Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
  • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

• a lightsensitive photographic color material comprising a redsensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on development by means of suitable color couplers, a cyan, a magenta and a yellow dye image are formed respectively.
• 3-acylamino-2-pyrazolin-5-one color couplers are not so stable to light, heat and humidity while others form dyes having unfavorable spectral characteristics eg dyes having too little green and too much red or blue absorption.
• l-substituted 2- pyrazolin-S-one color couplers are provided carrying in the 3- position a 2,4,6-triemthylphenylacylamino group viz a 2,4,6- trimethylphenylsulphonylamino or 2,4,6,-trimethylphenylcarbonylamino group.
• color couplers are provided corresponding to the following general formula:
• R stands for alkyl including substituted alkyl, aralkyl including substituted aralkyl, aryl including substituted aryl or a heterocycle including a substituted heterocycle,
• X stands for carbonyl or sulphonyl.
• the groups represented by R may be any of those customarily present in the Z-pyrazolin-S-one color couplers more particularly alkyl, aryl, aralkyl or heterocyclic groups. These groups may carry substituents favorable influencing the physical, spectral and/or sensitometric properties of the color couplers and the dyes formed therewith. If it is desired to make dyes that are fast to diffusion in the photographic colloid layer into which they are intended to be incorporated the substituent R preferably is or comprises a substituent of the formula -Y-D wherein Y stands for a chemical bond, oxygen, sulfur, sulphonyl, NHSO SO N(R,)with R hydrogen or lower alkyl, CONl-l.
• -NHCO-or -N(aklyl)-N(alkyl)- and D is an acylic aliphatic group rendering the color coupler fast to diffusion preferably having from five to 20 carbon atoms.
• 2- pyrazolin-S-one color couplers carrying substituents of the type represented by'R in the above general formula can be found in the literature; see for example United Kingdom Pat. Specification Nos. l,007,847, 1,044,959, 1,069,533 and 1,069,534, U.S. Pat. Specification No. 2,369,489, Japanese Pat. Publication No. 7039/57 and published Dutch Pat. application No. 671 1915.
• the color couplers of the present invention are distinguished from all known l-substituted 3-acylamino-2- pyrazolin-S-one color couplers by having attached to the 3- position a 2,4,6-trimethylphenylacylamino group.
• color couplers have useful properties not shared by couplers of similar structure except that they not contain such a 2,4,6- trimethylphenylacylamino group; one such useful property is that the dyes produced on color development have favorable spectral properties and another (particularly in the case of the 3-sulphonamido-2-pyrazolin-5-one color couplers of the invention) that they have an improved stability to humidity as compared with dyes similarly produced from the known I- substituted 3-acylamino-2-pyrazolin-5-one color couplers. Moreover, the color couplers of the invention furnish dye images with high color density and gradation.
• the color couplers of the invention apart from forming with the oxidation products of aromatic primary amino developing agents magenta dyes manifesting a favorable stability against light and heat and an excellent stability against humidity, the color couplers of the invention from magenta dyes having very good spectral characteristics in that they show markedly less blue-absorption than dyes formed with known 3-acylamino-2-pyrazolin-2- one color couplers.
• CH o c 1 a s O (CH:)1sCH; H, :c-NHco-om /N ⁇ CH cm l 1 Th 1 b d3(246' hlh 11' 2 e -su stitute -trimet yp eny acy ammo)- C NHS CHB pyrazolin-S-one color couplers according to the present inven- (IJHB tion can be prepared by condensation of 2,4,6-trimethylbenzoylchlorise or 2,4,6-trimethylphenylsulphonyl chloride O (CHZ)I5 CH3 with the appropriate l-substituted 3-amino-2-pyrazolin-5-one in the presence of anhydrous inert solvents and/or basic condensing agents such as pyridine preferably also in the presence of aluminum chloride as catalyst.
• anhydrous inert solvents and/or basic condensing agents such as pyridine preferably also in the presence of aluminum
