US2548574A - Sulfonamide substituted p-phenylenediamines containing o-alkoxy groups as silver halide photographic developers - Google Patents

Description

Patented Apr. 10, 1951 UNITED STATES PATENT OFFICE Arnold Weissberger, Dudley B. Glass, and Paul W. Vittum, Rochester, N. Y., assignors to Eastman tion of New Jersey N Drawing.

This invention relates to photographic developers and more particularly to photographicdevelopers of the substituted p-phenylenediamine yp This application isa. continuation-in-part of application Serial No.. 654,528, filed March 14, 1946, now abandoned.

It is known that p-phenylenediamine photographic developers are valuable compounds for producing fine grain black-and-white photographic images, and also, that these compounds, especially when they contain alkyl substituents, are useful as developers in processes for producing colored photographic images. The phenylenediamine developers, however, have several defects. A common 'difiiculty encountered when using these developers i their low activity and the low contrast and emulsion speed obtained with them. Other disadvantages are their low solubility in developing solutions and their allergenic character, that is, their poisonousness to the human skin. These latter defects have been solved, according to Weissberger U. S. Patent 2,193,015, by adding a sulfonamide group to one of the nitrogen atoms of p-phenylenediamine. Developers of this type, however, exhibit low developing activity.

A principal object of the present invention is, therefore, to provide new developing agents of the substituted p-phenylenediamine type having high developing activity and which are capable of giving high contrast and emulsion speed.

We have discovered that the rate of development with sulfonamide substituted p-phenylenediamines is remarkably increased by substituting an alkoxy group in the benzene ring in ortho position with respect to the primary amino group. These novel compounds have the following general formula:

HaN N Kodak Company, Rochester, N. Y., a corpora- Application February 27, 1947, 'Serial No. 731,420

11 Claims.

Specific compounds which we contemplate.

using include: 1 CiHt HiN N\ (CH2)2NHS OgCHa CgHs 4-amino-SethoXy-N-ethyI-N(fi-inethylsulfonamidoethyl) aniline 4-amino-N-methyl-N-(fi-methylsulfonamidoethyl)-mis dine 4-amino-N-ethy1-N- (B-methylsultonamidoethyl) -m-anisidine 4-amino-3-prop oxy-N-propyl-N- (fimethylsulfonamidoethyl) aniline 5 I v I CH3 (CHZMNHS OgCHa CH3 4-amin0-3-methoxy-5-methyl-N -etl1yl-N (B-methylsultonamidoethy1)-aniline 4-amino-3,5-diethoxy-N- (B-methylsulfonamidoethyl) aniline The preparation of these compounds is illus-.

trated by the preparation of 4-amino-3-ethoxy- N ethyl N r (E methylsu1fonamidoethyl).-

3 aniline, which may be synthesized by the following methods:

(a) N02 ND: NE:

C2H5I H:

catalyst OH OO:H OOzHs l 02H: I

NHC H:

or alternately: V O C2115 (b) COCHa..1

l nnoant NCzHs (CzHshSO (CH3CO)2O K hydrolyze OH OH BI'(CH9)2NH2.HBI

CHaCHiNHSQzCHs CH CH2NH3O2CH CHaCHaNHz NCzHa NC2H5 CzH HONO CHzSOzCl O CgHs O CzHs O CgHs H: catalyst CHzCHzN-HSOzCHg NCzHfl 002m; 1 I zy The preparation of 4-amino-N-ethyl-N-( 3- methylsulfonamido-ethyl) -m-phenetidine (Compound 1) may be illustrated-by the followin procedure:

N-ethyl-m+acetophenetida-A mixture of one mole of m-phenetidine and one mole of ethyl iodide was warmed in a waterbath to 40 at which temperature an exothermicreaction began. The temperature was allowed to risto 60 and then was maintained atthis temperature for one hour first by cooling and as the exothermic reaction subsided by Warming. After standing overnight, the reaction mixture was stirred with 200 m1. of water and 100 ml. of 40% caustic until all of the solid had gone into solution. The amines were extracted with ether, the ethereal solution was dried over solid sodium hydroxide and the ether was evaporatedx-The residue was added to 100 g. of acetic anhydr'id'with stirring and cooling so that the temperature did not rise above 50. This mixture was heated on the steam bath for thirty minutes, cooled and then stirred with 150 ml. of water until all of the excess anhydride had decomposed. The mixture was made alkaline with 40% caustic solution and the product was extracted with ether. The ethereal solution was dried oversolid sodium sulfate and the ether was evaporated. The residue was distilled under reduced pressurecollecting the portion that boiled 4 at 105-110/1 mm. as the desired product. The yield was 80 per cent.

N-ethyl-m-phenetidine.-One mole of N-ethylm-acetophenetide was boiled with 150 ml. of water and 150 ml. of concentrated hydrochloric acid for six hours. The reaction mixture was cooled, made alkaline with 200 m1. of 40% caustic solution and the amine was extracted with ether. The ethereal solution was dried over solid sodium hydroxide and the ether was evaporated. The residue was distilled under reduced pressure collecting the portion that boiled at l48-150/l7 as the desired product. The yield amounted to 90 per cent.

