US3733201A - Photographic compositions and elements comprising coupling compounds which on development release silver halidecomplexing materials and dyes - Google Patents

Abstract

A NOVEL CLASS OF SELENIUM AND TELLURIUM ORGANIC ETHER PHOTOGRAPHIC COUPLER COMPOUNDS HAVING UTILITY IN THE COLOR PHOTOGRAPHIC AREA, SUCH COMPOUNDS CONTAINING A RELEASABLY LINKED ORGANIC RADICAL ATTACHED AT A COUPLING SITE BY A DIVALNT SELENIUM OR TELLURIUM ATOM, PHOTOGRAPHIC EMULSIONS, DEVELOPING COMPOSITIONS AND PHOTOGRAPHIC ELEMENTS CONTAINING SUCH COMPOUNDS AS WELL AS A PROCESS FORDEVELOPING THE EXPOSED PHOTOGRAPHIC ELEMENTS.

Description

United States Patent Ofice 3,733,20l Patented May 15, 1973 U.S. Cl. 96--100 40 Claims ABSTRACT OF THE DISCLOSURE A novel class of selenium and tellurium organic ether photographic coupler compounds having utility in the color photographic area, such compounds containing a releasably linked organic radical attached at a coupling site by a divalent selenium or tellurium atom, photographic emulsions, developing compositions and photographic elements containing such compounds as well as a process for developing the exposed photographic elements.

The present invention relates to a new class of seleniumor tellurium-containing organic compounds of the ether type having utility in the photographic area. In particular, this invention relates to new color photographic coupler compounds, also photographic elements, photographic emulsions and developing compositions containing one or more of such compounds.

By way of background, colored photographic images are obtained in the photographic art by coupling a silver image development by-product (i.e., oxidized primary arornatic amino developing agents) with a color-forming coupler compound. The subtractive process of color formation is ordinarily employed and the resulting cyan, magenta or yellow image dyes are complementary to the primary colors. Coupler compounds employed to produce cyan photographic dyes, for instance, generally contain phenolic or u-naphtholic moieties, while S-pyrazolone-type couplers produce magneta, and open-chain ketomethylene couplers produce yellow dyes. A majority of color photographic couplers of the above types are known and described as four-equivalent couplers and are characterized in requiring the development of four light-exposed silver halide molecules in order to ultimately produce one molecule of dye.

A somewhat more efficient reaction is obtained through the use of so-called two-equivalent couplers in which non-chromophoric coupling off groups are substituted in coupling position. Such couplers are functionally characterized by requiring the development of only two exposed silver halide molecules during development to obtain one molecule of dye. Known two-equivalent couplers and methods for their utilization are disclosed, for instance, in U.S. Pats. 3,458,315 and 3,277,155 of Loria and Loria et al. respectively. The above type compounds may be either ditfusible (i.e., introduced into a color photographic system along with the color developer), or non-ditfusible (i.e., originally incorporated into a photographic element or material as part of or contiguous with an emulsion layer).

In addition to the amount of silver and general reactivity of a coupler, consideration must be given to other characteristics such as the color balance, contrast, grain size and general sharpness of the resulting photographic image. To a great extent, this problem is directly correlated to the amount and nature of development inhibitor releasing (DIR) couplers present in the system. In addition to producing dye, such self-regulatin g couplers contain releasable organic groups in the coupling position which are made functionally active for color photographic purposes when split off upon coupler reaction with oxidized developer. Such compounds are exemplified, for instance, by U.S. Pats. 3,265,506 of Weissberger et al. and U.S. Pat. 3,227,554 of Barr et al. A further type of coupler is the so-called image transfer coupler in which the releasable radical attached to the coupling position of a coupler compound is in itself a diifusible dye or dye precusor which is released upon reaction of the coupler and may thereafter be mordanted onto a receiving layer as a color image. Examples of such couplers are described, for instance, in U.S. Pats. 3,227,554 and 3,227,551 of Barr et al.

In addition to the above, modern photographic products and the underlying technology require a number of important ancillary characteristics. It is desirable, for instance, to utilize readily soluble couplers requiring minimal amounts of the higher-boiling organic coupler solvents and thereby obtain thinner and more durable photographic elements. In addition, the coupler should be stable and produce stable photographic dyes having precise spectral absorption characteristics upon reaction with oxidized developer. It is also important that non-diffusible couplers of the above types be precisely and homogeneously incorporated into a silver halide emulsion without adversely affecting emulsion viscosity, adhesion characteristics, or the unity of any particular emulsion layer during modern high speed multilayer application onto a film backing.

Undesired changes in viscosity of a melted gelatin photographic emulsion may be particularly troublesome when Fischer-type couplers (ref. U.S. Pat. 2,186,849) are utilized. Undesirable changes may also be caused by additives such as wetting agents, color components, etc.; such changes are capable of directly affecting the coating characteristics of the photographic emulsion. This fact is indicated, for instance, on page 250 of the text by Zelikman and Levi, entitled Making and Coating Photographic Emulsions, The Focal Press (1964).

Including antihalation and gelatin interlayers, up to eight or more separate layers may be applied to a film base to obtain a modern color photographic element (ref. Kirk- Ohmer, vol. 5, pages 812-845, Encyclopedia of Chemical Technology (1950). For this reason, major couplerinduced changes in the adhesion or coating characeteristics of a photographic layer may well be unacceptable.

In addition, the order of application of a coupler-containing layer in such an element it also important, depending upon the absorption properties of the particular dye to be obtained. For this reason, the optima spectra of characteristics for present day yellow, cyan and magenta dye-producing couplers may substantially differ.

The above-listed characteristics are not necessarily compatible or may otherwise be matched by disadvantages, since the color photographic technology of recent years is complex and functionally interrelated. In fact, some coupler characteristics considered advantageous in earlier photographic art may now even be considered undesirable. Moreover, with few exceptions, it is not possible to predict a particular desirable combination of functional coupler characteristics from molecular structure alone.

To ascertain suitable couplers for modern color photographic purposes, it is necessary to find which particular group of substituents favor a minimal number of undesirable characteristics while, at the same time, encourage a preconceived spectrum of favorable characteristics.

Thus far, the known prior art has completely failed to provide any realistic basis for associating selenium or tellurium ether derivatives of known couplers such as the yellow, etc., dye formers with a satisfactory spectrum of characteristics of the above type, or even suggest reactivity with oxidized developer to form dyes and to effect a controlled image formation.

3 In British Pat. 503,752, a single diffusible diphenyl selenide compound is listed as a coupler precursor, but the selenium atom and attached organic radical are not attached in the coupling position and there is no reason to assume that the moiety would be released as a result of a coupling reaction or effect control of image formation.

In U.S. Pat. 3,227,554, there is listed a class of coupler compounds which are substituted in the coupling position by a variety of displaceable sulfur-connected radicals. These compounds are not structurally or functionally equated to selenium or tellurium ethers of the present type.

U.S. Pat. 2,437,062 also fails to suggest the functional advantages in using thioalkyl or selenoalkyl substituents on the coupling position for controlled coupling reaction in addition to the above-listed ancillary advantages.

In U.S. Pat. 3,227,550, a number of linking groups inclusive of S-, -O-, -SS and N=N are utilized to attach various organic radicals to known coupler compounds. Here again, however, there is no indication of the functional properties of corresponding selenium or tellurium ethers.

It is an object of this invention to obtain a new class of selenium and tellurium ethers.

