Avermectins and avermectin monosacharides substituted in the 4′-and 4″ position having pesticidal properties

1. A compound of the formula

wherein the bond between carbon atoms 22 and 23 is a single or double bond;

m is 0 or 1;

R 1 is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl or C 2 -C 12 alkenyl; and either

(A) R 2 is —N(R 3 )R 4 , and

(1) X is O, wherein

R 3 is hydrogen, unsubstituted or mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl, aryl or heterocyclyl, and

R 4 is mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to penta-substituted C 3 -C 12 cycloalkyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl, unsubstituted or mono- to trisubstituted heterocyclyl, unsubstituted or mono- to pentasubstituted aryl, NH 2 , NHC 1 -C 12 alkyl, N(C 1 -C 12 alkyl) 2 , C 1 -C 6 alkyl-N(C 1 -C 12 alkyl) 2 SO 2 NH 2 , SO 2 NHC 6 H 5 , SO 2 Phenyl, SO 2 Benzyl, OH, —OC 1 -C 12 alkyl, —OC 1 -C 12 alkenyl or —OC 1 -C 12 alkynyl; or

(2) X is S, wherein

R 3 is hydrogen, unsubstituted or mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl; aryl or heterocyclyl, and

R 4 is hydrogen, unsubstituted or mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to pentasubstituted C 3 -Ci 12 cycloalkyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl, unsubstituted or mono- to trisubstituted heterocyclyl, unsubstituted or mono- to pentasubstituted aryl, NH 2 , NHC 1 -C 12 alkyl, N(C 1 -C 12 alkyl) 2 , SO 2 NH 2 , SO 2 NHC 6 H 5 , SO 2 Phenyl, SO 2 Benzyl, OH or —OC 1 -C 12 alkyl; or

(3) X is O or S, wherein R 3 and R 4 together are a three- to seven-membered alkylene or a four- to seven-membered alkenylene bridge, in which a CH 2 group may be replaced by S, C═O or NR 6 ;

in which the substituents of the alkyl-, alkenyl-, alkynyl-, alkylene-, alkenylene-, heterocyclyl-, aryl- and cycloalkyl-radicals mentioned under R 3 and R 4 are selected from the group consisting of halogen, halo-C 1 -C 2 alkyl, CN, SCN, NO 2 , C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl which is unsubstituted or substituted by one to three methyl groups; norbornylenyl; C 3 -C 8 cycloalkenyl which is unsubstituted or substituted by one to three methyl groups; C 3 -C 8 halocycloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkoxy, C 1 -C 12 alkoxy, C 3 -C 8 cycloalkoxy, C 1 -C 12 alkylthio, C 3 -C 8 cycloalkylthio, C 1 -C 12 haloalkylthio, C 1 -C 12 alkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 12 haloalkylsulfinyl, C 3 -C 8 halocycloalkylsulfinyl, C 1 -C 12 alkylsulfonyl, C 3 -C 8 cyclo-alkylsulfonyl, C 1 -C 12 haloalkylsulfonyl, C 3 -C 8 halocycloalkylsulfonyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, —N(R 6 ) 2 , wherein the two R 6 are independent of each other; —C(═O)R 7 , —O—C(═O)R 8 , —NHC(═O)R 7 , —S—C(═S)R 8 , —P(═O)(OC 1 -C 6 alkyl) 2 , —S(═O) 2 R 11 ; —NH—S(═O) 2 R 11 , —OC(═O)—C 1 -C 6 alkyl-S(═O) 2 R 11 ; heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy, arylthio, benzylthio or heterocyclylthio, each of which may be mono- to pentasubstituted by substituents selected from the group consisting of OH, halogen, CN, NO 2 , C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkylthio, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, dimethylamino-C 1 -C 6 alkoxy, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenoxy, phenyl-C 1 -C 6 alkyl, methylenedioxy, —C(═O)R 7 , 13 O—C(═O)—R 8 , —NH—C(═O)R 8 , —N(R 10 ) 2 , wherein the two R 10 are independent of each other; C 1 -C 6 alkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 3 -C 8 halocycloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 3 -C 8 cyclo-alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl and C 3 -C 8 halocycloalkylsulfonyl; or

(B) R 2 is OR 5 and X is O or S, wherein R 5 is mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl;

in which the substituents of the alkyl-, alkenyl-, alkynyl and cycloalkyl-radicals mentioned under R 5 are selected from the group consisting of OH, CN, SCN, NO 2 , C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl which is unsubstituted or substituted by one to three methyl groups; norbomylenyl; C 3 -C 8 cycloalkenyl which is unsubstituted or substituted by one to three methyl groups; C 3 -C 8 halocycloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkoxyC 1 -C 12 alkoxy, C 3 -C 8 cycloalkoxy, C 1 -C 12 alkylthio, C 3 -C 8 cycloalkylthio, C 1 -C 12 haloalkylthio, C 1 -C 12 alkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 12 haloalkylsulfinyl, C 3 -C 8 halocycloalkylsulfinyl, C 1 -C 12 alkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 12 haloalkylsulfonyl, C 3 -C 8 halocycloalkylsulfonyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, —N(R 6 ) 2 , wherein the two R 6 are independent of each other; —C(═O)R 7 , —O—C(═O)R 8 , —NHC(═O)R 7 , —S—C(═S)R 8 , —P(═O)(OC 1 -C 6 alkyl) 2 , —S(═O) 2 R 11 ; —NH—S(═O) 2 R 11 , —OC(═O)—C 1 -C 6 alkyl-S(═O) 2 R 11 ; aryl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy, arylthio, benzylthio or heterocyclylthio each of which may be mono- to pentasubstituted by substituents selected from the group consisting of OH, halogen, CN, NO 2 , C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkylthio, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, dimethylamino-C 1 -C 6 alkoxy, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenoxy, phenyl-C 1 -C 6 alkyl, methylenedioxy, —C(═O)R 7 , —O—C(═O)—R 8 , —NH—C(═O)R 8 , —N(R 10 ) 2 , wherein the two R 10 are independent of each other; C 1 -C 6 alkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 3 -C 8 halocycloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 6 haloalkylsulfonyl and C 3 -C 8 halocycloalkylsulfonyl;

