US2603656A - Photographic developing agents - Google Patents
Photographic developing agents Download PDFInfo
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- US2603656A US2603656A US213051A US21305151A US2603656A US 2603656 A US2603656 A US 2603656A US 213051 A US213051 A US 213051A US 21305151 A US21305151 A US 21305151A US 2603656 A US2603656 A US 2603656A
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- aniline
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- ethyl
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- 150000001875 compounds Chemical class 0.000 claims description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- -1 N- substituted aminoaniline Chemical class 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002832 nitroso derivatives Chemical class 0.000 description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000009935 nitrosation Effects 0.000 description 2
- 238000007034 nitrosation reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MKZHJJQCUIZEDE-UHFFFAOYSA-N 1-[(2-hydroxy-3-naphthalen-1-yloxypropyl)-propan-2-ylamino]-3-naphthalen-1-yloxypropan-2-ol Chemical compound C1=CC=C2C(OCC(O)CN(CC(O)COC=3C4=CC=CC=C4C=CC=3)C(C)C)=CC=CC2=C1 MKZHJJQCUIZEDE-UHFFFAOYSA-N 0.000 description 1
- JJFOBACUIRKUPN-UHFFFAOYSA-N 2-bromoethoxybenzene Chemical compound BrCCOC1=CC=CC=C1 JJFOBACUIRKUPN-UHFFFAOYSA-N 0.000 description 1
- QBLISOIWPZSVIK-UHFFFAOYSA-N 4-bromobutoxybenzene Chemical compound BrCCCCOC1=CC=CC=C1 QBLISOIWPZSVIK-UHFFFAOYSA-N 0.000 description 1
- QOLSAZPSEJXYSH-UHFFFAOYSA-N 6-bromohexoxybenzene Chemical compound BrCCCCCCOC1=CC=CC=C1 QOLSAZPSEJXYSH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- KKHWAYLPKGKYTI-UHFFFAOYSA-N n-ethyl-n-(2-phenoxyethyl)aniline Chemical compound C=1C=CC=CC=1N(CC)CCOC1=CC=CC=C1 KKHWAYLPKGKYTI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical class [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 210000003859 smegma Anatomy 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- An object. of. this invention is to provide a new class of. photographic developing agents.
- .A. further object is to provide a. new class of photographic developing agents. which are useful in chromogenic development and are free from, toxic effects.
- the more specifieobject is to provide a new class of N-alkyl-N(sulfophenyloxy) alkylanilines. Still other objects will be apparent from the-following: description of the invention.
- the new compounds ofthi's invention may be represented by the following general formula:
- alkoxy "alkoxy" group; n is a positive integer from 2 to '10- and alkyl contains irom 1 to 6 carbon atoms.
- useful alkyl radicals for R there may I be mentioned -CH3, C2H5, CH(CH3)2 and among the'useful substituted alkyl radicals R there may be mentioned-CHzQl-I and -CH2C1.
- R Suitable; specific alkoxy radicals for Ruinclude and --0C2Hs -OCI-I(CH3;)2.
- R preferably is hydrogen or an unsubstituted alkyl or alkoxyxradicaloi, 1.to 3 carbonatoms.
- tertiary mtrogen, atom and the .suliopheny-l group in theabove. compounds be separated by at least two. methylene (CH2) groups in order to obtain a high degree 4 Claims. (Cl. 260-509) loid silver halide emulsion layer andit is more difficult to Wash such compounds out oi the colloid silver halide emulsion layers.
- the compounds of Formula I may beprepared by the following series of chemical reactions: (a) preparation of an N.-alky1-N.-(phenoxyalkyl) aniline by reaction of an omega-halogen substituted alkyl. phenylether containing the halogen and ether groups on the opposite. ends 9 the straight chain. alkylene radical with N- alkylanilina'e. g;., N-methylaniline, N.-ethyla-- line or N-butylaniline. This reaction is us carried out under neutral to alkaline 091.
