Insecticidal hydrazine derivatives

BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to hyrazine derivatives represented by the following general formula (I) and agricultural and horticultural insecticides: ##STR2## wherein Ar.sup.1 and Ar.sup.2, which may be the same or different, are unsubstituted phenyl groups; substituted phenyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; unsubstituted 5- or 6-membered heteroaryl groups having 1 to 3 heteroatoms which may be the same or different and are selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom; or substituted 5- or 6-membered heteroaryl groups which are the same as the above unsubstituted 5- or 6-membered heteroaryl groups, except for having as the substituent(s) one or more halogen atoms or (C.sub.1-6)alkyl groups, which may be the same or different, R.sup.1 is a hydrogen atom, a (C.sub.1-6)alkyl group, a (C.sub.2-6)alkenyl group or a (C.sub.2-6)alkynyl group, A is ##STR3## [wherein R.sup.2 is a hydrogen atom, a (C.sub.1-6)alkyl group, a (C.sub.2-6)alkenyl group or a (C.sub.2-6)alkynyl group, B is an unsubstituted and linear or branched (C.sub.1-6)alkylene group, a substituted and linear or branched (C.sub.1-6)alkylene group having one or more halogen atoms or (C.sub.1-6)alkoxy groups as the substituent(s), an unsubstituted and linear or branched (C.sub.2-6)alkenylene group, a substituted and linear or branched (C.sub.2-6)alkenylene group having one or more halogen atoms or (C.sub.1-6)alkoxy groups as the substituent(s), an unsubstituted and linear or branched (C.sub.2-6)alkynylene group, or a substituted and linear or branched (C.sub.2-6)alkynylene group having one or more halogen atoms or (C.sub.1-6)alkoxy groups as the substituent(s), the branched alkylene, alkenylene or alkynylene group being able to form a ring having 3 to 7 carbon atoms by bonding of substituents on the same carbon atom to each other, n is zero or 1, Q is a cyano group; a nitro group; a (C.sub.2-6)alkenyl group; a (C.sub.2-6)alkynyl group; an unsubstituted phenyl(C.sub.2-6)alkenyl group; a substituted phenyl(C.sub.2-6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; an unsubstituted phenyl(C.sub.2-6)alkynyl group; a substituted phenyl(C.sub.2-6)alkynyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; a (C.sub.2-6)alkynyl(C.sub.2-6)alkenyl group; a (C.sub.2-6)alkenyl(C.sub.2-6)alkynyl group;
--OR.sup.3
(wherein R.sup.3 is a hydrogen atom; a (C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkyl group; a (C.sub.1-6)alkoxy(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylthio(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylsulfinyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylsulfonyl(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkylthio(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkylsulfinyl(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkylsulfonyl(C.sub.1-6)alkyl group; a cyano(C.sub.1-6)alkyl group; a (C.sub.3-6)cycloalkyl group; a (C.sub.3-6)cycloalkyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkoxycarbonyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylcarbonyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylcarbonyl group; an unsubstituted amino(C.sub.1-6)alkyl group; a substituted amino(C.sub.1-6)alkyl group having one or two substituents which may be the same or different and are selected from the group consisting of (C.sub.1-6)alkyl groups and (C.sub.1-6)alkylcarbonyl groups; an unsubstituted carbamoyl(C.sub.1-6)alkyl group; a substituted carbamoyl(C.sub.1-6)alkyl group having one or two substituents which may be the same or different and are selected from (C.sub.1-6)alkyl groups; an unsubstituted phenyl group; a substituted phenyl group having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; an unsubstituted phenyl(C.sub.1-6)alkyl group; a substituted phenyl(C.sub.1-6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; an unsubstituted phenyl(C.sub.2-6)alkenyl group; a substituted phenyl(C.sub.2-6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; an unsubstituted phenyl(C.sub.2-6)alkynyl group; a substituted phenyl(C.sub.2-6)alkynyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; a 5- or 6-membered heteroaryl group having 1 to 3 heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom; or a 5- or 6-membered heteroaryl(C.sub.1-6)alkyl group having 1 to 3 heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom); ##STR4## (wherein R.sup.3 is as defined above, and m is zero, 1 or 2);
--COOR.sup.4
(wherein R.sup.4 is a hydrogen atom, a (C.sub.1-6)alkyl group, a halo(C.sub.1-6)alkyl group, a (C.sub.2-6)alkenyl group, a halo(C.sub.2-6)alkenyl group, a (C.sub.2-6)alkynyl group or a halo(C.sub.2-6)alkynyl group); ##STR5## (wherein R.sup.4 is as defined above);
--CON(R.sup.5)R.sup.6
(wherein R.sup.5 is a hydrogen atom; a (C.sub.1-6)alkyl group; a (C.sub.2-6)alkenyl group; a (C.sub.2-6)alkynyl group; an unsubstituted phenyl group; or a substituted phenyl group having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups, and R.sup.6 is a hydrogen atom; a (C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkyl group; a (C.sub.2-6)alkenyl group; a (C.sub.2-6)alkynyl group; a (C.sub.1-6)alkoxy(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkoxy(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylthio(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkylthio(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylsulfinyl(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkylsulfinyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylsulfonyl(C.sub.1-6)alkyl group; a halo(C.sub.1-6)alkylsulfonyl(C.sub.1-6)alkyl group; a cyano(C.sub.1-6)alkyl group; a hydroxy(C.sub.1-6)alkyl group; a (C.sub.3-6)cycloalkyl group; a (C.sub.3-6)cycloalkyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkoxycarbonyl(C.sub.1-6)alkyl group; a (C.sub.1-6)alkylcarbonyl(C.sub.1-6)alkyl group; a carbamoyl(C.sub.1-6)alkyl group; a substituted carbamoylalkyl group having one or two substituents which may be the same or different and are selected from (C.sub.1-6)alkyl groups; an unsubstituted amino(C.sub.1-6)alkyl group; a substituted amino(C.sub.1-6)alkyl group having one or two substituents which may be the same or different and are selected from the group consisting of (C.sub.1-6)alkyl groups and (C.sub.1-6)alkylcarbonyl groups; or a 5- or 6-membered heteroaryl(C.sub.1-6)alkyl group having 1 to 3 heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, R.sup.5 and R.sup.6 being able to be taken together to represent a (C.sub.4-6)alkylene group which may contain, between adjacent carbon atoms of the carbon chain, --O--, --(SO).sub.m -- (wherein m is as defined above), or --N(R.sup.7)-- (wherein R.sup.7 has the meaning described below), and said alkylene group being able to have one or more substituents which may be the same or different and are selected from the group consisting of (C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxycarbonyl groups and phenyl group);
--SO.sub.2 N(R.sup.5)(R.sup.6)
(wherein R.sup.5 and R.sup.6 are as defined above);
--N(R.sup.7)R.sup.8
(wherein R.sup.7 and R.sup.8, which may be the same or different, are hydrogen atoms; formyl groups; cyano groups; (C.sub.1-6)alkyl groups; (C.sub.2-6)alkenyl groups; (C.sub.2-6)alkynyl groups; (C.sub.1-6)alkylcarbonyl groups; halo(C.sub.1-6)alkylcarbonyl groups; (C.sub.1-6)alkoxycarbonyl groups; halo(C.sub.1-6)alkoxycarbonyl groups; (C.sub.3-6)cycloalkylcarbonyl group; phenoxycarbonyl groups; (C.sub.1-6)alkylsulfonyl groups; unsubstituted carbamoyl groups; substituted carbamoyl groups having as the substituent(s) one or two (C.sub.1-6)alkyl groups which may be the same or different; unsubstituted carbamoyl(C.sub.1-6)alkyl groups; substituted carbamoyl(C.sub.1-6)alkyl groups having as the substituent(s) one or two (C.sub.1-6)alkyl groups which may be the same or different; unsubstituted thiocarbamoyl groups; substituted thiocarbamoyl groups having as the substituent(s) one or two (C.sub.1-6)alkyl groups which may be the same or different; unsubstituted sulfamoyl groups; substituted sulfamoyl groups having as the substituent(s) one or two (C.sub.1-6)alkyl groups which may be the same or different; unsubstituted (C.sub.1-6)alkoxycarboimidoyl groups; substituted (C.sub.1-6)alkoxycarboimidoyl groups having (C.sub.1-6)alkyl group as the substituent; unsubstituted (C.sub.1-6)alkylthiocarboimidoyl groups; substituted (C.sub.1-6)alkylthiocarboimidoyl groups having (C.sub.1-6)alkyl group as the substituent; unsubstituted phenyl groups; substituted phenyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; unsubstituted phenyl(C.sub.1-6)alkyl groups; substituted phenyl(C.sub.1-6)alkyl groups having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; unsubstituted phenylcarbamoyl groups; substituted phenylcarbamoyl groups having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; unsubstituted phenylcarbonyl groups; substituted phenylcarbonyl groups having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups; unsubstituted phenylsulfonyl groups; or substituted phenylsulfonyl groups having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups, halo(C.sub.1-6)alkylthio groups, (C.sub.1-6)alkylsulfinyl groups, halo(C.sub.1-6)alkylsulfinyl groups, (C.sub.1-6)alkylsulfonyl groups, halo(C.sub.1-6)alkylsulfonyl groups, (C.sub.1-6)alkoxycarbonyl groups, unsubstituted phenoxy group, substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, unsubstituted pyridyloxy group, substituted pyridyloxy groups having 1 to 4 substituents which may be the same or different and are selected from the group consisting of halogen atoms, (C.sub.1-6)alkyl groups and halo(C.sub.1-6)alkyl groups, dioxy(C.sub.1-3)alkylene groups, and dioxyhalo(C.sub.1-3)alkylene groups);
--C(R.sup.9).dbd.NOR.sup.4
(wherein R.sup.4 is as defined above, and R.sup.9 is a hydrogen atom, a (C.sub.1-6)alkyl group, a halo(C.sub.1-6)alkyl group, an unsubstituted phenyl group, or a substituted phenyl group having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups and halo(C.sub.1-6)alkylthio groups);
--C(R.sup.9).dbd.N--N(R.sup.7)(R.sup.8)
(wherein R.sup.7, R.sup.8 and R.sup.9 are as defined above); or
--O--N.dbd.C(R.sup.9)(R.sup.10)
(wherein R.sup.9 is as defined above, and R.sup.10 is a hydrogen atom, a (C.sub.1-6)alkyl group, a halo(C.sub.1-6)alkyl group, an unsubstituted phenyl group, or a substituted phenyl group having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (C.sub.1-6)alkyl groups, halo(C.sub.1-6)alkyl groups, (C.sub.1-6)alkoxy groups, halo(C.sub.1-6)alkoxy groups, (C.sub.1-6)alkylthio groups and halo(C.sub.1-6)alkylthio groups)], ##STR6## [wherein R.sup.2, B, Q and n are as defined above], ##STR7## [wherein R.sup.2, B, Q and n are as defined above], or ##STR8## [wherein R.sup.2, B, Q and n are as defined above], and W is an oxygen atom or a sulfur atom. More particularly, the hydrazine derivatives of the general formula (I) of the present invention include hydrazine derivatives represented by the following general formulas (I-1), (I-2), (I-3) and (I-4). ##STR9## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q and W are as defined above.
In the definition of the hydrazine derivatives of the general formula (I) of the present invention, the term "(C.sub.1-6)alkyl group", for example, means a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl or the like. The prefix "halo" is used for expressing that a group has as its substituent(s) one or more halogen atoms which may be the same or different and are selected from chlorine, bromine, iodine and fluorine atoms. The term "haloalkyl group" means a substituted alkyl group having as the substituent(s) one or more halogen atoms which may be the same or different and are selected from the group consisting of chlorine atom, bromine atom, iodine atom and fluorine atom. The term "heteroaryl" in "heteroaryl group" or "heteroarylalkyl group" means a 5- to 6-membered ring having 1 to 3 heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, hydrogen atom and nitrogen atom, for example, heterocyclic groups such as furyl group, thienyl group, oxazole group, thiazole group, pyrazole group, imidazole group, pyridine group, etc.
The hydrazine derivatives of the general formulas (I-1) and (I-3) of the present invention have geometrical isomers, i.e., E-form and Z-form. The present invention also includes the E-form, the Z-form, and mixtures thereof. The hydrazine derivatives of the general formulas (I-2) and (I-4) have optical isomers, i.e., R-form and S-form. The present invention also includes the R-form, the S-form, and mixtures thereof.
Of the hydrazine derivatives of the general formula (I), compounds having a preferable structure are the hydrazine derivatives of the general formula (I-1). As the substituents of the hydrazine derivatives of the general formula (I-1), Ar.sup.1 and Ar.sup.2 are preferably unsubstituted phenyl groups or substituted phenyl groups having 1 to 3 substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, alkyl groups, haloalkyl groups, alkoxy groups and haloalkoxy groups. R.sup.1 and R.sup.2, which may be the same or different, are preferably hydrogen atoms, or methyl groups. B is preferably a methylene, a ethylene or a propylene group, or n is preferably zero.
Q is preferably a substituent such as cyano group, --OR.sup.3, --S(O).sub.m R.sup.3, --COOR.sup.4, --CON(R.sup.5)(R.sup.6), or N(R.sup.7)(R.sup.8).
RELATED ART
Japanese Patent Unexamined Publication Nos. 5-4958, 5-17428, 5-32603 and 5-262712 and WO92/06076, etc. disclose hydrazines similar to those of the present inventions and discloses them as effective as insecticides.
SUMMARY OF THE INVENTION
The present inventors earnestly investigated for developing a novel agricultural and horticultural insecticide and consequently found that the hydrazine derivatives of the general formula (I) are novel compounds not concretely described in prior references and not known in any literature, and are insecticides which have an excellent insecticidal effect at a low dose and are harmless to environment, whereby the present invention has been accomplished.
The above-mentioned hydrazine of the general formula (I) of the present invention which is useful as an agricultural and horticultural insecticide can be produced, for example, by any of the following processes. ##STR10## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q and W are as defined above.
A hydrazine derivative of the general formula (I-1) can be produced by reacting a compound of the general formula (II) with a compound of the general formula (III) in the presence of an inert solvent and in the presence or absence of a catalyst.
As the inert solvent usable in this reaction, any inert solvent may be used so long as it does not markedly inhibit the progress of the reaction. There may be used, for example, alcohols such as methanol, ethanol, propanol, butanol, etc.; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc.; non-halogenated or halogenated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, etc.; nitriles such as acetonitrile, benzonitrile, etc.; acyclic or cyclic ethers such as Methyl Cellosolve, diethyl ether, diglyme, dioxane, tetrahydrofuran, etc.; carboxylic acids such as acetic acid, etc.; dimethylacetamide; dimethyl sulfoxide; and water. These inert solvents may be used singly or as a mixture thereof.
As the catalyst used in the reaction, there can be used, for example, inorganic acids such as hydrochloric acid, sulfuric acid, and the like; or organic acids such as p-toluenesulfonic acid and the like. As to the amount of the catalyst used, it is sufficient that the catalyst is present in the reaction system in an amount of 0.001 to 10% by weight based on the weight of the compound of the general formula (II).
Since the reaction is an equimolar reaction, it is sufficient that the reactants are used in equimolar amounts, though either of them may be used in excess.
The reaction temperature is chosen in the range of room temperature to the boiling point of the inert solvent used, and is preferably 70.degree. C. to 80.degree. C.
Although the reaction time is varied depending on the reaction temperature, the degree of the reaction, etc., it may be properly chosen in the range of several minutes to 48 hours.
After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, etc., and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.
The compound of the general formula (II) can be produced from a corresponding benzoic acid, benzaldehyde or acetophenone by a conventional process, and the compound of the general formula (III) can be produced by the following process: ##STR11## wherein Ar.sup.2, R.sup.1, R.sup.2 and W are as defined above, and V is a halogen atom or a leaving group such as (C.sub.1-6)alkoxy group, phenoxy group, p-nitrophenoxy group or imidazole group).
The compound of the general formula (III) can be produced by reacting a compound of the general formula (IX) with a hydrazine of the general formula (IV) in the presence of an inert solvent and a base. ##STR12## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q and W are as defined above, except that R.sup.1 is a hydrogen atom.
