US2819965A - Carboxymethylmercapto compounds as stabilizers for photographic emulsions - Google Patents

Carboxymethylmercapto compounds as stabilizers for photographic emulsions Download PDF

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US2819965A
US2819965A US567418A US56741856A US2819965A US 2819965 A US2819965 A US 2819965A US 567418 A US567418 A US 567418A US 56741856 A US56741856 A US 56741856A US 2819965 A US2819965 A US 2819965A
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emulsions
carboxymethylmercapto
compounds
photographic
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Thomas F Murray
James A Van Allan
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
    • A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/42—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/50—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
    • C07D253/07—1,2,4-Triazines having 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
    • C07D253/075—Two hetero atoms, in positions 3 and 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/74—Sulfur atoms substituted by carbon atoms
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • Fog depends both on the emulsion and the conditions of development; for a given emulsion it increases with the degree of development. With constant development conditions, it tends to increase with time, temperature and relative humidity of storage conditions; it is common practice to make accelerated tests of the stability of photographic emulsions by storage at increased temperature or humidity, or both. It 1s, of course, desirable to have emulsions as stable as possible under the conditions of high temperature and humidity which may occur in tropical climates, for example. Fog usually appears over the whole area of the sensitive coating, but when severe, it frequently is non-uniform. Fog may also be caused by exposure to chemicals, for example, hydrogen sulfide and other reactive sulfur compounds, hydrogen peroxide vapor, and strongly reducing materials.
  • antifoggants and stabilizers may protect, to some extent, against such efiects, it is normally understood that an antifoggant protects against spontaneous growth of fog during prolonged storage or storage at high temperatures and humidities, or during development to maximum contrast and speed, or both.
  • an object of the present invention to provide a method for stabilizing photographic emulsions.
  • a further object is to provide a means for reducing the fog produced upon keeping of such emulsions which have been sensitized, especially emulsions stored under tropical or other adverse conditions.
  • a still further object is to provide a means for stabilizing the speed and contrast of sensitized photographic emulsions.
  • heterocyclic nitrogen compounds containing a carboxymethylmercapto substituent have strong antifoggant and stabilizing effects when incorporated in photographic silver halide emulsions.
  • the optimum concentrations are generally higher than those of the corresponding mercaptans and are less critical with respect to desensitization.
  • Many of our antifoggant and stabilizing compounds have a sulfur or oxygen atom in the heterocyclic ring, in addition to the nitrogen atom.
  • simple heterocyclic compound we mean a compound wherein the heterocyclic atoms (i. e. atoms other than carbon) are members of a single heterocyclic ring, as contrasted with compounds containing fused or condensed heterocyclic rings in which the heterocyclic atoms are members of more than one heterocyclic ring.
  • Such simple heterocyclic nitrogen compounds include triazoles (e. g. 1,2,4-triazoles, especially those containing an amino substituent in addition to the carboxymethylmercapto substituent), diazoles (e.
  • R 1 N C-S- H-COOM wherein R represents a hydrogen atom or an alkyl group (e. g., methyl, ethyl, butyl, heptyl, etc.), M represents a hydrogen atom or an alkali metal atom (e. g., sodium, potassium, etc.), and Z represents the non-metallic atoms necessary to complete a simple heterocyclic ring as defined above.
  • R represents a hydrogen atom or an alkyl group (e. g., methyl, ethyl, butyl, heptyl, etc.)
  • M represents a hydrogen atom or an alkali metal atom (e. g., sodium, potassium, etc.)
  • Z represents the non-metallic atoms necessary to complete a simple heterocyclic ring as defined above.
  • alkyl e. g., methyl, ethyl, butyl, heptyl, etc.
  • the principal purpose of our invention is to provide a means for maintaining the sensitivity and fog of silver halide emulsions at or close to initial optimum values under conditions of high temperature or high humidity, or both.
  • the antifoggants of our invention are added to the emulsion at any stage during the process of manufacture prior to coating the emulsion.
  • the antifoggants can be added to the emulsion in solution in water or any convenient solvent not injurious to the emulsion, such as lower aliphatic alcohols, acetone, etc.
  • solutions of antifoggants which we employ when added in suitable concentration before coating to unsensitized or optically sensitized silver halide emulsions usually do not appreciably afiect the sensitivity and fog when measurements are made soon after coating. However, when sensitometric measurements are made after appreciable intervals of time under tropical or dry conditions of storage at elevated temperatures, the antifoggants do stabilize speed and maintain fog at a low level.
  • the preparation of silver halide emulsions involves three separate operations: (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, (3) the second digestion or after-ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942, page 3).
  • the fog inhibiting agents can be added at any stage, preferably after the final digestion.
  • the photographic emulsions which we use are of the developing-out type and best results have been obtained with gelatino-silver bromoiodide emulsions. sions of varying halide composition can be used.
  • the emulsions can be chemically sensitized by any of the accepted procedures.
  • the emulsions can be digested With naturally active gelatin, or sulfur compounds may be added such as those described in Sheppard U. S. Patent 1,574,944 and U. S. 1,623,499, and Sheppard and Brigham U. S. Patent 2,410,689.
  • the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum, all of which belong to group VIH of the. periodic table of elements and have an atomic weight greater than 100.
  • Representative compounds are. ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces anysubstantial fog inhibition, as described in Smith and Trivelli U. S. Patent 2,448,060, and as anti-foggants in higher amounts, as described in Trivelli and Smith U. S. Patents 2,556,245 and 2,566,263.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller and Dodd U. S. Patent 2,399,083, or stabilized with gold salts as described in Damschroder U. S. Patent 2,597,856 and Yutzy and Leermakers U. S. Patent 2,597,915.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and Z-aurosulfobenzothiazole methochloride.
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U. S. application Serial No. 319,611 (nowU. S. Patent 2,728,663, issued December 27, 1955); Carroll and Murray U. S. application Serial No. 319,612 (now U. S. Patent 2,728,664, issued December 27, 1955); and Leubner and Murray U. S. application SerialNo. 319,613 (now U. S. Patent 2,728,665, issued December 27, 1955), all filed November 8, 1952.
