US3615525A - Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition - Google Patents

Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition Download PDF

Info

Publication number
US3615525A
US3615525A US727358A US3615525DA US3615525A US 3615525 A US3615525 A US 3615525A US 727358 A US727358 A US 727358A US 3615525D A US3615525D A US 3615525DA US 3615525 A US3615525 A US 3615525A
Authority
US
United States
Prior art keywords
developing
photographic
group
hydroquinone
amino
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
US727358A
Other languages
English (en)
Inventor
Jozef Frans Willems
George Frans Van Veelen
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
Original Assignee
Agfa Gevaert NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Application granted granted Critical
Publication of US3615525A publication Critical patent/US3615525A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D215/38—Nitrogen atoms

Definitions

  • the invention relates to a process for the development of photographic materials, Containing exposed silver halide, and to developing compositions used therein.
  • R stands for lower alkyl comprising from one to five carbon atoms
  • R stands for lower alkyl comprising from one to five carbon atoms including substituted lower alkyl e.g. hydroxyalkyl, carboxyalkyl, the group R-NHSO R wherein each of R and R stands for lower alkyl, the group XSO; M wherein X stands for a straight chain or branched alkylene radical having from two to five carbon atoms in straight line and M stands for hydrogen, an alkali metal atom such as sodium or potassium, ammonium or an amine and R stands for hydrogen, lower alkyl comprising from one to live carbon atoms including substituted lower alkyl e.g. alkyl substituted as exemplified for R at most one of R and R being substituted alkyl.
  • the combinations of developing agents according to the invention show as compared with the developing combinations described in our British Pat. specification No. 989,383 a markedly higher development activity. In most cases they even have a higher activity than the developing combination of hydroquinone and 1-phenyl-3-pyrazolidinone.
  • the developing compositions of the invention have the further advantage of being stable to hydrolysis, even in strong alkaline medium whereas compositions with l-phenyl-3- pyrazolidinone hydrolyse in strong alkaline baths.
  • very stable developing solutions are obtained which is pahticularly interesting for preparing liquid developers.
  • the compounds corresponding to the above general formula can be added to the developing bath in the form of free bases as well as in the form of their salts e.g. as hydrochloride, as sulfate, etc.
  • the 6-aminc-tetrahydroquinoline derivatives of use according to the present invention can be prepared by alkylation of 6-amino-tetrahydroquinolines or by alkylation of 6-dialkylamino-tetrahydroquinolines.
  • the 6-dialkylaminotetrahydroquinolines are prepared by hydrogenation of the 6- dialkylaminoquinolines, which in their turn can be prepared as described in Bull. Soc. Chim. Fr. 27 1920) 430.
  • Preparation 1 Compound l
  • a solution of g. (0.4 mole) of o-diethylamino-quinoline in 400 ml. of anhydrous ethanol is hydrogenated, using 8 ml. of Raney nickel as catalyst, in a sealed tube at 70 C. and a hydrogen pressure of 1,500 p.s.i.
  • the uptake of hydrogen is complete after min.
  • the catalyst is filtered ofi and the filtrate is treated with 200 ml. of concentrated hydrochloric acid. After evaporation of the alcohol the residue is recrystallized from a mixture of ethanol and ethyl acetate. Melting point: C.
  • Preparation 2 Compound 2 40.4 g. (0.2 mole) of 6-diethylamino-l,2,3,4- tetrahydroquinoline and 18.2 g. (0.1 mole) of triethylphosphate are heated for 3 hours in an oil bath at 200 C. After having been cooled to 50 C. a solution of 15 g. of sodium hydroxide in 50 ml. of water is added and heating is continued for 90 min. The reaction mixture is treated with water and extracted with ether. After evaporation of the ether the residue is distilled. The l-ethyl-6diethylamino-l,2,3,4- tetrahydroquinoline has a boiling point of 184-l87 C./14 mm. It is converted into its dihydrochloride by treating the base, dissolved in ethanol, with alcoholic hydrochloric acid. Melting point: 172 C. (after recrystallization from a mixture of ethanol and ethyl acetate).
  • the undissolved sodium chloride is filtered off and the ethanol filtrate is evaporated.
  • the product is dried bisulfites, metabisulfites, sultites, and acids such as boric acid and citric acid.
  • the developing bath may further contain potassium bromide, water-softening agents such as polyphosphates or derivatives of ethylene diamine tetraacetic acid, antifogging agents and moistening agents, as well as other compounds known in the developing technique.
  • the pH of the baths can vary within wide limits, preferably between eight and 1 1, so that a rapid or slow development can be obtained at will resulting in high-contrast and low-contrast images respectively.
