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US2552241A - p-phenylenediamines containing alkylacylamidoethyl or alkylacylamidoethoxy ring substituents - Google Patents

p-phenylenediamines containing alkylacylamidoethyl or alkylacylamidoethoxy ring substituents Download PDF

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US2552241A
US2552241A US82282A US8228249A US2552241A US 2552241 A US2552241 A US 2552241A US 82282 A US82282 A US 82282A US 8228249 A US8228249 A US 8228249A US 2552241 A US2552241 A US 2552241A
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Weissberger Arnold
Dudley B Glass
Paul W Vittum
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

  • the allergenic properties of the p-phenylenediamine developers may be overcome by substituting a sulfonamide group or an amine sulfonyl group in the alkyl group on the nitrogen atom of p-phenylenediamine as described in Weissberger U. S. Patent 2,193,015, granted March 12, 1940.
  • These substituted p-phenylenediamine developers are sometimes too low in developing strength (or reduction poteninvention by the use as developing agents of compounds of the following general formulas:
  • R is a lower alkyl group such as methyl, ethyl or propyl
  • R is a lower alkyl group
  • X is the substituted acyl group -SO2R" or -COR" and R is a lower alkyl group.
  • lower alkyl group we mean a methyl
  • the nitrite was added during a period of 1 hour. Stirring was continued for 1 hour longer at 0.
  • This solution was further acidified by the addition of ml. of concentrated hydrochloric acid and the nitroso compound was reduced with 65 g. of zinc dust.
  • the zinc dust was added in portions, with stirring, while the temperature of the reaction mixture was maintainedat 15:5".
  • the excess zinc dust was filtered off and the solution was made alkaline with 400 ml. of ammonium hydroxide.
  • the diamine was extracted with 600 ml. of chloroform.
  • the chloroform solution was washed with water and dried over anhydrous sodium sulfate.
  • the chloroform was removed under reduced pressure and the diamine was distilled under reduced pressure. The portion that boiled at 190-195 at 1 mm. was collected as the desired product.
  • the chloroform solution was washed with water, dried over anhydrous sodium sulfate and the chloroform Was evaporated under reduced pressure.
  • the residue was dissolved in a mixture of ml. of concentrated hydrochloric acid and 400 ml. of water, and nitrosated 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 05 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 and dissolved in a mixture of 166 ml. of concentrated hydrochloric acid and 400 ml. of water.
  • Thearesidue- 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. Theresidue was'distilled under reduced pressure. The product boiled at 135-142 at 2 mm.
  • Thechloroform solution was driedover anhydrous-sodium sulfate and then the chloroform was removed under reduced pressure keeping the temperature of the nitroso compound at 20-25".
  • the nitroso compound after" recrystallized from :benzene melted at l24124.5.
  • N,N-- diethyl -3 (,8-methylsuljonamidoeth- 0wy)aniZine.
  • a mixture of 3-(B-aminoethoxy)- N,N-diethylaniline; (0.1 mole) and 40 ml. .of water was cooled to 1520 and stirred while 9 m1. of :methanesulfonyl chloride was added slowly. After. each quarter of the acid: chloride had been added,..one-fourth of'a So1ution'of'4-.5 g. of sodium hydroxide in 15 ml. of water was-added.
  • the temperature ofthe reaction mixture was main taine'd-at 15--20 during the reaction- After stirring at 20 for two hours, theprecipitate was .removed by filtrationand recrystallized: from: ml. Of'45 aqueousalcohol. After drying. in air, the product melted :at- 70-72".
  • Thetfollowing example illustrates a developingsolution which may beused accordingto -our invention.
  • the developing agents described in' the present application maybeused' to form photographic images by'development ofexposed'silvei' halide contained-in the usual gelatin carrier r-hr carrierssuch:ascollodiontwater-permeablecellulose 9 i 10 ester or water-permeable synthetic resins.
  • An amino compound having the formula developing agents may be used with photographic R 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.
  • a developing solution similar in composition to Part A in OOHCHNHBOR the above example is suitable.
  • NH It will be understood that the examples included herein are illustrative only and that our in- Where R and are lower. alkyl groups vention is to be taken as limited only by the scope An ammo compound having the formula of the appended claims.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

