US2992920A - Production of colored photographic images - Google Patents

Production of colored photographic images Download PDF

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Publication number
US2992920A
US2992920A US720013A US72001358A US2992920A US 2992920 A US2992920 A US 2992920A US 720013 A US720013 A US 720013A US 72001358 A US72001358 A US 72001358A US 2992920 A US2992920 A US 2992920A
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Prior art keywords
quinazolone
phenyl
acetamino
melting
color
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Expired - Lifetime
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US720013A
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Cat Arthur Henri De
Tavernier Bernard Hippoliet
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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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
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups

Definitions

  • Yellow colored images are usually obtained by de- Welopment in the presence of compounds which contain an active methylene group, particularly acylacetanilide derivatives.
  • a reducible "silver salt image is developed with ;an aromatic aminowdeveloping agent in the presence of a compound according to the formula: i
  • the ketodiazine nucleus may be for example 4-pyrirnidone or 4-quinazolone.
  • the sodium salt of anthranilic acid is condensed with 0-, mor p-nitrobenzoylchloride.
  • the resulting amide is treated with acetic anhydride, thus looses a molecule of water and is converted into a nitrophenylbenzoxazine compound.
  • This compound is converted with ammonium hydroxide and pyridine into nitrobenzoylanthranilamide which by boiling in diluted sodium hydroxide is converted into nitrophenylquinazolone.
  • the latter is reduced with hydrogen and Raney nickel to the corresponding aminophenyl quinazolone which by condensation with XCH COOC H gives the desired coupler.
  • metaand para-nit-robenzoylanthranilic acid obtained according to M. Bogert, R. Gortner and C. Amend, J.A.C.S. 33(1911), 952 may be converted into 2-(mand p-nitrophenyl)benzoxazine according to the same authors.
  • the corresponding o-compound may be obtained as follows: o-nitro-benzoylanthranilic acid obtained. according to H. Meyer, Ann. 351 (1907), 273, may be converted into 2-(o-nitrophenyl)benzoxazine according to G. schroeter and O. Eisleb, Ann. 367(1909), 132.
  • p-nitrobenzoylanthranilamide .melting at 242 C.
  • o-nitro-benzoylanthranilarnide melting at 192 C.
  • These anthranilamides may be converted into quinazolones.
  • m-nitrobenzoylanthranilamide is refluxed with sodium hydroxide N.
  • the reaction mixture is acidified with hydrochloric acid and the precipitate is recrystallized from dimethyl-formamide. Small yellow needles of Z-(m-nitrophenyl)quinazolone, melting above 300 C., are obtained.
  • 2-(p-nitrophenyl)-quinazolone is dissolved in a mixtune on? piperidine and Water (equal parts by volume) and reduced in the presence of Raney nickel by hydrogen under a pressure of 30 kg. per sq. cm. and at 75 C. until the theoretical absorption of hydrogen has taken place.
  • the reaction mixture is concentrated in vacuum and acidified with acetic acid.
  • 2-(m-nitrophenyl)quinazolone is reduced in sodium hydroxide N by hydrogen under a pressure of 3 "kg; per sq. .cm. at 5.0-" C; in the presence .ofRaney nickel.
  • the reaction mixture is acidified with hydrochloric acid A precipitate is formed by addition of ammonium hydroxide.
  • the resulting 2- (m-aminophenyDquinazolone melts at 251 C.
  • 2-(o-nitrophenyl)quinazolone is reduced in dimethylforrnamide in the presence of Raney nickel by hydrogen under a pressure of kg. per sq. cm. at 70 C.
  • the resulting 2-(o-aminophenyl)quinazolone melts at 27.5- 227 C.
  • couplers may be prepared as follows:
  • the said quinazolones are refluxed in dimethylformamide together with an excess of 10-15% of beta-ketcester.
  • the resulting beta-keto-anilide precipitates, is washed with methanol and recrystallized from glycolrnet'hyl ether or dimethyl-for-mamide.
  • color couplers may arise from adding to the developer a compound which differs from the color coupler only because in the active CH -grou-p one or two hydrogen atoms are replaced by a group capable of splitting off either before development occurs by the action of the alkali in the developing solution or during the color-development.
  • aromatic amino compounds which according to our invention are used as developing agents, comprise mono-, diand tri-amino aryl compounds, particularly NzN-dialkyl-para-phenylene diamines and derivatives such as NrN-dialkyl-N'-sulphomethyl-para-phenylene diamines.
  • mono-amino developers may be mentioned amino phenols and arnino-cresols and their halogen den'vatives, and also amino-naphthols.
  • An exposed photographic film strip coated with a silver halide emulsion layer is developed in a bath of the following composition:
  • One of the couplers 1 to' 7 prepared as described above 1 Water to 50 cmfi.
  • Solution B is added to'Solution A and water is added to the resulting solution to 1,000 cm.*.
  • a yellow image is obtained.
  • We claim: 7 1. Process for obtaining a colored photographic image, comprising developing an image consisting of a reducible silver salt with a color forming developer'com tainin-g an N,N-dialkyl-para-pheny1ene diamine as a developing agent, and a quinazolone color coupler selected from the group consisting of 2-(benzoyl-acetamino-phenyl)-4-quinazolone, 2-[m(p-anisoyl-acetamino)-phenyl]- 4 quinazolone, 2 (m-acetyl-acetamino-phenyl) -4-quinazolone, Z-[m-(alpha-furoyl-acetamino)phenyl]-4-quinazolone, and 2-[m-(alpha-thenoyl-acetamino)phenyl]-4- quinazolone.
  • Photographic developer containing an N,N-dialkylpara-phenylene diamine as a developing agent, and a quinazolone compound as a color coupler, said quinazolone compound being selected from the group consisting of Z-(benzoyl-acetamiino-phenyl)-4-quinazolone, 2-1[m-' (p-anisoyl-acetamino)phenyl]-4-quinazolone, 2 (m-acetyl-acetamino-phenyl) -4-quinazolone, 2 [m (alpha-furoyl-acetamino)phenyl]-4-quinazolone, and Z-[m-(alphathenoyl-acetamino)-pheny1] -4-quinazolone.
  • Process for obtaining a colored photographic image comprising developing an image consisting of a reducible silver salt with a color forming developer containing an N,N-dialkyl-para-phenylene diamine as a developing agent, and 2 (benzoyl-acetamino-phenyl)-4- quinazolone as a color coupler.
  • Photographic developer containing an N,N-dialkyl para-pheny-lene diamine as a developing agent, and 2- (benzoyl-acetamino-phenyl) 4-quinazolone as a color coupler.

