US2596978A - 8-hydroxy-1, 2, 3, 4-tetrahydroquinoline as a silver halide developer - Google Patents

8-hydroxy-1, 2, 3, 4-tetrahydroquinoline as a silver halide developer Download PDF

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US2596978A
US2596978A US774678A US77467847A US2596978A US 2596978 A US2596978 A US 2596978A US 774678 A US774678 A US 774678A US 77467847 A US77467847 A US 77467847A US 2596978 A US2596978 A US 2596978A
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hydroxy
tetrahydroquinoline
silver halide
solution
photographic
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US774678A
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Robert R Burtner
Robert T Dillon
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GD Searle LLC
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GD Searle LLC
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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
    • 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

Definitions

  • This invention relates :to anew photographic developer compositions and to solutions-thereof, and to the preparation of the ;,same. More particularly, the invention relates to photo rap i developer compositions containing --8-hydroxy- .l,2;3;4-etetrahydroquinoline' and homolo gs thereof for the developmentofa latentimage inasilver halide emulsion.
  • It-is an object of this 'inventionto. provide dry powder photographic'developer compositions. It isafurtherobject to-provide new developingisolutions .and .baths which may betreadily prepared and which are stable for extended periods of time. ltis still; another object-of .thisinvention to :prepare.single powder photographic developers which :contain both organic developing :agents and alkaline compounds which :are. suitable "for preparing stable aqueous-solutions.
  • a further object of this invention isitofproviderapidl-highenergy. develop ng solutions.
  • Our. invention is zfurtl'iercdisclosed .zby :the fol-'- lowing examples, which illustrate typicalneveloping solutions and compositions.
  • Our invention is not. to be construed .as limited by these examples, which 3 are'provided for purposes. of i'ill'ustrationonly. Itwill be apparent to lthosesk'illed in the photographic arts that a great number .of variations il'i'Lthe "'relative amounts of materials in the formulations may be made without departing from the scope of our invention.
  • Example 1 29 grams of fiehydroxyquinoline in, 125 .cc.. of dioxane are hydrogenated .in the presence, of Raney nickel at 20-50'lb. pressure at room temperature in 15-20 hours. The hydrogen up-take ceases when it reaches approximately .Q.4"mo1e. Then the catalyst is removed by filtration .and the solvent is evaporate'cl'under'reduced" pressure to about volume. 500 cccof cold. water .are added "and 'the precipitated "'8-hydroxy'- .I;2;3,”4-
  • B-hydroxyquinaldine can be reduced to 8-hydroxy-2-methyl-1,2,3,4etetrahydroquinoline.
  • Other solvents which are suitable include the lower alcohols and hydrocarbons of boiling point 50-150 C.
  • Example 2 A solution of 1.5 g. of 8-hydrdxy-l,2,3,1-tetrahydroquinoline in 10 milliliters of ethanol-is added to a solution of 25 g. of sodium sulfite, 25 g. of
  • Example 3 A solution of 1 g. of 8-hydroxy-1,2,3,4-tetrahydroquinolinein 10 ml. of ethanol is added to a solution of 25 g. of sodium sulfite and 2 to 5 g. of potassium bromide in 500 ml. of N/10 sodium hydroxide solution. After mixing, sufficient water is added to bring the volume to 1 liter. The resulting clear solution forms brown-black prints.
  • Example 4 k A solution of 0.5 g. of 8-hydroxy-1,2,3,4-tetra hydroquinoline and 0.5 g. of p-methylaminophenol in 10 ml. of ethanol is added to a solution of'25 g. of sodium'sulfite, 25 gpof sodium carbonate and 3 g. of potassium bromide in 800, ml. of water. The resulting solution is brought to 1 liter with additional water.
  • the clear solu- 'tion is a high energy developer which produces grey-black prints.
  • Example 5 A solution of 0.5 g. of 8-hydroxy-1,2,3,4-tetrahydroquinoline and 0.5 g. of hydroquinone in 10 ml. of ethanol is added to a solution of 25 g. of sodium sulfite and 2 to 5 g. of potassium bromide in'500 ml. of N/10 sodium hydroxide solution. After mixing, suflicient water is added to bring the volume to 1 liter. This developer gives black prints of good contrast and clear whites.
  • Example 6 A dry powder mixture is prepared by thoroughly mixing the following materials:
  • a photographic developing composition for the development of a. latent image in a silver halide emulsion comprising an 8hydroxy-1,2,3,4- tetrahydroquinoline and a soluble inorganic reducing agent containing tetravalent sulfur.
  • a photographic developing composition comprising an B-hydroxy-1,2,3,4-tetrahydroquinoline and sodium sulfite.
  • a photographic developing solution comprising an aqueous solution of an S-hydroxy- 1,2,3, i-tetrahydroquinoline, a hydroquinone and sodium sulfite.
  • a process of developing a latent image of an exposed silver halide emulsion the step which comprises treating said emulsion with an aqueous solution containing an 8-hydroxy-,1,2,3,4- tetrahydroquinoline and a soluble inorganic reducing agent containing tetravalent sulfur.
  • step- which comprises treating said emulsion with an aqueous solution containing an 8-hydroxy-1,2,3,4-.tetrajhydroquinoline and sodium sulfite.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

