Photographic products and processes employing azo dyes, azo dye-releasing compounds

Photographic elements, diffusion transfer assemblages and processes are described which employ a novel nondiffusible compound having a novel releasable azo dye. The dyes are azophenols, or precursors of azophenols, and have electron withdrawing groups in each of the positions ortho to the phenolic hydroxy group.

This invention relates to azo dyes and dye-releasing compounds useful in 
photography. In a particular aspect it relates to color diffusion transfer 
photography employing certain nondiffusible azo dye-releasing compounds, 
which, as a function of development of a silver halide emulsion layer, 
release a diffusible azo dye. 
Color diffusion transfer processes generally involve the use of a 
photographic element comprising a support, at least one silver halide 
emulsion layer and an image dye-providing material which is contained in 
or contiguous said layer. After exposure, the photographic element is 
treated with an alkaline processing solution to effect imagewise 
development of silver halide and imagewise dye discrimination. The 
imagewise dye discrimination is generally brought about by a monitoring or 
carrier group which, in the presence of the alkaline processing solution, 
is responsible for a substantial change in the diffusibility of at least 
the dye portion of the dye-providing material. As is known in the art, the 
dye-providing material can be initially immobile or initially mobile in 
the processing solution. In an element containing an initially immobile 
dye-providing material, alkaline processing results in release of a 
diffusible dye imagewise. In an element containing an initially mobile 
dye-providing material, alkaline processing results in the material being 
rendered insoluble (and thus immobile) in an imagewise fashion. 
It is well known in the art to utilize image dye-providing materials in a 
photographic element wherein an imagewise exposed element can be contacted 
with an alkaline processing solution to effect an imagewise difference in 
mobility of at least a portion of the dye-providing material, i.e., to 
effect release of a dye or dye precursor, to render said compound 
diffusible. Exemplary dye releasing compounds of this type, and 
photographic elements employing them, are described in U.S. Pat. No. 
4,076,529 issued Feb. 28, 1978; U.S. Pat. No. 3,980,479; U.S. Patent 
application Ser. No. 534,966 filed Dec. 20, 1974 and U.S. Patent 
application Ser. No. 775,025 filed Mar. 7, 1977. 
The yellow dye releasing compounds described in these and associated 
disclosures are highly useful. However, it would be desirable to provide 
improved compounds which release yellow dyes having improved stability to 
heat, light and chemical reagents and better hues. 
We have found that this can be accomplished with novel yellow azophenol 
dyes having electron withdrawing groups in each of the positions ortho to 
the phenolic hydroxy group and with novel nondiffusible compounds which 
release such azo dyes, or precursors of such azo dyes, as a function of 
silver halide development. Accordingly, our invention relates to novel 
dyes, novel nondiffusible dye releasing compounds, photographic elements 
and assemblages containing these dye releasing compounds and processes of 
forming photographic images employing these elements and assemblages. 
A photographic element in accordance with our invention comprises a support 
having thereon at least one photosensitive silver halide emulsion layer 
having associated therewith a nondiffusible compound having a releasable 
azo dye moiety which is diffusible under alkaline conditions when released 
from the compound, said compound having the formula: 
##STR1## 
wherein: 
D is an electron withdrawing group (i.e., a group having a Hammett para 
sigma value greater than 0, and preferably between 0 and +1.5); 
E is a strong electron withdrawing group (i.e., a group having a Hammett 
para sigma value greater than +0.3, and preferably between +0.3 and +1.5); 
Z represents the atoms necessary to complete an aromatic carbocyclic or 
heterocyclic nucleus having at least one ring of 5 to 7 atoms (e.g., 
phenyl, pyridyl, naphthyl, pyrazolyl, indolyl, etc.); 
G is hydroxy or a hydrolyzable precursor thereof; and, attached to one of 
the rings, a ballasted carrier moiety capable of releasing the diffusible 
azo dye under alkaline conditions as a function (either direct or inverse) 
of development of the silver halide emulsion layer. 
Exemplary Hammett para sigma values and procedures for their determination 
are set forth by J. Hine in Physical Organic Chemistry, 2nd edition, p. 
87, published in 1962; by H. VanBekkum, P. E. Verkade and B. M. Wepster in 
Rec. Trav. Chim, Volume 78, Page 815, published in 1959; by P. R. Wells in 
Chem. Revs., Volume 63, Page 171, published in 1963; by H. H. Jaffe, Chem. 
Revs., Volume 53, Page 191, published in 1953; by M. J. S. Dewar and P. J. 
Grisdale in J. Amer. Chem. Soc., Volume 84, Page 3548, published in 1962; 
and by Barlin and Perrin in Quart. Revs., Volume 20, Page 75 et seq., 
published in 1966. 
In a preferred embodiment of our invention, Z represents the atoms 
necessary to complete an aryl group such as a phenyl group which can be 
substituted with one or more non-interfering substituents such as halogen 
(e.g., chloro, fluoro, bromo, iodo), lower alkyl (e.g., methyl, ethyl, 
propyl, butyl), lower alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy), or 
acid or acid derivative substituents such as acids, esters and amides 
(e.g., sulfo, sulfonamido, sulfamoyl, carboxy, carboxamido or carbamoyl 
groups which can be unsubstituted or substituted with lower alkyl or lower 
aryl groups). As used herein lower alkyl and lower alkoxy refer to such 
groups containing 1 to 4 carbon atoms while lower aryl refers to aryl 
groups of 6 to 9 carbon atoms such as phenyl, benzyl, tolyl, 
methoxyphenyl, chlorophenyl and the like. In a particularly preferred 
embodiment the ballasted carrier moiety is attached to the ring completed 
by Z. 
In a preferred embodiment of our invention D is an electron withdrawing 
group selected from halogen, nitro, cyano, carboxy, sulfonyl, sulfamoyl, 
or lower perfluoroalkyl and E is a strong electron withdrawing group 
selected from nitro, cyano, carboxy, sulfonyl, sulfamoyl or lower 
perfluoroalkyl. The sulfamoyl group can be unsubstituted, substituted with 
lower alkyl, lower aryl or heterocyclic groups or can form a part of the 
ballasted carrier moiety which is cleaved from the carrier when the dye is 
released. The sulfonyl group can be substituted with a lower alkyl, lower 
aryl or heterocyclic groups or can form a part of the ballasted carrier 
moiety. 
In a preferred embodiment of our invention G is hydroxy or a hydrolyzable 
ester group of the formula 
##STR2## 
where each R.sup.1 is independently alkyl of 1 to 8 carbon atoms, aryl of 
6 to 12 carbon atoms or a group which together with the 
##STR3## 
is the ballasted carrier moiety. 
The azo dyes of our invention have the structure I, above, except that they 
do not contain a ballasted carrier moiety. The dyes can, however, contain 
a residue of a ballasted carrier moiety when, for example, they are 
released from the nondiffusible compound. When G is a hydroxy group the 
dyes are azophenols and typically are yellow in color. When G is a 
hydrolyzable precursor of a hydroxy group the absorption spectrum of the 
dye is shifted to shorter wavelengths and when such a G group is 
hydrolyzed, such as under alkaline conditions encountered during 
processing, the yellow color of the azophenol dye is obtained. 
There is great latitude in selecting a ballasted carrier moiety in the azo 
dye releasing compounds described above. Depending upon the nature of the 
ballasted carrier moiety selected, various groups may attach or link the 
carrier moiety to the azo dye. Such linking groups are considered to be a 
part of the ballasted carrier moiety in the above definition. It should be 
noted that when the dye moiety is released from the compound, cleavage may 
take place in such a position that part or all of a linking group, or even 
other parts of the ballasted carrier moiety, may remain attached to the 
dye. 
Ballasted carrier moieties useful in the invention are described in U.S. 
Pat. Nos. 3,227,550; 3,628,952; 3,227,552; and 3,844,785 (dye released by 
chromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dye 
released by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and 
3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No. 
3,728,113 (dye released from a hydroquinonylmethyl quaternary salt); U.S. 
Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release); and 
U.S. Pat. Nos. 3,245,789 and 3,980,497; Canadian Pat. No. 602,607; British 
Pat. No. 1,464,104; Research Disclosure 14447, April 1976; and U.S. 
application Ser. No. 775,025, filed Mar. 7, 1977 of Chasman et al (dye 
released by miscellaneous mechanisms), the disclosures of which are hereby 
incorporated by reference. 
In a further preferred embodiment of the invention, the ballasted carrier 
moiety may be represented by the following formula: 
EQU (BALL-CAR-LINK)- II 
wherein: 
(a) BALL is an organic ballasting radical of such molecular size and 
configuration as to render the compound nondiffusible in a photographic 
element during development in an alkaline processing composition; 
(b) CAR is an oxidizable acyclic, carbocyclic or heterocyclic moiety; 
(c) LINK represents a group which upon oxidation of said CAR moiety is 
capable of being hydrolytically cleaved to release the diffusible azo dye. 
For example, LINK may be the following groups: 
##STR4## 
wherein * represents the position of attachment to CAR. 
The ballast group in the above formula is not critical as long as it 
confers nondiffusibility to the compound. Typical ballast groups include 
long-chain alkyl radicals linked directly or indirectly to the compound as 
well as aromatic radicals of the benzene and naphthalene series indirectly 
attached or fused directly to the carbocyclic or heterocyclic nucleus, 
etc. Useful ballast groups generally have at least 8 carbon atoms such as 
substituted or unsubstituted alkyl groups of 8 to 22 carbon atoms, a 
carbamoyl radical having 8 to 30 carbon atoms such as 
--CONH(CH.sub.2).sub.4 --O--C.sub.6 H.sub.3 (C.sub.5 H.sub.11).sub.2, 
--CON(C.sub.12 H.sub.25).sub.2, etc, a keto radical having 8 to 30 carbon 
atoms such as --CO--C.sub.17 H.sub.35, --CO--C.sub.6 H.sub.4 (t--C.sub.12 
H.sub.25), a sulfamoyl radical having 8 to 30 carbon atoms such as 
--SO.sub.2 NHC.sub.12 H.sub.25, etc. 
For specific examples of BALL-CAR-LINK- moieties useful as the ballasted 
carrier moiety in this invention, reference is made to the November 1976 
edition of Research Disclosure, pages 68 through 74, and the April 1977 
edition of Research Disclosure, pages 32 through 39, the disclosures of 
which are hereby incorporated by reference. 
In one highly preferred embodiment of the invention, the ballasted carrier 
moiety is such that the diffusible azo dye is released as a direct 
function of development of the silver halide emulsion layer under alkaline 
conditions. This is ordinarily referred to as negative-working dye-release 
chemistry. In one such embodiment the ballasted carrier moiety is a group 
having the formula: 
##STR5## 
wherein: 
(a) Ballast is an organic ballasting radical of such molecular size and 
configuration (e.g., simple organic groups or polymeric groups) as to 
render the compound nondiffusible in a photographic element during 
development in an alkaline processing composition; 
(b) D' is OR.sup.2 or NHR.sup.3 wherein R.sup.2 is hydrogen or a 
hydrolyzable moiety and R.sup.3 is hydrogen or a substituted or 
unsubstituted alkyl group of 1 to 22 carbon atoms such as methyl, ethyl, 
hydroxyethyl, propyl, butyl, secondary butyl, tert-butyl, cyclopropyl, 
4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, 
octadecyl, octadecyl, dodecyl, benzyl, phenethyl, etc. (when R.sup.3 is an 
alkyl group of greater than 8 carbon atoms, it can serve as a partial or 
sole ballast); 
(c) --NHSO.sub.2 L-- is ortho or para to D'; 
(d) Y represents the atoms necessary to complete a benzene nucleus, a 
naphthalene nucleus, or a 5 to 7 membered heterocyclic ring such as 
pyrazolone, pyrimidine, etc.; 
(e) j is a positive integer of 1 to 2 and 2 when D' is OR.sup.2 or when 
R.sup.3 is hydrogen or an alkyl group of less than 8 carbon atoms; and 
(f) L is a linking group which is --[X--(NR.sup.4 --J).sub.q ].sub.m -- or 
--X--J--NR.sup.4 -- wherein: 
(i) X represents a bivalent linking group of the formula --R.sup.5 
--L'.sub.n --R.sup.5.sub.p -- where each R.sup.5 can be the same or 
different and each represents an alkylene radical having 1 to about 8 
carbon atoms, such as methylene, hexylene and the like; a phenylene 
radical; or a substituted phenylene radical having 6 to about 9 carbon 
atoms, such as methoxy phenylene; 
(ii) L' represents a bivalent radical selected from oxy, carbonyl, 
carboxamido, carbamoyl, imino, sulfonamido, ureylene, sulfamoyl, sulfinyl 
or sulfonyl; 
(iii) n is an integer of 0 or 1; 
(iv) p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that 
when p is 1 the carbon content of the sum of both R.sup.5 radicals does 
not exceed 14 carbon atoms; 
(v) R.sup.4 represents a hydrogen atom, or an alkyl radical having 1 to 
about 6 carbon atoms; 
(vi) J represents a bivalent radical selected from sulfonyl or carbonyl; 
(vii) q represents an integer of 0 or 1; and 
(viii) m represents an integer of 0, 1 or 2. 
Especially good results are obtained in the above formula when D' is OH, j 
is 2, and Y is a naphthalene nucleus. 
Examples of the ballasted carrier moiety in this highly preferred 
embodiment are disclosed in U.S. Published Patent Application No. B 
351,673; U.S. Pat. No. 3,928,312; French Patent 2,284,140; and German Pat. 
Nos. 2,406,664; 2,613,005; and 2,505,248, the disclosures of which are 
hereby incorporated by reference, and include the following: 
##STR6## 
In other highly preferred embodiments of the invention, the ballasted 
carrier moiety is such that the diffusible azo dye is released as an 
inverse function of development of the silver halide emulsion layer under 
alkaline conditions. This is ordinarily referred to as positive-working 
dye-release chemistry. In one of these embodiments, the ballasted carrier 
moiety can be a group having the formula: 
##STR7## 
wherein: 
Ballast is an organic ballasting radical of such molecular size and 
configuration as to render the compound nondiffusible in a photographic 
element during development in an alkaline processing composition; 
W.sup.2 represents the atoms necessary to complete a benzene nucleus 
(including various substituents thereon); 
R.sup.7 is an alkyl (including substituted alkyl) radical having 1 to about 
4 carbon atoms; 
X' is an alkylene group of 1 to 4 carbon atoms; and 
R.sup.4, J, q and m are as defined above. 
Examples of the ballasted carrier moiety of this formula include the 
following: 
##STR8## 
In a second embodiment of positive-working dye-release chemistry, the 
ballasted carrier moiety can be a group having the formula: 
##STR9## 
wherein: 
Ballast is an organic ballasting radical of such molecular size and 
configuration as to render the compound nondiffusible in a photographic 
element during development in an alkaline processing composition; 
W.sup.1 represents the atoms necessary to complete a quinone nucleus 
(including various substituents thereon); 
r is a positive integer of 1 or 2; 
R.sup.6 is an alkyl (including substituted alkyl) radical having 1 to about 
40 carbon atoms or an aryl (including substituted aryl) radical having 6 
to about 40 carbon atoms; 
k is a positive integer of 1 and 2 and is 2 when R.sup.6 is a radical of 
less than 8 carbon atoms; 
X" is a phenylene or substituted phenylene radical of 6 to 9 carbon atoms; 
and 
R.sup.4, J, q and m are as defined above. 
Examples of the ballasted carrier of this formula include the following: 
##STR10## 
For further details concerning the positive working ballasted carrier 
moieties of the two preceding general formulae, including synthesis 
details, reference is made to U.S. application Ser. No. 775,025 of Chasman 
et al, filed Mar. 7, 1977, the disclosure of which is hereby incorporated 
by reference. 