Description

United States Patent() 2,992,920 i PRODUCTION OF COLORED PHOTOGRAPHIC IMAGES i Arthur Henri De Cat, Antwerp, and Bernard Hippoliet Tavernier, Mortsel-Antwerp, Belgium, assiguors to .Gevaert Photo-Producten N.V., Mortsel, Belgium, a
Belgian company N Drawing. Filed Mar. 10, 1958, Ser. No. 720,013
Claims priority, application Great Britain 15, 1957 4 Claims. (CI. 96-55) developing agent and [forms a dyestufi which precipitates onto the developed silver grains.
Yellow colored images are usually obtained by de- Welopment in the presence of compounds which contain an active methylene group, particularly acylacetanilide derivatives.
It is an object of the present invention to provide a new'process of color development. It is another object of the present invention-to provide new photographic developers. It is a further objecttof the presentinvention to provide new colored photographic images. Still further objects will appear from the following description. @These ObjCClSflIG accomplished by the use as color couplers of a class of compounds, some members of which are preferable to the known compounds by combining high solubility in the developer, insolubilityof the resulting. dyestufis which do not bleed outand more over greater activity than is found with .otherjacylacetanilides.
According to the present invention, a reducible "silver salt imageis developed with ;an aromatic aminowdeveloping agent in the presence of a compound according to the formula: i
\ GAr-NH-CO-CHz-X wherein Y=the atoms necessary to complete a ketodiazine nucleus,
=o-, mor p-arylene, X=acyl.
The ketodiazine nucleus may be for example 4-pyrirnidone or 4-quinazolone.
Compounds containing a 4-quinazolone nucleus may be prepared as follows:
The sodium salt of anthranilic acid is condensed with 0-, mor p-nitrobenzoylchloride. The resulting amide is treated with acetic anhydride, thus looses a molecule of water and is converted into a nitrophenylbenzoxazine compound. This compound is converted with ammonium hydroxide and pyridine into nitrobenzoylanthranilamide which by boiling in diluted sodium hydroxide is converted into nitrophenylquinazolone. The latter is reduced with hydrogen and Raney nickel to the corresponding aminophenyl quinazolone which by condensation with XCH COOC H gives the desired coupler.
ice
Thus metaand para-nit-robenzoylanthranilic acid obtained according to M. Bogert, R. Gortner and C. Amend, J.A.C.S. 33(1911), 952, may be converted into 2-(mand p-nitrophenyl)benzoxazine according to the same authors. The corresponding o-compound may be obtained as follows: o-nitro-benzoylanthranilic acid obtained. according to H. Meyer, Ann. 351 (1907), 273, may be converted into 2-(o-nitrophenyl)benzoxazine according to G. schroeter and O. Eisleb, Ann. 367(1909), 132.
These benzoxazines may be converted into metaand para-nitrobenzoylanthranilamide as illustrated by the fo lowing example:
30 g. 2-m-nitro-phenylbenzoxazine are refluxed with 75 cm. pyridine and 40 cm. of concentrated ammonium hydroxide. After cooling, sucking oif the precipitate and recrystallizing firom a mixture of dioxane and water, the meta-nitrobenzoylanthranilamide, melting at 230 C. is obtained.
Likewise, p-nitrobenzoylanthranilamide, .melting at 242 C., and o-nitro-benzoylanthranilarnide, melting at 192 C., are obtained. These anthranilamides may be converted into quinazolones. For this purpose, m-nitrobenzoylanthranilamide is refluxed with sodium hydroxide N. The reaction mixture is acidified with hydrochloric acid and the precipitate is recrystallized from dimethyl-formamide. Small yellow needles of Z-(m-nitrophenyl)quinazolone, melting above 300 C., are obtained.
Likewise Z-(p-nitrophenyl)-quinazolone, also melting above 300 C. and 2-(o-nitrophenyl).-quinazolone, melting at 232 C.,qare obtained.
These nitrophenylquinazolones may be reduced as follows:
2-(p-nitrophenyl)-quinazolone is dissolved in a mixtune on? piperidine and Water (equal parts by volume) and reduced in the presence of Raney nickel by hydrogen under a pressure of 30 kg. per sq. cm. and at 75 C. until the theoretical absorption of hydrogen has taken place. The reaction mixture is concentrated in vacuum and acidified with acetic acid. The 2 -,(p-amiuo-pheny\l).- quinazolone, melting above 300 'C., precipitates.