Patented May 8, 1951 UNITED STATES PATENT OFFICE p-PHENYLENEDIAMINES CONTAINING AL- KYLACYLAMIDOETHYL OR ALKYLACYL- AMIDOETHOXY RING SUBSTITUENTS 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 No Drawing. Original application March 6, 1948,
Serial No. 13,526. Divided and this application March 18, 1949, Serial No. 82,282
pounds for producing fine grain black and white photographic images and also 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 sulfonamide group or an amine sulfonyl group in the alkyl group on the nitrogen atom of p-phenylenediamine as described in Weissberger U. S. Patent 2,193,015, granted March 12, 1940. These substituted p-phenylenediamine developers, however, are sometimes too low in developing strength (or reduction poteninvention by the use as developing agents of compounds of the following general formulas:
2 and o CHzCHgNHX where R is a lower alkyl group such as methyl, ethyl or propyl, R is a lower alkyl group, X is the substituted acyl group -SO2R" or -COR" 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 according to our invention are as follows:
1 CHHB 2 5 OH CH NHO 00H;
NH; 3- (B-a cetamidoethyl) 4-amino-N,N-diethylaniline 2 C 2H5 C 2B5 OHQCHzNHSOgOHa 4-amino-N,N-diethyl-3-(B-methyl-sulfonamidoethyl)- aniline 3-(B-acetamidoethoxy)-4-am1no-N,N-diethylanil1ne 4 C:H| CIHB The specific compounds illustrated above were prepared as follows:
1. 3 (p acetamidoethyl) 4 amino N,N diethylaniline was prepared from 3-nitrotoluene a by the followin series of reactions.
11. 3-nitrobenzyl briomide.-3-nitrotoluene (5 moles) was heated at 135i5 and bromine (5 H, moles) was dropped in during a period of 5 4-amin -N,N-diethy1-3-,(fi-methylsulfonamidoetho y)- h During, this time e reaction mixture aniline 10 was exposed to the lightiofa, 200 w; clear bulb. The reaction mixture was cooled, dissolved in ether and the ether was dried over anhydrous O CH2CHINHSO2CHI The preparation of our developers may be summarized by the following reaction schemes:
NO NH;
sodium sulfate. The ether wa evaporated and the residue was distilled under reduced pressure collecting the fraction that boiled at 120-150/2 mm. This crude product was redistilled under reduced pressure collecting the portion that boiled at 160-162/14 mm. This redistilled material was recrystallized from methanol and dried in air. Melting point 58-59".
I). 3-nitrophenylacetonitrile.-Sodium cyanide (1.0 mole) was dissolved in 80 ml. of water. Alcohol (280 ml.) was added and the mixture was cooled to 20. 3-nitrobenzyl bromide (0.8 mole) was added and the mixture was stirred and warmed slowly to 40. At this temperature the heating was stopped and the exothermic reaction allowed to proceed. The temperature was 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 ml. 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 160165/3 mm. The product was recrystallized from methanol. Melting point 61-62". A
c. 3 aminophenylacetonitrile. 3 nitro-' phenylacetom'trile (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 solution was made alkaline with 2 l. of 40 per cent 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 collectingthe fraction that boiled at 132-135/2 mm.
d. 3-(N,N-diethylamzfno) phenylacetom'trile. 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 reflux 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 under reduced pressure collecting the fraction that boiled at 125130/2 mm.