In a third embodiment of positive-working dye release chemistry, the 
ballasted carrier moiety can be a group having the formula: 
##STR11## 
wherein: 
Ballast, W.sup.2, R.sup.7, X', R.sup.4, J, q and m are as defined above. 
Examples of the ballasted carrier moiety of this formula include the 
following: 
##STR12## 
For further details concerning this ballasted carrier moiety, including 
synthesis details, reference is made to U.S. application Ser. No. 534,966 
of Hinshaw et al, filed Dec. 20, 1974, the disclosure of which is hereby 
incorporated by reference. 
In a fourth embodiment of positive-working dye release chemistry as 
referred to above, the ballasted carrier moiety can be a group having the 
formula: 
##STR13## 
wherein: 
Ballast, W.sup.2, r, R.sup.6, k, X", R.sup.7, J, q and m are as defined 
above; and 
K is OH or a hydrolyzable precursor thereof. 
Examples of the ballasted carrier moiety of this formula include the 
following: 
##STR14## 
For further details concerning this ballasted carrier moiety, including 
synthesis details, reference is made to U.S. Pat. No. 3,980,479 of Fields 
et al, issued Sept. 14, 1976, the disclosure of which is hereby 
incorporated by reference. 
Preferred nondiffusible compounds of our invention can be represented by 
the formula: 
##STR15## 
wherein: 
G is hydroxy or a hydrolyzable ester group having the formula 
##STR16## 
where each R.sup.1 is independently alkyl of 1 to 8 carbon atoms, aryl of 
6 to 12 carbon atoms or a group which together with the 
##STR17## 
is the ballasted carrier moiety; 
D is an electron withdrawing group selected from halogen, nitro, cyano, 
lower perfluoroalkyl, --SO.sub.2 R.sup.8, --SO.sub.2 N(R.sup.9).sub.2 or 
--COOR.sup.9 ; 
E is a strong electron withdrawing group selected from nitro, cyano, lower 
perfluoroalkyl, --SO.sub.2 R.sup.8, --SO.sub.2 N(R.sup.9).sub.2 or 
--COOR.sup.9 ; 
P is --COOR.sup.9, --SO.sub.2 N(R.sup.9).sub.2 or --CON(R.sup.9).sub.2 ; 
y is an integer of 0 to 2; 
R.sub.8 is lower alkyl or lower aryl; 
R.sub.9 is, independently, hydrogen, lower alkyl, lower hydroxyalkyl, lower 
carboxyalkyl, lower aryl, or one of R.sub.9 is a group which together with 
the 
##STR18## 
--SO.sub.2 N-- or --CON-- moiety to which it is attached is a ballasted 
carrier moiety; or both R.sup.9 radicals form a 5- or 6-membered 
heterocyclic ring with the nitrogen atom to which they are attached; 
Q is hydrogen, or a halogen, carboxy, lower alkyl or lower alkoxy 
substituent; and 
at least one of G, D, E or P contains the ballasted carrier moiety. 
Particularly preferred are those compounds of formula VIII where: 
G is hydroxy or a hydrolyzable ester having the formula --OCOR.sup.10 where 
R.sup.10 is alkyl of 1 to 8 carbon atoms or aryl of 6 to 12 carbon atoms; 
D is an electron withdrawing group selected from halogen, cyano, or 
--SO.sub.2 R.sup.8 where R.sup.8 is as defined above; 
E is a strong electron withdrawing group selected from nitro, cyano, 
--SO.sub.2 R.sup.8, or --SO.sub.2 N(R.sup.11).sub.2, where R.sup.8 is as 
defined above and each R.sup.11 is independently hydrogen, lower alkyl, 
lower hydroxyalkyl or lower carboxyalkyl, or together both R.sup.11 
radicals form a 5- or 6-membered heterocyclic ring with the nitrogen atom 
to which they are attached; 
Q is hydrogen, halogen, carboxy, lower alkyl or lower alkoxy; 
P is the ballasted carrier moiety; and 
y is 1. 
An especially preferred ballasted carrier moiety of the type represented by 
formula III, above, for use as P in formula VIII, above, can be 
represented by the structure: 
##STR19## 
wherein: 
Ballast is as previously defined; 
Y' represents the atoms necessary to complete a benzene or naphthalene 
nucleus; 
R.sup.5 is an alkylene radical having 1 to about 8 carbon atoms, a 
phenylene radical, or a substituted phenylene radical having 6 to about 9 
carbon atoms; 
R.sup.4 is a hydrogen atom or an alkyl group having 1 to about 6 carbon 
atoms; 
J is sulfonyl; and 
m is 0 or 1. 
Preferred azo dyes have the structure of formula VIII above, except that D, 
E and P do not contain a ballasted carrier moiety. Particularly preferred 
azo dyes have the structure: 
##STR20## 
wherein: 
G is hydroxy or a hydrolyzable ester having the formula --OCOR.sup.10 where 
R.sup.10 is as defined above; 
D is an electron withdrawing group selected from halogen, cyano, or 
--SO.sub.2 R.sup.8 where R.sup.8 is as defined above; 
E is a strong electron withdrawing group selected from nitro, cyano, 
--SO.sub.2 R.sup.8, or --SO.sub.2 N(R.sup.11).sub.2, R.sup.8 and R.sup.11 
are as defined above; 
Q is hydrogen, halogen, carboxy, lower alkyl or lower alkoxy; 
P is --COOR.sup.8, --SO.sub.2 N(R.sup.11).sub.2 or --CON(R.sup.11).sub.2 
where R.sup.8 and R.sup.11 are as defined above; and 
y is 1. 
Especially preferred nondiffusible azo dye releasing compounds and azo dyes 
of this invention are shown in the following Tables I and II. 
TABLE Ia 
__________________________________________________________________________ 
AZO DYE-RELEASING COMPOUNDS 
##STR21## 
Compound 
Number 
CAR.sup.2 
Attachment.sup.1 
Q D E G 
__________________________________________________________________________ 
1 A 4 H Cl NO.sub.2 OH 
2 A 3 H Cl CN OH 
3 B 3 H Cl NO.sub.2 OH 
4 B 5 2-Cl Cl SO.sub.2 NHC.sub.2 H.sub.5 
OH 
5 B 3 H Cl SO.sub.2 NHC(CH.sub.3).sub.3 
OH 
6 B 3 H Cl SO.sub.2 NHCH.sub.2 COOC.sub.2 H.sub.5 
OH 
7 B 3 H Cl SO.sub.2 NHCH.sub.2 COOH 
OH 
8 D 3 H Cl NO.sub.2 OH 
9 C.sup.1 
3 H Cl NO.sub.2 OH 
10 B 3 H Cl SO.sub.2 NHC.sub.2 H.sub.5 
OH 
11 E 3,5 H Cl NO.sub.2 OCOPh 
12 D 4 H Cl 
##STR22## OH 
13 D 3 H Cl SO.sub.2 N(C.sub.2 H.sub.5).sub.2 
OH 
14 C.sup.2 
4 H Cl CN OH 
15 D 5 2-OCH.sub.3 
Cl SO.sub.2 NHC(CH.sub.3).sub.3 
OH 
16 D 4 H Cl SO.sub.2 NHCH.sub.2 CH.sub.2 OH 
OH 
17 B 4 H Cl SO.sub.2 NHCH(CH.sub.3).sub.2 
OCOCH.sub.3 
18 F 4 H Cl SO.sub.2 NHCH.sub.3 
OCOCH.sub.3 
19 G 5 2-Cl Cl SO.sub.2 NHCH.sub.3 
OCOOCH.sub.2 C.sub.6 H.sub.5 
20 C.sup.3 
3 H Cl SO.sub.2 NHCH(CH.sub.3).sub.2 
OH 
21 C.sup.1 
4 H SO.sub.2 C.sub.6 H.sub.5 
SO.sub.2 C.sub.6 H.sub.5 
OH 
22 H 3 H Cl CN OH 
__________________________________________________________________________ 
table ib 
__________________________________________________________________________ 
AZO DYE-RELEASING COMPOUNDS 
##STR23## 
Compound 
Number CAR.sup.2 
P y Q E D G 
__________________________________________________________________________ 
23 J SO.sub.2 CH.sub.3 
1 H CAR Cl OH 
24 K SO.sub.2 CH.sub.3 
1 H SO.sub.2 NHCH.sub.3 
Cl CAR 
__________________________________________________________________________ 
##STR24## 
TABLE II 
__________________________________________________________________________ 
Dye 
P y Q D G E 
__________________________________________________________________________ 
1 5-SO.sub.2 NH.sub.2 
1 2-Cl 
Cl OCOCH.sub.3 
CN 
2 4-SO.sub.2 NH.sub.2 
1 2-Cl 
Cl OH SO.sub.2 NHC.sub.2 H.sub.5 
3 4-SO.sub.2 NH.sub.2 
1 H Cl OH SO.sub.2 C.sub.2 H.sub.5 
4 4-SO.sub.2 NH.sub.2 
1 H Cl OH SO.sub.2 CH.sub.3 
5 4-SO.sub.2 NH.sub.2 
1 H Cl OH SO.sub.2 NHC.sub.2 H.sub.5 
6 3,5-SO.sub.2 NH.sub.2 
2 H Cl OH SO.sub.2 NHC.sub.2 H.sub.5 
7 3-SO.sub.2 NHCOCH.sub.3 
1 H Cl OH CN 
8 4-SO.sub.2 NH.sub.2 
1 H SO.sub.2 CH.sub.3 
OH SO.sub.2 CH.sub.3 
9 4-SO.sub.2 NH.sub.2 
1 H COOH OH COOH 
10 3-COOCH.sub.3 2 H Cl OH CN 
5-SO.sub.2 NH.sub.2 
11 3-SO.sub.2 NH.sub.2 
2 H Cl OH CN 
5-COOH 
12 4-SO.sub.2 NH.sub.2 
1 H CN OH CN 
13 
##STR25## 1 2-Cl 
Cl OH SO.sub.2 NH(CH.sub.2).sub.2 NHSO.sub. 
