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476

Toshihiko

BULLETIN

OF THE

The

CHEMICAL

SOCIETY

HosHI

Yoshi@

VOL. 39

OF JAPAN

Absorption
Spectra
of the Component

and

TANIZAKI

476-480

[Vol.

(1966)

of Dyes. X.1) Note on the


Molecules
in the Complex

By Toshihiko

HOSHI

and

Yoshie

39, No. 3

Configuration
State*

TANIZAKI

Department of Chemistry, Tokyo Institute of Technology, Ookayama, Tokyo


(Received June 22, 1965)

The configuration of the component molecules in the complexes formed between Chrysophenine
G (G) and the direct dyes (P), such as Chlorazol Sky Blue FF, has been discussed qualitatively
with respect to the relation between the steric structure of the individual P molecules and the
enthalpy or the entropy changes in the complex formations. The electrons to be transferred from
1) Part IX of this series:
T. Hoshi,
Ando, This Bulletin, 38, 725 (1965).

Y. Tanizaki

and

N.

* Presented at the 7th Discussions on Dyeing Chemistry (May,


1965) held by the Chemical Society of Japan and the Society
of Fiber Sience and Technology, Japan.

March,

1966]

the

Steric

partner

those

(P)

of the

one

functional

comes,
must

more

exist

Such

has

this

been

clusion

respective

The

larger

the

charge

reached

combinations

series,

the

complex

arranged

the

in

the

by

such

the

partner

when

be

abbreviated

of

for

as

transfer

P)

to

the

curs1.3);

that

group

of

molecule

is,

the

MO

transfer,
in

change

(-H)

certain

charge

formations

directional

The
of

The

in

the

the

purpose

tively

the

and
the

same

results
of

the

equilibrium
The

in

I.

obtained

so

the

I,

dyes

used

here

the

usual

in

as

and

the

be

called

coupling
by

benzidine

tolidine

the

dichlorobenzidine
SS-acid
A

(S),

dye,

will

for

be

the

of

described

graph.
ed

the

1:2

they
to

Taken

from

The

could

spectral
complex

NB.

not
only

other

disazo

the

dyes

following
will
in

tail

of

(N),

and

3,

J-acid

chromotropic

change
formations.

be

one

dyes,

CT

and

acid

CCl

obtained
spot

when

on

However,

Se.u.

1:2

the

complex

FOR

COMPLEX

THE

1:1

FORMATIONS

3'-

in
the

pure

paper

because
to

to
there

In

with

G,

the

1:1

spectral

and

the

were

small

calculated.

some

2) T. Kobayashi, Y. Tanizaki and N. Ando, This Bulletin, 33,


661 (1960).
3) T. Kobayashi, K. Saito, Y. Tanizaki and N. Ando, ibid.,
35, 935 (1962).
4) Y. Tanizaki, T. Hoshi and N. Ando, ibid., 38, 264 (1965).

short

first
wave-

one

the

other

formation

at
for

K2

The

spectral
at
for

The

Kt

not

due

values

be

due

example,

persed

from

-18

be

as

to

chromato-

could.
to

to

isosbestic

the 1:2

complex

point

was

too

the

1:1
point

complex
was

too

calculated.

obtained

for

so

paper

to

calculated.

1:2

persed;

1:2
were

purified

the

isosbestic

change

to

1:1

the

respectively

be
on

the

at

constants

samples

be

the

formations,
to

equilibrium

1:1

to

formation

points

spot

not

well-defined

formations

change
the

did

the

corresponding

could

only
spectral

small

of

the

complex

sample

as

formation

complex

the

be

corre-

points.

to

isosbestic

not

change

indication

due

changes

The

small

g)

of

the

could

complex

the

for

The

graph

of

1:1

provide

f)

influence

too

spectral

isosbestic

1:2

too

and

at

constants

points

(C).

show-

the
because

were

the

the 1:2

spite

the

e)

to

appear

P's

well-defined

(J),

enough

due

not
of

equilibrium

the

chromato-

did

peaks

and

excluded

. 4.
points

The

d)

were

combined

corresponding

means

are

(530m).