e. 3 (p aminoethyl) N,N-diethyZaniline.-- 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.) and hydrogenated 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 therfraction that boiled at 148-150/10 mm.
1. 3 (,6 acetamidoethyl) 4 amino N,N- diethyZam'Zine.-3 (13 amino ethyl) N,N- diethylaniline (0.39 mole) was addedwith stirring and cooling to 40 n11. of acetic anhydride. The mixture was kept below a temperature of 50 during the addition and then was heated on the steam bath for 30 minutes. After cooling, the solution was 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, 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 continued for 1 hour longer at 0. This solution was further acidified by the addition of ml. of concentrated hydrochloric acid and the nitroso compound was reduced with 65 g. of zinc dust. The zinc dust was added in portions, with stirring, while the temperature of the reaction mixture was maintainedat 15:5". The excess zinc dust was filtered off and the solution was made alkaline with 400 ml. of ammonium hydroxide. The diamine was extracted with 600 ml. of chloroform. The chloroform solution was washed with water and dried over anhydrous sodium sulfate. The chloroform was removed under reduced pressure and the diamine was distilled under reduced pressure. The portion that boiled at 190-195 at 1 mm. was collected as the desired product.
2. 4 amino-N,N-diethyl 3 (,B-methylsulfonamidoethyl) aniline was prepared from 3-(-.B- aminoethyl) N,N-diethylaniline by the following method.
A mixture of 3-(fl-aminoethy1)-N,N-diethylaniline (0.36 mole) and water (150 ml.) was cooled to 15 and stirred vigorously while methanesulfonyl 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 throughout the addition. The mixture was stirred for 2 hours at room temperature and then extracted with ch10 roform. The chloroform solution was washed with water, dried over anhydrous sodium sulfate and the chloroform Was evaporated under reduced pressure. The residue was dissolved in a mixture of ml. of concentrated hydrochloric acid and 400 ml. of water, and nitrosated 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 05 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 and dissolved in a mixture of 166 ml. of concentrated hydrochloric acid and 400 ml. of water. This mixture was cooled to 15 and zinc dust (1 mole) was added in portions with stirring, keeping the temperature below 20. The excess zinc was removed 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 215220/ 1 mm. was collected as pure product.
3. 3 (B-acetamidoethoxy) 4 amino-N,N-diethylaniline was prepared by the following series of reactions.
a. 3 (.fl-chZoroetho-xy) -N,N-diethyZaniline.-A solution of 80 g. of sodium hydroxide in 2 1. of water was placed in a flask and melted 3-(N,N- diethylamino) phenol (3 moles) was added and the mixture was heated on a steam bath for 19 hours with stirring. At the end of this period the mixture was cooled and ml. of 40% sodium hydroxide solution was stirred in. The solution was extracted twice with ether. The
7: ether solution.waswashedwith water, dried-over. anhydrous.-;sodium sulfate. and; the ether was evaporated; Theoresidudwas distilled underzreduced pressure The: product boiled at 125-135 at'2.mm.
