TECHNICAL FIELD

The present invention belongs to the field of agricultural herbicides, and particularly relates to an isoxazoline compound with optical activity and use thereof.

BACKGROUND

CN105753853 has disclosed an isoxazoline compound having the following structural formula and herbicidal activity. However, it does not involve the report of an optical isomer of the compound, does not describe whether the herbicidal activity of optical isomers is the same or different, and even does not involve which optical isomer is more effective as the herbicidical active ingredient. It is difficult to predict the difference without specific experimental studies.

[Image Omitted]

SUMMARY

The purpose of the present invention is to provide an isoxazoline compound with optical activity and use thereof.

To achieve the above purpose, the present invention adopts the following technical solution:

The isoxazoline compound with optical activity, which has excellent herbicidal activity, in the present invention is shown in formula (I):

[Image Omitted]

Wherein:

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from C₁-C₄alkyl or C₁-C₄haloalkyl;

R₃and R₄are respectively selected from hydrogen, halogen, C₁-C₆alkyl or C₁-C₆alkoxy;

R₅is selected from hydrogen, cyano, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, phenyl, or phenyl substituted independently with 1-4 following substitutents: halogen, CN, NO₂, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio or C₁-C₆alkylsulfonyl;

R₆is selected from C₁-C₆alkyl CO₂R₇, CO₂R₇or CONR₈R₉;

R₇is selected from hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆alkoxy C₁-C₆alkyl, C₁-C₆alkoxycarbonyl C₁-C₄alkyl, C₁-C₆alkylcarbonyloxy C₂-C₄alkyl, and benzyl, furylidene, thiazomethylene, tetrahydrofuranmethylene or pyridinemethylene which is unsubstituted or further substituted with 1-4 groups independently selected from the following: halogen, CN, NO₂, C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkoxy, C₁-C₈haloalkoxy, C₁-C₈alkoxycarbonyl, C₁-C₈alkylthio or C₁-C₈alkylsulfonyl;

R₈and R₉are respectively selected from hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₄alkoxycarbonyl C₁-C₄alkyl.

The configuration at a central asymmetric carbon atom represented by * is S configuration.

A preferred compound in the present invention is: in the formula (I)

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from methyl, isopropyl, tert-butyl, trifluoromethyl, trichloromethyl, difluoromethyl or heptafluoroisopropyl;

R₃and R₄are respectively selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy or isopropoxy;

R₅is selected from hydrogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, phenyl, or phenyl substituted independently with 1-4 following substitutents: halogen, CN, NO₂, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio or C₁-C₄alkylsulfonyl;

R₆is selected from C₁-C₄alkyl CO₂R₇, CO₂R₇or CONR₈R₉;

R₇is selected from hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₄alkoxy C₁-C₄alkyl, C₁-C₄alkoxycarbonyl C₁-C₄alkyl, C₁-C₄alkylcarbonyloxy C₂-C₄alkyl, and benzyl, furylmethylene or tetrahydrofurylidene which is unsubstituted or further substituted with 1-4 groups independently selected from the following: halogen, CN, NO₂, C₁-C₆alkyl or C₁-C₆haloalkyl;

R₈and R₉are respectively selected from hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl or C₁-C₄alkoxycarbonyl C₁-C₄alkyl.

A further preferred compound in the present invention is: in the formula (I)

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from methyl, trifluoromethyl, trichloromethyl or difluoromethyl;

R₃and R₄are respectively selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxy, ethoxy or isopropoxy;

R₅is selected from hydrogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, phenyl or phenyl substituted independently with 1-4 following substitutents: halogen, CN, NO₂, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy or C₁-C₄haloalkoxy;

R₆is selected from C₁-C₄alkyl CO₂R₇, CO₂R₇or CONR₈R₉;

R₇is selected from hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₄alkoxy C₁-C₂alkyl, C₁-C₄alkoxycarbonyl C₁-C₂alkyl, C₁-C₄alkylcarbonyloxy C₂-C₄alkyl, and benzyl, furylmethylene or tetrahydrofurylidene which is unsubstituted or further substituted with 1-3 groups independently selected from the following: halogen, CN, NO₂, C₁-C₄alkyl or C₁-C₄haloalkyl;

R₈and R₉are respectively selected from hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl or C₁-C₄alkoxycarbonyl C₁-C₂alkyl.

