&agr;-unsaturated amines, their production and use

Details &agr;-unsaturated amines, their production and use &agr;-unsaturated amines, their production and use

1992-09-17

2002-06-18

Davis, Zinna Northington (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S280400, C546S334000

Reexamination Certificate

active

06407248

ABSTRACT:

This invention relates to agrochemically useful &agr;-unsaturated amines having insecticidal/miticidal activity, their production and use.
Among &agr;-unsaturated amines, such compounds as (i) cimetidine (described for example in Journal of Medicinal Chemistry 24, 913, 1981), (ii) ranitidine (described for example in Agents Actions 11, 160, 1981) and (iii) famotidine (described for example in Journal of Medicinal Chemistry 27, 849, 1984) are known as histamine H
2
receptor antagonists.
As agricultural insecticide/miticides, organophosphorus or carbamate pesticides which are highly toxic to warm-blooded animals have heretofore been employed. However, there has been an emergence of noxious insects, particularly of the order “Hemiptera”, which are resistant to these pesticides, and there has been a long-standing need for the development of a pesticide effective against these resistant pests.
Getting impetus from the aforementioned histamine H
2
receptor antagonists, the present inventors synthesized various &agr;-unsaturated amines and investigated their activities. As a result, we discovered surprisingly that compounds of the invention which have no alkylene group or only a short alkylene group in the side chain have agriculturally useful insecticidal/miticidal activity.
Based on the above finding, the present inventors conducted further research and have come up with the present invention.
The invention is, thus, concerned with:
(1) novel &agr;-unsaturated amines of the formula:
 wherein X
1
and X
2
are such that one is an electron-attracting group with the other being a hydrogen atom or an electron-attracting group; R
1
is a group attached through a nitrogen atom; R
2
is a hydrogen atom or a group attached through a carbon, nitrogen or oxygen atom; n is an integer equal to 0, 1 or 2; A° is a heterocyclic group, with the proviso that when R
2
is a hydrogen atom, R
1
is a group of the formula:
 wherein R
3a
is a hydrogen atom, C
1-4
alkyl, C
7-9
aralkyl or C
1-4
acyl and R
4a
is a hydrogen atom, C
1-4
alkyl, C
1-4
alkoxy-C
1-4
alkyl, (di-C
1-4
alkylamino)-C
1-4
alkyl, tri-C
1-4
alkylsilyl-C
1-4
alkyl, C
2-4
alkenyl, or pyridyl- or thiazolyl-C
1-2
alkyl wherein the pyridyl or thiazolyl moiety may optionally be substituted with a halogen atom, or R
3a
and R
4a
taken together with the adjacent nitrogen atom constitute pyrrolidino and A° is pyridyl, pyrazinyl or thiazolyl which may optionally be substituted with a halogen C
1-4
alkyl, C
1-4
alkylthio or C
1-4
alkoxy, or a salt thereof, and
(2) insecticidal/pesticidal compositions containing an &agr;unsaturated amine of the formula:
 wherein X
1
and X
2
are such that one is an electron-attracting group with the other being a hydrogen atom or an electron-attracting group; R
1
is a group attached through a nitrogen atom; R
2
is a hydrogen atom or a group attached through a carbon, nitrogen or oxygen atom; n is an integer equal to 0, 1 or 2; A is a heterocyclic group or a cyclic hydrocarbon group, with the proviso that when R
1
is &bgr;-N-pyrrolidinoethylamino and R
2
is a hydrogen atom, A is a group of the formula:
 wherein Hal is a halogen atom (e.g. Cl, Br, F, etc.), or a salt thereof, and their production.
Referring to the above formulas [I°] and [I], one of X
1
and X
2
is an electron-attracting group with the other being a hydrogen atom or an electron-attracting group. The electron-attracting group represented by X
1
and X
2
includes, among others, cyano, nitro, C
1-4
alkoxy-carbonyl (e.g. methoxycarbonyl, ethoxycarbonyl, etc.), hydroxycarbonyl, C
6-10
aryloxy-carbonyl (e.g. phenoxycarbonyl etc.), heterocycleoxycarbonyl wherein the heterocycle moiety is as mentioned below (e.g. pyridyloxycarbonyl, thienyloxycarbonyl, etc.), C
1-4
alkylsulfonyl which may be substituted with halogen (e.g. methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.), aminosulfonyl, di-C
