CN104530037A - Triazine heterocyclic compound with nematicidal activity as well as preparation method and application of triazine heterocyclic compound - Google Patents

Triazine heterocyclic compound with nematicidal activity as well as preparation method and application of triazine heterocyclic compound Download PDF

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CN104530037A
CN104530037A CN201510031222.4A CN201510031222A CN104530037A CN 104530037 A CN104530037 A CN 104530037A CN 201510031222 A CN201510031222 A CN 201510031222A CN 104530037 A CN104530037 A CN 104530037A
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yuan
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CN104530037B (en
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徐晓勇
李忠
王高磊
陈修雷
张经纬
邵旭升
须志平
周珍
陈琦
张梦婷
王容义
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East China University of Science and Technology
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Priority to PCT/CN2016/071608 priority patent/WO2016116058A1/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
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    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
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    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Abstract

The invention relates to a triazine heterocyclic compound with nematicidal activity as well as a preparation method and application of the triazine heterocyclic compound and particularly discloses a compound as shown in the formula (I) or an optical isomer, cis-trans isomer or pesticidally-acceptable salt of the compound and a preparation method of the compound or the optical isomer, cis-trans isomer or pesticidally-acceptable salt of the compound. The invention also discloses an agricultural composition containing the compound and application of the agricultural composition. The compound has excellent nematicidal activity.

Description

A kind of there is eelworm-killing activity triazine heterogeneous ring compound and method for making and purposes
Technical field
The invention belongs to pesticide field.Particularly, the present invention relates to a kind of there is eelworm-killing activity triazine heterogeneous ring compound and method for making and purposes.
Background technology
Plant nematode is the very harmful pathogenic micro-organism of a class, it has a very wide distribution, of a great variety, adaptive capacity to environment is strong, can colonize in the root system of plant, stem, leaf, seed, young shoot and fruit, by feeding activity, physical abuse is caused to host plant, and rob the nutrition of host plant, especially its esophageal gland secretory product can cause host plant that a series of pathology occurs, and also jointly can infect host plant with other pathogenic micro-organism, cause compound disease, cause production loss.In the world, the agricultural losses that plant nematode is caused every year, up to more than 1,000 hundred million dollars, seriously constrain the development of rural economy.
Agriculturally have a lot, at present based on chemical prevention to the means of prevention of nematode.The chemical nematicides of widespread use is mainly high toxicity, the organophosphorus of high residue or carbamate chemicals for agriculture, as cadusafos, ethoprop, fenamiphos, lythidathion, aldicarb, oxamyl and carbofuran etc., low to the security of the mankind and other non-target organism, also can cause pollution in various degree to soil, water source and agricultural-food.In addition, because kind is single, such nematocides by excessive, frequently use, caused serious resistance, the difficulty of prevention and cure of nematode increased day by day.Therefore, find the chemical nematicides of efficient, low toxicity and the good novel structure of Environmental compatibility, become the technical problem that this area is in the urgent need to address.
Summary of the invention
An object of the present invention is to provide chemical nematicides of a kind of efficient, low toxicity and the good novel structure of Environmental compatibility and its preparation method and application.
In a first aspect of the present invention, provide the compound that one has structure shown in general formula (I), or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science:
In formula:
X is O or S;
Y is O, S, S (=O) s (=O) 2 nH or covalent linkage;
Q is carbonyl thiocarbonyl group-amino thiocarbonyl group-amino-carbonyl or covalent linkage;
When L is substituted or unsubstituted C 1-6alkylidene group, substituted or unsubstituted C 1-6halogeno alkylen, substituted or unsubstituted C 2-6alkenylene, substituted or unsubstituted C 2-6haloalkenediyl, substituted or unsubstituted C 2-6alkynylene, substituted or unsubstituted C 2-6halo alkynylene, substituted or unsubstituted C 3-7cycloalkylidene, substituted or unsubstituted C 5-7mix fragrant two rings or three ring ring systems in sub-cycloalkenyl group, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylidene, substituted or unsubstituted 5 yuan or 6 yuan of sub-heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan Asias, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R " time; M is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R "; Or
When L is substituted or unsubstituted C 1-6alkyl, substituted or unsubstituted C 1-6haloalkyl, substituted or unsubstituted C 2-6thiazolinyl, substituted or unsubstituted C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, substituted or unsubstituted C 2-6halo alkynyl, substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R " time; M is nothing;
And A is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R ";
G represents the substituting group on any one or more positions of A, and G is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R ";
Wherein, R', R " is H, C independently of one another 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, hydroxyl, hydroxyl C 1-4alkyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4;
R 1for C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4;
R 2for H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl or C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4;
Wherein, R 3, R 4, R 6be H, C independently of one another 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl or C 2-6halo alkynyl;
R 5for C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl or C 2-6halo alkynyl;
M is 1 or 2;
N is 0,1,2,3,4 or 5.
In another preference, described compound is selected from lower group:
Above-mentioned various in, the definition of X, L, G, A, M and n is described above, and Y is O, S, S (=O), S (=O) 2or covalent linkage.
In another preference, X is O or S.
In another preference, L is substituted or unsubstituted C 1-6alkylidene group, substituted or unsubstituted C 1-6halogeno alkylen, substituted or unsubstituted C 2-6alkenylene, substituted or unsubstituted C 2-6haloalkenediyl, substituted or unsubstituted C 2-6alkynylene, substituted or unsubstituted C 3-7cycloalkylidene, substituted or unsubstituted C 5-7mix fragrant bicyclic ring system for sub-cycloalkenyl group, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylidene, substituted or unsubstituted 5 yuan or 6 yuan of sub-heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan Asias, and described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl; Or
L is substituted or unsubstituted C 1-6alkyl, substituted or unsubstituted C 1-6haloalkyl, substituted or unsubstituted C 2-6thiazolinyl, substituted or unsubstituted C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
In another preference, L is any group shown in L row in table 2 ~ table 6 in embodiment.
In another preference, M is nothing; Or M is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, Trimethylsilanylethynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
In another preference, M is any group shown in M row in table 2 ~ table 6 in embodiment.
In another preference, A is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, and described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4halogenated alkoxy, phenoxy group, amidosulfonic acid base, amido-carbonyl, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
In another preference, G is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, Trimethylsilanylethynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
In another preference, for in table 2 ~ table 6 in embodiment any group shown in row.
In another preference, described compound is compound cited in table 2 ~ table 6 in embodiment.
Provide a kind of agricultural composition in second aspect present invention, it comprises:
(1) acceptable salt or their combination in the optical isomer of the compound described in first aspect present invention of 0.001-99.99 % by weight or described compound, cis-trans-isomer or Pesticide Science; And
(2) acceptable carrier and/or vehicle in Pesticide Science.
