US3062653A - Photographic emulsion containing pyrazolone magenta-forming couplers - Google Patents

Photographic emulsion containing pyrazolone magenta-forming couplers Download PDF

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US3062653A
US3062653A US9467A US946760A US3062653A US 3062653 A US3062653 A US 3062653A US 9467 A US9467 A US 9467A US 946760 A US946760 A US 946760A US 3062653 A US3062653 A US 3062653A
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coupler
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couplers
pyrazolone
emulsions
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US9467A
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Weissberger Arnold
Loria Anthony
Ilmari F Salminen
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • 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

  • CURVE c a E g 80 CURVE 2 3 PERCENT rRANsN/rmNOE 0F COUPLER NO 3 g /-(2,6-D/CHLOR0 4 ME THOXYPHEA/YL) -3L5 M-PE'NMDECYLPHE/VOXY) BUTYRAM/DQ7-5- PYRAZOLO/VE '5 cum E BEFORE EXPOSURE TO XENON ARC LIGHT CURVEZAFTER 30HOUR$ EXPOSURE TO XENON ARC LIGHT u l 0 WAVELENGTH /N MILL/MICRONS Fig. 3
  • This invention relates to color photography and-par"- Another i? to P d ma co p r which f ticularly to substituted l-phenyl:3amidO-S-pyrazolbhe only Teadlly lllcorpoiaied .. ⁇ P ⁇ 9 j i fi magenta-forming uplers and photographic silve h lid layers but are free from wandering from the layer in w 1c emulsions containing these couplers.”
  • y 'p f 1 Formation of i-color'edphot'o graphic im 'ages'by' coupling 15 pil l r ge p qiegt vp l P Q QgIQPiQ g!
  • the couplers :used to produce resldPal -P h f 1 these dyes generally contain color forming g 0uP -.,0.. the s l a gii cgggf W111 become 111131921?nt fIOm t e 0 henolic,'h drox l, razolone or benzo l acetanilide 0 g lasses.
  • Tli ese gong render h c p bl i
  • the above ob ects and other; coupling with the oxidati prgduct f h 'f ob ects can be accomphshed by using the new classes 0 aromatic amino developing agent for d during photomagenta-forming couplers of our invention.
  • Our cougraphic development. plers can advantageously be represented by the following The use of various pyrazolone derivatives for the proformula?
  • Couplers are not as stable to J 9 light and heat a's is'desired 'Ihe'couplers are undolored but upori'decomposition form products that have some p color.
  • couplers incorporated in emulsions do I .j' x not have good stability, decomposition will occur producing a veryundesirable yellowing: or st aining of the pictures.
  • An'othe'r' effect fg'ener'ailyknown as print out will also resultin pictures made with emulsions containing '3 5 y i, 7
  • Print-out is. produced by the decomposition of I residual coupler that, was unused in ther'image dye iormation, and results in stain :in' the. area's containingresidual coupler.
  • A-further disadvantage ofthe couplers.incurrent use I is that'they form dyeshaving an excess red absorption and: Y i an inadequate greenabsorption.
  • Y is an alky'l group hgving 5 1 use are not soluble enough in coupler solvents to make it to 18 (who; atoms Such as y e h l f butyl z i z i h inlrphotlographic emulsions pentyl or hexyl heptyl octyl nony l'decyl dodecyl tri a e esire on e 7., i plers in use are hot aliva y h f rgfi n i v s l ari r ir ig if h e gi gfifgj gifg g ifijf P a
  • alkscleno group e:g.',”methylseleno, ethylse'leno, propylseleno, hexylseleno; etc, all of which may have from 1 t0-'-1;8
  • alkyl group may be secondary orv tertiary as well as primary, an aryl group e.g., phenyl, toly-l, etc, aryloxy group e.'g".,-' pheno"xy, etc, an arylthio group e.g'.;' phenylthio or an arylseleno group, 'e.g., phenylseleno, etc.;
  • Z, Z and Z each represents a hydrogen atom, a halogen atom or a Y group
  • I is an aromatic acyl amino group such as those of thel-Porter and Weissberger -Patent 2,369,- 489 includingfo'r'example'such groups as 35 werein;represents either 1 i
  • Another object of our invention provide i'a new class of magenta'-fornr1ing couplersflwhich are readily in corporated in photographic silver halide'emulsion layers with standard coupler solvents overga broad span Jot coupler .to coupler solvent ratios, and which reactduringj development withithef oxidized developing agent to pro ⁇ prise a magenta dye havingi'imp'rove'd lightabsorption characteristics? 1' ".1 I I a i 1 ..Another object is to provide'couplers which upon'deogfa velopment with oxidized developing agents produce-dyes 1 whose light absorption curves arezshifted toward the L shorter wavelengths in.
  • the preferred couplers have a ballasting group 2 h l r l y y as defined 'by I, our couplers can have any of the ballasting phenox-y) Duty ramldflm'benzamldo ⁇ groups attached to the 3-position on the 5-pyrazolone C 7 ring that are used in prior art couplers.
  • Our couplers are distinguished from the prior art couplers by having the 0 3 I H substituents X and Y attached to the 2, 4 and 6-positions of the l-phenyl group.
  • genatiqn f th a o riately substituted aniline hyd C I chloride conversion of this compound to the correspond- OHP ingp'henylhydrazine, then reacting the phenylhydrazine C1 0 0:93; with ethyl-fl-ethoxy-fi-iminopropionate to form the substitute' d l phenyl-3-amino-5-pyrazolone. followed by there- 01 30 action of this compound with the appropriate acylchloride.
  • the hot mixture was filtered through a sintered glass funnel and sulfur dioxide was slowly bubbled through the dark solution for 30 minutes.
  • Water (approximately 750 cc.) was added to the warm solution and the product allowed to crystallize slowly. After overnight standing the product was collected on a Biichner funnel, washed well with water and dried giving 381 g. of material with a melting point of l77-1 80 C.
  • the crude product was recrystallized from 1 liter of 95% ethyl alcohol, thus obtaining 172 g. of material as white flakes having a melting point of 1 85 -187 C.
  • the mixture was heated under reflux for 24 hours. "The alcohol was removed by distillation and the semi-solid residue stirred and cooled while being-neutralized with 28% ammonium hydroxide, The mixture was ether extracted 3 times, the combined ether extracts dried over magnesium sulfate, filtered and thesolvent distilled. The residual oil was distilled under reduced pressure (boiling point 116-119 C. /1-5 mm. Hg) giving 223 g. of white crystalline material having a melt? ing point of 40.5 to 42 C.
  • This pyrazolone was prepared by the method described for the'prep'aration of 1-(4,6-dichloro-Z-methoxyphenyl)- 3-amino5-pyrazolone, using an equivalent amount of 6-chl0ro-2,4-dimethylphenylhydrazine instead of 4,6-dichloro-2-methoxyphenylhydrazine.
  • the crude product was crystallized from 95% ethyl alcohol, and had a melting point of 158-160" C,
  • Coupler 6 STEP 1 -1(6-CHLORO-2,4-DIMETHYLPHENYL)-3- (3'NITROBENZAMIDO --PYRAZOLONE
  • the couplers of our invention are particularly adapted for incorporation in light, sensitive emulsion layers for color photography. These emulsions are of the developing-out type.
  • the emulsions 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. Patent 1,574,944, issued-March 2, 1926, Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard et a1- U.S. Patent 2,410,689, issued November 5, 1946.
  • the emulsions can also betreated with salts of the noble metals suchfas ruthenium, rhodium, palladium, iridium, and platinum.
  • Representative compounds are ammonium ,chloropalladate,,, potassium chloroplatinatc, and sodium clilor'opalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued August31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August 28, 1951.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller et a1.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaura'te, auric trichloride and 2-aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S.
  • the emulsions can alsobe optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White U.S. Patent 1,990,507, issued February 12, 1935; Brooker and White U.S. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued January 10, 1950 and 2,739,964, issued March 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950; Sprague U.S.
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955 Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955 the triazoles of Heimbach and Kelley US; Patent 2,444,608, issued July 6, 1948; the azaindenes of- Heimbach' and Kelley U.S. Patents 2,444,605 and 2,444,606, issued July 6, 1948; Heimbach U.S. Patents 2,444,607, issued July -6, 1948 and 2,450,397, issued September 28, I948; Heimbach and Clark U.S.
  • Patent 2,444,609 issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955, and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27,1956, and those disclosed by Birr in Z. wiss. Phot., vol.
  • the emulsions may also contain speed increasing compounds of the quaternary ammonium type of Carroll .5. Patent 2,271,623, issued February 3, 1942; Carroll and Allen US. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1959; and the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the thiopolymers of Graham and Sagal U.S. application SerialNo. 779,839, filed December 12, 1958, or Dann and Chechak U.S. application Serial No. 779,874, filed December 12, 1958.
