NOVEL SPINOSYN COMPOUNDS

Abstract

The present invention generally relates to the field of pesticides. More specifically, the present invention relates to novel spinosyn compounds having advantageous properties, processes for their preparation, and their use as pesticides.

Claims

1. A compound of general formula (I): ##STR00054## wherein the dashed line is a single bond, a double bond or an epoxide; X is NR.sub.2R.sub.3, NHR.sub.2, N.sup.+R.sub.1R.sub.2R.sub.3 or OR.sub.2; R.sub.1 is (CH.sub.2).sub.nOC(O)R.sub.1b, wherein: n is an integer ranging from 0 to 20; and R.sub.1b is selected from the group consisting of C(R.sub.2b).sub.3, N(R.sub.2b).sub.2, OH and OC(R.sub.2b).sub.3, wherein: each R.sub.2b is independently selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.2 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.3 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.4 is selected from the group consisting of unsubstituted butyl, unsubstituted 1-butenyl, unsubstituted 1,3-butadienyl and unsubstituted 3-hydroxy-1-butenyl; R.sub.5 is H; R.sub.6 is OR.sub.6 or OC(O)R.sub.6, wherein R.sub.6 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.6 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.6 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.7 is H or OR.sub.7, wherein R.sub.7 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.8 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.9 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; R.sub.10 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; and R.sub.11 is selected from the group consisting of hydrogen and substituted or unsubstituted C.sub.1-C.sub.2 alkyl; optionally in the form of a corresponding salt thereof.

2-15. (canceled)

16. The compound according to claim 1, wherein X is NR.sub.2R.sub.3.

17. The compound according to claim 1, wherein R.sub.2 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl; and/or R.sub.3 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

18. The compound according to claim 1, wherein R.sub.4 is unsubstituted 1-butenyl.

19. The compound according to claim 1, wherein R.sub.6 is OR.sub.6, wherein R.sub.6 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.6 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.6 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted.

20. The compound according to claim 1, wherein R.sub.6 is OC(O)R.sub.6, wherein R.sub.6 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.6 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.6 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted.

21. The compound according to claim 1, wherein R.sub.6 is unsubstituted C.sub.1-C.sub.2 alkyl.

22. The compound according to claim 1, wherein R.sub.7 is H.

23. The compound according to claim 1, wherein each of R.sub.8, R.sub.9, R.sub.10 and R.sub.11 is CH.sub.3.

24. The compound according to claim 1, which is selected from the group consisting of: ##STR00055## and corresponding salts thereof.

25. A composition comprising the compound according to claim 1, optionally in the form of a corresponding salt thereof, and one or more physiologically acceptable adjuvants.

26. A method for controlling a pest, comprising contacting a pest with a compound according to claim 1, optionally in the form of a corresponding salt thereof.

27. A method for protecting a plant against a plant pest, comprising applying a compound according to claim 1, optionally in the form of a corresponding salt thereof, to a plant in need thereof.

28. The method according to claim 27, wherein the plant pest is an insect or mite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0130] The present invention provides novel spinosyn compounds having advantageous properties. More specifically, the present invention provides novel spinosyn compounds showing improved solubility compared to existing spinosyn compounds such as butenyl spinosyn which represents a big advantage in preparation of formulations based on aqueous media. In addition, some of the novel spinosyn compounds of the present invention have also shown improved insecticidal activity compared to existing spinosyn compounds such as butenyl spinosyn, Spinosad and spinetoram.

[0131] In one aspect, the present invention provides a compound of general formula (I)

##STR00021## [0132] wherein [0133] the dashed line is a single bond, a double bond or an epoxide; [0134] X is NR.sub.2R.sub.3, NHR.sub.2, N.sup.+R.sub.1R.sub.2R.sub.3 or OR.sub.2; [0135] R.sub.1 is (CH.sub.2).sub.nOC(O)R.sub.1b, wherein [0136] n is an integer ranging from 0 to 20; preferably is an integer ranging from 1 to 10, more preferably is an integer ranging from 1 to 5; and [0137] R.sub.1b is selected from the group consisting of C(R.sub.2b).sub.3, N(R.sub.2b).sub.2, OH and OC(R.sub.2b).sub.3, wherein [0138] each R.sub.2b is independently selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; [0139] R.sub.2 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; preferably is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; more preferably is unsubstituted methyl; [0140] R.sub.3 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.1-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; preferably is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; more preferably is unsubstituted methyl; [0141] R.sub.4 is selected from the group consisting of unsubstituted ethyl, unsubstituted propyl, unsubstituted butyl, unsubstituted 1-butenyl, unsubstituted 1,3-butadienyl and unsubstituted 3-hydroxy-1-butenyl, preferably is unsubstituted ethyl or unsubstituted 1-butenyl, more preferably is unsubstituted 1-butenyl; [0142] R.sub.5 is H or unsubstituted methyl; preferably is H; [0143] R.sub.6 is OR.sub.6 or OC(O)R.sub.6, wherein R.sub.6 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.6 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.6 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted, preferably is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; more preferably is unsubstituted C.sub.1-C.sub.2 alkyl; most preferably is unsubstituted methyl; [0144] R.sub.7 is H or OR.sub.7, wherein R.sub.7 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; preferably R.sub.7 is H; [0145] R.sub.8 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.1-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; preferably is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; [0146] R.sub.9 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; preferably is optionally substituted C.sub.1-C.sub.2 alkyl; [0147] R.sub.10 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.12 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.20 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted; preferably is optionally substituted C.sub.1-C.sub.2 alkyl; and [0148] R.sub.11 is selected from the group consisting of hydrogen and substituted or unsubstituted C.sub.1-C.sub.2 alkyl; preferably is hydrogen or substituted or unsubstituted methyl; more preferably is hydrogen or unsubstituted methyl; most preferably is unsubstituted methyl; [0149] optionally in the form of a corresponding salt thereof.

[0150] According to some embodiments, X is NR.sub.2R.sub.3.

[0151] According to some embodiments, X is NHR.sub.2.

[0152] According to some embodiments, X is N.sup.+R.sub.1R.sub.2R.sub.3.

[0153] According to some embodiments, X is OR.sub.2.

[0154] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIa)

##STR00022## [0155] wherein the dashed line, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0156] optionally in the form of a corresponding salt thereof.

[0157] According to some embodiments, R.sub.1b is C(R.sub.2b).sub.3.

[0158] According to some embodiments, R.sub.1b is N(R.sub.2b).sub.2.

[0159] According to some embodiments, R.sub.1b is OH.

[0160] According to some embodiments, R.sub.1b is OC(R.sub.2b).sub.3.

[0161] According to some embodiments, each R.sub.2b is independently selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0162] According to some embodiments, each R.sub.2b is independently selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl.

[0163] According to some embodiments, each R.sub.2b is independently selected from the group consisting of hydrogen and substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0164] According to some embodiments, each R.sub.2b is independently selected from the group consisting of hydrogen and unsubstituted C.sub.1-C.sub.6 alkyl.

[0165] According to some embodiments, each R.sub.2b is independently selected from the group consisting of hydrogen and unsubstituted C.sub.1-C.sub.4 alkyl.

[0166] According to some embodiments, each R.sub.2b is independently selected from the group consisting of hydrogen and CH.sub.3.

[0167] According to some embodiments, n is an integer ranging from 1 to 10.

[0168] According to some embodiments, n is an integer ranging from 1 to 5.

[0169] According to some embodiments, n is 1, 2, 3 or 4.

[0170] According to some embodiments, n is 1, 2 or 3.

[0171] According to some embodiments, n is 1 or 2.

[0172] According to some embodiments, n is 1.

[0173] According to some embodiments, n is 2.

[0174] According to some embodiments, n is 3.

[0175] According to some embodiments, n is 4.

[0176] According to some embodiments, n is 5.

[0177] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIb)

##STR00023## [0178] wherein the dashed line, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0179] optionally in the form of a corresponding salt thereof.

[0180] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIc)

##STR00024## [0181] wherein the dashed line, R.sub.2, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0182] optionally in the form of a corresponding salt thereof.

[0183] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIIa)

##STR00025## [0184] wherein the dashed line, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0185] optionally in the form of a corresponding salt thereof.

[0186] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIIb)

##STR00026## [0187] wherein the dashed line, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0188] optionally in the form of a corresponding salt thereof.

[0189] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIIc)

##STR00027## [0190] wherein the dashed line, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0191] optionally in the form of a corresponding salt thereof.

[0192] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIId)

##STR00028## [0193] wherein the dashed line, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0194] optionally in the form of a corresponding salt thereof.

[0195] According to some embodiments, the compound of general formula (I) is a compound of general formula (IIIe)

##STR00029## [0196] wherein the dashed line, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein; [0197] optionally in the form of a corresponding salt thereof.

[0198] According to some embodiments, R.sub.2 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.1-C.sub.6 alkenyl, substituted or unsubstituted C.sub.1-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0199] According to some embodiments, R.sub.2 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0200] According to some embodiments, R.sub.2 is substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0201] According to some embodiments, R.sub.2 is unsubstituted C.sub.1-C.sub.6 alkyl.

[0202] According to some embodiments, R.sub.2 is unsubstituted C.sub.1-C.sub.2 alkyl.

[0203] According to some embodiments, R.sub.2 is CH.sub.3.

[0204] According to some embodiments, R.sub.3 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0205] According to some embodiments, R.sub.3 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0206] According to some embodiments, R.sub.3 is substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0207] According to some embodiments, R.sub.3 is unsubstituted C.sub.1-C.sub.6 alkyl.

[0208] According to some embodiments, R.sub.3 is unsubstituted C.sub.1-C.sub.2 alkyl.

