Патент USA US2407210код для вставки
Patented Sept. 3, ‘1946 a‘ ‘ e ._ 2,407,210 UNITED STATES -. PATENT 'ZOFFlCE‘ ‘COLOR COUPLERS Arnold Weissberger, Charles J. Kibler, and Paul W. Vittum, Rochester, N. Y., assignors to East man Kodak Company, Rochester, N. Y., a cor poration of New Jersey ' No Drawing. 7 Application April 14‘, 1944, Serial No. 531,124 17 Claims. (Cl..95--6) " This invention relates to photography, and particularly to color-forming coupler compounds. tinctorial' power than. dyes produced from cou 3 plers having only the ortho alkoxy substituent in The formation of' colored photographic images by coupling the developmentproduct of aromatic the‘benzoyl'nucleusa A-combination of the al koxy group- in ‘the ortho-‘pos'itio'n‘in thee-phenyl ‘amino developing ‘agents with color-forming or 5 ring of the benzoyl group, with chlorine in the Coupling compounds is Well knoWrl- In these ortho position in the phenyl ring of the aniline processes the subtractive process of 00101‘ formation is ordinarily used and the image’ dyes are intended to be of the Complementary primary colors cyan or blue-green, magenta, and yelloW- 10 The couplers Which produce the cyan dyes are usually phenols or naphthols, those producing-the magenta dyes are Ordinarily pyrazolones or oyano grourx-thefefqre, produces; couplers which‘résult in the formation of yellow dyes of improved color or light absorption characteristics and having high tinctorial strength. The couplers them selves interfere with: the dye stability to, a cone siderably diminished degree, ‘ Compounds illustrating our invention are as fol acetyl compounds, and those producing theyelv- lows: low dyes are ordinarily compounds containing a 15 1 methylene group having two carbonyl groups at- - ' ‘ ‘ tached to it. The dyes produced by coupling are Q . azomethines; indamines or indophenols, depend: developer. ‘ ‘ . ' ‘ [F OCHa ing upon the composition of the coupler and of the ~ o‘ooneooNn 2‘ CH3 20 ' One ofcompounds, the disadvantages encountered with coupler particularly coupler com-v ‘ Q_COCHQC,ONH pounds which are incorporated in sensitive emul sions, is that the residual couplers in the emul- 3 ' 0 ‘ sion layer interfere with the stability of the dyes 25 ' QOOCHQOQNHONHCOGH'OGQE formed upon development. Many coupler-saris OCH 3 either unstable and subject to discoloration 1‘ ' 4. themselves or interfere with the stability of the dye formed in the layers in which the couplers are incorporated. ‘ H3 _oo'oneo0NH<:? . CH3l ‘ ‘ 30 NH ' 'OmfH'OfO-mm It is, therefore, an object of the present inven- CH3 tion to provide a novel class of photographic'cou- i ‘ 5' 'pler compounds. ~COOH2CONHONHCOCH-OO-O?ig A. further objectlis to provide‘ ‘ novel couplers which do not interfere with the stability of the dyes formed from them. I I (‘ma Other 35 6- ‘ objects will appear from the following descrip- ‘ 0001120ONH-ONHG‘O-CH-O-O-OEHU tion of our invention. $2115 These objects are accomplished according‘to’ our invention by the use as coupler compounds 7. 45 . . —GOOH2CONH—<:>—NHCOCH-O-O-CsHu 1y compounds having the following structure: OR . 1 00m of ortho-alkoxy benzoyl acetanilides, particular- 40 Q-COCHzOONH-R' ' ' 003mm) OCHS (‘3H3 8- CgooomooNH-Osm-NO-cm 0H3 “ (11m): where R is an alkyl radical and R’ is .an aromatic nucleus of the benzene series. ' 7 . . . . While benzoyl acetanilide couplers are well known, We have found. that benzoyl acetanilide couplers having an ortho alkoxy substituent. in 50 the benzoyl nucleus produce improved yellow 001ors upon color development. and interfere with the stability of the yellow dyes thus formed to a considerably less degree than the unsubstituted benzoyl acetanilides. We have also found that a 55 chlorine substituent in the ortho position in the aniline nucleus produces dyes having a greater ' 9 ‘ ' 10 “ . p l ‘ o0 omooNn Q one. ' Q 01 CH3 I ooomo ONH on, - o1 2,407,210 4 11. 