A more preferred compound in the present invention is: in the formula (I)

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from trifluoromethyl, trichloromethyl or difluoromethyl;

R₃and R₄are respectively selected from hydrogen, fluorine, chlorine, bromine or isopropoxy;

R₅is selected from hydrogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, trifluoromethyl, difluoromethyl, phenyl, or phenyl substituted independently with 1-4 following substitutents: halogen, CN, NO₂, methyl, isopropyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, difluoromethoxy or trifluoroethoxy;

R₆is selected from C₁-C₄alkyl CO₂R₇, CO₂R₇or CONR₈R₉;

R₇is selected from hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, allyl, 2-methylallyl, 1,1-dimethylallyl, allyl carbinyl, propargyl, alkynyl butyl, cyclopropyl, cyclohexyl, C₁-C₃alkoxy C₁-C₂alkyl, C₁-C₄alkoxycarbonyl C₁-C₂alkyl, C₁-C₄alkylcarbonyloxy C₂-C₃alkyl, and benzyl, furylidene or tetrahydrofurylidene which is unsubstituted or further substituted with 1-3 groups independently selected from the following: halogen, CN, NO₂or C₁-C₄alkyl;

R₈and R₉are respectively selected from hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl or C₁-C₄alkoxycarbonyl C₁-C₂alkyl.

A more further preferred compound in the present invention is: in the formula (I)

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from trifluoromethyl, trichloromethyl or difluoromethyl;

R₃and R₄are respectively selected from hydrogen, fluorine, chlorine, bromine or isopropoxy;

R₅is selected from hydrogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, trifluoromethyl, difluoromethyl, phenyl, or phenyl substituted independently with 1-4 following substitutents: halogen, CN, NO₂, methyl, isopropyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, difluoromethoxy or trifluoroethoxy;

R₆is selected from CH₂CO₂R₇, CH₂CH₂CO₂R₇, CO₂R₇or CONR₈R₉;

R₇is selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, trifluoromethyl, difluoroethyl, heptafluoroisopropyl, allyl, propargyl, 2-methylallyl, 1,1-dimethylallyl, allyl carbinyl, propargyl, alkynyl butyl, cyclopropyl, cyclohexyl, methoxyethyl, ethoxyethyl, isopropoxyethyl, CH₃OCOCH₂, CH₃CH₂OCOCH₂, (CH₃)₂CHOCOCH₂, CH₃OCOCH₂CH₂, CH₃CH₂OCOCH₂CH₂, (CH₃)₂CHOCOCH₂CH₂, CH₃OCOCH(CH₃), CH₃CH₂OCOCH(CH₃), benzyl, furylidene or tetrahydrofurylidene which is unsubstituted or further substituted with 1-2 groups independently selected from the following: fluorine, chlorine, bromine, CN, NO₂, methyl, isopropyl or tert-butyl;

R₈is selected from hydrogen, C₁-C₄alkyl or C₁-C₄haloalkyl;

R₉is selected from hydrogen, C₁-C₄alkyl or C₁-C₄alkoxycarbonyl C₁-C₂alkyl.

A further more preferred compound in the present invention is: in the formula (I)

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from trifluoromethyl or difluoromethyl;

R₃and R₄are respectively selected from hydrogen, fluorine, chlorine, bromine or isopropoxy;

R₅is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

R₆is selected from CH₂CO₂R₇, CH₂CH₂CO₂R₇, CO₂R₇or CONR₈R₉;

R₇is selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, trifluoromethyl, difluoroethyl, heptafluoroisopropyl, allyl, propargyl, 2-methylallyl, 1,1-dimethylallyl, allyl carbinyl, propargyl, alkynyl butyl, cyclopropyl, cyclohexyl, methoxyethyl, ethoxyethyl, isopropoxyethyl, CH₃OCOCH₂, CH₃CH₂OCOCH₂, (CH₃)₂CHOCOCH₂, CH₃OCOCH₂CH₂, CH₃CH₂OCOCH₂CH₂, (CH₃)₂CHOCOCH₂CH₂, CH₃OCOCH(CH₃), CH₃CH₂OCOCH(CH₃), furanmethylene or tetrahydrofurylidene, and benzyl which is unsubstituted or further substituted with 1-2 groups independently selected from the following: fluorine, chlorine, bromine, CN, NO₂, methyl, isopropyl or tert-butyl;

R₈is selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, trifluoroethyl, difluoroethyl, 1-chloroethyl, 1-chloropropyl or 2-chloropropyl;

R₉is selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, CH₃OCOCH₂, CH₃CH₂OCOCH₂, (CH₃)₂CHOCOCH₂, CH₃OCOCH₂CH₂, CH₃CH₂OCOCH₂CH₂, (CH₃)₂CHOCOCH₂CH₂, CH₃OCOCH(CH₃) or CH₃CH₂OCOCH(CH₃).

