Maleimide derivatives with herbicidal activity, agricultural compositions thereof and uses thereof

Abstract

The present invention relates to novel maleimides having the general formula (I): and their use as herbicides.

Description

[0001] The present invention relates to novel maleimides having the general formula (I), their isomers, salts and hydrates:

[0002]

[0003] and their use as herbicides. Summary of the invention

[0004] The present invention relates to novel substituted maleimides.

[0005] More particularly, the present invention relates to novel substituted maleimides having high herbicidal activity and their use as herbicides for controlling weeds in crops.

[0006] Patent applications EP297378, US4,845,230 and more recently WO2016 / 071360 describe hydroxymaleimides having the following general formula for use as herbicides:

[0007]

[0008] Furthermore, maleimides in which the hydroxyl group is appropriately acylated have been described, for example, in patent applications EP286816, EP339390 or WO2014 / 180740.

[0009] However, the dosage indicated in the above patent application is extremely high, and therefore, in addition to causing phytotoxicity to the treated crops, there may also be problems associated with environmental impact.

[0010] The applicant has now surprisingly found that by appropriately modifying the substituents present on the maleimide ring, products with significant herbicidal activity can be obtained, which have significant herbicidal activity against a variety of weeds and can be used at significantly reduced dosages. At the same time, these products show low or no phytotoxicity to crops of agricultural significance and can therefore also be used as selective herbicides.

[0011] The present invention therefore relates to novel maleimides of the general formula (I):

[0012]

[0013] in

[0014] -R stands for C 3 -C 18 Cycloalkylcarbonyl, C 3 -C 18 Cycloalkylthiocarbonyl, C 7 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkoxycarbonyl, C3 -C 18 Cycloalkyl C 1 -C 6 Alkylcarbonyl, C 3 -C 18 Cycloalkyl C 1 -C 12 Alkylthiocarbonyl, C 1 -C 12 Alkoxy C 1 -C 12 Alkylcarbonyl, C 1 -C 12 Alkoxy C 1 -C 12 Alkylthiocarbonyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkylthiocarbonyl, C 1 -C 12 Alkylthio C 1 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkylsulfide C 1 -C 12 Alkylcarbonyl, C 1 -C 12 Alkyl carboxyl C 1 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkylcarboxyl C 1 -C 12 Alkylcarbonyl, C 1 -C 12 Alkylcarbonyl C 1 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkylcarbonyl C 1 -C 12 Alkylcarbonyl, C 1 -C 12 Alkoxy C 1 -C 12 Alkoxycarbonyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkoxycarbonyl, C 1 -C 12 Alkylthio C 1 -C 12Alkoxycarbonyl, C 3 -C 18 Cycloalkylthio C 1 -C 12 Alkoxycarbonyl, C 3 -C 18 Cycloalkylcarboxyl C 1 -C 12 Alkoxycarbonyl, arylC 1 -C 12 Alkoxycarbonyl, C 1 -C 12 Alkoxy C 2 -C 12 Alkyl, aryloxy C 1 -C 12 Alkyl, benzyloxy C 2 -C 12 Alkyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkyl, C 1 -C 12 Alkyl carboxyl C 1 -C 12 Alkyl, C 3 -C 18 Cycloalkylcarboxyl C 1 -C 12 Alkyl, C 1 -C 12 Alkylthio C 1 -C 12 Alkyl, C 3 -C 18 Cycloalkylthio C 1 -C 12 Alkyl, C 1 -C 12 Alkylcarbonyl C 1 -C 12 Alkyl, C 3 -C 18 Cycloalkylcarbonyl C 1 -C 12 Alkyl, C 1 -C 12 Alkoxycarbonyl C 1 -C 12 Alkyl, C 3 -C 18 Cycloalkoxycarbonyl C 1 -C 12 Alkyl, C 2 -C 6 Haloalkenylcarbonyl, R 3 R 4 R 5 Si group, CO-COOR3 Group, COCR 3 2 COOR 3 Group, bifunctional-SiR 3 R 4 (CH 2 ) m S i 3 R 4 -group, bifunctional -(CO-CO)-group, bifunctional -(COCR 3 2 CO)-group, bifunctional -[COO(CH 2 ) m OCO]-group;

[0015] -R 1 and R 2 The same or different from each other, representing a halogen atom, C 1 -C 12 Alkyl, C 1 -C 12 Haloalkyl, C 3 -C 18 Cycloalkyl, C 1 -C 12 Alkoxy, C 3 -C 18 Cycloalkoxy.

[0016] -Z represents an O atom, a S atom or NR 4 Group;

[0017] -Q represents O atom, S atom, NOR 3 Group, NR 3 R 4 Group, C=CR 3 R 4 Group;

[0018] -R 3 , R 4 , R 5 The same or different from each other, representing hydrogen atoms, C 1 -C 12 Alkyl, C 1 -C 12 Haloalkyl, C 3 -C 18 Cycloalkyl;

[0019] -m is an integer from 1 to 5;

[0020] -n is 1 or 2;

[0021] -G represents a 5- or 6-membered aromatic heterocycle selected from:

[0022]

[0023]

[0024] And among them:

[0025] -X represents a nitrogen atom or a CRa group;

[0026] -W represents an oxygen atom, a sulfur atom or an NRa group;

[0027] -Ra, Rb, Rc are the same as or different from each other and represent hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl, C 2 -C 12 Alkenyl, C 2 -C 12 Halogenated alkenyl, C 3 -C 18 Cycloalkenyl, C 3 -C 18 Cycloalkyl, C 2 -C 12 Alkynyl, C 1 -C 12 Haloalkyl, C 1 -C 12 Alkoxy, C 1 -C 12 Haloalkoxy, C 3 -C 18 Cycloalkoxy, CN group, B(OR 3 ) 2 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl;

[0028] The condition is that when:

[0029] (i) R represents cyclopropylcarbonyl, cyclohexylcarbonyl or 3-ketobutyryl, and

[0030] (ii) R 1 and R 2 are methyl, and

[0031] (iii) Q and Z are oxygen atoms, and

[0032] (iv) When n is equal to 1,

[0033] Then G is different from G in which Ra and Rb are both hydrogen or in which Ra is methyl and Rb is hydrogen 6 .

[0034] Preferred are compounds of formula (I) wherein:

[0035] -R means C 3 -C 12 Cycloalkylcarbonyl, C 3 -C 12 Cycloalkylthiocarbonyl, C 7 -C 12 Alkylcarbonyl, C 3 -C 12 Cycloalkoxycarbonyl, C 3 -C 12 Cycloalkyl C 1 -C 6 Alkylcarbonyl, C 3 -C 12 Cycloalkyl C 1 -C 6 Alkylthiocarbonyl, C 1 -C 6 Alkoxy C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxy C 1 -C 6 Alkylthiocarbonyl, C 3 -C 12 Cycloalkoxy C 1 -C 6 Alkylcarbonyl, C 3 -C 12 Cycloalkoxy C 1 -C 6 Alkylthiocarbonyl, C 1 -C 6 Alkylthio C 1 -C 6 Alkylcarbonyl, C 3 -C 12 Cycloalkylthio C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkyl carboxyl C 1 -C 6 Alkylcarbonyl, C 3 -C 12 Cycloalkylcarboxyl C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkylcarbonyl C 1 -C 6 Alkylcarbonyl, C 3 -C 12 Cycloalkylcarbonyl C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxy C1 -C 6 Alkoxycarbonyl, C 3 -C 12 Cycloalkoxy C 1 -C 6 Alkoxycarbonyl, C 1 -C 6 Alkylthio C 1 -C 6 Alkoxycarbonyl, C 3 -C 12 Cycloalkylthio C 1 -C 6 Alkoxycarbonyl, C 3 -C 12 Cycloalkylcarboxyl C 1 -C 6 Alkoxycarbonyl, arylC 1 -C 6 Alkoxycarbonyl, C 1 -C 6 Alkoxy C 2 -C 7 Alkyl group, aryloxy C 1 -C 6 Alkyl, benzyloxy C 2 -C 7 Alkyl, C 3 -C 12 Cycloalkoxy C 1 -C 6 Alkyl, C 1 -C 6 Alkyl carboxyl C 1 -C 6 Alkyl, C 3 -C 12 Cycloalkylcarboxyl C 1 -C 6 Alkyl, C 1 -C 6 Alkylthio C 1 -C 6 Alkyl, C 3 -C 12 Cycloalkylthio C 1 -C 6 Alkyl, C 1 -C 6 Alkylcarbonyl C 1 -C 6 Alkyl, C 3 -C 12 Cycloalkylcarbonyl C 1 -C 6 Alkyl, C 1 -C 12 Alkoxycarbonyl C 1 -C 12 Alkyl, C3 -C 12 Cycloalkoxycarbonyl C 1 -C 12 Alkyl, C 2 -C 6 Haloalkenylcarbonyl, R 3 R 4 R 5 Si-based, CO-COOR 3 Group, COCR 3 2 COOR 3 Group, bifunctional-SiR 3 R 4 (CH 2 ) m S i 3 R 4 -group, bifunctional -(CO-CO)-group, bifunctional -(COCR 3 2 CO)-group, bifunctional -[COO(CH 2 ) m OCO]-group;

