COLOR-FORMING PARA-SULFONAMIDODIPHENYLAMINE DYE PRECURSOR AND SULFONIMIDE DYE IN PHOTOGRAPHIC MATERIAL AND PROCESS

PRECURSEUR DE COLORANT A BASE DE PARA-SULFONAMIDODIPHENYLAMINE CHROMOGENE ET COLORANT DE SULFONIMIDE, UTILISES DANS DES PRODUITS ET PROCEDES PHOTOGRAPHIQUES

English Abstract

ABSTRACT OF THE DISCLOSURE
A color-forming para-sulfonamidodiphenylamine dye
precursor in a photographic material and process enables
formation of a dye image by means of cross-oxidation with-
out the need for a coupling reaction. The color-forming
para-sulfonamidodiphenylamine dye precursor is useful in a
photographic silver halide material for producing (i) a
dye image, or (ii) a dye image and silver image. The
exposed photographic material is processes to produce (a)
a positive dye image, (b) a negative dye and negative
silver image, (c) a negative dye image or (d) a positive
dye image and a positive silver image.

Claims

- 95 -
WHAT IS CLAIMED IS:
1. In a photographic element comprising a
support having thereon, in reactive association, in binder,
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precursor, a color-forming parasulfon-
amidodiphenylamine.
2. A photographic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamin is repre-
sented by the formula:
<IMG>
wherein:
R is in the meta or para position and is an electron
donating substituent selected from
<IMG>
alkoxy containing 1 to 20 carbon atoms, aryloxy
containing 6 to 20 carbon atoms, sulfonamido and
carboxamido groups;
R1 is in the ortho or meta position and is hydrogen,
alkyl containing 1 to 3 carbon atoms, carbamoyl,
alkoxy containing 1 to 3 carbon atoms, sulfonyl-
alkyl containing 1 to 3 carbon atoms, sulfonylaryl
containing 6 to 12 carbon atoms, chlorine,
bromine, iodine or fluorine;

-96-
R2 is hydrogen, alkyl containing 1 to 3 carbon atoms,
carbomoyl, alkoxy containing 1 to 20 carbon atoms,
sulfonylalkyl containing 1 to 5 carbon atoms,
sulfonylaryl containing 6 to 12 carbon atoms,
chlorine, bromine, iodine or fluorine;
R3 is hydrogen, alkyl containing 1 to 20 carbon
atoms, haloalkyl containing 1 to 20 carbon atoms,
alkoxy containing 1 to 20 carbon atoms, an ester
containing 1 to 20 carbon atoms, carboxy, carbox-
amido, chlorine, bromine, iodine, fluorine,
carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl
containing 1 to 5 carbon atoms, ureido or a carbo-
cyclic group containing 5 to 12 carbon atoms;
R4 is hydrogen, alkyl containing 1 to 20 carbon
atoms, alkoxy containing 1 to 20 carbon atoms, an
ester represented by the formula
<IMG> ,
carboxy, carboxamido, chlorine, bromine, iodine,
fluorine, carbamoyl, sulfonic acid, sulfamyl,
sulfonylakyl containing 1 to 3 carbon atoms,
ureido and a carbocyclic group containing 5 to 12
carbon atoms;
R5 is individually alkyl containing 1 to 20 carbon
atoms or aryl containing 6 to 20 carbon atoms;
R6 is hydrogen, alkyl containing 1 to 20 carbon atoms,
<IMG> ,
aryl containing 6 to 20 carbon atoms, or repre-
sents, with R7, atoms completing a 5- or
6-member heterocyclic group;

- 97 -
R7 is alkyl containing 1 to 20 carbon atoms,
carbamoyl, carboxamido, or represents, with R6,
atoms completing a 5- or 6-member heterocyclic
group;
R8 is alkyl containing 1 to 4 carbon atoms; and
R6A is alkyl containing 1 to 20 carbon atoms.
3. A photographic element as in Claim 2 wherein
R5 is 2,4,6-triisopropylphenyl.
4. A photgraphic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamine consists
essentially of 4-dihexylamino-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine represented by the formula:
<IMG>
5. A photographic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamine consists
essentially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine represented by the formula:
<IMG>

- 98 -
6. A photographic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamine consists
essentially of 4-dihexylamino-3'-methyl-4'-(2,4,6-triiso-
propylbenzenesulfonamido)diphenylamine represented by the
formula:
<IMG>
7. A photographic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamine consists
essentially of 4-dihexylamino-2'-methylsulfonyl-4'-
(2,4,6-triisopropylbenzenesulfonamido)diphenylamine repre-
sented by the formula:
<IMG>
8. A photographic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamine consists
essentially of 3-methanesulfonamido-4-methoxy-2'-pival-
amido-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenyl-
amine represented by the formula:

- 99 -
<IMG>
9. A photographic element as in Claim 1 wherein
said color-forming para-sulfonamidodiphenylamine consists
essentially of 4-[N-ethyl-N-(.beta.-methanesulfonamido-
ethyl)amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-tri-
isopropylbenzenesulfonamido) diphenylamine represented by
the formula:
<IMG>
10. A photographic element as in Claim 1 also
comprising (c) a cross-oxidizing photographic silver halide
developing agent.
11. A photographic element as in Claim 1 wherein
said binder is a gelatino binder.
12. In a photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,
(a) photosensitive silver halide; and

- 100 -
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precurso, a para-sulfonamidodi-
phenylamine consisting essentially of 4-dihexyl-
amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine.
13. In a photographic element comprising a
support having thereon, in reactive association, in a
gelatine binder,
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precursor, a color-forming parasulfon-
amidodiphenylamine consisting essentially of
4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine.
14. In a photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precursor, a color-forming sulfon-
amidodiphenylamine consisting essentially of
4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)-
amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-
triisopropylbenzenesulfonamido) diphenylamine
represented by the formula:

- 101 -
<IMG>
15. In a photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precursor, a color-forming sulfon-
amidodiphenylamine consisting essentially of
4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6-tri-
isopropylbenzenesulfonamido) diphenylamine
represented by the formula:
<IMG>

- 102 -
16. In a photographic composition comprising:
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
composition to a dye by cross-oxidation by means
of a cross-oxidizing silver halide developing
agent;
the improvement comprising
as said dye precursor, a color-forming parasulfon-
amidodiphenylamine.
17. A photographic composition as in Claim 16
also comprising a binder.
18. A photographic composition as in Claim 16
also comprising (c) a cross-oxidizing silver halide
developing agent.
19. A photographic composition as in Claim 16
also comprising (c) a 3-pyrazolidone cross-oxidizing silver
halide developing agent.
20. A photographic composition as in Claim 16
wherein said color-forming para-sulfonamidodiphenylamine is
represented by the formula:
<IMG>
wherein:
R is in the meta or para position and is an electron
donating substituent selected from
<IMG> ,

- 103 -
alkoxy containing 1 to 20 carbon atoms, aryloxy
containing 6 to 20 carbon atoms, sulfonamido and
carboxamido groups;
R1 is in the ortho or meta position and is hydrogen,
alkyl containing 1 to 3 carbon atoms, carbamoyl,
alkoxy containing 1 to 3 carbon atoms, sulfonyl-
alkyl containing 1 to 3 carbon atoms, sulfonylaryl
containing 6 to 12 carbon atoms, chlorine,
bromine, iodine or fluorine;
R2 is hydrogen, alkyl containing 1 to 3 carbon atoms,
carbamoyl, alkoxy containing 1 to 3 carbon atoms,
sulfonylalkyl containing 1 to 5 carbon atoms,
sulfonylaryl containing 6 to 12 carbon atoms,
chlorine, bromine, iodine or fluorine;
R3 is hydrogen, alkyl containing 1 to 20 carbon
atoms, haloalkyl containing 1 to 3 carbon atoms,
alkoxy containing 1 to 20 carbon atoms, an ester
containing 1 to 20 carbon atoms, carboxy, carbox-
amido, chlorine, bromine, iodine, fluorine,
carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl
containing 1 to 5 carbon atoms, ureido or a carbo-
cyclic group containing 5 to 12 carbon atoms;
R4 is hydrogen, alkyl containing 1 to 3 carbon atoms,
alkoxy containing 1 to 20 carbon atoms, an ester
represented by the formula:
- ? - O -R8 ,
carboxy, carboxamido, chlorine, bromine, iodine,
fluorine, carbamoyl, sulfonic acid, sulfamyl,
sulfonylalkyl containing 1 to 3 carbon atoms,
ureido and a carbocyclic group containing 5 to 12
carbon atoms;
R5 is alkyl containing 1 to 20 carbon atoms or aryl
containing 6 to 20 carbon atoms;

- 104 -
R6 is hydrogen, alkyl containing 1 to 20 carbon atoms,
<IMG> ,
aryl containing 6 to 20 carbon atoms, or repre-
sents, with R7, atoms completing a 5- or
6-membered heterocyclic group;
R7 is alkyl containing 1 to 20 carbon atoms,
carbamoyl, carboxamido, or represents, with R6,
atoms completing a 5- or 6-membered heterocyclic
group;
R8 is alkyl containing 1 to 4 carbon atoms; and
R6A is alkyl containing 1 to 20 carbon atoms.
21. A photographic composition as in Claim 16
wherein R5 is 2,4,6-triisopropylphenyl.
22. A photographic composition as in Claim 16
wherein said para-sulfonamidodiphenylamine consists essen-
tially of 4-dihexylamino-4'-(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine represented by the formula:
<IMG>
23. A photographic composition as in Claim 16
wherein said para-sulfonamidodiphenylamine consists essen-
tially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine represented by the formula:

- 105 -
<IMG>
24. A photographic composition as in Claim 16
wherein said para-sulfonamidodiphenylamine consists essen-
tially of 4-dihexylamino-3'-methyl-4'-(2,4,6-triiso-
propylbenzesulfonamido)diphenylamine represented by the
formula:
<IMG>
25. A photographic composition as in Claim 16
wherein said para-sulfonamidodiphenylamine consists essen-
tially of 4-dihexylamino-2'-methylsulfonyl-4'-(2,4,6-tri-
isopropylbenzenesulfonamido)diphenylamine represented by
the formula:

- 106 -
<IMG>
26. In a photographic composition comprising, in
a gelatino binder,
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precursor, a para-sulfonamidodi-
phenylamine consisting essentially of 4-dihexyl-
amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine.
27. In a photographic composition comprising, in
a gelatino binder,
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
element to a dye by cross-oxidation by means of a
cross-oxidizing silver halide developing agent;
the improvement comprising
as said dye precursor, a para-sulfonamidodiphenyl-
amine consisting essentially of 4-hexyloxy-3'-
methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine.
28. In a photographic composition comprising:
(a) photosensitive silver halide; and

- 107 -
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
composition to a dye by cross-oxidation by means
of a cross-oxidation silver halide developing
agent;
the improvement comprising
as said dye precursor, a para-sulfonamidodiphenyl-
amine consiting essentially of 4-[N-ethyl-N-
(.beta.-methanesulfonamidoethyl)amino]-2-methyl-
2',5'-dipivalamido-4'-(2,4,6-triisopropyl-
benzenesulfonamido) diphenylamine represented by
the formula:
<IMG>
29. In a photographic composition comprising:
(a) photosensitive silver halide; and
(b) a color-forming dye precursor which is imagewise
converted upon exposure and processing of said
composition to a dye by cross-oxidation by means
of a cross-oxidizing silver halide developing
agent;
the improvement comprising
as said dye precursor, a a para-sulfonamidodi-
phenylamine consisting essentially of 4-n-
hexyloxy-2',5'-dipivalamido-4'-(2,4,6-triiso-
propylbenzenesulfonamido) diphenylamine repre-
sented by the formula:

- 108 -
<IMG>
30. A process of producing a negative dye image
and a negative silver image in an imagewise exposed photo-
graphic element comprising a support having thereon, in
reactive association, in binder,
(a) photosensitive silver halide, and
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor which is converted upon processing of
said element to a dye by cross-oxidation by means
of a cross-oxidizing silver halide developing
agent;
said process comprising:
(A) developing said photographic element in an
alkaline, cross-oxidizing, photographic
silver halide developer composition to
produce a negative dye image and silver image.
31. A process as in Claim 30 wherein said alka-
line, cross-oxidizing developer composition comprises a
1-phenyl-3-pyrazolidone, cross-oxidizing, photographic
silver halide developing agent.
32. A process of producing a negative dye image
and a silver image in an imagewise exposed photographic
element comprising a support having thereon, in reactive
association, in a gelatino binder,
(a) photosensitive silver halide; and

- 109 -
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor consisting essentially of 4-dihexyl-
amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine;
said process comprising:
(A) developing said photographic element in an
aqueous, alkaline, cross-oxidizing, photogra-
phic silver halide developer solution
comprising a cross-oxidizing photographic
silver halide developing agent consisting
essentially of 4-methyl-4-hydroxymethyl-1-
phenyl-3-pyrazolidone.
33. A process of producing a negative dye image
and a silver image in an imagewise exposed photographic
element comprising a support having thereon, in reactive
association, in a gelatino binder,
(a) photosensitive silver halide;
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor consisting essentially of 4-hexyl-
oxy-3'-methyl-4'-(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine;
said process comprising:
(A) developing said photographic element in an
aqueous, alkaline, cross-oxidizing, photogra-
phic silver halide developer solution
comprising a cross-oxidizing photographic
silver halide developing agent consisting
essentially of 4-methyl-4-hydroxymethyl-
1-phenyl-3-pyrazolidone.
34. A process of producing a positive dye image
in an imagewise exposed photographic element comprising a
support having thereon, in reactive association, in binder,
(a) photosensitive silver halide; and

- 110 -
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor which is converted upon processing of
said element to a dye by cross-oxidation by means
of a cross-oxidizing photographic sllver halide
developing agent;
said process comprising the steps:
(A) developing a silver image in said photogra-
phic element by means of an alkaline, photo-
graphic silver halide developer in the
absence of a cross-oxidizing, photographic
silver halide developing agent;
(B) fogging the resulting element;
(C) producing a dye image in the photographic
element by means of an alkaline, cross-
oxidizing, photographic silver halide
developer; and
(D) bleaching and fixing the photographic element
by means of a silver halide bleaching and
fixing solution;
to produce a positive dye image in the photographic element.
35. A process as in Claim 34 wherein said fogging
is performed by means of a uniform flash exposure.
36. A process as in Claim 34 wherein ssid photo-
graphic element after step (A) and before step (B) is
treated by means of a photographic development stop bath.
37. A process of producing a positive dye image
in an imagewise exposed photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,
(a) photosensitive silver halide gelatino emulsion; and
(b) a color-forming sulfonamidodiphenylamine dye
precursor consisting essentially of 4-hexyl-
oxy-3'-methyl-4'-(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine;
said process comprising the steps:

- 111 -
(A) developing said photographic element in an
alkaline, photographic developer in the
absence of a cross-oxidizing, photographic
silver halide developing agent;
(B) treating the photographic element by means of
a photographic development stop bath;
(C) fogging the resulting element;
(D) producing a dye image in the photographic
element by means of an alkaline, cross-
oxidizing, photographic silver halide
developer comprising an alkaline solution of
4-methyl-4-hydroxymethyl-1-phenyl-3-pyra-
zolidone, and then
(E) bleaching and fixing the photographic element
in a silver halide bleaching and fixing
solution;
to produce a positive dye image in the photographic element.
38. A process of producing a positive dye image
in an imagewise exposed photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,
(a) photosensitive silver halide gelatino emulsion; and
(b) a color-forming sulfonamidodiphenylamine dye
precursor consisting essentially of 4-dihexyl-
amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine;
said process comprising the steps:
(A) developing said photographic element in an
alkaline, photographic silver halide
developer in the absence of a cross-oxidiz-
ing, photographic silver halide developing
agent;
(B) treating the photographic element by means of
a photographic development stop bath;
(C) fogging the resulting element;

- 112 -
(D) producing a dye image in the photographic
element by means of an alkaline, cross-
oxidizing, photographic silver halide
developer comprising an alkaline solution of
4-methyl-4-hydroxymethyl-1-phenyl-3-pyra-
zolidone, and then
(E) bleaching and fixing the photographic element
in a silver halide bleaching and fixing
solution;
to produce a positive dye image in the photographic element.
39. A process of producing a negative dye image
in an imagewise exposed photographic element comprising a
support having thereon, in reactive association, in binder,
(a) photosensitive silver halide, and
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor which is converted upon processing of
said element to a dye by cross-oxidation by means
of a cross-oxidizing silver halite developing
agent;
said process comprising:
(A) developing said photographic element in an
alkaline, cross-oxidizing, photographic
silver halide developer composition to
produce a negative dye image and silver
image; then
(B) removing at least part of the silver image
from the photographic element.
40. A process of producing a negative dye image
as in Claim 39 wherein said alkaline, cross-oxidizing
developer composition comprises a 1-phenyl-3-pyrazolidone,
cross-oxidizing, photographic silver halide developlng
agent.
41. A process of producing a negative dye image
in an imagewise exposed photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,

- 113 -
(a) photosensitive silver halide, and
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor consisting essentially of 4-dihexyl-
amino-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine;
said processing comprising:
(A) developing said photographic element in an
aqueous, alkaline, cross-oxidizing, photogra-
phic silver halide developer solution
comprising a cross-oxidizing photographic
silver halide developing agent consisting
essentially of 4-methyl-4-hydroxymethyl-1-
phenyl-3-pyrazolidone; then
(B) removing at least part of the silver image
from the photographic element.
42. A process of producing a negative dye image
in an imagewise exposed photographic element comprising a
support having thereon, in reactive association, in a
gelatino binder,
(a) photosensitive silver halide, and
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor consisting essentially of 4-hexyloxy-
3'-methyl-4'-(2,4,6-triisopropylbenzenesulfon-
amido)diphenylamine;
said process comprising:
(A) developing said photographic element in an
aqueous, alkaline, cross-oxidizing photogra-
phic silver halide developing solution
comprising a cross-oxidizing photographic
silver halide developing agent consisting
essentially of 4-methyl-4-hydroxymethyl-1-
phenyl-3-pyrazolidone; then
(B) removing at least part of the silver image
from the photographic element.

