US2981623A - Photographic developers - Google Patents

Photographic developers Download PDF

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Publication number
US2981623A
US2981623A US494221A US49422155A US2981623A US 2981623 A US2981623 A US 2981623A US 494221 A US494221 A US 494221A US 49422155 A US49422155 A US 49422155A US 2981623 A US2981623 A US 2981623A
Authority
US
United States
Prior art keywords
pyrazolone
amino
carboxylic acid
filtered
developer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US494221A
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English (en)
Inventor
Burgardt Lothar
Pelz Willibald
Wahl Ottmar
Sassmann Heinz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
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Agfa AG
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Publication date
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Publication of US2981623A publication Critical patent/US2981623A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in position 3 or 5
    • C07D231/22One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C07D231/24One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms having sulfone or sulfonic acid radicals in the molecule
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/48Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/50Acylated on said nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56Benzopyrazoles; Hydrogenated benzopyrazoles
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29Development processes or agents therefor
    • G03C5/30Developers
    • G03C5/3028Heterocyclic compounds
    • G03C5/3035Heterocyclic compounds containing a diazole ring

Definitions

  • the present invention relates to photographic developer substances and more especially to substances derived from 4-amino-pyrazolones-(S -As photographic developers, it has been the practice hitherto generally to employ substances which belong to the class of aromatic polyvalent hyd'roxy compounds, amino-hydroxy compounds or polyvalent amino compounds.
  • Compounds of the heterocyclic class are known to have developer properties (German Patent No. 646,516), inter alia, S-pyrazolones, substituted in the 4-position with an amino group, which S-pyrazolorles contain the m-aminoketone structurein the heterocyclic nucleus.
  • These aminopyrazolones are, however, exclusively substances which are alkylated in the 3-position.
  • These compounds have not been used in practice as developers, since they are quite unstable with relatively small intensity of development and show a strong tendency to fogging.
  • R may represent -OH, O-alkyl, O-aryl, O-aralkyl NH or substituted NH groups, NHNH or substituted hydrazide groups, NHOH or an azide group and also alkyl, aryl or aralkyl radicals.
  • R may represent hydrogen, alkyl, aralkyl, aryl groups or substituted aryl groups or heterocyclic radicals.
  • Such compounds represent excellent photographic developer substances, since they operate without fogging with a surprisingly high development intensity and are sufficiently stable in order to be used practically as developers.
  • the developer substances may either be used independently or with advantage in combination with known developer substances, whereby they either work more quickly owing to their great rapidity, i.e. develop images to the same gamma value in a shorter time, or they develop a specific photographic material to higher gamma values with the same development period.
  • the property of the present invention may be incorporated into silver super-additivity may also frequently be used with adhalide emulsion layers which are developed by alkaline solution containing, if desired, developer substances.
  • aminopyrazolones are produced according to known processes.
  • suitable pyrazolones may be transformed by treatment with nitrite into the isonitroso-compounds and the latter by reduction with tin into the associated amino compounds.
  • the reduction of the isonitroso-cornpounds may also be carried out according to other known processes, for example with zinc and glacial acetic acid or catalytically.
  • Another available method for the production of such compounds is based upon the reductive splitting of azo dyestuifs, which are obtained. by coupling suitable pyrazolones with diazonium salts.
  • the isonitroso compound can be reduced with tin sponge and hydrochloric acid according to the process described in Arch. Pharm., 278 (1940), p. 330.
  • 430 g. of the pyrazolone are dissolved in 1000 cc. of hydrochloric acid 1:1) at 50 C., the undissolved portion is separated by filtering and the solution is mixed at lO-15 C. with 170 g. of nitrite in 300 cc. of water. After filtering with suction, washing water and drying 380 g. of isonitroso derivative are obtained.
  • the deriva tive is mixed with 100 cc. of alcohol, reacted while stirring with 1000 cc. of hydrochloric acid and reduced by gradual addition of 250 g. of tin sponge within 5 hours.
  • the hydrochloride is filtered with suction, dissolved in 1000 Iclc. of hot water, filtered and precipitated in the cold wit cc. of hydrochloric acid. After filtering with suction, washing with little water and drying in vacuum.
  • 1-phenyl-4-amino-5-pyrazolone-3-carboxylic acid hydrazide can be prepared as follows:
  • reaction product is reduced with tin sponge and hydrochloric acid according to Arch. Pharm, 278 (1940), p. 330.
  • This aminopyrazolone is produced according to Arch. Pharm, 278 (1940), p. 330.
  • EXAMPLE 7 In the developer of Example 3, the hydrochloride of 4-amino-5-pyrazolone-3-carboxylic acid ester is replaced by 15 g. of 1-(p-sulfophenyl)-4-amino-5-pyrazolone-3- carboxylic acid ethyl ester.
  • the developer is of high stability and develops negatives brilliantly and free from fogging.
  • 34 g'. of the nitroso compound are mixed with stirring with 20 cc. ofalcohol and 120 cc. of hydrochloric acid and reduced with 24 g. of tin sponge as usual.
  • the aminopyrazolone is filtered with suction and recrystallized from water.
  • the ethanol amide is dissolved in sodium hydroxide solution (3%), mixed with 8 g. of nitrite, introduced with stirring into hydrochloric acid (10%), filtered with suction and recrystallized from alcohol.
  • EXAMPLE 9 1 (p-aminophenyl)-4-amino-5-pyrazolone-3-carboxylic acid ethyl ester hydrochloride g 3 Sodium sulfite anhydrous g 40 Hydroquinone g 6 Soda g 20 Potassium bromide -g 1 Water cc Up to 1000 Soft-acting negative developer for orthochromatic and panchromatic photographic materials; development period: 5 minutes.
  • EXAMPLE l1 1 (2'-tetrahydrothiophenesulfone)-4-amino-5-pyrazolone-3-carboxylic acid ethyl ester hydrochloride g 14 Sodium sulfite anhydrous g 125 Soda 6 Potassium bromide g 2.5 Water cc Up to 1000 Very soft fine-grain developer; development period: 12-14 minutes.
  • EXAMPLE 12 1 phenyl 4 amino 5 pyrazolone 3 carboxylic acid g 1.6 Sodium sulfite anhydrous g 45 Hydroquinone g 1.2 Soda g 8 Potassium-meta bi-sulfite (K S O g 4 Potassium bromide g 1 Water cc Up to 1000 Normal negative developer; development periods: 10 12 minutes.
  • the process of developing silver halide layers which comprises applying to said'layers a compound having a formula selected from the group consisting of and wherein R is a radical selected from the group consisting of OH, O-alkyl, O-aryl, O-aralkyl, NH NH-- NH and -NHOH, and R is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and Z-tetrahydrothiophene sulfone radicals, in an alkaline medium.
  • R is a radical selected from the group consisting of OH, O-alkyl, O-aryl, O-aralkyl, NH NH-- NH and -NHOH
  • R is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and Z-tetrahydrothiophene sulfone radicals, in an alkaline medium.
  • a photographic developing composition consisting essentially of a compound having a formula selected from the group consisting of wherein R is a radical selected from the group consisting of OH, O-alkyl, O-aryl, O-aralkyl, NH NHNH and NH-OH, and R is selected from the group consisting of hydrogen, alkyl, aralkyl, aryl and 2-tetrahydroth-iophene sul-fone radicals, plus a compound selected from the group consisting of pyrocatechol, hydroquinone,
  • a photographic developer comprising a silver halide developing compound having a formula selected from the class consisting of:
  • a photographic developer according to claim 3 wherein said silver halide developing agent is l-phenyl- 4-amino-5-pyrazolone-3-carboxylic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US494221A 1954-03-15 1955-03-14 Photographic developers Expired - Lifetime US2981623A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA19873A DE955025C (de) 1954-03-15 1954-03-15 Photographischer Entwickler