[0036] -R 1 and R 2 The same or different from each other, representing a halogen atom, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 3 -C 12 Cycloalkyl, C 1 -C 6 Alkoxy, C 3 -C 12 Cycloalkoxy;

[0037] -Z represents an O atom, a S atom or NR 4 Group;

[0038] -Q represents O atom, S atom, NOR 3 Group, NR 3 R 4 Group, C=CR 3 R 4 Group;

[0039] -R 3 , R 4 , R 5 The same or different from each other, representing hydrogen atoms, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C3 -C 12 Cycloalkyl;

[0040] -m is an integer from 1 to 5;

[0041] -n is 1 or 2;

[0042] -G represents a 5- or 6-membered aromatic heterocycle selected from:

[0043]

[0044]

[0045] And among them:

[0046] -X represents a nitrogen atom or a CRa group;

[0047] -W represents an oxygen atom, a sulfur atom or an NRa group;

[0048] -Ra, Rb, Rc are the same as or different from each other and represent hydrogen atoms, halogen atoms, C 1 -C 6 Alkyl, C 2 -C 7 Alkenyl, C 2 -C 7 Halogenated alkenyl, C 3 -C 12 Cycloalkenyl, C 3 -C 12 Cycloalkyl, C 2 -C 7 Alkynyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkoxy, C 3 -C 12 Cycloalkoxy, CN group, B(OR 3 ) 2 group, 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl;

[0049] The condition is that when:

[0050] (i) R represents cyclopropylcarbonyl, cyclohexylcarbonyl or 3-ketobutyryl, and

[0051] (ii) R 1 and R 2 are methyl, and

[0052] (iii) Q and Z are oxygen atoms, and

[0053] (iv) When n is equal to 1,

[0054] Then G is different from G in which Ra and Rb are both hydrogen or in which Ra is methyl and Rb is hydrogen 6 .

[0055] C 7 -C 12 Alkylcarbonyl refers to a group having the formula RxCO, wherein Rx has C 7 -C 12 The meaning of alkyl.

[0056] Examples of this group are heptanecarbonyl, octanecarbonyl, nonanecarbonyl, decanecarbonyl.

[0057] C 1 -C 12 Alkoxy C 1 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkylcarbonyl refers to a group having the formula RxORyCO, ​​wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0058] Examples of such radicals are methoxymethylcarbonyl, isopropoxymethylcarbonyl, cyclopropyloxymethylcarbonyl, methoxyethylcarbonyl, methoxypropylcarbonyl.

[0059] C 1 -C 12 Alkylthio C 1 -C 12 Alkylcarbonyl, C 3 -C 18 Cycloalkylthio C 1 -C 12 Alkylcarbonyl refers to a group having the formula RxSRyCO, ​​wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0060] Examples of such groups are methylthiomethylcarbonyl, isopropylthiomethylcarbonyl, cyclopropylthiomethylcarbonyl.

[0061] C 3 -C 18 Cycloalkyl C 1 -C 12 Alkylthiocarbonyl refers to a group having the formula RxRyCS, wherein Rx is C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0062] Examples of such groups are cyclopropyl-methylthiocarbonyl, cyclohexylmethylthiocarbonyl.

[0063] C 1 -C 12 Alkoxy C 1 -C 12 Alkylthiocarbonyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkylthiocarbonyl refers to a group having the formula RxORyCS, wherein Rx has C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0064] Examples of such groups are methoxymethylthiocarbonyl, isopropoxymethylthiocarbonyl, cyclopropyloxymethylthiocarbonyl.

[0065] C 1 -C 12 Alkyl carboxyl C 1 -C 12 Alkylcarbonyl and C 3 -C 18 Cycloalkylcarboxyl C 1 -C 12 Alkylcarbonyl refers to a group having the formula RxOCORyCO, ​​wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0066] Examples of such groups are methylcarboxymethylcarbonyl, ethylcarboxymethylcarbonyl, cyclohexylcarboxymethylcarbonyl.

[0067] C 1 -C 12 Alkylcarbonyl C1 -C 12 Alkylcarbonyl and C 3 -C 18 Cycloalkylcarbonyl C 1 -C 12 Alkylcarbonyl refers to a group having the formula RxCORyCO, ​​wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0068] Examples of such groups are acetylmethylcarbonyl, ethylcarbonylmethylcarbonyl, cyclopropylcarbonylmethylcarbonyl.

[0069] C 1 -C 12 Alkoxy C 1 -C 12 Alkoxycarbonyl and C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkoxycarbonyl refers to a group having the formula RxORyOCO, wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0070] Examples of such groups are methoxymethoxycarbonyl, ethoxymethoxycarbonyl, cyclopropyloxymethoxycarbonyl.

[0071] C 1 -C 12 Alkylthio C 1 -C 12 Alkoxycarbonyl and C 3 -C 18 Cycloalkylthio C 1 -C 12 Alkoxycarbonyl refers to a group having the formula RxSRyCOO, wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 Cycloalkyl.

[0072] Examples of such groups are methylthiomethoxycarbonyl, ethylthiomethoxycarbonyl, cyclopropylthiomethoxycarbonyl.

[0073] C 1-C 12 Alkyl carboxyl C 1 -C 12 Alkoxycarbonyl and C 3 -C 18 Cycloalkylcarboxyl C 1 -C 12 Alkoxycarbonyl refers to a group having the formula RxOCORyOCO, wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0074] Examples of such groups are methylcarboxymethoxycarbonyl, ethylcarboxymethoxycarbonyl, cyclopropylcarboxymethoxycarbonyl.

[0075] Aryl C 1 -C 12 Alkoxycarbonyl refers to a group having the formula ArRxOCO, wherein Rx is C 1 -C 12 The meaning of alkyl is given in R and Ar has the meaning of a mono-, bi- or tricyclic aromatic system consisting only of carbon atoms.

[0076] Examples of such groups are benzyloxycarbonyl, 2-phenoxycarbonyl.

[0077] C 1 -C 12 Alkoxy C 2 -C 12 Alkyl, aryloxy C 1 -C 12 Alkyl, benzyloxy C 2 -C 12 Alkyl, C 3 -C 18 Cycloalkoxy C 1 -C 12 Alkyl refers to a group having the formula RxORy, wherein Rx has C 1 -C 12 Alkyl, aryl, benzyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0078] Examples of such groups are ethoxymethyl, 2-phenoxyethyl, benzyloxymethyl, cyclopropyloxymethyl.