A hydrazine derivative of the general formula (I-1) can be produced by reacting a compound of the general formula (II) with a hydrazine of the structural formula (IV) in the presence of an inert solvent and in the presence or absence of a catalyst to obtain a compound of the general formula (V), and reacting the compound (V) with a compound of the general formula (VI) in the presence of an inert solvent and in the presence or absence of a catalyst after or without isolating the compound (V).
2-1. General formula (II).fwdarw.general formula (V)
As the inert solvent usable in this reaction, there can be used, for example, the inert solvents exemplified in production process 1. The kind and amount of the catalyst used in this reaction may be selected from those exemplified in production process 1.
The hydrazine of the structural formula (IV) may be used in the form of either any of various salts or an aqueous solution having a suitable concentration. As to the amount of this hydrazine used, the hydrazine can be used in an amount equimolar with or larger than the amount of the compound of the general formula (II). Preferably, the amount is properly chosen in the range of 2 to 10 moles per mole of the compound of the general formula (II).
The reaction temperature may be properly chosen in the range of room temperature to the boiling point of the inert solvent used, and is preferably 70.degree. C. to 100.degree. C.
Although the reaction time is varied depending on the degree of the reaction, the reaction temperature, etc., it may be chosen in the range of several minutes to 48 hours.
After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, or the like, and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.
The compound of the general formula (V) produced by this reaction may be subjected to the subsequent reaction either after isolation and purification by the above method, or without isolation.
2-2. General formula (V).fwdarw.general formula (I-1)
As the inert solvent usable in this reaction, there can be used, for example, the inert solvents exemplified in production process 1 except for the alcohols, the carboxylic acids and water. There can also be used esters such as ethyl acetate and the like and pyridines.
As the catalyst usable in the reaction, there can be used, for example, amines such as triethyamine. The amount of the catalyst used may be properly chosen in the range of a catalytic amount to excess moles over the compound of the general formula (V).
Since the reaction is an equimolar reaction, it is sufficient that the reactants are used in equimolar amounts, though either of them may be used in excess.
The reaction temperature may be chosen in the range of -20.degree. C. to the boiling point of the inert solvent used, and is preferably -10.degree. C. to room temperature.
Although the reaction time is varied depending on the degree of the reaction, the reaction temperature, etc., it may be chosen in the range of several minutes to 48 hours.
After completion of the reaction, the same treatment as in 2-1 is carried out, whereby the desired compound can be produced. ##STR13## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, R.sup.3, m and W are as defined above, and Hal is a halogen atom.
A hydrazine derivative of the general formula (I-1') can be produced by reacting a compound of the general formula (VII) with a compound of the general formula (VIII) in the presence of an inert solvent and a base. A hydrazine derivative of the general formula (I-1") can be produced by oxidizing the hydrazine derivative of the general formula (I-1') in the presence of an inert solvent and an oxidizing agent after or without isolating this compound.
3-1. General formula (VII).fwdarw.general formula (I-1')
As the inert solvent usable in this reaction, any inert solvent may be used so long as it does not markedly inhibit the progress of the reaction. There may be used, for example, alcohols such as methanol, ethanol, propanol, butanol, etc.; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc.; non-halogenated or halogenated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, etc.; nitriles such as acetonitrile, benzonitrile, etc.; carboxylic acids such as acetic acid, etc.; dimethylformamide; dimethylacetamide; dimethyl sulfoxide; and water. These inert solvents may be used singly or as a mixture thereof.
As the base used in the reaction, an inorganic base or an organic base may be used. As the inorganic base, there may be used, for example, hydroxides, carbonates or hydrogencarbonates of alkali metal atoms or alkaline earth metal atoms, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate, etc. As the organic base, there may be used triethylamine, pyridine, etc. The amount of the base used may be chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (VII).
Since the reaction is an equimolar reaction, it iS sufficient that the compound of the general formula (VII) and the compound of the general formula (VIII) are used in equimolar amounts, though either of them may be used in excess.
The reaction temperature is preferably chosen in the range of room temperature to the boiling point of the inert solvent used, and is more preferably a room temperature or thereabout.
Although the reaction time is varied depending on the reaction temperature, the degree of the reaction, etc., it may be properly chosen in the range of several minutes to 48 hours.
After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, or the like, and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.
3-2. General formula (I-1').fwdarw.general formula (I-1")
As the inert solvent usable in this reaction, the same inert solvent as used in 3-1 can be used and any of the alcohols or water is preferably used.
As the oxidizing agent, there can be used, for example, hydrogen peroxide, monopersulfate compounds (e.g. sodium peroxymonosulfate), benzoyl peroxide and m-chloroperbenzoic acid. Of these, monopersulfate compound or m-chloroperbenzoic acid is preferable. Although the amount of the oxidizing agent used is varied depending on the desired monooxide or dioxide compound, it is preferably chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (I-1'). Preferably, the oxidizing agent is used in excess.
The reaction temperature is preferably chosen in the range of room temperature to the boiling point of the inert solvent used, more preferably in the range of room temperature to 50.degree. C.
Although the reaction time is varied depending on the reaction temperature, the degree of the reaction, etc., it may be properly chosen in the range of several minutes to 48 hours.
After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, or the like, and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.
The compound of the general formula (VII), i.e., the starting material in the reaction can be produced according to J.O.C. 26, 5221 (1961).
Typical examples of the hydrazine derivatives of the general formula (I-1) produced by production processes 1, 2 and 3 are given in Table 1 but they are not intended in any way to limit the scope of the present invention. ##STR14##
TABLE 1__________________________________________________________________________(R.sup.1 = H, W = 0, Ph = phenyl) MeltingNo. Ar.sup.1 Ar.sup.2 R.sup.2 (B).sub.n Q point (.degree.C.)__________________________________________________________________________1 Ph 4-ClPh H CH.sub.2 OPh 1972 Ph 4-ClPh H CH.sub.2 SPh 2003 Ph 4-ClPh H CH.sub.2 SO Ph 191 (decomp.)4 Ph 4-ClPh H CH.sub.2 SO.sub.2 CH.sub.3 2325 Ph 4-ClPh H CH.sub.2 CONHPh 2186 Ph 4-BrPh H CH.sub.2 SO.sub.2 CH.sub.3 2327 Ph 4-CF.sub.3 Ph H CH.sub.2 OPh 1998 Ph 4-CF.sub.3 Ph H CH.sub.2 SPh 1979 Ph 4-CF.sub.3 Ph H CH.sub.2 SOPh 188 (decomp.)10 Ph 4-OCF.sub.3 Ph H -- CONH.sub.2 218 Z-form11 Ph 4-OCF.sub.3 Ph H -- CONH.sub.2 221 E-form12 Ph 4-OCF.sub.3 Ph H -- CONHCH.sub.3 178 Z-form13 Ph 4-OCF.sub.3 Ph H -- CONHCH.sub.3 115 E-form14 Ph 4-OCF.sub.3 Ph H -- CON(CH.sub.3).sub.2 17515 Ph 4-OCF.sub.3 Ph H -- 13116 Ph 4-OCF.sub.3 Ph H -- CONHPh-4-OCF.sub.3 19017 Ph 4-OCF.sub.3 Ph H -- ##STR15## 17518 Ph 4-OCF.sub.3 Ph H -- ##STR16## 15519 Ph 4-OCF.sub.3 Ph H -- ##STR17## Vitreous20 Ph 4-OCF.sub.3 Ph H -- ##STR18## 16121 Ph 4-OCF.sub.3 Ph H -- ##STR19## Vitreous22 Ph 4-OCF.sub.3 Ph H -- ##STR20## 18623 Ph 4-OCF.sub.3 Ph H -- CO.sub.2 CH.sub.3 13024 Ph 4-OCF.sub.3 Ph H CH.sub.2 CN 17925 Ph 4-OCF.sub.3 Ph H CH.sub.2 OCH.sub.3 13126 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh 18427 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-NO.sub.2 17228 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 190 E-form29 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 179 Z-form30 Ph 4-OCF.sub.3 Ph H CH.sub.2 SH 19131 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.3 18632 Ph 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 CH.sub.3 23233 Ph 4-OCF.sub.3 Ph H CH.sub.2 SC.sub.3 H.sub.7 -i 16334 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CCH 18435 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 12836 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCOCH.sub.3 17737 Ph 4-OCF.sub.3 Ph H CH.sub.2 SPh 19238 Ph 4-OCF.sub.3 Ph H CH.sub.2 SPh-4-Cl 19639 Ph 4-OCF.sub.3 Ph H CH.sub.2 SPh-4-NO.sub.2 18640 Ph 4-OCF.sub.3 Ph H CH.sub.2 SOPh 192 (decomp.)41 Ph 4-OCF.sub.3 Ph H CH.sub.2 SOPh-4-Cl 19042 Ph 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 Ph 21943 Ph 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 Ph-4-NO.sub.2 21844 Ph 4-OCF.sub.3 Ph H CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 20845 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHC.sub.4 H.sub.9 -t 17246 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh 270 (decomp.)47 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-Cl 24348 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-Br 27649 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-CN 18050 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-CH.sub.3 210 (decomp.)51 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4- 164 C.sub.3 H.sub.7 -i52 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-OCH.sub.3 18953 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-OCF.sub.3 18754 Ph 4-OCF.sub.3 Ph H CH.sub.2 N(CH.sub.3).sub.2 60 E-form55 Ph 4-OCF.sub.3 Ph H CH.sub.2 N(CH.sub.3).sub.2 210 Z-form56 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCHO 18157 Ph 4-OCF.sub.3 Ph H ##STR21## NHCHO 16758 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOCH.sub.3 22259 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOC.sub.3 H.sub.7 -i 20560 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCO.sub.2 C.sub.2 H.sub.5 15261 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCONHC.sub.2 H.sub.5 20162 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCON(C.sub.2 H.sub.5).sub.2 8663 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHPh 170 E-form64 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHPh 120 Z-form65 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh 19766 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-4-Cl 20267 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-2,4-Cl.sub.2 20768 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-4-NO.sub.2 23569 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-4-CN 18670 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHSO.sub.2 Ph-4-Cl 15071 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHSO.sub.2 Ph-4-CH.sub.3 15072 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CN 18173 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 OC.sub.2 H.sub.5 134.174 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHCHO 18575 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 N(CHO).sub.2 19876 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHCOCH.sub.3 21077 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHCO.sub.2 CH.sub.3 20878 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHCON(CH.sub.3).sub.2 18379 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHCOPh-4-Cl 22280 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHSO.sub.2 CH.sub.3 18881 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 NHSO.sub.2 N(CH.sub.3).sub.2 19182 Ph 4-OCF.sub.3 Ph H ##STR22## CN paste83 Ph 4-OCF.sub.3 Ph H ##STR23## NHCOPh 15084 Ph 4-OCF.sub.3 Ph H ##STR24## CN 14985 Ph 4-OCF.sub.3 Ph H ##STR25## SCH.sub.3 ##STR26##86 Ph 4-OCF.sub.3 Ph H ##STR27## SCH.sub.2 Ph ##STR28##87 Ph 4-OCF.sub.3 Ph H ##STR29## SCH.sub.2 Ph ##STR30##88 Ph 4-OCF.sub.3 Ph CH.sub.3 CH.sub.2 SO.sub.2 CH.sub.3 15789 Ph 4-OCF.sub.3 Ph CH.sub.3 ##STR31## SO.sub.2 CH.sub.3 paste90 Ph 4-SCF.sub.3 Ph H ##STR32## SCH.sub.3 paste91 2-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 145 Z-form92 2-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 127 E-form93 3-ClPh 4-OCF.sub.3 Ph H -- CO.sub.2 CH.sub.3 13494 3-ClPh 4-OCF.sub.3 Ph H -- CONH.sub.2 213 E:Z = 1:195 3-ClPh 4-OCF.sub.3 Ph H -- CONHCH.sub.3 191 Z-form96 3-ClPh 4-OCF.sub.3 Ph H -- CONHCH.sub.3 paste E-form97 3-ClPh 4-OCF.sub.3 Ph H -- CON(CH.sub.3).sub.2 13998 3-ClPh 4-OCF.sub.3 Ph H -- CON(C.sub.2 H.sub.5).sub.2 vitreous99 3-ClPh 4-OCF.sub.3 Ph H -- CONHC.sub.3 H.sub.7 -n 177 Z-form100 3-ClPh 4-OCF.sub.3 Ph H -- CONHC.sub.3 H.sub.7 -n paste E-form101 3-ClPh 4-OCF.sub.3 Ph H -- CON(C.sub.3 H.sub.7 -i).sub.2 185102 3-ClPh 4-OCF.sub.3 Ph H -- ##STR33## ##STR34##103 3-ClPh 4-OCF.sub.3 Ph H -- ##STR35## ##STR36##104 3-ClPh 4-OCF.sub.3 Ph H -- ##STR37## paste105 3-ClPh 4-OCF.sub.3 Ph H -- ##STR38## paste106 3-ClPh 4-OCF.sub.3 Ph H -- ##STR39## vitreous107 3-ClPh 4-OCF.sub.3 Ph H -- ##STR40## vitreous108 3-ClPh 4-OCF.sub.3 Ph H -- ##STR41## vitreous109 3-ClPh 4-OCF.sub.3 Ph H -- ##STR42## vitreous110 3-ClPh 4-OCF.sub.3 Ph H -- ##STR43## 204111 3-ClPh 4-OCF.sub.3 Ph H -- ##STR44## vitreous112 3-ClPh 4-OCF.sub.3 Ph H -- ##STR45## vitreous113 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-3-NO.sub.2 182114 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-NO.sub.2 120115 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 105116 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-COOCH.sub.3 220117 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-SCH.sub.3 201118 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-SOCH.sub.3 155119 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 NHCOC.sub.2 H.sub.5 192120 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 NHCOC.sub.3 H.sub.7 -n 157121 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 NHCOC.sub.3 H.sub.7 -i 203122 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 NHCOC.sub.4 H.sub.9 -t 157123 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 ##STR46## 198124 3-ClPh 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh 199125 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CN 158126 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CO.sub.2 C.sub.2 H.sub.5 111127 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 196128 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CON(CH.sub.3).sub.2 119129 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CON(C.sub.2 H.sub.5).sub.2 123130 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHC.sub.3 H.sub.7 -n 225131 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHCH.sub.2 CHCH.sub.2 215132 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHCH.sub.2 CN 230133 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHCH.sub.2 CONHCH.sub.3 225134 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHCH.sub.2 CO.sub.2 C.sub.2 H.sub.5 216135 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 ##STR47## 156136 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 ##STR48## 170137 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHCH.sub.2 Ph 223138 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 ##STR49## 215139 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 ##STR50## 156140 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 ##STR51## 168141 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.3 CN 152142 3-ClPh 4-OCF.sub.3 Ph H ##STR52## CN 57143 3-ClPh 4-OCF.sub.3 Ph H ##STR53## CONH.sub.2 218144 3-ClPh 4-OCF.sub.3 Ph H ##STR54## CONH.sub.2 66145 3-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.4 CN 169146 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh 4-NO.sub.2 180147 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 200148 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 SPh-4-NO.sub.2 190149 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 SPh-4-CH.sub.3 195150 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 SOPh-4-NO.sub.2 197151 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 SOPh-4-CH.sub.3 185152 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 Ph-4-NO.sub.2 230153 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 Ph-4-CH.sub.3 237154 4-ClPh 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh 190155 4-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 N(CH.sub.3).sub.2 125156 4-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 215157 4-ClPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.4 CN 180158 3-BrPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 209159 4-BrPh 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 210160 4-FPh 4-OCF.sub.3 Ph H -- CO.sub.2 CH.sub.3 paste Z-form161 4-FPh 4-OCF.sub.3 Ph H -- CO.sub.2 CH.sub.3 166 E-form162 4-FPh 4-OCF.sub.3 Ph H -- CONHCH.sub.3 168 Z-form163 4-FPh 4-OCF.sub.3 Ph H -- CONHCH.sub.3 vitreous E-form164 4-FPh 4-OCF.sub.3 Ph H -- CON(CH.sub.3).sub.2 152165 4-FPh 4-OCF.sub.3 Ph H -- CON(C.sub.2 H.sub.5).sub.2 vitreous166 4-FPh 4-OCF.sub.3 Ph H -- ##STR55## 154167 4-FPh 4-OCF.sub.3 Ph H -- ##STR56## 178168 4-FPh 4-OCF.sub.3 Ph H -- ##STR57## 215169 4-FPh 4-OCF.sub.3 Ph H -- ##STR58## 180170 3-NO.sub.2 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 190171 3-CH.