Pyrimidine derivatives, process and intermediate products for their preparation and pesticides or fungicides containing these derivatives

A pyrimidine compound I

• wherein
• X is C(CO2CH3)═NOCH3, C(CONHCH3)═NOCH3, C(CO2CH3)═CHOCH3, C(CO2CH3)═CHCH3 or N(CO2CH3)—OCH3;
• R1 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;
• R2 is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
• A is
• wherein the bond marked * is to Y;
• R3 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, phenoxy-C1-C4-alkyl, C3-C6-cycloalkyl, cyano, C1-C4-alkoxy, hydroxyl or halogen;
• R4 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C1-C6-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-oxoalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl or C1-C4-alkoxy;
• Y is hydrogen, hydroxyl, halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C3-C6-cycloalkoxy, C1-C4-alkylthio, C3-C6-cycloalkyl, C5-C8-cycloalkenyl, heterocyclyl, aryl, aryloxy, arylthio, aryl-C1-C4-alkyl, aryl-C2-C4-alkenyl, aryloxy-C1-C4-alkyl, aryl-C1-C4-alkoxy, hetaryl, hetaryloxy, hetarylthio, hetaryl-C1-C4-alkyl, hetarylthio-C1-C4-alkyl, hetaryl-C1-C4-alkoxy or hetaryl-C2-C4-alkenyl, wherein the cyclic radicals are unsubstituted or partially or completely halogenated and/or carry 1 to 3 of the following groups:
• cyano, nitro, hydroxyl, mercapto, amino, formyl, carboxyl, aminocarbonyl, aminothiocarbonyl,
• C1-C12-alkyl, C1-C6-haloalkyl, C1-C6-hydroxyalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylcarbonyl, C1-C6-alkylcarbonyloxy, C1-C6-alkoxycarbonyl, benzyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C(═NORb)—Zn—Rc, NRf—CO—D—R9, benzyl, benzyloxy, aryl, aryloxy, hetaryl or hetaryloxy, wherein the last 6 mentioned radicals are unsubstituted or partially or completely halogenated and/or carry 1 to 3 of the following groups:
• cyano, C1-C6-alkyl, C1-C6-alkoxycarbonyl, C1-C4-alkoxy, nitro, C1-C6-alkylcarbonyl, C1-C6-haloalkyl, hydroxyl, rhodano, formyl, aminocarbonylamino, methylsulfonylamino, aminocarbonyl and C1-C6-alkylaminocarbonyl;
• Z is oxygen, sulfur or nitrogen, the nitrogen bearing hydrogen or C1-C6-alkyl;
• D is a direct bond, oxygen or NRh;
• n is 0 or 1;
• Rb and Rc independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or benzyl;
• Rf is hydrogen, hydroxyl, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy or C1-C6-alkoxycarbonyl;
• Rg and Rh independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, aryl, aryl-C1-C6-alkyl, hetaryl or hetaryl-C1-C6-alkyl,
• R9 is hydrogen or C1-C6-alkyl;
• or a salt thereof.

A pyrimidine compound of the formula

• wherein
• X′ is C(═O)—CO2CH3, NO2, NH—OH or N(OH)—CO2CH3;
• R1 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;
• R2 is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
• A is
• wherein the bond marked * is to Y;
• R3 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, phenoxy-C1-C4-alkyl, C3-C6-cycloalkyl, cyano, C1-C4-alkoxy, hydroxyl or halogen;
• R4 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C1-C6-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-oxoalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl or C1-C4-alkoxy;
• Y is hydrogen, hydroxyl, halogen, unsubstituted or substituted aryl, hetaryl, cycloalkyl, cycloalkenyl, heterocyclyl, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, cycloalkyloxy or alkylthio.