[0079] C 1 -C 12 Alkyl carboxyl C1 -C 12 Alkyl and C 3 -C 18 Cycloalkylcarboxyl C 1 -C 12 Alkyl refers to a group having the formula RxOCORy, wherein Rx has C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0080] Examples of such groups are methylcarboxymethyl, cyclopropylcarboxymethyl.

[0081] C 1 -C 12 Alkylthio C 1 -C 12 Alkyl and C 3 -C 18 Cycloalkylthio C 1 -C 12 Alkyl refers to a group having the formula RxSRy, wherein Rx has C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0082] Examples of such groups are methylthiomethyl, cyclopropylthiomethyl.

[0083] C 1 -C 12 Alkylcarbonyl C 1 -C 12 Alkyl and C 3 -C 18 Cycloalkylcarbonyl C 1 -C 12 Alkyl refers to a group having the formula RxCORy, wherein Rx is C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0084] Examples of such groups are acetylmethylpropionylmethyl, cyclohexanoylmethyl.

[0085] C 1 -C 12Alkoxycarbonyl C 1 -C 12 Alkyl and C 3 -C 18 Cycloalkoxycarbonyl C 1 -C 12 Alkyl refers to a group having the formula RxOCORy, wherein Rx has C 1 -C 12 Alkyl and C 3 -C 18 The meaning of cycloalkyl is, and Ry has C 1 -C 12 The meaning of alkyl.

[0086] Examples of such groups are methoxycarbonylmethyl, isopropoxycarbonylmethyl, cyclopentyloxycarbonylmethyl.

[0087] C 2 -C 6 Haloalkenylcarbonyl refers to a group having the formula RxCO, wherein Rx has C 2 -C 6 The meaning of haloalkenyl.

[0088] Examples from this group are 3,3-difluoro-2-allylcarbonyl, 2,2-difluorovinylcarbonyl, 4,4-difluoro-3-butenecarbonyl, 5,5-difluoro-4-pentenecarbonyl, 6,6-difluoro-5-hexenecarbonyl.

[0089] Examples of halogen are fluorine, chlorine, bromine, iodine.

[0090] C 1 -C 12 Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3,3-dimethylbutyl.

[0091] C 1 -C 12 Examples of haloalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 4,4,4-trichlorobutyl, 4,4-difluoropentyl, 5,5-difluorohexyl.

[0092] C 3 -C 18 Examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

[0093] C 2 -C 12 Examples of alkenyl are: ethenyl, propenyl, butenyl.

[0094] C2 -C 12 Examples of haloalkenyl are: 2,2-dichloropropenyl, 1,2,2-trichloropropenyl.

[0095] C 2 -C 12 Examples of alkynyl are propargyl, 2-butynyl.

[0096] C 3 -C 18 Examples of cycloalkylcarbonyl are cyclopropanoyl, cyclopentanoyl.

[0097] C 3 -C 18 Examples of cycloalkylthiocarbonyl are cyclopropylthiocarbonyl, cyclopentylthiocarbonyl.

[0098] C 3 -C 18 Examples of cycloalkoxycarbonyl are cyclopropyloxycarbonyl, cyclohexyloxycarbonyl.

[0099] C 1 -C 12 Examples of alkoxy are methoxy, ethoxy.

[0100] C 1 -C 12 Examples of haloalkoxy are trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy.

[0101] C 3 -C 18 Examples of cycloalkyl are cyclopropyloxy, cyclopentyloxy.

[0102] R 3 R 4 R 5 Examples of Si groups are trimethylsilyl, triethylsilyl, dimethyl-tert-butylsilyl, dimethyl-phenylsilyl, respectively.

[0103] Aryl refers to a monocyclic, bicyclic or tricyclic aromatic system consisting only of carbon atoms, for example: phenyl, naphthyl, phenanthrenyl, anthracenyl.

[0104] All aryl and benzyl systems may be replaced by one or more selected from halogen, C 1 -C 12 Alkyl, C 1 -C 12 Haloalkyl, C 3 -C 18 Cycloalkyl, C 1 -C 12 Alkoxy, C 4 -C 18Cycloalkoxy, C 1 -C 18 The haloalkoxy group is substituted.

[0105] The present invention also includes:

[0106] a) Substituents R, R 1 -R 5 , any possible stereoisomers of compounds of the general formula (I) derived from the specific meanings of R, R, Rc, Z, Q and G;

[0107] b) salts of compounds of formula (I), for example salts obtained by addition of inorganic or organic acids;

[0108] c) any possible hydrates of the compounds of formula (I).

[0109] Specific examples of compounds of the general formula (I) having herbicidal activity are those wherein R, R 1 , R 2 , Z, n, Q and G have the meanings shown in Table 1:

[0110]

[0111] Table 1

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] Preferred compounds of formula (I) in terms of biological activity are those wherein:

[0127] -R means selected from C 3 -C 12 Cycloalkylcarbonyl, C 1 -C 18 Alkoxyalkylcarbonyl, C 1 -C 18 Alkoxy C 1 -C 18 Alkoxycarbonyl, R 3 R 4 R 5 A group of Si group or -(COCO)- group,

[0128] -Z represents an oxygen or sulfur atom,

[0129] -Q represents an oxygen atom or a NOH group,

[0130] -R 1 and R 2 The same means C 1 -C 4 alkyl,

[0131] -n is equal to 1 or 2 and

[0132] -G is selected from G 1 To G 6 , and represents a six- or five-membered heterocyclic ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur.

[0133] Even more preferred are compounds of formula (I) wherein:

[0134] -R represents a group selected from cyclopropylcarbonyl, methoxymethylcarbonyl, methoxy-ethoxycarbonyl, trimethylsilyl or -(COCO)-,

[0135] -R 1 and R 2 is methyl or ethyl,

[0136] -Z and Q represent oxygen atoms,

[0137] -n is equal to 1 or 2 and

[0138] -G is selected from G 1 To G 4 , and represents thiadiazolyl, isoxazolyl or pyrazolyl.

[0139] Particularly preferred are compounds of the general formula (I) wherein R, R 1 , R2 , Z, Q, G and n have the meanings shown in Table 2.

[0140] Table 2

[0141]

[0142]

[0143]

[0144] As will be clear to those skilled in the art, compounds of general formula (I) may be obtained in the form of two or more optical isomers.

[0145] One object of the present invention therefore relates to compounds of the general formula (I) in racemic form, isomerically pure or mixtures thereof in any ratio, wherein said mixtures may be obtained during the preparation of the compounds of the general formula (I) or result from incomplete separation of the same isomers.

[0146] Another object of the present invention relates to a process for preparing compounds of general formula (I).

[0147] In particular, compounds of general formula (I) can be prepared from corresponding compounds of formula (II) by functionalizing the ZH group with compounds RT of formula (III), wherein R has the meaning as indicated above, as shown in reaction scheme 1.

[0148] Route 1

[0149]

[0150] More specifically, when n has a value of 1 or 2, the reaction can be carried out in a suitable solvent, in the presence of an organic or inorganic base, with a compound RT having formula (III) treating a compound having formula (II), wherein in the above formula (III), T represents a leaving group, for example a halogen selected from Cl, Br, I, or a methanesulfonate, p-toluenesulfonate or trifluoromethanesulfonate group. The compound having formula (III) can be obtained as described, for example, in Theodora W. Greene "Protective Groups in Organic Synthesis" 3rd edition, pages 198-199. The above organic or inorganic base can be, for example, triethylamine, pyridine, sodium acetate, sodium hydride or potassium hydride, potassium bicarbonate or calcium bicarbonate, sodium hydroxide or potassium hydroxide. The above solvent can be, for example, dichloroethane, chloroform or dichloromethane, tetrahydrofuran. The above reaction can be carried out, for example, at a temperature of 0° C. to the reflux temperature of the selected solvent.