- 114 -
43. A process of producing a positive dye image
and a positive silver image in an imagewise exposed photo-
graphic element comprising a support having thereon, in
reactive association, in binder,
(a) direct-positive photographic silver halide t and
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor which is converted upon processing of
said element to a dye by cross-oxidation by means
of a cross-oxidizing silver halide developing
agent;
said process comprising:
(A) developing said photographic element in an
alkaline, cross-oxidizing photographic silver
halide developing composition; then
(B) fixing the resulting photographic element to
produce a positive dye image and a positive
silver image.
44. A process of producing a positive dye image
and a positive silver image in an imagewise exposed photo-
graphic element comprising a support having thereon, in
reactive association, in a gelatino binder,
(a) direct-positive photographic silver halide, and
(b) a color-forming para-sulfonamidodiphenylamine dye
precursor consisting essentially of 3-methane-
sulfonamido-4-methoxy-2'-pivalamido-4'-(2,4,6-
triisopropylbenzenesulfonamido) diphenylamine;
said process comprising:
(A) developing said photographic element in an
alkaline, cross-oxidizing photographic silver
halide developing composition comprising a
3-pyrazolidone silver halide developing
agent; then
(B) fixing the resulting photographic element to
produce a positive dye image and a positive
silver image.

- 115 -
45. In an exposed and processed photographic
element comprising a support having thereon a dye image,
the improvement comprising:
as said dye image, a dye consisting essentially of
a sulfonimide dye represented by the formula:
<IMG>
wherein:
R is in the meta or para position and is an electron
donating substituent selected from
<IMG> ,
alkoxy containing 1 to 20 carbon atoms, aryloxy
containing 6 to 20 carbon atoms, sulfonamido and
carboxamido groups;
R1 is in the ortho or meta position and is hydrogen,
alkyl containing 1 to 3 carbon atoms, carbamoyl,
alkoxy containing 1 to 3 carbon atoms, sulfonyl-
alkyl containing 1 to 3 carbon atoms, sulfonylaryl
containing 6 to 12 carbon atoms, chlorine,
bromine, iodine or fluorine;
R2 is hydrogen, alkyl containing 1 to 3 carbon atoms,
carbamoyl, alkoxy containing 1 to 3 carbon atoms,
sulfonylalkyl containing 1 to 5 carbon atoms,
sulfonylaryl containing 6 to 12 carbon atoms,
chlorine, bromine, iodine or fluorine;

- 116 -
R3 is hydrogen, alkyl containing 1 to 20 carbon
atoms, haloalkyl containing 1 to 3 carbon atoms,
alkoxy containing 1 to 20 carbon atoms, an ester
containing 1 to 20 carbon atoms, carboxy, carbox-
amido, chlorine, bromine, iodine, fluorine,
carbamoyl, sulfonic acid, sulfamyl, sulfonylalkyl
containing 1 to 5 carbon atoms, ureido or a carbo-
cyclic group containing 5 to 12 carbon atoms;
R4 is hydrogen, alkyl containing 1 to 3 carbon atoms,
alkoxy containing 1 to 20 carbon atoms, an ester
represented by the formula
<IMG> ,
carboxy, carboxamido, chlorine, bromine, iodine,
fluorine, carbamoyl, sulfonic acid, sulfamyl,
sulfonylalkyl containing 1 to 3 carbon atoms,
ureido and a carbocyclic group containing 3 to 6
carbon atoms;
R5 is alkyl containing 1 to 20 carbon atoms or aryl
containing 6 to 20 carbon atoms;
R6 is hydrogen, alkyl containing 1 to 20 carbon atoms,
<IMG> ,
or aryl containing 6 to 20 carbon atoms, or
represents, with R7, atoms completing a 5- or
6-member heterocyclic group;
R7 is alkyl containing 1 to 20 carbon atoms
carbamoyl, carboxamido, or represents, with R6,
atoms completing a 5- or 6-member heterocyclic
group;
R8 is alkyl containing 1 to 4 carbon atoms; and
R6A is alkyl containing 1 to 20 carbon atoms.

- 117 -
46. An exposed and processed photographic
element as in Claim 45 wherein R5 is 2,4,6-triisopropyl-
phenyl.
47. An exposed and processed photographic
element as in Claim 45 wherein said sulfonimide dye
consists essentially of 4-dihexylamino-4'-(2,4,6-triiso-
propyl benzenesulfonamido)diphenylamine represented by the
formula:
<IMG>
48. An exposed and processed photographic element
as in Claim 45 wherein said sulfonimide dye consists essen-
tially of 4-hexyloxy-3'-methyl-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine represented by the formula:
<IMG>
49. An exposed and processed photographic element
as in Claim 45 wherein said sulfonimide dye consists
essentially of 4-dihexylamino-3'-methyl-4'-(2,4,6-triiso-
propylbenzenesulfonamido)diphenylamine represented by the
formula:

- 118 -
<IMG>
50. An exposed and processed photographic element
as in Claim 45 wherein said sulfonimide dye consists essen-
tially of 4-dihexylamino-2'-methylsulfonyl-4'-(2,4,6-tri-
isopropylbenzenesulfonamido)diphenylamine represented by
the formula:
<IMG>
51. An exposed and processed photographic element
as in Claim 45 wherein said sulfonimide dye consists essen-
tially of 4-[N-ethyl-N-(.beta.-methanesulfonamidoethyl)-
amino]-2-methyl-2',5'-dipivalamido-4'-(2,4,6-triiso-
propylenzenesulfonamido) diphenylamine represented by the
formula:

- 119 -
<IMG>
52. An exposed and processed photographic element
as in Claim 45 wherein said sulfonimide dye consists essen-
tially of 4-n-hexyloxy-2',5'-dipivalamido-4'-(2,4,6- tri-
isopropylbenzenesulfonamido) diphenylamine represented by
the formula:
<IMG>
53. An exposed and processed photographic element
as in Claim 45 also comprising a silver image.
54. An exposed and processed photographic element
comprising a support having thereon, in reactive associa-
tion, in binder, developed silver image enhanced by a
sulfonimide dye image wherein said dye image consists
essentially of 4-dihexylamino-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine represented by the formula:

- 120 -
<IMG>
55. An exposed and processed photographic element
comprising a support having thereon, in binder, a developed
silver image enhanced by a sulfonimide dye image wherein
said dye image consists essentially of 4-hexyloxy-3'-
methyl-4'-(2,4,6-triisopropylbenzenesulfonamido)di-
phenylamine represented by the formula:
<IMG>

Description

1 ~;.'3691
-- 1 --
COLOR-FORMING PARA-SULFONAMIDODIPHENYLAMINE
DYE PRECURSOR AND SULFONIMIDE DYE IN
PHOTOGRAPHIC MATERIAL AND PROCESS
Field of the Invention
Thi& invention relate6 to a photographic material
and proce6s for producing images by means of photosensi-
tive silver halide and a color-forming para-sulfonamidodi-
phenylamine dye precuræor. One aspect of the invention
relates to a photographic element for producing such
images. Another aspect relates to a photographic composi-
tion comprising the dye precursor according to the inven-
tion. A further aspect relates to processes for producing
images in an imagewise expo6ed photographic material
comprising a color-forming para-sulfonamidodiphenylamine
dye precursor.
Description of the State cf the Art
Photographic materials for producing silver
images and dye images are known. The dye image in such
materiale is generally produced by a coupling reaction in
which a developing agent is oxidized upon development of
photosensitive 6ilver halide in the material, followed by
reaction of the resulting oxidized form of the developing
agent with a coupling agent to produce a dye image. It
has been desirable to provide alternative means for
producing a dye image, e~pecially a dye image that
enhances a silver image, other than by a coupling reac-
tion. The formation of dye images according to the inven-
tion by means of a dye precursor doe6 not involve a
coupling reaction.
Production of reversal color images, al60 known
as positive dye images, by developing a silver image in an
imagewise exposed photographic material is also known.
Such reversal color images and proce6se6 for producing
such images are described in, for example, U.S. Patent
4,035,184 and U.S. Patent 3,938,995. These patents
describe production of a negative dye image by means of a

~ 3~
leuco dye comprising the reaction product of a color-form-
ing coupler and an N,N-dialkyl-~-phenylenedismine.
Neither of these patents relate to the formation of a dye
image and silver image in which the dye is produced from a
color-forming para-sulfonamidodiphenylamine dye precur-
sor. The present invention also avoids the need for a
coupling reaction to produce a dye described in these
patents.
The term "photographic material" herein means
photographic elements and photographic compositions. For
instance, photographic material herein includes photo-
graphic elements and photographic compositions comprising
photosensitive silver halide and a color-forming
para-sulfonamidodiphenylamine dye precursor according to
the invention.
SUMMARY OF THE INVENTION
It has been found according to the invention that
a stable dye image, especially a dye image that enhances a
silver image, is produced by means of a photographic
material comprising, in reactive association, in binder:
(a) photosensitive silver halide, and (b) a color-forming
dye precursor which is imagewise converted upon expo~ure
and proces6ing of the photographic material to a dye by
cross-oxidation, preferably by means of a cross-oxidizing
silver halide developing agent. The color-forming dye
precursor according to the invention is a color-forming
para-sulfonamidodiphenylamine dye precursor.
An e6pecially useful color-forming sulfonamidodi-
phenylamine dye precursor according to the invention is
one that comprises a stabilizer group. The stabilizer
group provides increased light stability to the resulting
dye upon processing of the photographic material contain-
ing the color-forming sulfonamidodiphenylamine dye precur-
sor. The term stabilizer group herein means such 8 group
that provides increased light stability to the resulting
dye from the sulfonamidodiphenylamine upon processing of

~ 3~ ~1
the photographic material. Many stabilizer groups are
u~eful a~ a component of the sulfonamidodiphenylamine
according to the invention. An especially useful stabi-
lizer group is a 2,4,6-triisopropylbenzene 6tabilizing
S group bonded to a sulfonamido group of the para-sulfon-
amidodiphenylamine. A combination of stabilizer groups is
also useful.
It has also been found that a positive dye image
is provided in a photographic material according to the
invention by a process comprising (a) developing the
exposed photographic material in an alkaline photographic
developer in the absence of a cross-oxidizing silver
halide developing agent; then, (b) fogging the resulting
element, such as by uniformly exposing the resulting
element to a flash exposure of light or, alternatively, a
chemical fogging agent; followed by (c) developing the
photographic element in an alkaline cross-oxidizing devel-
oper, such as a 3-pyrazolidone cross-oxidizing developer;
and, then (d) bleaching and fixing the photographic
material in a silver halide bleaching and fixing compo6i-
tion to produce a positive dye image in the photographic
material. After step (a) and before step (b), optionally
the photographic process for producing a positive dye
image includes a stop bath treatment. This enable6 a
tesirable lowering of the pH of the development to a point
at which development of a negative silver image stops
quickly. This produces an improved dye image upon
processing .
A negative dye image and a negative ~ilver image
are produced in an imagewise exposed photographic material
comprising, in reactive association, in binder, (8) photo-
sensitive silver halide, and (b) a color-forming para-sul-
fonamidodiphenylamine dye precursor by developing the
photographic material in an alkaline, cross-oxidizing,
photographic 6ilver halide developer composition, prefer-
ably such a composition comprising a 3-pyrazolidone silver

3tj9
-- 4 --
halide developing agent. The negative dye i~age prefer-
ably enhances the negative silver image. Thi6 enables a
lower concentration of silver in the photographic material
before exposure than otherwise might be necessary to form
a similar developed image from silver halide alone. When
the negative, developed silver image is removed from the
photographic material, such as by means of a bleaching and
fixing composition, a negative dye image remains in the
proce~sed photographic material.
A positive dye image and a positive silver image
are produced in an imagewise exposed photographic material
according to the invention by means of direct-positive
photographic silver halide. A process for producing a
positive, dye image and a positive, silver image in an
imagewise exposed photographic material comprising, in
reactive association, in binder, (a) direct-positive
photographic silver halide, and (b) a color-forming
para-sulfonamidodiphenylamine dye precursor comprises (A)
developing the photographic element by means of an alka-
line, cross-oxidizing photographic silver halide develop-
ing composltion; then (B) fixing the resulting photogra-
phic element to produce a positive dye image and a po6i-
tive silver image.
In each of the photographic materials and
processes, the resulting dye in the image areas has
increased stability. The dyes according to the invention
containing a ~tabilizer group exhibit better stability
than dyes that do not contain a stabilizer group.
DETAILED DESCRIPTION OF THE INVENTION
Many para-sulfonamidodiphenylamines are useful
color-forming sulfonamidodiphenylamine dye precursors in
photographic materials and processes according to the
invention. Combinations of color-forming para-sulfon-
amidodiphenylamine dye precursors are also useful, if
desired. The color-forming para-sulfonamidodiphenylamine
dye precursor is selected to provide a dye image by means

-- 5 --
of a cross-oxidizing photographic silver halide developing
agent after imagewise exposure.
The term "para-sulfonamidodiphenylamine" herein
alternatively means 4'-sulfonamidodiphenylamine.
One illustrative class of color-forming para-sul-
fonamidodiphenylamine dye precursors is represented by the
formula:
Rl R3
y O / -NH--/ O \--NHSO2Rs
R2 R4
~herein:
R is in the meta or para position and is an
electron donating substituent selected from amino
groups represented by the formula:
~R
N
~R7
alkoxy containing 1 to 20 carbon atoms, such as
methoxy, ethoxy, propoxy, hexyloxy and octadecyl-
oxyj sulfonamido, such as R5ASo2NH; aryloxy
containing 6 to 20 carbon atoms, such as phenoxy,
3,4,5-trimethylphenoxy, 2,4-di-t-amylphenoxy and
halophenoxy; and carboxamido groups, such as
acetamido, N-methylacetamido and propionamido;
is in the ortho or meta position and is hydrogen,
alkyl containing 1 to 3 carbon atoms, such as
methyl, ethyl and propyl, carbamoyl, alkoxy
containing 1 to 3 carbon atoms, such as methoxy,
ethoxy and propoxy, sulfonylalkyl containing 1 to
3 carbon atoms, such as sulfonylmethyl, sulfonyl-

-- 6 --
ethyl, and sulfonylpropyl, sulfonylaryl contain-
ing 6 to 12 carbon atoms, such as sulfonylphenyl
and sulfonyl methylphenyl, chlorine, bromine,
iodine or fluorine; R2 is hydrogen, alkyl containing l to 3 carbon
atoms, such as methyl, ethyl and propyl, carba-
moyl, alkoxy containing 1 to 20 carbon atoms,
such as methoxy, ethoxy and propoxy, sulfonyl-
alkyl containing 1 to S carbon atoms, such as
sulfonylmethyl, sulfonylethyl, and sulfonyl-
propyl, sulfonylaryl containing 6 to 12 carbon
atoms, such as sulfonylphenyl and sulfonyl
methylphenyl, chlorine, bromine, iodine or
fluorine;S R3 is hydrogen, alkyl containing 1 to 20 carbon
atoms, such as methyl, ethyl and propyl, halo-
alkyl containing 1 to 3 carbon atoms, such as
tribromomethyl, trifluoromethyl, 2,2,2-trichloro-
ethyl, and 3,3,3-trichloropropyl, alkoxy contain-
ing 1 to 20 carbon atoms, such as methoxy,
ethoxy, propoxy and decyloxy, an ester containing
1 to 20 carbon atoms, such as formoxy, acetoxy,
butyroxy and stearoxy, carboxy, carboxamido, such
as acetamido, N-methylacetamido and propionamido,
chlorine, bromine, iodine, fluorine, carbamoyl,
sulfonic acid, sulfamyl, sulfonylalkyl containing
1 to 5 carbon atoms, such as sulfonylmethyl,
sulfonylethyl and sulfonylpropyl, ureido, or a
carbocyclic group containing 5 to 12 carbon `
atoms, such as cyclohexyl, cyclopentyl and
dimethylcyclohexyl;
R4 is hydrogen, alkyl containing 1 to 20 carbon
atoms, alkoxy containing 1 to 20 carbon atoms,
such as methoxy, ethoxy and propoxy, an ester
represented by the formula:

