CN113527129A - Trifluoroolefin compound with nematicidal activity and preparation method and application thereof - Google Patents

Trifluoroolefin compound with nematicidal activity and preparation method and application thereof Download PDF

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CN113527129A
CN113527129A CN202010286890.2A CN202010286890A CN113527129A CN 113527129 A CN113527129 A CN 113527129A CN 202010286890 A CN202010286890 A CN 202010286890A CN 113527129 A CN113527129 A CN 113527129A
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membered
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徐晓勇
李忠
张瑞峰
刘城
陈佃聪
邵旭升
须志平
程家高
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East China University of Science and Technology
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Abstract

The invention relates to a compound containing trifluoroolefin with nematicidal activity, a preparation method and application thereof. Specifically, the invention discloses a compound with a formula (I) or an optical isomer, a cis-trans isomer or an agriculturally and pharmaceutically acceptable salt thereof, and a preparation method thereof. The above compounds have excellent nematicidal activity.

Description

Trifluoroolefin compound with nematicidal activity and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticides. In particular to a trifluoroalkene compound with nematicidal activity and a preparation method and application thereof.
Background
Plant parasitic nematodes are pathogenic microorganisms with great harm, have wide distribution range, various varieties and strong environmental adaptability, can be parasitic in roots, stems, leaves, seeds, buds and fruits of plants, can cause mechanical damage to the host plants through feeding activities, and graze the nutrition of the host plants, particularly esophageal gland secretions of the host plants can cause a series of pathological changes to the host plants, and can infect the host plants together with other pathogenic microorganisms to cause compound diseases and yield loss. The agricultural loss caused by plant parasitic nematodes is over 1000 billion dollars each year in the world, and the development of agricultural economy is severely restricted.
There are many agricultural means for preventing and controlling nematodes, and chemical prevention is the main point at present. The widely used chemical nematicides are mainly high-toxicity and high-residue organophosphorus or carbamate pesticides, such as cadusafos, ethoprophos, phenthoate, fosthiazate, aldicarb, oxamyl, carbofuran and the like, have low safety to human beings and other non-target organisms, and cause pollution to soil, water sources and agricultural products to different degrees. In addition, because of single variety, the nematicide is used excessively and frequently, so that serious drug resistance is caused, and the control difficulty of the nematodes is increased day by day. Therefore, the search for a chemical nematicide with high efficiency, low toxicity and good environmental compatibility and novel structure is a technical problem which needs to be solved urgently in the field.
In view of the foregoing, there is a strong need in the art to develop new compounds having nematicidal activity.
Disclosure of Invention
The invention aims to provide a chemical nematicide with novel structure, high efficiency, low toxicity and good environmental compatibility.
Another object of the present invention is to provide a preparation method and application of the chemical nematicide.
In a first aspect, the present invention provides a compound of formula (I), or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof:
Figure BDA0002448851040000021
in the formula (I), the compound is shown in the specification,
n is an integer from 0 to 5, preferably an integer from 1 to 3, more preferably 1;
a is an oxygen or sulfur atom;
g is selected from the group consisting of: H. substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C3-6Cycloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-or 6-membered aliphatic heterocyclic group;
m is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring or a 9-12 membered fused aromatic heterocyclic ring, or a substituted or unsubstituted 5-7 membered aliphatic heterocyclic ring, CH2SN2、CO、 SO，SO2、(CH2)mWherein m is an integer of 0 to 5; the substituents of the ring M are selected from the group consisting of: H. halogen, substituted or unsubstituted C1-6Alkyl or alkoxy, substituted or unsubstituted C3-6Cycloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-or 6-membered aliphatic heterocyclic group;
q is a substituted or unsubstituted 5-12 membered aromatic ring, a substituted or unsubstituted 5-12 membered carbocyclic ring, a substituted or unsubstituted 5-12 membered aromatic heterocyclic ring, a substituted or unsubstituted 5-12 membered alicyclic heterocyclic ring (including fully or partially unsaturated alicyclic heterocyclic rings), a substituted or unsubstituted alkenyl group, or a group selected from the following U-1 to U-34:
Figure BDA0002448851040000031
wherein p is an integer from 0 to 7, preferably an integer from 0 to 5, most preferably an integer from 0 to 3;
wherein R is1Selected from the group consisting of: o, substituted or unsubstituted C1-6Alkyl or alkoxy, halogen, substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-or 6-membered aliphatic heterocyclic group.
In a preferred embodiment, Q is a 5-12 membered aromatic or heteroaromatic ring.
In a further preferred embodiment, Q is a 5-12 membered benzoheteroaromatic or a 5-12 membered benzoheteroaromatic.
In a specific embodiment, the compound is of formula I-I, I-II, I-III or I-IV:
Figure BDA0002448851040000041
wherein m, n, A, G and Q are as defined above.
In a specific embodiment, the compound is represented by formula I-I,
wherein m is 0 or 1;
n is an integer of 1 to 3;
a is an oxygen atom or a sulfur atom;
g is H, substituted or unsubstituted C1-6Alkyl or alkoxy (preferably halogen-substituted alkyl), five or six membered aromatic heterocyclic ring;
q is a substituted or unsubstituted 5-12 membered aromatic ring, a substituted or unsubstituted 5-12 membered aromatic heterocycle, a substituted or unsubstituted 5-12 membered aliphatic heterocycle.