[0151] When Z and Q have the meaning of oxygen, the compound of formula (II) can be prepared by reducing the corresponding precursor (IV) as shown in Reaction Scheme 2, for example using sodium borohydride or lithium aluminum hydride as a reducing agent, in a suitable alcohol solvent (e.g. methanol, ethanol, propanol, isopropanol) or in a halogenated hydrocarbon solvent (e.g. dichloromethane, dichloroethane or chloroform) or in an ether such as dioxane or tetrahydrofuran.

[0152] The reaction may conveniently be carried out at a temperature of from 0°C to room temperature for a period of from 1 to 12 hours.

[0153] Route 2

[0154]

[0155] When Z represents an S atom or NR 4 When Q is oxygen, compounds of formula (II) can be prepared starting from compound (V) wherein T represents a leaving group, for example a halogen selected from Cl, Br, I, or a mesylate, p-toluenesulfonate or triflate group, as described in reaction scheme 3 and in the literature, for example in EP0297378 and EP0339390, by reacting a compound of formula R 4 NH 2 The amine or salt (such as KSH or NaSH) is substituted.

[0156] Route 3

[0157]

[0158] Alternatively, when Z represents an oxygen atom, the compound of general formula (I) can be obtained according to Reaction Scheme 4 by reacting a compound of general formula (VI) (wherein T represents a leaving group, such as a halogen selected from Cl, Br, I, or mesylate, p-toluenesulfonate or triflate) with a compound R-ZH of formula (VII).

[0159] Route 4

[0160]

[0161] The reaction can be carried out in the presence of an organic or inorganic base (e.g. triethylamine, pyridine, sodium acetate, sodium or potassium hydride, potassium or calcium bicarbonate, sodium or potassium hydroxide) in a suitable solvent (e.g. dichloroethane, chloroform, dichloromethane or tetrahydrofuran) at a temperature ranging from 0°C to the reflux temperature of the selected solvent, typically in the range of 0°C to 90°C, as described, for example, in Plouvier, B et al., "Journal of Medicinal Chemistry", 2007, Vol. 50, pp. 2818-2841 or Campbell S. et al., "Journal of Medicinal Chemistry, 1988, Vol. 31, pp. 516-520 or in Kyasa S. et al., "Journal of Organic Chemistry", 2015, Vol. 80, pp. 12100-12114.

[0162] When Q and Z have the meaning of oxygen, the compound of formula (IV) can be reacted with a compound of formula (IX) G-NH by appropriate maleic anhydride (VIII) 2 (G has G 1 -G 6 In the case of acidic environment (such as glacial acetic acid), in the presence or absence of solvent, at a temperature range of 0°C to the reflux temperature of the solvent used, usually at a temperature in the range of 0°C-90°C, as shown in reaction scheme 5 and described, for example, in EP0297378 or EP0286816.

[0163] Route 5

[0164]

[0165] Alternatively, when Q and Z have the meaning of oxygen, the compound of the general formula (IV) can be obtained by reaction of an appropriate maleimide (X) with a compound TG of the general formula (XI) wherein G has G 1 -G 6 The meaning of and T is a leaving group having the above meaning, for example in Wolfe RMW et al., "Organic Letters", 2017, Vol. 19, pp. 996-999, and proceed as shown in Reaction Scheme 6.

[0166] Route 6

[0167]

[0168] Alternatively, the compound of general formula (II) can be obtained by reacting a suitable hydroxypyrrolidone (XII) with a compound TG of general formula (XI) wherein Q and Z represent oxygen atoms, wherein T represents a halogen atom selected from Cl, Br, I, and G has G 1 -G 6 The meaning of transition metal complexes (such as Pd 2 (dba) 3 (Tris(dibenzylideneacetone)dipalladium(0)) or Pd(OAc) 2 (acetate Pd (II)), possibly in the presence of a ligand such as Xantphos or Brettphos, in the presence or absence of a base (such as potassium carbonate or cesium carbonate) and in an inert solvent (such as toluene), as described in the literature, for example, Yin J. et al., "Organic Letters", Vol. 2, No. 8, 2000, 1101-1104, according to Reaction Scheme 7.

[0169] Route 7

[0170]

[0171] Compounds of formula (IV) wherein Q and Z have the meaning of oxygen and R 1 and R 2 different from each other and having a halogen atom such as Cl or Br, for example as described in WO2014180740, according to reaction scheme 8, using Alg 2 By halogenation of the intermediate (XIII) as a reagent, wherein Alg is, for example, Br or Cl.

[0172] Route 8

[0173]

[0174] When Q and Z have the meaning of oxygen and when R 1 and R 2 When different from the halogen atom, the hydroxypyrrolidone of formula (II) can be prepared by reacting a compound of formula (IX) G-NH 2 (G has G 1 -G 6The compound of formula (XVI) is then converted into intermediates (XVIIIa) and (XVIIIb) by Horner-Wadsworth-Emmons reaction in the presence of a compound of general formula (XVII), which cyclizes under acidic conditions to provide intermediates of formula (II), according to reaction scheme 9 and, for example, as described in WO2014180740.

[0175] Route 9

[0176]

[0177] When Q has the meaning of S(Ia), compounds of the general formula (I) can be prepared by reacting the corresponding compounds of the general formula (I) in which Q has the meaning of oxygen with a suitable reagent, such as Lawessons reagent or phosphorus pentasulfide as clearly described in the literature, for example, as described in El-Sharief, A. et al., "Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry", 1981, Vol. 20; nb. 9, pp. 751-754, or in Psutka K. et al., "RSC Advances", 2016, Vol. 6; nb. 82, pp. 78784-77890, according to reaction scheme 10.

[0178] Route 10

[0179]

[0180] When Q has NOR 3 (Ib) means that the compound of the general formula (I) can be reacted with the compound of the formula NH 2 OR 3 (XIX) is prepared by reacting the reagents as described in the literature, for example in Poon Steve F. et al., "Bioorganic and Medicinal Chemistry Letters" (2005), Vol. 15; nb. 9; pp. 2259-2263, according to Reaction Scheme 11:

[0181] Route 11

[0182]

[0183] When Q has CR 3 R 4 When the term "compound" is used herein, the compounds of the general formula (I) can be prepared as described, for example, in patent application EP403891.

[0184] When Q has NR 3 R 4 In the sense of the term, compounds of the general formula (I) can be prepared, for example, by reacting an amine NHR 3 R 4 and a solution of a compound of formula (II) in toluene is refluxed until water is completely removed from the reaction medium. Water is removed from the reaction medium using a Dean-Stark apparatus or by a dehydrating agent such as sodium sulfate or by acid catalysis.

[0185] G has G 1 -G 6 The meaning of the compound of formula (IX) NH 2 G, when for a specific G 1 -G 6 When it is not commercially available, it can be prepared by methods known in the literature, for example, as described in Katrizky AR "Comprehensive Heterocyclic Chemistry: The Structure, Reactions, Synthesis and Uses of Heterocyclic Compounds" 1998, Elsevier Science & Technology Books.

[0186] As already indicated, the compounds of the general formula (I) have high herbicidal activity, which makes them suitable for use in the agricultural sector for protecting useful crops from weeds.

[0187] Therefore, another object of the present invention relates to the use of compounds of the general formula (I) in racemic form, isomerically pure or mixtures thereof or compositions containing them as herbicides.

[0188] In particular, the compounds of the invention are effective both in the pre-emergence and post-emergence control of weeds, especially monocotyledonous and dicotyledonous weeds.

[0189] Furthermore, the compounds of the general formula (I) can be used for controlling weeds which are resistant to herbicidal compounds having a different mechanism of action, such as sulfonylureas, glyphosate or 4-hydroxyphenylpyruvate-dioxygenase (4-HPPD) inhibitors.

