Multi-stage preparation of 2-(2-hydroxyphenyl)-2-alkoxyimino-acetami des in high yield, for use as intermediates for pesticidal pyrimidine derivatives

摘要

Preparation of 2-(2-hydroxyphenyl)-2-alkoxyimino-acetamides (I) involves reacting an alkoxyimino-acetate ester (II) (possibly without isolation) with an amine (III), where (II) has been prepared by one of four specific methods. Some oximino-acetate ester intermediates (VII) are new compounds. Preparation of alkoxyimino-acetamide derivatives of formula (I) involves reacting an alkoxyimino-acetate ester of formula (II) (possibly without isolation) with an amine of formula R6NH2 (III) (optionally in presence of a diluent), where (II) has been prepared by one of methods (A)-(D). (A) involves reacting a 2- oximino-benzofuran-3-one of formula (IV) with an alcohol of formula R7OH (V) and a carbonyl compound (which forms an oxime to bind the hydroxylammonium chloride formed in the reaction) in presence of an acid or acidic ion exchanger; and either (i) reacting the obtained phenylglyoxylic acid derivative of formula (VI) with a hydroxylammonium salt (optionally in presence of a diluent and/or an acid or acid acceptor) to give an oximino-acetate ester of formula (VII) then reacting with an alkylating agent of formula R5-X (VIII) (optionally in presence of a diluent and/or a base); or (ii) reacting (VI) with an alkoxyamine of formula R5ONH2 (IX) or its acid addition salt (optionally in presence of a diluent and/or an acid or acid acceptor). (B) involves reacting (IV) with (IX) or its acid addition salt (optionally in presence of a diluent and/or an acid or acid acceptor). (C) involves reacting (IV) with (V) in presence of an acid or acidic ion exchanger and optionally a hydroxylammonium salt to give (VII), which is converted into (II) as in (A) (i). (D) involves reacting a 2,3-bis-(oximino)-benzofuran of formula (X) with (V) in presence of an acid or acidic ion exchanger and optionally a carbonyl compound (which forms an oxime to bind the hydroxylammonium chloride formed in the reaction) [Image] [Image] [Image] R1-R4H, halo, CN or NO2; or alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl (all optionally substituted by halo); R5, R7optionally substituted alkyl; R6H or optionally substituted alkyl; X : halo or OSO2OR5. Independent claims are included for: (i) (VII) as new compounds, with the exception of (VII; R1-R4 = H; R7 = Et); (ii) the preparation of 4-(2-((alkoxyimino)(carbamoyl)-methyl)-phenox y)-pyrimidine derivatives of formula (XI) from (I) prepared the present method, by: (E) reacting with a pyrimidine derivative of formula (XII) (optionally in presence of a diluent and/or a base) then reacting the product of formula (XIII) with Z'-Q-H (XIV) (optionally in presence of a diluent, an acid acceptor and/or a catalyst); or (F) reacting with a pyrimidine derivative of formula (XV) (optionally in presence of a diluent and/or a base); (iii) the isomerization of (XI) by treatment with an acid, optionally in presence of a diluent; and (iv) the preparation of (VI) from (IV) as in step (A). [Image] [Image] Z' : optionally substituted cycloalkyl, aryl or heterocyclyl; Q : O or S; Y, T1, T2halo.