US3884700A - Silver halide emulsions containing two-equivalent benzoylacetanilide photographic couplers - Google Patents

Abstract

Two-equivalent benzoylacetanilide photographic couplers containing ballasting groups attached to an aromatic ring thereof characterized by a halogen atom in ortho position in the benzoyl residue and a halogen atom as a substituent in the reactive methylene which are substantially free of fog and produce yellow dyes substantially without orange coloration upon color development.

Description

United States Patent Quaglia May 20, 1975 SILVER HALIDE EMULSIONS [56] References Cited CONTAINING TWO-EQUIVALENT UNlTED STATES PATENTS BENZOYLACETANIUDE PHOTOGRAPH": 3,056,675 l0/l962 Hoffstadt 96/100 COUPLERS 3,369,895 2/1968 Loria et a]. 96/100 3,664,84] 5/1972 lwama et al. 96/100 [75] lnvfimo" figs Mare 3,669,671 6/l972 Iwama et al. 96/100 [73] Assignec: Minnesota Mining and Primary Examiner-J. Travis Brown Manufacturing Company, St. Paul, Attorney, Agent, or Firm-Alexander, Sell, Steldt & Minn. DeLaI-lunt [22] Flledz Dec. 26, 1972 [57] ABSTRACT PP 3181561 Two-equivalent benzoylacetanilide photographic couplers containing ballasting groups attached to an aro- [30] Foreign Application Prioriy Data matic ring thereof characterized by a halogen atom in D 28 1971 k 1 ortho position in the benzoyl residue and a halogen a y atom as a substituent in the reactive methylene which are substantially free of fog and produce yellow dyes 96/100 96/56 substantially without orange coloration upon color de- [58] Field of Search 96/100, 55

3 Claims, No Drawings US. Pat.

1 SILVER HALIDE EMULSIONS CONTAINING TWO-EQUIVALENT BENZOYLACETANILIDE PHOTOGRAPHIC COUPLERS The present invention relates to two-equivalent benzoylacetanilide couplers for color photography and to colored photographic elements containing them.

More specifically the present invention relates to two-equivalent benzoylacetanilide couplers which give rise to yellow dyes upon color development with pphenylene diamine type developers.

The present invention further relates to photographic emulsions containing such couplers. to photographic elements including such emulsions and to photographic elements containing the dyes derived from such couplers upon color development.

Colored photographic elements normally include at least three emulsion layers which are sensitive to the blue, to the green and to the red region and contain, respectively, a yellow, a magenta and a cyan coupler.

It is recognized in the art that couplers used in photographic elements should not be excessively reactive. This will prevent undesired color formations.

[t is also known that couplers must give rise upon color development to dyes having a given desired absorption curve to obtain images with balanced colors It may be useful, for instance, to obtain yellow dyes substantially without orange colorations, i.e., with a low absorption in the green region.

Benzoylacetanilide type couplers are capable of reacting with the oxidation product of p-phenylene diamine type developers to form yellow images in light exposed silver halide photographic elements.

Upon color development with p-phenylene diamine type developers, a molecule of such couplers normally give rise to a molecule of a dye by the reduction of four silver ions struck by the light. If however one of the hydrogens of the reactive methylene in the coupler is substituted with a suitable substituent, a molecule of a dye can be obtained by the reduction of only two silver ions.

The couplers which exhibit such characteristics are commonly called two-equivalent couplers: the meaning of this expression is clear. Obviously they are very useful in color photographic industry because they allow a lower consumption of silver in color photographic emulsions which employ incorporated couplers.

Benzoylacetanilide couplers include a benzoyl residue (phenyl-CO) and an aniline residue (NH-phenyl) joined by a carboxymethylene bridge (CHg-CO). This methylene group is called reactive methylene" be cause the coupling reaction occurs on it.

Two-equivalent benzoylacetanilide couplers are described for instance in the French Pat. No. 991,453; in Nos. 2,407,210; 2,728,658; 3,408,194; 3,447,928 and in the British Pat. No. 1,092,506.

Such two-equivalent benzoylacetanilide couplers have some drawbacks which make their practical employment in colored photographic elements difficult and sometimes impossible. These difficulties drive from their excessive reactivity which enables them to react with the developer even in absence of exposed silver halide, thus giving rise to undesired coloration commonly called fog. Furthermore, some two-equivalent benzoylacetanilide couplers known in the art are much more expensive than four-equivalent couplers from LII ' low-cost couplers substantially free of fog can be obtained by the combination of a halogen substituent (Y) in ortho position in the benzoyl and a halogen substituent (X) in the reactive methylene.

lt was further found that a fluorine atom as a substituent in ortho position in the benzoyl and a halogen atom as a substituent in the reactive methylene yield low-cost benzoylacetanilide couplers, substantially free of fog, which give rise to yellow dyes substantially without orange coloration upon color development with pphenylene diamines.

The halogen substituent (X) produces low-cost twoequivalent couplers, and the halogen substituent (Y), combined with it, yields two-equivalent couplers substantially free of fog.

The halogen substituent in ortho position in the benzoyl is an essential substituent for the purposes of the present invention. It enables one to obtain, free of fog, two-equivalent benzoylacetanilide couplers of the type having a hydrogen of the reactive methylene substituted with a halogen.

Other substituents can obviously be introduced into the benzoyl and aniline residues to provide the couplers or the dyes deriving therefrom upon color development with desired characteristics. For example, these characteristics may relate to the solubility of the couplers, to their non-diffusing properties, to the stability of the dyes deriving therefrom and to their absorption characteristics. Such substituents however are thought to be of secondary importance for the main purpose of the present invention. The man ordinarily skilled in the art can select them readily, so that the advantages of the present invention can be achieved and the requirements of particular usages satisfied everytime.