[0190] At the same time, the compounds of the general formula (I) can exhibit compatibility or lack of toxic effects with respect to useful crops in the pre-emergence and / or post-emergence treatment.

[0191] Therefore, in terms of the amount of active ingredient used, the compound of the present invention can be used as both a total herbicide and a selective herbicide.

[0192] Examples of weeds that can be effectively controlled using the compounds of formula (I) are: Abutilon theofrasti, Alisma plantago, Amaranthus spp., Amni maius, Capsella bursa pastoris, Chenopodium album, Convolvulus sepium, Galium aparine, Geranium dissectum, Heterantheraspp., Ipomea spp., Matricaria spp., Papaver rhoaes, Phaseolus aureus, Polygonum persicaria, Portulaca oleracea, Setaria viridis, Sida spicata, spinosa, Sinapsis arvensis, Solanum nigrum, Stellaria media, Veronica spp., Viola spp., Xanthium spp., Alopecurus myosuroides, Anisanta spp., Apera spica-venti, Avena spp., Cyperus spp., Digitaria sanguinalis, Eleusine spp., Echinochloa spp., Eleocharisavicularis, Lolium spp., Panicum spp., Poa spp., Scirpus spp., Sorghum spp., etc.

[0193] Many of the above compounds are active against one or more important agricultural crops, such as wheat ( Triticum sp. ),barley( Hordeum vulgare ),corn( Zea mays )、Soybean( Glycine max ) showed no toxic effects.

[0194] Another object of the present invention relates to a method for controlling weeds in cultivated land, which comprises applying an effective dose of at least one compound of general formula (I) or a composition comprising the compound to target crops.

[0195] The amount of compound to be applied to obtain the desired effect (effective dose) may vary depending on various factors, for example, the compound used, the crop to be preserved, the weeds to be controlled, the degree of infestation, climatic conditions, soil characteristics, method of application, etc.

[0196] Doses of from 1 g to 1,000 g of compound per hectare will usually provide adequate control.

[0197] In order to apply at least one compound of general formula (I) as a herbicide to weeds or crops, the compound of general formula (I) is formulated in the form of a composition, which, in addition to the above-mentioned compound, also contains: at least one solvent medium and / or an inert diluent medium. The inert diluent can be in solid or liquid form. The composition can optionally contain at least one agronomically acceptable excipient.

[0198] Therefore, another object of the present invention relates to a herbicidal composition comprising at least one compound of the general formula (I) in racemic form, isomerically pure or a mixture thereof, at least one inert solvent and / or diluent and optionally at least one agronomically acceptable excipient.

[0199] The inert diluent can be solid or liquid. Kaolin, alumina, silica, talc, bentonite, gypsum, quartz, dolomite, attapulgite, montmorillonite, diatomaceous earth, cellulose, starch, etc. or mixtures thereof can be used as, for example, solid diluents, also called carriers.

[0200] Liquid inert diluents that can be used are, for example, water or organic solvents, such as aromatic hydrocarbons (mixed xylenes, mixtures of alkylbenzenes, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), halogenated aromatic hydrocarbons (chlorobenzene, etc.), alcohols (methanol, propanol, butanol, octanol, etc.), esters (isobutyl acetate, etc.), ketones (acetone, cyclohexanone, acetophenone, isophorone, ethyl amyl ketone, etc.), vegetable oils, mineral oils or mixtures thereof.

[0201] The at least one agriculturally acceptable excipient is preferably selected from the group consisting of surfactants, dispersants, stabilizers and mixtures thereof.

[0202] Surfactants which can be used are, for example, nonionic (polyethoxylated alkylphenols, polyethoxylated fatty alcohols, etc.), anionic (alkylbenzenesulfonates, alkylsulfonates, etc.) or cationic (quaternary salts of alkylammonium, etc.) wetting agents and emulsifiers.

[0203] Lignin and its salts, cellulose derivatives, alginates etc. can also be added, for example, as dispersants.

[0204] For example, an antioxidant, an ultraviolet absorber, etc. may be added as a stabilizer.

[0205] The formulations suitable for agricultural use may be in the following forms: dry powder, wettable powder, emulsifiable concentrate, microemulsion, paste, granules, solution, suspension, etc. The type of composition is selected according to the specific use.

[0206] In order to broaden the scope of action of the above-mentioned composition, one or more other active ingredients compatible with the compound of general formula (I) may be added thereto, for example, herbicides, fungicides, insecticides, miticides, fertilizers, plant protection agents (safeners) and the like other than the compound of general formula (I).

[0207] Herbicides other than compounds of general formula (I) may be added to the composition containing at least one compound of general formula (I) to broaden the spectrum of action and possibly produce synergistic compositions, examples of which are as follows:

[0208] Acetochlor, acifluorfen, benitobutyl, alachlor, amethoxam, amitriptyline, amitriptyline, amino-cyclopyrachlor, aminopyralid, cypermethrin, cypermethrin, sulfamethoxam, atrazine, oxazolidinone, tetrazosulfuron, aziprotryne, fluazifop-butyl, bencarbazone, chloranil, furazolidinone, dimethoate, bentazon, bispyribac, bispyribac, pyrasulfuron, pyrasulfuron, bicyclopyrone, cypermethrin, bispyribac, bromophenoxime, bromoxynil, butachlor, fluazifop-butyl, chloranil, butachlor, chloranil, butachlor, chloranil, butachlor , butycloprop-butyl, butycloprop-butyl, mesotrione, mesotrione, mesotrione-butyl, methoxyfenoxate, chlorbromid, chlorpyrifos, chloranil, chlorthalid, chloranil, chlorotoluron, chloranil, chlorprop-butyl, chlorsulfuron, chlorthalid, chlorsulfuron, cinidon ethyl ester, cyproconazole, chlorsulfuron, chlorthalid, chlorsulfuron, ethyl cinidon, cyproconazole, chlorsulfuron, clacyfos, clethodim, clodinafop, isothiocarb, clomethalin, clopyralid, clodinafop, benzylpyridin, cyanazine, cyclopyrimorate, cyprosulfuron, cyfluthrin, cyprosulfamide, 2,4-D, 2,4-D butyric acid, cyprothiocarb, cyprosulfuron , betaine, dichlorvos, dicamba, dichlorvos nitrile, 2,4-dichlorprop, 2,4-dichlorprop, diclofop, bisclosulam, acetochlor, cypermethrin, difenac, fluazifop, flufenac, oxazolidinone, dimethoate, isopentyl, dimethoate, dimethoate, dimethoate, dimethoate, diquat, fluthiopyr, 1-diuron, eglinazine, endosulfan, endosulfan, pentazocyl, ethylbutyric acid, ethametsulfuron-methyl, sulfathiocarb, ethidium bromide, ethoxysulfuron, ethidium bromide, oxazolidinone, oxazolidinone, fenoxasulfone, fenoxasulfone, f enquinotrione, tetrazopyralid, fenamid, flufenpyr, high-efficiency flufenpyr, fluazolamide, fluazifop-butyl, fluazolamide, flufenpyr-butyl ...glufosinate-P, glyphosate, halauxifen, halofosulphonate-methyl, fluazifop-p-butyl, fluazifop-p-butyl, hexazinone, imazapic acid, imazapic acid, imazapic acid, imazaquin acid, imazapic acid, azole pyrasulfuron, indaziflam, iodosulfuron, iofensulfuron, iobenzonitrile, ipfencarbazone, isoproturon, isoxaluron, isoxadiazine, isoxadiazine, isoxadiazine, isoxadiazine, isoxadiazine, isoxadiazine, lactofosulphonate, cypermethrin, linuron, 2-Methyl-4-chloro-4-thioester, 2-Methyl-4-chloro-butyric acid, 2-Methyl-4-chloro-propionic acid, 2-Methyl-4-chloro-4-thioester Propionic acid, mefenacet, mesosulfuron, mesotrione, oxadiazine, metamitron, pyraclostrobin, metazosulfuron, methylbenzenesulfuron, chlorpyrifos, methiozolin, methoxypropyl, methylthiazol, pyranuron, bromosulfuron, isopropylamine, s-isopropylamine, sulfamethoxazole, methoxythiocarb, methicillin, metribuzin, metsulfuron, chlorpyrifos, chlorpyrifos, naphthamide, naphthamide, naphthamide-M, naphthamide, chlorpyrifos, nicosulfuron, fluazifop, fluazifop, pyralid, orthosulfamuron, amoxicillin, oxadiazine, oxadiazine, oxadiazine, oxadiazine, oxyfluorfen, paraquat, chlorpyrifos, pendimethalin, Penoxsulam, meclofenamide, cyclopentadione, pethoxamid, betaquinolin, amilpyridinium, chlorpyrifos, pyrasulfotole, pretilachlor, primisulfuron, amilpyridinium, fluazifop, cyproconazole, pyridafol, pyridafol, pyridafol, pyridafol, pyridafol, pyridafol, pyridafol-methyl, pyrimisul fan, pyroxasulfone, pyrosulfuron, quinclorac, clomaquinone, quizalofop-p-ethyl, quizalofop-p-ethyl, quizalofop-p-ethyl, sulfasulfuron-methyl, benzylsulfuron, sethoxydim, cypermethrin, simazine, simethoxam, sulfosulfuron, sulfosulfuron-methyl, sulfosulfuron-methyl, chlorpyrifos, sodium trichloroacetate, oxadiazine, tefuryltrione, tembotrione, pyraclostrobin, terbuthion, terbuthion, terbuthion, terbuthion, dimethoate, thiosulfuron, thiamethoxam, thiencarbazone, thifensulfuron-methyl, thiamethoxam, tiafenacil, tefuryltrione, tembotrione, pyraclostrobin, terbuthion, terbuthion, terbuthion, dimethoate, thiosulfuron, thiamethoxam, thiencarbazone, thifensulfuron-methyl, thiamethoxam, tiafenacil, tefenacil,tioclorim, tolpyralate, topramezone, triafamone, wild wheat dapoxetine, bensulfuron-methyl, triazine fluazifop, bensulfuron-methyl, triclopyr, trifloxysulfuron, trifludimoxazin, trifloxysulfuron, trifloxysulfuron-methyl ...