22. coomc om: QooomcoNH-QNHcocmsooom SOaN-O-CH: CH: (13H: 01 CH: ‘The couplers used according to our invention with the exception of 20 and 22 are prepared by treating the appropriate amine with the appro priate o-alkoxybenzoylacetic ester. For exam ple, the coupler 21 is prepared as follows: 12. qoocmc ONH on. NHcooH-o-O-cm, 41H’ 1 1 ooorno om; 14. (‘1H1 1 15 -OOCH|CONH CHI N-[3-(2"-methoxybenzoy1acetamino)-4-chlorosu1fonyl]-N-(‘y-phenyl n-propyD-p-toluidme Oa-NOC] OCH; ’ C300 cmo oicim+mNCl ONO JIHI 1 1 soar-Q0113 —» CH: (CHM 20 somn 15- Qcocmcomr CH: "CE' co CHgOONHUSOgN-O-CHH-CQERO 011 (i?zh 1 16. QoocmwNHQmNH-O-O ' 17. ~CH: A 500 cc. three-necked ?ask ?tted with a stir rer, an addition funnel used for solids, and a 10" distilling column, was charged with 29 cc. (32 1 coomoomr 00H. - grams, 0.15 mole) of ethyl o-methoxybenzoyl oaNH-O-cmnc) ' 1 acetate and 60 cc. of bromobenzene. The flask was immersed in an oil bath maintained at 170 200°, stirring was begun, and 4'? grams (0.11 mole) 1' 18. Qcoomoomr CH: 19. of N-(3-amino-4-chlorobenzenesulfonyl) -N-('y phenyl-n-propyl) -p-toluidine was added portion NHsoOcm 1 wise during one hour. Alcohol distills and the temperature at the head of the distilling column remains at 75-80” until the reaction is complete. ‘ vCOOHaC ONHQSOaNG-CH: C 41H: CH: ' H: After a total reaction time of 1.5 hours, the tem 40 perature of the vapors dropped to ca. 60°. ‘The reaction mixture was cooled and diluted with 350 cc. of petroleum ether. The oil which separated crystallized when stirred for a short time. The CH: Cells yield of crude product amounted to 65.7 g., M. P. 45 99-101°. It was recrystallized twice from 500 cc. 20. 0 CH: > of alcohol; yield, 44 g. (66%), M. P. 119.5-122". Q0 O-CH-CONHP-SOr \cmcmonro CH: (In 21. Molecular weights 1 N/OCF“ cocmoomz? CH!cHICH:-<:> . 50 Ethyl o-methoxybenzoylacetate _________ __ 222 N-(3-amin0-4-chlorobenzenesulfonyl) -N ('y-phenylpropyl)-p-toluidine ________ __ 414.5 For \ 1 CHI _ . Product 55 590.5 The appropriate esters and amines are listed in the following table: ‘ Ester Coupler Amine Ethyl o-methoxybenzoylacetate ___________ -. Ethyl 2-methoxy-?amethylbeuzoylaoeta Aniline num ber _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ _ _. 2 li-P-(y-ten-butylphenoxy)propionamido aniline" Do ___________________________ _. _ 3- a-E?-ten-butylphenoxy)propionamido aniline“ Ethyl o-propoxybenzoylacetate__._ Ethyl o~methoxybenmylacetate____ Do ........................ _. 1 --___do Ethyl o-methoxybenzoylacetate._-. 3 4 . 4» c- 4’-ter.-butylphenoxy)propionamido aniline“ _ 4- a-E'Y-ten-amylphenoxy)butyramido]ani1ine__.__ ___ _ 5 6 4-[a- 4’-ter.-amylphenoxy)propionamidolaniline ______________ __ 7 Do ____________________________________ -. N 21(p-arninobenzenesulfonyl)-N-('y-phenyl-n- propyl) -p-tolui- 8 me. Do o-Chlomanilinn ____ Ethyl 2-methoxy-5-methylbenzoylacetate ____do Ethyl o-methoxybenmylacetate ______ __ Do ________________________ _- 4-amino-3-chlorobenzenesulfonmethyl- -toluide____ 4-[a-(4’rter.-butylphenoxy)propionami 01-3-ch10r0a Do.___ Do_-__ Do.__. Do..-. N-(4’-aminc-3-chlorobcnzensu1fonyl)-4-ter.amylani1ine_ . D0 .................................. __ 9 _____ _. 10 11 12 4—amino-3~chl0robenzenesu1fonmethyl-p-chlol'oanilide____ _ 4»amino~3-chlorobenzenesulfonmethylanilide _________________ __ 4-amino~3-chlorobenzenesulfon-p-toluide ________ __ 4-(4’-amino-B-chlorobenzeuesulfonamido)diphenyl. . ___ Do. Do. ___ _ I 13 14 15 16 17 4-(4’toluenesulfonamido)-2'chloroaniline _____________________ __ 18 N-(4~amino‘3'chlorobenzenesu1lonyl)-N-(y-phenyl-n-propyl)- i9 p-toluidine. ‘12,407,210 5 jCoupler '20 is prepared by chlorinating coupler 19 with sulfuryl chloride in chloroform solution. Coupler 22 is prepared by condensing 4(2’ methoXy-benzoylacetamino) 3-chloroaniline with acetylthioglycolyl chloride with a suitable con densing agent such ‘as sodium acetate or quinoline. Our couplers may be used in processes in which the coupleris incorporated in the developingsolu tion such as those described in Mannes and Godowsky U. S. Patent 2,113,329, granted April 5, 1938, or. Mannes, Godowsky and Wilder U. S. Patent 2,252,718,.granted- August 19, 1941, or may “the jiproduction of colored photographic images 'inllayers of gelatin or other water-permeable .col loidal'carriers, such as albumimcollodion organic esters of cellulose, or synthetic resins. The car rier may be supported by a transparentmedium such as glass,.a cellulose ester or synthetic resin or a non-transparent re?ecting medium such ‘as paper or an opaque cellulose ester. The emul sion may be coated as a single layer on the sup port or as