~ ~3~
-- 7 --
- C - O - R8
carboxy, carboxamido, chlorine, bromine, iodine,
fluorine, carbamoyl, sulfonic acid, sulfamyl,
sulfonylalkyl containing 1 to 3 carbon atoms,
such as sulfonylmethyl, sulfonylethyl and sulfon-
ylpropyl, ureido, and a carbocyclic group
containing 5 to 12 carbon atoms, such as cyclo-
pentyl, cyclohexyl and dimethylcyclohexyl; or
atoms necessary to complete a naphthyl ring with
the ad;oining phenyl ring containing NHSo2R5;
Rs and R5A are individually alkyl containing 1 to
20 carbon atoms, such as methyl, ethyl, propyl,
decyl, eicosyl and benzyl, aryl containing 6 to
20 carbon atoms, such as phenyl, naphthyl, halo-
phenyl, 2,4,6-triisopropylphenyl, 2,6-di-methyl-
phenyl, p-tolyl, 2,4,6-trimethylphenyl and
2,6-diisopropylphenyl;
R6 is hydrogen, alkyl containing 1 to 20 carbon
atom8, 8uch a8 methyl, ethyl, propyl, hexyl,
decyl, and eicosyl,
O
CR6A
or aryl containing 6 to 20 carbon atom6, such as
phenyl, tolyl and trimethylphenyl, or represents,
with R7, atoms 6uch as carbon, oxygen, 6ulfur
and nitrogen atoms completing a heterocyclic
group, including a 5- or 6-member heterocyclic
group, such as a pyridino, morpholino or piper-
idino group;
R7 is alkyl containing 1 to 20 carbon atoms, 6uch a6
methyl, ethyl, propyl and decyl, carbamoyl,

'3~gl
carboxamido, or represents, wi~h R6, atoms ~uch
as carbon, oxygen, sulfur and nitrogen atomæ
completing a heterocyclic group, including a
5- or 6-member heterocyclic group;
R~ is alkyl containing 1 to 4 carbon atoms, such as
methyl, ethyl, propyl and butyl; and
R6A i8 alkyl containing 1 to 20 carbon atoms, such as
ethyl, octyl and decyl.
The terms "alkyl" and "aryl" herein mean un6ub-
stituted alkyl and unsubstituted aryl. The terms "alkyl"
and "aryl" herein also mean ~ubstituted alkyl and substi-
tuted aryl wherein the alkyl and aryl are substituted by
groups which do not adversely affect the sulfonamidodi-
phenylamines or the corresponding sulfonimide dyes accord-
ing to the invention. Example~ of suitable substitutedalkyl groups include alkyl contsining a sulfonamido group,
such as CH3S02NHCHzCH2-, a carboxamido group, an
alkoxy group, such as methoxy or ethoxy, a carboxyl
t-COOH), an aryl group, such as a benzyl group, and
carbonyl. An alkyl group containing an aryl substituent
is also known as an aralkyl group. Examples of suitable
substltuted aryl groups include phenyl containing an
alkoxy group, such as methoxy and ethoxy, carboxyl, alkyl
such as methyl, ethyl, propyl and butyl, and hydroxy. An
especially useful substituted aryl group is an alkyl
substituted aryl group, such as tolyl, Z,4,6-triisopropyl-
phenyl and t-butylphenyl. An alkyl substituted aryl group
is also known as an alkaryl group.
Especially useful para-sulfonamidodiphenylamines
and corresponding sulfonimide dyes in imaging materials
and processes are those which comprise a stabilizer
group. The term stabilizer group herein means a group
that is substituted on the sulfonamidodiphenylamine to
provide increased stability to the sulfonamidodiphenyl-
amine and the corresponding sulfonimide dye. A partic-
ularly useful stabilizer group is a 2,4,6-triisopropyl-
phenyl group represented by the formula:

~ .3æ~
CH3
CH3 - CH CH3
~'\ 0 /-CH
t
CH3 - CH CH3
CH3
This group is alternatively herein repre~ented by the
formula:
\._.
_ / 0 /-_\
While a 2,4,6-triisopropylphenyl group is a particularly
useful stabilizer group, other stabilizer group6 are also
useful .
Examples of useful color-forming para-sulfon-
amidodiphenylamine dye precursors according to the inven-
tion include:
4-Dihexylamino-4'-(2,4,6-trii60propylbenzenesulfona
mido) diphenylamine represented by the formula:
CH3
CH 3 -CH CH 3
C 3 ( ) ~ 0\- -NH--\ 0 \--NHS0 2 --~O~-CH
CH 3 -CH CH 3
CH3

3~
- 10 -
4-Hexyloxy-3'-methyl-4'-(2,4,6-triisopropylben-
zenesulfonamido) diphenylamine represented by the formula:
CH3
CH3 CH3-CH CH3
CH3(CH2)sO--\ 0 /--NH--/ 0 /--NHS02--/ Q /--CH
CH3-CH CH3
CH3
4-N,N-diethylamino-4'-(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine represented by the formula:
CH3
CH3 CH 3 -CH CH3
--/ 0 /--NH--\ 0 /--NHSO2--\ 0 /--CH
CH3-CH CH3
CH3
4-N,N-dihexylamino-2'-methylsulfonyl-4'-~2,4,6-
triisopropylbenzenesulfonamido) diphenylamine represented
by the formula:
CH3
CH3-CH CH3
C ( ) ~ 0~--NH-~0~--NHSO2-/0~-CH
S02 CH3 CH3-CH CH3
CH3

l~t;9~1
- 11 -
An especially useful embodiment iB a photographic
element comprising a support having thereon, in reactive
association, in a gelatino binder: (a) photosensitive
silver halide gelatino emulsion; and (b) a color-forming
S dye precursor which is imagewise converted upon exposure
and processing of the element to a dye by cross-oxidation
by means of a cross-oxidizing developing agent wherein the
color-forming dye precursor is a para-sulfonamidodiphenyl-
amine consisting essentially of 4-dihexylamino-4'-(2,4,6-
triisopropylbenzenesulfonamido) diphenylamine.
Another illustrative class of color-forming
para-sulfonamidodiphenylamine dye precursor6 that are
useful in a photographic material is the class of color-
forming para-sulfonamidodiphenylamines represented by the
formula:
I o
R R' 2
20~~~\~ ~ ~--NH--\ O /-NHSO2RI 4
Rl I Rl 3
wherein:
R9 is in the meta or para position and is an elec-
25tron donating substituent selected from
~Rl s
\Rl 6
alkoxy containing 1 to 20 carbon atom~, such aR
methoxy, ethoxy, propoxy and hexyloxy, aryloxy
containing 6 to 12 carbon atoms, such as phenoxy
and naphthoxy, sulfonamido, and carboxamido
groups such as acetamido, butyramido, N-methyl-
acetamido and n-octylureido;

91
- 12 -
Rl is in the ortho or meta position and is hydro~en,
alkyl containing 1 to 3 carbon atoms, such as
methyl, ethyl and propyl, carbamoyl, alkoxy
containing 1 to 3 carbon atoms, such as methoxy,
ethoxy and propoxy, sulfonylalkyl containing 1 to
3 carbon atoms, such as sulfonylmethyl, sulfonyl-
ethyl and sulfonylpropyl, sulfonylaryl containing
6 to 12 carbon atoms, such as sulfonylphenyl and
sulfonylmethylphenyl, chlorine, bromine, iodine
or fluorine~ or in the meta position is sulfon-
amido;
Rll is hydrogen, alkyl containing 1 to 3 carbon
atoms, such as methyl, ethyl and propyl,
carbamoyl, alkoxy containing 1 to 3 carbon atoms,
such as methoxy, ethoxy and propoxy, sulfonyl-
alkyl containing 1 to 3 carbon atoms, such as
sulfonylmethyl, sulfonylethyl and sulfonylpropyl,
sulfonylaryl containing 6 to 12 carbon atoms,
such as sulfonylphenyl and sulfonylmethylphenyl,
chlorine, bromine, iodine or fluorine;
Rl2 is hydrogen, alkoxy containing 1 to 20 carbon
atoms, or carboxamido, such as acetamido,
propionamido, pivalamido and ureido;
Rl 3 iS hydrogen, alkoxy containing 1 to 20 carbon
atoms, or carboxamido, such as acetamido,
propionamido, pivalamido and ureido;
Rl 4 iS alkyl containing 1 to 20 carbon atoms, such as
methyl, ethyl, propyl, decyl and eicosyl, aryl
containing 6 to 20 carbon atoms, such as phenyl
tolyl, 2,4,6-triisopropylphenyl and
2,4,6-trimethylphenyl;
Rl 5 iS hydrogen or alkyl containing 1 to 20 carbon
atoms, such as methyl, ethyl, propyl, decyl and
eicosyl; and,

~ 1~i9~ ~1
Rl 6 iS hydrogen, alkyl containing l to 20 carbon
atoms, such aæ methyl, ethyl, propyl, decyl and
eicosyl, or aryl containing 6 to 12 carbon atoms,
such as phenyl and tolyl.
Particularly useful compounds are those within the above
formula wherein when Rl3 is carboxamido, then Rl2 is
carboxamido.
The term "sulfonamido" herein means a substituent
group represented by the formula:
-NHS02Rl 7
wherein Rl 7 iS a substituent which does not adver~ely
affect the diphenylamine compound or imide dye according
to the invention. Rl 7 iS, for example, alkyl containing
1 to 20 carbon atoms, such as methyl, ethyl, propyl,
butyl, decyl, and eicosyl, or aryl containing 6 to 20
carbon atoms, æuch as phenyl, tolyl and 2,4,6-triiso-
propylphenyl. Examples of such groups include 2,4,6-tri-
isopropylsulfonamido, methylsulfonamido and tolyl6ulfon-
amido.
Examples of us~ful color-forming para-sulfon-
amidodiphenylamine dye precursors within the above formula
containing carboxamido groups include:
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-
2-methyl-2',5'-dipivalamido-4'-(2,4,6-triisopropylbenzene-
sulfonamido) diphenylamine repre6ented by the formula:
0 CH3
il I
/CH3 HNCC(CH3)3 CH3-CH CH3
/N--\ 0 /--NH--\ 0 /--NHS02--~ 0 /--CH
CH3S02NHCH2CH2 t t--
(CH3)3CCNH H3C-CH CH3
Il I
0 CH3

;9
- 14 -
4-n-Hexyloxy-2',5'-dipivalamido-4'-(2,4,6-triiso-
propylbenzenesulfonamido)diphenylamine repre6ented by the
formula:
0 CH3
Il I
HNCC(CH3)3 H3C-CH CH3
1 . .
n-C6H13O-/ ~ ~--NH-/ Q ~- NHSO2--/ O \--CH
HN H3C-CH CH 3
C - CH3
C(CH3)3
A further illustrative clas~ of color-forming
para-~ulfonamidodiphenylamine dye precur~ors is repre-
sented by the formula:
0 CH3
R2~S02 ~ NHCRI9 CH3-CH CH3
-NH--~ O /--NHS02~/ O ~--CH
-- -T T--
R20 CH3-CH CH3
CH3
wherein:
Rl 8 i6 alkyl containing 1 to 20 carbon atoms, such as
methyl, ethyl, propyl, decyl and eicosyl, alkoxy
containing 1 to 20 carbon atom6, such a6 methoxy,
ethoxy and dodecyloxy, or an appropriate amino
group, such as
/R2 2
N\R2 3

- 15 -
Rl9 is alkyl containing 1 to 20 carbon atoms, such ~æ
methyl, ethyl, propyl, decyl and eico6yl, aryl
containing 6 to 12 carbon atoms, such a6 phenyl
and tolyl, alkoxy containing 1 to 4 carbon atom6,
such as methoxy, ethoxy, and butoxy, aryloxy
containing 6 to 12 carbon atoms, such a6 phenoxy
and 3,4,5-trimethylphenoxy, or NH-R2 4;
R20 i6 hydrogen or
o
NHCR2 5
R2 1 i8 alkyl containing 1 to 12 carbon atom6, such as
methyl, ethyl, propyl and dodecyl;
R2 2 i8 hydrogen or alkyl containing 1 to 2~ carbon
atoms, such as methyl, ethyl, propyl and decyl;
R2 3 iB hydrogen, alkyl containing 1 to 20 carbon
atoms, such as methyl, ethyl, propyl and hexyl,
or aryl containing 6 to 12 carbon atoms, such as
phenyl and tolyl;
R2 4 iB alkyl containing 1 to 20 carbon atoms, such as
methyl, ethyl and decyl, aryl containing 6 to 12
carbon atoms, such as phenyl and tolyl, alkoxy
containing 1 to 4 carbon atoms, such as methoxy,
ethoxy and butoxy, or aryloxy containing 6 to 12
carbon atoms, such a6 phenoxy and 3,4,5-tri-
methylphenoxy;
R2s is alkyl containing 1 to 20 carbon atoms, such as
methyl, ethyl, propyl and decyl, aryl containing
6 to 12 carbon atoms, such as phenyl and tolyl,
alkoxy containing 1 to 4 carbon atoms, such as
methoxy and butoxy, or aryloxy containing 6 to 12
carbon atoms, such as phenoxy and 3,4,5-tri-
methylphenoxy.
Examples of suitable color-forming para-sulfon-
amidodiphenylamine dye precursors within this formula
include:

~ 3
- 16 -
3-Methanesulfonamido-4-methyl-2'-palmitamido-4'-
(2,4,6-triisopropylbenzene~ulfonamido)diphenylamine repre-
sented by the formula:
0 CH3
Il l
NHS02CH3 NHCClsH3l CH3-CH CH3
! . !_. ! .
H3C--\ 0 /- NH - \ 0 /. NHS02 / Q \--CH
CH3-CH CH3
CH3
3-Methanesulfonamido-4-methoxy-2'-pivalamido-4'-
(2,4,6-triisopropylbenzenesulfonamido) diphenylamine
represented by the formula:
0 CH3
Il I
NHS02CH3 NHCC(CH3)3 CH3-CH CH3
CH30--/ 0 \--NH--/ 0 /- NHS02 - / 0 \--CH
CH3-CH CH3
CH3
The color-forming para-sulfonamidodiphenylamine
dye precursors are prepared generally by one of four
methods. The first method (Method 1) involves condensa-
tion of a phenylenediamine compound or ether-substituted
aniline with a sub~tituted halonitrobenzene wherein the
nitro group is ortho or para with respect to a halogen
atom on the benzene ring, followed by reduction of the
nitro group and subsequent sulfonylation of the inter-
35 . mediate amine.

The second method (Method 2) involves condensa-
tion of a halonitroaniline with 6ulfonyl chloride,
followed by condensation with a phenylenediamine or
aniline. The resulting intermediate i8 then reduced,
S followed by acylation of the intermediate amine to yield a
carboxamido-sub6tituted sulfonamidodiphenylamine. The
sulfonylation step is avoidable by using a halonitro6ul-
fonamidobenzene that condenses directly with the phenyl-
enediamine or aniline.
The third method of preparation (Method 3)
involves condensation of a 6ubstituted aniline with a
sulfonyl chloride, followed by oxidative coupling. Thiæ
oxidative coupling is with a phenylenediamine in the
pre6ence of ferricyanide and base to yield a dye that is
subsequently reduced, such as by hydrogenation in the
presence of a suitable palladium-charcoal catalyst, to
form the corresponding leuco form of the compound.
Carboxamido groups are introduced prior to oxidative
coupling.
The fourth method of preparation (Method 4)
involves a Smlles rearrangement method for those cases in
which the direct nucleophilic condensation, such as in
Method 1, is not entirely satisfactory.
An illustrative preparation for preparing a
compound by Method 1 is the preparation of 4-dihexyl-
amino-4'-benzenesulfonamidodiphenylamine. This illustra-
tive preparation i8 as follows:
A Rample of N,N-dihexyl-~-phenylenediamine-di-~-
eoluenesulfonic acid salt (30.8 grams, 0.05 mole) in
dimethylformamide (150 ml) is stirred under nitrogen
atmosphere as succes6ive additions of sodium bicarbonate
(16.8 grams) and para-fluoronitrobenzene (7.05 grams, 0.05
mole) are made. After stirring overnight at 90 to lOO~C,
the reaction mixture is poured into ice water and
extracted with ethyl acetate. The extract is washed with
water, dr~ed and freed of solvent. The filtrate residue

~ 3 ~ ~ ~
- 18 -
i~ then chromatographed from an appropriate 6ilica gel,
using benzene as eluent, to provide 4-dihexylamino-4'-
nitrodiphenylamine that is characterized by nuclear
magnetic resonance. This nitro intermediate is reduced to
the corresponding amine by hydrogenation over palladium-
charcoal catalyst in a suitable hydrogenation apparatu6.
The corre~ponding amine is converted to its benzenesulfon-
amide derivative by means of benezenesulfonyl chloride.
The resulting color-forming sulfonamidodiphenylamine dye
precursor is purified by methods known in the organic
synthesi~ art, such a6 by recrystallization from an appro-
priate solvent, such as methanol.
Another illustrative preparation is the prepara-
tion of 4-diethylamino-4'-benzenesulfonamidodiphenylamine
according to Method 1. This method is as follows:
A solution of N,N-dimethyl-~-phenylenediamine
(16.4 gramR, 0.18 mole) and ~-fluoronitrobenzene (14.1
grams, 0.10 mole) in 200 ml of dimethylformamide i~
stirred overnight with sodium bicarbonate (16.8 grams,
0.20 mole) at 85 to 90~C under a nitrogen atmosphere.
This reaction mixture i5 poured into ice water and
extracted with ethyl acetate. Evaporation of the 601vent
provides 4-diethylamino-4'-nitrodiphenylamine which is
recrystallized from ethanol to provide red violet leaflets
having a melting point of 139 to 141~C. This nitro inter-
mediate (5.7 grams) in tetrahydrofuran (100 ml) is hydro-
genated over a palladium-charcoal catalyst (1.2 gram6) in
a 6uitable hydrogenation apparatus (40 pBi hydrogen
pressure). The corresponding amine is converted to the
desired benezenesulfonamide compound by means of reaction
with benzenesulfonyl chloride. The product is recry6tal-
lized from methanol to provide a gray 601id having a melt-
ing point of 145 to 146C.
A further preparation that illu6trate6 the
Method 1 is the preparation of 4-methoxy-4'-benzene6ulfon-
amidodiphenylamine. Thi6 preparation i6 a6 follow6:

A solution of ~-anisidine (49.2 grams, 0.4 mole)
and ~-fluoronitrobenzene (28.2 grams, 0.2 mole) in
dimethylsulfoxide was stirred for 24 hours on a steam
bath. The resulting red reaction mixture was poured into
water (500 ml) and extracted with ethyl acetate. The
extract wa6 washed with water, dried over magnesium
sulfate and evaporated to dryness. The residue was
slurried in ligroin and filtered to provide a brick red
solid. This was di6601ved in ethyl acetate, warmed with
charcoal, and the filtrate filtered. The filtrate was
evaporated and the re6idue recrystallized from ethyl
acetate to provide 4-methoxy-4'-nitrodiphenylamine having
a melting point of 149 to 151C. A solution of the
resulting nitro compound (24.4 grams, 0.1 mole) in ethyl
acetate (250 ml) is converted to the corresponding amine
by hydrogenation over a palladium-charcoal catalyst at 60
psi hydrogen pressure. After filtration, the solvent i6
removed under vacuum and the light purple solid dis601ved
in pyridine (150 ml). This i6 reacted with benzenesul-
fonyl chloride (17.7 grams, 0.1 mole) by stirring for 3hours under a nitrogen atmosphere at 25C. After dilution
with water (500 ml), the organic phase is washed with
water, dried over magne6ium sulfate and freed of solvent.
The red oil resulting is dissolved in chloroform and
filtered through an appropriate filtering composition.
The filtrate residue is purified, 6uch as by recrystalli-
zation three time6 from chloroform-ligroin, to provide a
desired white powder having a melting point of 133 to
135~C.
A further example of a method of preparing a
compound according to Method 1 is the preparation of
4-dihexylamino-4'-(2,4,6-triisopropylbenzenesulfonamido)-
diphenylamine. This method is carried out as follows:
A sample (5.24 grams, 0.013 mole) of the compound
4-dihexylamino-4'-nitrodiphenylamine is reduced by hydro-
genation in a suitable hydrogenation apparatus in try

- 20 -
tetrahydrofuran (100 ml) containing palladium-charcoal
catalyst (1.2 grams). The resulting filtrate i6 freed of
solvent under vacuum, and the resulting 4'-amino deriva-
tive di6solved in dry pyridine (25 ml) and reacted at 5C
with 2,4,6-triisopropylbenzenesulfonyl chloride (4.5
gram6, 0.015 mole). After stirring for three hours at
25C, the reaction mixture is poured into chloroform (200
ml) and ice water. The organic phase iB waehed five times
with water, dried, concentrated to about 50 ml volume and
chromatographed on an appropriate silica gel. The chloro-
form eluate i6 freed of solvent, and the filtrate residue
recrystallized from methanol. The crystalline product i6
purified by washing with an appropriate 601vent, 6uch as a
methanol-water mixture, and dried to provide the de6ired
product having a melting point of 127 to 129C.
An illustrative preparation according to Method 2
i6 the preparation of 4-[N-ethyl-N-(~-methane6ulfon-
amidoethyl)amino]-2-methyl-2'-octanamido-4'-(2,4,6-tri-
isopropylbenzene6ulfonamido)diphenylamine. This prepara-
tlon is as follows:
The following preparation of a desired inter-
mediate i6 carried out:
F S02Cl F
i/ + \i/o~ \ Pyridine i/O\i~
\ . / . I \
NH2 / \ NHS02--~ O /---\
_ --
A 601ution of 4~fluoro-3-nitroaniline (15.6
gram6, 0.1 mole) in pyridine (400 ml) is 6tirred at room
temperature and 2,4,6-triisopropylbenzenesulfonyl chloride
(30.2 grams, 0.1 mole) is added in bulk. The resulting

j,t~
- 21 -
æolution is 6toppered tightly and 6tirred at room tempera-
ture (about 20C) overnight (about 18 hour6). The reac-
tion mixture i6 then poured over an ice hydrochloric acid
(aqueou6) mixture (500 gram6 of ice and 500 ml of concen-
trated aqueou6 hydrogen chloride). An oily solidseparates and i6 removed by filtration. Repeated recry6-
tallization from methanol and water provides light golden
cry6tal6 having a melting point of 151 to 152C. The
desired intermediate product i6 identified by methods
known in the chemical analytical art, such as by elemental
analy6is.
The following reaction is then carried out:
F C2HsNCH2CH2NHSO2CH3
1S I o ,/NO2 i CH3
NH NH2
SO2
-J~
i~0,i
/i~
C2H5NCH2CH2NHSO2CH 3
iOi
~ \CH 3
NH
/ \ /NO2
i,O l~
NHSO2 \ O ,---,

- 22 -
This reaction iB carried out as follow6:
42.2 grams ~0.1 mole) of 2-fluoro-5-(2,4,6-tri-
isopropylbenzenesulfonamido)nitrobenzene in 275 ml of
l-picoline is stirred at reflux under nitrogen for three
days with 40.6 grams (0.15 mole) of 4-amino-3-methyl-N-
ethyl-N-(~-methanesulfonamidoethyl) aniline (in the form
of a free base). The reaction solution is allowed to cool
to room temperature and i6 poured over an ice water
mixture (1.5 liters). The mixture is allowed to stand
until a red-brown oil separates. The aqueous layer is
decanted from the oil. The oil is di~solved in
CH2Cl2 (about 400 ml). The methylene chloride
solution is then washed with vigorous agitation with 5
percent hydrochloric acid (50 ml concentrated HCl plus
380.5 ml of water) four times (500 ml), then with 5
percent NaHCO3 (four times, 500 ml) and finally with
500 ml of water (four times). The methylene chloride
layer is dried by means of sodium sulfate and then swirled
with a filtering composition (Florisil) to remove a purple
residue. Evaporation of the solvent provides a red oil
which is taken up in about 150 ml of boiling methsnol.
The methanol solution is allowed to cool to room tempera-
ture (about 20C) overnight. A yellow-orange crystalline
product having a melting point of 164 to 166C is
produced. Thin layer chromatography on silica gel-glass
and recrystallization from ethyl acetate provide~ the
desired pure product which is identified by methods known
in the chemical analytical art, such as by elemental
analysis.

- 23 -
The following reaction iB then carried out:
C2HsNCH2CH2NHSO2CH3 C2HsNCH2CH2NHSO2CH3
i/O\i i O`i
I \CH3 \T/ ~ H3
NH NH
/ \ /N02 H2 ~ H 2
i O i Pd/C i O I + C7Hl5CCl+Ca(OH)2
\./ THF
NH NH
S02 S02
_J ' ,!_ i~o,i
C2HsNCH2CH2NHSO2CH3
i`O i
~/ \CH3
~ !NH o
i o i-NHCC7Hl 5 -n
\./
NH
S02
! ! !
i O i
~ /
/ \
6.7 grams (0.01 mole) of the nitro compound in
35 about 75 ml of tetrahydrofuran is reduced over 10 percent
palladium on charcosl at 40 pounds psi in a hydrogen
- .

(3
- 24 -
atmosphere until the hydrogen uptake ceases (within about
2.5 hours). The reaction mixture is blanketed with nitro-
gen and removed from the hydrogen atmosphere. No attempt
i~ made to remove the catalyst at this point. The calcium
S hydroxide (0.41 grams, 0.055 mole), used as an HCl
6cavenger, i~ added in bulk to the reaction mixture.
Next, octanoyl chloride (1.8 grams, 0.011 mole) i6 added
in bulk to the reduction mixture. The resulting reaction
mixture is stoppered tightly and allowed to be fitirred at
room temperature (about 21C) for three hours. No
exothermic properties are observed. The catalyst and
calcium salts are removed by filtration. The solvent is
evaporated to yield a brown oil. The oil iB taken up in
boiling ether. The oil is dissolved and a precipitate
begins to form. Filtering provides a colorless solid with
a strong octanoyl chloride odor. The solid is re-6us-
pended in boiling ether (100 ml), then filtered and vacuum
dried at room temperature (about 21C) to yield 6.0 grams
of a very faintly yellow-tinted 601id having a melting
point of 98 to 100C. Thin layer chromatogrsphy with
silica gel on glass shows one component with a variety of
solvents (ethyl acetate, methylene chloride, acetone and
acetonitrile). The compound i8 further characterized by
methods known in the chemical anslytical art, such as
infrared analysis, nuclear magnetic resonance, mass
spectrography and elemental analysi~. Oxidation with
aqueous potassium ferricyanide yield6 a green dye.
Another illustrative preparation according to
Method 2 is the preparation of 3-methanesulfonamido-2'-
octanamido-4'-(2,4,6-triisopropylbenzenesulfonamido)di-
phenylamine. This preparation is carried out a8 follows:

~ ~ ~ 9~ 9
- 25 -
NHS02CH3 N02 ~!
/ 0 \--NH2+ F--/ 0 /--NHS02--\ 0 / - \ (heat)
NHS02CH3 N02 _!
! . ! . \. .
. ~ Q, . -NH- . ~ Q, . -NHso 2 - ~ Q, - ~
H2 l Pd/C
0
n-C7Hl5CCl THF
NHS02CH 3 NHCC7Hs
1 . 1 . \. .
/O ~--NH- ~0 ~--NHSO2- ,Q ,-- ,
.
A mixture of meta-methanesulfonamidoaniline (1.86
gram6, 0.01 mole) and 2-fluoro-5-(2,4,6-triisopropylben-
zenesulfonamido)nitrobenzene (4.2g grams, 0.01 mole) in 25
ml of a-picoline i8 refluxed for 29 hours. Thi6 mixture
is poured into a mixture of 100 gram6 of ice and 100 ml of
lN hydrochloric acid, and the 6eparated oil extracted with
100 ml of ethyl acetate. The extract i8 washed with
water, dried by means of anhydrou6 60dium 8ul fate, and
freed of solvent. The re6ulting oil is chrom~tographed on
Woelm'6 6ilica gel using methylene chloride as the

91
- 26 -
eluent. The column held material is eluted w~th 1:1 parts
by volume methylene chlorideethyl acetate, freed of
601vent, and character$zed as 3-methanesulfonamido-2'-
nitro-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenyl-
emine. Thi6 compound is identified by, for example,nuclear magnetic re60nance. 2.9 grams of the oily product
i6 di6601ved in 150 ml of 1:1 methanoltetrahydrofuran and
reduced by hydrogen over a palladium-charcoal catalyst.
After removal of catalyst and 601vent, the 601id product
is characterized, 6uch as by nuclear magnetic resonance,
a6 3-methane6ulfonamido-2'-amino-4'-(2,4,6-trii60propyl-
benzenesulfonamido)diphenylamine. 1.5 gram6 (0.003 mole)
of this compound are then dis601ved in 20 ml of dry pyri-
dine and reacted at 5uC with 6.5 gram6 of octanoyl
chloride in 20 ml of dry tetrahydrofuran. After 18 hours
at 25C, the reaction mixture i6 poured into ice and 20 ml
of concentrated hydrochloric acid, and the separated oil
extracted with methylene chloride. The extract is washed
with 10 percent 60dium bicarbonate in water, tried, and
freed of solvent. The resulting oil i6 purified by high
pressure liquid chromatography to yield 1.3 grams of a
glass that is recrystallized from etherhexane to give
white leaflets. The desired product is characterized,
such a6 by nuclear magnetic resonance, and ha6 a melting
point of 146 to 148~C. A sample of thi6 compound i6
oxidized in butyl acetate with potassium ferricyanide in
pH 10 buffer, yielding a yellow dye possessing a maximum
absorption of 429 nm.
A preparation which illustrates preparation of a
compound by Method 3 is the preparation of 4-~N-ethyl-N-
(~-methanesulfonamidoethyl)amino]-2-methyl-2',5'-di-
pivalamido-4'-(2,4,6-trii60propyl-benzenesulfonamido)di-
phenylamine. This preparation according to Method 3 is as
follows:

~ 3~ ~ 1
NH2 S02Cl
5l 0 1 + I 0 i Pyridine
\j/ \./
N02
101, /NHS02 \ 0 /---
!,0,! ./
.
N02
\ -
NHS02 -~Q,-- ~
20i 0 i 2
~./
N0z
15.3 grams (0.1 mole) of the 4-nitro-o-phenylene-
diamine are dissolved in 200 ml of pyridine snd the solu-
tion cooled in an ice bath. After one hour, a solution of
31.2 grams (0.1 mole) of 2,4,6-triisopropylbenzenesulfonyl
chloride in 100 ml of tetrahydrofuran are added to the
amine solution. The resulting mixture is stirred over-
night at room temperature and is next poured over ice (400
grams) plus 300 ml of glacial acetic acid. An oil sepa-
rates and solidifies upon standing. The crude solid is
removed by filtration. The resulting solid is recrystal-
lized twice from methanol-water to yield a yellow crystal-
line solid (27.6 grams) having a melting point of 187 to

3~9
- 28 -
191C. Thin layer chromatography on 6ilica gel (hexane:-
ethyl acetate; 3:2 by volume) indlcates a major ~nd minor
component mixture, a~ indicated by the 6tructure~ above.
The de6ired intermediate i6 identified by elemental
S analysi6-
The following reaction is then carried out:
NH2 \._. NHSO2- ~ O /--~/
~NHS02- ~Ø~ - \ I ~ \ 11
N02
N02
N(CH3)2 NHCC(CH3)3 \ /
i/0 i TN~ i i-NHso2 \- /
N02
21.0 gram6 (0.05 mole) of the crude amine mixture
are dis601ved in 250 ml of tetrahydrofuran and 6.6 gram~
(0.05 mole) of the acid scavenger, N,N-dimethylaniline,
are added in bulk. To this 601ution is added, dropwise in
15 minutes, 6.6 grams (0.05 mole) of the pivaloyl
chloride. After stirring at room temperature overnight
(at about 20UC), thin layer chromatography indicates an
incomplete reaction. Thu6, an additional 5 millimoles of
acid chloride and base are added, and the mixture is
stirred overnight again. The mixture is diluted with
methanol (100 ml), then quenched in one liter of water.
An oil separates and solidifies. The solid obtained is

- 29 -
recry6tallized from methanol-water to provide 24.6 grams
of 601id having a melting point of 160 to 162~C. Thi6
material contain6 a small amount (less than 2 percent) of
the following i~omeric compound:
!
0 lNHS02 \ 0
~.0~
N02
The de6ired product i6 identified by elemental
analy~is.
The following reaction i6 then carried out:
NHCC(CH 3 ) 3
_ / 10% Pd/C
N02
NHCC(CH 3 ) 3 o
i/0 i- NHS02--/ 0 ~---/ + (CH3)3CCCl +
NH2

1~;9t~
- 30 -
N(CH3)3 NHCC(cH3)3_
i/O\i ~ i\O i~lS2 ~.0/--~
NHCC(CH3)3
10.1 grams (0.02 mole) of the nitro compound is
reduced 8t room temperature in 125 ml of tetrahydrofuran
over 10 percent palladium on charcoal at 40 psi hydrogen
preæ~ure until hydrogen uptake cea6eæ (1.5 hours). The
15 catalyst is then removed by filtration. 2.5 grams (0.021
mole) of the acid scavenger, N,N-dimethylaniline, ig added
in bulk; followed by bulk addition of 2.5 grams (0.021
mole) of pivaloyl chloride. The mixture iæ stoppered and
stirred overnight at room temperature. Solvent is then
20 evsporated to yield an amber oil. The oil is crystsllized
irom ethanol-water to yield 10.2 grams of colorle~s solid
having a melting point of 196C. This desired inter-
mediate iB identified, such as by elemental analy6is.
The structure of the intermediate is confirmed by
25 making the same compound by an alternate synthetic route:
NH2 0 NHCC(CH3) 2
! ~02 ll ! N02
30 t/O j (CH3)3CCCl t/O\t' H2
Et3N \./ Pd/C, THF
NH2 NHCC(CH3)3
O

3~1
- 31 -
\ NHCC(CH3)
/o i - NHS0
i
\ /---\ NHCC(CH3)3
/---\ O /--S02Cl 0
\._
CH3 11 NHS02- ~Q `- ~ C2Hs~NCH2CH2NHS02CH3
+H i\/l 0 CH \I/ \CH
NHC + CH 3 NH2
CH 3
(A) (B)
i O i
--' '1' '--
+ K3Fe(CN)6 ~ K2C03 ~ S02 0
N 11 CH3
~ HC + CH3
CH31l i1 i1 CH3
CH3 ¦ CNH/ ~i1/
CH3 N
i /0~ i /
\./
C2HsNCH2CH2NHS02CH3