[0209] According to some embodiments, R.sub.3 is CH.sub.3.

[0210] According to some embodiments, R.sub.4 is unsubstituted ethyl or unsubstituted 1-butenyl.

[0211] According to some embodiments, R.sub.4 is unsubstituted 1-butenyl.

[0212] According to some embodiments, R.sub.5 is H.

[0213] According to some embodiments, R.sub.5 is CH.sub.3.

[0214] According to some embodiments, R.sub.6 is OR.sub.6.

[0215] According to some embodiments, R.sub.6 is OC(O)R.sub.6.

[0216] According to some embodiments, R.sub.6 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0217] According to some embodiments, R.sub.6 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.2 alkyl.

[0218] According to some embodiments, R.sub.6 is substituted or unsubstituted C.sub.1-C.sub.2 alkyl.

[0219] According to some embodiments, R.sub.6 is unsubstituted C.sub.1-C.sub.2 alkyl.

[0220] According to some embodiments, R.sub.6 is unsubstituted methyl.

[0221] According to some embodiments, R.sub.7 is H.

[0222] According to some embodiments, R.sub.7 is OR.sub.7.

[0223] According to some embodiments, R.sub.7 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0224] According to some embodiments, R.sub.7 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl.

[0225] According to some embodiments, R.sub.7 is selected from the group consisting of hydrogen and substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0226] According to some embodiments, R.sub.7 is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; preferably is CH.sub.3.

[0227] According to some embodiments, R.sub.8 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0228] According to some embodiments, R.sub.8 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl.

[0229] According to some embodiments, R.sub.8 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0230] According to some embodiments, R.sub.8 is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; preferably is CH.sub.3.

[0231] According to some embodiments, R.sub.9 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0232] According to some embodiments, R.sub.9 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl.

[0233] According to some embodiments, R.sub.9 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0234] According to some embodiments, R.sub.9 is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; preferably is CH.sub.3.

[0235] According to some embodiments, R.sub.10 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0236] According to some embodiments, R.sub.10 II) is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl.

[0237] According to some embodiments, R.sub.10 is hydrogen or substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0238] According to some embodiments, R.sub.10 is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; preferably is CH.sub.3.

[0239] According to some embodiments, each of R.sub.8, R.sub.9 and R.sub.10 is substituted or unsubstituted C.sub.1-C.sub.6 alkyl.

[0240] According to some embodiments, each of R.sub.8, R.sub.9 and R.sub.10 is unsubstituted C.sub.1-C.sub.6 alkyl.

[0241] According to some embodiments, each of R.sub.8, R.sub.9 and R.sub.10 is CH.sub.3.

[0242] According to some embodiments, R.sub.11 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.12 cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.10 aryl, substituted or unsubstituted C.sub.5-C.sub.10 heterocyclyl, (C.sub.1-C.sub.6 alkyl)-(C.sub.3-C.sub.12 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.6 alkyl)-(C.sub.6-C.sub.10 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.6 alkyl)-(C.sub.5-C.sub.10 heterocyclyl) with the heterocyclyl being optionally substituted.

[0243] According to some embodiments, R.sub.11 is selected from the group consisting of hydrogen, substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl and substituted or unsubstituted C.sub.2-C.sub.6 alkynyl.

[0244] According to some embodiments, R.sub.11 is hydrogen or substituted or unsubstituted methyl.

[0245] According to some embodiments, R.sub.11 is hydrogen.

[0246] According to some embodiments, R.sub.11 is substituted or unsubstituted methyl.

[0247] According to some embodiments, R.sub.11 is CH.sub.3.

[0248] According to some embodiments, the dashed line is a double bond.

[0249] According to some embodiments, the dashed line is a single bond.

[0250] According to some embodiments, the dashed line is an epoxide.

[0251] According to some embodiments, the compound is selected from the group consisting of

##STR00030##

and corresponding salts thereof.

[0252] According to some embodiments, the compound is selected from the group consisting of

##STR00031##

and corresponding salts thereof.

[0253] According to some embodiments, the compound is

##STR00032##

or a corresponding salt thereof.

[0254] According to some embodiments, the compound is

##STR00033##

or a corresponding salt thereof.

[0255] According to some embodiments, the compound is

##STR00034##

or a corresponding salt thereof.

[0256] According to some embodiments the compound is selected from the group consisting of

##STR00035##

or a corresponding salt thereof.

[0257] The present invention further provides a composition comprising a compound according the present invention, optionally in the form of a corresponding salt thereof, and one or more physiologically acceptable adjuvants.

[0258] Composition of the present invention include concentrated versions, in which the present active agent is present in a concentration of from 0.001 to 98.0 percent, with the remaining content being physiologically acceptable carriers. Such compositions, especially those with less than 50 percent of the present compound, can sometimes be used directly, but these compositions can also be diluted with other physiologically acceptable carriers to form more dilute treating formulations. These latter compositions can include the active agent in lesser concentrations of from 0.001 to 0.1 percent. Compositions are prepared according to the procedures and formulas which are conventional in the agricultural or pest control art. The compositions may be concentrated and dispersed in water or may be used in the form of a dust, bait or granular formulation. The dispersions are typically aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. The water-soluble or water-suspension or emulsifiable formulations are either solids, wettable powders, or liquids, known as emulsifiable concentrates or aqueous suspensions. Wettable powders may be agglomerated or compacted to form water dispersible granules. These granules comprise mixtures of compound, inert carriers and surfactants. The concentration of the compound is typically between about 0.1% to about 90% by weight. The inert carrier is typically attapulgite clays, montmorillonite clays and the diatomaceous earths or purified silicates. Surfactants comprise typically about 0.5% to about 10% of the wettable powder. Surfactants include sulfonated lignins, condensed napthalenesulfonates, the napthalenesulfonates, alkyl-benenesulfonates, alkysulfonates or nonionic surfactants such as ethylene oxide adducts of alkylphenols or mixtures thereof. Emulsifiable concentrates of the derivatives of the invention typically range from about 50 to about 500 grams of spinosyn derivative per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is a mixture of a water immiscible solvent and emulsifiers. Organic solvents include organics such as xylenes, and petroleum fractions such as high-boiling naphthlenic and olefinic portions of petroleum which include heavy and aromatic naphtha. Other organics may also be used such as terpenic solventsrosin derivatives, aliphatic ketones such as cyclohexanone and complex alcohols. Emulsifiers for emulsifiable concentrates are typically mixed ionic and/or nonionic surfactants such as those mentioned herein or their equivalents. Aqueous suspensions may be prepared containing water-insoluble spinosyn derivatives, where the compounds are dispersed in an aqueous vehicle at a concentration typically in the range of between about 5% to about 50% by weight. The suspensions are prepared by finely grinding the compound and vigorously mixing it into a vehicle of water, surfactants, and dispersants. Inert ingredients such as inorganic salts and synthetic or natural gums may also be employed to increase the density and/or viscosity of the aqueous vehicle as is desired. Precipitated flowables may be prepared by dissolving at least one spinosyn derivative of the invention in a water-miscible solvent and surfactants or surface active polymers. When these formulations are mixed with water, the active spinosyn derivative precipitates with the surfactant controlling the size of the resulting micro-crystalline precipitate. The size of the crystal can be controlled through the selection of specific polymer and surfactant mixtures. The spinosyn derivatives may also be applied as a granular composition that is applied to the soil. The granular composition typically contains from about 0.5% to about 10% by weight of the derivative. The spinosyn derivative is dispersed in an inert carrier which is typically clay or an equivalent substance. Generally, granular compositions are prepared by dissolving the compounds of the invention in a suitable solvent and applying it to a granular carrier which has been pre-formed to the desirable particle size. The particle size is typically between about 0.5 mm to 3 mm. The granular compositions may also be prepared by forming a dough or paste of the carrier and compound, drying the combined mixture, and crushing the dough or paste to the desired particle size.

[0259] The spinosyn compounds may also be combined with an appropriate organic solvent. The organic solvent is typically a bland petroleum oil that is widely used in the agricultural industry. These combinations are typically used as a spray. More typically, the spinosyn compounds are applied as a dispersion in a liquid carrier, where the liquid carrier is water. The compounds may also be applied in the form of an aerosol composition. The compound is dissolved in an inert carrier, which is a pressure-generating propellant mixture. The aerosol composition is packaged in a container, where the mixture is dispersed through an atomizing valve. Propellant mixtures contain either low-boiling halocarbons, which may be mixed with organic solvents or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons. The compounds may be applied to any locus inhabited by an insect or mite. Such locus typically is cotton, soybean and vegetable crops, fruit and nut trees, grape vines, houses and ornamental plants. The amount of the spinosyn compound applied to the loci of insects and mites can be determined by those skilled in the art. Generally, the concentrations of from about 10 ppm to about 5,000 ppm provide the desired control. For crops such as soybeans and cotton, the rate of application is about 0.01 to about 1 kg/ha, where the spinosyn derivative is applied in a 5 to 50 gal/A spray formulation.

[0260] The composition can be formulated in a liquid concentrate, ready-to-use (RTU) liquid spray, dust, or solid form. The formulation chosen will depend on the use of the product. The following general treatment methods are preferably suitable for carrying out the seed treatment, or plant propagation material treatment, according to the invention: dry treatments (preferably with addition of adhesion promoters such as, for example, liquid paraffin or talc), and, if appropriate, colorants, slurry treatments (preferably with addition of wetters, dispersants, emulsifiers, adhesives, inert fillers and colorants), aqueous liquid treatments (preferably with addition of emulsifiers, dispersants, thickeners, antifreeze agents, polymers, adhesives and colorants), solvent-based liquid treatments (with addition of solvents and colorants), emulsion treatments (with addition of emulsifiers, solvents and colorants).

