Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/30—Developers
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/30—Developers
  • G03C5/3028—Heterocyclic compounds
  • G03C5/3035—Heterocyclic compounds containing a diazole ring
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
• • 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

Definitions

• R represents a hydrogen atom or the carboxy, or amino-carbonyl (NI-I CO--) radicals or a monovalent organic radical, such as an alkylhaving 1 to 12 carbon a o (m th l; e y p py buty a y (p y a n phenyl, acyl-aminophenyl); aralkyl (benzyl); cycloalkyl (cyclohexyl); a heterocyclic radical (a-furyl, yy-pyridyl), 'a-COOR', NR R" or OR group in which R and R" each represent a hydrogen atom or analkyl radical andthe benzene ring (designated A in the foregoing formula) maybe substituted by an alkyl, aryl or aralkyl radical as defined above, a halogen atom, .an alkoxy, aroxy, OH, NH COQH or SO H group
• the amino-pyrazolino-benzimidazoles may be prepared by introducing an amino group into the pyrazolino-ben'zimidazoles described in our copending United States patent application Serial No. 819,066, filed June 9, 1959, by treating them in an acid aqueous solution with nitrous acid followed by reduction at temperatures of about to C.', as for instance by means of hydrogen in the presmeant a catalyst, such as Raney nickel.
• the [aforementioned pyrazolino-b'enzimidazoles may be coupled in an. alkaline to neutral aqueous solution with :diaz onium salts and the resulting products reduced as disclosedto give the amido pyrazolino-benzimidazoles.
• the aqueous solutions of the new heterocyclic compounds develop exposed silver halide emulsion layers into strong silver images in the presence of alkali, such as alkali-metal carbonates or hydroxides,.the pH values of the solutions being preferably adjusted to about 10-12.
• the solutions may contain the usual preservatives or antioxidants, such as sodium sulfite, sodium bisulfit'e, sodium metabisulfite or the corresponding potassium salts, preferably in amounts of l to 10 grams per liter of solution.
• the new developer substances are excellently. suitable for use as color developers in the process of chromogenic development. I'nQthis'pr'ooess the oxidation products which are formed during the development of the latent silver image react with the color couplers which are present to form ayesmfis.
• eeuplers' it is possible to u e a'ny of the known color couplers described in the lite a'unfe' which can react with the oxidation prodlit o'f a rimary arematicainino ('l'- vloper to yield a dyestu'lf, such as aromatic and nil phenols; naphthols; pyraz'olones, exaz'o1ons,-cyan acetic acid and acetoacetic aid 0'1 a'royl acetic acid esters and amides, 1,3-diketones and hydroxythionaph'th'enes'.
• a dyestu'lf such as aromatic and nil phenols; naphthols; pyraz'olones, exaz'o1ons,-cyan acetic acid and acetoacetic aid 0'1 a'royl acetic acid esters and
• Typical color couplers or coupling compounds are exemplified v e. formu a h e af r, e gna ed .1 ingo the eho ceetthe produce a wide range of ellow through redandblue to gre
• the particular advanta e of 11; 'ge dyi tained in color development using the new aminopyraiolino-benzimidazoles lies in the fact that they form metal dyestuff complexes with numerous metals. in the form of their salts or soluhle sam le); compounds, which com; plexesare characterized by high fastn'ess to light, The complex may be produced either by treating.
• Suitable metal salts are, for instance, the sulphates, chlorides and. nitrates of Cr, Ni, Zn, Mn, Mg, Cd, Ca, Sr, Ba, whichsalts are preferably used in the form of 5% aqueous solutions, as illustrated in Exam- P h a t r. H I a 4 t.
• developer 'AQor 7.5 o'f'developer B (the preparation of developer A rmaarinspwamltnort.5;1'2'1- benzimidazole-3-carboxylic acid) and developer B (3- phenyl 4-aminopyrazolino[ l .5:1'.2]benzimidazole-5- sulphonic acid) are described following exem ts s hereinafter)
• the material is thereafter and the usual manner. A strong silver image is obtained.
• EXAMPLE '2 A photographic silver iodobromideeinul sionlayeron 2 minutes.
• a film support is exposed and developed in a developer having the following composition:
• EXAMPLE 3 A photographic silver bromide emulsion layer which contains one of the diffusion-resisting color couplers I-VII (represented by formulae following Example 12 hereinafter) is exposed and developed in the developing solution described in Example 1. It is then rinsed, bleached and fixed in the usual manner. Details concerning the colors of the images thus obtained are included in the table hereinafter.
• EXAMPLE 4 The processing is initially as described in Example 3. Thereafter, the material is washed for 5 minutes in a sodium hydroxide solution and thereafter rinsed for The hues of the resulting color images are indicated in the table hereinafter.
• EXAMPLE 5 A photographic silver bromide emulsion layer which contains one of the color couplers I-VII (represented by formulae following Example 12 hereinafter) is initially processed as described in Example 3. The material is then washed for 5 minutes in a 5% magnesium sulphate solution or 5% zinc sulphate solution or 5% cobalt sulphate solution or a 5% nickel sulphate solution and thereafter rinsed for 5 minutes. Depending on which bath is used, color images having the colors indicated in the table hereinafter are obtained with the different color couplers.