Substituents which can be usefully introduced into the molecule of the couplers of the present invention are for instance alkyl groups (having for instance from 1 to 18 carbon atoms), halogen (for instance Cl, Br, F), alkoxy groups (having for instance from I to 18 carbon atoms), dialkylamino groups (having from 2 to 19 carbon atoms), arylaminosulphoxy groups (for instance phenylaminosulphoxy, alkylphenylaminosulphoxy, oand p-alkylphenylaminosulphoxy, oand palkoxyphenylaminosulphoxy, wherein the alkyl or alkoxy group has from 1 to 18 carbon atoms), aryloxyacylamino group (for instance phenyloxyacylamino, phenyloxyacetylamino, alkylphenyloxyacylamino, 2,4- dialkyl-phenyloxyacylamino, 2,4- dialkylphenylacetylamino, wherein the alkyl group or the alkyl groups have altogether from i to 18 carbon atoms, acyl group having from 1 to l8 carbon atoms, arylsulphonamido (for instance phenylsulphonamido, alkylphenylsulphonamido, alkoxyphenylsulphonamido, oand p-alkylphenylsulphonamido, oand p-alkoxyphenylsulphonamido, wherein the alkyl or alkoxy group has from 1 to 18 carbon atoms) and every other substituent known to the man ordinarily skilled in the art. The applicant has observed that the best substituent combination to obtain, within the scope of the present invention. two-equivalent couplers free of fog which give rise to yellow dyes substantially without orange coloration upon color development with pphenylene diamine type developers is the combination of a fluorine atom in the ortho position in the benzoyl, a halogen in the reactive methylene and an electron donor of the alkyl, alkoxy group, dialkylamino type and their equivalents in ortho position in the aniline residue. Very stable couplers within the present invention can be further obtained if in combination with the halogen, particularly fluorine atom in ortho position in the benzoyl, the halogen in the reactive methylene and the electron donor of the alkyl, alkoxy group and dialkylamino type in 2 (ortho) position in the aniline residue, an arylsulphonamiclo or arylaminosulphoxy group in S-position in the aniline residue (for instance phenylaminosulphoxy, alkylphenylaminosulphoxy, alkoxylaminosulphoxy, oand palkylphenylaminosulphoxy, oand palkoxyphenylaminosulphoxy, phenylsulphonamido, alkylphenylsulphonamido, alkoxyphenylsulphonamido, and p-alkylphenylsulphonamido, oand p-alkoxyphenylsulphonamido, wherein the alkyl or alkoxy group has from 1 to 18 carbon atoms) is used.

It is desirable for a corect employment of the couplers of the present invention in silver halide photographic emulsions to provide them with ballasting groups which prevent them from wandering through the emulsion layers that compose the silver halide photographic elements. In view of this, the coupler is intended to mean a non-diffusing coupler," Le, a coupler carrying at least a ballasting group capable of imparting non-diffusing properties to the said coupler. The ballasting groups or anti-diffusing chains, as they are often called. (generally comprising high-molecular weight alkyl groups, e.g., having from to 18 carbon atoms) can be introduced as substituents either into the benzoyl residue or into the aniline residue of the couplers of the present invention, because it does not appear that they substantially affect the coupler characteristics necessary for the purposes of the present invention. On account of preparation ease, and therefore of cost, the ballasting group is preferably introduced into the aniline residue, preferably into the phenyl ring in ortho (2) and/or in meta (5) position to the carbon atom carrying the amino group (briefly: in ortho and/or in meta position in the aniline residue).

In the case where the couplers of the present invention must be incorporated into photographic emulsions in aqueous solution, they must be made water-soluble by means of the SO H and COOH type. In the case where they must be incorporated into the emulsion by the solvent dispersion technique, the couplers must be soluble in substantially water-immiscible organic solvents (see: C. E. Kenneth Mees and T. H. James, The Theory of Photographic Process, third edition, page 303).

Such techniques, which are now preferred, are described for instance in US. Pat. Nos. 2,322,027; 2,801,170; 2,80l,l7l; 2,870,0[2 and 2,991,177. Briefly the solvent dispersion technique involves first dissolving a coupler in a substantially water-immiscible organic solvent and then dispersing the so-prepared solution as extremely fine droplets in a hydrophilic colloidal binder. Gelatin is the preferred hydrophilic colloidal binder but other polymeric colloidal binder materials known to the art can also be used. Obviously, when the couplers are incorporated into the emulsion by the solvent dispersion technique, the dyes deriving therefrom upon color development are also contained dispersed in the emulsion dissolved in the substantially water-immiscible organic solvent.

Briefly, the present invention refers, in its most general aspects, to non-diffusing benzoylacetanilide couplers including a halogen atom in the reactive methylene and in ortho position in the benzoyl residue as expressed by the following formula:

B-CH-CO-A wherein: B is a benzoyl residue bearing a halogen substituent in the phenyl in the ortho position to the carbon atom carrying the carbonyl; X represents a halogen atom and A is an aniline residue.

In its more particular aspect, the present invention refers to non-diffusing benzoylacetanilide couplers containing a halogen substituent in the reactive methylene and a fluorine atom in ortho position in the benzoyl. More particularly, the present invention relates to non-diffusing couplers of the benzoylacetanilide type including a halogen atom, and in particular a fluorine atom, in ortho position in the benzoyl, a halogen atom in the reactive methylene and an electron donor of the alkyl group, alkoxy group, dialkylamino group type in ortho position in the aniline residue. More particularly, the present invention refers to non-diffusing couplers of the benzoylacetanilide type including a halogen atom, and in particular a fluorine atom, in ortho position in the benzoyl residue, a halogen atom in the reactive methylene, an electron donor of the alkyl group, alkoxy group, dialkylamino group type in 2-position in the aniline residue and a group of the arylsulphonamido or arylaminosulphoxy type in S-position in the same aniline residue.