The most preferred compound in the present invention is: in the formula (I)

* represents an asymmetric carbon atom with configuration S;

R₁is selected from CH₃or NH₂;

R₂is selected from trifluoromethyl or difluoromethyl;

R₃and R₄are respectively selected from hydrogen, fluorine, chlorine or isopropoxy;

R₅is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

R₆is selected from CH₂CO₂R₇, CH₂CH₂CO₂R₇or CO₂R₇;

R₇is selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, trifluoromethyl, difluoroethyl, heptafluoroisopropyl, allyl, propargyl, 2-methylallyl, 1,1-dimethylallyl, allyl carbinyl, propargyl, alkynyl butyl, cyclopropyl, cyclohexyl, methoxyethyl, ethoxyethyl, isopropoxyethyl, CH₃OCOCH₂, CH₃CH₂OCOCH₂, (CH₃)₂CHOCOCH₂, CH₃OCOCH₂CH₂, CH₃CH₂OCOCH₂CH₂, (CH₃)₂CHOCOCH₂CH₂, CH₃OCOCH(CH₃), CH₃CH₂OCOCH(CH₃), furanmethylene or tetrahydrofurylidene, and benzyl which is unsubstituted or further substituted with 1-2 groups independently selected from the following: fluorine, chlorine, bromine, CN, NO₂, methyl, isopropyl or tert-butyl.

In the definitions of the compounds of the formula (I) provided above, the terms used in the collection are generally defined as follows:

Halogen: fluorine, chlorine, bromine or iodine. Alkyl: linear or branched alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl. Cycloalkyl: substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl and halogen. Haloalkyl: linear or branched alkyl on which hydrogen atoms can be partially or fully replaced by halogen atoms, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl. Alkoxy: linear or branched alkyl, bonded to the structure through an oxygen atom. Haloalkoxy: linear or branched alkoxyl, and hydrogen atoms on the alkoxyl can be partially or fully replaced by halogen atoms, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy and trifluoroethoxy. Alkylthio: linear or branched alkyl, bonded to the structure through a sulfur atom. Halogenated alkylthio: linear or branched alkylthio, and hydrogen atoms on the alkyls can be partially or fully replaced by halogen atoms, such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio and chlorofluoromethylthio. Alkenyl: linear or branched alkene, such as vinyl, 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomers. The alkenyl also comprises polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. Alkylsulfonyl: linear or branched alkyl, connected to the structure through sulfonyl (—SO₂—), such as methylsulfonyl. Aloalkylsulfonyl: linear or branched alkylsulfonyl, and hydrogen atoms on the alkyl can be partially or fully replaced by halogen atoms. Alkylsulfinyl: linear or branched alkyl, connected to the structure through sulfonyl (—SO—), such as methylsulfinyl. Aloalkylsulfonyl: linear or branched alkylsulfinyl, and hydrogen atoms on the alkyl can be partially or fully replaced by halogen atoms. Alkoxycarbonyl: alkoxyl, connected to the structure through carbonyl, such as CH₃OCO— or CH₃CH₂OCO—. Alkoxyalkyl: alkyl-O-alkyl-, such as CH₃OCH₂—. Alkylcarbonyloxy alkyloxycarbonyl: alkyl-CO—O-alkyl-OCO—, such as CH₃COOCH₂OCO—, CH₃COOCH₂CH₂OCO— or C₂H₅COOCH₂CH₂OCO—. Alkylcarbonyl: alkyl, connected to the structure through carbonyl, such as CH₃CO— or CH₃CH₂CO—. Haloalkylcarbonyl: haloalkyl, connected to the structure through carbonyl, such as CF₃CO— or CF₂HCO—. Cycloalkylcarbonyl: cycloalkyl, connected to the structure through carbonyl, such as cyclopropanoyl or cyclohexylformyl. Halocycloalkylcarbonyl: halocycloalkyl, connected to the structure through carbonyl, such as 1-chlorocyclopropanoyl. Alkylaminosulfonyl: alkyl-NH—SO₂—, such as CH₃NHSO₂— or C₂H₅NHSO₂—. Dialkylaminosulfonyl: dialkyl-N—SO₂—, such as (CH₃)₂NSO₂— or (C₂H₅)₂NSO₂—. Alkylaminocarbonyl: alkyl-NH—CO—, such as CH₃NHCO— or C₂H₅NHCO—. Dialkylaminocarbonyl: dialkyl-N—CO—, such as (CH₃)₂NCO— or (C₂H₅)₂NCO—. Dialkylaminothiocarbonyl: dialkyl-N—CS—, such as (CH₃)₂NCS— or (C₂H₅)₂NCS—. Alkylthioalkylcarbonyl: alkyl-S-alkyl-CO, such as CH₃SCH₂CO or CH₃SCH₂CH₂CO. Aryl: polyaromatic group, such as phenyl and naphthyl. Heteroaryl is a five-membered or six-membered ring containing one or more N, O and S hetero atoms, such as furyl, pyrazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, and the like. The central carbon atom at mark * is an asymmetric carbon atom or a chiral carbon atom. Four different substituents on the central carbon atom can be R configuration or S configuration according to the R—S systematic nomenclature adopted by IUPAC.

