US2289805A

US2289805A - Sulphonic ester coupler

Info

Publication number: US2289805A
Application number: US358493A
Authority: US
Inventors: Porter Henry Dudley; Weissberger Arnold
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1940-01-03
Filing date: 1940-09-26
Publication date: 1942-07-14
Anticipated expiration: 1959-07-14
Also published as: GB537921A; FR928785A

Description

Patented July 14, 1942 UNITED v STATES u sULrnoNIc E Henry Dudley Porter Roe PATENT "OFF-ICE srsa COUPLER and Arnold Weissberger,

heater, N. Y., assignor to Eastman Kodak Company, Roeheste New Jersey N. Y., a corporation oi No Drawing. Application September 20, 1940, Se-

. rial No. 358,493; In

15 Claims.

a colored compound ondevelopment. The

colored compound thus formed is deposited adjacent to the silver grains of the silverimage during the development. It is also known that a colored image may be formed by adding to certain developer solutions or by incorporating in the gelatino-silver-halideemulsion before or after exposure a compound which couples during development with the oxidation productof the developing agent and forms a coloring substance which is likewise-deposited adjacent to the silver grains of the silver image during deve1opment.- Such ,a compound, which is employed in conjunction with a developins'agent for the silver and which couples with the oxidag component or The present invention concerns newer im-.- proved color forming developers comprising a primary aromatic compound, serving as the developing ageniuand a coupler as herein:

after defined and also includes a new or improved 4 color development process which consists in developing a reducible silver salt image in a photographic element with the aid of a primary aromatic amine compound in the presence of a coupler as hereinafter defined. 'It. also includes photographic sensitive elements having such a coupler incorporated in one or more emulsion layers. a

In BritishPatent 503,752 sulphonic ester coli- 7 piers are described which are obtained by the reaction of. a-naphthol sulphonic acid chloride with phenols having a high molecular substituted amino or hydroxy group. In these couplers the hydroxyl group of the naphthol constitutes the K Q0ocHiconnOsmcmcmosm-O-mxcocmco-G 20 tion product thereof during development, is referredto herein .as a vcouplin coupler.-

Great Britain January 8,

alcohol or an alkoxy or aryloxy alcohol, or witha, phenol. According to: the molecular size and solubility of these compounds, they may be incorporated either in photographic emulsions or in developing solutions. The introduction of the sulphonic ester group tends to confer better dispersabillty on the coupler molecule, which is. a

' desirable proper y when the coupler is to be incorporated in emulsions. The compounds which we propose the following general formula:

n-soz-o-Yp wherein R=an aroyl acetamlnobenzene Y' '-alkyl, aryl, alkoxy alkyl, or aryloxy alkyl cording to our invention are the following:

wnoocmc-Q 'Methylp-(benzoylscetamino) benzenesulphonate U OcocmconnGsmcm Itthyl p-(benzoylacetamino) benzenesulphonate n-Iropyl p-(benloylaeetamino) benzeneslilphonate Ococmo oNraOsmcmcmocnn B-Etlioxyethyl p-benaoylacetamino) benzenesulphonate' B-Benzyloxyethyl p-(benzoylacetamino) benzenesulphonate Ethylene 1.8 di-(p-benzoylscetamino) benzenesulphonate pared by treating a sulphonic acid chloride of a yellow coupler with an alcohol, such as ethyl o NEG 011180 OaCsHu n-a'mylp-(benroylaoetaminm benzenesulphousfm tousehave Specific compounds which may be used acs Ocodmdonfi-O-smcmcmocm-C) compounds, the former.

a o O,

ll Nniio'mcQ smcmomocmomocm-O fl-(fi-Benzyloxyethoxyyethyl p(benzoylaoetamlno) benzenesulphonate i NBC (limb-O to alkoxy and aryloxy groups, it is to be understood that these groups may be further substituted-provided that the other requirements with respect to coupling are met.

The aromatic amino developing agents used with the coupler compounds of our invention include the mono-, di and tri-amlnoaryl compounds and their derivatives formed by substitue tion in the amino group as well as in the ring, such as alkylphenylenediamines and alkyltoluylenediamines. These compounds are usually used in the salt form, such as the hydrochloride or the sulphate, which are more stable than the amines themselves. Suitable compounds are diethyL-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediaminehydrochloride, dimethyl-p-pheny1enediaminehydrochloride and dimethyl-p-phenylenediamine sulphate. The

p-aminophenols 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 products of the developer to couple NHC O CHaC O op-00H" din 2,4-diamylphenyl p (benzoylaoetamino)-benzsnesulphonate with the color forming compounds to form a dye image.

, The following developer formula may be used with the compounds of our invention:

A. p-Aminodiethylaniline sulphate grams 2 Our development process may be employed for the productionot colored photographic images in layers of gelatin or other carrier such as collodion, organic esters of cellulose or synthetic resins. The carrier may be supported by a trans- (12) t-CrHO-OCHaCBaOSih-QNHC OCHsC GOO CHI fi-(p-t-Butylphenoxy-ethyl p-enlsoylacetamino-benzeneaulphonate n-A myl panisoylocetemino-benzenesulphonate The couplers made according to our invention may-be dissolved in the developing solution or may be incorporated in the emulsion layer according to their solubility characteristics. Compounds 1 to 4 are suitable for use in the developing solution and compounds 5 to 13 may be incorporated in the emulsion layer.

As stated above, the coupler must contain a coupling function, which in this case is a reactive methylene group. By coupling function we mean a functior.al or reactive group common to coupler compounds which-react with primary aromatic amino developing agents. By reactive methylene we v mean a CH2 group which is reactive in the coupling process. The CH2 group is usually present between two ne ative centers as in the groups -COCH2--CO or -CO-CH2CN, in the case of the present One of the hydrogen atoms of the methylenegroup may, in general, be substituted without destroying the chemical activity of the group.