It is another object of this invention to provide novel photographic elements and processes using such ethers as color couplers capable of reacting with oxidized color developing agent to form photographically active selenide or telluride compounds as well as dyes.

It is another object of this invention to provide new photographic elements and processes using new photo graphic color couplers that release diffusible development inhibitors on reaction with oxidized photographic color developing agents.

It is a still further object of this invention to provide a new method for controlling contrast, grain, size and sharpness in processing photographic silver halide emulsions.

It is also an object of this invention to provide novel photographic elements useful for preparing positive color images within the diffusion transfer area.

It is another object of this invention to provide novel photographic elements containing selenideor tellurideforming couplers useful for color correction purposes.

It is likewise an object of this invention to provide a novel method for processing black and white emulsions.

It is an additional object of this invention to provide photographic elements containing novel photographic couplers that release silver halide complexing materials as well as dyes when reacted with oxidized photographic color developing agents.

These and other objects of the invention are attained with selenideor telluride-releasing couplers having the general formula wherein:

COUP represents a color photographic coupler moiety capable of reacting with oxidized color developing agent, such as an oxidized aromatic primary amino color developing agent to form a dye and to split off the XR group, wherein X represents a divalent selenium or tellurium atom substituted in a coupling position of COUP; and R is an alkyl, an aryl, or a heterocyclic group linked to X at a carbon atom. More specifically, compounds of interest within the present invention consists of a class defined by Formula 1, supra, in which the radical, COUP, is a color photographic coupler moiety such as a 5-pyrazolone magenta dye-forming coupler moiety, a phenolic or an anaphtholic cyan dye-forming coupler moiety, or an openchained ketomethylene yellow dye-forming coupler moiety, the divalent seleno or telluro group (-X-) being generally attached at the #4 ring position on the 5- pyrazolone and the phenolic or the a-naphtholic rings, or attached onto the active oc-methylene moiety 0 i P3CH2- *Denoting the coupling position.

of an open-chain yellow dye-forming ketomethylene coulet.

p A wide variety of organic groups or radicals are found suitable in defining the R radical of Formula 1, it being required, however, that R does not itself couple with oxidized color developing agent to form a dye. Preferably, R is an alkyl radical (generally an alkyl radical having up to about 30 carbon atoms) such as methyl, hexyl,-octadecyl, eicosyl, 4-methylpentyl or the like aliphatic alkyls as well as cycloalkyls generally having 5 to 6 carbon atoms like cyclohexyl or cyclopentyl; an aryl radical exemplified by a phenyl or a naphthyl group and including the alkyland/or alkoxy-substituted aryl having 1-20 carbons; or a carbon-containing heterocyclic group having a 5- to 6-membered heterocyclic nucleus ring with at least one hetero-nitrogen, oxygen or sulfur atom, and preferably containing 1 to 4 hetero-nitrogen atoms. Further suitable substituents for such aryl or heterocyclic radicals include, for instance, nitro, chloro, alkyl, alkylamido, alkoxy, alkylsulfoamido, -chloroacetylthio, alkylcarbamyl, amino, and the like. Examples of suitable heterocyclic groups include, for instance, a tetrazolyl, triazinyl, triazolyl, oxazolyl, oxadiazolyl, diazolyl, thiazyl, thiadiazolyl, benzoxazolyl, benzotriazolyl, benzothiazolyl, pyrimidv pyridinyl or a quinolinyl group.

By utilizing additional ballasting and solubilizing groups, corresponding seleniumand tellurium-containing couplers suitable for a wide variety of purposes can be prepared. For instance, the couplers can be either nondilfusible and initially incorporated into an emulsion layer, or diffusible and introduced into a photographic element after exposure as part of an aqueous alkaline photographic processing composition. Similarly, the selenide or telluride or the dye formed on reacting the subject couplers with oxidation product of color developing agents can be made either dilfusible or non-diffusible, or soluble in aqueous alkaline photographic processing compositions. The nature of the ballasting and solubilizing groups used on the COUP moiety or the R moiety of Formula 1 can be widely varied. Usefully included among the substituents favoring non-diffusibility are bulky organic moieties such as alkyl radicals or groups of alkyl radicals typically not less than about 14 and preferably about 14- 30 or more carbon atoms. Also includable are solubilizing groups such as acidic groups exemplified by carboxyl, sulfonyl, ionizable sulfonamido and hydroxyl-substituted groups which lend negative charges to the moieties being solubilized.

Various functional or potentially functional groups are conveniently attached together with the Se or -Tegroups onto the coupling position of the COUP moiety and released upon coupler reaction with oxidized developer. For example, 4-substituted compounds within the scope of Formula 1 can be usefully incorporated into an emulsion layer of a photographic element or contiguous thereto for improving sharpness and minimizing grain size in color photographic images. Such compounds generally favor a definition of R as a heterocyclic group. Other compounds includable within the definition of Formula 1 are dye-producing two-equivalent couplers, Where the substituent R group is a non-chromophoric aryl or alkyl group and will not react with oxidized de veloper to form a dye. Also included within the present invention are compounds which utilize an R group which is itself a diffusible dye or dye precursor.

Useful RX- groups of the above types include the alkylcarbamylphenyl selenide or telluride and, desirably,

the 3-alkylcarbamylphenyl derivative thereof in which the alkyl moiety has about 6 to 22 carbon atoms, exemplified by 3-hexylcarbamylphenylor 3-octadecylcarbamylphenyl-selenide or telluride; 1-phenyl-5-tetrazolylor nitrophenyl-selenide or telluride such as the Z-nitrophenyland 4-nitrophenyl-selenide or telluride; also aminophenyl such as the 2-aminophenyl-, 4-aminophenyl-selenide or telluride, or the Z-benzothiazolyl and 5-phenyl-1,3,4- oxadiazolyl-Z-selenide or telluride derivatives.

For purposes of the above general description and as hereinafter used, it is understood that the term nonditfusible as applied to couplers and products derived from couplers has the meaning commonly applied to the term in color photography, denoting materials which for all practical purposes do not migrate or wander through a photographic hydrophilic colloid layer, such as gelatin, particularly during processing with aqueous alkaline solutions. The same meaning is also attached to the term immobile, while the terms dilfusible and mobile have the converse meaning.

Preferred couplers within the present invention are further conveniently described in the following formulae: (2) SOLCOUP'-X-R' wherein:

X is defined as above;

COUP is a color photographic coupler moiety defined as COUP in Formula 1;

BALL represents at least one photographically inert organic ballasting group, such ballastiug group being further defined as having a molecular size and configuration to render the coupler non-diffusible in a color photographic element exposed to alkaline color developing solution;

SOL is either a hydrogen atom or an acidic solubilizing group (i.e., when the coupler is developed in the presence of a photographic alkaline color developing composition containing an aromatic primary amino color developing agent having an acidic solubilizing agent), SOL always being defined as the latter when a color developing agent free of any acidic solubilizing group is utilized;

R can be an alkyl group having 1 to 13 carbon atoms, an unballasted aryl group such as phenyl or naphthyl, or an unballasted carbon-containing heterocyclic group with at least one heteronitrogen, -oxygen, or sulfur atom and as defined above for R;

R" can be a ballasted organic radical including an alkyl group having at least 14 carbon atoms, preferably about 14-30 carbon atoms, an aryl group inclusive of a sub stituted phenyl or substituted naphthyl group or a carbon-containing ballasted heterocyclic group with at least one hetero-nitrogen, -oxygen or -sulfur atom. R adds ballast and non-diifusibility to the R-X-- moiety that splits otf when reacted with oxidized color developing agent.