isosbestic

parentheses;

Ref

calculated

c)

diazo
hereforth

(D)

NW-acid
and

1:1

AND

THE

isosbestic

sponding

NW-acidsbenzidineNW-acid,
by

indicate
The

symmetric

dianisidine

and
(H)

example,

represented

because
form

(Cl),
H-acid

so

quantities

experi-

treatment
been

indicated

(T),

for

and

previous
the

a)

which

notations

calculated,

therefore

regarding

have

from

components,

the

(B),

the

be

qualita-

of

far,

and

way

which

Hkcal./mol.

lengths

were

in

AND

retain

The

to

large

points

must

before.4)

prepared

indicate

for

formed.

same

not
isosbestic

peculiar

the

basis

complexes

were

did

the

exist

b)
data

G
at

thermodynamic

Table

absorption

the

were
affected
concentrations;

configuration.
to

the

procedure

for

absorption

(PG+GGPG)

Experimental
experimental

for

first

wavelengths
its higher

constants

estimated

the

The

the

constants
estimated

of

may

is

the

supplement

accumulated

an

electron

quantities

on

be

with

with

changes

(P+GPG)

suitable

study

with

given,

not

at

ND
to

(-S).

present

be

it

molecules

change

the

time,

configuration

such

component

connection

will

mental

to

shifts

thermodynamic

in

discussion

than
due

equilibrium

dyes

combined

reliable

TABLE

density

and

free

deformation.

could

at shorter
tail
of G

should

there

entropy

of

consider

At

of

transfer.

reflected

to

property,

when
spectral

enthalpy

the

the

the

some

enough

shown

important

electron
as

which

or

forma-

almost

of

for

reasons;

in

are

magnitude

complex

there

complex

deformed
state

the

be-

that

(NW-aciddianisidine

more

combinations

on.

lowest

formation

the

the

the

than

group

certainty

to

are

more

charge

the

Moreover,

configuration

configuration
be

by

the
the

an

complex

group.
the

to

plays

oc-

functional

Since

force,

the

affected

possesses

G.1)

known,

for

functional

transfers

of

well

the

is

and

have

the

G)

on

intermolecular

directly

the

(to

(Chrysophenine

molecule

is

the

partner

electron

(G*)

as

role

the

the

vacant

be

from

with

ND

complex

to

others
charge

and

the

dye
functional

said

peculiar
G

groups

the

effective
be

peaks
at 530m
by the
absorption

component

side

an

of

several

con-

(hydroxy)
of

may

molecules

477

State

functional

It

proportion

formation

to

state,

side

of

configuration

Chrysophenine

According

the

combination

which

Complex

components

density

the

increases

and

of

coupling

component

for

the

complex

dyes

electrons

the

is increased.

the

of
to

the

direct

on

are

of
seen

which

in

(-H)

maybe

studied.1-4)

molecules

change

equilibrium

Molecules

the

the

(-S)

disazo

are

configuration

of

Dye

when

other

shifts

in
the

molecule

enthalpy

certain

change

Hitherto
between

the

For
the

entropy

of

groups

a configuration

NW-acid).
state,

the

group.

the

ition.

to

inner-side

Structure

were
the

to

-23.

-H

extensively
values

diswere

dis-

478

Toshihiko

formation
the

of

the

P+GPG

PG+GGPG

type,

and

HosHI

1:2,

and

that

of

type.

Yoshie

TANIZAKI

pair

electrons,

tion

in

because

the

and

cule

Discussion

The

thermodynamic

formations

of

GPG)

are

for

the

can

be

the

effect

summarized

and

the

in
H

by

of

series

means

the

III,

of

and,

that

for

1:2

Tables

II

the

complex

and

III
There

data

in

Table

II

for

means

diazo

HS

of

the

the

data

components.

FoR

II.

THE

THE

AND

ENTHALPY
SERIES;

H2,

H1,

S2

FoR

AND

ENTROPY

S1

FoR

strongly
functional

are

reason
groups

attached

with

P+2GGPG.

