US3369899A - Photographic materials containing aroylacetanilide type color couplers - Google Patents

Description

United States Patent 3,369,899 PHOTOGRAPHIC MATERIALS CONTAINING ARO- YLACETANILIDE TYPE COLOR COUPLERS Arthur Henri De Cat, Mortsel-Antwerp, Marcel Hendrik Verbrugghe, WiIrijk-Antwerp, and Raymond Albert Roosen, Mortsel-Antwerp, Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel, Belgium, a company of Belgium No Drawing. Filed July 8, 1964, Ser. No. 381,230 Claims priority, application Belgium, July 9, 1963, 42,767, Patent 634,665 7 Claims. (CI. 96-74) This invention relates to the production of photographic color images, to color couplers for yellow of use therefor and to photographic materials incorporating said color couplers.

It is known that for the production of photographic color images in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a color coupler which reacts with the oxidation product of the developing substance to form a dyestuff on the areas corresponding to the silver image.

In the subtractive tri-color photography there is generally employed a photographic light-sensitive color material comprising a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wheren on color development, by use of approprate color couplers, a cyan, a magenta, and a yellow image is respectively formed.

It is known that color couplers should meet various requirements according to the way wherein the color material is prepared and the purpose for which it is used.

For preparing a usable photographic multilayer color material comprising in the dilferently sensitized silver halide emulsion layers the color couplers for the different color separation images,. the color couplers have to be incorporated into the hydrophilic silver halide emulsion layers in non-migratory form. This can be achieved e.g. by using a color coupler which is sufiiciently watersoluble and which is provided with a sufiiciently large organic radical for inhibiting migration of the color coupler into the hydrophilic silver halide emulsion layer or by using a lipophilic color coupler which, dissolved in an organic solvent, is dispersed into the silver halide emulsion layer.

For the production of color images, more especially positive color images, for instance on a paper support, it is important to dispose of color couplers which on color development form dyestuffs which are resistant to the action of light, humidity and heat.

A class of color couplers for yellow of the known ketomethylene type, more especially of the aroyl acetarylide type has now been found, which color couplers on color development with an aromatic primary amine developing substance form dyestuffs which possess besides a very good stability against light an exceptionally good stability against humidity and heat.

These ketomethylene color couplers of the aroyl acetarylide type are characterized by the presence of at least one sulphonic acid group in the aroyl part of the molecule, by an arylide part which may be further substituted by one or more substituents which have not a watersolubilizing character, and by the presence of a group inhibiting migration either in the aroyl part or in the arylide part of the molecule. The sulphonic acid group(s) may be bound directly to the aromatic nucleus of the aroyl group or may be present on an aromatic nucleus which is linked to the aromatic nucleus of the aroyl group by means of a bivalent radical.

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Examples of color couplers for yellow according to the invention wherein at least one sulphonic acid group is directly bound to the aromatic nucleus of the aroyl group correspond to the following general formula:

R1 Ra wherein R represents a sulphonic acid group or salt form thereof,

R represents a hydrogen atom, a substituent having either a water-solubilizing character or not such as a halogen atom, an alkoxy group and a sulphonic acid group or salt formthereof, or a group inhibiting migration such as a n-hexadecyloxy group,

R represents a hydrogen atoms, a substituent having no water-solubilizing character, for instance a group inhibiting migration for instance the group -XR, wherein X represents a chemical bond, an oxygen atom, a sulphur atom, a sulphonyl group, a SO NH group, a ,NHSO group, a CONH group or a NHCO group, and R represents an acyclic aliphatic hydrocarbon radical containing from 5 to- 20 carbon atoms, and

R represents a hydrogen atom, a substituent having no water-solubilizing character such as an alkoxy group, a halogen atom, an alkyl sulphonyl group or a substituted alkyl sulphonyl group such as a -SO CHF group, or the atoms necessary to form a fused aromatic system which may be'further substituted such as an aromatic system of the naphthalene series, at .least one of R and R being a group inhibiting migration.

Examples of color couplers for yellow according to means of a bivalent radical correspond to the following general formula:

Y-RI1 wherein R R and R have the same significance 'as set forth Y represents a bivalent radical such as a -CONH group, a 4O NH-- group and a -NH-CONH- group.

whereupon by deacylation in acid medium the corresponding fl-ketoester derivatives are formed (c). These fi-ketoester derivatives are condensed with aromatic amines whereupon the fluorosulphonyl-substituted benzoyl acetanilides obtained (d) are converted into the corresponding sulphonic acid derivatives (e) by alkaline hydrolysis.

The following reaction scheme illustrates the different steps of the preparation:

1 NBOSOI oo-om-oo-xm- -o O-CHaOO-NHU CO-OHz-OO-NH SOaNa SOsNa a 2) lS NEOSOF COCH2CONH 0 CH Cia s:

( O-(CH2)1iCHa I The following description illustrates more detailedly how the intermediate compounds of use for the preparation of color couplers for yellow according to the invention are prepared.

