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Publication numberUS2993791 A
Publication typeGrant
Publication dateJul 25, 1961
Filing dateOct 31, 1957
Priority dateOct 31, 1957
Also published asDE1073308B
Publication numberUS 2993791 A, US 2993791A, US-A-2993791, US2993791 A, US2993791A
InventorsColes Robert F, Heinz Schulze
Original AssigneeGen Aniline & Film Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Color couplers containing long chain alkylaminoisophthalicester groups
US 2993791 A
Abstract  available in
Images(6)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent C COLOR COUPLERS CONTAINING LONG C ALKYLAMINOISOPHTHALICESTER GROUPS Robert F. Coles, North St. Paul, Minn., and Heinz Schulze, Cincinnati, Ohio, assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 31, 1957, Ser. No. 693,509

9Claims. (Cl. 96-55) This invention relates to color photography and particularly to color-forming compounds.

The use in color photography of color-forming compounds, which react with the oxidation or development product of primary aromatic amino developing agents to form colored images upon photographic development, is well-known. The colored compound thus formed is deposited next to the silver grains of the silver image during development. The coupler compounds as employed above may be added to the color developer solutions or they may be incorporated in the gelatino silver-halide emulsion.

When used in photographic emulsions, the couplers may be dissolved directly in the gelatin or other hydrophilic colloid. In such case, the couplers must have groups rendering them alkali soluble such as carboxylic acid or sulfonic acid groups.

Alternately, the couplers may be incorporated in a photographic emulsion by dissolving them in a waterimmiscible or oily organic solvent and dispersing the resulting solutions in the photographic emulsion.

In the manufacture of emulsions containing couplers,

considerable difficulty is encountered in obtaining couplers of high purity, particularly couplers containing carboxylic or sulfonic acid groups. In the case of couplers that are added to emulsions in the form of dispersions, problems are experienced in obtaining couplers of sufficient solubility in organic solvents. Similarly, many couplers have a tendency to diffuse in the medium in which they are incorporated. Finally, many of the couplers mentioned in the prior art give rise to colored photographic images of undesirable spectral characteristics.

It is, therefore, an object of the present invention to provide color formers which can be readily purified by recrystallization.

A further object is to provide color formers which containing the functional or reactive group which reacts with the oxidation products of the primary amino aromatic developing agents to yield color images, said reactive groups comprising a reactive methylene group, such as ketomethylene, i.e., COCH CO;

--CO-CH CN- C 0CHif]J N etc., or a reactive phenolic hydroxyl group, e.g.,

CIJH C=C e.g., phenols and naphthols, which are reactive in the ortho or para position relative to the hydroxyl group; X represents a CO- or SO group; Z represents hydrogen, halogen, e.g., chlorine, bromine and iodine, an

H 1 it i Q --ONOO @omom alkyl group, e.g., methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, n-hexyl, etc., an aryl group, e.g., phenyl, halophenyl, e.g., chlorophenyl, bromophenyl, etc., naphthyl, etc., an alkoxyl group, e.g., methoxy, ethoxy, npropoxy, n-butoxy, etc.; R and R are short chain alkyl groups such as methyl or ethyl and Alk is an alkyl group of at least 10 carbon atom, i.e., decyl, dodecyl, tetradecyl, octadecyl, etc.

The following compounds illustrate the isophthalic esters which may be used according to our invention.

I COiCH soluble salts, i.e., sodium, potassium, ammonium, etc.

can be incorporated in gelatin emulsions either directly or by dispersing a solution of the coupler in organic solvents.

A still further object is to provide color couplers which are fast to diffusion in the emulsion.

Other objects will appear herein as the description A-CONH X-III-Alk wherein A represents that part of the coupler molecule CO2CH3 and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

( C OsOHa I n n SOr-N OOzCHa and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

CO2CHa and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

OCH:

and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

Cl COICHa and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

ll 1 o-N- C ieHa-l COzCHa and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

H GIEHM and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

a? l r OOHz-ON OCH:

CrsHa1 SOs-N? GOQOHE C OnCHa and the corresnondmg dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

O E I II I Q I C1s a1 O-- -CO1CHa n 0 and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

ll OH ll l SOz-N COQCH! and the corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc.