  • the emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murray U.S. application Serial No. 588,951, filed June 4, 1956, now U.S. Patent 2,960,404, issued November 15, 1960; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate as described in Milton U.S. application Serial No. 662,564, filed May 31, 1957, now U.S. Patent 2,904,424, issued September 15, 1959; bis(ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No. 604,333, filed August 16, 1956, now
  • the emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene-2,3,5, 6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfouic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll U.S., Patents 2,725,294, and 2,725,295, both issued November 29, 1955; a cyclic 1,2-diketone such as cyclopentane-1,2-dione as described in Allen and Byers U.S.v Patent 2,725,305, issued November 29, 1955; a bis
  • the emulsions may contain a coating aid such as saponin; a lauryl or oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, ,1958; .a salt of a sulfated and alkylated polyethylene glycolether as described in Knox and Davis U.S. Patent 2,719,087, issuedSeptember 27, 1955;;an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl taurine as describedmin Knox, Twardokus and Davis U.S.
  • a coating aid such as saponin
  • a lauryl or oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, ,1958
  • .a salt of a sulfated and alkylated polyethylene glycolether as described in Knox and Davis U.S. Patent 2,719,087, issuedSeptember 27, 1955
  • Patent 2,739,891 issued March '27, 1956; the reaction product of a dianhyclride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a Water-soluble maleopimarate and .a substituted glutamate salt as described in Knox and Fowler U.S.
  • Patent 2,823,123 issued February 11, 1958;,an alkali metal salt of a substituted amino acid such as disodium N-(carbo-ptert. octylphenoxypentaethoxy)-glutamate as described in Knox and Wilson U.S. Patent application Serial No. 600,679, filed July 30, 1956; or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate asdescribed in Knox and Stenberg U.S. Patent application Serial No. 691,125, filed October 21, 1957, now U.S. Patent 2,992,108, issued July 11, 1961,
  • the couplers which we have described may be used in various kinds of photographic emulsions. They may be added to the emulsions before or after any sensitizing dyes which are used.
  • Various silver salts may be used asthe sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the agents may be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other .13 color-generating material emulsions of the r nixed-packet type, such as described in Godowsky US.
  • Patent 2,698,794 issued January 4, 1955; oriemuls'ions of the mixed-grain type, such as described in Carroll and Hanson US. Patent 2,592,243, issued April 8, 1952. These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form inside the silver halide crystal, such as those described in Davey and Knott US. Patent 2,592,250, issued April 8, 1952.
  • gelatin in the preparation ployed for preparing silver halide emulsions, there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, -a polyvinyl compound.
  • colloidal albumin a cellulose derivative
  • synthetic resin for instance, -a polyvinyl compound.
  • colloids which may be usedare polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Patent 2,286,215, sued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in US.
  • Patent 2,768,154 issued Octoberv 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest US. Patent 2,808,331, issued October 1,1957; or a polymeric material which results from polymerizing a protein or a saturatedacy lated protein with a monomer having .a vinyl group as described in US. Patent 2,852,382 of lllingsworth Dann and Gates-issued September 16, 1958.
  • compatible mixturesjof two or more of these colloids may be employed for dispersing the silver halide in its preparation.
  • Couplers are readily soluble in conventional types of coupler solvents such as those described in Jelley Tand Vitturn US. Patent 2,322,027, and can be used over a rangejofc'oupler to coupler ⁇ solvent ratios of from 1:0 to 1:2, ;Our couplers do not crystallize when used in dispersions of high coupler to coupler solvent ratios.
  • the preferred ratio is 111 /2. t t
  • the preferred couplers of our invention are free from wandering from the layer in which they are incorporated. However, if it is "desirable to make these couplers diffusible this can be readily done by changing the ballasting group substituted on the 3-position of the pyrazolone ring.
  • Photographic emulsions containing our couplers can be developed by any ofthe conventional primary amino developing compositions.
  • the'preferred developing agents are developers suchas 2-amino-5-diethylaminotoluene hydrochloride; and N-ethyl-fi-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate.
  • Typical delatent images. predominantly of the silver halide dispersions em- -14" velopers containing these developing agents are follows:
  • EXAMPLE VIII f A gelatin dispersion containing 0.50 g. of coupler No. 1 in tri-o-cresyl phosphate was added to 5 ml. of a greensensitized medium-speed silver bromoiodide emulsion, the mixture was coated on a suitably subbed cellulose acetate support and dried. The coating was exposed in a spec,- trograph to tungsten illumination and developed In Developer No; 1 to form'a negative silver Image and a magenta dye image. The silver image andthe res dual silver halide were then removedtwith ferricyanide bleach and a hypo-fixer leaving a magenta dye image hay nga maximum absorption at 538 mu. f
  • a photographic emulsion was made as in Example VIII, but Coupler No. 3 was used instead of coupler No. 1.. Two samples of this emulsion were exposed, one'of them was developed in Developer No. 1 and the second in Developer No. 2. After bleaching and fixing, both samples "had good magenta dye images having a maximum absorption ata wavelength of 543' mu.
  • EXAMPLE XII Similarly, photographic emulsions containing Coupler No. 5 were prepared, exposed,'developed, bleached and -fixed to produce good magneta dye images. Developer N0 1 and Developer N0. 2 produced magneta dye images havl'ng'rnaximurn light absorption at wavelengths of 538 mu and 539 mu, respectively.
  • Coupler "No. 7 was incorporated in a photographic emulsion in place of Coupler No. 1- of Example VIII good magenta dye images were produced after exposure, development, bleaching and fixing, the dye images formed by Developer No. 1 and by Developer No. 2 had maximum light absorption at wavelengths of 544 mu and 542 mu, respectively.
  • FIGURE 1 shows the spectrophotometric curves for the dye images produced upon the development of our emulsion containing Coupler No. 2 in Example IX and for the dye image produced with an emulsion made, exposed and processed in the same way but containing the prior art coupler l-(2,4,6-trichlorophenyl)-3-[3-(2,4-diamylphen'oxyacetamido)LS-pyrazolone in place of our Coupler No. 2. From these curves it is apparent that thedye from our coupler has less absorption in the red gron of the spectrum and considerably more absorption in the green region of the spectrum. The maximum absorption of our dye occurs at a wavelength of 533 as compared to 550 for the prior art dye.
  • FIGURES 2 and 3 are percent transmittance curves showing the effect produced upon the transmission characteristic of our Coupler No. 3, 1-(2,6-dichlor o-4-methoxyphenyl) 3 [a-(meta-pentadecylphenoxy)-butyramido]-5Py razolone, and of the coupler 1-( .2,5 -dichloro-4-- methoxyphenyl 3 [a-(meta-pentadecylphenoxy)-butyramidol-5-pyrazolone, respectively by hoursof exposure to a xenon are light.
  • FIGURES 2 and 3 illustrate the criticalness of the substituents in the 2,4,6- posi'tion's' over those in the 2,4,5-positions on the l-phenyl group of the pyrazolone coupler.
  • Couplers are not only valuable in their own right, but also as parent couplers for making valuable colored couplers and other types of couplers which are used in color photography.
  • Colored couplers for example may be readily made by replacing one of the hydrogens on the 4-carbon of the S-pyrazolone ring with a phenylazo group or any of the other splittable groups which are used in colored couplers.
  • novel 2,4-6-substituted l-phenyl pyrazolone couplers of our invention are valuable for use in color photography. They are distinguished from other couplers which have substituents in the 2,4,5-positions on the l-phenyl ring by having unexpectedly greater stability to light and heat and thus have greatly improved print-out characteristics when used in'photographic emulsions.
  • a photographic emulsion containing our Coupler No. 3 loses only 8.5% in its light transmission after being subject to 30 hours exposure to xenon light as compared to a 15% loss in transmission
  • a photographic emulsion containing the 2,4,5-substituted l-phenyl analogue of our coupler when subjected to the same treatment.
  • Our couplers produce dyes having improved light absorption characteristics which avoid the excessive red absorption and the inadequate green absorption of the dyes in current use. These dyes have satisfactory light and heat stability and are well adapted for use in color photography.
  • couplers are readily soluble in standard coupler solvents over a broad range of coupler to coupler solvent ratios and give dispersions which are free from crystallization at high coupler to coupler solvent ratios. Furthermore, our couplers are free from wandering from the emulsion layer they are incorporated in. Not only are our couplers valuable per se but also for use as parent couplers in making colored couplers which are also characterized by having all of the desirable properties of the parent coupler.
  • N C--J wherein W represents a member selected from the class consisting of groups having the formulas:
  • Q is a member selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; n is from 0 to 2; m is from 0 to l; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
  • Y is a member selected
  • Q is a member selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; 11 is from 0 to 2; m is from O to 1; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
  • X is a halogen atom
  • R is selected from the class consisting of alkyl groups having from 1 to 6 carbon atoms; where said X and said R groups are substituted on the carbon atoms in the 2, 4 and 6-positions of the l-phenyl group
  • J is a member selected from t class having the formulas:
  • Q is a member selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; n is from 0 to 2; m is from O to 1; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
  • N C-I R2 ll 0 wherein X is a halogen atom; R is an alkoxy group having from 1 to 6 carbon atoms, where said X group and said R group are substituted on the carbon atoms in the 2, 4 and 6-positions of the l-phenyl group; J is a member selected from the class having the formulas:
  • a hydrogen atom selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; 11 is from 0 to 2; m is from O to 1; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.

