US2474293A - 1-naphthol-2-carboxylic acid amide couplers for color photography - Google Patents

Description

Patented June 28, 1949 UNITED STATES PATENT OFFICE l-NAPHTHOL-Z-CARBOXYLIQ ACID AMIDE COUPLERS roacomnrnoroomrnn No Drawing.

This invention relates to photography and particularly to compounds which form dye bycoupling with the developing agent to produce colored images.

It is known thatcolored photographic images may be formed by using a developer which produces a colored compound on development. The colored'compound thus formed is deposited adjacent the silver grains of the silver image during development. It is also known that a colored imagemay be formed by adding to certain developing solutions or by incorporating in the silver halide emulsion a compound which couples during development with the oxidation product of the developing agent and forms a colored compound which is likewise deposited adjacent the silver grains of the silver image during development. Such a compound which is employed in conjunction with a developing agent for the silver and whichcouples with the oxidation product of the developing agent during development is referred to herein as a coupling compound or coupler.

The present invention concerns new and improved color-forming couplers for use with a primary aromatic amino developing agent and also includes anew and improved color development process which consistsin developing a reducible silver salt image in a photographic emulsion with the aid of a primary aromatic amino developer and in the presenceof a coupler as'hereinafter defined. The invention also includes photograph-'- ic sensitive elements having'such coupler in one or more of thesensitive emulsion layers.

We have foundthat compounds of the follow ing structureare valuable couplers for color pho-' tography and'produce blue-green images of high purity and stability on photographic development.

CONH-(CH2)(NHCOCH2),OC R' Ca n 1-hydroxy-2- 6 (2' ,4='-di-tert. amylphenoxy) -n-butyl] naphthamide Application September 10, 1947, Serial No."773,290

7 Claims.

coNmcHicmNH-co-oHi-o?cn1u" sHii 1-hydroxy-2-{ 2' Eaten. diainylplienory) acetamido1 60 ethyl}-naphthainide' it b. in

1-l1ydroxy-2- [B- 2',4'-tert. diamylphenoxy) acetamido ethyl] -4-chloro-naphthamide 1-hydroxy-2-{ [8-(2,4'-tert. diamyl phenoxy) acetamid01- n-butyl naphthamide These couplers contain a coupling function which in this case is a phenolic hydroxyl group. Coupling is believed to occur in a position para to the hydroxyl group of the naphthol radical and in case a chlorine atom is present in this position, it is split off during the coupling.

Our compounds may be prepared by reacting a ,8-2,4-TERT.DIAMYLPHENOXYPRQPIONITRILE cine-Q01: OHFCHON cant-Q0 cmomoN 5H In a 200-cc. round-bottomed flask was placed 47 g. (0.2 mole) of diamylphenol (alkali-washed) and 32 g. of redistilled acrylonitrile. The temperature rose from 24 to 26.5". To this solution was added 4 cc. of trimethylbenzyl ammonium hydroxide solution. The quaternary hydroxide solution failed to mix with the ether until 25 cc. of dioxane had been added also.

The solution stood in a stoppered flask for 3 days, after which it was removed, drowned in 400 cc. of water, extracted with three 200-cc. portions of ether, the emulsion being broken with 4 g. of barium chloride. The ether solution was washed with three 200-00. portion of water, dried over sodium or magnesium sulfate, filtered, and concentrated by distillation on a steam bath.

The residual liquid was distilled in vacuo at 136-142/1 mm. Yield =47 g. (82%).

Molecular weights Diamylphenol 234 Acrylonitrile 53 3-2,4-tert.-diamylphenoxypropionitrile 287 7- (2,4-TERT.-DIAMYLPHENOXYPROPYL) -AMINE lsHu with the 4-chloro derivative to give compound 2.

