i c k b o r n ,

Tetrahedron, 18, 917 (1962).

54. K . Bowden and R. S t e w a r t , Tetrahedron, 21^, 261 (1965).

55. C. H. Rochester, J. Chem. S o c , 676 (1965).

 162

56. R . S t e w a r t and A . B u c k l e y , unpublished results from this

laboratory.

57. E . C . S t e i n e r and J . M. G i l b e r t , J. Am. Chem. S o c . ,

87, 382 ( 1 9 6 5 ) .

58. J. B . Conant and G . W. W h e l a n d , J. Am. Chem. S o c , 54,

1212 (1932).

59. W. K . McEwen, J. Am. Chem. S o c , 58, 1124 (1936).

60. A. Streitwieser, Jr., J. I. Brauman, J. H . Hammons and

A . H . P u d j a a t m a k a , J . Am. Chem. S o c , 8 7 , 384 ( 1 9 6 5 ) .
61. A . S t r e i t w i e s e r , J r . , D . E . Van S i c k l e a n d W. C .
L a n g w o r t h y , J . Am. Chem. S o c , 84, 244 ( 1 9 6 2 ) .

62. A . I . S h a t e n s h t e i n , i n "Advances i n P h y s i c a l Organic

C h e m i s t r y " , V o l . 1, Academic P r e s s , London, 1963,
p. 156.

63. (a) A . S t r e i t w i e s e r , J r ; and D . E . Van S i c k l e , J . Am.

Chem. S o c , 8 4 , 2 4 9 , 254 ( 1 9 6 2 ) .

(b) A. Streitwieser, Jr., W. C . L a n g w o r t h y a n d D . E .

Van S i c k l e , J. Am. Chem. S o c , 84, 251 (1962).

64. S. Andreades, J. Am. Chem. S o c , 86, 2003 (1964).

65. J. E . Hofmann, A. Schriesheim and R. E . Nichols,

Tetrahedron L e t s . 1745 (1965).

66. L . Ebert, Monatsh., 8 0 , 788 (1949).

67. R. G . B a t e s and G . D . P i n c h i n g , J. Am. Chem. S o c ,

72, 1393 ( 1 9 5 0 ) .
68. R. P . B e l l , " T h e P r o t o n i n C h e m i s t r y " , C o r n e l l University
P r e s s , I t h a c a , New Y o r k , 1 9 5 9 , C h a p . V I I .
69. R. S t e w a r t and J . P . O ' D o n n e l l , C a n . J . C h e m . , 42,
1694 ( 1 9 6 4 ) .
70. D . J . C r a m , R . R i c k b o r n , C . A . K i n g s b u r y and P .
H a b e r f i e l d , J . Am. Chem. S o c , 8 3 , 3678 ( 1 9 6 1 ) .

71. H . L . S c h l a f e r and W. S c h a f f e r n i c h t A n g e w . Chem.,

72, 618 ( 1 9 6 0 ) .

72. " D i m e t h y l s u l f o x i d e - R e a c t i o n Medium and R e a c t a n t " ,

Crown Z e l l e r b a c h , C o r p . , Camas. W a s h i n g t o n , 1962.
 163

73. R. S t e w a r t , Can. J . Chem., 35, 766 (1957).

74. W. K . M u s k e r , J. Am. Chem. S o c , 86, 960 (1964).

75. G . A . Harlow, Anal. Chem., 34, 1487 (1962).

76. J. P. O'Donnell, P h . D .Thesis, University of British

Columbia, 1962.

77. J. M. G . Cowie and P . M. T o p o r o w s k i , Can. J . Chem.,

39, 2240 ( 1 9 6 1 ) .

78. H . H . J a f f e and R. W. G a r d n e r , J. Am. Chem. S o c , 80,

319 ( 1 9 5 8 ) .

79. S . - J . Yeh a n d H . H . J a f f e , J. Am. Chem. S o c , 8JL,

3274 ( 1 9 5 9 ) .

80. H . H . J a f f t ? and M. O r c h i n , " T h e o r y and A p p l i c a t i o n s o f

U l t r a v i o l e t S p e c t r o s c o p y " , J o h n W i l e y and S o n s , I n c . ,
New Y o r k , 1962, C h a p . 2 0 .