R 6 is H, C 1 -C 8 alkyl, hydroxy-C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, benzyl, —C(═O)R 7 , or —CH 2 —C(═O)—R 7 ;

R 7 is H, OH, SH, —N(R 10 ) 2 , wherein the two R 10 are independent of each other; C 1 -C 24 alkyl, C 2 -C 12 alkenyl, C 1 -C 8 hydroxyalkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 12 alkylthio, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy, NH—C 1 -C 6 alkyl-C(═O)R 9 , —N(C 1 -C 6 alkyl) -C 1 -C 6 alkyl-C(═O)—R 9 , —O—C 1 -C 2 alkyl-C(═O)R 9 , —C 1 -C 6 alkyl-S(═O) 2 R 9 ; or aryl, benzyl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy, each of which are unsubstituted or mono- to trisubstituted in the ring independently of one another by halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy;

R 8 is H, C 1 -C 24 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 hydroxyalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, N(R 10 ) 2 , wherein the two R 10 are independent of each other; —C 1 -C 6 alkyl -C(═O)R 10 , —C 1 -C 6 alkyl-S(═O) 2 R 9 , or aryl, benzyl or heterocyclyl, each of which may be mono- to trisubstituted by substituents selected from the group consisting of OH, halogen, CN, NO 2 , C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio and C 1 -C 12 haloalkylthio;

R 9 is H, OH, C 1 -C 24 alkyl which is optionally subsituted with OH, or —S(═O) 2 -C 1 -C 6 alkyl; C 1 -C 12 alkenyl, C 1 -C 12 alkynyl, C 1 -C 12 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 2 -C 8 alkenyloxy, aryl, aryloxy, benzyloxy, heterocyclyl, heterocyclyloxy or —N(R 10 ) 2 , wherein the two R 10 are independent of each other;

R 10 is H, C 1 -C 6 alkyl, which is optionally substituted with one to five substituents selected from the group consisting of halogen, C 1 -C 6 alkoxy, hydroxy and cyano; C 1 -C 8 -cycloalkyl, or aryl, benzyl or heterocyclyl, each of which may be mono- to trisubstituted by substituents selected from the group consisting of OH, halogen, CN, NO 2 , C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio and C 1 -C 12 haloalkylthio;

or, an E/Z isomer, E/Z isomer mixture and/or tautomer thereof, or a salt thereof.

2. A pesticide composition which contains at least one compound of the formula (I) as described in claim 1 as active compound and at least one auxiliary.

3. A method for controlling pests wherein a composition as defined in claim 2 is applied to the pests or their habitat.

4. A process for preparing a composition as defined in claim 2 which contains at least one auxiliary, wherein the active compound is mixed intimately and/or ground with the auxiliary(s).

5. A method for protecting plant propagation material against damage by a pest, wherein the propagation material or the location where the propagation material is planted is treated with a composition as defined in claim 2 .

6. The compound of claim 1 , wherein R 2 is —N(R 3 )R 4 , and X is O.

7. The compound of claim 1 , wherein R 2 is —N(R 3 )R 4 , and X is S.

8. The compound of claim 1 , wherein R 2 is —N(R 3 )R 4 , and X is O or S, wherein R 3 and R 4 together are a three- to seven-membered alkylene or a four- to seven-membered alkenylene bridge, in which a CH 2 group may be replaced by O, S, C═O or NR 6 .

9. The compound of claim 1 , wherein R 2 is OR 5 and X is O or S.

10. The compound of claim 1 , wherein:

R 2 is —N(R 3 )R 4 ,

X is O;

R 3 is hydrogen; and

R 4 is mono- to pentasubstituted C 1 -C 12 alkyl, or unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl.

11. The compound of claim 1 , wherein:

R 2 is —N(R 3 )R 4 ,

X is O;

R 3 is hydrogen; and

R 4 is unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, or unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl.

12. The compound of claim 1 , wherein:

R 2 is —N(R 3 )R 4 ,

X is O;

R 3 is hydrogen; and

R 4 is unsubstituted or mono- to trisubstituted heterocyclyl, or unsubstituted and mono- to pentasubstituted aryl.

13. The compound of claim 1 , wherein:

R 2 is —N(R 3 )R 4 ,

X is S;

R 3 is hydrogen; and

R 4 is hydrogen, mono- to pentasubstituted C 1 -C 12 alkyl, or unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl.

14. The compound of claim 1 , wherein:

R 2 is —N(R 3 )R 4 ,

X is S;

R 3 is hydrogen; and

R 4 is unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, or unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl.

15. The compound of claim 1 , wherein:

R 2 is —N(R 3 )R 4 ,

X is S;

R 3 is hydrogen; and

R 4 is unsubstituted or mono- to trisubstituted heterocyclyl unsubstituted, or mono- to pentasubstituted aryl.

16. The compound of claim 1 , wherein:

R 2 is OR 5 , and

R 5 is mono- to pentasubstituted C 1 -C 12 alkyl, or unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl.

17. The compound of claim 1 , wherein:

R 2 is OR 5 , and

R 5 is unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, or unsubstituted or mono- to pentasubstituted alkynyl.

18. The compound of claim 1 , wherein the configuration at the ε-position is (R).

19. The compound of claim 1 , wherein the configuration at the ε-position is (S).