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 160172 3-CH.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh 194173 3-CH.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 231174 4-CH.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 N(CH.sub.3).sub.2 170175 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CO.sub.2 CH.sub.3 141 Z-form176 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CO.sub.2 CH.sub.3 137 E-form177 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CHC(CH.sub.3).sub.2 131178 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CON(CH.sub.3).sub.2 vitreous179 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CONHC.sub.4 H.sub.9 -t 160 Z-form180 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CONHC.sub.4 H.sub.9 -t 169 E-form181 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CONHPh paste Z-form182 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CONHPh 140 E-form183 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR59## 148184 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR60## 102185 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR61## paste186 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR62## 98187 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR63## 107188 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR64## 157189 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CON(CH.sub.2 CN).sub.2 101190 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR65## paste191 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CONHCH.sub.2 CH.sub.2 OCH.sub.3 146 Z-form192 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- CONHCH.sub.2 CH.sub.2 OCH.sub.3 85 E-form193 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR66## 194194 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR67## 188195 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR68## 189196 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR69## paste197 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 OCH.sub.3 142198 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 165199 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SC.sub.3 H.sub.7 -i 164200 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 C.sub.3 H.sub.7 -i 224201 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SC.sub.4 H.sub.9 -t 209202 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR70## 180203 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR71## 214204 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CHCH.sub.2 131205 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SOCH.sub.2 CHCH.sub.2 188206 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CCH 155207 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CN 182208 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CH.sub.2 CN 123209 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 145210 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SOCH.sub.2 CO.sub.2 CH.sub.3 197211 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5 134212 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 133213 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SOCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 166214 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CONH.sub.2 178215 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CONHC.sub.3 H.sub.7 -i 212216 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 CONHC.sub.4 H.sub.9 -t 178217 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCH.sub.2 COCH.sub.3 164218 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SOCH.sub.2 COCH.sub.3 182219 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCOCH.sub.3 173220 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 SCN 169221 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 163222 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHC.sub.4 H.sub.9 -t 171223 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR72## 197224 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 CONHPh-4-CN 174225 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR73## 224226 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh 197227 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-2-Cl 214228 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-3-Cl 189229 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-4-Cl 207230 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-4-NO.sub.2 205231 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCO.sub.2 Ph 194232 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CN 156233 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 203234 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 COOC.sub.2 H.sub.5 153235 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CON(C.sub.2 H.sub.5).sub.2 148236 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 ##STR74## 160237 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR75## OPh-4-CN ##STR76##238 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR77## CON(C.sub.2 H.sub.5).sub.2 142239 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR78## ##STR79## vitreous240 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.3 CN 175241 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.3 CO.sub.2 C.sub.2 H.sub.5 151242 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.3 CONH.sub.2 177243 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR80## CO.sub.2 C.sub.2 H.sub.5 ##STR81##244 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR82## CO.sub.2 C.sub.2 H.sub.5 ##STR83##245 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR84## CN 153246 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR85## CONH.sub.2 165247 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR86## CO.sub.2 C.sub.2 H.sub.5 paste248 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.4 CONH.sub.2 194249 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.4 CN 169250 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.5 CN 139251 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.10 CN 100252 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H ##STR87## SCH.sub.3 142253 4-CF.sub.3 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 203254 3-OCH.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 OPh-4-CN 180255 3-OCH.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCHO 180256 3-OCH.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh 181257 3-OCH.sub.3 Ph 4-OCF.sub.3 Ph H CH.sub.2 NHCOPh-4-CH.sub.3 189258 Ph 4-ClPh H -- SCH.sub.3 114259 Ph 4-ClPh H -- SCH.sub.2 PhCO.sub.2 C.sub.4 H.sub.9 -t 150260 Ph 4-ClPh H -- SO.sub.2 CH.sub.3 191261 Ph 4-ClPh H -- SCH.sub.2 Ph-4-NO.sub.2 133262 Ph 4-ClPh H -- SOCH.sub.3 159263 Ph 4-ClPh H CH.sub.2 NO.sub.2 181264 Ph 4-OCF.sub.3 Ph H -- ##STR88## 130265 Ph 4-OCF.sub.3 Ph H -- ##STR89## ##STR90##266 Ph 4-OCF.sub.3 Ph H -- ##STR91## ##STR92##267 Ph 4-OCF.sub.3 Ph H -- ##STR93## 212268 Ph 4-OCF.sub.3 Ph H -- CHNOH 164269 Ph 4-OCF.sub.3 Ph H -- ##STR94## ##STR95##270 Ph 4-OCF.sub.3 Ph H -- ##STR96## ##STR97##271 Ph 4-OCF.sub.3 Ph H -- CHNOC.sub.3 H.sub.7 -i 150272 Ph 4-OCF.sub.3 Ph H -- CHNNHCO.sub.2 C.sub.2 H.sub.5 100273 Ph 4-OCF.sub.3 Ph H -- CHNOCH.sub.2 CCH 169 E-form274 Ph 4-OCF.sub.3 Ph H -- CHNOCH.sub.2 CCH 115 Z-form275 Ph 4-OCF.sub.3 Ph CH.sub.3 -- SCH.sub.3 paste276 Ph 4-OCF.sub.3 Ph H -- SCH.sub.3 105277 Ph 4-OCF.sub.3 Ph H -- SOCH.sub.3 136278 Ph 4-OCF.sub.3 Ph H -- SC.sub.3 H.sub.7 -i 122279 Ph 4-OCF.sub.3 Ph H -- SOC.sub.3 H.sub.7 -i paste280 Ph 4-OCF.sub.3 Ph H -- SO.sub.2 C.sub.3 H.sub.7 -i 124 (decomp.)281 Ph 4-OCF.sub.3 Ph H -- SCH.sub.2 CH.sub.2 CH.sub.2 paste282 Ph 4-OCF.sub.3 Ph H -- SCH.sub.2 CCH 85283 Ph 4-OCF.sub.3 Ph H -- SCH.sub.2 CO.sub.2 CH.sub.3 80284 Ph 4-OCF.sub.3 Ph H -- S(CH.sub.2).sub.3 COCH.sub.3 paste285 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR98## 157286 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR99## 180287 Ph 4-OCF.sub.3 Ph H CH.sub.2 ONC(CH.sub.3).sub.2 140288 Ph 4-OCF.sub.3 Ph H CH.sub.2 P(O)(OCH.sub.3).sub.2 153289 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR100## 222290 Ph 4-OCF.sub.3 Ph H CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2 210291 Ph 4-OCF.sub.3 Ph H CH.sub.2 ##STR101## 145292 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONHPh-4-OCF.sub.3 237293 Ph 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 203294 Ph 4-OCF.sub.3 Ph H CHCH CONHPh-4-OCF.sub.3 231295 3-ClPh 4-ClPh CH.sub.3 -- SPh-4-Cl 148296 3-ClPh 4-ClPh CH.sub.3 -- SPh 128297 3-ClPh 4-ClPh H (CH.sub.2).sub.2 CONH.sub.2 206298 3-ClPh 4-BrPh H (CH.sub.2).sub.2 CONH.sub.2 214299 3-ClPh 4-FPh H (CH.sub.2).sub.2 CONH.sub.2 201300 3-ClPh 3,5-Cl.sub.2 Ph H (CH.sub.2).sub.2 CONH.sub.2 193301 3-ClPh 4-CNPh H (CH.sub.2).sub.2 CONH.sub.2 219302 3-ClPh 4-NO.sub.2 Ph H (CH.sub.2).sub.2 CONH.sub.2 232303 3-ClPh 4-CF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 218304 3-ClPh 4-CF.sub.3 Ph CH.sub.3 -- SPh 130305 3-ClPh 4-OC.sub.3 H.sub.7 -i-Ph H (CH.sub.2).sub.2 CONH.sub.2 202306 3-ClPh 4-SCH.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 210307 3-ClPh 4-SCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 228308 3-ClPh 4-OCHF.sub.2 Ph H (CH.sub.2).sub.2 CONH.sub.2 210309 3-ClPh 4-OCHF.sub.2 Ph CH.sub.3 -- SPh 96310 3-ClPh 4-OCF.sub.3 Ph H -- ##STR102## paste311 3-ClPh 4-OCF.sub.3 Ph CH.sub.3 -- SPh-4-Cl 119312 3-ClPh 4-OCF.sub.3 Ph CH.sub.3 -- SPh 107313 3-ClPh 4-OCH.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 219314 3-BrPh 4-BrPh H (CH.sub.2).sub.2 CONH.sub.2 228315 3-BrPh 4-OCF.sub.3 Ph H -- ##STR103## 117316 3-BrPh 4-OCF.sub.3 Ph H -- ##STR104## 121317 3-BrPh 4-OCF.sub.3 Ph H -- ##STR105## 107318 3-BrPh 4-OCF.sub.3 Ph H -- CON(CH.sub.3).sub.2 paste319 3-BrPh 4-OCF.sub.3 Ph H -- ##STR106## paste320 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR107## 201321 3-BrPh 4-OCF.sub.3 Ph H -- ##STR108## 171322 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR109## 147323 3-BrPh 4-OCF.sub.3 Ph H -- ##STR110## paste324 3-BrPh 4-OCF.sub.3 Ph H -- ##STR111## paste325 3-FPh 4-OCF.sub.3 Ph H -- CON(CH.sub.3).sub.2 174326 3-FPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 196327 4-FPh 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 206328 3-CF.sub.3 Ph 4-BrPh H (CH.sub.2).sub.2 CONH.sub.2 208329 3-CF.sub.3 Ph 4-NO.sub.2 Ph H (CH.sub.2).sub.2 CONH.sub.2 246330 3-CF.sub.3 Ph 4-OC.sub.3 H.sub.7 -i-Ph H (CH.sub.2).sub.2 CONH.sub.2 234331 3-CF.sub.3 Ph 4-OCH.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 225332 3-CF.sub.3 Ph 4-SCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 230333 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR112## paste334 3-CF.sub.3 Ph 4-OCHF.sub.2 Ph H (CH.sub.2).sub.2 CONH.sub.2 209335 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.3 -- ##STR113## paste336 3-CF.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR114## 221337 3-CF.sub.3 Ph 4-CF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 233338 4-OCH.sub.3 Ph 4-OCF.sub.3 Ph H -- ##STR115## 150339 ##STR116## 4-OCF.sub.3 Ph H (CH.sub.2).sub.2 CONH.sub.2 230__________________________________________________________________________
Table 2 shows .sup.1 H-NMR data of compounds having physical properties expressed by the word "paste" or "vitreous" in Table 1.
TABLE 2______________________________________No. .sup.1 H--NMR [CDCl.sub.3 /TMS, .delta. value (ppm)]______________________________________19 1.70(bs, 1H), 2.65-3.85(m, 8H), 7.16-7.75(m, 10H), 8.25(bs, 1H).21 2.25-3.90(m, 8H), 3.51(s, 2H), 7.15-7.70(m, 14H), 8.22(bs, 1H), 8.32(bs, 1H).82 1.57(d, 3H), 3.89(q, 1H), 7.10-7.60(m, 9H), 8.03 (bs, 1H), 8.34(bs, 1H).86 1.19-1.48(m, 4H), 3.99(s, 2H), 7.13-7.90(m, 14H), 8.27(bs, 1H), 8.73(bs, 1H).87 1.11-1.40(m, 4H), 3.79(s, 2H), 7.10-7.60(m, 15H), 8.22(bs, 1H).89 1.77(d, 3H), 2.84(s, 3H), 2.97(s, 3H), 4.14(q, 1H), 7.12-7.68(m, 9H), 9.21(bs, 1H).90 1.17-1.45(m, 4H), 2.10+2.30(s, 3H), 7.15-7.90(m, 9H), 8.27+8.34+8.42+8.78(bs, 2H).96 2.97(d, 3H), 6.75(m, 1H), 7.13-7.57(m, 8H), 7.92 (bs, 1H), 8.23(bs, 1H).98 1.04(t, 3H), 1.32(t, 3H), 3.18(q, 2H), 3.60(q, 2H), 7.18-7.70(m, 8H), 8.18(bs, 1H), 8.27(bs, 1H).100 0.98(t, 3H), 1.62(m, 2H), 3.33(q, 2H), 6.75(t, 1H), 7.11-7.53(m, 8H), 7.93(bs, 1H), 8.25(bs, 1H).103 1.10-2.12(m, 10H), 3.88(m, 1H), 6.60(bd, 1H), 7.10-7.56(m, 8H), 7.96(bs, 1H), 8.19(bs, 1H).104 0.95-1.96(m, 10H), 2.72+3.03(s, 3H), 3.23+4.55(m, 1H), 7.17-7.70(m, 8H), 8.16+8.18+8.21+8.25(bs, 2H).105 1.23(t, 3H), 2.53(m, 1H), 3.12(m, 2H), 3.45(m, 2H), 4.11(q, 2H), 4.40(m, 2H), 7.19-7.68(m, 8H), 8.18(bs, 1H), 8.62(bs, 1H).106 3.22-3.87(m, 8H), 7.18-7.95(m, 8H), 8.17(bs, 1H), 8.96(bs, 1H).107 1.70(bs, 1H), 2.60-3.90(m, 8H), 7.10-7.70(m, 9H), 8.15(bs, 1H).108 3.20-3.85(m, 8H), 3.73(s, 3H), 7.18-7.79(m, 8H), 8.15(bs, 1H), 8.54(bs, 1H).109 2.07+2.24(s, 3H), 3.20-3.90(m, 8H), 7.20-7.70(m, 8H), 8.15+8.55+8.58(bs, 2H).111 1.15(t, 3H), 3.20-3.87(m, 10H), 4.41(bt, 1H), 7.18-7.70(m, 8H), 8.17(bs, 1H), 8.56(bs, 1H).112 1.12(t, 6H), 3.05-3.85(m, 8H), 3.22(q, 4H), 7.18- 7.70(m, 8H), 8.17(bs, 1H), 8.62(bs, 1H).160 3.92(s, 3H), 7.08-7.64(m, 8H), 8.23(bs, 1H), 11.50(bs, 1H).163 2.97(d, 3H), 6.70(bq. 1H), 7.15-7.58(m, 8H), 7.92 (bs, 1H), 8.11(bs, 1H).165 1.02(t, 3H), 1.30(t, 3H), 3.18(q, 2H), 3.61(q, 2H), 7.10-7.72(m, 8H), 8.19(bs, 2H).178 2.90(s, 3H), 3.18(s, 3H), 7.18-7.92(m, 8H), 8.16 (bs, 1H), 8.37(bs, 1H).181 7.12-8.05(m, 13H), 7.89(bs, 1H), 8.08(bs, 1H), 11.90(bs, 1H).185 3.22-3.80(m, 11H), 7.18-7.91(m, 8H), 8.18(bs, 1H), 9.12(bs, 1H).190 3.01+3.13(s, 3H), 4.34+4.53(s, 2H), 7.21-8.26(m, 8H), 7.92(bs, 1H), 9.86(bs, 1H).196 1.08+1.38(d, 3H), 3.07-5.10(m, 6H), 7.13-7.97(m, 8H), 8.18+8.20(bs, 1H), 9.25+9.28(bs, 1H).237 1.19+1.87(d, 3H), 5.34+5.64(q, 1H), 7.80-8.20(m, 12H), 7.75+8.05+9.63+10.20(bs, 1H).239 1.29(d, 3H), 2.72(dd, 1H), 3.20-3.90(m, 10H), 7.10-8.30(m, 9H), 9.94(bs, 1H).244 1.25(t, 3H), 1.42(d, 3H), 2.80-3.00(m, 1H), 4.10- 4.30(m, 2H), 7.10-7.80(m, 8H), 7.51(bs, 1H), 8.40 (bs, 1H).247 1.10-1.95(m, 4H), 1.22(t, 3H), 4.22(q, 2H), 7.80- 8.30(m, 8H), 7.97(bs, 1H), 8.65(bs, 1H).275 2.19(s, 3H), 3.40(s, 3H), 7.10-7.16(m, 2H), 7.45- 7.60(m, 7H), 7.87(bs, 1H).279 1.27+1.34(d, 3H), 1.31+1.46(d, 3H), 2.68+3.22 (septet, 1H), 7.15-7.20(m, 2H), 7.35-7.66(m, 7H), 8.03+8.31(bs, 1H), 8.90+12.27(bs, 1H). (Z:E=3:2)281 4.73(d, 2H), 4.92-5.04(m, 2H), 5.60-5.75(m, 1H), 7.15-7.20(m, 2H), 7.43-7.74(m, 7H), 8.12(bs, 1H), 8.71(bs, 1H).284 1.73(m, 2H), 2.08(s, 3H), 2.46(t, 2H), 2.70(t, 2H), 7.12-7.17(m, 2H), 7.41-7.77(m, 9H), 8.11(bs, 1H), 8.17(bs, 1H).310 3.26-3.85(m, 8H), 7.21-7.65(m, 8H), 8.19(bs, 1H), 9.47(bs, 1H).318 2.89(s, 3H), 3.11(s, 3H), 7.18-7.81(m, 8H), 8.20 (bs, 1H), 8.85(bs, 1H).319 1.02-1.06(m, 6H), 2.45(septet, 1H), 7.16-7.74(m, 8H), 8.60(bs, 1H), 9.58(bs, 1H), 10.05(bs, 1H).323 2.86(s, 3H), 3.87(s, 3H), 4.30(s, 2H), 7.16-7.87 (m, 8H), 8.21(bs, 1H), 9.32(bs, 1H).324 0.76-1.41(m, 11H), 2.81(bt, 2H), 3.08(s, 3H), 7.20-7.81(m, 8H), 8.17(bs, 1H), 8.50(bs, 1H).333 2.28(t, 1H), 2.43(t, 2H), 2.66(t, 2H), 3.27-3.33 (m, 4H), 3.86(t, 2H), 7.17-7.23(m, 2H), 7.54-7.88 (m, 6H), 8.17(bs, 1H), 8.79(bs, 1H).335 2.29(s, 3H), 2.80-3.05(m, 2H), 3.19(s, 3H), 3.25- 3.35(m, 4H), 3.50(s, 3H), 3.55-3.70(m, 2H), 7.18- 7.24(m, 2H), 7.50-7.89(m, 6H), 8.72(s, 1H).______________________________________ ##STR117## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q and W are as defined above).
