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Publication numberUS3725067 A
Publication typeGrant
Publication dateApr 3, 1973
Filing dateJan 15, 1971
Priority dateJan 15, 1970
Also published asCA957684A, CA957684A1, US3705896, US3758309
Publication numberUS 3725067 A, US 3725067A, US-A-3725067, US3725067 A, US3725067A
InventorsJ Bailey, E Knott, P Marr
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Silver halide emulsion containing 1-h-pyrazolo(3,2-c)-s-triazole color couplers
US 3725067 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent 3,725,067 SILVER HALIDE EMULSION CONTAINING l-H- PYRAZOL0[3,2-c]-s-TRIAZOLE COLOR COUPLERS Joseph Bailey, Harrow Middlesex, and Edward B. Knott, Bushey Heath, England, and Peter A. Marr, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y.

No Drawing. Continuation-impart of application Ser. No. 778,329, Nov. 22, 1968. This application Jan. 15, 1971, Ser. No. 106,892

Claims priority, application Great Britain, Jan. 15, 1970,

Int. Cl. dose 7/00, 7/40 US. 01. 96-565 7 Claims ABSTRACT OF THE DISCLOSURE 1-H-pyrazolo[3,2-c]-s-triazoles having utility as photographic color couplers possessing good coupling activity and forming dyes of good spectral absorption characteristics and also utility as precursors in the formation of various methine sensitizing dyes.

This application is a continuation-in-part of US. Ser. No. 778,329 filed on Nov. 22, 1968 and relates to photography, and particularly to color photography including color-forming couplers, light-sensitive photographic materials containing color-forming couplers, developer compositions containing color-forming couplers and processes for forming photographic dye images.

Formation of colored photographic images in photographic elements by the coupling of the oxidation products of primary aromatic amine developing agents, formed during photographic development of silver salt emulsions, with color couplers is well known. In the subtractive process of color photography, the image dyes formed from the color couplers are of complementary primary colors, cyan (blue-green), magenta and yellow. The color couplers used to produce the cyan dyes are usually phenols or naphthols, those used to produce the magenta dyes are usually pyrazolones and those used to produce the yellow dyes are usually open-chain compounds containing a methylene group having one or two carbonyl groups attached to it. In photographic elements for three-color photograpy wherein the couplers are incorporated in the emulsions the cyan-forming couplers are usually in the red-sensitive emulsion, the magentaforming couplers are usually in the green-sensitive emulsion and the yellow-forming couplers are usually in the blue-sensitive emulsion. Sometimes the couplers are incorporated in the color developing baths.

Oolor couplers whose solubility or dispersibility is sufiicient to enable them to be usefully incorporated in aqueous color developing baths are referred to as diffusible-type couplers. Color couplers of such high molecular weight and/or complex molecular structure that they are capable of remaining, during color development, in photographic hydrophilic colloid-silver emulsion layers in which they have been incorporated are referred to as non-diffusing couplers. Non-diffusing couplers having carboxylic or sulfonic groups rendering them soluble in aqueous alkali are referred to as Fischer-type couplers. Non-diffusing couplers having no such solubilizing groups are somewhat hydrophobic and are generally incorporated in hydrophilic colloid-silver halide emulsions with the aid of high-boiling solvents.

When the dye image formed on color development is to be used in situ, e.g., as, or as part of, a color transparency or color print, the coupler must be one which gives a substantially non-diffusing dye. The dye image used for image transfer processes should be ditfusible but capable of being mordanted or fixed in the receiving 3,725,067 Patented Apr. 3, 1973 sheet. For this purpose, a coupler is selected which will produce this type of dye.

Color couplers have a reactive group, usually a reactive methylene group, which reacts with the oxidation products of the primary aromatic amino developing agent producing azo-methines, indamines or indophenols depending upon the nature of the color coupler and of the developing agent. If the reactive group is an unsubstituted reactive methylene group, then for the formation of each equivalent of dye there are required the oxidation products resulting from the development of 4 equivalents of silver. These couplers are referred to as 4-equivalent couplers. Couplers which have one of the hydrogen atoms of the reactive methylene group replaced by a coupling-of group, such as, a halogen atom, are referred to as Z-equivalent couplers because they require the oxidation products resulting from the production of only 2- equivalents of silver.

British patent specification 918,128 describes pyrazolino-benzimidazole color couplers which form magenta dyes on coupling with oxidized color developers. However, when incorporated into silver halide emulsions in the form of a dispersion obtained by dissolution of the coupler in an organic solvent and dispersing the solution in an aqueous solution of a hydrophilic colloid, such as gelatin, the couplers give inadequate color images. The couplers have the disadvantage of relatively low coupling activity in normal color developer solutions.

The magenta dyes formed from some of the prior art S-pyrazolone couplers have unwanted absorption, for example, unwanted absorption of blue light. The magenta dyes formed from certain of the S-pyrazolones do not have as sharp a cutting spectral absorption curve on the long wavelength side as desired. There has been a continuing search for new magenta dye-forming couplers which will produce magenta dyes having the desired spectral absorption characteristics and couplers which have good coupling activity in the usual color developer solutions.

It is therefore an object of our invention to provide a novel class of couplers which have good coupling activity in normal color developer solutions and which produce dyes having improved spectral absorption characteristics.

Another object of our invention is to provide a novel class of dye-forming couplers, some of which are used to produce improved magenta dyes and others of which are used to produce yellow dyes for color photography.

Another object of our invention is to provide lightsensitive photographic emulsions containing our novel dye-forming couplers for use in photographic elements.

Another object of our invention is to provide novel photographic color developer compositions comprising a primary aromatic amine color developing agent and one of our novel dye-forming couplers.

Still another object of our invention is to provide a novel photographic color process for forming magenta dye images and for forming yellow dye images.

Still other objects of our invention will become apparent from a consideration of the following specification and claims.

These and still other objects of our invention are accomplished by making and using our novel dye-forming couplers which are derived from lH-pyrazolo[3,2-c]-striazoles in which the carbon in the 7 position of the ring appears to be the reactive coupling position and which is substituted with hydrogen or any of the usual couplingolf groups used in photographic dye-forming couplers and in which the carbons in the 3 and 6 positions of the ring are substituted with hydrogen or any of the conventional substituents used in the non-coupling positions on photographic dye-forming couplers such as ballasting groups, solubilizing groups, etc.

Included among the lH-pyrazolo[3,2-c]-s-triazole couplers of our invention are those represented by the folwherein R represents a hydrogen, an esterified carboxy group, such as a 0 II R500- group in which R is an alkyl group (substituted or not), 2 particularly an alkyl having from 1 to 22 carbon atoms (e.g., methyl, benzyl, phenethyl, 2-chloroethyl, 2-methoxyethyl, ethyl, butyl, hexyl, dccyl, pentadecyl octadecyl, docosyl, etc.), and a phenyl group (substituted or not), e.g., phenyl, tolyl, methoxyphenyl, 2-chlorophenyl, 2,4,6-trichlorophenyl, etc.; and any group used on conventional photographic dye-forming couplers which splits off during color development with an oxidized primary aromatic amine color developing agent, including a halogen atom (e.g., Cl, Br, 1, etc.); the sulfo group; a watersoluble salt of the sulfo group, such as, an alkali metal (Na, K, etc.) salt, the ammonium salt, etc.; the carboxy group; a water-soluble salt of the carboxy group, such as, an alkali metal (Na, K, etc.) salt, the ammonium 5 salt, etc.; a R O group in which R represents an alkyl group, particularly an alkyl group having from 1 to 22 carbon atoms (e.g., methyl, benzyl, ethyl, phenethyl, 2-chlor0ethyl, methoxypropyl, propyl, decyl, dodecyl, heptadecyl, docosyl, etc.), an aryl group, such as, 0 a phenyl group (e.g., phenyl, tolyl, alkylsulfonylphenyl, arylsulfonylphenyl, N-alkylsulfamylphenyl, N,N-dialkylsulfamylphenyl, N-arylsulfamylphenyl, N-alkyl-N-arylsulfamylphenyl, sulfamylphenyl, nitrophenyl, acetamidophenyl, halophenyl, methoxyphenyl, octadecyloxyphenyl, hydroxyphenyl, sulfophenylazophenyl, an N-alkylcarbamylphenyl (e.g., N-octadecylcarbamylphenyl, N-methylcarbamylphenyl, etc.), carboxyphenyl, sulfophenyl, etc.), a naphthyl group (e.g., tit-naphthyl, ,B-naphthyl, etc.), and a heterocyclic group having from 5 to 6 atoms in the heterocyclic ring, such as, a pyridyl group, a quinolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group (e.g., S-tetrazolyl, l-phenyl-S-tetrazolyl, etc.); a R S in which R, is as described previously; a R N=N group in which R represents a radical of a diazotizable amine, such as, an aryl amine, e.g., a phenyl amine (in which the phenyl moiety is phenyl, tolyl, pentadecylphenyl, 4-carboxymethylphenyl, me thoxyphenyl, 4-carboxy methoxyphenyl, octadecyloxyphenyl, sulfomethylphenyl, sulfophenyl, 2,4-dinitrophenyl, 4-acetamidophenyl, Z-methoxy 4 nitrophenyl, etc.), a naphthyl amine (in which the naphthyl moiety is tit-naphthyl, it-naphthyl, 4-sulfo-a-naphthyl, 4-methoxya-naphthyl, 4-chloro-u-naphthyl, etc.) and a heterocyclic amine having from 5 to 6 atoms in the ring (in which the heterocyclic moiety is Z-benzothiazolyl, 2-thiazolyl, 2-quinolyl, 4-quino1yl, a pyrazolyl group (e.g., pyrazolyl, 3-methyl-S-pentadecylpyrazolyl, etc.); an acyloxy group, such as, an alkylcarbonyloxy group in which the alkyl moiety represents a straight or branched chain alkyl group having from 1 to 30 carbon atoms that is unsubstituted or substituted with any of the conventional substituents used, such as, halogen, nitro, hydroxyl, carboxyl, amino, substituted amino, aryl, carboxy esters (e.g., carboethoxy, carbophcnoxy, etc.), amido (e.g.,