Publications (1)

Publication Number Publication Date
US2981623A true US2981623A (en) 1961-04-25

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US494221A Expired - Lifetime US2981623A (en) 1954-03-15 1955-03-14 Photographic developers

Country Status (6)

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US (1) US2981623A (fr)
BE (1) BE536351A (fr)
CH (1) CH335940A (fr)
DE (1) DE955025C (fr)
FR (1) FR1124976A (fr)
GB (1) GB765286A (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3178441A (en) * 1961-12-19 1965-04-13 Ilford Ltd Pyridyl-pyrazolidine 3-ones
US3285150A (en) * 1961-05-16 1966-11-15 Wunder Phot Inc Combined photographic and development apparatus
US3295975A (en) * 1962-09-15 1967-01-03 Agfa Ag Black-and-white developer for photographic reversal processes
US3386825A (en) * 1957-07-02 1968-06-04 Polaroid Corp Photographic product containing zinc
US5187050A (en) * 1986-11-07 1993-02-16 Fuji Photo Film Co., Ltd. Method for automatic processing of silver halide photographic material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1029229B (de) * 1956-12-22 1958-04-30 Agfa Ag Photographischer Entwickler
BE563474A (fr) * 1956-12-31 1960-06-17
BE578539A (fr) * 1958-05-10
US3034891A (en) * 1958-07-31 1962-05-15 Gen Aniline & Film Corp Procedure for the production of yellow dye images by color development

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1937844A (en) * 1931-03-23 1933-12-05 Goodrich Co B F Photographic developer and method of developing
US2139870A (en) * 1935-08-31 1938-12-13 Agfa Ansco Corp Photographic developers
US2637732A (en) * 1953-05-05 Process for the manufacture of
US2731473A (en) * 1956-01-17 New pyrazolone derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2637732A (en) * 1953-05-05 Process for the manufacture of
US2731473A (en) * 1956-01-17 New pyrazolone derivatives
US1937844A (en) * 1931-03-23 1933-12-05 Goodrich Co B F Photographic developer and method of developing
US2139870A (en) * 1935-08-31 1938-12-13 Agfa Ansco Corp Photographic developers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386825A (en) * 1957-07-02 1968-06-04 Polaroid Corp Photographic product containing zinc
US3285150A (en) * 1961-05-16 1966-11-15 Wunder Phot Inc Combined photographic and development apparatus
US3178441A (en) * 1961-12-19 1965-04-13 Ilford Ltd Pyridyl-pyrazolidine 3-ones
US3295975A (en) * 1962-09-15 1967-01-03 Agfa Ag Black-and-white developer for photographic reversal processes
US5187050A (en) * 1986-11-07 1993-02-16 Fuji Photo Film Co., Ltd. Method for automatic processing of silver halide photographic material

Also Published As

Publication number Publication date
BE536351A (fr) 1955-09-09
DE955025C (de) 1956-12-27
GB765286A (en) 1957-01-09
FR1124976A (fr) 1956-10-22
CH335940A (de) 1959-01-31

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