The purposes of agricultural composition described in acceptable salt in the optical isomer of compound described in first aspect present invention or described compound, cis-trans-isomer or Pesticide Science or second aspect present invention is provided, for killing or prevent nematode or for the preparation of nematicidal agent composition in third aspect present invention.
In another preference, for killing or prevent agriculture and forestry plant parasitic nematode or for the preparation of the nematicidal agent composition killing or prevent agriculture and forestry plant parasitic nematode.
The preparation method of acceptable salt in the optical isomer of compound described in a kind of first aspect present invention or described compound, cis-trans-isomer or Pesticide Science is provided in fourth aspect present invention,
(A) described method comprises step:
(1) in inert solvent, formula (a) compound and two (trichloromethyl) carbonic ether (BTC) are carried out ring closure reaction, obtain formula (b) compound:
(2) in inert solvent, formula (b) compound and volatile salt are carried out ring-opening reaction, obtain formula (c) compound:
(3) in inert solvent, by formula (c) compound through diazotization reaction, ring closure reaction, formula (d) compound is obtained:
(4) in inert solvent, in the presence of a base, formula (d) compound and BrCH 2(CH 2) nbr reacts, and obtains formula (e) compound;
(5) in inert solvent, formula (e) compound and formula (f) compound or formula (p) compound (H-Y-Q-L-M) are reacted, thus obtain formula (I) compound:
Or (B) described method comprises step:
(4') in inert solvent, in the presence of a base, formula (d) compound and BrCH 2(CH 2) nc ≡ CH reacts, and obtains formula (g) compound:
(5') in inert solvent, formula (g) compound and formula (h) compound are reacted, thus obtain formula (I) compound:
Or (C) described method comprises step:
(4 ") in inert solvent, in the presence of a base, formula (d) compound and BrCH 2(CH 2) nyH reacts, and obtains formula (i) compound:
(formula (i) compound and formula (k) compound, in inert solvent, react by 5 "), thus obtain formula (I) compound:
Or (D) described method comprises step:
(5 " ') in inert solvent, in the presence of a base, formula (e) compound and formula (m) compound are reacted, then obtain formula (n) compound through deprotection:
(6) in inert solvent, formula (n) compound and formula (o) compound are reacted, thus obtain formula (I) compound:
Or (E) described method comprises step:
(6'), in inert solvent, formula (n) compound and formula (o') compound react, and obtain formula (I) compound:
Or (F) described method comprises step:
(5 " ") in inert solvent, in the presence of a base, formula (e) compound and formula (p) compound react, and obtain formula (I) compound:
Above-mentioned various in, the definition of X, Y, Q, L, M, A, G and n is described above.
In a fifth aspect of the present invention, provide a kind of nematicide and/or anti-nematode method, described method comprises step: the compound described in first aspect present invention or the agricultural composition described in second aspect are put on and suffer maybe may suffer in the plant materials of nematode evil, the soil around it or environment.
In a sixth aspect of the present invention, provide the method preparing agricultural composition described in second aspect present invention, described method comprises step: by acceptable salt or their combination in compound, its optical isomer, cis-trans-isomer or the Pesticide Science described in (1) first aspect present invention; Mix with acceptable carrier and/or vehicle in (2) Pesticide Science, thus the agricultural composition described in being formed.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Embodiment
The present inventor, through long-term and deep research, is surprised to find that and has synthesized a series of novel structure, has the triazine heterogeneous ring compound of remarkable insecticidal activity.On this basis, contriver completes the present invention.
group definition
Term " C 1-6alkyl " refer to the straight or branched alkyl with 1-6 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or similar group.
Term " C 2-6thiazolinyl " refer to the thiazolinyl of the straight or branched with 2-6 carbon atom, such as vinyl, allyl group, 1-propenyl, pseudoallyl, 1-butylene base, crotyl or similar group.
Term " C 2-6alkynyl " refer to the alkynyl of the straight or branched with 2-6 carbon atom, such as ethynyl, proyl or similar group.
Term " C 3-7cycloalkyl " refer to the cyclic alkyl with 3-7 carbon atom, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl or similar group.
Term " C 5-7cycloalkenyl group " refer to that there is 5-7 carbon atom, that there is one or more double bond cyclic alkenyl radical, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1，3-cyclohexadiene base, 1，4-cyclohexadiene base or similar group.
As used herein, term " C 1-4alkoxyl group " refer to the straight or branched alkoxyl group with 1-4 carbon atom, such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy or similar group.
Term " halogen " refers to fluorine, chlorine, bromine or iodine.Term " halo " refers to the group replaced by identical or different one or more above-mentioned halogen atom, such as trifluoromethyl, pentafluoroethyl group, seven fluorine sec.-propyls or similar group.
Term " ring " or " ring system " refer to carbocyclic ring or heterocycle.
Term " heterocycle " finger-type becomes at least one atom in the atom of described heterocyclic skeleton not to be carbon, is nitrogen, oxygen or sulphur.Usually, heterocycle comprises and is no more than 4 nitrogen, is no more than 2 oxygen and/or is no more than 2 sulphur.Except as otherwise noted, heterocycle can be saturated, part is undersaturated or complete undersaturated ring.
Term " ring system " refers to two or more rings and condensed ring together.
As used herein, term " 5 yuan or 6 yuan of heterocyclic radicals " refers to be selected from nitrogen containing one or more, heteroatomic five yuan or the six-ring of oxygen or sulphur, such as pyridyl, thiazolyl, isothiazolyl, thienyl, furyl, pyrryl, pyrazolyl, pyrimidyl, tetrahydrofuran base, 4, 5-thiazoline-2-base, 2-cyanoimino-4-oxygen-1, 3-thiazolidine-3-base, 2-cyanoimino-4-oxygen-1, 3-thiazan-3-base, oxazolyl, isoxazolyl, 1H-TETRAZOLE base, 1H-1, 2, 3-triazolyl, 4H-1, 2, 4-triazolyl, 1, 2, 3-thiadiazolyl group, 1, 2, 4-thiadiazolyl group, 1, 3, 4-thiadiazolyl group, 1, 2, 4-oxadiazolyl, 1, 2, 5-oxadiazolyl, 1, 3, 4-oxadiazolyl or tetrazyl etc.
At least one ring in term " heterocycle ring system " finger ring system is the ring system of heterocycle.
At least one ring in term " hetero-aromatic ring ring system " finger ring system is the system of aromatic ring.