  • the ratio of hydroquinone to a G-amino-tetrahydroquinoline derivative used in the present invention can be chosen in such a way that the bath composition is suited for the development of all kinds of materials including materials having silver chloride emulsion layers of low sensitivity as well as materials having sensitive silver bromoiodide emulsion layers.
  • the ratio of hydroquinone to the 6-amino-tetrahydroquinoline derivatives used in the present invention can vary within wide limits.
  • the amounts are, however, generally chosen in such a way that the hydroquinone strongly outweighs the said derivatives.
  • a strong superadditive effect is already obtained with a ratio of 50 mg. of a said derivative used in this invention to 5 g. of hydroquinone per liter.
  • the amount of hydroquinone is comprised between 1 and 30 g. per litre and the amount of 6-amino-tethydroquinoline derivative between 5 mg. and 2 g. per liter.
  • Combinations of developing agents used in this invention may also be applied in the treating solution and/or in the lightsensitive material and/or in the image-receiving material used in the application of the silver complex diffusion transfer process, the principle of which is described in British Pat. specification Nos. 614,155 and 654,630 and in German Pat. specification No. 887,733.
  • the different embodiments of the materials and apparatus used therein there can be referred to Progress in Photography 1955-1958, p. 24-36 and the patent literature cited therein.
  • Example 1 Strips of a photographic material comprising a light'sensitive silver bromoiodide emulsion layer, coated on material comprising triacetate support, are exposed through a grey filter with light-quantity (E) which corresponds to the shoulder part ofthe density/log E curve.
  • E light-quantity
  • sodium carbonate sodium hexametaphosphate 1.0 g. sodium sulfite "0.0 g. potassium bromide 0.5 g. hydroquinone 4.4 8. water up to 1.000 ml.
  • the results of these developing tests are listed in table 1.
  • the densities are determined after a development time of 30, 6060 and 90 sec.
  • Example 2 5 ing the following composition:
  • boric acid 5.0 g. borax I0.0 g. sodium hexametaphosphate 1.0 g. sodium sulfite 20.0 g. potassium bromide 0.5 g. hydroquinone 4.4 g.
  • the densities are determined after 1, 3 and 5 respectively Table 2 Developing bath Density after a developing time of l min. 3 min. 5 min bath 8 0.04 0.04 0.04 bath B+ mg. of compound 1 0.20 1.20 1.60 bath B+ mg. of compound 2 0.80 1.45 1.70 bath B+l05 mg. of compound 3 0.05 0.84 1.25 bath B+70 mg. of l-methyl-oamino-l,Z.3,4-tetruhydroquinoline oxalate 0.05 0.46 1.00 bath B+l07 mg. of N.N-diethyl-N- propyl-N-3-sulphopropyl-p-phenylene diamine 0.05 0.17 0.58 bath B+50 mg. of l-phenyl-3- pyrazolidinone 0.05 0.46 1.10
  • Example 3 Strips of a photographic material comprising a silver bromoiodide emulsion layer were exposed through a step wedge and developed for 2 minutes in a developing bath C having the following composition:
  • Photographic developing composition comprising hydroquinone and a derivative of 6-amino-l,2,3,4- tetrahydroquinoline corresponding to the following general formula, in the form of the free base or in its salt form 3 R1 ?H2 ⁇ N CH: 0 R2 Hz wherein R is an alkyl group comprising from one to five carbon atoms.
  • R is an alkyl group comprising from one to five carbon atoms
  • R is hydrogen, or an alkyl group comprising from one to five carbon atoms
  • R R and R being substituted alkyl.
  • Photographic developing composition according to claim 1 wherein one of R,, R and R is a hydroxyalkyl group, a carboxyalkyl group, or the group R-NHSO R wherein each of R and R is a lower alkyl group, the group -X-SO M wherein X is a straight or branched alkylene group having from two to five carbon atoms in straight line, and M is hydrogen, an alkali metal, ammonium or an amine.
  • Photographic developing composition according to claim 1 wherein each of R and R is a lower alkyl group having from one to five carbon atoms, and R is hydrogen, a lower alkyl group having from one to five carbon atoms or the group -X-SO M wherein X is a straight or branched alkylene group having from two to five carbon atoms in straight line, and M is hydrogen, an alkali metal, ammonium or an amine.
  • Photographic-developing composition according to any of claim 1, wherein the said hydroquinone is present in an amount of from 1 to 30 g. per litre and the said 6-aminol,2,3,4-tetrahydroquinoline derivative in an amount offrom 5 mg. to 2 g. per litre.
  • Photographic-developing method comprising developing and exposed silver halide emulsion layer of a photographic material an means of hydroquinone and a 6- aminol,2,3,4tetrahydroquinoline derivative as defined in claim 1.
  • Photographic-developing method for application in the silver complex diffusion transfer process wherein the exposed light-sensitive material is developed with an aqueous alkaline solution in the presence of hydroquinone and a o-amino-l,2,3,4-tetrahydroquinoline derivative as defined in claim 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US727358A 1967-05-24 1968-05-07 Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition Expired - Lifetime US3615525A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB24191/67A GB1191535A (en) 1967-05-24 1967-05-24 Improvements in or relating to Photographic Development