• EXAMPLE 6 A photographic silver bromide emulsion layer which contains one of the color couplers I-VTI (represented by formulae following Example 12 hereinafter) is initially processed as described in Example 3 and thereafter washed for 5 minutes in an ammoniacal 1% copper sulphate solution. It is then rinsed for 5 minutes and color images are obtained, the color of which is specified in the table hereinafter.
• Example 7 The photographic material of Example 5 is initially processed as described in Example 5. It is thereafter washed for 5 minutes in a 10% sodium hydroxide solution and then rinsed for 2 minutes. There are obtained color images, the colors of which, when using magnesium sulphate solution, are set out in the table hereinafter.
• EXAMPLE 8 A photographic silver iodobromide emulsion layer coated on a film support is exposed and developed at 20 C. in a developer having the following composition:
• the material is thereafter rinsed and fixed in the usual manner.
• the silver image thus obtained is twice as fast as a silver image obtained under comparable conditions in a developer in which the developer B had been replaced by an equimolar amount of hydroquinone.
• Developer A 4-amino-pyrazolin0[1.5:1'.2]-benzimz'dazole-3-carboxylic acid. 10 g. of pyrazolinobenzimidazole-3-carboxylic acid are dissolved in 50 cc. of a 10% aqueous sodium hydroxide solution and 3.8 g. of sodium nitrite are added thereto. The solution thus obtained is introduced dropwise at a temperature of from 0 C. to 5 C. into 30 cc. of 20% hydrochloric acid. The nitroso product is filtered with suction, dissolved in isopropanol with addition of ammonia (pH 8) and hydrogenated in the, presence of Raney nickel at 50 C. and 50 atm. gauge. The product is filtered into 40% acetic acid and filtered off with suction.
• the pyrazolinobenzimidazole-3-carboxylic acid is obtained as follows:
• Developer B 3-phanyl-4-amin0-pyraz0li1z0[1.5:1.2]- benzimidazole-5'-sulph0nic acid.--12 g. of 3-phenylpyrazolinobenzimidazole-S'-sulphonic acid are dissolved in 50 cc. of 10% sodium hydroxide solution and 27 cc. of a 10% sodium nitrite solution are added thereto. The solution is added dropwise at a temperature of from 0 C. to 5 C. to 50 cc. of a 20% solution of sulphuric acid. The nitroso product is separated by suction filtration and dissolved in cc. of isopropanol and 50 cc.
• Decomposition of the compound begins at 320 C.
• decomposition of the compound begins at C. 12 g. of the latter compound are dissolved in 100 cc. of a 4% aqueous sodium hydroxide solution, mixedlyvith 35 cc. of a 10% aqueous sodium nitrite solution and added dropwise to 50 cc. of a 20% solution of sulphuric acid at a temperature of 5? C. to"0 vC.
• the nitroso product obtained is separated .by suction filtration and dissolved in a mixture of100 cc. of water, 100 cc.'of methanol and cc. of ammonia (25%.).
• the product is hydrogenated at 50 C. and 50 atm.
• nitroso is hydrogenated after beingmi'xjed with 350 cc. of methanol and 50 cc. 'of'25% ammonia in the pressure of Raney v nickel era temperaturecf 50"C.” and 'a pressure of 50 atm., acidifiedwith 250 cc. of 20% sulphuric acid, cooled and separated by suction filtration. Inorder to purify the amino product thus obtained, it is recrystallized from 2000 cc. of water in the presence'of activated carbon.
• the 3-methylpyrazolinobenzimidazole is obtained from 1-o-aminophenyl-3-methylpyrazolone by melting "with aniline according to the procedure 'desc'ribed'hereinbefore in Example 9.
• the compounds of Examples 9 to 12 are silver halide black/white and color developers, and may be used instead of the developers A and B in the solutions of Examples 1, 2 and 8. i
• the compounds whose formulae follow are difiusionresisting color couplers or coupling compounds that were referred to in the description hereirrbefore.
• the compounds designated from I to VII were referred to specifically in Examples'3 to 7. These compounds are referred to in the table which follows hereinafter by these Roman-numeral desianafims- COOH ina-pyridyl, the benzene ring A being a benzene ring sel lected from the group consisting of an unsubstituted ben- 01 (31 :0 zene ring, and a benzene ring substituted by at least one g I 1 radical selected from the group consisting of carboxy and P 0 0Na 5 sulfo.
• S 4
• a process for developing an exposed photographic silver halide emulsion which comprises developing the said exposed photographic silver halide emulsion in an aqueous alkaline solution of a silver halide developing substance that comprises a 4-aminopyrazolino[l.5:l'.2]- benzirnidazole.
• An aqueous alkaline color developer consisting essentially of a solution of a 4-amino-pyrazolin0-[ 1.5 1.2']- benzimidazole and a color-coupler capable of reacting with the oxidation product of a primary aromatic amine developer to form a dyestutf.
• R represents a substituent selected from the group consisting of hydrogen, alkyl having up to 12 carbon atoms, phenyl, aminophenyl, carboxy, aminocarbonyl, benzyl, cyclohexyl, alpha-furyl and gamhalide developer substance is 4-arnino-pyrazolino- [1.5 1'.2']-benzimidazole-3,5'-dicarboxylic acid.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Plural Heterocyclic Compounds (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (6)

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Citations (5)

• 0
  • BE BE584545D patent/BE584545A/xx unknown
• 1958
  • 1958-11-12 DE DEA30730A patent/DE1099349B/de active Granted
• 1959
  • 1959-11-06 US US851267A patent/US3079255A/en not_active Expired - Lifetime
  • 1959-11-11 CH CH8046059A patent/CH383161A/de unknown
  • 1959-11-12 FR FR809893A patent/FR1247498A/fr not_active Expired
  • 1959-11-12 GB GB38448/59A patent/GB918129A/en not_active Expired

Patent Citations (5)

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