In a preferred embodiment, the aromatic ring is a substituted or unsubstituted aromatic ring-to-aromatic ring, preferably a substituted or unsubstituted phenyl-to-phenyl group;
in a preferred embodiment, the aromatic heterocycle is a nitrogen-containing aromatic heterocycle, a five-or six-membered aromatic heterocycle, an aromatic-ring (preferably a benzene ring) aromatic heterocycle, a fused aromatic heterocycle, an aromatic-heterocycle-to-aromatic heterocycle, an aromatic-ring-to-aromatic heterocycle;
in a preferred embodiment, the five-membered aromatic heterocycle includes, but is not limited to: substituted or unsubstituted oxazole, substituted or unsubstituted thiadiazole, substituted or unsubstituted oxadiazole, substituted or unsubstituted isoxazole, substituted or unsubstituted isoxazoline;
the six-membered heterocyclic ring includes, but is not limited to: substituted or unsubstituted pyridine, substituted or unsubstituted triazine ring, substituted or unsubstituted oxadiazoline;
the aromatic fused heterocyclic ring is a benzoaromatic heterocyclic ring, including but not limited to: benzoxazole, benzotriazole, benzoquinonedione ring;
the fused aromatic heterocycles include, but are not limited to: thiazolopyrazole, triazolothiadiazole;
the aromatic-ring heteroaromatic ring includes, but is not limited to, a benzene heteroaromatic ring such as benzene pyrazole, benzene thiazole (oxa) zole, or benzene isoxazoline;
the aromatic heterocyclic-aromatic heterocyclic includes but is not limited to: pyrazinopyradine and pyridinylpyrazole.
In a specific embodiment, the compound is represented by formula I-I,
wherein m is 0 or 1;
n is an integer of 1 to 2;
a is an oxygen atom or a sulfur atom;
g is H, substituted or unsubstituted C1-6Alkyl or alkoxy (preferably C)1-3Alkyl or alkoxy);
q is substituted or unsubstituted five-membered or six-membered aromatic heterocycle, substituted or unsubstituted five-membered or six-membered aliphatic heterocycle, substituted or unsubstituted 5-12 membered aromatic ring (preferably benzene ring) aromatic heterocycle, substituted or unsubstituted 5-12 membered aromatic heterocycle, substituted or unsubstituted 5-12 membered aromatic ring.
In a specific embodiment, the compound of formula I-I is a compound selected from the group consisting of:
Figure BDA0002448851040000051
Figure BDA0002448851040000061
Figure BDA0002448851040000071
Figure BDA0002448851040000081
Figure BDA0002448851040000091
Figure BDA0002448851040000101
Figure BDA0002448851040000111
Figure BDA0002448851040000121
Figure BDA0002448851040000131
the compounds of formulae I-II are selected from the group consisting of:
Figure BDA0002448851040000132
Figure BDA0002448851040000141
the compounds of formulae I-III are selected from the group consisting of:
Figure BDA0002448851040000142
the compounds of formulae I-IV are selected from the following:
Figure BDA0002448851040000143
Figure BDA0002448851040000151
in a second aspect, the present invention provides a pesticidal composition comprising a compound of the first aspect, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, and optionally an agriculturally pharmaceutically acceptable excipient.
In a third aspect, the present invention provides the use of a compound of the first aspect, or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof, for nematicidal or for the preparation of a nematicidal pesticide composition.
In a fourth aspect, the present invention provides the use of a pesticidal composition according to the second aspect for killing nematodes.
In a fifth aspect, the present invention provides a method of controlling and exterminating nematodes, the method comprising the step of administering an effective amount of a compound according to the first aspect, or an optical isomer, cis-trans isomer or agriculturally pharmaceutically acceptable salt thereof, or a pesticidal composition according to the second aspect to a plant or crop in need of control and extermination of nematodes.
In a sixth aspect, the present invention provides a process for the preparation of a compound according to the first aspect, prepared using the following synthetic route:
1) when M is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring, orSubstituted or unsubstituted 5-7 membered heterocycle, (CH)2)mWherein when m is 0-5, the compound is prepared by adopting a method shown in the following reaction formula:
Figure BDA0002448851040000161
a) chloridizing a compound shown as a formula 1-1 to obtain a compound shown as a formula 1-2;
b) reacting the compound shown in the formula 1-2 with corresponding amine or sulfamide in the presence of alkali or a condensing agent to obtain a compound shown in the formula 1-3;
c) reacting a compound shown as a formula 1-3 with a bromide in the presence of a catalyst to generate a compound shown as a formula 1-4;
or
2) When M is CH2SN2The preparation method is characterized by comprising the following steps:
Figure BDA0002448851040000162
a) acylating and chlorinating the compound shown in the formula 2-1 to obtain a compound shown in the formula 2-2;
b) reacting the compound shown in the formula 2-2 with corresponding ammonium thiocyanate to obtain corresponding isothiocyanate, namely the compound shown in the formula 2-3; and
c) reacting the compound shown in the formula 2-3 with an amino compound to generate a compound shown in the formula 2-4;
or
3) When M is SO2The preparation method is characterized by comprising the following steps:
Figure BDA0002448851040000171
a) reacting the compound shown in the formula 3-1 with corresponding sulfamide in the presence of a condensing agent to obtain a compound shown in a formula 3-2;
b) reacting the compound shown as the formula 3-2 with a bromide in the presence of a base to generate the compound shown as the formula 3-3.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 shows the construction concept of the compounds of the present invention;
fig. 2 shows the manner of grading calculation of disease index.