The present invention also relates to silver halide photographic emulsions containing such couplers preferably introduced by the solvent dispersion technique and to photographic elements comprising such emulsions. The present invention further relates to exposed and developed silver halide photographic elements containing dyes derived from the said couplers upon coupling reaction with p-phenylene diamine type compounds.

Useful couplers within the scope of the present invention are for instance the following:

1) G CO-CH-CO-NHQ c a t I 01 NH-CO7CH20- c n t coca-001m oc n 1 c1 SO2NH OCH3 ,co-en-comr o NH-CO-CH -O-C H 1-t.

Prior art couplers useful for a comparison with the couplers according to the present invention are for example the following.

A) CO-CH-CO-NH c1 ocn I CO-CH-(IO-NH N'H-CO -CH O 0 1-1 1:

C H t c Q I 01 SOQNHQ OC18H37 1 D) CO-CH-CO-NH oso cn 0 G The following examples further illustrate the practice of the present invention:

EXAMPLE 1 a-( Z-chlorobenzoyl)-a-chloro-5-[ oz-( 2-4-ditertamylphenoxyl)-acetamide1-2-chloroacetanilide intermediate l; 3-nitro-4-chloro-a-(2-4-ditertamylphenoxy )-acetanilide 0 1mg S12E25 5L7 g. (0.3 moles) of 3-nitro-4-chloro-aniline, 29.5 g. (0.36 moles) of sodium acetate anhydrous and 450 m]. of glacial acetic acid were mixed in a multi-neck flask of 1 liter provided with a stirrer and a refluxecondenser. The mixture was stirred till a complete solution was reached and 93.2 g. (0.3 moles of 24-- ditertamyLphenoxy-acetyl-chloride were added thereto. The solution was stirred for l hour at room temperature and further at 70C for half an hour. The hot solution was poured into icy water and the precipi tate filtered, washed. dried and crystallized from ethanol, thus obtaining 1 12.4 g. of a white product melting at 154-155C.

Analysis: Found Calculated Intermediate 2: 3-amino-4-chloro-o:-(2-4-ditertamylphenoxy)-acetanilide 44.6 g. (0.1 moles) of the intermediate 1 were put into a 500 m1. autoclave with 250 ml. of ethanol and Ni Raney in catalytic quantities. The mixture was held under stirring for 10 h at a H pressure of 40 atm. and at a temperature of 50C. The Ni was removed from the solution by filtration, the solution was then dried and the residue crystallized from ligroin, thus obtaining 31.8 g. of a white product melting at l 10-l 12C.

Analysis: Nl-l 98.7 Intermediate 3: a-( 2-chlorobenzoyl )-5-[ a-( 2-4- ditertamylphenoxylacetamidel-2-chloro-acetanilide 41.7 g. (0.1 moles) of the intermediate 2 and 200 ml. of xylene were mixed into a multi-neck flask provided with a stirrer and a Liebig condenser. To the solution brought to boil, 10 ml. ofa solvent distilled and 24.9 g. (0.11 moles) ethyl o-chlorobenzoyl acetate, prepared according to the method described in J.A.C.S. 37, 1259. were added thereto. The solution was boiled gently for 3 h, thus obtaining 40 ml. of distillate. The precipitate thus formed was filtered. washed with dried methanol and recrystallized from methanol, thus obtaining 33.5 g. of a white product melting at 108-1 10C.

Calculated 11.87

Found Cl% Titration from CH 99.88.

Preparation of the coupler 20.8 g. (0.0348 moles) of a-(2-chlorobenzoyl)-5-[a- (2-4-ditertamylphenoxy)acetarnide]-2' chloroacetanilide and 100 ml. of anhydrous chloroform were mixed into a 250 m1. multi-neck flask provided with a stirrer and a refluxe-condenser. The solution was cooled at some 5C and 4.4 g. (0.034 moles) of pure sulphorylchloride all at once added thereto. The mix ture was held under stirring for 3 h at room temperature, afterwards the solvent was distilled under vacuum and the molten residue dissolved in boiling methanol. The precipitation of a white-rosy product was obtained by cooling the solution. The precipitate was recrystallized from methanol, thus obtaining 17.5 g. of a white product melting at 9598C.

a-( 2-chlorobenzoyl )-a-chloro-Z-methoxy-5-[a-(2-4- ditertamylphenoxy)-acetamide]-acetanilide lntermediate 4; d-(2-chlorobenzoyl)-2-methoxy-5- nitro-acetanilide 50.5 g. (0.3 moles) of Z-methoxy-S-nitro-aniline and 200 ml. of xylene were mixed into a 500 ml. multi-neck flask provided with a stirrer and a Liebig condenser. The mixture was brought to boil and when some 10 ml. of solvent were distilled, 81.6 g. (0.36 moles) of ethyl Z-chlorobenzoylacetate were added thereto. The solution was boiled gently for 4 h., thus obtaining 35 ml. of distillate and afterwards cooled at room temperature and then at 35C for 2 h.

The precipitate thus formed was filtered, washed first with xylene and then with petroleum ether, dried and finally recrystallized from acetone, thus obtaining g. of a crystalline straw-colored product melting at Found 1011 Calculated 10. l 7

Intermediate 5: amino-acetanilide A 250 ml. methylcellosolve and Ni Raney (in catalytic quantities) solution of 34.8 g. (0.1 moles) of the intermediate 4 was poured into a 500 ml. autoclave. The mixture was stirred for 18 h at room temperature at a H pressure of 35 atm.