~ 6 9 ~
10.5 grams (0.02 mole) of the coupler (A) and 5.4
grams (0.02 mole) of the reducing agent (B) are dissolved
in 200 ml of tetrahydrofuran. With rapid stirring, the
aqueous potassium carbonate 601ution (11.0 grams, 0.08
mole in 50 ml of water) is added to the tetrahydrofuran
solution of (A) and (B). Finally, the aqueous potassium
ferricyanide solution (26.3 grams, 0.08 mole in 150 ml of
water) is added dropwise to the above solution. A green
dye began to form during the addition. Following the
addition, the reaction mixture is stirred for 45 minutes
and then is quenched in one liter of water. The dye is
extracted into methylene chloride, washed well with water,
and dried by means of sodlum sulfate. It is then evapo-
rated to yield a green oil. The oil is chromatographed in
Woelm'~ silica gel with an ethyl acetate-hexane (8:2 parts
by volume) eluent to yield 12.0 grams of green dye as a
8reen glass (maximum absorption in butyl acetate of 672
nm). The gla6s is used directly without further
purification.
The following reaction is carried out:
I O 1
/- I \ H2
S02 0 10% Pd/C,
U ~ C ¦ CH3
Il / \ / CH3
30CH3 ¦ CNH il
CH3 N
/~ /CH3
~0-1
\./
C2HsNCH2CH2NHSOzCH3

;'3ti~
- 33 -
i'O`I
s /'' 't ~
S02 o
NH 1I CH3
NHC ~ H 3
Il / \O/ CH3
CH3 ¦ CNH t
CH3 NH
,!, /CH3
\/-
C2HsNCH2CH2NHS02CH3
The glass obtained above i~ dissolved in tetra-
hytrofuran and reduced over 10 percent palladium on char-
coal at room temperature (sbout 20~C) and 40 p8i hydrogenpressure until hytrogen uptake cea6es (about 5 minutes).
The catalyst is removed by filtration and the solvent i6
evaporated at reduced pressure to yield a light blue oil.
The oil is recrystallized from ether-hexane (2:5:1 parts
by volume) to yield 8 grams of colorless solid having a
melting point of 166 to 168C. The desired product i~
identified, such as by elemental analysis.
A further preparation illustrating preparation of
a compound according to Method 3 is the preparation of
4-diethylamino-2-methyl-2'-methoxy-5'-pivalamido-4'-
(2,4,6-triisopropylbenzenesulfonamido)diphenylamine. This
method is carried out as follows:
/l~ /NHCC(C~3)3 /J\ /NHcc(cH3)3
CH30 ~-/ 10% Pd/C CH30/ ~-/

- 34 -
$02Cl
_J J l_ l
\i/o\i/ Pyridine I O~i
/ \ S02 o
NH "
/o\ /NHCC(CH3)3
CH30/ \-/
13.3 grams (O.OS mole) of the nitro compound in
150 ml of tetrahydrofuran is reduced at 40 pBi hydrogen
lS pressure over 10 percent palladium on charcoal at room
temperature (about 20C) until hydrogen uptake ceases (1.5
hours). The catalyst is removed by filtration, and the
solvent by evaporation, to yield a colorless crystalline
solid which is the desired amine. This amine is used
directly. The colorle~s solid is dissolved in 250 ml of
pyridine, and the resulting solution cooled in an ice
bath. Next, triisopropylbenzenesulfonyl chloride (15.1
grams, O.OS mole) i8 added portion-wise to yield a
bright-yellow solution which is allowed to warm to room
temperature and is stirred overnight (about 18 hours).
The mixture is poured into a mixture of ice (400 grams)
and concentrated hydrogen chloride (300 ml) to produce a
colorless solid. Filtration and recrystallizAtion from
acetonitrile produce~ 18.6 grams of a colorless crystal-
line solid having a melting point of 177 to 178~C. Thisdesired intermediate is identified, such as by elemental
analysis.

~6~91
- 35 -
Then the following reaction is carried out:
CH30 NHSO2 - '\ 0 /-~-\ N(C2Hs)2
CH3~cNH~i/o\i ~ + i O i +
\-/ \OCH3 \t/ \CH
NH2 HCl
K3Fe(CN)s+K2CO3
'/Oi
-t
SO2 0
!I~ /NHC +
I.l Ii H2
CH30/ \iI/ 10% Pd/C
N THF
CH3
i\o/i
N(C2Hs)2

ti 91
- 36 -
i O 1
- T i t -
NH 1l
!, ,NHC +
o ,! O !
NH
,CH3
iOi
\./
N(C2Hs)2
CH3
The designation l herein means - C - CH3
CH3
The following solution~ are prepared:
Solution A: 10.0 grams (0.02 mole) of the start-
ing intermediate in 150 ml of tetrahydrofursn;
Solution B: 4.2 grams (0.02 mole) of N,N-di-
ethyl-3-methyl-~-phenylenediamine hydrochloride in 60 ml
of water;
Solution C: 26.3 gram6 (0.08 mole) of potassium
ferricyanide in 125 ml of water; and,
Solution D: 11.0 gram6 (0.08 mole) of potassium
carbonate in 25 ml of water.
Addition of Solution A and then Solution B to
Solution D produces no color change. Next, Solution C i6
added to the previous mixture dropwise in 15 minutes. A

~ 3~ 9
- 37 -
green dye is formed. The mixture is stirred for two hours
following the addition and then diluted to one liter with
water. The dye is extracted into methylene chloride,
washed well with water, dried by means of sodium sulfate
and evaporated under reduced pressure to yield the crude
green dye as a thick oil (approximately 15 grams). The
crude dye is dissolved in tetrahydrofuran and reduced over
10 percent palladium on charcoal at 40 psi hydrogen
pressure, at room temperature ~about 20C), until hydrogen
uptake ceases (30 minutes). Filtration provides a brown-
magenta solution. Solvent i6 evaporated and replaced with
methylene chloride (about 300 ml). The magenta-brown
solution is 61urried with a filtering composition
(Florisil) (10 grams) and filtered to yield a pale green
solution. The solvent is evaporated to yield a crude pale
green solid. Recrystallization from methanol-water fails
to remove the trace of dye present. The sample i6
repeatedly recrystallized from ether- hexane until
constant melting point i6 reached. The melting point of
the desired product is 201 to 202UC.
The color-forming para-sulfonamidodiphenylamine
dye precursor~ and their corresponding sulfonimide dyes
are pre6ent in a photographic material and process accord-
ing to the invention in their ~alt form or non-salt form.
The color-forming sulfona~idodiphenylamine dye precursors
and their corresponding dyes herein include either of the
appropriate forms. Examples of suitable salt6 of the
color-forming para-sulfonamidodiphenylamine dye precursor6
include para-toluenesulfonate, 1,5-naphthalenedisulfonate
and benzenesulfonate salts.
The color-forming para-sulfonamidodiphenylamine
dye precursors are useful in a photographic material and
process according to the invention in a range of concen-
trations. Selection of an optimum concentration of
color-forming para-sulfonamidodiphenylamine dye precursor
or combination of 6uch dye precursor6 depends upon the

- 38 -
desired image, the particular photographic material,
processing steps and conditions, other components in the
photographic material, and the particular para-sulfon-
amidodiphenylamine. A useful concentration of para-sul-
fonamidodiphenylamine is generally within the range ofabout 0.1 to about 0.6 mole of para-6ulfonamidodiphenyl-
amine per mole of photosensitive silver halide in the
photographic material. An especially useful concentration
of para-sulfonamidodiphenylamine is within the range of
about 0.1 to about 0.2 mole of para-sulfonamidodiphenyl-
amine per mole of silver halide in the photographic
material. In a photographic element, a useful concentra-
tion of color-forming para-sulfonamidodiphenylamine dye
precursor is within the range of about 0.5 to about 22 mg
Of color-forming para-sulfonamidodiphenylamine dye precur-
sor per square decimeter of support, such as a concentra-
tion within the range of about S to about 11 mg per square
decimeter of support.
The hue of the dye produced from the color-form-
ing para-sulfonamidodiphenylamine dye precursor will vary,
depending upon such factors as the particular groups on
the color-forming para-sulfonamidodiphenylamine dye
precursor, processing conditions, other components in the
photographic material such as disper6ion solvent6, and
whether a combination of dyes is present in the photogra-
phic material or not. The color-forming para-sulfonamido-
diphenylamine dye precursor in the photographic material
is preferably colorless prior to exposure and processing.
Some of the suitable color-forming para-sulfonamidodi-
phenylamine dye precursor~ have a slight color, such as aslight yellow color, in the photographic material. This
slight color is not considered unacceptable.
The term "colorless" herein means that the
color-forming para-sulfonamidodiphenylamine dye precursor
in the photographic material does not absorb radiation to
an unde6ired degree in the visible region of the electro-

- 39 -
magnetic 6pectrum. In some photographic materials, the
color-forming para-sulfonamidodiphenylamine dye precursor
absorbs radi~tion in certain areas of the electromagnetic
~pectrum which do not adversely affect the desired
properties or the desired image formed upon proces6ing.
The color-forming para-sulfonamidodiphenylamine
dye precursor generally absorbs electromagnetic radiation
outside the visible region of the electromagnetic spectrum
before imagewise expo6ure and proces6ing of the photogra-
phic material. The nature of the absorption and degree ofabsorption of the color-forming pars-sulfonamidodiphenyl-
amine dye precursor depend6 upon the nature, for the mo6t
part, of the substituent group~ on the para-sulfonamidodi-
phenylamine.
The photographic materials according to the
invention comprise a photosensitive component which
consists essentially of photographic silver halide.
Examples of useful photographic silver halides are silver
chloride, silver bromide, silver bromoiodide, silver
chlorobromoiodide, silver iodide and mixtures thereof.
The photographic silver halide is generally present in the
photographic material in the form of an emulsion which is
a dispersion of the photographic silver halide in a
suitable binder. The photographic silver halide is
present in a range of grain sizes from fine grain to
coarse grain. A compo6ition containing the photographic
silver halide is prepared by any of the well known
procedures in the photographic art, such as described in
Research Disclosure, December 1978, Item No. 17643.
The photographic material according to the inven-
tion contains addenda commonly found to be useful in
silver halide photographic materials. These addenda
include chemical 6ensitizers, brighteners, antifoggants,
emul6ion stabilizers, light absorbing and scattering
materials, hardener6, coating aid6, pla6ticizer6, lubri-
cants, antistatic materials, matting agents, and develop-

- 40 -
ment modifiers, as described in esearch Disclosure,
December 1978, Item No. 17643.
The photographic silver halide is generally
spectrally senæitized by means of spectral sensitizing
dyes, a6 described in, for example, Research Disclosure,
December 1978, Item No. 17643. Useful spectrsl sensitiz-
ing dyes in photographic materials according to the inven-
tion include such dyes as polymethine dyes which include
the cyanines, merocyanines, complex cyanines and mero-
cyanines (including tri, tetra and polynuclear cyanines
and merocyanines), as well as oxonols, hemioxonols,
styryls, merostyryls and streptocyanines. Combinations of
spectral sensitizing dyes are also useful in photographic
materials according to the invention.
The photographic silver halide is useful in A
range of concentrations in a photographic material sccord-
ing to the invention. An optimum concentration of photo-
graphic silver halide depends upon such factors as the
de8ired image, processing conditions, particular sulfon-
amidodiphenylamine dye precursor, other components of the
photographic material and particular photographic silver
halide. A useful concentration of photographic 6ilver
halide in the photographic material ~ccording to the
invention is generally within the range of about 2 to
about 7 moles of photographic silver halide per mole of
color-forming sulfonamidodiphenylamine dye precursor in
the photographic material. The coverage of photographic
silver halide is less than otherwise might be useful, due
to the enhancing properties of the dye produced upon
processing of the photographic material according to the
invention.
The color-forming para-sulfonamidodiphenylamine
dye precurBor iB in any suitable location in a photogra-
phic material according to the invention which produces
the desired dye upon processing. The color-forming para-
sulfonamidodiphenylamine dye precursor is, if desired, in

- 41 -
a layer contiguous to the layer comprising the photosensi-
tive ~ilver halide. The term "in reactive association"
herein means that the photo~ensitive silver halide and the
color-forming sulfonamidodiphenylamine dye precursor are
in a location with respect to each other which enable~ the
photographic material according to the invention upon
processing to produce a desired dye image and a desired
silver image.
Many developing agent6 are useful for developing
an image in a photographic material according to the
invention. Any ~ilver halide developing agent is useful
according to the invention, provided it comprise6 a
cross-oxidizing developing agent which will cross-oxidize
with the color-forming para-sulfonamidodiphenylamine dye
precursor. Such a silver halide developer, called herein
a cros6-oxidizing developing agent, becomes oxidized
during development by reducing exposed silver halide to
silver metal. The oxidized developer then cross-oxidizes
the color-forming para-sulfonamidodiphenylamine dye
precursor to form the deslred dye.
A cross-oxidizing developing agent (COD) enables
the color-forming para-sulfonamidodiphenylamine dye
precursor to become oxidized without the color-forming
para-sulfonamidodiphenylamine dye precursor itself
developing ~ilver. The color-forming sulfonamidodiphenyl-
amine dye precursor is viewed alternatively as an electron
transfer agent which shuttles electrons between the
developing silver halide and the para-sulfonamidodiphenyl-
amine dye precursor.
The color-forming para-sulfonamidodiphenylamine
dye precursor is frequently immobilized in an oil phase in
the photographic material. This enables the dye precursor
to be dispersed satisfactorily. Alternatively, the
color-forming para-sulfonamidodiphenylamine dye precursor
is dispersed in a dispersion solvent to produce a desired
photographic material. Coupler solvent~ known in the

- 42 -
photographic art are useful for aiding di~persion of the
color-forming para-sulfonamidodiphenylamine dye precur-
sor. Examples of useful coupler solvents include
~-n-butylacetanilide, diethyl lauramide, di-n-butyl
phthalate and 2,4-di-tertiaryamylphenol. The color-form-
ing para-sulfonamidodiphenylamine dye precursor is also
usefully loaded into a latex or a non-solvent dispersion
is prepared, if desired.
The requirementæ for a cro6s-oxidizing developing
agents generally are: (a) the developing agent must have
sufficient electrochemical potential under the conditions
of use to develop exposed silver halide, (b) in its
oxidized form, the developing agent must be of such
electrochemical potential as to oxidize the color-forming
para-sulfonamidodiphenylamine dye precursor, and (c) in
its oxidized form, the developing agent must be stable to
decomposition by other chemical reactions for a sufficient
period to undergo the redox reaction with the color-form-
ing para-sulfonamidodiphenylamine dye precursor. Whether
a developing agent is a cross-oxidizing developing agent
or not depend~ upon whether the oxidized form is
sufficiently stable and the oxidizing potential is such
that an effective transferral of electrons occurs through
whatever phase barriers exist during cross-oxidizing
development. Whether a particular developing agent meets
these requirements depends upon the conditions under which
development occurs. Other fsctors influence whether a
particular developing agent is a cross-oxidizing
developer, including the pH of the developing composition,
the temperature of the development process and the length
of development time. Examples of developing agents which
are useful as cross-oxidizing developing agents include
3-pyrazolidone developers, such as 1-phenyl-3-pyrazoli-
done, l-phenyl-4,4-dimethyl-3-pyrazolidone and 4-hydroxy-
methyl-4-methyl-1-phenyl-3-pyrazolidone. Such
cross-oxidizing developing agents are described in, for

- 43 -
example, U.S. Patent 3,938,995. Combinations of non-
cross-oxidizing developing agents and cros~-oxidizing
developing agent6 are useful, provided a minor proportion
of the non-cros~-oxidizing developing agent i6 pre6ent,
6uch as less than about 10 percent of the total combina-
~ion is non-cro6s-oxidizing developing agent. Examples of
combinations of a non-cross-oxidizing developing agent and
a cross-oxidizing developing agent include 4-hydroxy-
methyl-4-methyl-1-phenyl-3-pyrazolidone with a minor
proportion of at least one of the following non-cross-
oxidizing developing agent~:ascorbic acid, hydroquinoneand pyrimidine. Selection of an optimum cross-oxidizing
silver halide developing agent or developing agent combi-
nation will depend upon such factors as the desired image,
the particular photosensitive silver halide, processing
conditions, and the particular color-forming para-sulfon-
amidodiphenylamine dye precursor.
A silver halide developing agent or silver halide
developing agent combination i8 incorporated in the photo-
graphic material according to the invention, if desired.
Generally, the silver halide developing agent i8 mo6t
useful in a processing solution in which the photographic
material according to the invention i6 processed after
exposure .
The developing agent is useful in a range of
concentration in the photographic material or in a
proces~ing compo~ition in which the photographic material
according to the invention is proce6sed. A concentration
of developing agent in the photographic material is
generally within the range of about 0.01 to about 1.0 mole
of developing agent per mole of color-forming para-sulfon-
amidodiphenylamine dye precursor in the photographic
material. A useful concentration of developing agent in a
process~ng solution for proces6ing a photographic material
containing a color-forming para-sulfonamidodiphenylamine
dy~ precursor is within the range of about 0.5 to about 2
grams of developing agent per liter of processing solution