[0261] The present invention further provides the use of a compound, optionally in the form of a corresponding salt thereof, or composition according to the present invention as a pesticide.

[0262] The present invention further provides the use of a compound according to the present invention, optionally in the form of a corresponding salt thereof, or a composition according to the present invention as an insecticide.

[0263] The present invention further provides the use of a compound, optionally in the form of a corresponding salt thereof, or composition according to the present invention in controlling a pest, such as a plant pest.

[0264] The present invention further provides the use of a compound, optionally in the form of a corresponding salt thereof, or composition according to the present invention in protecting a plant against a plant pest.

[0265] The present invention further provides a method for controlling a pest, such as a plant pest, comprises contacting a pest, such as a plant pest, with a compound, optionally in the form of a corresponding salt thereof, or composition of the present invention.

[0266] The present invention further provides a method for protecting a plant against a plant pest, comprising the step of: applying a compound, optionally in the form of a corresponding salt thereof, or composition of the present invention to a plant in need thereof.

[0267] The compound or composition as defined above may be used on any plant in need of being protected against a plant pest. The plant may be an angiosperm or gymnosperm. According to some embodiments, the plant is an angiosperm. According to some embodiment, the plant is a gymnosperm. The plant may be a dicot or monocot. According to some embodiments, the plant is a dicot. According to some embodiment, the plant is a monocot. The plant may be a food plant (i.e. a plant some parts of which provides food for animal or human consumption), such as fruit plant.

[0268] The plant may be a crop plant, such as a food crop plant. According to certain embodiments, the plant is a food crop plant selected from the group consisting of pepper plant, cocoa plant, tomato plant, potato plant, maize plant, wheat plant and rice plant. The plant may be a tobacco plant, such as Nicotiana tabacum.

[0269] The plant pest can be an insect, such as a herbivorous insect, an arachnid or a nematode. Therefore, according to certain embodiments, the plant pest is an insect.

[0270] According to some embodiments, the plant pest is a herbivorous insect.

[0271] According to some embodiments, the insect is of the order Coleoptera, Lepidoptera, Diptera, Hemiptera, Orthoptera, Hymenoptera, Thysanoptera or Blattodea.

[0272] According to some embodiments, the insect is of the order Coleoptera or Lepidoptera.

[0273] According to some embodiments, the insect is of the order Coleoptera.

[0274] According to some embodiments, the insect is of the order Lepidoptera.

[0275] According to some embodiments, the insect is of the family Aphididae, Aleyrodidae, Agromizydae, Byturidae, Chrysomelidae, Cicadellidae, Crambidae, Curculionidae, Drosophilidae, Elateridae, Eriophyidae, Pentatomidae, Plutellidae, Gelechiidae, Gracillariidae, Hadeninae, Thripidae, Tortricidae, Nitidulidae, Noctuidae, Pyralidae, Pieridae, Scarabeidae or Tetranychidae.

[0276] According to some embodiments, the insect is of the genus Aphis, Agriotes, Anarsia, Bermisia, Byturus, Bactrocera, Crioceris, Chilo, Cydia, Cnaphalocrocis, Chrysodeixis, Ceratitis, Dacus, Diabrotica, Diatraea, Drosophila, Euschistus, Eupoecillia, Frankliniella, Halyomorpha, Helicoverpa, Heliothis, Heliothrips, Hercinothrips, Leptinotarsa, Lilioceris, Limothrips, Lobesia, Myzus, Melolontha, Nilaparvata, Ostrinia, Phyllotreta, Phyllocnistis, Popillia, Plutella, Pieris, Sesamia, Spodoptera, Thrips, Tribolium, Trialeurodes, Trichoplusia, Tortrix, Tetranychus, Tuta, Grapholita, Clysia, Popillia, Anthonomus, Meligethes, Rhopalosiphum, Macrosiphum, Acrosternum, Nezara or Piezodorus.

[0277] According to some embodiments, the insect is Aphis gossypii, Anarsia lineatella, Agriotes spp., Agriotes lineatus, Agriotes obscurus, Agriotes ustulatus, Agriotes sputator, Bemisia tabaci, Byturus tomentosus, Bactrocera carambolae, Bactrocera invadens, Bactrocera cucurbitae, Bactrocera dorsalis complex, Chilo suppressalis, Cydia pomonella, Crioceris duodecimpunctata, Ceratitis capitate, Ceratitis rosa, Ceratitis cosyra, Ceratitis fasciventris, Chrysodeixis includens, Cydia pomonella, Diabrotica virgifera virgifera, Dacus frontalis, Dacus bivittatus, Dacus vertebratus, Dacus ciliates, Diatraea venostata, Drosophila suzukii, Eupoecillia ambliguella, Frankliniella occidentalis, Halyomorpha halys, Helicoverpa zea, Helicoverpa armigera, Hercinothrips bicinctus, Hercinothrips femoralis, Leptinotarsa decemlineata, Lilioceris merdigera, Lilioceris lilii, Limothrips cerealium, Lobesia botrana, Melolontha melolontha, Myzus persicae, Nilaparvata lugens, Ostrinia nubilialis, Panonychus ulmi, Phyllotreta spp., Phyllotreta cruciferae, Phyllotreta striolata, Popillia japonica, Phyllocnistis citrella, Plutella xylostella, Pieris brassicae, Peridroma saucia, Sesamia Sesamia, Spodoptera litura, Spodoptera frugiperda, Thrips simplex, Thrips palmi, Thrips tabaci, Tribolium castaneum, Trialeurodes vaporariorum, Tuta absoluta, Tetranychus urticae, Sesamia nonagrioides, Sopdoptera exigua, Spodoptera eridania, Trichoplusia ni, Heliothis virescens; Grapholita molesta, Clysia ambiguella, Popillia japonica, Anthonomus grandis, Meligethes aeneus, Ceutorhynchus napi, Psylliodes chrysocephala, Sitobion avenae, Rhopalosiphum padi, Macrosiphum euphorbiae, Acrosternum hilare, Nezara viridula or Piezodorus guildinii.

[0278] The plant pest may be a larva or an imago of the insect. According to some embodiments, the plant pest is a larva of the insect. The larva may be in any stage of larval development, such as a larval stage selected from the group consisting of L1, L2, L3, L4, and L5. According to some embodiments, the plant pest is an imago of the insect.

[0279] The present invention further provides the use of a compound, optionally in the form of a corresponding salt thereof, or composition according to the present invention in agriculture.

[0280] Generally, the compound or composition can be applied to a plant in need thereof in any suitable dose, frequency and method of administration.

[0281] The compound or composition may suitably be in liquid form, and may be applied by spraying, drenching or dropping onto the plant. According to some embodiments, the compound or composition is applied by drenching. According to some embodiments, compound or composition is applied by spraying. According to some embodiments, the composition is applied by dropping.

[0282] The compound, either as raw material or in the form of a composition, may be applied at any effective amount, for example, at a concentration ranging from about 0.1 ?M to about 100 mM. Generally, a effective amount is one at which the active spinosyn compound shows insecticidal activity. The effective amount may thus vary depending on the actual active spinosyn compound employed and can be determined by the skilled person.

[0283] The compound or composition may be applied at least once a week. For example, it may be applied 1 to 3 times a week, such as two times a week. The compound may be applied at least once a day. For example, it may be applied 1 to 3 times a day, such as twice a day.

[0284] In a further aspect, the present invention provides a process for the preparation of a compound of general formula (I) as defined herein (with R.sub.6 being H or OR.sub.6), said process comprising reacting a compound of formula (p-I)

##STR00036##

with SeO.sub.2 to obtain a compound according to general formula (I-xi)

##STR00037##

optionally further reacting the resulting compound of general formula (I-xi) with a compound of a general formula R.sub.6Z to obtain a compound of general formula (I-xii)

##STR00038## [0285] optionally further reacting the compound of general formula (I-xii) with hydrogen (H.sub.2); [0286] wherein Z is a halogen, preferably Cl, Br or I, R.sub.6 is substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.6 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.6 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted, preferably is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; more preferably is unsubstituted C.sub.1-C.sub.2 alkyl; most preferably is unsubstituted methyl; and X, R.sub.4, R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein.

[0287] In a further aspect, the present invention provides a process for the preparation of a compound of general formula (I) as defined herein (with R.sub.6 being OC(O)H), said process comprising reacting a compound of formula (p-I)

##STR00039## [0288] with SeO.sub.2 in the presence of formic acid to obtain a compound according to general formula (I-xxi)

##STR00040## [0289] optionally further reacting the compound of general formula (I-xxi) with hydrogen (H.sub.2); wherein X, R.sub.4, R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein.

[0290] In a further aspect, the present invention provides a process for the preparation of a compound of general formula (I) as defined herein (with R.sub.6 being OC(O)R.sub.6), said process comprising reacting a compound of formula (p-I)

##STR00041## [0291] with SeO.sub.2 to obtain a compound according to general formula (I-xi)

##STR00042## [0292] further reacting the resulting compound of general formula (I-xi) with a compound of a general formula R.sub.6C(O)Z or a compound of a general formula R.sub.6C(O)O(O)CR.sub.6 to obtain a compound of general formula (I-xxxi)

##STR00043## [0293] optionally further reacting the compound of general formula (I-xxxi) with hydrogen (H.sub.2); [0294] wherein Z is a halogen, preferably Cl, Br or I, R.sub.6 is substituted or unsubstituted C.sub.1-C.sub.6 alkyl, substituted or unsubstituted C.sub.2-C.sub.6 alkenyl, substituted or unsubstituted C.sub.2-C.sub.6 alkynyl, substituted or unsubstituted C.sub.3-C.sub.6 cycloalkyl, substituted or unsubstituted C.sub.3-C.sub.6 aryl, substituted or unsubstituted C.sub.3-C.sub.12 heterocyclyl, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 cycloalkyl) with the cycloalkyl being optionally substituted, (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.6 aryl) with the aryl being optionally substituted, and (C.sub.1-C.sub.4 alkyl)-(C.sub.3-C.sub.12 heterocyclyl) with the heterocyclyl being optionally substituted, preferably is substituted or unsubstituted C.sub.1-C.sub.2 alkyl; more preferably is unsubstituted C.sub.1-C.sub.2 alkyl; most preferably is unsubstituted methyl; and X, R.sub.4, R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are as defined herein.