The Ni was then removed by filtration and the solvent distilled under vacuum. The oily residue was dissolved in boiling methanol. By cooling the solution, a white crystalline precipitate was obtained. The precipitate was then filtered washed and dried, thus obtaining 25.6 g. of a product melting at 124-l26C.

oz-( 2-chlorobenzoyl )-2-methoxy-5 Calculated l l l 2 Found 1 1.14

intermediate 6: a-(2-chlorobenzoyl)-2-methoxy-5-[a- (2-4-ditertarnyl-phenoxy)-acetamide l-acetanilide 9.2 g. (0.13 moles) of sodium acetate anhydrous were dissolved into 400 ml. of glacial acetic acid in a l 1. multi-neck flask provided with a stirrer and refluxe condenser.

30 g. (0.094 moles) of the intermediate 5 and further 29.2 g. (0.094 moles) of 2-4-ditert-amyl-phenoxyacetylchloride were then added to the solution. It was then stirred for 1 h at room temperature and U2 h at 60-70C, the mixture was then poured into icy water under stirring. The precipitate thus formed was filtered, washed with water, dried and recrystallized from ethanol, thus obtaining 40.6 g. of a white product melting at l31133C.

This coupler was prepared in the manner described in Example 1.

26.1 g. of a white product, recrystallized from ethanol, were obtained from 29.7 g. (0.05 moles) of the intermediate 6 and 6.8 g. (0.05 moles) of sulphoryl chloride. M. P. 96-98C.

a-( Z-bromobenzoyl )-a-chloroa-( 2-4-ditertamylphenoxy)-acetamide]-2-chloroacetanilide Intermediate 7: ethyl 2-bromobenzoylacetate This compound was prepared as was ethyl 2- chlorobenzoylacetate according to the method described in J.A.C.S. 37, 1259.

The product. thus obtained, is an oily straw-colored liquid boiling at l55158C/2 mm Hg. Intermediate 8: a-( Z-bromobenzoyl )-5-[ a-( 2-4- ditertamylphenoxy )-acetamide l-2-chloro-acetanilide This product was prepared in the same manner as intermediate 3.

33.4 g. of a white product, recrystallized from ethanol, were obtained from 61 g. (0.143 moles) of intermediate 2 and 43.3 g. (0.16 moles) of intermediate 7.

Analysis: Found Calculated C% 61.84 61.73 H% 6.04 5.97 N% 4.44 4.36

Coupler 3 This coupler was obtained in the same manner as coupler 1.

23 g. of the product, recrystallized from heptane, were obtained from 25.7 g. (0.04 moles) of intermediate 8, dissolved in 100 ml. of chloroform and 5.4 g. (0.04 moles) of sulphoryl chloride. M. P. l06-108C.

Analysis. Found Calculated Cl% 10.4 1 .48 Br% 1 l .79 1 1.81

Titration from CH% 99.0.

EXAMPLE 4 a-(2-fluorobenzoyl)-a-chloro-5-[a-( 2-4-ditertamylphenoxy)-acetamide]-2 -chloroacetanilide Found Analysis: Calculated Cl% Titration from CH 99% Coupler 4 This coupler was prepared in the same manner as coupler 1.

23.2 g. of a white product, recrystallized from methanol, were obtained from 23.2 g. (0.04 moles) of intermediate lO. dissolved in 100 ml. of chloroform anhydrous and 5.4 g. (0.04 moles) of sulphoryl chloride.

Found 11.37

Titration from CH% 99.19.

EXAMPLE 5 a-( 2-chlorobenzoyl)-a-ch1oro-2-cetoxyacetani1ide Intermediate 1 l; Z-cetoxy-nitrobenzene 8.3 g. (0.36 moles) of metallic sodium were added in small portions into a 1 l. multi-neck flask provided with a stirrer, a thermometer, a dropping funnel and refluxe-condenser and containing 325 ml. of cellosolve. The mixture was stirred till a complete solution was reached and cooled at 20C. 50 g. (0.36 moles) of onitrophenol were then added thereto in small portions. After 30 minutes of stirring, 110.5 g. (0.36 moles) of cetyl bromide were added thereto dropwise, the mixture was boiled for 5 h. and then poured into icy water. The precipitate, thus obtained, was filtered, washed til Br was removed completely, dried and recrystallized from ethanol, thus obtaining 152 g. of a product melting at 3335C.

Found 72.70 10.25

Calculated 72.69 10.26

Analysis:

Calculated 6.90

Found 6.88

Analysis:

Cl% Titration from CH 99.35%.

Coupler This coupler was prepared in the same manner as coupler l. r

27 g. of a crystalline white product, recrystallized from isopropylic alcohol, were obtained from 50.8 g. (0.06 moles) of intermediate 13 and 8.1 g. (0.06 moles) of sulphoryl chloride. M.P. 5860C.

intermediate 14: a-(2-fluorobenzoyl )-2-cetoxyacetanilide This product was prepared in the same manner as intermediate 3.

32.3 g. of a product, crystallized first from ethanol and afterwards from ligroin, were obtained from 27.6 g. (0.0828 moles) of 2-cetoxyaniline (intermediate 12) dissolved in 200 ml. of xylene and 17.4 g. (0.0828 moles) of ethyl Z-fluorobenzoylacetate (intermediate 9). M.P. 7072C.

Analysis: Titration from CH 98.2 percent. Coupler 6 This coupler was prepared in the same manner as coupler l.

29 g. of a white product, crystallized from isopropylic alcohol, were obtained from 30.7 g. (0.0616 moles) of intermediate 14, dissolved in 150 ml. of dry chloroform and 8.3 g. (0.0616 moles) of sulphoryl chloride. M.P. 80-82C.

Analysis: Found Calculated Cl% 6.64 6.66 Titration from- CH 98.6%.

EXAMPLE 7 a-( 2-chlorobenzoyl )-a-ch1oro-2-( N-methyl-N- octadecylamino)-S-sulphanilide-acetanilide Analysis: Found Calculated C% 46.09 46.08 H% 2.78 2.90 N% 9.12 8.95 Cl% 1 1.26 1 1.33

Titration from NO, 99.15%.