The couplers described above in 'Formula 2 are diffusible couplers of the type suitable for use in developing compositions; such compounds release ditfusible dyes plus the indicated selenide or telluride group upon reaction with oxidized color developing agents.

The coupler of Formula 3, however, is a non-difiusible coupler of the type initially incorporated into a photographic element and which forms a non-diffusible dye and a ditfusible selenide or telluride compound in the presence of oxidized color developing agent. Couplers of Formula 4, on the other hand, are non-dififusible couplers of the type utilized in photographic elements which form diffusible dyes and non-ditfusible selenides or telluride compounds upon reaction with oxidized color developing agent. The ditfusible selenide or telluride compounds formed when couplers of Formulae 2 and 3 are reacted with oxidized color developing agents can be used as development inhibitors for silver halide to improve such properties as sharpness of image. The diffusible dyes formed when couplers of Formula 4 are reacted with oxidized color developing agents can be used in color diffusion transfer processing of the type disclosed in Whitmore et al. US. Pat. 3,227,550.

Particular compounds within the present invention are also conveniently described in accordance with the formulae R3XNAOLCONA NAOL and PHOL are defined as cyan dye-forming photographic coupler moieties respectively of the a-naphthol and phenol type having at least the two indicated substituent groups directly attached onto the a-naphthol or phenol ring, wherein X is a divalent selenium or tellurium atom;

R is an alkyl group having about 1-30 carbon atoms and particularly a lower alkyl having about 1-8 carbon atoms such as methyl, isopropyl and octyl; an aryl group such as a phenyl or a naphthyl group, in cluding substituted aryl such as an arylazophenyl, an alkylphenyl, an alkoxyphenyl and corresponding naphthyls; or a heterocyclic group containing at least one oxygen, sulfur or nitrogen atom such as a tetrazolyl, triazinyl, oxazolyl, oxadiazolyl, diazolyl, thiazyi, thiadiazolyl, benzoxazolyl, benzotriazolyl, benzothiazolyl, pyrimidyl, pyridinyl, oxazinyl, morpholino, or a quinolinyl group which definitions include one or more substituent groups such as a nitro, halo, including chloro, also aryl groups such as phenyl, an alkyl having up to about 20 carbon atoms, alkylamido such as methyl or butyl carbonamido, an alkylcarbonamido phenyl, including phenoxy-lower alkylcarbonamido groups such as meta-alkyl phenoxy lower alkyl groups, alkoxy, alkylsulfonamido, an alkylcarbamyl wherein the alkyl moieties preferably contain up to 20 carbon atoms, and an amino group. Of particular interest is the definition of R as a tetrazolyl group inclusive of a 5-phenyl-, 5-alkylcarbonamidophenyl-, or 5-alkylphenoxyalkylcarbonarnidophenyltetrazolyl substituent;

R is a hydrogen atom or an alkyl group, including an alkyl group having about 1-20 carbon atoms such as methyl, butyl, octadecyl, isopropyl or eicosyl;

A is defined as an alkyl group preferably alkyl having up to about 22 carbon atoms including secondary or tertiary alkyls, also including a substituted alkyl group such as an aryloxy alkyl group demonstrated by a phenoxy alkyl, an alkylphenoxyalkyl, a dialkylphenoxyalkyl, or a corresponding naphthoxyalkyl. A is also usefully defined as an aryl group such as a phenyl or a naphthyl group inclusive of a substituted aryl such as an alkylphenyl, an alkylnaphthyl, an alkoxyphenyl and a carboxy-substituted phenyl group; the

and

s I ICOA substituent groups of Formulae 5 and 6 being attached onto the No. 2 ring carbon and the -X-R substituent 7 group attached onto the No. 4 ring carbon of NAOL and PHOL;

PY of Formula 7 is defined as a magenta dye-forming 5- pyrazolone photographic coupler moiety containing at least three substituent groups attached onto the pyrazolone ring, of which Ar is defined as an aryl group such as a phenyl or a naphthyl group, including substituted phenyl or naphthyl moieties, such as a chlorophenyl (Ex.: trichlorophenyl), an alkylcarbonarnidophenyl inclusive of substituted alkyl moieties such as a phenoxy lower alkylcarbonamido group, also an arylcarbonamidophenyl such as a phenylearbonamidophenyl group inclusive of one or more substituents promoting solubility such as a carboxy, sulfo, or corresponding salts thereof exemplified by sodium sulfophenylcarbonamidophenyl;

R of the -XR group is an alkyl having up to about 30 carbon atoms, and preferably a lower alkyl of 1-8 carbons such as methyl, isopropyl or octyl, an aryl group such as a phenyl or a naphthyl group, inclusive of an alkylcarbamylphenyl group, or a substituted phenyl or naphthyl having an attached chromophoric group containing radical such as an arylazophenyl group, or a heterocyclic group such as defined above for the R group in Formula 1; and

R is defined as an alkylcarbonamido group inclusive of one having an alkyl moiety of up to about 30 carbons, particularly a lower alkyl of 1-8 carbons and substituted alkyls demonstrated by an aryl-oxyalkyl-, such as phenoxy lower alkyl or an alkylphenoxy lower alkyl group attached onto the carbonamido moiety, R also includes an alkoxy group having up to about 22 carbon atoms such as methoxy, isopropyloxy, or octadecyloxy, an amino group including substituted amino such as an aryl amine exemplified by a phenyl amine, a naphthylamine and a carboxyphenylamine; as a 5-6- membered nitrogen-containing heterocyclic group which can be attached to PY by a nitrogen atom such as a pyrrole group; and R is additionally defined as an aryl carbonamido group such as a phenyl or substituted phenylcarbonamido group of the formula --NHCO-Ar in which Ar is defined as above;

In Formula 8,

A is usefully defined as an alkyl group of 1-22 carbon atoms including a secondary and tertiary alkyl such as methyl, isopropyl and eicosyl, an aryl group demonstrated by a phenyl or a naphthyl group such as phenyl and naphthyl, also inclusive of a substituted aryl such as an aryloxy alkylcarbonamidophenyl or an alkyl-substituted aryloxy alkylcarbonamidophenyl;

Ar is defined as an aryl group such as a phenyl group or a naphthyl group including substituted aryl exemplified by an alkyl carbonamidophenyl, an aryloxyalkylcarbonamidophenyl such as a phenoxyalkylcarbonamidophenyl, an alkoxyphenyl, an N-alkyl-, or a N,N-

dialkyl-sulfonamido substituted phenyl; and R is an aryl group exemplified by a phenyl group or a naphthyl group and including substituted aryl such as an alkylphenyl inclusive of a carboxy alkylphenyl, an arylazophenyl group, and a heterocyclic group as defined for R (supra) containing at least one nitrogen atom and at least one carbon atom, such as a S-tetrazolyl group or a benzothiazolyl group.