Publications (1)

Publication Number Publication Date
US3615525A true US3615525A (en) 1971-10-26

Family

ID=10207836

Family Applications (1)

Application Number Title Priority Date Filing Date
US727358A Expired - Lifetime US3615525A (en) 1967-05-24 1968-05-07 Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition

Country Status (5)

Country Link
US (1) US3615525A (en:Method)
BE (1) BE715500A (en:Method)
DE (1) DE1772490A1 (en:Method)
GB (1) GB1191535A (en:Method)
NL (1) NL6807365A (en:Method)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767403A (en) * 1970-12-01 1973-10-23 Agfa Gevaert Nv Tetra-alkyl p-phenylene diamine with aromatic primary amino color developing agent
US3970454A (en) * 1974-01-10 1976-07-20 Eastman Kodak Company Photographic developing agents

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767403A (en) * 1970-12-01 1973-10-23 Agfa Gevaert Nv Tetra-alkyl p-phenylene diamine with aromatic primary amino color developing agent
US3970454A (en) * 1974-01-10 1976-07-20 Eastman Kodak Company Photographic developing agents

Also Published As

Publication number Publication date
DE1772490A1 (de) 1971-04-22
BE715500A (en:Method) 1968-11-22
GB1191535A (en) 1970-05-13
NL6807365A (en:Method) 1968-07-25

Similar Documents

Publication Publication Date Title
EP0458708B1 (en) High contrast photographic element including an aryl sulfonamidophenyl hydrazide containing an alkyl pyridinium group
DE69225166T2 (de) Verfahren zur Erzeugung von extrem hochkontrastreichen negativen Bildern und silberhalogenidhaltiges Material und Entwickler, welche dafür verwendet werden
US3811887A (en) Photographic material comprising bisacylhydrazinium compounds
US3954478A (en) Silver halide emulsion containing an alkenyl benzothiazolium salt as stabilizer
US3247201A (en) 1-carbocyclic aryl-2-tertiary amino-3, 4-hydrocarbon and carbocyclic aryl-3-pyrazolidones
US3984243A (en) Photographic developer compositions for obtaining high contrast images
DE69126821T2 (de) Photographisches Hochkontrastelement, das ein Ethylenoxygruppen enthaltendes Arylsulphonamidophenylhydrazid einschliesst
US3794495A (en) Prevention of static in light-sensitive photographic materials using bisaminimide compounds
US3157502A (en) Stabilized physical developers containing ionogenic surfactants
US3615525A (en) Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition
US3265502A (en) Photographic developing compositions
US3252798A (en) Stabilized physical developments
US3740221A (en) Development of photographic material
EP0324391A2 (en) Method for the formation of high-contrast images
US3002997A (en) Photographic products, processes and compositions
US3563747A (en) Photographic developing combinations
US3723117A (en) Method for developing silver halide emulsions
US3666457A (en) Photographic product,composition and process
US3236642A (en) Process for producing direct positives by the silver salt diffusion process
US3713827A (en) Process for the development of photographic material
US3804624A (en) Method for developing silver halide photosensitive material
JPH03259240A (ja) ハロゲン化銀写真感光材料
US3061434A (en) Novel substituted silver halide developing agents
US3801323A (en) Method of developing silver halide photosensitive material
US3645731A (en) Silver salt diffusion alkaline bath of trisodium phosphate and a polyalcohol