Part of compounds in the present invention can be illustrated by specific compounds listed in Table 1, but the present invention is not limited to the compounds. In the table, the compound R₁=CH₃, R₂=CF₃, and other groups are shown in Table 1.

[Image Omitted]

TABLE 1

No.
R₃
R₄
R₅
R₆

1
F
Cl
CH₃
CO₂H

2
F
Cl
CH₃
CO₂CH₃

3
F
Cl
CH₃
CO₂C₂H₅

4
F
Cl
CH₃
CO₂C₃H₇

5
F
Cl
CH₃
CO₂C₄H₉

6
F
Cl
CH₃
CO₂(cyclo-C₃H₅)

7
F
Cl
CH₃
CO₂(iso-C₃H₇)

8
F
Cl
CH₃
CO₂(tert-C₄H₉)

9
F
Cl
CH₃
CO₂CH₂C≡CH

10
F
Cl
CH₃
CO₂CH₂CH═CH₂

11
F
Cl
CH₃
CO₂CH₂C(CH₃)═CH₂

12
F
Cl
CH₃
CO₂CH₂CH₂OC₂H₅

13
F
Cl
CH₃
CO₂CH₂CH₂OCH₃

14
F
Cl
CH₃
CO₂CH₂CH₂OCOCH₃

15
F
Cl
CH₃
CO₂CH₂Ph

16
F
Cl
CH₃
CO₂CH₂(4-Cl—Ph)

17
F
Cl
CH₃
CO₂CH₂(2,6-2F—Ph)

18
F
Cl
CH₃
CO₂CH₂(2,6-2C1—Ph)

19
F
Cl
CH₃
CO₂CH₂CF₃

20
F
Cl
CH₃
CO₂CH₂CH(CH₃)₂

21
F
Cl
CH₃

[Image Omitted]