(1) PREPARATION OF ACID CHLORIDE I (CF. TABLE 1) (a) 3-flu0rosulphonylhenzoyl chloride ('0) 4-fluorosulphonyl benzoylchloride This compound is prepared as described in J. prakt. Chemie (2) 117 (1927) 29.

(c) 3 -fluorosul phonyl-4-ch lorobenzoyl chloride o1-Qo or SOzF (1) 3-chlorosulphenyl-4-chlor0benz0ic acid.The synthesis of this product occurs analogously to the preparation of sulphonyl chlorides from amines according to the method of Meerwein et a1., Ber. 90 (1957) 841. When starting from 84 g. of 3-amino-4-chlorobenzoic acid (Bamberger Ber. 35 (1902) 3709), 98 g. of a white to light brown crystalline product melting at 171 C., are obtained after diazotation and treatment of the diazonium compound with sulphurous acid anhydride in acetic acid medium in the presence of copper (I) chloride.

(2) 3-fluor0sulphonyl-4-chlorobenzoic acid.-The sulphonyl chloride prepared above is dissolved in dioxan and converted into the sulphonyl fluoride by stirring for 3 h. at 45 C. in an aqueous potassium fluoride solution. When pouring the reaction mixture into water a white crystalline product is formed melting at 196 C.

(3) 3-fluorosulphonyl-4-chl0robenzoyl chloride.-The conversion of the acid into the acid chloride occurs by reaction with thionyl chloride at reflux temperature. After evaporating the excess of thionyl chloride the residue is distilled off in a vacuum of 0.5 mm. Hg. Boiling point: 120122 C.

(d) 3,5 -difluorosul phonyl benzoy lchloride SORF (1) 3,5-difluorosulph0nyl benzoic acid.This compound is prepared in an analogous way as given under (1)(c) (2), starting from 3,5-dichlorosulphonyl benzoic acid (Bell, Bennett, J. Chem. Soc. 1930-, 3). A white crystalline product melting at 176*177 C. is obtained.

(2) 3,5-difluorosulph0nyl benz0ylchloride.-The conversion of the acid into the acid chloride occurs as given under (1)(c)(3) with thionyl chloride. After distillation in a vacuum of 0.5 mm. Hg, a white crystalline product melting at 51 C. and boiling at 145 C. is obtained.

(e) 3-fluorosulph0nyl-4-n-hexadecyloxy-benzoylchloride SIO 2F (1) 3-sulpho-4-n-hexadecyloxy benzoic acid.This compound is obtained by sulphonation of p-n-hexadecyloxy-benzoic acid (as described in British patent specification 808,276) with sulphurtrioxide in tetrachloroethane. The reaction is carried out at 95100 C. for 1 h.

After cooling the reaction mixture and adding hexane a light grey precipitate is obtained melting at 158 C.

By recrystallization from acetone the melting point raises to C.

(2) 3-chlorosulphonyl-4-n-hexadecyloxy-benzoic acid.- 3-sulpho-4-n-hexadecyloxy-benzoic acid is converted into the diacid chloride by treatment with thionyl chloride in the presence of dimethyl formamide. After distilling off the excess of thionyl chloride, formic acid of 8.5% is added and the reaction mixture is boiled for 15 min, whereby only the carboxylic acid chloride group is hydrolyzed. After cooling and Washing the precipitate with acetonitrile a white crystalline product is obtained. Melting point: 88 C.

(3) 3-fluorosulpltonyll-n-hexadecy loxy-benzoic acid.- Thesulphonyl chloride derivative prepared above is converted into the sulp'honyl fluoride by reaction with potassium fluoride in acetic acid. After cooling the reaction mixture the precipitate obtained is treated with isopropyl ether and recrystallized from acetic acid. The white crystalline product formed melts at 92 C.

(4) 3 fluorosulphonyl-4-n-hexadecyloxy-benzoylchloride.-The acid obtained in the previous step is converted into the acid chloride by means of thionyl chloride. After distilling off the excess of thionyl chloride the residue is recrystallized from n-hexane. The white crystalline product formed melts at 48 C.

(1) Z-methoxy-5-fluorosulphonyl-benzoylchloride F o z s (1) 2-methoxy-S-fluorosulphonyl-benzoic acid-This product is obtained by stirring for 3 h. at 45-50 C. a solution of 2-methoxy-5-chlorosulphonyl-benzoic acid (Meldrurn, Shah, J. Indian Chem. Soc. 8 (1931) 575) in dioxan with an aqueous solution of potassium fluoride. After pouring the reaction mixture into water and recrystallization of the precipitate from a mixture of ethyl alcohol and carbon tetrachloride a white crystalline product is obtained melting at 167 C.

(2) 2-methoxy 5 fluorosulphonyl-benzoylchloride. The acid obtained above is converted into the acid chloride by means of thionyl chloride. The product formed is recrystallized from a mixture of benzene and hexane. A white coarsely crystalline product is obtained. Melting point: 76 C.

