Classifications

• • 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
• • 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

Definitions

• Diffusible couplers are used in alkaline developer solutions containing the primary aromatic amino color developing agent to color develop color photographic elements that do not contain the color forming couplers.
• the coupler and developing agent as well as other materials in the color developer solution diffuse into the color photographic element being developed with the imagewise formation of oxidized color developer and the subsequent coupling to produce a nondiffusing dye image in the element.
• Desirable couplers for color photography must have good coupling activity, and produce dye images in the color developed photographic elements that have the needed spectral absorption characteristics, and dye images that have good stability to prolonged exposure to light. In addition to this, it is important that the coupler and its reaction products not produce yellow stain in the' highlight or D min. areas of the developed photographic elements.
• magenta-forming couplers now in use have good activity and produce dyes with good absorption characteristics but do not produce dyes with the desired light stability. Furthermore, these couplers tend to produce undesirable yellow stain in the D min. areas of the developed elements. Many of the prior art S-anilino-S-pyrazolone magenta-forming couplers are un acceptable because of low coupling activity and undesirable spectral absorption characteristics of the dyes produced from them.
• Another object of my invention is to provide, for use in color photography, valuable magenta-image-forming developer solutions containing my 1-aryl-3-aniliano-5- pyrazolone couplers, said solutions producing unexpectedly low yellow stain in the D min. areas of color photographic elements processed through them.
• Another object is to provide valuable magenta-image forming developer solutions which produce magenta dye images having unexpectedly good stability to prolonged exposure to light.
• Another object is to provide a color process that uses my valuable l-aryl-3-anilino-5-pyrazolone couplers in a magenta-image-forming developer solution.
• My couplers exhibit good coupling activity in magenta-forming developer solutions during color development reactions and produce in the color element being developed, magenta images having desirable sensitometric characteristics, i.e., good D min., D max. and contrast.
• the use of my couplers in magenta-forming developer solutions results in a substantial reduction in the yellow stain in the D min. areas of color photographic elements developed with them.
• This valuable improvement shown by my couplers over certain l-aryl-3-anilino-5-pyrazolone outside my invention is unexpected.
• the dyes formed from my couplers have good spectral absorptions characteristics and are unexpectedly stable upon prolonged exposure to light.
• the 1-aryl-3-anilino-5-pyrazolone couplers of my invention are represented advantageously by the following formula:
• I represents a group selected from the class consisting of the chlorine atom, the nitro group and the cyano group
• W represents a group selected from the class consisting of the hydrogen atom, and the chlorine atom
• X represents a group selected from the class consisting of the hydrogen atom, the cyano group and the nitro group
• Y represents a group selected from the class consisting of the hydrogen atom, the chlorine atom, the cyano group and the methylsultonyl group
• Z represents a group selected from the class consisting of the hydrogen atom, and the cyano group, such that at least one of the groups, W, X, Y and Z represents a group other than the hydrogen atom.
• My 1-aryl-3-anilino-5-pyrazolones are used advantageously in aqueous alkaline color developer solutions containing primary aromatic amino developing agents to produce the magenta dye image in the image exposed multicolor photographic element during color development.
• the improvement according to my invention comprises the use in said magenta developer solution of one of my laryl-3anilino-S-pyrazolone couplers as the magenta image-forming coupler.
• the couplers of my invention are prepared advantageously by a general synthesis for making 1-aryl-3- anilino-S-pyrazolone couplers.
• an aryl hydrazine is. mixed and heated with a methyl ,G-methyh mercapto-fi-aryliminopropionate. This reaction is believed to occur according to the following equations:
• the reaction is used to advantage with any isothiocyanate which is not attacked irreversibly by the sodio acetoacetic ester at another substituent.
• the isothiocyanates used can be prepared by any of several methods, the most commonly used methods for making aryl isothiocyanates being the method described by Dyson, Organic Synthesis, coll. vol. 1, p. 165, and the method described by Dains, Brewster and Olander, Organic Synthesis, coll. vol. 1, p. 447.