As used herein, term " 8 yuan to 12 yuan assorted fragrant bicyclic ring systems " or " 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems " can be selected from lower group: cumarone, benzo [b] thiophene, indoles, quinoline, isoquinoline 99.9, 1H-indazole, 1H-benzo [d] imidazoles, benzo [d] thiazole, benzo [d] oxazole, benzo [d] isoxazole, benzo [d] [1,2,3] thiadiazoles, 2,3-glyoxalidine is [1,2-a] pyridine also, quinazoline, quinoxaline, cinnolines, phthalazines, 1,8-naphthyridines, 4,5,6,7-tetrahydro benzo [b] thiophene, benzo [b] thiophene-1,1-dioxy alkane, 8H-indeno [2,1-b] thiophene, 7,8-dihydro-6H-ring penta [4,5] thieno-[2,3-d] pyrimidine, 3,5,6,7-tetrahydrochysene-4H-ring penta [4,5] thieno-[2,3-d] pyrimidin-4-one, spiral shell [indoline-3,2'-[1,3] dioxolane]-2-ketone, spiral shell [indoline-3,2'-[1,3] dioxane]-2-ketone, or indoline-2,3-diketone etc.
Term " alkyl " refers in alkane molecule the group minusing a hydrogen atom; Term " alkylidene group " refers in alkane molecule the group minusing two hydrogen atoms.Similarly, the definition of " alkenylene ", " alkynylene ", " cycloalkylidene ", " sub-cycloalkenyl group ", " phenylene ", " naphthylidene ", " sub-heterocyclic radical " or " sub-assorted fragrant two rings or three ring ring systems " is similar.
Group of the present invention is " substituted or unsubstituted " unless stated otherwise, otherwise the substituting group that group of the present invention all can be selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, hydroxyl, hydroxyl C 1-4alkyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4deng, wherein, described R 3, R 4, R 5, R 6definition the same, m is 1 or 2.
Inert solvent refers to all kinds of SOLVENTS do not reacted with raw material, comprises the alcohol of various straight chain, side chain or ring-type, ether or ketone, haloalkane, Isosorbide-5-Nitrae-dioxane, acetonitrile, tetrahydrofuran (THF), DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO) etc.
Compound of the present invention can contain one or more asymmetric center, and therefore occurs with the form of raceme, racemic mixture, single enantiomer, diastereomeric compound and single diastereomer.The asymmetric center that can exist, depends on various substituent character on molecule.Each this asymmetric center will produce two optically active isomers independently, and all possible optically active isomer and non-enantiomer mixture and pure or partial-purified compound comprise within the scope of the present invention.The present invention includes all isomeric form of compound.
In formula I of the present invention, when Y or Q is covalent linkage, represent that the group of Y or Q both sides is connected by covalent linkage.
the eelworm-killing activity of active substance of the present invention
Term " active substance of the present invention " or " active compound of the present invention " refer to acceptable salt in the compound of structure shown in general formula (I), its optical isomer, cis-trans-isomer or Pesticide Science.It, containing the heterocycle structure of N, S, has significant eelworm-killing activity, and nematicide spectrum is wide, stability is strong.
Term " in Pesticide Science acceptable salt " refer to the negatively charged ion of this salt formed nematocides pharmacy acceptable salt time be understood with acceptable.Preferably, this salt is water miscible.Suitable, comprise by the acid salt of the compound formation of formula (I) salt that mineral acid formed, such as hydrochloride, phosphoric acid salt, vitriol, nitrate; And comprise the salt of organic acid formation, and as acetate, benzoate etc.
Actives mass-energy of the present invention is used as control and eliminate agriculture and forestry plant parasitic nematode widely.In this manual, " nematocides " is the general designation of the material with the effect preventing and treating all plant nematodes mentioned in this article.
The example of plant nematode includes but not limited to: root knot nematode, as peanut root-knot nematode (Meloidogynearenaria), Qi Shi root knot nematode (Meloidogyne chitwoodi), short and small root knot nematode (Meloidogyneexigua), M hapla (Meloidogyne hapla), Meloidogyne incognita (Meloidogyne incognita), javanese root knot nematode (Meloidogyne javanica), and other Meloidogyne (Meloidogyne); Cyst roundworm, as globodera rostochiensis (Globodera rostochiensis), G.pallida (Globodera pallida), tobacco cyst roundworm (Globodera tabacum), and other cyst roundworm belongs to (Globodera); Golden nematode, as cereal cyst nematode (Heterodera avenae), soy bean cyst roundworm (Heterodera glycines), beet cyst roundworm (Heterodera schachtii), trifolium cyst roundworm (Heterodera trifolii), and other Heterodera (Heterodera); Plant knurl nematode, as shear retention factor (Anguina funesta), wheat anguina (Anguinatritici) and other Turbatrix (Anguina); Stem and leaf bud nematode, as aphelenchoides besseyi (Aphelenchoidesbesseyi), strawberry aphelenchoides (Aphelenchoides fragariae), chrysanthemum aphelenchoides (Aphelenchoidesritzemabosi), and other Aphelenchoides (Aphelenchoides); Thorn nematode, as weeds thorn nematode (Belonolaimus longicaudatus) and other acupuncture Turbatrix (Belonolaimus); Loose ends worm, as pine wood nematode (Bursaphelenchus xylophilus) and other Bursaphelenchus (Bursaphelenchus); Annular nematode, as ring grain Turbatrix (Criconema), little loop wire Eimeria (Criconemella), Criconemoides (Criconemoides) and Middle Ring Line Eimeria (Mesocriconema); Bulb eelworm, as rot stem nematodes (Ditylenchus destructor), sweet potato stem nematode (Ditylenchus dipsaci), mushroom stalk nematode (Ditylenchus myceliophagus), and other Ditylenchus (Ditylenchus); Cone nematode, as cone Turbatrix (Dolichodorus); Helicotylenchus, as Spiral namatodes (Helicotylenchus dihystera), Pratylenchus penetrans (Helicotylenchus multicintus), and other spiral-line Eimeria (Helicotylenchus); Sheath nematode, as sheath Turbatrix (Hemicycliophora) and half Criconemoides (Hemicriconemoides); Hat nematode, as Colombia tie nematode (Hoploaimus columbus) and other tie Turbatrix (Hoploaimus); Pseudo-knot nematodes, as abnormal pearl nematode (Nacobbus aberrans) and other pearl curve Eimeria (Nacobbus); Needlework worm, as ease removes minute hand nematode (Longidorus elongatus) and other minute hand Turbatrix (Longidorus); Nail nematode, as nail Turbatrix (Paratylenchus); Pratylenchus, as most short-tail Pratylenchidae (Pratylenchus brachyurus), coffee pot handle (Pratylenchus coffee), corn lesion nematode (Pratylenchus zeae), Cobb root (Pratylenchus penetrans), and other Pratylenchidae belongs to (Pratylenchus); Similes thorne, as radopholus similes thorne (Radopholus similis) and other perforation line Eimeria (Radopholus); Kidney shape nematode, as Rotylenchulus reniformis (Rotylenchus robustus) and other kidney shape Turbatrix (Rotylenchus); Undesirable root nematode, as original burr nematode (Trichodorus primitivus) and other burr Turbatrix (Trichodorus); Species of Tylenchorhynchus Nematodes, as Clayton's species of Tylenchorhynchus Nematodes (Tylenchorhynchus claytoni), indefinite species of Tylenchorhynchus Nematodes (Tylenchorhynchus dubius), and other Tylenchorhynchus (Tylenchorhynchus); Citrus nematode, as citrus Tylenchulus Semipenetrans (Tylenchulus semipenetrans) and other pulvinulus sword Turbatrix (Tylenchulus); Sword nematode, as X. radicicola (Xiphinema americanum), standard sword nematode (Xiphinemaindex), split tail sword nematode (Xiphinema diversicaudatum), and other Xiphinema (Xiphinema).