N-(fi aminoethyl) -N-ethyl-m phenetidine. A mixture of 1 mole of N-ethyl-m-phenetidine and 0.5 mole of p-bromoethylamine hydrobromide was stirred and heated at 140-150" for two and one-half hours. At the end of this time the reaction mixture was cooled and 225 ml. of water and ml. of 40% caustic solution were added. After all of the organic salts had dissolved, the product was extracted with ether. The ethereal solution was dried over solid sodium hydroxide and the ether was evaporated. The residu was distilled under reduced pressure collecting the portion that boiled at 157-160/6 mm. as the desired product. The yield was per cent.

N ethyl N-(p methylsuljonamzdoethyl)emphenetidina-A mixture of 0.625 mole of N-(flaminoethyl) -N-ethyl-m-phenetidine and 250 ml. of water was stirred vigorously, and 80 g. (0.7 mole) of methane-sulfonyl chloride was added during a period of 30 minutes, the temperature of the reaction mixture being kept at 15:5" during the addition of the chloride. After each quarter of the acid chloride had been admitted, onefourth of a solution of 28 g. (0.7 mole) of sodium hydroxide in '75 ml. of water'was introduced. The mixture was then stirredfor two hours at 20-25 and made alkaline with ammonium hyadroxide. The amide was extracted with chloroxform, the chloroform solution was washed'with water and dried over sodium sulfate. The chloroform was evaporated under reduced pressure. The residue of crude amide amounted to per cent.

N -ethyl N (,8-metitylsuljonamidoethyl) -4,-nitroso-m-phenetz'dine.0ne half mole of N-ethyl- N-(p methylsulfonamidoethyl) -m. phenetidine was dissolved in a mixture of ml. of concentrated hydrochloric acid and 500 ml. of hot water. This solution was cooled quicklyto 5 and. maintained at this temperatureiwhile', a solutionof 39. g. (0.56 mole) of sodium nitrite in 50ml. of water was added, withstirring, during a period of"20f minutes. After standing" at 5? for one hourgthe" reaction mixture was made alkalinelwith. ammo--. nium hydroxide. The precipitate, wa'sfiltered with suctionand washed With'jwater. I The moist produce .was' recrystallized twice from 500 m l. por tions of "Sf-A' alcohol and dried in air. The yield was85pe'rce'ntl' l -amino N ethyl-N-(p-methylsulfonamido ethyl) -m-phenetidine omalata one-half mole of N ethyl N (,B-methylsulfonamidoethyl) -4-nitroso-m-phenetidine was dissolved" in 500 ml. of absolute alcohol and reduced in the presence of Raney nickel at a hydrogen pressure of 4=5 lbs./in, anda temperature of60. After the reduction was complete, the catalyst was filtered off and 0.5-' mole of powdered, anhydrous oxalic acid was added. The mixture was warmed until all or the oxalic acid had dissolved and then, was cooled to;

1 0 and allowed to stand until crystallization was" complete. The crystals were filtered ofi, washed with absolute alcohol and dried in avacuum desiccator over sulfuric acid. The yield was 80 per cent. 4-.-amino-N-ethyl-N-(,B-methylsulfonamidoethy1).-m'-anisidine (Compound 3), 4-amino-3,5-diethoxy N-ethyl-N-(B-methylsulfonamidoethyl) aniline (Compound 6) and 4-amino-3-methoxyfi-methyl-N-ethyl-N (fi-methylsulfonamidoethyl)-aniline (Compound 5) can be prepared by this procedure from m-anisidine, 3,5.-diethoxyaniline and 3-methoxy-5-methylaniline respectively.

. 4 amino N -,methyl N (,8 methylsulfonamidoethyD-m-anisidine (Compound-'2) can be prepared from meanisidine and 4 amino 3 propoxy N propyl N (B methylsulfonamidoethyl) aniline (Compound 4) from 3- propoxyaniline by this procedure if instead of using ethyl iodide-inthe first. step of the syntheses, methyl iodide is used for the first compound and propyl iodide'is used for the second.

The introduction of more 'than, one ethoxy group in the ortho positions with respect to the primaryamino group as well as the introduction of an alkyl group in one ortho position and. an alkoxy group in the other mustbe considered part of the present invention. Instead of ethoxy groups, other alkoxy groups may be used, including alkoxy groups with additional substituents in the aliphatic radical, such as OH, Cl, OR, etc.

When used for the formation of colored photographic images, the developers of our invention may be used in conjunctionwith any well known coupler compounds such as those described in Fischer U. S. Patent 1,102,028, June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602, February 15, 1938; Mannes, Godowsky and Peterson U. S. Patent 2,115,934, April 26, 1938; and Mannes, Godowsky and Peterson U. S. Patent 2,126,337, August 9, 1938.