Description

Nov. 6, 1962 Filed Feb. 1 1960 OPT/CAL DENSITY A. WElSSBERGER ETAL PHOTOGRAPHIC EMULSION CONTAINING PYRAZOLONE MAGENTA-FORMING COUPLERS 2 Sheets-Sheet 1 Fig.
CURVE MAGENTA DYE FROM THE -/4,6 -D/CHLOR-2- ME 7' HOX YPHE/VYL} 5 -PYRAZOL0/VE COUPLER x cuRvEz MAGENTZI DYE mom THE (2,4,6-TR/CHL0R0P/1'E/VYL) 5-Pm4z0L0/vE COUPLER (PRIOR ART) l l 60 0'0 500 6'0 0'0 6'00 20 4'0 00750 WAVELENGTH 11v mum/moms ANTHONY LOR/A ILMAR/ E SALMINE/V ATTORNEYS Nov. 6, 1962 A. WEISSBERGER ETAL 3,062,653
PHOTOGRAPHIC EMULSION CONTAINING PYRAZOLONE MAGENTA-FORMING COUPLERS Filed Feb. 18. 1960 2 Sheets-Sheet 2 Fig. 2
CURVE c: a E g 80 CURVE 2 3 PERCENT rRANsN/rmNOE 0F COUPLER NO 3 g /-(2,6-D/CHLOR0 4 ME THOXYPHEA/YL) -3L5 M-PE'NMDECYLPHE/VOXY) BUTYRAM/DQ7-5- PYRAZOLO/VE '5 cum E BEFORE EXPOSURE TO XENON ARC LIGHT CURVEZAFTER 30HOUR$ EXPOSURE TO XENON ARC LIGHT u l 0 WAVELENGTH /N MILL/MICRONS Fig. 3
CURVE m E 500 E I g PERCENT TRANSMITTANCE 0F COUPLER /-(2,O-OIONLORO-4-NErN0xYP//ENrL)-3L7 -/m-PENTAOE0YLPHEN0XY/ BUTYRAM/DQ7-5-PYRAZOLO/VE g CURVE BEFORE EXPOSURE TO XENON ARC LIGHT E CURVEZ AFTER /400175 EXPOSURE TO XENON ARC LIGHT I l 1 1 1 1 l l l l l A WAVELENGTH //V MILL/MICRO/VS ANTHONY LOR/A ILMAR/ E SALM/NEN ARNOLD WEISSBERGER INVENTORS A T TOR/VE Y 5 6 pr 3,062,653 United States Patent 1C6 Famed No 1962 i avoid excessr'ed absorption and inadequate green absorp- 3,062,653 tion of the dyes in current use, PHOTOGRAPHIC EMULSION CONTAINING PY- Another object is toprovide a new class of magenta RAZOLONE MAGENTA-FURMING COUPLERS forfnin'g' coupler's'which are not only readily soluble .111
W $b r 9 r m 0 9. 1 a v 3 1 5 couplr'solvents but give dispersions which arevfre'e from; Rochester; ass-ignors tdlEasa-tman'kodak coupler ciystalliz'ation at high coupler to coupler solvent gompany, Rochester,s N.Y .,'"a" corporation of New v5 ratios g r I v I V ersey I i i I A further object is to provide a new class 'of'mag'en'tafggg i fgifij forming couplers which give dyes of good light and heatstability. g This invention relates to color photography and-par"- Another i? to P d ma co p r which f ticularly to substituted l-phenyl:3amidO-S-pyrazolbhe only Teadlly lllcorpoiaied ..\P}9 j i fi magenta-forming uplers and photographic silve h lid layers but are free from wandering from the layer in w 1c emulsions containing these couplers." y 'p f 1 Formation of i-color'edphot'o graphic im 'ages'by' coupling 15 pil l r ge p qiegt vp l P Q QgIQPiQ g! the development productiof primary aromatic amino de- ISIOIIS 'avg m c rup r l n onlypro 1196 1 veloping agents with olor f i or coupling dyes having superior light absorptlon characteristics, dtylespounds is well known, In th processes h bt tfiy that have good stability to light and heat, and dyes t at process of color formation is ordinarily used and the are free from Wandefmg, but elm-11810115 Whlch h P image dyes are of the c m h m f primary colors, essed and stored have low print-out and yellowmg from y agenta and yellow. The couplers :used to produce resldPal -P h f 1 these dyes generally contain color forming g 0uP -.,0.. the s l a gii cgggf W111 become 111131921?nt fIOm t e 0 henolic,'h drox l, razolone or benzo l acetanilide 0 g lasses. Tli ese gong: render h c p bl i We have discovered that the above ob ects and other; coupling with the oxidati prgduct f h 'f ob ects can be accomphshed by using the new classes 0 aromatic amino developing agent for d during photomagenta-forming couplers of our invention. Our cougraphic development. plers can advantageously be represented by the following The use of various pyrazolone derivatives for the proformula? v duction of the magenta image in v thre e' c'olor photography Jjf' 4 N=' --l is well known, and the use of l-phenyl-B-acylamino-S- 1 pyrazolones for this purpose ,is described in Porter and I Weissberger U.S. Patent 2,369,489. -Q
Some of the prior art couplers are not as stable to J 9 light and heat a's is'desired 'Ihe'couplers are undolored but upori'decomposition form products that have some p color. Thus, if couplers incorporated in emulsions do I .j' x not have good stability, decomposition will occur producing a veryundesirable yellowing: or st aining of the pictures. An'othe'r' effect fg'ener'ailyknown as print out will also resultin pictures made with emulsions containing '3 5 y i, 7
couplers which are unstable upon exposure to heat and i .j light. "Print-out is. produced by the decomposition of I residual coupler that, was unused in ther'image dye iormation, and results in stain :in' the. area's containingresidual coupler.
A-further disadvantage ofthe couplers.incurrent use I is that'they form dyeshaving an excess red absorption and: Y i an inadequate greenabsorption. Some of the couplersin X halogen atom. Y is an alky'l group hgving 5 1 use are not soluble enough in coupler solvents to make it to 18 (who; atoms Such as y e h l f butyl z i z i h inlrphotlographic emulsions pentyl or hexyl heptyl octyl nony l'decyl dodecyl tri a e esire on e 7., i plers in use are hot aliva y h f rgfi n i v s l ari r ir ig if h e gi gfifgj gifg g ifijf P a hssm l a s laggh t gga g ggs apentoxy, hexoxy, he ptoxyy tride y, hexadecoxy, m, rated as lsdeslred' I 5 an alkthio group, e.g., methylthio, ethylthio, butylthio,
hexylthio, octylthio, decylthio, tridecylthio, *etc., an alkscleno group e:g.',"methylseleno, ethylse'leno, propylseleno, hexylseleno; etc, all of which may have from 1 t0-'-1;8
carbon *atoms in the alkyl part of these 'groups'and in which the alkyl group may be secondary orv tertiary as well as primary, an aryl group e.g., phenyl, toly-l, etc, aryloxy group e.'g".,-' pheno"xy, etc, an arylthio group e.g'.;' phenylthio or an arylseleno group, 'e.g., phenylseleno, etc.;
Z, Z and Z each represents a hydrogen atom, a halogen atom or a Y group; I is an aromatic acyl amino group such as those of thel-Porter and Weissberger -Patent 2,369,- 489 includingfo'r'example'such groups as 35 werein;represents either 1 i It is, therefore, an object of our invention to provide 5 a new class of magenta-forming couplers whichhave good stability to heat and light and which can be incorporated in photographic emulsions that will therefore not be subject to print-out or yellowing. 1"
Another object of our invention provide i'a new class of magenta'-fornr1ing couplersflwhich are readily in corporated in photographic silver halide'emulsion layers with standard coupler solvents overga broad span Jot coupler .to coupler solvent ratios, and which reactduringj development withithef oxidized developing agent to pro{ duce a magenta dye havingi'imp'rove'd lightabsorption characteristics? 