  • the antifoggants of our invention are effective in the presence or absence of optical sensitizing dyes. Since optical sensitizing can atfect stability of emulsions with respect to sensitivity, fog and latent image changes, the action of the antifoggants is not completely independent of optical sensitizing or other emulsion variables. We have found, however, that both unsensitized emulsions and emulsions sensitized with cyanine or merocyanine dyes, or both, can be treated with the antifoggant comspeed,,gamma and fog, before and after incubation of each of the samples, are given in the following table. Kodak Developer D-19 has the following composition:
  • Kodak Developer SD-28 has the following composition:
  • the quanuty of antifoggant compound employed can N- nethyl-p-ammophenol sulfate 1.5 be vaned, dependmg upon the particular silver hahde Hydroqumone 1.3 employed, degree of ripening, presence or absence of Sodium sulfite (des1ccated) 75 other emulsion addenda, etc.
  • the quanuty of Borax 4.5 anhfoggant can vary from about 0.01 to 3.0 grams per Potassmm brom1de 0.4 gram mole of s1lver halide 1n the emulsion.
  • the stabilizing action afiorded by the antifoggants of our invention was determined by incubation of the emulsions for a period of 1 to 2 weeks at 120 F. (as indicated below) and at constant humidity. The speeds were measured in terms of 30/E Where E is the exposure in meter candle seconds required to produce a density of 0.2 above fog.
  • the antifoggants were added to a panchromatically-sensitized, high speed silver bromiodide emulsion which had been chemically sensitized with a sulfur compound, such as described in Sheppard U. S. Patent 1,574,944 and potassium chloroaurate.
  • the emulsions were then coated on a cellulose acetate support and the coatings exposed on an Eastman lb Sensitometer and processed for the time indicated below in a developer of the type indicated below. The results of these tests for to stabilize photographic silver halide emulsions, either in the presence or absence of chemical sensitizers.
  • these antifoggants can be incorporated in a colloid layer, such as a gelatin overcoating layer or interlayer, in contact with the emulsion.
  • the fog-inhibiting agents which we have described can be used in various kinds of photographic emulsions. In addition to being useful in non-sensitized emulsions, they can also be used in orthochromatic, panchromatic, and X-ray emulsions. if used with sensitizing dyes they can be added to the emulsion before or after the dyes are added.
  • Various silver halides can be used as the lightsensitive material, including silver bromide, silver iodide, silver chloride, silver bromiodide, silver chlorobromide, silver chlorobromiodide, etc.
  • the antifoggants of our .7 invention cantbe used in emulsions intended for color photography, for example, emulsions containing colorforming couplers, or emulsions to be developed by solutions containing couplers.
  • the dispersing agents can be gelatin, or other colloids, such as collodion, albumen, cellulose derivatives, synthetic resins, etc.
  • carboxymethylrnercapto compounds can, as mentioned above, be obtained from the corresponding mercapto compounds by condensing an alkali metal salt of the mercapto compound with an alkaline solution containing an alkali metal chloroacetate.
  • This method of making the carboxymethylmereapto compounds of our invention is illustrated in U. S. Patent 2,527,265, issued October 24, 1950. Other examples follow.
  • Example A -2 carboxymethylmercapto-I -phenylz'midazole KIJaHs HC-N
  • a mixture of 3.5 grams of 1-phenyl-2(3H)-imidazolethione, 3.0 grams of sodium chloroacetate and 15 ml. of water was heated on the water bath for 15 minutes, then 2.0 grams of sodium carbonate was added, and the mixture refluxed 0.5 hour. The clear solution was filtered, and acetic acid was added. The product separated as a white precipitate which was filtered, washed and dried. Yield, 3.5 grams, M. P. l48-50 C.
  • Z-carboxymethylmercapto 4,5,6 triaminopyrimidine (compound 8) was prepared by replacing the pyrimidine compound used in Example B by a molecularly equivalent amount of 2-mercapto-4,S,6-triaminopyrimidine.
  • Example C.2-carboxymethylmercapro 4 amino-fi-hydroxypyrimidine N ?NH: HOOGCHzS-(J CH N-c-OH
  • Example D.2-carboxymethylmercaptopyrimidine li H A mixture of 4.0 grams of Z-mercaptopyrimidine and 4.5 grams of sodiumchloroacetate in 50 ml. of water was heated on the steam bath 15 minutes, 3.5 grams of sodium bicarbonate added, and the heating continued one hour. After cooling, the solution was acidified with hydrochloric acid, and the solid collected and recrystallized from water to give 1.5 grams of the product, M. P. 198-200 C.
  • Hi l -SCH2CO0H H0C N
  • Example F --2-carboxymethylmercaptobenzoxazale C-SCHgCO OH
  • a mixture of 15.1 grams of Z-mercaptobenzoxazole and 13.0 grams of sodium chloroacetate in ml. of water was heated to reflux, and dilute sodium bicarbonate was slowly added until solution was complete, then refluxed for 10 minutes. The clear, yellow solution was filtered hot, and the filtrate was acidified with acetic acid. A nicely crystalline, yellow precipitate slowly separated from the aqueous phase. After standing overnight, the precipitate was collected by filtration and dried to give 12 grams of product, M. P. 1645 C.
  • 2-carboxymethylmercaptobenzothiazole (compound 16) was prepared by replacing the Z-mercaptobenzoxazole employed in Example F by a molecularly equivalent amount of 2-mercaptobenzothiazole.
  • the desired product was obtained as crystals melting at 162-3 C.
  • Example H -carboxymethylmercapto-3,4-diamin0-1,2, 4-triaz0le l o-somooon
  • Example ]-2-carboxymezhylmercapt0-4,6-diaminas-triazine acetic acid were then added to the colorless solution with stirring until solution was obtained. The clear solution was then stirred for an additional 21 hours, no change in appearance taking place during this time. A small amount of activated carbon and a filtering agent were added to the clear solution, which was then filtered. The clear filtrate was acidified with dilute acetic acid to give a white precipitate. This precipitate was collected on a filter and dried. Yield, 5.7 g. (94.5%). A small amount of the solid was recrystallized in sodium hydroxide solution, filtered, and reprecipitated in acetic acid. The dried product had a decomposition point of about 250 C.
  • compound 4 was obtained by heating together 102 g. of Z-mercaptoimidazoline and g. of sodium chloroacetate in 200 cc. of water. 102 g. of the desired product were obtained. In like manner, compound 3 was obtained from the corresponding mercapto compound. See Johnson and Edens-JACS, vol. 64 (1942), page 2708).