(2) PRREPARATION OF fl-KETOESTER DERIVATIVES (CF. TABLE 1) (a) Substituted a-benzoyl-acetyl-acetic acid ethyl esters (reaction Step A) General procedure: To a suspension of 64.32 g. (0.2 mole) of the copper salt of acetyl acetic acid ethyl ester (cf. Conrad, Guthzeit, Ber. 19 (1886) 21) in 200 ccs. of chloroform 0.2 mole of fluorosulphonyl benzoylchloride is added in 15 min. time. The reaction mixture is stirred for 4 h. at room temperature. According to the solubility of the copper salt in chloroform the preparation is carried out in two different ways.

First method (the copper salt is soluble in chlorof0rm ).-The reaction mixture is acidified with hydrogen chloride. From the copper salt the a-fiuorosulphonylbenzoylaacetyl-acetic acid ethyl ester is set free. The chloroform layer is separated, washed with water until acid-free and evaporated till an oily residue remains. This residue is converted for purification purposes into the copper salt by means of a solution of copper (II) acetate in alcohol, and after separation of-the green precipitate formed set free again with acid. Finally the fi-dicarbonyl compound is obtained either as an oil which is distilled off or as a solid product which is treated with hexane.

Second method (the copper salt is insoluble in chlorof0rm).'1"he copper salt is separated and washed with 3,369,899 7 8 ethanol and with water. After treatment with acid the white crystalline product is obtained. Melting point: fi-dicarbonyl compound is set free from the copper salt, ll7-ll8 C. extracted with chloroform and evaporated till an oily This product is hydrolyzed for 3 h. at boiling temperaresidue remains. This residue is treated with hexane. A ture by means of a mixture of ethanol and concentrated crystalline product is formed. hydrogen chloride. Then the reaction mixture is neutralized with an aqueous solution of sodium hydroxide whereupon after cooling the precipitate formed is washed with water and recrystallized from acetonitrile. The 2- Gelleml Procedure! H1016 the a-bellzoyl yl methoxy-S-n-hexadecylarninosulphonylaniline is obtained acetic acid ethyl esters are refluxed for 3 i a in the form of a white crystalline product. Melting point:

(b) Substituted benzoyl acetic acid ethyl esters (reaction Step B) mixture of 50 ccs. of ethanol and 5 cos. of acetic acid. 84 C, After evaporating the solvent the residue is distilled off Z-chloro-S-n-hexadecylaminosulphonyl -aniZine.- First or recrystallized from an appropriate solv' the 2 chloro-5-n-hexadecylaminosulphonylnitrobenzene In the following Table 1 some benzoyl acetic acid ethyl i prepared i an analogous way as the 2-methoxy-5- esters are listed which were synthetized starting from acid n-hexadecylaminosulphonyl-acetanilide starting from 3- hl lid s i n d under P n chloro-4-nitrobenzene sulphonylchloride (Fischer, Ber.

TABLE 1 Substituted rrbQIlZOyl-ECGlZYl acetic acid Substituted benzoyl acet ic acid ethyl ester (0) ethyl ester (b) N 0. Formula of the acid chloride (:1)

Method Boiling point or melting Recrystallizing Boiling point or melting applied point agent point 1 3-fluorosulph0nyl benzoylchloride 1st Boiling point: 140-142" C. Boiling point: 158 C.

l (0.4 mm. Hg). (1.5 mm. Hg). 2 -fiuorosulphonyl benzoylchlonde 2nd Melting point; 62 C Boiling pOinEtI: 143-144" C.

.1 mm. 3 3fiuorosulphonyl4-ehlorobenzoylchloride Melting point: 56 C Ethanol Melting point? 65 C. 4 3,5-d1fluorosulphonyl benzoylchlonde. 2 Melting oint; 100 C do Melting point: 96 0. 5 3-tlu0rosulphonyl-icetyloxybenzoylchlor de Melting point: iZ- id O Methanol Melting point: 60 C. 6 2-meth0xy-5-fluor0sulphonylbenzoylchloride Melting point: 75-7 6 C l Ether/n-hexane... Melting point: 43-45 C.

(3) PREPARATION OF FLUOROSULPHONYL-SUB- 24 (1891) 3190) and n-hexadecylamine. After recrystal- STITUTED BENZOYLACETANILIDES D 0 lization from benzene a yellow crystalline product is ob- KALINE HYDROLYSIS THEREOF TO SUL- tained. Melting point: 92 C.

PHONIC ACI DERI A VE This product is hydrogenated in ethanol medium in the presence of Raney nickel as a catalyst at 80 C. and

a pressure of 105 kg./ sq. crn. After the calculated amount of hydrogen has been used up the catalyst is filtered ofi.

