Butyramides and butyrates

#Buchanan, U.S. Pat. No. 3,530,220, issued Sept. 22, 1970, discloses a class of alkyl 1-carbamoyl-N-(substituted carbamoyloxy)thioformimidates such as methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl) which can be represented by the formula ##STR2## The compounds are useful as nematocides, acaricides and insecticides.

#Fuchs and Loux, U.S. Pat. No. 3,694,431, issued Sept. 26, 1972, discloses a method of making the compounds of U.S. Pat. No. 3,530,220 which involves nitrosating an acetoacetamide to produce a 2-hydroxyiminoacetoacetamide, e.g. ##STR3## then chlorinating, reacting with a mercaptan, and carbamylating. The 2-hydroxyiminoacetoacetamides are also starting materials for making the substituted 2-hydroxyimino-3-iminobutyramides of the present invention.

#Buchanan U.S. Pat. No. 3,557,190, issued Jan. 19, 1971, discloses a method of making the compounds of U.S. Pat. No. 3,530,220 which involves reacting a 2-hydroxyimino ester with two moles of an amine in the presence of water or an alcohol to give the corresponding amide. The amide is then reacted further to give the desired compounds, e.g., ##STR4## This amination procedure also is useful for the conversion of the 3-imino-2-hydroxyiminoacetoacetates and propionylacetates of this invention to the corresponding 2-hydroxyimino-3-iminobutyramides and 2-hydroxyimino-3-iminovaleramides.

#The procedures for synthesis of the compounds of this invention are further illustrated in the following examples wherein parts and percentages are by weight unless otherwise noted.

#To a stirred mixture of 336 parts of N,N-dimethyl-2-hydroxyiminoacetoacetamide (a compound of Formula III), 1500 parts ethanol and 203 parts of methoxyamine hydrochloride were added dropwise 210 parts of pyridine over one-half hour while maintaining the reaction mixture at 10.degree. C. by external cooling. The mixture was allowed to warm slowly to 25.degree. C. and maintained at this temperature for 18 hours. Finally, it was stirred and refluxed for one-half hour. The solvent was removed under reduced pressure (15 mm.) at 40.degree. C. bath temperature. Approximately 2000 parts of ice water were added, which caused the residue to solidify. The solid was filtered, washed twice with ice water, filtered, and dried. There was obtained 340 parts of N,N-dimethyl-2-hydroxyimino-3-methoxyiminobutyramide (a compound of Formula II), m.p. 144-147, which is of satisfactory quality for use as an intermediate. The product was, however, recrystallized from ethyl acetate, whereupon it melted at 146.degree.-148.degree..

#This procedure can be repeated by substituting comparable molar amounts of the indicated compound of Formula III in Table I below and the amine (either used as free amine or released through use of pyridine or sodium carbonate) to produce the indicated compound of Formula II. A slight-to-moderate excess of amine is desirable for best yields (one to two moles amine per mole of compound of Formula III). External heating is not always required, especially when the reaction is exothermic.