Alpha-unsaturated amines, their production and use

Claim 1

An α-unsaturated amine of the formula: wherein: one of X¹ and X² is an electron-attracting group and the other is a hydrogen atom or an electron-attracting group, wherein the said electron-attracting group is cyano, nitro, C₁₋₄ alkoxy carbonyl, carboxyl, C₆₋₁₀ aryloxy-carbonyl, heterocycleoxycarbonyl, C₁₋₄ alkylsulfonyl which may be substituted with halogen, aminosulfonyl, di-C₁₋₄ alkoxyphosphoryl, C₁₋₄ alkanoyl which may be substituted with halogen, C₁₋₄ alkylsulfonylthiocarbamoyl, carbamoyl or halogen, or X¹ and X² together with the carbon atom to which they are attached form a ring of the formula: R¹ is a group of the formula: in which: R³ is hydrogen, C₁₋₂₀ alkyl, C₆₋₁₀ aryl, C₇₋₉ aralkyl, heterocycle, C₁₋₄ alkanoyl, C₆₋₁₀ aryl-carbonyl, C₁₋₄ alkoxy-carbonyl, C₆₋₁₀ aryloxy-carbonyl, heterocycleoxycarbonyl, C₆₋₁₀ arylsulfonyl, C₁₋₄ alkylsulfonyl, di-C₁₋₄ alkoxyphosphoryl, C₁₋₄ alkoxy, hydroxy, amino, di-C₁₋₄ alkylamino, C₁₋₄ alkanoylamino, C₁₋₄ alkoxycarbonylamino, C₁₋₄ alkylsulfonylamino, di-C₁₋₄ alkoxyphosphorylamino, C₇₋₉ aralkyloxy or C₁₋₄ alkoxy-carbonyl-C₁₋₄ alkyl; and R⁴ is hydrogen, C₁₋₂₀ alkyl, C₃₋₆ cycloalkyl, C₂₋₆-alkenyl, C₃₋₆ cycloalkenyl or C₂₋₆ alkynyl, wherein each of the radicals defined for R⁴ except for hydrogen may optionally be substituted by 1 to 3 substituents selected from the group consisting of hydroxy, C₁₋₄ alkoxy, halogen, di-C₁₋₄ alkylamino, C₁₋₄ alkylthio, C₁₋₃ alkanoylamino, C₁₋₄ alkylsulfonylamino, tri-C₁₋₄ alkylsilyl, pyridyl and thiazolyl, and each of the pyridyl and thiazolyl may further be substituted by halogen, or R³ and R⁴ together with the adjacent nitrogen atom constitute a cyclic amino group of the formula: R² is (1) hydrogen, (2) a group attached through a carbon atom selected from the class consisting of C₁₋₄ alkanoyl, C₁₋₂₀ alkyl, C₂₋₆ alkenyl, C₃₋₆ cycloalkyl, C₆₋₁₀ aryl, C₇₋₉ aralkyl and 3- or 4-pyridyl, the said group attached through a carbon atom being optionally substituted by 1 to 3 substituents selected from the class consisting of C₁₋₄ alkylthio, C₁₋₄ alkoxy, mono- or di-C₁₋₄ alkylamino, C₁₋₄ alkoxy-carbonyl, C₁₋₄ alkylsulfonyl, halogen and C₁₋₄ alkanoyl, (3) a group attached through an oxygen atom selected from the class consisting of C₁₋₄ alkoxy, C₃₋₆ cycloalkoxy, C₂₋₄ alkenyloxy, C₃₋₆ cycloalkenyloxy, ethynyloxy, C₆₋₁₀ aryloxy, thienyloxy and hydroxy, the said group attached through an oxygen atom being optionally substituted by 1 to 3 substituents selected from the class consisting of halogen and phenyl, or (4) a group attached through a nitrogen atom of the formula: wherein R³ and R⁴ have the meanings given above; n is an integer of 0, 1 or 2; A o is heterocycle; wherein