, phenol.
Patented May 20, 1952 1 STATES OFF-I CE '*8 HYDRXY- 1;2;3,4-TETRAHYDROQUINO- LINE AS A SILVER HALIDE DEVELOPER Robert RJBurtneUSkokie, and .Robertt la Dillon, Wilmette, 111., -assignors to" G. .'D.I Searle & 00.,
.Skokie, 111., a corporation .ofllllinois NoDravving. "ApplicationSeptember-17,1947,
' "Serial- No. 774;678
This invention relates :to anew photographic developer compositions and to solutions-thereof, and to the preparation of the ;,same. More particularly, the invention relates to photo rap i developer compositions containing --8-hydroxy- .l,2;3;4-etetrahydroquinoline' and homolo gs thereof for the developmentofa latentimage inasilver halide emulsion.
It-is an object of this 'inventionto. provide dry powder photographic'developer compositions. It isafurtherobject to-provide new developingisolutions .and .baths which may betreadily prepared and which are stable for extended periods of time. ltis still; another object-of .thisinvention to :prepare.single powder photographic developers which :contain both organic developing :agents and alkaline compounds which :are. suitable "for preparing stable aqueous-solutions. A further object of this invention isitofproviderapidl-highenergy. develop ng solutions.
We have discoveredv that photographic developer-"compositions containing 8ehydroxy+ l',2j3,4- tetrahydroquinoline and homologs thereo'f :are extraordinarily stable. in neutral and alkaline solutions, .rand produce extremely rapid photographic :developers of .;high energy. We have further discovered that compositions containing 8-.hydroxy-1;2,3,4-tetrahydroquinoline are useful photographic compositions in a variety'iof solutions, either alone .or in combination with other developing agents such as hydroquinone, pyrogallol, :catechol, paminophenol; p=methylaminophenoLo-"and p phenylenediamine, chloroh-ydro- 'quinone, "bromohydroquinone, and 'ZA-diam'ino- Other 8-hydroxytetrahydroquinolines which are rsuitable ;for the preparation of photographic I-developer compositions. includ f8 h ydroxy-i2-methyl-1,2,3Aetetrahydroquinoline ,iand 'BGI'IydIOXY-"G-mGthyI -'l,2,3,4 tetrahydroquinoline. The range of tones'which can beproducedzwith photographic developer solutions. containing 8-hydroxy-I,2,3,4-tetrahydroquinoline runs from brown in the weaker solutions to black in the more concentrated solutions. For this reason the developing solutions which comprise this invention :are particularly useful for developing bromide prints. Developing solutions containing fi-hydroxy 1,2,3A tetrahydroquinoline exhibit unusual stalbilityf for example, a solutionmade with 'sodium sulfite of pH of' about 8 is stablefor at least one month. Solutions-of higher'pHare.
somewhat 'less stable, as" would be expected, but
even thosemadewith "free sodium hydroxide'have 2 tions. At higher pH's the 8-hydroxy-1,2:,3-,4- tetrahydroquinoline is'moresoluble, and solutions are morereadilyprepared. Similarly, .the speed of development is greater at higherJT'pI-I "values than at neutrality. Inwurtdevloper compositions," we have 'found that a variety of alkali'es 'aresuitable, such .as sodium carbonate, potassium carbonate, sodium hydroxide, trisodium phosphate, 'borax. sodium sulfite, sodium lm'etaborate and triethanolamine. Inorganic reducing agents which have been found satisfactory for incorporation. into our photographic developer solutions include. sodium sulfite, sodium .bisulfite, potassium thiocyanate, sodium thiocyanate, organic sulfinates, potassium .metabisulfite, -.and potassium ferric oxalate.
Wefhave also discovered that 8'-hydroxy-l,2 .3,4- tetrahydroquinolines can be readilyand e'fiiciently obtained by the catalytic hydrogenation of the corresponding S-hydroxyquindlines. .Themeactions can be carried out in any of the solvents known to besuitable for hydrogenation, such as the lower alcohols, thelowersaturatedhydrocarbons, dioxane, certain non-volatileethersand other inert solvents. As catalystsrwe preferto use Raney nickel because of its ready availability, convenience and efiiciency. Other nickel catalysts are also efiective, among them being supported nickelcatalysts such as nickel onakieselguhr. Noble metal catalysts are suitablewalso.
among them being platinum oxide, palladium black, palladium on charcoal, platinum sponge and the like. The hydrogenation may be carried out. over a' wide range of temperature :and prossure. Forexa'mple temperatures :of 20=to 1009C.
and pressures? of 20 lb..to. 500*10. 'aresuitable.
Our. invention is zfurtl'iercdisclosed .zby :the fol-'- lowing examples, which illustrate typicalneveloping solutions and compositions. Our invention is not. to be construed .as limited by these examples, which 3 are'provided for purposes. of i'ill'ustrationonly. Itwill be apparent to lthosesk'illed in the photographic arts that a great number .of variations il'i'Lthe "'relative amounts of materials in the formulations may be made without departing from the scope of our invention.