A hydrazine derivative of the general formula (I-2) can be produced by reducing a hydrazine derivative of the general formula (I-1) in the presence of a reducing agent.
This reduction reaction can be carried out by the use of a suitable reducing agent, or it can be carried out by catalytic reduction in the presence of a suitable catalyst. As the reducing agent, there can be used, for example, NaBH.sub.3 CN and NaBH.sub.4.
The amount of the reducing agent used may be chosen so that its number of moles in terms of the number of moles of hydride as reducing agent may be equal to or larger than that of the hydrazine derivative of the general formula (I-1).
As an inert solvent usable in the reaction, any inert solvent may be used so long as it does not markedly inhibit the progress of the reaction. There can be exemplified alcohols such as methanol, ethanol, propanol, butanol, etc.; chain ethers such as diethyl ether, etc.; cyclic ethers such as dioxane, tetrahydrofuran, etc.; Cellosolves such as Methyl Cellosolve, etc.; esters such as ethyl acetate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc.; diglyme; dimethylformamide; dimethylacetamide; dimethyl sulfoxide; sulfolane; and water. These inert solvents may be used singly or as a mixture thereof.
The reaction is carried out under acidic or neutral conditions in the pH range of 1 to 7. The pH is preferably in the range of 4 to 6 and is adjusted by adding hydrogen chloride, hydrogen bromide or the like to the reaction system.
It is also possible to carry out the reaction in the presence of a Lewis acid such as titanium tetrachloride (TiCl.sub.4) in the reaction system for the purpose of accelerating the reaction.
The reaction temperature may be properly chosen in the range of -20.degree. C. to the boiling point of the inert solvent used.
Although the reaction time is varied depending on the degree of the reaction, the reaction temperature, etc., it is several minutes to 48 hours.
After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, or the like, and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.
When catalytic reduction is carried out as the reduction reaction, it is carried out according to, for example, the conventional method described in Shin Jikken Kagaku Koza, Vol. 15-II, Maruzen Co., Ltd., etc. As an inert solvent usable in this case, there can be exemplified alcohols such as methanol, ethanol, propanol, butanol, etc.; Cellosolves such as Methyl Cellosolve, etc.; cyclic ethers such as dioxane, tetrahydrofuran, etc.; hydrocarbons such as hexane, cyclohexane, etc.; fatty acids or esters thereof, such as acetic acid, ethyl acetate, etc.; and amides such as N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. These inert solvents may be used singly or as a mixture thereof.
As the catalyst used in the reaction, there can be used typical catalysts for catalytic reduction, for example, palladium-carbon, palladium black, platinum dioxide and Raney nickel. The amount of the catalyst used may be properly chosen in the range of 0.0001 to 20% by weight based on the weight of the hydrazine derivative of the general formula (I-1).
The hydrogen pressure in the reaction can be chosen in the range of atmospheric pressure to 300 atmospheres, and is preferably in the range of atmospheric pressure to 50 atmospheres.
The reaction temperature may be properly chosen in the range of room temperature to the boiling point of the inert solvent used, and is preferably in the range of room temperature to 80.degree. C.
Although the reaction time is varied depending on the degree of the reaction, the reaction temperature, etc., it is several minutes to 80 hours.
After completion of the reaction, a reaction solution containing the desired compound is treated in the same manner as in the case of using the reducing agent, whereby the desired compound can be produced.
Examples of the hydrazine derivative of the general formula (I-2) produced by production process 4 are given in Table 3 but they are not intended in any way to limit the scope of the present invention. ##STR118##
TABLE 3__________________________________________________________________________(R.sup.1, R.sup.2 = H, W = O) MeltingNo. Ar.sup.1 Ar.sup.2 (B).sub.n Q point (.degree.C.)__________________________________________________________________________340 Ph 4-OCF.sub.3 Ph CH.sub.2 CN 169341 Ph 4-OCF.sub.3 Ph CH.sub.2 OPh-4-NO.sub.2 138342 Ph 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN 176343 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.3 174344 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 ClCH 157345 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 143346 Ph 4-OCF.sub.3 Ph CH.sub.2 SPh-4-Cl 188347 Ph 4-OCF.sub.3 Ph CH.sub.2 SPh-4-NO.sub.2 167348 Ph 4-OCF.sub.3 Ph CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 186349 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOCH.sub.3 202350 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOPh 227351 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOPh-2,4-Cl.sub.2 180352 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOPh-4-NO.sub.2 227353 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCONHC.sub.2 H.sub.5 160354 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CN 168355 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.2 OC.sub.2 H.sub.5 162356 Ph 4-OCF.sub.3 Ph SCH.sub.3 paste357 Ph 4-OCF.sub.3 Ph ##STR119## CN 171358 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 OPh-3-NO.sub.2 70359 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 OPh-4-NO.sub.2 160360 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 OPh-4-SCH.sub.3 paste361 3-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CN 174362 3-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CONH.sub.2 164363 3-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CON(C.sub.2 H.sub.5).sub.2 132364 3-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CONHCH.sub.2 CHCH.sub.2 148365 3-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.2 ##STR120## 113366 3-ClPh 4-OCF.sub.3 Ph ##STR121## CN paste367 3-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.4 CN 165368 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 OPh-4-NO.sub.2 200369 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN 200370 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 SPh-4-NO.sub.2 180371 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 SPh-4-CH.sub.3 190372 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 NHCOPh 230373 4-ClPh 4-OCF.sub.3 Ph (CH.sub.2).sub.4 CN 168374 4-BrPh 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN 190375 3-NO.sub.2 Ph 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN 190376 3-CH.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN 155377 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN paste378 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 SC.sub.3 H.sub.7 -i 127379 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 ##STR122## 108380 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 CHCH.sub.2 107381 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 CH.sub.2 CN 80382 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 CO.sub.2 CH.sub.3 95383 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 100384 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 SCH.sub.2 CONHC.sub.4 H.sub.9 -t 70385 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 135386 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOPh 199387 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOPh-2-Cl 195388 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 NHCOPh-4-NO.sub.2 193389 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CN 173390 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.2 CONH.sub.2 135391 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.3 CN 135392 3-CF.sub.3 Ph 4-OCF.sub.3 Ph ##STR123## CN paste393 3-CF.sub.3 Ph 4-OCF.sub.3 Ph ##STR124## CONH.sub.2 159394 3-CF.sub.3 Ph 4-OCF.sub.3 Ph ##STR125## SCH.sub.3 paste395 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.4 CN 134396 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.4 CONH.sub.2 180397 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.5 CN 129398 3-CF.sub.3 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.10 CN 113399 3-OCH.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 OPh-4-CN 185400 Ph 4-OCF.sub.3 Ph CH.sub.2 ##STR126## 230401 Ph 4-OCF.sub.3 Ph ##STR127## 175__________________________________________________________________________
Table 4 shows .sup.1 H-NMR data of compounds having physical properties expressed by the word "paste" or "vitreous" in Table 3.
TABLE 4______________________________________No. .sup.1 H--NMR [CDCl.sub.3 /TMS, .delta. value (ppm)]______________________________________356 0.70-1.04(m, 4H), 1.74(s, 3H), 3.52(d, 1H), 4.51 (d, 1H), 6.08(bs, 1H), 6.95-7.55(m, 9H), 8.72(bs, 1H).360 2.41(s, 3H), 4.15(m, 2H), 4.33(m, 1H), 5.52(bs, 1H), 6.57(bs, 1H), 6.90-7.80(m, 12H), 8.89(bs, 1H).366 1.29(d, 3H), 1.70-1.90(m, 1H), 2.10-2.20(m, 1H), 2.40-2.60(m, 1H), 4.08(dt, 1H), 4.50(d, 1H), 6.35 (bs, 1H), 7.10-7.60(m, 8H), 8.15(bs, 1H).377 4.25(d, 2H), 4.44(m, 1H), 4.75(bs, 1H), 6.85(bs, 1H), 6.90-7.80(m, 12H), 8.08(bs, 1H).392 1.30(d, 3H), 1.70-1.90(m, 1H), 2.10-2.20(m, 1H), 2.40-2.60(m, 1H), 4.10(dt, 1H), 4.30(d, 1H), 6.48 (bs, 1H), 7.10-7.60(m, 8H), 8.19(bs, 1H).394 0.75-1.03(m, 4H), 1.62(s, 3H), 3.35(bs, 1H), 4.40 (bs, 1H), 6.30(bs, 1H), 6.96-7.53(m, 8H), 8.64 (bs, 1H).______________________________________ ##STR128## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q and W are as defined above).
A hydrazine derivative of the general formula (I-3) can be produced by reacting a compound of the general formula (XI) and a condensing agent with a compound of the general formula (XII) in the presence or absence of an inert solvent and/or in the presence of a base.
As the inert solvent usable in this reaction, there can be used, for example, acetone, methyl ethyl ketones, pyridine, etc. in addition to the inert solvents usable in production process 3.
As the condensing agent, there can be used, for example, halogenating agents (e.g. thionyl chloride, phosphorus trichloride and phosphorus pentachloride), carbodiimidazole, dicyclohexylcarbodiimide, and 2-chloro-1-methylpyridinium iodide. The amount of the condensing agent used may be properly chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (XII).
It is also possible to carry out the reaction by addition of a catalytic amount of triethylamine, pyridine or dimethylformamide for the purpose of accelerating the reaction.
As the base used in the reaction, an inorganic base or an organic base may be used. As the inorganic base, there may be used, for example, hydroxides, carbonates or alcoholates of alkali metal atoms or alkaline earth metal atoms (e.g. sodium, potassium, magnesium and calcium), and hydrides of alkali metals, such as sodium hydride, etc. As the organic base, there may be used triethylamine, pyridine, N,N-dimethylaniline, 2,6-dimethylpyridine, 4-N,N-dimethylaminopyridine, 1,8-diazabicyclo[5,4,0]-7-undecene (DBU), etc. The amount of the base used may be chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (XII).
The reaction temperature may be properly chosen in the range of room temperature to the boiling point of the inert solvent used.
Although the reaction time is varied depending on the degree of the reaction, the reaction temperature, etc., it is several minutes to 48 hours.
After completion of the reaction, the same treatment as in production process 1 is carried out, whereby the hydrazine derivative of the general formula (I-3) can be produced.
The compound of the general formula (XI) can be produced by the following process: ##STR129## wherein Ar.sup.1, R.sup.2, B, n, Q, W and Hal are as defined above).
A compound of the general formula (XI) can be produced by reacting a compound of the general formula (XIII) with a halide of the general formula (XIV) to obtain a compound of the general formula (XV), and reacting the compound (XV) with a compound of the general formula (XVI) after or without isolating the compound (XV). ##STR130## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q, W and Hal are as defined above.
A hydrazine derivative of the general formula (I-3) can be produced by reacting a compound of the general formula (XVII) with a halide of the general formula (XIV) in the presence or absence of an inert solvent and in the presence of a base.
As the inert solvent and the base which are usable in this reaction, there can be used, for example, the inert solvents and bases which are exemplified in production process 4. The amount of the base used may be chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (XIV).
Since the reaction is an equimolar reaction, it is sufficient that the reactants are used in equimolar amounts, though either of them may be used in excess.
The reaction temperature may be chosen in the range of 0.degree. C. to the boiling point of the inert solvent used.
Although the reaction time is varied depending on the degree of the reaction, the reaction temperature, etc., it may be chosen in the range of several minutes to 48 hours.
After completion of the reaction, a reaction solution containing the desired compound is treated in the same manner as, for example, in production process 1, whereby the hydrazine derivative of the general formula (I-3) can be produced.
The compound of the general formula (XVII) used in the reaction can be produced by the following process: ##STR131## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, and W are as defined above.
The compound of the general formula (XVII) can be produced by reacting a compound of the general formula (XIII) with a compound of the general formula (XVI) to obtain a compound of the general formula (XVIII), and reacting the compound (XVIII) with a compound of the general formula (XII) after or without isolating the compound (XVIII).
Typical examples of the hydrazine derivatives of the general formula (I-3) produced by production processes 5 and 6 are given in Table 5 but they are not intended in any way to limit the scope of the present invention. ##STR132##
TABLE 5__________________________________________________________________________(R.sup.1, R.sup.2 = H, W = O) MeltingNo. Ar.sup.1 Ar.sup.2 (B).sub.n Q point (.degree.C.)__________________________________________________________________________402 Ph 4-OCF.sub.3 Ph -- COPh-4-CN 144.4-148.1403 Ph 4-OCF.sub.3 Ph -- COPh-4-CH.sub.3 152-154404 Ph 4-ClPh CH.sub.2 CONHPh 253-255405 Ph 4-OCF.sub.3 Ph CH.sub.2 CONHPh 243-245406 Ph 4-OCF.sub.3 Ph CH.sub.2 CO.sub.2 CH.sub.3 137.8407 Ph 4-OCF.sub.3 Ph CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 129-131408 Ph 4-OCF.sub.3 Ph (CH.sub.2).sub.2 SOPh 118-119409 Ph 4-OCF.sub.3 Ph CO.sub.2 CH.sub.3 nD 1.5545 (20.degree. C.)410 3-ClPh Ph CH.sub.2 CHCHPh 160.5-161.1411 3-ClPh 4-ClPh CH.sub.2 CHCHPh 178.1-180.3412 3-ClPh 4-CNPh CH.sub.2 CONHPh-4-Cl 252.9-253.5413 3-ClPh 4-CNPh CH.sub.2 CONHPh-4-OCF.sub.3 257.1414 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CHCH.sub.2 79-81415 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CCH 126416 3-ClPh 4-OCF.sub.3 Ph -- ##STR133## nD 1.5575 (25.degree. C.)417 3-ClPh 4-OCF.sub.3 Ph -- SO.sub.2 Ph-4-Cl 121.0-122.7418 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 OCH.sub.3 99.3419 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHCH.sub.2 CN 228.4420 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONH.sub.2 221421 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh 225.4-228.0422 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-3-Cl 218.9-220.4423 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-Cl 227.7-229.4424 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-Br 244.5425 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-NO.sub.2 187.5426 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-CN 227.9-228.7427 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-CH.sub.3 227.6-230.9428 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-OCH 239-242429 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-3-CF.sub.3 188430 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-OCF.sub.3 218.6-220.5431 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 ##STR134## 227.1432 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CHCHPh 152433 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CHCHPh-4-Cl paste E- or Z-form434 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CHCHPh-4-Cl 155-156 Z- or E-form435 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 ##STR135## 99-101436 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 ##STR136## 142-144437 4-ClPh 4-ClPh CH.sub.2 CONHPh-4-OCF.sub.3 257.4-260.1438 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-OCF.sub.3 247.4439 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 CHCHPh-4-CN paste__________________________________________________________________________
Table 6 shows .sup.1 H-NMR data of compounds having physical properties expressed by the word "paste" or "vitreous" in Table 5.
