US2524741A - Magenta phenazonium dyestuff images from 6-substituted-8-hydroxyquinoline couplers - Google Patents
Magenta phenazonium dyestuff images from 6-substituted-8-hydroxyquinoline couplers Download PDFInfo
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- US2524741A US2524741A US793533A US79353347A US2524741A US 2524741 A US2524741 A US 2524741A US 793533 A US793533 A US 793533A US 79353347 A US79353347 A US 79353347A US 2524741 A US2524741 A US 2524741A
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- Prior art keywords
- phenazonium
- hydroxyquinoline
- magenta
- acid
- color
- Prior art date
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- -1 6-substituted-8-hydroxyquinoline Chemical class 0.000 title claims description 16
- 239000000975 dye Substances 0.000 title claims description 10
- 239000000839 emulsion Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- JSYBAZQQYCNZJE-UHFFFAOYSA-N 1,2,4-benzenetriamine Natural products NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IMUJTAIQEBHAMT-UHFFFAOYSA-N 6-bromoquinolin-8-ol Chemical compound C1=CN=C2C(O)=CC(Br)=CC2=C1 IMUJTAIQEBHAMT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 2
- HVXPHYSLKISNEG-UHFFFAOYSA-N 8-hydroxyquinoline-6-sulfonic acid Chemical compound C1=CN=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HVXPHYSLKISNEG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- MFSHNFBQNVGXJX-UHFFFAOYSA-N 2-oxo-1,2-dihydroquinoline-4-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC(=O)NC2=C1 MFSHNFBQNVGXJX-UHFFFAOYSA-N 0.000 description 1
- RTNBZBKSKPBOHJ-UHFFFAOYSA-N 3-amino-4-methyl-5-(octadecanoylamino)benzenesulfonic acid Chemical compound NC1=C(C(=CC(=C1)S(=O)(=O)O)NC(CCCCCCCCCCCCCCCCC)=O)C RTNBZBKSKPBOHJ-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- MDHKUUWRECHNAX-UHFFFAOYSA-N 6-bromo-2-methylquinolin-8-ol Chemical compound C1=C(Br)C=C(O)C2=NC(C)=CC=C21 MDHKUUWRECHNAX-UHFFFAOYSA-N 0.000 description 1
- ZUVRWEGJVKUIKO-UHFFFAOYSA-N 6-bromo-8-hydroxy-2-(3-nitrophenyl)quinoline-4-carboxylic acid Chemical compound [N+](=O)([O-])C=1C=C(C=CC1)C1=NC2=C(C=C(C=C2C(=C1)C(=O)O)Br)O ZUVRWEGJVKUIKO-UHFFFAOYSA-N 0.000 description 1
- YFKDOLPRGYKULB-UHFFFAOYSA-N 6-chloroquinolin-8-ol Chemical compound C1=CN=C2C(O)=CC(Cl)=CC2=C1 YFKDOLPRGYKULB-UHFFFAOYSA-N 0.000 description 1
- BVBQGQLGXJDKLZ-UHFFFAOYSA-N 6-nitroquinolin-8-ol Chemical compound C1=CN=C2C(O)=CC([N+]([O-])=O)=CC2=C1 BVBQGQLGXJDKLZ-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- FJNCXZZQNBKEJT-UHFFFAOYSA-N 8beta-hydroxymarrubiin Natural products O1C(=O)C2(C)CCCC3(C)C2C1CC(C)(O)C3(O)CCC=1C=COC=1 FJNCXZZQNBKEJT-UHFFFAOYSA-N 0.000 description 1
- 108010039224 Amidophosphoribosyltransferase Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100353161 Drosophila melanogaster prel gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- VDRWNKIQBYUKGD-UHFFFAOYSA-N octadecane-1-sulfonyl chloride Chemical compound CCCCCCCCCCCCCCCCCCS(Cl)(=O)=O VDRWNKIQBYUKGD-UHFFFAOYSA-N 0.000 description 1
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- G03C7/32—Colour coupling substances
- G03C7/3244—Couplers forming azinic dyes; Specific developers therefor
Definitions
- the present invention relates to the production of phenazonium dyestufi images by color development of exposed silver halide emulsions by means of derivatives of ortho-phenylene diam ine, and more particularly to the employment in such process of color formers which directly yield the phenazonium dyestufi images by such color development.