The compound that the present invention relates to especially has good prevention effect to Meloidogyne incognita (Meloidogyne incognita).
containing the nematicidal agent composition of active substance of the present invention
Active substance of the present invention can be prepared into nematicidal agent composition in a conventional way.These active compounds can make conventional preparation, such as solution, emulsion, suspensoid, pulvis, foaming agent, paste, granule, aerosol, with the natural of active substance dipping and the material of synthesis, microcapsule in polymer, for seed dressing compound and with combustion unit one piece of preparation used, such as sootiness cartridge case, sootiness tank and sootiness dish, and the cold mist of ULV (Cold mist) and hot mist (Warmmist) preparation.
These preparations can be produced by known method, such as, active compound mix with expansion agent, these expansion agent be exactly liquid or liquefied gas or the diluent or carrier of solid, and tensio-active agent and emulsifying agent and/or dispersion agent and/or formation of foam agent can be selected arbitrarily.Such as when using water as expansion agent, organic solvent also can be used as auxiliary agent.
When making diluent or carrier with liquid solvent, be suitable substantially, as: arene, such as dimethylbenzene, toluene or alkylnaphthalene; The fragrance of chlorination or the fat hydrocarbon of chlorination, such as chlorobenzene, vinylchlorid or methylene dichloride; Fat hydrocarbon, such as hexanaphthene or paraffin, such as mineral oil fractions; Alcohols, such as ethanol or ethylene glycol and their ether and lipid; Ketone, such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or cyclohexanone; Or the polar solvent be of little use, such as dimethyl formamide and dimethyl sulfoxide (DMSO), Yi Jishui.
The diluent or carrier of liquefied gas, refers to and will become the liquid of gas at normal temperatures and pressures, such as aerosol propellants, as hydro carbons and butane, propane, nitrogen and the carbonic acid gas of halogenation.
Solid carrier can with the natural mineral substance ground, such as kaolin, clay, talcum, quartz, atlapulgite, polynite or diatomite; With the mineral substance of the synthesis ground, the silicic acid of such as high dispersing, aluminum oxide and silicate.Solid carrier for particle is that pulverize with natural zircon that is classification, such as calcite, marble, float stone, sepiolite and rhombspar, and the particle of inorganic and organic meal synthesis, and the particle etc. of organic materials such as wood sawdust, Exocarpium cocois (Cocos nucifera L), corn cob and tobacco stems.
Emulsification row that are non-ionic and negatively charged ion can be used as emulsifying agent and/or formation of foam agent.Such as polyoxyethylene-fatty esters of gallic acid, polyoxyethylene-fatty alcohol ethers, such as alkaryl polyoxyethylene glycol ethers, alkyl sulfonates, alkyl sulfuric ester class, aromatic yl sulphonate class and albumin hydrolysate.Dispersion agent comprises lignin sulfite waste liquor and methylcellulose gum.
Can tackiness agent be used in the formulation, such as carboxymethyl cellulose and with the natural of powder, particle or emulsion form and synthesis polymer, such as gum arabic, polyvinyl alcohol and polyvinyl acetate.
Can with coloring agents as inorganic dyestuff, as ferric oxide, oxidation bore and Prussian blue; Organic dye, as azoic dyestuff or metallized phthalocyanine dye; With use trace nutritional agent, as the salt etc. of iron, manganese, boron, copper, cobalt, aluminum and zinc.
These active compounds of the present invention can be made a kind of mixture with other active compounds and be present in their commercial preparation or from use formulation prepared by these preparations, and these other active compound is sterilant, sterilant, mycocide, weedicide, growth control agent etc.Sterilant comprises, and such as phosphoric acid ester, amino formate, chlorinated hydrocarbons and the material produced by microorganism, as Avrmectin etc., mycocide comprises methoxy acrylic, amides, triazole species etc.
In addition, these active compounds of the present invention also can be made a kind of mixture with synergistic agent and be present in their commercial preparation or from use formulation prepared by these preparations, these synergistic agent are the compounds improving active compound effect, because active compound itself has activity, also synergistic agent can be added.
These preparations usually containing the 0.001-99.99 % by weight accounting for described nematicidal agent composition gross weight, preferred 0.01-99.9 % by weight, the more preferably active compound of the present invention of 0.05-90 % by weight.Commercial preparation or use the concentration of the active compound in formulation can change in wide scope.Use the concentration of the active compound in formulation can from 0.0000001-100% (g/v), preferably between 0.0001 and 1% (g/v).
the preparation method of the compounds of this invention
Shown in general formula of the present invention (I), compound obtains by following method, but the condition of the method, the amount, temperature of reaction, reaction required time etc. of such as reactant, solvent, alkali, compound used therefor are not limited to explanation below.Various synthetic method that describe in this manual or known in the art can also optionally combine and obtain easily by the compounds of this invention, and such combination can be easy to carry out by those skilled in the art in the invention.
In the preparation process in accordance with the present invention, each reaction, usually in inert solvent, is carried out under temperature of reaction-20 ~ 120 DEG C (preferably-10 ~ 0 DEG C or 20 ~ 30 DEG C or 80 ~ 100 DEG C).Reaction times is generally 2 ~ 24 hours, is preferably 4 ~ 18 hours.