3~:i91
- 44 -
The term "developing agent" herein includes
compound~ which are developing agents or developing agent
precursors. That i6, those compound~ are included which
are not developing agent~ in the photographic material
until a condition occurs, such a~ contact with A suitable
activator for the photographic material.
The tone of the silver image and dye image
produced in a photographic material according to the
invention will vary, depending upon such factors a~ the
silver morphology of the developed silver image, the
covering power of the 6ilver materials, the particular dye
formed, the particular developing agent, processing condi-
tions, and other components in the photographic material.
In photographic materials according to the invention that
provide a brown silver image, a dye produced iR especially
useful which i~ complementary in hue to the silver image.
A combination of dyes and a ~ilver image that produce a
neutral-appearing image are generally most useful.
The photographic materials according to the
invention comprise a varlety of binders alone or in combi-
nation. The binders include both naturally occurring
substances, such as proteins, for example, gelatin,
gelatin derivatives, cellulose derivativeR, polysaccha-
rides, such as dextran, and gum arabic; but also include
synthetic polymeric materials, such as water-soluble poly-
vinyl compounds, like poly(vinylpyrrolidone) and acryl-
amide polymer~. Examples of useful binders include tho6e
de~cribed in, for instance, Research DiscloRure, December
1978, Item No. 17643.
The photographic elements according to the inven-
tion generally contain an overcoat layer, and/or inter-
layer, and/or ~ubbing layer to provide de~ired
properties. The overcoat layer, for example, increases
resi6tance to abrasion and other markings on the element.
The overcoat layer, interlayer or Rubbing layer contain,
alone or in combination, the described binders.

i..~ 3~1
- 45 -
A photographic element according to the invention
comprises a variety of ~upports. Useful supports include
those that are resistant to adver6e changes in structure
due to proces6ing conditions and which do not adversely
affect the desired sen6itometric properties of the photo-
graphic materials. Examples of useful supports include
cellulose ester, poly(vinylacetal), poly(ethylene tere-
phthalate) and polycarbonate films, as well as related
films and resinous materials. Glass, paper and metal
supports are also useful. A flexible support is generally
most useful.
Photographic materials according to the invention
are generally coated on a suitable support by procedures
known in the photographic art. Such procedures include,
for example, immersion or dip coating, roller coating,
reversal roll coating, airknife coating, doctor blade
coating, spray coating, extrusion coating, bead coating,
stretch flow coating and curtain coating.
Photographic elements according to the invention
are imagewise exposed by means of vsrious forms of energy
to produce a developable image. Such orms of energy
include those to which the photo6ensitive 8ilver halide is
sensitive, and encompass ultraviolet, visible and infrared
regions of the electromagnetic 6pectrum, as well as
electron beam and beta radiation, gamma ray, X-ray, alpha
particle, neutron radiation and other forms of corpuscular
wave-like radiant energy in either coherent or non-
coherent forms. Lasers are useful, for example.
Exposures are monochromatic, orthochromatic or panchro-
matic, depending on the spectral sensitization of thephotosensitive silver halide. Imagewise exposure is
generslly for a sufficient time and intensity to produce a
developable latent image in the photographic material.
A photographic element according to the invention
is processed in (a) a process which produces a positive
dye image, (b) in a process which produces a negative dye

691
- 46 -
image and negative silver image, (c) in a process which
produces a negative dye image, or (d) in a process which
processes a po~itive dye image and a positive silver
image. The light-sensitive silver halide in the photogra-
phic material according to the invention i~ processedfollowing exposure to form a visible image. This is done,
for example, by associating the silver halide at one stage
of the process with an aqueous alkaline medium in the
presence of a cross-oxidizing developing agent contained
in the medium and/or in the photographic material.
To produce a positive dye image, also known as a
rever~al dye image, according to the invention, it is
generally desirable to process the exposed photographic
material by means of a non-cros~-oxidizing developing
composition as a first development step. During this
step, the exposed silver halide is reduced to elemental
silver by the non-cross-oxitizing developing composition.
The non-cross-oxidizing developing composition does not,
when oxidized, oxidize the color-forming para-sulfonamido-
diphenylamine dye precursor to its corresponding dye.
The non-cross-oxidizing developer composition
useful in this step 18 generally an alkaline solution,
preferably an aqueous solution comprising a non-cross-
oxidizing developing agent. Non-cross-oxidizing develop-
ing agents are known in the photographic art and includemany silver halide developing agents which will reduce
exposed photosensitive silver halide to silver, but will
not oxidize the color-forming para-sulfonamidodiphenyl-
amine dye precursor to a corresponding dye. Examples of
useful non-cross-oxidizing developing agents are described
in, for example, Research Disclosure, December 1978, Item
No. 17643. Useful non-cross-oxidizing developers include
developer compositions comprising ascorbic acid, hydro-
quinone, pyrimidine developing agents and a combination of
hydroquinone and N-methyl-~-aminophenol.

~ 91
In a 6econd step of a proce6s for forming a posi-
tive dye im~ge according to the invention, fogging of the
photographic material i8 accomplished by expo6ing the
photographic material to light or by chemical fogging by
mean6 of chemical fogging agent6 known in the photographic
art.
Following the described fogging step, a second
silver halide developing 6tep i6 carried out. Thi6 i6
carried out by means of a cross-oxidizing developing
compo6ition. It i6 in this 6tep that the color-forming
para-sulfonamidodiphenylamine dye precursor is converted
to a dye in the image areas. Any silver halide developing
composition is useful in thi6 6tep, provided that it
cross-oxidizes the color-forming para-sulfonamidodiphenyl-
amine dye precur60r to a de6ired dye. Such silver halidedeveloping compo6itions include alkaline 601ution6
comprising a cross-oxidizing silver halide developing
agent, preferably a 3-pyrazolidone cros6-oxidizing silver
halide developing agent. Thi6 cross-oxidizing developing
agent becomes oxidized during development by reducing
exposed or fogged silver halide to 6ilver metal. The
oxidized developing agent then cros6-oxidizes the color-
forming para-sulfonamidodiphenylamine dye precursor to a
desired dye. The photographic material, upon processing,
contains a concentration of dye in inverse proportion to
the amount of exposure of the photographic element. That
is, a positive dye image, also described herein a6 a
rever6al dye image, is formed.
An especially useful process for producing a
positive dye image in an imagewise exposed photographic
element according to the invention compri6es: (a) develop-
ing the exposed photographic element in an alkaline photo-
graphic developer in the absence of a cross-oxidizing
silver halide developing agent, and then (b) uniformly
exposing the resulting element to a flash exposure of
light, followed by (c) developing the photographic element

- 48 -
in an alkaline, cross-oxidizing developer, comprising an
aqueous, alkaline solution of 4-methyl-4-hydroxymethyl-1-
phenyl-3-pyrazolidone, and (d) bleaching and fixing the
photographic element in a silver haiid~ bleaching and
fixing 601ution to produce a positive dye image in a
photographic element. It iB generally useful to treat the
photographic element by mean6 of a development stop bath
after step (a) and before step (b).
Photographic elements according to the invention
are also useful for producing negative dye images. Such
negative dye images are produced in an expoæed photogra-
phic element comprising a support having thereon, in
reactive as60ciation, in binder, (a) photosen6itive silver
halide, and (b) a color-forming para-6ulfonamidodiphenyl-
amine dye precursor by ~A) developing the photographicelement in an alkaline, cro6s-oxidizing photographic
silver halide developer composition to produce a negative
dye image and silver image; then (B) removing at least
part of the silver image from the photographic element,
such as by bleaching and fixing the silver from the
element. Removal of the silver is accompllshed by means
of bleaching and fixing compositions known in the photo-
graphic art. The optimùm bleaching and fixing composi-
tions are selected to provide the desired dye image.
Suitable bleaching and fixing composition6 are described
in Grant Haist, Modern Photographic Processing, Vol. 2,
Chapter 10 (1979).
Photographic elements according to the invention
compri6ing direct-po6itive photographic silver halide are
useful for forming positive, dye images and positive,
silver images. A process of producing a positive, dye
image and a positive, silver image in an imagewise exposed
photographic element comprising a support having thereon,
in reactive association, in binder, (a) direct-positive
photographic silver halide, and (b) a color-forming para-
sulfonamidodiphenylamine dye precursor, comprising (A)
developing the photographic element in an alkaline,

- 49 -
cross-oxidizing photographic silver halide developing
composition; then (B) fixing the resulting photographic
element to produce a positive, dye image and a positive,
6ilver image. Useful direct-positive silver halide is
described in, for example, Research Disclosure, December
1978, Item No. 17643, page6 22 through 31. Fixing the
photographic element is accomplished by means of fixing
compositions known in the photographic art, such as a
sodium thiosulfate fixing composition.
An advantage of the photographic material and
process according to the invention is that the dye images
produced upon processing po6sess de6ired stability to
post-processing conditions and visible light expoRure. A
simple test is useful for establishing the degree of
stability which is desired for a dye image produced from a
color-forming sulfonamidodiphenylamine dye precursor
according to the invention. One such test is a test well
known ln the photographic art in which a processed photo-
graphic element is exposed to a Simulated Average North
American Skylight (SANS) with continuous 5400 LUX of
exposure at an average temperature of 21~C at 45 percent
relative humidity. A comparison of the stability of the
tested dye is then observed. This test is described with
respect to specific compounds in the following examples.
When a cross-oxidizing silver halide developing
agent is present in the photographic material according to
the invention, a developed image is produced after image-
wise exposure of the photographic material by contacting
the material with an alkaline activator solution which
enables development of the exposed silver halide, as well
as production of the desired dye. Many alkaline
activators are useful for developing an image in a photo-
graphic material according to the invention compri6ing an
incorporated cross-oxidizing silver halide developing
agent. Alkaline activators which are known to be useful
in the photographic art, such as in stabilization process-
ing, are useful for developing an image in the de6cribed

gl
- so -
photographic material according to the invention.
Examples of useful alkaline activator~ include ~odium
hydroxide, potassium hydroxide, tri60dium phos-
phate l2H20 (pH 12), 60dium metabora~e (pH 12),
di60dium phosphate and monosodium phosphate. An optimum
alkaline activator will depend upon such factor6 a6 the
desired image, the particular cross-oxidizing developing
agent, proce66ing condition6 and the particular color-
forming para-sulfonamidodiphenylamine dye precursor. An
e6pecially u6eful alkaline activator compri6es trisodium
pho6phate (pH 12).
The alkaline activator is useful in a range of
concentrations. A generally u6eful concentration of alka-
line activator is within the range of about 10 to about 50
grams per liter of activator solution which produces a pH
within the range of about 11 to about 12. An optimum
concentration of alkaline activator will depend upon such
factor6 as the de6ired image, the particular activator,
proces6ing condition6, particular cro6~-oxidizing
developing agent, particular photosen6itive silver halide
and particular color-forming para-sulfonamidodiphenylamine
dye precursor.
After exposure and processing of the photographic
material according to the invention, the photographic
material comprise6 a 6ulfonimide dye image or,
alternatively, a 6ulfonimide dye image and a silver
image. The 6ulfonimide dye image con6i6t~ e66entially of
a 6ulfonimide dye repre6ented by the formula:
Rl ~3
n -~ o ~ -N~-\ /--NS02Rs
t ~
R2 R4

t;~6
- 51 -
wherein R, Rl, R2, R3, R4 and Rs are as
defined. Preferably, R5 in this dye is a stabil-
izer group, 6uch as a 2,4,6-trlisopropylphenyl group.
Examples of useful sulfonimide dyes in ex-
posed and processed photographic materials according
to the invention are as follows:
N-(4-dihexylaminophenyl)-N'-(2,4,6-triisopro-
pylbenzenesulfonyl)-p-benzoquinonediimine repre-
sented by the formula:
CH3
CH3-CH CH3
CH3 (CH2) 5 ! -. I
~N - . /0 ~. -N-. / \. 5NS02 - . / O \ . - CH
CH 3 - CH 3
CH3
N-(4-hexyloxyphenyl)-N'-(2,4,6-triisopropylben-
zenesulfonyl)-3-methyl-~-benzoquinonediimine represented
by the formula:
CH3
~C~3 CH3-CH CH3
CH3 ( CH2 ) s O - . / O / . -N~ . 5NSO2 - . ~ O ~ . - CH
CH 3-CH CH3
C~13
N-dihexylaminophenyl)-N'-(2,4,6-triisopropylben-
zene6ulfonyl)-3-methyl-~-benzoquinonediimine represented
by the formula:

3~91
CH3
CH3 CH3-CH ~H3
CH3(CH2) /N- \ 0 /--N--\ /--NS02--/ 0 \ CH
CH3-CH CH3
CH3
N-S4-dihexylaminophenyl)-N'-(2,4,6-triisopropyl-
benzenesulfonyl)-2-methylsulfonyl-p-benzoquinonediimine
represented by the formula:
CH3
S02CH3 CH3-CH CH 3
CH3(CH2)s\ /---\
/N--\ 0 /--N=-\ /-=NS02--~ 0 /--CH
CH3-CH CH3
CH3
N-(4-dihexylaminophenyl)-N'-(2,4,6-triisopropyl-
benzenesulfonyl)-2-pivalamido-~-benzoquinonediimine
represented by the formula:
0 CH3
Il l
30(CH3)3CCNH CH3-CH CH3
N-.\ 0 /--N=., ~-~NS02--/ 0 /--CH
CH3-CH CH3
CH3

11~'3~91
- s3 -
N-(4-hexyloxyphenyl)-N'-(2,4,6-trii60propylben-
zenesulfonyl)-~-benzoquinonediimine represented by the
formula:
CH3
CH3-CH CH3
CH3(CH2)sO--/ O /--N=-\ /-=NSO2--/ Q /--CH
CH3-CH CH3
CH3
N-[4-N-ethyl-N-(~-methane6ulfonamidomethyl)- amin
o]-N'-(2,4,6-triisopropylbenzenesulfonyl)-2,5-dipival-
amido-~-benzoquinonediimine represented by the formula:
O CH3
Il I
C2Hs /CH3 HNCC(CH3)3 CH3;cH CH
~N--~ O /-~N''-~ /-~-NS02- ~ O / CH
CH3SO2NHCH2CH2 -- ~ I_- CH
(CH3)3CCNH H3C-CH 3
Il I
O CH3

~'3~ 9
- 54 -
N-(4-n-hexyloxyphenyl)-N'-t2,4,6-trii60propyl-
benzenesulfonyl)-2,5-dipivalamido-~-benzoquinonediimine
repre6ented by the formula:
0 CH3
Il I
HNCC(CH3)3 H3C-CH CH3
n-C6HI30--\ 0 /--N==-~ NS02--\ 0 /--CH
HN H3C-CH CH3
C ~ CH3
C(CH3)3
N-(4-methyl-3-methane6ulfonamidophenyl)-N'-
(2,4,6-trii60propylbenzene6ulfonyl)-2-palmitamido-~-benzo-
quinonediimine repre6ented by the formula:
0 CH3
11
NHS02CH3 NHCClsH3l CH3-CH CH
1 . ~............... 1 . ,
H3C-- ~Q `._ N ~NS02 - / 0 /--CH
CHs-CH CH3
CH3

- 55 -
N-(4-methoxy-3-methanesulfonamidophenyl) -N ' -
(2,4,6-triisopropylbenzenesulfonyl)-2-pivalamido-~-
benzenequinonediimine represented by the formula:
CH3
CH3S02HN Nycc(cH3) 3 CH3-CH CH3
CH3 0- - / O \- -N ~ NS0 2 - ,O, - -CH
CH3 -CH CH 3
CH3
The following examples are included for a further
understanding of the invention.

l.~t;~1i5~1
- 56 -
Example 1 -- Reversal Proce~sing to Produce a Positive
Dye Image
Thi6 illustrates the invention.
A silver bromide gelatino photographic emulsion
was prepared containing a dispersion of the following
S color-forming sulfonamidodiphenylamine dye precursor which
iB 4-diethyl~mino-4'-(2,4,6-triisopropylbenzenesulfon-
amido)diphenylamine:
H3C\ CH3
o C~ CH3
(C2Hs)2N--\ 0 \--N--\ 0 /--NHS--/ 0 /--CH
CH CH3
CH3 ~H3
(Dye Number le)
dispersed in N-n-butylacetanilide. The emulsion was
coated on a film support at a silver (Ag+) coverage of
104 mg/ft2 (corresponding to 11.2 mg/dm2), 45 mg/ft2
of Compound le and 90 mg/ft2 of N-n-butylacetanilide
(corresponding to 4.9 and 9.7 mg/dm2, respectively). A
sample of the resulting photographic film was imagewise
exposed to light in a commercial sensitometer for 10-4
seconds through a 1.0 neutral density filter to produce a
developable latent image in the film. Processing of the
exposed film was carried out as follows:
1. Develop for 60 seconds in the following developer
solution:
(a) sodium hexametaphosphate2.0 g
(b) N-methyl-~-aminophenol sulfate 6.0 g
(c) sodium sulfite (anhydrous) 50.0 g
(d) sodium carbonate (anhydrous) 30.0 g
(e) hydroquinone 6.0 g
(f) potassium bromide 2.0 g
(g) sodium thiocyanate 1.3 g

