US2313498A - Cyanoacetyl coupler - Google Patents

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Patented Mar. 9, 1943 CYANOACETYL COUPLER I Charles F. H. Allen and Paul W. Vittum, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N Drawing. Application December 23, 1940, Se-

rial No.'371,396. In Great Britain January 2,

21 Claims.

This invention relates to photography and more particularly to compounds which form dyes by coupling with the developing compound on development.

The method of forming colored photographic images by depositing a colored compound in the photographic layer adjacent to the silver image has been described in numerous prior patents. The present invention relates to a process in which the color-forming compound is contained preferably in the developing solution, but might also be in the sensitive material, and forms a dye concurrently in the region adjacent to silver formed on development of the silver image by coupling; with the oxidation product of the photographic developer. In U. S. Patent No. 2,115,394, granted April 26, 1938, to Mannes, Godowsky and Peterson, there are disclosed cyanoacetyl compounds useful as coupler com-- pounds in photographic developers. In U. S.

Patents Nos. 2,113,330; granted April 5, 1938 m Mannes and Godowsky, and 2,108,602, granted February 15, 1938, -to Mannes and Godowsky, other cyanoacetyl compounds are disclosed.

We have found that there are certain cyanoacetyl coupler compounds which have better (5) ciHi Cn zs These compounds, according to their molecular size and solubility, maybe incorporated either in photographic emulsions or indeveloping soluphotographic characteristics than those which have hithertobeen known. These new, cyanoacetyl couplers which we describe have sharper absorption bands and considerably higher transmissions in-a region of the spectrum such as the blue, with the result that satisfactory colors for subtractive color processes are obtained upon coupler development.

The compounds which we contemplate using have the general formula:

Where X is a.CN or COOR: group, R3 is alkyl,

Z is NHRi or alkoxy, Ri'and R2 are H, alkyl or aryl, Y is oxygen, sulfur or NR4, where R4 is H,

alkyl, or aryl.

Compounds which fall under this general clas- Cyanoacetyl urea (2) NEH-O 0-NH-0 O-CH2C 0 0 0 2H: I Ethyl malonyl urea a Nnr-o-NH-c 0-o Ha-CN Oyanoacetyl guanidine (4) 04m NH-C ONH-C O-CHi-GN Butyl eyanoacetyl urea tions. Usually the less highly N substituted compounds (those compounds having substituents of lower molecular weight) are used in developers.

Compounds 1-5 and 7-9 are suitable for use in a developing solution and compound 6. may be incorporated into an emulsion layer. These couplers must contain a coupling function, which is in this case a reactive methylene group. By

coupling function" we mean afunctional or reactive group commori to coupler compounds which react with primary aromatic amino developers. By reactive methylene we mean aCH z group which is reactive in the coupling process. The reactive methylene group is present between two negative centers as in the groups CO- CH2- CO- or COCH2CN. One of the atoms of the methylene group may, in general be substituted without destroying the chem ical activity of the group, if the substituentis one which is split off easilysuch as halogen or carboxyl.

The aromatic amino developing agents used with the coupler compounds of our,invention include the mono-, di-, and tri-aminoaryl com-- pounds and their derivatives formed by substitution in the amino group as well as in the ring, such as alkylphenylenediamines and alkyltoluenediamiries. These compounds are usually used in the salt form, such as the hydrochloride or the sulfate, which are more stable than the amines themselves. Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride and dimethyl p phenylenediamine sulfate.

may also be used where the amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables oxida- Thep-aminophenols and their substitution products I color forming compounds to form a dye image.

- where R is alkyl, and R1 and R2 are selected from the group consisting of H, alkyl and aryl, Y

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

A. p-Aminodiethyl aniline sulfate grams 2 Sodium sulfite anhydrous do 5 Sodium carbonate anhydrous do 20 Potassium bromide do 2 Water to "liter..- 1

B. Coupler grams 1-5 Solvent (acetone or isopropyl alcohol) cc 100 Add B to A.

Our development process may be employed for the production of colored photographic images in layers of gelatin or other carrier such as collodion, organic esters of cellulose or synthetic resins. The support for the emulsion may be a transparent material such as glass, a cellulose ester, or an opaque material such as paper or an opaque cellulose ester. The superimposed layers may be sensitized to record different regions of the spectrum.

The cyanoacetyl couplers which we use are, in general, prepared by the interaction of cyanoacetic acid and ureas, guanidines, cyanamide or urethane in the presence of a dehydrating agent such as phosphorous oxychloride or acetic anhydride in a manner similar to that described in the German, Patents Nos. 175,415 and 115,253. The-malonyl urea couplers are prepared by the interaction of an acid chloride of malonic ester and a urea, thiourea, guanidine, etc. as described in the German Patent No. 193,447.

The methods and compounds set forth in the present specification are illustrative only and it is to be understood that our invention is limited only by the scope of the appended claims.