Intermediate l6: 3-nitro-4-(N-methyl-N-octadecylamino)-benzensulphanilide 31.2 (0.1 moles) of 3-nitro-4-chlorobenzensulphanilide (intermediate 15) and 60 ml. of n-propanol were mixed into a 500 ml. multi-neck flask provided with a stirrer and refluxe condenser. The mixture was heated till a complete solution was reached and an n-propanol (60 ml.) hot solution of 56.7 g. (0.2 moles) of methylocatadecylamine was added thereto. The solution was refluxed for 15 h., poured into icy water and the pH value arranged at 3- 4 with HCl. The orangecolored solid, which separated, was filtered. washed and extracted with ethyl ether.

The ethereal solution was dried and evaporated and the yellow residue, thus obtained, was crystallized first from ethanol and then from heptane, thus obtaining 28 g. of a crystalline product under the form of gleaming yellow scales. M.P. 6l-63C.

Analysis: Found Calculated Intermediate 17: 3-amino-4-(N-methy1,N-

Analysis: Found Calculated Cl% 4.93 4.99 Acidimetric titration from CH 97.2% Acidimetrit: titration from -SO,NH 97% Coupler 7 This coupler was prepared in the same manner as coupler l.

21 g. of the product were obtained from 25 g. (0.035 moles) of intermediate 18 and 4.7 g. (0.035 moles) of sulphoryl chloride. M.P. 4347C.

Analysis: Found Calculated EXAMPLE 8 a-( 2-chlorobenzoyl )-a-chloro-5-[(4-dodecyl-phenylamino)-sulphoxy l-2-methoxy-acetanilide Intermediate 19: 3-nitro-4-methoxy-benzensulpho-4- dodecylanilide 13.1 g. (0.05 moles) of paradodecylaniline, ml. of tetrahydrofuran and 7.6 g. (0.075 moles) of triethylamine were mixed into a 250 m1. multi-neck flask provided with a stirrer, a refiuxe-condenser and a dropping funnel. The solution was cooled at C and a tetrahydrofuran (30 ml.) solution of 12.5 g. (0.05 moles) of 3-nitro-4-methoxybenzensulphochloride was added in minutes thereto dropwise under stirring and maintaining a temperature ranging from 5 to 10C.

After such an addition. the suspension was stirred at 5l0C for still another hour and then at 50C for onehalf h. After having been cooled in icy water. the mixture was filtered to remove the white precipitate which deposited and the filtrate was dried by evaporation under vacuum. The yellow oily residue was resolved in 200 ml. of ethyl ether and the solution shaken into a separatory funnel with 200 ml. of current water containing 1.5 ml. of concentrated HCl and washed with water till it became neutral. The water was removed with sodium sulphate anhydrous and the remaining so lution dried. The residue was then resolved in 500 ml. of petroleum ether. A white solid was immediately formed which was filtered and recrystallized from ligroin, thus obtaining 15.6 g. of a product melting at 8284C.

Analysis: Titration from --NO 99.71 percent. Intermediate 3-amino-4-rnethoxy-benzensulpho-4- dodeeylanilide 19 g. (0.04 moles) of intermediate 19, 120 ml. of 90 percent acetic acid and 60 ml. of ethanol were mixed into a 500 ml. multi-neck flask provided with a stirrer and refluxe-condenser. The mixture was brought to boil and 22.4 g. (0.4 moles) of pulverized iron were added thereto cautiously in small portions and control ling the addition speed so that the mixture could be kept under light spontaneous boiling. After the additions, the mixture was boiled for another one-half h., filtered when it was boiling and the filtrate was poured, when hot, into icy water. The granulose product which deposited, was isolated, dried and crystallized from methanol, thus obtaining 12.3 g. of a pink-colored product melting at 121-123C.

Analysis: Titration from NH 100.0 percent. Intermediate 21: a-( 2-chlorobenzoyl)-5-[ (4- dodecylamino)sulphol-2-methoxyacetanilide This product was obtained in the same manner as intermediate 18.

40.1 g. (0.09 moles) of intermediate 20 and 21.4 g. (0.04 moles) of ethyl O-chlorobenzoylaeetate were mixed and heated up to 145C in a rotating flask under vacuum for 2 h. The amber-colored molten reaction mixture was crystallized from cyclohexane, thus ob taining 28.6 g. of a product melting at 60-65C.

Found 5 68 Analysis: Calculated Analysis: Found Calculated Acidimetric titration from-*CH and so,NH 99% EXAMPLE 9 0H 2 chlorobenzoyli-a-chloro-Z-methyl-S-lauonoylacetanilide Analysis: Found Calculated N% 4.36 4.39 C% 7 l l 6 7 l .44 H9? 9 .26 9. l 5

Intermediate 23: 2-methyl-5-lauroyl-aniline This product was obtained in the same manner as intermediate 20.

27.5 g. of the product, crystallized from ethanol, were obtained from 32 g. (0.1 moles) of intermediate 22, dissolved in 300 ml. of glacial acetic acid and 150 ml. of toluolated ethanol, and 55.8 g. of pulverized iron. MP. 66-68C.

Analysis: Found Calculated N% 4.75 4.84 C% 78.4 78.84 H% 10.87 10.8

Intermediate 24: a-(2-chlorobenzoyl)-2-methyl-5- lauroylacetanilide This product was obtained in the same manner as intermediate 18.

38.2 g. of a white product, crystallized from heptarie, were obtained from 32.7 g. (0.1 16 moles) of intermediate 23 and 27.6 g. (0.122 moles) of ethyl 2- chlorobenzoylacetate. MP. 77-79C.

Analysis: Found Calculated (1% 7.63 7.54 Acidintetrir titration from CH 98% Coupler 9 This product was obtained in the same manner as coupler 1.