Compounds within the present invention are conveniently obtained, for instance, in accordance with the general equation NAOLOONlI-A H202 I:

I-NAOL-UONi-t-A 11 0;

Ra-X-NAO L-C O NII-A wherein I- and R X are attached to NAOL in the No. 4 coupling position and X, NAOL, A and R are defined as above. Suitable reactions of general applicability are also demonstrated with respect to Couplers XV, XXXI and XXXV as follows:

SYNTHESIS l (COUPLER XV) Oil CONHQ A 100i +N IN OCnHz I acetone N: l I

I out!" A 1 N= (XV) A stirred suspension of 0.5 g. (0.00082 mole) of l-hydroxy 4 iodo-N-[o-tetradecyloxyphenyl]-2-naphthamide (obtained from the corresponding 2-carbamyl-a-naphthal by oxidative iodination with H 0 and Iodine); plus 0.21 g. (0.00083 mole) of potassium-l-phenyltetrazolyl- 5-selenide, and 0.12 g. (0.00007 mole) potassium carbonate are heated to reflux in 100 ml. dry acetone. After one hour the reaction mixture is cooled and Water added to dissolve the potassium carbonate. Acidification with diluted hydrochloric acid produces a white precipitate which is collected and dried (M.P. 3690 C.). The resulting product is then recrystallized from ethanol (M.P. 95- 96 C.), and identified as Coupler XV.

SYNTHESIS II (COUPLER XXX!) M n r- S Tetrahydrofurano A Solvent N N-CaHr i I? N N N N o=o c-N s SeSe- +3n1 N-N N-N e E lam 473 15 N N-QH,

N=N (XXXI) I 0.6 mole of the above 1-phenyl-5-selenotetrazole (ob- Coupler I tained by reacting chloro-1-phenyl tetrazole with hydro- H gen selenide in an alcohol reaction solvent at room tem perature) is admixed, in the presence of K CO with .02 'H M Q mole of the 4-iodo pyrazolone reactant (obtained by reacting the corresponding unsubstituted pyrazolone with CHwt iodine in the presence of KI in alkaline solution as de- 5' scribed, for instance, in Weissberger Pyrazolones, Pyrazolidones and Derivatives," page 81 (1964), and in Chemical Abstracts 44 1490 (1950), in tetrahydrofuran reac- 1 tion solvent and stirred for 2 hours). The reaction product is filtered, the filtrate concentrated and added to eth- Coupler II anol, and then refiltered. The second filtrate is added to ligroin to obtain a yellow solid (M.P. 134-l36 C.) on

identified as Coupler XXXV. This product couples to CONHwHmO CHwt produce the expected magenta dye. For the above pur-- pose, the 4-unsubstituted pyrazolone precursor is con- HM veniently obtained by reacting pyrrolidine with a suitable 1-p-nitrophenyl-pyrazolone, hydrogenating the resulting 3- pyrrolidino-S-pyrazolone with palladium catalyst to obtain the amine, and reacting this intermediate with u-(2,4- di-tert.-amylphenoxy) butyryl chloride in acetontrile as described, for instance, in Belgian Pat. 747,827.

SYNTHESIS III (COUPLER XXXV) (CHaCN) (CHa)aCCOCHCO-NH 051M N 1;:

N=N (XXXV) About 13.7 gm. (.05 mole) of the potassium salt of phenyl selen-o tetrazol is admixed with gm. (.05 mole) of a-chloro a (pivalyl-5-[2,4 di tert.-amylphenoxy) OH butyramido] 2- chloroacetanilide (obtained by conventional chlorination of Compound 10 of US. Pat. 3,265,- CONHQ 506 with sulfuryl chloride). After 2 hours an insoluble F KCl by-product is filtered otf and the oily filtrate concentrated by evaporation. After treatment with ligroin, there Se is obtained a light yellow solid identified as Coupler XXXV and having a MP. of 72-76 C. This product gave the expected yellow dye when reacted with 4-amino-N- t ethyl, N-hydroxy ethyl aniline. NHCO OiHn SYNTHESIS IV Corresponding tellurium analogs of couplers XV, XXXI and XXXV are also conveniently obtained in the above- 011 described manner.

A suitable preparation for compounds of Formulae 1-6 CONE is also described in detail in the copending concurrentlyfiled US. patent application Ser. No. 185,833 by H. W.

Cressman entitled Synthesis of 4-Thioether Naphthoic 7 'ie Couplers.

Compounds of the above-described types within the N scope of the present invention are further exemplified as follows: NBC 0 08H Coupler III Coupler IV Coupler V 011 Gun" Co H OOH Coupler VI OH 0 1131 00 OH CON I 'I"e C4110 Coupler VII OH C O OH C OOH ?a 0 N C;

Coupler VIII 0H 00 OH OOH I 'lle 0 N Coupler IX OH CO OH CzH5 OOH

C ONHCnHu Coupler X OH COOH I (ih s 5 0 K COOH CONHCmHav Coupler XI OH CONHCHzCHaQ K/ NHCOCH;

Coupler XII wonnomcmQ K/ NHCOCHa e CzHg Coupler XIII CONH(CH:)4O Cn n 5Hn-l;

So I

(HI NHCOCH;

Coupler XIV OH NHCOCH;

Coupler XLI (CHa)aCCO(|3HCONH Coupler XLII CO CIIHCN lzHs Coupler XLIII g8 mzoownno-Q- The ballasted non-difiusible type couplers of the present invention, inclusive of development inhibitor-releasing couplers, image transfer couplers, preformed dye image transfer couplers and two-equivalent type couplers, are usefully incorporated into light-sensitive photographic silver halide emulsion layers or adjacent layers and applied onto an emulsion support or film base in a singleor multilayer color photographic material by known methods (example: the solvent and Fisher fat-tail methods) as described, for instance, in Marines et al. in U.S. 2,304- 939-40 and Jelley et al. in U.S. Pat. 2,322,027, in which high-boiling organic solvents are used to dissolve the coupler. Further useful procedures are described, for instance, in Vittum et a1. U.S. Pat. 2,801,170; Fierke et al. U.S. Pat. 2,801,171 (July 57); and Julian U.S. Pat. 2,479,- 360 (August 60), whereby low-boiling or water-soluble organic solvents are used with or in place of a high-boiling solvent. In the case of multi-layer photographic materials or elements, the non-difiusible coupler compounds are generally incorporated into the red-sensitive silver halide emulsion layer and preferably utilize minimal amounts of high-boiling solvents.

A useful coupler concentration can vary from about -200 mg./ft. of coated material, a range of -50 mg./ ft. being generally satisfactory for use in photographic paper, with overlapping and higher concentrations found useful in color photographic films.

In the image transfer art (ref. Couplers IX-X, XX- XXI, XXX, XXXIII-XXXIV), a useful concentration conveniently varies from about .5%-8% by weight of gelatin or other media utilized as incorporating layer.

A variety of color coupler-containing photographic materials and elements are obtainable utilizing the abovedescribed family of couplers. Generally speaking, however, such photographic materials and elements will comprise the following main components:

(A) A support such as cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, poly- (ethylene terephthalate) film, polyethylene film, polypropylene film and related films of resinous materials as well as paper, polyethylene coated paper, glass, and others. The terms include paper or other flexible fibrous material which can be partially acetylated or coated with baryta or some other hydrophobic film or surface which repels and 18 does not absorb or adsorb water. A support layer having a hydrophobic surface can also include hydrophobic resin layers which have been subject to a corona treatment as described, for instance, in British Pats. 971,058, 1,060,526 and U.S. Pats. 2,864,755 and 2,864,756 to improve adhesion of hydrophilic colloid layers coated over them.