acetamido, butyramido, ethylsulfonamido, N-propylbenzamido, etc.), carbamyl (e.g., N-methylcarbamyl, N-octadecylcarbamyl, N-methyl-N-phenylcarbamyl, etc.), sulfamyl (e.g., N-propylsulfamyl, N-tolylsulfamyl, etc.), alkoxy (e.g., ethoxy, octadecyloxy, etc.), aryloxy (e.g., phenoxy, tolyloxy, etc.), sulfo, sulfo esters (e.g., methylsulfonyl, octadecylsulfonyl, phenylsulfonyl, tolylsulfonyl, phenoxysulfonyl, etc.), an arylcarbamyloxy group, in which the aryl moiety is a phenyl group (e.g., phenyl and substituted phenyl in which the substituents are any of those defined for the alkyl moiety in the acyloxy group), and a naphthyl group (e.g., naphthyl and substituted naphthyl in which the substituents are any of those defined for the alkyl moiety in the acyloxy group), and a heterocyclylcarbamyloxy group in which the heterocyclic moiety has from 5 to 6 atoms in the ring, such as:

a benzofuranyl group, a furanyl group, a thiazolyl group,

0 a benzothiazolyl group,

a naphthothiazolyl group, an oxazolyl group,

a benzoxazolyl group,

an imidazolyl group,

a benzimidazolyl group,

a quinolinyl group, etc.;

a substituted sulfonyloxy group, such as, an alkylsulfonyloxy group havin an alkyl moiety, an alkyl group substituted or not and especially those of from 1 to 22 carbon atoms (e.g., methyl, ethyl, octadecyl, 2-carboxyethyl, 4- sulfobutyl, S-hydroxypentyl, 2-chloroethyl, t-butyl, 3- carbethoxypropyl, 4-methoxybutyl, etc.), an arylsulfonyloxy group in which the aryl group is substituted or not and is preferably a group such as a phenyl group (e.g., phenyl, 3-aminophenyl, 4-aminophenyl, S-carboxyphenyl, 4-sulfophenyl, 3-hydroxyphenyl, 4-cyanophenyl, 3-nitrophenyl, 2-chlorophenyl, 4-ethoxyphenyl, 3-octadecylcarbamylphenyl, 4 butyramidophenyl, 3 docosylphenyl, etc.); thiocyano; a benzotriazolyl group (e.g., benzotriazolyl, S-chlorobenzotriazolyl, 6-methylbenzotriazolyl, 5- methoxybenzotriazolyl, etc.; R represents a R CH: group in which R represents an alkyl group, e.g., methyl, ethyl, butyl, phenethyl, etc., and an aryl. group, such as, a phenyl group, e.g., phenyl, tolyl, ethylphenyl, methoxyphenyl, dimethylarninophenyl, etc.; R and R each represent the same or a different group, such as, hydrogen; an alkyl group that is straight chain or branched chain preferably having from 1 to 22 carbon atoms unsubstituted or substituted with any of the usual substituents used on photographic couplers as solubilizing groups, ballasting groups, etc., such alkyl groups include methyl, ethyl, n-propyl, isopropyl, sec. butyl, t-butyl, t-amyl, hexyl, dodecyl, docosyl, 2-chlorobutyl, Z-hydroxyethyl, Z-phenylethyl, 2-(2,4,6-trichlorophenyl)ethyl, an alkyl group containing a non-coupling phenolic stabilizer moiety such as a 4-substituted phenol as described in French Pat. No. 1,529,896, delivered May 13, 1968, including for example:

2- u- 3-t-butyl-4-hydroxyphenoxy tetradecanamidoethyl],

2- a- 3-t-butyl-4-hydroxyphenyl hexanamidoethyl] fi-(2,Z-dimethyl-6-hydroxy-7-octadecyl-4-chromanyl) propionamidoethyl,

5 'y-(4,7-dioctyl-6-hydroXy-2-methyl-2-chromanyl) butyramidoethyl, fl- (2,4-dioctyl-6-hydroXy-2-methyl-7-chromanyl) propionamidoethyl, etc.;

an aryl group that is unsubstituted or substituted with any of the substituents used on photographic couplers as solubilizing groups, ballasting groups, etc., in which the aryl group is a naphthyl group, e.g., tat-naphthyl, fi-naphthyl, 2-chloro-a-naphthyl, Z-methoxylnaphthyl, etc., a phenyl group (e.g., 4-methylphenyl, 2,4,6-trichlorophenyl, 3,5-dibromophenyl, 2-, 3- or 4-trifluoromethylphenyl, a phenyl group containing a non-coupling phenolic stabilizer moiety, such as, a 4-substituted phenol, as described in French Pat. No. 1,529,896, delivered May 13, 1968, including for example:

4- a- 3-t-butyl-4-hydroxyphenoxy tetradecanamido] -2,6-

dichlorophenyl,

4- [a- 3-t-butyl-4-hydroxyphenyl hexanamidophenyl] 4- u- 3-t-butyl-4-hydroxyphenoxy heptanamido phenyl,

3- ['y (4,7 -dioctyl-6-hydroxy-2-methyl-2-chromanyl) butyramido] phenyl,

fl- 2,4-diocty1-6-hydroxy-2-methyl-7-ehromanyl) propionamidophenyl, etc.;

and a heterocyclic group, particularly those having from 5 to 6 atoms in the ring (e.g., a pyridyl group, thienyl group, a quinolyl group, etc.); amino; substituted amino (e.g., methylamino, diethylamino, n-docosylamino, phenylamino, tolylamino, 4 (3 sulfobenzamido) anilino, 4- cyanophenylamino, 2-trifluoromethylphenylamino, benzothiazoloamino, 4[a-(3-t-butyl-4-hydroxyphenoxy) tetra decanamido1anilino, 2-chloro-4-[ti-(2,2-dimethyl 6 hydroxy-7-octadecyl 4 chromanyl)propionamidolanilino, etc.); acylamido radicals (e.g., ethylcarbonamido, ndecylcarbonamido, phenylethylcarbonamido, phenylcarbonamido, 2,4,6-trichlorophenylcarbonamido, 4-methylphenylca-rbonamido, 2-ethoxyphenylcarbonamido, 2- [(2,4-di-tert amylphenoxy)acetamido]benzamido, 11-, B- naphthylcarbonamido, a-(3-t-blJtYl-4 hydroxyphenoxy) tetradecanarnido, 3-[a-(3-t-butyl 4 hydroxyphenoxy) tetradecanamido benzamido, 3-['y-(4,7-diOCtYl-6-11YdrOXY- Z-methyl 2 chromanyl)butyramido1benzamido, etc.; hydroxy; an alkoxy group, e.g., methoxy, ethoxy, nbutoxy, n-hexoxy, etc., carboxy; or an esterified c-arboxy; or an esterified carboxy radical, such as, a

group, R represents an alkyl group (e.g., methyl, ethyl, butyl, etc.) or an aryl group (e.g., phenyl, tolyl, ethylphenyl, chlorophenyl, etc.).

For purposes of the present invention, R and R may also be separately and individually defined as an alkylthio group, the alkyl moiety of which includes alkyl groups containing up to about 22 carbon atoms, exemplified by methyl, octyl, dodecyl, eicosyl, and preferably lower alkyls.

The compounds of the present invention are mostly colorless but may themselves be colored, couple with oxidized photographic color developing agents, e.g., pphenylene diamines to form dyes. Those compounds wherein R is H or a splittable group are believed to couple at position 7 to form magenta dyes. They are twoequivalent couplers except when R is hydrogen, then they are four-equivalent couplers. Those compounds wherein R is an esterified carboxy group form a yellow dye but the mechanism of this reaction is not fully understood.

The compounds of the present invention are advantageously prepared by ring closure of a compound of Formula III in the presence of POCl in an inert solvent, e.g., benzene, toluene, xylene, etc., according to the following equation:

III. IV. R

JJOORa LII Alternatively, the present compounds are advantageously prepared by ring closure of a compound of Formula V in the presence of bromine and sodium acetate in acetic acid according to the following equation:

When the compounds of Formula IV or VI are treated with sulfuric acid the group R is hydrolyzed leaving a free carboxy group or, if the treatment is continued, the carboxy group is split off leaving the free base of the following formula:-

wherein R R and R are alkyl, aralkyl or aryl radicals which can be substituted as described previously.

Another alternative process for obtaining compounds within the present invention is disclosed in copending application Ser. No. 106,893 of Bailey, Knott and Marr which is a continuation-in-part of abandoned application 778,333, filed on Nov. 22, 1968, and describes fusion of an isothiocarbohydrazide with a keto ester, to directly obtain a bi-cyclic product. This reaction can be exemplified by the following equation:

X. B XI.

wherein R is defined as an alkylthio group having up to 20 carbon atoms, and R is an alkyl, such as methyl, tertiary butyl, octyl, eicosyl, etc., alkylthio, such as lower alkylthio, and particularly branched alkyl such as tertiary lower alkyl, and X is an acid anion exemplified by a halogen ion such as I; while R is an alkyl group such as methyl, octyl and eicosyl, particularly lower alkyl groups.

This reaction is eifected at an elevated temperature, convenientlylat reflux temperatures typically varying from about 75 130 C., depending upon the particular reactants and/0r reaction solvents employed and particularly at 78-l20 C. Any substituent required at the 7-position can be subsequently introduced by well-known methods. By way of example, a smiple halo substituent such as a bromine or chlorine atom is introduced on to the 7-position of a compound of Formula I, in which R is hydrogen, by direct treatment with a halogenating agent such as bromine or sulphuryl chloride.

In the above reaction, the compound of Formula X, for instance, can be prepared by reacting known thiocarbohydrazides with an alkyl or substituted alkyl halide (RI), optionally in an organic solvent such as a lower aliphatic alcohol such as amyl alcohol, for better control of the reaction.

If, for example, it is desired to make a compound of Formula I in which R is defined as represents a pyrazolo-triazole residue, two moles of the appropriate compound of Formula I, in which R is hydrogen, are reacted with one mole of a compound such as is used in the preparation of symmetrical cyanine dyes. Examples of such compound include ethyl ortho-formate (n=) and 1,1,3-trimethoxy-3-ethoxy propane (n=1).