Example 1 29 grams of fiehydroxyquinoline in, 125 .cc.. of dioxane are hydrogenated .in the presence, of Raney nickel at 20-50'lb. pressure at room temperature in 15-20 hours. The hydrogen up-take ceases when it reaches approximately .Q.4"mo1e. Then the catalyst is removed by filtration .and the solvent is evaporate'cl'under'reduced" pressure to about volume. 500 cccof cold. water .are added "and 'the precipitated "'8-hydroxy'- .I;2;3,"4-
tetrahydroquinoline is"collected on afi'lter and dried. After recrystallization from benzene the product melts at C.
In a similar way, B-hydroxyquinaldine can be reduced to 8-hydroxy-2-methyl-1,2,3,4etetrahydroquinoline. Other solvents which are suitable include the lower alcohols and hydrocarbons of boiling point 50-150 C.
Example 2 A solution of 1.5 g. of 8-hydrdxy-l,2,3,1-tetrahydroquinoline in 10 milliliters of ethanol-is added to a solution of 25 g. of sodium sulfite, 25 g. of
sodium carbonate and 2 to g. of potassium bromide in 800 m1. of water. After mixing, suffiv This mixture can be dissolved with slight warming in.4 liters of water to make a stable stock developer solution which is unchanged for at 1' least a week. The dry powder may be stored for cient water is added to bring the volume to 1 liter. The resulting clear solution develops prints" of brownish color especially suitable for gold tones.'-
Example 3 A solution of 1 g. of 8-hydroxy-1,2,3,4-tetrahydroquinolinein 10 ml. of ethanol is added to a solution of 25 g. of sodium sulfite and 2 to 5 g. of potassium bromide in 500 ml. of N/10 sodium hydroxide solution. After mixing, sufficient water is added to bring the volume to 1 liter. The resulting clear solution forms brown-black prints.
Example 4 k A solution of 0.5 g. of 8-hydroxy-1,2,3,4-tetra hydroquinoline and 0.5 g. of p-methylaminophenol in 10 ml. of ethanol is added to a solution of'25 g. of sodium'sulfite, 25 gpof sodium carbonate and 3 g. of potassium bromide in 800, ml. of water. The resulting solution is brought to 1 liter with additional water. The clear solu- 'tion is a high energy developer which produces grey-black prints.
Example 5 A solution of 0.5 g. of 8-hydroxy-1,2,3,4-tetrahydroquinoline and 0.5 g. of hydroquinone in 10 ml. of ethanol is added to a solution of 25 g. of sodium sulfite and 2 to 5 g. of potassium bromide in'500 ml. of N/10 sodium hydroxide solution. After mixing, suflicient water is added to bring the volume to 1 liter. This developer gives black prints of good contrast and clear whites.
Example 6 Eivample 8 A dry powder mixture is prepared by thoroughly mixing the following materials:
I Grams B-hydroxy-1,2,3,4-tetrahydroquinoline 6 Hydroquinone 24' Sodium carbonate monohydrate 216 Potassium metabisulfite 111 Potassium bromide '12 Sodium sulfite 90 several months without change.
Example 9 To a solution of l g. of 8-hydroxy-1,2,3,4-tetrahydroquinolinein 200 ml. of N/10 sodium hydroxide solution are added 25 g. of sodium sulfite and 5 g. of potassium bromide in 500 ml. of water. After thorough mixing the resulting clear solution is diluted to 1 liter with water. It develops 'light-hued brown prints.
l. A photographic developing composition for the development of a. latent image in a silver halide emulsion comprising an 8hydroxy-1,2,3,4- tetrahydroquinoline and a soluble inorganic reducing agent containing tetravalent sulfur.
2. A photographic developing composition comprising an B-hydroxy-1,2,3,4-tetrahydroquinoline and sodium sulfite. v
' 3. A photographic developing composition for the development of a latent image in a silver halide emulsion comprising an 8-hydroxy-1,2,3,4- tetrahydroquinoline, a hydroquinone and a soluble inorganic sulfite.
4. A photographic developing composition comprising an 8-hydroxy-1,2,3,4=-tetrahydroquinoline, a hydroquinone and sodium sulfite.
5. A photographic developing solution comprising an aqueous solution of an 8-hydroxy- 1,2,3,4-tetrahydroquinoline and sodium sulfite.
6. A photographic developing solution, comprising an aqueous solution of an S-hydroxy- 1,2,3, i-tetrahydroquinoline, a hydroquinone and sodium sulfite.
.7. In a process of developing a latent image of an exposed silver halide emulsion, the step which comprises treating said emulsion with an aqueous solution containing an 8-hydroxy-,1,2,3,4- tetrahydroquinoline and a soluble inorganic reducing agent containing tetravalent sulfur.
8. In aprocess of developing a latent image of an exposed silver halide emulsion, the step which comprises treating said emulsion with an aqueous solution containing an 8-hydroxy-1,2,3,4 tetrahydroquinoline, a hydroquinone and a so1u ble inorganic sulfite.
9. In a process of developing a latent image of an exposed silver halide emulsion, thestep-which comprises treating said emulsion with an aqueous solution containing an 8-hydroxy-1,2,3,4-.tetrajhydroquinoline and sodium sulfite. v1'
ROBERT R. BURTINERQ ROBERT T. DILLON.
REFERENCES CITED Y The following references are of record in the file of this patent:
UNITED STATES PATENTS 'Date Sease et al Aug. 31, 1943