A pyrimidine compound of the formula

• wherein
• X′ is C(═O)—CO2CH3, NO2, NH—OH or N(OH)—CO2CH3;
• R1 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;
• R2 is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
• A is
• wherein the bond marked * is to Y;
• R3 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, phenoxy-C1-C4-alkyl, C3-C6-cycloalkyl, cyano, C1-C4-alkoxy, hydroxyl or halogen;
• R4 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C1-C6-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-oxoalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl or C1-C4-alkoxy;
• Y is hydrogen, hydroxyl, halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C3-C6-cycloalkoxy, C1-C4-alkylthio, C3-C6-cycloalkyl, C5-C8-cycloalkenyl, heterocyclyl, aryl, aryloxy, arylthio, aryl-C1-C4-alkyl, aryl-C2-C4-alkenyl, aryloxy-C1-C4-alkyl, aryl-C1-C4-alkoxy, hetaryl, hetaryloxy, hetarylthio, hetaryl-C1-C4-alkyl, hetarylthio-C1-C4-alkyl, hetaryl-C1-C4-alkoxy or hetaryl-C2-C4-alkenyl, wherein the cyclic radicals are unsubstituted or partially or completely halogenated and/or carry 1 to 3 of the following groups:
• cyano, nitro, hydroxyl, mercapto, amino, formyl, carboxyl, aminocarbonyl, aminothiocarbonyl,
• C1-C12-alkyl, C1-C6-haloalkyl, C1-C6-hydroxyalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylcarbonyl, C1-C6-alkylcarbonyloxy, C1-C6-alkoxycarbonyl, benzyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C(═NORb)—Zn—Rc, NRf—CO—D—R9, benzyl, benzyloxy, aryl, aryloxy, hetaryl or hetaryloxy, wherein the last 6 mentioned radicals are unsubstituted or partially or completely halogenated and/or carry 1 to 3 of the following groups:
• cyano, C1-C6-alkyl, C1-C6-alkoxycarbonyl, C1-C4-alkoxy, nitro, C1-C6-alkylcarbonyl, C1-C6-haloalkyl, hydroxyl, rhodano, formyl, aminocarbonylamino, methylsulfonylamino, aminocarbonyl and C1-C6-alkylaminocarbonyl;
• Z is oxygen, sulfur or nitrogen, the nitrogen bearing hydrogen or C1-C6-alkyl;
• D is a direct bond, oxygen or NRh;
• n is 0 or 1;
• Rb and Rc independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or benzyl;
• Rf is hydrogen, hydroxyl, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy or C1-C6-alkoxycarbonyl;
• Rg and Rh independently of one another are hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, aryl, aryl-C1-C6-alkyl, hetaryl or hetaryl-C1-C6-alkyl, and
• R9 is hydrogen or C1-C6-alkyl.

A process for preparing a compound I

• wherein
• X is C(CO2CH3)═NOCH3,
• R1 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;
• R2 is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
• A is
• wherein the bond marked * is to Y;
• R3 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, phenoxy-C1-C4-alkyl, C3-C6-cycloalkyl, cyano, C1-C4-alkoxy, hydroxyl or halogen;
• R4 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C1-C6-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-oxoalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl or C1-C4-alkoxy;
• Y is hydrogen, hydroxyl, halogen, unsubstituted or substituted aryl, hetaryl, cycloalkyl, cycloalkenyl, heterocyclyl, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, cycloalkyloxy or alkylthio,
• which comprises reacting an α-oxopyrimidinylacetic acid IIa
• with methoxyamine or methoxyamine hydrohalide.

A process for preparing a compound I

• wherein
• X is C(CONHCH3)═NOCH3,
• R1 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;
• R2 is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
• A is
• wherein the bond marked * is to Y;
• R3 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, phenoxy-C1-C4-alkyl, C3-C6cycloalkyl, cyano, C1-C4-alkoxy, hydroxyl or halogen;
• R4 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C1-C6-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C1-C4-oxoalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl or C1-C4-alkoxy;
• Y is hydrogen, hydroxyl, halogen, unsubstituted or substituted aryl, hetaryl, cycloalkyl, cycloalkenyl, heterocyclyl, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, cycloalkyloxy or alkylthio,
• which comprises reacting a 2-oximinopyrimidinylacetic acid IIb
• with methylamine.

A process for preparing a compound I

• wherein
• X is C(CO2CH3)═CHOCH3 or C(CO2CH3)═CHCH3,
• R1 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;
• R2 is hydrogen, C1-C4-alkyl or C1-C4-haloalkyl;
• A is
• wherein the bond marked * is to Y;
• R3 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, phenoxy-C1-C4-alkyl, C3-C6-cycloalkyl, cyano, C1-C4-alkoxy, hydroxyl or halogen;
• R4 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, C1-C6-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl C1-C4-oxoalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl C3-C6-cycloalkyl-C1-C4-alkyl or C1-C4-alkoxy;
• Y is hydrogen, hydroxyl, halogen, unsubstituted or substituted aryl, hetaryl, cycloalkyl, cycloalkenyl, heterocyclyl, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, cycloalkyloxy or alkylthio, and
• wherein A is not —O— when X is C(CO2CH3)═CHOCH3, which comprises reacting an α-oxopyrimidinylacetic acid IIa
• with a Wittig reagent IIc or IId
• wherein Ph is phenyl and Hal is iodine, bromine, chlorine or fluorine.