We claim:

1. A color forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and a coupler compound having the-formula:

where X is selected from the group consisting of CN and COOR: where Ra is-alkyl, Z is selected from the group consisting of NHR1 and alkoxy R1 and R2 are selected from the group consisting of H, alkyl and aryl, Y is selected from the group consisting of oxygen, sulfur and NR4, where R4 is selected from the group consisting of H, alkyl and aryl.

2. A color forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and a coupler compound having the formula:

4 pound containing a primary amino group and cyanoacetyl guanidine. Y

. 4. A color forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and,

a coupler compound having the formula:

is selected from the group consisting of oxygen, sulfur and NR4, where R; is selected from the group consisting of H, alkyl and aryl.

5. A color forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and ethyl malonyl urea.

6. A color forming photographic developer comprising an aromatic amino developing agent containing a primary amino group and a coupler compound having the formula:

R; l lH( 3I lOOCHaCN where R1 and R2 are selected from the group consisting of H, alkyl and aryl, Y is selected from the group consisting of oxygen and sulfur.

'7. A color forming photographic developer comprising an aromatic amino developing compound containing a primary amino group and cyanoacetyl urea.

8. The method of producing a colored photographic image in a light sensitive silver halide emulsion layer which comprises exposing the layer and developing it with an aromatic amino developing compound containing a primary amino group in the presence of a coupler compound having the formula:

where X is selected from the group consisting of CN and COORa where R: is alkyl, Z is selected from the group consisting of NHR1 and alkoxy R1 and R2 are selected from the group consisting of H, alkyl and aryl, Y is selected from the group consisting of oxygen, sulfur and NR4 where R4 is selected from the group consisting of H, alkyl and aryl.

9. The method of producing a colored photographic image in a light sensitive silver halide emulsion layer which comprises exposing the layer and developing it with an aromatic amino developing compound containing a primary amino group in the presenceof a coupler compound having the formula:

where R1, R2 and R4 are selected from the group consisting of H, alkyl and aryl.

10. The method of producing a colored photographic image in a light sensitive silver halide emulsion layer which comprises exposing the layer and developing it with an aromatic amino developing compound containing a primary amino group in the presence of cyanoacetyl guanidine.

11. The method of producing a colored photographic image in a light sensitive silver halide emulsion layer which comprises exposing the layer and developing it with an aromatic amino developing compound containing a primary amino group in the presence of a coupler compound having the formula:

1 i 1 NH-i-N-CO-CHPCOOR where R is alkyl, and R1 and R2 are selected from the group consisting of H, alkyl and aryl,

Y is selected from the group consisting of oxygen, sulfur and NR4, where R4 is selected from the group consisting of H. alkyl and aryl.

12. The method of producing a colored photographic image in a light sensitive silver halide emulsion layer which comprises exposing the.

layer and developing it with an aromatic amino developing compound containing a primary amino group in the presence of ethyl malonyl urea. e

13. The method of producing a colored photo,- graphic image in a light sensitive'silver halide emulsion layer which comprises exposing the layer and developing it with-an aromatic amino developing compound containing a primary amino group in the presence of a coupler com pound having the. formula;

i" i f NHCNCOCH:CN

where R1 and R2 are selected from the group consisting of H, alkyl and aryl, Y is selected from the group consisting of. oxygen and sulfur.

14. The method of producing a colored photoemulsion having incorporated therein a coupler compound having the formula:

' R1 NR4 R2 v where Rn-R2, and R4 are selected from the group consisting of H, alkvl and aryl, R4 is selected from the group consisting of H, alkyl and aryl.

17. A photographic emulsion for forming colored images comprising a gelatino silver halide emulsion having incorporated therein cyanoacetyl guanidine.

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

r i r NH-CN-C0CHz-CO0R where'R is alkyl, and R1 and-R's are selected from the group consisting of H, alkyl and aryl,

graphic image in a light sensitive silver halide emulsion layer which comprises exposing the layer and developing it with an aromatioamino developing compound containing a primary amino group in the presence of cyanoacetyl urea.

15. Aphotographic emulsion for forming colored images comprising a carrier containing a sensitive silver halide and a coupler compound having the formula:

where X is selected from the group consisting of CN and CQORa where R; is alkyl, 2 is selected from the group consisting of NHR1 and alkoxy R1 and R2 are selected from the group consist-- ing of H, alkyl and aryl,-Y is selected from the group consisting of oxygen, sulfur and NR4 where R; is selected from the group consisting of H, alkyl and aryl. g

16. A photographic emulsion for forming colored images comprising a gelatino silver halide Y is selected from the group consisting of oxygen, sulfur and NR4, where Rr'is selected from the group consisting of H, alkyl' and aryl.

19. A photographic emulsion for forming colorcd images comprising a gelatino silver halide emulsion having incorporated therein ethyl emulsion having incorporated therein cyanoacetyl urea. CHARLES E. H. ALIEN.

PAUL W. V1'1I'UM'.-