CH.sub.3 
__________________________________________________________________________ 
dyes of this invention can be prepared by known techniques such as 
described in Fierz-David and Blangley, Process of Dye Chemistry, 
Intersciences Publishers, Inc., 1949. 
A preferred procedure for preparing the 2-halo-6-sulfamoylphenol 
intermediates used to prepared the dyes in compounds such as numbers 2, 5, 
6 and 13 is described in the copending application of our coworkers Stern 
and Lestina U.S. Patent application Ser. No. 850,178, filed Nov. 10, 1977, 
and entitled 2-Halo-6-Sulfamylphenols And A Process For Their Preparation. 
Some of the dyes in which both D and E are strong electron-withdrawing 
groups cannot be made in the conventional manner, because the group 
deactivates the phenol so that it will not couple with diazonium salts. In 
these cases the azophenol is prepared by reacting the appropriate 
arylazomalonaldehyde derivative (Chem. Ber. 97, 96-109, 1964) with the 
appropriate 1,3-disubstituted acetone. For example, 
##STR26## 
The non-diffusible azo dye-releasing compounds of this invention can be 
prepared by reacting an appropriate derivative of the dye with an 
appropriate derivative of the desired carrier by procedures described in 
the patents and applications referred to above showing specific classes of 
carriers. 
Photographic color images can be prepared with elements of this invention 
by treating the element to form an imagewise distribution of diffusible 
azo dye as a function of the imagewise exposure of the silver halide 
emulsion. Images can be formed employing the imagewise released diffusible 
dye, or the remaining imagewise distribution of nondiffusible compound, or 
both. The released diffusible dye can be allowed to diffuse to a receiver 
sheet or layer to form a transfer image. Alternatively, it can merely be 
removed from the element and not made further use of. Whether the 
imagewise pattern of diffusible dye is used to form an image or not, the 
remaining nondiffusible compound can be used as a retained image in the 
layer in which it was initially coated. This could include removing 
residual silver and silver halide by any conventional procedure known to 
those skilled in the art, such as a bleach bath followed by a fix bath, a 
bleach-fix bath, etc. In the event that the azo dye in the nondiffusible 
compound is a shifted dye, the process for forming a retained image would 
include the step of converting it to the desired dye, for example, by 
hydrolysis. Alternatively, once the initially formed diffusible dye is 
removed from the element, the residual nondiffusible compound can be 
employed to form a transfer image by oxidizing it (e.g. by cross 
oxidation, or otherwise) to yield a second distribution of diffusible dye 
which can be transferred to a suitable receiver sheet or layer. 
A process for producing a photographic image in color according to our 
invention comprises: 
(a) treating an imagewise-exposed photographic element as described above 
with an alkaline processing composition in the presence of a silver halide 
developing agent to effect development of each of the exposed silver 
halide emulsion layers, 
(b) the dye-releasing compound then releasing the diffusible azo dye as 
described above imagewise as a function of the development of each of the 
silver halide emulsion layers; and 
(c) at least a portion of the imagewise distribution of the azo dye 
diffusing out of the layer in which it is coated. 
In a preferred embodiment of our invention, a process for producing a 
photographic transfer image in color according to our invention comprises: 
(a) treating an imagewise-exposed photographic element as described above 
wherein the ballasted carrier moiety has the formula: 
##STR27## 
D', Y, L and j being defined as above; with an alkaline processing 
composition in the presence of a silver halide developing agent to effect 
development of each of the exposed silver halide emulsion layers, thereby 
oxidizing the developing agent; 
(b) the oxidized developing agent thereby cross-oxidizing the dye-releasing 
compound; 
(c) the cross-oxidized dye-releasing compound then cleaving as a result of 
alkaline hydrolysis to release the diffusible azo dye imagewise as a 
function of the imagewise exposure of each of the silver halide emulsion 
layers; and 
(d) at least a portion of the imagewise distribution of the azo dye 
diffusing to a dye image-receiving layer. 
After processing the photographic element described above, there remains in 
it after transfer has taken place an imagewise distribution of azo dye in 
addition to developed silver. A color image comprising residual 
nondiffusible compound may be obtained in this element if the residual 
silver and silver halide are removed by any conventional manner well known 
to those skilled in the photographic art, such as bleach bath followed by 
a fix bath, a bleach-fix bath, etc. The imagewise distribution of azo dye 
may also diffuse out of the element into these baths, if desired, rather 
than to an image-receiving element. 
The photographic element in the above-described process can be treated with 
an alkaline processing composition to effect or initiate development in 
any manner. A preferred method for applying processing composition is by 
use of a rupturable container or pod which contains the composition. In 
general, the processing composition employed in this invention contains 
the development agent for development, although the composition could also 
just be an alkaline solution where the developer is incorporated in the 
photographic element, image-receiving element or process sheet, in which 
case the alkaline solution serves to activate the incorporated developer. 
A photographic film unit which can be processed in accordance with this 
invention is adapted to be processed by passing the unit between a pair of 
juxtaposed pressure-applying members, such as would be found in a camera 
designed for in-camera processing, and comprises: 
(1) a photographic element as described above; 
(2) a dye image-receiving layer; and 
(3) means for discharging an alkaline processing composition within the 
film unit, such as a rupturable container which is adapted to be 
positioned during processing of the film unit so that a compressive force 
applied to the container by the pressure-applying members will effect a 
discharge of the container's contents within the film unit; 
the film unit containing a silver halide developing agent. 
The dye image-receiving layer in the above-described film unit can be 
located on a separate support adapted to be superposed on the photographic 
element after exposure thereof. Such image-receiving elements are 
generally disclosed, for example, in U.S. Pat. No. 3,362,819. When the 
means for discharging the processing composition is a rupturable 
container, it is usually positioned in relation to the photographic 
element and the image-receiving element so that a compressive force 
applied to the container by pressure-applying members, such as would be 
found in a typical camera used for in-camera processing, will effect a 
discharge of the container's contents between the image-receiving element 
and the outermost layer of the photographic element. After processing, the 
dye image-receiving element is separated from the photographic element. 