Alkali used in reaction comprises (but being not limited to): triethylamine, diisopropyl ethyl amine, diethylamine, piperidines, piperazine, morpholine, N-methylmorpholine, triethylene diamine (DABCO), 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), 1,5-diazabicylo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene (DBN), salt of wormwood, saleratus, sodium carbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, or its combination.
In a preference, the method synthesis of starting materials of formulae (d) compound of the present invention by comprising the steps:
Above-mentioned various in, X, A, G are as hereinbefore defined;
(1) in inert solvent, under certain temperature (as-10 ~-5 DEG C), by formula (a) compound and BTC reaction, thus formula (b) compound is obtained.
(2) in inert solvent, under certain temperature (as 55 ~ 60 DEG C), by formula (b) compound and volatile salt reaction, thus formula (c) compound is obtained.
(3) in inert solvent, under certain temperature (as-5 ~ 0 DEG C), by formula (c) compound and NaNO 2dilute hydrochloric acid solution reaction, thus obtain formula (d) compound.
Preferably, described method comprises step:
(1) formula (a) compound is added in appropriate tetrahydrofuran (THF), be down to-10 DEG C.Temperature control-10 ~-5 DEG C, slowly drips the tetrahydrofuran solution of BTC, finishes, react under being placed in room temperature, TLC follows the tracks of reaction process, after reaction terminates, and removal of solvent under reduced pressure, in residual solids, add anhydrous diethyl ether fully stir, suction filtration, dry formula (b) compound.
(2) formula (b) compound is added in appropriate Isosorbide-5-Nitrae-dioxane, add volatile salt, be heated to 55 ~ 60 DEG C of reactions, TLC follows the tracks of reaction process, after reaction terminates, is cooled to room temperature, removal of solvent under reduced pressure, add appropriate saturated sodium bicarbonate aqueous solution, extraction into ethyl acetate, organic phase anhydrous sodium sulfate drying, removal of solvent under reduced pressure, obtains formula (c) compound.
(3) by NaNO 2add in appropriate 0.5M dilute hydrochloric acid, be down to-5 DEG C.Temperature control-5 ~ 0 DEG C, the DMF solution of slow dropping formula (c) compound, finish, react under being placed in room temperature, TLC follows the tracks of reaction process, treat that (c) reacts completely, adjust pH=8 ~ 10 with ammoniacal liquor, rear hydrochloric acid adjusts pH=2 ~ 5, suction filtration, by large water gaging flush cake, dry formula (d) compound.
In another preference, shown in general formula of the present invention (II), compound synthesizes by following method:
Above-mentioned various in, as hereinbefore defined, n is the integer of 0-5 for X, Y, L, M, G and A;
(1) under alkali (as salt of wormwood etc.) exists, solvent is made with inert solvent (as acetone), formula (d) compound and BrCH 2(CH 2) nbr reacts for some time (as 5 ~ 10 hours) under certain temperature (as backflow), after reaction terminates, be cooled to room temperature, remove solvent under reduced pressure, add water in residue, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (e) compound.
(2) under potassiumiodide exists, with inert solvent (as DMF) for solvent, formula (e) compound and formula (f1) compound react for some time (as 10 ~ 15 hours) under certain temperature (as 80 ~ 90 DEG C), after reaction terminates, be cooled to room temperature, remove solvent under reduced pressure, dilute hydrochloric acid is added in residue, with dichloromethane extraction, organic phase saturated common salt water washing, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (II) compound;
Or, under alkali (as salt of wormwood etc.) exists, with inert solvent (as DMF or acetone) for solvent, formula (e) compound and formula (p1) compound react for some time (as 8 ~ 12 hours) under certain temperature (as 80 ~ 90 DEG C or reflux), after reaction terminates, be cooled to room temperature, remove solvent under reduced pressure, add water in residue, with dichloromethane extraction, organic phase saturated common salt water washing, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (II) compound.
Or compound is synthesized by following method shown in general formula (II):
Above-mentioned various in, as hereinbefore defined, n is the integer of 0-5 for X, Y, L, M, G and A;
(1) under alkali (as salt of wormwood etc.) exists, solvent is made with inert solvent (as acetone), formula (d) compound and BrCH 2(CH 2) nc ≡ CH reacts for some time (as 5 ~ 8 hours) under certain temperature (as backflow), after reaction terminates, be cooled to room temperature, remove solvent under reduced pressure, add water in residue, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (g) compound.
(2) under alkali (as triethylamine etc.) exists, solvent is made with inert solvent (as acetonitrile), take CuI as catalyzer, formula (g) compound and formula (h1) compound at room temperature react for some time (as 2 ~ 4 hours), after reaction terminates, remove solvent under reduced pressure, residue post is separated, obtains formula (II) compound.
In another preference, shown in general formula of the present invention (III), compound synthesizes by following method:
Above-mentioned various in, as hereinbefore defined, n is the integer of 0-5 for X, L, M, G and A;
(1) under alkali (as salt of wormwood etc.) exists, solvent is made with inert solvent (as acetone), formula (d) compound and BrCH 2(CH 2) noH reacts for some time (as 5 ~ 8 hours) under certain temperature (as backflow), after reaction terminates, be cooled to room temperature, remove solvent under reduced pressure, add water in residue, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (i1) compound.
(2) under alkali (as triethylamine etc.) exists, with inert solvent (as methylene dichloride) by formula (i1) compound dissolution, formula (k1) compound is added under room temperature, finish, continue reaction for some time (as 2 ~ 4 hours), after reaction terminates, add saturated sodium bicarbonate aqueous solution fully to stir, separate organic phase, aqueous phase methylene dichloride extracts 2 times again, merges all organic phases, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (III) compound.
In another preference, shown in general formula of the present invention (IV), compound synthesizes by following method:
Above-mentioned various in, as hereinbefore defined, n is the integer of 0-5 for X, L, M, G and A;
(1) under alkali (as salt of wormwood etc.) exists, with inert solvent (as DMF) for solvent, formula (e) compound and formula (m1) compound react for some time (as 8 ~ 12 hours) under certain temperature (as 50 ~ 60 DEG C), after reaction terminates, add water in residue, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (q) compound.
(2) in inert solvent (as ethanol), formula (q) compound and hydrazine hydrate react for some time (as 6 ~ 10 hours) under certain temperature (as refluxed), after reaction terminates, suction filtration, filtering insolubles, solvent under reduced pressure in filtrate is steamed and removes, saturated sodium bicarbonate aqueous solution is added in residue, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, remove solvent under reduced pressure, obtain yellow oily liquid-type (n1) compound.