FoR

THE

AND

ENTHALPY
SERIEs;

H2,

AND

H1,

S2

ENTROPY

S,

FOR

FoR

CHANGES

sense.

P+GPG,

ficulty
The

the

hydroxyl

group,

the

proton

dissociation

figures

pH

that

the

of

lone

SS-acid

link

due

Fig.

1.5)

must,
G

pair

(S)

formation

Change.-It

the

of

the

On

of
the

hydroxyl

transfer,
the
other
groups

as

the

hydroxyl

responsible

for

provided

the

above-mentioned
hand,
of

all
H

and

shown

SD

amino
C

for
and/or

have

S.
the

type

lone

As

it

is

positions

densities

of
D

same

as

that

of

Bulletin,

38,

the

soluof

of

be

the

same
charge

dyes

arranged

coupling

the

the
the

of

of

the

condition

in

the

components,

corresponds
the

the

well-including

magnitude

of

the

-H's

II.

In

the

series,

acid,

is

the

common

kinds

of

substituents

the

at

electron

on

ing

to

of

the
the

This

of
the

inner
n

component,

H-

is

of

correlated

the

hydroxyl

the

substituent

conjugate

the

3, 3'positions

be

hydroxyl

electron

assumption

the

must

effect

the

coupling

ingredient;therefore,

skeleton
density

This

order
in

the

a
the

Indeed,

mentioned
of

in

plausible

groups

plausibly

that

Table

case,

N. Ando,

dissociated

components,*

hydroxyl
may

just

here
also

because

series

resonance

H. Inoue and

used

(ND)<JD<SDHDCD.

order

charge

5) Y. Tanizaki,
1419 (1965).

water

preserved
the

to

approximate

N<JS<H<C

of

dis-

found

a halfofCand

that

is

the

order

i.e.,

is

dif-

group.
the

been

the

be

assumed

coupling

biphenyl

of SS

the
the

for

has

the

density

ND-with

Fig. 1. The type of the hydrogen


bonding
acid, H acid and chromotropic
acid.

usual'
charge

more

value

solvent

ofJcould

groups

in

the
the

where

nearly

Accordingly,

If

the

the

The

comparable

of

pH

the

in

the

indicate

of6,

hydroxyl

in

molecule

situation
the

SD

be

larger

erouns

parentheses

value

charge

tion.
in

groups
the

pH

solution.

bond

is

in

amount

the

hydrogen

of

alone

group

naphthalene

with
groups.

the

starting

hvdroxvl

vaiues.5)
a

small

clarified

amino

the

type,

electrons
be

been

the
to

intramolecular

The

charge

on

conjugate

NcH-O

therefore,

allows

electrons

cannot

to

has

the

the

it

relative

C(4.2)<J(5.6)<N(6.2)<S(8.0)H(8.4),

had
Enthalpy

of
of

dyes;

above,

density

that

groups.

the

will

charge

of

order

the

The

hydroxyl

be

sociation
be

connection

can

of

the

described

in

said

rate,.

discussed

hydroxyl

such

total

any

be

explain

density

the

naphthalene

of

the

It

density

P+2GGPG.

of

The

functional

At

groups

to

electron

that

of

will

findings

of

end

found.

just

of-H

relative

THE

the

the

mind.

possible

densities

with

in

of
groups)

transfer.

the

groups

SD,
This

electrons

ring

be

of

order.

charge

outside
not

H's

hydroxyl

on

therefore,

be

magnitude

III.

the

facts

to
to

electron

the

functional

are,

According

TABLE

to

above

here

ought

for

could

efTective

used

(the

hydroxyl

the

The

the

molecule.

the
same

only

molewith

SD

the

groups

CD

groups

however,
in

forma-

respectively

the

the

electrons

ineffective

P+GPG,

and

as

that

the

internal

HD

nearly

responsible

why

bond
form

functional

II,

are

internal
of

the

many

Table

CD

hydrogen

O-HO

electrons

suggests

are
CHANGES

to

and

the
TABLE

as

pair

According

(P+2G

differences
by

the

the

and

respectively.