81. E . C . S t e i n e r and J . M. G i l b e r t , J. Am. Chem. S o c ,

85, 3054 ( 1 9 6 3 ) .

82. G. A. Russell, E . G . J a n z e n , H . - D . B e c k e r and F . J .

Smentowski, J . Am. Chem. S o c , 8 4 , 2652 ( 1 9 6 2 ) .

83. H . S . H a r n e d and B . B . Owen, " T h e P h y s i c a l Chemistry

of E l e c t r o l y t i c S o l u t i o n s " , t h i r d e d i t i o n , R e i n h o l d
P u b l i s h i n g C o r p o r a t i o n , New Y o r k , 1958, C h a p . 1 5 .

84. A. I. Biggs and R . A . R o b i n s o n , J. Chem. S o c , 388 (1961),

85. M. A . P a u l , J. Am. Chem. S o c , 76, 3236 (1954).

86. F . E . Condon, J. Am. Chem. S o c , 87, 4481 (1965).

87. J. C . Hindman, J. Chem. Phys., 36, 1000 (1962).

88. E. Glueckauf, Tran. Faraday S o c , 51, 1235 (1955).

89. R. F u c h s , G . E . McCrary and J . J. Bloomfield, J. Am. Chem,

S o c , 83, 4281 (1961) .

90. E . Tommila and M . - L . M u r t o , Acta Chem. Scand., 17, 1947

(1963).

91. J. K e n t t a m a a and J . J. Lindberg, Suomen Kemistilehti,

B 3 3 , 98 ( 1 9 6 0 ) .
 164

92. T . Ackermann, Disc. Faraday S o c , 24, 180 (1957).

93. G . W. B r a d y , J. Chem. Phys., 28, 464 (1958).

94. J. L . Kavanau, "Water and S o l u t e - W a t e r I n t e r a c t i o n s " ,

H o l d e n - D a y , I n c . , San F r a n c i s c o , 1964; (a) p . 8 f f ;
(b) p . 5 7 f f .

95. H . S. Frank, J. Phys. Chem., 67, 1554 (1963).

96. W. D r i n k a r d and D . K i v e l s o n , J. Phys. Chem., 62,

1494 ( 1 9 5 8 ) .

97. G . C . P i m e n t e l and A . L . M c C l e l l a n , " T h e Hydrogen

B o n d " , W. H . Freeman a n d C o . , San F r a n c i s c o , 1 9 6 0 ,
p. 143ff.

98. W. R o b e r t s a n d M. C . W h i t i n g , J. Chem. S o c , 1290 (1965).

99. D. D. Roberts, J. O r g . Chem., 29, 2039 (1964).

100. C. A . Kingsbury, J. O r g . Chem., 29, 3262 (1964).

101. R. G . B a t e s and G . S c h w a r z e n b a c h , Helv. Chim. Acta,

38, 699 (1955).

102. I. M. K o l t h o f f and S . B r u c k e n s t e i n , J. Am. Chem. S o c ,

78, 1 ( 1 9 5 6 ) .

103. J. E . L e f f l e r a n d E . G r u n w a l d , " R a t e s and E q u i l i b r i a

of O r g a n i c R e a c t i o n s " , J o h n W i l e y and S o n s , I n c . ,
New Y o r k , 1963; (a) p . 1 7 3 : (b) p . 214; (c) p . 211;
(d) p . 2 1 9 f f .

104. H. H. Jaffe, Chem. R e v . , 53, 191 (1953).

105. A. I. Biggs and R. A . R o b i n s o n , J. Chem. S o c , 388

(1961).

106. W. A . S h e p p a r d , J. Am. Chem. S o c , 87, 2410 (1965).

107. L . P a u l i n g , "The Nature of the Chemical B o n d " , third

e d i t i o n , C o r n e l l U n i v e r s i t y P r e s s , I t h a c a , New Y o r k ,
1960; (a) p p . 8 8 - 1 0 3 ; (b) p . 2 9 6 .