(a) Amino derivatives applied (cf. Table 2, col. 2) 2-n-hexadecyloxyaniline (CA. 46 (1952) 3976) z'n'hexadecylthloamhne 9 51 (i957) 12850) On cooling a white crystalline precipitate of 2-chloro-5- 2'n-h?Xadecylsulphonyl'anlhne (Belglan Paient P n-hexadecylarnino-sulphonyl-aniline is formed in the filcatlm trate. Melting point: 90 C. 4-I1-hf1Xadecylslllphoilyl-anlllne (Belglan Patent Pec1fi Z-n-hexadccylthio 5 difluoromcthylsulphonyl anicatlon 584,152) line.First 4 difluorornethylthiochlorobenzene is pre- 3'n'hexadecylsulphony1am1n"an11me pared analogously to the method described in J. Org. For the preparation of this product equimolar amounts Chem- 25 (1960) 2009/12 starting from P- i f m-nit oaniline d n hexadecyisulphonyl chloride phenol and chlorodifluoromethane in a solutio of sod1urn (sprague, J hn on Am Chem 59 1937 1837) hydroxide in dioxan. A colorless liquid is obtained. Boilare allowed to react in pyridine solution. The reaction mg P mixture is kept for 2 h. at 90 0 and for 3 h. at 115 c. Then the 4-dlfluor01pethylsulphonyl-chlorolqenzene 18 Then the pyridine is distilled off under reduced pressure P from the Prevlmls compound according "Q an and the residue is treated with methanol and washed with Pxldatlon Process analQgOuslY to the method decnbed water. After recrystallization from methanol 3-n-hexa- 25 Thsfefoi the -f decylsulphonylamino-nitrobenzene which is a white crysmethylthlwnlombenzelle 1S dissolved 1n afetlc tanine product is obtained Melting point: treated with an excess of a 30% aqueous hydrogen per- This product is hydrogenated in ethanol medium in the oxlde Solution and 1991166 r 3 h. After pouring into presence of Raney nickel as a catalyst at Q and a water a white crystalline precipitate of l-(llflllOl'Ol'l'lCillYlpressure of 105 an After the calculated amount sulphonyl-chlorobenzene is formed. Melting point: 67 C. of hydrogen is used up the catalyst is filtered off. On cool- This product is nitrated in an analogous way as the ing a white precipitate of 3-11-hexadecylsu1phonylaminopreparation of 4-difluoromethylsulphonyl-2-nitrobromoaniline is formed in the filtrate which is recrystallized benZeIle described in Chem- 25 The obtained. Melting point: 82 C. product is dissolved in concentrated sulphuric acid, N-n-hexadecyl m i il i Thi product i pretreated with portions of potassium nitrate and the reaction pared by reaction of isatic anhydride and n-hexadecylr is kept for 2 h. at 85 C. After pouring over amine i a t t fl temperature Aft t lice, filtering off the precipitate formed and washing with lization from methanol a white crystalline product is Water light YBHOW Crystals of 2-11itf0-4difiu0T0mahl/1- obtained. Melting point: 82 C, sulphonyl-chlorobenzene are obtained. Melting point:

3-palrnitoylamino-aniline (Belgian patent specification 3-n-hexadecylsulphonyl-aniline 2-rnethoxy-5-n-hexad'ecylaminosulphonyl-aniline This nitrated chlorobenzene derivative is allowed to react at boiling temperature with a solution of the lead salt of n-hexadecylmercaptane in dimethyl formamide. After refluxing for 2 h. the lead chloride formed is For the preparation f this product 1 filtered oil and the filtrate is poured out into methanol. sulphonylacetanilide (Child, J. Chem. Soc. 1932, 715-20 The preclrltate formed lsfiltered oft and recrystalhzed and n-hexadecylamine are refluxed in acetone while neufrom P 'P Light Yellow cfysiflis 0f y tralizing the hydrogen hl id get f i h 2 N di thio-S-difiuoromethylsulphonyl-nitrobenzene are obtainedhydroxide. After cooling the precipitate formed is washed Melting point: 8889 C. with water and recrystallized from ethanol. 2-rnethoxy-5- This nitro compound is reduced with iron and hydrogen n-hexadecylaminosulphonylacetanilide in the form of 7 chloride. The reduction is carried out in ethanol medium.

9 After the reduction the mixture is filtered off in warm state. On cooling a precipitate is formed in the filtrate which may be recrystallized from a mixture of methanol and ethanol. From white to yellow crystals of 2-n-hexal reaction is slowly distilled off till the temperature reaches 138 C. which takes about 1 h.

Then the remaining xylene is distilled oil under reduced pressure. To the residue 200 ccs. of hexane are decylthio-S-difiuoromethylsulphonyl-aniline are obtained. added. The precipitate formed is filtered otf and recrystal- Melting point: 7374 C. p lized from an appropriate solvent.