(3) under alkali (as triethylamine etc.) exists, with inert solvent (as methylene dichloride) by formula (n1) compound dissolution, formula (o1) compound is added under room temperature, finish, continue reaction for some time (as 2 ~ 4 hours), after reaction terminates, add saturated sodium bicarbonate aqueous solution fully to stir, separate organic phase, aqueous phase methylene dichloride extracts 2 times again, merges all organic phases, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains formula (IV) compound.
In another preference, shown in general formula of the present invention (V-VI), compound synthesizes by following method:
Above-mentioned various in, as hereinbefore defined, n is the integer of 0-5 for X, L, M, G and A;
In inert solvent (as acetonitrile), formula (n1) compound and formula (o'1) compound at room temperature react for some time (as 8 ~ 12 hours), after reaction terminates, and suction filtration, filter cake dehydrated alcohol recrystallization, obtains formula (V) compound.
In inert solvent (as methylene dichloride), formula (n1) compound and formula (o'2) compound at room temperature react for some time (as 8 ~ 12 hours), after reaction terminates, suction filtration, filtrate is concentrated, post is separated, and obtains formula (VI) compound.
Preferably, in described reaction mixture, the content of described intermediate product is 10-99.99wt%; Be preferably 20-90wt%; Be more preferably 50-80wt%.
Therefore, contriver by after this intermediate purification, then can carry out next step reaction; The reaction mixture comprising this compound directly can certainly be carried out next step reaction.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number calculate by weight.
Embodiment 1 2-cyanoimino-3-(N-3-(4-oxygen-7-chlorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group))-1,3-thiazoles alkane-4-ketone
1.1 preparation 7-chlorobenzenes also [d] [1,2,3] triazine-4 (3H)-one
1.1.1 preparation 7-chloroisatoic anhydride
6.864g (40mmol) 2-amino-4-chloro-benzoic acid is added in 100ml tetrahydrofuran (THF), stirring makes it into suspension, be down to-10 DEG C, temperature control-10 ~-5 DEG C, the 20ml tetrahydrofuran solution of slow dropping 11.88g (40mmol) BTC, finish, react under being placed in room temperature, TLC follows the tracks of reaction process.After reaction terminates, remove solvent under reduced pressure, in residual solids, add 150ml anhydrous diethyl ether fully stir, suction filtration, filter cake anhydrous diethyl ether washs, dry white solid 6.718g, yield 85%. 1H NMR(400MHz,DMSO-d 6)δ11.84(s,1H),7.92(d,J＝8.4Hz,1H),7.30(dd,J 1＝8.4Hz,J 2＝1.6Hz,1H),7.14(d,J＝1.6Hz,1H)； 13CNMR(100MHz,DMSO-d 6)δ159.1,146.9,142.5,141.1,130.9,123.6,114.7,109.5.
1.1.2 2-amino-4-chlorobenzamide is prepared
5.928g (30mmol) 7-chloroisatoic anhydride added in 120ml Isosorbide-5-Nitrae-dioxane, add 14.40g (150mol) volatile salt, stir and make it into suspension, be heated to 60 DEG C of reactions, TLC follows the tracks of reaction process.After reaction terminates, remove solvent under reduced pressure, in residue, add 120ml saturated sodium bicarbonate aqueous solution, be extracted with ethyl acetate (60ml × 3), organic phase anhydrous sodium sulfate drying, removes solvent under reduced pressure, obtain brown solid 4.197g, yield 82%. 1H NMR(400MHz,DMSO-d 6)δ7.78(br,1H),7.54(d,J＝8.4Hz,1H),7.15(br,1H),6.83(s,2H),6.74(d,J＝2.0Hz,1H),6.49(dd,J 1＝8.4Hz,J 2＝2.0Hz,1H)； 13C NMR(100MHz,DMSO-d 6)δ170.4,151.5,136.3,130.6,115.1,114.0,112.4.
1.1.3 7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one is prepared
By 3.450g (50mmol) NaNO 2be dissolved in 200ml 0.5M dilute hydrochloric acid, be down to-5 DEG C, temperature control-5 ~ 0 DEG C, slowly drip the 15ml DMF solution of 4.265g (25mmol) 2-amino-4-chlorobenzamide, finish, react under being placed in room temperature, TLC follows the tracks of reaction process.After reaction terminates, adjust pH=10 with ammoniacal liquor, fully stir 15 minutes, rear hydrochloric acid adjusts pH=2, fully stirs 15 minutes, suction filtration, by large water gaging flush cake, dry, obtains white solid 3.860g, yield 85%. 1H NMR(400MHz,DMSO-d 6)δ15.10(s,1H),8.29(d,J＝2.0Hz,1H),8.21(dd,J 1＝8.4Hz,J 2＝1.6Hz,1H),7.94(dd,J 1＝8.4Hz,J 2＝2.0Hz,1H)； 13C NMR(100MHz,DMSO-d 6)δ155.0,145.0,139.9,132.7,127.1,126.6,119.1.
1.2 preparation 3-(3-bromopropyl)-7-chlorobenzenes also [d] [1,2,3] triazine-4 (3H)-one
By 3.632g (20mmol) 7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one adds in 120ml acetone, add 24.24g (120mmol) 1 again, 3-dibromopropane and 5.520g (40mmol) salt of wormwood, stirring makes it into suspension, is heated to back flow reaction, and TLC follows the tracks of reaction process.After reaction terminates, remove solvent under reduced pressure, add 200ml water in residue, with dichloromethane extraction (80ml × 2), organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains light yellow solid 3.150g, yield 52%. 1H NMR(400MHz,DMSO-d 6)δ8.35–8.30(m,1H),8.25(d,J＝8.4Hz,1H),7.96(ddd,J 1＝8.4Hz,J 2＝2.0Hz,J 3＝0.8Hz,1H),4.50(t,J＝6.8Hz,2H),3.63(t,J＝6.4Hz,2H),2.42-2.33(m,2H)； 13C NMR(100MHz,DMSO-d 6)δ154.4,144.5,139.7,132.9,127.1,126.8,118.3,48.0,31.6,31.2.
1.3 preparation 2-cyanoimino-4-oxygen-1,3-thiazoles alkane-3-sylvite
Add in 120ml ethanol by 11.68g (80mmol) N-dimethyl cyanodithioimidoacrbonate and 4.220g (44mmol) volatile salt, stir and make it into suspension, be heated to 60 DEG C of reactions, TLC follows the tracks of reaction process.Treat that N-dimethyl cyanodithioimidoacrbonate reacts completely, add 7.15ml (80mmol) Methyl Thioglycolate and 8.960g (80mmol) the 50%KOH aqueous solution, be heated to back flow reaction 8 hours, be cooled to room temperature, suction filtration, filter cake absolute ethanol washing, dry, obtain light yellow solid 10.12g, yield 71%.