- the phenazonium dye images produced in this way are extremely desirable from the standpoint of transmission spectra and stability.
- the phenazonium dyes of such images are only formed by a special after-treatment with acids or alkalies of the green dye image, presumably of a quinoneimine, resulting from the color forming development step.
- the value of the phenazonium dye as a photographic image is therefore somewhat ofiset by the fact that additional time and chemicals are necessary in order to obtain the image thereof.
- R is halogen, i. e.,-bromine, chlorine, iodine, or the like, nitro, sulfo, or an arsonic acid radical
- R1 is hydrogemalkyl or a mononuclear carb cyc ic a ma c rad cal such as phenyl, i
- R2 is hydrogen, -COOH or --CONHR3 and R3 is a sulfonated aliphatic 5 radical containingat least carbon atoms or a sulfonated aromatic radical substituted by an aliphatic radical containing at least 10 carbon atoms.
- compound No. 9 may be 2 obtained by treating equimolecular quantities of 2- -(B-ammophenyl)-6-bromo-8-hydroxycmchomnlc acid phenyl 6 bromo s hydroxycinchoninic acid and 14. 00 6-amino-2-stearoylaminotoluene-4-sulfonic acid 0 in pyridine solution ,with an excess of phosphorus Br NBA-017E trichloride.
- C O O H i IIIH :
- Example 1 A photographic silver bromide emulsion is exposed and then color developed for 5 to minutes in a solution of the following color developer:
- Example 2 .5 gram of compound No. 9 is dissolved in 1.4 ml. of 0.05 N-lithium hydroxide, the solution diluted to 17 ml. with water and then neutralized with dilute acetic acid. The resulting solution is added to 35 grams of a photographic silver bromide emulsion and the emulsion coated on a film base.
- the emulsion is then exposed and color developed with the developer of Example 1, excepting that the 6-bromo-8-hydroxyquinoline is omitted therefrom.
- a brilliant magenta phenazonium dyestuff image of excellent stability is directly produced in the development step.
- R is a member of the class consisting of halogen, nitro, sulfo and arsonic acid radicals
- R1 is a member of the class consisting of hydrogen, alkyl and a mononuclear carbocyclic aromatic radical
- R2 is a member of the class consisting of H, -COOH and CONHR3
- R3 is a member selected from the class consisting of sulfonated aliphatic radicals containing at least 10 carbon atoms, and sulfonated aromatic radicals substituted by an aliphatic radical containing at least 10 carbon atoms.
- R. is a member of the class consisting of halogen, nitro, sulfo and arsonic acid radicals
- R1 is a member of the class consisting of hydrogen, alkyl and a mononuclear carbocyclic aromatic radical
- R2 is a member of the class consisting of H, COOH and --CONH-Ra
- R3 is a member selected from the class consisting of sulfonated aliphatic radicals containing at least 10 carbon atoms, and sulfonated aromatic radicals substituted by an aliphatic radical containing at least 10 carbon atoms.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Quinoline Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Patented Oct. 3., 1950 MAGENTA PHENAZONIUM DYESTUFF IMAGES FROM G-SUBSTITUTED-S-HY- DROXYQUINOLINE COUPLERS Vsevolod Tulagin, Phillipsburg, N. .-I., and Robert F. Coles, Easton, Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a
corporation of Delaware No Drawing. Application December 23, 1947, Serial No. 793,533
5 Claims The present invention relates to the production of phenazonium dyestufi images by color development of exposed silver halide emulsions by means of derivatives of ortho-phenylene diam ine, and more particularly to the employment in such process of color formers which directly yield the phenazonium dyestufi images by such color development.