  • carboxymethylmercapto compounds of our invention can also be employed to advantage as stabilizers in photographic silver halide emulsions.
  • compounds containing a carbalkoxylmethylmercapto group or a carbamylmethylmercapto group can sometimes be employed to advantage in photographic emulsions.
  • the following two examples will describe the preparation of two compounds of these types which can be employed to advantage in photographic emulsions.
  • Example N.2-carbethoxymethylmercaptoimidazolium hydrochloride 2O C-SOHiCOOCzHr A mixture of 10.2 g. of ethylenethiourea and 13.0 g. (11.3 ml.) of ethyl chloroacetate in 30 ml. of absolute alcohol was refluxed for 3 hours after which 60 ml. of acetone was added to the reaction mixture. The product which had separated was filtered off and recrystallized from isopropanol to give 21 g. of Z-carbethoxymethylmercaptoimidazolium hydrochloride, M. P. 1423 C.
  • antifoggant and stabilizing compounds of our invention which contain a benzene ring can have substituents on the benzene ring, such as chlorine, bromine, methyl, ethyl, phenyl, etc. These compounds can be prepared in exactly the manner shown in the above examples.
  • a photographic silver halide emulsion containing a monoheterocyclic nitrogen compound selected from those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom and an alkyl group
  • M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom
  • Z represents the non-metallic atoms necessary to complete a heterocyclic ring.
  • V N o-s-omooon wherein M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete an imidazoline heterocyclic ring.
  • M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a pyrimidine heterocyclic ring.
  • M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a 1,2,4-triazine heterocyclic ring.
  • M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a benzoxazole heterocyclic ring.

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Description

CARBOXYMETHYLMERCAPTO COMPOUNDS AS FOR PHOTOGRAPHIC EMUL- Thomas F. Murray, George A. Reynolds, and James A. Van Allan, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application February 23, 1956 Serial No. 567,418
14 Claims. (Cl. 96-409) tion; in this invention, we are not concerned with the latter.
Fog depends both on the emulsion and the conditions of development; for a given emulsion it increases with the degree of development. With constant development conditions, it tends to increase with time, temperature and relative humidity of storage conditions; it is common practice to make accelerated tests of the stability of photographic emulsions by storage at increased temperature or humidity, or both. It 1s, of course, desirable to have emulsions as stable as possible under the conditions of high temperature and humidity which may occur in tropical climates, for example. Fog usually appears over the whole area of the sensitive coating, but when severe, it frequently is non-uniform. Fog may also be caused by exposure to chemicals, for example, hydrogen sulfide and other reactive sulfur compounds, hydrogen peroxide vapor, and strongly reducing materials. While antifoggants and stabilizers may protect, to some extent, against such efiects, it is normally understood that an antifoggant protects against spontaneous growth of fog during prolonged storage or storage at high temperatures and humidities, or during development to maximum contrast and speed, or both.
It is, therefore, an object of the present invention to provide a method for stabilizing photographic emulsions. A further object is to provide a means for reducing the fog produced upon keeping of such emulsions which have been sensitized, especially emulsions stored under tropical or other adverse conditions. A still further object is to provide a means for stabilizing the speed and contrast of sensitized photographic emulsions. Other objects will become apparent from a consideration ofthe following description and examples.
It is known that certain mercaptans, and particularly compounds having mercapto substitution on a heterocyclic ring, have an antifoggant and stabilizing effect when incorporated in photographic silver halide emulsions. In general, these compounds are relatively strongly antifoggant at low concentrations but they are also desensitizing, and the concentration at which desensitization is largely avoided may be so low that the antifoggant action is weak. Conversion of the mercapto group to a thioether (alkylor arylmercapto) group usually reduces the photographic activity by a large factor. Consequently, thioethers as a class have little usefulness in photographic emulsions.
States atent O We have found that heterocyclic nitrogen compounds containing a carboxymethylmercapto substituent have strong antifoggant and stabilizing effects when incorporated in photographic silver halide emulsions. The optimum concentrations are generally higher than those of the corresponding mercaptans and are less critical with respect to desensitization. Many of our antifoggant and stabilizing compounds have a sulfur or oxygen atom in the heterocyclic ring, in addition to the nitrogen atom.
According to our invention we provide a method for stabilizing photographic silver halide emulsions by incorporating therein a simple heterocyclic nitrogen compound containing a carboxymethylmercapto substituent. By simple heterocyclic compound we mean a compound wherein the heterocyclic atoms (i. e. atoms other than carbon) are members of a single heterocyclic ring, as contrasted with compounds containing fused or condensed heterocyclic rings in which the heterocyclic atoms are members of more than one heterocyclic ring. Such simple heterocyclic nitrogen compounds include triazoles (e. g. 1,2,4-triazoles, especially those containing an amino substituent in addition to the carboxymethylmercapto substituent), diazoles (e. g.,imidazoles, benzimidazoles, imidazolines, etc.), pyrimidines (especially those wherein the carboxymethylmercapto group is in the 2-position), 1,2,4-triazines, s-triazines, mono-azoles (e. g. benzoxazo'les, benzothiazoles, etc.), etc. These carboxymethylmercapto compounds can, in general, be obtained from the corresponding mercapto compounds by the well known Williamson synthesis, wherein the alkali metal salt of the mercapto compound is condensed with an alkaline solution of chloroacetic acid (salt). This method is further illustrated below.
These simple heterocyclic compounds can advantageously be represented by the following general formula:
R 1 N C-S- H-COOM wherein R represents a hydrogen atom or an alkyl group (e. g., methyl, ethyl, butyl, heptyl, etc.), M represents a hydrogen atom or an alkali metal atom (e. g., sodium, potassium, etc.), and Z represents the non-metallic atoms necessary to complete a simple heterocyclic ring as defined above.