- N methyl, ethylnmstoluidine, N-methyl, ethyl-m-anisldine, or similarly nuclear substifluted N-alkyl amines are. used in p a e. of; N- alkyl aniline in the above syntheses one bta n the. corresp din ly substitu ed. derelopers,
- N -ethyZ-N [omega- (p-sulfophenoxy) prom/Z] aniline
- N-ethyl-N- (omega-phenoxypropyl) aniline 51 grams was added in a thin stream to 45 ml.
- the product was treated with a little sodium hydrosulfite and a decolorizing charcoal and --filtered.
- the pH of the solution. was adjusted "to 6 which caused the product to separate as asyrupr
- the water was separated and the syrup was rubbed'with dioxane to cause Yield, 86 grams (82%).
- N -ethyZ-N- (4-phenoscybutyl) aniline phenoxybutyl bromide (168 grams) and N- 'ethyl aniline (178 grams) were heated three 1 1 hours at 125 C.
- the product was cooled and shaken with 32 grams of sodium hydroxide in 500 cc. of water.
- the amine was separated,
- N-ethyl-N-.(fi-phenoxyhexyllaniline was i 43.5 grams '6; N -ethyl-N- i6- (p-sulfophenomy'lhexyll aniline N-ethyl-Nr fi-phenoxyhexyllaniline (4]. grams) was added to 33 milliliters of sulfuricaacidwith stirring. The-temperaturexwas. kept at 9010. during the addition and the mixture was then heated: at 90-95 C. for'0.5 hour.
- Block speed is an arbitrary figure indicating the speed of the developer. If a developer has a block speed one unit less than another, this means that the photographic film will require about twice the degree of exposure to give an image of the same density as the second under the same conditions of development.
- Gamma is defined in Neblette, Photography, page 412 (published by D. Van Nostrand Com- ;pany, 1942). Values of block speed and/or gamma comparable or superior to those of the commercial developer, p-amino-N,N-diethyl aniline, are important. Increases are shown in the table for certain of these values. Particularly important is the fact that the new developers cause less fog than the p-amino-N,N-diethyl aniline.
- the compounds of this invention when used as photographic developing agents may be employed alone or in admixture of alkali salts such as sodium carbonate.
- sodium sulfite or other conventional agents of photographic developers may be used as the free acid or as a suitable derivative of the sulfonic acid group, e. g., the alkali metal or ammonium salt, according to the solubility requirements of the system.
- the developing agents may be used in developer formulations containing color formers for color development of exposed silver halide contained in gelatin or synthetic water-permeable colloid binding agents for silver halide grains. They may be used in the color development of photographic films containing immobile color formers in the light-sensitive silver halide emulsion layers, particularly films of the type described in U. S. Patent No. 2,397,864.
- the compounds of Formula I are not limited in their use as photographic developing agents. To the contrary, they are useful chemical intermediates and may serve as a basis for the preparation of various other chemical com- 7 v esn m ny widely diffe ent em o imentsie i v n io can h -ma e -wiih u eb ng mm the spirit and scope-thereof, it is tcbe nderstood that the invention is not to be limited except as defined by the claims.
- Ft isc a. member taken frona the groub consisting of hydrogen, alkyl radicals of 1 to3 carbon atoms and alkoxy radicals of 1 m3 carbon atoms,
- alkyl contains 1 to 6 carbon atoms and n is e 7 cardinal number from 2 to 6 inclusive.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented July 15, 1952 UNIT ED STATES PATENT OFF-l CE;
2,603,656 PHOTOGRAPHIC DEVELOPING AGENTS. Elmore Louis Martin, Wilmington, Del., assignor to E. 1.. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application February 27', 1951, Serial No. 213,051
This invention pertains to a new class of, N- substituted aminoaniline derivatives. More par.- ticularly it pertains to N=alkyl-N-.(sulfphenyloxy)all ylanilines. These compounds are useful 'as photographic developing agents.