If it is desired to make a compound of Formula I or II in which R and R are respectively and Whereln= ifand= are heterocyclic groups of the kind present in cyanine and related sensitizing dyes and n is 0-3, then an appropriate compound of Formula I, in which R is hydrogen can be reacted with a compound having the desired nucleus and substituted with a group which will provide, on reaction, the required linkage. If this linkage is a direct one, an alkoxy or alkylthio group will serve. If a single methine group linkage is required, an aldehyde or alkoxymethylene group is used. If a two-carbon methine chain is required, an acylanilidovinyl group is utilized; if a three-carbon chain is required, an alkoxyallylidene group is used; and if a four-carbon chain is required, an acylanilidobutadienyl group is utilized.

A halogen atom may also be advantageously introduced at position 7 by treating the compound of Formula VII with halogen in acetic acid.

A sulfo group is advantageously introduced at position 7 by sulfonating with oleum.

A phenylthio group is advantageously introduced at position 7 by condensing the compound of Formula VII with the appropriately substituted compound R4501 (wherein R is as defined previously) in the presence of a base and an inert solvent.

A substituted sulfonyloxy group is advantageously introduced at position 7 by reaction of the 7-bromo derivative of the compound of Formula VII, with the silver salt of the alkyl or aryl sulfonic acid.

An acyloxy group is advantageously introduced at position 7 by reacting the 7-bromo derivative of the compound of Formula VII with the appropriate organic acid or alkali metal salt of the organic acid. It is preferable that the reactants be anhydrous. An amine such as triethylamine is used advantageously as a condensing agent in this reaction when the acylating agent is an organic acid.

A phenoxy group is advantageously introduced at position 7 by reaction of the 7-bromo derivative of the compound of Formula VII with sodium phenate.

The thiocyano group is substituted at the position 7 by reacting a coupler of Formula VII with the product of the reaction of an alkali metal or ammonium thiocyanate with bromine.

A benzotriazol 2 yl group is advantageously substituted at the position 7 by preparing the 7-(2-nitrophenylazo) derivative of a coupler of Formula VII and heating this in aqueous ethanol containing sodium hydroxide while zinc dust is added. Refiuxing is continued until the solution turns colorless after which the excess zinc is removed by filtration and the reaction mixture is advantageously acidified with hydrochloric acid to form the coupler.

A 5-tetrazolylthio group such as a 1-phenyl-5-tetrazolylthio group is advantageously substituted at the position 7 by reacting a coupler of Formula V-II with a compound prepared by treating 5,5'-bis(1 phenyltetrazolyl) disulfide (Ber. 28, 77-81) suspended in dry carbon tetrachloride with dry chlorine gas.

Further substituent groups are advantageously introduced by known methods.

The compound of Formula III is advantageously obtained by condensation of a compound of Formula VIII with an acid chloride in the presence of a base, e.g., pyridine, according to the following equation:

vnr.

NNH

01001:, R. -NHNH:

h on

o III. NNH

H01 R. NHNHCOR1 The compound of Formula V is advantageously prepared as described in H. Beyer et al., Ber. 89, 2552 (1956).

When it is desired to replace R, by a group NH--R step (3) is replaced by the addition to a compound of Formula VIII of an isocyanate of the Formula RqNCO in an inert solvent according to the following equation:

NNH

I CON-R7 --r B5 -NHNHI C JOORa VIII.

N-NH

R NHNHCONHR1 I COOR! A compound of Formula IX is then used in place of a compound of Formula III in step (1).

The following examples are included for a further understanding of our invention.

EXAMPLE 1 7-cthoxycarbonyl-6-methyl-3-phenyl-1H-pyrazolo- [3,-2-c1-s-triazole A solution of bromine (0.64 gram) in glacial acetic acid (5 ml.) is added portionwise over 5 minutes to a mixture of benzaldehyde 4 ethoxycarbonyl 3 methylpyrazol-S-yl hydrazone (0.96 gram) [H. Beyer et al., Ber. 89, 2552 (1956)], sodium acetate (0.3 gram) in acetic acid (15 ml.). The mixture is stirred at room temperature for minutes, warmed on a steam bath for further 15 minutes, cooled and poured with stirring into water ml.). The sticky yellow-brown precipitate hardens on standing overnight. It is collected by filtration, washed with water and dried in the atmosphere. It is recrystallized from aqueous ethanol. The product (0.81 gram 85%) is obtained as pale yellow needles, M.P. 172 C. C H N O requires 62.2% C; 5.2% H; 20.7% N; sample on analysis gives 62.5% C; 5.35% H; 20.4% N. The reaction product couples with a 2-amino-5-diethylaminotoluene by hydrochloride developer solution oxidized with potassium persulfate to give a yellow dye having )1 max. in ethyl acetate at 435 my, 460 m and shoulder at 480 mp.

9 EXAMPLE 2 6-methyl-3-phenyl-1H-pyrazolo[3,2-c]-s-triazole 7 ethoxycarbonyl 6 methyl 3 phenyl 1H- pyrazolo-[3,2-c]-s-triazole (1 gram) and sulfuric acid (sp.gr. 1.84; 8 ml.) is warmed on a steam bath at 60- 70 C. for 45 minutes. The clear reaction solution is cooled and poured into Water (200 ml.). The thick colorless precipitate is collected by filtration, Washed with sulfuric acid (3 N, 25 ml.) and then with water (50' ml.). The product is recrystallized from aqueous ethanol and obtained as buff needles. The yield is 0.4 gram (55%). C H -N requires 66.7% C; 5.1% H; 28.3% N; sample on analysis gives 66.8% C.; 5.3% H; 27.85% N.

The product couples with a 2-amino-5-diethylaminotoluene hydrochloride developer solution oxidized with potassium persulfate to give a magenta dye A max. ethyl acetate at 550 mg, with a similarly oxidized N-ethyl-N- fl-methanesulfonamidoethyl 3 methyl 4 aminoaniline sulfate developer solution to give a magenta dye A max. ethvl acetate at 543 mp.

EXAMPLE 3 6-methyl-3-p-tolyl-lH-pyrazolo[3,2-c] -s-triazole The method of preparation is similar to Example 2 using the appropriate intermediate. The intermediate used is prepared by reacting p-tolualdehyde with 4-ethoxycarbonyl 3 methyl-pyrazol 5 yl-hydrazine and ring closure of the resulting hydrazone by the method described in Example 1. The product which is obtained in 53% yield melts at 230 C. and couples with the oxidized developer solution of Example 1 to give a dye which has a max. in methanol at 562 m in ethylacetate at 549 mi and in cyclohexane at 540 ml and 516 m EXAMPLE 4 3 -o-chlo rophenyl-6-methyllH-pyrazolo [3 ,2-c] -striazole-7-carboxylic acid The method of preparation is similar to Example 2 using the appropriate intermediate. The intermediate used is prepared by reacting o-chlorobenzaldehyde with 4- ethoxycarbonyl-3-methylpyrazol-S-yI-hydrazine and ring closure of the resulting hydrazone by the method described in Example 1. The product which melts at 156 C. couples with the oxidized developer solution of EX- ample 1 to give a dye which has a x max. in ethyl acetate at 540 mu.

EXAMPLE 5 3-p-dimethylaminophenyl-6-methyl-lH-pyrazolo- [3,2-c] -s-triazole The method of preparation is similar to Example 2 using the appropriate intermediate. The intermediate used is prepared by reaction of p-dimethylaminobenzaldehyde with 4-ethoxycarbonyl 3 methylpyrazol 5 ylhydrazine and ring closure of the resulting hydrazone by the method described in Example 1. The product melts at 175 C. and couples with the oxidized developer solution of Example 1 to give a dye which has a A max. in ethyl acetate at 559 m EXAMPLE 6 3,6-dimethyl-1H-pyrazolo [3,2-c] -s-triazole 4 ethoxycarbonyl 3 methylpyrazol 5 yl-hydrazine [I-I. Beyer et al., Ber. 89, 2552 (1956)] (3.09 grams) is mixed with acetic acid (10 ml.) and acetic anhydride (1.5 ml.) and heated on steam bath for 1 hour. The solution is cooled, poured into water (50 ml.) and the crystalline acethydrazide is collected, after chilling overnight, washed with ice cold water and dried. The product which weighs 3.14 grams (98%) MP. 130 C., is heated under reflux with dry benzene (125 ml.) and phosphorus oxychloride (2.7 ml.) for 4 hours and then stood overnight at room temperature. The benzene is removed by distillation and the residual oil stirred with water (100 ml.). The mixture is extracted with ethyl acetate (3 x 150 ml.). The ethyl acetate solution is dried over calcium sulfate and then concentrated to dryness yielding a pale yelow solid which is recrystallized from ethanol. The product which weighs 2.05 grams and melts at 1723 C. is treated with concentrated sulfuric acid (16 ml.) and heated on a steam bath for 75 minutes. The solution is then cooled and poured into water ml.) and, after chilling, is basified to pH 10 with 40% sodium hydroxide solution. The solution is extracted with ethyl acetate (3 x ml.) and the organic layer separated, dried over calcium sulfate and, after removing the solvent by distillation, a pale yellow solid is obtained. The product Weighs 1.1 gram and melts at C. It couples with the oxidized developer solution of 'Example 1 to give a dy which has a x max. in ethyl acetate at 528 mu.

EXAMPLE 7 6-methyl-3-(2,4,4-trimethylpentyl) -1'H-pyrazolo- [3,2-c] -s-triazole 4 ethoxycarbonyl 3 methylpyrazol 5 yl-hydrazine (2.33 grams) in pyridine (30 ml.) is treated at room temperature with 3,5,5-trimethylhexanoyl chloride (2.24 grams) and the mixture is heated on a steam bath for 1 hour. After cooling, it is poured into water (250 ml.). The oil is extracted into ethyl acetate (3 x 100 ml.). The ethyl acetate solution is dried over calcium sulfate and the solvent removed in vacuo. The thick yellow residual oil which weighs 4.1 grams (98%) is treated in dry benzene 125 ml.) with phosphorus oxychloride (3.9 grams) under reflux for 5 hours. The product is Worked up as in the previous example by extraction with ethyl acetate. The obtained oil (3.0 grams) is heated on a steam bath with concentrated sulfuric acid (20 ml.) for 90 minutes after which the mixture is cooled and poured into water (250 ml.). The oil is extracted into ethyl acetate which is then dried over calcium sulfate. After removal of the solvent an oil results which weighs 2.2 grams. It is stirred with 10% sodium carbonate solution (50 ml.) and then with water (50' ml.) after which it solidifies. The product is recrystallized from ethanol/ water mixture to give a buff solid (0.4 gram), M.P. 148 C.