22
F
Cl
CH₃
CH₂CH₂CO₂CH₃

23
F
Cl
CH₃
CH₂CH₂CO₂C₂H₅

24
F
Cl
CH₃
CH₂CO₂CH₃

25
F
Cl
CH₃
CH₂CO₂C₂H₅

26
F
Cl
CH₃
CONH₂

27
F
Cl
CH₃
CONHCH₃

28
F
Cl
CH₃
CONHC₂H₅

29
F
Cl
CH₃
CONHC₃H₇

30
F
Cl
CH₃
CONH(iso-C₃H₇)

31
F
Cl
CH₃
CONH(cyclo-C₃H₅)

32
F
Cl
CH₃
CONH(tert-C₄H₉)

33
F
Cl
CH₃
CON(CH₃)₂

34
F
Cl
CH₃
CON(C₂H₅)₂

35
F
Cl
CH₃
CON(C₃H₇)₂

36
F
Cl
CH₃
CONHCH₂Ph

37
F
Cl
CH₃
CONHCH₂CO₂CH₃

38
F
Cl
CH₃
CONHCH(CH₃)CO₂CH₃

39
F
Cl
CH₃
CONHCH₂CH₂CO₂CH₃

40
F
Cl
CH₃
CONHCH₂CO₂C₂H₅

41
F
Cl
CH₃
CONHCH(CH₃)CO₂C₂H₅

42
F
Cl
CH₃
CONHCH₂CH₂CO₂C₂H₅

43
F
Cl
H
CO₂H

44
F
Cl
H
CO₂CH₃

45
F
Cl
H
CO₂C₂H₅

46
F
Cl
H
CO₂C₃H₇

47
F
Cl
H
CO₂C₄H₉

48
F
Cl
H
CO₂(cyclo-C₃H₅)

49
F
Cl
H
CO₂(iso-C₃H₇)

50
F
Cl
H
CO₂(tert-C₄H₉)

51
F
Cl
H
CO₂CH₂C≡CH

52
F
Cl
H
CO₂CH₂CH═CH₂

53
F
Cl
H
CO₂CH₂C(CH₃)═CH₂

54
F
Cl
H
CO₂CH₂CH₂OC₂H₅

55
F
Cl
H
CO₂CH₂CH₂OCH₃

56
F
Cl
H
CO₂CH₂CH₂OCOCH₃

57
F
Cl
H
CO₂CH₂Ph

58
F
Cl
H
CO₂CH₂(4-Cl—Ph)

59
F
Cl
H
CO₂CH₂(2,6-2F—Ph)

60
F
Cl
H
CO₂CH₂(2,6-2Cl—Ph)

61
F
Cl
H
CO₂CH₂CF₃

62
F
Cl
H
CO₂CH₂CH(CH₃)₂

63
F
Cl
H

[Image Omitted]

64
F
Cl
H
CH₂CH₂CO₂CH₃

65
F
Cl
H
CH₂CH₂CO₂C₂H₅

66
F
Cl
H
CH₂CO₂CH₃

67
F
Cl
H
CH₂CO₂C₂H₅

68
F
Cl
H
CONH₂

69
F
Cl
H
CONHCH₃

70
F
Cl
H
CONHC₂H₅

71
F
Cl
H
CONHC₃H₇

72
F
Cl
H
CONH(iso-C₃H₇)

73
F
Cl
H
CONH(cyclo-C₃H₅)

74
F
Cl
H
CONH(tert-C₄H₉)

75
F
Cl
H
CON(CH₃)₂

76
F
Cl
H
CON(C₂H₅)₂

77
F
Cl
H
CON(C₃H₇)₂

78
F
Cl
H
CONHCH₂Ph

79
F
Cl
H
CONHCH₂CO₂CH₃

80
F
Cl
H
CONHCH(CH₃)CO₂CH₃

81
F
Cl
H
CONHCH₂CH₂CO₂CH₃

82
F
Cl
H
CONHCH₂CO₂C₂H₅

83
F
Cl
H
CONHCH(CH₃)CO₂C₂H₅

84
F
Cl
H
CONHCH₂CH₂CO₂C₂H₅

85
H
Cl
CH₃
CO₂H

86
H
Cl
CH₃
CO₂CH₃

87
H
Cl
CH₃
CO₂C₂H₅

88
H
Cl
CH₃
CO₂C₃H₇

89
H
Cl
CH₃
CO₂C₄H₉

90
H
Cl
CH₃
CO₂(cyclo-C₃H₅)

91
H
Cl
CH₃
CO₂(iso-C₃H₇)

92
H
Cl
CH₃
CO₂(tert-C₄H₉)

93
H
Cl
CH₃
CO₂CH₂C≡CH

94
H
Cl
CH₃
CO₂CH₂CH═CH₂

95
H
Cl
CH₃
CO₂CH₂C(CH₃)═CH₂

96
H
Cl
CH₃
CO₂CH₂CH₂OC₂H₅

97
H
Cl
CH₃
CO₂CH₂CH₂OCH₃

98
H
Cl
CH₃
CO₂CH₂CH₂OCOCH₃

99
H
Cl
CH₃
CO₂CH₂Ph

100
H
Cl
CH₃
CO₂CH₂(4-Cl—Ph)

101
H
Cl
CH₃
CO₂CH₂(2,6-2F—Ph)

102
H
Cl
CH₃
CO₂CH₂(2,6-2Cl—Ph)

103
H
Cl
CH₃
CO₂CH₂CF₃

104
H
Cl
CH₃
CO₂CH₂CH(CH₃)₂

105
H
Cl
CH₃

[Image Omitted]