The dye image-receiving layer in the above-described film unit can also be 
located integral with the photographic element between the support and the 
lowermost photosensitive silver halide emulsion layer. One useful format 
for integral receiver-negative photographic elements is disclosed in 
Belgian Pat. No. 757,960. In such an embodiment, the support for the 
photographic element is transparent and is coated with an image-receiving 
layer, a substantially opaque light-reflective layer, e.g., TiO.sub.2, and 
then the photosensitive layer or layers described above. After exposure of 
the photographic element, a rupturable container containing an alkaline 
processing composition and an opaque process sheet are brought into 
superposed position. Pressure-applying members in the camera rupture the 
container and spread processing composition over the photographic element 
as the film unit is withdrawn from the camera. The processing composition 
develops each exposed silver halide emulsion layer and dye images are 
formed as a function of development which diffuse to the image-receiving 
layer to provide a positive, light-reading imge which is viewed through 
the transparent support on the opaque reflecting layer background. For 
other details concerning the format of this particular integral film unit, 
reference is made to the above-mentioned Belgian Pat. No. 757,960. 
Another format for integral negative-receiver photographic elements in 
which the present invention can be employed is disclosed in Belgian Pat. 
No. 757,959. In this embodiment, the support for the photographic element 
is transparent and is coated with the image-receiving layer, a 
substantially opaque, light-reflective layer and the photosensitive layer 
or layers described above. A rupturable container containing an alkaline 
processing composition and an opacifier is positioned adjacent the top 
layer and a transparent top sheet which has thereon a neutralizing layer 
and a timing layer. The film unit is placed in a camera, exposed through 
the transparent top sheet and then passed through a pair of 
pressure-applying members in the camera as it is being removed therefrom. 
The pressure-applying members rupture the container and spread processing 
composition and opacifier over the negative portion of the film unit to 
render it light-insensitive. The processing composition develops each 
silver halide layer and dye images are formed as a result of development 
which diffuse to the image-receiving layer to provide a positive, 
right-reading image which is viewed through the transparent support on the 
opaque reflecting layer background. For further details concerning the 
format of this particular integral film unit, reference is made to the 
above-mentioned Belgian Pat. No. 757,959. 
Still other useful integral formats in which this invention can be employed 
are described in U.S. Pat. Nos. 3,415,644; 3,415,645; 3,415,646; 
3,647,437; and 3,635,707. In most of these formats, a photosensitive 
silver halide emulsion is coated on an opaque support and a dye 
image-receiving layer is located on a separate transparent support 
superposed over the layer outermost from the opaque support. In addition, 
this transparent support also preferably contains a neutralizing layer and 
a timing layer underneath the dye image-receiving layer. 
Another embodiment of the invention uses the image-reversing technique 
disclosed in British Pat. No. 904,364, page 19, lines 1 through 41. In 
this process, the dye-releasing compounds are used in combination with 
physical development nuclei in a nuclei layer contiguous to the 
photosensitive silver halide negative emulsion layer. The film unit 
contains a silver halide solvent, preferably in a rupturable container 
with the alkaline processing composition. 
The film unit or assembly used in the present invention may be used to 
produce positive images in single- or multicolors. In a three-color 
system, each silver halide emulsion layer of the film assembly will have 
associated therewith a dye-releasing compound which releases a dye 
possessing a predominant spectral absorption within the region of the 
visible spectrum to which said silver halide emulsion is sensitive, i.e., 
the blue-sensitive silver halide emulsion layer will have a yellow or 
yellow-forming dye-releaser associated therewith, the green-sensitive 
silver halide emulsion layer will have a magenta or magenta-forming 
dye-releaser associated therewith, and the red-sensitive silver halide 
emulsion layer will have a cyan or cyan-forming dye-releaser associated 
therewith, the yellow dye-releasers being a compound in accordance with 
the present invention. The dye-releaser associated with each silver halide 
emulsion layer may be contained either in the silver halide emulsion layer 
itself or in a layer contiguous to the silver halide emulsion layer. 
The concentration of the dye-releasing compounds that are employed in the 
present invention may be varied over a wide range, depending upon the 
particular compound employed and the results which are desired. For 
example, the dye-releasers of the present invention may be coated in 
layers by using coating solutions containing between about 0.5 and about 8 
percent by weight of the dye-releaser distributed in a hydrophilic 
film-forming natural material or synthetic polymer, such as gelatin, 
polyvinyl alcohol, etc., which is adapted to be permeated by aqueous 
alkaline processing composition. 
Depending upon which ballasted carrier moiety is used in the present 
invention, a variety of silver halide developing agents can be employed. 
In certain embodiments of the invention, any silver halide developing 
agent can be employed as long as it cross-oxidizes with the dye-releasers 
described herein. The developer may be employed in the photosensitive 
element to be activated by the alkaline processing composition. Specific 
examples of developers which can be employed in this invention include: 
N-methylaminophenol 
Phenidone (1-phenyl-3-pyrazolidone) 
Dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidone) 
aminophenols 
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 
N,n-diethyl-p-phenylenediamine 
N,n,n',n'-tetramethyl-p-phenylenediamine 
3-methyl-N,N-diethyl-p-phenylenediamine 
3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc. 
The non-chromogenic developers in this list are preferred, however, since 
they avoid any propensity of staining the dye image-receiving layer. 
In one of the preferred embodiments of the invention, the silver halide 
developer employed in the process becomes oxidized upon development and 
reduces silver halide to silver metal. The oxidized developer then 
cross-oxidizes the dye-releasing compound. The product of cross-oxidation 
then undergoes alkaline hydrolysis, thus releasing an imagewise 
distribution of diffusible azo dye which then diffuses to the receiving 
layer to provide the dye image. The diffusible moiety is transferrable in 
alkaline processing composition either by virtue of its self-diffusivity 
or by having attached to it one or more solubilizing groups, for example, 
a carboxy, sulpho, sulphonamido, hydroxy or morpholino group. 
In using the dye-releasing compounds according to the invention which 
produce diffusible dye images as a function of development, either 
conventional negative-working or direct-positive silver halide emulsions 
may be employed. If the silver halide emulsion employed is a 
direct-positive silver halide emulsion, such as an internal-image emulsion 
designed for use in the internal image reversal process or a fogged, 
direct-positive emulsion such as a solarizing emulsion. which is 
developable in unexposed areas, a positive image will be obtained on the 
dye image-receiving layer in those embodiments in which dye is released as 
a direct function of development. After exposure of the film unit, the 
alkaline processing composition permeates the various layers to initiate 
development of the exposed photosensitive silver halide emulsion layers. 
The developing agent present in the film unit develops each of the silver 
halide emulsion layers in the unexposed areas (since the silver halide 
emulsions are direct-positive ones), thus causing the developing agent to 
become oxidized imagewise corresponding to the unexposed areas of the 
direct-positive silver halide emulsion layers. The oxidized developing 
agent then cross-oxidizes the dye-releasing compounds and the oxidized 
form of the compounds then undergoes a base-catalyzed reaction to release 
the dyes imagewise as a function of the imagewise exposure of each of the 
silver halide emulsion layers. At least a portion of the imagewise 
distributions of diffusible dyes diffuse to the image-receiving layer to 
form a positive image of the original subject. After being contacted by 
the alkaline processing composition, a pH-lowering layer in the film unit 
or image-receiving unit lowers the pH of the film unit or image receiver 
to stabilize the image. 
Internal-image silver halide emulsions useful in this invention are 
described more fully in the November 1976 edition of Research Disclosure, 
pages 76 through 79, the disclosure of which is hereby incorporated by 
reference. 
The various silver halide emulsion layers of a color film assembly employed 
in this invention can be disposed in the usual order, i.e., the 
blue-sensitive silver halide emulsion layer first with respect to the 
exposure side, followed by the green-sensitive and red-sensitive silver 
halide emulsion layers. If desired, a yellow dye layer or a yellow 
colloidal silver layer can be present between the blue-sensitive and 
green-sensitive silver halide emulsion layers for absorbing or filtering 
blue radiation that may be transmitted through the blue-sensitive layer. 