Such resin layers or films may be either self-supporting or may be coated over another support layer. Specific supports having useful hydrophobic surfaces include polyethylene terephthalate films electron-bombarded to have a contact angle less than 45 (U.S. Pat. 3,220,842), a corona-treated surface comprising a chromium halide (U.S. Pat. 3,117,865), or corona-treated hardened gelatin coated papers (Belgian Pat. 671,661), etc. The support layer may also contain various functional additives such as titanium dioxide, Zinc oxide, and silica as suggested in U.S. Pats. 2,992,101 and 2,701,245, and anti-static agents as described, for instance, in U.S. Pat. 3,253,922;

(B) An antihalatiou layer such as a dye-containing gelatin, starch, etc., as described, for instance, in Glafkides Photographic Chemistry, volume 1, pages 470-471, Arrowsmith Ltd. 1958;

(C) One or more, preferably three light-sensitive and difierently-sensitized color coupler-containing silver halide emulsion layers coated onto the support, optionally with one or more gelatin spacer layers between. The support is conveniently coated in succession with a red-sensitive layer containing one or more of the above-defined class of cyan-dye-producing coupler, a green-sensitive layer and a blue-sensitive layer, either with or without a Carey-Lea filter layer between the blueand greensensitive layers. The three differently color-sensitized layers can also be arranged in any other order over one another that is desirable, with the exception that a Carey-Lea filter layer cannot be placed over a blue-sensitive layer.

The light-sensitive silver halide emulsions can include coarse, regular, or fine grain silver halide crystals or mixtures thereof such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide and mixtures thereof. Both conventional negative-type silver halide emulsions and direct positive silver halide emulsions can be utilized in preparing the photographic elements within this invention. Such emulsions are described, for instance, in The Photographic Journal, volume LXXIX, May 1939, pages 330-338; Journal of Photographic Science, volume l2, #5, Sept/Oct. 1964, pages 242-251, and also in U.S. Pats. 2,184,013, 2,456,953, 2,541,472, 2,563,785, 2,592,250, 3,367,778 and 3,501,307. In addition to the above-described couplers, such emulsions used in greenand blue-sensitive layers can also include twoand four-equivalent magentaand yellow-dye-producing couplers of the type described, for instance, in U.S. Pats. 2,453,661, 2,449,966, 2,521,908, 2,908,573, 3,311,476, 3,476,563, 3,152,896 and 3,062,653. Ballasted two-equivalent couplers of the present invention are usefully incorporated within gelatin, colloidal albumin, cellulose derivatives or synthetic resins, as described in U.S. Pat. 2,286,- 215 or 2,327,808, water-soluble ethanol amine cellulose acetates as described in U.S. Pat. 2,322,085, also suitable polyacrylamides having a combined acrylamide content of 3060% and a specific viscosity of 25-15 on an imidized polycerylamide of similar acrylamide content and viscosity such as described in U.S. Pat. 2,541,474, in zeil as described in US. Pat. 2,563,791, into a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in US. Pat. 2,768,154, or one containing cyano-acetyl groups, exemplified by vinyl alcoholvinyl cyanoacetate copolymers as described in US. Pat. 2,808,331, a polymeric material from a protein polymerisate or a saturated acylated protein with a monomer having a vinyl group described in US. Pat. 2,852,382.

(D) One or more gelatin spacer layers between the light-sensitive emulsion layers or the emulsion layers and Carey-Lea filter layer as above described; and

(E) A protective water-permeable overcoat layer, such as gelatin, poly-N-vinyl lactam, gum arabic, hydrophilic copolymer of N-acrylamidoalkyl betain (ref. US. Pat. 2,833,650), cellulose ethers and esters, alkali soluble polyvinyl phthalate (ref. US. Pat. 2,798,004); also watersoluble polymers having varying degrees of solubility, such as polyvinyl alcohol (optimally with surfactant), polyvinyl pyrrolidone polyalkylene oxides, polyvinyl alcohol and its derivatives such as partial esters, ethers and acetals exemplified by hydrolyzed polyvinylacetate, polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal, polyvinyl sodium o-sulfobenzaldehyde acetal, polyvinyl disodium 2,4-disulfobenzaldehyde acetal; and water-soluble copolymers and interpolymers exemplified by copoly- (methyl vinyl ether/maleic anhydride), copoly(acrylic acid/methacrylic acid ethyl ester-maleic anhydride) and copoly(maleic anhydride/acrylic acid/vinyl acetate). The overcoat may conveniently contain aldehyde scavenger such as described, for instance, in US. Pats. 3,236,652, 3,287,135, 3,220,839, 2,403,927 and British Pat. 623,448 and other ingredients such as buffering agents (elg. an acidic or basic material), and ultra-violet light absorbers such as 2,2 di hydroxy 4,4 dimethoxybenzophenone, 4,4-dimethoxybenzophenone, 4,4'-diazidostilbene-2,2' disulfonic acid sodium salt and sodium-fi-phenylhydrazone.

In addition, photographic materials and elements utilizing the present couplers can usefully contain brighteners such as stilbenes, triazines, oxazoles and coumarins as described, for instance, in German 'Pats. 972,067, 115,024, and in U.S. Pat. 2,933,390; they may also contain spectral sensitizing dyes to impart additional sensitivity to light-sensitive silver halide emulsion layers.

The above-described photographic elements or materials can also be conveniently modified for use with diffusiontransfer-type couplers within the present invention which contain dyes or dye precursors in the manner of the systems generally described, for instance, in US. Pats. 3,362,819, 3,415,644-6 and 3,484,238, and in accordance with the techniques disclosed in British Pats. 1,157,501- 1,157,510 and US. Pats. 2,559,643, 2,661,293, 2,698,244, 2,698,798 and 2,774,668.

Suitable light-sensitive emulsions for purposes of the present invention can also contain speed-increasing compounds of the quaternary ammonium and polyethylene glycol type as found, for instance, in US. Pats. 2,271,623, 2,288,226, 2,334,864 and 2,708,162.

The photographic elements of the invention are developed with photographic alkaline color developing solutions containing aromatic primary amino color developing agents. Such developing agents are well known in the art and typically are p-phenylenediamines. Suitable color developing agents include p-amino-N,N-diethylaniline HCl 4-amino-3-methyl-N,-N-diethylaniline HCl 4-amino-N-ethyl-N-fl-hydroxyethylaniline H SO 4-amino-N-butyl-N-w-sulfobutylaniline 4-amino-3-methyl-N-ethyl-N-p-hydroxyethylaniline H SO 4-amino-3-methyl-'N-ethyl-N-fl-( methane sulfonamido) ethylaniline 3/ 2 H SO H O 4-amino-3-B-(methanesulfonamido)ethyl-N,N-diethylaniline HCl 20 4-amino-3-methoxy-N-ethyl-N-fi-hydroxyethylaniline 2HCl, and N,N-diethyl-3 (Z-hydroxyethyl) -p-phenylenediamine 2HCl, while reference is also made to Bent et al., JACS 73, 3100- 3125 (1951) for additional typical suitable color developing agents.

As earlier indicated, diflusible-unballasted or lightlyballasted selenide or telluride couplers of the invention, as exemplified by couplers VII-VIII, XI-XII, and XLI- XLII, are conveniently utilized in the color developing solution, rather than initially incorporating them into a photographic element. More specifically, such couplers are usefully introduced into a photographic element during processing by dissolving or otherwise incorporating them into an aqueous alkaline aromatic primary amino color developer solution generally at a concentration of 1.5 to 1.7 grams per liter, although the concentration of such couplers in color developers can vary widely. These are exemplified by the general formulation:

G./1. Development accelerator 0-50 Color developing agent 1.3- Alkali metal bromide 0-100 Antifoggant 01.0 Alkali metal iodide 0-1.0 Alkali metal chloride 0-25 Soluble ditfusible competing coupler 0-500 Buffer 0-100 Silver halide solvent 0-50 Antioxidant 0-50 pH range 8.0 to 14.0.

wherein the pH is conveniently adjusted with an alkali metal or ammonium hydroxide.