b: N-,N.- Methyl-. 3 (fi phthalimidoethoxy) amline.zA- mixture of 3-(fi-chl0roethoxy9 -N,=Ndiethylaniline. (1.01 moles), potassium phthalate (1.07 moles) and; diethyleneglycol' (2 1.) was stirred slowly andheated at--1.40-150 for hours. Thexsolution was poured into 1 l. of coldwa-ter and allowed to standfor 10-12 hours at 0. The precipitate; was. removed by filtration, washed with alcohol and recrystallized from a mixture of 850 ml; of 3A and 760 ml. of ethylacetate; T-hepro duct meltedat 127--129.
c. 3- (fi-ammoerhorys).-N,N-diethyZaniZme:-A mixtureof N,Na-diethyl-3-'(d+phthalimidoethoxy.) aniline (0.43 mole), 85% hydrazine (0.43 mole) and 300ml.- of alcohol was boiled under reflux for 30.:minutes. The mixture was cooledsomewhat 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 off and the filtrate was concentrated under reduced pressure until the alcohol had been removed. Thearesidue-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. Theresidue was'distilled under reduced pressure. The product boiled at 135-142 at 2 mm.
d. 3 (,8 acetamz'doethoxw N,N diethylaniline.3 3 aminoethoxy) N ,N-diethylaniline (0.07) 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 stillhot'and allowed to cool. The crystals were removed by filtration and dried in air. Melting point 66.5-67".
e; 3- (,Beaceiamidoethoazy) -N,N-diethyZ-4-m'trosoaniline.3 (o acetamidoethoxy) -N,N-diethylaniline (0.07 mole) was dissolved in 140ml. of water and'21 ml. of concentratedhydrochloric acid. The solution was cooled to 0 and nitrosated with a solutionof 5.0 g. of sodium nitrite in 35 ml. of water. After standing at 0 for minutes the reaction mixture Was made alkaline with ammonium hydroxide and the nitroso compound .Was extracted with chloroform. Thechloroform solution was driedover anhydrous-sodium sulfate and then the chloroform was removed under reduced pressure keeping the temperature of the nitroso compound at 20-25". The nitroso compound after" recrystallized from :benzene melted at l24124.5.
f. 3- (.fi-acetamidoethoxy) -4-a.mino -N,N-di'eth ylaniline.3 (B-acetamidoethoxy) -N,N-diethyl- 4-nitrosoaniline (0:06 mole) and. 50ml. of absolute alcohol were placed in a Parr hydrogenation apparatus-andreduced in the presenceof Raney nickel at a' temperature of 60 and a hydrogenpressure of 3 atmospheres. Theca-talyst was re-' moved by filtration and the alcohol wasevaporated under reduced pressure. The residue was distilled under reduced pressure. The portion that boiled at 112 11? at 1 mm. was diluted with 25 ml. of petroleum ether. Aiter standing at 0 for. 16 hourskthe product. wasfiltered ofitanfi 8 dried; in: a: vacuum desiccator. 50-51";
4. 4'-- amino -N,N diethyl;3-(fi-methylsulfonamidoethoxyl-aniline was prepared from 34paminoethoxy) -N,N-diethylaniline by the followingniethodz.
a; N,N-- diethyl -3 (,8-methylsuljonamidoeth- 0wy)aniZine.A mixture of 3-(B-aminoethoxy)- N,N-diethylaniline; (0.1 mole) and 40 ml. .of water Was cooled to 1520 and stirred while 9 m1. of :methanesulfonyl chloride was added slowly. After. each quarter of the acid: chloride had been added,..one-fourth of'a So1ution'of'4-.5 g. of sodium hydroxide in 15 ml. of water was-added. The temperature ofthe reaction mixture was main taine'd-at 15--20 during the reaction- After stirring at 20 for two hours, theprecipitate was .removed by filtrationand recrystallized: from: ml. Of'45 aqueousalcohol. After drying. in air, the product melted :at- 70-72".