106
H
Cl
CH₃
CH₂CH₂CO₂CH₃

107
H
Cl
CH₃
CH₂CH₂CO₂C₂H₅

108
H
Cl
CH₃
CH₂CO₂CH₃

109
H
Cl
CH₃
CH₂CO₂C₂H₅

110
H
Cl
CH₃
CONH₂

111
H
Cl
CH₃
CONHCH₃

112
H
Cl
CH₃
CONHC₂H₅

113
H
Cl
CH₃
CONHC₃H₇

114
H
Cl
CH₃
CONH(iso-C₃H₇)

115
H
Cl
CH₃
CONH(cyclo-C₃H₅)

116
H
Cl
CH₃
CONH(tert-C₄H₉)

117
H
Cl
CH₃
CON(CH₃)₂

118
H
Cl
CH₃
CON(C₂H₅)₂

119
H
Cl
CH₃
CON(C₃H₇)₂

120
H
Cl
CH₃
CONHCH₂Ph

121
H
Cl
CH₃
CONHCH₂CO₂CH₃

122
H
Cl
CH₃
CONHCH(CH₃)CO₂CH₃

123
H
Cl
CH₃
CONHCH₂CH₂CO₂CH₃

124
H
Cl
CH₃
CONHCH₂CO₂C₂H₅

125
H
Cl
CH₃
CONHCH(CH₃)CO₂C₂H₅

126
H
Cl
CH₃
CONHCH₂CH₂CO₂C₂H₅

127
H
Cl
H
CO₂H

128
H
Cl
H
CO₂CH₃

129
H
Cl
H
CO₂C₂H₅

130
H
Cl
H
CO₂C₃H₇

131
H
Cl
H
CO₂C₄H₉

132
H
Cl
H
CO₂(cyclo-C₃H₅)

133
H
Cl
H
CO₂(iso-C₃H₇)

134
H
Cl
H
CO₂(tert-C₄H₉)

135
H
Cl
H
CO₂CH₂C≡CH

136
H
Cl
H
CO₂CH₂CH═CH₂

137
H
Cl
H
CO₂CH₂C(CH₃)═CH₂

138
H
Cl
H
CO₂CH₂CH₂OC₂H₅

139
H
Cl
H
CO₂CH₂CH₂OCH₃

140
H
Cl
H
CO₂CH₂CH₂OCOCH₃

141
H
Cl
H
CO₂CH₂Ph

142
H
Cl
H
CO₂CH₂(4-Cl—Ph)

143
H
Cl
H
CO₂CH₂(2,6-2F—Ph)

144
H
Cl
H
CO₂CH₂(2,6-2Cl—Ph)

145
H
Cl
H
CO₂CH₂CF₃

146
H
Cl
H
CO₂CH₂CH(CH₃)₂

147
H
Cl
H

[Image Omitted]

148
H
Cl
H
CH₂CH₂CO₂CH₃

149
H
Cl
H
CH₂CH₂CO₂C₂H₅

150
H
Cl
H
CH₂CO₂CH₃

151
H
Cl
H
CH₂CO₂C₂H₅

152
H
Cl
H
CONH₂

153
H
Cl
H
CONHCH₃

154
H
Cl
H
CONHC₂H₅

155
H
Cl
H
CONHC₃H₇

156
H
Cl
H
CONH(iso-C₃H₇)

157
H
Cl
H
CONH(cyclo-C₃H₅)

158
H
Cl
H
CONH(tert-C₄H₉)

159
H
Cl
H
CON(CH₃)₂

160
H
Cl
H
CON(C₂H₅)₂

161
H
Cl
H
CON(C₃H₇)₂

162
H
Cl
H
CONHCH₂Ph

163
H
Cl
H
CONHCH₂CO₂CH₃

164
H
Cl
H
CONHCH(CH₃)CO₂CH₃

165
H
Cl
H
CONHCH₂CH₂CO₂CH₃

166
H
Cl
H
CONHCH₂CO₂C₂H₅

167
H
Cl
H
CONHCH(CH₃)CO₂C₂H₅

168
H
Cl
H
CONHCH₂CH₂CO₂C₂H₅

The compound with optical activity in the formula I in the present invention can be prepared from amino compound II with optical activity by the method reported in known literature, such as CN105753853, CN108570041 or WO2016095768.

