US2902366A - Acylated 3-aminopyrazolone couplers - Google Patents

Acylated 3-aminopyrazolone couplers Download PDF

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Publication number
US2902366A
US2902366A US617681A US61768156A US2902366A US 2902366 A US2902366 A US 2902366A US 617681 A US617681 A US 617681A US 61768156 A US61768156 A US 61768156A US 2902366 A US2902366 A US 2902366A
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United States
Prior art keywords
mls
gms
pyrazolone
solution
mole
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Expired - Lifetime
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US617681A
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English (en)
Inventor
Joseph A Sprung
Robert M Lindquist
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GAF Chemicals Corp
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General Aniline and Film Corp
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Priority to BE561850D priority Critical patent/BE561850A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US617681A priority patent/US2902366A/en
Priority to GB32627/57A priority patent/GB833596A/en
Priority to DEG23193A priority patent/DE1051638B/de
Application granted granted Critical
Publication of US2902366A publication Critical patent/US2902366A/en
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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

  • This invention relates to the production of photographic dye images by color development, and more particularly 7 to pyrazolone coupler compounds therefor.
  • p p The formation of colored photographic images by using a primary aromatic amino developing agent which couples with color-forming compounds has long been known to the photographic art and much efi ort has been directed toward a workable practicalsystem based on these principles. Modern methods of color photography are based upon the subtractive color principle, in which differently sensitized silver halide emulsions are arranged in superimposed layers, 'each layer containing the color forming components which, upon development with a primary aromatic amino developing agent, yieldthe subtrac tively colored dyestufi images, yellow, cyan and magenta.
  • magenta images are frequently produced by conplers derived from pyrazolones and the present invention relates to couplers of this type.
  • a further object is to provide pyrazolone couplers capable of incorporation in photographic emulsionlayers.
  • pyrazolone color forming compounds oontem-" plated herein are acylated derivatives of 3-amir 1o-lphenyl-S-pyrazolone and can be represented by the following general formula:
  • B represents hydrogen, a carbamyl group, i.e., carbamyl, ethyl carbamyl, diethyl carbamyl, or a sulfamyl gro up, i.e., .sulfamyl,
  • dimethyl sulfamyl or such groups in which the nitrogen atom of the sulfamyl group is part of a saturated 5 or 6 membered heterocyclic ring system of thefollowing general structure:
  • SO5N Z tem such as pyrrolidine, piperidine, morpholine, .hy q i o a d the e and A i a some the following general; structure:
  • D stands for CO-, COQH or 1 *C CH 1 l i and K is selected from the class consisting of hydrogen, ammonium and the alkali metals.
  • pyrazolone couplers are the 21501- lowing:
  • 'rnary amino groups acylated with a slight excess of an a-sjulfoalkyl carboxylic acid of from 10 to 20 carbon atoms in'the presence of a basic solvent such as pyridine while using phosphorous trichloride as a catalyst.
  • the substituted hydrozines used in the synthesis of dhe pyrazolone intermediates i.e., the 3-amino-1-aryl-5- pyrazolones, were prepared by reduction of the corre- :SpOnding diazonium salts. Two general methods of reiduction were employed, depending on the type of reduciing agent. The sodium sulfite procedure is given in Organic Synthesis (Collective Vol. I, page 432) while the stannous chloride procedure is described in CA.
  • aromatic primary amino color developing agents may be mentioned 4-amin0aniline, 4-ethylaminoaniline, 2-diethylaminoaniline, 4dialkylaminoaniline, e.g., 4-dimethylaminoaniline, 4-diethylarninoaniline, 4- [N-(fi-hydroxyethyl)-N-ethyl]-aminoaniline,' 4-amino-N- ethyl-N-(fl-methanesulfonamidoethyl) 2 methylaniline sulfate and the like.
  • the above developing agents are preferably used in the form of their salts, such as the hydrochloride or hydrosulfate, as they are more soluble and stable than the free bases.
  • the oxidation products of these aromatic primary amino developing agents then couple with the pyrazolone color former to form a dye image of the azomethine type in the emulsion. After removal of the silver image by bleaching and fixing in a manner well known to the art, the color image remains in the emulsion.
  • a suitable developing solution can be prepared as follows:
  • the exposed silver halide emulsions containing the described pyrazolone color formers are developed in the above solution in the usual manner. If a reversal type image is desired, a black and white first developer and second exposure are then required.