(15) OH CH3 0 H. n C' -N COaOHs and the. corresponding dicarboxylic acid and its watersoluble salts, i.e., sodium, potassium, ammonium, etc. The compounds hereof are prepared by condensing a 5-alkylaminoisophthalate with an acid chloride or sulfonlychloride of the following general formulae:

NO S0201 with Z representing the same groups as above. The condensations are advantageously carried out in an inert solvent like benzene or xylene at elevated temperatures so that the hydrogen chloride formed during the reaction is discharged immediately. After reduction of the nitro group, the resulting amine is condensed with a carboxylic acid derivative of the color-forming residue by known methods. Naturally, the esters can be hydrolyzed and their carboxylic acids used as color formers in the same Way as used herein. The above compounds may be used in the form of their esters or their acids. If the esters are employed, they are dissolved in a suitable solvent such as a mixture of 50 parts phenethyl alcohol, 40 parts of tricresyl phosphate and 10 parts of n-butyl phthalate and the resulting solution incorporated in the emulsion as a fine dispersion. If the acids are employed, they are 5 introduced into the emulsion directly as an alkali metal salt such as the sodium salt.

I Example 1 Compound (1) is prepared as follows: Dlmethyl 5-(3-nltro-N-octadecylbenzamtdo)tsophthalate C O O OH: (lliaHw Q II I N02 COUCH-a Dlmethyl B-amtno-N-octadecylbenzamido) tsophthalate C 0 O CH:

NH COOCHa 80 grams of the foregoing product was hydrogenated with platinum oxide in 100 ml. oflmethanol at 50 C. More methanol was added and the'solution filtered hot from the catalyst and a small quantity of an insoluble white residue. The solvent was evaporated on a steam bath in vacuum. Yield 66 g. of a slightly brownish viscous oil.

Analysis: Calc.72.40% 72.22% C, 9.17% H.

C, 8.96% H. Found- 1-h drox -3-[N-(3 5-dlcarbomethoxyphenyl)-N-(octadecyl) y y carbamyH-Z-naphthamHde COOCHI (EOOCH:

- 18.3 grams (0.03 mole) of the foregoing product and 9 g. (0.033 mole) of phenyl 1-hydroxy-2-naphthoate.

Example II Compound (2) was prepared in the same way as Compound (1) while substituting the isomeric p-nitrobenzoy-l chloride for the m-nitrobenzoyl chloride.

1- Compound (2) melted at 139-140 C.

zenesulfonyl chloride.

Example III I Compound (3) was prepared as follows:

Dlmethyl S-p-nltro-N-octadecylphenylsulfonamidolsophthslate C O O CH: CraHn Dirnethyl 5-0ctadecylaminoisophthalate was condensed with 4-nitrobenzenesulfonyl chloride in' 'refluxing xylene according to Example I. The condensation product melted at 9191.5 C.

Dimethyl 5-pamino-N-octadecglphenylsultonamldolsop a e OOCHs hthal c o 0 0H- (liisHu HiN-SO2N I c o 0 cm The nitro compound was reduced to the corresponding amine using platinum oxide as catalyst; M.P. 91-915 C.

N (3,5-dlcarbomethoxyphenyl)-N'-ootadecy1-N- (l-hydroxy- 2-naphthy1)su1fanilam1de C 0 O CH CiaHu OOCHI Example IV Dlmethyl 5-(4-chlore3-n1tropl1enyl-N-octadecylsultonamtdo) tsophthalate C O O CH: (IJ1aHa1 Ol-Q-SOa-N N02 60 O CH:

In a 1 liter 3-necked flask, equipped with a reflux condenser and stirrer was placed a solution of 92.4 g. (0.2 mole) of octadecylaminoisophthalic acid dimethyl ester in 500 ml. of dry toluene. 5 drops of pyridine was added followed -by 51.2 g. (0.2. mole) of 4echloro-3-nitroben- Thesolution was refluxed for 18 hours and the solvent then removed at reduced pressure. The 4-ch-loro-3-nitrobenzenesulfonyl chloride used above was prepared from the potassium salt of the con-responding acid using phosphorous pentachloride as the chlorinating agent and phosphorous oxychloride as a solvent. The residual oil was crystallized from about 1200 ml. of petroleum ether; B.P. -100 C. The resulting product was digested with 1 liter of boiling methanol, cooled and filtered. Yield g., M.P. 93-94 C.