• the l-substituted 3-amino-Z-pyrazolon-S-one compounds used in said methods can be prepared according to the 7 methods known by those skilled in the art and described in the H10 C 1 ⁇ HSOZ CH3 literature i.e. by cyclization of the appropriately substituted hydrazine with e.g. the ethyl ester of B-imino-B-ethoxy propionic acid. in this connection there can be referred to United Kingdom Pat Specification Nos. 1,007,847. 1,044,959, 1,069,533, 1,069,543 and 1,086,988 and published Dutch Pat.
• the reaction mixture is poured into 14 liters of ice-cold water and the precipitate formed is filtered off and a washed with water until acid free
• the product is dissolved in N 2 liters of dichloromethane, the aqueous layer is separated and z 2 5 the organic layer is dried over anhydrous sodium sulfate.
• PREPARATION 3 COMPOUND 3
• PREPARATION 4 COMPOUND 4 1-(p-hexadecylsulphamoylpheny1)-3-(2,4,6-trimethylphenylsulphonamido)-2-pyrazolin-5-one
• This compound is prepared in an analogous way as compound 3 by condensation of 47.8 g. (0.1 mole) of l-(p-hexadecylsulphamoylphenyl)-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specificationv No 1,007,847) with 21.9 g. (0.1 mole) of 2,4,6-trimethylbenzene sulphochloride in a mixture of 100 ml. of pyridine and 13.4 g. of aluminum chloride. Recrystallization occurs from acetic acid.
• PREPARATION 5 COMPOUND 5 1-(2-trif1uoromethyl-4-N-methy1-N-hexadecylsulphamoylphenyl)-3-(2,4,6-trimethylphenylsulphonamido)- 2-pyrazolin-5-one
• This compound is prepared in an analogous way as compound- 3 by condensation of 28 g. (0.05 mole) of 1-(2 trifluoromethyl-4-N-methyl-N-hexadecylsu1phamoylphenyl)- 3-amino-2-pyrazolin-5-one with 12 g. (0.055 mole) of 2,4,6- trirnethylbenzene sulphochloride in a mixture of 6.7 g. (0.05 mole) of anhydrous aluminum chloride and 50 ml. of pyridine. Recrystallization occurs from hexane. Melting point: 105 C.
• PREPARATION 6 COMPOUND 6 1-(o-hexadecylsulphonylphenyl)-3-(2,4,6-trimethylphenylsulphonamido)-2-pyrazolin-5-one
• This compound is prepared in an analogous way as compound 3 by condensation of 32.4 g. (0.07 mole) of 1-(o-hexadecylsulphonylphenyl)-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specification No. 1,044,959) with 16.8 g. (0.077 mole) of 2,4,6-trimethylbenzene sulphochloride in a solution of 9.4 g. (0.7 mole) of anhydrous aluminum chloride in m1. of pyridine. Recrystallization occurs from methanol. Yield: 30 g. (66%). Melting point: 152C.
• PREPARATION 7 COMPOUND 7 1-(m-hexadecyloxypheny1)-3-(2,4,6-trimethylphenylsulphonamido) 2-pyrazolin-5-one
• l-(m-hexadecyloxyphenyl)-3-amino-2-pyrazolin-5-one prepared as described in United Kingdom Pat. Specification No. 1,007,847
• 10 g. (0.075 mole) of anhydrous aluminum chloride in 37.5 ml. of nitrobenzene and 18.7 ml. ofpyridine 16.4 g. (0.075 mole) of 2,4,6-trimethylbenzene sulphochloride are added.
• reactionmixture is stirred for 4 hours at 50 C. whereupon it is poured into 500 m1; of5 N hydrochloric acid. The precipitation formed is recrystallized from 2-ethoxy-ethanol. Yield: 60%. Melting point: 147 C.
• PREPARATION 8 COMPOUND 8 a. l-(2-hexadecyloxy-S-chlorophenyl)-3-amino-2-pyrazolin-5 -one 126 g. of 2-hexadecy1oxy-S-chloro-phenylhydrazine (preparedas described in United Kingdom Pat. Specification No. 1,086,988) and 66 g. of B-ethoxy-B-amino-acrylic acidethyl ester are heated for 3 hours at 40 C. in the presence of 1 ml. of acetic acid. A sodium methylate solution prepared from 15.2 g. ofsodium and 200 ml. of methanol is added. The solution is kept for 30 min.
• reaction mixture is heated for'5 hours at'50 C.
• the reaction mixture is poured into 1 liter of boiling 5 N hydrochloric acid.
• PREPARATION l0 COMPOUND 10 1-(2 ,2,2-trifluoroethyl)-3-( 2,4,6-trimethylpheny1- sulphonamido )-2-pyrazolin-5 -one from ethanol. Yield: 22 g. (60%). Melting point: 208 C.
• PREPARATION 1 l COMPOUND l l l[-hexadecyl-N-methylsulphamoyl)-2-pyridyl]-3-(2,4,6- trimethylphenylsulphonamido)2-pyrazolin-5-one
• anhydrous aluminum chloride 14.8 g. (0.03 mole) of I-[S-(N-methyl-N-hexadecyl-sulphamoyl)-2-pyridyl]-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specification No. 1,069,534) in 6.56 g.
• PREPARATION l2 COMPOUND 12 1-( m-hexadecyloxyphenyl )-3-( 2,4,6-trim ethylbenzoylamino 2-pyrazolin-5-one
• a solution of41.5 g. (0.1 mole) of l-(m-hexadecyloxyphenyl)-3-amino-2-pyrazolin-5-one and 18.3 g. (0.1 mole) of 2,4,6-trimethylbenzoyl chloride in 100 ml. of dioxan is refluxed for 2 hours.