Various aryle'nediamines have been used as photographic developing agents, but the most .importantof them, namely, para-phenylenediamine and its lower- N,N-dialky1 derivatives.- have the disadvantage that. they are readily absorbed .by-the skin and give rise to dermatitis. Since these. agents are strong photographic developers and, readily couplewith, color formers during the development of latent silver halide images to produce quinoneimine or azomethine dye images insitu.withthe silver images-they are used in mostcommercial. processes of color photography. The, compounds, however, due. to their toxicity constitute a health hazard in. photographic. de-
{veloping laboratories.
An object. of. this invention is to provide a new class of. photographic developing agents.
.A. further object is to provide a. new class of photographic developing agents. which are useful in chromogenic development and are free from, toxic effects. The more specifieobject is to provide a new class of N-alkyl-N(sulfophenyloxy) alkylanilines. Still other objects will be apparent from the-following: description of the invention.
The new compounds ofthi's invention may be represented by the following general formula:
alkoxy" group; n is a positive integer from 2 to '10- and alkyl contains irom 1 to 6 carbon atoms. Among the useful alkyl radicals for R there may I be mentioned -CH3, C2H5, CH(CH3)2 and among the'useful substituted alkyl radicals R there may be mentioned-CHzQl-I and -CH2C1.
Suitable; specific alkoxy radicals for Ruinclude and --0C2Hs -OCI-I(CH3;)2. R, however, preferably is hydrogen or an unsubstituted alkyl or alkoxyxradicaloi, 1.to 3 carbonatoms.
It is important: that the tertiary mtrogen, atom and the .suliopheny-l group in theabove. compounds be separated by at least two. methylene (CH2) groups in order to obtain a high degree 4 Claims. (Cl. 260-509) loid silver halide emulsion layer andit is more difficult to Wash such compounds out oi the colloid silver halide emulsion layers.
The compounds of Formula I may beprepared by the following series of chemical reactions: (a) preparation of an N.-alky1-N.-(phenoxyalkyl) aniline by reaction of an omega-halogen substituted alkyl. phenylether containing the halogen and ether groups on the opposite. ends 9 the straight chain. alkylene radical with N- alkylanilina'e. g;., N-methylaniline, N.-ethyla-- line or N-butylaniline. This reaction is us carried out under neutral to alkaline 091. tions; (22) preparation of; N-alliy -N-iem sa-s fophenyloxyalkyl):anilines by the reaction oi the tertiary aminederivative obtained in stepq with a sulionating agent. e, g... hot. concentrated suliuric acid; (.6). preparation (lithe. orresponding P- r -N-a kyln-N- (omega.- su ioehenrlexralmula I.
when N methyl, ethylnmstoluidine, N-methyl, ethyl-m-anisldine, or similarly nuclear substifluted N-alkyl amines are. used in p a e. of; N- alkyl aniline in the above syntheses one bta n the. corresp din ly substitu ed. derelopers,
s invention will be further. illu t tediby thefollowing examples. They exe liiy sui able sp i me ods for he p epar n hecoinpounds and illustrate heir uses n pr pert e but, are, not intended to limit the invention.
E AMP E. 1'
P-AMINO-N-ETH'YL-N EOMEGAW- g-Swmo mmqgyy PiioPYMANmINE- A. N-ethyl-N- ('omegawhenowypropyl) aniline ome a-bro osro vl phenyl ethe 2115513 0.5 mol) and N-ethyla-nil-ine (242 gra ns, 1- were heated one steam a for 15: ou s, u' lh product was washed with-a solutionoi 22 grams of sodium hydroxide in 300 milliliters of iollowed by a water wash, and dried, Dis llation gave 209 grams (92%) at 186-8" 331,; n =1.5753.
B. N -ethyZ-N [omega- (p-sulfophenoxy) prom/Z] aniline N-ethyl-N- (omega-phenoxypropyl) aniline (51 grams) was added in a thin stream to 45 ml. of
sulfuric, acid in a stirred flask. The mixture was kept at;90 C. for 0.5 hour, then cooled and poured onto 75 grams of ice. The aqueous layer was removed from the syrup which separated and replaced with '75 milliliters of water. The product crystallized on standing. It .Was recrystallized from water; yield 32 grams, M. P. 222-4 C.