Dlmethyl 5- (3-amluo-4-chloropl1enyg-N-oetadecylsultonsmtdo) e A mixture of 30 g. (0.044 mole) of the above nitro compound and 200 ml. of methanol were reduced in a low pressure heated hydrogenator with Raney nickel The condensation product weaver Dtmethyl 6-(3 u-benzoylacetamIdmkchIorophenyl-N-octadecylsulfonamldo)isophthalate.

c 0 on: l iaHn Qantas- 3:

' doc cm.

In a 1" liter-3mecked flask, equipped with a stirrer, vertical steam jacketed condenser and dropping funnel, was placed a solution of. the above amine (48 g., 0.074 mole) in 500 ml. oi. dry'xylene. The solution was treated dropwise at reflux with etyl-benzoylacetate (17.3 g., 0.09 mole), and the resulting solution was refluxed for 8 hours. After removal of the solvent; on a steam bath at reduced pressure, the residual oil was dissolved in 800 ml. of methanol, treated with charcoal and filtered. The filtrate was decanted from a small amount of dark oil, treated again with charcoal and filtered. The filtrate was cooled, the product collected and washed with cold methanol. Yield 25 g-,, M.P. 107-108 C.

Example. V Compound (9) was' 'prepared by condensing dimethyl" (3-amino 4"-chlorophenyl N- octadecylsulfonamidof 3 Compound 10) was I prepared as: follows-2 Dimethyl 6*- (3 nttrophenyl N-octadecylsultonamtdo) lso= I phthalate' COOiCHa'. 13 31.

l N01 C O 0 CH3 In lei-500ml. 3'-necked flask, equipped with a stirrerand a reflux condenser, were placed 200 ml. of dry xylene, and.46.2-. g...(-.( ).Ol mole) of, 3-octadeoylaminoisophthalic acid dimethyl; ester: 3-nitrobenzenesulfonyl chloride (22.21g.-,,0.l+ mole) was added and the solution heated at gentle reflux. for 18 hours. ,Thes'olvent was removed from the dark solutionatreduced pressure and the residue triturated' with methanol (l50=ml.). After cooling the-solution, the solid was collected-by filtration andiwashed with methanol. The product was dissolved in 200' ml. of' petroleum ether; B.P. 90-l00 C. The. solutionwas treated withv charcoal and filtered. The:

filtrate was diluted with an equal volume of petroleum etliefyFiPEU-GO' Alter cooling, theswhitef cnystal line solid was collected by filtration and waswashed with petroleum ether. The product was recrystallized from 400 ml. methanol; M.P. 74-75 6.

Dtmeth'yr 5-(e amtnophenyl moctadecylsulfonamidoltam phthalate v oooon. OraHn NH: O 0 CHI Amixture-of' Z7.7-'g., (0.043 mole) of theabovenitro compound in 200'. ml. of methanol were reduced'in" a low pressure hydrogenator with platinum oxide catalyst.

The white crystalline solid obtained. was dissolved in 50 m1. of hot petroleum'ether; B.P. 30-60 C. The solution was cooled inice-and the crystalline solid which separated. was collected' by filtration and dried. Yield" 21 g., M.P. 76-78 C.

l-hydrox -8-[N- 8,5-dicarbomcthox hen 1)-N-(octadec l) y tiulta'myllQ naphthiiQiMdiL' y CO 0 CH;

A mixture of the amine' prepared as above (4.5 g., 0.017 mole) wasxheated at reduced pressure (5-10 mm.) on a metal bath first-at-140--l50 C. for A hour and then at 160-l70 C. for hour. Methanol (100 ml.) was added to the hot melt. After tri-turating' for a short time, the oil crystallized. The warm mixture wasfiltered and T the solid was crystallized from petroleum .ether; B.P.

C. Yield 7.8 g., M.P. l l4ll5 C.

Analysis: Calc.--68.70% C, 7.38% 68.74% C, 7.39% H.