Compounds 3 and 4 are prepared as follows:

Ethylenimine and 2,4 tert. diamylphenol are condensed hot to give p-2,4-tert.-diamylphenoxyethylamine. The amine is condensed with an equivalent amount of l-naphthol-Z-carboxylio acid phenyl ester to give compound 3, or with the 4- chloro derivative to give compound 4.

Compound 5 is prepared as follows:

2,4-tert.-diamylphenol is condensed with acrylonitrile in the presence of alkali, giving ea-2,4- tert.-diamylphenoxypropionitrile. The nitrile is reduced catalytically to the amine, which is condensed with l-naphthol-2-carboxylic acid phenyl ester to yield compound 5.

Compounds 6 and 7 are prepared like compounds 1 and 2, with the use of commercial amylbutylphenol for 6 and p-tert-amylphenol for 7.

Compound 8 is prepared as follows:

1-naphthol-2-carboxylic acid phenyl ester is condensed with ethylene diamine, giving l-hydroxy-2-fi-aminoethylnaphthamide. The aminonaphthamide is condensed with 2,4-tert.-diamylphenoxyacetyl chloride to ive compound 8.

Compound 9 is prepared like compound 8, with the use of 4-chloro-l-naphthol-2carboxylic acid phenyl ester.

Compound 10 is prepared like compound 8, with the use of tetramethylene diamine.

The detailed preparation of compound 5, for example, is as follows:

In the low-pressure shaker was placed 40 g. (0.1 mole) of 5-2,4-diamylphenoxypropionitrile, 150 cc. of white label methanol and Raney nickel which had been washed four times with distilled water, followed by four times with methanol. The mixture was heated with steam and reduced while shaking. Reduction wa rapid, the hydrogen pressure dropping from 59 to 35 lbs. in 1 hr. Only 1 lb. more was absorbed during an additional half hour.

The mixture was filtered from Raney nickel. The filtrate was concentrated by distillation up to an oil bath temperature of The 38.6 g. of residual liquid was distilled in vacuo, fractions being collected as follows:

No. 1, B. P. 113-l30/1 mm 6.0 g. m 1.5092 No. 2, B. P. 13l139/1 mm 25.3 g. m 1.5090 No.3, B. P. 150/l mm 3.8 g. m c 1.5058 No. 4, residue 3.2 g. H230 1.5112

Molecular weights ;3-2,4-tert.-diamylphenoxypropionitrile 287 'y-(2,4-tert.-diamylphenoxypropyl),-amine 291 Cn n Q cmomomum @o 0.0 00115 Ii n oorreomomomoO-mm 05115011 In a Claisen flask, set up for vacuum distillation, was placed 6.0 g. (0.02-mole) of 'y(2',4- tert.-diamylphenoxypropyl)-amine (fraction No. 2) and 5.3 g. (0.02 mole) of phenyl l-hydroxy-Z- naphthoate. The fiasl: was immersed in a preheated oil bath at 145-150 for one-half hour. Vacuum was applied to the amber melt and phenol removed by distillation. After 5 mins. 1.65 g. of distillate had been collected. Following another 15 mine, the temperature of the bath having risen to 160, 2.85 g. of distillate had been collected. The cooled reaction mixture was diluted with cc. of petroleum ether and seeded with product from a previous preparation. Some solid appeared. The mixture stood overnight in an open flash, the solvent evaporating and leaving behind a pale yellow semi-crystalline residue. This residue was stirred for 1 hr. with 100 cc. of petroleumether, cooled in an ice bath and illtered at 5 C. The solid was Washed on the funnel with three 5-cc. portions of cold petroleum ether. Yield: 4.5 g. (50%); M. P. 91-533. Recrystallization of the product from hexane or ligroin gave better looking crystals but did not raise the melting point.