TABLE 6______________________________________No. .sup.1 H--NMR [CDCl.sub.3 /TMS, .delta. value (ppm)]______________________________________433 3.68(d, 2H), 6.17(ddd, 1H), 6.50(d, 1H), 690- 7.80(m, 12H), 8.10(s, 1H), 8.92(s, 1H).439 4.79(d, 2H), 6.33(ddd, 1H), 6.44(d, 1H), 6.95(s, 1H), 7.20-7.70(m, 12H), 8.55(s, 1H).______________________________________ ##STR137## wherein Ar.sup.1, Ar.sup.2, R.sup.1, R.sup.2, B, n, Q and W are as defined above.
A hydrazine derivative of the general formula (I-4) can be produced by reducing a hydrazine derivative of the general formula (I-3) in the presence of a reducing agent.
This reaction is carried out in the same manner as in production process 4, whereby the hydrazine derivative of the general formula (I-4) can be produced.
Typical examples of the hydrazine derivative of the general formula (I-4) produced by production process 7 are given in Table 7 but they are not intended in any way to limit the scope of the present invention. ##STR138##
TABLE 7__________________________________________________________________________(R.sup.1, R.sup.2 = H, W = 0) MeltingNo. Ar.sup.1 Ar.sup.2 (B).sub.n Q point (.degree.C.)__________________________________________________________________________440 Ph 4-OCF.sub.3 Ph CH.sub.2 CONHPh 180.5-180.8441 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-OCF.sub.3 171.5442 3-ClPh 4-CNPh CH.sub.2 CONHPh-4-OCF.sub.3 207.5-209.3443 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-CN 183.2-184.6444 3-ClPh 4-OCF.sub.3 Ph CH.sub.2conh-Ph-3-CF.sub.3 131.9-133.2445 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 CONHPh-4-OCF.sub.3 151-153446 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 CHCHPh 99.3447 4-ClPh 4-OCF.sub.3 Ph CH.sub.2 CHCHPh-4-Cl 85-87448 3-CF.sub.3 Ph 4-OCF.sub.3 Ph CH.sub.2 CHCHPh-4-CN paste449 3-ClPh 4-OCF.sub.3 Ph CH.sub.2 paste__________________________________________________________________________
Table 8 shows 1H-NMR data of the compounds having properties expressed by the word "paste" or "vitreous" in Table 7.
TABLE 8______________________________________No. .sup.1 H--NMR [CDCl.sub.3 /TMS, .delta. value (ppm)]______________________________________448 3.75(s, 2H), 4.30(d, 2H), 6.31(ddd, 1H), 6.65(d, 1H), 7.00-7.70(m, 13H), 8.65(s, 1H).449 1.22(s, 9H), 3.63(s, 2H), 4.02(d, 2H), 5.73(d, 1H), 5.94(ddd, 1H), 6.90-7.50(m, 9H), 8.72(s, 1H).______________________________________

Typical examples concerning the hydrazine derivatives of the general formula (I) of the present invention are described below, but they should not be construed as limiting the scope of the invention.
EXAMPLES
Example 1
1-1. Production of .alpha.-(4-cyanophenoxy)acetophenone ##STR139##
In 50 ml of acetone were dissolved 1.10 g (5.5 mmoles) of .alpha.-bromoacetophenone and 0.72 g (6.1 mmoles) of 4-cyanophenol, after which 0.76 g (5.5 mmoles) of anhydrous potassium carbonate was added to the resulting solution, and the reaction was carried out at room temperature for 2 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction mixture containing the desired compound. Water was added to the residue and the desired compound was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the solvent, whereby 1.10 g of the desired compound was obtained.
Physical property: m.p. 162.degree. C. Yield: 84%.
1-2. Production of 2-[2-(4-cyanophenoxy)-1-phenylethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound Nos. 28 and 29) ##STR140##
In 30 ml of methanol were dissolved 0.53 g (2.2 mmoles) of the .alpha.-(4-cyanophenoxy)acetophenone obtained in 1-1 and 0.53 g (2.2 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out at room temperature for 8 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution. Water was added to the residue and the desired compound was extracted with ethyl acetate. The organic layer was washed with water, dried, and distilled to remove the solvent, whereby a crude product was isolated. The crude product obtained was purified and separated by a silica gel column chromatography (dichloromethane) to obtain two isomers of the desired compound, i.e., 0.46 g of Z-isomer and 0.40 g of E-isomer.
Z-isomer: Physical property m.p. 190.degree. C. Yield 45%.
E-isomer: Physical property m.p. 179.degree. C. Yield 39%.
Example 2
2-1. Production of .gamma.-chloro-(3-trifluoromethyl)butyrophenone ##STR141##
Under ice-cooling, 85 g (82 mmoles) of .gamma.-chlorobutyronitrile was added dropwise to a solution in 100 ml of ether of a Grignard reagent prepared from 4.0 g (160 mmoles) of magnesium and 18.5 g (82 mmoles) of 3-bromobenzotrifluoride. After completion of the dropwise addition, the reaction was carried out with refluxing for 2 hours.
After completion of the reaction, the reaction solution was poured into ice water and neutralized with concentrated hydrochloric acid. The desired compound was extracted with ethyl acetate and the organic layer was washed with water, dried and then distilled under reduced pressure to remove the solvent, whereby 9.0 g of the desired compound was obtained.
Physical property: oil. Yield: 44%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 2.23 (quintet, 2H), 3.20 (t, 2H), 3.67 (t, 2H), 7.5-8.26 (m, 4H).
2-2. Production of .alpha.-bromo-.gamma.-chloro-(3-trifluoromethyl)butyrophenone ##STR142##
In 100 ml of acetic acid was dissolved 4.1 g (16 mmoles) of .gamma.-chloro-(3-trifluoromethyl)butyrophenone, after which 2.9 g (18 mmoles) of bromine was added to the resulting solution, and the reaction was carried out at 50.degree.-60.degree. C. for 2 hours.
After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted with ethyl acetate. The organic layer was washed with an aqueous sodium thiosulfate solution and then an aqueous sodium hydrogencarbonate solution, dried over magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 4.8 g of the desired compound was obtained.
Physical property: oil. Yield: 89%. .sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 2.55-2.64 (m, 2H), 3.74-3.90 (m, 2H), 5.40-5.50 (m, 1H), 7.60-8.35 (m, 4H).
2-3. Production of (3-trifluoromethylphenyl) (1-methylthiocyclopropyl)ketone ##STR143##
After 10 ml of a 50% aqueous sodium hydroxide solution and 2.8 g (6.1 mmoles) of a 15% aqueous methyl mercaptan sodium salt solution were mixed and then added to 30 ml of toluene, 10 mg of tetra-n-butylammonium bromide was added. Then, 1.0 g (3.0 mmoles) of .alpha.-bromo-.gamma.-chloro-(3-trifluoromethyl)butyrophenone was added dropwise at room temperature, and the reaction was carried out for 2 hours.
After completion of the reaction, water was added to the reaction mixture and the desired compound was extracted with ethyl acetate. The organic layer was washed with water, dried, and then concentrated under reduced pressure. The resulting residue was purified by a silica gel column chromatography (ethyl acetate: n-hexane=1:10) to obtain 0.40 g of the desired compound.
Physical property: oil. Yield: 51%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 1.28-1.60 (m, 4H), 2.06 (s, 3H), 7.55-8.35 (m, 4H).
2-4. Production of .alpha.-(1-methylthiocyclopropyl)-3-trifluoromethylbenzylidene-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 252) ##STR144##
In 30 ml of methanol was dissolved 0.40 g (1.5 mmoles) of (3-trifluoromethylphenyl) (1-methylthiocyclopropyl)ketone, after which 0.43 g (1.9 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide and a drop of concentrated sulfuric acid were added to the resulting solution, and the reaction was carried out at 50.degree.-60.degree. C. for 8 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction mixture containing the desired compound. The resulting residue was purified by a silica gel column chromatography (ethyl acetate: n-hexane=1:4) to obtain 0.55 g of the desired compound as a mixture of E-form and Z-form.
Physical property: m.p. 142.degree. C. Yield: 55%.
Example 3
3-1. Production of N,N-diethyl-4-fluorophenylglyoxamide ##STR145##
In 20 ml of tetrahydrofuran was dissolved 10 ml of diethylamine, after which a solution of 1.0 g (5.4 mmoles) of 4-fluorophenylglyoxylyl chloride in 3 ml of tetrahydrofuran was added dropwise at room temperature, and the reaction was carried out for 2 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution. Water was added to the residue and the desired compound was extracted with ethyl acetate. The organic layer was washed with diluted hydrochloric acid and an aqueous sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (ethyl acetate: n-hexane=1:2) to obtain 0.62 g of the desired compound.
Physical property: paste. Yield: 52%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 1.16 (t, 3H), 1.29 (t, 3H), 3.23 (q, 2H), 3.35 (q, 2H), 7.13-7.22 (m, 2H), 7.93-8.03 (m, 2H).
3-2. Production of 2-[.alpha.-(N,N-diethylcarbamoyl)-4-fluorobenzylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 165) ##STR146##
In 30 ml of methanol were dissolved 0.40 g (1.8 mmoles) of N,N-diethyl-4-fluorophenylglyoxamide and 0.42 g (1.8 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out at 40.degree.-50.degree. C. for 16 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution. The resulting residue was purified by a silica gel column chromatography (ethyl acetate: n-hexane=2:3) to obtain 0.32 g of the desired compound.
Physical property: vitreous. Yield: 40%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 1.02 (t, 3H), 1.30 (t, 3H), 3.18 (q, 2H), 3.61 (q, 2H), 7.10-7.72 (m, 8H), 8.19 (bs, 2H).
Example 4
4-1. Production of 1-(phenylglyoxylyl)piperazine ##STR147##
In 30 ml of methanol were dissolved 5.0 g (58 mmoles) of anhydrous piperazine and 0.80 g (4.9 mmoles) of methyl phenylglyoxylate, and the reaction was carried out at room temperature for 8 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution containing the desired compound. Water was added to the resulting residue and the desired compound was extracted with ethyl acetate (50 ml.times.3). The organic layer was washed with water, dried and then distilled under reduced pressure to remove the solvent, whereby 0.95 g of the desired compound was obtained.
Physical property: paste. Yield: 89%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 1.78 (bs, 1H), 2.82 (t, 2H), 2.97 (t, 2H), 3.32 (t, 2H), 4.74 (t, 2H), 7.48-8.00 (m, 5H).
4-2. Production of 1-methoxycarbonyl-4-(phenylglyoxylyl)piperazine ##STR148##
In 30 ml of tetrahydrofuran was dissolved 0.35 g (1.6 mmoles) of 1-(phenylglyoxylyl)piperazine, after which 0.5 ml of methyl chloroformate and 1 ml of triethylamine were added to the resulting solution, and the reaction was carried out at room temperature for 2 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution. Water was added to the resulting residue and the desired compound was extracted with ethyl acetate. The organic layer was washed with diluted hydrochloric acid and an aqueous sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 0.37 g of the desired compound was obtained.
Physical property: paste. Yield: 83%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 3.30-3.85 (m, 8H), 3.72 (s, 3H), 7.48-8.00 (m, 5H).
4-3. Production of 2-[.alpha.-[(4-methoxycarbonylpiperazino )carbonyl]benzylidene]-N-[4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 22) ##STR149##
In 30 ml of methanol were dissolved 0.37 g (1.3 mmoles) of 1-methoxycarbonyl-4-(phenylglyoxylyl)piperazine and 0.32 g (1.3 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out at 40.degree.-50.degree. C. for 24 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution. The resulting residue was purified by a silica gel column chromatography (ethyl acetate: n-hexane=1:1) to obtain 0.25 g of the desired compound.
Physical property: m.p. 186.degree. C. Yield: 38%.
Example 5
5-1. Production of .alpha.-(N,N-diformylamino)-3-chloroacetophenone ##STR150##
In 20 ml of acetonitrile was dissolved 20 g (86 mmoles) of .alpha.-bromo-3-chloroacetophenone, after which 8.14 g (86 mmoles) of sodium diformamide was added to the resulting solution, and the reaction was carried out at room temperature for 3 hours.
After completion of the reaction, the reaction mixture containing the desired compound was filtered under reduced pressure and the filtrate was concentrated. The desired compound was extracted with ethyl acetate, and the extracted solution was dried and then distilled under reduced pressure to remove the solvent, whereby 3.0 g of the desired compound was obtained.
Physical property: m.p. 71.degree. C. Yield: 15%.
5-2. Production of .alpha.-amino-3-chloroacetophenone hydrochloride ##STR151##
In 6N HCl aqueous solution was suspended in 12.7 g (56 mmoles) of .alpha.-(N,N-diformylamino)-3-chloroacetophenone, and the reaction was carried out with refluxing for 30 minutes.
After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the crystals precipitated were washed with a small volume of ether to obtain 11.2 g of the desired compound.
Physical property: m.p. 223.degree. C. Yield: 97%.
5-3. Production of 3-chloro-.alpha.-benzoylaminoacetophenone ##STR152##
In 10 ml of tetrahydrofuran were dissolved 0.68 g (4.9 mmoles) of benzoyl chloride and 1.47 g (14.6 mmoles) of triethylamine, after which 1.0 g (4.9 mmoles) of .alpha.-amino-3-chloroacetophenone hydrochloride was added to the resulting solution, and the reaction was carried out at room temperature for 2 hours.
After completion of the reaction, the desired compound was extracted from the reaction mixture with ethyl acetate, and the extracted solution was washed with water, dried, and then distilled under reduced pressure to remove the solvent, whereby 0.60 g of the desired compound was obtained.
Physical property: m.p. 105.degree. C. Yield: 43%.
5-4. Production of 2-[2-benzoylamino-1-(3-chlorophenyl)ethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 124) ##STR153##
In 5 ml of ethanol was suspended 0.50 g (1.7 mmoles) of 3-chloro-.alpha.-benzoylaminoacetophenone, after which a drop of concentrated sulfuric acid was added to the resulting suspension, and the reaction was carried out at room temperature for 6 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction mixture. The desired compound was extracted from the resulting residue with ethyl acetate, and the extracted solution was washed with water, dried and then distilled under reduced pressure to remove the solvent, whereby 0.60 g of the desired compound was obtained.
Physical property: m.p. 190.degree. C. Yield: 68%.
Example 6
6-1. Production of S-[2-oxo-(3-trifluoromethylphenyl)ethyl]acetate ##STR154##
In 300 ml of ether was dissolved 4.3 g (56 mmoles) of thioacetic acid, followed by adding thereto 5.7 g (56 mmoles) of triethylamine. A solution of 15 g (56 mmoles) of .alpha.-bromo-3-trifluoromethylacetophenone in 50 ml of ether was added dropwise at room temperature over a period of 15 minutes. After completion of the dropwise addition, the reaction was carried out with refluxing for 1.5 hours.
After completion of the reaction, the insoluble materials were filtered off and the filtrate was concentrated under reduced pressure to obtain 15.4 g of the desired compound.
Physical property: crystals. Yield: 87%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 2.43 (s, 3H), 4.40 (s, 2H), 7.64-8.26 (m, 4H).
6-2. Production of .alpha.-(2-propynylthio)-3-trifluoromethylacetophenone ##STR155##
In 50 ml of methanol was dissolved 0.16 g (7.1 mmoles) of metallic sodium, and into the resulting solution was slowly dropped a solution of 1.0 g (5.2 mmoles) of S-[2-oxo-(3-trifluoromethylphenyl)ethyl]acetate in 10 ml of methanol. After completion of the dropping, the reaction was carried out for another 1.5 hours. Then, a solution of 0.71 g (6.0 mmoles) of 2-propynyl bromide in 15 ml of methanol was added to the reaction solution, and the resulting mixture was subjected to reaction for 1 hour.
After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 0.95 g of the desired compound was obtained.
Physical property: oil. Yield: 97%.