• the reaction mixture is poured into water and the precipitate formed is filtered off and recrystallized from ethyl acetate. Melting point: 98-100 C.
• the color couplers For manufacturing an appropriate photographic multilayer color material containing color couplers for each color separation image in the differently optically sensitized silver halide emulsion layers, the color couplers must be present in the hydrophilic silver halide emulsion layers or other colloid layers in water-permeable relationship therewith in a nondiffusible form.
• the substituent in the l-position of the 2-pyrazolin-5- one color couplers of the invention can contain as already said above a ballasting group rendering the molecule fast to diffusion into photographic colloid layers.
• the color couplers according to the present invention can be incorporated into the photographic material according to any technique known by those skilled in the art for incorporating photographic ingredients, more particularly color couplers into colloid compositions.
• the water-soluble color couplers can be incorporated into the coating composition of the layer in question from an aqueous solution or alkaline aqueous solution and the water-insoluble or insufficiently water-soluble color couplers from a solution in the appropriate water-miscible or water-immiscible high-boiling or low-boiling organic solvents or mixtures thereof whereupon the solution obtained is dispersed, if necessary in the presence of a wetting or dispersing agent, in a hydrophillic colloid composition forming or forming part of the binding agent of the colloid layer.
• the hydrophilic colloid composition may of course comprise an addition to the colloid carrier all other sorts of ingredients.
• solutions of the color couplers of the above general formula need not necessarily be dispersed or dissolved directly in the coating composition of the silver halide emulsion layer or other water-permeable layer.
• Said solution may advantageously be first dispersed or dissolved in an aqueous nonlight-sensitive hydrophilic colloid solution whereupon the resultant mixture, if necessary after the removal of the organic solvents employed, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.
• Another interesting method of rendering the color couplers fast to diffusion is to use the color couplers in polymeric form e.g. by copolymerization of monomeric color couplers corresponding to the general formula above wherein R comprises e.g. a substituent of the formula wherein Z stands for hydrogen, halogen, lower alkyl, araklylor aryl, with one or more noncolor forming monomers containing at least one ethylenic group.
• the polymeric color couplers can be incorporated into photographic colloid compositions according to any technique known by those skilled in the art for incorporating polymeric photographic color couplers into colloid compositions.
• hydrophilic colloid compositions forming or forming part of the binding agent of the colloid layer.
• the polymeric color couplers can also be incorporated into hydrophilic colloid compositions in the form of latices, primary latices as well as secondary latices.
• the color couplers according to the present invention may be used in conjunction with various kinds of photographic emulsions.
• Various silver salts may be used as the sensitive salt, such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
• the couplers can be used in emulsions of the mixed-packet type as described in US. Pat. Specification No. 2,698,794 or emulsions of the mixed grain type as described in U.S. Pat. Specification No. 2,592,243.
• the color couplers can be used with emulsions wherein latent images are formed predominantly on the surface of the silver halide crystal, or with emulsions wherein latent images are formed predominantly inside the silver halide crystal.
• the hydrophilic colloid used as the vehicle for the silver halide may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinylalcohol, poly-N-vinyl-pyrrolidone etc. If
• compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide.
• the light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as optically sensitized. They may be chemically sensitized by effecting the ripening in the presence of amounts of sulfur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate etc.