If desired, the selectively sensitized silver halide emulsion layers can 
be disposed in a different order, e.g., the blue-sensitive layer first 
with respect to the exposure side, followed by the red-sensitive and 
green-sensitive layers. 
The rupturable container employed in certain embodiments of this invention 
can be of the type disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 
2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In general, such 
containers comprise a rectangular sheet of fluid- and air-impervious 
material folded longitudinally upon itself to form two walls which are 
sealed to one another along their longitudinal and end margins to form a 
cavity in which processing solution is contained. 
Generally speaking, except where noted otherwise, the silver halide 
emulsion layers employed in the invention comprise photosensitive silver 
halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; 
the dye-releasers are dispersed in an aqueous alkaline solution-permeable 
polymeric binder, such as gelatin, as a separate layer about 0.2 to 7 
microns in thickness; and the alkaline solution-permeable polymeric 
interlayers, e.g., gelatin, are about 0.2 to 5 microns in thickness. Of 
course, these thicknesses are approximate only and can be modified 
according to the product desired. 
Scavengers for oxidized developing agent can be employed in various 
interlayers of the photographic elements of the invention. Suitable 
materials are disclosed on page 83 of the November 1976 edition of 
Research Disclosure, the disclosure of which is hereby incorporated by 
reference. 
Any material can be employed as the image-receiving layer in this invention 
as long as the desired function of mordanting or otherwise fixing the dye 
images will be obtained. The particular material chosen will, of course, 
depend upon the dye to be mordanted. Suitable materials are disclosed on 
pages 80 through 82 of the November 1976 edition of Research Disclosure, 
the disclosure of which is hereby incorporated by reference. 
Use of a pH-lowering material in the film units employed in this invention 
will usually increase the stability of the transferred image. Generally, 
the pH-lowering material will effect a reduction in the pH of the image 
layer from about 13 or 14 to at least 11 and preferably 5 to 8 within a 
short time after imbibition. Suitable materials and their functioning are 
disclosed on pages 22 and 23 of the July 1974 edition of Research 
Disclosure and pages 35 through 37 of the July 1975 edition of Research 
Disclosure, the disclosures of which are hereby incorporated by reference. 
A timing or inert spacer layer can be employed in the practice of this 
invention over the pH-lowering layer which "times" or controls the pH 
reduction as a function of the rate at which alkali diffuses through the 
inert spacer layer. Examples of such timing layers and their functioning 
are disclosed in the Research Disclosure articles mentioned in the 
paragraph above concerning pH-lowering layers. 
The alkaline processing composition employed in this invention is the 
conventional aqueous solution of an alkaline material, e.g., alkali metal 
hydroxides or carbonates such as sodium hydroxide, sodium carbonate or an 
amine such as diethylamine, preferably processing a pH in excess of 11, 
and preferably containing a developing agent as described previously. 
Suitable materials and addenda frequently added to such compositions are 
disclosed on pages 79 and 80 of the November 1976 edition of Research 
Disclosure, the disclosure of which is hereby incorporated by reference. 
While the alkaline processing composition used in this invention can be 
employed in a rupturable container, as described previously, to 
conveniently facilitate the introduction of processing composition into 
the film unit, other methods of inserting processing composition into the 
film unit could also be employed, e.g., interjecting processing solution 
with communicating members similar to hypodermic syringes which are 
attached either to a camera or camera cartridge. The processing 
composition may also be applied by means of a swab or by dipping in a 
bath, if so desired. 
The alkaline solution-permeable, substantially opaque, light-reflective 
layer employed in certain embodiments of photographic film units used in 
this invention are described more fully in the November 1976 edition of 
Research Disclosure, page 82, the disclosure of which is hereby 
incorporated by reference. 
The supports for the photographic elements used in this invention can be 
any material as long as it does not deleteriously affect the photographic 
properties of the film unit and is dimensionally stable. Typical flexible 
sheet materials are described on page 85 of the November 1976 edition of 
Research Disclosure, the disclosure of which is hereby incorporated by 
reference. 
While the invention has been described with reference to layers of silver 
halide emulsions and dye image-providing materials, dotwise coating, such 
as would be obtained using a gravure printing technique, could also be 
employed. In this technique, small dots of blue-, green- and red-sensitive 
emulsions have associated therewith, respectively, dots of yellow, magenta 
and cyan color-providing substances. After development, the transferred 
dyes would tend to fuse together into a continuous tone. 
The silver halide emulsions useful in this invention, both negative-working 
and direct-positive ones, are well known to those skilled in the art and 
are described in Product Licensing Index, Volume 92, December 1971, 
publication 9232, page 107, paragraph I, "Emulsion types"; they may be 
chemically and spectrally sensitized as described on page 107, paragraph 
III, "Chemical sensitization", and pages 108 and 109, paragraph XV, 
"Spectral sensitization", of the above article; they can be protected 
against the production of fog and can be stabilized against loss of 
sensitivity during keeping by employing the materials described on page 
107, paragraph V, "Antifoggants and stabilizers", of the above article; 
they can contain development modifiers, hardeners, and coating aids as 
described on pages 107 and 108, paragraph IV, "Development modifiers"; 
paragraph VII, "Hardeners"; and paragraph XII, "Coating aids", of the 
above article; they and other layers in the photographic elements used in 
this invention can contain plasticizers, vehicles and filter dyes 
described on page 108, paragraph XI, "Plasticizers and lubricants", and 
paragraph VIII, "Vehicles", and page 109, paragraph XVI, "Absorbing and 
filter dyes", of the above article; they and other layers in the 
photographic elements used in this invention may contain addenda which are 
incorporated by using the procedures described on page 109, paragraph 
XVII, "Methods of addition" , of the above article; and they can be coated 
by using the various techniques described on page 109, paragraph XVIII, 
"Coating procedures", of the above article, the disclosures of which are 
hereby incorporated by reference. 
The term "nondiffusing" used herein has the meaning commonly applied to the 
term in photography and denotes materials that for all practical purposes 
do not migrate nor wander through organic colloid layers such as gelatin 
in an alkaline medium, in the photographic elements of the invention and 
preferably when processed in a medium having a pH of 11 or greater. The 
same meaning is to be attached to the term "immobile". The term 
"diffusible" as applied to the materials of this invention has the 
converse meaning and denotes materials having the property of diffusing 
effectively through the colloid layers of the photographic elements in an 
alkaline medium in the presence of "nondiffusing" materials. "Mobile" has 
the same meaning. 
The term "associated therewith" as used herein is intended to mean that the 
materials can be in either the same or different layers so long as the 
materials are accessible to one another.

The following examples further illustrate this invention. 
EXAMPLE 1 
Synthesis of Compound 1 (Table 1) 
##STR28## 
To a slurry of 3.0 g ground sodium carbonate in 25 ml dry dimethyl 
sulfoxide, under nitrogen, was added 
2-chloro-4-(4-fluorosulfonyl-phenylazo)-6-nitrophenol (1.80 g, 5 mmol) 
followed by the addition of 
4-amino-N-[4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide (2.55 g, 
5.2 mmol). The reaction mixture was heated to 90.degree. C. After 2 hours 
an additional 3.0 g ground sodium carbonate was added and the reaction 
mixture stirred at 90.degree. C. overnight. After cooling to room 
temperature, the reaction mixture was poured over ice and hydrochloric 
acid resulting in a green precipitate, which was filtered off, washed with 
water, and then air dried. This material was dissolved in 80 ml 
tetrahydrofuran, slurried with anhydrous magnesium sulfate, the suspension 
filtered, and the filtrate poured into 800 ml hexane. The resulting 
precipitate was filtered off, washed with hexane, and air dried. The yield 
was 2.73 g (66%). 
The dye was purified by column chromatography from 70 ml chloroform on 
silica gel. Elution with 10% hexane in chloroform removed a first 
component, whereupon elution with chloroform gave the purified product, 
m.p. 148.degree.-50.degree. C., .epsilon.=3.22.times.10.sup.4. 
