US2592364A - p-phenylenediamine developer containing alkylacylamidoethyl or alkylacylamidoethoxyring substituents - Google Patents

Description

?atented Apr. 8, 1952 p-PHENYLENEDIAMINE DEVELOPER CON- TAINING ALKYLACYLAMIDOETHYL 10R AIZKYLACYLAIVHPOETHPX? RING SUB- STITUENTS Arnold Weissberger, Dudley B. Glass, and Paul W. Vittum, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N i Application March e, 1948, ferial No. 1532 5 26 6 Claims. 1 ,This invention relates to photographic developers and more particularly to photographic developers containing alkylacylamidoeth'yl or alkylacylamidoethoxy ring substituents.

It is known that photographic developers of the p-phenylenediamine type are valuable compoundsfor producingiilnglgrain black and white photographic images'an'dalso that these compounds, especially when they contain alkyl substituents on one of the nitrogen atoms, are useful as developers in producing colored photographic images. A serious disadvantage of the p-phenylenediamine developers is that they are highly allergenic, that is, they are poisonous to the human skin and are therefore somewhat dangerous to use.

The allergenic properties of the p-phenylenediamine developers may be overcome by substituting .a su1fonamide group or an amino sulfonyl group in the alkyl'group on the nitrogen atom of p-phenyle'nediamine as described in Weissberger U. S. Patent 2,193,015 granted March 12, 1940. 'Ihesesubstituted p-phenylenediamine developers, however, are sometimestoo low in developing strength (or reduction potential) so that it is diflicult to obtain, with them, dye images of suifici'entlyrhigh density and contrast.

It is-therefore an object oi. the present-invention to provide a new class of photographic developing agents ofthe p-phenylenediamine type.

A further object is to provide developing agents of the p-phenylenediamine type which produce dye images having the desired characteristics.

These objects are accomplished by the present invention by the use as developing agents of compounds of the followinggeneral formulas:

and

where R is a lower alkyl group such as methyl, ethyl or propyl, B is ,a lower alkyl r up, X is the substituted acyl group -SO2R" or' CQ and R is a lower alkyl group.

By lower alkyl group, we mean a methyl, ethyl or propyl group.

Compounds of this class which may be used acording'toour invention areas followsf 1. C:Ha\ /C:H|

omqmNHoo on,

3- (B-acetamidoethyl) -4-am ino-N,N-dlethy1aniline 2, C;Ha\ /C1H| CHaCEhNI-ISOzQH:

4-amino-N,N-diethyl-3-(B-methylsulfonamidoethyl)- aniline V 3. CiHt @2136 N .pCmCmNHCQQm 40 Ma thead:dete m e esessg s fle -4-Amino-N;N-diethyl-3-(B-methylsulfonamldoethoxyr v l'. w t. 4 ..:,;V': M: xial. s I

The preparation of our developers may be the residue was distilled under reduced pressure summarized by the following reaction schemes: collecting the fraction that boiled at 120-150/2 N: NO: NO: NH, N r

H: Br; NaCN SnCh CaHd NHKLiq) CH CHaBr OHgCN CHiCN CHICN ickel H omco o HONO Nlci rel CE|CH NH CHICHINHCOCHI CH|CH3NHCOCH| CH CHgNHCOCH:

NO NH:

GIH! CIHI CIH! 01H; CIHI CIHI 2 0 C111:

ems 0,01 HONO H,

---o -o o omomNH, omomNHsmcm cmcmNHs 0.0m Nick omonmnsmcm N O N H:

(as above in 1) 3. CIHI C13] 2 61B;

NK CaHa CaHl aHl CIHI ll 0H ocmomol p C CO 0 v oomonm O ILNHIO H:

O CH: C HQNH] Ha HONO Nickel OCHgCHgNHCOCH: OCHICHZNHCOCHI OOHzCHzNHCOCHI N O NH:

CIHI C2H| 1H: ClHl IHi 1H: CiHl CaHl OCHgCHzNH: OCHICHQNHBOQCHI OCHgCH|NHSO1CH| OCHzCHzNHSOnCH:

NO NH:

The specific compounds illustrated above were mm. This crude product was redistilled under prepared as follows: reduced pressure collecting the portion that 1. 3-(p-Acetamidoethyl)-4-amino-N.N-dieth- 65 boiled at 160-162/l4 mm. This redistilled maylaniline was prepared from 3-nitrotoluene by terial was recrystallized from methanol and dried the following series of reactions. in air. Melting point 58-59".

