US2865748A - 3-acylamido-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography - Google Patents

3-acylamido-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography Download PDF

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US2865748A
US2865748A US619151A US61915156A US2865748A US 2865748 A US2865748 A US 2865748A US 619151 A US619151 A US 619151A US 61915156 A US61915156 A US 61915156A US 2865748 A US2865748 A US 2865748A
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pyrazolone
couplers
coupler
acylamido
hydroxyethyl
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US619151A
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Feniak George
Warren A Reckhow
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to GB32419/57A priority patent/GB865721A/en
Priority to FR1196010D priority patent/FR1196010A/fr
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    • 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

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  • This invention relates to 3-acylamiclo-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography and more particularly to those pyrazolones and pyrazoles having hydroxyalkyl and acyloxyalkyl groups in the l-poSitiOn.
  • 3-acylamido-5.-pyrazolone couplers for color photography have previously been described and more particularly certain 1 alkyl 3 acylamido pyrazolone couplers.
  • certain S-acyloxy pyrazole couplers have previously been described.
  • the couplers of the present invention are distinct in having the l-hydroxyalkyl or l-acyloxyalkyl substituents which confer special properties upon the dyes obtained therefrom in,
  • R represents a member of the class consisting of; a hydrogen atom and a carboxylic acid acyl group such as a phenoxyacetyl', heptoyl, benzoyl'groupgetc Ry and R each represent a carboxylic acid acyl group such as a phenoxyacetyl, lauroyl, tetracosyl, benzoyl, palmitoyl, heptoyl group, etc., and R represents a hydrogen atom, and alkyl group preferably containing from 1 to 4 carbon atoms e. g. methyl, ethyl, n-propyl'and n-butyl, or a monocyclic aryl group of the benzene series such as phenyl. and nuclear-substituted phenyl.
  • Couplers having these structures are as follows:
  • R represents an alkyl group of from about. 110.- 20 carbon atoms and one of the groups X. and: Y rep resents a hydrogen atom and the other represents; an. organic acid acylamido group.
  • t 1 1 A particular group of these benzoylacet-o-alko)kyanilide couplers elficacious for use with the above couplers of the lnvention have the above general formula wherein R represents an alkyl group of from'about 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents the group.
  • R p g -NHC o (1114)- can CrHn I wherein R alkyl group of from about 1 to 4 carbon atoms.
  • benzoyl ⁇ -2-methoxyacetanilide represents either a hydrogen atom or an couplers ⁇
  • the reason why the couplers of the invention are particularly useful with the benzoylacet-o-alkoxyanilide couplers above will be apparent from consideration of thespectral absorption curves shown in the drawing.
  • Curve 2 illustrates the region of absorption of a similar methoxy (2',4' di -tertdye made by coupling the same color developing agent i with a typical l-alkyl 3 acylamido-S-pyrazolone coupler 1-methyl-3- [4-(2,4-di-tert.-amylphenoxyacetamido phenoxybutyramido) -5-pyrazolone
  • Curve 3 illustrates the region of absorption of a similar dye made from the same color developing agent and one of the couplers of the invention (Coupler No. NII).
  • Curve 4 illustrates the region of absorption of a dye made from typical known magenta coupler 1-(2,4,6-trichlorophenyl) -3-[ 3 (2,4-di-tert-amylphenoxyacetamido) benzamidol] 5 -pyrazolone (U. S. 2,600,788) using the same developing.
  • the couplers of the invention may be prepared in the following manner:
  • l-(fi-hydroxyethyl) 3 (p-nitrophenoxyacetamido)- S-pyrazolone was prepared in the same manner as was 1 (B-phenyl-p-hydroxyethyl) 3 (p-nitrophenoxyacetamido)-5-pyrazolone.IX except that l-(B-hy'droxyethyD- 3-amino-5-pyrazolone was used in place of l-(fl-phenylp-hydroxyethyl) 3 amino-S-pyrazolone. This material was reducedin glacial acetic acid, over 10%. palladium on charcoal at ca. C. with hydrogen at a pressure of ca. 30 lbs. per sq. in..
  • This material was acylated with two equivalents ot octanoyl chloride, in the presence of 2 equivalents of N,N-dimethylaniline in dry acetonitrile.
  • the product after recrystallization from methanol, melted at -2" C.
  • COUPLER IV 1 (B-phenylacetoxyethyl)-3-(2,4-di-n-amylphenoxy-acetamido) -5- (phenylacetoxy pyrazole
  • This compound was prepared in the same manner as was Coupler III except that phenylacetyl chloride was used in place of octanoyl chloride. It melts at 72-3".
  • COUPLER X I-(B-hyaroxypropyl) 3 (p-nitrophenoxyacetamido)-5- pyrazolone 1-(18-hydroxypropyl) 3 amino-S-pyrazolone was prepared by the method used in the preparation of l-(B- hydroxyethyl) 3 amino-S-pyrazolone except that p-hydroxypropylhydrazine (I. Am. Chem. Soc. 76, 1283, (1954), was used in place of B-hydroxyethylhydrazine.
  • the product was acylated with p-nitrophenoxyacetyl chloride by the method used in the acylation of l-(B-hydroxy-B-phenylethyl)-3-amino-5-pyrazolone.
  • the prod uct was recrystallized from butanol (M. P. 255-6).
  • the oil layer was then taken up in 500 ml. of 3A alcohol containing 16.8 g. of potassium hydroxide and allowed to stand two hours at room temperature.
  • the mixture was acidified by the addition of 20 ml. of acetic acid contained in ml. of water, and the solid which precipitated was filtered, washed well with water, and air dried.
  • the product was crystallized from toluene twice, getting white needles melting between -106 C.
  • COUPLER XIV This compound is prepared from Coupler X by reduction of the nitro group and reaction with 2,4-di-tertamylphenoxyacetyl chloride.
  • COUPLER XV 1 (fl-h yd roxyeth yl -3-tetracosanamid0-5-pyraz0lone This compound was prepared by the same method used for .preparing l-(fl-hydroxyethyl)-3-[a-(2,4-di-tertamylphenoxy)acetamido]-5-pyrazolone XI. It too was s crystallized from toluene and had a melting point between 167-169" C.
  • Couplers Nos. IX, X, XIII, XVI, XVII, XVIII are most useful in color developing solutions for the development of multilayer color films in which some or all of the emulsion layers are devoid of coupler compounds.
  • a typical color developing solution in which such couplers can be incorporated is as follows:
  • the couplers can be incorporated into the developer compositions by first dissolving them in a solvent such as isopropyl alcohol and adding this solution to an alkaline developer composition. About 3 grams of the couplers of the invention are suitable for use in developer compositions such as the above.
  • Color developing solutions thus containing the couplers of the invention are used in well known subtractive color processes.
  • a color film containing at least one emulsion layer and preferably two or three emulsion layers sensitized to different regions of the spectrum is exposed to a subject, developed in a black-and-white developer followed by selective reversal exposure and the exposed emulsion layer color developed with the above developing solution containing one of the coupler compounds appropriate for the particular emulsion layer which has been reversal exposed.
  • Couplers Nos. I-VIII and XI-XV can be dispersed in an emulsion layer such as a gelatino silver halide emulsion layer by means of coupler solvents including cellulose esters, natural and synthetic resins and organic crystalloidal materials having a boiling point above about 170 C., as described in the Marines etal. U. S.
  • the couplers of the invention can be employed in a multilayer color film in conjunction with the benzoylaceto-alkoxyanilide couplers for the purposes mentioned as follows:
  • a multilayer film was prepared using emulsion melts made in a manner similar to that described in the single layer example above: (1) a gelatin dispersion of a cyan coupler, l-hydroxy-Z-[6(2,4-di-tert.amylphenoxy)- n-butyll -naphthamide dissolved in tricresylphosphate was added to a red-sensitive gelatin silver-halide emulsion and coated as the bottom layer, (2) a gelatin dispersion of a magenta coupler, I-Efl-(ZA-di-n-amylphenoxyacetoxy) ethyl] 3 (2,4 di n amylphenoxyacetamido) 5 (2,4 di namylphenoxyacetoxy) parazole (Coupler II),
  • a gelatin dispersion of a yellow coupler t" ⁇ 3-[DC-(2,4-di-tCI'L-3IHYL phenoxy) acetamidolbenzoyl ⁇ 2 methoxyacetanilide dissolved in di-n-butylphthalate, was added to an unsensitized gelatin silver-halide emulsion and coated as the top sensitive layer over a Carey Lea silver yellow filter interlayer. The film was exposed and processed as in the same manner as the single layer material above.
  • FIG. 2 A multilayer color film prepared as just described is illustrated in Fig. 2 in the drawings wherein layer 20 represents a support such as a cellulose ester film base, layer 21 represents a red-sensitive silver halide emulsion layer containing a cyan coupler, layer 22 represents a green-sensitive silver halide emulsion layer containing the coupler compound of the invention, layer 23 represents a yellow filter layer such as a Carey-Lea silver filter layer and layer 24 represents a blue-sensitive silver halide emulsion layer containing the mentioned benzoylacet-o-alkoxyanilide coupler.
  • a film can be developed directly to a color negative or indirectly to a color positive by well known reversal methods.
  • the 3-acylamido-S-acyloxypyrazole couplers of the invention can be used in emulsion or color developing solutions in substantially the same manner as described for the S-pyrazolone couplers of the invention above.
  • These pyrazole couplers are particularly useful in that they have lower melting points and higher solubility in coupler solvents than the corresponding -pyraz'olones,
  • the color developing agents used for development of emulsion layers in the presence of the novel coupler compounds include the well known primary aromatic amino silver halide developing agents such as the phenylenediamines including the alkyl phenylenediamines and alkyl toluene diamines as well as the p-aminophenols in which the amino group is unsubstituted.
  • the N-alkyl sulfonamido alkyl-p-phenylenediamine developing agents of U. S. Patent 2,193,015 are particularly useful for the development of emulsion layers in the presence of the couplers of the invention.
  • the silver halide component of the emulsion layers is not especially critical and may be, for example, silver bromoiodide, silver bromide or silver chloride, etc., depending upon'the results desired.
  • the emulsions which are developed in the presence of the novel couplers may consist of single-layer o1 differentially sensitized multilayer films.
  • the hydrophilic colloid vehicle of the emulsions may be selected from known types including gelatin, hydrolyzed cellulose esters, polyvinyl alcohol and other natural and synthetic organic colloids.
  • a photographic silver halide emulsion containing a coupler compound of the class consisting of those having the general formulas I R3 C CH wherein R represents a carboxylic acid acyl group.
  • a multilayer color film comprising a support having thereon a silver halide emulsion designated in claim 1 sensitive to green light and a silver halide emulsion sensitive to blue light containing a coupler compound having the general formula wherein R represents an alkyl group of from 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents an organic acid acylamido group.
  • a multilayer color film comprising a support having thereon a silver halide emulsion designated in claim 1 sensitive to green light and a silver halide emulsion sensiphenoxy- 11 tive to blue light containing a coupler compound having the general formula wherein R represents an alkyl group of from 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents the group R! NHCO (in-0005B i CsHu wherein R represents a member of the class consisting of a hydrogen atom and an alkyl group of from 1 to 4 car bon atoms.
  • a multilayer color film comprising a support having thereon a silver halide emulsion designated in claim 1 and sensitive to green light, and a silver halide emulsion sensitive to blue light containing a coupler compound of the class consisting of a ⁇ 3 [1x (2,4 di n amylphenoxy)butyramido] benzoyl ⁇ -2-methoxyacetanilide 3 benzoylacetamino 4 methoxy (2',4' di tertamylphenoxy)-acetanilide a- ⁇ 3- oz- (2,4-di-tert-amylphenoxy) acetamido] -benzoy1 ⁇ -2- methoxyacelanilide a ⁇ 3 [a (2,4 di tamylphenoxy)butyramido] ben zoyl ⁇ -2-methoxyacetanilide a Benzoyl 5 [at (2,4 di tert.
  • a method of producing a colored photographic image in a developable silver halide emulsion layer which comprises developing said layer with a primary aromatic amino silver halide developer in the presence of a coupler compound of the class consisting of those havingthe wherein R represents a member of the class consisting of a hydrogen atom and a carboxylic acid acyl group, R and R each represent a carboxylic acid acyl group and R represents a member of the class consisting of a hydrogen atom, an alkyl group of from 1 to 4 carbon atoms and a monocyclic aryl group of the benzene series.