Detailed Description
The inventor designs and synthesizes a series of trifluoroolefin-containing compounds with novel structures and remarkable insecticidal activity through long-term and intensive research. The compound has the advantages of high efficiency, low toxicity, good environmental compatibility and the like. On this basis, the inventors have completed the present invention.
Radical definition
The term "C1-6Alkyl "means a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The term "C2-6Alkenyl "means a straight or branched chain alkenyl group having 2 to 6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or the like.
The term "C2-6Alkynyl "means a straight or branched chain alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl, or the like.
The term "C3-7Cycloalkyl "refers to a cyclic alkyl group having 3 to 7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.
The term "C5-7Cycloalkenyl "refers to a cyclic alkenyl group having 5 to 7 carbon atoms with one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1, 3-cyclohexadienyl, 1, 4-cyclohexadienyl, or similar groups.
As used herein, the term "C1-4Alkoxy "means a straight or branched chain alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.
The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted with one or more of the above halogen atoms, which may be the same or different, such as trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or the like.
The term "ring" or "ring system" refers to a carbocyclic or heterocyclic ring.
The term "heterocycle" means that at least one of the atoms forming the skeleton of the heterocycle is not carbon, but a heteroatom such as nitrogen, oxygen or sulfur. As known to those skilled in the art, heterocycles can be divided into two main classes, namely aliphatic heterocycles and aromatic heterocycles; the heterocyclic ring typically contains no more than 4 nitrogens, no more than 2 oxygens, and/or no more than 2 sulfurs. Unless otherwise indicated, the heterocyclic ring may be a saturated, partially unsaturated, or fully unsaturated ring.
The term "ring system" refers to fused rings where two or more rings are joined together.
As used herein, the term "5-or 6-membered heterocyclyl" refers to a five-or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, for example, pyridyl, thiazolyl, isothiazolyl, thienyl, furyl, pyrrolyl, pyrazolyl, pyrimidinyl, tetrahydrofuryl, 4, 5-dihydrothiazol-2-yl, 2-cyanoimino-4-oxo-1, 3-thiazolidin-3-yl, 2-cyanoimino-4-oxo-1, 3-thiazinan-3-yl, oxazolyl, isoxazolyl, 1H-tetrazolyl, 1H-1,2, 3-triazolyl, 4H-1,2, 4-triazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, tetrazolyl, or the like.
The term "heterocyclic ring system" refers to a ring system in which at least one ring in the ring system is heterocyclic.
The term "heteroaromatic ring system" refers to systems in which at least one ring in the ring system is aromatic.
The term "alkyl" refers to a group derived from an alkane molecule by the removal of one hydrogen atom; the term "alkylene" refers to a group derived from an alkane by subtracting two hydrogen atoms from the molecule. Similarly, "alkenylene", "alkynylene", "cycloalkylene", "cycloalkenylene", "phenylene", "naphthylene", "heterocyclylene" or "heteroarylene bicyclic or tricyclic ring system" are defined analogously.
Unless specified to be "substituted or unsubstituted", the groups of the present invention may be substituted with a substituent selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Halogenated alkynyl, hydroxy C1-4Alkyl, OR ', Si (R')3、 NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR’、S(O)2NR’R"、OC(O)R’、 OC(O)NR’R"、OS(O)2R’、OS(O)2NR’R"、N(R”)C(O)R’、NCH2R’、N(R”)C(O)NR’R"、 N(R”)S(O)2R 'or N (R') S (O)2NR 'R', etc.;
wherein, R 'and R' are each independently H, C1-6Alkyl or cycloalkyl, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl or C2-6A haloalkynyl group.
The inert solvent refers to various solvents which do not react with the raw materials, including various straight chain, branched chain or cyclic alcohols, ethers or ketones, alkyl halides, 1, 4-dioxane, acetonitrile, tetrahydrofuran, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like.
Compounds of the invention having nematicidal activity
The term "active substance according to the invention" or "active compound according to the invention" means a compound of the structure shown by the general formula (I) or an agriculturally pharmaceutically acceptable salt.
In a specific embodiment, the compounds of the invention are of formula I:
Figure BDA0002448851040000191
wherein n, A, G, M and Q are as described above.
In a further embodiment, the compounds of the invention can be divided into several different types of compounds, depending on the type of connecting bridge M in formula I:
when M is (CH)2)mWherein m is 0 to 5, the amide compound I-I is obtained, and the specific structure of the amide compound I-I is shown as the above;
when M is
Figure RE-GDA0002604393530000192
Then, sulfonamide compounds I to II, specific examples of which are shown above, are obtained;
when M is
Figure RE-GDA0002604393530000201
Then, the thiosemicarbazide compounds I-III are obtained, and specific examples thereof are shown above;
when M is a six-membered aromatic (hetero) ring, compounds I-IV are obtained in which when Q is
Figure RE-GDA0002604393530000202
Specific examples of the bisamide compound obtained by the reaction are as shown above.
The active substance of the invention can be used for controlling and killing a wide range of parasitic nematodes of agricultural and forestry plants. In the present specification, "nematicide" is a collective term for substances having an effect of controlling all of the plant-parasitic nematodes mentioned herein.
