US 5,256,679 A · Substituted guanidine derivatives, their preparation and use

Abstract

Novel substituted nitroguanidine derivatives and salts thereof having the following formula: ##STR1## wherein R.sup.1 is a substituted or unsubstituted heterocyclic group; R.sup.2 is a group attached through a sulfur atom, a group attached through a phosphorus atom, cyano, --CO--OR.sup.6 wherein R.sup.6 is a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group, or --CO--NR.sup.7 R.sup.8 wherein R.sup.7 and R.sup.8, which are the same or different, are each independently hydrogen, a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group, or R.sup.7 and R.sup.8, taken together with the nitrogen atom to which they are attached are a cyclic amino group; R.sup.3 is hydrogen, a substituted or unsubstituted hydrocarbon group (except for one substituted with an oxo group at the binding site), a group attached through a sulfur atom, a group attached through a phosphorus atom, cyano, --CO--R.sup.9 wherein R.sup.9 is hydrogen, a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group, --CO--OR.sup.10 wherein R.sup.10 is a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group, or --CO--NR.sup.11 R.sup.12 wherein R.sup.11 and R.sup.12, which are the same or different, are each independently hydrogen, a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group, or R.sup.11 and R.sup.12, taken together with the nitrogen atom to which they are attached are a cyclic amino group; and R.sup.4 is hydrogen or a lower alkyl group; which have unexpectedly potent pesticidal activity and very low toxicity.

A compound of the formula:

##STR113## wherein R.sup.1 is a heterocyclic group having a single or fused ring with 5 to 8 ring members in each ring and having from 1 to 5 heteroatoms in each ring independently selected from the group consisting of oxygen, nitrogen, and sulfur, wherein said heterocyclic group may optionally be substituted with 1 to 5 substituents which may be the same or different selected from the group consisting of C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-10 alkynyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
nitro;
hydroxyl;
mercapto;
oxo;
thioxo;
cyano;
carbamoyl;
carboxyl;
C.sub.1-4 alkoxycarbonyl;
sulfo;
halogen;
C.sub.1-4 alkoxy optionally substituted with 1 to 5 substituents selected from the group consisting halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.6-10 aryloxy optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.1-4 alkylthio optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.6-10 arylthio optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.1-4 alkylsulfinyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.6-10 arylsulfinyl optionally substituted with 1 to 5 substitutents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.1-4 alkylsulfonyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.6-10 arylsulfonyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
amine optionally substituted with 1 to 2 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-6 acylamino;
mono- or di-C.sub.1-4 alkylamino optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-6 cycloalkylamino optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.6-10 arylamino optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-4 acyl;
C.sub.6-10 arylcarbonyl;
and 5 to 6 membered heterocyclic containing from 1 to 4 heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
R.sup.2 is cyano;
--CO--OR.sup.6 wherein R.sup.6 is a hydrocarbon group selected from the group consisting of C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkyl, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-10 alkynyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substitutents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
and C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkythio, and phenylthio;
or R.sup.6 is a heterocyclic group as defined for R.sup.1 ;
or --CO--NR.sup.7 R.sup.8 wherein R.sup.7 and R.sup.8, which are the same or different, are each independently hydrogen, a hydrocarbon group selected from the group consisting of C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-10 alkynyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
and C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
or a heterocyclic group as defined for R.sup.1 ;
or R.sup.7 or R.sup.8, taken together with the nitrogen atom to which they are attached are a cyclic amino group selected from the group consisting of aziridino, azetidino, pyrrolidino, piperazino, piperidino, morpholino, and thiomorpholino which may optionally be substituted with 1 to 4 C.sub.1-4 alkyl groups;
R.sup.3 is hydrogen, a hydrocarbon group except for one substituted with an oxo group at the binding site selected from the group consisting of C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-10 alkynyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkenyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
and C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
--S(O).sub.n --R.sup.13 wherein n is an integer selected from the group consisting of 0, 1, and 2 and R.sup.13 is selected from the group consisting of a heterocyclic group as defined for R.sup.1 ;
C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxy, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 and 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-10 alkynyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
and C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
--P(.dbd.O)R.sup.14 R.sup.15 wherein R.sup.14 and R.sup.15 are each independently a heterocyclic group as defined for R.sup.1 ;
C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.2-10 alkynyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
and C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
cyano;
--CO--R.sup.9 wherein R.sup.9 is hydrogen, a hydrocarbon group selected from the group consisting of C.sub.1-15 alkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.2-10 alkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio;
C.sub.3-10 cycloalkenyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
C.sub.6-10 aryl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
and C.sub.7-10 aralkyl optionally substituted with 1 to 5 substituents selected from the group consisting of halogen, hydroxyl, C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 alkylthio, and phenylthio;
or R.sup.9 is a heterocyclic group as defined for R.sup.1 ;
--CO--OR.sup.6 as defined above;
or
--CO--NR.sup.7 R.sup.8 as defined above;
and
R.sup.4 is hydrogen or a lower alkyl group;
or a salt thereof.

86 more elements

Substituted guanidine derivatives, their preparation and use

Life of this patent

Substituted guanidine derivatives, their preparation and use

Life of this patent

Abstract

Claims42