4-n-hexadecylaniline (CA. 55 (1961) 426)2-n-hex- In Table 2 (col. 34) the results are given of the adecyloxy-I-naphthylamine.First, 2 n-hexadecyloxy-lcondensations of amines with fi-ketoesters mentioned in nitronaphthalene is prepared by allowing to react for 1 Table 1. h. at reflux temperature equimolar amounts of n-hexadecylbromide and 1-nitro-2-naphthol-sodium salt disg? Alkilme lzfg y 2f hfluamsulzhonyl-substztuted solved in ethylene glycol monomethyl ether. After the 'l gf g es to Sup Omc de'lvatwes reaction the potassium bromide formed is filtered oil. In the filtrate f Preclpltate of g General procedure.--0.1 mole of fluorosulphonyl denaphthalene formed recrystalwanzn fi rivative in 400 ccs. of acetone is heated till boiling temf hght Xeuow crystanme Product 18 0 tamed perature. Whilst stirring, 60 ccs. of 5 N sodium hydroxide g i q g 1 d h d d t are slowly added, thus producing an exothermic reaction. 50 15 lutronap h a I' 1 efwatlved 15 y rogenatef The reaction mixture is heated at boiling temperature for k m g so utlonf er a p f i 0 t 3 h. Whilst stirring. Then the reaction mixture is acidified A i if alley 2? 6 5 with acetic acid and cooled till room temperature. The a is er ur er ma e conven Iona Way 'P' precipitate formed is washed with water and recrystallized hexadecyloxy-l-naphthylamlne 1n the form of a white t d bt d M C from an appropriate solvent. crys a me Pro uc 0 mm 6 mg Pol In Table 2 (cols. 5-6) the results of these alkaline (1)) Preparation of the corresponding benzoylacetanilides hydrolyses are given (col. 6 refers to the numbers of the (reaction Step C) structural formulae of the color couplers).

TABLE 2 ikrizpltied Substituted benzoylacetanilide Sulphonic acid derivative (sodium salt) e 0 Applied amino derivative ester Melting Structural dteriva- Recrystallizing agent potent, Recrystallizing agent formula ive 2-n-liexadecyloxyaniline 1 Isopropanol 94 Water 1 Do 2 do 96 Isopropanol/water 2 Do. 1 Hexane 73 Ethanol/water 3 2-n-hexadecylsulphonylanilin 1 Ethanol 98 E thanol 4 -n hexadecylsulphonylaniline 2 Dichloroethane/hexane 146 Etlt gleneglycol monomethyl- 5 e 61'. 3-n-hexadecylsulphonylaniline 1 do 87 Methanol/water 6 N-n-hexadeeylanthranilamide 2 Etltlgleneglycol monomethyl- Ethanol/water 7 8 6!. 3-palmitoylamino-aniline 1 Dichlcroethane 128 Isopropanol/water 8 2-n-hexadecylthioaniline 3 8182 Ethan0l/water 9 3 n-hexadeeylsulphonylaniline 4 122 o 10 Aniline 5 114 Methanol/water... 11 2-methoxy-5-n-hexadecylaminosulphonyl-aruline 2 Isopropanol 151 Isopropanol/water 12 Z-chloro-fi-n-hexadecyleminosulphonyl-aniline 1 Dichloroethane/hexane Elllgl61t2gfiy00% monomethyl- -13 e ere 8.110. r Z-n-hexadeeylthio-fi-dlfluoromethylsulphonyl- 1 Ethanol 97 Methanol/water 14 8111 H19. -n-hexadeoyl-aniline 6 Dichloroethane. 138 Ethanol/water 15 z-n-hexadecyloxyJ-napthylamine 3 V Isopropanol Methanol/water 16 1 The numbers refer to the numbers of Table 1, col. 1.

General procedure. O.l mole of amine derivative, 0.1 mole of B-ketoester derivative and 0.2 g. of anhydrous sodium acetate are placed in 100 ccs. of anhydrous xylene.

The reaction mixture is heated till reflux temperature 50 and a mixture of xylene and ethanol formed during the Specific examples of color couplers for yellow according to the present invention wherein a .sulphonic acid group in the aroyl part of the molecule is bound to an aromatic nucleus which is linked to the aromatic nucleus of the aroyl part by means of a bivalent radical, are:

NO OOCH2COOC2H5 NH2- N01 OOCHzOONH- O C s:

F SO 2 F802 WNH-Oc0orncorna@ wherein:

Z represents a -COCl radical, a SO Cl radical or a -NCO radical, and

W a CO- radical, a SO radical or a -NHCO radical.

| NaO SO2 -WNH000Hz0 0 NHO (A) INTERMEDIATE COMPOUNDS APPLIED (a) a- 3 -amin0benz0yl -2 -n-hexadecy loxyacetani lid e O Cm aa First, the a-(3'-nitrobenzoyl)-2-n-hexadecyloxyacetanilide (a') is prepared analogously to the general pro cedure as described above under (312), starting from 33.3 g. of 2-n-hexadecyloxy-aniline and 23.7 g. of 3-nitrobenzoyl acetic acid ethyl ester. After recrystallization from a mixture of benzene and n-hexane, a light yellow crystalline product is obtained. Melting point: 90 C.