Schmidt and Tulagin copending' application Ser. No. 640,382, filed January 10, 1946, now Patent No. 2,486,440, describes the production of phenazonium dyestuff images by color developing an exposed silver halide emulsion with a color developer comprising a developer of the orthophenylene diamine type in the presence of 8- hydroxy-quinoline as the color former.
'The phenazonium dye images produced in this way are extremely desirable from the standpoint of transmission spectra and stability. However, the phenazonium dyes of such images are only formed by a special after-treatment with acids or alkalies of the green dye image, presumably of a quinoneimine, resulting from the color forming development step. The value of the phenazonium dye as a photographic image is therefore somewhat ofiset by the fact that additional time and chemicals are necessary in order to obtain the image thereof.
It has now been found-that such dye images can be directly produced by the color forming development step, i. e., without an additional after-treatment if there be employed as the color former B-hydroxy-quinolines (including 8-hydroxy cinchomnic acids) containing in the 6 position of the quinoline ring a substituent which is eliminated during the color forming development as a negative ion. The utilization of such color formers in the production of phenazonium dyestufi images and silver halide emulsions containing the same accordingly constitute the purposes and objects of the present invention.
The color formers contemplated herein are characterized by the following general formula: I
wherein R is halogen, i. e.,-bromine, chlorine, iodine, or the like, nitro, sulfo, or an arsonic acid radical, R1 is hydrogemalkyl or a mononuclear carb cyc ic a ma c rad cal such as phenyl, i
nitrophenyl, aminophenyl, stearoylaminophenyl, octadecanesulfonamidophenyl, chlorophenyl, tolyl, anisyl and the like, R2 is hydrogen, -COOH or --CONHR3 and R3 is a sulfonated aliphatic 5 radical containingat least carbon atoms or a sulfonated aromatic radical substituted by an aliphatic radical containing at least 10 carbon atoms.
Examples of compounds embraced by the above 10 formula are the following:
6-bromo-8-hydroxyquin0line SOQH I OH 6-sulfo-8-hydroxyquinoline moms-m 6-arsono-s-hydroxyquinoline OzN I N CH 6-nitro-8-hydroxyquinoline 40 5. v COzH 2-phenyl-6-bromo-8-hydroxycinchoninic acid 6. CODE 6sulfo-S-hydroxyclnchoninic acid Br- IYHS-CmHu N i 6-chloro-8-hydroxyquinoline 0H 8 2- (3-octade canesulfonamidqpheny l) -6-bromo-8- Br hydr'oxycinchoumle acid 10 16. C 0 OH CH3 1 N 6-bromo-8-hydroxyquinaldine 2&(4-ohldroph'eny1I-6-bromo'8-hydroxycinch0ninic acid 17. C O OH 6-stearoylamino-2-(2-pheny1-6-bromo-8-l1ydrpxycinchoninoyl) aminotoluene -sulfonlc acid 18.
---N-UuaHa1v 2-'(4-methoxypheny1) -'6-'br0mo-8-hydroxycinchoninic acid 1 It willbe apparentthat in thecompounds listed- 2-phenyl-6-ch10ro-8-hydroxycinchoninoyloctadecyltaurine above, those containingvthe Ilongaliphatianhain W Wil1 .-be-;n0n.-.migratory when located in. photographic emulsions. Consequentlywhen the em- AT-N, ploymentof these compounds is desired, they are 40 most. advantageously dispersed in emulsions.
OC10Hn Theiothercompounds, however, may be employed.
either. in ,the developer or in the emulsion-a1-v AOSH though it ispreferred thatthey be added-to the.
developer.
The color vdeveloperswvhichare utilized are, as
stated, of-thezortho-phenylene diamine type,. a
large numberv of example .of which are referred 6-decoxy-3-(2-pl1e11yl-6-br0mo-8-hydroxycinch0ninoy1)- to in the aforesaid Schmidt and Tu1aginappli-- ammobenzenesulfomc and cation. Suitable developers of thisclass are, for 00 OH 0. example:
4,6 diani1ino-metanilic acid 4-(o-methoxy phenylamino) 6 (p methoxy- 55, phenylamino) -metani1ic acid 4,6-'bis-(o-methoxy phenylamino) -metanilic acid 4- (p-sulfo-phenylamino) -6 dimethylamino-metanilic acid.