108. A. Streitwieser, Jr. and H . F . K o c h , J. Am. Chem. S o c .

86, 404 ( 1 9 6 4 ) .

109. R. A . R o b i n s o n , J. Res. N . B . S . , 68A, (Phys. and Chem.)

159 ( 1 9 6 4 ) .
 165

110. L . A . Cohen and W. M. J o n e s , J . Am. Chem. S o c , 85, 3397

(1963).

111. H . S t i l l s o n , D . W. Sawyer a n d C . K . H u n t , J . Am.

Chem. S o c , 6 7 , 303 ( 1 9 4 5 ) .

112. L. J. Bellamy, H . E . H a l l a m and R. L . Williams,

Trans. F a r a d a y S o c , 54, 1120 (1958).

113. A. I. Biggs, Trans. F a r a d a y S o c , 52, 35 (1956).

114. G . W. W h e l a n d , R . M. B r o w n e l l and E . C . Mayo, J . Am.

Chem. S o c , 70, 2492 (1948).

115. B . M. W e p s t e r , Rec. trav. chim., 76, 335, 357 (1957).

116. U . Tamres and S . S e a r l e s s , J. Am. Chem. S o c , 81,

2100 ( 1 9 5 9 ) .
117. M. M. F i c k l i n g , A . F i s c h e r , B . P . Mann, J . P a c k e r a n d
J . V a u g h n , J . Am. Chem. S o c , 8 1 , 4226 ( 1 9 5 9 ) .
118. D . D . P e r r i n , " D i s s o c i a t i o n Constants of Organic
B a s e s i n Aqueous S o l u t i o n " , B u t t e r w o r t h s , L o n d o n , 1 9 6 5 .
119. E . Hogfeldt and L . L e i f e r , Arkiv. K e m i . , 2JL_, 285 (1963).

120. E . S . G o u l d , " M e c h a n i s m and S t r u c t u r e i n O r g a n i c Chemistry",

H o l t , R i n e h a r t a n d W i n s t o n , New Y o r k , 1960, p p . 4 5 2 -
456.

121. J. D . F a r r , C . C . B a r d a n d G . W. W h e l a n d , J . Am.
Chem. S o c , 7 1 , 2013 ( 1 9 4 9 ) .

122. R. B o l t o n , J. Miller and A . J . Parker, Chem. a n d I n d .

(London), 1026 (1960).

123. M. R . Crampton and V . G o l d , Proc Chem. S o c , 298 (1964).

124. R. E . M i l l e r and W. F . K . W y n n e - J o n e s , J. Chem. S o c ,

2375 (1959).

125. C. H . Rochester, Trans. Faraday S o c , 59, 2820 (1963).

126. B. D. Pearson, Proc Chem. S o c , 78 (1962).

127. S . W. B e n s o n , J. Am. Chem. S o c , 80, 5151 (1958).

128. K. Yates and H . W a i , J . Am. Chem. S o c , 8 6 , 5408 (1964).

 166

129. M. A n b a r , M. B o b t e l s k y , ' D . S a m u e l , B . S i l v e r and G .

Y a g i l , J . Am. Chem. S o c , 8 5 , 2380 (1963)

130. C . W. M u t h , J . C . E l l e r s a n d 0. F . F o l m e r , J. Am.
Chem. S o c , 7 9 , 6500 ( 1 9 5 7 ) .

131. C . W. M u t h , N . Abraham, M. L . L i n f i e l d , R. B . Wotring

and E . A . P a c o f s k y , J . O r g . Chem., 25, 736 (1960).

132. J. D . Loudon and G . T e n a n t , Quart. R e v . , 18, 389 (1964)

133. W. T . M i l l e r , Jr., J. H. Fried and H . G o l d w h i t e , J . Am.

Chem. S o c , 82, 3091 ( 1 9 6 0 ) .
134. (a) H . Normant, T . G u v i g n y , J . Normant, and B . Angelo,
B u l l . Soc. Chim. F r a n c e , 1561 ( 1 9 6 5 ) .

(b) H . Normant and B . A n g e l o , B u l l . S o c Chi)n. France,

354 ( 1 9 6 0 ) ; 1988 ( 1 9 6 1 ) ; 810 ( 1 9 6 2 ) .