35.2 g. (0.075 moles) of intermediate 24 were brought to react with i0.1 g. (0.075 moles) os sulphorylchloride, thus obtaining 26.8 g. of the product. M.P. -89C.

Analysis: Found Calculated EXAMPLE l Coupler a-( 2-chlorobenzoyl )-a-bromo-5-[a-( 2-4- Analysis: Found Calculated (Wr 10.0 10.48 Br% 1 L88 1 [.Bl Titration from --CH 98.5%

EXAMPLE l l a-( Z-fluorobenzoyl)-achloro-5-( 4-cetylbenzensulphonamide )-2-acetanilide Intermediate 25: u-(2-fluorobenzoyl)-2-methoxy-5- nitroacetanilide This product was prepared in the same manner as intermediate 4.

162.6 g. of a straw-colored crystalline product were obtained from 137.2 g. (0.652 moles) of ethyl 2- fluorobenzoylacetate (intermediate 9) and 109.6 g. (0.652 moles) of 2*methoxy-5-nitroaniline. M.P.

Titration from NO 989% Analysis:

Titration from CH 995% provided with a stirrer, a refluxe condenser, a thermometer and a dropping funnel. The mixture was heated up to 50C and a solution of 123.5 g. (0.308 moles) of 4-cetylbenzensulphochloride in 150 ml. of anhydrous dioxane was dropped thereinto in one-half h. The solution, thus obtained, was stirred for 2 h. at 50C and then poured into 3 liters of icy water under stirring and very slowly. A brown'colored product deposited and further was crystallized twice from ethanol, thus obtaining 133.6 g. of a whitish product melting at 9193C.

Analysis:

Coupler preparation:

This coupler was prepared in the same manner as coupler l.

61.5 g. of a white product, crystallized first from methanol and further from ethanol, were obtained from 69.3 g. (0.103 moles) of intermediate 27 dissolved in 250 ml. of dry chloroform and 14 g. (0.103 moles) of pure sulphorylchloride. M.P. 104-l05C.

Analysis: Found Calculated C% 65. l 8 65.06 Cl% 5.10 5.06 H% 7.14 7.18 N% 3.95 3.99

EXAMPLE 12 a-( 2-fluorobenzoyl )-a-chloro-5- a-( 2-4- ditertamylphenoxy )-acetamidel-2-methoxyacetanilide Intermediate 28: a-(2-fluorobenzoyl)-5-[a-(2-4- ditertam ylphenoxy )-acetamide Z-methoxyac etanilide This product was obtained like intermediate 6.

g. of a white product, crystallized from ethanol, were obtained from 102 g. (0.3374 moles) of intermediate 26, from 33.3 g. of anhydrous sodium acetate dissolved in 900 ml. of glacial acetic acid and from 104.9 g. (0.3374 moles) of 2-4-ditertamyl'phenoxyacetylchloride. M.P. 101-103C.

Analysis: Titration from CH2 =99.8 percent. Coupler preparation:

The above-described product was chlorinated with sulphorylchloride like the previously described couplers.

102 g. of a white product, crystallized from ethanol, were obtained from 1 16 g. (0.201 moles) of intermediate 28 dissolved in 400 m1. of dry chloroform and 27.1 g. (0.201 moles) of pure sulphorylchloride. M.P. 76-80C.

Analysis: Found Calculated Cl% 5.72 5.79 Titration from CH 99.32%.

EXAMPLE 13 a-( 2fluor0benzoyl)-a-chloro-5-[(4-dodecyl-phenylamino)-sulphoxy]-2-methoxy-acetanilide Analysis: Titration from CH, 98.9%

Titration from -SO,NH 99.4%.

Coupler preparation:

This coupler was prepared like what is described in the above-mentioned couplers.

Analysis: Found Calculated C% 66.02 66.84 Cl% 5.20 5.50 H% 6.72 6.55 N% 4.28 4.34

EXAMPLE 14 o:( Z-fluorobenzoyl )-oz-chloro-[ 2-cetoxyphenylamino)-sulfoxy]-2-metoxyacetanilide Intermediate 30: 4-metoxy-benzensulfochloride.

This product was prepared according to the method described in J. A.C.S. 70, 375. The product melted at 42-43C. Intermediate 3l:

ride.

This product was prepared according to the method described in the 1. pr. Chem. [2 74, I05. The product had a M.P. 59-61C.

Intermediate 32: 3-nitro-4-metoxy-benzensulfo-(2- cetoxy )-anilide.

166.7 (0.5 M) of intermediate l2, l,000 ml. of anhydrous dioxane, 89.5 g. (0.6 M) of N,N-diethylaniline were mixed into a multi-neck flask provided with a thermometer, a stirrer and refluxe condenser and, when a complete solution thereof was obtained, 125.8 g. (0.5 M) of intermediate 31 added thereto. The brown-colored solution was heated at 80zt5C for 3 h. under stirring and further diluted with 5 liters of ice water. The pH value of the suspension, thus obtained, was arranged at 3 4 with diluted HCI and the browncolored solute was filtered on a Buchner filter, dried and crystallized from 2,500 ml. of ligroine, thus obtaining 240 g. of a beige product having a M.P. =73-74C.

3-nitro-4-metoxy-benzensulfochlo- Analysis: Titration from NO Analysis: Titration from -Nl-l,%

Intermediate 34: a-( 2-fluorobenzoyl H 5-( 2-cetoxyphenylamino)-sulfoxy1-2-metoxyacetanilide.

This product was obtained like intermediate 3.

38.1 g. of a white product were obtained from 4L5 g. (0.08 M) of intermediate 33, 200 ml. of xilol and 16.8 g. (0.08 M) of ethyl 2-fluorobenzoylacetate. The product was then crystallized from methyl alcohol and ligroin. M.P. 77-79C.