The nitro product obtained is reduced in the presence of Raney nickel as catalyst in a dioxan solution under a pressure of 105 kg./sq. cm. of hydrogen at 70 C. Once the calculated amount of hydrogen has been used up the catalyst is filtered oil. In the filtrate a precipitate is formed which is filtered off and recrystallized from benzene. The a (3' aminobenzoyl) 2-n-hexadecyloXy-acetanilide (b') is obtained in the form of white crystals. Melting point: 112 C.

(b) 3-flu0r0sulph0nyl-benzoylchloride (cf. 1.a)

(c) 3-flu0r0su[phonylbenzenesulphochloride This compound is prepared analogously to the general method for preparing sulphonyl chlorides from amino derivatives (Maerwein et al., Ber. (1957) 841). Starting from 3-fluorosulphonylaniline (British patent specification 808276) a colorless oil is obtained after diazotation in the conventional way and a treatment with a sulphur dioxide solution in acetic acid in the presence of copper (I) chloride. Boiling point: 137 C. (0.9 mm. Hg).

(d) 3-flu0r0sulph0nylphenylisocyanate The synthesis of this product occurs analogously to the preparation of p-nitrophenylisocyanate described in Org. Synth. Coll. vol. II (1943) 453. A solution of 3- finorosulphonylaniline in ethylacetate is treated with an excess of phosgene. After reaction the solvent is distilled off under nitrogen atmosphere. The residue is vacuum distilled yielding a colorless liquid. Boiling point: 102 C. (1.2 mm. Hg).

(B) REACTION OF a-(T-AMINOBENZOYL)-2-n- HEXADECYLOXYACETANILI-DE WITH VAR- IOUS SULPHONYL FLUORIDES (c) (a) With 3-flu0r0sulph0nylbenzoylchloride 9.88 g. of amino derivative is dissolved in a tenfold amount of acetonitrile. To this solution an equivalent amount of 3-fluorosulphonyl-benzoylchloride is added whereupon the reaction mixture is refluxed for 5 h.

Hydrogen chloride is gradually set free and the initially formed precipitate of amine hydrochloride dissolves slowly. After the said reflux period a clear light yellow solution is obtained wherein on cooling till room temperature a white granular product precipitates which is separated and recrystallized from acetonitrile, Melting point: 104 C.

(b) With 3-flu0r0sulphonylbenzenesulphochloride 9.88 g. of amino derivative are dissolved in an eightfold amount of acetic acid comprising 1.7 g. of anhydrous sodium acetate. To this solution is added an equivalent amount of 3-fluorosulphonylbenzenesulphochloride whereupon the reaction mixture is refluxed for 30 min. After adding water and cooling till room temperature a White crystalline product is obtained. This product is separated and subsequently recrystallized from a mixture of benzene and hexane and from methanol. Melting point: 96 97 C.

(0) With S-fluorosulphonylphenylisocyanate 9.88 g. of amino derivative are dissolved in an eightfold amount of anhydrous dioxane. To this solution is added an equivalent amount of 3-fluorosulphonylphenylisocyanate whereupon the reaction mixture is heated for 3 h. at 8090 C. On cooling till room temperature a precipitate is formed which is separated and recrystallized from ethanol. A white crystalline product melting at 136 C. is obtained.

(C) ALKALINE HYDROLYSIS TO SULPHONIC ACID DERIVATIVES (d') The alkaline hydrolysis of the sulphofluoride derivatives is carried out as indicated above in the procedure under (30).

In the following Table 3 the results of some alkaline hydrolyses of the corresponding fluorosulphonyl derivatives are given.

TABLE 3 Sulphofiuoride derivative applied I Recrystallizing No. of the agent structural F502 WNH C OCHzCONH- formula C O Ethanol/water- 17 -S O i- Ethanol 18 NH O 0 Ethanol/water- 19 The color couplers need not necessarily be separated in the form of sulphonic acid derivatives before their addition to the silver halide emulsion. The sulphonic acid derivatives formed in situ from the sulphofiuoride derivatives by dissolving the latter derivatives in alkali can be added as such to the emulsion. Preferably 1 mole of sulphofluoride derivative is hydrolyzed therefor in an aqueous solution of 3 mole of sodium hydroxide and the resulting clear solution, after adjusting the pH to agree with the pH of the emulsion applied, is added to the silver halide emulsion in the form of a 5 to aqueous solution.

During the preparation of the light-sensitive color material, the non-migratory color couplers for yellow according to the above-mentioned general formulae are mixed homogeneously in dissolved state with the lightsensitive silver halide emulsion, preferably immediately before the coating of the emulsion. They may also be added to the composition of a water-permeable nonlight-sensitive layer, which is in direct contact with the light-sensitive silver halide emulsion layer or they may be incorporated into a non-light-sensitive layer, which is separated from the light-sensitive layer by a waterpermeable non-light-sensitive layer. The silver halide emulsion contains'the usual colloids such as gelatin, poly- (vinyl alcohol), collodion or other suitable natural or synthetic colloids. The photographic emulsion may further contain usual ingredients such as hardeners, chemical sensitizing agents, optical sensitizing agents, plasticizers, development accelerators, stabilizing agents and wetting agents.