2-(m-nitrophenyl)quinazolone is reduced in sodium hydroxide N by hydrogen under a pressure of 3 "kg; per sq. .cm. at 5.0-" C; in the presence .ofRaney nickel. The reaction mixture is acidified with hydrochloric acid A precipitate is formed by addition of ammonium hydroxide. The resulting 2- (m-aminophenyDquinazolone melts at 251 C.
2-(o-nitrophenyl)quinazolone is reduced in dimethylforrnamide in the presence of Raney nickel by hydrogen under a pressure of kg. per sq. cm. at 70 C. The resulting 2-(o-aminophenyl)quinazolone melts at 27.5- 227 C.
From these aminophenylquinazolones, couplers may be prepared as follows:
The said quinazolones are refluxed in dimethylformamide together with an excess of 10-15% of beta-ketcester. The resulting beta-keto-anilide precipitates, is washed with methanol and recrystallized from glycolrnet'hyl ether or dimethyl-for-mamide.
In this way the following compounds, for example, were obtained:
(1) 2 (p benzoyl acetamino phenyl) 4 quinazolone, melting above 300 C.
(2) 2 (m benzoyl acetamino phenyl) 4 quinazolone, melting at 275-277 C.
(3) 2 (o benzoyl acetamino phenyl) 4 quinazolone, melting at 240-241 C.
(4) 2 [m alpha furoyl acetamino)phenyl] 4 (6) 2 [m (p anisoyl acetamino)phenyl] 4 quinazolone, melting at 245 C. (7) 2 (in acetylacetamino phenyl) 4 -quinazolone, melting at 202-205 C. i
The presence, during color development, of color couplers according to the present invention, may arise from adding to the developer a compound which differs from the color coupler only because in the active CH -grou-p one or two hydrogen atoms are replaced by a group capable of splitting off either before development occurs by the action of the alkali in the developing solution or during the color-development.
The aromatic amino compounds, which according to our invention are used as developing agents, comprise mono-, diand tri-amino aryl compounds, particularly NzN-dialkyl-para-phenylene diamines and derivatives such as NrN-dialkyl-N'-sulphomethyl-para-phenylene diamines. As mono-amino developers may be mentioned amino phenols and arnino-cresols and their halogen den'vatives, and also amino-naphthols.
The following example serves to, illustrate the invention without, however, limiting the scope thereof.
An exposed photographic film strip coated with a silver halide emulsion layer is developed in a bath of the following composition:
One of the couplers 1 to' 7 prepared as described above 1 Water to 50 cmfi.
Before use, Solution B is added to'Solution A and water is added to the resulting solution to 1,000 cm.*. The
4 developed image is rinsed for thirty minutes and the silver is bleached in the following bath:
G. Potassium ferricyanide Potassium bromide V 3 Water to 1000 cmfi.
The image is rinsed again for ten minutes and then fixed for twenty minutes in the following bath: 7 G
Sodium thiosulphate -i 250 Water to 1000 01 11.
and again rinsed for thirty minutes.
A yellow image is obtained. We claim: 7 1. Process for obtaining a colored photographic image, comprising developing an image consisting of a reducible silver salt with a color forming developer'com tainin-g an N,N-dialkyl-para-pheny1ene diamine as a developing agent, and a quinazolone color coupler selected from the group consisting of 2-(benzoyl-acetamino-phenyl)-4-quinazolone, 2-[m(p-anisoyl-acetamino)-phenyl]- 4 quinazolone, 2 (m-acetyl-acetamino-phenyl) -4-quinazolone, Z-[m-(alpha-furoyl-acetamino)phenyl]-4-quinazolone, and 2-[m-(alpha-thenoyl-acetamino)phenyl]-4- quinazolone. j
2. Photographic developer containing an N,N-dialkylpara-phenylene diamine as a developing agent, and a quinazolone compound as a color coupler, said quinazolone compound being selected from the group consisting of Z-(benzoyl-acetamiino-phenyl)-4-quinazolone, 2-1[m-' (p-anisoyl-acetamino)phenyl]-4-quinazolone, 2 (m-acetyl-acetamino-phenyl) -4-quinazolone, 2 [m (alpha-furoyl-acetamino)phenyl]-4-quinazolone, and Z-[m-(alphathenoyl-acetamino)-pheny1] -4-quinazolone.
3. Process for obtaining a colored photographic image, comprising developing an image consisting of a reducible silver salt with a color forming developer containing an N,N-dialkyl-para-phenylene diamine as a developing agent, and 2 (benzoyl-acetamino-phenyl)-4- quinazolone as a color coupler.
4. Photographic developer containing an N,N-dialkyl para-pheny-lene diamine as a developing agent, and 2- (benzoyl-acetamino-phenyl) 4-quinazolone as a color coupler.
References Cited in the file of this patent V UNITED STATES PATENTS.