structural

components,

Table

for

(P+GPG)

discussed

coupling
in

quantities

1:1

is,

twice

lone

the

or

That

have

type

of

N-HO

(Fig.1).5)

Results

[Vol. 39, No. 3;

will
from

system.
of

adequate

except

the

groups.

group

density

the

with

hinder
migrat-

If

the

The

this

is

hydroxyl

in

the

case

the

group

of

ND

because,
as will be shown
in the following
section,
all of the
dyes in the D series
but
ND are affected
by some steric effects
and,
consequently,
the relative
situation
of the charge
densities
of the hydroxyl
groups
could not be altered.
At present,
however, no reason can be found
for arranging
ND on the left side
as above.

March,
will

1966]

be

larger

in

that

of

tion

HB

probability

become
of

Steric
case

of

HT.
of

larger

the

the

and

in

magnitude

HD

and

of Dye Molecules
HCl

than

Consequently,

PG

than

Structure

in

the

of

the

the

former

case
the

-H's

in

fact,

Table

479

State

in

transi-

In

latter.

in the Complex

will
order

III

comes

up to this expectation.
The above consideration can equally be applied to both the PG (1:1) and the GPG (1:2)
(complexes.
In the 1:2 complex state, the two G molecules
have been considered to be equivalent to one
another.1,2) This is not inconsistent with the magnitude

of

for

all

the

cases,

values

the

obtained

here,

-2H1-H2

because,

relation

is always

maintained.
Entropy

Change.-First

the

value,

ang

relations

it is
which

for

the

ND-G

for

the

JD-G

of

interesting
appear

in

concerning

notice

the

Table

system:
and

all,

to

S1

SD-G

follow-

II;
S20

(1)

systems:
2S1=S2

for-the

HD-G

and

CD-G

(2)

systems:
-251<-S2

and

for

both

S1

and

(3)

Fig.

S2

2.

Steric

shadings
0

Relation

suffered

from

S(CD)

implies

that

any

ND

(4)

and

structural

have

not

restriction

by

be

Relation

PG)and

the

Relation

the

first
In

order
the
the

to

the

than

in

directional
For

that
required

the

the

above

shown
the

sort

R1

may

be

in

of

descrlbed

above

component

into

torsional

coupling

be

us

and.R2

it

change.

the

other
order

components,

in

independent.

In

the

R0

case

2),the

(R2=0),

the
the
sum

to

in

of

is

bond

HD

the

negative

fhe

fbrmation

SD;

electrons

of

hydrogen

fbrce

of

say,

the

the

on

the

the

of

the

bond,

the

group

with
group

and

of

and

that

the

ND

the

complex

that
the

of

tortional

the

entropy

and

onance

ND

also

the

naphthalene
a

H
the
force

increase

of
the

to

be

that

of
the

could

increase

C-N

bond

(R2)

density

of

biphenyl.

charge
coupled

the

amino

case

group

has
effect

the
to

In

HD.6)
end
HD

increases

while

charge

adjacent

while

that.7)

the

as
the

resonance

position

do

amino

at

The

slightly

component,
cannot

R2

links,

positions.
of J

considered

of

groups

opposite

diazo

of

amino

deformed
conformation.

been

order

any

assumption,

ideal

previously

end

the

this

somewhat
an

same

has

keeps

formation,
without

to

become

have

molecule

complexes

such

group

at
the

to

the

amino

therefore,

the

fbrce

R2

group

of

HD.

exceeds

to

be

and

the

R2=50-60.6)

R2(ND)R2(HD)relation

Y. Tanizaki

the

density

the

have

CD

of
at

of
the

and

the

JD,
res-

could

azo-nitrogen

For

that

N. Ando,

angle

of

The
as

JD

may

order

follows

become

of the

torsion

(R2(SD)

will

smaller

reason,
than

angles
not

that

is considered
be

considered

here):