D. N,N- diethyl- --3- (ii-methylsulfonamidoeth 0mg) -4-'-nitrosoam'line-.A solution of N ,N dieth yl-3- (fi-methylsulfonamidoethoxy) 'anilin'e' (0.058 mole) in 50ml. of: water and 17 ml. of concen trated hydrochloric acid was cooled to 0 and nitrosatedby the addition ofa-solution of4.1 g; of sodiumzni-trite 111.15 ml. of-water. The solution 'waststirred at. 0? *for minutes, dilutediwith 50 ml. of water and made alkaline with1ammonium hydroxide. The. precipitate: was removed by filtration and:recrystallizedzfromr100 ml..of 50% aqueous alcohoL. Thetproduct was dried in air.
c. 4- ami'no NgN- Methyl-3 .-(p-methylsuljonamidoethoxy) aniZine.-N,N-diethyl-3-(flamethyls'ulfonamid'oethoxy) 4 nitrosoaniline (0.0365 mole) and .75 ml. of absolute alcohoLw'ereiplac'ed inv a Pair: hydrogenation apparatus andreduced in theipresence of :Raney: nickel at a temperature of? andlahydrogenzpressure.of .3 atmospheres. The catalystiwasmemoved by filtration and the filtrate. was: concentrated to a syrup underreducedpressurez The residue was-recrystallized fromaqueous alcohol. The produczt, dried'in a vacuni'desiccator, melted'at 89-01 Whenlused for .the=.formation of colored 'photo graphic: images,.. the developers of our in'- vention.v may. be used in conjunctionwith any well ekno-wnicou-plerl compoundssuch as thosedescribeddn Fisher U. .S; Patent '1,'102,028, grantedJune 30, 1914, .Mannesand Godowsky-U. S5 Patent 2,100,602, granted Fe'bruary' w, 1938; or Marines; .Godowsky. and Peterson U. 6. Patents 2,115,394,. granted: April 26',- 1933, and 2,126,337, granted August 9, 1938.
Thetfollowing exampleillustrates a developingsolution which may beused accordingto -our invention.
Melting; point 4a- -amino-N;N-diethyl -3 (B=m'ethylsulfona-midoethyl aniline grams 2.5
Sodium sulfite' do' 2 Sodiumcarbonate" do-' 30 Potassiumbromide do 2 Waterto l-liter Coupler (o-phenylphenol) do 2 Sodium hydroxide (10%.solution) cc 20 F0r-use,-B isadded to A;
The developing agents described in' the present application maybeused' to form photographic images by'development ofexposed'silvei' halide contained-in the usual gelatin carrier r-hr carrierssuch:ascollodiontwater-permeablecellulose 9 i 10 ester or water-permeable synthetic resins. Our 4. An amino compound having the formula developing agents may be used with photographic R 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 developing solution similar in composition to Part A in OOHCHNHBOR the above example is suitable. NH It will be understood that the examples included herein are illustrative only and that our in- Where R and are lower. alkyl groups vention is to be taken as limited only by the scope An ammo compound having the formula of the appended claims.
We claim: 02H: C255 1. An amino compound having a formula of N the class consisting of omomNHooom NH: CHCHNHX 6. An amino compound having the formula 0 H c H and 2 5/ 2 5 R\ /R N 80 CHiCHjNHSO CHg O 0 H10 HiNHX NH:
NH 7. An amino compound having the formula where R and R are lower alkyl groups, X is CHE 01H selected from the class consisting of SO2R" and COR" groups, and R" is a lower alkyl N group.
2. An amino compound having the formula R\ /R1 ocmcmunsoicm ARNOLD WEISSBERGER. CH CH NHSO RII B. I PAUL W. VI'ITUM. NH: Where R, R and R" are lower alkyl groups. REFERENCES CITED An ammo compound havmg the formula The following references are of record in the file of this patent:
N/ UNITED STATES PATENTS Number Name Date 2,193,015 Weissberger Mar. 12, 1940 CECHNHCOR" 2,304,953 Peterson Dec. 15, 1942 FOREIGN PATENTS NH:
Number Country Date where R, R and R" are lower alkyl groups. 294,085 Germany Sept. 13, 1916

