Avermectin b1 and avermectin b1 monosaccharide derivatives having an alkoxymethyl substitutent in the 4"-or 4'-position

A compound of formula

• wherein
• n is 0 or 1;
• A-B is —CH═CH— or —CH2—CH2—;
• R1 is C1-C12-alkyl, C3-C8-cycloalkyl or C2-C12-alkenyl;
• R2 is C1-C12-alkyl, C2-C12-alkenyl, C2-C12-alkinyl;
• or C1-C12-alkyl, C2-C12-alkenyl or C2-C12-alkinyl, which are substituted with one to five substituents selected from the group consisting of OH, halogen, CN, —N3, —NO2, C3-C8-cycloalkyl which is optionally substituted with one to three C1-C6-alkyl-groups, C3-C8-cycloalkenyl which is optionally substituted with one to three C1-C6-alkyl-groups, norbornylenyl-, C3-C8-halocycloalkyl, C1-C12-alkoxy, C1-C6-alkoxy-C1-C6-alkoxy, C3-C8-cycloalkoxy, C1-C12-haloalkoxy, C1-C12-alkylthio, C3-C8-cycloalkylthio, C1-C12-haloalkylthio, C1-C12-alkylsulfinyl, C3-C8-cycloalkylsulfinyl, C1-C12-haloalkylsulfinyl, C3-C8-halocycloalkylsulfinyl, C1-C12-alkylsulfonyl, C3-C8-cycloalkylsulfonyl, C1-C12-haloalkylsulfonyl, C3-C8-halocycloalkylsulfonyl, —NR4R6, —X—C(═Y)—R4, —X—C(═Y)-Z-R4, —P(═O)(OC1-C6-alkyl)2, aryl, heterocyclyl, aryloxy, arylthio and heterocyclyloxy;
• wherein the aryl, heterocyclyl, aryloxy, arylthio and heterocyclyloxy groups are optionally—depending on the substitution possibilities on the ring—substituted with one to five substituents selected form the group consisting of OH, Halogen, CN, NO2, C1-C12-alkyl, C3-C8-Cycloalkyl, C1-C12-Haloalkyl, C1-C12-alkoxy, C1-C12-Haloalkoxy, C1-C12-alkylthio, C1-C12-haloalkylthio, C1-C6-alkoxy-C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkinyl, Si(C1-C12-alkyl)3, —X—C(═Y)—R4, —X—C(═Y)-Z-R4, aryl, aryloxy, heterocyclyl and heterocyclyloxy;
• or
• R2 is aryl, heterocyclyl C3-C8-Cycloalkyl, C3-C8-Cycloalkenyl;
• or aryl, heterocyclyl C3-C8-Cycloalkyl or C3-C8-Cycloalkenyl, which are optionally—depending on the substitution possibilities on the ring—substituted with one to five substituents selected from the group consisting of OH, halogen, CN, NO2, C1-C12-alkyl, C3-C8-cycloalkyl, C1-C12-haloalkyl, C1-C12-alkoxy, C1-C12-haloalkoxy, C1-C12-alkylthio, C1-C12-haloalkylthio, C1-C6-alkoxy-C1-C6-alkyl, dimethylamino-C1-C6-alkoxy, C2-C8-alkenyl, C2-C8-alkinyl, methylendioxy, aryl, aryloxy, heterocyclyl and heterocyclyloxy;
• R3 is H, C1-C12-alkyl or C1-C12-alkyl which is substituted with one to five substituents selected from the group consisting of OH, halogen, CN, —N3, —NO2, C3-C8-Cycloalkyl which is optionally substituted with one to three C1-C6-alkyl groups, norbornylenyl-, C3-C8-Cycloalkenyl which is optionally substituted with one to three methyl groups;
• C3-C8-halocycloalkyl, C1-C12-alkoxy, C1-C6-alkoxy-C1-C6-alkoxy, C3-C8-cycloalkoxy, C1-C12-haloalkoxy, C1-C12-alkylthio, C3-C8-cycloalkylthio, C1-C12-haloalkylthio, C1-C12-alkylsulfinyl, C3-C8-cycloalkylsulfinyl, C1-C12-haloalkylsulfinyl, C3-C8-halocycloalkylsulfinyl, C1-C12-alkylsulfonyl, C3-C8-cycloalkylsulfonyl, C1-C12-haloalkylsulfonyl, C3-C8-halocycloalkylsulfonyl, —NR4R6, —X—C(═Y)—R4, —X—C(═Y)-Z-R4, —P(═O)(OC1-C6-alkyl)2, aryl, heterocyclyl, aryloxy, arylthio and heterocyclyloxy;