(c) H . Normant and T . C u v i g n y , B u l l . S o c Chim.

F r a n c e , 1866, 1881 ( 1 9 6 5 ) .

(d) T . C u v i g n y and H . Normant, Bull. S o c . Chim.

F r a n c e , 1872 ( 1 9 6 5 ) .

135. J. E . Hofmann, A. Schriesheim and D . D . Rosenfeld,

J. Am. Chem. S o c , 87, 2523 (1965).

136. J. E . Gordon; (a) J. Am. Chem. S o c , 86, 4492 (1964).

(b) J. Am. Chem. S o c , 87, 1499 (1965).

(c) J. Am. Chem. S o c , 87, 4347 (1965).

(d) J. O r g . Chem., 30, 2760 (1965).

137. P. Grammaticakis, Bull. S o c . Chim. F r a n c e , 99 (1954).

138. F. Scardiglia and J . D . R o b e r t s , J. O r g . Chem., 23_,

629 (1955).

139. A . Calm, B e r . , 1<3, 2787 (1883).

140. J. Cymerman-Craig, W. P . R o g e r s and M. E . Tate,

Australian J . Chem., 9 , 397 ( 1 9 5 6 ) .
141. I. Goldberg, B e r . , 40, 4541 ( 1 9 0 7 ) .
 167

142. H . Burton and C . S . G i b s o n , J . Chem. S o c , 2241 (1926).

143. A . W . Chapman; (a) J. Chem. S o c , 121, 1676 (1922).

(b) J. Chem. S o c , 127, 1992 (1925).

(c) J. Chem. S o c , 1743 (1927).

(d) J. Chem. S o c , 569 (1929).

144. J. W. S c h u l e n b e r g and S . A r c h e r , " T h e Chapman R e -

a r r a n g e m e n t " , i n O r g a n i c R e a c t i o n s , V o l . 14, John
W i l e y and S o n s , I n c . . New Y o r k , 1 9 6 5 , p . I f f .

145. A . W. Chapman and C . H . P e r r o t t , J. Chem. S o c ,

2462 (1930).

146. L . A. Elson and C . S . G i b s o n , J . Chem. S o c , 294 (1931).

147. N. L . Smith, J. O r g . Chem., 15, 1125 (1950).

148. H . H . Hodgson and D . P . Dodgson, J. Chem. S o c , 1004
(1948).

149. W. E . T r u c e a n d C . W. V r i e s e n , J. Am. Chem. S o c , 7_5,

5032 ( 1 9 5 3 ) .

150. E . A. Nodiff, S. L i p s c h u l t z , P. N. C r a i g and M. G o r d o n ,

J. O r g . Chem., 25, 60 (1960).

151. F . U l l m a n n and R . Dahmen, B e r . , 41, 3744 (1908).

152. B . T . T o z e r and S . S m i l e s , J . Chem. S o c , 2052 ( 1 9 3 8 ) .

153. I . H e i l b r o n , A . H . C o o k , H . M. B u n b u r y and D . H . H e y ,
" D i c t i o n a r y o f O r g a n i c Compounds", f o u r t h e d i t i o n , E y r e
and S p o t t i s w o o d e , L t d . , L o n d o n , 1 9 6 5 .

154. E. J. Hoffmann and P . A . Dame, J. Am. Chem. S o c ,

41, 1013 ( 1 9 1 9 ) .

155. W. A . S c h r o e d e r , P . E . W i l c o x , K . N . T r u e b l o o d , a n d
O . A . D e k k e r , A n a l . C h e m . , 2 3 , 1740 ( 1 9 5 0 ) .

156. M. F r e i f e l d e r and G . R. S t o n e , J. O r g . Chem., 26, 1477

(1961).

157. L . Friedman and H . S c h e c t e r , J. O r g . Chem., 26, 2 5 2 2 (1961).

 168

158. C . W. F e r r y , J . S . Buck a n d R. B a l t z l y , Org. S y n . , Coll.

V o l . I l l , 239 ( 1 9 5 5 ) .