6-3. Production of 2-[2-(2-propynylthio)-1-(3-trifluoromethylphenyl)ethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 206) ##STR156##
In 10 ml of ethanol was dissolved 0.95 g (5.0 mmoles) of .alpha.-(2-propynylthio)-3-trifluoromethylacetophenone, after which 1.23 g (5.25 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide and a drop of concentrated sulfuric acid were added to the resulting solution, and the reaction was carried out at room temperature for 6 hours.
After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 1.1 g of the desired compound was obtained.
Physical property: m.p. 155.degree. C. Yield: 54%.
Example 7
7-1. Production of 4-(3-trifluoromethylphenyl)-4-oxobutanamide ##STR157##
To a solution of 5.00 g (28.7 mmoles) of 3-trifluoromethylbenzaldehyde in 18 ml of dimethylformamide was added 0.28 g (5.7 mmoles) of powdered sodium cyanide, and the reaction was carried out at 45.degree. C. for 30 minutes. Subsequently, a solution of 1.30 g (24.5 mmoles) of acrylonitrile in 2 ml of dimethylformamide was added dropwise to the reaction mixture over a period of 20 minutes. After completion of the dropwise addition, the resulting mixture was subjected to reaction for 4 hours. Then, 1 ml of acetic acid was added to the reaction mixture and the reaction was carried out for 10 minutes.
After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (n-hexane: ethyl acetate=10:1) to obtain 5.63 g of 4-(3-trifluoromethylphenyl)-4-oxobutanenitrile.
Physical property: oil. Yield: 72.8%. .sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 2.81 (t, 2H), 3.43 (t, 2H), 7.60-8.20 (m, 4H).
To 40 ml of concentrated sulfuric acid was added 5.50 (21.9 mmoles) of the obtained 4-(3-trifluoromethylphenyl)-4-oxobutanenitrile on an ice water bath, and the reaction was carried out at 0.degree. C. for 30 minutes and then at room temperature for 5 hours.
After completion of the reaction, the reaction mixture was poured into 150 ml of ice water and the desired compound was extracted with chloroform. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (n-hexane: ethyl acetate=2:1) to obtain 2.70 g of the desired compound.
Physical property: m.p. 133.degree. C. Yield: 45.6%.
7-2. Production of 2-[3-carbamoyl-1-(3-trifluoromethylphenyl)propylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 233) ##STR158##
To a solution of 1.0 g (4.1 mmoles) of 4-(3-trifluoromethylphenyl)-4-oxobutanamide and 0.96 g (4.1 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide in 15 ml of tetrahydrofuran was added 15 ml of ethanol and then two drops of concentrated sulfuric acid, and the reaction was carried out at room temperature for 15 hours.
After completion of the reaction, the reaction solution was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (ethyl acetate) to obtain 1.14 g of the desired compound.
Physical property: m.p. 203.degree. C. Yield: 60.4%.
Example 8
8-1. Production of 4-(3-trifluoromethylphenyl)-4-oxobutanoic acid ##STR159##
In 180 ml of dimethylformamide was dissolved 24.8 g (0.143 mole) of 4-trifluoromethylbenzaldehyde, after which 1.05 g (0.021 mole) of powdered sodium cyanide was added to the resulting solution, and the reaction was carried out at 45.degree. C. for 30 minutes. Subsequently, a solution of 11.4 g (0.114 mole) of ethyl acrylate in 20 ml of dimethylformamide was added dropwise to the reaction mixture over a period of 20 minutes, and the resulting mixture was subjected to reaction for 4 hours. Then, 3 ml of acetic acid was added to the reaction mixture and the reaction was carried out for 30 minutes.
After completion of the reaction, the reaction mixture was poured into 300 ml of ice water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby a crude product was obtained. The obtained crude product was purified by a silica gel column chromatography (n-hexane: ethyl acetate=3:1) to obtain 24.6 g of ethyl 4-(3-trifluoromethylphenyl)-4-oxobutanoate.
Physical property: crystals. Yield: 63.0%.
In 200 ml of methanol was dissolved 20.0 g (73 mmoles) of the obtained ethyl 4-(3-trifluoromethylphenyl)-4-oxobutanoate, after which a solution of 8.2 g (0.20 mole) of lithium hydroxide monohydrate in 100 ml of water was added to the resulting solution, and the reaction was carried out for 10 hours.
After completion of the reaction, the reaction solution was concentrated under reduced pressure and adjusted to pH 2 with 6N hydrochloric acid. The crystals precipitated were collected by filtration and dried under reduced pressure to obtain 18.0 g of the desired compound.
Physical property: m.p. 88.degree. C. Yield: 100%.
8-2. Production of N,N-diethyl-4-(3-trifluoromethylphenyl)-4-oxobutanamide ##STR160##
A mixture of 1.0 g (4.1 mmoles) of 4-(3-trifluoromethylphenyl)-4-oxobutanoic acid, 1.20 g (4.7 mmoles) of 2-chloro-1-methylpyridinium iodide and 0.36 g (4.9 mmoles) of diethylamine was dissolved in 20 ml of dichloromethane, followed by adding thereto 0.84 g (8.3 mmoles) of triethylamine, and the reaction was carried out with refluxing for 8 hours.
After completion of the reaction, the reaction mixture was poured into ice water and acidified with 2N hydrochloric acid. Then, the desired compound was extracted with methylene chloride, and the extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby a crude product was obtained.
The obtained crude product was purified by a silica gel column chromatography (n-hexane: ethyl acetate=1:1) to obtain 1.15 g of the desired compound.
Physical property: nD 1.5012 (21.6.degree. C.).
Yield: 94%.
8-3. Production of 2-[3-(N,N-diethylcarbamoyl)-1-(3-trifluoromethylphenyl)propylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 235) ##STR161##
To 15 ml of tetrahydrofuran were added 0.67 g (2.2 mmoles) of N,N-diethyl-4-(3-trifluoromethyl)-4-oxobutanamide and 0.52 g (2.2 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, and then 15 ml of ethanol and two drops of concentrated sulfuric acid, after which the reaction was carried out for 15 hours.
After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby a crude product was obtained.
The obtained crude product was purified by a silica gel column chromatography (n-hexane: ethyl acetate=2:1) to obtain 0.74 g of the desired compound.
Physical property: m.p. 148.degree. C. Yield: 64%.
Example 9
9-1. Production of 4-oxo-4-phenyl-N-(4-trifluoromethoxyphenyl)-2-butenamide ##STR162##
In 300 ml of tetrahydrofuran (THF) was dissolved 4.0 g (16 mmoles) of 3-bromo-4-oxo-4-phenylbutanoic acid, after which 2.0 g (19 mmoles) of ethyl chloroformate was added to the resulting solution, and then a solution of 4.7 g (47 mmoles) of triethylamine in 2 ml of THF was dropped thereinto slowly. Thereafter, the reaction was carried out at room temperature for 30 minutes. Subsequently, 3.3 g (19 mmoles) of 4-trifluoromethoxyaniline was added to the reaction mixture and the resulting mixture was subjected to reaction for 4 hours.
After completion of the reaction, water was added to the reaction mixture and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 2.8 g of the desired compound as crystals.
Physical property: m.p. 188.degree. C. Yield: 60%.
9-2. Production of 2-[1-phenyl-3-[N'-(4-trifluoromethoxyphenyl)carbamoyl]-2-propenylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 294) ##STR163##
In 30 ml of methanol was dissolved 0.40 g (1.2 mmoles) of 4-oxo-4-phenyl-N-(4-trifluoromethoxyphenyl)-2-butenamide, after which a drop of concentrated sulfuric acid and 0.36 g (1.8 mmoles) of N-(4-trifluoromethoxyphenyl)-2-butenamide were added to the resulting solution, and the reaction was carried out with refluxing for 6 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure and the desired compound was extracted from the residue with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 0.30 g of the desired compound as crystals.
Physical property: m.p. 237.degree. C. Yield: 73%.
Example 10
10-1. Production of (2-propynyloxyimino)acetophenone ##STR164##
In 20 ml of acetonitrile were dissolved 3.0 g (19 mmoles) of isonitrosoacetophenone and 2.3 g (19 mmoles) of 2-propargyl bromide, after which 3.9 g (28 mmoles) of potassium carbonate was added to the resulting solution, and the reaction was carried out at room temperature for 3 hours.
After completion of the reaction, the reaction mixture was poured into water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 2.5 g of the desired compound as paste.
Physical property: paste. Yield: 83%.
10-2. Production of 2-[1-phenyl-2-(2-propynyloxyimino)ethylene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound Nos. 273 and 274) ##STR165##
In 10 ml of ethanol were dissolved 0.50 g (2.5 mmoles) of (2-propynyloxyimino)acetophenone and 0.60 g (2.5 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out at room temperature for 5 hours.
After completion of the reaction, the reaction solution was poured into water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and freed of the solvent under reduced pressure. The residue was purified by a silica gel column chromatography (ethyl acetate: n-hexane=1:2) to obtain two forms of the desired compound, i.e., E-form and Z-form.
Physical property E-form: m.p. 169.degree. C. Amount (yield) 0.23 g (22%). Z-form: m.p. 115.degree. C. Amount (yield) 0.37 g (38%).
Example 11
11-1. Production of ethyl 2-(2-phenyl-2-oxoethylene)hydrazinecarboxylate ##STR166##
In ethanol were dissolved 1.0 g (7.5 mmoles) of phenylglyoxal and 1.6 g (15 mmoles) of ethyl carbamate, and the resulting solution was subjected to reaction at room temperature for 4 hours.
After completion of the reaction, the reaction solution was poured into water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 0.40 g of the desired compound.
Physical property: m.p. 139.degree. C. Yield: 27%.
11-2. Production of ethyl 2-[2-phenyl-2-[[N-(4-trifluoromethoxyphenyl)carbamoyl]hydrazono]ethylene]hydrazinecarboxylate (compound No. 272) ##STR167##
In 10 ml of ethanol were dissolved 0.30 g (1.4 mmoles) of ethyl 2-(2-phenyl-2-oxoethylene)hydrazinecarboxylate and 0.38 g (1.6 mmoles) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out at room temperature for 5 hours.
After completion of the reaction, the reaction solution was poured into water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 0.26 g of the desired compound.
Physical property: m.p. 100.degree. C. Yield: 42%.
Example 12
Production of 2-[2-(O,O-dimethoxyphosphoryl)-1-phenylethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 288) ##STR168##
In 20 ml of methanol were dissolved 0.20 g (0.88 mmole) of dimethyl 2-oxo-2-phenylethanephosphonate and 0.21 g (0.88 mmole) of N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out with heating under reflux for 3 hours.
After completion of the reaction, the reaction solution was allowed to cool and distilled under reduced pressure to remove the solvent, and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain crude crystals. The crude crystals were washed with ether to obtain 0.16 g of the desired compound.
Physical property: m.p. 222.degree. C. Yield: 41%.
Example 13
13-1. Production of 4-phenylglyoxylylmorpholine ##STR169##
In 30 ml of tetrahydrofuran was dissolved 1.1 g (13 mmoles) of morpholine, after which a solution of 0.70 g (4.2 mmoles) of phenylglyoxylyl chloride in 5 ml of tetrahydrofuran was added dropwise to the resulting solution. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, water was added to the reaction solution and the desired compound was extracted with ethyl acetate. The extracted solution was washed with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 0.70 g of the desired compound was obtained as paste.
Physical property: paste. Yield: 77%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 3.38 (t, 2H), 3.65 (t, 2H), 3.70 (s, 4H), 7.50-8.00 (m, 5H).
13-2. Production of 2-(.alpha.-morpholinocarbonylbenzylidene)-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 18) ##STR170##
In 30 ml of methanol was dissolved 0.7 g (3.2 mmoles) of 4-phenylglyoxylylmorpholine, after which 10 ml of hydrazine hydrate and a drop of concentrated sulfuric acid were added to the resulting solution, and the reaction was carried out at 40.degree.-50.degree. C. for 4 hours.
After completion of the reaction, the reaction solution was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby a hydrazone was obtained as an intermediate.
The obtained hydrazone was dissolved in 30 ml of tetrahydrofuran, after which 5 ml of pyridine and 0.58 g (2.9 mmoles) of 4-trifluoromethoxyphenyl isocyanate were added to the resulting solution at room temperature, and the reaction was carried out for 8 hours.
After completion of the reaction, the reaction solution was concentrated under reduced pressure, followed by purification by a silica gel column chromatography (ethyl acetate: n-hexane=2:3), whereby 0.30 g of the desired compound was obtained.
Physical property: m.p. 155.degree. C. Yield: 30%.
Example 14
14-1. Production of N,N-dimethyl-2-hydrazono-2-phenylethanesulfonamide ##STR171##
In 40 ml of ethanol were dissolved 1.0 g (4.4 mmoles) of N,N-dimethyl-2-oxo-2-phenylethanesulfonamide and 0.44 g (8.8 mmoles) of hydrazine hydrate, after which a drop of concentrated sulfuric acid was added to the resulting solution, and the reaction was carried out with heating under reflux for 2 hours.
After completion of the reaction, the reaction solution was allowed to cool and distilled under reduced pressure to remove the solvent, and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 0.73 g of the desired compound as crystals.
Physical property: crystals. Yield: 69%.
14-2. Production of 2-[2-N',N'-dimethylaminosulfonyl)-1-phenyl]ethylidene-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 290) ##STR172##
In a mixed solvent of 15 ml of tetrahydrofuran and 15 ml of pyridine was dissolved 0.50 g (2.1 mmoles) of N,N-dimethyl-2-hydrazono-2-phenylethanesulfonamide, followed by adding thereto 0.42 g (2.1 mmoles) of 4-trifluoromethoxyphenyl isocyanate, and the reaction was carried out at room temperature for 2 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure and the crude crystals thus obtained were washed with toluene to obtain 0.60 g of the desired compound.
Physical property: m.p. 210.degree. C. Yield: 65%.
Example 15
15-1. Production of 2-thiobenzoyl-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide ##STR173##
In 30 ml of tetrahydrofuran was dissolved 0.90 g (5.9 mmoles) of thiobenzhydrazide, and 0.5 ml of pyridine was added to the resulting solution. Then, a solution of 1.08 g (5.3 mmoles) of 4-trifluoromethoxyphenyl isocyanate in 2 ml of tetrahydrofuran was added dropwise, and the reaction was carried out at room temperature for 4 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.18 g of the desired compound.
Physical property: m.p. 191.degree. C. Yield: 62%.
15-2. Production of 2-(.alpha.-isopropylthiobenzylidene)-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 278) ##STR174##
In 30 ml of acetone was suspended 1.5 g (4.2 mmoles) of 2-thiobenzoyl-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which 0.72 g (4.2 mmoles) of isopropyl iodide and 1.5 g of anhydrous potassium carbonate were added to the resulting suspension, and the reaction was carried out at room temperature for 1 hour.
After completion of the reaction, the solvent was distilled off under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure to obtain 1.3 g of the desired compound as crystals.
Physical property: m.p. 122.degree. C. Yield: 79%.
15-3. Production of 2-(.alpha.-isopropylsulfinylbenzylidene)N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 279) and 2-(.alpha.-isopropylsulfonylbenzylidene)-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 280) ##STR175##
In 20 ml of methanol was dissolved 0.50 g (1.3 mmoles) of 2-(.alpha.-isopropylthiobenzylidene)-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which a suspension of 2.0 g (3.3 mmoles) of sodium peroxymonosulfate in 10 ml of water was added to the resulting solution, and the reaction was carried out at room temperature for 30 minutes.
After completion of the reaction, the reaction mixture was poured into water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then freed of the solvent under reduced pressure. The product thus obtained was purified by a silica gel column chromatography (ethyl acetate: n-hexane=1:2) to obtain the desired compound.
Physical property Sulfoxide product: paste. Amount (yield) 0.23 g (44%). Sulfone product: m.p. 124.degree. C. (decomp.). Amount (yield) 0.10 g (19%).