1' ".1 I I a i 1 ..Another object is to provide'couplers which upon'deogfa velopment with oxidized developing agents produce-dyes 1 whose light absorption curves arezshifted toward the L shorter wavelengths in. such a wayasl-to enableone' to i -T A i v IRE 3 a 4 and the group Coupler 4 r (H) w (I) CI C2115 TNHC( JNH(OHi)q /N=o-NHiJ-d o R II C IJH i sHn(n) Qis a hydrogen atom or a lower alkyl group having in If fromlto6carbonatoms;nisfrom0to2;mis0or1; I II II I R is an alkyl group having from 1 to 20 carbon atoms; -(4 m-Z- y p 'e li-li-[ -p ti1 er and q is 1 Ito 3 phenoxy)butyr amido]--pyrazolone The preferred couplers of our invention can be repre- Collplel' 5 sented by the formula: I 01 M-I5 N= C'NH-GOl I-O =C-J I CH N. g N\ G1 I H 151-131(11) o om H Y n v I m 1-(6-chloro -2,4dlmethylphenyl)-3-[a.:(m-pentadecyl- 1n which X, Y and J are as defined above and where X and p y)bHtyri1mld0]-5-pyrazolone Y occupy the 2, 4 and 6-positions of the l-phenyl ring. Coupler 6 on O rho-mud CH: -N\ I 5]) CiHs o- H, NHo-dn-o 61 n Ciu M Although the preferred couplers have a ballasting group 2 h l r l y y as defined 'by I, our couplers can have any of the ballasting phenox-y) Duty ramldflm'benzamldo} groups attached to the 3-position on the 5-pyrazolone C 7 ring that are used in prior art couplers. Our couplers are distinguished from the prior art couplers by having the 0 3 I H substituents X and Y attached to the 2, 4 and 6-positions of the l-phenyl group. Our couplers are not only charor 'N acterized by this novel structural arrangement but are "H1169 charcterized far more significantly by the greatly improved 1 0 OH: I] print-out properties that result from this structural I I I I I 0 I r I djfig g gg, 1- 2methoy=5imttlathyl'3 4,fifrlcgioroghenyl 13% a- (in-pen ta The following representative couplers will illustrate our P enoxymce am 'pyrazo one invention. However, it is to be understood that our ino Coupler compounds are prepared by m h l ventlon is not limited to these specific couplers. genatiqn f th a o riately substituted aniline hyd C I chloride, conversion of this compound to the correspond- OHP ingp'henylhydrazine, then reacting the phenylhydrazine C1 0 0:93; with ethyl-fl-ethoxy-fi-iminopropionate to form the substitute' d l phenyl-3-amino-5-pyrazolone. followed by there- 01 30 action of this compound with the appropriate acylchloride. I CHHM) The following examples will illustrate specific synthesis OCH "3-OH= of representative couplers of our invention 0 1 -(4,MichloroZ-methoxyphenyl)-3-[a-(1n-pntadecy1- EXAMPLE I phenoxy)butyra1mdo]-5pyraz0lone I I Coupler I Coupler 2 seer- 1.-4,6-DliCfiLORO-2-METHOXYANILINE HYDRO- O CHLORIDE ll o In a 3-liter flask, fitted with a stirrer, a condenser, a g I T- 6O thermometer, and a dropping funnel was placed 160 g. 6 (n) (1.0 mole) of o-anisidine hydrochloride. The flask was cooled in an ice water bath and 500 cc. of sulfuryl chlo- OOH l I ride was added in one portion through the condenser with "t"'.Ati luen'o wa bt'ed 1-(4,G-dichloro-2-methoxypheny1)-3-[a-.(m-pentadecyl- 35: a g g e S 3 w s f phenoxy)acetamido1-5-pyrazolone a c ange u y mass 3 a 6 mmu es 0 st rring. After stirring from 15 to 20 minutes, a second Coupler 3 250 cc. portion of sulfuryl chloride was added and the O 5 H rniii'tu're was stirred an additional 15 minutes. Anhydrous O1 v H 5 ether was then added and the suspended material collected N:C 'NH C H on a Biichner funnel, washed well with dry ether, and CHBO N I I H dr ed giving 210 g. of a gray-White solld.
The crude product was dissolved in 1500 cc. of meth- 5 C911:
1 I! anol by warming, stlrred for 15 minutes with decolorizmg I carbon such as Nuchar, filtered and the clear filtrate confiigg5$2jgglgjgi ggg centrated to /2 its original volume. The solution was from 10 parts of methyl alcohol to'produce 84 g."
lone (171 g., 0.623 .mole') was' p laced flask equipped with.
dilutedwithe liters of cold water and the 4,6-dichlor o-2 methoxyaniline which separated as an oil was extracted with-ether. f I i 'The'ether'extract was then saturated with gaseous hydrogen chloride.
product'wereobtainedupon filtration and drying.
.STE .2..-+ s:DICHL RQ I X H Y HYDRAZINE "In a 12 liter flask fitted with a stirrer, and dropping funnel -were- -placed 500 g. of 4,6-dichloro-2-methoxyaniline hydrochloride,'.665 cc. of distilled water and 1330 cc. of concentrated hydrochloricacid. The mixture was vigorously stirred for 30 minutes at room temperature and then cooled to C. to 2 C. by'a Dry lce bath. A solution of 160 g. of sodium nitrite in 500 cc. of water wasintroduced through a tube below the surface of the cold stirred suspension. Excess nitrous acid was destroyed with sulfamic acid.- The diazonium solution was filtered and poured rapidly into a" stirred solution of 1830 g. of stannous chloride dissolved in 20 liters of distilled water and liters of'concentrated hydrochloric acid contained in a lg5-ga-llon crock. The reaction mixture was stirred for.- l'hour' and the supernatant-liquid was removed by filtration.rThe solid was triturated with ;-;gallons of distilled water'andthe'supernatant liquid was--again removed by filtration.v Thewet, solid'residuewas suspended in 15; liters of.-distilled:water,,stirred and made strongly basic with .4,0 'sodium'hydroxide.-- -;The mixture was extracted 4--.times with l-literflportions of ethyl ether and-the combined extnac'tswere driedover sodium sulfate. The dried ether solution was evaporated to dryness. The crude hydrazine, was recrystallized from hexane 1o produce 348 g. of light orange crystals having a melting point of 9'() 92-(:I
dried over magnesium sulfate and 160 g. of
i I sm le 3. r-. ae-nrcnLonoe-MwrHoxmPiiENYL-a V A anarNo-s-rYaazoLomn Ina 3'-liter, 3-n'eck flask were placed 139 g. (.67 mole) of ':4,6-dichloro-2 methoxyphenylhydrazine and '107' ,g. (.67 mole) of ethyl fi-ethoxy-fi iminopropionate.' Thetwo 's'olids' were' mixed by rotating thefiask manually .for 2-3 minutes and then '3 ml. of glacialacetic acidJWas added' andmanual rotation was eon 'nued untilthe material comple'telydissolved. After minutes to 1 hour, the mate'- rial solidified and the temperature of-the solution rose to 44?. The-.fiaskwasthen placed the temperaturecontrolled water bath at to 45 C, and evacuatedby r'rieans or an evaporator suchfasahinco evaporator for l ho'ur. The'flaslt'wasre'moved from, the evaporator and a freshly prepared solutionot l 5 g. of sodium in 750 ce. of ahs olute ethyl alcohol was added. The reaction mixt ur'e'f-vna's =boiled under reflux fortwo hours, the excess alcohol was removed in vacuo and'th'el remaining solid was dissolved in 1500 cc. of water.
extracted 3 timesf with ethyl ether and the aqueous phase was filtered through a" previously prepared cake of decolor-izir'ig' carbon such as Nuchar; The filtrate was cooled to 20 C; and','.with:stirring,"was acidified with glacial-acetic acid. The precipitate'was washed, filtered and dried; 'l'llere'was obtained 136' g. of dry product, with This was recrystallized of crystalline product having aimeltin'g point of.2l8220. C.
PENTADECYLPHENOXY)BUTYRAMIDO] P E l 4,6-dichloro 2-methoxy)phenyl-3-amino 5 pyrazo inaS-liter, 3-nec'lc a stirrer, a condenser, a thermometer, The flask was placed in a'95% :5 BYRAZO- and a dropping funnel.
ethyllalcoholbath, 2500 cc. of acetonitrile was added and Ithe temperature was raised to *C. to obtain a complete' solution,; 'deeylphenoxy)butyryl chloridew-as added in IO-rninutes.
and 260 g; (0.63 molel-of a-(meta-penta- The solution was I 6 When the addition was complete,
was stirred under reflux overnight. The 'reaotion-mhw ture was cooled externally with water to 25 C. Thesupernatant liquor was poured off, andthe crude product was heated in a waterbath at--50crunder-vaeuurm to removeas much of the acetonitrile as possible; residue was dissolved in a solution of'SOO ccuof absolutealcohol, .30 g.' of sodiurn'hydroxide pellets"; and"20"c'c; of distilled water and stirred for 2 hours. The solution was poured into a stirred solution of1100 cc. of concentrated hydrochloric acid and Slite'rs of ice water. Thefine, whit-e precipitate was suction-filtered,'washedslightly with water, and dissolved in 500 cc. of ethyl .ether.- The ethereal solution was dried for 2 hours over sodium sul; fate, filtered, and'coucentrated. The residue was dissolved 3 liters of acetonitrile, the solution filtered through a filter cake composed of a mixture of filter aid and decol'orizing carbon, and allowed to crystallize slowly overnight. There was obtained26-0 g. of producthaving a melting point of to C.