[0209] Examples of safeners that may be added to the composition comprising at least one compound of general formula (I) are as follows: fenoxac, cloquintocet-mexyl, fenoxac, mefenpyr-butyl, metamphenifen.

[0210] The concentration of the active substance, i.e. the concentration of the compound of formula (I) in the above-mentioned composition can vary within a wide range, depending on the active compound, its intended application, environmental conditions and the type of formulation adopted. In general, the concentration of the active substance is preferably 1 to 90%.

[0211] Some examples are now provided which should be considered illustrative and not limiting of the present invention.

[0212] In order to better illustrate the present invention, the following examples are now provided, which should be regarded as illustrative rather than limiting.

[0213] Example 1

[0214] Preparation of 1-(5-tert-butylisoxazol-3-yl)-2-cyclopropanecarbonyloxy-3,4-dimethyl-2H-pyrrol-5-one.

[0215] [Compound No. 4]

[0216] a) Preparation of 1-(5-tert-butylisoxazol-3-yl)-3,4-dimethylmaleimide [intermediate having the general formula (IV) body]

[0217] A solution of 15.00 g of 3-amino-5-tert-butyl-isoxazole (107.1 mmol) - a compound of formula (IX) - and 17.60 g of 2,3-dimethylmaleic anhydride (139.2 mmol) - a compound of formula (VIII) in 250 ml of glacial acetic acid was heated under reflux for 5 hours. The system was cooled to room temperature and left under stirring for 16 hours. After the reaction was completed, it was confirmed by GC-MS control, the solvent was evaporated and the residue was dissolved in water. The aqueous solution was extracted with dichloromethane, and the combined organic phases were washed with 10% potassium carbonate solution. The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated. 28.09 g of the desired product was obtained, which was used in the next step without further purification. Quantitative yield

[0218] GC-MS: M +=248

[0219] b) Preparation of 1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-3,4-dimethyl-2H-pyrrol-5-one [having the general formula (II) intermediate]

[0220] At room temperature, under an inert atmosphere, a solution of 20.00 g of 1-(5-tert-butylisoxazol-3-yl)-3,4-dimethylmaleimide (80.6 mmol) - a compound of formula (IV) - in 400 ml of anhydrous methanol was stirred for a few minutes. 1.83 g of sodium borohydride (48.4 mmol) was carefully added to the solution in portions.

[0221] The system was stirred at room temperature for 16 hours. After the reaction was completed, the solvent was evaporated and the residue was dissolved in an aqueous solution containing 4.61 ml of glacial acetic acid (80.6 mmol). The aqueous solution was extracted with dichloromethane and the combined organic phases were washed with water and saturated NaCl solution. After drying over anhydrous sodium sulfate and filtering, the organic phase was concentrated to obtain 17.93 g of the desired product. Yield: 89.0%

[0222] GC-MS: M + =250

[0223] c) Preparation of 1-(5-tert-butylisoxazol-3-yl)-2-cyclopropanecarbonyloxy-3,4-dimethyl-2H-pyrrol-5-one Preparation

[0224] [Compound No. 4]

[0225] A solution of 2.00 g of 1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-3,4-dimethyl-2H-pyrrol-5-one (8.0 mmol) (compound of formula (II))-1.67 ml of triethylamine (12.0 mmol) (compound of formula (III)) in 65 ml of anhydrous dichloromethane was cooled to about 0°C with an ice bath. 1.09 ml of cyclopropanecarbonyl chloride (12.0 mmol) was added dropwise to the solution. After addition, the solution was warmed to room temperature and left under stirring for 16 hours. After the reaction was completed, 60 ml of water was added to the solution to obtain a two-phase system, which was confirmed by GC-MS control. After separation of the organic phase, the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with a saturated NaCl solution, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 2.95 g of oil. The material thus obtained was purified by silica gel chromatography, eluting with a heptane:ethyl acetate solution 9:1. 2.49 g of the desired product was obtained. Yield: 98%

[0226] GC-MS: M + =318

[0227] LC-MS: MH + =319

[0228] Example 2

[0229] Preparation of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-3,4-dimethyl-2-methoxyacetate-2H-pyrrol-5-one. [Compound Nr.2]

[0230] a) Preparation of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-2,3-dimethylmaleimide [having the general formula (IV) intermediate]

[0231] 0.45 g of pyrrolidine (6.4 mmoles) and 0.38 g of glacial acetic acid (6.4 mmoles) were added to a solution of 10.00 g of 2-amino-5-tert-butyl-1,3,4-thiadiazole (63.6 mmoles) - a compound of formula (IX) - and 8.02 g of 2,3-dimethylmaleic anhydride (63.6 mmoles) - a compound of formula (VIII) - in 60 ml of toluene. The solution was refluxed for 2 hours and 30 minutes. After the reaction was completed, 50 ml of a 10% aqueous solution of HCl was added to the solution to obtain a two-phase system. After separation of the organic phase, the aqueous phase was extracted with ethyl acetate. The combined organic phase was washed with 10% HCl solution, water and saturated NaCl solution, dried over anhydrous sodium sulfate, filtered and concentrated. The solid thus obtained was washed with cold heptane. 15.98 g of the desired product was obtained.

