Patent GB-1334400-A (GB)
Title: Phosphourus-containing derivatives of acetyl hydrazides and their use as pesticides
IPC: C07F9/165
Filed: 1971-04-23
Abstract: 1334400 Phosphorus-containing acetyl hydrazides; intermediates therefor ESSO RESEARCH & ENG CO 23 April 1971 [24 April 1970] 11042/71 Headings C2P and C2C The invention comprises compounds of Formula I where each of R and R 1  is C 1-6  alkyl, alkoxy or alkylthio, C 2-6  alkoxyalkyl, or phenyl, phenoxy or phenylthio optionally substituted by halogen, nitro or C 1-6  alkyl, R 2 , R 3  and R 4  are hydrogen, C 1-6  alkyl optionally substituted by halogen, C 1-6  alkoxy, C 1-6  alkylthio, C 2-6  alkylthioalkyl, alkoxyalkyl or mono- or dialkylamino alkyl, or phenyl optionally substituted by halogen, nitro or C 1-6  alkyl, X and X<SP>1</SP> are oxygen or sulphur, n is 1 to 3, R 5  and R 6  are optionally substituted aryl or heteroaryl or are groups of formula or -Y-A, Z is H, CN, COOR 2 , CONR 2 (R 3 ), NO 2 , SO 2 NR 2 (R 3 ), trihaloalkyl or -C(O)R 2 , L is O, S, SO, SO 2 , NR 2 , -C(O)-, -C(S)- or >C=NR 2 , Y is -C(O)-, -C(S)-, SO or SO 2 , A is OR 2 , SR 2  or NR 2 (R 3 ) and a is 1 to 6, and when n is greater than 1 and/or when in R 5  and R 6  a is greater than 1, the CR 2 (R 3 ) groupings present in the chains so formed may be the same or different, provided that when R 5  is the same as R 2 , R 6  cannot be R 2  except when R 5  or R 6  is aryl or heteroaryl and that R 5  and R 6  may not simultaneously be alkyl. The compounds of Formula I may be prepared according to the reaction scheme: where M is potassium, sodium, triethylammonium or ammonium, or by a reaction exemplified by the reaction scheme: Starting materials are prepared as follows: 1 - methyl - 1 - (2 - cyanoethyl) - 2 - acryloylhydrazide is prepared by reacting acryloyl chloride with 1-methyl-1-(2-cyanoethyl) hydrazine; 1 - methyl - 1 - (2 - cyanoethyl)-2-(2- bromo-propionyl) hydrazide is prepared by reacting 2 - bromopropionylbromide with 1-methyl- 1 - (2 - cyanoethyl) hydrazine; 1 - R 5  - 1 - R 6 - 2-chloroacetylhydrazides are prepared by reacting chloroacetic anhydride or chloroacetyl chloride with the corresponding hydrazine; 1-methyl-1- (2 - cyanoethyl) - 2 - (2 - ethylthioacetyl) hydrazide is prepared by reacting ethyl mercaptan with 1 - methyl - 1 - (2 - cyanoethyl) - 2 - (2 - chloroacetyl) hydrazide; 1 - methyl - 1 - (2 - cyanopropyl or 2-cyanoethyl) hydrazine is prepared by reacting methylhydrazine with acrylonitrile or methacrylonitrile; 1 - methyl - 1 - (6 - chloro - 2- pyridyl) hydrazine is prepared by reacting methyl hydrazine with 2,6-dichloropyridine; 1-methyl- 1 - cyanomethyl hydrazine is prepared by reacting methyl hydrazine with cyanomethyl benzene sulphonate; 1 - methyl - 1 - (2 - ethoxyethyl) hydrazine is prepared by reacting methyl hydrazine with 2-chloroethyl ethyl ether; 1-methyl- 1 - (carbomethoxy or carboethylthio) hydrazine is prepared by reacting methyl hydrazine with methyl chloroformate or ethyl chlorothioformate; 2 - methyl - 4 - (phenyl or methyl) semicarbazide is prepared by reacting phenyl or methyl isocyanate with methyl hydrazine. The compounds of Formula I have insecticidal and miticidal properties, and may be used as the active ingredients in conventional pesticidal compositions.