Claims (1)

1. A PHOTOGRAPHIC DEVELOPING COMPOSITION FOR THE DEVELOPMENT OF A LATENT IMAGE IN A SILVER HALIDE EMULSION COMPRISING AN 8-HYDROXY-1,2,3,4TETRAHYDROQUINOLINE AND A SOLUBLE INORGANIC REDUCING AGENT CONTAINING TETRAVALENT SULFUR.
US774678A 1947-09-17 1947-09-17 8-hydroxy-1, 2, 3, 4-tetrahydroquinoline as a silver halide developer Expired - Lifetime US2596978A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2691588A (en) * 1952-03-14 1954-10-12 Eastman Kodak Co Photographic developers containing 8-hydroxyquinolines
US3397983A (en) * 1961-02-17 1968-08-20 Gevaert Photo Prod Nv Photographic materials producing a color change by reacting a metal salt with tetrahydroquinoline
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
US20120165370A1 (en) * 2007-08-21 2012-06-28 Tang Johnny Cheuk-On Quinoline derivatives as anti-cancer agents

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2108243A (en) * 1935-07-24 1938-02-15 Agfa Ansco Corp Photographic developer
US2163820A (en) * 1936-04-23 1939-06-27 Agfa Ansco Corp Photographic developer
US2194399A (en) * 1940-03-19 Tetbahydroquinoune derivative
US2251922A (en) * 1940-08-22 1941-08-12 Eastman Kodak Co Nu-nitroaryl tetrahydroquinoline compounds and material colored therewith
US2328034A (en) * 1940-12-14 1943-08-31 Du Pont Photographic element and process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2194399A (en) * 1940-03-19 Tetbahydroquinoune derivative
US2108243A (en) * 1935-07-24 1938-02-15 Agfa Ansco Corp Photographic developer
US2163820A (en) * 1936-04-23 1939-06-27 Agfa Ansco Corp Photographic developer
US2251922A (en) * 1940-08-22 1941-08-12 Eastman Kodak Co Nu-nitroaryl tetrahydroquinoline compounds and material colored therewith
US2328034A (en) * 1940-12-14 1943-08-31 Du Pont Photographic element and process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2691588A (en) * 1952-03-14 1954-10-12 Eastman Kodak Co Photographic developers containing 8-hydroxyquinolines
US3397983A (en) * 1961-02-17 1968-08-20 Gevaert Photo Prod Nv Photographic materials producing a color change by reacting a metal salt with tetrahydroquinoline
US3981732A (en) * 1971-08-19 1976-09-21 Fuji Photo Film Co., Ltd. Granular p-phenylenediamine color developing agent
US20120165370A1 (en) * 2007-08-21 2012-06-28 Tang Johnny Cheuk-On Quinoline derivatives as anti-cancer agents
US9493419B2 (en) * 2007-08-21 2016-11-15 The Hong Kong Polytechnic University Quinoline derivatives as anti-cancer agents

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