and. .the. like: Many of i the: color formers "previously referred to are .known' compounds. Those which are not describedin. the literature, such as compounds 9 tov 18;.areprepared by methods conventional in the art. For instance, compound No. 9 may be 2 obtained by treating equimolecular quantities of 2- -(B-ammophenyl)-6-bromo-8-hydroxycmchomnlc acid phenyl 6 bromo s hydroxycinchoninic acid and 14. 00 6-amino-2-stearoylaminotoluene-4-sulfonic acid 0 in pyridine solution ,with an excess of phosphorus Br NBA-017E trichloride. Compounds'10...and 11 can be prel r pared by similar procedures-using the appropriate intermediates. N Compound 7 12can be-prepared by heating a H mixture of I 2=amino-5-bromophenol, m-nitrobenzaldehyde and pyruvic acid in ethyl alcohol. 2 (3 iiligifi figfi i ifii $3 8 C poun -1 c be p p ed by y o e a in 2- (3-nitrophenyl) -6-bromo-8-hydroxycinchoninic acid 13. C O O H i IIIH:
4,6-bis-. (mmethoxy-phenylamino) -metanilic acid compound 12 dissolved in aqueous sodium hydroxide using a platinum oxide catalyst. Compounds 14 and 15 can be prepared by reacting compound 13 in pyridine solution with octadecanoyl chloride and octadecanesulfonyl chloride respectively. Compounds 16, 17 and 18 can be prepared by employing the procedure described for compound 12 using p-chlorobenzaldehyde, pmethylbenzaldehyde and p-methoxybenzaldehyde respectively in place of m-nitrobenzaldehyde.
The invention is illustrated by the following examples, but it is to be understood that these examples are illustrative and not limitative of the invention.
Example 1 A photographic silver bromide emulsion is exposed and then color developed for 5 to minutes in a solution of the following color developer:
Sodium carbonate monohydrate grams 60 Potassium bromide do-.. 2 Sodium sulfite do 40 Pyridine cc 12 4,6-dianilino-metanilic acid grams 4 6-bromo-8-hydroxyquinoline do 2 Water cc 1000 A magenta phenazonium dyestuff image is directly produced by this development. By further processing the film in the usual manner, images of an excellent transmission spectra and stability are obtained.
Example 2 .5 gram of compound No. 9 is dissolved in 1.4 ml. of 0.05 N-lithium hydroxide, the solution diluted to 17 ml. with water and then neutralized with dilute acetic acid. The resulting solution is added to 35 grams of a photographic silver bromide emulsion and the emulsion coated on a film base.
The emulsion is then exposed and color developed with the developer of Example 1, excepting that the 6-bromo-8-hydroxyquinoline is omitted therefrom. A brilliant magenta phenazonium dyestuff image of excellent stability is directly produced in the development step.
Various modifications of the invention will occur to workers in this art, and we therefore do not intend to be limited in the patent granted except as necessitated by the prior art and the appended claims.
We claim:
1. The process of producing magenta phenazonium dyestuif images by color forming development which comprises exposing a silver halide emulsion and developing the same with a 2,4- diaminoaniline developer in the presence of a color former having the following formula:
wherein R is a member of the class consisting of halogen, nitro, sulfo and arsonic acid radicals, R1 is a member of the class consisting of hydrogen, alkyl and a mononuclear carbocyclic aromatic radical, R2 is a member of the class consisting of H, -COOH and CONHR3 and R3 is a member selected from the class consisting of sulfonated aliphatic radicals containing at least 10 carbon atoms, and sulfonated aromatic radicals substituted by an aliphatic radical containing at least 10 carbon atoms.