Example VII Compound (11) was prepared by condensing dimethyl 5-(3 aminophenyl-N-octadeeylsulfonamido) isophthalate (10 g., 0.016 mole) with ethyl benzoylacetate (3.8 g., 0.02 mole) in 100 ml. of dry xylene, following the procedure used to prepare Compound (8).

The" amine was the same used for the preparation of Compound (10).

H. Found A solution of 1.5 'g. of Compound (5) wasdissolved in 6.0 g. of a mixture consisting of 50 parts phenethylalcohol, 40' parts of tricresyl phosphate "and 10 parts of n butyl phthalate-and the resulting solution dispersed'iin' 20ml. of a 6% gelatin solution containing 0.05 of" Einulsification was efiected by high-speed.

lauryl' sulfate; I agitation in a small' Waring Blendor. The" above dispersion of coupler was mixed. with..50 g. of a melted silverhalide gelatin emulsion andthen coated on a suitable support, set and 'dried in theusual manner. On exposure aIIdfd'CVGlOPIILBHlZEOfTfl'fi emulsion witha developingsolir tion employing Z-aminoeidiethylaminotoluene as the de I veloping agent and'subsequent removal of-' silven'a yellow 75' image was obtained.

Compound was treated with alcoholic KOH to convert the di-ester into the corresponding potassium salt. The salt was dissolved in alkali and methanol and added to a silver-halide emulsion according to the procedure of U.S. Patent 2,186,849.

Various photographic developing agents can be employed with the couplers of our invention. The primary aromatic amino developing agents are generally suitable including the phenylenediamines and aminophenols. Suitable compounds are 4-aminoaniline, 4-ethylaminoaniline, 4-dialkylaminoaniline, e.g., 4-dimethylaminoaniline, 4-diethylaminoaniline, 4-[N-(p-hydroxyethyD-N- ethyl] aminoaniline, 4 amino N-ethyl-N-(fi-methanesulfonamidoethyl)-2-methylaniline sulfate, and the like. The above developing agents are preferably used in the form of their salts such as the hydrochloride or hydro sulfate as they are more soluble and stable than the free bases. All of these compounds have a primary amino group which enables the oxidation product of the developer to couple with the color compounds to form dye images. After removal of the silver image by bleaching and fixing in a manner well-known to the art, the color image remains in the emulsion.

A suitable developing solution can be prepared as follows:

G. 2-amino-5-diethylaminotoluene 2 Sodium carbonate (anhydrous) 20 Sodium sulfite (anhydrous) 2 Potassium bromide 0.2

Water to make 1 liter.

The exposed silver-halide emulsions containing the color formers are developed in the above solution in the usual manner.

It will be understood that the examples and modifications set forth herein are illustrative only and our invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A silver-halide emulsion containing a coupler compound of the following general formula:

Z A-CONH ROOC COOR wherein A is an organic color forming residue of the type capable of color coupling with the oxidation products of a primary aromatic amino silver halide developing agent, said color forming residue having a grouping selected from the class consisting of a l-hydroxy-Z-phenyl group, 1-hydroxy-2-naphthyl group and a benzoylmethylene group; X is selected from the class consisting of CO-- and --SO Z is selected from the class consisting of hydrogen, halogen, lower alkyl, lower alkoxyl and an arcmatic hydrocarbon radical of the benzene and naphthalene series; R and R are selected from the class consisting of hydrogen, lower alkyl, an alkali metal, ammonium and Alk is an alkyl group of from to 18 carbon atoms.

2. The article as defined in claim 1 wherein the organic color forming residue A is a l-hydroxy-Z-phenyl group.

3. The article as defined in claim 1 wherein the organic color forming residue A is a benzoylmethylene group.

4. The article as defined in claim 1 wherein the organic color forming residue is a l-hydroxy-Z-naphthyl group.

COOCH;

6. A silver-halide emulsion containing a coupling compound of the following formula.

C O O CH: C") (ilisHu C-N O OCH:

1 N-H (i=0 7. The method of producing a colored photographic image in a silver-halide emulsion layer which comprises exposing the layer and developing said layer with a primary aromatic amino developing agent in the presence of a coupler compound of the following formula:

Z A-CONH ROOC COOR' wherein A is an organic color forming residue of the type capable of color coupling with the oxidation products of a primary aromatic amino silver halide developing agent, said color forming residue having a grouping selected from the class consisting of a l-hydroxy-Z-phenyl group, l-hydroxy-Z-naphthyl group and a benzoylmethylene group; X is selected from the class consisting of CO- and -SO Z is selected from the class consisting of hydrogen, halogen, lower alkyl, lower alkoxyl and an aromatic hydrocarbon radical of the benzene and naphthalene series; R 'and R are selected from the class consisting of hydrogen, lower alkyl, an alkali metal, ammonium and Alk is analkyl group of from 10 to =18 carbon atoms.