- 57 -
(h) sodium hydroxide 2.0 g
(i) potas6ium iodide (0.1 percent
solution) 6.0 ml
(j) water to 1 li,ter (pH 10.1 to 10.3)
2. Wash in water for 60 second6.
3. Re-expose by means of a uniform flash to light.
4. Develop 30 seconds in a pH 12 buffered developer
containing:
(a) 4-hydroxymethyl-4-methyl-1-
phenyl-3-pyrazolidone (cross-
oxidizing developing agent) l g/Q
(b) pota6sium bromide l g/Q
(c) benzyl alcohol 10 m1/Q
(d) water to 1 liter
5. Wash in water for 60 seconds.
6. Soak in the following bleaching and fixing compo-
sition (composition B-F~ for 60 seconds:
(a) (NaFe or NH4Fe) ethylene-
diaminetetraacetic acid 40.0 g
(b) ethylenediaminetetraacetic
acid (EDTA) 4.0 g
(c) potassium iodide 1 g
(d) ammonia (20 percent aqueous
solution) 10 ml
(e) ammonium thiosulfate,
crystalline 100 g
(f) sodium sulfite, anhydrous 2 g
(g) sodium or ammonium thio-
cyanate (20 percent
aqueous solution) 50 ml
(h) water to 1 liter (pH 6.2 to 6.5)
7. Wash 120 seconds in water, and
8. Dry at 22C in room air.
A dye only image which was a cyan po6itive image
was produced in the photographic film. The cyan dye image
had a maximum density of 1.41 and a minimum density of

;9~
- 58 -
0.17. The dye image had a maximum absorption at 680 nm.
Examples 2 through 11
Dye images were also produced by the procedure of
Example 1, with the exception that some of the color-forming
sulfonamidodiphenylamine dye precursors from the following
Table I were used in place of Dye Number le in Example 1.
The absorptions of the resulting dyes are given in the follow-
ing Table I. These values were obtained by the following
procedure:
A sample of the proposed color-forming sulfon-
amidodiphenylamine dye precursor (3 to 18 mg, based on
anticipated value of 1.0 for optical density of a solution)
was dissolved in butyl acetate (50 ml) or a similar solvent
for the dye precursor. This was mixed vigorously with a
solution of excess K3Fe(CN)6 in pH 12 phosphate buffer.
The organic phase was washed three times with water and
then diluted to 100 ml with butyl acetate for spectrophoto-
metric assay. This procedure ls useful for pre-screening
color-forming sulfonamidodiphenylamine dye precursors,
because the hue, ~-max (wavelength of maximum absorption)
and molar extinction (~) values obtained are comparable
to the properties of the image dye produced in a photographic
element. It is not probable that a proposed color-forming
sulfonamidodiphenylamine dye precursor is useful in a photo-
graphic element to form an image dye if the procedure of
reaction with K3Fe(CN)6 produces no suitable dye.

_ 59 ~L~L6~ 9
^~,
~C o
0
,` ,
o o
X X
C~l
a~
o=v~=o
~; æ
~ 11 -
C ~ / / \ / ~
U~ 11
~ ~ Z
.-, a~
JJ ~ -
U /\
.
~ ~ ~10 1
O C,~
0 \/
~a c~ cq -
l S
_
V~ ~ ~7
00 6q
)J
O O
~0 ~ ~
O
O
'~,
Z Z
C~
O = U~ = O
_I :C
~ Z
,f:/ \
O \ /
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The color-forming ~-sulfonamidodiphenyl~mine dye
precursors from which the dyes in Table I are derived are
named as follows:
Color-Forming Sulfonamidodiphenylamine Dye
Dye Precursors Correspondi.ng to Noted Dyes in
Number Table I:
~ .
la 4-Dihexylamino-4' (2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine
lb 4-Dihexylamino-3'-methyl-4'-~2,4~6 tr~iso-
propylbenzenesulfonamido)diphenylamine
lc 4-Dihexylamino-2'-methylsulfonyl-4'-(2,4,6-
triisopropylbenzenesulfonamido)diphenylamine
ld 4-Dihexylamino-2'-[~-(2,4-di-tert-amyl-
phenoxy)butylsulfamyl]-4'-benzenesulfonamido-
diphenylamine
lf 4-Diethylamino-4 7 - (4-n-dodecyloxybenzenesul-
fonamido)diphenylamine
lg 4-Hexyloxy-4'-(2,4,6-triisopropylbenzenesul-
fonamido)diphenylemine
lh 4-Hexyloxy-3'-methyl-4'-(2,4~6-triisopropyl-
benzenesulfonamido)diphenylamine
li 4-Dihexylamino-4'-(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine
lj 4-Dihexylamino-3l-methyl-4'-benzenesulfon-
amidodiphenylamine
lk 4-Hexyloxy-4'-benzenesulfonamidodiphenylamlDe
Examples 12 ~hrou~h 21 -- Fixing of .lements Comprising
Dyes of Sulfonamido_~phenylamines
Film strips (I) prepared as described in
Example 1 containing photographic silver halide and
containing the color-forming sulfonamldodiphenylamine dye
precursors described in the following Table II were
processed as follows:

3~;91
- 64 -
1. Fixed in the following liquid fix 601ution (fix
composition A) for 30 seconds:
(a) 60dium thiosulfate (cry6talline)
(or ammonium thiosulfate at 120.0 g)
160.0 g
(b) potassium metabisulfite 20.0 g
(c) water to 1 liter,
2. Wa~hed well in water for 120 6econds,
3. The color-forming 6ulfonamidodiphenylamine dye
precur~or wa6 oxidized by immer6ing the film into
the following composition:
(a) K3Fe(CN)6 (one percent by
weight in benzyl alcohol) 20 g
(b) Water to 1 liter (buffered to pH 12), and
4. Washed 120 æecond6 in water.
A æecond æet of comp~rative film 6trip6 (II)
containing the same color-forming æulfonamidodiphenylamine
dye precur~or6 were processed in the same way a6 described
for film 6trips (I), with the exception that the strips
were also reflxed in fix composltion A for 30 second6
following step 4, and then washed in water for 120 seconds.
The percentage den6ity 1088 on fixing for the
dyes waæ calculated aæ follow6:
% Denæity Lo6æ on Fixing ~ I D II x 100
where DI and DII were densities to complementary light
of film strip6 I and II, reæpectively.
.

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- 68 -
Table II demonstrates that only a 6 to 9 percent
dye density loss occurs for the 4'-triisopropylbenzene
~ulfonamido cyan dye formers la and lb relative to the 46
to 100 percent losses experienced for the non-ballasted
homologs. Comparison of the re~pective los6es (16 versu6
~6 percent) for Compounds le and lf demonstrate the
importance of a 4'-ballast with isopropyl groups in both
ortho positions of the benzene ring. The excellent
stability of Compound ld (4 percent loss~ demonstrates
that a bulky sub~tituent in the 2'-ring position conveys
stabilization of the image dye after fixing. Furthermore,
comparisons of the respective den6ity losses (O versus 33
percent) for the magenta dye precursor lh and the dye
precursor 2b show the value of the introduction of a tri-
isopropylbenzene sulfonamido ballast at the 4'-position.
Examples 22 through 29 -- Processing of Photographic
Elements
A. Film strips prepared as in Example 1 containing
photographic silver halide and containing the
color-forming sulfonsmidodiphenylamine dye
precursor descrlbed in the following Table III-A
were chemically processed at 22.2C according to
the sequence:
(l) 30-second fix in fix composition A,
(2) 60-second water wash,
(3) 30 seconds in pH 12.0 Na ~04 buffer
containing 10 g/liter K3Fe(CN)6, 10
ml/liter benzyl alcohol, 1 g/liter KBr and
water to l liter,
(4) 5-minute wash in water, and ~
3 (5) lO seconds in Kodak Photo-Fl~ , followed
by distilled water wash for 120 seconds.
The processed strips were then mounted on aperture cards
and exposed (emulsion side to light source) at 21~C and 45
percent relative humidity in a SANS test a6 described
~Ising 5400 ~UX irradiation for one, three and seven days.
Percentage fade of the dyes was calculated as follows:

3~i91
- 69 -
% Fade D
initial
where D is the density to complementary light after n
days. The term SANS herein means Simulated Aver~ge
Northern American Skylight.
B. Film 6trips prepared as in Example 1 containing
photographic silver halide and containing the
color-forming sulfonamidodiphenylamine dye
precur60rs described in Table III-B were photo-
graphically processed at 22.2C according to the
sequence:
(1) Imagewise expo6e to provide developable
latent image,
(2) Activate in the following developer:
pH 12 Na3P04 buffer containing 1 gram
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolido
ne, 10 ml benzyl alcohol, 1 gram K8r, water
to 1 liter, for 30 seconds,
(3) 2-minute wash in water,
(4) 30-second fix in fix composition A,
(5) 2-minute wash in water~ and
(6) dry in room air.
The dried strip6 were mounted and exposed to SANS irradia-
tion, as described above.

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- 76 -
The SANS fade results summarized in Table III-A
(for coatings chemically oxidized without development)
demonstrate the advantage of the triisopropylbenzenesul-
fonamido ballast. The respective seven-day dye loss for
la was about 23 percent, compared to almost complete
fading (83 to 100 percent) for the non-bsllasted dye6.
Similarly, the seven-day loss for lb was 9 percent versus
59 percent for the non-ballasted 1~ cyan dye; and, again,
a 19 percent loss for Compound le as contrasted to 100
percent destruction of the dye of Example 20. The
ballasted magenta dye-former lh faded 4.5 percent in
seven-day SANS, whereas the unballasted compound of
Example 22 showed 58 percent dye fade.
Density values of the images produced for the
listed dyes are as follows (see Table III-B):
Density
Example
Number Dye Silver (Ag)Silver ~Ag) with Dye
lb 0.42 1.56
20 36 la 0.43 1.68
37 ld 0.45 1.03
38 lh 0.37 1.40
39 lg 0.47 1.03
Example 40
A disper~ion of a color-forming para-sulfonamido-
d1phenylamine dye precursor, as designated in the follow-
ing Table IV-A, was prepared by dissolving one part of the
dye precursor in two parts of ethyl acetate and two parts
of N-n-butylacetanilide (coupler solvent~. This organic
mixture was combined with an aqueous gelatin solut~on and
passed through a colloid mill five times. The resulting
disper6ion was mixed with a gelatino photographic silver
halide emulsion and coated at about 11.7 mgs of ~ilver per
dm2 on a clear poly(ethylene terephthalate) film

~l t;~ ;'31
- 77 -
~upport. The resulting photographic element was lmagewise
expo6ed to light through a 1.0 neutral density filter in a
commercial sensitometer to provide a developable latent
image in the element.
The exposed photographic element was proce6sed
for 30 seconds at 22C in a developer composition
comprising:
4-methyl-4-hydroxymethyl-1-phenyl-3-
pyrazolidone (cross-oxidizing develop-
0 ing agent) 1 g
Na3P0412H 2 47 . 52 g
KBr 1 g
Water to 1 liter
The photographic element was then fixed for two
15 minute6 in an aqueou6 solution of 5-(2-hydroxyethyl)tetra-
hydro-S-triazine-2(lH)-thione represented by the formula:
-N
Ho-cH2cH2-N~ N/ ~S
H
The photographic element was then washed in water for five
minutes. The following Table IV-A identifies the color-
5 forming sulfonamidodiphenylamine dye precursor, a8 well asthe maximum absorption of the corresponding dye produced
upon proces 8 ~ng.
TABLE IV-A
Example Dye Absorption:
NumberNumber Dmax DminAmax, nm
Control None 0.19 0.14 (black)
40a 0.59 0.08 460
41a 0.53 0.07 535
42 42A 1.16 0.20 720
43 43a 0.48 0.08 430

~6!~6~3
- 78 -
Example Dye Color-Forming
Number Number Dye Precursor
1-methoxy-4'-benzenesulfonamido-
diphenylamine
41 41a 4-hexyloxy-3'-methyl-4'-benzene-
8ul fonamidodiphenylamine
42 42a 4-dihexylamino-4'-benzenesulfon-
amidodiphenylamine
43 43a 4-methyl-4'-~-tolylsulfonamido-
diphenylamine
Example 44 -- Use in Direct Positive Photographic Silver
Halide Material
A photographic element was prepared by coating
the following composition on a poly(ethylene terephtha-
late) film support:
Silver chloroiodide gelatino
emulsion (0.4 mole percent I,
0.24 micron cubic grsins, surface
chemically sensitized, internally
doped) 9.7 mg/dm2
(as Ag)
gelatin ~hardened by means of
bis(vinylsulfonylmethyl)ether]43.2 mg/dm2
color-forming dye precursor:
(dispersed in di-n-butylphthalate~ 5.4 mg/dm 2
CH3 _.
CH3CH2~ / 0 \--NH--/ 0 /--NHS02--~ 0 / -
CH3S02NH(CH2)2 -- t
NHCC7HIs-n
0
.

~ 9f;91
- 79 -
The resulting emulsion layer was overcoated with 10.8
mg/dm2 of gelatin hardened with bis(vinylsulfonylmethyl)
ether. The resulting photographic element according to
the invention was imagewise exposed to light in a commer-
cial senæitometer to produce a developable image in the
emulsion layer. Then the exposed photographic element was
processed as follows:
(1) 30 seconds activation in the following
composition:
0 phosphate buffer (pH 12)
4-hydroxymethyl-4-methyl-1-phenyl-
3-pyrazolidone 1 g/L.
benzyl alcohol (1 percent by
volume),
(2) 60-second wash in water,
(3) 30-second fix (pH 10) in a fixing composition; snd
(4) 120-second wash in water.
This produced a dye image and silver image in the emulæion
layer. The processed element w~s permitted to dry in
air. The density of the resulting image was (read through
B red filter): Dmax 1.57, Dmin 0.41. A reversal image
was produced.
A second sample of the imagewise exposed photo-
graphic element was fixed and oxidized by means of potas-
sium ferricyanide to produce a maximum density of 1.40.
Example 45 -- Illustrative Developeræ
A. The following photographic composition was coated
on a poly(ethylene terephthalate) film support:
AgBr octahedral grains)9.4 mg/dm2
gelatin (binder) 43.2 mg/dm2
bis(vinylæulfonylmethyl) ether
(hardener) 0.4 mg/dm2
di-n-butyl phthalate (coupler
~olvent) 5.4 mg/dm2

~ ~6'36~:~
- 80 -
color-formlng para-sulfonamidodi-
phenylamine dye precursor: 5.4 mg/dm2
NHCC7HIs _./
CH3SO2NH(CH2) ~ ~.0 ~ NH- \ 0 ~--NHSO2 -/ 0 \---~
(Compound 45A) (Cyan)
potas6ium nitrate 0.6 mg/dm2
The resulting emul6ion layer was then overcoated by means
of gelatin (10.8 mg/dm2) hardened by bis(vinylsulfonyl-
methyl) ether (0.108 mg/dm2). The re6ulting photo-
graphic element was imagewise exposed to light through a
conventional step tablet in a commercial sensitometer to
produce a developable latent image in the emulsion layer.
Processing was carried out at 22C as follows with agita-
tion oi the processing solutions:
(a) Development for 30 seconds in the following
developer solution:
Na3P04-12H20 47.5 g
Na2S3 5.0 g
N,N-diethylhydroxylamine
(85 percent in H20) 1.0 ml
4,4-dimethyl-1-phenyl-3-
pyrazolidone 5 mM
KBr 1~0 g
Water (to one liter)
(pH 12.0);

1~6'3691
(b) Rinse for 60 second~ in water;
(c) Fix for 30 seconds in the following compo~ition:
Na2S2o3 5H20 248 g
Na2C03-H20 30.0 g
NaHC03 g
Water to one liter
(pH 10.0);
(d) Wash for five minutes in water; and
(e) air dry.
A cyan image was produced.
The procedure was repeated, with the exception
that the following color-forming sulfonamidodiphenylamine
dye precursor was used in place of Compound 45A:
11
NHCC(CH 3 ) 3 . /
! . \. .
C6Hl30--/ 0 /--NH--\ ~ ~ - -NHSO 2 - ~0
(Compound 45B) (Magenta)
Compound 45B was coated in the emulsion layer at 9.6
mg/dm2 with 9.6 mg/dm2 of the coupler solvent.
The image produced with the Compound 45B had a
maximum density of 1.25 to green light and a density of
0.41 in the eleventh step of the image. The image
produced with the Compound 45A had a maximum den~ity of
1.12 to red light and a density of 0.80 in the eleventh
step of the image.