• the emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Pat, Specification No. 1,146,955 and in Belgian Patv Specification No. 568,687, imino-amino methane sulfinic acid compounds as described in United Kingdom Pat. Specification No. 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium. They may be optically sensitized by means of cyanine and merocyanine dyes.
• the said emulsions may also comprise compounds which sensitize the emulsions by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in US. Pat. Specification Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. Specification Nos. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat.
• the emulsions may be stabilized with heterocyclic nitrogen-containing thioxo' compounds such as benzothiazoline-Z-thione and l-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Pat. Specification Nos. 524,121 and 677,337, published Dutch Pat. application No. 6715932 and in US. Pat. Specification 3,179,520.
• heterocyclic nitrogen-containing thioxo' compounds such as benzothiazoline-Z-thione and l-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type
• mercury compounds such as the mercury compounds described in Belgian Pat. Specification Nos. 524,121 and 677,337, published Dutch Pat. application No. 6715932 and in US. Pat. Specification 3,179,520.
• the light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agents, etc.
• the color couplers for magenta described in the present invention are 'usually incorporated into a green-sensitized silver halide emulsion for forming one of the differently sensitized silver halide emulsion layers of a photographic multilayer color material.
• a photographic multilayer color material usually comprises a support, a red-sensitized silver halide 45 emulsion layer with a cyan forming color coupler, a green-sensitized silver halide emulsion layer with a magenta-forming color coupler and a blue-sensitive silver halide emulsion layer with a yellow color former.
• emulsions can be coated on a wide variety of photo- 50 graphic emulsion supports.
• Typical supports include cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, and relatedfilmsor resinous materials, as well as paper and glass.
• an exposed silver halide emulsion layer is developed preferably with an aromatic primary amine developing substance in the presence of a color coupler according to the present invention.
• Suitable developing agents are aromatic compounds such as p-phenylenediamine, N,N-dialkyl-p-phenylenediamines such as N,N-diethyl-p-phenylenediamine, and derivatives such as N,N-dialkyl-N'-sulphomethyl-p-phenylenediamines and N,N- dialkyl-N'-carboxymethyl-p-phenylenediamines.
• magenta color formers of the invention form on color development with aromatic primary amines such as N,N- diethyl-p-phenylenediamine magenta dyes having favorable light-absorption characteristics and showing good resistance to heat and humidity.
• the following table I gives a clear idea about the light-absorption characteristics of dyestuffs formed on color development by reaction of the oxidation product of N.N-diethyl-pphenylenediamine with color couplers according to the present invention and analogous color couplers comprising common acylamino groups in the 3-position.
• the dyes formed according to the invention have less side-absorption in the blue and red region of the spectrum than the dyes formed with analogous color couplers carrying known 3-acylamino-substituents.
• the side-absorptions are given in percent relative to absorption in the green region of the spectrum.
• trimethylphenylacylamino group is a 2.4.6-trimethylphenylsulphonamido group.
• a photographic element comprising at least one silver halide emulsion layer and a 2-pyrazolin-5-one color coupler containing the 3-position a 2,4,-trimethylphenylacylamino group 7.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=10364414

Family Applications (1)

Country Status (4)

Cited By (2)

• 1968
  • 1968-07-18 GB GB3433968A patent/GB1265155A/en not_active Expired
• 1969
  • 1969-06-19 US US834873A patent/US3615504A/en not_active Expired - Lifetime
  • 1969-06-19 DE DE19691931058 patent/DE1931058A1/de active Pending
  • 1969-07-18 BE BE736251D patent/BE736251A/xx unknown

Also Published As

Similar Documents