• any arylhydrazine can be used to advantage. If the hydrazine molecule contains a free sulfo or carboxy group, the method is modified to include a mole of a tertiary amine, such as, pyridine or triethylamine, to keep the hydrazine in solution in the refluxing methyl alcohol.
• a tertiary amine such as, pyridine or triethylamine
• This synthesis is used to advantage for the preparation of a wide variety of l-aryl-3anilino-S-pyrazolone couplers, including for example, the ditiusible couplers with or without solubilizing groups, ballasted or nondiifusible couplers with or without solubilizing groups, colored couplers (i.e., couplers that are colored), etc.
• sulfo groups can be introduced by sulfonation of the 5-pyrazolone after its synthesis by my new method.
• a sulfo group is introduced into the anilino ring under mild conditions, and a sulfo group is introduced into the l-phenyl ring at about to C.
• Ballast groups can be introduced by use of ballasted arylhydrazines or aryl thiocyanates, or by any of several methods which have been described previously.
• 1-aryl-3anilino-S-pyrazolones of my invention are the following illustrative examples.
• 1-aryl-3-anilino5-pyrazolone couplers of the invention are used to advantage in color developing solutions to develop magenta images in light-sensitive elements (which do not contain the color-forming coupler) used for color photography.
• any of the well known primary aromatic amino color-forming silver halide developing agents such as, the phenylenediamines, e.g., N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-di nethyl-pphenylenediamine hydrochloride, 2-amino-5-N,N-diethylaminotoluene hydrochloride, Z -amino-S-(N ethyI-N-Iauryl)t0luene.
• the phenylenediamines e.g., N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-di nethyl-pphenylenediamine hydrochloride, 2-amino-5-N,N-diethylaminotoluene
• N ethyl [3 methanesulfonamidoethyl 3- methyl-4-aminoalinine sulfate, N-ethyl-fl-methanesulfonamidoethyl 4 aminoaniline, 4 N ethyl N ,8 hydroxyethylaminoaniline, etc., the p-aminophenols, and their substitution products when the amino group is unsubstituted may be used in the alkaline developer solution with my couplers.
• Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc.
• a multilayer, multicolor photographic material comprising a support coated in succession with a red-sensitive cyan-forming silver halide emulsion layer, a greensensitive magenta-forming silver halide emulsion layer,
• a yellow filter layer, and a blue-sensitive yellow-forming silver halide emulsion layer was exposed to a step wedge in a sensitometer.
• Pieces of this element were processed as follows: l-minute treatment in a conventional alkali metal bisulfite-formalin prehardener, washing, 2 /2-minute development in a conventional p-methylaminophenol sulfate-hydroquinone black-and-white developer, washing, fogging the unexposed and undeveloped silver halide, 7-minute treatment in magenta color developer solutions, Washing, bleaching, fixing and Washing.
• the magenta color developer solutions used had the composition:
• Magenta Color Developer Sodium hexametaphosphate g 1.0 Sodium sulfite g 5.0 ,4-amido-N-ethyl-N-(B-methanesulfonamidoethyl)-m-toluidine' sesquisulfate monohydrate g 40.0 Trisodium phosphate 40.0 Potassium bromide Sodium sulfate Potassium iodide C-itrizinic acid communique Sodium thiocyanate 1.0 Coupler mole .006 Carbowax 4000 g 1.0 Ethylenediamine sulfate g 3.0
• magenta. color developer container the magenta-forming coupler indicated in the following table.
• the coupler 1 (2,4,6 triclilorophenyl) 3 (4 nitroanilino) 5- pyrazolone which is outside our invention was used as the control.
• the processed and dried elements were cornpared for yellow stain by determining the optical density in the D min. areas withlight through a blue filter having a cutoff point at 442 mg.
• the optical density values of each of the processed strips were determined With light through a green filter.
• the strips were then exposed to a tungsten are light for 3 days and the density values measured again with light through the green filter.
• the percent fading of the magenta dye at a density of 1.0 and the yellow stain levels in each strip are tabulated This table shows that the magenta dyes formed from my couplers were all more stable upon prolonged exposure to light than was the control.
• the yellow stain found in the D min. areas of the processed elements was from 23.5 to 35.3% lower than the stain in the control strip.
• coupler 5 which is position isomer of the control coupler (that is, coupler Sis 1-2,4,6-trichlorophenyl)-3-(3- nitroanilino)-5-pyrazolone and the control is l-(2,4,6-trichlorophenyl -3- (4-nitroanilino 5-pyrazolone)
• the couplers in Example 1 all exhibited good coupling activity, that is they formed go d dye images having desirable sensitometric curves (curve relating developed dye density to log exposure).
• the coupler 1-(2,4,6-trichlorophenyl)-3-anilino-5-pyrazolone which is outside our invention was used in a magenta developer composition described in Example 1.
• My couplers are designed for use in processes in which the coupler is incorporated in the developing solution such as those described in Mannes and Godowsky, US. Patent 2,113,329, issued April 5, 1938, Marines, Godowsky and Wilder, US. Patent 2,252,718, issued August 19, 1941, etc. ,7
• Example 2 Multilayer, multicolor photographic elements were exposed as in Example 1 and given the complete reversal process described previously. This process included the steps: treatment in a conventional alkali metal bisulfite formalin prehardener, water washing, development in a conventi nal p-methylaminophenol sulfate hydroquinone black and white developer, Water washing, selective reexposure of the red-sensitive layer with a red light, treatment with an aqueous alkaline cyan developer solution containing a cyan-forming coupler and a primary aromatic amino developing agent, water Washing, selective re-exposure of the blue-sensitive layer, treatment with an aqueous alkaline yellow developer solution containing a yel-.
• Coupler 1 was prepared as follows. To a methanolic solution of sodium methoxide prepared from 2.3 g. (0.10
• the amide hydrazone (44.8 g., 0.10 mole) was added to a solution of 10.8 g. (0.20 mole) of sodium methoxide in 350 ml. methanol. The mixture was refluxed for about 1 hour (30-45 after solution was obtained), cooled, 350 ml. of water added, and the solution acidified with acetic acid. The precipitate was separated by filtration, washed with water, and dried. After recrystallization from acetonitrile, the coupler 1 had a melting point of 267-269 C.
• Coupler 2 was prepared by the method used to make coupler 1, but 16.0 g. (0.10 mole) of 4-cyanophefi'ylisothiocyanate was used in place of 4-methylsulfonylphenylisothiocyanate tomake the amide hydrazone.
• Coupler 3 was prepared by the'method used to make coupler 1 but 16.0 g. (0.10 mole) of 3-cyanophenylisothi- Jocyanate was used in place of 4-methylsulfonylphenylisothiocyanate to make the amide hydrazone.
• Coupler 4 was prepared by the method used to make coupler l but 19.5 g. (0.10 mole) of 2-chloro-5- cyanophenylisothiocyanate was used in place of 4-methylsulfonylphenylisothiocyanate to make the amide hydrazone.
• the coupler made by cycliz'ation of the amide hydrazone was recrystallized from "acetic acid togive a product with a melting point of 259-262 C. (dec.).
• Coupler 5 was prepared by the method used to make coupler 1 but 18.0 g. (0.10 mole) of 3-nitropheny1isothiocyanate was used in the reaction to make the amide hydrazone.
• the coupler made from the cyclization of the amide hydrazone was recrystallized from methanol to give a product melting at 250251 C.
• Coupler 6 was prepared by the method used for coupler 1 but 20.4 g. (0.10 mole) of 2,4-dichlorophenylisothiocyanate was used and the final period of reflux was 72-96 hours.
• the reaction mixture was then filtered to remove a small amount of by-product (apparently the hydrazide formed by reaction of the uncyclized amide hydrazone and excess hydrazine).
• the filtrate was then added to a solution of 2 parts of sodium methoxide in methanol, refluxed for 30 min. and an equal volume of water added.
• the reaction mixture was then extracted with ether to remove some dark tarry material.
• the aqueous solution was acidified with acetic acid, and the precipitate was separated by filtration, washed well with water, and dried. After three recrystallizations from acetonitrile there was obtained a 24 percent yield of product; M.P. 197-201 C.
• Coupler 7 was prepared by the method used for coupler 1 but equivalent amounts of 2,4-dichlorophenylisothiocyanate and 2,6-dichloro-4-nitrophenylhydrazine were used. The cyclized coupler was recrystallized from glacial acetic acid to yield the product; M.P. 229-231 C. (dec.).
• Coupler 8 was prepared by the method used for were used.
• the cy'clized coupler was recrystallized from glacial acetic acid to yield the product; M.P. 258-261" C. (dec.).
• the arylisothiocyana'tes used were prepared by reaction of, the appropriate amine with thiophosgene in an aqueous suspension. The procedure was adapted for use with high melting amines by using high-speed stirring in a Morton flask, thus eliminating the need for an organic solvent. Consistently higher yields than are reported in the literature were obtained by this revised procedure. Most of these compounds have been described in the literature, for example, 4-methylsulfonylphenylisothiocyanate (L.
• 2,4,6-trichlorophenylhydrazine is available commercially.