Examples of plant parasitic nematodes include, but are not limited to: root-knot nematodes, such as peanut root-knot nematodes (melodogyne arenaria), Meloidogyne chia (melodogyne chilo di), Meloidogyne pumila (melodogyne exigua), Meloidogyne hapla (melodogyne hapla), Meloidogyne incognita (melodogyne incognita), Meloidogyne javanica (melodogyne japonica), and other Meloidogyne species (melodogyne); cyst nematodes, such as potato gold nematode (Globodera rostochiensis), potato white nematode (Globodera pallida), tobacco cyst nematode (Globodera tabacum), and other cyst nematodes (Globodera); heterodera species, such as Heterodera graminicola (Heterodera avenae), Heterodera glycines (Heterodera glycines), Heterodera betacellularis (Heterodera schachtii), Heterodera trifolii (Heterodera trifolii), and other Heterodera species (Heterodera); nodorworms, such as pratylenchus glumae (Anguina funesta), Triticum tritici (Anguina tritici) and other Ditylenchus (Anguina); stem and leaf bud nematodes, such as Aphelenchoides besseyi (Aphelenchoides besseyi), Aphelenchoides fragaria (Aphelenchoides fragaria), Chrysanthemum Aphelenchoides (Aphelenchoides ritzemabosi), and other Aphelenchoides (Aphelenchoides); nematoda, such as weed nematoda (Belololaimus longicaudatus) and other nematoda (Belololaimus); pine nematodes, such as pine wood nematodes (Bursaphelenchus xylophilus) and other species of Gliocladium spp (Bursaphelenchus); ring nematodes, such as Trichinella (Criconema), Trichinella (Criconemoides), and Mesocronium (Mesocroniema); globodera, such as the rot culm nematode (Ditylenchus destructor), Ditylenchus dipsaci (Ditylenchus dipsaci), Leptodermia lentis (Ditylenchus myceliophagus), and other Steptophora species (Ditylenchus); conus nematodes, such as the genus Conidiobolus (Dolichodorus); helicopterides, such as helicoptera palaestina (helicoptera), helicoptera plecoglosa (helicoptera multicinctus), and other helicoptera species (helicoptera); sheath nematodes, such as coleoptera (Hemiclilophora) and Hemicconemoides (Hemicconomodes); coronaries, such as Nematoda Columbus (Hoploaimus columbus) and other Nematoda species (Hoploaimus); pseudorhizomatoid nematodes, such as anovulus margarita (Nacobb aberrans) and other Anemonchus species (Nacobbus); nematodes such as the nematode longerongatus (longidrorus) and other longerongatus (longidrorus); stapled nematodes, such as the genus nematode (Paratylenchus); root-rot nematodes, such as Pratylenchus brachyurus, Pratylenchus coffei (Pratylenchus coffei), Pratylenchus zea (Pratylenchus zeae), Pratylenchus penetrans (Pratylenchus penatrans), and other Pratylenchus species (Pratylenchus); perforactidae, such as Radopholus similis (Radopholus similis) and other Perforactidae (Radopholus); reniform nematodes, such as reniform nematodes (Rotylenchus robustus) and other reniform nematodes (Rotylenchus); residual root nematodes, such as primitive Bursaphelenchus (Trichoderma primaivus) and other Bursaphelenchus (Trichoderma); dwarf nematodes, such as Kleinhovia dwarfis (Tylenochlornchus clavytoni), Amylophilus dwalus (Tylenochlornchus dubius), and other species of dwarfing nematodes (Tylenochlornchus); citrus nematodes, such as citrus hemiptera (Tylenchulus semipenenetrans) and other species of Tylenchulus tenuis (Tylenchulus); sword nematodes, such as American sword nematode (Xiphilinema americanum), standard sword nematode (Xiphilinema index), cleft tail sword nematode (Xiphilinema diversicaudate), and other Sword nematodes (Xiphilinema).
The compound provided by the invention has a good control effect on Meloidogyne incognita.
Nematicide compositions comprising an active substance according to the invention
The active substances according to the invention can be prepared in a customary manner to form nematicide compositions. These active compounds can be formulated in the customary formulations, for example as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substance, microcapsules in polymers, coating compositions for seeds, and formulations for use with combustion devices, for example smoking cartridges, smoking pots and smoking trays, and ULV Cold mist (Cold mist) and hot mist (Warm mist) formulations.
These formulations can be produced by known methods, for example by mixing the active compound with extenders, that is, liquid or liquefied gases or solid diluents or carriers, and optionally surfactants, that is emulsifiers and/or dispersants and/or foam formers. Organic solvents may also be used as an auxiliary agent, for example when water is used as extender.
When a liquid solvent is used as the diluent or carrier, it is basically suitable, for example: aromatic hydrocarbons such as xylene, toluene or alkyl naphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as ethanol or ethylene glycol, and ethers and lipids thereof; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less commonly used polar solvents such as dimethylformamide and dimethylsulfoxide, and water.
The diluent or carrier of the liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, for example, aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
The solid carrier may be a finely divided natural mineral such as kaolin, clay, talc, quartz, attapulgite, montmorillonite or diatomaceous earth; and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates. Solid carriers for granules are crushed and classified natural zircon, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic coarse powders, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stalks, and the like.