8. A photographic emulsion for forming colored images comprising a gelatino silver-halide emulsion having incorporated therein a coupling compound of the following formula:

C O O CH! 0 raHn SOs-N- 9. A photographic emulsion for forming colored images comprising a gelatino silver-halide emulsion hav- 1'1? 7' 12 Mg incorporated 'therein-a' coupliiagcompound o'f the fdl- RfrencesrCite-drin thezfile'of this patent lowmg formula UNITED STATES PATENTS 0 018B" fi 2,186,849 Wilmanns et a1 Jan. 9, 19,40 n 1, 2,498,466 Thompson Feb. 21, 19 50: 7 2,652,329 McCrossen et a1 Sept. 15, 1953 2,657,134 Graham et a1. Oct. 27, 1953. OOOH:

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2186849 *Aug 5, 1936Jan 9, 1940Agfa Ansco CorpManufacture of photographic silver halide emulsions
US2498466 *May 9, 1946Feb 21, 1950Gen Aniline & Film CorpPhenolic color formers
US2652329 *Jul 31, 1952Sep 15, 1953Eastman Kodak CoColor couplers containing isophthalic acid radicals
US2657134 *Dec 5, 1951Oct 27, 1953Eastman Kodak CoPhotographic emulsion with colored couplers containing isophthalic ester groups
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3226230 *Oct 31, 1960Dec 28, 1965Gevaert Photo Prod NvLight-sensitive emulsions containing non-migratory n-substituted 1-hydroxy-2-naphthamide color couplers
US3419564 *Mar 30, 1964Dec 31, 1968Basf AgProduction of bis(1-arylureido)-benzene-p- or m-dicarboxylic acid dialkyl esters
US4250251 *Jul 11, 1979Feb 10, 1981Eastman Kodak CompanyCoupler solvent particles for forming a microcrystalline dye having broadened infrared absorption spectra
US7566790Jun 10, 2005Jul 28, 2009Life Technologies CorporationChemically reactive carbocyanine dyes incorporating an indolium ring moiety that is substituted at the 3-position by a reactive group or by a conjugated substance
US7671214Feb 14, 2007Mar 2, 2010Molecular Probes, Inc.Modification of the indolium ring to permit a reactive group or conjugated substance at the 3 ring position unexpectedly mitigates the problems of quenching, difficulty in preparing, strong tendency to self-associate (stack); fluorescent dyes; biomarking; uniformity; intensity; photostability
US7790893 *Dec 20, 2005Sep 7, 2010Life Technologies Corporationincorporating indolium ring moiety substituted at 3-position improves spectral properties; for detection of ligands; hybridization probes
US7820824 *Feb 14, 2007Oct 26, 2010Life Technologies CorporationAs labeling reagents for a variety of biological applications
US7927830May 29, 2008Apr 19, 2011Life Technologies CorporationModified carbocyanine dyes and their conjugates
US8252932Oct 18, 2010Aug 28, 2012Life Technologies CorporationModified carbocyanine dyes and their conjugates
US8569506Jul 24, 2012Oct 29, 2013Life Technologies CorporationModified carbocyanine dyes and their conjugates
US8614302May 29, 2008Dec 24, 2013Life Technologies CorporationModified carbocyanine dyes and their conjugates
Classifications
U.S. Classification430/376, 562/457, 430/553, 560/45, 560/47, 430/557, 430/556, 562/435, 562/455, 430/388, 430/389, 560/13, 562/430, 430/552, 430/385, 562/833, 560/48, 564/86, 560/10, 560/21, 430/384
International ClassificationG03C7/32, C07K1/00
Cooperative ClassificationG03C7/3212, C07K1/006
European ClassificationC07K1/00B, G03C7/32B