superposed layers on one or both sides of the support. The superposed layers may be differentially sensitized and the dyes formed ,be incorporated in the sensitive emulsion layer therein by coupling may be bleached by ‘an oxi as described in Fisher U. S. Patent 1,055,155, dizing agent such as chromiclacid to. colorless Mannes and Godowsky U. S. Patent 2,304,940, 15 soluble compounds. The destruction of the dye granted December 15, 1942,»and J elley and Vittum in this way .doesnot destroy thesilver image and U. S. Patent 2,322,027, granted June 15, 1943. a silver image may be developed, bleached-and The following example illustrates a developing developed to color images in superposed layers solution containing a coupler according to our vas described, for example, in Mannes and Go invention: 20 .dowsky U. S.‘Patent No. 2,113,329. The examples and compounds set forth in the A. 2-amino-5-diethylamino toluene HCl present speci?cation are illustrative only‘and it 7 > ‘ grams__ 2 is to be understood that our invention is to be taken as limited only by the scope of the append-y 1 25 ed claims. We claim: 1 ‘ Sodium sul?te (anhydrous) ____-___do____‘ 2 ‘Sodium carbonate (anhydrous)___do____ 20 Potassium bromide _____________ __do___’_ Water to _____________________ __liters__ B. Orthomethoxy benzoyl acetanilide ' . grams“ Sodium hydroxide (10% solution)___cc__ (For use, B is added to A.) 2 10 30 - The foregoing example refers to the addition of. the coupler compound to the developing solution itself. The coupler may also be added to the emulsion layer. Inythe case of multilayer coat 35 ings, it is- desirable» to ‘provide means to prevent diffusion of the coupler and the adjacent layers. Also dispersing agents may be used for incorpo~ 1. A color-forming photographic ‘developer comprising a primary aromatic amino developing agent and an o-alkoxybenzoyl-acetanilide cou plercompo‘und. " , ' , , . i 2. A colorgforming “ photographic developer comprising a primary aromatic amino developing agent and a coupler compound having "the fol lowing probable formula: I I ' ' ' ‘ . Q00 ongo ONE-4R’ ' ‘ R rating the'coupler compound in the emulsion and in certain cases‘the coupler maybe absorbed or 40 where R is an alkylradical and .R’ is an aromatic adsorbed to the sensitive saltor may be combined nucleus of the benzene series. » , 3. A color-forming photographic developer with the sensitive salt as a chemical combina; tion. Certain of the-couplercom‘pounds described comprising a primary aromatic amino develop ing agent and a coupler compound having the above such as Nos. 3, 4, 5, 6, '7, 8, 1‘1, .12, .13, .14, 1'7, 19, 20 and 21, are} in themselves non-diffusing and ‘may be incorporated in the photographic following probable formula: Y ' layer without the use of additional agents ‘to pre vent di?‘usion. These couplers may also be ‘in corporated in the emulsion layer according to ‘the OR methods of Mannes and Godowsky U. S. .Batent 50 2,304,940 and Jelley and Vittum U. S. Patent where R is an alkyl radical and Y is an acid 2,322,027 referred to above. amide group. In the development of exposed photographic ‘ 4. A color-forming photographic developer silver halide emulsion layers using the couplers comprising a primary aromatic amino develop of our invention, any color-forming developer ing agent and .a coupler compound ‘having the containing a primary amino ‘group maybe used. followingprobable formula: ‘ These include developers having two primary amino groups as well as those having one of the I amino groups substituted orhaving substituents in the ring, such‘as the alkyl phenylene di'amines. 60 These compounds are usually used in the salt form, such as the hydrochloride or the’ sulfate which are more stable than the amines them selves. The suitable compounds are diethyl-p phenylenediamine hydrochloride, monomethyl--p phenylenediamine hydrochloride, dimethyl-p phenylene-diamine hydrochloride, and Z-arnino 5-diethylaminotoluene hydrochloride. Th'e ,p~ amino phenols and their substitution products oR ‘ Y or where R is an alkyl radical and Y is an .acid amide group. . ' 5. A color-forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound having .the fol lowing probable formula: ' ‘ Q00 omoonnQ-soat-iv may also be used where ‘the amino