Preparation of Intermediates 
4-Amino-N-[4-(2,4-di-t-pentylphenoxy)-butyl]-1-hydroxy-2-naphthamide 
1-Hydroxy-N-[4-(2,4-di-t-pentylphenoxy)-butyl]-2-naphthamide was coupled 
with a diazotized p-anisidine 
##STR29## 
The azo group of the compound thus prepared was then reduced with sodium 
dithionite (Na.sub.2 S.sub.2 O.sub.4) to the corresponding amine. 
2-Chloro-4-(4-fluorosulfonylphenylazo)-6-nitrophenol 
Solid 2-Chloro-4-(4-fluorosulfonylphenylazo)phenol (7.5 g. 23 mmol) was 
added rapidly to a vigorously stirred mixture of 15 ml concentrated nitric 
acid and 15 ml concentrated sulfuric acid, cooled to -30.degree. C. After 
13 minutes of stirring, the reaction mixture was poured into 400 ml ice 
water with vigorous stirring. The resulting precipitate was filtered off 
and washed with water. During drying on the funnel the solid softened and 
became tarry. When the tar was dissolved in acetic acid and then carefully 
and slowly diluted with water, a fine precipitate separated and was 
filtered off. This process was repeated with the filtrate until the 
resulting precipitate no longer separated as a solid. The collected solids 
were combined and air dried. Yield: 3.1 g, (37%) m.p. 
129.degree.-133.degree. C. 
2-Chloro-4-(4-fluorosulfonylphenylazo)phenol 
Sulfanilyl fluoride (17.5 g, 0.1 mole) was dissolved in 75 ml warn 
saturated methanolic HCl, and the resulting solution was cooled in a 
methanol-ice bath. Sodium nitrite (7.0 g, 0.1 mole), dissolved in 25 ml 
water was then added dropwise, and the solution stirred 5 minutes more. 
The diazonium salt solution was then added dropwise to a cold (cooled in 
an ice bath) solution of o-chlorophenol (12.8 g, 0.099 mole) dissolved in 
150 ml pyridine. The reaction mixture was stirred an additional 15 minutes 
and then poured over ice and hydrochloric acid. The resulting precipitate 
was filtered off, washed with water, and air dried. The yield was 20.0 g 
(64%), m.p. 133.degree.-134.degree. C. 
EXAMPLE 2 
Synthesis of Compound 2 (Table I) 
##STR30## 
This compound was prepared from 
2-chloro-6-cyano-4-(3-fluorosulfonylphenylazo)phenyl acetate by the method 
of Example 1. The crude brown product was purified by column 
chromatography. It was added to a silica gel column in chloroform, the 
components separated with 5% acetone in chloroform and the purified dye 
eluted with acetone. The yield, after evaporation of the solvent was 17%, 
m.p. 183.degree.-186.degree. C. .epsilon.=3.1.times.10.sup.4. 
Preparation of Intermediates 
2-Chloro-6-cyano-4-(3-fluorosulfonylphenylazo)phenyl acetate 
3-Chloro-5-(3-fluorosulfonylphenylazo)-2-hydroxybenzaldehyde oxime (22.5 g, 
0.063 mol) was added to 150 ml acetic anhydride and heated to 95.degree. 
C. Sodium acetate (3.0 g) was added. After 21/2 hours, the reaction 
mixture was poured into 750 ml water and stirred at room temperature until 
anhydride fully hydrolysed. The resulting precipitate was filtered off. 
The solids which became gummy on standing were dissolved in 75 ml 
chloroform and poured onto a silica gel column. Elution with 10% hexane in 
chloroform gave the desired dye as the first component. Removal of the 
solvents under reduced pressure gave an oil which hardened on standing but 
did not crystallize. Yield: 16.8 g (70%). 
3-Chloro-5-(3-fluorosulfonylphenylazo)-2-hydroxybenzaldehyde oxime 
3-Chloro-5-(3-fluorosulfonylphenylazo)-2-hydroxy-benzaldehyde (23.8 g, 0.07 
mol) was added to 250 ml ethanol, followed by hyroxylamine hydrochloride 
(5.04 g, 0.072 mol) and sodium hydroxide (2.88 g, 0.072 mol). The reaction 
was brought to reflux for 30 minutes and then cooled to room temperature. 
The mixture was then poured into ice and hydrochloric acid, resulting in 
the formation of a precipitate which was filtered off, washed with water, 
and dried in a vacuum oven (55.degree. C.). The yield was 22.5 g (90%). 
3-Chloro-5-(3-fluorosulfonylphenylazo)-2-hydroxy benzaldehyde 
m-Aminobenzenesulfonyl fluoride hydrochloride (21.1 g, 0.099 mol) was 
slurried in hot 10% HCl (300 ml) and then cooled to 0.degree. C. Sodium 
nitrite (7.0 g, 0.1 mol) was dissolved in 30 ml water and added dropwise 
to the acidic solution. Vigorous stirring was required to prevent the 
slurry from coagulating. The diazonium slurry was then added slowly to 500 
ml of pyridine containing 3-chloro-2-hydroxy-benzaldehyde (16.0 g, 0.10 
mol) at 0.degree. C. The mixture was stirred 30 minutes and then slowly 
added to 1500 ml ice and hydrochloric acid. The resulting precipitate 
coagulated into one lump. The liquid was decanted off and the remaining 
tarry solid crushed and slurried in 50% HCl. The resulting solid was 
filtered off, washed with water and air dried, (21.1 g). Upon standing 72 
hours, the decanted solution yielded an additional 2.8 g. Yield: 23.8 g 
(70%). 
m-Aminobenzenesulfonyl fluoride hydrochloride 
m-Nitrobenzenesulfonyl fluoride (41.0 g, 0.20 mol) was dissolved in 200 ml 
dr tetrahydrofuran, Pd/carbon catalyst added, and the mixture was shaken 
under hydrogen for 6 hours at room temperature. The solution was filtered 
and the solvent removed under reduced pressure, resulting in an oil. The 
oil was dissolved in benzene into which dry halogen chloride gas was 
bubbled. The resulting precipitate was filtered off, washed with 
additional benzene and dried in a vacuum oven (55.degree. C.). The yield 
was 42.1 g (100%), m.p. 198.degree.-199.degree. C. 
3-Chloro-2-hydroxybenzaldehyde 
A sodium hydroxide solution (266 g, 6.65 mol in 1000 ml water) in a 3000 ml 
round bottom flask, equipped with a mechanical stirrer, addition funnel 
(250 ml), and a reflux condenser was warmed to 60.degree. C. 
o-Chlorophenol (126 g, 0.98 mol) was added, dissolving instantly. 
Chloroform (262 g, 2.20 mol) was then introduced slowly over a one-hour 
period. After stirring at 60.degree. C. for an additional two hours, the 
temperature was raised to 80.degree. C. for sixteen hours. The excess 
chloroform was then allowed to distill off, the reaction acidified with 6 
N sulfuric acid, and the mixture steam distilled. Six liters of distillate 
were extracted with ether, the ethereal solution dried with MgSO.sub.4, 
the slurry filtered, and the solvent evaporated under reduced pressure. A 
yellow oil composed of both the desired product and 
3-chloro-4-hydroxybenzaldehyde remained. Pouring the oil into 500 ml of 
vigorously stirred hexane generated a white precipitate of 
3-chloro-4-hydroxybenzaldehyde which was filtered off. Yield: 8%. The 
hexane filtrate was evaporated under reduced pressure yielding an oil 
which crystallized upon standing at room temperature for 24 hours. The 
yield of 3-chloro-2-hydroxybenzaldehyde was 8.01 g (5%), m.p. 
51.degree.-53.degree. C. 
EXAMPLE 3 
Dyes released from compounds of Table I and dyes of Table II were tested 
for absorption and light stability. 