[0232] Yield 94.8%

[0233] GC-MS: M + =265

[0234] b) Preparation of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-3,4-dimethyl-5-hydroxy-5H-pyrrol-2-one [Intermediate having the general formula (II)]

[0235] A solution of 15.00 g of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-2,3-dimethylmaleimide (56.6 mmol) - a compound of formula (IV) - in 270 ml of anhydrous methanol was stirred at room temperature for several minutes in an inert atmosphere. 1.29 g of sodium borohydride (34.0 mmol) was carefully added to the solution in batches. The system was stirred at room temperature for 16 hours. After the reaction was completed, it was confirmed by GC-MS control, the solvent was evaporated, and the residue was dissolved in an aqueous solution containing 3.24 ml of glacial acetic acid (56.6 mmol). The aqueous solution was extracted with dichloromethane, and the combined organic phases were washed with water and a saturated NaCl solution. After drying with anhydrous sodium sulfate and filtering, the organic phase was concentrated to obtain 13.22 g of the desired product. Yield: 87.4%

[0236] GC-MS: M + =267

[0237] c) Preparation of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-3,4-dimethyl-2-methoxyacetate-2H-pyridine Pyrrol-5-one [Compound Nr.2]

[0238] 0.29 ml of methoxyacetic acid (3.74 mmol)-compound of formula (III) was added to a solution of 1.00 g of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-3,4-dimethyl-5-hydroxy-5H-pyrrole-2-one (3.74 mmol)-compound of formula (II) in 15 ml of anhydrous dichloromethane. After the solution was cooled to 0°C with an ice bath, 0.77 g of dicyclohexylcarbodiimide (3.74 mmol) was added to the system. After addition, the solution was warmed to room temperature and left under stirring for 16 hours. After completion of the reaction, the solution was filtered and concentrated to obtain 2.16 g of oil, confirmed by GC-MS control. The material thus obtained was purified by silica gel chromatography, eluting with a dichloromethane: ethyl acetate solution of 7:3. 1.20 g of the desired product was obtained. Yield>95%

[0239] GC-MS: M + =339

[0240] LC-MS: MH + =340

[0241] Example 3

[0242] Preparation of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-3,4-dimethyl-2-methoxyethyl carbonate-2H- Pyrrol-2-yl-5-one [Compound Nr.3]

[0243] A solution of 1.00 g of 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-3,4-dimethyl-5-hydroxy-5H-pyrrol-2-one (3.74 mmol)-compound of formula (II) and 0.57 ml of triethylamine (4.12 mmol) in 15 ml of anhydrous dichloromethane was cooled to about 0°C with an ice bath. 0.48 ml of 2-methoxyethyl chloroformate (4.12 mmol)-compound of formula (III)-was added dropwise to the solution. After addition, the solution was warmed to room temperature and left under stirring for 16 hours. After the reaction was completed, confirmed by control in LC-MS, 60 ml of water was added to the solution to obtain a two-phase system. After separation of the organic phase, the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with saturated NaCl solution, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 1.22 g of oil. The material thus obtained was purified by silica gel chromatography, eluting with a heptane:ethyl acetate solution 9:1. 0.80 g of the desired product was obtained. Yield 90%

[0244] LC-MS: MH + =240

[0245] Example 4

[0246] Preparation of 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-pyridin-2-yl]-2-cyclopropanecarbonyloxy-3,4-dimethyl-2H-pyrrol-5-one [Compound No. 110]

[0247] a) 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-pyridin-2-yl]-3,4-dioxaborolan-2-yl Preparation of methylmaleimide [intermediate having the general formula (IV)]

[0248] A solution of 10.00 g of 2-amino-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (45.44 mmol) and 7.45 g of 2,3-dimethylmaleic anhydride (59.06 mmol) in 100 ml of glacial acetic acid was refluxed for 5 hours. The system was cooled at room temperature and placed under stirring for 16 hours. After the reaction was completed, the solvent was evaporated and the residue was dissolved in water, as confirmed by LC-MS control. The aqueous solution was extracted with dichloromethane, and the combined organic phase was washed with 10% potassium carbonate solution. The organic phase was washed with anhydrous sodium sulfate, filtered and concentrated. 15.00 g of the desired product was obtained, which was directly used in the next step without further purification. Quantitative yield.

[0249] GC-MS: M + =328.

[0250] b) 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]-2-hydroxy- Preparation of 3,4-dimethyl-2H-pyrrol-5-one [intermediate having general formula (II)]

[0251] Under an inert atmosphere, a solution of 10.00 g of 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]-3,4-dimethylmaleimide (30.50 mmol) in 150 ml of anhydrous methanol was stirred at room temperature for a few minutes. 0.69 g of sodium borohydride (18.3 mmol) was carefully added to the solution. The system was stirred at room temperature for 4 hours. After the reaction was completed, the solvent was evaporated and the residue was dissolved in an aqueous solution containing 1.75 ml of glacial acetic acid (30.5 mmol). The aqueous solution was extracted with dichloromethane, and the combined organic phases were washed with water and a saturated NaCl solution. After drying with anhydrous sodium sulfate and filtering, the organic phase was concentrated to obtain 8.05 g of the desired product. Yield: 80.0%

[0252] GC-MS: M + =330

[0253] c) Preparation of 1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)-2-cyclopropanecarbonyloxy-3,4-dimethyl-2H-pyrrol-5-one [Compound No. 110]

[0254] A solution of 8.00 g of 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl]-2-hydroxy-3,4-dimethyl-2H-pyrrole-5-one (24.24 mmol) and 3.7 ml of triethylamine (26.66 mmol) in 250 ml of anhydrous dichloromethane was cooled to about 0°C with an ice bath. 2.42 ml of cyclopropanecarbonyl chloride (26.66 mmol) was added dropwise to the solution. After addition, the solution was warmed to room temperature and left under stirring for 16 hours. After the reaction was completed, 250 ml of water was added to the solution to obtain a two-phase system, as confirmed by LC-MS control. After separation of the organic phase, the aqueous phase was extracted with dichloromethane. The combined organic phase was washed with a saturated NaCl solution, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 10.2 g of oil. The material thus obtained was purified by silica gel chromatography, eluting with a heptane:ethyl acetate solution 9:1. 8.8 g of the desired product were obtained. Yield 91%

[0255] GC-MS: M + =398

[0256] LC-MS: MH + =399

[0257] Example 5

[0258] Preparation of compounds Nrs.11, 14, 18, 22, 100, 101, 109, 110, 113, 114, 117-119

[0259] By operating similarly to the above examples, compounds 11, 14, 18, 22, 100, 101, 109, 110, 113, 114, 117-119 of formula (I) shown in Table 3 were obtained.

[0260] Table 3

[0261]

[0262]

[0263] Table 4 shows the results of LC-MS analysis of compounds 11, 14, 18, 22, 100, 101, 109, 110, 113, 114 and 117-119.

[0264] Table 4

[0265]

[0266]

[0267] Example 6

[0268] Determination of pre-emergence herbicidal activity and phytotoxicity.

[0269] The pre-emergence herbicidal activity of the compounds of the present invention was evaluated according to the following operating mode.

[0270] Plant species of interest (weeds or crops) were sown in pots 10 cm in diameter and 10 cm in height containing sandy soil. Six pots were used for each plant.

[0271] Water was added to each pot in an amount suitable for seed germination. The pots were then divided into two groups, each containing 3 pots for each weed or crop.

[0272] One day after sowing, the first set of pots was treated with a dispersion having the following composition:

[0273] - 200 mg of the compound of formula (I)

[0274] - 56 ml water

[0275] - 14 ml of acetone

[0276] -Tween 20 0.5% (w / w)

[0277] The dispersion was prepared by adding the desired dose of the compound according to the invention to an acetone-water solution containing 20% ​​by volume of acetone and 0.5% by weight of Tween 20, relative to the total weight of the dispersion, and applied to a surface of 2 square meters.

