Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
  • C07D213/72—Nitrogen atoms
  • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
  • C07D333/30—Hetero atoms other than halogen
  • C07D333/32—Oxygen 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups

Definitions

• Beta-keto amides especially those belonging to the aromatic series, are valuable and important chemical intermediates and are extensively used in the dying and related arts. These compounds are particularly useful in the realm of color photography where they are employed as couplers for providing yellow dye images.
• a coupler or color forming component reacts with the oxidation product of the developing agent. It is the common practice to employ a phenolic or naphthol compound for producing a cyan image or the red aspects of the subject; a pyrazolone coupler to form a magenta image, or green aspects, and a beta-keto amide to reproduce the yellow image or blue aspects.
• the beta-keto ester coupling component is prepared by reacting an aroylacetic ester with a primary aromatic amine such as aniline, whereby alcohol is eliminated with concomitant formation of the beta-keto amide.
• This reaction which constitutes the only general method for arriving at beta-keto amide couplers, is a reliable reaction and normally provides good yields. Nevertheless, it suffers from one serious drawback.
• the requisite aroylbenzylacetic ester starting material is difiicult to obtain except for a few relatively simple derivatives.
• beta-keto amides can readily be produced by reacting a methylarylketone with an arylisocyanate or the urethane derivatives thereof in the presence of a strongly basic condensing agent, a reaction which yields directly the basic salt of the beta-keto amide. Acidification of the coupler salt gives the free beta-keto amide.
• beta-keto amides prepared in accordance with my invention can be depicted formulistically as follows:
• R and R each represents an aromatic nucleus such as phenyl, cyanophenyl, aminophenyl, halophenyl, e.g., chlorophenyl, dichlorophenyl, trichlorophenyl, fluorophenyl, bromophenyl, etc., hydroxyphenyl, alkoxyphenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, hexoxyphenyl, decoxyphenyl, heptoxyphenyl, decoxyphenyl, undecoxyphenyl, pentadecoxyphenyl, heptodecoxyphenyl, etc., alkylphenyl, e.g., methylphenyl, ethylphenyl, propylphenyl, butylphenyl, amylphenyl, heptylphenyl, octylphenyl, undecylphenyl, methyl
• Beta-keto amide couplers falling within the ambit of formula can be illustrated as follows:
• R has the significance as defined in Formula I.
• exemplary methyl ketones falling within the scope of Formula I include the following:
• amide portion of the couplers described herein can be supplied by either a urethane or an isocyanate. Although both of these components react with about equal facility, the urethaues are preferred because they are more readily procurable. ing formulae:
• R represents a lower alkyl group, i.e., methyl, ethyl, propyl, etc.
• Typical structures contemplated within the confines of Formulae IIIa and Hlb can be depicted as follows:
• 1 prefer to add the basic condensing agent to the isocyanate or urethane to form the above-mentioned adduct, after which the ketone is then introduced and forms the salt of the beta-keto amide. Acidificaton of the reaction mixture liberates the free or acid form of the beta-keto amides which can then be readily purified by the usual techniques.
• the solvent medium for carrying out these reactions is desirably an inert solvent such as the aromatic hydrocarbons, i.e., benzene, toluene, Xylene, mesitylene, etc.
• an inert solvent such as the aromatic hydrocarbons, i.e., benzene, toluene, Xylene, mesitylene, etc.
• Chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene are useful, especially if it is desired to run the reaction at a higher temperature, a condition which is made possible by the higher boiling points of these chlorinated solvents.
• Other inert media include tertiary heterocyclic bases such as pyridine, quinoline, and other tertiary amines exemplified by dimethyl aniline, diethyl aniline, dipropyl aniline and the like.
• the choice of the solvent is mainly determined by the reaction conditions such as temperature and solvent properties needed to effect dissolution of the reacting components. It is deemed to be evident that the choice of the solvent is a matter which falls within the routine knowledge of the skilled artisan in the organic chemical field.
• the product was purified by crystallization from aqueous methanol.
• The. melting point of the purified product was 105107 C. (Mixed MP. with an authentic sample of benzoyl acetanilide was 106108 C.
• the infrared spectra of the two samples were identical.
• EXAMPLE 7 2- (4-Diethylaminobenz0yl)Acetanilide
• equal molecular proportions of paradiethylamino acetophenone and phenyl urethane were reacted under conditions as set forth in the first example.
• the yield of beta-keto ester amide corresponding to the above formula approximated the yield as obtained in the first example.
• EXAMPLE 12 4 -F luoro-Z- -M ethoxy-Z-T heonyl Acezanilide S-methoxy methyl-Z-theonyl ketone and parafluorophenyl urethane were combined in equal molecular portions following the procedure enunciated in Example 1. In general, the results and yield approximately those of the first example.
• R and R are each selected from the class consisting of an aromatic ring, thiazolyl, methylthiazolyl, thienyl, benzothiazolyl, pyridyl, furyl, quinolyl and quinoxalinyl, which comprises heating in a substantially anhydrous inert solvent in the presence of a highly basic condensing agent containing an alkali metal atom a methyl aryl ketone of the following formula:
• R has the values as above designated with a compound selected from the class represented by the following formulae:
• R has the values as above designated and R represents a lower alkyl group, whereby is formed a complex of the basic condensing agent with the beta-keto amide, acidifying the complex to produce the free betaketo amide.
• R has the values as above designated and R represents a lower alkyl group and treating the resultant 15 16 adduct which contains an alkali metal atom with amethyl 9.
• solvent is pyridine.
• a process according to claim 6 wherein the basic condensing agent is an alkali metal alkoxide. 0 5 11.
• the heatwherein R has the values as above designated, whereby ing i i d out t steam bmh temperature is formed a complex of the basic condensing agent with the beta-keto amide, and acidifying the complex to pro- R fer n s Cited in the file of this patent prise the free beta'keto'amlde- Comanducci et al.: Chemical Abstracts, vol. 16, page 7.
• R and R 10 3476 (1922) are aromatlc- Kocwa: Chemical Abstracts, vol. 31, pages 18034 8.
• a process according to claim 6 wherem the inert (1937) solvent is Xylene.

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Cited By (2)

• 0
  • BE BE616867D patent/BE616867A/xx unknown
• 1961
  • 1961-05-02 US US107035A patent/US3130228A/en not_active Expired - Lifetime
• 1962
  • 1962-03-28 GB GB11863/62A patent/GB954269A/en not_active Expired
  • 1962-05-01 CH CH519962A patent/CH401026A/de unknown

Non-Patent Citations (1)

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