159. A . I. V o g e l , " P r a c t i c a l Organic Chemistry", t h i r d e d i t i o n ,

Longmans, L o n d o n , 1 9 6 1 ; (a) p . 6 1 5 ; (b) p . 1 9 9 .

160. G . M. D y s o n , H . J . George and R. F . H u n t e r , J . Chem.

S o c . , 3041 ( 1 9 2 6 ) .

161. J. B . Cohen and H . G . B e n n e t t , J. Chem. S o c , 87, 320

(1905) .

162. T. Zincke, B e r . , 27, 537 (1894).

163. N . S. J o h a r y , S . S . Guha and P . C . G u h a , J . Ind.

I n s t . S c i . , 34, 387 ( 1 9 5 2 ) .
164. A . T . P e t e r s , F . M. Rowe and D . M. S t e a d , J. Chem.

S o c , 233 (1943) .

165. B . M. W e p s t e r , R e c trav. chim., 76, 335 (1957).

166. H . T . Page a n d B . R . Heasman, J. Chem. S o c , 123,

3238 ( 1 9 2 3 ) .
167. B . M. W e p s t e r and P . E . V e r k a d e , R e c trav. chim.,

68, 77 (1949).

168. B . M. W e p s t e r , R e c trav. chim., 73, 809 (1954).

169. L . Ross, C. Barclay and E . E . B e t t s , Can. J . Chem.,

33 , 672 ( 1 9 5 5 ) .
170. J . B u r g e r s , M. A . H o e f n a g e l , P . E . V e r k a d e , H . V i s s e r ,
and B . M. W e p s t e r , R e c . t r a v . c h i m . , 77_, 491 ( 1 9 5 8 ) .
171. J . B u r g e r s , W. v a n H a r t i n g s v e l d t , J . van K e u l e n , P .
E . V e r k a d e s , H . V i s s e r and B . M. W e p s t e r , R e c
t r a v . c h i m . , 75,- 1329 ( 1 9 5 6 ) .

172. B . M. W e p s t e r and P . E . V e r k a d e , Rec. trav. chim., 68,

88 (1949) .

173. L . I. S m i t h and F . J . Dobrovolny, J. Am. Chem. S o c ,

48, 1420 ( 1 9 2 6 ) .

174. C . E . Ingham and G . C . Hampson, J. Chem. S o c , 981 (1939).

 169

175. R. H . B i r t l e s and G . C . Hampson, J. Chem. S o c ,

10 ( 1 9 3 7 ) .

176. I. J. P a c h t e r a n d M. C . K l o e t z e l , J. Am. Chem. S o c ,

74, 1321 ( 1 9 5 2 ) .

177. R. L . L a n t z a n d P . O b e l l i a n n e , Bull. S o c . Chim. France,

311 ( 1 9 5 6 ) .

178. T . Kagayama and K . T a k a h a s h i , J a p a n e s e P a t e n t 9326

(1955); taken from Chemical A b s t r a c t s , 52, 1231a
(1958) .

179. W. K . T . G l e i m , U . S . P a t e n t 2 , 7 6 6 , 2 7 7 ( 1 9 5 6 ) ; taken
from Chemical A b s t r a c t s , 5 1 , 11381f ( 1 9 5 7 ) .

180. A. Bell a n d M. B . K n o w l e s , U . S . P a t e n t 2 , 6 9 2 , 287 (1954);

taken from Chemical A b s t r a c t s , 5 0 , 2666f ( 1 9 5 6 ) .

181. P. E . Verkade, H. Nijon, F . D. T o l l e n a a r , J. H . van R i j ,

and M. v a n L e e u w e n , Rec. trav. chim., 71_, 1007 (1952).

182. F . G . Mann a n d J . Watson, J. O r g , Chem., ] J 3 , 502 (1948).

183. W. A . S c h r o e d e r , P. E . Wilcox, K . N . T r u e b l o o d and

A. O. Dekker, Anal. Chem., 23, 1740 (1951).

184. E. J. Forbes and R . T . W r a g g , Tetrahedron, 8, 79 (1960).

185. R. F o s t e r , D . L . Hammick, G . M. Hood and A . C . E .

Sanders, J. Chem. S o c , 4865 (1956).