Nonionic and anionic emulsifying trains may be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. The dispersant comprises lignin sulfite waste liquid and methyl cellulose.
Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, may be used in the formulations.
Colorants such as inorganic dyes, e.g., iron oxide, cobalt oxide, and prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and with trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, and the like.
The active compounds according to the invention can be present in their commercial formulations or in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, fungicides, herbicides, growth control agents, etc. The insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons and substances produced by microorganisms, such as avermectins and the like, and the fungicides include methoxypropenoates, amides, triazoles and the like.
Furthermore, the active compounds according to the invention can also be present in their commercial preparations in a mixture with synergists, which are compounds which increase the action of the active compounds, or in the use forms prepared from these preparations, it being possible for no synergists to be added, since the active compounds themselves are active.
These formulations generally contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight, of the active compound according to the invention, based on the total weight of the nematicide composition. The concentration of the active compound in the commercial preparations or dosage forms can vary within wide limits. The concentration of active compound in the dosage form to be used may be from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1% (g/v).
Process for the preparation of the compounds of the invention
The compounds represented by the general formula of the present invention can be prepared by the following method, however, the conditions of the method, such as the reactants, the solvent, the base, the amount of the compound used, the reaction temperature, the time required for the reaction, and the like, are not limited to the following explanation. The compounds of the present invention can also be conveniently prepared by optionally combining various synthetic methods described in the present specification or known in the art, and such combination can be easily performed by those skilled in the art to which the present invention pertains. If feasible, the reagents may be purchased commercially.
Typical embodiments of the compounds of the invention may be synthesized using the general reaction scheme described below. It is obvious from the description given herein that the general scheme can be modified by substituting other materials with similar structures to obtain correspondingly different products. Synthetic methods can be used as needed to provide large scale production. The starting materials can be obtained commercially or synthesized using published methods. The examples given herein, through simple testing procedures, the characteristics of the final product often make the characteristics of the necessary starting materials apparent.
Synthesis reaction parameters the compounds of the present invention may be prepared from readily available starting materials using, for example, the following general methods and procedures. It will be appreciated that where typical or optimized process conditions (i.e., reaction temperatures, times, molar ratios of reactants, solvents, catalysts, pressures, etc.) are given, other process conditions may also be used, unless otherwise indicated. Optimal reaction conditions may vary with the particular reactants or solvents used, but such conditions may be determined by one skilled in the art by routine optimization procedures.
The starting materials for the following reactions are generally known compounds or can be prepared by known procedures or obvious modifications thereof. For example, many of the starting materials are available from commercial suppliers, others may be prepared by procedures described in the text of standard references or obvious modifications.
In the preparation method of the invention, each reaction is usually carried out in an inert solvent at a reaction temperature of-20 to 120 ℃ (preferably-10 to 0 ℃ or 20 to 30 ℃ or 80 to 100 ℃). The reaction time is usually 2 to 24 hours, preferably 4 to 18 hours, and can be appropriately prolonged according to the reaction requirement, and the specific reaction time is determined according to the reaction degree.
Bases used in the reaction include (but are not limited to): triethylamine, pyridine, diisopropylethylamine, diethylamine, piperidine, piperazine, morpholine, N-methylmorpholine, triethylenediamine (DABCO), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, or a combination thereof.
Condensing agents used in the reaction include (but are not limited to): 4-dimethylaminopyridine (4-DMAP, PyBop), diphenylphosphoryl azide (DPPA), Dicyclohexylcarbodiimide (DCC), HATU, diphenylphosphinic chloride (DPP-Cl).
The synthetic route is as follows:
when M is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring, or a substituted or unsubstituted 5-7 membered heterocyclic ring, (CH)2)mWherein m is 0-5, the method in scheme one is adopted.
Scheme 1:
Figure BDA0002448851040000241
in one embodiment, 1-1 is chlorinated and then reacted with the corresponding amine or sulfonamide in the presence of a base or condensing agent to give 1-3, which is then reacted with a bromide in the presence of a base to give compound 1-4.
When M is CH2SN2The method in scheme two is adopted.
Scheme II:
Figure BDA0002448851040000242
in one embodiment, 2-1 is chlorinated and then reacted with the corresponding ammonium thiocyanate to provide the corresponding isothiocyanate 2-3, 2-3 which is then reacted with the amino compound to form compound 2-4.
When M is SO2The method adopts a third scheme:
Figure BDA0002448851040000243
in one scheme, 3-1 reacts with corresponding sulfamide in the presence of a condensing agent to obtain 3-2, and then the 3-2 reacts with bromide in the presence of alkali to generate a compound 3-3.
Synthetic examples
1. Preparation of Compounds I to I
Take the example of the preparation of I-I-2N- (5-chlorothiazol-2-yl) -4,5, 5-trifluoropenten-4-amide.
(1) And preparing an I-I-2 intermediate.
Synthesis of 4,5, 5-trifluoropentenecarboxylic chloride
Figure BDA0002448851040000251
2mmol of 4,5, 5-trifluoropenteneacyl chloride and 15mL of dichloromethane are added into a 50mL single-neck bottle, a dichloromethane solution of 2.5mmol of oxalyl chloride is dropwise added in an ice bath, and 0.05mL of DMF is added after the dropwise addition. Stirred at room temperature for 3 h. After the reaction, dichloromethane was distilled off to obtain crude 4,5, 5-trifluoropenteneacyl chloride with a yield of 91%. The reaction was directly carried out in the next step without purification.