Claims (2)

1. AN AMINO COMPOUND HAVING A FORMULA OF THE CLASS CONSISTING OF
2. AN AMINO COMPOUND HAVING THE FORMULA
US82282A 1947-05-23 1949-03-18 p-phenylenediamines containing alkylacylamidoethyl or alkylacylamidoethoxy ring substituents Expired - Lifetime US2552241A (en)

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US750178A US2566271A (en) 1947-05-23 1947-05-23 Photographic developer containing substituted sulfonamide groups
US13525A US2592363A (en) 1947-05-23 1948-03-06 P-phenylenediamine developer containing nu-alkylacetamido ethyl substituent
US13526A US2592364A (en) 1947-05-23 1948-03-06 p-phenylenediamine developer containing alkylacylamidoethyl or alkylacylamidoethoxyring substituents

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Cited By (8)

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US2811555A (en) * 1955-05-02 1957-10-29 Eastman Kodak Co Reduction of 2-nitroso-5-diethylaminotoluene
US2824872A (en) * 1955-02-05 1958-02-25 Lab Dausse Morpholino phenyl carbamates and production thereof
US2830008A (en) * 1954-04-30 1958-04-08 May & Baker Ltd Amines
US2879293A (en) * 1957-02-19 1959-03-24 Hoffmann La Roche Benzylamine derivatives
US2911410A (en) * 1954-10-01 1959-11-03 Ici Ltd N (p-aminophenyl) phthalimides as photographic developers
US2927132A (en) * 1955-05-19 1960-03-01 May & Baker Ltd 1-(4-amino-2-alkoxyphenoxy)-benzamidoalkanes
US3647462A (en) * 1969-02-19 1972-03-07 Eastman Kodak Co Methods and materials for replenishment of developers for color photographic films (b)
US6303816B1 (en) * 1997-02-04 2001-10-16 Eli Lilly And Company Sulphonamide derivatives

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US2727062A (en) * 1954-05-26 1955-12-13 Gen Aniline & Film Corp Storage stable 4, 6-diamino metanilic acids
US3658525A (en) * 1970-12-03 1972-04-25 Eastman Kodak Co Reversal color photographic processes
US3656950A (en) * 1970-12-03 1972-04-18 Eastman Kodak Co Color photographic processes

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US2389575A (en) * 1942-07-08 1945-11-20 Du Pont Immobile n-substituted naphthylamine dye intermediates
US2449919A (en) * 1947-07-05 1948-09-21 Eastman Kodak Co 3-methylsulfonamido-4-amino dimethyl aniline photographic developer
US2552242A (en) * 1948-03-06 1951-05-08 Eastman Kodak Co p-phenylenediamines containing n-alkylacetamido ethyl substituent
NL2007777C2 (en) * 2011-11-11 2013-05-14 Assembleon Bv COMPONENT POSITIONING DEVICE EQUIPPED WITH A MACHINE FRAME AND AT LEAST TWO COMPONENT CONTAINING UNITS, AND METHOD FOR DRIVING SUCH COMPONENT INSTALLATION DEVICE.

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US2304953A (en) * 1941-08-08 1942-12-15 Eastman Kodak Co Photographic developer

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830008A (en) * 1954-04-30 1958-04-08 May & Baker Ltd Amines
US2911410A (en) * 1954-10-01 1959-11-03 Ici Ltd N (p-aminophenyl) phthalimides as photographic developers
US2824872A (en) * 1955-02-05 1958-02-25 Lab Dausse Morpholino phenyl carbamates and production thereof
US2811555A (en) * 1955-05-02 1957-10-29 Eastman Kodak Co Reduction of 2-nitroso-5-diethylaminotoluene
US2927132A (en) * 1955-05-19 1960-03-01 May & Baker Ltd 1-(4-amino-2-alkoxyphenoxy)-benzamidoalkanes
US2879293A (en) * 1957-02-19 1959-03-24 Hoffmann La Roche Benzylamine derivatives
US3647462A (en) * 1969-02-19 1972-03-07 Eastman Kodak Co Methods and materials for replenishment of developers for color photographic films (b)
US6303816B1 (en) * 1997-02-04 2001-10-16 Eli Lilly And Company Sulphonamide derivatives
US6596716B2 (en) * 1997-02-04 2003-07-22 Eli Lilly And Company 2-propane-sulphonamide derivatives
US20060030599A1 (en) * 1997-02-04 2006-02-09 Arnold Macklin B Sulphonamide derivatives
US7135487B2 (en) * 1997-02-04 2006-11-14 Eli Lilly And Company Sulphonamide derivatives

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US2592363A (en) 1952-04-08
GB663101A (en) 1951-12-19
GB651909A (en) 1951-04-11
GB653284A (en) 1951-05-09

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