  • p-Hydrazinobenzenesulfonamide 86.0 grams (0.50 mole) of sulfanilamide were dissolved in 131 mls. of concentrated hydrochloric acid (sp. gr. 1.138) and then cooled to 9 C. To this mixture were added gms. of cracked ice after which a cold solution (0 C.) of 36 gms. (9.50 mole) of sodium nitrite dissolved in 75 mls. of water was allowed to run in slowly from a separatory funnel while maintainmg good stirring; the temperature was kept at C. The above diazonium salt solution was added rapidly with strong agitation to a solution of 310 gms.
  • the free base was obtained by treating an aqueous solution of the salt with sodium bicarbonate.
  • the yield of tan product was 41.3 gms. and the melting point was 155-156 C.
  • Example 11 IIIH-N H2 p-Hydra z ino-N,N-dimethylbenzenesulfonamide The same procedure was used as in Example I.
  • the same procedure was used as in Example I.
  • the powdered solid was suspended in 300 mls. of 70% aqueous ethanol, and the suspension was warmed to about 55 C. Then 35 mls. or 40% aqueous sodium hydroxide were added, causing immediate solution. The solution was poured into 50 mls. of glacial acetic acid. The light yellow solid was removed and was washed with ethanol and with ether. Thedried product weighed 15 gms. and melted at 260 C. with decomposi- B-p-nitrophenoxyacetamidoel-phenyl-dpyrazclone The same procedure was used as in the preparation of the product of Example V, excepting that nitro phenoxy acetic acid was used in lieu of the nitro benzoic acid.
  • the color former was dissolved in about 200 mls. of water by adding aqueous sodium hydroxide. About 15 mls. of pyridine were added and the solution was heated on a steam bath for 2 hours. the filtrate was cooled and was acidified with hydrochloric acid. The white precipitate was removed and washed thoroughly with water. The product was dissolved in hot acetic acid by adding potassium acetate. p-Toluenesulfonic acid was added to the hot solution and the product crystallized out. The suspension was cooled and the precipitate was removed and washed with acetic acid, with methanol (twice), with Water, and again with methanol. The dried product was a light tan in color and weighed 7.2 gms.
  • Example VIII l-PHENYL-S- (4'-a-SULFO STEARAMIDO) -BENZAMID 0-5- PYRAZOLONE 11.9. grams (0.0405 mole) of 3-(4'-am-inobenzamido)- 1 phenyl-5-pyrazolone and 17.2 gms. (0.0446 mole) of a-sulfostearic acid, monosodium salt were dissolved in a mixture of 100 mls. of dry pyridine and 150 mls. of dry benzene and the resulting mixture dried by azeotropic distillation, after which 170 mls. of solvent were distilled 0E.
  • a coating of the material showed the presence of a very slight amount of black and white fogging agent.
  • the color former was dissolved in 200 mls. of water by adding aqueous alkali. About mls. of pyridine were added and the mixture was heated on a steam bath for 2 hours. The solution was cooled and the product was precipitated with hydro- After filtration, v
  • Example IX (Alternate method) A 1-PHENYL-3- (4'-a- SULFO STEARAMIDO -BENZAMIDO-5- PYRAZOLONE 7.25 grams (0.0414 mole) of 3-amino-1-phenyl-5-pyrazolone and 20 gms. (0.0414 mole) of 4-(a-sulfosteramido) benzoic acid were dissolved in a mixture of mls. of dry pyridine and mls.
  • Example X 1-PHENYIr3- re-SULFOsTEARAMIDO)rmmrLAcn'r AMIDO-S-PYRAZOLONE
  • Ten gms. (0.0325 mole) of 3 (4 aminophenylacetamido)-1-phenyl-5-pyrazolone and 13.2 gms. (0.034 mole) of a-sulfostearic acid, monosodium salt were dissolved in a mixture of 100 mls. of dry pyridine and 160 mls. of dry benzene and the resulting mixture dried by azeotropic distillation, after which 170 mls. of solvent were distilled off. After cooling to room temperature, a solution of 2.48 gms.
  • R represents a member selected from the class consisting of alkyl groups of from 8 to 18 carbon atoms
  • B is selected from the class consisting of hydrogen, carbamyl groups and sulfamyl groups
  • A is wherein D is selected from the class consisting of --CO, --COCH and -COCH O-, and K is selected from the class consisting of hydrogen, ammonium and the alkali metals.
  • R represents a member selected from the class consisting of alkyl groups of from 8 to 18 carbon atoms
  • B is selected from the class consisting of hydrogen, carbamyl groups and sulfamyl groups
  • A is CwHaaCH-C ONH 6.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US617681A 1956-10-23 1956-10-23 Acylated 3-aminopyrazolone couplers Expired - Lifetime US2902366A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE561850D BE561850A (enrdf_load_stackoverflow) 1956-10-23
US617681A US2902366A (en) 1956-10-23 1956-10-23 Acylated 3-aminopyrazolone couplers
GB32627/57A GB833596A (en) 1956-10-23 1957-10-18 Photographic silver halide emulsion
DEG23193A DE1051638B (de) 1956-10-23 1957-10-23 Photographische Halogensilberemulsion mit einem Gehalt an Pyrazolonkupplern

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US617681A US2902366A (en) 1956-10-23 1956-10-23 Acylated 3-aminopyrazolone couplers

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US2902366A true US2902366A (en) 1959-09-01

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BE (1) BE561850A (enrdf_load_stackoverflow)
DE (1) DE1051638B (enrdf_load_stackoverflow)
GB (1) GB833596A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3080233A (en) * 1959-04-30 1963-03-05 Gen Aniline & Film Corp Method of incorporating metal salts of color couplers in photographic emulsions
US3110717A (en) * 1959-08-07 1963-11-12 Ilford Ltd Pyrazolone color couplers for color photography
US3112198A (en) * 1959-06-18 1963-11-26 Gen Aniline & Film Corp Non-diffusing color formers in which the long aliphatic chain thereon is provided with a terminal sulfo group
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
US3171740A (en) * 1960-02-11 1965-03-02 Agfa Ag Process for the production of colored photographic non-transparent or transparent images
US3199983A (en) * 1961-02-01 1965-08-10 Agfa Ag 3-indazolone color couplers
US3476560A (en) * 1964-07-28 1969-11-04 Fuji Photo Film Co Ltd Inhibiting fogging action during color development
CN107573266A (zh) * 2017-09-19 2018-01-12 黑龙江鑫创生物科技开发有限公司 一种对肼基苯磺酰胺盐酸盐的合成方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1155979B (de) * 1961-10-24 1963-10-17 Eastman Kodak Co Farbentwicklungsverfahren mit 5-Pyrazolonderivatfarbkupplern und hierfuer verwendete photographische Emulsionen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2186849A (en) * 1935-08-07 1940-01-09 Agfa Ansco Corp Manufacture of photographic silver halide emulsions
CH232384A (de) * 1938-02-05 1944-05-31 Ig Farbenindustrie Ag Verfahren zur Herstellung von farbigen photographischen Bildern.
US2829975A (en) * 1956-04-26 1958-04-08 Gen Aniline & Film Corp 3-alpha-sulfo acylamino pyrazolone color formers in which the acyl group contains a long aliphatic chain

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE726611C (de) * 1936-02-21 1942-10-16 Ig Farbenindustrie Ag Verfahren zur Herstellung von Halogensilberemulsionsschichten mit Farbstoffbildnern fuer Farbenphotographie
DE736867C (de) * 1940-08-08 1943-06-30 Ig Farbenindustrie Ag Verfahren zum Herstellen photographischer Farbenbilder durch Farbentwicklung von Halogensilberemulsionsschichten, die als Farbstoffbildner 1-Phenyl-5-pyrazolone enthalten
DE759642C (de) * 1941-07-01 1952-10-27 Ig Farbenindustrie Ag Verfahren zur Herstellung von photographischen Farbenbildern
US2369489A (en) * 1941-09-25 1945-02-13 Eastman Kodak Co Acylated amino pyrazolone couplers
US2511231A (en) * 1949-03-26 1950-06-13 Eastman Kodak Co 1-cyanophenyl-3-acylamino-5-pyrazolone couplers for color photography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2186849A (en) * 1935-08-07 1940-01-09 Agfa Ansco Corp Manufacture of photographic silver halide emulsions
CH232384A (de) * 1938-02-05 1944-05-31 Ig Farbenindustrie Ag Verfahren zur Herstellung von farbigen photographischen Bildern.
US2829975A (en) * 1956-04-26 1958-04-08 Gen Aniline & Film Corp 3-alpha-sulfo acylamino pyrazolone color formers in which the acyl group contains a long aliphatic chain

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3080233A (en) * 1959-04-30 1963-03-05 Gen Aniline & Film Corp Method of incorporating metal salts of color couplers in photographic emulsions
US3112198A (en) * 1959-06-18 1963-11-26 Gen Aniline & Film Corp Non-diffusing color formers in which the long aliphatic chain thereon is provided with a terminal sulfo group
US3110717A (en) * 1959-08-07 1963-11-12 Ilford Ltd Pyrazolone color couplers for color photography
US3171740A (en) * 1960-02-11 1965-03-02 Agfa Ag Process for the production of colored photographic non-transparent or transparent images
US3199983A (en) * 1961-02-01 1965-08-10 Agfa Ag 3-indazolone color couplers
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
US3476560A (en) * 1964-07-28 1969-11-04 Fuji Photo Film Co Ltd Inhibiting fogging action during color development
CN107573266A (zh) * 2017-09-19 2018-01-12 黑龙江鑫创生物科技开发有限公司 一种对肼基苯磺酰胺盐酸盐的合成方法

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DE1051638B (de) 1959-02-26
BE561850A (enrdf_load_stackoverflow)
GB833596A (en) 1960-04-27

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