The color couplers for yellow according to the abovementioned general formulae are added usually to a bluesensitive silver halide emulsion. According to the most conventionally applied procedure this silver halide emulsion is coated as the last color coupler-containing layer of a photographic multilayer color material. Such photographic multilayer color material usually consists in the given sequence of a support, a red-sensitized siver halide emulsion layer with a color coupler for cyan, a greensensitized silver halide emulsion layer with a color coupler for magenta and a blue-sensitive silver halide emulsion layer with a color coupler for yellow. The support of this multilayer material may consist of paper, glass, cellulose nitrate, a celluose ester such as cellulose triacetate, polyester, polystyrene or another synthetic or natural resin.

Between the silver halide emulsion layer containing a color coupler for yellow and the green-sensitized silver halide emulsion layer a yellow filter layer is generally present which comprises usually colloidal silver dispersed in gelatin.

The sulphofiuoride derivatives may be applied as color couplers for yellow according to the present invention in the so-called droplet emulsions. .(cf.. U.S..Patent 2,304,940). 7

For the production of photographic color images according to the present invention an exposed silver halide emulsion layer is developed with an aromatic primary amino dveloping substance in the presence of a color coupler for yellow according to the present invention.

All color developing substances capable of forming azomethine dyes can be utilized as developers. The color couplers for yellow according to the present invention form on color development with aromatic primary amines such as N-diethyl-p-phenylenediamine yellow dyes which excel by their favorable light absorption in the blue region of the spectrum and little absorption in the other regions. Further, the dyes formed on color development show good resistance to heat, humidity and light which is proved by comparative tests, the description and results of which are given hereinafter.

The resistance to humidity and heat of the dyes to be examined is determined from the decrease in density Maximum density Maximum density Percentage Formula of the color coupler at the beginning after storing for I decrease in oi the test 10 days at 0. maximum and 87% RH. density (I) CisHaa mosmQ-ooomcoma 1.2 1.2 o

O Cm aa NaOSO CONH- COCHzCONH- 1.2 1.2 0

ClaHaaO-Q-C 0 0 mo ONHO-S O3N3.

(Color coupler for yellow according to British patent specification 808,276.)

15 of a developed wedge print after having stored said Wedge print for a certain time (e.g., days) at a specific temperature (e.g., 35 C.) and relative humidity (e.g., 87%), While being protected from light.

The preceding table gives a clear idea about the resistance to humidity and heat of dyestufrs formed on color development by reaction of the oxidation product of N-diethyl-p-phenylenediarnine with color couplers according to the present invention and a known color coupler of British patent specification 808,276 respectively.

The resistance to light of the dyestuffs formed on development with N-diethyl-p-phenylenediamine and which are to be examined is determined from the decrease in density of a developed wedge print on exposing it for a certain time (e.g., 16 h.) to light of a Xenon Arc Fadeometer (daylight spectrum).

The following table gives a clear idea about the resistcoupler for yellow of the aroylacetanilide type wherein the aroyl part of the aroylacetanilide molecule comprises at least one sulfonic acid group, the anilide part of the aroylacetanilide molecule contains only substituents selected from the group consisting of hydrogen and a hydrophobic group, and the aroylacetanilide molecule contains a group for inhibiting migration in a member of the group consisting of the aroyl part and anilide part of the molecule.

3. Photographic multilayer color material comprising, in non-migratory state, in a member selected from the group consisting of a light-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent to a silver halide emulsion layer a color coupler for yellow corresponding to the following general formula:

ance to light of a dyestufi formed on development by RH reaction of the oxidation product of N-diethyl-p-phenylenediamine with a color coupler according to the present 20 Z OH CO NH invention and known color couplers for yellow respectively. R4

Maximum density Maximum density Percentage Formula of the color coupler at the beginning after exposing for decrease in of the test 16 h. in Xenon maximum Are Fadeometer density NaOSO: COOH:CONH -NHO 00 11 1.20 1.10 8.5

C H O ONHO-C OCH-2C ONH- -SO;H 1. 20 1. 02 15 (Color coupler for yellow described in the British patent; pecification ClbHnC ONH -COOH:C ONE COOH 1.20 0.99 17.5

(Color coupler for yellow described in th (British patent specification In connection with the structure of the color couplers wherein:

according to the present invention there has to be remarked that, where the term sulphonic acid group or sulphonic acid substituent is used, the acid form :as well as the salt form of this group or substituent are intended, the salt form carrying preferably as cation an alkali metal cation, an ammonium group or an amine salt group.

Wherever in the specification the term group or substituent having no water-solubilizing character is used :there is intended group or substituent having a hydrophobic character.