1.4 preparation 2-cyanoimino-3-(N-(3-(4-oxygen-7-chlorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group))-1,3-thiazoles alkane-4-ketone
By 0.606g (2mmol) 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one adds in 10mlDMF, add 0.332g (2mmol) potassiumiodide and 0.358g (2mmol) 2-cyanoimino-4-oxygen-1 again, 3-thiazolidine-3-sylvite, stirring makes it in suspension, is heated to 90 DEG C of reactions 10 hours, removes solvent under reduced pressure, add dilute hydrochloric acid, with dichloromethane extraction, organic phase saturated common salt water washing, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains light yellow solid 0.305g, yield 42%. 1h NMR (400MHz, DMSO-d 6) δ 8.35 (d, J=2.0Hz, 1H), 8.25 (dd, J 1=8.4Hz, J 2=2.0Hz, 1H), 7.97 (dd, J 1=8.4Hz, J 2=2.0Hz, 1H), 4.40 (t, J=7.2Hz, 2H), 4.29 (s, 2H), 3.74 (t, J=7.2Hz, 2H), 2.20-2.09 (m, 2H); 13c NMR (100MHz, DMSO-d 6) δ 179.6,172.9,154.8,144.9,140.3,133.6,127.7,127.3,118.6,114.0,47.3,40.8,36.1,26.0.HRMS (ES+) C 14h 11n 6o 2naS 35cl (M+Na) +, calculated value: 385.0250, measured value: 385.0258; C 14h 11n 6o 2naS 37cl (M+Na) +, calculated value: 387.0221, measured value: 387.0232.
Embodiment 2 2-cyanoimino-3-(N-(4-(4-oxygen-7-fluorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) butyl))-1,3-thiazoles alkane-4-ketone
The synthesis of target compound and the step 1.4 of embodiment 1 similar, difference is, with 3-(4-brombutyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Yellow solid, yield 53%. 1h NMR (400MHz, DMSO-d 6) δ 8.33 (dd, J 1=8.8Hz, J 2=5.6Hz, 1H), 8.07 (dd, J 1=8.8Hz, J 2=2.4Hz, 1H), 7.81 (td, J 1=8.8Hz, J 2=2.4Hz, 1H), 4.39 (t, J=6.8Hz, 2H), 4.31 (s, 2H), 3.65 (t, J=6.8Hz, 2H), 1.90-1.75 (m, 2H), 1.69-1.56 (m, 2H); 19f NMR (376MHz, DMSO-d 6) δ-101.9 (td, J 1=8.6Hz, J 2=5.6Hz) .HRMS (ES-) C 15h 12n 6o 2fS (M-H) –, calculated value: 359.0726, measured value: 359.0723.
Embodiment 3 2-cyanoimino-3-(N-(5-(4-oxygen-6-methyl benzo [d] [1,2,3] triazine-3 (4H)-Ji) amyl group))-1,3-thiazoles alkane-4-ketone
The synthesis of target compound and the step 1.4 of embodiment 1 similar, difference is, with 3-(5-bromine amyl group)-6-methyl benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Light yellow solid, yield 65%. 1h NMR (400MHz, DMSO-d 6) δ 8.09 (d, J=8.0Hz, 1H), 8.05 (s, 1H), 7.90 (d, J=8.4Hz, 1H), 4.35 (t, J=6.8Hz, 2H), 4.31 (s, 2H), 3.59 (t, J=6.8Hz, 2H), 2.55 (s, 3H), 1.89-1.73 (m, 2H), 1.67-1.50 (m, 2H), 1.41-1.24 (m, 2H); 13c NMR (100MHz, DMSO-d 6) δ 179.6,173.0,155.2,144.1,142.5,136.9,128.3,124.2,119.5,114.3,49.2,43.1,36.0,28.3,26.4,23.6,21.8.HRMS (ES-) C 17h 17n 6o 2s (M-H) –, calculated value: 369.1134, measured value: 369.1137.
Embodiment 4 2-cyanoimino-3-(N-(6-(4-oxygen-7-methoxyl group benzo [d] [1,2,3] triazine-3 (4H)-Ji) hexyl))-1,3-thiazoles alkane-4-ketone
The synthesis of target compound and the step 1.4 of embodiment 1 similar, difference is, with 3-(6-bromine hexyl)-7-methoxyl group benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Light yellow solid, yield 41%. 1h NMR (400MHz, DMSO-d 6) δ 8.15 (d, J=8.8Hz, 1H), 7.62 (d, J=2.4Hz, 1H), 7.47 (dd, J 1=8.8Hz, J 2=2.4Hz, 1H), 4.39-4.27 (m, 4H), 3.99 (s, 3H), 3.58 (t, J=7.2Hz, 2H), 1.86-1.73 (m, 2H), 1.59-1.46 (m, 2H), 1.40-1.24 (m, 4H); 13c NMR (100MHz, DMSO-d 6) δ 179.1,172.5,164.3,154.3,145.9,126.3,122.3,113.7,112.7,108.5,56.3,48.8,42.7,35.5,28.1,26.2,25.6,25.5.HRMS (ES+) C 18h 21n 6o 3s (M+H) +, calculated value: 401.1396, measured value: 401.1396.
Embodiment 5 2-cyanoimino-3-(N-(3-(4-oxygen-6-thiotolene is [3,2-d] [1,2,3] triazine-3 (4H)-Ji also) propyl group))-1,3-thiazoles alkane-4-ketone
The synthesis of target compound and the step 1.4 of embodiment 1 similar, difference is, with 3-(3-bromopropyl)-6-thiotolene also [3,2-d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Yellow solid, yield 18%.HRMS (ES+) C 13h 13n 6o 2s 2(M+H) +, calculated value: 349.0541, measured value: 349.0538.
Embodiment 6 2-cyanoimino-3-(N-(3-(4-oxygen-5,6,7,8-tetrahydro benzo [4,5] thiophene [2,3-d] [1,2,3] triazine-3 (4H)-Ji) propyl group))-1,3-thiazoles alkane-4-ketone
The synthesis of target compound and the step 1.4 of embodiment 1 similar, difference is, with 3-(3-bromopropyl)-5,6,7,8-tetrahydro benzo [4,5] thiophene [2,3-d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Light yellow solid, yield 30%.HRMS (ES+) C 16h 17n 6o 2s 2(M+H) +, calculated value: 389.0854, measured value: 389.0858.