EXAMPLE 8 6-methyl-3-n-pentadecyl-lH-pyrazolo[3,2-c]-striazolyl-7-carboxylic acid 4 ethoxycarbonyl 3 methylpyrazol 5 yl-hydrazine (6 grams) is dissolved in pyridine (100 ml.) and treated at room temperature with palmitoyl chloride (8.9 grams). After standing for 10 minutes, the mixture is heated on a steam bath for 1 hour. After cooling the reaction mixture is poured into water (400 ml.) and the colorless precipitate is collected by filtration and dried. The yield is 11.6 grams. The product is treated with phosphorus oxychloride (8.19 grams) in dry benzene (400 ml.) under reflux for 7 hours and worked up as in the previous examples. The yield of ester is 10 grams. It is hydrolyzed by heating in concentrated sulfuric acid (80 ml.) on a steam bath for 45 minutes. After cooling, the reaction mixture is poured into water (400 ml.). The precipitate is collected by filtration, washed with water and recrystallized twice from methanol yielding 2.5 grams of buff-colored solid, M.P. 113 C.

EXAMPLE '9 3-n-butylamino-6-methyllH-pyrazolo 3,2-c] -s-triazole 4 ethoxycarbonyl 3 methylpyrazol 5 yl-hydrazine (2.1 grams) is treated with n-butylisocyanate (1.14 grams) in boiling benzene (10 ml.) for 3 hours. Dioxan (50 ml.) is added and heating continued for 1 hour. After standing overnight the colorless crystals formed are collected by filtration yielding 1.1 gram. A second crop (0.7 gram) is taken by concentrating the benzene solution and recrystallizing the residue from ethanol.

The first crop material is treated with phosphorus oxychloride (1.2 gram) in benzene (250 ml.) under reflux for 6 hours during which time a gum separates. The mixture is held overnight and then water (150 ml.) is added. The benzene is separated and the gum extracted into ethyl acetate (3 x 150 ml.). The organic layers are combined and washed with water (2 x 100 ml.) dried over calcium sulfate and concentrated. The residue is recrystallized from ethanol/water mixture yielding 0.63 gram (60%) of buff crystals, M.P. 130-132 C. The product is heated in concentrated sulfuric acid (4 ml.) on a steam bath for 90 minutes, after cooling, is poured into water (50 ml.) to yield a butt precipitate which is collected by filtration, washed with water (2 x 25 ml.) and dried. The product weighes 0.33 gram, M.P. 68 C. and couples with the oxidized developer solution of Example 1 to give a dye with x max. in ethyl acetate at 538 m EXAMPLE 10 The following compounds are prepared by ring closure of the corresponding hydrazone by methods analogous to that used in Example 1. The necessary hydrazones are obtained from the appropriate aldehyde and 4-ethoxycarbonyl-3-methylpyrazol-S-yl-hydrazine (which can be obtained in 80% yield by treatment of the corresponding hydrochloride (22 grams) in methanol (100 ml.) with triethylamine (14 ml.), warming to effect solution, chilling and collection of the free base). Hydrolysis and decarboxylation is effected by the method of Example 2.

(A) 6-methy1-3-n-propyl-1H-pyrazolo[3,2-c]-s-triazole,

(B) 6-methyl-3-isopropyl-1H-pyrazolo[3 ,2-c] -s-triazole,

(C) 3-hexyl-6-methyl-lH-pyrazolo[3,2-c1-s-triazole,

M.P. ll1l1 (D) 6-methyl-3-undecyllH-pyrazolo [3 ,2-c] -s-triazole,

(E) 6-methyl-3,4'-pyridyl-1H-pyrazolo[3,2-c]-s-triazole,

(F) 3-p-methoxyphenyl-6-methyl-lH-pyrazolo[3,2-c]-striazole, M.P. 290

(G) 3-(2,6-dichlorophenyl)-6-methyl-lH-pyrazolo [3,2-c]-s-triazole-7-carboxylic acid, M.P. 260.

EXAMPLE 11 The following compounds are prepared by a method analogous to that of Example 7 starting from 4-ethoxycarbonyl-3-methyl-pyrazol-5-yl-hydrazine and the appropriate acid chloride.

(H) 3-heptadecyl-6-methyl-lH-pyrazolo [3 ,2-c] -s-triazole,

(I) 3-[4-(2,4-ditertiaryamylphenoxy)butyl]-6-methyllH-pyrazolo[3,2-c1-s-triazole, M.P. 203.

EXAMPLE 12 6-methyl-3-phenylamino-lH-pyrazolo [3 ,2-c] -s-triazole The compound is prepared by the method of Example 9 starting from 4-ethoxycarbonyl-3-methylpyrazol-5- yl-hydrazine and phenylisocyanate. The product melts at 273.

EXAMPLE 13 The following compounds are prepared by treating the appropriate pyrazolotriazole (unsubstituted in the 7-position) (2 grams) in acetic acid (30 ml.) with sulphuryl chloride (0.7 gram) in acetic acid ml.) at 40-50 for 15 minutes and then warmed on a steam bath for 5 minutes. After 1 hour at room temperature the solution is diluted with water (200 ml.) and the product collected by filtration or extracted into benzene (3 x 50 ml.). The benzene extracts are dried over magnesium sulfate and the product obtained by removing the benzene by distillation. The product is recrystallized from petroleum ether (B.P. 4060). The yields are of the order of 80%.

(K) 7-chloro-6-methyl-3-undecyl-1H-pyrazolo[3,2-c]- s-triazole, M.P. 48 buff crystals (L) 7-chloro-6-methyl-3-pentadecyl-lH-pyrazolo[3,2-c]- s-triazole, M.P. 57 buff crystals (M) 7-chloro-6-methyl-3-heptadecyl-lH-pyrazolo[3,2-c]- s-triazole, M.P. 7678 buff crystals (N) 7-chloro-3-[4-(2,4-ditertiaryamylphenoxy)butyl]- 6-methyl-1H-pyrazolo[3,2-c]-s-triazole, M.P. 134 pale yellow solid.

EXAMPLE 14 7-bromo-3-[4-(2,4-ditertiaryamylphenoxy)butyl]- 6-methyl-1H-pyrazolo[3,2-c1-s-triazole 3 [4 (2,4 ditertiaryamylphenoxy)butyl]-6-methyl- 1H-pyrazolo[3,2-c]-s-triazole (0.6 gram), sodium acetate (0.25 gram) in cetic acid (20 ml.) and bromine (0.25 gram) are kept at room temperature for 40 minutes and then warmed on a steam bath for 20 minutes. The mixture after standing at room temperature for 30 minutes, is poured into water (100 ml.) and the product is extracted into benzene. The product is obtained on concentration of the dried benzene extracts and after recrystallization from petroleum ether (B.P. 60 80) is obtained in 50% yield as a pale yellow solid, M.P. 176.

EXAMPLE 15 6-methyl-7- [2,4-dinitrophenylthio] -3-(4-pyridy1) -pyrazolo [3 ,2-c] -s-triazole 6 methyl 3-(4-pyridyl)-1H-pyrazolo[3,2-c1-s-triazole (0.3 gram), 2,4-dinitrophenylsulphenylchloride (0.35 gram) in benzene (50 ml.) are heated under reflux for 5 hours and cooled overnight. The product is collected by filtration and washed with benzene. The yellow solid product yield) melts at 218 and couples with oxidized 2-amino-5-diethylaminotoluene hydrochloride developer solution to give a magenta dye having an max. ethyl acetate at 558 nm.

EXAMPLE 16 The following compounds (0), (P) and (Q) are prepared by methods analogous to those described in Examples 4, 8 and 9, respectively starting from 4-ethoxycarbonyl-pyrazol-5-yl-hydrazine instead of 4-ethoxycarbonyl- 3-rnethylpyrazol-5-yl-hydrazine. The required hydrazine is advantageously prepared from the corresponding amino pyrazole by diazotization followed by reduction with sodium sulfite as outlined for the preparation of 4-ethoxycarbonyl-3-methy1pyrazol-5-yl-hydrazine, H. Beyer et a1. Ber. 89, 2552 (1956).

EXAMPLE 17 The following compounds (R) and (S) are prepared by methods analogous to those described in Examples 4 and 8, respectively, starting from 4-ethoxycarbonyl-3-propyl-pyrazol-S-yl-hydrazine instead of 4-ethoxycarbonyl-3- Inethylpyrazol-5-yl-hydrazine. The required hydrazine is advantageously prepared by the method for the synthesis of 4-ethoxycarbonyl-3-methyl-pyrazol-5-y1-hydrazine, H. Beyer et al. Ber. 89, 2552 (1956) using ethyl-2-chlorobutyrylacetate instead of ethyl-2-chloroacetoacetate.

The product (M.P. 135 decomp.) couples with oxidized 2-amino-S-diethylaminotoluene developer to give a dye having x max. ethyl acetate at 544 nm.

(S) 3-hexyl-6-n-propyl 1H pyrazolo]3,2-c]-s-triazolyl- 7-carboxylic acid The product couples with oxidized 2-amino-5-diethylaminotoluene developer to give a dye having A max. ethyl acetate at 530 nm.

EXAMPLE 18 7 -o-methoxyphenylazo-6-methyl-3-phenyllH-pyrazolo [3,2-c]-s-triazole o-Anisidine (25 mg.) is diazotized in 10% hydrochloric acid (1 milliliter) and the resulting diazonium salt solution is added to a pyridine (2 ml.) solution of 6-methyl-3- phenyl-lH-pyrazolo[3,2-c] -s-triazole (25 mg.). The colored coupler which precipitates on dilution with Water, is collected by filtration and washed with water. It has an absorption max. in ethanol at 436 III/1..

EXAMPLE 19 7-(m-lauramidophenylthio)-6-methyl-3-propyl-1H- pyrazolo[3,2-c1-s-triazole This coupler is advantageously prepared by a method similar to that used in Example 15 but using equimolar amounts of 6-methyl-3-propyl-lH-pyrazolo[3,2-c]-s-triazole and m-lauramidophenylsulphenylchloride as the intermediates.

