IL45113A - 6-substituted-2-benzoxyzolinone derivatives and their preparation - Google Patents

Description

derivatives and their preparation IHSTITUT NATIONAL DE LA SANTE ET DE LA RECHERCHE MEDICALE The inventors Charles LESPAGNOL Daniel BONTE 43204 This invention relates to atives and their According to the present invention there are provided compounds of formula in which represents a hydrogen an unsubstituted or halogen substituted alkyl group containing 1 to 6 carbon atoms or a phenyl or a benzyl or a thienyl R2 represents a hydrogen or an alkyl group ing 1 to 6 carbon and X represents a hydrogen atom and represents a hydroxy group or X and Y together represent an oxo Preferred conpounds are those wherein is as defined for I represents a hydrogen atom or a group and X and Y together represent an oxo According to another preferred grouping represents a hydrogen is as defined for formula I and X and Y together represent an oxo Of particular interest are those of formula I in wh ch represents a hydrogen atom or a chl benzyl or thienyl and represents a hydrogen or a The compounds of formula I may be prepared by reacting the presence of polyphosphoric of formula R is as defined with an acid of the formula is as defined or a functional deriva anhydride or to form a compound of formula I wherein X and Y together an oxo group if a of formula I wherein X represents a hydrogen atom and represents a hydroxy group is selectively reducing the said oxo group to the corresponding To prepare a compound of formula I wherein represents a hydrogen the compound of II is formylated with the aid of hexamethylene tetramine in the presence of the polyphosphoric This produces a compound of formula I which carries a group in the represents a hydrogen atom and X and Y represent n oxygen This be reduced to the corresponding alcohol if of the of in the present preparative process has been found in the presence of polyphosphoric Use of ional Crafts catalysts generally results in a total absence of reaction or in extremely The polyphospboric acid acts both as catalyst and solvent for the present The reduction of of I wherein X and Y together represent an oxo group of course be carried out without reduction of the keto group of the one This can be carried out in known for with the aid of sodium The of I are valuable in the chemical particularly in pharmaceutical for the preparation of compounds are difficult to prepare by conventional For example the compounds of the invention may be used to prepare nones with other substituents in the in particular benzoxaaolinones In addition the of I X and Y together represent an oxo group may by alkaline hydrolysis be converted to which themselves are useful These are described in our French Patent Publication The invention is further illustrated in the following EXAMPLE 1 0 g Acetic acid are added slowly and with stirring to a solution of g benzoxazolinone in polyphosphoric acid The mixture is progressively heated to and kept at this temperature for 2 After the reaction mixture is poured into iced water and stirred The precipitate obtained is extracted and recrystallised from ethyl alcohol Melting EXAMPLE 5 31 0 obtained according to Example 1 are dissolved in 50 ml of a 3 aqueous sodium hydroxide There is added slowly and with stirring 60 g 015 of sodium Stirring is continued for 3 hours and on the mixture is acidified with hydrochloric The precipitate formed extracted and recrystallised from Melting EXAMPLE 3 g 0 Hexamethylenetetramine are added to a solution of g 0 linone in 100 g polyphosphoric The mixture is heated to and stirred for 10 at this It is cooled rapidly and the reaction mixture poured into iced water with vigorous The precipitate obtained is washed with water and The mother liquors are treated several times with The combined ethereal solutions are washed with dried over sodium sulphate and the ether is evaporated A second fraction of the product is thus recovered and this combined with the Recrystallisation from ethyl alcohol is carried to Melting In the following Table compounds according to the invention are Compounds 1 to 12 were prepared by the method of Example compounds 13 to 16 by the method of Example 2 and compounds 17 and l8 by the method of Example Compound X Y Melting Point ion solvent 1 1 0 H 228 Alcohol 2 0 H 205 Alcohol 3 0 H Benzene 0 H 17 Benzene 5 0 II Alcohol 6 0 H 253 Alcohol 95 0 Alcohol 8 0 Alcohol 95 9 0 Alcohol 95 10 0 Benzene 11 0 179 Alcohol 95 12 0 158 Alcohol TABLE Compound X Y Rl Melting Recrystall Point ion solvent 13 K OK H Water H OH H 156 Wa er 15 H OH H 159 Alcohol 16 H OH H 179 Alcohol 17 3 0 H Alcohol 95 18 0 H H 190 Water insufficientOCRQuality

Claims (1)

1. CLAIMS in wh represents a hydrogen an unsubstituted Rl or halogen substituted alkyl group containing 1 to 6 carbon atoms or a phenyl or a benzyl or a thienyl represents a hydrogen atom or an alkyl group aining 1 to carbon and represents a hydrogen and Y represents a hydroxy or and Y together represent an oxo Compound according to 1 in which represents a hydrogen or a methyl group Y together represent an oxo according to 1 in which represents a hydrogen and and represent an oxo Co pound according claim 1 in which represents a chloro eth benzyl or thienyl and represents a hydrogen or methyl Any one of the numbered 2 to to 16 and 18 specifically identified Process for preparing a according to any one of the preceding which process reacting in the presence of polyphosphoric acid a of the is as defined in claim with an acid of formula is as defined in claim or a functional derivative thereof to forra compound of formula I wherein X and Y together represent an oxo group if of fornula I wherein X represents hydrogen atom and Y represents a hydroxy group is selectively reducing the said oxo group to the corresponding Process according to claim to prepare a compound wherein represents a hydrogen wherein the compound of formula II is the aid of te Process for preparing a of formula X as defined in 1 substantially as described reference to any oae of the Compounds of formula as defined in claim 1 whenever by the process in any one of f to insufficientOCRQuality