" This/material gave the 'followi'ngrarralysisz u i Analysis. 1'
' '65: s as. s
.v COP This coupler was preparedgby lthel sarne nmethod lused for preparing Couplerl excepting that a-(meta-pentadecylphenoxy) acetyl chloride was used in 'Step, 4 in place-pf ot-(meta pentadecylphenoxy) hutyryl chloride,
The product obtained was ofiwhite ,-in color, haying a melting .point of. l 1'9--l29 "v It had the following J lHEX TA M: iris in "j I Coupler 3" STEP 11 2 ,ti-DICHnOROfi-iMFETHQXYANILINEY l v A saturated solutionf gas in methanol was prepared'by'bubbling dry HCl' in methanol with cooling.- To 2.4 liters'ofj thi'ssaturated solution was slowly added 290 g. of p-nitrosophenol- (M.P. 142-'l43 C.) over a one-hour period, maintaining the temperature at 15' to melting point of'72 73 C. as in Step 2 of Example 1 to-produce the corresponding .20? C. with an ice waterhajth. DI'YJHCI was continually bubbled thr ugh the mixture during the. addition. Stirring was continued an additional 30 minutes while HCl 'gas' was huhbledinto the'suspension. The product was collected on a sintered glass funnel; washed with ether and-"dried, giving a yield of g.
The crude hydrochloride was dissolved in 1.4 liters of refluxing methanol plus cc. of water, treated with Nuchar and the filtrate'd'rownedin 10 liters of cold water. The solid whichformedwas collected by'fil'tration and crystallized from" 700 of methanol giving 192 gfof "2,6-dichloro4-rnethoxyaniline as white needles with a This amine diaz'oti'zed phenylhydrazine' which was then carried through Steps :3
and 4 of Example 1 to-pro'duce the white coupler (3) "the. reaction mixture STEP 1.- 4,6-DICHLORO-2-METHYLACETANILIDE In a -liter flask equipped with a mechanical stirrer, a reflux condenser and a gas-addition tube were placed 450 g. (3.0 moles) of o-acetotoluidide, 492 g. of anhydrous sodium acetate (6.0 moles), 1.5 liters of glacial acetic acid, and g. of iron powder. The mixture was heated to 90 on a steam bath and chlorine gas bubbled through the suspension for 4 /2 hours with continued heating and stirring. The hot mixture was filtered through a sintered glass funnel and sulfur dioxide was slowly bubbled through the dark solution for 30 minutes. Water (approximately 750 cc.) was added to the warm solution and the product allowed to crystallize slowly. After overnight standing the product was collected on a Biichner funnel, washed well with water and dried giving 381 g. of material with a melting point of l77-1 80 C. The crude product was recrystallized from 1 liter of 95% ethyl alcohol, thus obtaining 172 g. of material as white flakes having a melting point of 1 85 -187 C.
STEP 2.-4,6-DICHLORO-2-METHYLANILINE A mixture of 352 g. (1.62 moles) of 4,6-dichloro-2- methylac'et'anilide, 1.9 liters: of 95%"ethyl alcohol (3A alcohol) and 2.1 liters of concentrated hydrochloric acid in a l2-liter flask were refluxed overnight. The alcohol was removed by distillation and the semi-solid residue stirred and cooled while being neutralized with 28% ammonium hydroxide. The mixture was extracted 3 times with ether, the combined extracts water washed, dried overma'gnesiunr sulfate, filtered, and the solvent distilled. The residual oil was distilled under reduced pressure (the main fraction boiling point was 128-130 13 mm. Hg) giving 175 g. of a white crystalline material having a melting point of 48-49" C.- l
STEP 3.54,G-DICHLOROPZ-METHYLPHENYLHYDRAZINE This compound was preparedby'the same method given for the preparation of 4,6-dichloro-2-methoxyphenylhydrazine using 4,6-dichloro-Z-methylaniline instead of 4,6-dichloro-2-methoxyaniline as starting material. Crystallized from 1400 cc. of methanol, it had a melting point of 120.5 to 122 C.
STEP ,.4.1- 4,6-DICHLORO '2METHYLPHENYL) -3- AMINO-5-PYRAZOLONE This .compound was prepared by the same method given for the preparation of 1-(4,6-dichloro-2-methoxyphenyl)-'3-amino -5-pyrazolone, using an equivalent of 4,6-dichloro-2-methylphenylhydrazine instead of 4,6-dichloro-Z-methoxyphenylhydrazine as starting material. The crude product was recrystallized from 7.5 parts of ,ethyl acetate using 1.5 partsof ethanol to obtain complete solution. A yield of 94 g. was obtained having a melting point of l95-196 C.
dichloro Z-methylphenyl)-3-amino-5-pyrazolone, 123 g.
(0.3 mole) of ot-(meta-pentadecylphenoxy)butyryl chloride and 1500 ml. of anhydrous acetonitrile. The mixture was stirred and refluxed for 4 hours. On slow cooling overnight, with stirring, a solid separated and was collected on .a filter, washed with a small portion of cold acetonitrile and dried. The crude product weighed 163 g. and was recrystallized from 30 parts of n-hexane yielding 78 g. of coupler No. 4 as a white solid having a melt ing point of 90-92 C. The analysis of this material was 5 as follows:
Analysis I O7 H N Calculated 66. 8 7. 8 6.6
EXAMPLE V Coltpler 5 STEP 1.7-6-CHLORO-2,4-DIMETHYLACETANILIDE A 5-liter flask equipped with a mechanical stirrer, reflux condenser and gas addition tube was charged with .489 g. (3.0 mole) of 2,4-dimethylacetanilide, 246g. (3.0 moles) of anhydrous sodium acetate dissolved in 1.5 liters of glacial acetic acid, and 10 grams of iron powder. The mixture was heated to C. on a steam bath and chlorine gas was bubbled through the mixture for 3 hours with continued heating and stirring. The hot'mixture was filtered through a sintered "glass funnel and sulfur dioxide was bubbled through the dark filtrate for -5 minutes. Water was added to the warm solution until a precipitate began toform (approximately 750 cc.). The mixture was allowed to stand overnight, filtered and the solid washed well with water and dried. The crude product was recrystallized from 1 100 cc. of ethyl alcohol as white flakes with a melting point of 201-202? C. STEP 2. s-cnr.ono-arnnunrnrmisrnmn In a 12-liter flask equipped with a reflux condenser was placed 361 g. (1.82 moles) of 6-chloro-2,4-dimethylacet-l anilide, 1900 cc. of 3A alcohol and 2100 cc. of concentrated'hydrochloric acid. The mixture was heated under reflux for 24 hours. "The alcohol was removed by distillation and the semi-solid residue stirred and cooled while being-neutralized with 28% ammonium hydroxide, The mixture was ether extracted 3 times, the combined ether extracts dried over magnesium sulfate, filtered and thesolvent distilled. The residual oil was distilled under reduced pressure (boiling point 116-119 C. /1-5 mm. Hg) giving 223 g. of white crystalline material having a melt? ing point of 40.5 to 42 C. a STEP3.6-CHLORO-2,4-DIMETHYLPHENYLHYDRAZINE This hydrazine was prepared by the same method given for the preparation of 4,6- dichloro-2-methoxyphenylhydra'zine, using an equivalent quantity of 6-chloro-2,4-dimethylaniline instead of 4,6-dich1oro-2 methoxyaniline". The product was crystallized from hexane, from which it cameout as tan colored needles having a melting point arms-775 c.
STEP 4.-1-te-cnnoaoaenmmnmnunrr. -3-
This pyrazolone was prepared by the method described for the'prep'aration of 1-(4,6-dichloro-Z-methoxyphenyl)- 3-amino5-pyrazolone, using an equivalent amount of 6-chl0ro-2,4-dimethylphenylhydrazine instead of 4,6-dichloro-2-methoxyphenylhydrazine. The crude product was crystallized from 95% ethyl alcohol, and had a melting point of 158-160" C,
STEP 5.--1-(6 CHLORO 2,4 DIMETHYLPHENYL)? [a -(3-n-PENTADECYLPHE NOXY BUTYRYLA-MIDQ -5- PYRAZOLON'E In a 1-liter flask equipped with a mechanical stirrer and a reflux condenser were placed 25.5 g. (0.107 mole) of 1 (6 chloro-2,4-dimethylphenyl) -3-amino-5-pyrazolone, 48.3 g. (0.118 mole) of a-(3en-pentadecylphenoxy)t butyryl chloride and '600 cc. of anhydrous acetonitrile. The mixture was stirred and refluxed for 4 hours. On slow cooling overnight with stirring, a solid separated which was collected on a Biichner funnel, washed with seems Analysls Calculated Found EXAMPLE VI Coupler 6 STEP 1.--1(6-CHLORO-2,4-DIMETHYLPHENYL)-3- (3'NITROBENZAMIDO --PYRAZOLONE A solution of 23.8 g. (0.1 mole) of 1-(6-chloro-2,4- dimethylphenyl)-3-amino-5-pyrazolone prepared as in Step 4 of Example V, and 20.4 g. of recrystallized 3-nitrobenzoylchloride (0.l1 mole) in 500 cc. of acetonitrile was refluxed for 16 hours. After 30 minutes of refluxing solid material separated. The solid was collected, washed with acetonitrile and dried. It was crystallized from methanol to give'material having a melting point of 262-264? C. f Y STEP 2.1'-.(G-CHLORO2,4 DIMETHYLPHENYL) -3- [u; (3-11- PENTADECY'LPHENOXY BUTYRAMIDO 1 BENZAMIDO-' s-rynazonoNn r A suspension of 6.5 (0.017 mole) of'the purified 1-(6- chloro 2,4 dimethylphenyl) 3 [3 nitrobenzamido] 5 pyrazolone in 50 cc. of glacial acetic .acid was treated with 0.5 g. of palladium on carbon and shaken under hydrogen. The required 'volume of hydrogen was absorbed in 15 minutes. The catalyst was filtered off and the filtrate heated to 65 C. 7.8 g. (0.019 mole) of a- (S-n-pentadecylphenoxy)butyryl chloride dissolved in '10 cc. of acetic acid were added followedby 2.5 g. (0.03 mole) of anhydrous acid with stirring. Sodium chloride precipitated. The solution was poured into water with stirring. The yellow solid formed was collected, dried overnight, and crystallized from acetonitrile. The product had a melting-point of. 106-108 C.