C. p Nitroso N ethyl N [omega (17- sulfophenoxy) -propyll aniline D. p -Amino-N ethyl N-[omega-(p-sulfophenoay) propyll aniline Ninety-one-grams of the above nitroso compound was dissolved in grams of NaOH plus 130 milliliters of water,charged into a shaker tube with 2 grams of palladium-on-charcoal catalyst and hydrogenated at 25-55 C. and 200- 1000 lbs/sq. in. for one-hour.
The product was treated with a little sodium hydrosulfite and a decolorizing charcoal and --filtered. The pH of the solution. was adjusted "to 6 which caused the product to separate as asyrupr The water was separated and the syrup was rubbed'with dioxane to cause Yield, 86 grams (82%).
iir-Amho-N-Errrrrl N [4 (P-StJLFoPHErIoxfl "ANILINE l I v 'A,4-phen 0:l:11/batg/Z bromide. i 2.11m, smegma flasli' 'equipped witha Ustirr'er, condenser and dropping funnel were;
"placed 158 "grams of 88% phenol, 402' grams of tetramethylenedibroinide and 750 'milliliters of (water; .Thei mixture was refluxed and during 0.5 hour 57 grams of sodium hydroxide in 190 milliliters of waterwas 'added- The mixture was refluxed five hours longer, after, which it was'cooled, the organic layer was separated, dried and distilled. A 50% yield (169 grams) of 4-,phenoxybutyl bromide boiling at 166-170 C./20 mm. was obtained.-
B. N -ethyZ-N- (4-phenoscybutyl) aniline phenoxybutyl bromide (168 grams) and N- 'ethyl aniline (178 grams) were heated three 1 1 hours at 125 C. The product was cooled and shaken with 32 grams of sodium hydroxide in 500 cc. of water. The amine was separated,
dried and distilled and 81% yield (159 grams) boiling at 226-9 C.
/2 mm. was obtained; n =1.5709.
it to crystallize,
-- D. p-Nitroso-N- C. N-ethyl-N- [4- (saljophe-nomy) butyl] aniline N ethyl N (4 phenoxybutyhaniline (159 grams) was run in a thin stream into 127 milliliters of sulfuric acid with cooling so that the temperature did not rise above 90 Cf. v The solution was heated on a' steam bath at 90-96 C. for 0.5 hour. The mixture was poured onto 200 grams of ice and the solution of the sulfonated products, which was completely soluble in sodium hydroxide solution, was used directly for nitrosation.
ethyZ-N- [4- (p-snljophenory) butyl] aniline The above solution was mixed with 75 milliliters'of hydrochloric acid and stirred at 0-5" C. while 43 grams of sodium nitrite in 60 milliliters of water was added dropwise. Crystallization was started by scratching the product. After the mixture had stirredforjone hour, the nitroso "compound was filtered off and washed with water. "The yield was 174 grams or 78%. The compound 'may be crystallized in small portions from water.
ethyZ-N- 4 (p-salfophe mi ne 1 Eighty-five grams of the above nitroso 'c ompound was dissolved in 120 milliliters oflwater containing 9 grams of sodium hydroxide and E. p-Amino-N- norwcharged-into a shaker tube'with 2 gramsof-palladium-on-charcoal catalyst. Hydrogenation for one hour. The product "Wasmixed with50 milliliters of hydrochloric acid and the'catalyst wasfiltered off with theaid of a silicous flltering aid. A small amountof sodium hydrosulilte was added to the filtrate and sodium hydroxide 'solution was added to a pH of about 6. 7 Ayield of 62.5 grams of the amino acid separated. The amino acid was recrystallized from water. The
; compound had water of crystallization which was pears that the c0 "1.00. Found: 6.94, 6.84.