The coupling compounds used according to our invention may contain other substituents which do not affect the coupling properties of the compound. Where we refer in the general formula parent medium such as glass, a cellulose ester, or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or as superposed layers on one or both sides of the support. The superposed layers may be differentially sensitized to form natural color photographic images in the well known manner.

The couplers which we propose to, use are pre- I pared, in general, by the interaction of the sulphonyl chloride of the coupler with the appropriate alcohol in the presence of one equivalent of pyridine. For example, to prepare methyl: p-(benzoylacetamino) -ben zenesulphonate, one equivalent weight of p-(benzoylacetamino)- benzene-sulphonyl chloride is reacted with an excess methyl alcohol in the presence of one equivalent weight of pyridine. In the case of the couplers prepared from the sulphonyl chloride of the coupler-and a phenol, the sulphonyl chloride is reacted with the sodium salt of the phenol in xylene solution. For example, Compound 11, 2,4-diamylphenyl-p-(benzoylacetamino) -benzenesulphonate, the coupler was obtained by the reaction of p-(benzoylacetamino)- benzene sulphonyl chloride on the sodium salt of 2,4-diamylphenol in xylene solution.

The sulphonyl chlorides of thecouplers are prepared as described in our copending applica- I tion Serial No. 358.494, filed September 26, 1940, by treating the appropriate acetanilide with chlorosulphonic acid at' a temperature below about 10 C. and permittingthe reaction to proceed fora, short time, that is, of the order of a few days. For example, p-benzoylacetamino benzenesulphonyl chloride is prepared as follows:

ExAmrLn- -p-Benzoylacetaminobeneenesulphonyl chloride One part of benzoylacetanilide is added to 2 volumes ofchlorosulphonic acid while keeping the temperature below 10 C. Thereaction mixture is allowed to warm slowly to room temperature, and, after standing overnight, is decomposed by pouring onto ice. The product. is filtered, washed with water, dried in ether solution, and recrystallized 149-151" C.

The example and compounds set forth in the present specification are illustrative only and it from benzene. M. P.

isto be understood that our'invention is limited.

only by the scope of the appended claims.

We claim: 1. A color forming photographic develope comprising a primary aromatic amino developing agent formula R-SOe-O-Y where R is an aroyl acetaminobenzene and Y is selected from the group consisting of alkyl,

aryl, alkoxyalkyl and aryloxyalkyl radicals.

is selected from the; group consisting of alkyl, aryl, alkoxyalkyl and aryloxyalkyl radicals.

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

a coupler where R is a p-benzoyl acetamino benzene and Yis selected from the group consisting of alkyl,

aryl, alkoxyalkyl and aryloxyalkyl radicals.

' where R is a p-benzoylacetaminobenzene andY is an alkyl radical.

and a coupler compound having the 2. A color forming photographic developer.

comprising a'primary aromatic amino developing agent and acouplercompound having the forv is an alkyl radica1.

4. A color forming photographic developer comprisinga primary aromatic aminodeveloping agent and a coupler compound having the formula; V

R SOr--O--Y where R is a p-benzoylacetaminobenzene and Y i is an alkoxyethyl radical.

5. A color forming photographic developer 8. The method ofproducing a colored photo graphic image in a gelatino silver halide emulsion layer which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:

9. The method of producing a colored photographic image in a geiatino silver halide emul-'.

sion layer which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence of I a coupler compound having the formula:

' R-SOa-OY I where R is a p-benzoylacetaminobenzene and Y -is an alkoxyethyl radical.

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

O 0 ocmcoNHGsor-d-Y where Y is selected from the group consisting of alkyl, aryl, valkoxyalkyl, and aryloxyalkyl radicals.

comprising a primary aromatic amino developing agent and a coupler compound having the formula:

11. A photographic emulsion for forming colored images comprising acarrier containing a sensitive silver halide and a having the formula:

coupler compound I where- R. is an aroyl acetaminobenzene andY is selected from the group consisting of alkyl, aryl, alkexyaikyl and aryloxyalkyl radicals.

12. A photographic emulsion for forming colored images comprising a gelatino silver halide emulsion having incorporated therein a coupler compound of the general formula:

where R is a p-benzoylacetaminobenzene and Y 'is selected from the group consisting of alkyl,

' aryl, alkoxyaikyl and aryloxyalkyl radicals.

where Y is selected fromthe group consisting I of aliryl, aryl, alkoxyalkyl, and aryloxyalkyl radicals. 6. The method of producing a 'coloredphotographic image in a gel tino silver halide emulsion layer which comprises exposing the layer and developing it with a primary aromatic amino of a coupler developing agent in the presence compound having the formula:

I .R-S02-OY where R is an aroyl acetaminobenzene' and Y 13. A photographic emulsion for forming col-' ored images comprising'a gelatino silver halide emulsion having incorporated therein a coupler compound of the general formula:

R-- SO2-OY where'l't is a p-benzoylacetaminobenzene and Y is an alkyl radical/ 1 14. A photographic emulsion for forming colored images comprising a gelatino silver halide emulsion having incorporated therein a coupler compound of the general formula:

4- i 2,289,805 where R is a p-benzoylacetami'nobenzene and Y where Y is selected from the. group consisting of is an alkoxyethyl radical. alkyl, aryl, alkoxyalkyl, and aryloxyalkyl rad- 15. A photographic emulsion for forming oolicals. ored images comprising a gelatino silver halide HENRY DUDLEY PORTER.

emulsion having incorporated therein a coupler 5 ARNOLD WEISSBERGER. compound of the general formula: v I

OcocmcomxO-sm-o-v