2. The process as defined in claim 1 wherein the color former is 6-sulfo-8-hydroxy quinoline.
3. The process as defined in claim 1 wherein the color former is 6-bromo-8-hydroxy-quinoline.
4. A photographic silver halide emulsion containing as a color former capable of directly yielding magenta phenazonium dyestuif images when color developed with a 2,4-diamino aniline developer, a compound of the following formula:
wherein R. is a member of the class consisting of halogen, nitro, sulfo and arsonic acid radicals, R1 is a member of the class consisting of hydrogen, alkyl and a mononuclear carbocyclic aromatic radical, R2 is a member of the class consisting of H, COOH and --CONH-Ra and R3 is a member selected from the class consisting of sulfonated aliphatic radicals containing at least 10 carbon atoms, and sulfonated aromatic radicals substituted by an aliphatic radical containing at least 10 carbon atoms.
5. A photographic silver halide emulsion containing as a color former a compound of the following formula:
VSEVOLOD TULAGIN. ROBERT F. COLES.
REFERENCES CITED The following references are of record in the file of this patent:
FOREIGN PATENTS
Claims (1)
1. THE PROCESS OF PRODUCING MAGENTA PHENAZONIOUM DYESTUFF IMAGES BY CCOLOR FORMING DEVELOPMENT WHICH COMPRISES EXPOSING A SILVER HALIDE EMULSION AND DEVELOPING THE SAME WITH A 2,4DIAMINOANILINE DEVELOPER IN THE PRESENCE OF A COLOR FORMER HAVING THE FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US640382A US2486440A (en) | 1946-01-10 | 1946-01-10 | Production of phenazonium dyestuff images |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2524741A true US2524741A (en) | 1950-10-03 |
Family
ID=41210569
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US640382A Expired - Lifetime US2486440A (en) | 1946-01-10 | 1946-01-10 | Production of phenazonium dyestuff images |
| US793534A Expired - Lifetime US2525502A (en) | 1946-01-10 | 1947-12-23 | Production of phenazonium dyestuff images |
| US793533A Expired - Lifetime US2524741A (en) | 1946-01-10 | 1947-12-23 | Magenta phenazonium dyestuff images from 6-substituted-8-hydroxyquinoline couplers |
| US793536A Expired - Lifetime US2524725A (en) | 1946-01-10 | 1947-12-23 | Magenta phenazonium dyestuff images from 8-hydroxyquinoline couplers |
| US793535A Expired - Lifetime US2525503A (en) | 1946-01-10 | 1947-12-23 | Production of phenazonium dyestuff images |
| US101913A Expired - Lifetime US2570116A (en) | 1946-01-10 | 1949-06-28 | Color developers for the production of azine dye images |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US640382A Expired - Lifetime US2486440A (en) | 1946-01-10 | 1946-01-10 | Production of phenazonium dyestuff images |
| US793534A Expired - Lifetime US2525502A (en) | 1946-01-10 | 1947-12-23 | Production of phenazonium dyestuff images |
Family Applications After (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US793536A Expired - Lifetime US2524725A (en) | 1946-01-10 | 1947-12-23 | Magenta phenazonium dyestuff images from 8-hydroxyquinoline couplers |
| US793535A Expired - Lifetime US2525503A (en) | 1946-01-10 | 1947-12-23 | Production of phenazonium dyestuff images |
| US101913A Expired - Lifetime US2570116A (en) | 1946-01-10 | 1949-06-28 | Color developers for the production of azine dye images |
Country Status (6)
| Country | Link |
|---|---|
| US (6) | US2486440A (en) |
| BE (6) | BE470459A (en) |
| CH (5) | CH280516A (en) |
| DE (6) | DE851163C (en) |
| FR (6) | FR939497A (en) |