Development accelerators for use in the above-type formulation include, for instance:

benzyl alcohol p-cresol phenyl ethyl alcohol p-n-amyl phenol n-octyl alcohol, and p-sec.-butyl phenol Useful antifoggant components for purposes of the present invention are demonstrated, for instance, by benzotriazole, S-nitrobenzimidazol nitrate, S-nitroindazole, 1- phenyl-S-mercaptotetrazole, S-methylbenzotriazole, and N-methylbenzothiazolium-p-toluene sulfonate, etc.

Useful buffers in color developing formulations can include alkali metal salts such as:

K PO K HPO KH PO Na CO an alkali metal salt of boric acid, etc., or organic buffers, such as described in Bard et al., U.S. Pat. 3,305,364, etc.

Useful siliver halide solvent for the above purpose includes:

NaCNS NH OH ethylenediamine dithiooctanediol thiourea isopropylamine, and n-butylamine, etc.; and

useful antioxidants include:

hydroxylamine sulfate diethylhydroxylamine sodium sulfite dextrose p-hydroxyphenyl glycine ascorbic acid oxytetronic acids and dihydroxyacetone; while suitable optional soluble competing couplers are exemplified, for instance, by

additional competing couplers of this type are further described in US. patent application Ser. No. 52,721, now

US. Pat. 3,647,452, of Hendess et al. filed on July 6, 20

22 and B, coating (2) contains couplers A and B, and coating (3) contains A and B as described below. After drying, the strips are sensitometrically exposed through a graduated density test object developed for 3 minutes with the Color Developing Composition, stop fixed, washed, silver bleached, washed, fixed, Washed, and dried in the conventional manner and the developed strips are read spectrophotometrically to determine the relative effectiveness of development inhibitor-releasing couplers of the present invention as opposed to corresponding oxy ether or 4-unsubstituted couplers. In coating (1), red and blue densities are measured. In coating (2), blue density is measured and compared with the blue density of the check, and in coating (3), the red density is measured and compared with the red density of the check. Coating (l), which is the control, contains couplers common to both experimental coatings. The dye densities of the couplers in common in coatings 1) and (2) or (1) and (3) are measured and compared so that differences in the reactivity of couplers A and A for example, are not mistaken for reduced development due solely to the DIR 1970. effect (i.e., development inhibitor releasing).

A OK A cyan dye-forming cou ler as described in Coupler U.S. Pat. 2,822,027. p

nHzs C ler B---. Cl A yellow dye-forming eou ler as described in mm U.S. Pat. 3,408,194. p

(CH3)3CCOCHCONH-- NHCO(OH2)OQCsHn-t sHirt C0upletA1 Obtained in accordance with the synthesis OH I o o NEE-Q CnHzn t N=N Coupler 131 01 described on pages 15, 15b and 150 supra;

e NHCO (CH2) 0-Qomm) a Of the invention.

This invention is further described, although not limited, by the following examples:

EXAMPLE I Three test film coatings identified as (1)-(3) and containing couplers A, A B and B are prepared by coating on a transparent cellulose acetate film support gelatine silver bromide emulsion layer containing per ft. of film, 270 mg. silver, 400 mg. gelatin, 61 mg. of a cyan dyetforming coupler or a 105 mg. of a yellow dye-forming coupler, as identified below, dissolved in a tri-cresyl phos- COLOR DEVELOPING COMPOSITION Water to 1 liter.

phate coupler solvent. Coating (1) contains couplers A 75 pH 68 F. (20 C.)==10.75.

TABLE I equivalents seleno ether couplers of the invention were used. Coating Dmnx. Dmnx- T BLE II 2.9 .1 2.3 .1 Microcon- .3 .09 trast or 1.1 .15 Coupler D sharpness A (control) i m d IOVO EXAMPLE n 0 p Four test coatings invdividually containing couplers A,

O 2H5 NH-C o-rb-o-Q-mnm" a 51111 (t) Coupler C I C- H [I H O H Coupler XVI-2:2: 0H

C2115 NH0 0 CEO-Q0131? CH O sHn Coupler XXII /N=CNHC O NHCO CH 0 o- -H 2 [I A 0 e 151131 8 Compound C is pre ared from the corresponding 2-amino-5-methoxy phenol (Bcil. XIII) which is reacted with the desired acid oh orlde in dioxa-ne to complete the No. 2 substituent group.

b Ref. U.S. Pats. 2,369,489 and 2,600,788.

A B and B are prepared as in Example I, and then ex- TABLE I11 posed to light in progressively narrower strips (i.e., coupler D 10 100 and 1000p.) for running microdensitometric C 6; traces of the dye densities to determine relative changes ""7 in microcontrast attributable to the efiective presence of g (mvenuon) the development-inhibitor releasing couplers of Example I (ref. Photographic Science and Engineering, vol. 13, XXII (mvennon) No. 4 (1969) pages 74-80). The light-exposed film is This invention has been described in detail with developed and the results qualitatively observed and reparticular reference to certain preferred embodiments ported in Table II as density differences attributed to thereof, but it will be understood that variations and diffusion of the released thioor selenoheterocyclic modifications can be effected within the spirit and scope development inhibitor between the center and outside of the invention.

ears or edges of the exposed strip, a indicating a We claim:

substantial change in density between the center and the 1. A light-sensitive photographic element comprising edges of the exposed and processed coatings. a support layer having coated thereon a photographic silver halide emulsion layer and containing at least one EXAMPLE HI coupler compound of the formula Four coatings comprising a single silver bromoiodide emulsion containing per ft. of film, 75 mg. coupler inwhich (identified in Table 11 below), 39 mg. di-n-butyl COUP represents a color photographic coupler moiety phthalate as coupler. solvent, 450 mg. gelatin, and 136 capable of reacting with oxidized color developing mg. silver are sensitometrically exposed and developed agent to form a dye and to split off -XR;

in the manner described in Example I and evaluated Xrepresentsadivalent selenium or tellurium atom; and

spectrophotometrically. The results are reported in R represents an alkyl, an aryl or a heterocyclic group Table III below. Higher D resulted when the twolinked to X at a carbon atom.

25 2. A light-sensitive color photographic element comprising a support layer having coated thereon a photo graphic silver halide emulsion layer and containing at least one coupler compound of the formulae BALLCOUPX-R' SOLCOUP'X wherein:

X is a divalent selenium or tellurium atom;

COUP' is a color photographic coupler moiety capable of reacting with oxidized color developing agent to form a dye and having --XR', or substituted in a. coupling position thereon;

BALL represents at least one photographically inert organic ballasting substituent group;

SOL is either a hydrogen atom or an acidic solubilizing group, SOL being defined as the latter when a color deveolping agent free of any acid solubilizing group is utilized;

R is an alkyl group having 1 to 13 carbon atoms, an

unballasted aryl group, or an umballasted heterocyclic group; and

R" is an alkyl group having at least 14 carbon atoms, a ballasted aryl group, or a ballasted heterocyclic group.

