New classes of phosphorus-containing dyes

TetrahedronLetters No. 6, pp. 199-205,1961. Pergamon Press,Inc. Printed in the United States of America.

NEW CLASSES OF PHOSPHORUS-CONTAINING DYES H. Depoorter,J. Nys and A. Van Dormael Chemical Research Laboratories,Gevaert Photo-ProductenN.V. Mortsel, Belgium (Received6 March 1961) IN the course of a research program for photographicsensitizingdyes, a new class of dyes containinga C=Pc auxochromehas been discovered. 1 subdivisedinto several subclasses.

It may be

It is our intention,in this pre-

liminary communication,to bring a short record of the principalroutes by which the new dyes may be obtained. A first class of new phosphorus-containing dyes, which we propose to call "phosphinines",by analogy with the structurallyrelated cyanine dyes, is characterizedby the auxochromophoricsystem: f&-(CH=CH),

- CH=b-Pi +'

t-,

+=(CH-CH!n

= Cl-&'<

These new dyes may be synthesizedin a variety of ways.

Starting with

cyclopentadienylene-triphenylphosphorane (I), whose nucleophilic propertieshave been pointed out recently by Ramirez and Levy', the symmetricaldye II may be obtained, e.g. by refluxingwith ethyl orthoformate or orthoacetatein acetic anhydride.

1 Gevaert, Belg.Pat. 583.922 (prior.G.-B. 2.4.10.58) and A.Van Dormael, J.Nys and H. Depoorter,Sci. & Ind. Phot. (2) & 389 (1960) 2

F. Ramirez and S. Levy, J.Amer.Chem.Sot. 29, 6167 (1957)

199

New classes

200

HC--$H I(tC .cY Y C6H5-y-C,;H5

of

phosphorus-containing

Rc(OC2H5$ -p AcZO

HCAH He, )

- !

'gH5

X- =

hmax

I-;

will

be noticed

link

results

was

observed

dipyrrylmethene

that in

the

of

introduction

a bathochromic

by Brunings

rnp

analogously

shift,

and Corwin

a methyl-group

3

in

the

in

to

same

the

the

shift

conditions

with

dyes.

The same acrolein

I

477 ny *

=

II : R = CH3; X' = C104-;A,,.ax= 488

which

X'

II

II : R = H;

methine

I.+ C6H5-T-C6H5

'gH5

I

It

= ':;i,H

s C6H5-f'-C6H5

'gH5

No.6

dyes

anil

a trimethine

I condensed

cyclopentadienylene-phosphorane (III, link

n = 1) between

leads both

to

the

corresponding

with

dye

p-anilino

IV (n = 1) with

nuclei.

a-NH-(CH+H),-cH+f-(a I

III Ac20 (NaClO4) HCTH HC--CH c104E(cH-cH),-Hc~,~JH HE. / F It H5c6-7'c6H5 H5C6-P-C6H5 C6H5 'gH5 ! Iv

* 3 K.J.

All

optical

Brunings

data

were

and A.H.

determined

Corwin,

J.

in Amer.

ethanolic Chem.

solution. Sot.

2,

593

(194.2)

New

No.6

201

classes of phosphorus-containing dyes

The phosphoraneI yields the correspondingpentamethinehomologue IV (n = 2) by reactionwith the anil of 1-anilino_pentadien(1,3)-al(5) (III, n = 2).

The absorptiondata are t dye IV (n = l), Am,, = 597 rnp

and dye IV (n = 2), A,,, = 695 rnp. I, when allowed to Furthermore,the cyclopentadienylene-phosphorane

react with various electrophilicreagents ordinarilyused in the chemistry of cyanine and merocyaninedyes, yields asymmetricaldyes which we might characterizedby the followingauxochromophoric

ho', call "p s system I

$P=k(CH=CH),-CH=k

M +

;P&(CH-CH),=CH-k+

As an example, I reacts with 2-methylmercapto-3-methyl-benzothiazolium methylsulphate(V) in ethanol to produce the dye VI (Amax = 398 myI.

The

reaction is catalyzedby triethylamine.