[0295] If not commercially available, the necessary starting materials for the processes of the invention may be made by procedures which are selected from standard organic chemistry techniques, techniques which are analogous to the synthesis of known structurally similar compounds, or techniques, which are analogous to the procedures described in the examples.

[0296] The reaction between a compound of formula (p-I) and SeO.sub.2 is preferably carried out in a suitable solvent, preferably dioxane, at a suitable temperature, such as between room temperature and the reflux temperature, preferably between 90? C. and 110? C. Generally, the reaction may be carried out for any period of time suitable for the formation of a compound of the invention. Suitably, the reaction is carried out for at least 3 hours, such as from 3 to 12 hours.

[0297] Optionally, the reaction between a compound of formula (I-xi) or (I-xxi) and the compound R.sub.6Z is preferably carried out in a suitable solvent, preferably tetrahydrofuran (THF), preferably in the presence of sodium hydride (NaH), at a suitable temperature, preferably at 20? C. Generally, the reaction may be carried out for any period of time suitable for the formation of a compound of the invention. Suitably, the reaction is carried out for at least 3 hours, such as from 3 to 6 hours.

[0298] Optionally, a compound of formula (I-xii), (I-xxi) or (I-xxxi) may be reacted with hydrogen in the presence of a suitable catalyst, preferably chloridotris(triphenylphosphine)rhodium(I) (Wilkinson's catalyst), preferably dissolved in a suitable solvent (homogeneous catalysis) to obtain a saturated ring. Generally, the reaction may be carried out for any period of time suitable for the formation of a compound of the invention. Suitably, the reaction is carried out for at least 3 hours, such as from 3 to 42 hours. Generally, the reaction may be carried out at any pressure. Suitably the reaction is carried out at increased pressure of at least 1.1 bar, such as from 1.1 bar to 5 bar, most suitably 3 bar.

[0299] Alternatively, the reaction can also be carried out in the presence of the Pearlman's catalyst (moist Pd(OH)2/C) (heterogeneous catalysis) and a suitable solvent, preferably ethanol. Generally, the reaction may be carried out for any period of time suitable for the formation of a compound of the invention. Suitably, the reaction is carried out for at least 1 hour, such as from 1 to 6 hours. Generally, the reaction may be carried out at any pressure. Suitably the reaction is carried out at increased pressure of at least 1.1 bar, such as from 1.1 bar to 5 bar, most suitably 3 bar.

[0300] It is to be understood that the methodology described for compounds of general formula (I) applies mutatis mutandis to obtain corresponding compounds according to general formula (IIa), (IIb), (IIc), (IIIa), (IIIb), (IIIc), (IIId) and (IIIe).

[0301] The process of the present invention may further comprise an purification step after completion of any of the reactions. The purification step may include any conventional procedure for purification of chemical compounds from a reaction. Well-known purification procedures include centrifugation or filtration, precipitation, and chromatographic methods such as e.g. ion exchange chromatography, gel filtration chromatography, etc.

Certain Definitions

[0302] In the context of this invention, a pesticide is a compound or composition that is meant to control a plan pests, and includes insecticide, nematicide and molluscicide.

[0303] In the context of this invention, a insecticide is a compound or composition used for reducing or eliminating insects harmful to cultivated plants.

[0304] In the context of this invention, alkyl is understood as meaning saturated, linear or branched hydrocarbons, which may be unsubstituted or substituted once or several times. It encompasses e.g. CH.sub.3 and CH.sub.2CH.sub.3. In these radicals, C.sub.1-C.sub.2 alkyl represents C1- or C2-alkyl, C.sub.1-C.sub.3 alkyl represents C1-, C2- or C3-alkyl, C.sub.1-C.sub.4 alkyl represents C1-, C2-, C3- or C4-alkyl, C.sub.1-C.sub.5 alkyl represents C1-, C2-, C3-, C4-, or C5-alkyl, C.sub.1-C.sub.6 alkyl represents C1-, C2-, C3-, C4-, C5- or C6-alkyl, C.sub.1-C.sub.7-alkyl represents C1-, C2-, C3-, C4-, C5-, C6- or C7-alkyl, C.sub.1-C.sub.8 alkyl represents C1-, C2-, C3-, C4-, C5-, C6-, C7- or C8-alkyl, C.sub.1-C.sub.10 alkyl represents C1-, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10-alkyl, C.sub.1-C.sub.18-alkyl represents C1-, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9-, C10-, C11-, C12-, C13-, C14-, C15-, C16-, C17- or C18-alkyl, and C.sub.1-C.sub.20-alkyl represents C1-, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9-, C10-, C11-, C12-, C13-, C14-, C15-, C16-, C17-, C18-, C19 or C20-alkyl. The alkyl radicals are preferably methyl, ethyl, propyl, methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, 1-methylpentyl, if substituted also CHF.sub.2, CF.sub.3 or CH.sub.2OH etc. Preferably alkyl is understood in the context of this invention as C.sub.1-C.sub.8 alkyl like methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; more preferably as C.sub.1-C.sub.6 alkyl like methyl, ethyl, propyl, butyl, pentyl, or hexyl; and most preferably as C.sub.1-C.sub.4 alkyl like methyl, ethyl, propyl or butyl.

[0305] Alkenyl is understood as meaning unsaturated, linear or branched hydrocarbons, which may be unsubstituted or substituted once or several times. It encompasses groups like e.g. CH?CHCH.sub.3. The alkenyl radicals are preferably vinyl (ethenyl), allyl (2-propenyl). Preferably in the context of this invention alkenyl is C.sub.1-C.sub.10 alkenyl or C.sub.1-C.sub.8 alkenyl like ethylene, propylene, butylene, pentylene, hexylene, heptylene or octylene; or is C.sub.1-C.sub.6 alkenyl like ethylene, propylene, butylene, pentylene, or hexylene; or is C.sub.1-C.sub.4 alkenyl, like ethylene, propylene, or butylenes.

[0306] Alkynyl is understood as meaning unsaturated, linear or branched hydrocarbons, which may be unsubstituted or substituted once or several times. It encompasses groups like e.g. C?CCH.sub.3 (1-propinyl). Preferably alkynyl in the context of this invention is C.sub.1-C.sub.10 alkynyl or C.sub.2-8-alkynyl like ethyne, propyne, butyene, pentyne, hexyne, heptyne, or octyne; or is C.sub.1-C.sub.6 alkynyl like ethyne, propyne, butyene, pentyne, or hexyne; or is C.sub.1-C.sub.4 alkynyl like ethyne, propyne, butyene, pentyne, or hexyne.

[0307] In connection with alkyl (also in alkylaryl, alkylheterocyclyl or alkylcycloalkyl), alkenyl and alkynylunless defined otherwisethe term substituted in the context of this invention is understood as meaning replacement of at least one hydrogen radical on a carbon atom by halogen (F, Cl, Br, I), cyano, hydroxy, amino or carboxyl. More than one replacement on the same molecule and also on the same carbon atom is possible with the same or different substituents. This includes for example 3 hydrogens being replaced on the same C atom, as in the case of CF.sub.3, or at different places of the same molecule, as in the case of e.g. CH(OH)CH?CHCHCl.sub.2.

[0308] In the context of this invention haloalkyl is understood as meaning an alkyl being substituted once or several times by a halogen (selected from F, Cl, Br, I). It encompasses e.g. CH.sub.2Cl, CH.sub.2F, CHCl.sub.2, CHF.sub.2, CCl.sub.3, CF.sub.3 and CH.sub.2CHCl.sub.2. Preferably haloalkyl is understood in the context of this invention as halogen-substituted C.sub.14-alkyl representing halogen substituted C1-, C2-, C3- or C4-alkyl. The halogen-substituted alkyl radicals are thus preferably methyl, ethyl, propyl, and butyl. Preferred examples include CH.sub.2Cl, CH.sub.2F, CHCl.sub.2, CHF.sub.2, and CF.sub.3.

[0309] In the context of this invention haloalkoxy is understood as meaning an O-alkyl being substituted once or several times by a halogen (selected from F, Cl, Br, I). It encompasses e.g. OCH.sub.2Cl, OCH.sub.2F, OCHCl.sub.2, OCHF.sub.2, OCCl.sub.3, OCF.sub.3 and OCH.sub.2CHCl.sub.2. Preferably haloalkyl is understood in the context of this invention as halogen-substituted OC.sub.1-C.sub.4 alkyl representing halogen substituted C1-, C2-, C3- or C4-alkoxy. The halogen-substituted alkyl radicals are thus preferably O-methyl, O-ethyl, O-propyl, and O-butyl. Preferred examples include OCH.sub.2Cl, OCH.sub.2F, OCHCl.sub.2, OCHF.sub.2, and OCF.sub.3.