a. 3-Nitr0benzyl Bromide.--3-Nitroto1uene b. 3-NitrophenylacetonitriZe.-Sodium cyanide moles) was heated at 135:5" and bromide (5 (1.0 mole) was dissolved in 80 ml. of water. Almoles) was dropped in during a period of 5 70 cohol (280 ml.) was added and the mixture was hours. During this time the reaction mixture cooled to 3-Nitrobenzyl bromide (0.8 mole) was exposed to the light of a 200 W clear bulb. was added and the mixture was stirred and The reaction mixture was cooled, dissolved in warmed slowly to At'this temperature the ether and the ether was dried over anhydrous heating was stopped and the exothermic reacsodium sulfate. The ether was evaporated and tion allowed to proceed. The temperature was diseases not allowed to rise above 60-65". After the spontaneous reaction was over, the reaction mixture was boiled for 1 hour. The alcohol was removed under reduced pressure and the residue was dissolved in 250 m1. of water plus 300 ml. of ether. The layers were separated, and the ether layer was washed with water and dried over anhydrous sodium sulfate. The ether was evaporated and the residue was distilled under reduced pressure collecting the fraction that boiled at 160- 165/3 mm. The product was recrystallized from methanol. Melting point 61-62.

c. 3-AminophenylacetonitriZe.-3 Nitrophenylacetonitrile (0.9 mole) was added to a solution of stannous chloride (2.7 moles) in concentrated hydrochloric acid (700 ml.) The temperature of the reaction mixture was maintained at 35- 40", by cooling, until the exothermic reaction subsided. After stirring for 2 hours, the so1u tion was made alkaline with 2 l. of 40 percent sodium hydroxide solution. This mixture was diluted with 1 l. of water and the product extracted with ether. The ether solution was washed with water, dried over anhydrous sodium sulfate and the ether was evaporated. The residue was: distilled under reduced pressure collecting the fraction that boiled at l3-2-135/-2' d. 3-(N,N-Diet-hylamino) phenylacetonitrila A mixture of 3-amino-phenylacetonitrile (0.75 mole). alcohol (400 ml.). sodium carbonate (1.0 mole), water (100 ml.) and ethyl iodide (1.8 moles) was boiled under refiux for 6 hours. The alcohol was removed under reduced pressure and the residue was dissolved in a mixture of water (500 ml.) and ether (500 ml.). The ether layer was separated, washed with water and dried over anhydrous sodium sulfate. The ether was evaporated and the residue was distilled un der reduced pressure collecting the fraction that boiled at 125-130/2 mm.

e. 3-(p-Aminoethyl)-N,N diethylcmilt'ne.3- (N,N diethylamino) -phenylacetonitrile (0.66 mole) was placed in a high pressure reduction apparatus with liquid ammonia (250 ml.) and methanol (150 ml.) andhydrogenated at 110 in the presence of Raney nickel (10 g.) and a hydrogen pressure of 1500 lbs./in. The product was distilled under reduced pressure collecting the fraction that boiled at 148-150f/1.0 mm.

,f. 3-08 Acetamidoethyl)-4-amino-N;N-diethylaniline. 3 -(fi-Amino-ethyl) N,N diethylani line (0.39 mole) was added with stirring andcooling to 40 ml. of acetic anhydride. The mixture was kept below a temperature of 50 during the addition and thenwas heated on the steambath for 30 minutes. After cooling. the solutionwas stirred with 400 ml. of water until the: excess. acetic anhydride had decomposed. The solution was made; acid with 100 m1. of concentrated hydrochloric acid. cooled to. 0",v and nitrosated by the. addition of a solution of 28 g. of sodium nitrite in 50, ml. of water. The nitrite. was: added during a period. of 1 hour. Stirring, was. 6011. tinued for 1 hour longer at 0. This solution was: further: acidified by the: addition of 8.0. ml. ofconcentrated. hydrochloric acid and the. nitroso compound was reduced with. 65 g; of zincv dust. The zinc-dust was added in portions, with stirring, while. the temperature of the reaction mixture was, maintained at :5"; Theexcess zinc dust was filtered. off. and the solution, wasmadealkaline with 400 ml. of ammonium; hydroxide. The diamine was extracted with 600 of chloroform. The chloroform. solutions. was washed with water and dried over anhydrous sodium sulfate. The chloroform was removed under-ro duced pressure and the diamine was distilled under reduced pressure. The portion that boiled at 190-l95 at 1. mm. was collected as the de sired product. 2. i-Amino N,N-diethyl' 3-(B-methylsulfon amidoethy-l) aniline was prepared from 3 (5- aminoethyl)-N,N-diethylaniline by the renowing method.