Claims (1)

1. PROCESS FOR OBTAINING A COLORED PHOTOGRAPHIC IMAGE, COMPRISING DEVELOPING AN IMAGE CONSISTING OF A REDUCIBLE SILVER SALT WITH A COLOR FORMING DEVELOPER CONTAINING AN N,N-DIALKYL-PARA-PHENYLENE DIAMINE AS A DEVELOPING AGENT, AND A QUINAZOLONE COLOR COUPLER SELECTED FROM THE GROUP CONSISTING OF 2-(BENZOYL-ACETAMINO-PHENYL)-4-QUINAZOLONE, 2-(M-(P-ANISOYL-ACETAMINO)-PHENYL)4-QUINAZOLONE, 2-(M-ACETYL-ACETAMINO-PHENYL)-4-QUINAZOLONE, 2-(M-(ALPHA-FUROYL-ACETAMINO)PHENYL)-4-QUINAZOLONE, AND 2-(M-(ALPHA-THENOYL-ACETAMINO)PHENYL)-4QUINAZOLONE.
US720013A 1957-03-15 1958-03-10 Production of colored photographic images Expired - Lifetime US2992920A (en)

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GB8588/57A GB856158A (en) 1957-03-15 1957-03-15 Improvements in or relating to the production of coloured photographic images

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3161512A (en) * 1959-12-23 1964-12-15 Ilford Ltd Colour couplers and their production and use in colour photography
US3645742A (en) * 1968-01-05 1972-02-29 Agfa Gevaert Nv Color photography
US4057432A (en) * 1970-12-26 1977-11-08 Konishiroku Photo Industry Co., Ltd. Acylacetanilide coupler with heterocyclic diacyl amino coupling-off group
US20100137387A1 (en) * 2007-05-03 2010-06-03 Neurosearch A/S Beta-keto-amide derivatives useful as ion channel modulators

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI70036C (en) * 1980-01-31 1986-09-12 Ciba Geigy Ag CHROMOGENE QUINAZOLINE INFOERING

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500487A (en) * 1948-11-09 1950-03-14 Gen Aniline & Film Corp Yellow diffusion-fast color formers of the benzimidazole class
US2668112A (en) * 1950-12-20 1954-02-02 Gevaert Photo Prod Nv Manufacture of photographic color images

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500487A (en) * 1948-11-09 1950-03-14 Gen Aniline & Film Corp Yellow diffusion-fast color formers of the benzimidazole class
US2668112A (en) * 1950-12-20 1954-02-02 Gevaert Photo Prod Nv Manufacture of photographic color images

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3161512A (en) * 1959-12-23 1964-12-15 Ilford Ltd Colour couplers and their production and use in colour photography
US3645742A (en) * 1968-01-05 1972-02-29 Agfa Gevaert Nv Color photography
US4057432A (en) * 1970-12-26 1977-11-08 Konishiroku Photo Industry Co., Ltd. Acylacetanilide coupler with heterocyclic diacyl amino coupling-off group
US20100137387A1 (en) * 2007-05-03 2010-06-03 Neurosearch A/S Beta-keto-amide derivatives useful as ion channel modulators

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FR1201538A (en) 1959-12-30
BE565656A (en)
GB856158A (en) 1960-12-14

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