EXAMPLE 20 3-(3,5-dicarboxyphenyl)-6-heptadecyl-lH-pyrazolo [3,2-c1-s-triazole The coupler is advantageously prepared by reacting 3, S-diethoxycarbonylbenzoyl chloride with 4ethoxycarbonyl-3-heptadecylpyrazol-5-yl hydrazine, cyclizing the resulting product to form 3-(3,S-diethoxycarbonylphenyl)- 7 ethoxycarbonyl-6-heptadecy1-lH-pyrazolo[3,2-c]-s-triazole followed by hydrolysis with sulfuric acid as described in Example 2.

EXAMPLE 21 3-hexyl-6-methyl-lH-pyrazolo[3,2-c]s-triazo1yl-7- sulfonic acid This coupler is advantageously prepared by sulfonating the coupler of Example 10 (C) with oleum.

EXAMPLE 22 6-methyl-3-p entadecyl-7-phenoxy- 1 H-pyrazolo 3 ,2-c] s-triazole This coupler is advantageously prepared by making 7- bromo-6 methyl-3-pentadecyl-1H-pyrazolo[3,2-c]-s-triazole by a method similar to that described for Example 14 but using 6-methyl-3-pentadecyl-lH-pyrazolo[3,2-c]-striazole (in place of the intermediate used in Example 14) and then reacting the 7-bromo derivative with sodium phenate.

EXAMPLE 23 3-hexyl-6-methyl-7-( l-phenyl-S-tetrazolylthio)-1H- pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by reacting the 3 hexyl 6 methyl-lH-pyrazolo[3,2-c]-s-triazole made in Example 10(C) with the compound prepared by treating 5,5 bis (l-phenyltetrazolyl)disulfide (Ber. 28, 7781) suspended in dry carbontetrachloride with dry chlorine gas.

EXAMPLE 24 6-methyl-3-phenyl-7- 3'-pyridylazo lH-pyrazolo [3,2-c1-s-triazole This coupler is advantageously prepared by reacting the 14 coupler made in Example 2 with the diazonium salt prepared from 3-pyridylamine.

EXAMPLE 25 7-acetoxy-6-methyl-3-pentadecyl-1H-pyrazolo[3,2-c]- s-triazole This coupler is advantageously prepared by reacting 7 bromo 6 methyl 3 pentadecyl-lH-pyrazolo[3, 2-c] s triazole with sodium acetate. The 7 bromo 6- methyl-3-pentadecyl-lH-pyrazolo-[3,2-c]-s-triazole is prepared by the reaction shown in Example 14 but using 6- methyl 3 pentadecyl 1H pyrazolo[3,2-c]-s-triazole (in place of the triazole derivative used in Example 14).

EXAMPLE 26 3 {4-[u-(3-tertiarybutyl-4-hydroxyphenoxy)tetradecanamido] 2 chlorophenyl} 6 methyl 1H pyrazolo [3,2-c]-s-t-riazole This compound is advantageously prepared by stirring a solution of 3 {4-[a-acetoxy-3-t-butylphenoxy)tetradecanamido] 2 chlorophenyl} 6 methyl-lH-pyrazolm [3,2-c]-s-triazole and sodium hydroxide in methanol under nitrogen, followed by acidification with concentrated hydrochloric acid, dilution with water and separation by filtration. The 3 {4 [0c (4acetoxy-3-t-butylphenoxy) tetradecanamido] 2 chlorophenyl}-6-methyl-lH-pyrazolo[3,2-c]-s-triazole is prepared by adding a solution of a (4-acetoxy-3-t-butylphenoxy)tetradecanoyl chloride in acetic acid to a mixture of 3- (4amino-2-chlorophenyl)-6- methyl lH-pyrazolo[3,2-c1-s-triazole and anhydrous sodium acetate in acetic acid, stirring, diluting with water and recrystallizing the solid coupler from acetonitrile. Intermediate 4, a (4-acetoxy-3-t-butylphenoxy)-tetradecanoyl chloride, is advantageously prepared by the following series and reactions used to make intermediates 1, 2, 3 and 4.

Intermediate 1.2-t-butyl-4-(a-carbethoxytridecyloxy)phenol A mixture of 41 g. of t-butyl hydroquinone, '86 g. of ethyl a-bromotetradecanoate, and 40 g. of potassium carbonate in 500 ml. of acetone is refluxed for 3 days, after which time the solution is poured into a mixture of 1 liter of diethyl ether and 500 ml. of water. The ether layer is separated from the water, dried and concentrated in vacuo. The residue is distilled under reduced pressure and the fraction which boils at 225 C. at a pressure of 0.4 mm. is collected. This solid is recrystallized from acetonitrile to yield the product.

Intermediate 2.--2-t-butyl-4-(a-carboxytetradecyloxy)phenol A mixture of 21 g. of Intermediate 1 above and 11 g. of potassium hydroxide in 250 ml. of methyl alcohol is refluxed for /2 hour, after which time the clear solution is neutralized by the addition of dilute hydrochloric acid. The solid which separated is collected and recrystallized from hexane to yield the product.

Intermediate 3. -a-(4-acetoxy-3-t-butylphenoxy)tetradecanoic acid A mixture of 10 g. of Intermediate 2 above and 2 drops of concentrated sulfuric acid in 40 ml. of acetic anhydride is heated on the steam bath under a drying tube for 2 hours. To the resultant solution is added 250 ml. of water. The oil-water mixture is heated for 10 minutes at 60 C. with stirring, after which time the clear solution is cooled in an ice bath; whereupon a solid separates, is collected, dried, and recrystallized from petroleum ether to yield the product.

Intermediate 4.a-(4-acetoxy-3-t-butylphenoxy) tetradecanoyl chloride A mixture of 41 g. of Intermediate 3 above and g. of phosphorous pentachloride in 200 ml. of dry petroleum ether is refluxed for 2 hours, after which time the clear solution is concentrated in vacuo. The residual solid is recrystallized twice from acetonitrile to yield the product.

EXAMPLE 27 7-butylmethylene-6-methyl-3-(2'-chlorophenyl)-1H- pyrazolo[3,2-c1-s-triazole This coupler is advantageously prepared by reacting 6- methyl-3-(2'-chlorophenyl) 1H pyrazolo[3,2-c]-s-triazole with butyraldehyde in dry benzene.

EXAMPLE 28 7-benzylidene-6-methyl-3-2(2'-chlorophenyl)-1H- pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by the method described in Example 27 but using benzaldhyde in place of butyraldehyde.

EXAMPLE 29 6-methyl-3-pentadecyl-7-thiocyanato- 1 H-pyrazolo- [3 ,2-c] -s-triazole This coupler is advantageously prepared by reacting 6- methyl 3 pentadecyl-1H-pyrazolo[3,2-c]-s-triazole with the product of reaction of sodium thiocyanate and bromide.

EXAMPLE 30 7-benzotriazol-2-yl-6-methyl-3-pentadecyl-1H- pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by reacting 6 methyl 3 pentadecyl-lH-pyrazolo[3,2-c1-s-triazole with the diazonium salt prepared from 2-nitroaniline to prepare 7-(2-nitrophenylazo)-6-methyl-3-pentadecyl-1H- pyrazolo[3,2-c]-s-triazole. The 7-(2-nitrophenylazo) derivative is then heated in aqueous ethanol containing sodium hydroxide while zinc dust is added. Refiuxing is continued until the solution turns colorless after which excess zinc is removed by filtration and the reaction mixture is acidified with hydrochloric acid to form the coupler.

EXAMPLE 31 6-methyl-7-methylsulfonoxy-3-pentadecyl-1H- pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by reacting 7- bromo 6 methyl-3-pentadecyl-lH-pyrazolo[3.2-c] striazole with the silver salt of methylsulfonic acid.

EXAMPLE 32 3-heptadecyl-6-methyl-7-(2-aminophenylazo)-1H- pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by reacting the coupler of Example 11 (H) with the diazonium salt prepared from 2-nitroaniline and then reducing the 7-(2-nitrophenylazo) derivative to the immediate coupler by reduction in the presence of sodium sulfide.

EXAMPLE 33 7-butylaminomethyl-6-methyl-3-undecyl-1H- pyrazolo [3,2-c] -s-triazole This coupler is advantageously prepared by reacting the coupler made in Example 10 (D) with a mixture of formaldehyde, potassium hydroxide and butylamine.

EXAMPLE 34 3-(p-acetamidophenyl) -1H-pyrazolo [3,2-c1-s-triazole This coupler is advantageously prepared by first preparing 3-(4-nitrophenyl) 1H pyrazolo[3,2-c]-s-triazole by ring closing 4 nitrobenzaldehyde-4-ethoxycarbonylpyrazole-S-yl hydrazone by a reaction similar to that shown in Example 1 then removing the 7-ethoxycarbonyl group by a hydrolysis reaction such as is illustrated by Example 2. The 3-(4-nitrophenyl) derivative is converted to the corresponding 3-(4-aminophenyl) derivative by a conventional reduction step and this compound reacted with acetic anhydride to make the immediate coupler.

EXAMPLE 35 3- (p-trifluoromethylphenyl)-1H-pyrazolo[3,2-c] s-triazole This coupler is advantageously prepared by ring closing 4 trifluoromethylbenzaldehyde 4 ethoxycarbonyl pyrazol-S-yl hydrazone by a reaction similar to that of Example 1 followed by hydrolysis of the 7-ethoxycarbonyl group from the coupler as described in Example 2.

EXAMPLE 36 3-(a-naphthyl)-lH-pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by ring closing a-naphthaldehyde-4-ethoxycarbonylpyrazol 5 yl hydrazone followed by removal of the 7-ethoxycarbonyl group by hydrolysis as described for similar reactions in Examples 1 and 2, respectively.

EXAMPLE 37 3-(2'-thienyl)-1H-pyrazolo[3,2-c]-s-triazole This coupler is advantageously prepared by ring clos ing 2-thienyl-4-ethoxycarbony]pyrazol-S-yl hydrazone followed by removal of the 7-ethoxycarbonyl group by hydrolysis as described for similar reactions in Examples 1 and 2, respectively.

EXAMPLE 38 3-hydroxy-6-methyl-lH-pyrazolo[3,2-c] -s-triazole This coupler is advantageouly produced by reacting 4- ethoxycarbonyl-3-methylpyrazol-5-yl hydrazine with urea and cyclizing the resulting product to form 7-ethoxycarbonyl-3-hydroxy 6-methyl 1H pyrazolo[3,2 c]-s-triazole and then removing the 7-ethoxycarbonyl group by hydrolysis in sulfuric acid as described previously.