A mixture of 3-(5 aminoethyD-NN-diethyl aniline (0.36 mole) and water (150 ml.) was cooled to 15 and stirred vigorously while meth' anesu-lfonyl chloride (0.41 mole) was dropped in during the course of 30 minutes. After each fifth of the methanesulfonyl chloride had been added, one-fifth of a solution of sodium hydroxide (0.41 mole) in water (50 ml.) was added. The temperature was held at 15-20" throughoutthe addition. The mixture was stirred for-2 hours at room temperature and then extracted with chloroform. The chloroform solution was washed with water, dried over anhydrous sodium sulfate and the chloroform was evaporated under reduced pressure. solved in a mixture of ml. of concentrated hydrochloric acid and 100 ml. of water, and n-itrosated at 0 by the addition of 22.5 g. of solid sodium nitrite during a period of 1 hour. The mixture was stirred for 1 hour at 0-5 and then made alkaline with ammonium hydroxide. The mixture was stirred thoroughly and the aqueous portion was decanted from the gummy product. The gum was washed with water ana'd dissolved in a mixture of 166 ml. of concentrated hydrochloric acid and 400ml. of water. This mixture was cooled to 15 and zinc dust (1' mole) was added in portions with stirring, keeping the tem-- perature below 20. The excess zinc was re moved by" filtration and the filtrate made alkaline with ammonium hydroxide. The diamine was extracted with chloroform. The chloroform solution was washed with water, dried over anhydrous sodium sulfate and the chloroform was removed under reduced pressure. The residue was distilled under reduced pressure. The fraction that boiled at 21 5-220 1 mm. was collected as pure product.

3. 3- 9 Acetamidoethoxy) --4 amino N,N- diethylaniline was prepared by the followingseries of reactions.

at. 3- (B Chloroathory) --N,N-diethylaniZine.-- A solution of 80 a; of sodium hydroxidein 21. of water was placed in a. flask and melted 3-(N,N

diethylamino)pheno1 (3 moles) was added with stirring. Ethylene dichloride (amen): was added and. the mixture was heated on a steam bath for l9hours with stirring; At the end ofthis period the mixture was cooled and ml. of 40% 60- dium hydroxide solution was stirred in. The sol'u-- ti'on was extracted twice with ether. The-ether solution was washed with water, dried over an precipitate was" removed by filtration; washed with alcohoiand' recrystallized from amixture-of The residue was dis- 7 850 ml. of 3A and 760 ml. of ethylacetate. The product melted at 127-129".

0. 3 8 Aminoethoxy) N,N diethylani- Zine.A mixture of N,N-diethyl-3-( B-phthali midoethoxy) aniline (0.43 mole), 85% hydrazine (0.43 mole) and 300 ml. of alcohol was boiled under reflux for 30 minutes. The mixture was cooled somewhat and 140 ml. of concentrated hydrochloric acid was added. The mixture was then boiled under reflux for 30 minutes cooled and diluted with 750 ml. of water. The hydrazide was filtered oil and the filtrate was concentrated under reduced pressure until the alcohol had been removed. The residue was made alkaline with ammonium hydroxide. The amine was extracted with ether. The ether solution was dried over anhydrous sodium sulfate and the ether was evaporated. The residue was distilled under reduced pressure. The product boiled at 135142 at 2 mm.

d. 3 (13 Acetamidoethory) N,N diethylaniline.3 8 Aminoethoxy) N,N diethylaniline (0.07 mole) was added to 15 ml. of acetic anhydride and the solution was heated on a steam bath for 30 minutes. The solution was stirred with 70 ml. of water until the excess anhydride had decomposed and then was concentrated to a thick syrup under reduced pressure. The syrup was dissolved in 150 ml. of boiling ligroin. The ligroin solution was filtered while still hot and allowed to cool. The crystals were removed by filtration and dried in air. Melting point 66.5 67".

6. 3 (,8 Acetamz'doethomy) N,N diethyl 4 nitrosoam'lz'na-ii (p Acetamidoethoxy) N,N-diethylaniline (0.07 mole) was dissolved in 140 ml. of water and 21 ml. of concentrated hydrochloric acid. The solution was cooled to and nitrosated with a solution of 5.0 g. of sodium nitrite in 35 ml. of water. After standing at, 0 for 20 minutes the reaction mixture was made alkaline with ammonium hydroxide and the nitroso compound was extracted with chloroform. The chloroform solution was dried over anhydrous sodium sulfate and then the chloroform was removed under reduced pressure keeping the temperature of the nitroso compound at 2025. The nitroso compound after recrystallized from benzene melted at 124124.5.

,f. 3 (p Acetamidoethowy) 4 amino -N,N

diethylamflina-3 (,B Acetamidoethoxy) N,N-

diethyl-i-nitrosoaniline (0.06 mole) and 50 m1. of absolute alcohol were placed in a Parr hydrogenation apparatus and reduced in the presence of Raney nickel at a temperature of 60 and a hydrogen pressure of 3 atmospheres. The catalyst was removed by filtration and the alcohol was evaporated under reduced pressure. The residue was distilled under reduced pressure. The portion that boiled at 112-114" at 1 mm. was diluted with 25 ml. of petroleum ether. After standing at 0 for 16 hours, the product was filtered off and dried in a vacuum desiccator. Melting point 50-51.