| GB (5) | GB644863A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2691588A (en) * | 1952-03-14 | 1954-10-12 | Eastman Kodak Co | Photographic developers containing 8-hydroxyquinolines |
| US2701766A (en) * | 1952-06-14 | 1955-02-08 | Gen Aniline & Film Corp | Developers for and method of producing phenazonium dyestuff images with p-dialkylaminoaniline developing agents |
| US3099559A (en) * | 1959-08-31 | 1963-07-30 | Gen Aniline & Film Corp | Silver-free color reproduction process and composition therefor |
| US4503141A (en) * | 1983-03-28 | 1985-03-05 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive materials containing couplers with a hydroxyl substituted aromatic heterocyclic sulfonyl group in the ballast group |
| US4680299A (en) * | 1984-04-30 | 1987-07-14 | E.I. Du Pont De Nemours And Company | 2-phenyl-4-quinolinecarboxylic acids and pharmaceutical compositions thereof |
| US4847381A (en) * | 1987-08-31 | 1989-07-11 | American Cyanamid Company | 2-Phenyl-4-quinoline carboxylic acids |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2611785A (en) * | 1952-09-23 | N-substituted x | ||
| CH277023A (en) * | 1949-05-03 | 1951-08-15 | Ciba Geigy | Process for the production of an intermediate product. |
| US2575027A (en) * | 1949-10-29 | 1951-11-13 | Gen Aniline & Film Corp | N-substituted 4, 6-diamino metanilic acids |
| US2596926A (en) * | 1949-12-16 | 1952-05-13 | Gen Aniline & Film Corp | Preparation of azine dye images |
| US2594917A (en) * | 1949-12-16 | 1952-04-29 | Gen Aniline & Film Corp | Suppression of proximity development with azine color developers |
| US2623823A (en) * | 1950-03-21 | 1952-12-30 | Gen Aniline & Film Corp | Energizers for aromatic triamino developing agents and suppression of proximity development in azine color developers |
| US2618559A (en) * | 1950-03-21 | 1952-11-18 | Gen Aniline & Film Corp | Stain preventing shortstop bath for photographic azine dye images |
| US2687431A (en) * | 1950-12-20 | 1954-08-24 | Gen Aniline & Film Corp | Process of preparing nitro phenylenediamines |
| BE508676A (en) * | 1951-01-26 | |||
| BE526742A (en) * | 1953-02-24 | |||
| GB802553A (en) * | 1955-11-18 | 1958-10-08 | Gen Aniline & Film Corp | Improvements in or relating to colour photographic materials and processes |
| US2945761A (en) * | 1957-07-29 | 1960-07-19 | Eastman Kodak Co | Reactivity of couplers incorporated in photographic emulsions |
| BE576817A (en) * | 1958-04-03 | |||
| BE594935A (en) * | 1959-09-11 | |||
| US3050394A (en) * | 1959-09-30 | 1962-08-21 | Gen Aniline & Film Corp | Method of incorporating color couplers in hydrophlic colloids |
| US3077403A (en) * | 1960-05-31 | 1963-02-12 | Gen Aniline & Film Corp | Color former containing bis coupling functions |
| US4511569A (en) * | 1982-08-26 | 1985-04-16 | Schering Corporation | Tricyclic lactams and derivatives useful in increasing cardiac contractility |
| SE8302361D0 (en) * | 1983-04-27 | 1983-04-27 | Astra Laekemedel Ab | NEW TRICYCLIC AMINES |
| US5260177A (en) * | 1988-03-16 | 1993-11-09 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| US5223386A (en) * | 1989-03-04 | 1993-06-29 | Konica Corporation | Cyan coupler |
| EP0386931A1 (en) * | 1989-03-04 | 1990-09-12 | Konica Corporation | A novel cyan coupler |
| US4990436A (en) * | 1990-01-23 | 1991-02-05 | Eastman Kodak Company | Cyan dye-forming couplers and photographic recording materials containing same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB178986A (en) * | 1921-02-11 | 1922-05-04 | John Augustus Ward | Improvements in and relating to advertising apparatus |