the heterocycle in the said heterocycle carbonyl for X¹ and X², the said heterocycle for R³, the heterocycle in the said heterocycleoxycarbonyl for R³, and the said heterocycle for A o are a member selected from the class consisting of thienyl, furyl, pyrrolyl, pyridyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, N-oxidopyridyl, pyrimidinyl, N-oxidopyrimidinyl, pyridazinyl, pyrazinyl, N-oxidopyridazinyl, benzofuryl, benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl, tetrazo[1,5-b]pyridazinyl, triazolo[4,5-b]pyridazinyl, oxoimidazinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperazinyl, benzimidazolyl, quinolyl, isoquinolyl, indolizinyl, quinolizinyl, 1,8-naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl and phenoxazinyl, the said heterocycle being optionally substituted by 1 to 5 substituents selected from the group consisting of: (i) C₁₋₄ alkyl, (ii) C₃₋₆ cycloalkyl, (iii) C₆₋₁₀ aryl, (iv) C₁₋₄ alkoxy, (v) C₃₋₆ cycloalkyloxy, (vi) C₆₋₁₀ aryloxy, (vii) C₇₋₁₂ aralkyloxy (viii) C₁₋₄ alkylthio, (ix) C₃₋₆ cycloalkylthio, (x) C₆₋₁₀ arylthio, (xi) C₇₋₁₂ aralkylthio, (xii) mono-C₁₋₄ alkylamino, (xiii) di-C₁₋₄ alkylamino, (xiv) C₃₋₆ cycloalkylamino, (xv) C₆₋₁₀ arylamino, (xvi) C₇₋₁₂ aralkylamino, (xvii) halogen, (xviii) C₁₋₄ alkoxycarbonyl, (xix) C₆₋₁₀ aryloxycarbonyl, (xx) C₃₋₆ cycloalkyloxycarbonyl, (xxi) C₇₋₁₂ aralkyloxycarbonyl, (xxii) C₁₋₅ alkanoyl, (xxiii) C₁₋₁₅ alkanoyloxy, (xxiv) carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-ethylcarbamoyl, N,N-diethylcarbamoyl N-phenylcarbamoyl, pyrrolidinocarbamoyl, piperidinocarbamoyl, piperazinocarbamoyl, morpholinocarbamoyl or N-benzylcarbamoyl, (xxv) N-methylcarbamoyloxy, N,N-dimethylcarbamoyloxy, N-ethylcarbamoyloxy, N-benzylcarbamoyloxy, N,N-dibenzylcarbamoyloxy or N-phenylcarbamoyloxy, (xxvi) C₁₋₄ alkanoylamino, (xxvii) C₆₋₁₀ arylcarbonylamino, (xxviii) C₁₋₄ alkoxycarbonylamino, (xxix) C₇₋₁₂ aralkyloxycarbonyl, (xxx) methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino, naphthalenesulfonylamino, trifluoromethanesulfonylamino, 2-chloroethanesulfonylamino or 2,2,2-trifluoromethanesulfonylamino, (xxxi) pyrrolidinyl, pyrrolyl, pyrazolyl, imidazolyl, furyl, thienyl, oxazolyl, isoxazolyl, isothiazolyl, thiazolyl, piperidinyl, pyridyl, piperazinyl, pyrimidinyl, pyranyl, tetrahydropyranyl, tetrahydrofuryl, indolyl, quinolyl, 1,3,4-oxadiazolyl, thieno[2,3-d]pyridyl, 1,2,3-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, tetrazolyl, 4,5-dihydro-1,3-dioxazolyl, tetrazolo[1,5-b]-pyridazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl or benzothienyl, (xxxii) heterocyclethio, heterocycleoxy, heterocycleamino or heterocyclecarbonylamino group which is derived by attachment of any of