Each dye was incorporated in a viscous solution, the composition of which 
was per liter: 5.times.10.sup.-3 moles dye, 20 g sodium hydroxide (0.5 M) 
and 30 g hydroxyethylcellulose. The solution was spread between a 
polyester film cover sheet and a receiving element containing a mixture of 
gelatin and a mordant, 
poly[styrene-co-N-vinylbenzyl-N-benzyl-N,N-dimethylammonium 
sulfate-co-divinylbenzene], each at 2.2 g/m.sup.2, the mixture coated as a 
latex on a polyester support. 
The sandwich formed by the cover sheet, the viscous dye solution and the 
receiving element was passed between a pair of juxtaposed pressure rollers 
set so that the viscous dye solution was 0.1, 0.2 and 0.4 .mu.m thick on 
separate samples. After a 2-minute transfer time, the laminate was peeled 
apart and the receiving element washed and dried. Actual surface pH 
measurements have shown the final pH to be about 8. The three samples of 
the receiving element offer a choice of 3 densities, one of which was 
selected for spectra and fading tests. 
Table III shows absorption and light stability data for the dyes released 
from the compounds of Table I, and Table IV shows the same data for the 
dyes of Table II. In Table III, Z represents the portion of the carrier 
remaining on the dye after release. 
The hue of the dye is represented by the wavelength of maximum optical 
density (.lambda..sub.max) of the absorption spectrum and the "half band 
width" (1/2 B.W.) which is the width of the spectrum band at one-half of 
the density of the peak at .lambda..sub.max. 
Light stability was determined by exposure to a "simulated average northern 
skylight" test for 21 days: a high intensity 6000 w xenon arc lamp unit 
irradiating the sample with 5280 lux at 21.degree. C. and 45% relative 
humidity. The optical density was measured at .lambda..sub.max both before 
(D.sub.o) and after (D) exposure. 
TABLE III 
______________________________________ 
Dye 
From Absorption Light Stability 
Cpd. .lambda.max 
1/2 BW D 
No. Residue of CAR (nm) (nm) D.sub.o 
D Loss 
______________________________________ 
1 4-SO.sub.2 NH.sub.2 
424 118 1.06 0.86 0.20 
2 3-SO.sub.2 NHCOCH.sub.3 
440 143* 1.55 1.51 0.04 
3,8,9 
3-SO.sub.2 NH.sub.2 
418 117 0.93 0.81 0.12 
4 5-SO.sub.2 NH.sub.2 
446 109 1.48 1.36 0.12 
6 3-SO.sub.2 NH.sub.2 
437 100 1.73 1.51 0.22 
7 3-SO.sub.2 NH.sub.2 
439 107 1.51 1.34 0.17 
11 3,5-[-SO.sub.2 NH(CH.sub.2).sub.3 - 
442 116 1.88 1.48 0.40 
SO.sub.2 NH.sub.2 ].sub.2 
12 4-SO.sub.2 NH.sub.2 
461 101 1.22 1.13 .09 
13 3-SO.sub.2 NH.sub.2 
454 95 1.86 1.73 .13 
14 4-SO.sub.2 NH--.sub.m C.sub.6 H.sub.4 - 
441 &gt;150** 
1.31 1.24 .07 
SO.sub.2 NH.sub.2 
15 5-SO.sub.2 NH.sub.2 
443 109 1.70 1.59 .11 
21 4-SO.sub.2 NH.sub.2 
420 145** 
1.85 1.62 .23 
______________________________________ 
*There is a secondary absorption peak in ultraviolet which does not affec 
the visible color but does extend 1/2 B.W. 
**Estimated by extrapolation of a portion of the absorption curve below 
400 nm which was off the scale. 
TABLE IV 
______________________________________ 
Absorption 
(Unblocked 
Dye) Light 
Dye 1/4 Stability Density 
No. max (nm) BW D.sub.o 
D Loss 
______________________________________ 
1 452 109 1.52 1.17 0.35 
2 456 116 0.86 0.78 0.08 
3 446 103 0.95 0.84 0.11 
4 438 100 1.33 1.28 0.05 
5 444 107 1.02 0.93 0.09 
6 447 105 0.86 0.79 0.07 
7 (See Table III, Dye from Compound No. 2) 
8 418 &gt;150* 2.00 1.71 .29 
9 386 110* 1.97 1.74 .23 
11 440 101 1.62 1.52 .10 
12 383 &gt;150* 1.76 1.56 .20 
13 440 108 1.23 1.06 .17 
______________________________________ 
*Estimated by extrapolation of a portion of the absorption curve below 40 
nm which was off the scale. 
EXAMPLE 4 
An integral multicolor photosensitive element was prepared by coating the 
following layers in the order recited on a transparent poly(ethylene 
terephthalate) film support. Coverages are shown in parentheses and are in 
g/m.sup.2 unless specified otherwise: 
1. image-receiving layer of a latex of 
poly[styrene-co-N-vinylbenzyl-N-benzyl-N-benzyl-N,N-dimethylammonium 
sulfate-co-divinylbenzene] (2.2) and gelatin (1.1); 
2. reflecting layer of titanium dioxide (16) and gelatin (2.6); 
3. opaque layer of carbon black (1.9) and gelatin (3.3); 
4. cyan dye-releasing compound (0.59) having the formula: 
##STR31## 
and gelatin (1.1); 
5. red-sensitive, direct positive internal-image gelatin-silver bromide 
emulsion (1.3 silver; 1.3 gelatin), potassium 
2-octadecylhydroquinone-5-sulfonate (16 g/mole silver) and nucleating 
agent 1-p-formylhydrazinophenyl-3-phenyl-2-thiourea (3.8 mg/mole silver); 
6. interlayer of gelatin (1.6) and 2,5-di-sec-dodecylhydroquinone (1.3); 
7. magenta dye-releasing compound (0.54) having the formula: 
##STR32## 
and gelatin (1.2); 
8. green-sensitive, direct positive internal-image gelatin-silver bromide 
emulsion (1.25 silver, 1.3 gelatin), potassium 
2-octadecylhydroquinone-5-sulfonate (16 g/mole silver) and nucleating 
agents 
1-acetyl-2{4-[5-amino-2-(2,4-di-t-pentylphenoxy)benzamido]phenyl}hydrazine 
and 1-formylhydrazinophenyl-3-phenyl-2-thiourea (34 mg and 2.7 mg/mole 
silver, respectively); 
9. interlayer of gelatin (1.6) and 2,5-di-sec-dodecylhydroquinone (1.3); 
10. yellow dye-releasing compound 22 (0.65) having the formula: 
##STR33## 
and gelatin (1.45); 
11. blue-sensitive internal-image gelatin-silver bromide emulsion (1.25 
silver, 1.3 gelatin), potassium 2-octadecylhydroquinone-2-sulfonate (16 
g/mole silver) and nucleating agents 
1-acetyl-2-{4-[5-amino-2-(2,4-di-t-pentylphenoxy)benzamido]phenyl}hydrazin 
e and 1-p-formylhydrazinophenyl-3-phenyl-2-thiourea (24 mg and 2.7 mg/mole 
silver, respectively); 
12. overcoat of gelatin (0.9) and 2,5-didoceylhydroquinone (0.11). 
The above photosensitive element was then exposed to a tungsten light 
source through a graduated-density multicolor test object. A processing 
composition in a pod is spread between each photosensitive element and a 
processing cover sheet by passing the transfer "sandwich" between a pair 
of juxtaposed pressure rollers. The sample was maintained at 23.degree. C. 
during processing. The processing composition and the cover sheet are 
described in Example 2 of Ducharme and Hannie, U.S. Ser. No. 676,947, 
filed Apr. 14, 1976. 
After about 3 hours sensitometric curves were obtained by reflection 
densitometry with the following results: 
______________________________________ 
Maximum Density Minimum Density 
Red Green Blue Red Green Blue 
______________________________________ 
2.10 2.16 2.27 0.20 0.24 0.30 
______________________________________ 
This invention has been described in detail with particular reference to 
preferred embodiments thereof, but it will be understood that variations 
and modifications can be effected within the spirit and scope of the 
invention.