[0310] In the context of this invention cycloalkyl is understood as meaning saturated and unsaturated (but not aromatic) cyclic hydrocarbons (without a heteroatom in the ring), which can be unsubstituted or once or several times substituted. Furthermore, C.sub.3-C.sub.12 cycloalkyl represents C3-, C4-, C5-, C6-, C7-, C8-, C9-, C10-, C11- or C12-cycloalkyl, C.sub.3-C.sub.4cycloalkyl represents C3- or C4-cycloalkyl, C.sub.3-C.sub.8 cycloalkyl represents C3-, C4- or C5-cycloalkyl, C.sub.3-C.sub.6 cycloalkyl represents C3-, C4-, C5- or C6-cycloalkyl, C.sub.3-C.sub.7 cycloalkyl represents C3-, C4-, C5-, C6- or C7-cycloalkyl, C.sub.3-C.sub.8 cycloalkyl represents C3-, C4-, C5-, C6-, C7- or C8-cycloalkyl, C.sub.4-C.sub.5 cycloalkyl represents C4- or C5-cycloalkyl, C.sub.4-C.sub.6 cycloalkyl represents C4-, C5- or C6-cycloalkyl, C.sub.4-C.sub.7 cycloalkyl represents C4-, C5-, C6- or C7-cycloalkyl, C.sub.5-C.sub.6 cycloalkyl represents C5- or C6-cycloalkyl and C.sub.5-C.sub.7 cycloalkyl represents C5-, C6- or C7-cycloalkyl. Examples are cyclopropyl, 2-methylcyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cycloheptyl, cyclooctyl, and also adamantly. Preferably in the context of this invention cycloalkyl is C.sub.3-C.sub.8 cycloalkyl like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl; or is C.sub.3-C.sub.7 cycloalkyl like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl; or is C.sub.3-C.sub.6 cycloalkyl like cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, especially cyclopentyl or cyclohexyl.

[0311] Aryl is understood as meaning 3 to 12 membered mono or polycyclic ring systems with at least one aromatic ring but without heteroatoms even in only one of the rings. Examples are phenyl, naphthyl, fluoranthenyl, fluorenyl, tetralinyl or indanyl, 9H-fluorenyl or anthracenyl radicals, which can be unsubstituted or once or several times substituted. Preferably, the aryl is a monocyclic aryl. More preferably the aryl is a 5, 6 or 7 membered monocyclic aryl. Even more preferably the aryl is a 5 or 6 membered monocyclic aryl. Most preferably aryl is understood in the context of this invention as phenyl, naphtyl or anthracenyl, preferably is phenyl.

[0312] A heterocyclyl radical or group (also called heterocyclyl hereinafter) is understood as meaning 3 to 12 membered mono or polycyclic heterocyclic ring systems, with at least one saturated or unsaturated ring which contains one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring. A heterocyclic group can also be substituted once or several times.

[0313] Examples include non-aromatic heterocyclyls such as tetrahydropyrane, oxazepane, morpholine, piperidine, pyrrolidine as well as heteroaryls such as furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phthalazine, thiazole, benzothiazole, indole, benzotriazole, carbazole and quinazoline.

[0314] Subgroups inside the heterocyclyls as understood herein include heteroaryls and non-aromatic heterocyclyls: [0315] the heteroaryl (being equivalent to heteroaromatic radicals or aromatic heterocyclyls) is an aromatic 3 to 12 membered mono or polycyclic heterocyclic ring system of one or more rings of which at least one aromatic ring contains one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring; preferably is an aromatic 3 to 12 membered mono or polycyclic heterocyclic ring system of one or two rings of which at least one aromatic ring contains one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring, more preferably is selected from furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phthalazine, benzothiazole, indole, benzotriazole, carbazole, quinazoline, thiazole, imidazole, pyrazole, oxazole, thiophene and benzimidazole; [0316] the non-aromatic heterocyclyl is a 3 to 12 membered mono or polycyclic heterocyclic ring system of one or more rings of which at least one ringwith this (or these) ring(s) then not being aromaticcontains one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring; preferably is a 3 to 12 membered mono or polycyclic heterocyclic ring system of one or two rings of which one or both ringswith this one or two rings then not being aromaticcontain/s one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring, more preferably is selected from oxazepam, pyrrolidine, piperidine, piperazine, tetrahydropyran, morpholine, indoline, oxopyrrolidine, benzodioxane, oxetane, especially is benzodioxane, morpholine, tetrahydropyran, piperidine, oxopyrrolidine, oxetane and pyrrolidine.

[0317] Preferably, the heteroaryl is a monocyclic heteroaryl. More preferably the heteroaryl is a 5, 6 or 7 membered monocyclic heteroaryl. Even more preferably the heteroaryl is a 5 or 6 membered monocyclic heteroaryl.

[0318] Preferably, the non-aromatic heterocyclyl is a monocyclic non-aromatic heterocyclyl. More preferably the non-aromatic heterocyclyl is a 4, 5, 6 or 7 membered monocyclic non-aromatic heterocyclyl. Even more preferably the non-aromatic heterocyclyl is a 5 or 6 membered monocyclic non-aromatic heterocyclyl.

[0319] Preferably in the context of this invention heterocyclyl is defined as a 5 to 10 membered mono or polycyclic heterocyclic ring system of one or two saturated or unsaturated rings of which at least one ring contains one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring.

[0320] Preferred examples of heterocyclyls include oxetane, oxazepan, pyrrolidine, imidazole, oxadiazole, tetrazole, pyridine, pyrimidine, piperidine, piperazine, benzofuran, benzimidazole, indazole, benzodiazole, thiazole, benzothiazole, tetrahydropyrane, morpholine, indoline, furan, triazole, isoxazole, pyrazole, thiophene, benzothiophene, pyrrole, pyrazine, pyrrolo[2,3b]pyridine, quinoline, isoquinoline, phthalazine, benzo-1,2,5-thiadiazole, indole, benzotriazole, benzoxazole oxopyrrolidine, pyrimidine, benzodioxolane, benzodioxane, carbazole and quinazoline, especially is pyridine, pyrazine, indazole, benzodioxane, thiazole, benzothiazole, morpholine, tetrahydropyrane, pyrazole, imidazole, piperidine, thiophene, indole, benzimidazole, pyrrolo[2,3b]pyridine, benzoxazole, oxopyrrolidine, pyrimidine, oxazepane, oxetane and pyrrolidine.

[0321] In connection with aromatic heterocyclyls (heteroaryls), non-aromatic heterocyclyls, aryls and cycloalkyls, when a ring system falls within two or more of the above cycle definitions simultaneously, then the ring system is defined first as an aromatic heterocyclyl (heteroaryl) if at least one aromatic ring contains a heteroatom. If no aromatic ring contains a heteroatom, then the ring system is defined as a non-aromatic heterocyclyl if at least one non-aromatic ring contains a heteroatom. If no non-aromatic ring contains a heteroatom, then the ring system is defined as an aryl if it contains at least one aryl cycle. If no aryl is present, then the ring system is defined as a cycloalkyl if at least one non-aromatic cyclic hydrocarbon is present.

[0322] In the context of this invention alkylaryl is understood as meaning an aryl group (see above) being connected to another atom through a C.sub.1-6-alkyl (see above) which may be branched or linear and is unsubstituted or substituted once or several times. Preferably alkylaryl is understood as meaning an aryl group (see above) being connected to another atom through 1 to 4 (CH.sub.2) groups. Most preferably alkylaryl is benzyl (i.e. CH.sub.2-phenyl).

[0323] In the context of this invention alkylheterocyclyl is understood as meaning an heterocyclyl group being connected to another atom through a C.sub.1-6-alkyl (see above) which may be branched or linear and is unsubstituted or substituted once or several times. Preferably alkylheterocyclyl is understood as meaning an heterocyclyl group (see above) being connected to another atom through 1 to 4 (CH.sub.2) groups. Most preferably alkylheterocyclyl is CH.sub.2-pyridine.

[0324] In the context of this invention alkylcycloalkyl is understood as meaning an cycloalkyl group being connected to another atom through a C.sub.1-6-alkyl (see above) which may be branched or linear and is unsubstituted or substituted once or several times. Preferably alkylcycloalkyl is understood as meaning an cycloalkyl group (see above) being connected to another atom through 1 to 4 (CH.sub.2) groups. Most preferably alkylcycloalkyl is CH.sub.2-cyclopropyl.

[0325] Preferably, the cycloalkyl is a monocyclic cycloalkyl. More preferably the cycloalkyl is a 3, 4, 5, 6, 7 or 8 membered monocyclic cycloalkyl. Even more preferably the cycloalkyl is a 3, 4, 5 or 6 membered monocyclic cycloalkyl.

[0326] In connection with aryl (including alkyl-aryl), cycloalkyl (including alkyl-cycloalkyl), or heterocyclyl (including alkyl-heterocyclyl), substituted is understoodunless defined otherwiseas meaning substitution of the ring-system of the aryl or alkyl-aryl, cycloalkyl or alkyl-cycloalkyl; heterocyclyl or alkyl-heterocyclyl with one or more of halogen (F, Cl, Br, I), cyano, hydroxy, amino, carboxyl, haloalkyl, haloalkoxy, linear or branched, substituted or unsubstituted C.sub.1-6-alkyl; a saturated or unsaturated, linear or branched, substituted or unsubstituted C.sub.1-6-alkyl; a saturated or unsaturated, linear or branched, substituted or unsubstituted OC.sub.1-6-alkyl (alkoxy); a saturated or unsaturated, linear or branched, substituted or unsubstituted SC.sub.1-6-alkyl; a saturated or unsaturated, linear or branched, substituted or unsubstituted C(O)C.sub.1-6-alkyl-group; a saturated or unsaturated, linear or branched, substituted or unsubstituted C(O)OC.sub.1-6-alkyl-group; NH-Boc and -Boc. Preferably, suitable substituents are 1, 2 or 3 substituents independently selected from fluoro, chloro, bromo, iodo, cyano, nitro, amino, carboxyl, methylamino, dimethylamino, hydroxy, methyl, ethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, phenyl, NH-Boc and -Boc.

