Patent GB-1287899-A (GB)
IPC: A01N47/18
Filed: 1969-09-04
Abstract: 1287899 1,2,4-Triazole derivatives ROHM & HAAS CO 4 Sept 1969 [4 Sept 1968 3 July 1969] 43799/69 Heading C2C Novel pesticidal compounds have Formula XII, XIII or XIV below, or are a tautomer or tautomer derivative of such compounds in which the tautomer or tautomer derivative is of Formula III, V or VA given hereinbelow, or are acid salts of any such compounds wherein A is (a) hydrogen, (b) C 1 -C 5  alkyl or C 1 -C 5  alkyl substituted by (1) halogen, C 1 -C 5  alkoxy, cyano, hydroxy, or nitro; (2) aryloxy or alkoxy-, alkyl-, halo-, or nitro-substituted aryloxy; (3) aryl or alkoxy-, alkyl-, halo- or nitro-substituted aryl; or (4) benzoyl or halo-, alkoxy-, alkyl- or nitro-substituted benzoyl; (c) the group -C(X)R<SP>4</SP> wherein X is O or S and R<SP>4</SP> is aryl or C 1 -C 5  alkyl-substituted aryl, C 1 -C 5  alkoxy-substituted aryl, halo- or nitrosubstituted aryl, furyl or the group -NR<SP>5</SP>R<SP>6</SP> wherein R<SP>5</SP> and R<SP>6</SP> are hydrogen or C 1 -C 5  alkyl; (d) the group -CH 2 C(O)NR<SP>5</SP>R<SP>6</SP> wherein R<SP>5</SP> and R<SP>6</SP> are as defined above; (e) the group -CH(OH)R<SP>7</SP> wherein R<SP>7</SP> is hydrogen, C 1 -C 5  alkyl or halo-substituted C 1 -C 5  alkyl; (f) the group wherein C and D each represent hydrogen or a meta-directing group with the proviso that only one of C and D may be hydrogen; or (g) a saltforming metal; when A is hydrogen, R<SP>8</SP> is C 3 -C 18  alkyl which may be substituted with one or more halo, C 1 -C 5  alkoxy, hydroxy or nitro groups; or C 3 -C 8  cycloalkyl which may be substituted with one or more halo, hydroxy or nitro groups; when A is methyl, R<SP>8</SP> is C 3 -C 18  alkyl which may be substituted with one or more halo, C 1 -C 5  alkoxy, hydroxy or nitro groups; aralkyl of up to 10 carbon atoms; or aralkyl of up to 10 carbon atoms in which the aryl group is substituted with C 1 -C 5  alkyl, halo or nitro groups; when A is carbamoylmethyl, benzyl, nitrobenzyl or sodium, R<SP>8</SP> is C 1 -C 18  alkyl which may be substituted with one or more halo, C 1 -C 5  alkoxy, hydroxy or nitro groups; aralkyl of up to 10 carbon atoms; or aralkyl of up to 10 carbon atoms in which the aryl group is substituted with C 1 -C 5  alkyl, halo or nitro groups; when A is all other values, R<SP>8</SP> is C 1 - C 18  alkyl which may be substituted with one or more halo, C 1 -C 5  alkoxy, hydroxy or nitro groups; C 3 -C 8  cycloalkyl which may be substituted with one or more halo, hydroxy or nitro groups; aralkyl of up to 10 carbon atoms; aralkyl of up to 10 carbon atoms substituted in the aryl group with C 1 -C 8  alkyl, halo or nitro groups; aryl; or C 1 -C 5  alkyl-, halo- or nitrosubstituted aryl; and R<SP>9</SP> is hydrogen; C 1 -C 18  alkyl which may be substituted with one or more halo, C 1 -C 5  alkoxy, hydroxy or nitro groups; furyl; or the group -COOB wherein B is hydrogen, C 1 -C 12  alkyl, ammonium, ammonium monosubstituted with C 1 -C 5  alkyl or C 1 -C 5  hydroxyalkyl, ammonium disubstituted with C 1 -C 5  alkyl or C 1 -C 5  hydroxyalkyl, ammonium trisubstituted with C 1 -C 5  alkyl or C 1 -C 5  hydroxyalkyl, quaternary ammonium or a salt-forming metal; R<SP>10</SP> is C 3 -C 18  alkyl exclusive of the n-butyl group; and R<SP>11</SP> is C 2 -C 18  alkyl which may be substituted with one or more halo, alkoxy, hydroxy, or nitro groups, or C 3 -C 8  cycloalkyl, exclusive of unsubstituted cyclohexyl, but which may be substituted with one or more halo, hydroxy or nitro groups. Preparative methods include: (1) for compounds of Formula XIII, the reaction of N,N-dimethylformamide or diformhydrazide with R<SP>10</SP>NH 2  or the oxidative removal of SH from 3-mercaptotriazoles; (2) alkaline cyclization of R<SP>9</SP>CONHNHCSNHR<SP>8</SP>; (3) reaction of R<SP>8</SP>NHCSNHNH 2  with R<SP>9</SP>COOEt or HOCOOEt in the presence of an alkali metal alkoxide; (4) decarboxylation of 1,2,4-triazoles in which R<SP>9</SP> is COOH; (5) conversion of compounds in which A is H to compounds in which A has other values, e.g. by reaction with A-hal, R<SP>5</SP>NCO, R<SP>5</SP>NCS (giving A as -CONHR<SP>5</SP> or -CSNHR<SP>5</SP>) or an olefinic nitrile (where A is cyanoalkyl), the last process tending to give isomers of Formula V; (6) standard methods of salt formation. Intermediates prepared are from 4-n-butylthio-semicarbazide and ethyl formate; by reaction of 4-cyclohexylthiosemicarbazide and formic acid; 1-(2-furoyl)-4-methylthiosemicarbazide from 4-methylthiosemicarbazide and furoyl chloride; and from diethyl oxalate, hydrazine hydrate and n-butyl isothiocyanate.