Example 16
Production of 2-[2-(4-cyanophenoxy)-1-phenylethyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 342) ##STR176##
In a mixed solvent of 15 ml of methanol and 15 ml of tetrahydrofuran was dissolved 0.30 g (0.66 mmole) of 2-[2-(4-cyanophenoxy)-1-phenylethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which 0.20 g (3.2 mmoles) of sodium cyanoborohydride (NaBH.sub.3 CN) was added to the resulting solution. The resulting mixture was maintained at pH 4 to 6 with hydrogen chloride (a methanolic solution) with stirring. After confirming the completion of the reaction by a thinlayer chromatography, the solvent was distilled off under reduced pressure and water was added to the residue, followed by neutralization with sodium hydrogencarbonate. The desired compound was extracted with ethyl acetate, and the organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 0.32 g of the desired compound was obtained.
Physical property: m.p. 176.degree. C. Yield: 76%.
Example 17
Production of 2-[2-benzoylamino-1-(4-chlorophenyl)ethyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 372) ##STR177##
In 10 ml of methanol was suspended 0.30 g (0.59 mmole) of 2-[2-benzoylamino-l-(3-chlorophenyl)ethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, and 0.07 g (1 mmole) of sodium cyanoborohydride was added to the resulting suspension. The resulting mixture was adjusted to pH 4 to 6 with a methanolic solution of hydrogen chloride at room temperature and subjected to reaction.
After confirming the completion of the reaction by a thin-layer chromatography, the desired compound was extracted with ethyl acetate, and the organic layer was washed with an aqueous sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 0.20 g of the desired compound was obtained.
Physical property: m.p. 230.degree. C. Yield: 67%.
Example 18
Production of 2-[2-(2-propynylthio)-1-phenylethyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 344) ##STR178##
In 10 ml of methanol was suspended 0.50 g (1.2 mmoles) of 2-[2-(2-propynylthio)-1-phenylethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, and 0.37 g (4.7 mmoles) of sodium cyanoborohydride was added to the resulting suspension. The resulting mixture was adjusted to pH 4 to 6 with a methanolic solution of hydrogen chloride at room temperature and subjected to reaction.
After confirming the completion of the reaction by a thin-layer chromatography, the desired compound was extracted with ethyl acetate, and the organic layer was washed with an aqueous sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 0.36 g of the desired compound was obtained.
Physical property: m.p. 157.degree. C. Yield: 73%.
Example 19
Production of 2-[3-carbamoyl-1-(3-trifluoromethylphenyl)propyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. 390) ##STR179##
In a mixed solvent of 15 ml of tetrahydrofuran and 15 ml of methanol was dissoved 0.46 g (1.0 mmole) of 2-[3-carbamoyl-1-(3-trifluoromethylphenyl)propylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide, after which to the resulting solution were added 0.46 g (7.7 mmoles) of sodium cyanoborohydride and then 5 drops of a saturated methanolic solution of hydrochloric acid, and the reaction was carried out for 36 hours.
After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (methanol: ethyl acetate) to obtain 0.35 g of the desired compound.
Physical property: m.p. 135.degree. C. Yield: 76%.
Example 20
20-1. Production of 2-phenyl-2-(N-phenylcarbamoylmethyl)hydrazonoacetic acid ##STR180##
To 30 ml of toluene were added 3.00 g (27.8 mmoles) of phenylhydrazine, 4.71 g of chloroacetanilide and 2.81 g (27.8 mmoles) of triethylamine, and the reaction was carried out with heating under reflux for 13 hours.
After completion of the reaction, 50 ml of water was added to the reaction mixture and the desired compound was extracted with ethyl acetate (50 ml.times.2). The extracted solution was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 5.43 g of a crude product of 2-(1-phenylhydrazino)acetanilide was obtained.
In a mixed solvent of 50 ml of ethanol and 10 ml of dioxane was dissolved 2.50 g (10.4 mmoles) of the obtained 2-(1-phenylhydrazino)acetanilide, after which to the resulting solution was added 1.73 g (9.3 mmoles) of a 40% aqueous glyoxylic acid solution under ice-cooling, and the reaction was carried out at room temperature for 2 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution containing the desired compound, and the residue was washed with ether to obtain 1.13 g of the desired compound.
Physical property: m.p. 193.degree.-194.degree. C. Yield: 33%.
20-2. Production of 2-phenyl-2-(N-phenylcarbamoylmethyl)hydrazono-(4-trifluoromethoxy)acetanilide (compound No. 405) ##STR181##
To 10 ml of dried carbon tetrachloride were added 0.40 g (1.4 mmoles) of 2-phenyl-2-(N-phenylcarbamoylmethyl)hydrazonoacetic acid and 0.32 g (2.7 mmoles) of thionyl chloride, and the reaction was carried out with heating under reflux for 1 hour.
After completion of the reaction, the reaction solution was allowed to cool and distilled under reduced pressure to remove the solvent and the excess thionyl chloride. The resulting concentrate was added dropwise to a solution of 0.26 g (2.5 mmoles) of triethylamine and 0.22 g (1.3 mmoles) of 4-trifluoromethoxyaniline in dried tetrahydrofuran, and the reaction was carried out at room temperature for 5 hours.
After completion of the reaction, 80 ml of water was added to the reaction solution and the desired compound was extracted with ethyl acetate (100 ml.times.2). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The crystals thus obtained were washed with an ether-ethyl acetate mixed solution to obtain 0.35 g of the desired compound.
Physical property: m.p. 243.degree.-245.degree. C. Yield: 60%.
Example 21
21-1. Production of 2-(3-chlorophenyl)hydrazinoacetic acid ##STR182##
In 50 ml of ethanol was dissolved 15.0 g (0.11 mole) of 3-chlorophenylhydrazine, followed by adding dropwise thereto 19.5 g (0.11 mole) of a 40% aqueous glyoxylic acid solution and a solution of 4.2 g (0.11 mole) of sodium hydroxide in 20 ml of water under ice-cooling, and the reaction was carried out at room temperature for 2 hours.
After completion of the reaction, 80 ml of water was added to the reaction solution and the desired compound was extracted with ethyl acetate (100 ml.times.2). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The crystals thus obtained were washed with an ether-ethyl acetate mixed solution to obtain 12.2 g of the desired compound.
Yield 58.4%.
.sup.1 H-NMR [CDCl.sub.3 /TMS, .delta. values (ppm)] 2.05 (bs, 1H), 6.98-7.01 (m, 2H), 7.08 (s, 1H), 7.18-7.25 (m, 2H), 8.50 (s, 1H).
21-2. Production of 2-(3-chlorophenyl)hydrazono-(4-trifluoromethoxy)acetanilide ##STR183##
In 150 ml of dried dichloromethane was dissolved 8.9 g (50 mmoles) of 4-trifluoromethoxyaniline, and 12.9 g (50 mmoles) of 2-chloro-1-methylpyridinium iodide was added to the resulting solution. Then, a solution of 12.7 g (130 mmoles) of triethylamine and 10.0 g (50 mmoles) of 2-(3-chlorophenyl)hydrazonoacetic acid in 50 ml of dried tetrahydrofuran was added dropwise at room temperature. After completion of the dropwise addition, the reaction was carried out at room temperature for 10 hours.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution, and 100 ml of water was added to the residue. The desired compound was extracted with ethyl acetate (200 ml.times.2), and the organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (n-hexane: ethyl acetate=3:1) to obtain 5.64 g of the desired compound.
Physical property: m.p. 196.degree.-197.degree. C. Yield: 31.6%.
21-3. Production of 2-allyl-2-(3-chlorophenyl)hydrazono-(4-trifluoromethoxy)acetanilide (compound No. 414) ##STR184##
In 15 ml of dried dimethylformamide was dissolved 0.60 g (1.7 mmoles) of 2-(3-chlorophenyl)hydrazono-(4-trifluoromethoxy)acetanilide, and 0.08 g (2.0 mmoles) of 60% sodium hydride was added to the resulting solution under ice-cooling and stirred for 10 minutes. Then, 0.22 g (1.9 mmoles) of 3-propenylbromide was added dropwise and the reaction was carried out at room temperature for 1 hour.
After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted with ethyl acetate (50 ml.times.2). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (n-hexane: ethyl acetate=3:1) to obtain 0.27 g of the desired compound.
Physical property: m.p. 79.degree.-81.degree. C. Yield: 40%.
Example 22
Production of 2-(3-chlorophenyl)-2-[N-(4-cyanophenylcarbamoylmethyl)]hydrazino-(4-trifluoromethoxy)acetanilide (compound No. 443) ##STR185##
In a mixed solvent of 1 ml of dried tetrahydrofuran and 3 ml of methanol was dissolved 0.18 g (0.35 mmole) of 2-(3-chlorophenyl)-2-[N-(4-cyanophenylcarbamoylmethyl)]hydrazono-(4-trifluoromethoxy)acetanilide, followed by adding thereto 0.09 g (1 mmole) of sodium cyanotrihydroborate and 3 ml of a saturated methanolic solution of hydrochloric acid under ice-cooling, and the reaction was carried out at room temperature for 1 hour.
After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction mixture, and 30 ml of a saturated aqueous sodium hydrogencarbonate solution was added to the residue. The desired compound was extracted with ethyl acetate (300 ml.times.2), and the organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The resulting residue was purified by a silica gel column chromatography (n-hexane: ethyl acetate=1:1) to obtain 0.17 g of the desired compound.
Physical property: m.p. 183.2.degree.-184.6.degree. C. Yield: 94%.
Example 23
23-1. Production of S-Phenyl 3-chloro-N-methylbenzhydrazonethioate. ##STR186##
In 30 ml of dimethylformamide was dissolved 2.0 g (8.1 mmoles) of 3-chloro-N-methylbenzhydrazonoyl bromide, after which 1.1 g (9.7 mmoles) of thiophenol and 2.0 g (14 mmoles) of anhydrous potassium carbonate was added to the resulting solution, and the reaction was carried out at room temperature for 4 hours.
After completion of the reaction, the reaction mixture was poured into ice water and extracted with ether. The extracted solution was dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 1.7 g of the desired compound was obtained as oil.
Physical property: nD 1.6621 (29.degree. C.). Yield: 99%.
23.2. Production of 2-(3-chloro-.alpha.-phenylthiobenzylidene)-N-(4-difluoromethoxyphenyl)-1-methylhydrazinecarboxamide. (Compound No. 309) ##STR187##
In 20 ml tetrahydrofran was dissolved 0.43 g (2.0 mmoles) of S-phenyl 3-chloro-N-methylbenzhydrazonethioate, after which 0.5 ml of pyridine was added to the resulting solution. Subsequently, a solution of 0.36 g (1.9 mmoles) of 4-difluoromethoxyphenyl isocyanate in 1 ml tetrahydrofran solution was added dropwise to the reaction mixture. The reaction was carried out at room temperature for 2 hours.
After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent, whereby a crude product was obtained. The obtained crude product was purified by a silica-gel column chromatography (n-hexane: ethyl acetate=4:1) to obtain 0.32 g of desired compound as crystals.
Physical property: m.p. 96.degree. C. Yield: 41%.
Agricultural and horticultural insecticides containing the hydrazine derivative of the general formula (I) of the present invention as an active ingredient are suitable for controlling various insect pests such as agricultural insect pests, forest insect pests, horticultural insect pests, stored grain insect pests, sanitary insect pests, nematodes, etc. They have an insecticidal effect also, for example, on LEPIDOPTERA including summer fruit tortrix (Adoxophyes orana fasciata), smaller tea tortrix (Adoxophes sp.), Manchurian fruit moth (Grapholita inopinata), oriental fruit moth (Grapholita mlesta), soybean pod border (Leguminivora glycinivorella), mulberry leafroller (Olethreutes mori), tea leafroller (Caloptilla thevivora), Caloptilia sp. (Calopilia zachrysa), apple leafminer (Phyllonorycter rengoniella), pear barkminer (Spulerina astaurota), common white (Piers rapae crucivora), tabacco budworm (Heliothis armigera), codling moth (Laspeyresia pomonella), diamondback moth (Plutella xylostella), apple fruit moth (Argyresthia conjugella), peach fruit moth (Carposina niponensis), rice stem borer (Chilo suppressalia), rice leafroller (Cnaphalocrocis medinalis), tabacco moth (Ephestia elutella), mulberry pyralid (Glyphodes pyloalis), yellow rice borer (Scirpophaga incertulas), rice skipper (Parnara guttata), rice armyworm (Pseudaletia separata), pink borer (Sesamia inferens), common cutworm (Spodoptera litura), beet armyworm (Spodoptera exigua), etc.; HEMIPTERA including aster leafhopper (Macrosteles fascifrons), green rice leafhopper (Nephotettix cincticeps), brown rice planthopper (Nilaparvata lugens), whitebacked rice planthopper (Sogatella furcifera), citrus psylla (Diaphorina citri), grape whitefly (Aleurolobus taonabae), sweetpotato whitefly (Bemisia tabaci), greenhouse whitefly (Trialeurodes vaporariorum), turnip aphid (Lipaphis erysimi), green peach aphid (Myzus persicae), Indian wax scale (Ceroplastes ceriferus), cottony citrus scale (Pulvinaria aurantii), camphor scale (Pseudaonidia duplex), San Jose scale (Comstockaspis perniciosa), arrowhead scale (Unaspis yanonensis), etc.; COLEOPTERA including soybean beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica), tabacco beetle (Lasioderma serricorne), powderpost beetle (Lyctus brunneus), twenty-eight-spotted ladybird (Epilachna vigintioctopunctata), adzuki bean weevile (Callosobruchus chinensis), vegetable weevil (Listroderes costirostris), maize weevil (Sitophilus zeamais), boll weevil (Anthonomus grandis grandis), rice water weevil (Lissorphoptrus oryzophilus), cucurbit leaf beetle (Aulacophora femoralis), rice leaf beetle (Outlema oryzae), striped flea beetle (Phyllotreta striolata), pine shoot beetle (Tomicus piniperda), Colorado potato beetle (Leptinotarsa decemilineata), Mexican bean beetle (Epilachna varivestis), corn rootworm (Diabrotica sp.), etc.; DIPTERA including melon fly (Dacus(Zeugodacus) cucurbitae), oriental fruit fly (Dacus(Bactrocera) dorsalis), rice leafminer (Agnomyza oryzae), onion maggot (Delia antiqua), seedcorn maggot (Delia platura), soybeanpod gall midge (Asphodylia sp.), muscid fly (Musca domestica), house mosquito (Culex pipiens), etc.; and TYLENCHIDA including root-lesion nematode (Pratylenchus sp.), coffer root-lesion nematode (Pratylenchus coffeae), potato cyst nematode (Globodera rostochiensis), root-knot nematode (meloidogyne sp.), citrus nematode (Tylenchulus semipenetrans), Aphelenchus sp. (Aphelenchus avenae), chrysanthemum foliar (Aphelenchoides ritzemabosi), etc. The insecticides are markedly effective particularly against insect pest belonging to LEPIDOPTERA, COLEOPTERA and the like.
The zoological names and the like are in accordance with Applied Zoology and Entomology Society of Japan, "List of Agricultural and Forest Injurious Animals and Insects", published in 1987.
The agricultural and horticultural insecticide containing the hydrazine derivative of the general formula (I) of the present invention as an active ingredient has a marked insecticidal effect on the above-exemplified insect pests, sanitary insect pests, and/or nematodes, which are inurious to paddy rice, fruit trees, vegetables and other crops, and flowers and ornament plants. Therefore, the desired effect of the insecticide of the present invention can be obtained by applying the insecticide to the paddy field water, stalks and leaves of fruit trees, vegetables, other crops, flowers and ornament plants, soil, etc., or to the inside of a house or ditches around a house, in which the above-exemplified sanitary insect pests injurious to men and beasts appear or are expected to appear. The application is carried out at a season at which the insect pests, sanitary pests or nematodes are expected to appear, before their appearance or at the time when their appearance is confirmed. The present invention however should not be limited to these embodiments.
When the hydrazine derivative of the general formula (I) of the present invention is used as an agricultural and horticultural insecticide, it is generally prepared into conveniently usable forms according to an ordinary manner for preparation of agrochemicals.
That is, the hydrazine derivative of the general formula (I) of the present invention and, optionally, an adjuvant are blended with a suitable inert carrier in a proper proportion and prepared into a suitable preparation form such as a suspension, emulsifiable concentrate, soluble concentrate, wettable powder, granules, dust or tablet through dissolution, dispersion, suspension, mixing, impregnation, adsorption or sticking.