| FR836144A (en) * | 1935-03-21 | 1939-01-11 | Kodak Pathe | Improvements to color photography processes and in particular to chromogenic developers |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1782356A (en) * | 1927-11-14 | 1930-11-18 | Firm J R Geigy S A | Manufacture of acid dyestuffs of the phenonaphthosafranine series |
| US1886809A (en) * | 1929-09-04 | 1932-11-08 | Gen Aniline Works Inc | Arylated safranines and process of preparing them |
| BE369421A (en) * | 1929-09-09 | |||
| DE767652C (en) * | 1936-05-27 | 1953-03-02 | Ig Farbenindustrie Ag | Process for the color development of halogen silver emulsions |
| US2356475A (en) * | 1936-07-07 | 1944-08-22 | Eastman Kodak Co | Phenolic and naphtholic couplers containing sulphonamide groups |
| US2306410A (en) * | 1936-07-07 | 1942-12-29 | Eastman Kodak Co | Color development |
| US2196739A (en) * | 1938-09-23 | 1940-04-09 | Eastman Kodak Co | Photographic developer for color photography |
| GB531312A (en) * | 1939-03-31 | 1941-01-01 | Eastman Kodak Co | Improvements in and relating to colour forming developers and processes of colour development |
| US2193015A (en) * | 1939-05-24 | 1940-03-12 | Eastman Kodak Co | Developer containing sulphonamide groups |
| GB536939A (en) * | 1939-08-24 | 1941-06-03 | Eastman Kodak Co | Improvements in and relating to photographic colour development |
| BE442586A (en) * | 1940-07-31 | |||
| FR956696A (en) * | 1941-08-08 | 1950-02-02 | ||
| FR956698A (en) * | 1941-09-11 | 1950-02-02 | ||
| GB553064A (en) * | 1941-09-25 | 1943-05-06 | Eastman Kodak Co | Improvements in photographic developers |
| US2364350A (en) * | 1941-11-06 | 1944-12-05 | Eastman Kodak Co | Photographic developer |
| US2400872A (en) * | 1942-09-01 | 1946-05-28 | Eastman Kodak Co | Diamino-nu-alkyl phenazinium salts |
| US2394527A (en) * | 1942-11-04 | 1946-02-05 | Du Pont | Color photography |
| GB576891A (en) * | 1944-05-12 | 1946-04-25 | John David Kendall | Improvements in or relating to colour photography |
| BE465025A (en) * | 1945-01-27 | |||
| US2489440A (en) * | 1945-05-03 | 1949-11-29 | Naylor Brothers Ltd | Conveyer |
| US2445252A (en) * | 1947-04-10 | 1948-07-13 | Gen Aniline & Film Corp | Photographic elements containing urethanes of nu-substituted j acids as color formers |
-
1946
- 1946-01-10 US US640382A patent/US2486440A/en not_active Expired - Lifetime
- 1946-12-11 GB GB36617/46A patent/GB644863A/en not_active Expired
-
1947
- 1947-01-03 FR FR939497D patent/FR939497A/en not_active Expired
- 1947-01-10 BE BE470459D patent/BE470459A/xx unknown
- 1947-12-23 US US793534A patent/US2525502A/en not_active Expired - Lifetime
- 1947-12-23 US US793533A patent/US2524741A/en not_active Expired - Lifetime
- 1947-12-23 US US793536A patent/US2524725A/en not_active Expired - Lifetime
- 1947-12-23 US US793535A patent/US2525503A/en not_active Expired - Lifetime
-
1948
- 1948-12-10 FR FR61005D patent/FR61005E/en not_active Expired
- 1948-12-10 FR FR61007D patent/FR61007E/en not_active Expired
- 1948-12-10 FR FR61004D patent/FR61004E/en not_active Expired
- 1948-12-10 FR FR61006D patent/FR61006E/en not_active Expired
- 1948-12-10 FR FR58855D patent/FR58855E/en not_active Expired
- 1948-12-14 GB GB32321/48A patent/GB647638A/en not_active Expired
- 1948-12-14 DE DEP24686D patent/DE851163C/en not_active Expired
- 1948-12-14 DE DEP24684D patent/DE854889C/en not_active Expired
