New phosphorylated thiophene compounds, processes for their preparation and pesticidal compositions containing them

摘要

1511413 Phosphorus esters containing a substituted thiophene group ROUSSEL-UCLAF 13 Feb 1976 [14 Feb 1975] 05698/76 Headings C2P and C2C The invention comprises compounds (I) of the formula wherein R 1 is C 1 -C 4 alkyl, R 2 is C 1- C 4 alkyl or -alkoxy, or a radical -NRSP1/SPRSP11/SP wherein RSP1/SP and RSP11/SP are H or C 1 -C 4 alkyl, R 3 is CN, -COOC 1 -C 4 alkyl, or -COZ where Z is C 1 -C 4 alkyl or phenyl, R 4 is C 1 -C 6 alkyl, -alkoxy or -alkythio, phenyl, N-morpholinyl, N-piperidinyl or -COOC 1 -C 4 alkyl, and X is O or S. They may be obtained by reacting in compound (II) with ClP(X)(OR 1 )R 2 preferably in the presence of a basic agent. The compounds (I) have insecticidal, acaricidal and nematocidal properties and may be used as active ingredients in conventional pesticidal compositions. Compounds (II) of the above formula in which R 3 is cyano and R 4 is methoxy, N- morpholino, ethylthio, n-butoxy and n-propyl respectively are stated to be novel and are obtained by reacting a compound (IV) of the formula wherein R 4 SP1/SP corresponds to the specified R 4 group and alk is an alkyl radical with chloroacetonitrile. The compounds (IV) in which R 4 SP1/SP is methoxy and n-butoxy respectively are also stated to be novel and are prepared by reacting 0-methyl- or 0-n-butyl-2-ethoxycarbonyl imidoacetate hydrochloride respectively with H 2 S. Examples are given for the production of the said novel compounds II and IV. The imidoacetate hydrochlorides are also stated to be novel and are prepared in examples by reacting ethyl cyanacetate with methanol or n-butanol respectively in the presence of HCl gas. Ethyl 3-thioxohexanoate is obtained by bubbling H 2 S into ethyl 3-oxo-hexanoate in ethanol saturated with HCl gas at - 10‹ C. and is converted to 2 - cyano - 3 - hydroxy - 5 - propylthiophene by reaction with chloroacetonitrile as above.