• 2,6 dichl0r0-4-nitrophenylhydrazine is prepared by chlorinating 4-nitroaniline by a conventional reaction then diazotizing the 2,6-diehloro-4-nitroaniline with nitrosyl sulfuric acid at 40 C. and reducing the diazo compound to the corresponding hydrazine compound by treating it with stannou's chloride and hydrochloric acid.
• 2,6-dichloro 4-cyanophenylhydrazine is prepared by chlorinating 4-cyanoaniline, diazotizing the amine with isoamyl nitrite at 0 C. and then reducing the diazo compound'to the hydrazine derivative as described above.
• the 1-aryl-3-anilino-5-pyrazolone couplers of my invention are valuable for use incolor photography.
• My couplers are distinguished from certain other 1-aryl-3- anilino-5-pyrazolone couplers by having good coupling reactivity. They are distinguished from other 1-aryl-3- anilino-5-pyrazolone couplers by producing up to 35.3% less yellow stain in D. min. areas of photographic elements processed through them.
• the magnet image dyes formed by my couplers have unexpectedly better light stability than couplers outside the invention.
• a difiusible magnets-forming coupler having this formula:
• Y represents a group selected from the class consisting of the hydrogen atom, the chlorine atom, the cyano group and the methylsulfonyl group
• Z represents a group selected from the class consisting of the hydrogen atom, and the cyano group, such that at least one' of the groups W, X, Y, and Z represents a group other'than the hydrogen atom.
• magenta-forming coupler 1 2,4,6-trichlorophenyl) -3 -(4-cyanoanilino) -5 -pyrazolone.
• J represents a group selected from the class consisting of the chlorine atom, the nitro group, and the cyano group
• W represents a group selected from the class consisting of the hydrogen atom, and the chlorine atom
• X represents a group selected from the class consisting of the hydrogen atom, the cyano group, and the nitro group
• Y represents a group selected from the class consisting of the hydrogen atom, the chlorine atom, the cyano group and the methylsulfonyl group
• Z represents a group selected from the class consisting of the hydrogen atom, and the cyano group, such that at least one of the groups W, X, Y, and Z represents a group other than the hydrogen atom.
• J represents a group selected from the class consisting of the chlorine atom, the nitro group, and the cyano group
• W represents a group selected from the class consisting of the hydrogen atom, and the chlorine atom
• X represents a group selected from the class consisting of the hydrogen atom, the cyano group, and the nitro group
• Y represents a group selected from the class consisting of the hydrogen atom, the chlorine atom, the cyano group and the methylsulfonyl group
• Z represents a group selected from the class consisting of the hydrogen atom, and the cyano group, such that at least one of the groups W, X, Y, and Z represents a group other than the hydrogen atom.
• washing (6) selectively re-exposing the unexposed and undeveloped silver halide in the said blue-sensitive layer
• the improvement comprising the use in the magenta color developing step of an aqueous alkaline solution containing a primary aromatic amino developing agent and a coupler having the formula:
• I represents a group selected from the class consisting of the chlorine atom, the nitro group, and the cyano group
• W represents a group selected from the class consisting of the hydrogen atom, and the chlorine atom
• X represents a group selected from the class consisting of the hydrogen atom, the cyano group, and the nitro group
• Y represents a group selected from the class consisting of the hydrogen atom, the chlorine atom, the cyano group and the methylsulfonyl group
• Z represents a group selected from the class consisting of the hydrogen atom, and the cyano group, such that at least one of the groups W, X, Y, and Z represents a group other than the hydrogen atom.

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• Organic Chemistry (AREA)
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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

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Citations (4)

• 1963
  • 1963-02-18 US US259392A patent/US3152896A/en not_active Expired - Lifetime
• 1964
  • 1964-02-13 BE BE643777A patent/BE643777A/xx unknown
  • 1964-02-13 GB GB6024/64A patent/GB1059146A/en not_active Expired
  • 1964-02-15 DE DEE26411A patent/DE1176478B/de active Pending
  • 1964-02-17 DK DK77064AA patent/DK113756B/da unknown
  • 1964-02-17 CH CH184564A patent/CH429444A/fr unknown
  • 1964-02-17 ES ES296535A patent/ES296535A1/es not_active Expired
  • 1964-02-18 SE SE01932/64A patent/SE333500B/xx unknown
  • 1964-02-18 NL NL6401438A patent/NL6401438A/xx unknown
• 1967
  • 1967-12-31 MY MY1967160A patent/MY6700160A/xx unknown

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