Analysis: Titration from CH,% l00.56

Preparation of the Coupler This product was obtained like Coupler No. I.

36.5 g. of a white product were obtained from 44.1 g. (0.0646) of intermediate 34, dissolved in ml. of anhydrous chloroform and 8.72 g. (0.646 M) of pure sulforyl chloride. The product was then crystallized from methyl alcohol and ligroin. M.P. 68-70C.

a-{2fluoro-4-[a-( 2,4-ditertamylphenoxy acetamido1-benzoyl }-a-chloro-Z-metoxyacetanilide Intermediate 35: ethyl 2-fluoro-4-nitrobenzoylacetate This intermediate was prepared according to a method similar to the one followed to produce ethyl 2- chlorobenzoylacetate described in .l.A.C.S. 37, 1259.

68.4 g. of a yellow oil, which was thermically unstable (at C it turns black without distillation), were obtained from 90 g. (0.443 M) of 2-fluoro-4- nitrobenzoylchloride prepared according to the method described in Helv. Chim. Acta 51 (I934), 1350. Such an oil was used as it was for the preparation of the next intermediate. With a series of operations similar to those described for other couplers of the present invention, we successively obtained the following intermediates:

-a-( 2fluoro-4-nitro-benzoyl )-2-metoxy-acetanilide; -a-( 2-fluoro-4-aminobenzoyl)-2-metoxy-acetanilide;

and -a-{2-fluor0-4-[a-(2,4-ditertamylphenoxy)- acetamide l-benzoyl }-2-metoxy-acetanilide.

The coupler of example 15 was obtained upon reaction of the last intermediate with sulforyl chloride at room temperature with chloroform as a solvent, like that described for the hereinbefore described couplers.

The final coupler was a white powder crystallized from methanol. M.P. l37-139C.

Analysis: Titration from -CH 99.14

Calculated Found C% 66.82 66.94 1 1% 6.60 6.66 N% 4.58 4.51 CI% 5.80 5.83

The couplers of the present invention may be used in conjunction with many types of silver halide emulsions suitable for color photography. They can be used for instance in silver bromide, silver chloride or silver iodide emulsions or in those emlsions containing a halide mixture, such as silver bromoiodide or silver chlorobromide emulsions. The couplers can also be used in those emulsions which are described in U.S. Pat. Nos. 2,592,243 and 2,698,794. Such couplers can still be used in those emulsions capable of forming an image on the surface or in the interior of the silver halide grains, such as those described in U.S. Pat. No. 2,592,250.

As it is known to the man skilled in the art, the abovementioned emulsions can be chemically sensitized either by addition of sulphur compounds, as described for instance in U.S. Pat. Nos. 1,574,944; 1,623,469 and 2,410,689; and by addition of noble metal salts, such as rhutenium, rhodium, iridium, palladium and platinum. Such emulsions can be chemically sensitized by addition of Au salts, as described in U.S. Pat. No. 2,399,083. They can be stabilized with An salts as described in U.S. Pat. Nos. 2,597,856 and 2,587,915. The above-mentioned emulsions can be optically sensitized with apomerocyanine dyes as those described in German Pat. No. 1,009,020; in British Pat. No. 734,792; in French Pat. Nos. 1,559,295 and 2,018,196; in U.S. Pat. No. 3,574,631 and in Belgian Pat. Nos. 746,342 and 747,781.

The emulsions can contain organic stabilizers and anit-foggants of the cyclic amine type; iminoazoles, such as mercaptobenzimidazole; triazoles, such as those described in U.S. Pat. No. 2,444,608; azaindenes,

such as those described in U.S. Pat. Nos. 2,444,605; 2,444,606; 2,444,609; 2,450,397; 2,723,541; 2,716,062; 2,735,769; 2,743,181; 2,756,147;

2,772,164 and E. .1. Birr, Z. Wiss, Phot. 472 (1952); tetrazoles, such as l-phenyI-S-mercapto-tetrazole; thiazoles and benzothiazoles, such as l-methylbenzothiazole and benzothiazole quaternary salts, as described in US. Pat. No. 2,131,038; mercaptobenzothiazoles, such as l-methyl-mercaptobenzothiazole; oxazoles, thiosemicarbazydes; primidines; iodonium derivatives; benzensulphyn acids; inorganic stabilizers of the zinc and cadmium salt type, such as those described in U.S. Pat. Nos. 2,839,405.

The emulsions can further contain any suitable plasticizer, known to the man skilled in the art, such as glycerm.

The emulsion may be hardened with any suitable hardener for gelatin, known to the man skilled in the art, such as aldehyde of the formaldehyde, glyoxale, succinic, glutaric and resorcylic aldehyde type; and halogen substituted aliphatic acids, such as mucochloric and mucobromic acids, as described in U.S. Pat. No. 2,080,019; or mixtures thereof, as described in U.S. Pat. No. 2,591,542.

The emulsions may have been supplied with a coating aid, known to the man skilled in the art, such as saponin. Any suitable base type, known to the man skilled in the art, can be used, such as cellulose triacetate, polyester, paper, polytenated paper. In the preparation of the silver halide dispersions, employed for preparing silver halide emulsions, there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or another water-permeable means of the colloidal albumin type, a cellulose derivative, or a synthetic resin of the polyvinyl type. Such material types are described in U.S. Pat. Nos. 2,286,215; 2,328,808; 2,322,085; 2,527,872; 2,541,474; 2,563,791; 2,768,154; 2,808,331; 2,852,382.

If desired a mixture of two or more of these colloids may be employed for dispersing the silver halide in its preparation.