We claim:

1. A photographic material comprising a silver halide emulsion layer and a color coupler for yellow of the .aroylacetanilide type wherein aroyl part or the aroyl- :acetanilide molecule comprises at least one sulfonic acid group, the anilide part of the aroylacetanilide molecule contains only substituents selected from the group consisting of hydrogen and a hydrophobic group, and the aroylacetanilide molecule contains a group for inhibiting migration in a member of the group consisting of the aroyl part and anilide part of the molecule;

2. Photographic multilayer color material comprising, in non-migratory state, in a member selected from the group consisting of a light-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent to a silver halide emulsion layer a color Z is a sulfonated benzoyl group;

R represents a member selected from the group consisting of a hydrogen atom and a hydrophobic group;

R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and the atoms necessary to form a fused aromatic nucleus, said color coupler having at least one group for inhibiting migration.

4. Photographic multilayer color material comprising, in non-migratory state, in a member selected from the group consisting of a light-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent to a silver halide emulsion layer a color coupler for yellow corresponding to the following general formula:

Y represents a bivalent radical selected from the group consisting of CONH, SO NH, and

1 7 R' represents a sulfonated aromatic nucleus, R represents a member selected from the group consisting of a hydrogen atom, a hydrophilic group and a hydrophobic group,

R represents a member selected from the group consisting of a hydrogen atom, and a hydrophobic group,

R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and the atoms necessary to form a fused aromatic nucleus, at least one of R and R being a group inhibiting migration.

5. Photographic multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized wherein a member selected from the group consisting of the blue-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent thereto incorporates, in non-migratory state, a color coupler for yellow of the aroylacetanilide type wherein the aroyl part of the aroylacetanilide molecule comprises at least one sulfonic acid group, the anilide part of the aroylacetanilide molecule contains only substituents selected from the group consisting of hydrogen and a hydrophobic group, and the aroylacetanilide molecule contains a group for inhibiting migration in a member of the group consisting of the aroyl part and anilide part of the molecule.

6. Photographic multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized wherein a member selected from the group consisting of the blue-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent thereto incorporates, in non-migratory stateTa color coupler for yellow corresponding to the following general formula:

wherein:

Z is a sulfonated benzoyl group; R represents a member selected from the group consisting of a hydrogen atom and a hydrophobic group; R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and 18 the atoms necessary to form a fused aromatic nucleus, said color coupler having at least one group for inhibiting migration.

7. Photographic multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized wherein a member selected from the group consisting of the blue-sensitive silver halide emulsion layer and a non-light-sensitive water-permeable colloid layer adjacent thereto incorporates, in non-migratory state, a color coupler for yellow corresponding to the following general formula:

wherein:

Y represents a bivalent radical selected from the group consisting of CONH--, SO NH, and

NH(|f-NH o R represents a sulfonated aromatic nucleus, R represents a member selected from the group consisting of a hydrogen atom, a hydrophilic group and a hydrophobic group, R represents a member selected from the group consisting of a hydrogen atom, and a hydrophobic group, R represents a member selected from the group consisting of a hydrogen atom, a hydrophobic group and the atoms necessary to form a fused aromatic nucleus, at least one of R and R being a group inhibiting migration.

References Cited UNITED STATES PATENTS 2,662,913 12/1953 Eberhart et al. 260507 2,836,620 5/1958 Bersworth et al. 260-507 2,933,391 4/1960 Feniak et al. 96--100 2,983,608 5/1961 Beavers 96100 2,350,138 5/ 1944 Weissberger 96-56.6 2,704,709 3/ 1955 Sprung 969 2,895,825 7/1959 Pelz et al. 9656.6

NORMAN G. TORCHIN, Primary Examiner.

J. T. BROWN, Assistant Examiner.

Claims (1)

1. 5. PHOTOGRAPHIC MULTILAYER COLOR MATERIAL COMPRISING THREE SILVER HALIDE EMULSION LAYERS WHICH ARE DIFFERENTLY OPTICALLY SENSITIZED WHEREIN A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE BLUE-SENSITIVE SILVER HALIDE EMULSION LAYER AND A NON-LIGHT-SENSITIVE WATER-PERMEABLE COLLOID LAYER ADJACENT THERETO INCORPORATES, IN NON-MIGRATORY STATE, A COLOR COUPLER FOR YELLOW OF THE AROYLACETANILIDE TYPE WHEREIN THE AROYL PART OF THE AROYLACETANILIDE MOLECULE COMPRISES AT LEAST ONE SULFONIC ACID GROUP, THE ANILIDE PART OF THE AROYLACETANILIDE MOLECULE CONTAINS ONLY SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND A HYDROPHOBIC GROUP, AND THE AROYLACETANILIDE MOLECULE CONTAINS A GROUP FOR INHIBITING MIGRATION IN A MEMBER OF THE GROUP CONSISTING OF THE AROYL PART AND ANILIDE PART OF THE MOLECULE.