Synthesis of 2-amino-4-chlorothiazole
Figure BDA0002448851040000252
5mmol of 2-aminothiazole, 10mL of acetic acid and 6mmol of NCS were added to a 100mL single-neck flask, the reaction was stirred at room temperature, followed by TLC, and after completion of the reaction, the reaction mixture was poured into 50mL of distilled water, and the pH was adjusted to 7 with a saturated aqueous solution of sodium bicarbonate. Extraction was performed with dichloromethane (15 mL. times.3), and the organic layers were combined, dried over anhydrous sodium sulfate, filtered with suction, and the filtrate was concentrated. The petroleum ether/ethyl acetate 3/1 column chromatography obtains the pure 2-amino-4-chlorothiazole product with the yield of 72 percent.
(2) Preparation of I-I-2
Figure BDA0002448851040000253
N- (5-Chlorothiazol-2-yl) -4,5, 5-trifluoropentene-4-amide is exemplified. 3mmol of 2-amino-5-chlorothiazole, 3mmol of 4,5, 5-trifluoropentoyl chloride, 4.5mmol of triethylamine and 20mL of dichloromethane are added into a single-neck bottle, and the reaction is stirred at room temperature. TLC tracking, after the reaction is finished, removing the solvent under reduced pressure, adding 30mL of saturated ammonium chloride aqueous solution into the residue, extracting with dichloromethane (15mL multiplied by 3), combining organic phases, drying with anhydrous sodium sulfate, filtering, collecting and concentrating filtrate, and performing petroleum ether ethyl acetate column chromatography to obtain the pure product N- (5-chlorothiazol-2-yl) -4,5, 5-trifluoropentene-4-amide.
2. Preparation of Compounds I-II
Preparation of I-II-14, 5, 5-trifluoro-N- (thiazol-2-ylsulfonyl) pent-4-enamine
Figure BDA0002448851040000261
Adding 1.7mmol of thiazole-2-sulfonamide, 3mmol of 4,5, 5-trifluoropentenoic acid, 4.5mmol of triethylamine and 20mL of dichloromethane into a single-neck bottle, and stirring at room temperature for reaction. TLC tracking, after the reaction is finished, removing the solvent under reduced pressure, adding 30mL of saturated ammonium chloride aqueous solution into the residue, extracting with dichloromethane (15mL multiplied by 3), combining organic phases, drying with anhydrous sodium sulfate, filtering, collecting and concentrating filtrate, and performing petroleum ether ethyl acetate column chromatography to obtain the pure product N- (5-chlorothiazol-2-yl) -4,5, 5-trifluoropentene-4-amide.
3. Preparation of Compounds I to III
Preparation of I-III-14, 5, 5-trifluoro-N- (2- (thiazol-2-yl) hydrazine-1-thiocarbonyl) pent-4-enamide
(1) Preparation of intermediate 4,5, 5-trifluoropent-4-enoyl isothiocyanate
Figure BDA0002448851040000262
2mmol of ammonium thiocyanate, 2mmol of 4,5, 5-trifluoropentoyl chloride and 20mL of dimethyl carbonate are added into a single-neck bottle, stirred and heated to reflux. After 30min, the heating was stopped and the temperature was cooled to room temperature. The solvent was removed under reduced pressure, and 30mL of a saturated aqueous solution of sodium chloride was added to the residue, followed by extraction with methylene chloride (15 mL. times.3), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered under suction, and the filtrate was collected and concentrated to give a crude 4,5, 5-trifluoropent-4-enoyl isothiocyanate.
(2) Preparation of 4,5, 5-trifluoro-N- (2- (thiazol-2-yl) hydrazine-1-thiocarbonyl) pent-4-enamide
Figure BDA0002448851040000263
Adding 2mmol of 4,5, 5-trifluoro-pent-4-enoyl isothiocyanate, 2mmol of 2-thiazole hydrazine and 20mL of ethyl acetate into a single-neck bottle, and stirring and cooling to 0 ℃ for reaction. And tracking by TLC, after the reaction is finished, adding 30mL of saturated sodium chloride aqueous solution, extracting, combining organic phases, drying by using anhydrous sodium sulfate, performing suction filtration, collecting and concentrating a filtrate, and performing column chromatography to obtain 4,5, 5-trifluoro-N- (2- (thiazole-2-yl) hydrazine-1-thiocarbonyl) pent-4-enamide.
4. Preparation of Compounds I to IV
To prepare I-IV-6N2,N6Examples of (e) -bis (4,5, 5-trifluoropent-4-en-1-yl) pyrazin-2, 6-amide
Figure BDA0002448851040000271
1.5mmol of 2, 6-diaminopyrazine, 3mmol of 4,5, 5-trifluoropentenoic acid, 4.5mmol of pyridine and 20mL of dichloromethane were added to a single-neck flask, and the reaction was stirred at room temperature. TLC tracking, after reaction, removing solvent under reduced pressure, adding saturated ammonium chloride aqueous solution 30mL into residue, extracting with dichloromethane (15mL × 3), mixing organic phases, drying with anhydrous sodium sulfate, suction filtering, collecting and concentrating filtrate, and performing petroleum ether ethyl acetate column chromatography to obtain pure product N2,N6-bis (4,5, 5-trifluoropent-4-en-1-yl) pyrazin-2, 6-amide.