EXAMPLE 3 9 3-ethoxy- 6-methyllH-pyrazolo [3 ,2-c] -s-triazole This compound is advantageously prepared by reacting the compound prepared in Example 18 with diethyl sulfate in alkaline solution.

EXAMPLE 40 3-{-2-chloro-4[fi-(2,2-dimethyl 6 hydroxyoctadecyl-4- chromanyl)propionamidoJanilino} 1H pyrazolo[3,2- c] -s-triazole This coupler is advantageously prepared by reacting the coupler, 3-(4'-aminoanilino) 1H pyrazolo[3,2-c]-s-triazole with the intermediate, fl-(6-acetoxy-2,2-dimethyl-6- octyl-4-chromanyl)-propionyl chloride in acetic acid using sodium acetate as the condensing agent, and then converting the 4-acetoxy group to the 4-hydroxy group by alkaline hydroylsis, i.e., mixing with sodium hydroxide in water and methyl alcohol at room temperature under nitrogen. The B-(6-acetoxy 2,2 dimethyl-7-octadecyl-4-chromanyl) propionyl chloride is advantageously prepared by adding 6-carboxy-2-methyl-2,4-hexadiene to a heated mixture of acetic acid, octadecyl hydroquinone and zinc chloride catalyzed by two drops of sulfonic acid, followed by reaction with acetic anhydride and subsequently by reaction with thionyl chloride.

1 7 EXAMPLE 41 3 {[oc (3 t butyl 4 hydroxyphenoxy) tetradecanamido]-ethyl} 6 pentadecyl 1H pyrazolo[3,2-c]- s-triazole EXAMPLE 42 S-methylthio 6 phenyl-lH-pyrazolo[3,2-c]-s-triazole, Compound 42 Ethyl benzoylacetate (9.6 grams) and S-methyl isothiocarbohydrazide hydriodide (12.4 grams were heated together at |1 l C.-1'15 C. for 25 minutes. During the last minutes of the heating, the volatile reactants were distilled off in vacuo. The reaction mixture was cooled and then heated with sufiicient boiling 10% sodium carbonate solution (about 300 ml.) to effect solution of most of the reaction mass. A small amount of oily residue remained which was removed by filtration. 0n cooling the hot clear carbonate solution the product crystallized and was collected by filtration. It was recrystallized from benzene as tiny buff-coloured needles. The yield of product which melted at 179 C. was 5 grams. It coupled with oxidized Z-amino-S-diethylaminotoluene developer to give a dye which had A max. ethyl acetate at 565 nm. The S-methyl isothiocarbohydrazide hydriodide was prepared by adding methyl iodide (18 grams) to a well stirred suspension of thiocarbohydrazide (12 grams) in boiling ethanol (400 ml.) and heating under reflux for 2 hours. The product was isolated by cooling the hot filtered solution and collection of the separated product by filtration. Concentration of the ethanol solution to about half volume gave a second crop. The yield of colourless crystals was 70%. The product melted at 145 (with decomposition).

EXAMPLE 43 3-methylthio-6-m-nitrophenyl-lH-pyrazolo- [3,2-c1-s-triazole Ethyl m-nitrobenzoyl acetate (2.4 grams) and S-methyl isothiocarbohydrazide hydriodide 2.5 grams) were heated at 120 C. for 15 minutes. The reaction mass was treated with carbonate solution as described in the previous example. The dark yellow solid product, which separated was collected, melted at 2l4-2l7 C. and coupled with oxidized 2-amino-5-diethylaminotoluene developer to give a dye having A max. ethyl acetate at 5 85 nm.

18 EXAMPLE 44 6-heptadecyl-3-methylthiolH-pyrazolo [3 ,2-c] -s-triazole A solution of ethyl stearoylacetate (2.1 grams) and S-methyl isothiocarbohydrazide hydriodide (1.6 grams) in n-amyl alcohol (25 ml.) was heated under reflux for 2 hours. On cooling some solid material separated and was collected by filtration. Ether was added to the amyl alcohol solution to precipitate more solid material which was also filtered oif. Neither solid coupled with oxidized developers. The solution was concentrated to leave an oil which was treated with benzene ml.) and the solvent again removed. The residual gum (2 grams) coupled with oxidized Z-amino-S-diethylamino toluene developed to give a dye having A max. ethyl acetate at 541 nm.

EXAMPLE 45 S-methylthio-6-n-nitrophenyllH-pyrazolo [3 ,2-c] -s-triazole Ethyl p-nitrobenzoylacetate (2.26 grams) and S-methylisothiocarbohydrazide hydriodide (2.36 grams) were heated in boiling amyl alcohol (40 cc.) for 35 minutes. The reaction mixture was cooled and the product which precipitated as yellow crystals was collected by filtration and recrystallised from amyl alcohol. The purified product was collected, washed with ethanol and dried. The yield of product which melted at 277 C. was 1 gram. It coupled with oxidised 2-amino-5-diethylaminotoluene developed to give a dye with A max. ethyl acetate at 58 nm.

EXAMPLE 46 3-methylthio-6-propyll'H-pyrazolo [3,2-c1-s-triazole This compound was prepared similarly to Example 42 using a proportionate amount of ethyl butyrylacetate instead of ethyl stearoylacetate. The product which was obtained as a gum coupled with oxidised 2-an1ino-5-diethylaminotoluene developed to give a dye with A max. ethyl acetate at 541 nm.

EXAMPLE 47 6,2-furyl-3-methylthio-lH-pyrazolo 3,2-c1-s-triazole This compound was prepared as Example 44 using ethyl-Z-furoylacetate instead of ethyl stearoylacetate. The product which was obtained as a gum coupled with oxidised Z-amino-S-diethylaminotoluene developer to give a dye having 7\ max. ethyl acetate at 567 nm.

1 9 EXAMPLE 4:;

CHaS N O-ethyl-S-methyl asymmetric diethiomalonate (1.78 grams) (Laakso, Soumen Kemistilehte, 1944, 17B, 1-6) and S-methyl isothioearbohydrazide hydroiodide (2.36 g.) were heated in boiling amyl alcohol (25 ml.) for 30 minutes and worked up as in Example 3. The product which was obtained as a gum coupled with oxidised 2-amino-5- diethylamino toluene developer to give a dye having A max. ethyl acetate at 533 nm.

EXAMPLE 49 7-bromo-3-methylthio-6-phenyl-lH-pyrazolo[3,2-c1- s-triazole H B r Compound 42 (1 gram), sodium acetate (0.42 gram) were dissolved in acetic acid (30 ml.) and the solution was treated with bromine (0.8 gram) in acetic acid (4 ml.) portionwise. The mixture was allowed to stand at room temperature for 40 minutes and then heated on a steam bath for 20 minutes, after which it was cooled back to room temperature and poured into water (150 ml.) The precipitated product was collected by filtration, washed with water and dried. It weighed 1.1 grams, melted at 152153 and coupled with oxidised 2-amino-5-diethylamino toluene developer to give a magenta dye.

EXAMPLE 50 7-chloro-3-methylthio-6-phenyl-1H-pyrazolo[3,2-c]- s-triazole l H Cl Compound 42 (1 gram) was dissolved in acetic acid (15 ml.) and sulphuryl chloride (0.65 gram) were slowly added to the solution, the mixture was heated on the steam bath for 5 minutes and allowed to stand at room temperature for 1 hour. The mixture was then poured into water (200 ml.) and the precipitated product was collected by filtration and dried. It weighed 0.9 gram and melted at 150.

EXAMPLE 51 7-(3-methylthio-6-phenyl-7H-pyrazolo[3,2-c] s triazol- 7-ylidene)-methylene-3-methylthio 6 phenyl 1H- pyrazolo [3 ,2-c] -s-triazo1e l u a a :CH 1. 1'. l H CHaS kN NJ SCHa Compound 42 (0.1 gram), ethylorthoformate (1 ml.) and acetic acid (4 ml.) were heated at boiling point for minutes. The product which crystallized from the hot reaction mixture was isolated after cooling by filtration. It

20 was washed with ethanol, dried and obtained in almost theoretical amount. It has an absorption maximum in methanol in the presence of triethylamine at 494 nm.

EXAMPLE 52 7,3'-(3-methylthio-6-phenyl-7H pyrazolo[3,2 c] striazol-7-ylidene)allylidene-3-methylthio-6-phenyl 1H- pyrazolo[3,2-c1-s-triazole (Compound 52) A solution of Compound 42 (0.23 gram) and 1,1,3-trimethoxy-3-ethoxypropane (0.2 ml.) in acetic acid (5 ml.) was heated under reflux for 2 minutes. The solid dye product separated from solution and after cooling it was collected and recrystallized in almost quantitative yield from methanol. The product was obtained as dark green metallic crystals x max. methanol at 554 nm.

EXAMPLE 53 3-ethyl-2-(3-methylthio-6-phenyl-7H-pyrazolo[3,2 c] s triazole-7-ylidene)benzthiazoline (Compound 5 3) EXAMPLE 54 3-methylthio-7-p-nitrobenzylidene-6-phenyl-7H-pyrazolo [3 ,2-c] -s-triazole CaHs Compound 42 (0.23 gram), p-nitrobenzaldehyde and acetic acid (5 ml.) were heated under reflux for 10 mins. After cooling the product was precipitated by dilution with water (25 ml.) and collected by filtration. It was twice recrystallised from ethanol and obtained in 20% as pale yellow crystals. It coupled with oxidized Z-amino- S-diethylamino toluene developer to give a dye A max. ethyl acetate at 565 nm.

EXAMPLE 55 7- 1-ethyl-2,5 -dimethy1-3 -pyrryl) methylene-B-methylthio- 6-phenyl-7H-pyrrazolo [3, 2-c] -s-triazole l ill l...

CHaS dim Compound 42 (0.46 gram), 1-ethyl-2,S-dimethylpyrrol- 3-aldehyde (0.3 gram) were dissolved in boiling ethanol (10 ml.) and triethylamine (1 ml.) was added and the solution was reflux for 10 minutes. The solution was concentrated to ml. and Well chilled when the dye product (0.25 gram) separated. It was twice recrystallised from methanol giving 0.15 gram orange needles. The dye has 7t max methanol at 447 nm.

EXAMPLE 56 5 (3 methylthio-6-ph'enyl-1'H-pyrrazo1o['3,2-c]-s-triazol- 7 yl)methylene-3-phenyl-2-thiothiazolid-4-one (C-ompound 56) A mixture of Compound 42 (0.23 gram), 5-ethoxymethylene-S-phenylrhodanine (0.26 gram), triethylamine (0.42 ml.) and ethanol (20 ml.) was heated under reflux for minutes. About half the ethanol was removed by distillation, water (10 ml.) added, and the mixture made slightly acid with hydrochloric acid. The dye precipitated as a gum which rapidly hardened. A'fter collection by filtration the product was recrystallised from a mixture of benzene and petroleum ether. The dye which was obtained in 55% yield had A max methanol at 495 nm.

EXAMPLE 57 3 ethyl-2,2'-(3-methylthio-6-phenyl-lH-pyrazolo [3,2-c]- s triazole 7-ylidene)ethylidenebenzoxazoline (Comsound 57) A mixture of Compound 42 (.23 gram) 2,2'-acetanilidovinylbenzoxazole ethiodide (0.45 gram), triethylamine (0.42 ml.) and ethanol (20 ml.) was heated under reflux for 10 minutes. Water (20 ml.) was added to the cooled reaction solution and the product which was obtained in almost quantitative yield was recrystallised from methanol as yellow crystals having A max methanol at 480 nm.

EXAMPLE 5 8 3 ethyl-2,2-(3-methylthio-6-phenyl-7H-pyrazolo[3,2-c]- s triazol 7 ylidene)ethylidenebenzthiazoline (Compound 58) CaHa CzHs CHaS N/ Compound 42 (0.46 gram) 2,2-acetanilidovinylbenzthiazole ethiodide (0.9 gram), triethylamine (1 ml.) and ethanol (30 ml.) were heated together on a steam bath for 10 minutes. The reaction mixture was cooled and the separated product was collected by filtration. It was recrystallised twice from methanol. The purified product weighted 0.2 gram and has A max methanol at 521 nm.

22 EXAMPLE 59 7,3 (1,3 diethyl-4,6-dioxo-hexahydro-2-thiopyrimid-5- ylidene)allylidene 3 methylthio-G-phenyl-lH-pyrazolo [3,2-c] -s-triazole EXAMPLE 6O 3 ethyl-2,4-(3-methylthio-6-phenyl-7H-pyrazolo[3,2-c]- s triazol 7-ylidene) but-2'-enylidenebenzthiazoline (Compound 60) Compound 42 (0.46 gram), 2,4-acetanilidobutadienylbenzthiazole ethiodide (0.95 gram) were dissolved in boiling ethanol (70 ml.) Triethylamine (1 ml.) was added and a deep blue dye was formed. The mixture was heated under reflux for 5 minutes and on chilling dark blue needles separated. The product (0.6 gram) was collected and recrystallised twice from methanol. The dye had max methanol at 619 nm.

The diifusible couplers of our invention, such as couplers of Examples 6, 7, 9, 10A, 10B, 10C, 16F, 16Q, 17S, 21, 23, 34, 35, 37, 38, 39, 42, 46 and 48 are used to advantage in developer compositions for color photo graphy. Our developer compositions comprise one of our couplers and any of the primary aromatic amine color developing agents known in the art including for example: N,N-diethyl-6-phenylenediamine hydrochloride, N-methylp phenylenediamine hydrochloride, N,N dimethyl-pphenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, Z-amino 5 (N-ethylN-lauryl) toluene, N-ethyl-N-fi-methanesulfonamidoethyl-3-methyl- 4-aminoaniline sulfate, N-ethyl-N-fl-methanesulfonamidoethyl 4-aminoaniline, 4-N-ethyl-N-fi-hydroxyethylaminoaniline, 3 methyl 4-N-ethyl-N-;i-hydroxyethyl-aminoaniline, N (2 amino-5-diethyl-aminophenylethyl)menthanesulfonamido hydrochloride or the p-aminophenols and their substitution products where the amino group is unsubstituted. In addition to the mixture of coupler and developing agent, our developer compositions comprise alkali, such as, alkali metal carbonate, alkali metal hydroxide, etc., water, antioxidant, such as, an alkali metal sulfite, and any of the usual addenda such as alkali metal bromides, antifoggants, thickening agents, such as, carboxymethyl cellulose, hyroxyethyl cellulose, etc., used in making viscous developer compositions, etc.

The diffusible couplers of our invention are used to advantage in emulsion layers when incorporated by the methods described in Mannes et al. US. Pat. 2,304,940, issued Dec. 15, 1940.

The other coupler examples used to illustrate our invention are nondifiusing and are used to advantage in photographic emulsion layers. The coupler of Example 20 illustrates a Fischer-type coupler. The other nondiffusing couplers are incorporated in emulsion layers by methods such as are described by Mannes et al. U.S. Pat. 2,304,939, issued Dec. 15, 1942, Jelley et al. U.S. Pat. 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents are used to dissolve the coupler, and by methods described in Vittum et al. U.S. Pat. 2,801,170, and Fierke et al. U.S. Pat. 2,801,171, both issued July 30, 1957, and Julian U.S. Pat. 2,949,360, issued Aug. 16, 1960, in which low-boiling or watersoluble organic solvents are used with or in place of the high-boiling solvent.

The present couplers which have solubilizing groups in one or more non-coupling positions and which have all or a substantial position of the ballast attached to the coupling-off group are advantageously employed in color diffusion transfer processes wherein diffusible dyes are formed and transferred imagewise to an image-receiving sheet which preferably contains a mordanted layer. Diffusion transfer processes are described patents such as U.S. Pat. 3,227,554.

Our couplers are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type either in the color developer solution or in the emulsion layer. The emulsions advantageously contain silver chloride, silver b;omide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodide, etc., as the light-sensitive material.

Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which are used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in U.S. Pat. 2,286,215, of Lowe; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in U.S. Pat. 2,327,808 of Lowe and Clark, a water-soluble ethanolamine cellulose acetate as described in U.S. Pat. 2,322,085 of Yutzy; a polyacrylamide having a combined acrylamide content of 30-60% and a specific viscosity of 0.25-1.5 on an imidized polyacrylamide of like acrylamide content and viscosity as described in U.S. Pat. 2,541,474 of Lowe, Minsk and Kenyon; zein as described in U.S. Pat. 2,563,791 of Lowe; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Pat. 2,768,154 of Unruh and Smith, or containing cyanoacetyl groups, such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in U.S. Pat. 2,808,331 of Unruh, Smith and Priest; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in U.S. Pat. 2,852,382 of Illingsworth, Dann and Gates.

The emulsions used in the photographic element of our invention can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard, U.S. Pat. 1,574,994; Sheppard and Punnett, U.S. Pat. 1,623,499; and Sheppard and Brigham, U.S. Pat. 2,410,689.

The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Pat. 2,488,060, and as antifoggants in higher amounts, as described in Trivelli and Smith, U.S. Pats. 2,566,245 and 2,566,263.

The emulsions can also be chemically sensitized with gold salts as described in Waller, Collins and Dodd, U.S. Pat. 2,399,083 or stabilized with gold salts as described in Damschroder, U.S. Pat. 2,597,856 and Yutzy and The emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll, U.S. Pat. 2,487,850), polyamines, such as diethylene triamine (Lowe and Jones U.S. Pat. 2,518,698), polyamines, such as spermine (Lowe and Allen U.S. Pat. 2,521,925), or bis(B-aminoethyl)sulfide and its water-soluble salts (Lowe and Jones, U.S. Pat. 2,521,926).

The emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker, U.S. Pats. 1,846,301; 1,846,302; and 1,942,- 854; White, U.S. Pat. 1,990,507; Brooker and White, U.S. Pats. 2,112,140; 2,165,338; 2,493,747; and 2,739,- 964; Brooker and Keyes, U.S. Pat. 2,493,748; Sprague, U.S. Pats. 2,503,776 and 2,519,001; Heseltine and Brooker, U.S. Pat. 2,666,761; Heseltine, U.S. Pat. 2,734,- 900; Van Lare, U.S. Pat. 2,739,149; and Kodak Limited, British 450,958.

The emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carrol, U.S. Pat. 2,271,623; Carroll nad Allen, U.S. Pat. 2,288,- 226; and Carroll and Spence, U.S. Pat. 2,334,864; and the polyethylene glycol type of Carroll and Beach, U.S. Pat. 2,708,162.

The above-described emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthaate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass and others.

Usually our emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a red-sensitive layer, a green-sensitive layer and a bluesensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.

The folowing examples are included for a still further understanding of our invention.

EXAMPLE 61 6-methyl-3-n-pentadecyl-lH-pyrazolo[3,2-c] s triazolyl-7-carboxylic acid (0.194 gram) is dissolved in N, N-diethyl lauramide (0.39 ml.) at C. A hot solution (80 C.) of 10% inert bone gelatin (12.8 ml.) and 5% triisopropylnaphthalene sulfonate (1.2 ml.) is added to the coupler solution and the mixture is homogenised using an ultrasonic probe. Water (8.8 ml.) and 7.5% solution of saponin (0.9 ml.) are added and the mixture is filtered. A bromoiodide emulsion (6.77 grams containing 0.69 gram silver) is added to the filtrate and the mixture is coated on film base giving silver, coupler and gelatin spreads of 150, 40 and 425 mg./sq. ft. dry weight respectively and the light-sensitive material so obtained is exposed at /25 second and then developed for 10 minutes at 20 C. in a color developer of the following composition:

Water-800 ml. Anhydrous sodium sulfite2.0 grams 2-amino-5-diethylaminotoluenehydrochloride-2.0 grams Sodium carbonate monohydrate--20.0 grams Sodium 'bromide1.73 grams Water to make 1000 ml. and pH adjusted to 10.86 (22 The development is followed by acid stop-fix, ferricyanide bleach and finally fixation stages when a magenta image is obtained in the exposed regions by the formation of a dye having an absorption maximum at 540 m Other developing agents are advantageously used, for example, N,N-diethyl p phenylenediamine hydrochloride gives a dye with absorption maximum at 531 m 3-methyl-4-amino-N-fl-methylsulfonamidoethylaniline gives a dye with absorption maximum at 536 m EXAMPLE 62 6-methyl-3-phenyl-lH-pyrazolo[3,2-c1-s-triazole is dispersed and coated in a similar way to that described in Example 61 at a coupler: solvent ratio of 1:3 and processed under similar conditions giving a dye with absorption maximum at 564 III/1..