gradually lost on heating in an oven,' but-1t apmpound separates with two molecules of water. I 1
Analysis calculated for A stirred mixture of 300 grams of hexamethyl- 'ene dibromide, 105 grams of 88% phenol and 500 milliliters of water was refluxed while 37.5 grams of sodium hydroxide in 125 milliliters of water was added during 0.5 hour. After five hours of reflux, the mixture was cooledand the organic layer was separated, dried and distilled. The yield of 6-phenoxyhexyl bromide, boiling at m-awas 63- r ms or. 2
B. Ma t -N-aaiamhmmmzaq, phenoxyhexyl1bromide I 51.5 grams, 0.2 mol) i and N-ethyl aniline" (48.5 grams,"0.4"mol) ==were heated for 15 hours on a steam bath. 'I'l1e;prodnot was shaken with 10 grams 01 sodium hydroxide in millilitersof Water and the amine layer was separated, "dried and distilled. 1 The -=yield of N-ethyl-N-.(fi-phenoxyhexyllaniline was i 43.5 grams '6; N -ethyl-N- i6- (p-sulfophenomy'lhexyll aniline N-ethyl-Nr fi-phenoxyhexyllaniline (4]. grams) was added to 33 milliliters of sulfuricaacidwith stirring. The-temperaturexwas. kept at 9010. during the addition and the mixture was then heated: at 90-95 C. for'0.5 hour. The sulfonated product was cooled and poured onto 100 grams 6 types-of compound's of thisinvention as compared witl r those of' p-amino-NN-di'ethy-l aniline are set forth inthe fbllowingtable:
Taib-le v zHr't.
MONOLAYER COATINGS V 7 Block Speed Gamma Base-l-Fog CD-I 1r= 2" n=3 n=4 n=6 OD-l n=2 n=3 n=-t ;n=6 OD-l n=2 n==3 n=4 n=6 Oyan..- 5.0- s. 1 4: s: 4.7-; 5.0 3': 70' "2.55 4.23 4:24 K4505 0.13" 11* o-. 13 :13 "0;1'4 Magenta 6. 7 4. 2 6:2 5. 7, 7. O 2314.; 2 1. 25 2.51.' L 73" (1171. 0". 20, 0.15" 20. 19 O. 12 1' 0.16 Yellow; 6. 0 3. 0 4'. 6 4'. 7 5. 4 1.93 0. 1 42 1 1 3 2 1. 5& 0.119,. 0. 0. 06- 0..08 0. (19
MUIJTILAY E R 00mm.
Cyan 5. 2 3. 7 4. 8 4. 7 5. 3 3. 36 2. 57 3. 72 3. S3 3. 29 0. 12 D. 11 0. 15 0. 10 O. 32 Magenta 4. 5 1. 6 3. 3 3. 5 4. 3 2. 48 0. 62 2. 27 2. 69 2. 34 0. 11 O. 09 0. 12 0. 12 O. 28 Yellow 4. 6 1. 8 3. 5 3. 9 3. 6 1. 44 0. 32 1. 64 1. 34: 1. O0 0. 14 0. O9 0. 09 O. 14 0. 26
CD-1 p-Amino-NiN-diethyl aniline. of ice. This solution was used directly for nitrosation after 50 milliliters of water and 120 milliliters of hydrochloric acid were added.
D. p-Nitroso-N-ethyZ-N- [6- (p-sulfophenoxy) hexyl] aniline To the above solution was added with stirring 10 grams of sodium nitrite in 15 milliliters of water at 0-5 C. The mixture was stirred for one hour, 400 milliliters of water was added, and the inside of the flask was scratched to induce crystallization. After two additional hours of stirring, the nitroso compound was filtered off and washed with water. The yield was 39 grams or '7 0%. The compound was recrystallized from water.
E. p-Amino -N-ethyZ-N- [6- (sulfophenoxy) hexyl] aniline Thirty grams of the above nitroso compound was dissolved in a solution of 3 grams of sodium hydroxide in 100 milliliters of water and charged into a shaker tube with 2 grams of palladium-oncharcoal catalyst and hydrogenated at 50-60 C. and 1500 lbs/sq. in. for 1.5 hours. The product was filtered and one equivalent of hydrochloric acid was added to precipitate the amino acid as a syrup. The syrup was rubbed with dioxane to cause it to crystallize. The yield was 21 grams. The product was recrystallized from water.