-

SCH3

CH3S04-

CH3 V

-His CH3

c lob-

H5C&C6H5 ‘SH5 VI

Similarly,the reaction of (I) with 2-(p-acetanilido-vinyl)-3-ethylbenzoxazoliumethylsulphate(VII) yields the dye VIII (A,,, =,!+80rnp).

202

New classes

of

phosphorus-containing

dyes

No.6

I CH=CH-F/-e_3 co dH3

C2H5

I

C2H5S04-

(NaC104) 1

VII

- = CH

CH -H!;:::

clo _ 4

H5C6-f-C6H5

C2H5

‘gH5

I

VIII Chain-substituted

phospho-cyanine

p-alkyl-p-methylmercaptovinyl 5.0

m$

is

dyes may be obtained

derivatives

by using

such as IX whereby

dye X (I,,,

=

obtained.

Ix

X The cyclopentadienylene-phosphorane methylene anhydride,

derivatives

of

ketomethylene

whereby merocyanine-like

“meroohosohiniqss”

is

I also

proposed.

nuclei

systems

reacts

with

acetanilido-

in the presence are obtained,

for

of

acetic

which the name

New classes

No.6 These namely

dyes,

too,

of

display

phosphorus-containing

dyes

a new characteristic

203

auxochromophoric

pattern,

1 >P~-(cH=CH)~-$-

~P-&=(CH-CH)n~+ 0'

-

0 Thus, dye XII

reaction

(aax

I

+

=

of

I with

the rhodanine-intermediate

XI yields

the new

~$86m$ .

a-;

-

CH

=

COCH3

2-i o=C,,cs

l

T C2H5 XI

HC----CH H8, ,'! -

CH

C

=

C--s od.

H5Cb-+H5

,ks

Y 'zH5

‘SH5

XII Aromatic in acetic

aldehydes

anhydride)

react

to yield

E -dimethylaminobenzaldehyde

I

+

with

I in appropriate

another (XIII),

new series e.g.

conditions of

dye XIV is

(refluxing

polymethine

dyes.

obtained

(Xmax =

‘With

495 my).

Ac20

OCH-

HC==-=CH Hd, ,h = C

CH

clo _ 4

ti5c6-+6H5

I

‘gH5

XIV

20-4

New classes Still

starting (‘max

mere complex

of phosphorus-containing

dye-systems

frorr the quaternized

= 606 m$

is

obtained

merocyanine by reaction

2H5

dye with

XV, the complex dye XVI I in pyridine.

!

= C----s

I

CH3S0,+-

Opd \ ,kSCH3 k

As an example,

may be synthesized.

;H2 -C6H5


No.6

dyes

T+ C2H5

(NaI)

Pyridine

xv

C2H5

XVI Finally, other

instead

phosphoranes

may be used. benzothiazoline

of

cyclopentadienylene-triphenyl-phosphorane

(I), 4 (XVII)

such as carbethoxymethylene-triphenyl-phosphorane

By reaction

with

(XVIII)in acetic

the

anil

of 2-formylmethylene-3-ethyl-

anhydride,

dye XIX is

obtained

(A,,,

A-S =CH-CH==N-0

+

4 0. Isler, H. Guttmann, M. Montavon, Helv. Chim. Acta @, 124.2 (1957).

H5C200C-CH=PP(C6H5

R.Ruegg,

G. Ryser

I3

and P.Zeller,

= 446 m$.

No.6

New classes

of

phosphorus-containing

205

dyes

Ac20 ? (NaC104)

a

S

COOC2H5 -CH=CHb =

/C6H5 P-C6H5 "6H5

I+ c2H5

c104I

XIX A detailed dyes

will

these

dyes

description

be published have

been

5 H.

Depoorter, preparation.

6 A. Van Dormael,

J.

of elsewhere,5

discussed

the

synthesis whilst

the

the

optical

properties data

of of

the

some of

recently.6

Nys and A. Van Dormael,

Chimia

and

l.J,

67 (1961).

&ll.Soc.Chim.Belq.

in

new