[Image Omitted]

The amino compound II with optical activity can be obtained by resolving the racemic amino compound III using a chiral column. The racemic amino compound III can be prepared by referring to the method in CN105753853.

[Image Omitted]

Unless otherwise stated, the definitions of the groups in the reaction formula are the same as above.

An application of the compound of the formula (I) in control for weeds is provided.

The compound of the formula (I) can control various weeds, and can also be used to control resistant weeds.

The compound of the formula (I) can effectively control various broad-leaved weeds, grass weeds, and Cyperaceae weeds, such as Echinochloa crusgalli, Setaria viridis, Cyperus difformis, Juncellus serotinus, Cyperus esculentus, Digitaria sangunalis, Arthraxon hispidus, Abutilon theophrasti, Zinnia elegans, Amaranthus retrofluxes, Portulaca oleracea, Xanthium sibiricum, Solanum nigrum, Cassia tora, Hibiscus trionum, Glycine soja, Amaranthus palmeri, Amaranthus rudis, Bidens pilosa, Kochia scoparia, Pharbitis purpurea, Eleusine indica, Euphorbia cyathophora, Fagopyrum cymosum, Setaria glauca, Pseudosorghum zollingeri, Conyza canadensis, Alopecurus aequalis, Alopecurus myosuroides, Avena fatua, Poa annua, Avena sterilis, Chenopodium album, Phalaris minor, Raphanus raphanistrum, Stellaria media, Centaurea cyanu, Galium spurium, Lamium maculatum, Tanacetum Parthenium, Papaver rhoeas, Fallopia convolvulus, Veronica persica, Viola tricolor, Festuca arundinacea, Cynodon dactylon, Emilia sonchifolia, Acalypha australis, Commelina communis, Polygonum convolvulus, Sida acuta, Panicum miliaceum, Brachiaria villosa, Celosia argentea, Euphorbia lathyris, and so on. The present invention compounds can effectively control weeds even at lower doses. Moreover, various resistant weeds can be controlled, such as weeds resistant to the herbicides of Acetyl-CoA carboxylase inhibitors, photosystem I, II inhibitors, synthetic auxins, triazines, glyphosate and acetolactate synthase inhibitors.

The compound has certain safety to wheat, corn, rice, soybean, sugar beet and other crops. The compound can be used as a selective herbicide in crop fields in agriculture, and can also be used as a non-selective herbicide in non-cultivated land, fallow land, woodland, orchards and ridges.

The compound of the present invention can be used to control the weeds pre- and post-emergence, and can also be used for soil treatment. Therefore, the present invention also comprises use of the compound of the formula (I) for controlling the weeds.

In addition, the compound of the formula (I) of the present invention is also applicable to drying and/or defoliating plants.

A herbicidal composition uses the compound of the formula (I) as an active ingredient, and the weight percentage of the active ingredient in the composition is 0.1-99%.

An application of the herbicidal composition in control for weeds is provided.

DESCRIPTION OF THE INVENTION IN DETAIL The following specific examples are used to further illustrate the present invention, but the present invention is not limited to these examples (unless otherwise specified, the raw materials used are commercially available).

PREPARATION EXAMPLE
Example 1 the Preparation of Compound 3

[Image Omitted]

1) Preparation of (S)-3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4,5-dihydro-5-isoxazole carboxylic acid ethyl ester

25 g of Amylose tris(3,5-dimethylphenylcarbamate) silica gel was loaded into a chromatographic column; 5 ml of dichloromethane solution containing 1 g of 3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4,5-dihydro-5-isoxazole carboxylic acid ethyl ester (prepared according to the method in CN105753853) was adsorbed onto the chromatographic column; Biotage Purification Instrument(Isolera™) was used to separate and collect corresponding components to respectively obtain 0.47 g of optical isomer (R)-3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4,5-dihydro-5-isoxazole carboxylic acid ethyl ester (with optical purity of 99.8% and melting point of 105-106° C.) and 0.46 g of (S)-3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4,5-dihydro-5-isoxazole carboxylic acid ethyl ester (with optical purity of 99.4% and melting point of 104-105° C.).

Optical rotation (Shenguang WZZ-2S/2SS, sodium lamp wavelength: 589.44 nm, solvent: acetonitrile): S isomer [α]^{26° C.}_{589.44 nm}=150.65°, R isomer [α]^{26° C.}_{589.44 nm}=−111.66°.