the heterocyclic groups (xxxi) defined above to the S, O, N atom or a carbonylamino group, (xxxiii) di-C₁₋₄ alkylphosphinothioylamino, (xxxiv) methoxyimino , ethoxyimino, 2-fluoroethoxyimino, carboxymethoxyimino, 1-carboxy-1-methylethoxyimino, 2,2,2-trichloroethoxycarbonylmethoxyimino, 1-(2,2,2-trichloroethoxycarbonyl)-1-methylethoxyimino, (2-aminothiazol-4-yl)methoxyimino or (1H-imidazol-4-yl)methoxyimino, (xxxv) C₁₋₄ alkylsulfonyloxy, (xxxvi) C₆₋₁₀ arylsulfonyloxy, (xxxvii) di-C₆₋₁₀ arylphosphino-thioylamino, (xxxviii) thiocarbamoylthio, N-methylthiocarbamoylthio, N,N-dimethylthiocarbamoylthio, N-ethylthiocarbamoylthio, N-benzylthiocarbamoylthio, N,N-dibenzylthiocarbamoylthio or N-phenylthiocarbamoylthio, (xxxix) trimethylsilyloxy, t-butyldimethylsilyloxy, t-butyldiphenylsilyloxy or dimethylphenylsilyloxy, (xL) trimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl or dimethylphenylsilyl, (xLi) C₁₋₄ alkylsulfinyl, (xLii) C₆₋₁₀ arylsulfinyl, (xLiii) C₁₋₄ alkylsulfonyl, (xLiv) C₆₋₁₀ arylsulfonyl, (xLv) C₁₋₄ alkoxy-carbonyloxy, (xLvi) halo-C₁₋₄ alkyl, (xLvii) halo-C₁₋₄ alkoxy, halo-C₁₋₄ alkylthio, halo-C₁₋₄ alkylsulfinyl or halo-C₁₋₄ alkylsulfonyl, (xLviii) cyano, nitro, hydroxyl, carboxyl, sulfo, phosphono, (xLix) C₁₋₄ alkyloxysulfonyl, (L) C₆₋₁₀ aryloxysulfonyl, (Li) C₇₋₁₂ aralkyloxysulfonyl, and (Lii) di-C₁₋₄ alkyloxyphosphoryl group, with the proviso that when R² is a hydrogen atom, R¹ is a group of the formula: [wherein R 3a is hydrogen, C₁₋₄ alkyl, C₇₋₉ phenylalkyl or C₁₋₄ alkanoyl and R 4a is a hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy-C₁₋₄ alkyl, (di-C₁₋₄ alkylamino)-C₁₋₄ alkyl, tri-C₁₋₄ alkylsilyl-C₁₋₄ alkyl, C₂₋₄ alkenyl or pyridyl- or thiazolyl-C₁₋₂ alkyl wherein 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 o is pyridyl, pyrazinyl or thiazolyl, each of which may optionally be substituted with a halogen, C₁₋₄ alkyl, C₁₋₄ alkylthio or C₁₋₄ alkoxy), and with the proviso that when is O₂N-CH=; R¹ is R³ is hydrogen, C₁₋₅ alkyl or C₃₋₆ cycloalkyl; R⁴ is hydrogen, C₁₋₅ alkyl, C₃₋₆ cycloalkyl, benzyl or pyrimidinylmethyl; or R³ and R⁴ together with the adjacent nitrogen atom constitute a cyclic amino group of pyrrolidinyl or piperazinyl; and R² is hydrogen, C₁₋₅ alkyl or C₃₋₆ cycloalkyl, A⁰ is not a pyridyl subsituted by C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, C₁₋₄ haloalkylthio, C₁₋₄ haloalkylsulfinyl, C₁₋₄ haloalkylsulfonyl, cyano, nitro or hydroxyl, or a salt thereof.

Claim 15

A method of combatting undesirable insects or mites, which comprises applying an insecticidal or miticidal effective amount of the compound of the formula [I o ] defined in any one of claims 1 to 12 or a salt thereof to the said insects or mites or their habitat.