Analysis calculated for C2oH2aN2O4S.2H2O2 N, 6.56. Found: N, 6.64, 6.69.
EXAMPLE IV P-AMmo-N-ErHYL-N [BETA- (P-SULFOPHENOXVY) ETHYL] ANILINE When the general procedure of Example I was repeated except that beta-bromoethyl phenyl ether was employed in place of the omega-bromopropyl phenyl ether there was obtained upon condensation with aniline, N-ethyl-N-(beta-phenoxyethyl) aniline, B. P. 154-156/3 mm.; n =1.5860.
Treatment with sulfuric acid gave N-ethyl- Nibeta- (p-sulfophenoxy) ethyl] aniline. Treatment of the latter under acid conditions with sodium nitrite gave p-nitroso-N-ethyl-N-[beta- (p-sulfophenoxy)ethyllaniline, which upon reduction gave the corresponding amino compound. The hydrochloride had the following analysis:
Calculated for C1oH21N204SI N, 7.53; S, 8.60. Found: N, 7.58; S, 9.09.
The photographic developing properties of the In the foregoing table the cyan, magenta and yellow coatings were dispersions of light-sensitive silver iodobromides in polyvinyl acetal color formers of aromatic halides of the type described in U. S. Patents 2,397,864 and 2,380,033 and U. S. applications Ser. Nos. 9,330, filed February 18, 1948, now U. S. Patent No. 2,513,190, issued June 27, 1950, and 29,921, filed May 28, 1948, and now U. S. Patent No. 2,538,257, issued January 16, 1951. In the table gamma refers to the development factor and fog relates to the density of development in the'unexposed portion of the photographic film. Block speed is an arbitrary figure indicating the speed of the developer. If a developer has a block speed one unit less than another, this means that the photographic film will require about twice the degree of exposure to give an image of the same density as the second under the same conditions of development. Gamma is defined in Neblette, Photography, page 412 (published by D. Van Nostrand Com- ;pany, 1942). Values of block speed and/or gamma comparable or superior to those of the commercial developer, p-amino-N,N-diethyl aniline, are important. Increases are shown in the table for certain of these values. Particularly important is the fact that the new developers cause less fog than the p-amino-N,N-diethyl aniline.
The compounds of this invention when used as photographic developing agents may be employed alone or in admixture of alkali salts such as sodium carbonate. sodium sulfite or other conventional agents of photographic developers. They may be used as the free acid or as a suitable derivative of the sulfonic acid group, e. g., the alkali metal or ammonium salt, according to the solubility requirements of the system. The developing agents may be used in developer formulations containing color formers for color development of exposed silver halide contained in gelatin or synthetic water-permeable colloid binding agents for silver halide grains. They may be used in the color development of photographic films containing immobile color formers in the light-sensitive silver halide emulsion layers, particularly films of the type described in U. S. Patent No. 2,397,864.
The compounds of Formula I, however, are not limited in their use as photographic developing agents. To the contrary, they are useful chemical intermediates and may serve as a basis for the preparation of various other chemical com- 7 v esn m ny widely diffe ent em o imentsie i v n io can h -ma e -wiih u eb ng mm the spirit and scope-thereof, it is tcbe nderstood that the invention is not to be limited except as defined by the claims.