Nuclear magnetic data of the target compound:
table 5: nuclear magnetic data for Compounds I-I
Figure BDA0002448851040000273
Figure BDA0002448851040000272
Figure BDA0002448851040000281
Figure BDA0002448851040000291
Figure BDA0002448851040000301
Figure BDA0002448851040000311
Figure BDA0002448851040000321
Figure BDA0002448851040000331
Figure BDA0002448851040000341
Figure BDA0002448851040000351
Table 6: nuclear magnetic data for compounds I-II:
Figure BDA0002448851040000353
Figure BDA0002448851040000352
Figure BDA0002448851040000361
table 7: nuclear magnetic data for Compounds I-III
Figure BDA0002448851040000363
Figure BDA0002448851040000362
Figure BDA0002448851040000371
Table 8: nuclear magnetic data for compounds I-IV:
Figure BDA0002448851040000373
Figure BDA0002448851040000372
Figure BDA0002448851040000381
test examples nematicidal Activity of Compounds of the invention
The root-knot nematode belongs to phylum nematoda, order of Tylenchida, suborder of Tylenchida, heterodermic superfamily, heterodermic family (Heterodermida), suborder of root-knot nematode (Meloidogyniae) and genus Meloidogyninella, and is a plant parasitic nematode with serious harm.
Activity in vivo
Southern root-knot nematode (Meloidogyne incognita) is used as a test object, cucumber seedlings are used as test hosts, and a test tube planting method is adopted for testing.
The operation process is as follows: preparing a sample to be tested into liquid medicine according to the required concentration for standby application, and preparing enough root-knot nematode second-instar larvae. After planting cucumber seedlings of one week old in test tubes, adding a proper amount of prepared liquid medicine into the test tubes, and inoculating about 2000 larvae into each test tube. And (3) culturing the test tube under the illumination of 10 hours at the temperature of 20-25 ℃, investigating the result after 45 days, and counting the root knot number on the root system of each plant. The test was repeated 3 times for each sample, and 4 replicates were made for each sample per test.
Distilled water is used as a blank control, distilled water and root-knot nematode are used as negative controls, and abamectin solution is used as a positive control.
The grading calculation of disease index is shown in FIG. 2.
Live nematicidal activity of the compounds:
table 9: in vivo Activity of Compounds I-I:
Figure BDA0002448851040000392
Figure BDA0002448851040000391
Figure BDA0002448851040000401
Figure BDA0002448851040000411
table 10: in vivo Activity of Compounds I-II:
Figure BDA0002448851040000413
Figure BDA0002448851040000412
Figure BDA0002448851040000421
table 11: in vivo Activity of Compounds I-III:
Figure BDA0002448851040000424
Figure BDA0002448851040000422
table 12: in vivo Activity of Compounds I-IV:
Figure BDA0002448851040000425
Figure BDA0002448851040000423
in vitro Activity
The southern root knot nematode (melodogyne incognita) was used as the test subject and the ex vivo test was performed in 96-well plates.
The test compound was diluted with acetone to a solution of a certain concentration and then diluted with a certain amount of water to the test concentration. Adding the liquid medicine and a certain amount of second instar larvae of Meloidogyne incognita into a 96-well plate, wherein not less than 50 larvae are in each well. After the preparation was completed, the 96-well plate was placed in a 25 ℃ incubator, and nematode mortality was observed and recorded for 72 hours. In the test, each compound was assayed in duplicate, with an aqueous solution of acetone as a blank and fluensulfone as a positive control. Mortality rates are shown in the table below.
Compound in vitro nematicidal activity:
table 13: compound I-I activity ex vivo:
Figure BDA0002448851040000432
Figure BDA0002448851040000431
Figure BDA0002448851040000441
Figure BDA0002448851040000451
Figure BDA0002448851040000461
Figure BDA0002448851040000471
table 14: compound I-II activity ex vivo:
Figure BDA0002448851040000474
Figure BDA0002448851040000472
table 15: ex vivo Activity of Compounds I-III
Figure BDA0002448851040000475
Figure BDA0002448851040000473
Table 16: compound I-IV activity ex vivo:
Figure BDA0002448851040000482
Figure BDA0002448851040000481
as can be seen from the activities summarized in the above table, the compounds of the present invention have very good nematicidal activity and show significant nematicidal effect at concentrations as low as 40 ppm.
All documents referred to herein are incorporated by reference into this application as if each had been individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined in the appended claims.