• wherein the aryl, heterocyclyl, aryloxy, arylthio and heterocyclyloxy groups are optionally—depending on the substitution possibilities on the ring—substituted with one to five substituents selected form the group consisting of OH, Halogen, CN, NO2, C1-C12-alkyl, C3-C8-Cycloalkyl, C1-C12-Haloalkyl, C1-C12-alkoxy, C1-C12-Haloalkoxy, C1-C12-alkylthio, C1-C12-haloalkylthio, C1-C6-alkoxy-C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkinyl, Si(C1-C12-alkyl)3, —X—C(═Y)—R4, —X—C(═Y)-Z-R4, aryl, aryloxy, heterocyclyl and heterocyclyloxy;
• or
• R2 and R3 together are a three- to seven-membered alkylen- or a four- to seven-membered alkenylenbridge, wherein one or two CH2-groups may independently of each other be replaced by a group —C(═O)—, —C(═S)—, O, S, —NR5, —OC(═O)—O, —OC(═O)S—, —OC(═O)N(R5)—, —C(═O)O—, —C(═O)S, —C(═O)N(R5)—, —N(R5)C(═O)S—, —N(R5)C(═O)N(R5)—, and wherein the alkylene or alkenylenbridge may be independently of each other substituted with one or two substituents selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy and C1-C4-halogenalkyl;
• X is O, NR5 or a bond;
• Y is O or S;
• Z is O, S or NR5
• R4 is H, C1-C12-alkyl which is optionally substituted with one to five substituents selected from the group consisting of halogen, hydroxy, C1-C6-alkoxy and CN;
• C2-C8-alkenyl, C2-C8-alkinyl, aryl, heterocyclyl, aryl-C1-C12-alkyl, heterocyclyl-C1-C12-alkyl;
• or aryl, heterocyclyl, aryl-C1-C12-alkyl or heterocyclyl-C1-C12-alkyl, which are—depending on the substitution possibilities—optionally substituted in the ring with one to five substituents selected from the group consisting of halogen, C1-C6-alkoxy, C1-C6-haloalkyl and C1-C6-haloalkoxy;
• R5 is H, C1-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkinyl, benzyl or —C(═O)—C1-C12-alkyl;
• R6 is H, C1-C12-alkyl which is optionally substituted with halogen, C1-C6-alkoxy, CN, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkinyl, C1-C12-Haloalkenyl, —X—C(═Y)—R9, —X—C(═Y)-Z-R9, —SO2—R9, aryl, heterocyclyl, aryl-C1-C12-alkyl, heterocyclyl-C1-C12-alkyl;
• or aryl, heterocyclyl, aryl-C1-C12-alkyl or heterocyclyl-C1-C12-alkyl, which are—depending on the substitution possibilities—optionally substituted in the ring with one to five substituents selected from the group consisting of halogen, C1-C6-alkoxy, C1-C6-haloalkyl or C1-C6-haloalkoxy;
• or
• R4 and R6 together are a three- to five membered alkylene bridge, wherein one of the methylene groups may be replaced by O, S or SO2;
• and
• R9 is H, C1-C12-alkyl which is optionally substituted with one to five substituents selected from the group consisting of halogen, hydroxy, C1-C6-alkoxy and CN;
• C2-C8-alkenyl, C2-C8-alkinyl, aryl, heterocyclyl, aryl-C1-C12-alkyl, heterocyclyl-C1-C12-alkyl;
• or aryl, heterocyclyl, aryl-C1-C12-alkyl or heterocyclyl-C1-C12-alkyl, which are—depending on the substitution possibilities—optionally substituted in the ring with one to five substituents selected from the group consisting of halogen, C1-C6-alkoxy, C1-C6-haloalkyl and C1-C6-haloalkoxy;
• and, where applicable, to E/Z isomers, mixtures of E/Z isomers and/or tautomers, in each case in free form or in salt form;
• with the proviso, that the compound is not an Avermectin B1a or B1b derivative when n is 1, R3 is H, and R2 is —CH2—CH2—OCH3 or —CH2—CH2—O-phenyl;
• is not the B1a or B1b derivative when n is 2, R3 is H, and R2 is —CH2—CH2—O-phenyl;
• is not the B1a or B1b derivative when n is 1, and R2 and R3 together are usubstituted —CH2—CH2—CH2—;
• and is not the B2a or B2b derivative when n is 1, R3 is H, and R2 is —CH2—CH2—OCH3.