[0327] Additionally to the above-mentioned substitutions, in connection with cycloalkyl (including alkyl-cycloalkyl), or heterocyclyl (including alkylheterocyclyl) namely non-aromatic heterocyclyl (including non-aromatic alkyl-heterocyclyl), substituted is also understoodunless defined otherwiseas meaning substitution of the ring-system of the cycloalkyl or alkyl-cycloalkyl; non-aromatic heterocyclyl or non aromatic alkyl-heterocyclyl with

##STR00044##

[0328] A ring system is a system consisting of at least one ring of connected atoms but including also systems in which two or more rings of connected atoms are joined with joined meaning that the respective rings are sharing one (like a spiro structure), two or more atoms being a member or members of both joined rings.

[0329] The term salt is to be understood as meaning any form of the compound according to the invention in which it assumes an ionic form or is charged and is coupled with a counter-ion (a cation or anion), or is in solution. By this are also to be understood complexes of the compound with other molecules and ions, in particular complexes via ionic interactions.

[0330] Salts can be formed with anions or acids and in the context of this invention is understood as meaning salts of at least one of the compounds according to the invention with at least one, preferably inorganic, anion. Non-limiting examples of an anion include chloride, sulfate, nitrate, phosphate, citrate, tartrate, acetate, lactate, propionate, gluconate and others.

[0331] Salts can also be formed with cations or bases and in the context of this invention is understood as meaning salts of at least one of the compounds used according to the inventionusually a (deprotonated) acidas an anion with at least one, preferably inorganic, cation. The salts of the alkali metals and alkaline earth metals are particularly preferred, and also those with NH.sub.4, but in particular (mono)- or (di)sodium, (mono)- or (di)potassium, magnesium or calcium salts.

[0332] Where a numerical limit or range is stated herein, the endpoints are included. Also, all values and sub ranges within a numerical limit or range are specifically included as if explicitly written out.

[0333] Having generally described this invention, a further understanding can be obtained by reference to certain specific examples, which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.

EXAMPLES

Example 1: Synthesis of Compound A1

[0334] A sample of butenyl spinosyn ?1 (1.0 g, 1.32 mmol) was dissolved in a mixture of solvents comprise of 20 mL dioxane and 2 mL of water. Selenium dioxide (293 mg, 2.64 mmol) was added and the mixture was heated to 100? C. and stirred for 12 hours. After the reaction was completed the mixture was cooled to room temperature and concentrated by using rotary evaporator. The residue was purified by preparative HPLC on C18 reversed phase column. Chromatographically pure fractions were dried by lyophilization and subjected to LCMS and .sup.1H NMR analysis. The structure was determined to be 7-hydroxy butenyl spinosyn ?1 (compound A1) as a light yellow solid (236 mg, 23.1%).

##STR00045##

Analytical Data for Compound A1:

[0335] .sup.1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.79 (s, 1H), 6.12 (dd, 1H, J=2.2, 9.9 Hz), 5.93 (dd, 1H, J=3.1, 9.7 Hz), 5.67 (td, 1H, J=6.2, 15.4 Hz), 5.31 (dd, 1H, J=7.4, 15.3 Hz), 5.0-5.1 (m, 1H), 4.88 (d, 1H, J=0.9 Hz), 4.4-4.5 (m, 2H), 3.6-3.7 (m, 1H), 3.4-3.6 (m, 13H), 3.3-3.4 (m, 1H), 3.1-3.3 (m, 3H), 3.0-3.1 (m, 1H), 2.3-2.4 (m, 1H), 2.25 (s, 8H), 2.0-2.1 (m, 3H), 1.9 (m, 2H), 1.6-1.9 (m, 5H), 1.5-1.6 (m, 6H), 1.4-1.5 (m, 2H), 1.2-1.4 (m, 8H), 1.20 (d, 3H, J=6.8 Hz), 0.95 (t, 3H, J=7.4 Hz).

[0336] LCMS (ESI+): m/z 774.5 [M+H].sup.+.

Example 2: Synthesis of Compound H1

[0337] A sample of 7-hydroxylated butenyl spinosyn ?1 (250 mg, 323 ?mol) was dissolved in 6.25 mL of tetrahydrofuran and sodium hydride (19.4 mg, 484 ?mol, 60% purity) was added. After 10 minutes of mixing iodomethane (68.8 mg, 484 ?mol) was added and stirred at 20? C. for 5 hours. The reaction solution was quenched with water and purified by preparative HPLC to obtain pure 7-methoxy butenyl spinosyn ?1 (63.1 mg, 24.8% yield, 99.7% purity) as a white solid. The structure of the compound was determined using LCMS and .sup.1H NMR.

##STR00046##

Analytical Data for Compound H1:

[0338] 1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.77 (br s, 1H), 6.04 (dd, J=2.4, 9.8 Hz, 1H), 5.92 (dd, J=2.8, 9.8 Hz, 1H), 5.68 (td, J=6.3, 15.3 Hz, 1H), 5.30 (dd, J=7.3, 15.4 Hz, 1H), 5.12-4.99 (m, 1H), 4.85 (s, 1H), 4.44 (br d, J=7.5 Hz, 1H), 4.31 (q, J=6.9 Hz, 1H), 3.71-3.46 (m, 16H), 3.39-3.28 (m, 2H), 3.21-3.08 (m, 5H), 3.04 (br s, 1H), 2.54-2.19 (m, 8H), 2.18-2.07 (m, 2H), 2.06-1.87 (m, 3H), 1.79 (dt, J=6.5, 12.7 Hz, 3H), 1.72-1.43 (m, 9H), 1.38-1.13 (m, 11H), 0.95 (t, J=7.4 Hz, 3H).

[0339] LCMS (ESI+): m/z 788.6 [M+H].sup.+.

Example 3: Synthesis of Compound H2

[0340] A sample of 7-hydroxylated butenyl spinosyn ?1 (300 mg, 387.6 ?mol) was dissolved in 6 mL of dimethylformamide and sodium hydride (23.3 mg, 581.4 ?mol, 60% purity) was added. After 10 minutes of mixing ethyl iodide (90.7 mg, 581.4 ?mol) was added and stirred at 20? C. for 3 hours. The reaction mixture was further purified by preparative HPLC to obtain pure 7-ethoxy butenyl spinosyn al (86.1 mg, 27.7% yield, 99.6% purity) as a white solid. The structure of the compound was determined using LCMS and .sup.1H NMR.

##STR00047##

Analytical Data for Compound H2:

[0341] .sup.1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.78 (br s, 1H), 6.10-5.98 (m, 1H), 5.89 (br dd, J=2.8, 9.8 Hz, 1H), 5.75-5.62 (m, 1H), 5.31 (br dd, J=7.1, 15.4 Hz, 1H), 5.11-5.00 (m, 1H), 4.85 (s, 1H), 4.43 (br d, J=7.1 Hz, 1H), 4.35-4.22 (m, 1H), 3.76-3.43 (m, 16H), 3.43-3.24 (m, 4H), 3.19-3.09 (m, 2H), 3.04 (br s, 1H), 2.50-2.33 (m, 1H), 2.24 (s, 7H), 2.17-2.06 (m, 3H), 2.05-1.94 (m, 3H), 1.91-1.72 (m, 4H), 1.69-1.41 (m, 7H), 1.28 (br dd, J=6.2, 9.9 Hz, 7H), 1.19 (br d, J=6.6 Hz, 3H), 1.09 (br t, J=6.9 Hz, 3H), 1.02-0.89 (m, 3H).

[0342] LCMS (ESI+): m/z 802.5 [M+H].sup.+.

Example 4: Synthesis of Compound J1A-H1

[0343] To a solution of H1 (200 mg, 254 ?mol) in acetonitrile (3 mL), iodomethyl 2,2-dimethylpropanoate (0.8 M, 635 ?L, 508 ?mol) and 1,2,2,6,6-pentamethylpiperidine (79 mg, 92 ?L, 508 ?mol) were added. The mixture was stirred at 60? C. for 6 hours. The reaction mixture was filtered and crude product was purified by reversed phase preparative HPLC. pH of the elution solution was adjusted to 7 with 0.5% aqueous ammonia and lyophilized to give white solid. The solid was triturated in acetonitrile and filtered to remove ammonium chloride. The filtrate was lyophilized to give J1A-H1 (100.6 mg, 40.9% yield, 97.0% purity) as a light yellow solid. The structure of the compound was determined using LCMS and .sup.1H NMR.

##STR00048##

Analytical Data for Compound J1A-H1:

[0344] .sup.1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.79 (s, 1H), 6.03 (m, 1H), 5.90 (m, 1H), 5.73-5.85 (m, 2H), 5.65-5.73 (m, 1H), 5.30 (m, 1H), 5.04 (br t, J=8.25 Hz, 1H), 4.86-4.92 (m, 1H), 4.85 (d, J=0.88 Hz, 1H), 4.32 (m, 3H), 3.72 (br d, J=9.38 Hz, 1H), 3.55-3.63 (m, 4H), 3.46-3.54 (m, 8H), 3.24-3.44 (m, 8H), 3.15 (s, 3H), 3.00-3.14 (m, 3H), 2.40 (br d, J=10.01 Hz, 1H), 2.19-2.36 (m, 2H), 2.07-2.18 (m, 2H), 1.96-2.05 (m, 2H), 1.78-1.91 (m, 3H), 1.52-1.70 (m, 8H), 1.37-1.49 (m, 1H), 1.28-1.34 (m, 10H), 1.19-1.28 (m, 4H), 1.15 (br d, J=6.75 Hz, 3H), 0.95 (t, J=7.44 Hz, 3H).

[0345] LCMS (ESI+): m/z 902.5 [M+H].sup.+.