group is un 70 substituted. All of these developers have an un-' '0 CH3 substituted amino group which enables the oxida tion products of the developer to couple with the .where R’ is an aromatic nucleus of the benzene color-forming compounds to form a dye image. series, and X is selected from the class consist . Our development process may be employed for . I 01 ing of hydrogen, alkyl, and aralkyl groups. ‘ v. 2,407,210 8 7 developing agent in the presence of a coupler compound having the probable formula: 6. A color-forming ‘photographic developer ‘comprising a primary aromatic amino developing agent and a coupler compound having the fol lowing probable formula: QooomooNHQeomE-R' Q-o 0 011,0 ONHQ-SOzNH-R 0 H3 ' CH 5 C1 where R’ is an aromatic nucleus of the benzene series. 01 where R is an aromatic nucleus of the benzene 13. A photographic emulsion for forming col 10 series. ored images comprising a water-permeable, col 7. The method of producing a yellow photo loidal carrier containing a sensitive silver halide graphic image in a gelatino-silver halide emul and a coupler compound having the probable sion layer, which comprises exposing said layer formula: and developing it with a primary aromatic amino developing agent in the presence of an o-alkoxy 15 benzoyl-acetanilide couplerv compound. CFC o omo ONH-R' 8. The method of producing a yellow photo R graphic image in a gelatino-silver halide emul— Where R is an alkyl radical and R’ is an arc sion layer, which comprises exposing said layer and developing it with a primary aromatic amino 20 matic nucleus of the benzene series. 14. A photographic emulsion for forming c01 developing agent in the presence of a coupler ored images comprising a water-permeable, col compound having the probable formula: loidal carrier containing a sensitive silver halide and a coupler compound having the probable for " QCOCHzCONH-R’ OR 25 mula: , Y where R is an alkyl radical and R’ is an aro matic nucleus of the benzene series. 9. The method of producing a yellow photo OR graphic image in a gelatino-silver halide emulsion 30 where R is an alkyl radical and Y is an acid layer,.which comprises exposing said layer and amide group. developing it with a primary aromatic amino de 15. A photographic emulsion for forming col veloping agent in the presence of a coupler com ored images comprising a water-permeable, col pound having the probable formula: 35 loidal carrier containing a sensitive silver halide and a coupler compound having the probable for Y QCOCIEHCONHU mula: Y R Q0 0 011,0 ONH—< Where R is an alkyl radical and Y is an acid 40 amide group. 10. The method of producing a yellow photo graphic image in a gelatino-silver halide emul ; 1 OR where R is an alkyl radical and Y is an acid amide group. sion layer, which comprises exposing said layer 16. A photographic emulsion for forming col and developing it with a primary aromatic amino 45 ored images comprising a water-permeable, col developing agent in the presence of a coupler loida1 carrier containing a sensitive silver halide compound having the probable formula: and a coupler compound having the probable for mula: Y Q0 0 CH2C ONHQ OR 01 Where R is an alkyl radical and Y is an acid amide group. 11. The method of producing a yellow photo graphic image in a gelatino-silver halide emul sion layer, which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the probable formula: Q00 0113c ONHQ-iIOni-RI OCH; Cl where R’ is an aromatic nucleus of the benzene series, and X is selected from the class consist ing of hydrogen, alkyl, and aralkyl groups. 12. The method of producing a yellow photo graphic image in a gelatino-silver halide emulsion layer, which comprises exposing said layer and developing it with a primary aromatic amino X 50 Q-oo c1120 oNHQsmn-R' on; or where R’ is an aromatic nucleus of the benzene series, and X is selected from the class consist ing of hydrogen, alkyl, and aralkyl groups. 1'7. A photographic emulsion for forming col ored images comprising a water-permeable, col 60 loidal carrier containing a sensitive silver halide and a coupler compound having the probable for mula: QoooniooNn©-somn_nr OCHa Cl where R’ is an aromatic nucleus of the benzene series. ARNOLD WEISSBERGER. CHARLES J. KIBLER. PAUL W. VI'ITUM.