Claims (10)

1. A compound of formula (I), or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof:
Figure FDA0002448851030000011
in the formula (I), the compound is shown in the specification,
n is an integer from 0 to 5, preferably an integer from 1 to 3, more preferably 1;
a is an oxygen or sulfur atom;
g is selected from the group consisting of: H. substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C3-6Cycloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-or 6-membered aliphatic heterocyclic group;
m is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring or a 9-12 membered fused aromatic heterocyclic ring, or a substituted or unsubstituted5-7 membered lipoheterocyclic, CH2SN2、CO、SO，SO2、(CH2)mWherein m is an integer of 0 to 5; the substituents of the ring M are selected from the group consisting of: H. halogen, substituted or unsubstituted C1-6Alkyl or alkoxy, substituted or unsubstituted C3-6Cycloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-or 6-membered aliphatic heterocyclic group;
q is a substituted or unsubstituted 5-12 membered aromatic ring, a substituted or unsubstituted 5-12 membered carbocyclic ring, a substituted or unsubstituted 5-12 membered aromatic heterocyclic ring, a substituted or unsubstituted 5-12 membered alicyclic heterocyclic ring (including fully or partially unsaturated alicyclic heterocyclic rings), a substituted or unsubstituted alkenyl group, or a group selected from the following U-1 to U-34:
Figure FDA0002448851030000021
wherein p is an integer from 0 to 7, preferably an integer from 0 to 5, most preferably an integer from 0 to 3;
wherein R is1Selected from the group consisting of: o, substituted or unsubstituted C1-6Alkyl or alkoxy, halogen, substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-or 6-membered aliphatic heterocyclic group.
2. The compound of claim 1, or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof, wherein the compound is of formula I-I, I-II, I-III, or I-IV:
Figure FDA0002448851030000031
wherein m, n, A, G and Q are as defined in claim 1.
3. The compound of claim 2, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, wherein the compound is according to formula I-I,
wherein m is 0 or 1;
n is an integer of 1 to 3;
a is an oxygen atom or a sulfur atom;
g is H, substituted or unsubstituted C1-6Alkyl or alkoxy (preferably halogen-substituted alkyl), five-or six-membered aromatic heterocycle;
q is a substituted or unsubstituted 5-12 membered aromatic ring, a substituted or unsubstituted 5-12 membered aromatic heterocycle, a substituted or unsubstituted 5-12 membered aliphatic heterocycle.
4. The compound of claim 3, or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt thereof,
wherein m is 0 or 1;
n is an integer of 1 to 2;
a is an oxygen atom or a sulfur atom;
g is H, substituted or unsubstituted C1-6Alkyl or alkoxy (preferably C)1-3Alkyl or alkoxy);
q is substituted or unsubstituted five-membered or six-membered aromatic heterocycle, substituted or unsubstituted five-membered or six-membered aliphatic heterocycle, substituted or unsubstituted 5-12 membered aromatic ring (preferably benzene ring) aromatic heterocycle, substituted or unsubstituted 5-12 membered aromatic heterocycle, substituted or unsubstituted 5-12 membered aromatic ring.
5. The compound of claim 2, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, wherein the compound of formula I-I is a compound selected from the group consisting of:
Figure FDA0002448851030000041
Figure FDA0002448851030000051
Figure FDA0002448851030000061
Figure FDA0002448851030000071
Figure FDA0002448851030000081
Figure FDA0002448851030000091
Figure FDA0002448851030000101
Figure FDA0002448851030000111
Figure FDA0002448851030000121
the compounds of formulae I-II are selected from the group consisting of:
Figure FDA0002448851030000122
the compounds of formulae I-III are selected from the group consisting of:
Figure FDA0002448851030000123
Figure FDA0002448851030000131
the compounds of formulae I-IV are selected from the following:
Figure FDA0002448851030000132
Figure FDA0002448851030000141
6. a pesticidal composition comprising a compound of any one of claims 1-5, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, and optionally an agriculturally pharmaceutically acceptable excipient.
7. Use of a compound according to any one of claims 1 to 5, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, for nematicidal or for the preparation of a nematicidal pesticide composition.
8. Use of the pesticidal composition of claim 6 for nematicidal purposes.
9. A method for controlling and eliminating nematodes comprising the step of administering an effective amount of a compound according to any one of claims 1 to 5, or an optical isomer, cis-trans isomer or agriculturally pharmaceutically acceptable salt thereof, or a pesticidal composition according to claim 6 to a plant or crop in need of control and elimination of nematodes.
10. A process for the preparation of a compound according to any one of claims 1 to 5, wherein said compound is prepared by the following synthetic route:
1) when M is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring, or a substituted or unsubstituted 5-7 membered heterocyclic ring, (CH)2)mWherein when m is 0-5, the compound is prepared by the method shown in the following reaction formula:
Figure FDA0002448851030000142
a) chloridizing a compound shown as a formula 1-1 to obtain a compound shown as a formula 1-2;
b) reacting the compound shown in the formula 1-2 with corresponding amine or sulfamide in the presence of alkali or a condensing agent to obtain a compound shown in the formula 1-3;
c) reacting a compound shown as a formula 1-3 with a bromide in the presence of a catalyst to generate a compound shown as a formula 1-4;
or
2) When M is CH2SN2The preparation method is characterized by comprising the following steps:
Figure FDA0002448851030000151
a) acylating and chlorinating the compound shown in the formula 2-1 to obtain a compound shown in the formula 2-2;
b) reacting the compound shown in the formula 2-2 with corresponding ammonium thiocyanate to obtain corresponding isothiocyanate, namely the compound shown in the formula 2-3; and
c) reacting the compound shown in the formula 2-3 with an amino compound to generate a compound shown in the formula 2-4;
or
3) When M is SO2The preparation method is characterized by comprising the following steps:
Figure FDA0002448851030000152
a) reacting the compound shown in the formula 3-1 with corresponding sulfamide in the presence of a condensing agent to obtain a compound shown in a formula 3-2;
b) reacting the compound shown as the formula 3-2 with a bromide in the presence of a base to generate the compound shown as the formula 3-3.
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