2) Preparation of compound 3

0.45 g (1.5 mmol) of (S)-3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4,5-dihydro-5-isoxazole carboxylic acid ethyl ester and 0.46 g (1.8 mmol) of ethyl (Z)-3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoate (prepared according to the method in CN108570041) were added to a reaction flask containing 20 ml of acetic acid in sequence, the mixture was then heated to reflux, and maintained at the temperature for 6 h; the mixture was concentrated under reduced pressure, followed by adjusting to a pH of 7 using sodium bicarbonate solution, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate and concentrated under reduced pressure, then 0.45 g (3.24 mmol) of potassium carbonate and 50 ml of N,N-dimethylformamide were added in sequence to the residue, the mixture was cooled to 0° C., 0.51 g (3.6 mmol) of iodomethane was added dropwise to the mixture, and then the mixture was raised to room temperature and stirred for 6 h. After the TLC monitored that the reaction was finished, the reactants were poured into water and extracted with ethyl acetate, the organic phase was washed with a saturated brine solution, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified through silica column (ethyl acetate:petroleum ether=1:5, as an eluent) to obtain compound 3: 0.48 g of oil.

Optical rotation of compound 3 (Shenguang WZZ-2S/2SS, sodium lamp wavelength: 589.44 nm, solvent: acetonitrile): [α]^{20° C.}_{589.44 nm}=68.06°.

¹H-NMR (300 MHz, CDCl₃): δ 7.68 (d, J=9.0 Hz, 1H, Ph-H), 7.35 (d, J=9.0 Hz, 1H, Ph-H), 6.36 (s, 1H, Ar—H), 4.26 (q, J=7.1 Hz, 2H, OCH₂), 4.00 (d, J=17.4 Hz, 1H, —CH₂—), 3.56 (s, 3H, N—CH₃), 3.39 (d, J=17.4 Hz, 1H, —CH₂—), 1.71 (s, 3H, CH₃), 1.32 (t, J=7.1 Hz, 3H, CH₃).

Test of Biological Activity Example 2 Bioassay of Herbicidal Activity in Greenhouse

The test method of the herbicidal activity of the compound in the present invention is as follows:

Quantitative grass weed (Echinochloa crusgalli and Setaria viridis) and broad-leaved weed (Abutilon theophrasti and Zinnia elegans) seeds were sown in paper cups having a diameter of 7 cm and containing nutrient soil, after sowing, the seeds were covered with 1 cm of soil, the soil was pressed and watered, and then the seeds were cultivated in a greenhouse according to a conventional method. The grass weeds grew to 2-3 leaf stages, the broad-leaved weeds grew to 2-4 leaf stages, stem and leaves were sprayed. Before emergence, the soil was sprayed within 24 hours after sowing. According to the design dose of the test, spray treatment was carried out on a track-type crop sprayer (designed and produced by British Engineer Research Ltd.) (spray pressure is 1.95 kg/cm², spray volume is 500 L/hm²and track speed is 1.48 km/h). The test was repeated for three times. The test material was treated and then placed in an operation hall. The medicinal liquid was naturally dried in the shade, and then was placed in a greenhouse and managed according to the conventional method. The response of the weeds to the test compound was observed and recorded. After treatment, the control effects of the test compound on the weeds were visually inspected regularly.

The grading standards of the control effects: 0 represents no control effect and 100% represents that the weeds are completely killed or greatly controlled.

It is found through the herbicidal activity test that the post-emergence treatment of the compound 3 at a dose of 4-8 g a.i./hm²has high herbicidal activity on Abutilon theophrasti, Zinnia elegans, Echinochloa crusgalli, Setaria viridi, and the activity is significantly better than that of the compound 6 in CN105753853 (Table 2-Table 3).

The specific structural formula of the compound 6 in CN105753853 is as follows:

[Image Omitted]

TABLE 2

Control Test Results of Grass Weed

Dose
Echinochloa
Setaria

g a.i./hm²
crusgalli
viridis

3
4
90
75

8
98
85

CN105753853
4
45
25

Compound 6
8
50
55

TABLE 3

Control Test Results of Broad-Leaved Weed

Dose
Zinnia
Abutilon

g a.i./hm²
elegans
theophrasti

3
4
100
90

CN105753853
4
90
60

Compound 6