Example 5: Synthesis of Compound J7-H1

[0346] To a solution of H1 (200 mg, 0.254 mmol) in acetonitrile (4 mL), chloromethyl isopropyl carbonate (0.8 M, 1.6 mL, 1.28 mmol), NaI (190 mg, 1.27 mmol) and 1,2,2,6,6-pentamethylpiperidine (78.8 mg, 92 uL, 0.508 mmol) were added. The mixture was stirred at 60? C. for 6 hours. The reaction mixture was filtered and crude product was purified by reversed phase preparative HPLC. The elution solution was adjusted to pH 7 with 0.5% aqueous ammonia and lyophilized to give white solid. The solid was triturated in acetonitrile and filtered to remove ammonium chloride. The filtrate was lyophilized to give J7-H1 (105.3 mg, 43.3% yield, 98.1% purity) as a light yellow solid. The correct structure of the compound was determined by LC-MS and 1H NMR analysis.

##STR00049##

Analytical Data for Compound J7-H1:

[0347] .sup.1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.78 (s, 1H), 6.03 (m, 1H), 5.89 (m, 1H), 5.74-5.83 (m, 2H), 5.69 (m, 1H), 5.29 (m, 1H), 5.00-5.07 (m, 1H), 4.96 (m, 1H), 4.87 (m, 1H), 4.84 (d, J=1.13 Hz, 1H), 4.25-4.40 (m, 2H), 4.03 (br d, J=6.88 Hz, 1H), 3.71 (br d, J=9.51 Hz, 1H), 3.54-3.62 (m, 4H), 3.48-3.54 (m, 8H), 3.38-3.48 (m, 6H), 3.23-3.37 (m, 2H), 3.14 (s, 3H), 3.07-3.12 (m, 1H), 3.01-3.06 (m, 1H), 2.39 (br d, J=10.13 Hz, 1H), 2.20-2.32 (m, 2H), 2.07-2.16 (m, 2H), 1.97-2.03 (m, 6H), 1.88 (br d, J=12.13 Hz, 1H), 1.72-1.82 (m, 2H), 1.62-1.71 (m, 4H), 1.52-1.59 (m, 2H), 1.39-1.48 (m, 1H), 1.36 (d, J=6.25 Hz, 6H), 1.28 (d, J=6.25 Hz, 3H), 1.08-1.24 (m, 5H), 0.95 (t, J=7.44 Hz, 3H).

[0348] LCMS (ESI+): m/z 904.4 [M+H].sup.+.

Example 6: Synthesis of Compound H6

[0349] A solution of A1 (350 mg, 0.45 mmol) in DMF (3 mL) was cooled to 0? C. and NaH (108 mg, 2.7 mmol, 60% purity) was added and the mixture was stirred at 0? C. for 10 minutes. Additionally, 3-bromoprop-1-ene (164 mg, 1.35 mmol) was added and the reaction mixture was stirred at 25? C. for 2 hours. Then the mixture was cooled down to 0? C., and the reaction was quenched with water (1 mL) at 0? C. The product was purified by reversed phase preparative HPLC and lyophilized to give H6 (87.4 mg, 23.5% yield, 100% purity) as a white solid.

##STR00050##

Analytical Data for Compound H6:

[0350] .sup.1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.78 (br s, 1H), 6.04 (m, 1H), 5.80-5.96 (m, 2H), 5.68 (m, 1H), 5.21-5.34 (m, 2H), 5.00-5.11 (m, 2H), 4.84 (s, 1H), 4.43 (br d, J=7.50 Hz, 1H), 4.32 (m, 1H), 3.87 (br d, J=4.00 Hz, 2H), 3.63-3.70 (m, 1H), 3.57-3.62 (m, 1H), 3.55 (s, 4H), 3.45-3.53 (m, 8H), 3.37-3.45 (m, 1H), 3.27-3.37 (m, 1H), 3.08-3.18 (m, 2H), 2.99-3.07 (m, 1H), 2.39 (m, 1H), 2.26 (s, 7 H), 2.07-2.19 (m, 2H), 1.93-2.06 (m, 3H), 1.75-1.92 (m, 4H), 1.42-1.59 (m, 7H), 1.28 (m, 7H), 1.15-1.24 (m, 4H), 0.95 (t, J=7.44 Hz, 3H).

[0351] LCMS (ESI+): m/z 814.4 [M+H].sup.+.

Example 7: Synthesis of Compound H9C

[0352] A solution of A1 (250 mg, 0.32 mmol) in dimethylformamide (DMF, 2 mL) was cooled to 0? C. and NaH (129 mg, 3.2 mmol, 60% purity) was added and the mixture was stirred at 0? C. for 10 minutes. Additionally, 2-(bromomethyl)oxirane (221 mg, 1.62 mmol) was added and stirred at 25? C. for 2 hours. The reaction was quenched with saturated ammonium chloride solution (2 mL) and the mixture was concentrated under reduced pressure. The product was purified by reversed phase preparative HPLC and lyophilized to give H9C (80.9 mg, 30.2% yield, 98.9% purity) as a white solid.

##STR00051##

Analytical Data for Compound H9C:

[0353] .sup.1H NMR (400 MHz, CDCl.sub.3): ? ppm 6.77 (br s, 1H), 5.99-6.07 (m, 1H), 5.90-5.97 (m, 1H), 5.68 (m, 1H), 5.30 (m, 1H), 5.00-5.10 (m, 1H), 4.85 (d, J=4.50 Hz, 1H), 4.43 (br d, J=7.13 Hz, 1H), 4.25-4.38 (m, 1H), 3.63-3.70 (m, 1H), 3.58-3.62 (m, 1H), 3.54-3.57 (m, 4H), 3.44-3.53 (m, 9H), 3.26-3.44 (m, 3H), 3.09-3.18 (m, 2H), 3.00-3.08 (m, 2H), 2.71-2.79 (m, 1H), 2.53-2.66 (m, 1H), 2.39 (m, 1H), 2.26 (br s, 6H), 2.11-2.19 (m, 2H), 1.95-2.10 (m, 4H), 1.72-1.94 (m, 4H), 1.59-1.67 (m, 4H), 1.43-1.54 (m, 3H), 1.22-1.34 (m, 8H), 1.19 (d, J=6.75 Hz, 3H), 0.92-0.99 (m, 3H).

[0354] LCMS (ESI+): m/z 830.4 [M+H].sup.+.

Example 8: Synthesis of Compound H9B

[0355] A solution of A1 (250 mg, 0.32 mmol) in dimethylformamide (DMF, 2 mL) was cooled to 0? C. and NaH (129 mg, 3.2 mmol, 60% purity) was added and the mixture was stirred at 0? C. for 10 minutes. Additionally, (bromomethyl)cyclopropane (219 mg, 1.62 mmol) was added and stirred at 25? C. for 2 hours. At the end of the reaction 54% of product H9B was detected by LC-MS analysis.

##STR00052##

Analytical Data for Compound H9B:

[0356] LCMS (ESI+): m/z 828.4 [M+H].sup.+.

Example 9: Synthesis of Compound H11

[0357] To a solution of H1 (100 mg, 0.127 mmol) in tetrahydrofuran (THF, 2 mL), Pd/C catalyst (0.5 eq) was added and H.sub.2 was supplied to the reaction mixture under atmospheric pressure for 30 minutes at 25? C. At the end of the reaction all H1 was consumed and product H11 was detected in the reaction mixture by LC-MS analysis.

##STR00053##

Analytical Data for Compound H11:

[0358] LCMS (ESI+): m/z 794.8 [M+H].sup.+.

Example 10: Evaluation of Kinetic Solubility of Spinosyn Compounds

[0359] Solubility of the compounds of the invention was assessed using kinetic solubility assay and compared to solubility of butenyl spinosyn. Stock solutions of spinosyn compounds were prepared in DMSO at 10 mM concentration). 10 uL of the stock solutions were added into 490 of in K.S. 5.4 buffer of pH 5.4 (80 mM phosphoric acid, acetic acid, boric acid buffer, adjusted the pH to pH 5.4 with 1 N HCl and 1N NaOH) or K.S. 7.4 buffer with pH of 7.4 (80 mM phosphoric acid, acetic acid, boric acid buffer, adjusted the pH to pH 7.4 with 1 N HCl and 1N NaOH). The solutions were incubated with shaking at room temperature (25?2? C.) for 24 hours. 200 uL of each solution were then transferred into a new MultiScreen filter plate (Membrane of polycarbonate) and filtered by millipore vacuum manifold, and the filtrate was collected. The concentrations of tested compounds in the filtered samples were analyzed by HPLC analysis calibrated by a standard curve generated by injection of 3 standard solutions of the relevant compound with concentrations of 1, 20, 200 ?M. The results of the testing are presented in Table 1. The conditions of HPLC analysis are presented in Table 2.

TABLE-US-00001 TABLE 1 Comparison of solubility of spinosyn compounds at pH 5.4 and 7.4. Kinetic Kinetic K.S 5.4 Solubility K.S 7.4 Solubility Dose Conc pH = 5.4 Dose Conc pH = 7.4 Compound (?M) (?M) (?M) (?M) Butenyl spinosyn 200 183.17 200 3.52 A1 200 192.40 200 186.57 H1 200 182.65 200 77.12 H2 200 166.38 200 7.68

TABLE-US-00002 TABLE 2 Conditions of the HPLC analysis for determination of kinetic solubility. Instrument Agilent 1200 Detector DAD Mobile phase A: Water containing 0.37 TFA B: Acetonitrile containing 0.19 TFA Time B Flow rate Gradient (min) (%) (mL/min) 0.00 5 1.0 2.00 90 1.0 2.50 90 1.0 3.01 5 1.0 4.00 5 1.0 Column Xbridge C18 (2.1 ? 50 mm, 5 ?m) Injection Volume 20 ?L

[0360] These results show that the compounds of the invention are significantly more soluble in the neutral pH values (7.4) compared to butenyl spinosyn, which represents a big advantage in preparation of formulations based on aqueous media.