[0278] The weighing of each compound of the present invention corresponds to an effective dose of 1,000 g / ha.

[0279] The second group was treated only with an aqueous acetone solution containing 20% ​​by volume of acetone and 0.5% by weight of Tween 20 and used as a comparison (control).

[0280] All pots were observed in a regulated environment (greenhouse) under the following environmental conditions:

[0281] - Temperature: 24℃ during the day, 18℃ at night

[0282] -Relative humidity: >50%

[0283] - Photoperiod: 16 hours;

[0284] -Light intensity: 12,000 Lux.

[0285] Water the pots evenly as needed to ensure sufficient humidity for good plant growth.

[0286] Twenty-one days after the treatment, the herbicidal activity was assessed according to the percentage injury (rating 0-100%) found on the treated plants in comparison with the untreated plants (control):

[0287] -0% = no effect on plants

[0288] -100% = Plants completely dead

[0289] Table 5 shows the results obtained with Comp.Nrs.4 and 2 for the plant species indicated below and compared with a dispersion containing the compound CR1 described in EP0297378 instead of the compound of general formula (I):

[0290] CR1=1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-3,4-dimethyl-2H-pyrrol-5-one

[0291] Table 5 :Pre-emergence herbicidal activity at a dose of 250g / ha

[0292]

[0293] Example 7

[0294] Determination of post-emergence herbicidal activity and phytotoxicity

[0295] The post-emergence herbicidal activity of the compounds of the present invention was evaluated according to the following operating mode.

[0296] Plant species of interest (weeds or crops) were sown in pots greater than 10 cm in diameter and 10 cm in height containing sandy soil. Six pots were used for each plant.

[0297] Water was added to each pot in an amount suitable for seed germination. The pots were then divided into two groups, each containing 3 pots for each weed or crop.

[0298] When the phenological stage of plants with 1-2 expanded leaves (BBCH 11-12) was reached, the first set of pots was treated with the same acetone-water dispersion as in Example 6 containing 20% ​​by volume acetone, the desired dose of the test compound and 0.5% by weight Tween 20.

[0299] The second group was treated only with an aqueous acetone solution containing 20% ​​by volume of acetone and 0.5% by weight of Tween 20 and used as a comparison (control).

[0300] All pots were observed in a regulated environment (greenhouse) under the following environmental conditions:

[0301] - Temperature: 24℃ during the day, 18℃ at night

[0302] -Relative humidity: >50%

[0303] - Photoperiod: 16 hours;

[0304] -Light intensity: 12,000 Lux.

[0305] Water the pots evenly as needed to ensure sufficient humidity for good plant growth.

[0306] Twenty-one days after the treatment, the herbicidal activity was assessed according to the percentage injury (rating 0-100%) found on the treated plants in comparison with the untreated plants (control):

[0307] -0% = no effect on plants

[0308] -100% = Plants completely dead

[0309] Table 6 shows the results obtained for the treatment of the plant species indicated below with Comp.Nrs.11, 4, 2, 3 and compared with an acetone-water dispersion containing compound CR1 described in EP0297378.

[0310] CR1=1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-3,4-dimethyl-2H-pyrrol-5-one

[0311] Table 6 :Post-emergence herbicidal activity at a dose of 250g / ha

[0312]

Claims

1. A compound of general formula (I) or a salt thereof: in: -n is 1 or 2; -When n is 1, R represents C3-C 12 Cycloalkylcarbonyl, C3-C 12 Cycloalkoxycarbonyl, C3-C 12 Cycloalkylmethylcarbonyl, methoxymethylcarbonyl, methoxyethoxycarbonyl, or when n is 2, R represents a difunctional -(CO-CO)- group; -R 1 and R 2 represents a methyl group; -Z represents an O atom; -Q represents an O atom; G stands for And among them: -W represents oxygen atom; -Rb represents a tert-butyl group and Rc represents a hydrogen atom.

2. Compounds of general formula (I): Among them, R 1 , R 2 , Z, n, Q and G have the following meanings:

3. The compound of general formula (I) according to claim 1, wherein: - When n is 1, R represents a compound selected from C3-C 12 a cycloalkylcarbonyl group, a methoxyethoxycarbonyl group, or when n is 2, R represents a -(CO-CO)- group, -Z represents an oxygen atom, -Q represents oxygen atom, -R 1 and R 2 represents a methyl group, and - G has G as defined in claim 1 3 meaning.

4. The compound of general formula (I) according to claim 1, wherein: - when n is 1, R represents a group selected from cyclopropylcarbonyl, methoxymethylcarbonyl, methoxyethoxycarbonyl, or when n is 2, R represents a -(COCO)- group, -R 1 and R 2 Methyl, - Z and Q represent oxygen atoms, and - G has G as defined in claim 1 3 meaning.

5. The compound of general formula (I) according to claim 1, wherein: R, R 1 , R 2 , Z, Q, G, and n have the following meanings:

6. A herbicide composition comprising: at least one compound of general formula (I) according to any one of claims 1 to 5; at least one solvent and / or at least one diluent; optionally, at least one agronomically acceptable excipient.

7. A herbicide composition according to claim 6, comprising at least one active ingredient compatible with the compounds of general formula (I), selected from: herbicides different from those of general formula (I), fungicides, insecticides, miticides, fertilizers, plant protection agents and mixtures thereof.

8. The herbicidal composition according to claim 6, wherein the compound of general formula (I) is present in a concentration of 1% to 90% by weight relative to the total weight of the composition.

9. Use of a compound of general formula (I) according to any one of claims 1 to 5 or a composition according to any one of claims 6 to 8 as a herbicide for controlling at least one weed in crops.

10. The use according to claim 9 for controlling at least one weed in crops before or after emergence.

11. The use according to claim 9 or 10, wherein the weeds are selected from the group consisting of: Abutilon theofrasti, Alisma plantago, Amaranthus spp., Amnimaius, Capsella bursa pastoris, Chenopodium album, Convolvulus sepium, Galium aparine, Geranium dissectum, Heterantheraspp., Ipomea spp., Matricaria spp., Papaver rhoaes, Phaseolus aureus, Polygonum persicaria, Portulaca oleracea, Setaria viridis, Sida oleracea, spinosa, Sinapsis arvensis, Solanum nigrum, Stellaria media, Veronica spp., Viola spp., Xanthium spp., Alopecurus myosuroides, Anisanta spp., Apera spica-venti, Avena spp., Cyperus spp., Digitaria sanguinalis, Eleusine spp., Echinochloa spp., Eleocharis avicularis, Lolium spp., Panicum spp., Poa spp., Scirpus spp., Sorghum spp.

12. The use according to claim 9, wherein the crop plant is selected from the group consisting of wheat (Triticum sp.), barley (Hordeum vulgare), corn (Zea mays), and soybean (Glycine max).

13. A method for controlling at least one weed in a crop plant, comprising: At least one effective dose of at least one compound of the general formula (I) according to any one of claims 1 to 5 or at least one herbicide composition according to any one of claims 6 to 8 is applied to the crop plants.

14. The method according to claim 13, wherein the compound of general formula (I) or the herbicidal composition is applied to crops at a dosage of the compound of general formula (I) in the range of 1-1000 g / ha.

15. A method for preparing a compound of general formula (I) according to claim 1, comprising the step of reacting a compound of general formula (II) with at least one compound of general formula (III) in the presence of at least one base according to the following route: Where R, R 1 , R 2 , Z, Q, n and G have the meanings defined in claim 1, and T represents a leaving group.

16. A method for preparing a compound of general formula (I) according to claim 1, comprising the step of reacting a compound of general formula (VI) with at least one compound of general formula (VII) in the presence of at least one base according to the following route: Where R, R 1 , R 2 , Z, Q, n and G have the meanings defined in claim 1 and T represents a leaving group.

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