4. 4 Amino N,N diethyl 3 (5 methylsulfonamidoethoxy)-aniline was prepared from 3-(B-aminoethoxy) -N,N-diethylaniline by the following method.

- a. N,N Diethyl 3 (,3 methylsulfonamidoethomy)aniZine.-A mixture of 3 (,3 aminoethoxy) -N,N-diethy1aniline (0.1 mole) and 40 ml. of water was cooled to 15-20 and stirred while 9 m1. of methanesulfonyl chloride was added slowly. After each quarter of theacid chloride hadbeen added, one-fourth of a solution of 4.5 g. of sodium hydroxide in 15 m1. of water was added.

8 The temperature of the reaction mixture was maintained at 15-20 during the reaction. After stirring at 20 for two hours, the precipitate was removed by filtration and recrystallized from 110 ml. of aqueous alcohol. Alter drying in air, the product melted at 7 0-72".

I). N,N Diethyl 3 (p methylsuljonamzdoethoccy) 4 nitrosoamline.-A solution of N,N- diethyl 3 (,8 methylsulfonamidoethoxy) aniline (0.058 mole) in ml. of water and 17 ml.

of concentrated hydrochloric acid was cooled to 0 and nitrosated by the addition of a' solution of 4.1 g. of sodium nitrite in 15 ml. of water. The solution was stirred at 0 for 20 minutes, diluted with 50 ml. of water and made alkaline with ammonium hydroxide. The precipitate was removed by filtration and recrystallized from 100 ml. of 50% aqueous alcohol. The product was dried in air.

0. 4-Amino-N,N-diethyl 3 (B-methylsuljon amidoethozty) aniZine.-N,N Diethyl 3 (B- methylsulfonamidoethoxy) 4 nitrosoanlline (0.0364 mole) and 75 ml. of absolute alcohol were placed in a Parr hydrogenation apparatus and reduced in the presence of Raney nickel at a temperature of and a hydrogen pressure of 3 atmospheres. The catalyst was removed by iiitration and the filtrate was concentrated to a syrup under reduced pressure. The residue was recrystallized from aqueous alcohol. The product, dried in a vacuum desiccator, melted at 89-91.

When used for the formation of colored photo A. 4 Amino N,N diethyl 3 (,8 methylsulfonamidoethyl) aniline grams 2.5 Sodium sulfite do 2 Sodium carbonate do 30 Potassium bromide do 2 Water to 1 liter B. Coupler (o-phenylphenol) grams 2 Sodium hydroxide l0 solution) cc.. 20 For use, B is added to A.

The developing agents described in the present application may be used to form photographic images by development of exposed silver halide contained. in the usual gelatin carrier or in carriers such as collodion, water-permeable cellulose ester or water-permeable synthetic resins. Our

developing agents may be used with photographic films containing the coupler in the emulsion layer as described in Mannes and Godowsky U. S. Patent 2,304,940, granted December 15, 1942 or Jelley and Vittum'U. S. Patent 2,322,027, granted June 15, 1943; When used in this way, a developingsolution similar in. composition to Part A in the above example is suitable.

It will be understood that the examples included herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.

We claim: .1. A photographic silver halide developing solution comprising as the developing agent a compound of the group consisting of CHzCHzNHX and O CHICBINHX where R and R are lower alkyl groups, X is selected from the class consisting of --SO2R" and COR" groups, and R" is a lower alkyl group, and a compound which couples with the oxidation product of the developing agent to form a colored image.

2. A photographic silver halide developing solution which contains, as a developing agent, a substantial amount of 3-(fi-acetamidoethyl) -4- amino N,N diethyla-niline, and a compound which couples with the oxidation product of the developing agent to form a colored image.

3., A photographic silver halide developing solution which contains, as a developing agent, a substantial amount of 4-amino-N,N-diethyl-3-(flmethyl-sulfonamidoethyl) -aniline. and a. compound which couples with the oxidation product of the developing agent to form a colored image.

4. A photographic silver halide developing solution which contains, as a developing agent, a substantial amount of 3-(p-acetamidoethoxy) -4 amino-N,N-diethylaniline, and a compound which couples with the oxidation product of the developing agent to form a colored image.

5, A silver halide developing solution for producing a colored photographic image comprising a developing agent having the formula:

where R and R. are lower alkyl groups, X is selected from the class consisting of SO:R" and -COR" groups, and R" is a lower alkyl group, and a compound which couples with the oxidation product of the developing agent to form a colored image.

6. A silver halide developing solution for producing a colored photographic image comprising a developing agent having the formula:

REFERENCES orrEn 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 2,414,491 Tulagin Jan. 21, 1947 2,449,919 Weissberger Sept. 21, 1948

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE DEVELOPING SOLUTION COMPRISING AS THE DEVELOPING AGENT A COMPOUND OF THE GROUP CONSISTING OF