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  • General Physics & Mathematics (AREA)
  • Cosmetics (AREA)
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US619151A 1956-10-30 1956-10-30 3-acylamido-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography Expired - Lifetime US2865748A (en)

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BE561952D BE561952A (pt) 1956-10-30
US619151A US2865748A (en) 1956-10-30 1956-10-30 3-acylamido-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography
GB32419/57A GB865721A (en) 1956-10-30 1957-10-17 Improvements in and relating to photographic colour development and photographic emulsions containing colour couplers
FR1196010D FR1196010A (fr) 1956-10-30 1957-10-28 Procédé de photographie en couleurs et nouveaux produits pour sa mise en oeuvre

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998314A (en) * 1956-09-18 1961-08-29 Agfa Ag Color photography
US3498789A (en) * 1967-03-13 1970-03-03 Eastman Kodak Co Photographic element having a novel filter layer thereon
US3945829A (en) * 1973-07-19 1976-03-23 Agfa-Gevaert Aktiengesellschaft Color photographic multilayer material with improved color density
US4062683A (en) * 1975-05-30 1977-12-13 Agfa-Gevaert N.V. Photographic material containing 3-anilino-5-pyrazolylalkylcarbonate or arylcarbonate couplers
US4283472A (en) * 1980-02-26 1981-08-11 Eastman Kodak Company Silver halide elements containing blocked pyrazolone magenta dye-forming couplers
US4308343A (en) * 1979-09-05 1981-12-29 Fuji Photo Film Co., Ltd. Process and material for forming color photographic image
US4310618A (en) * 1980-05-30 1982-01-12 Eastman Kodak Company Silver halide photographic material and process utilizing blocked dye-forming couplers
WO1982002198A1 (en) * 1980-12-29 1982-07-08 Kodak Co Eastman A method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
US4374253A (en) * 1981-09-28 1983-02-15 Eastman Kodak Company Method for preparing 1-aryl-3-arylamino-2-pyrazolin-5-ones from N-aryl-3-arylamino-3-oximinopropionamides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721798A (en) * 1953-09-02 1955-10-25 Eastman Kodak Co Compounds containing an isophthalate group useful in photography
US2772161A (en) * 1954-10-14 1956-11-27 Eastman Kodak Co Photographic emulsions and new coupling compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721798A (en) * 1953-09-02 1955-10-25 Eastman Kodak Co Compounds containing an isophthalate group useful in photography
US2772161A (en) * 1954-10-14 1956-11-27 Eastman Kodak Co Photographic emulsions and new coupling compounds

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998314A (en) * 1956-09-18 1961-08-29 Agfa Ag Color photography
US3498789A (en) * 1967-03-13 1970-03-03 Eastman Kodak Co Photographic element having a novel filter layer thereon
US3945829A (en) * 1973-07-19 1976-03-23 Agfa-Gevaert Aktiengesellschaft Color photographic multilayer material with improved color density
US4062683A (en) * 1975-05-30 1977-12-13 Agfa-Gevaert N.V. Photographic material containing 3-anilino-5-pyrazolylalkylcarbonate or arylcarbonate couplers
US4308343A (en) * 1979-09-05 1981-12-29 Fuji Photo Film Co., Ltd. Process and material for forming color photographic image
US4283472A (en) * 1980-02-26 1981-08-11 Eastman Kodak Company Silver halide elements containing blocked pyrazolone magenta dye-forming couplers
US4310618A (en) * 1980-05-30 1982-01-12 Eastman Kodak Company Silver halide photographic material and process utilizing blocked dye-forming couplers
WO1982002198A1 (en) * 1980-12-29 1982-07-08 Kodak Co Eastman A method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
US4345085A (en) * 1980-12-29 1982-08-17 Eastman Kodak Company Method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
US4374253A (en) * 1981-09-28 1983-02-15 Eastman Kodak Company Method for preparing 1-aryl-3-arylamino-2-pyrazolin-5-ones from N-aryl-3-arylamino-3-oximinopropionamides

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GB865721A (en) 1961-04-19
FR1196010A (fr) 1959-11-20

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