1-4
alkoxyphosphoryl (e.g. diethoxyphosphoryl, etc.), C
1-4
acyl which may be substituted with halogen (e.g. a C
1-4
alkylcarbonyl such as acetyl, trichloroacetyl, trifluoroacetyl, etc.), C
1-4
alkylsulfonylthiocarbamoyl (e.g. methylsulfonylthiocarbamoyl, etc.), carbamoyl and so on. One of X
1
and X
2
may be a halogen atom such as fluorine, chlorine, bromine or iodine, and X
1
and X
2
may join together with the adjacent carbon atom to form a ring such as, for example,
Preferred examples of the group
are O
2
NCH═.
Referring to the above formulas [I°] and [I], R
1
may be a group attached through a carbon, oxygen or sulfur atom, but a group attached through a nitrogen atom is preferred. Thus, for example, a group of the formula
can be used. In the above formula, R
3
is for example a hydrogen atom, an alkyl group (for example, a C
1-6
alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-hexyl, etc.), an C
6-10
aryl group (for example, phenyl, etc.), an C
7-9
aralkyl group (for example a phenylalkyl such as benzyl, etc.), a heterocyclic group as mentioned below (for example, pyridyl, etc.), a C
1-4
acyl group (for example, formyl, acetyl, propionyl, etc.), a C
6-10
arylcarbonyl (for example, benzoyl, etc.), an alkoxycarbonyl group (for example, C
1-4
alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, etc.), a C
6-10
aryloxy-carbonyl group (for example, phenoxycarbonyl, etc.), a heterocycleoxycarbonyl group wherein the heterocycle moiety is as mentioned below (for example, furyloxycarbonyl, etc.), a C
6-10
arylsulfonyl group (for example, phenylsulfonyl, etc.), an alkylsulfonyl group (for example, C
1-4
alkylsulfonyl groups such as methylsulfonyl, etc.), a dialkoxyphosphoryl group (for example, di-C
1-4
alkoxyphosphoryl groups such as diethoxyphosphoryl, etc.), an alkoxy group (for example, C
1-4
alkoxy groups such as methoxy, ethoxy, etc.), a hydroxy group, an amino group, a dlalkylamino group (for example, di-C
1-4
alkylamino group such as dimethylamino, diethylamino, etc.), an acylamino group (for example, C
1-4
acylamino groups such as formylamino, acetylamino, propionylamino, etc.), an alkoxycarbonylamino groups (for example, C
1-4
alkoxy-carbonylamino groups such as methoxycarbonylamino, etc.), an alkylsulfonylamino group (for example, C
1-4
alkylsulfonylamino groups such as methylsulfonylamino, etc.), a di-alkoxyphosphorylamino group (for example, di-C
1-4
alkoxyphosphorylamino groups such as diethoxyphosphorylamino, etc.), an C
7-9
aralkyloxy group (for example, benzyloxy, etc.), an alkoxycarbonylalkyl group (for example, C
1-4
alkoxy-carbonyl-C
1-4
alkyl groups such as methoxycarbonylmethyl, etc.) or the like. R
4
is for example a hydrogen atom, or an alkyl (for example, C
1-4
alkyl groups such as methyl, ethyl, etc.), cycloalkyl (for example, C
3-6
cycloalkyl groups such as cyclohexyl, etc.), alkenyl (for example, C
2-4
alkenyl groups such as vinyl, allyl, etc.), cycloalkenyl (e.g. C
3-6
cycloalkenyl groups such as cyclohexenyl, etc.) or alkynyl (for example, C
2-4
alkynyl groups such as ethynyl, etc.) group which may optionally be substituted by 1 to 3 substituents (e.g. hydroxyl, C
1-4
alkoxy such as methoxy, halogen such as fluorine, di-C
1-4
alkylamino such as dimethylamino, C
1-4
alkylthio such as i-propylthio and n-propylthio, C
1-3
acylamino such as acetylamino, C
1-4
alkylsulfonylamino such as methylsulfonylamino, tri-C
1-4
alkylsilyl such as trimethylsilyl, pyridyl or thiazolyl which may optionally be substituted with a halogen atom, etc.). Furthermore, R
3
and R
4
may, taken together with the adjacent nitrogen atom, constitute a 5- or 6-membered cyclic amino group such as
and so on.
The group attached through a nitrogen atom, represented by R
1
, includes an amino group which may optionally be substituted (for example by any of the alkyl, aryl, aralkyl, heterocyclic, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocycleoxycarbonyl, arylsulfonyl, alkylsulfonyl, dialkoxyphosphoryl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl groups mentioned in the above definition of R
3
and R

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