The inert carrier in this invention may be either solid or liquid. As the solid carrier, there can be exemplified soybean flour, cereal flour, wood flour, bark flour, saw dust, powdered tobacco stalks, powdered walnut shells, bran, powdered cellulose, extraction residues of vegetables, powdered synthetic polymers or resins, clays (e.g. kaolin, bentonite, and acid clay), talcs (e.g. talc and pyrophyllite), silica powders or flakes [e.g. diatomaceous earth, silica sand, mica and white carbon, i.e. synthetic, high-dispersion silicic acid, also called finely divided hydrated silica or hydrated silicic acid, some of commercially available products contain calcium silicate as the major component)], activated carbon, powdered sulfur, powdered pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate powder, calcium phosphate powder and other inorganic or mineral powders, chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride), and compost. These carriers may be used alone or as a mixture thereof.
The liquid carrier is that which itself has solubility or which is without such solubility but is capable of dispersing an active ingredient with the aid of an adjuvant. The following are typical examples of the liquid carrier and can be used alone or as a mixture thereof. Water; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; ethers such as ethyl ether, dioxane, Cellosolve, dipropyl ether and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and mineral oils; aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha and alkylnaphthalene; halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate and dioctyl phthalate; amides such as dimethylformamide, diethylformamide and dimethylacetamide; nitriles such as acetonitrile; and dimethyl sulfoxide.
The following are typical examples of the adjuvant, which are used depending upon purposes and used alone or in combination in some cases, or need not to be used at all.
To emulsify, disperse, dissolve and/or wet an active ingredient, a surfactant is used. As the surfactant, there can be exemplified polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonates and higher alcohol sulfate esters.
Further, to stabilize the dispersion of an active ingredient, tackify it and/or bind it, there may be used adjuvants such as casein, gelatin, starch, methyl cellulose, carboxymethyl cellulose, gum arabic, polyvinyl alcohols, turpentine, bran oil, bentonite and lignin sulfonates.
To improve the flowability of a solid product, there may be used adjuvants such as waxes, stearates and alkyl phosphates.
Adjuvants such as naphthalenesulfonic acid condensation products and polycondensates of phosphates may be used as a peptizer for dispersible products.
Adjuvants, e.g. silicon oils may also be used as a defoaming agent.
The content of the active ingredient may be varied as required. In dusts or granules, the suitable content thereof is from 0.01 to 50% by weight. In emulsifiable concentrates or flowable wettable powders, it is also from 0.01 to 50% by weight.
An agricultural and horticultural insecticide containing the hydrazine derivative of the general formula (I) of the present invention as an active ingredient is used to control a variety of insect pests in the following manner. That is, it is applied to the insect pests or a site where appearance or growth of the insect pests is undesirable, as it is or after being properly diluted with or suspended in water or the like, in an amount effective for control of the insect pests.
The applying dosage of the agricultural and horticultural insecticide containing the hydrazine derivative of the general formula (I) of the present invention as an active ingredient is varied depending upon various factors such as a purpose, insect pests to be controlled, a growth state of a plant, tendency of insect pests appearance, weather, environmental conditions, a preparation form, an application method, an application site and an application time. It may be properly chosen in the range of 0.01 g to 5 kg (in terms of the active ingredient) per 10 ares depending upon purposes.
The agricultural and horticultural insecticide containing the hydrazine derivative of the general formula (I) of the present invention as an active ingredient may be used in admixture with other insecticides or fungicides in order to expand both spectrum of controllable insect pest species and the period of time when effective applications are possible or to reduce the dosage.
Typical preparation examples and test examples of the present invention are described below but they should not be construed as limiting the scope of the invention.
In the preparation examples, parts are all by weight.
______________________________________Formulation Example 1______________________________________Each compound of the invention 50 partsXylene 40 partsMixture of polyoxyethylene 10 partsnonylphenyl ether and calciumalkylbenzenesulfonate______________________________________
An emulsifiable concentrate was prepared by mixing uniformly the above ingredients to effect dissolution.
______________________________________Formulation Example 2______________________________________Each compound of the invention 3 partsClay powder 82 partsDiatomaceous earth powder 15 parts______________________________________
A dust was prepared by mixing uniformly and grinding the above ingredients.
______________________________________Formulation Example 3______________________________________Each compound of the invention 5 partsMixed powder of bentonite and clay 90 partsCalcium lignin sulfonate 5 parts______________________________________
Granules were prepared by mixing the above ingredients uniformly, and kneading the resulting mixture together with a suitable amount of water, followed by granulation and drying.
______________________________________Formulation Example 4______________________________________Each compound of the invention 20 partsMixture of kaolin and synthetic, 75 partshigh-dispersion silicic acidMixture of polyoxyethylene 5 partsnonylphenyl ether and calciumalkylbenzenesulfonate______________________________________
A wettable powder was prepared by mixing uniformly and grinding the above ingredients.
Test Example 1
Insecticidal effect on common cutworm (Spodoptera litura)
A piece of cabbage leaf (cultivar; Shikidori) was immersed for about 30 seconds in a liquid chemical prepared by diluting a preparation containing each compound of the present invention as an active ingredient to adjust the concentration to 500 ppm.
After air-drying, it was placed in a plastic Petri dish with a diameter of 9 cm and inoculated with second-instar larvae of common cutworm, after which the dish was closed and then allowed to stand in a room thermostated at 25%.
Eight days after the inoculation, the dead and alive were counted. The mortality was calculated according to the following equation and the insecticidal effect was judged according to the criterion shown below.
The test was carried out with triplicate groups of 10 insects.
______________________________________ ##STR188## Criterion:______________________________________ Effect Mortality (%)______________________________________ A 100 B 99-90 C 89-80 D 79-50______________________________________
The results obtained are shown in Table 9.
TABLE 9______________________________________Compound ConcentrationNo. (ppm) Judgement______________________________________2 500 A3 500 A4 500 D5 500 A6 500 C7 500 B8 500 D10 500 A11 500 A12 500 A13 500 A14 500 A15 500 A16 500 A17 500 A18 500 A19 500 A20 500 A26 500 D31 500 A32 500 A33 500 A34 500 A35 500 C39 500 D41 500 B45 500 A46 500 A47 500 A48 500 A49 500 A21 500 A22 500 A23 500 A25 500 A29 500 C50 500 A51 500 C52 500 A53 500 A54 500 A55 500 A56 500 A57 500 A58 500 A59 500 A60 500 A61 500 A62 500 A65 500 A66 500 A67 500 A68 500 A69 500 A70 500 A72 500 A73 500 A74 500 A75 500 A76 500 A77 500 A78 500 A79 500 A80 500 A81 500 A82 500 C83 500 A84 500 D85 500 A86 500 A87 500 A88 500 A89 500 A90 500 A92 500 A93 500 A94 500 A95 500 A96 500 D97 500 A98 500 A99 500 A100 500 A101 500 D103 500 A104 500 B105 500 A106 500 A107 500 A108 500 A109 500 A110 500 B111 500 A112 500 A113 500 A114 500 B115 500 A116 500 A117 500 A118 500 A119 500 A120 500 A121 500 A122 500 A123 500 A124 500 A125 500 A126 500 A127 500 A128 500 A129 500 A130 500 A131 500 A132 500 A133 500 A134 500 A135 500 A136 500 A137 500 A138 500 A139 500 A140 500 A141 500 D142 500 A143 500 A144 500 A145 500 A147 500 A148 500 C150 500 C152 500 C154 500 A155 500 A156 500 A157 500 A158 500 A159 500 A160 500 A161 500 A162 500 A163 500 A164 500 A165 500 A166 500 A167 500 A168 500 A169 500 A170 500 A171 500 A172 500 A173 500 A174 500 A175 500 A176 500 A177 500 A178 500 A179 500 A180 500 A181 500 A182 500 D183 500 A184 500 A185 500 A186 500 A187 500 A188 500 A189 500 D190 500 A191 500 C192 500 D193 500 A195 500 A196 500 A197 500 A198 500 A199 500 A200 500 A201 500 A202 500 A203 500 A204 500 A205 500 A206 500 A207 500 A208 500 A209 500 A210 500 A211 500 A213 500 D214 500 A215 500 A216 500 A217 500 A218 500 A219 500 A220 500 A222 500 A223 500 A224 500 A225 500 A226 500 A227 500 A228 500 A229 500 A230 500 A231 500 A232 500 A233 500 A234 500 A235 500 A236 500 A237 500 A238 500 A239 500 A240 500 A241 500 A242 500 A243 500 A244 500 A245 500 B246 500 A247 500 A248 500 A249 500 A250 500 A251 500 A252 500 A253 500 A254 500 A255 500 A256 500 A257 500 A258 500 A259 500 C261 500 B262 500 A264 500 A265 500 A266 500 A267 500 C268 500 A269 500 A270 500 A271 500 A272 500 A274 500 A275 500 D276 500 A277 500 A278 500 A279 500 A280 500 A281 500 A282 500 B285 500 A286 500 A287 500 A288 500 A289 500 A290 500 A291 500 A292 500 A293 500 A294 500 D295 500 D296 500 A297 500 A298 500 A300 500 A301 500 A302 500 D303 500 A304 500 A305 500 D307 500 A308 500 A309 500 A310 500 A311 500 A312 500 A314 500 A315 500 A316 500 A317 500 A318 500 A319 500 D320 500 D321 500 A322 500 A323 500 A324 500 A325 500 A326 500 A327 500 A328 500 A329 500 C330 500 D332 500 A333 500 A334 500 A335 500 A336 500 A337 500 A338 500 A341 500 C343 500 A344 500 A345 500 B349 500 A350 500 A352 500 A354 500 A356 500 A357 500 A359 500 A360 500 A361 500 A362 500 A363 500 A364 500 A365 500 A366 500 A367 500 A368 500 A369 500 A370 500 A371 500 B372 500 A373 500 A374 500 A375 500 A376 500 A377 500 A378 500 A379 500 A380 500 A381 500 A382 500 A384 500 A386 500 A387 500 A388 500 A389 500 A390 500 A391 500 A392 500 A393 500 A394 500 A395 500 A396 500 A397 500 A398 500 A399 500 A401 500 A403 500 A405 500 C406 500 A407 500 A408 500 A409 500 C410 500 B411 500 A412 500 D413 500 A414 500 B415 500 B416 500 A418 500 A419 500 A420 500 A421 500 A422 500 A423 500 A424 500 A425 500 A426 500 A427 500 B428 500 A429 500 A430 500 A431 500 A432 500 A433 500 D434 500 B436 500 B437 500 B438 500 B440 500 A441 500 A442 500 D443 500 A444 500 A445 500 A446 500 A447 500 A448 500 A449 500 A______________________________________
Test Example 2
Insecticidal effect on adult maize weevil (Sitophilus zeamais)
Brown rice grains were immersed for about 30 seconds in a liquid chemical prepared by diluting a preparation containing each compound of the present invention as an active ingredient to adjust the concentration to 200 ppm.
After air-drying, it was placed in a glass Petri dish with a diameter of 4 cm and inoculated with adult maize weevil, after which the dish was closed and then allowed to stand in a room thermostated at 25%.
Eight days after the inoculation, the dead and alive were counted. The mortality was calculated in the same manner as in Test Example 1 and the insecticidal effect was judged according to the criterion shown in Test Example 1.
The test was carried out with triplicate groups of 10 insects.
The results obtained are shown in Table 10.
TABLE 10______________________________________ Concen- Concent-Compound tration Judge- Compound ration Judge-No. (ppm) ment No. (ppm) ment______________________________________5 200 D 29 200 A10 200 A 30 200 A12 200 A 31 200 A14 200 A 32 200 A17 200 A 33 200 A18 200 A 34 200 A21 200 C 36 200 A22 200 C 37 200 B24 200 D 39 200 C25 200 C 45 200 A27 200 A 47 200 A28 200 A 49 200 A50 200 A 80 200 A53 200 A 82 200 D54 200 A 85 200 A56 200 A 86 200 A57 200 C 87 200 A58 200 A 88 200 C59 200 A 89 200 A60 200 A 90 200 A62 200 A 92 200 A65 200 A 93 200 A66 200 A 94 200 A67 200 A 95 200 A68 200 A 96 200 A69 200 A 97 200 A73 200 A 98 200 A74 200 A 99 200 A75 200 A 100 200 A76 200 A 101 200 A77 200 A 104 200 A78 200 C 105 200 D79 200 A 106 200 A108 200 A 139 200 A109 200 A 141 200 A112 200 C 142 200 A113 200 C 143 200 A114 200 A 144 200 A115 200 A 145 200 A117 200 D 146 200 C118 200 A 147 200 C119 200 A 153 200 D120 200 C 154 200 A121 200 C 157 200 A122 200 C 158 200 A124 200 A 160 200 A125 200 A 162 200 A127 200 C 164 200 A128 200 A 165 200 A129 200 A 166 200 A130 200 C 167 200 C131 200 A 169 200 A137 200 A 170 200 A138 200 C 172 200 C173 200 D 201 200 A174 200 A 202 200 A175 200 A 203 200 A177 200 A 204 200 A178 200 A 206 200 A179 200 A 207 200 A180 200 C 208 200 A183 200 A 209 200 A184 200 A 210 200 C185 200 A 211 200 A186 200 A 212 200 A187 200 C 214 200 A188 200 D 215 200 A190 200 A 216 200 A194 200 A 217 200 A195 200 A 218 200 A196 200 C 219 200 A197 200 A 220 200 A198 200 A 221 200 A199 200 A 222 200 A200 200 A 225 200 A226 200 A 247 200 A227 200 A 248 200 A228 200 A 249 200 A229 200 A 250 200 A230 200 A 251 200 A231 200 A 252 200 A232 200 A 254 200 C233 200 A 256 200 A234 200 A 258 200 A235 200 A 259 200 A236 200 C 268 200 A237 200 A 269 200 A238 200 C 270 200 A239 200 A 271 200 A240 200 A 272 200 A241 200 A 274 200 D242 200 A 276 200 A243 200 A 278 200 A244 200 A 279 200 A245 200 A 281 200 C246 200 A 282 200 A283 200 D 321 200 A288 200 A 322 200 A290 200 D 323 200 A291 200 A 324 200 D292 200 A 325 200 A293 200 A 326 200 A294 200 C 327 200 A297 200 A 328 200 A298 200 A 329 200 A302 200 C 332 200 A303 200 A 333 200 A305 200 C 334 200 A307 200 C 335 200 D308 200 D 336 200 A310 200 A 337 200 A314 200 A 339 200 A315 200 D 341 200 A316 200 A 342 200 A317 200 A 343 200 A318 200 A 344 200 A320 200 C 345 200 A349 200 A 378 200 A350 200 A 379 200 A351 200 D 380 200 A352 200 C 381 200 A354 200 A 382 200 A355 200 A 383 200 A356 200 A 384 200 C358 200 C 385 200 D359 200 A 386 200 A360 200 A 387 200 A361 200 A 388 200 A362 200 A 389 200 A363 200 A 390 200 A364 200 C 391 200 A365 200 A 392 200 A366 200 A 393 200 A368 200 A 394 200 A371 200 A 396 200 A372 200 A 397 200 A375 200 D 398 200 A377 200 A 399 200 D400 200 A 428 200 D401 200 A 429 200 A406 200 D 430 200 A410 200 C 432 200 A411 200 A 433 200 D412 200 A 434 200 A414 200 A 435 200 C415 200 A 436 200 A417 200 A 437 200 A418 200 A 438 200 A419 200 A 439 200 A420 200 C 441 200 A421 200 A 442 200 A422 200 A 443 200 A423 200 A 444 200 A424 200 A 445 200 A425 200 A 446 200 A426 200 A 447 200 A427 200 A 449 200 A______________________________________

Number	Name	Date
3558654	Bamford et al.	Jan 1971
3712914	Tilles	Jan 1973
3753680	Tilles	Aug 1973
4606987	Matsuura et al.	Aug 1986
5118830	Findeisen et al.	Jun 1992
5182303	Daub et al.	Jan 1993
5376685	Stanek et al.	Dec 1994
5395855	Stanek et al.	Mar 1995

Number	Date	Country
0462456	Dec 1991	EPX
0486937	May 1992	EPX
5-17428	Jan 1993	JPX
5-4958	Jan 1993	JPX
5-32603	Feb 1993	JPX
5-262712	Oct 1993	JPX
7-53501	Feb 1995	JPX
9206076	Apr 1992	WOX
94-06758	Mar 1994	WOX
94-08954	Apr 1994	WOX

Insecticidal hydrazine derivatives

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Entry
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