Compounds useful in practicing our invention include those represented by the following formulas (R means carboxymethylmercapto) 2-carboxymethylmercapto-4-methylimidazo1ine C-Rr 2-carboxymethylmercaptoimtdazollne Pa tented Jan. 14, 1958 2.-carboxymethylmereapto-l-phenylimidazole H2O NCH2CO 0H H cl 2-carboxymethylmercaptoimldazoline chloroacetate Z-CarboXymethyImercaptoA,G-diaminopyrimidlne (8.) N
HQN Wen HsNl/ I THg Z-carboxymethylmercapto-4,5,G-triaminopyrtmldine I NHg 4am:ino-2rcarboxymethylmercapto-6-hydroxypyr1midine (10.), N
k/IR.
2-carboxymethylmercaptopyrimidine 11. N H3O YR].
I OH
2-carboxymethylmercaptol-hydroxy-fimethylpyrimidine 11m, V 2-carboxymethylmercapto-4,6-diamino-s-triaztne NH, 4,6-dlamino-2-(l-carhoxyoctylmercapto)-s-triazine Z carbQxymethylmercaptobenzoxazole C-Rg 2-carboaymethylmercaptobenzothiazole C-Rt 2-carboxymethylmercaptobenzimidazole By carboxymethylmercapto we mean the group:
or such a group having a simple substituent, such as alkyl (e. g., methyl, ethyl, butyl, heptyl, etc.), attached to the CH carbon atom.
The principal purpose of our invention is to provide a means for maintaining the sensitivity and fog of silver halide emulsions at or close to initial optimum values under conditions of high temperature or high humidity, or both. Preferably, the antifoggants of our invention are added to the emulsion at any stage during the process of manufacture prior to coating the emulsion. The antifoggants can be added to the emulsion in solution in water or any convenient solvent not injurious to the emulsion, such as lower aliphatic alcohols, acetone, etc.
The solutions of antifoggants which we employ when added in suitable concentration before coating to unsensitized or optically sensitized silver halide emulsions usually do not appreciably afiect the sensitivity and fog when measurements are made soon after coating. However, when sensitometric measurements are made after appreciable intervals of time under tropical or dry conditions of storage at elevated temperatures, the antifoggants do stabilize speed and maintain fog at a low level.
The preparation of silver halide emulsions involves three separate operations: (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, (3) the second digestion or after-ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942, page 3). The fog inhibiting agents can be added at any stage, preferably after the final digestion.
The photographic emulsions which we use are of the developing-out type and best results have been obtained with gelatino-silver bromoiodide emulsions. sions of varying halide composition can be used.
The emulsions can be chemically sensitized by any of the accepted procedures. The emulsions can be digested With naturally active gelatin, or sulfur compounds may be added such as those described in Sheppard U. S. Patent 1,574,944 and U. S. 1,623,499, and Sheppard and Brigham U. S. Patent 2,410,689.
The emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum, all of which belong to group VIH of the. periodic table of elements and have an atomic weight greater than 100. Representative compounds are. ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces anysubstantial fog inhibition, as described in Smith and Trivelli U. S. Patent 2,448,060, and as anti-foggants in higher amounts, as described in Trivelli and Smith U. S. Patents 2,556,245 and 2,566,263.
The emulsions can also be chemically sensitized with gold salts as described in Waller and Dodd U. S. Patent 2,399,083, or stabilized with gold salts as described in Damschroder U. S. Patent 2,597,856 and Yutzy and Leermakers U. S. Patent 2,597,915. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and Z-aurosulfobenzothiazole methochloride.
The. emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U. S. Patent 2,487,850), polyamines such as diethylene triamine (Lowe and Jones U. S. Patent 2,518,698), poly-- However, emul amines such as spermine (Lowe and Allan U. S. Patent 2,521,925), or bis-(,B-aminoethyDsulfide and its watersoluble salts (Lowe and Jones U. S. Patent 2,521,926).
The emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U. S. application Serial No. 319,611 (nowU. S. Patent 2,728,663, issued December 27, 1955); Carroll and Murray U. S. application Serial No. 319,612 (now U. S. Patent 2,728,664, issued December 27, 1955); and Leubner and Murray U. S. application SerialNo. 319,613 (now U. S. Patent 2,728,665, issued December 27, 1955), all filed November 8, 1952.
The antifoggants of our invention are effective in the presence or absence of optical sensitizing dyes. Since optical sensitizing can atfect stability of emulsions with respect to sensitivity, fog and latent image changes, the action of the antifoggants is not completely independent of optical sensitizing or other emulsion variables. We have found, however, that both unsensitized emulsions and emulsions sensitized with cyanine or merocyanine dyes, or both, can be treated with the antifoggant comspeed,,gamma and fog, before and after incubation of each of the samples, are given in the following table. Kodak Developer D-19 has the following composition:
Water, about 125 F cc 500 Water to make one liter.
Kodak Developer SD-28 has the following composition:
pounds represented by Formula I above. Grams The quanuty of antifoggant compound employed can N- nethyl-p-ammophenol sulfate 1.5 be vaned, dependmg upon the particular silver hahde Hydroqumone 1.3 employed, degree of ripening, presence or absence of Sodium sulfite (des1ccated) 75 other emulsion addenda, etc. In general, the quanuty of Borax 4.5 anhfoggant can vary from about 0.01 to 3.0 grams per Potassmm brom1de 0.4 gram mole of s1lver halide 1n the emulsion. These Water to make one llter.