Analysis C H N Calculated 71. o 7. s 7. Found; 70.8 r 8.1 7. 3
EXAMPLE VII Coupler 7 STEP I. 2-METHOX Y-5-METHYLACETANILIDE A solution of 326g. (2.4 mole) of 2-methoxy-5-methyl aniline in 500 cc. of glacial acetic acid was treated with 240 g. (2.4 mole) of acetic anhydride. The temperature rose to 90 C. The mixture was stirred for 30 minutes at this temperature then cooled and poured into ice water. The white solid formed was collected, washed thoroughly in water and dried. The damp white solid was recrystallized directly from alcohol and Water (about 48% ethyl alcohol). 340 g. of product were obtained having a melting point of 110-113" C.
STEP 2.---2 METHO XY-5-METHYL-3Afi-TRICHLORO- ACETANILIDE A solution of 195 g. (1 mole) of Z-methoxy-S-methylacetanilide inl liter of acetic acid was treated with 405 g. (3 mole) of sulfuryLchloride keeping the temperature at 35-40 C. The reaction, mixture was stirred for 3 hours at room temperature and then poured into water. The solid product was collected and washed thoroughly with water. The damp solid was recrystallized from sodium acetate in 15 cc. of acetic i methanol (3 liters) producing 100 g. of material having a melting point of 206208 C. STEP 3.2-METHOXY-5-METHYL-3,4,6TRICHLORO4 ANILINE 2-methoxy-5-methyl-3,4,6-trichloroacetanilide dissolved in ethyl alcohol and concentrated hydrochloric acid, was hydrolyzed under reflux by the same procedure used in Step 2 of Example V to produce the corresponding aniline derivative.
STEP 4.-2-E\1ETHOXY-5-METHYL-3,4,6-TRICHLORO- PHENYLHYDRAZINE v 2 methoxy 5 methyl 3,4,6 trichloroaniline was converted into the corresponding phenylhydrazine by the same procedure used in Step 3 of Example V using equimolecular portions of thereactants.
STEP 5.-1-(2-METH0XY-5-METHYL-3,4,6-TRICHL0R0- PHENYL)-3-AMINO-5-PYRAZOLONE 2-methoxy-5-methyl-3,4,6-trichlorophenylhydrazine was reacted with ethyl-p-ethoxy-fi-iminopropionate in acetic acid according to.the procedure used in Step 4 of Example V. g STEP 6.--1-(2-METHOXY 5 METHYL-3,4,6-TRICH-LORO- .PHENYL) -3- a.-'(META PENTADECYLPHENOXY )ACE'L AMIDO]-5-PYRAZOLONE The 1 (2 methoxy 5 methyl 3,4,6 trichloro phenyl) -3-amino-5-pyrazolone was reacted with tit-(metapentadecylphenoxy)acetyflchloride in anhydrous acetoni trile under reflux by the procedure used inStep 5 of Ex p 1: -i The recrystallized productwas off-white in color hav; ing a-melting point of 139-140.5 C.
Analysis C H .N
i The couplers of our invention are particularly adapted for incorporation in light, sensitive emulsion layers for color photography. These emulsions are of the developing-out type.
The emulsions 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. Patent 1,574,944, issued-March 2, 1926, Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard et a1- U.S. Patent 2,410,689, issued November 5, 1946. The emulsionscan also betreated with salts of the noble metals suchfas ruthenium, rhodium, palladium, iridium, and platinum. Representative compounds are ammonium ,chloropalladate,,, potassium chloroplatinatc, and sodium clilor'opalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued August31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August 28, 1951.
The emulsions can also be chemically sensitized with gold salts as described in Waller et a1. U.S. Patent 2,399, 083, issued April 23, 1946, or stabilized-with gold salts as described in Damschroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaura'te, auric trichloride and 2-aurosulfobenzothiazole methochloride. y The emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S. Pat ent 2,487,850, issued November 15, 1949),'po1yamines, such as diethyl triamine (Lowe and. Jones U.S. Patent 2,518,698, issued AugustlS, 1950), polyamines, such as 11- spermine (Lowe and Allen U. S, Patent 2,521,925, issued September 12, 1950), or bis(;iarninoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926, issued September 12, 1950).
The emulsions can alsobe optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White U.S. Patent 1,990,507, issued February 12, 1935; Brooker and White U.S. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued January 10, 1950 and 2,739,964, issued March 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950; Sprague U.S. Patents 2,503,776, issued April 11, 1950 and 2,519,001, issued August 15, 1950; Heseltine and Brooker U.S. Patent 2,666,761, issued January 19, 1954; Heseltine U.S. Patent 2,734,900, issued February 14, 1956; Van- Lare U.S. Patent 2,739,149, issued March 20, 1956; and Kodak Limited British Patent 450,958, accepted July 15, 1936.
The emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955 Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955 the triazoles of Heimbach and Kelley US; Patent 2,444,608, issued July 6, 1948; the azaindenes of- Heimbach' and Kelley U.S. Patents 2,444,605 and 2,444,606, issued July 6, 1948; Heimbach U.S. Patents 2,444,607, issued July -6, 1948 and 2,450,397, issued September 28, I948; Heimbach and Clark U.S. Patent 2,444,609, issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955, and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27,1956, and those disclosed by Birr in Z. wiss. Phot., vol. 47, 1952, pages 228; the disulfides of Kodak Belgian Patent 569,317, issued July 31, 1958; the quaternary benzothiazolium compounds of Brooker and Stand U.S. Patent 2,131,038, issued September 27, 1938, or the polymethylene bis-ben'zothiazolium salts of Allen and Wilson U.S. Patent 2,694,716, issued November decamethylene-bis-benzothiazolium perchlorate); or the zinc and cadmium salts of Jones U.S. Patent 2,839,405, issued June 17, 1958; and the carboxymethylmercapto compounds of Murray, Reynolds and Van Allen U.S. Patent 2,819,965, issued January 14, 1958.
The emulsions may also contain speed increasing compounds of the quaternary ammonium type of Carroll .5. Patent 2,271,623, issued February 3, 1942; Carroll and Allen US. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1959; and the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the thiopolymers of Graham and Sagal U.S. application SerialNo. 779,839, filed December 12, 1958, or Dann and Chechak U.S. application Serial No. 779,874, filed December 12, 1958.
The emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murray U.S. application Serial No. 588,951, filed June 4, 1956, now U.S. Patent 2,960,404, issued November 15, 1960; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate as described in Milton U.S. application Serial No. 662,564, filed May 31, 1957, now U.S. Patent 2,904,424, issued September 15, 1959; bis(ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No. 604,333, filed August 16, 1956, now
U.S. Patent 2,940,854, issuedJune14, 1960, or a polymeric hydrosol as results fron'rthe emulsion polymerization of a mixture of an amide of an acid of the acrylic acid series, an acrylic acid ester and a styrene-type compound as described in T ong U.S. Patent 2,852,386, issued September 16, 1958. Theplasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.
The emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene-2,3,5, 6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfouic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll U.S., Patents 2,725,294, and 2,725,295, both issued November 29, 1955; a cyclic 1,2-diketone such as cyclopentane-1,2-dione as described in Allen and Byers U.S.v Patent 2,725,305, issued November 29, 1955; a bisester of methane-sulfonic acid such as 1,2-di-(methanesulfonoxy)-ethane as described in Allen and Laakso U S. Patent 2,726,162, issued December 6, 1955 1,3-dihydroxymethylbenzimidazol-Z -one as described in July, Knott and Pollak U.S. Patent 2,732,316, issued January 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as fl-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness U.S.Patent application Serial No. 556,031, filedDecember 29, 1955 ;*a hisaziridine carboxamide such as trimethylene bis( l-aziridine carboxamide) as described in Allen and Webster U.S. patent application Serial No. 599,891, filed July 25,1956, now U.S. Patent 2,950,197, issued August 23,1960; or 2,3-dihydroxy dioxane asdescribed in Jeffreys U.S. Patent 2,870,013, issued January 20, 1959-.