Example 11: Evaluation of Biological Activity of Spinosyn Compounds

[0361] Insecticide activities of the compounds of this invention were assessed in comparison with commercially available samples of spinosad (LGC (Dr. Ehrenstorfer); Product code: DRE-C16972830) and spinetoram (LGC (Dr. Ehrenstorfer); Product code: DRE-C16972770) Solutions of spinosyn compounds were prepared by adding 0.05% Tween 80, lowering pH to 5.95 and sonicating. Two concentrations of each compound were used, 0.1 ?g/mL and 0.3 ?g/mL, with each condition tested in four parallels.

[0362] Freshly collected corn leaves were dipped into the prepared solutions. After dipping leaves were left to dry at room temperature for 1 hour. Each dry leaf was then infested with 4 larvae (development stage L1), and the experimental device was incubated at 21? C.-23? C. for 24 h in order to optimize insect development. At two timings post infestation (3 days and 6 days), the insecticide efficacy is evaluated from the number of living larvae using the Henderson-Tilton method. Untreated control was integrated for normalization and validation of larvae health.

TABLE-US-00003 TABLE 3 Comparison of efficacy of tested spinosyn compounds Dose % Efficacy Treatment (?g a.i./ml) 3 days 6 days SPN 0.1 25% 46% 0.3 63% 100% Spinoteram 0.1 58% 81% 0.3 85% 96% Butenyl 0.1 33% 56% spinosyn 0.3 79% 100% A1 0.1 2% 2% 0.3 15% 19% H1 0.1 27% 89% 0.3 58% 100%

[0363] These results show that the compound H1 shows extremely potent insecticidal activity on Ostrinia nubilalis larvae. The activity is comparable or superior to Spinosad and spinetoram.

Example 12: UV-Stability of Spinosyn Compounds

[0364] Synthesized spinosyn compounds were used to prepare 5 mM solutions in acetonitrile. The solution was divided in 2 aliquots and one aliquot was exposed to UV light at 254 nm and the other aliquot was incubated in the same conditions without UV light exposure. Quantities of remaining starting compounds were determined by HPLC after 0 h, 1 h, 5 h and 10 h. The results are presented in Table 4.

TABLE-US-00004 TABLE 4 shares of remaining compounds after exposure to UV light. Purity Compound/treatment 0 h 1 h 5 h 10 h changing Butenyl spinosyn 90.0% 88.6% 70.9% 59.6% ?30.4% (1) under UV Butenyl spinosyn 90.6% 90.7% 89.4% ?0.6% (1) without UV A1 under UV 90.7% 86.6% 71.3% 52.2% ?38.5% A1 without UV 90.7% 90.8% 90.9% +0.2% H1 under UV 96.0% 95.6% 87.5% 73.5% ?22.5% H1 without UV 96.5% 96.9% 96.7% +0.7% H2 under UV 93.2% 87.6% 67.8% 39.7% ?53.5% H2 without UV 93.6% 93.7% 92.3% ?0.9%

Example 13: Evaluation of Biological Activity of Additional Spinosyn Compounds

[0365] Insecticide activities of the compounds of this invention were assessed in comparison with commercially available samples of spinosad (LGC (Dr. Ehrenstorfer); Product code: DRE-C16972830) and spinetoram (LGC (Dr. Ehrenstorfer); Product code: DRE-C16972770) Solutions of spinosyn compounds were prepared by adding 0.05% Tween 80, lowering pH to 5.95 and sonicating. Two concentrations of each compound were used, 0.1 ?g/mL and 0.3 ?g/mL, with each condition tested in four parallels.

[0366] Freshly collected corn leaves were dipped into the prepared solutions. After dipping leaves were left to dry at room temperature for 1 hour. Each dry leaf was then infested with 4 larvae (development stage L1), and the experimental device was incubated at 21? C.-23? C. for 24 h in order to optimize insect development. At two timings post infestation (3 days and 6 days), the insecticide efficacy is evaluated from the number of living larvae using the Henderson-Tilton method. Untreated control was integrated for normalization and validation of larvae health.

TABLE-US-00005 TABLE 5 Comparison of efficacy of tested spinosyn compounds Dose % Efficacy Treatment (?g a.i./ml) 3 days 6 days SPN 0.1 25% 46% 0.3 63% 100% H1a 0.1 15% 41% 0.3 64% 93%

[0367] These results show that the compound H1a shows lower insecticidal activity on Ostrinia nubilialis larvae than its natural precursor spinosad. It is surprising that an equivalent chemical modification, addition of a methoxy group at position 7, reduces the activity of spinosyn A while, in contrast it increases the activity when added to the butenyl spinosyn scaffoldsee Example 11.

Example 14: Toxicity of Compounds on Honey Bees

[0368] Toxicity of the compounds of this invention towards honey bees (Apis melifera carnica, Pollman 1879) was assessed in comparison with commercially available samples of spinosad (LGC (Dr. Ehrenstorfer); Product code: DRE-C16972830) and the naturally produced compound butenyl spinosyn alpha 1. Solutions of spinosyn compounds were prepared in 100 mM ammonium acetate, pH=5, and later diluted in 50% (500 g/L) sucrose solution in water to final concentrations. Two final concentrations were used for each compound, 7.76 ?mol/L and 15.53 ?mol/L.

[0369] Single dose acute oral toxicity tests were conducted on adult worker bees according to previously described standard methods (Medrzycki at el., (2013)). Each compound and condition were tested in two parallels. Briefly, each parallel experiment consisted of 5 cages with 20 honey bees per cage. Each cage was supplied with 200 ?L of spinosyn compound-containing solution, prepared as described above, resulting in the oral dose of the active spinosyn compound 0.078 nmol or 0.155 nmol per honey bee, which corresponds to previously established 100% LD.sub.50 (0.057 ?g/bee) and 200% LD.sub.50 (0.114 ?g/bee) for Spinosad. After uptake of the solutions honey bees were supplied with standard 50% sucrose solution and observed at 24 h and 48 h and the number of dead and live bees was estimated. Ammonium acetate solution with pH 5 was used as the negative control. Results are presented in Table 6.

TABLE-US-00006 TABLE 6 Percentage of surviving honey bees at different time points after application of a single dose of butenyl spinosyn and its derivatives/prodrugs J1A-H1 and J7-H1. % of surviving honey bees Negative 0.078 nmol/bee 0.155 nmol/bee Time after control butenyl butenyl application / spinosyn J1A-H1 J7-H1 spinosyn J1A-H1 J7-H1 24 h 94 57 98 87 32 86 78 48 h 94 37 73 69 6 26 30

[0370] Conclusion: Naturally occurring butenyl spinosyn showed higher toxicity to honey bees in acute oral toxicity test compared to the derivatives provided by this invention.

LIST OF CERTAIN REFERENCES CITED IN THE DESCRIPTION

[0371] Donald R. Hahn, Gary Gustafson, Clive Waldron, Brian Bullard, James D. Jackson and Jon Mitchell; Butenyl-spinosyns, a natural example of genetic engineering of antibiotic biosynthetic genes; J Ind Microbiol Biotechnol.; 33(2):94-104 (2006) https://doi.org/10.1007/s10295-005-0016-9 [0372] Chao Guo, Weiqun Guo, Yuchun Liu and Chao Wang; Complete genome sequence of butenyl-spinosyn-producing Saccharopolyspora strain ASAGF58; Annals of Microbiology; 70, 46 (2020) https://doi.org/10.1186/s13213-020-01587-4 [0373] Paul Lewer, Donald R. Hahn, Laura L. Karr, Dennis O. Duebelbeis, Jeffrey R. Gilbert, Gary D. Crouse, Thomas Worden, Thomas C. Sparks, Pat McKamey, Rex Edwards abd Paul R. Graupner; Discovery of the butenyl-spinosyn insecticides: novel macrolides from the new bacterial strain Saccharopolyspora pogona; Bioorg Med Chem.; 17(12):4185-96 (2009) https://doi.org/10.1016/j.bmc.2009.02.035 [0374] John Daeuble, Thomas C. Sparks, Peter Johnson and Paul R. Graupner; Modification of the butenyl-spinosyns utilizing cross-metathesis; Bioorg Med Chem.; 17(12):4197-205 (2009) https://doi.org/10.1016/j.bmc.2009.02.036Get [0375] Herbert A Kirst; The spinosyn family of insecticides: realizing the potential of natural products research; J Antibiot; 63:101-111 (2010) https://doi.org/10.1038/ja.2010.5 [0376] Carl V. DeAmicis, James E. Dripps, Chris J. Hatton, and Laura L. Karr; Physical and Biological Properties of the Spinosyns: Novel Macrolide Pest-Control Agents from Fermentation; ACS Symposium Series; Vol. 658, Chapter 11: 144-154 (1997) https://doi.org/10.1021/bk-1997-0658.ch011 [0377] Da-You Ma, Long-Long Wang, Qin Lai, Kun-Jian Peng, Xuan Li, Zeng-Xia Li, Li-Jun Liu, Zhi-Yong Luo and Su-You Liu; Synthesis and antiproliferative activities of novel quartenary ammonium spinosyn derivatives; Bioorg Med Chem Lett.; 28(20):3346-3349 (2018) https://doi.org/10.1016/j.bmcl.2018.09.005 [0378] Raghavendra Ramachanderan and Bernd Schaefer; Spinosyn insecticides; ChemTexts; 6, 20 (2020) https://doi.org/10.1007/s40828-020-00113-y