Molecular weights 'y-(2,4-tert.-diamylphenoxypropyl) -amine 291 Our compounds may be used either in the developing solution or in the sensitive emulsion layer. Where the compounds are of suitable molecular size as in the case of compounds 1 to 10, they may be incorporated in the sensitive emulsion layer or in one of the layers of a multi-layer coating. When incorporated in a photographic emulsion layer, we prefer to incorporate the couplers in the manner described in Mannes and Godowsky U. S. Patent 2,304,940 or Jelley and Vittum U. S. Patent 2,322,027.

The aromatic amino developing agents used with the coupler compounds of our invention include the p-plienylene diamine type or their derivatives formed by substitution in one of the amino groups or in the ring such as the alkyl phenylene diamine and alkyl toluene diamines. These compounds are usually used in the salt form such as the hydrochloride or the sulfate which is more stable than the amines themselves. Suitable compounds are diethyl p-phenylene diamine hydrochloride, dimethyl-p-phenylene diamine hydrochloride and 2-amino-5-diethylamino toluene hydrochloride. Developing agents containing heterocyclic systems as described in U. S. Patent 2,196,739 are also suitable. The p-amino phenols and their substitution products may also be used where the amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation product of the developer to couple with the color-forming compounds to form a dye image.

The: 'followin'g- 'example' illustrates. a developing solution which may be used with the compounds of our invention where the compounds are incorporated in the emulsion layer.

Water to oneliter.

Our development process may-be" employed a for the production oi colored photographic images in -layers of gelatin or-other carrier for the silver halide such as'coIlodion; organic esters of celluloseor synthetic resins; The support'ior the emulsion maybe atransparent material such as glass,- cellulose esteror-a-non-'-transparent reflecting material-'such'as' paper or an-opaque cellulose ester. The-"'emulsionmay be coated as a-single layeron the support or as oneofa series of superposed layers on one 'or bothsids of the support. The superposed layer may be differentially sensitized to record natural color photographic images in 'the'-well"know'n manner.

The examples and compounds set forth in the present specification are illustrative only and it is to be understood that our invention is to be taken as limited only Joy-the'scopeof the append ed claims.

We claim:

1. A'photographic emulsion-for forming colored images comprisin a silver halide emulsionhavin'g incorporated:therein 'a coupler compound having the formula:

-o ON'H-(CHah-(NHC o eBa -0GB where Z is selected from the class consisting of hydrogen and chlorine, R and R are alkyl groups of from 1 to 5 carbon atoms, 12 is an integer from 2 to 4, and y is selected from the class consisting of 0 and 1.

2. A photographic emulsion for forming colored images comprising a silver halide emulsion having incorporated therein a coupler compound having (BEER 4. A light-sensitive emulsion for producing a colored image comprising a gelatino silver halide emulsion containing finely divided liquid particles of a mixture of a coupler compound having the formula:

where Z is selected from the class consisting of hydrogen and chlorine, R and R are alkyl groups of from 1 to 5 carbon atoms, 71 is an integer from 2 to 4, and y is selected from the class consisting of and 1 and a substantially water-insoluble low molecular weight organic crystalloidal material having a boiling point above about 175 C.

5. The method of producing a colored photographic image in a silver halide emulsion layer which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:

where Z is selected from the class consisting of hydrogen and chlorine, R. and R are alkyl groups of from 1 to carbon atoms, n is an integer from 2 to 4, and y is selected from the class consisting of 0 and 1.

6. The method of producing a colored photographic image in a silver halide emulsion layer which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:

c ornament-0GB ing the formula:

CONmCHamQGBHH ARNOLD WEISSBERGER. ILMARI F. SALMINEN. PAUL W. VI'ITUM.

N 0 references cited.

Certificate of Correction Patent No. 2,474,293. June 28, 1949.

ARNOLD WEISSBERGER ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 3, Compound 9, for that portion of the structural formula reading 7 a V on OK read Compound 10, same column, line 17, for that portion of the name under the structural formula reading n-butyl naphthamide read n-butyl }naphthamide;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 22nd day of November, A. D. 1949.

THOMAS F. MURPHY,

Assistant aomm-issioner of Patents.