0 R2(ND)<R2(JD)<R2(HD)R2(CD)

(5)

can

Relation
6) T. Kobayashi,
(1960).

that

approach

nearly

positions

the

repulsion

sulfbnic

azo

bonding
C-N

here

expected

is possible

electrostatic

charge

Ione-pair

rcsonance
That

hydrogcn

while

between

the

electrons.

order

According

JD

atom
Fig.

state

form

dyes

and
have

i.e.,

dependent

though

free

for

can

to

JD

of

about
are

assume

However,

that

them,

angles

be

the

conformation

entropy

to

chemical

secn

betwecn

may

between

the

because

molecules

similar

in

ideal

these

take

R1

R2,

the

in

each
has

may

2, as R0,

almost

with

configuration

dyes

the

Fig.

take
of

originally

been

structures
in

to

groups

overiap

differences

differences

in

conditions.

the

some

on

has
ofc

three-dimensional

and

and

pair

the-S(ND)-S(HD)
it

exists

Let
larger

transfer

must

both

of

is

hydroxyl

orbital

dhange

ail

structures,

to

for

Though

(see

HD

lone

change.

(P+G

(PG+GGPG),

charge

p
as

reason,

suitable

bonds

ND,

type

of

first

second.

the

of

the

property,

are

the

of

orbital

Besides,

the

to

Therefore,

parallelism

com-

amount

the

deformation

the

orbital

G*

other.

the
to

process

that

enable

that

distributed

second

3,

process

place,
and

2,

is equally

correlated

relation.

been

the

well

angle,
fbrmation;

defbrmation

and

of

the

S(ND)<-S(JD)<-S(SD)
<-S(HD)

plex

structures

indicate

ibid.,

5 coincides

with

Relation

4 except

33, 913
7)

H. Baba and S. Suzuki, ibid., 34, 82 (1961).

for

[Vol. 39, No. 3,

480
SD.

If

be

said

R2(JD)
SD

is

and

R2(HD),
fairly

of

because
has

the
been

bond

is

Fig.

2,
In

Table

in

R,

just

in

series,

since

invariant

III

ND

As

be
may

R0

and
of

attributed
seen

of
type

R2

can

the
to
from

the
the

pair

electrons

in

the

the

of

chlorine

than

zero.6)

the
in

in

can

HB

therefore,

latter.

Thus,

appearing
HCl),

in
can

the

to

similar
be

and

for

and

as

well..

the

than
change

(HB,

HD

HT

R,

larger

be

for

for

angles

classes,

Also,

consideration..

larger

entropy

reasonably

lone-

involving

into
be

to
of

type
atom.

perhaps

the
two

the

taken

become

due

hindrance

situation

may

torsion

will,

is mainly

steric

azo-nitrogen
a

effects
for

RL

the

relation

the

corresponding

class

of
or

HCl,

atom

HCl
The

torsion

of

case

steric

molecule

the

group

the

former

those

for

difference

HT)

and

(HD,

explained.

assumed
coupling

entropy

methoxy

2,

repulsion

substituent

is
be

the

Fig.

Such

shown

common

in

electrostatic

those

hydrogen

SD

HD

the

and

emphasized,
SD

of

the
in

be

be
the

molecule

angle

difference

may

of

of

intramolecular

R2

because
the

values.

the
the

fact

of
the

the
group

must

an

like
i,e.,

with
existence

between

image

of

R2

the

The

must

the

together

hydroxyl

mentioned

which

formed

components,
of

the

it

between

that

implies

acting
of

conventional

that,

the

be

2,

atom.

SD

parallel,
positioned

This,

Fig.

force

one

are
be

indicating

azo-nitrogen

structure

can

in

electrons

the

and

large.

SD

repulsive

1:ne-pair

to

R2(SD)

of

some

that

also

drawing

of

Relations

change
difference
drawing

of

the

express

One

his

hearty

Sankyo

Co.,

Ltd.,

present

authors

thanks
for

his

to

(T.
Dr.

encouragement

H.)

wishes

Harutada

Negoro,
and

advice.

to