EXAMPLE 63 6 methyl 3 (2,4,4 trimethylpentyl) 1H pyrazolo [3,2-c]-s-triazole is dispersed and coated out as described in Example 61 at a coupler: solvent ratio ofv 1:3. After processing as in Example 61 a dye having an absorption maximum at 540 mg is obtained.

Similar results are obtained when Example 61 is repeated using in place of the coupler of Example 8, couplers of Examples 3,4, 5, 10C, 10D, 10E, 10F, 10G, 11H, III, 12, 13K, 13L, 13M, 13N, 14, 15, 160, 16, 17R, 18, 19, 22, 24, 25, 26, 27, 28, 29, 30, 3 1, 32, 33, 36, 40 and 41. In each instance good magenta dye images are obtained characterized by having unusually low light absorption in the blue region of the spectrum.

When Example 61 is repeated using the coupler of Example 1, a useful yell-ow colored dye is produced upon color development.

1 EXAMPLE 64 A magenta-forming developer solution having thefor- 6 methyl 3(2,4,4-trimethylpentyl) 1H pyrazolo [3,2-c]-s-triazole (in ethanol sufficient to dissolve coupler) 1.5

Water to 1 liter.

pH adjusted to 11.5 with NaOH solution is used to color develop a magenta image in a strip of image exposed film coated with a layer of silver halide emulsion. The silver in the strip is converted to silver halide by treating it with a ferricyanide-bromide bleach and then the silver halide is removed by treating the strip with a hypo fix bath to leave a good magenta dye image having an absorption maximum at 541 m Similar results are obtained when Example 64 is repeated using in place of 6-methyl-3(2,4,4-trimethylpentyl)-1H-pyrazolo[3,2-c1-s-triazole couplers of Example Nos. 6, 7, 9, 10A, 10B, 10C, 16F, 16Q, 17S, 21, 23, 34, 35, 37, 38 and 39. In each instance good magenta dye images are developed in the imageexposed silver halide emulsion layer by color processing using our developer solutions.

EXAMPLE 65 A sensitizing amount of each of dye compounds 52, 57, 56, 58, 53 and 60 indicated in the table below was added to separate portions of a negative-type, developing out gelatino silver chlorobromide emulsion. Each of these emulsions was coated onto a piece of cellulose ester film support and dried. Spectrographic exposures were made on each coating at & second and these were developed the following compositions:

Grams p-Methyl aminophenol sulphate 2.0 Sodium sulphite desiccated 90.0 Hydroquinone 8.0 Sodium carbonate monohydrate 52.5 Potassium bromide 5.0

Water to make 1 litre.

fixed in a conventional sodium thiosulphate fixing bath, washed and dried. The following table summarizes the wavelength of light to which the maximum sensitivity is produced, and the longest wavelength light to which each emulsion is sensitized.

Wavelength of light in mm. to which:

(ii) Dye (i) Dye produces sensitizes max. senemulsion Compound No. sitivity EXAMPLE 66 6-heptadecyl-3-methylthio-IH-pyrazolo[3,2-c] s triazole (0.2 gram) was dissolved in dibutyl phthalate (0.4 ml.) at C. A hot solution (80 C.) of 10% inert bone gelatin (12.8 ml.) and 5% tri-isopropylnaphthalene sulphonate (1.2 ml.) were added to the coupler solution and the mixture was homogenized using an ultrasonic probe. Water (8.8 ml.) and 7.5% solution of saponin (0.9 ml.) were added and the mixture was filtered. A gelatino bromo-iodide emulsion (6.8 grams containing 0.69 gram silver) was added to the filtrate and the mixture was coated on a cellulose acetate film base at 425 mg. gelatin/sq. ft. dry weight and the light-sensitive material so obtained was exposed and then developed for 10 minutes at 20 C. in a colour developer of the following composition:

Water-800 ml.

Anhydrous sodium sulphite-2.0 grams 2-amino-S-diethylaminotoluene hydrochloride-2.0 grams Sodium carbonate monohydrate-20.0 grains Sodium bromide-1.73 grams Water to make 1,000 m1. and pH adjusted to 10.9

The development was followed by acid stop-fix, ferricyanide bleach and finally fixation stages when a magenta image was formed in the exposed regions by the formation of a dye having an absorption maximum at 559 nm. Other developing agents can be used for example, 3- methyl 4 amino N 9 methylsulphonamidoethyl-N- ethylaniline gives a dye with absorption maximum at 555 EXAMPLE 67 A colour developer solution having the formula:

Grams Sodium sulphite 2 2-amino-5-diethylamino toluene hydrochloride 2 Sodium carbonate 20 Potassium bromide 2 Compound 46 (in ethanol suificient to dissolve coupler) 1.5 Water to 1 litre.

pH adjusted to 11.5 with sodium hydroxide solution was used to colour develop a magenta image in a strip of image exposed film coated with a layer of silver halide emulsion. The silver in the strip was converted to silver halide by treating it with a ferricyanidebromide bleach and then the silver halide was removed by treating the strip with a hypo fix bath to leave a magenta dye image having an absorption maximum at 557 nm. A magenta dye image having an absorption maximum at 570 nm. was obtained when 3-methylthio-6-phenyl-lH-pyrazolo[3, 2-c]-s-triazole (Compound 42) is used as the coupler and N,N-diethyl-p-phenylenediamine as the developing agent in the above formula.

Our couplers are valuable for use in color photography. Certain of them are dilfusible and are used to advantage in color developer compositions While the other couplers are non-diffusible and used to advantage in light-sensitive silver halide emulsion layers of photographic elements. Couplers of this invention which have an esterified carboxy group in the coupling-01f position, for instance, are characterized by forming good yellow dyes for color hotography. Other couplers of our invention tform good magenta dyes which are characterized by having low absorption of light in the blue region of the spectrum. A further utility of the herein disclosed compounds is as an intermediate for various azamethine, azo and cyanine photographic sensitizing dyes. The compounds of this invention are also characterized by having good coupling reactivity with oxidized primary aromatic amine color developing agents.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be elfected within the spirit and scope of the invention.

What is claimed is:

1. A light-sensitive hydrophilic colloid containing silver halide and a compound of the formula N-NR7 l H R1 wherein R is hydrogen;

wherein R is an alkyl or a phenyl group; halo; sulfo; carboxy; corresponding water soluble salt of a sulfo or carboxy group;

R -S- wherein R is individually defined as an alkyl,

phenyl, naphthyl, pyridyl, quinolyl, triazolyl, benzotriazolyl or tetrazolyl group;

R N=N- wherein R is a phenyl, naphthyl, benzothiazolyl, thiazolyl, quinolyl or pyrazolyl radical; alkylcarbonyloxy; alkylsulfonyloxy; arylsulfonyloxy group; or thiocyano group; and

R and R, each represent a member selected from the class consisting of a hydrogen, alkyl, alkylthio, aryl, heterocyclic group having from 5-6 atoms in the ring, amino, acylamido, hydroxy, alkoxy, carboxy, or

Ra-O-C- ll wherein R represents an alkyl or a phenyl group.

28 2. A photographic dye-forming developer composition comprising a primary aromatic amine color developing agent and a coupler compound having the formula:

wherein R represents a member selected from the group consisting of a hydrogen;

0 Ego-( lwherein R is an alkyl or a phenyl group; halo; sulfo or corresponding water soluble salt thereof; carboxy group or corresponding water soluble salt thereof;

R --S-- wherein R is defined as an alkyl, phenyl, naphthyl, pyridyl, quinolyl, triazolyl, benzotriazolyl and tetrazolyl group;

R N=N- wherein R is a phenyl, naphthyl, benzothiazolyl, thiozolyl, quinolyl or pyrazolyl radical; alkylcarbonyloxy; alkylsulfonyloxy; and benztriazolyl group;

and

R and R, are individually defined as a member selected from the group consisting of a hydrogen, alkyl, alkylthio, alkoxy, phenyl, naphthyl, pyridyl, thienyl, quinolyl, amino, acylamido, hydroxyl, carboxy and the Rs-O-(igroup.

3. A light-sensitive hydrophilic colloid containing silver halide and 6-methyl-3-pentadecyl-lH-pyrazolo [3,2-c]-s-triazolyl-7-carboxylic acid.

4. A light-sensitive hydrophilic colloid containing silver halide and 6 methyl-3-phenyl-lH-pyrazolo[3,2-cJ-s-triazole.

* 5. A light-sensitive hydrophilic colloid containing silver halide and 6 methyl-3-(2,4,4-tri'methylpentyl)-1H-pyrazolo- [3 ,2-c] -s-triazole.

6. A light-sensitive hydrophilic colloid containing silver halide and 3,6 di(methylthio)-lH-pyraziolo[3,2-c-]-s-triazole.

7. A photographic dye-forming developer composition comprising a primary aromatic amine color developing agent and 6-methyl 3 (2,4,4trimethylphenyl)-1H-pyrazolo[3,2-c]-s-triazole.

References Cited UNITED STATES PATENTS 3,061,432 10/1962 Menzel et al. 96-100 3,079,255 2/1963 Wahl et al. 96100 3,369,897 2/1968 Menzel et al. 96l00 3. TRAVIS BROWN, Primary Examiner US. Cl. X.R.

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Classifications
U.S. Classification430/476, 548/181, 430/558, 544/300, 548/217, 548/159, 548/262.4
International ClassificationG03C1/10, C09B23/06, G03C1/83, C07D487/04, G03C7/38, C09B23/08, G03C7/384, C09B23/10, G03C7/305, C09B23/04, C09B23/01
Cooperative ClassificationG03C1/10, C09B23/04, C09B23/0091, C09B23/06, G03C1/83, G03C7/3835, G03C7/30529, C07D487/04, C09B23/10, C09B23/105, C09B23/107, G03C7/384, C09B23/083
European ClassificationG03C1/83, C09B23/08B, C09B23/00S, C09B23/10B, G03C1/10, G03C7/305B1M, C09B23/10, C09B23/04, C09B23/06, G03C7/38H2N4, C09B23/10D, G03C7/384, C07D487/04