What is claimed is:
Twhere Ft isc a. member taken frona the groub consisting of hydrogen, alkyl radicals of 1 to3 carbon atoms and alkoxy radicals of 1 m3 carbon atoms,
noxy) propyllaniline. I v v 3. p Arnino-N-ethyl-N- [-(p-sulfophenoxy) buty1]am1ine.' I 5 i 4; p --Ax'nino-N-e'thy1j-N-[6 (pesuifophenoxyihexyl] aniline v ELMORE LOUIS MAR'IIIEVN. REFERENCES CITED The following references are of record in the r 9? t i e n i UNITED STATES PATENTS Number 1 2,163,166 2,241,769
alkyl contains 1 to 6 carbon atoms and n is e 7 cardinal number from 2 to 6 inclusive. 1
Name Date WiIm'anns et a1. June 20, 1939 Dickey et a1 May 13, 1941
Claims (1)
1. THE CHEMICAL COMPOUNDS OF THE GENERAL FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US213051A US2603656A (en) | 1951-02-27 | 1951-02-27 | Photographic developing agents |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US213051A US2603656A (en) | 1951-02-27 | 1951-02-27 | Photographic developing agents |
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| Publication Number | Publication Date |
|---|---|
| US2603656A true US2603656A (en) | 1952-07-15 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US213051A Expired - Lifetime US2603656A (en) | 1951-02-27 | 1951-02-27 | Photographic developing agents |
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| Country | Link |
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| US (1) | US2603656A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4022762A (en) * | 1969-03-14 | 1977-05-10 | Produits Chimiques Ugine Kuhlmann | Water-soluble acid azo dyestuff containing a N-(p-sulphophenoxyalkyl)-N-alkyl amino group |
| US4063881A (en) * | 1969-03-14 | 1977-12-20 | Produits Chimiques Ugine Kuhlmann | Synthetic polyamide fibres colored with acid azobenzene dyestuffs, containing a N-alkyl (or substituted alkyl)-n-sulphophenoxyalkylamino radical in the para position to the azo linkage |
| US4066457A (en) * | 1974-12-10 | 1978-01-03 | Gaf Corporation | Color developer for diffusion transfer |
| US4113491A (en) * | 1975-02-10 | 1978-09-12 | Konishiroku Photo Industry Co., Ltd. | Color photographic developing composition |
| US4322492A (en) * | 1976-03-27 | 1982-03-30 | Agfa-Gevaert Aktiengesellschaft | Process for the development of color photographic images with p-dialkylaminoaniline color developers |
| EP0459210A1 (en) * | 1990-05-14 | 1991-12-04 | Fuji Photo Film Co., Ltd. | Color developing agent and process for forming image |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2163166A (en) * | 1936-05-27 | 1939-06-20 | Agfa Ansco Corp | Photographic developer |
| US2241769A (en) * | 1939-03-29 | 1941-05-13 | Eastman Kodak Co | Sulphonic acid derivatives of aryl diamines |
-
1951
- 1951-02-27 US US213051A patent/US2603656A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2163166A (en) * | 1936-05-27 | 1939-06-20 | Agfa Ansco Corp | Photographic developer |
| US2241769A (en) * | 1939-03-29 | 1941-05-13 | Eastman Kodak Co | Sulphonic acid derivatives of aryl diamines |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4022762A (en) * | 1969-03-14 | 1977-05-10 | Produits Chimiques Ugine Kuhlmann | Water-soluble acid azo dyestuff containing a N-(p-sulphophenoxyalkyl)-N-alkyl amino group |
| US4063881A (en) * | 1969-03-14 | 1977-12-20 | Produits Chimiques Ugine Kuhlmann | Synthetic polyamide fibres colored with acid azobenzene dyestuffs, containing a N-alkyl (or substituted alkyl)-n-sulphophenoxyalkylamino radical in the para position to the azo linkage |
| US4066457A (en) * | 1974-12-10 | 1978-01-03 | Gaf Corporation | Color developer for diffusion transfer |
| US4113491A (en) * | 1975-02-10 | 1978-09-12 | Konishiroku Photo Industry Co., Ltd. | Color photographic developing composition |
| US4322492A (en) * | 1976-03-27 | 1982-03-30 | Agfa-Gevaert Aktiengesellschaft | Process for the development of color photographic images with p-dialkylaminoaniline color developers |
| EP0459210A1 (en) * | 1990-05-14 | 1991-12-04 | Fuji Photo Film Co., Ltd. | Color developing agent and process for forming image |
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