- 1948-12-14 GB GB32322/48A patent/GB646490A/en not_active Expired
- 1948-12-14 DE DEP24685D patent/DE817554C/en not_active Expired
- 1948-12-14 GB GB32257/48A patent/GB646348A/en not_active Expired
- 1948-12-14 GB GB32258/48A patent/GB649811A/en not_active Expired
- 1948-12-14 DE DEP24683A patent/DE850385C/en not_active Expired
- 1948-12-14 DE DEP24682A patent/DE837959C/en not_active Expired
- 1948-12-20 CH CH280516D patent/CH280516A/en unknown
- 1948-12-21 BE BE486430D patent/BE486430A/xx unknown
- 1948-12-21 BE BE486433D patent/BE486433A/xx unknown
- 1948-12-21 BE BE486434D patent/BE486434A/xx unknown
- 1948-12-22 CH CH280517D patent/CH280517A/en unknown
- 1948-12-22 CH CH283788D patent/CH283788A/en unknown
- 1948-12-22 CH CH280518D patent/CH280518A/en unknown
- 1948-12-22 CH CH283787D patent/CH283787A/en unknown
-
1949
- 1949-01-01 DE DEP29268A patent/DE848155C/en not_active Expired
- 1949-01-15 BE BE486432D patent/BE486432A/xx unknown
- 1949-01-15 BE BE486431D patent/BE486431A/xx unknown
- 1949-06-28 US US101913A patent/US2570116A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB178986A (en) * | 1921-02-11 | 1922-05-04 | John Augustus Ward | Improvements in and relating to advertising apparatus |
| FR836144A (en) * | 1935-03-21 | 1939-01-11 | Kodak Pathe | Improvements to color photography processes and in particular to chromogenic developers |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2691588A (en) * | 1952-03-14 | 1954-10-12 | Eastman Kodak Co | Photographic developers containing 8-hydroxyquinolines |
| US2701766A (en) * | 1952-06-14 | 1955-02-08 | Gen Aniline & Film Corp | Developers for and method of producing phenazonium dyestuff images with p-dialkylaminoaniline developing agents |
| US3099559A (en) * | 1959-08-31 | 1963-07-30 | Gen Aniline & Film Corp | Silver-free color reproduction process and composition therefor |
| US4503141A (en) * | 1983-03-28 | 1985-03-05 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive materials containing couplers with a hydroxyl substituted aromatic heterocyclic sulfonyl group in the ballast group |
| US4680299A (en) * | 1984-04-30 | 1987-07-14 | E.I. Du Pont De Nemours And Company | 2-phenyl-4-quinolinecarboxylic acids and pharmaceutical compositions thereof |
| US4847381A (en) * | 1987-08-31 | 1989-07-11 | American Cyanamid Company | 2-Phenyl-4-quinoline carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| US2486440A (en) | 1949-11-01 |
| BE486432A (en) | 1949-01-15 |
| CH280518A (en) | 1952-01-31 |
| CH280517A (en) | 1952-01-31 |
| CH283787A (en) | 1952-06-30 |
| US2524725A (en) | 1950-10-03 |
| GB646490A (en) | 1950-11-22 |
| BE486434A (en) | 1949-01-15 |
| FR58855E (en) | 1954-04-06 |
| DE851163C (en) | 1952-10-02 |
| DE817554C (en) | 1951-10-18 |
| DE850385C (en) | 1952-09-25 |
| CH283788A (en) | 1952-06-30 |
| DE854889C (en) | 1952-11-06 |
| US2525502A (en) | 1950-10-10 |
| CH280516A (en) | 1952-01-31 |
| GB644863A (en) | 1950-10-18 |
| US2525503A (en) | 1950-10-10 |
| FR61005E (en) | 1955-03-23 |
| FR939497A (en) | 1948-11-16 |
| GB646348A (en) | 1950-11-22 |
| BE486431A (en) | 1948-12-21 |
| GB649811A (en) | 1951-01-31 |
| BE486433A (en) | 1949-01-15 |
| GB647638A (en) | 1950-12-20 |
| DE848155C (en) | 1952-11-04 |
| BE486430A (en) | 1949-01-16 |
| FR61007E (en) | 1955-03-23 |
| DE837959C (en) | 1952-05-05 |
| BE470459A (en) | 1947-02-28 |
| FR61006E (en) | 1955-03-23 |
| US2570116A (en) | 1951-10-02 |
| FR61004E (en) | 1955-03-23 |
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