Equilibrium NH-acidity of polyfluorinated arylamines and benzanilides

561

EQUILIBRIUM

NH-ACIDITY

OF

POLYFLUORINATEO

ARYLAMINES

AND

BENZANILIOES

V.M.

Vlaso,

G.G.

Institute

M.I.

of

Yakobson

Organic

Terekhova,

E.S.

Physico-Chemical

Equilibrium amlnes

and

on

nitrogen

the

type

(USSR)

NH-acidity

of

range

been

18.51

by

and

been

correlations

for

these

of

for

Investigated

non-fluorinated

NH-acids

C6FS-group

group

from

fying

effects

acids

[from

to 6.5

5

thoxyethane Influence

1. of

to

shows

neighboring 7.5

pK

of

C6FS

to

6’pK

units

This

Is -group

attributed on

the

to in

(X

=

these

have

been

found. and

acidifying

The

the to acidity

[APK)

that

been

results the

Examirespective

of

difference

have

of

Increase both

CH-

of

data

effect more

same

dimethyl

Me2N,Me0,Me,H,

From

are

9-

NH-acids

OMSO.

Ph-groups from

4-CSF4N1

compounds that

units. and

[C6FS, relation method

N-H-bond

-

C6F5

series

Karpov

luoroaromatic

para-substituted

in

nation

of

In

p-XC6F4NHC[OIPh

determined

values

polyf

overmetallatlon

Hammet

pK

of

ArF-group

of

(USSR)

L.Ya.

established

Acidity

K+l.

has

the

containing has

p-XC6F4NHC6FS

F,C1,Br,CF31

Shatenstein,

Moscow

atom

(cation

A.I.

Novosibirsk

Institute,

[pk

sulfoxide

630090,

Petrov,

benzanilides

phenylfluorene

the

Chemistry,

Ph-

of found PK

S

acidiin in

CHdlme-

of

inductive

and

NH-acids.

562

The

pK

correlations

-6

Series

Equation

p-XC6FqNHC6F5

PK r

p-XC6F4NHC(OIC6H5

The lides

in

pK

values

OTIS0

(cation

of

=

12.6

-0.972, = -2,926;

s

0.33, n + 13.6

6

PK r

-0.966,

s

0.25,

6

polyfluorinated K+)

l

P

arylamines

relative

to

Compound

PK

c6FFsNH2

23.1

4-Nn2C5F4N

19.2

C6F5NHPh

19.2

4-Me2NC6F6F4NHC6FS

13.6

4-MeC6F4NHC6F5

13.3

4-HC6F4NHC6F5

12.6

C6F5NHC6F5

12.6

4-BrC6F4NHC6F5

12.2

4-C1C6F4NHC6F5

12.0

C6F5NHC10F7-

11.6

4-CF3C6F4NHC6F5

10.6

4-NCC6F4NHC6F5

-3.45&

9.1

4-MeOC6F4NHC(OlPh

14.1

4-MeC6F4NHC(OlPh

14.2

4-HC6F4NHC(0)Ph

13.6

C6F5NHC[OlPh

13.0

4-CF3C6F4NHC[OIPh

11.8

C,F,NHC(OIC,F5

10.8

n

and

S-phenylfluorene(pK

benzani18.51