The developing baths to be used in conjunction with the couplers of the invention are well-known to the man skilled in the art. They contain a developer of the p-phenylene diamine type, a development restrainer of the potassium bromide type, an antioxidant, such as sodium sulphite and an alkaline agent of the alkali hydrate or carbonate type. They may further contain both an antifoggant of the benzimidazole type and derivatives, of the benzothiazole type and derivatives, of the triazole and tetrazole type and derivatives, such as mercapto-derivatives; and an anticalcium substance of the alkaline phosphate and alkylendiaminopolyacetic acid type, such as for instance EDTA. Compounds known to the man skilled in the art, of the p-penylene diamine type are those described for instance in U.S. Pat. Nos. 2,193,015; 2,656,273; 2,875,049 and in C. E. Kenneth Mees and T. H. James, The Theory of the Photographic Process, third edition, table 13.4, pages 264-295.

Suitable developers, which can be employed to develop photographic elements, containing the couplers of the present invention, are the sulphites, the hydrochlorides and the sulphates of:

a. N,N-diethyl- P- phenylene diamine;

b. N-ethyl,N-B-methansulphonamido-ethyl-3-methyl-4-aminoaniline;

c. N-ethyl, N-hydroxyethyl-Z-methylpphenylene diamine;

d. N-ethyl, N- ydroxyethyl-pphenylene diamine;

e. N,N-diethyl-Z-methyl-p-phenylene diamine.

EXAMPLE 16 6 g. of each coupler of the present invention and of the couplers A, B, C and D of the type known in the prior art were dissolved in 10 ml. of dibutylphtalate and 16 ml. of ethyl acetate and each solution was emulsified with 60 ml. of a 4 percent gelatin solution.

5 ml. ofa 10 percent anionic surfactant solution were further added thereto and the emulsions, thus obtained, were diluted with ml. of water. A fraction thereof containing 3 mM of a coupler was further mixed with 50 g. of a 7 percent gelatin silver chloro-bromide photographic emulsion which had not been optically sensitized.

The resulting emulsion was coated on a transparent cellulose acetate base and dried.

Two series of specimens were obtained therefrom: series A was incubated for 7 days at 22C and 40-45 percent RH. and series B for 7 days at 50C and 10-15 percent R.1-1. Such specimens were then exposed through a grey step wedge and further developed with a developer corresponding to the following formula:

sodium-hexamctaghosphale sodium sulphite an ydrous Z-amino-S-diethylamino toluenhydrochloride sodium carbonate monohydrate 2 potassium bromide water to make 1,000 ml.

The same specimens were then bleached and fixed and the fog and maximum optical density (Dmax) values read.

The specimens of series A were then exposed to a Xenon lamp in a fadeometer for 10 h. and the per cent decrease of optical density (A calculated.

The following table shows both the for values for each coupler examined in both specimen series A and B and the values corresponding to the fog differences (A V) between both series.

The same table also shows the maximum absorption (A max), the maximum density (Dmax), and the A D% (wherein D 1.5) values referring to the specimens of series A.

Table Coupler Fog A Fog B AV- Amax Dmax A091:

m TABLE- Continued Coupler Fog A Fog B AV Amax Drnax AD% B 0.28 0.55 0.27 448 2.15 31 C 0.22 1.32 1.10 446 2.09 S D 0.22 1.18 0.96 446 2.2 10

1 claim:

l. A silver halide photographic emulsion containing at least one two-equivalent benzoylacetanilide photographic coupler carrying on an aromatic ring thereof at least one ballasting group capable of imparting nondiffusing properties to said coupler, characterized by the fact that the coupler has a halogen atom in ortho position in the benzoyl residue, a chlorine or bromine atom as a substituent in the. reactive methylene, and a hydrogen or halogen atom, or an alkyl, alkoxy, or dialkylamino group as substituent in the 2-position in the aniline residue, and a hydrogen atom or an acylamino, acyl, aryloxyacrylarnino, arylaminosulfoxy or arylsulfonamido group as substituent in the 5-position in the aniline residue, the said 2-position and S-position substituents together including alkyl groups having a total of at least 10 carbon atoms.

2. Silver halide photographic emulsions containing dispersed therein at least a coupler of claim 1 dissolved in a substantially water-imiscible organic solvent.

3. Photographic elements including. a base and at least one layer of silver halide photographic emulsion of claim 1.

IF 1' 111 I

Claims (3)

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING AT LEAST ONE TWO-EQUIVALENT BENZOYLACETANILIDE PHOTOGRAPHIC COUPLER CARRYING ON AN AROMATIC RING THEREOF AT LEAST ONE BALLASTING GROUP CAPABLE OF IMPARTING NON-DIFFUSING PROPERTIES TO SAID COUPLER, CHARACTERIZED BY THE FACT THAT THE COUPLER HAS A HALOGROUP AND AT LEAST ONE OF A NONFLUORINATED BETAINE OF N-OXIDE OR BROMINE ATOM AS A SUBSTITUENT IN THE REACTIVE METHYLENE, AND A HYDROGEN OR HALOGEN ATOM, OR AN ALKYL, ALKOXY, OR DIALKYLAMINO GROUP AS SUBSTITUUENT IN THE 2-POSITION IN THE ANILINE RESIDUE, AND A HYDROGEN ATOM OR AN ACYLAMINO, ACYL, ARYLOXYACRYLAMINO,ARYLAMINOSULFOXY OR ARYLSULFONAMIDO GROUP AS SUBSTITUENT IN THE 5-POSITION IN THE ANILINE RESIDUE THE SAID 2-POSITION AND 5-POSITION SUBSTITUENTS TOGETHER INCLUDING ALKYL GROUPS HAVING A TOTAL OF AT LEAST 10 CARBON ATOMS.

2. Silver halide photographic emulsions containing dispersed therein at least a coupler of claim 1 dissolved in a substantially water-imiscible organic solvent.

3. Photographic elements including a base and at least one layer of silver halide photographic emulsion of claim 1.