The emulsions may contain a coating aid such as saponin; a lauryl or oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, ,1958; .a salt of a sulfated and alkylated polyethylene glycolether as described in Knox and Davis U.S. Patent 2,719,087, issuedSeptember 27, 1955;;an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl taurine as describedmin Knox, Twardokus and Davis U.S. Patent 2,739,891, issued March '27, 1956; the reaction product of a dianhyclride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a Water-soluble maleopimarate and .a substituted glutamate salt as described in Knox and Fowler U.S. Patent 2,823,123, issued February 11, 1958;,an alkali metal salt of a substituted amino acid such as disodium N-(carbo-ptert. octylphenoxypentaethoxy)-glutamate as described in Knox and Wilson U.S. Patent application Serial No. 600,679, filed July 30, 1956; or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate asdescribed in Knox and Stenberg U.S. Patent application Serial No. 691,125, filed October 21, 1957, now U.S. Patent 2,992,108, issued July 11, 1961,
The couplers which we have described may be used in various kinds of photographic emulsions. They may be added to the emulsions before or after any sensitizing dyes which are used. Various silver salts may be used asthe sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide. The agents may be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other .13 color-generating material emulsions of the r nixed-packet type, such as described in Godowsky US. Patent 2,698,794, issued January 4, 1955; oriemuls'ions of the mixed-grain type, such as described in Carroll and Hanson US. Patent 2,592,243, issued April 8, 1952. These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form inside the silver halide crystal, such as those described in Davey and Knott US. Patent 2,592,250, issued April 8, 1952.
In the preparation ployed for preparing silver halide emulsions, there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, -a polyvinyl compound. Some colloids which may be usedare polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Patent 2,286,215, sued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in US. Patent'2,327,808 of Lowe and Clark, issued August 24, 1943; a water-soluble ethanolamine cellulose acetate as described in-Yutzy- U.S.--'Patent 2,322,085, issued June 15, 1943; a'polyacrylamide-or an imidiz ed polyacrylamide as described in Lowe, Minsk and Kenyon U. S.,Patent 2,541,474, issued February 13, 195 1 .;ein as described in Lowe US, Patent 2,563,791, issued August 7,, 1951; a vinyl alcohol polymer containing urethane 'carboxylic' acid groups of the type described in Unruh and Smith US. Patent 2,768,154, issued Octoberv 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest US. Patent 2,808,331, issued October 1,1957; or a polymeric material which results from polymerizing a protein or a saturatedacy lated protein with a monomer having .a vinyl group as described in US. Patent 2,852,382 of lllingsworth Dann and Gates-issued September 16, 1958.
If desired, compatible mixturesjof two or more of these colloids may be employed for dispersing the silver halide in its preparation. Combinations of theseantifoggants, sensitizers, hardeners, etc.-, maybe used.- i
The coupler compounds of our invention may be dis= persed-in any water permeable hydrophilic material such as gelatin, albumin, gum, acacia, etc, 'or synthetic ma.- terials such'asorganic'es'ters of. cellulose, synthetic resins, etc. that are 'u'sed'for making photographic emulsions, Photographic emulsions containing these couplers maybe coatedaon transparenf sup-ports such-as glass, cellulose esters or- 'on a non-transparent reflecting material, such as paper or on opaque cellulose esters.
Our couplers are readily soluble in conventional types of coupler solvents such as those described in Jelley Tand Vitturn US. Patent 2,322,027, and can be used over a rangejofc'oupler to coupler} solvent ratios of from 1:0 to 1:2, ;Our couplers do not crystallize when used in dispersions of high coupler to coupler solvent ratios. The preferred ratiois 111 /2. t t
The preferred couplers of our invention are free from wandering from the layer in which they are incorporated. However, if it is "desirable to make these couplers diffusible this can be readily done by changing the ballasting group substituted on the 3-position of the pyrazolone ring. Photographic emulsions containing our couplers can be developed by any ofthe conventional primary amino developing compositions. Among the'preferred developing agents are developers suchas 2-amino-5-diethylaminotoluene hydrochloride; and N-ethyl-fi-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate. Typical delatent images. predominantly of the silver halide dispersions em- -14" velopers containing these developing agents are follows: A
Developer 1 G. 2-amino-S-diethylaminotoluene hydrochloride 2.5 Sodium sulfite (anhydrous) 5 Sodium carbonate (anhydrous) 20 Potassium bromide water to 1 liter.
' Developer 2 G.
N ethyl [3 methanesulfonamidoethyl 3 methyl- 4-aminoaniline sulfate -2 Sodium sulfite .5. Sodium carbonate 30 Water to 1 liter.
The following examples will illustrate the use ofout couplers in photographic emulsions.
EXAMPLE VIII f A gelatin dispersion containing 0.50 g. of coupler No. 1 in tri-o-cresyl phosphate was added to 5 ml. of a greensensitized medium-speed silver bromoiodide emulsion, the mixture was coated on a suitably subbed cellulose acetate support and dried. The coating was exposed in a spec,- trograph to tungsten illumination and developed In Developer No; 1 to form'a negative silver Image and a magenta dye image. The silver image andthe res dual silver halide were then removedtwith ferricyanide bleach and a hypo-fixer leaving a magenta dye image hay nga maximum absorption at 538 mu. f
"Another sample of the above emulsion coating treated in the same manner but developed with Developer No. resulted in the formation of a magenta image having a maximum light absorption at a wave-length of 5381 1111.
EXAMPLE'IX A photographic emulsion was made as in Example VIII but Coupler No. 2 was used in place of Coupler No. I. This was exposed, developed with Developer No. 1, bleached and ,fixed as in Example VIII to produce a good magenta dye image having a maximum absorption at a wavelength of 535. mu. g I t Another sample'of this emulsion was exposed, developed with Developer vN0. 2, bleached and fixed to pro duce good magenta dye-image having a-maximum absorption at 533-mu.
A photographic emulsion was made as in Example VIII, but Coupler No. 3 was used instead of coupler No. 1.. Two samples of this emulsion were exposed, one'of them was developed in Developer No. 1 and the second in Developer No. 2. After bleaching and fixing, both samples "had good magenta dye images having a maximum absorption ata wavelength of 543' mu.
EXAMPLE XI EXAMPLE XII Similarly, photographic emulsions containing Coupler No. 5 were prepared, exposed,'developed, bleached and -fixed to produce good magneta dye images. Developer N0 1 and Developer N0. 2 produced magneta dye images havl'ng'rnaximurn light absorption at wavelengths of 538 mu and 539 mu, respectively.
p EXAMPLE XIII When Coupler "No. 7 was incorporated in a photographic emulsion in place of Coupler No. 1- of Example VIII good magenta dye images were produced after exposure, development, bleaching and fixing, the dye images formed by Developer No. 1 and by Developer No. 2 had maximum light absorption at wavelengths of 544 mu and 542 mu, respectively.
The valuable characteristics of our couplers and the dyes formed from them are further illustrated by the accompanying drawings in FIGURES l, 2 and 3.
FIGURE 1 shows the spectrophotometric curves for the dye images produced upon the development of our emulsion containing Coupler No. 2 in Example IX and for the dye image produced with an emulsion made, exposed and processed in the same way but containing the prior art coupler l-(2,4,6-trichlorophenyl)-3-[3-(2,4-diamylphen'oxyacetamido)LS-pyrazolone in place of our Coupler No. 2. From these curves it is apparent that thedye from our coupler has less absorption in the red reglon of the spectrum and considerably more absorption in the green region of the spectrum. The maximum absorption of our dye occurs at a wavelength of 533 as compared to 550 for the prior art dye.
All of these characteristics mentioned above make our dye more desirable than the corresponding prior art dye.
FIGURES 2 and 3 are percent transmittance curves showing the effect produced upon the transmission characteristic of our Coupler No. 3, 1-(2,6-dichlor o-4-methoxyphenyl) 3 [a-(meta-pentadecylphenoxy)-butyramido]-5Py razolone, and of the coupler 1-( .2,5 -dichloro-4-- methoxyphenyl 3 [a-(meta-pentadecylphenoxy)-butyramidol-5-pyrazolone, respectively by hoursof exposure to a xenon are light. Curve No. l in each figure shows the percent transmittance for the respective couplers at wavelengths of 400 to 700 mu before exposure to the Xenon and curve No. 2 shows the corresponding percent transmittance after the 30 hours of exposure. A comparison of the differences between the curves 1 and 2 of the FIGURE 2 and of the differences between these two curves in FIGURE-3 shows that our Coupler No. 3 produces considerably less print out than the corresponding coupler of the prior art type. These two couplers have tructures' which differ only in the position on the l-phenyl ring at which a chlorine atom is substituted.