Ineu- Development Fresh Tests Incubation Tests Compound batlon Example (gJmol. Time .AgX) (wks.) Time Developer /E Gamma Fog 30/E Gamma Fog (Mms.) Speed Speed Control.-. 1 5 DK-50 5, 350 1. 12 .19 2, 100 .96 .45 1. (1.5)--.- 1 5 DK-50 4, 350 1.15 .15 2,950 1.03 .20 Control 1 5 DK-50 5, 350 1. 22 15 4, 050 1. 05 .24 2. .3) 1 5 DK-50 5,350 1.23 .13 4,350 1.12 .15 Control--. 1 5 DK-5O 6, 900 1. 00 10 6, 400 1. 03 19 1 5 DK-50 6, 400 1. 06 11 3, 150 1.17 12 1 5 DK-50 6, 900 1.00 10 6, 400 1. 03 .19 1 5 DK-5O 5, 100 1. 02 09 4,450 1. 01 10 2 12 SD-28 3, 450 .92 .09 2, 200 .74 .24 2 12 sD-2s 3, 450 .96 10 2, 600 77 .20 1 5 DK-5O 6, 700 1. 00 15 5, 700 .90 20 1 5 DK-SO 6, 900 1. 05 14 3, 950 1. 00 15 1 5 DK-50 5, 209 1. 13 17 2, 600 1. 02 33 1 5 DK-50 4, 350 1. 14 16 3, 100 1. 04 22 1 6. 5 s1) 2s 2, 200 .83 11 1, 090 65 .19 1 6. 5 SD-28 2, 200 .73 12 1, 440 .67 16 1 5 DK-50 7, 050 1. 0s 10 6, 700 94 16 1 5 DK-50 7,700 1. 04 .07 6, 150 .99 .12 1 4 D-19 2, 800 1. 19 3, 800 1.59 .23 1 4- D-19 3, 350 1.50 .17 3, 600 1. 30 .20 1 5 DK- 7, 050 1. 0s 10 6, 700 .94 16 1 5 Inc-50 2,1100 1. 14 .07 3,000 1.10 .08 1 5 DK-5O 6,700 1. 00 15 5, 700 90 20 1 5 DK-50 6, 400 1. 02 14 6, 250 .90 17 2 5 DK-50 4, 850 1. 14 13 4, 750 1.18 .26 2 5 DK-50 3, 100 93 15 2, 350 1. 02 22 2 5 DK-50 4, 350 1. 25 16 2, 150 95 .36 15. (.75)--. 2 5 DK-50 4, 750 1.26 .14 2,450 .99 .20. Control--. 2 4 D-19 4,350 1.32 .12 1,730 .83 .62 16. (.15)--. 2 4 D-19 3,950 1.23 .11 2,000 .93 .52
amounts can be used in combmanon with one or more in a manner similar to that illustrated in the above of the chem1cal sens1t1z1ng and stabilizing agents listed examples, other compounds of our 1nvent1on can be used above.
The stabilizing action afiorded by the antifoggants of our invention was determined by incubation of the emulsions for a period of 1 to 2 weeks at 120 F. (as indicated below) and at constant humidity. The speeds were measured in terms of 30/E Where E is the exposure in meter candle seconds required to produce a density of 0.2 above fog. The antifoggants were added to a panchromatically-sensitized, high speed silver bromiodide emulsion which had been chemically sensitized with a sulfur compound, such as described in Sheppard U. S. Patent 1,574,944 and potassium chloroaurate. The emulsions were then coated on a cellulose acetate support and the coatings exposed on an Eastman lb Sensitometer and processed for the time indicated below in a developer of the type indicated below. The results of these tests for to stabilize photographic silver halide emulsions, either in the presence or absence of chemical sensitizers.
Instead of incorporating the antifoggants in the photographic silver halide emulsion, these antifoggants can be incorporated in a colloid layer, such as a gelatin overcoating layer or interlayer, in contact with the emulsion.
The fog-inhibiting agents which we have described can be used in various kinds of photographic emulsions. In addition to being useful in non-sensitized emulsions, they can also be used in orthochromatic, panchromatic, and X-ray emulsions. if used with sensitizing dyes they can be added to the emulsion before or after the dyes are added. Various silver halides can be used as the lightsensitive material, including silver bromide, silver iodide, silver chloride, silver bromiodide, silver chlorobromide, silver chlorobromiodide, etc. The antifoggants of our .7 invention cantbe used in emulsions intended for color photography, for example, emulsions containing colorforming couplers, or emulsions to be developed by solutions containing couplers.
The dispersing agents can be gelatin, or other colloids, such as collodion, albumen, cellulose derivatives, synthetic resins, etc.
These carboxymethylrnercapto compounds can, as mentioned above, be obtained from the corresponding mercapto compounds by condensing an alkali metal salt of the mercapto compound with an alkaline solution containing an alkali metal chloroacetate. This method of making the carboxymethylmereapto compounds of our invention is illustrated in U. S. Patent 2,527,265, issued October 24, 1950. Other examples follow.
Example A.-2 carboxymethylmercapto-I -phenylz'midazole KIJaHs HC-N A mixture of 3.5 grams of 1-phenyl-2(3H)-imidazolethione, 3.0 grams of sodium chloroacetate and 15 ml. of water was heated on the water bath for 15 minutes, then 2.0 grams of sodium carbonate was added, and the mixture refluxed 0.5 hour. The clear solution was filtered, and acetic acid was added. The product separated as a white precipitate which was filtered, washed and dried. Yield, 3.5 grams, M. P. l48-50 C.
Example B.2-carboxymethylmercapto 4,6 diaminopyrimidine N-C-NH: HOOCCHzS-(il ("3H N=CNH:
A mixture of 15 grams each of 4,6-diamino-2-mercaptopyrimidine and sodium chloroacetate, 10 grams of sodium bicarbonate in 100 ml. of water was heated on the steam bath. After 0.5 hour, complete solution ensued. Heating was continued for one hour. The reaction mixture was treated with decolorizing carbon, filtered, and acidified with acetic acid. The precipitate was filtered and dried to give 17 grams of product, M. P. 2703 C.
Analysis for C H O N S: Calcd: C, 36.0; H, 4.0. Found: C, 35.5; H, 4.1.
In a manner similar to that illustrated in Example B above, Z-carboxymethylmercapto 4,5,6 triaminopyrimidine (compound 8) was prepared by replacing the pyrimidine compound used in Example B by a molecularly equivalent amount of 2-mercapto-4,S,6-triaminopyrimidine.
Example C.2-carboxymethylmercapro 4 amino-fi-hydroxypyrimidine N=?NH: HOOGCHzS-(J CH N-c-OH A mixture of 14 grams each of 4-amino-6-hydroxy-2- mercaptopyrimidine and sodium chloroacetate in 150 ml. of water was refluxed for 1.5 hours, then 3 grams more of sodium chloroacetate in 50 ml. of water was added. After a further hour on the steam bath, the precipitate which formed was filtered from the hot solution and dried to give 14 grams of product. The crude product was recrystallized from 800 ml. of water to give 10 grams of pure product, M. P. 241-2" C.
Example D.2-carboxymethylmercaptopyrimidine li H A mixture of 4.0 grams of Z-mercaptopyrimidine and 4.5 grams of sodiumchloroacetate in 50 ml. of water was heated on the steam bath 15 minutes, 3.5 grams of sodium bicarbonate added, and the heating continued one hour. After cooling, the solution was acidified with hydrochloric acid, and the solid collected and recrystallized from water to give 1.5 grams of the product, M. P. 198-200 C.
Analysis calcd for C H NO S: C, 42.4; H, 3.5; N, 16.5. Found: C, 43.2; H, 2.8; N, 16.8.
Example E.-2 carboxymethylmercapto 4 hydroxy-fi methylpyrimidine H:CC-N
Hi l -SCH2CO0H H0C=N A mixture of 28 grams each of 4-hydroxy-2-rnercapto- G-methylpyrimidine and sodium chloroacetate and 30 grams of sodium bicarbonate in 300 ml. of water were refluxed for 1.5 hours. Complete solution ensued. The reaction mixture was filtered through a filter aid (e. g., Filter Cal), and the filtrate was acidified with concentrated hydrochloric acid. The precipitate was filtered and dried. Yield, 33 grams, M. P. 213-15 C. A sample was recrystallized from water. Heavy needle-like crystals, M. P. 213-14 C. were obtained.
Analysis for CqHgOgNzS: Calcd: C, 42.0; H, 4.0. Found C, 42.0; H, 4.4.
Example F .--2-carboxymethylmercaptobenzoxazale C-SCHgCO OH A mixture of 15.1 grams of Z-mercaptobenzoxazole and 13.0 grams of sodium chloroacetate in ml. of water was heated to reflux, and dilute sodium bicarbonate was slowly added until solution was complete, then refluxed for 10 minutes. The clear, yellow solution was filtered hot, and the filtrate was acidified with acetic acid. A nicely crystalline, yellow precipitate slowly separated from the aqueous phase. After standing overnight, the precipitate was collected by filtration and dried to give 12 grams of product, M. P. 1645 C.
Analysis for C9H7O3NS1 Calcd: C, 51.5; H, 3.3. Found: C, 51.3; H, 3.8.
In a manner similar to that illustrated in Example F above, 2-carboxymethylmercaptobenzothiazole (compound 16) was prepared by replacing the Z-mercaptobenzoxazole employed in Example F by a molecularly equivalent amount of 2-mercaptobenzothiazole. The desired product was obtained as crystals melting at 162-3 C.
Analysis for CgHqOgNSzZ Calcd: C, 48.0; H, 3.1. Found: C, 47.7; H, 3.2.
Example G.-4-amino-5-carboxymethylmercapta-S-phenyl-1,2,4-rriazole IFTH:
20 g. of 4-amino-5-mercapto-3-phenyl-1,2,4-triazole (1. C. 8.," 1952, page 4814), 15 g. of sodium chloroacetate, and 15 g. of sodium carbonate in 200 cc. of water were refluxed 18 hours. While still warm, the reaction mixture was acidified with hydrochloric acid and then cooled. It was filtered and then washed with water. Yield 16.6 g. The product melted at 184-6" C...(sintered at 144 C.).
Analysis calcd: C, 48.0; H, 4.0; N, 22.4; S, 12.8. Found: C, 47.5; H, 3.9; N, 22.4; S, 12.8.
Example H.-carboxymethylmercapto-3,4-diamin0-1,2, 4-triaz0le l o-somooon A mixture of 5 g. of 5-hydroxy-3-mercapto-6-methyl- 1,2,4-triazabenzene (Compt rend, vol. 186, page 1216), 4.1 g. of sodium chloroacetate, 30 cc. of water and 30 cc. of ethanol was boiled under reflux for 15 minutes and allowed to cool. The liquid and precipitated solid were heated on a steam bath, allowed to cool and acidified with hydrochloric acid. It was then chilled, and the solid filtered ofi. The filtrate was recrystallized from aqueous dimethylformamide, digested in ethanol and cooled. 1.0 g. of solid melting at 176-8 C. was obtained.
Another useful carboxymethylmercapto compound, 3- carboxymethylmercapto 6 methyl-S-phenyl-l,2,4-triazabenzene was prepared in substantially the same manner. It was obtained as a pale orange solid.
Example ].-2-carboxymezhylmercapt0-4,6-diaminas-triazine acetic acid were then added to the colorless solution with stirring until solution was obtained. The clear solution was then stirred for an additional 21 hours, no change in appearance taking place during this time. A small amount of activated carbon and a filtering agent were added to the clear solution, which was then filtered. The clear filtrate was acidified with dilute acetic acid to give a white precipitate. This precipitate was collected on a filter and dried. Yield, 5.7 g. (94.5%). A small amount of the solid was recrystallized in sodium hydroxide solution, filtered, and reprecipitated in acetic acid. The dried product had a decomposition point of about 250 C.
Example K.4,6-diamin0-2-( 1 -car.boxyoctylmercapt0)- s-triazine new C-SCHCOOH N 01111: l NH,
4.74 g. of m-bromopelargonic acid, 2.86 g. of 4,6-di amino-2-mercaptopyrimidine, and 1.76 g. of sodium hydroxide were dissolved in 50 cc. of distilled water. The clear solution was stirred for 20 hours, treated with activated carbon and a filtering agent, and then filtered. The filtrate was acidified with acetic acid, whereupon a white precipitate separated. It was collected on a filter and dried in air.
- The product was redissolved in aqueous sodium hydroxide, filtered and reprecipitated in acetic acid. The precipitate was collected on a filter and dried. Yield, 5 g. (83.5%). The dried product was washed several times with petroleum ether and then dried.
In a manner similar to that illustrated in Example K above, compound 4 was obtained by heating together 102 g. of Z-mercaptoimidazoline and g. of sodium chloroacetate in 200 cc. of water. 102 g. of the desired product were obtained. In like manner, compound 3 was obtained from the corresponding mercapto compound. See Johnson and Edens-JACS, vol. 64 (1942), page 2708).
Example L.2-carboxymethylmercaptoimidazoline ch loroacetate N Bio C-SCHZCOOH HzC/NCH2C O OH 4 g. of Z-mercaptoimidazoline and 6 g. of chloroacetic acid in 15 cc. of water were heated to boiling for 5 minutes and then cooled in an ice chest. The desired product separated as white crystals. Yield 3.1 g. On recrystallization from water, it melted at 134 C.
Calcd for C H O N SCl: C, 33.1; H, 4.3. C, 33.4; H, 4.5.
We have also found that certain derivatives of the carboxymethylmercapto compounds of our invention can also be employed to advantage as stabilizers in photographic silver halide emulsions. For example, compounds containing a carbalkoxylmethylmercapto group or a carbamylmethylmercapto group can sometimes be employed to advantage in photographic emulsions. The following two examples will describe the preparation of two compounds of these types which can be employed to advantage in photographic emulsions.
Found Example M.2-carbamylmethylmercaptoimidazoline hydrochloride 2C-IIIH H2O CS CH2 (L-NHLHCI yield of 2-carbamylmethylmercaptoimidazoline, M. P.
139-40 C., was 16 g.
Analysis for C H ON S.HCl: Calcd: C, 30.7; H, 5.1. Found: C, 30.9; H, 5.4.
Example N.2-carbethoxymethylmercaptoimidazolium hydrochloride 2O C-SOHiCOOCzHr A mixture of 10.2 g. of ethylenethiourea and 13.0 g. (11.3 ml.) of ethyl chloroacetate in 30 ml. of absolute alcohol was refluxed for 3 hours after which 60 ml. of acetone was added to the reaction mixture. The product which had separated was filtered off and recrystallized from isopropanol to give 21 g. of Z-carbethoxymethylmercaptoimidazolium hydrochloride, M. P. 1423 C.
11 1 Analysis for C H O N SCI: Caled: C, 37.4; H, 5.8. Found: C, 37.6; H, 5.7.
In general, compounds such as those represented by Examples M and N above, are not nearly so useful in photographic emulsions as are the carboxymethylmercapto compounds illustrated above.
The antifoggant and stabilizing compounds of our invention which contain a benzene ring can have substituents on the benzene ring, such as chlorine, bromine, methyl, ethyl, phenyl, etc. These compounds can be prepared in exactly the manner shown in the above examples.
What we claim as our invention and desire secured by Letters Patent of the United States is:
1. A photographic silver halide emulsion containing a monoheterocyclic nitrogen compound containing a substituent selected from the group consisting of a carboxy methylmercapto group and a salt of a carboxymethylmercapto group, said substituent being attached to said monoheterocyclic nitrogen compound in the a-position with respect to the nitrogen atom of said nitrogen compound.
2. A photographic silver halide emulsion containing a monoheterocyclic nitrogen compound selected from those represented by the following general formula:
bl b-s-bn-ooorr wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group, M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a heterocyclic ring.
3. A photographic gelatino-silver-halide-developing-out emulsion containing a monoheterocyclic nitrogen compound selected from those represented by the following general formula:
I l N wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group, M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a heterocyclic ring.
5. A photographic silver halide developing-out emulsion containing a compound selected from those represented by the following general formula:
V N o-s-omooon wherein M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete an imidazoline heterocyclic ring.
8. A photographic gelatino-silver-halide developingout emulsion containing Z-carboxymethylmercaptoimidazoline.
9. A photographic silver-halide developing-out emulsion containing a compound selected from those represented by the following general formula:
16 b-s-crnoooivr wherein M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a pyrimidine heterocyclic ring.
10. A photographic gelatino-silver-halide developingout emulsion containing 2-carboxymethylmercapto-4,6- diaminopyrimidine.
11. A photographic silver-halide developing-out emulsion containing a compound selected from those represented by the following general formula:
I It -s omoooM wherein M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a 1,2,4-triazine heterocyclic ring.
12. A photographic gelatino-silver halide developingout emulsion containing 3-carboxymcthylmercapto-5- hydroxy-fi-methyl-l,2,4-triazine.
13. A photographic silver-halide developing-out emulsion containing a compound selected from those represented by the following general formula:
rt b-S-CHICOOM wherein M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom and Z represents the non-metallic atoms necessary to complete a benzoxazole heterocyclic ring.
14. A photographic gelatino-silver-halide developingout emulsion containing 2-carboxymethylmercaptobenzoxazole.
References Cited in the file of this patent FOREIGN PATENTS 699,888 Great Britain Nov. 18, 1953

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A MONOHETEROCYCLIC NITROGEN COMPOUND CONTAINING A SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF A CARBOXYMETHYLMERCAPTO GROUP AND A SALT OF CARBOXYMETHYLMERCAPTO GROUP, SAID SUBSTITUENT BEING ATTACHED TO SAID MONOHETEROCYCLIC NITROGEN COMPOUND IN THE A-POSITION WITH RESPECT TO THE NITROGEN ATOM OF SAID NITROGEN COMPOUND.
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Cited By (30)

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US2919985A (en) * 1958-08-15 1960-01-05 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US2939789A (en) * 1958-06-06 1960-06-07 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US2948615A (en) * 1958-03-13 1960-08-09 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US2952539A (en) * 1958-10-23 1960-09-13 Gen Aniline & Film Corp Photographic emulsions and developers stabilized with purine compounds
US2976152A (en) * 1958-12-19 1961-03-21 Gen Aniline & Film Corp Photographic gelatin layers containing triazine hardeners
US2981624A (en) * 1957-06-05 1961-04-25 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsion
US3042521A (en) * 1957-12-26 1962-07-03 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsion
US3051570A (en) * 1958-10-01 1962-08-28 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3068239A (en) * 1959-12-28 1962-12-11 Monsanto Chemicals Benzothiazole-, benzoxazole- and benzimidazole-2-thioacrylates and process
US3081170A (en) * 1958-10-06 1963-03-12 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3084044A (en) * 1960-12-09 1963-04-02 Gen Aniline & Film Corp Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer
US3136689A (en) * 1959-12-28 1964-06-09 Monsanto Co Heterocyclic esters effective against micro-organisms
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives
US3252799A (en) * 1962-06-09 1966-05-24 Agfa Ag Stabilized silver halide emulsions
US3325287A (en) * 1963-11-26 1967-06-13 Fuji Photo Film Co Ltd Photographic gelatin hardening composition
US3365294A (en) * 1963-04-27 1968-01-23 Agfa Ag Photographic material containing yellow fog-preventing agents
DE2222297A1 (en) * 1971-05-11 1972-11-23 Agfa Gevaert Ag Silver halide photographic material
JPS4972735U (en) * 1972-10-14 1974-06-24
US3896129A (en) * 1972-03-31 1975-07-22 American Home Prod (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides
US3901887A (en) * 1972-03-31 1975-08-26 American Home Prod (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides
US3940394A (en) * 1972-03-31 1976-02-24 Santilli Arthur A 2-pyrimidinylthio)alkanoic acids, esters, amides and hydrazides
US4009029A (en) * 1973-06-05 1977-02-22 Eastman Kodak Company Cyanoethyl-containing blocked development restrainers
US4111697A (en) * 1976-03-29 1978-09-05 Agfa-Gevaert, N. V. Novel antifogging and/or stabilizing compounds for silver halide photography
US4116697A (en) * 1976-12-17 1978-09-26 E. I. Du Pont De Nemours And Company Sulfur-substituted isothioureas in silver halide emulsions
US4351896A (en) * 1980-12-12 1982-09-28 Eastman Kodak Company Mesoionic silver halide stabilizer precursor and use in a heat developable and heat stabilizable photographic silver halide material and process
US4404390A (en) * 1980-12-12 1983-09-13 Eastman Kodak Company Mesoionic 1,2,4-triazolium silver halide stabilizer precursors
US4696763A (en) * 1984-05-11 1987-09-29 Ciba-Geigy Corporation Compositions containing heterocyclic corrosion inhibitors
EP0323146A2 (en) * 1987-12-29 1989-07-05 Smithkline Beecham Corporation Dopamine-beta-hydroxylase inhibitors
US5478721A (en) * 1995-01-31 1995-12-26 Eastman Kodak Company Photographic elements containing emulsion stabilizers
CN115477613A (en) * 2022-10-28 2022-12-16 陕西师范大学 Method for synthesizing 2-amino imidazoline compound

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FR2332708A1 (en) * 1975-11-26 1977-06-24 Fisons Ltd (1,2,4)-Triazolium salt plant protection agents - with fungicidal, herbicidal and plant growth regulating activity
US4390538A (en) * 1980-09-12 1983-06-28 Ciba-Geigy Corporation Pesticidal triorgano-tin triazines

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB699888A (en) * 1951-01-26 1953-11-18 Du Pont Photographic materials and processes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB699888A (en) * 1951-01-26 1953-11-18 Du Pont Photographic materials and processes

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2981624A (en) * 1957-06-05 1961-04-25 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsion
US3042521A (en) * 1957-12-26 1962-07-03 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsion
US2948615A (en) * 1958-03-13 1960-08-09 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US2939789A (en) * 1958-06-06 1960-06-07 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US2919985A (en) * 1958-08-15 1960-01-05 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3051570A (en) * 1958-10-01 1962-08-28 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3081170A (en) * 1958-10-06 1963-03-12 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US2952539A (en) * 1958-10-23 1960-09-13 Gen Aniline & Film Corp Photographic emulsions and developers stabilized with purine compounds
US2976152A (en) * 1958-12-19 1961-03-21 Gen Aniline & Film Corp Photographic gelatin layers containing triazine hardeners
US3068239A (en) * 1959-12-28 1962-12-11 Monsanto Chemicals Benzothiazole-, benzoxazole- and benzimidazole-2-thioacrylates and process
US3136689A (en) * 1959-12-28 1964-06-09 Monsanto Co Heterocyclic esters effective against micro-organisms
US3084044A (en) * 1960-12-09 1963-04-02 Gen Aniline & Film Corp Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer
US3220839A (en) * 1961-08-25 1965-11-30 Eastman Kodak Co Photographic emulsions containing isothiourea derivatives
US3252799A (en) * 1962-06-09 1966-05-24 Agfa Ag Stabilized silver halide emulsions
US3365294A (en) * 1963-04-27 1968-01-23 Agfa Ag Photographic material containing yellow fog-preventing agents
US3325287A (en) * 1963-11-26 1967-06-13 Fuji Photo Film Co Ltd Photographic gelatin hardening composition
DE2222297A1 (en) * 1971-05-11 1972-11-23 Agfa Gevaert Ag Silver halide photographic material
US3896129A (en) * 1972-03-31 1975-07-22 American Home Prod (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides
US3901887A (en) * 1972-03-31 1975-08-26 American Home Prod (2-pyrimidinylthio) alkanoic acids, esters, amides and hydrazides
US3940394A (en) * 1972-03-31 1976-02-24 Santilli Arthur A 2-pyrimidinylthio)alkanoic acids, esters, amides and hydrazides
JPS4972735U (en) * 1972-10-14 1974-06-24
US4009029A (en) * 1973-06-05 1977-02-22 Eastman Kodak Company Cyanoethyl-containing blocked development restrainers
US4111697A (en) * 1976-03-29 1978-09-05 Agfa-Gevaert, N. V. Novel antifogging and/or stabilizing compounds for silver halide photography
US4116697A (en) * 1976-12-17 1978-09-26 E. I. Du Pont De Nemours And Company Sulfur-substituted isothioureas in silver halide emulsions
US4351896A (en) * 1980-12-12 1982-09-28 Eastman Kodak Company Mesoionic silver halide stabilizer precursor and use in a heat developable and heat stabilizable photographic silver halide material and process
US4404390A (en) * 1980-12-12 1983-09-13 Eastman Kodak Company Mesoionic 1,2,4-triazolium silver halide stabilizer precursors
US4696763A (en) * 1984-05-11 1987-09-29 Ciba-Geigy Corporation Compositions containing heterocyclic corrosion inhibitors
EP0323146A2 (en) * 1987-12-29 1989-07-05 Smithkline Beecham Corporation Dopamine-beta-hydroxylase inhibitors
EP0323146A3 (en) * 1987-12-29 1991-01-30 Smithkline Beecham Corporation Dopamine-beta-hydroxylase inhibitors
US5478721A (en) * 1995-01-31 1995-12-26 Eastman Kodak Company Photographic elements containing emulsion stabilizers
CN115477613A (en) * 2022-10-28 2022-12-16 陕西师范大学 Method for synthesizing 2-amino imidazoline compound
CN115477613B (en) * 2022-10-28 2024-04-26 陕西师范大学 Method for synthesizing 2-amino imidazoline compound

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BE555210A (en)
GB859143A (en) 1961-01-18

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