3. A light-sensitive color photographic element comprising a photographic support having coated thereon a photographic silver halide emulsion layer containing a nondifiusible coupler that forms a diflusible dye and a nondilfusible selenide or telluride compound when reacted with oxidized color developing agent, said coupler having the formula SOLCOUP'X wherein X is a divalent selenium or tellurium atom;

COU P' is a color photographic coupler moiety comprising a S-pyrazolone magenta dye-forming coupler moiety, a phenolic or an a-naphtholic cyan dye-forming coupler moiety, or an open-chained ketomethylene yellow dye-forming coupler moiety, having substituted thereon in coupling position the --XR" substituent group;

SOL is an acidic solubilizing group; and

R is a ballasted organic radical selected from the group consisting of an alkyl group having at least 14 carbon atoms, an aryl group, and a carbon-containing heterocyclic group with at least one heteronitrogen, -oxygen, or -sulfur atom.

4. A light-sensitive photographic element comprising a photographic support having coated thereon a photographic silver halide emulsion layer containing a nondiffusible coupler that forms a non-difiusible dye and a dilfusible selenide or telluride compound when reacted with oxidized color developing agent, said coupler having the formula BALLCOUP'XR' wherein X is a divalent selenium or tellurium atom;

COUP' is a color photographic coupler moiety comprising a S-pyrazolone magenta dye-forming coupler moiety, a phenolic or a-naphtholic cyan dyeforming coupler moiety, or an open-chained ketomethylene yellow dye-forming coupler moiety, having substituted thereon in coupling position the --X--R substitutent group;

R is an organic radical that forms a ditfusible selenide or teluride when said non-diirusible coupler is reacted with oxidized aromatic primary amino color developing agent and is selected from the group consisting of an alkyl group having about il-l3 carbon atoms, an unballasted aryl group and an unballasted carbon- 26 containing heterocyclic group with at least one heteronitrogen, -oxygen or -sulfur atom.

5. A light-sensitive color photographic element comprising a support layer having coated thereon at least one photographic silver halide emulsion layer and a conpler of the formulae NAOL and PHOL are defined as a cyan dye-forming photographic coupler moiety respectively of the otnaphthol and phenol type having at least the two indicated substituent groups directly attached onto the a-naphthol or phenol ring, wherein X is a divalent selenium or tellurium atom;

R is an alkyl group, an aryl group or a heterocyclic group containing at least one one oxygen, sulfur, or nitrogen atom in the hetero ring;

R is a hydrogen atom or an alkyl group;

A is an alkyl group or an aryl group, the

substituent groups being attached onto the No. 2 ring carbon of NAOL and PHOL and the XR substituent group attached onto the No. 4 ring carbon of NAOL and PHOL;

PY is defined as a magenta dye-forming S-pyrazolone photographic coupler moiety containing at least three substituent groups attached onto the pyrazolone ring, of which Ar is defined as an aryl group;

R is an alkyl group having up to about 30 carbon atoms, an aryl group or a heterocyclic group, and

R is an alkyl carbonamido group, an aryl carbon amido group, an alkoxy group, and a heterocyclic group containing a 56 membered heterocyclic ring;

A is an alkyl group or an aryl group;

Ar is an aryl group;

R is an aryl or a heterocyclic group containing at least one oxygen, sulphur or nitrogen atom in the hetero ring.

6. A light-sensitive color photographic element of claim 2 wherein COUP' is a phenolic or a-naphtholic cyan dye-forming coupler radical, a 5-pyrazolone magenta dyeforming coupler radical, or an open-chain ketomethylene yellow dye-forming coupler radical;

R is a lower alkyl having 1-10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group containing a 56-membered heterocyclic ring having at least one nitrogen, oxygen or sulfur atom in the hetero ring.

7. A light-sensitive color photographic element comprising a support layer having coated thereon a photographic silver halide emulsion layer containing a coupler of the formulae i a RPS 8-NAO L-C ON-A.

wherein NAOL and PHOL, in combination with their substituent groups, are defined respectively as a non-diffusible a-naphthol and a phenol cyan dye-forming photographic coupler;

R is an alkyl group of l430 carbon atoms, an aryl group, or a heterocyclic group containing a -6 membered heterocyclic ring;

R; is a hydrogen atom or an alkyl group of about l-20 carbon atoms; and

A is an alkyl group having 1 to 22 carbon atoms; a

phenyl group or a naphthyl group; the

-C ON--A.

and the -NC O-A substituents being attached onto the No. 2 ring carbon and the -SeR substituent being attached onto the No. 4 ring carbons of NAOL and PHOL.

8. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula Se I - H-CO-Ar in which Ar is a phenyl group or a naphthyl group;

9. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula wherein A is an alkyl group, a phenyl, or a naphthyl group;

Ar is a phenyl or a naphthyl group; and

R is a phenyl group, a naphthyl group or a heterocyclic group containing at least one oxygen, sulfur, or nitrogen atom and at least one carbon atom.

10. A photographic element of claim 1 wherein X is a divalent selenium atom.

11. A photographic element of claim 2 wherein X is a divalent selenium atom.

12. A photographic element of claim 10 wherein COUP' is a S-pyrazolone magneta dye-forming coupler moiety.

13. A photographic element of claim 10 wherein COUP' is a phenolic or an ot-naphtholic cyan dye-forming coupler moiety.

14. A photographic element of claim 10 wherein COUP is an open-chained ketomethylene yellow dye-forming coupler moiety.

15. A light-sensitive color photographic element comprising a support having coated thereon a photographic 28 silver halide emulsion layer containing a coupler of the formula CONH 16. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer and containing a coupler of the formula (onmoooonoonnQ 17. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer and containing a coupler of the formula (i oomaomomQ NHCOCH a 18. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula OH G0NH(CHz)4O -C H1rt N N-CuH 19. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula N=CO H C2 5 OCHzCONH- N G OVHM C-C-H ll g 20. A light-sensitive color pohotographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula (CHa)aCCO CHCONH 21. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula (32115 NHCOCHO-QCJLF C1130 OsHn-t 22. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula i CH3 NHCOCHzO 23. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the csHu-t 24. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula 30 25. A light-sensitive color photographic element com prising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula l I (i Se C ONHCmHu 26. A light-sensitive color photographic element comprising a support having coated thereon a photographic silver halide emulsion layer containing a coupler of the formula X is a divalent selenium or tellurium atom;

COUP is a color photographic coupler moiety capable of reacting with oxidized color developing agent to form a dye and having XR substituted in coupling position thereon;

SOL is a hydrogen atom or an acidic solubilizing group, SOL bieng the latter when said color developing agent is free of any acid solubilizing group; and

R is an alkyl group having 1 to 13 carbon atoms, an

unballasted aryl group or an unballasted heterocyclic group, said -X--R' substituted forming a dilfusible selenide or telluride silver halide-development-inhibiting compound.

28. A developing composition of claim 27 wherein X is a divalent selenium atom.

29. A developing composition of claim 27 wherein X is a divalent tellurium atom.

30. A developing composition of claim 27 wherein the dilfusible coupler is a compound of the formula 31 31. A developing composition of claim 27 wherein the diffusible coupler is a compound of the formula OH COOH CODE 34. A light-sensitive silver halide photographic emulsion containing a coupler compound of the formulae BALL-COUP'-X-R' or 40 X is a divalent selenium or tellurium atom;

COUP is a color photographic coupler moiety capable of reacting with oxidized color developing agent to form a dye and having XR' or XR' substituted in coupling position thereon;

BALL represents at least one photographically inert organic ballasting substituent group;

SOL is either a hydrogen atom or an acidic solubilizing group, SOL being defined as the latter when a color developing agent free of any acid solubilizing group is utilized;

R is a lower alkyl group having 1 to 13 carbon atoms, an unballasted aryl, or an unballasted heterocyclic group; and 55 R" is an alkyl group having at least 14 carbon atoms,

a ballasted aryl group, or a ballasted heterocyclic group.