Our coupler has greater stability to print-out as evidenced by the 8.5% decrease in transmittance as compared to the 15% decrease in transmittance that occurs when the other coupler is used. This valuable improvement shown by our couplers is unexpected in view of the relatively small diiference in structure between it and the coupler of the prior art type. FIGURES 2 and 3 illustrate the criticalness of the substituents in the 2,4,6- posi'tion's' over those in the 2,4,5-positions on the l-phenyl group of the pyrazolone coupler.
Not only do our couplers show good stability to light but they also have good heat stability. The dyes formed from them have good stability to heat and light.
Our couplers are not only valuable in their own right, but also as parent couplers for making valuable colored couplers and other types of couplers which are used in color photography. Colored couplers for example may be readily made by replacing one of the hydrogens on the 4-carbon of the S-pyrazolone ring with a phenylazo group or any of the other splittable groups which are used in colored couplers.
The valuable characteristics imparted by substituents on the 2,4,6-positions of the l-phenyl ring of our couplers are also imparted to corresponding colored couplers.
The novel 2,4-6-substituted l-phenyl pyrazolone couplers of our invention are valuable for use in color photography. They are distinguished from other couplers which have substituents in the 2,4,5-positions on the l-phenyl ring by having unexpectedly greater stability to light and heat and thus have greatly improved print-out characteristics when used in'photographic emulsions. For
16' example, a photographic emulsion containing our Coupler No. 3 loses only 8.5% in its light transmission after being subject to 30 hours exposure to xenon light as compared to a 15% loss in transmission Shown by a photographic emulsion containing the 2,4,5-substituted l-phenyl analogue of our coupler when subjected to the same treatment. Our couplers produce dyes having improved light absorption characteristics which avoid the excessive red absorption and the inadequate green absorption of the dyes in current use. These dyes have satisfactory light and heat stability and are well adapted for use in color photography. Our couplers are readily soluble in standard coupler solvents over a broad range of coupler to coupler solvent ratios and give dispersions which are free from crystallization at high coupler to coupler solvent ratios. Furthermore, our couplers are free from wandering from the emulsion layer they are incorporated in. Not only are our couplers valuable per se but also for use as parent couplers in making colored couplers which are also characterized by having all of the desirable properties of the parent coupler.
The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim: 1. A photographic silver halide emulsion containing a magenta forming coupler having the formula:
N=C--J wherein W represents a member selected from the class consisting of groups having the formulas:
z X z Y l I z. and XQ Z: Y Z: Y
Q is a member selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; n is from 0 to 2; m is from 0 to l; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
2. A photographic silver halide emulsion containing a magenta forming coupler having the formula:
and
Y is a member selected Q is a member selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; 11 is from 0 to 2; m is from O to 1; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
3. A photographic silver halide emulsion containing a magenta forming coupler having the formula:
wherein X is a halogen atom; R is selected from the class consisting of alkyl groups having from 1 to 6 carbon atoms; where said X and said R groups are substituted on the carbon atoms in the 2, 4 and 6-positions of the l-phenyl group; J is a member selected from t class having the formulas:
Q is a member selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; n is from 0 to 2; m is from O to 1; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
18 4. A photographic silver halide emulsion containing a magenta forming coupler having the formula:
N=C-I R2 ll 0 wherein X is a halogen atom; R is an alkoxy group having from 1 to 6 carbon atoms, where said X group and said R group are substituted on the carbon atoms in the 2, 4 and 6-positions of the l-phenyl group; J is a member selected from the class having the formulas:
selected from the class consisting of a hydrogen atom, and a lower alkyl group having from 1 to 6 carbon atoms; 11 is from 0 to 2; m is from O to 1; R is an alkyl group having from 1 to 20 carbon atoms, and q is from 1 to 3.
5. A photographic silver halide emulsion containing the magenta forming coupler 1-(4,6-dich1oro-2-methoxyphenyl) 3 [a-(m-pentadecylphenoxy)butyramido]-5- pyrazolone.
6. A photographic silver halide emulsion containing the magenta forming coupler 1-(4,6-dichloro-2-methoxyphenyl) 3 [a (m-pentadecylphenoxy)acetamido1-5- pyrazolone.
7. Aphotographic silver halide emulsion containing the magenta forming coupler 1-(2,6-dichloro-4-methoxyphenyl) 3 [a (m-pentadecylphenoxy)butyramido] -5- pyrazolone.
8. A photographic silver halide emulsion containing the magenta forming coupler 1-(4,6-dichloro-2-methylphenyl) 3 [a (m-pentadecylphenoxy)butyramido]-5- pyrazolone.
9. A photographic silver halide emulsion containing the magenta forming coupler 1-(6-chloro-2,4-dimethylphenyl) 3 [a (m-pentadecylphenoxy)butyramido]-5- pyrazolone.
Q is a member References Cited in the file of this patent UNITED STATES PATENTS 2,354,552 Schneider et al July 25, 1944 2,803,544 Greenhalgh Aug. 20, 1957 2,817,666 Beaver et a1. Dec. 24, 1957 2,897,206 Fukiu et al. July 28, 1959

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A MAGENTA FORMING COUPLER HAVING THE FORMULA:
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619195A (en) * 1968-11-01 1971-11-09 Eastman Kodak Co Photographic coupler dispersions
US3939176A (en) * 1972-07-03 1976-02-17 Minnesota Mining And Manufacturing Company Magenta 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
US4409323A (en) * 1980-02-15 1983-10-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
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EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
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US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
EP0684515A1 (en) 1994-05-27 1995-11-29 Eastman Kodak Company Photographic element and process incorporating a high dye-yield image coupler providing improved granularity
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US5571661A (en) * 1994-06-09 1996-11-05 Konica Corporation Silver halide light-sensitive color photographic material
EP0779544A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
EP0779543A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
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US6509500B2 (en) 2001-05-24 2003-01-21 Eastman Chemical Company Continuous preparation of incorporated photographic amides
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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844794A (en) * 1969-06-13 1974-10-29 Minnesota Mining & Mfg Magenta couplers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2354552A (en) * 1940-08-08 1944-07-25 Gen Aniline & Film Corp Color photographic image
US2803544A (en) * 1953-02-13 1957-08-20 Ici Ltd Colour couplers for use in colour photography
US2817666A (en) * 1956-10-29 1957-12-24 Monsanto Chemicals N(3-methyl-5-pyrazolone)-halo-carboxanilides
US2897206A (en) * 1958-06-24 1959-07-28 Nippon Shinyaku Co Ltd Dialkylamides of alpha-(4-antipyrylamino)-fatty acids and their n-alkyl derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2354552A (en) * 1940-08-08 1944-07-25 Gen Aniline & Film Corp Color photographic image
US2803544A (en) * 1953-02-13 1957-08-20 Ici Ltd Colour couplers for use in colour photography
US2817666A (en) * 1956-10-29 1957-12-24 Monsanto Chemicals N(3-methyl-5-pyrazolone)-halo-carboxanilides
US2897206A (en) * 1958-06-24 1959-07-28 Nippon Shinyaku Co Ltd Dialkylamides of alpha-(4-antipyrylamino)-fatty acids and their n-alkyl derivatives

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619195A (en) * 1968-11-01 1971-11-09 Eastman Kodak Co Photographic coupler dispersions
US3939176A (en) * 1972-07-03 1976-02-17 Minnesota Mining And Manufacturing Company Magenta couplers
US4409323A (en) * 1980-02-15 1983-10-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
US4345085A (en) * 1980-12-29 1982-08-17 Eastman Kodak Company Method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
EP0067845A1 (en) * 1980-12-29 1982-12-29 Eastman Kodak Co A method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles.
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
EP0200878A1 (en) 1982-02-24 1986-11-12 Konica Corporation Light-sensitive silver halide color photographic material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0200502A2 (en) 1985-04-30 1986-11-05 Konica Corporation Light-sensitive silver halide color photographic material
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0452984A1 (en) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic material for photographing use
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes
EP0684515A1 (en) 1994-05-27 1995-11-29 Eastman Kodak Company Photographic element and process incorporating a high dye-yield image coupler providing improved granularity
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
US5571661A (en) * 1994-06-09 1996-11-05 Konica Corporation Silver halide light-sensitive color photographic material
EP0695968A2 (en) 1994-08-01 1996-02-07 Eastman Kodak Company Viscosity reduction in a photographic melt
EP0698816A1 (en) 1994-08-26 1996-02-28 Eastman Kodak Company Photographic paper formed with low molecular weight polyvinyl alcohol having low oxygen permeability
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers
EP0779536A1 (en) 1995-12-04 1997-06-18 Konica Corporation Light-and heat-sensitive recording material and recording method by use thereof
EP0779544A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
EP0779543A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
US6509500B2 (en) 2001-05-24 2003-01-21 Eastman Chemical Company Continuous preparation of incorporated photographic amides
WO2013032827A1 (en) 2011-08-31 2013-03-07 Eastman Kodak Company Motion picture films to provide archival images

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