1:~L6'3~91
- 82 -
B. The procedure in A. was repeated, with the excep-
tion that N-(p-hydroxyphenyl) pyrrolidine waæ used in
place of 4,4-dimethyl-1-phenyl-3-pyrazolidone. The image
produced with Compound 45B had a maximum den6ity of 1.41
and an eleventh step density of 0.43. The image produced
with Compound 45A had a maximum density of 1.56 and an
eleventh step density of O.S9.
C. The procedure in A. was repeated, with the excep-
tion that ~-N,N-dimethyl-~-aminophenol was used in place
of 4,4-dimethyl-1-phenyl-3-pyrazolidone. The image
produced with Compound 45B had a maximum density of 0.80
and an eleventh step density of 0.21. The image produced
with Compound 45A had a maximum den6ity of 1.42 and an
eleventh 6tep density of 0.28.
D. The procedure in A. was repeated, with the excep-
tion that N,N,N',N'-tetramethyl-~-phenylenediamine
dihydrochloride wa6 used in place of 4,4-dimethyl-1-
phenyl-3-pyrazolidone. The image produced with
Compound 45B had a maximum density of 1.30 and an eleventh
step den~ity of 0.38. The image produced with
Compound 45A h~d a maximum density of 1.34 and an eleventh
step denslty of 0.72.
E. The procedure in A. wa~ repeated, with the
exception that 6-amino-1-hydroxyethyl-2,2,4-trimethyl-
tetrahydroquinoline dihydrochloride wa6 u6ed in place of4,4-dimethyl-1-phenyl-3-pyrazolidone. The image produced
with Compound 45B had a maximum density of 1.23 and an
eleventh step den6ity of 0.22. The image produced with
Compound 45A had a maximum den6ity of 1.32 and an eleventh
step density of 0.40.
The maximum density valuefi for each of the images
produced in Examples 45A, B, C, D and E comprised about
0.40 neutral metallic silver den6ity.
Example 46 -- Mixed Dye Precursor6
A dispersion of 4-dihexylamino-4'-(2,4,6-triiso-
propylbenzenesulfonamido)diphenylamine (see Dye la in

- 83 -
Example 1) was prepared by di~æolving 3.0 gram6 of this
fir6t color-forming dye precur60r in 8.0 gram6 of
N-n-butylacetanilide. The re6ulting di6per6ion was
designated Di6persion 46A. A dispersion of 4-hexyloxy-
3'-methyl-4'-(2,4,6-trii60propylbenzenesulfonamido)diphenyla
mine (6ee Dye lh in Example 1) wa6 prepared by dis601ving
4.0 gram6 of this 6econd color-forming dye precur60r in
8.0 grams of N-n-butylacetanilide and 8.0 gram6 of ethyl
acetate. The resulting dispersion wa6 designated
Disper6ion 46B.
The following fir6t photographic 6ilver bromide
composition was coated on a poly(e~hylene terephthalate)
film 6upport:
red-sen6itized gelatino photo-
graphic 6ilver bromide emul6ion 9.7 mg/dm2
Disper6ion 46A:
4-dihexylamino-4'-(2,4,6-tri-
isopropylbenzene-
sulfonamido)diphenylamine
(dye precursor) 4.1 mg/dm 2
N-n-butylacetanilide 1008 mg/dm 2
gelatin (binder) 43.2 mg/dm 2
bis(vinylsulfonylmethyl) ether
(hardener) 0.4 mg/dm2
The following interlayer was coated on the
resulting fir6t layer:
2,5-di-s-dodecyl-1,4-dihydroxy-
benzene 12.9 mg/dm 2
gelatin (binder) 16.8 mg/dm2
bis(vinylsulfonylmethyl)ether
(hardener) 0.17 mgldm 2

~ 3
- 84 -
Then the following second photographic silver
bromide compo~i~ion was coated on the re6ulting interlayer:
green-sensitized gelatino photo-
graphic silver bromide emulsion 9.7 mg/dm2
Di6persion 46B:
4-hexyloxy-3'-methyl-4'-
(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine
(dye precur60r) 5.4 mg/dm2
N-n-butylacetanilide 10.8 mg/dm2
gelatin (binder) 43.2 mg/dm 2
bis(vinylsulfonylmethyl) ether0.4 mg/dm
The re6ulting photographic element was de6ignated a6
Element 46I. A 6imilar photographic element wa6 prepared,
with the exception that 2,5-dl-s-dodecyl-1,4-dihydroxy-
benzene was omitted. This photographic element was
designated a6 Element 46II. Each of the photographic
element6 wa6 imagewi6e exposed to light by mean6 of a
commercial wedge 6pectrograph to produce a developable
latent image in the element6. Then the element6 were
proces6ed at 22~C. a6 follows:
(1) Activated 30 seconds in the following composition:
Na3P04 (pH 12) (buffer)
4-hydroxymethyl-4-methyl-1-
phenyl-3-pyrazolidone 1 g
benzyl alcohol 10 ml
KBr 1 g
Water to 1 liter;

1~9~9~
- 85 -
(2) Wa6hed two minutes in water;
(3) Fixed for 30 second6 in the following fixing
composition:
Sodium thiosulfate (or
ammonium thio6ulfate 120.0 g) 160.0 g
Pot~sium metabisulfite 20.0 g
Water to 1 liter (pH 4.7);
(4) Wa6~ed two minute6 in water; and
(5) Air dried.
The photographic element6 produced a developed silver and
dye image. The following tran6mi6sion maximum and minimum
dye den6ities (negative) were ob6erved for the image~
produced in each e}ement when read by white, red and green
light:
Element 46I. Dmax Dmin
White 1.47 0.23
Red 1.66 0.39
Green 0.31 0.09
Element 46II: Dmax Dmin
White 1.47 0.10
Red 1.62 0.17
Green 0.74 0.09
The data demon6trateæ that the photographic
Elements 46I and 46II provide an overall blue dye-enhanced
silver image.
Compari60n of the maximum density values for
green light indicates color contamination occurred for
Element 46II which was a consequence of wandering of the
oxidized form of the 3-pyrazolidone developing agent
between layers of the element. In Element 46I, pure color
separation was ob6erved with no evidence of interlayer
oxidized 3-pyrazolidone developing agent wandering.

- 86 -
Example 47 -- Comparison of Stability in Photogrsphic
Material
The following color-forming 6ulfonamidodiphenyl-
amine dye precursors were compared regarding the 6tability
5 of the corresponding 6ulfonimide dyes formed in a silver
halide photographic material according to the invention:
47A 4-Hexyloxy-4'-(2,4,6-triisopropylbenzene6ul-
fonamido)diphenylamine
47B 4-n-Hexyloxy-2'-pivalamido-4'-(2,4~6-triisopropyl-
benzene6ulfonamido)diphenylamine
47C 4-Hexyloxy-3'-pivalamido-4'-(2,4,6-trii60propyl-
benzenesulfonamido)diphenylamine
47D 2',5'-Dipivalamido-4-n-hexyloxy-4'-(2,4,6-trii60-
propylbenzene6ulfonamido)diphenylamine
15 Each one of these dye precur60rs wa6 incorporated in a
photographic 6ilver halide element compri6ing a subbed
poly(ethylene terephthalate) film support having thereon a
layer comprising:
(1) 6ilver bromide (0.8 micron grain size, octahedral
grains, chemlcally sensitized by means of 8ulfur
and gold sensitizers) (9.7 mg/dm2) (90
mg/ft2), and
(2) gelatin (400 mg/ft2) (43.2 mg/dm2) hardened
with bi6(vinyleulfonylmethylether) (one percent
by weight) (binder).
The color-forming para-~ulfonamidodiphenylamine dye
precur- 60r was di6per6ed in 601vent (1:1 to 1:2 part6 by
weight) in the layer at 35 to 150 mg/ft 2 (3.0 to 16.2
mg/dm2). Each of the photographic element6 wa6
30 uniformly exposed to light in a commercial 6en6itometer to
produce a developable image in the element. Then each
photographic element wa6 proce~6ed at 22C a6 follow6:
(a) Activated for 30 seconds in the following
composition:
4-methyl-4-hydroxymethyl-
l-phenyl-3-pyrazolidone 1 g

~ 9
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potassium bromide 1 g
benzyl alcohol 10 ml
Na3P04-12H20 47.5 g
H20 to one liter
pH ad~u6ted to 12.0
(b) Washed for 30 6econds in water;
(c) Fixed for 30 6econds in the following composition:
Na2S203-5~ 0 248 g
Na2C03-H20 30.0 g
NaHC03 5.0 g
Water to 1 liter (pH 10.0); and
(d) Wa6hed for two minute6 in water.
A dye image and a silver image were formed in each of the
photographic elements. The developed images had the
following maximum and minimum density values:
Dmax Dmin
(Measured at(Derived from
Maximum Unexpo6ed
Dye AbsorptionPhotographic
Precur60r Wavelength)Element at ~max of dye)
47A 1.03 0.08
47B 0.72 0.08
47C 1.49 0.07
47D 1.71 0.08
Each of the photographic elements after processing was
exposed to light in a SANS test. After seven days, the
percentage fade of the dye image wa6 observed. The
following result6 were obtained:

;969
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Dye Precur60r Percent Fade
47A 13.3
47B 5.6
47C 26.2
47D 0
This illustrates the degree of stability to light
exhibited by dye image6 according to the invention.
A separate sample of each of the photogr&phic
elements after processing was exposed to a "wet oven test"
in which the photographic element was placed in an oven at
60C and 70 percent humidity. After 6even days, the
percentage fade of the dye image was observed. The
following re6ults were obtained:
Dye Precursor Percent Fade
20 47A 100.0
47B 6.3
47C 100.0
47D +1.9
(The dye image for 47D
increased in density.)
This illustrates that the sulfonimide dye images produced
from dye precursors 47B and 47D are more stable than the
sulfonimide dye~ produced from Compound6 47A and 47C.
The foll~wing dye precursors were also found to
produce corresponding 6ulfonimide dyes according to the
invention:
Example 48
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino~-
2-methyl-2~,5~-pivalamido-4~-(2,4,6-trii60propylbenzenesul-
fonamido)diphenylamine

l~i9~
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Example 49
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-
2-methyl-3'-pivalamido~4'-(2,4,6-triisopropylbenzenesul-
fonamido)diphenylamine
Example 50
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-
2-methyl-2',5'-dipivalamido-4'-(2,4,6-trii60propylbenzene-
sulfonamido)diphenylamine
Example 51
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino]-
2-methyl-2'-octanamido-4'-(2,4,6-triisopropylbenzenesul-
fonamido)diphenylamine
Example 52
4-Diethylamino-2-methyl-2'-methoxy-5'-pival-
amido-4'-(2,4,6-triisopropylbenzenesulfonamido)diphenyl-
amine
Example 53
4-Hexyloxy-2'-(N-methyl)acetamido-4'-(2,4,6-
triisopropylbenzenesulfonamido)diphenylamine
Example 54
4-Methoxy-2-methyl-2'-octanamido-4'-(2,4,6-tri-
isopropylbenzene6ulfonamido)diphenylamine
Example 55
4-Methoxy-2-methyl-2'-n-hexylureido-4'-(2,4,6-
triisopropylbenzene6ulfonamido)diphenylamineExample 56
4-Hexyloxy-2'-[~-(2,4-di-t-amylphenoxy)hexan-
amido]-4'-(2,4,6-triisopropylbenzene6ulfonamido)di-
phenylamine
Example 57
4-Dihexylamino-3'-pivalamido-4'-(2,4,6-triiæo-
propylbenzenesulfonamido)diphenylamine
Example 58
4-[N-ethyl-N-(~-methanesulfonamidoethyl)amino~-
2-methyl-2',5'-didodecyloxy-4'-(2,4,6-triisopropylbenzene-
sulfonamido)diphenylamine

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Example 59
The following photographic ~ilver halide compo~i-
tion was prepared and coated on a poly(ethylenetere-
phthalate) film support:
photographic silver bromide gelatino 9.7 mg/dm2
emulsion (0.8 micron grain, octa-
hedral grains, sulfur and gold
chemically sensitized)
gelatin 43.2 mg/dm2
bis(vinylsulfonylmethyl) ether0.43 mg/dm 2
(hardener)
N-n-butylacetanilide (coupler6.5 mg/dm2
solvent)
3-methanesulfonamido-2'-octan-6.5 mg/dm2
amido-4'-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine
(dye precursor)
The resulting photographic element was imagewise exposed
to light through a step tablet and a neutral density
filter in a commercial sensitometer to provide a develop-
able latent image in the photographic silver bromide
layer. The exposed element was then processed at 22~C as
fcllows:
(1) Activated for 30 seconds in the following
composition:
4-hydroxymethyl-4-methyl-
l-phenyl-3-pyràzolidone 1 g
benzyl alcohol 10 ml
pH 12, Na3P04 buffered water to 1 liter;

91
- 91 -
(2) Fixed until cleared in the following fixing
composition:
NaHC03 0.5 g
Na2C3 40 g
Na2S23 100 g
Water to 1 liter
This provided a developed 6ilver image and dye image
having a maximum density of 0.92. The maximum absorption
(~ max) was 435 nm. The procedure was repeated, with
the exception that in place of fixing the developed photo-
graphic element in the noted fixing composition, the
photographic element was treated in a bleach-fix
composition.
lS This removed the silver image. The resulting dye image
had a maximum density of 0.3 at 435 nm.
Examples 60 through 78
The following color-forming para-sulfonamidodi-
phenylamlne dye precursors also provided corresponding
sulfonimide dyes similar to the dye image produced in
Example 59. In each case, the dye precursor was prepared
as a dispersion in N-n-butylacetanilide (weight ratio of
1:1 to 1:2) and coated in the photographic silver halide
layer at 3.8 to 16.2 mg/dm2 at the appropriate concen-
tration to produce a dye and silver image density of about2Ø The development step was carried out at 26 to 27C
in an aqueous proces~ing solution (buffered to pH 12.2)
containing 1 gram per liter of 4-hydroxymethyl-4-methyl-
l-phenyl-3-pyrazolidone (cross-oxidizing developing
agent). The maximum absorption wavelength of each of the
corresponding sulfonimide dyes formed is given for each of
the dye precursors. Many of the ionizable 3-sulfonamido
sub6tituted dye precursors gave improved reactivity.
Example 60
3-Methanesulfonamido-4-methoxy-2'-octanamido-
4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine
(475 nm)

- 92 -
Example 61
3-(N-methyl)methaneæulfonamido-4-methoxy-2'-
octanamido-4'-(2,4,6-triisopropylbenzene6ulfonamido)-
dlphenylamine (472 nm)
_xample 62
3-Methanesulfonamido-4-methoxy-2'-pivalamido-
4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine
(478 nm)
Example 63
4-Methyl-2~-palmitamido-4'-(2,4,6-triisopropyl-
benzenesulfon~mido)diphenylamine (489 nm)
Example 64
3-Methanesulfonamido-2'-octanamido-4'-(2,4,6-
triisopropylbenzenesulfonamido)diphenylamine (429 nm)
Example 65
3-(N-methyl)methanesulfonamido-2'-octanamido-
4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine
(430 nm)
Example 66
3-Methane~ulfonamido-2'-palmitamido-4'-(2,4,6-
triisopropylbenzene~ulfonamido)dlphenylamine (429 nm)
Example 67
3-Methanesulfonamido-4-methyl-2'-palmitamido-4'-
(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (438
nm)
Example 68
3-Methanesulfonamido-4,6-dimethyl-2'-palmitamido-
4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine
(433 nm)
Example 69
3-Methanesulfonamido-6-methoxy-2'-octanamido-4'-
(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (419
nm)
Example 70
3-Acetamido-2'-octanamido-4~-(2,4,6-triisopropyl-
benzenesulfonamido)diphenylamine (429 nm)

1~ ~ 9~ 9
- 93 -
_xample 71
4-[N-(~-methylsulfonamido)ethyl-N-ethyl~-
amino-2-methyl-2'-octanamido-4'-(2,4,6-trii60propyl-
benzenesulfonamido)diphenylamine (641 nm)
Example 72
4-~N-(g-N'-methylmethylsulfonamido)ethyl-N-
ethyl]amino-2-methyl-2'-octanam~do-4'-(2,4,6-tri-
isopropylbenzenesulfonamido)diphenylamine (642 nm)
Example 7_
3-(4-Dodecyloxybenzene)sulfonamido-4~-(2,4,6-
triisopropylbenzenesulfonamido)diphenylamine (484 nm)
Example 74
3-(2,4-Ditert-amylphenoxy)acetamido-4'-(2,4,6-
triisopropylbenzenesulfonamido)diphenylamine (479 nm)
Example 75
4-Methoxy-2-methyl-2'-octanamido-4'-(2,4,6-
triisopropylbenzenesulfonamido)diphenylamine (515 nm)
Example 76
4-n-Hexyloxy-2'-L~-dodecyl-a-(3-tertbutyl-
4-acetoxyphenoxy)acetamido]-4'-(2,4,6-trli80propylben-
zenesulfonamido)diphenylamine ~505 nm)
Example 77
4-n-Hexyloxy-2'-[~-dodecyl--(3-tertbutyl-
4-hydroxyphenoxy)acetamido]-4'-(2,4,6-triisopropylben-
zenesulfonamido)diphenylamine (504 nm)Example 78
2,4-Dimethoxy-2'-octanamido-4'-(2,4,6-triiso-
propylbenzenesulfonamido)diphenylamine (533 nm)
Other color-forming para-6ulfonamidodi-
phenyl~mine dye precursors that are useful for form-
ing sulfonimide dyes are described in copending
Canadian Application Serial No. 403,954, of R. S.
Gabrielsen, P. A. Graham, J. E. Kli~anowicz and M. H.
Stern, filed May 28, 1982 entitled "Color-Forming
Sulfonamidodiphenylamine6 and Corresponding
Sulfonimide Dyes".
<
.~

- 94 -
The invention has been described in detail with
particular reference to preferred embodiments thereof, but
i.t will be understood that variations and modifications
can be effected within the spirit and scope of the
invention.