35. A light-sensitive silver halide photographic emulsion containing a coupler compound of the formula wherein X is a divalent selenium or tellurium atom;

COUP is a color photographic coupler moiety comprising a 5-pyrazolone magenta dye-forming coupler moiety, a phenolic or wnaphtholic cyan dye-forming coupler moiety, or an open-chained ketomethylene yellow dye-forming coupler moiety, having substituted thereon in coupling position the XR substituent group;

R is an organic radical that forms a diffusible selenide or telluride when said coupler is reacted with oxidized aromatic primary amino color developing ag t, R ng a member selected from the group consisting of an alkyl group having about 1-13 carbon atoms, an unballasted aryl group and an unballasted carbon-containing heterocyclic group with at least one heteronitrogen, oxygen or sulfur atom.

36. A light-sensitive silver halide photographic emulsion containing a coupler compound of the formulae NAOL and PHOL, in combination with their substituent groups, are defined respectively as a uon-diffusible u-naphtholand a phenol-cyan dye-forming photographic coupler;

R is an alkyl group of 14-30 carbon atoms, an aryl group, or a heterocyclic group containing a 5-6 membered heterocyclic ring;

R is a hydrogen atom or an alkyl group of 1-20 carbon atoms; and

A is an alkyl group of 1-22 carbon atoms, a phenyl group or a naphthyl group; the

0 CONA and the Il a NC O-A substituents being attached onto the No. 2 ring carbon and the SeR substituent being attached onto the No. 4 ring carbon of NAOL and PHOL.

37. A light-sensitive silver halide photographic emulsion containing a coupler compound of the formulae wherein A is an alkyl group of 1-22 carbon atoms, a phenyl group, or a naphthyl group; and

Ar is a phenyl group, or a naphthyl group; and

R is a phenyl group, a naphthyl group or a heterocyclic group containing at least one oxygen, sulfur, or nitrogen atom and at least one carbon atom.

38. A light-sensitive silver halide photographic emulsion containing a coupler compound of the formula wherein PY in combination with substituent groups is defined as a non-ditfusible S-pyrazolone magenta dye-forming photographic coupler;

R is an alkyl group having 1-30 carbon atoms, a heterocyclic group, phenyl, naphthyl, or substituted phenyl or naphthyl group in which a substituent group is an alkyl carbamyl or an aryl azo group; and

R is an alkyl carbonamido group, an alkoxy group, an

aryl amino group or in which Ar is a phenyl group, or a naphthyl group;

39. The process of developing an exposed photographic element comprising a photographic support having coated thereon a photographic silver halide emulsion layer containing a non-diffusible coupler that forms a non-ditfusible dye and a non-diifusible selenide or telluride when reacted with oxidized color developing agent, said coupler having the formula wherein wherein X is a divalent selenium or tellurium atom;

X is a divalent selenium or tellurium atom; COUP is a color photographic coupler moiety compris- COUP' is a color photographic coupler moiety comprising a S-pyrazolone magenta dye-forming coupler moiety, a phenolic or u-naphtholic cyan dye-forming coupler moiety, or an open-chained ketomethylene yellow dye-forming coupler moiety having substituted thereon in coupling position the ing a S-pyrazolone, magenta dye-forming coupler moiety, a phenolic or'an u-naphtholic cyan dye-forming coupler moiety, or an open-chained ketomethylene yellow dye-forming coupler moiety, having substituted thereon in coupling position the -X-- substituent group;

R is an organic radical that forms a dilfusible selenide or telluride when said non-ditfusible coupler is reacted with oxidized aromatic primary amino color developing agent and is selected from the group consisting of an alkyl group having about 1-13 carbon atoms, an unballasted aryl group and an unballasted carbon-containing heterocyclic group with at least one hetero-nitrogen, -oxygen or -sulfur atom.

substituent groups; SOL is an acidic solubilizing group; and R is a ballasted organic radical selected from the group consisting of an alkyl group having at least 14 carbon atoms, and a'ryl group, and a carbon-contain- 15 ing heterocyclic group with at least one hetero-nitrogen, -oxygen or -sulfur atom; which comprises treat ing said exposed photographic element with an aqueous alkaline photographic color developing composition containing an aromatic primary amino color developing agent, developing exposed silver halide of said element, and producing oxidized color developing agent with said coupler to form a diffusible dye with said SOL-COUP'moiety and a non-diffusible selenide or telluride of the formula H-Z- NORMAN G. TORCHIN, Primary Examiner 40. The process of developing an exposed photographic element comprising a photographic support having coated SURO PICO Assistant Exammer thereon a photographic silver halide emulsion layer containing a non-diffusible coupler that forms a non-diffusible dye and a diffusible selenide or telluride when reacted 96--22, 29 D, 55, 109 with oxidized color developing agent, said coupler having the formula References Cited UNITED STATES PATENTS 9/ 1964 Whitmore et al 96-55 3/ 1972 Carlson et a1 96-3 U .3. Cl. X.R.

"W950 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION patent NO 3, 733, 201 Dated May 15, 1973 Inventor) Charles R. Barr It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 41, "'magneta" should read --magenta---;

Column 2, lines 7-8, "precusor" should read ---precursor--;

Column 2, line 47, "it" should read --is---;

Column 4, line 33, after "pyrimidyl", insert Column 9, line 26, "acetontrile" should read ---acetonitrile---;

Column 16, approximate columnar line 27, that part of formula reading:

should read Q Column 16, line 44, that part of formula reading: "N= should read ---N=N--- Column 16, line 71, that part of formula reading: "CCH should read --OCH Column 20, line 55, "siliver" should read --silver--;

zgigg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Page 2 Patent No. 3 733 Dated May 15 1973 Inventor-(s) Charles arr It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 21, the formula for Coupler A, "CO H should read Column 23, line 2, "Dmax." (second occurrence) should read --Dmin.---;

Column 24, line 1, "equivalents" should read ---equivalent-- Column 25, line 71, (claim 4) "teluride" should read ---tel1uride---;

Column 26, line 17, (claim 5), that part of formula reading; "CC" should read ---CO---;

Column 27, line 67(claim l2) "magneta" should read --magenta--;

Column 28, line 10, (claim 15), that part of formula reading: "Sc" should read --Se-;

Column 28, line 71, (claim 19), that part of formula reading: "C H" should read --C H Column 30, line 47, (claim 27) "bieng" should read ---being--;

Column 30, line 51, (claim 27) "substituted" should read ---substituent-- Column 31, line 41, (claim 34) that part of formula reading: COUP. -R" should read ---COUP' -X-R"--;

Column 31, line 45, (claim 34) "-XR' (second occurrence) should read -XR" $3233? UNITED STATES PATENT OFFICE Page 5 CERTIFICATE OF CORRECTIQN Patent No. 3 733 2 May 15 1973 Dated Charles R. Barr Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 32, line 9, (claim 36) between the two formulae insert ---or-;

Column 33, line 15, (claim 39) "and" (first occurrence) should read ---an---;

Column 33, line 23, (claim 39) after "agent" insert reacting the oxidized color developing agent---;

Column 33, line 25, (claim 39) HZR" should read --H-XR"---;

Signed and sealed this 1st day of April 1975.

test 0. I-ZARSHALL Darn:

RUTH C. MASON Commissioner of Patents attesting Officer and Trademarks