The following examples, which are illustrative only, indicate developing solutions which may be used according to our invention.

Example 1 A 4-amino-3 -ethoxy-N-ethy1-N- (ft-methylsulfonamidoethyl) -aniline grams 1 Sodium sulfite do 0.5 Sodium carbonate do 20 Water to cubic centimeters 1000 Coupler grams 1 Acetone cubic centimeters 50 Add B to A Example 2 For the formation of a fine grain black-andwhite image, the following developing solution may be used:

4-amino-N-ethyl-N- (p-methylsulfonamidoethyl) -m-anisidine grams 5 Sodium sulfite do 30 Sodium carbonate do 30 Water to cubic centimeters 1000 While we have given numerous examples of compounds illustrating our invention, it is obvious that various modifications can be made without departing from the spirit thereof. The specific alkoxy and alkyl substituents may be varied and different combinations of these substituents may be employed. Although these compounds are of particular value as photographic developers, they have other utility as in the dyeing of fur and hair.

Having thus described our invention, what we now claim and desire to secure by U. S. Letters Patent is: v

1. A developing solution for producing a colored photographic image comprising as a silver halide developing agent, a i-amino-3-alkoxy-N- (,B-alkylsulfonamidoalkyl)-aniline, and a compound which couples with the oxidation product of said developing agent at the primary amino group to form'a colored image on development.

2. The method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion layer containing a latent image, with a solution containing a compound of the following general formula:.

l \RZNHSO2R3 Y wherein X represents a member selected from the group consisting of hydrogen, alkyl groups, alkoxy groups and substituted alkoxy groups; Y represents a member selected from the group consisting of alkoxy groups and substituted alkoxy groups; R1 representsa member selected from the group consisting of hydrogen, alkyl groups and substituted alkyl groups; R2 represents an alkylene radical selected from the group consisting of ethylene and propylene; and R3 represents a member selected from the group consisting of alkyl groups and hydrogen, for a suilicipnt time to develop the latent image to a visible silver image.

3. The method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion layer containing a latent image, with a solutioncontaining a p-phenylenediamine having an alkoxy substituent in the ortho position with respect to the primary nitrogen atom of the p-phenylenediamine and a suli'onamidoalkyl substituent attached to the secondary nitrogen atom of the p-phenylenediamine, for a sufficient time to develop the latent image to a visible silver image.

4. The method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion layer containing a latent image, with a solution containing a 4-amino-3- alkoxy N alkyl N (,8 alkylsulfonamidoalkyl) -aniline, for a sufiicient time to develop the latent image to a visible silver image.

5. The method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion layer containing a latent image, With a solution containing a 4-alkyl-N- (,B-alkylsulfonamidoalkyl)-aniline, for a sumimage, with a solution containing 4-amino-3- ethoxy N ethyl N (l8 methylsulfonamido- 7 ethyl) -aniline, for a sofficient time to develop the latent image to a visible silver image.

8. A developing solution for producing a colcred photographic image comprising as a silver halide developing agent a compound of the following general formula:

pound which couples with the oxidation product of said developing agent at the primary amino 7 group to form a colored image on development.

'9. A developing solution for producing a colored photographic image comprising as a silver halide developing agent a 4-amino-3,5 dialkoxy- N alkyl N (5 alkylsulfonamidoalkylianiline and a compound which couples with the oxidation product of said developing agent at the primary amino group to form a colored image on development.

10. A developing solution for producing a colored photographic image comprising as a silver halide developing agent a 4-aminoe3-alkoxy-5- alkyl N alkyl N (B alkylsulfonamidoalkyl) -aniline and a compound which couples with the oxidation product of said developing agent at the primary amino :group to form a colored image on development.

11. A developing solution for producing a colored photographic image comprising as a silver halide developing agent 4-amino-3-ethoxy-N- ethyl N (e methylsulfonamidoethyl) -aniline and a compound which couples with the oxidation product of said developing agent at the primary amino group to form a colored image on development.

ARNOLD WEISSBERGER. DUDLEY B. GLASS. PAUL W. V'IT'I'UM.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,193,015 Weissberger Mar. 12, 1940 2,304,953 Peterson Dec. 15, 1942 2,364,350 Dickey Dec. 5, 1944 2,374,337 Dickey Apr. 24, 1945 FOREIGN PATENTS Number Country Date 804,473 France Aug. 3, 1936 536,577 Great Britain May 20, 1941 541,328 Great Britain Nov. 24, 1941

Claims (1)

1. 2. THE METHOD OF DEVELOPING A SILVER HALIDE EMULSION WHICH COMPRISES TREATING AN EXPOSED SILVER HALIDE EMULSION LAYER CONTAINING A LATENT IMAGE, WITH A SOLUTION CONTAINING A COMPOUND OF THE FOLLOWING GENERAL FORMULA: