Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/18—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/20—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/20—Oxygen atoms
  • C07D215/24—Oxygen atoms attached in position 8
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/36—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/38—Nitrogen atoms

Definitions

• the present invention relates to a process for the preparation of quinoline-5,8-diones which find application as intermediates, in particular in the pharmaceutical industry.
• Bracher Heterocycles, 29, 2093, 1989
• This process requires a double functionalization of the quinoline nucleus and therefore uses raw materials that are not very accessible and expensive.
• S. Ghosh J. Fluorine Chem., 1994; 67: 53-56 describes quinoline-5-8diones derivatives obtained by cycloaddition between p-benzoquinone and a substituted diene.
• 4-chloroquinoline-5,8-dione is described as an intermediate for the synthesis of more complex tri or tetracyclic compounds (M. Croisy-Delsey et al., J. Heterocyclic Chem. 1993; 30: 55-60), while the 2-methoxy-quinoline-5,8-dione is a presented as a secondary product of N-alkylation of 2,5,8 (1 / - /) - quinolinet one (C. Avendano et al. Synthesis 1991; 727- 730).
• 4-hydroxy-5,8-quinoline-quinone can be synthesized from 2,5-dimethoxy aniline and the ester of methyl acrylic acid (P. Withopf et al.
• Quinoline-5.8 dione and 2-chloro-4-methyl-quinoline-5.8-dione are the starting materials used for the synthesis of azaanthraquinone derivatives (KT Potts et al., J. Org. Chem ., 1986: 2011 -2021).
• Antimalarial agents derived from 6-amino-5,8-dimethoxyquinolines are prepared from 2-trifluoro-4-methyl or from 2-4 dimethyl quinoline-5,8-dione (C. Temple et al., J. Med Chem., 1974; 17 (6): 615-619).
• EP 0433 679 describes quinoline-5,8-diones derivatives as inhibitors of the Maillard reaction in the organism, the latter being responsible (by denaturation of proteins by sugars) for several consequences of the diabetic disease (neuropathies, retinopathies ).
• the subject of the present invention is a process for the preparation of quinoline-5,8-diones of formula:
• Ri, R 2 and R 3 are chosen from hydrogen, a halogen atom, a CC 6 alkyl group , -CHO, -OH, -OR, -COOH, -CN, -C0 2 R, -CONHR, -CONRR'-, -NH 2 , -NHCOR, -CH 2 N-COOR, CH 2 -N-COOR, morpholino and
• R and R ' being chosen from dC 6 alkyl groups and Ar being a C 6 -C ⁇ 4 aryl group, in which one oxidizes with oxygen under the action of actinic radiation in solution in an organic solvent and in the presence of a catalytic amount of a sensitizer, an 8-hydroxyquinoline of formula:
• the oxidation reaction with oxygen is carried out in an organic solvent in which the starting 8-hydroxyquinoline of formula II is soluble.
• the solvent is advantageously chosen in such a way that the sensitizer is also soluble therein.
• the sensitizer can in particular be tetraphenylporphine (or TPP), in which case the solvent can be in particular dichloromethane.
• DCN dicyanonaphthalene
• DCA dicyanoanthracene
• DCB dicyano-benzene
• the reaction is advantageously carried out near ambient temperature (15 to 25 ° C) under irradiation, with visible light under oxygen bubbling, for a period which can be from 2 to 8 hours.
• the hydroperoxide formed of formula III decomposes spontaneously with stirring, in particular in the presence of Na 2 S0 4 .
• a subject of the present invention is also the quinoline-5,8-diones of formula:
• Ri, R 2 and R 3 are chosen from hydrogen, a halogen atom, a d-Ce alkyl group, -CHO, -OH, -OR, -COOH, -CN, -C0 2 R, -CONHR , - CONRR'-, -NH 2 , -NHCOR, -CH 2 N-COOR, CH 2 -N-COOR, morpholino and II
• R and R ′ being chosen from CC 6 alkyl groups and Ar being a C 6 -Cu aryl group, with the exception of the compounds in which:
• Ri H
• R2 H
• R 3 is chosen from H, CH 3 , CN and CHO.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Quinoline Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Steroid Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1999
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• 2000
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