Verfahren zur Herstellung von Estern einiger Saeuren des Phosphors

摘要

1,051,965. Esters of phosphorus acids. BOEHRINGER INGELHEIM G.m.b.H. Feb. 17, 1965 [Feb. 27, 1964; June 9, 1964], No. 6873/65. Heading C2C. Compounds of the general formula where R is an alkyl group having 1-4 carbon atoms; R1 is an alkyl group which may be substituted by at least one halogen atom or an alkoxy carbonyl group and/or be interrupted by an oxygen or sulphur atom, an alkenyl or alkynyl group, a substituted or unsubstituted aralkyl group in which an oxygen or sulphur atom may be present between the aliphatic and aromatic moieties or may interrupt the aliphatic moiety, or a substituted or unsubstituted aryl group; and R2 is a hydrogen atom, a substituted or unsubstituted alkyl, aryl or aralkyl group, or a group OR3 where R3 is an alkyl or alkenyl which may have at least one halogen atom, alkoxycarbonyl and/or carbamoyl group as substituent and/or be interrupted by an oxygen or sulphur atom, or a substituted or unsubstituted aralkyl or aryl group; are prepared by reacting a salt of the formula in the presence of a solvent or diluent with an orthoformate of the formula where Kt+ is a cation, and Hal is a halogen atom. The cation may be an alkali metal, ammonium, or the ion of an organic amine, sodium and potassium being preferred. The solvent may be benzene or a lower aliphatic ketone such as acetone, methylethylketone, or methyl isobutylketone, and the reaction is preferably effected at elevated temperatures, e.g. at the reflux temperature of the reaction mixture. Several examples are given and the specified products include the following compounds: methyl- (and ethyl-) 2,2-dichlorovinyl-3-alkyl. thio - n - propyl - phosphates; 3 - alkylthion-propyl- (and bromoethyl- and ethoxyethyl-) methyl - 1 - methoxycarbonyl - 1 - propen - 2- ylphosphates; methyl- (and ethyl-) 2,2-dichlorovinylbromoethyl- (and ethoxyethyl-) phosphates; methyl- 2-bromoethylphosphite; and the invention also includes such compounds per se.