Embodiment 7 2-cyanoimino-3-(N-(3-(4-sulphur-6-nitro benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group))-1,3-thiazoles alkane-4-ketone
The synthesis of target compound and the step 1.4 of embodiment 1 similar, difference is, with 6-nitro benzo [d] [1,2,3] triazine-4 (3H)-thioketones replaces 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Yellow solid, yield 28%.HRMS (ES-) C 14h 10n 7o 3s 2(M-H) –, calculated value: 388.0287, measured value: 388.0291.
The chloro-1-of embodiment 8 5-(4-(4-oxygen-7-trifluoromethoxy benzo [d] [1,2,3] triazine-3 (4H)-Ji) butyl) indoline-2,3-diketone
3-(4-brombutyl)-7-trifluoromethoxy benzo [d] [1,2,3] 3-(3-bromopropyl)-7-chlorobenzene also [d] [1 in the preparation method of triazine-4 (3H)-one and embodiment 1,2,3] preparation of triazine-4 (3H)-one is similar, difference is, with 7-trifluoromethoxy benzo [d] [1,2,3] triazine-4 (3H)-one replaces 7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one, 1,3-dibromopropane is replaced with Isosorbide-5-Nitrae-dibromobutane.
By 0.732g (2mmol) 3-(4-brombutyl)-7-trifluoromethoxy benzo [d] [1,2,3] triazine-4 (3H)-one adds in 15ml DMF, add 0.399g (2.2mmol) 5-chlorisatide and 0.414g (3mmol) salt of wormwood again, stirring makes it in suspension, be heated to 80 DEG C of reactions 8 hours, remove solvent under reduced pressure, add water, with dichloromethane extraction, organic phase saturated common salt water washing, through anhydrous sodium sulfate drying, concentrated, post is separated, obtain yellow solid 0.486g, yield 52%.HRMS (ES+) C 20h 15n 4o 4f 3 35cl (M+H) +, calculated value: 467.0734, measured value: 467.0738; C 20h 15n 4o 4f 3 37cl (M+H) +, calculated value: 469.0704, measured value: 469.0768.
Embodiment 9 1-(4-(4-oxygen-7-nitro benzo [d] [1,2,3] triazine-3 (4H)-Ji) butyl) spiral shell [indoline-3,2'-[1,3] dioxolane]-2-ketone
9.1 prepare spiral shell [indoline-3,2'-[1,3] dioxolane]-2-ketone
2.94g (20mmol) isatin, 22ml ethylene glycol and 0.38g (1mmol) p-methyl benzenesulfonic acid are added in 160ml toluene, is heated to back flow reaction 12 hours.Be cooled to room temperature, remove solvent under reduced pressure, add saturated aqueous sodium carbonate, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains light yellow needles 2.636g, yield 69%. 1H NMR(400MHz,DMSO-d 6)δ10.43(s,1H),7.37-7.28(m,2H),7.01(td,J 1＝7.6Hz,J 2＝0.8Hz,1H),6.83(d,J＝7.6Hz,1H),4.40-4.30(m,2H),4.30-4.20(m,2H)； 13C NMR(100MHz,DMSO-d 6)δ174.4,142.8,131.6,124.9,124.6,122.3,110.5,101.6,65.4.
9.2 preparation 1-(4-(4-oxygen-7-nitro benzo [d] [1,2,3] triazine-3 (4H)-Ji) butyl) spiral shell [indoline-3,2'-[1,3] dioxolane]-2-ketone
3-(4-brombutyl)-7-nitro benzo [d] [1,2,3] 3-(3-bromopropyl)-7-chlorobenzene also [d] [1 in the preparation method of triazine-4 (3H)-one and embodiment 1,2,3] preparation of triazine-4 (3H)-one is similar, difference is, with 7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one replaces 7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one, 1,3-dibromopropane is replaced with Isosorbide-5-Nitrae-dibromobutane.
By 0.327g (1mmol) 3-(4-brombutyl)-7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one adds in 10mlDMF, add 0.210g (1.1mmol) spiral shell [indoline-3 again, 2'-[1,3] dioxolane]-2-ketone and 0.207g (1.5mmol) salt of wormwood, stir and make it in suspension, be heated to 80 DEG C of reactions 10 hours.Be cooled to room temperature, remove solvent under reduced pressure, add water, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains yellow solid 0.323g, yield 74%. 1h NMR (400MHz, DMSO-d 6) δ 8.90 (d, J=2.0Hz, 1H), 8.59 (dd, J 1=8.8Hz, J 2=2.0Hz, 1H), 8.46 (d, J=8.8Hz, 1H), 7.44-7.32 (m, 2H), 7.15-7.03 (m, 2H), 4.44 (t, J=6.8Hz, 2H), 4.39-4.30 (m, 2H), 4.30-4.22 (m, 2H), 3.66 (t, J=6.8Hz, 2H), 1.93-1.78 (m, 2H), 1.77-1.61 (m, 2H); 13cNMR (100MHz, DMSO-d 6) δ 172.5,153.9,151.3,143.7,143.4,131.7,127.2,126.2,124.6,124.1,123.4,123.2,122.9,109.5,101.4,65.5,49.0,38.5,25.4,23.8.HRMS (ES-) C 21h 18n 5o 6(M-H) –, calculated value: 436.1257, measured value: 436.1260.
Embodiment 10 1-(4-(4-oxygen-7-vinyl benzo [d] [1,2,3] triazine-3 (4H)-Ji) butyl)-6-bromine spiral shell [indoline-3,2'-[1,3] dioxane]-2-ketone
The synthesis of target compound and the step 9.2 of embodiment 9 similar, difference is, with 3-(4-brombutyl)-7-vinyl benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(4-brombutyl)-7-vinyl benzo [d] [1,2,3] triazine-4 (3H)-one, with 6-bromine spiral shell [indoline-3,2'-[1,3] dioxane]-2-ketone replacement spiral shell [indoline-3,2'-[1,3] dioxolane]-2-ketone.White solid, yield 88%.HRMS (ES+) C 24h 24n 4o 4 79br (M+H) +, calculated value: 511.0981, measured value: 511.0985; C 24h 24n 4o 4 81br (M+H) +, calculated value: 513.0960, measured value: 513.0958.
Embodiment 11 3-((1-(4-p-methoxy-phenyl)-1H-1,2,3-triazole-4-yl) methyl) benzo [d] [1,2,3] triazine-4 (3H)-one
11.1 preparation 3-(2-propine-1-base) benzo [d] [1,2,3] triazine-4 (3H)-one
By 7.350g (50mmol) benzo [d] [1,2,3] triazine-4 (3H)-one and 8.28g (60mmol) salt of wormwood add in 200ml acetone, stirring makes it in suspension, add 8.925g (75mmol) 3-propargyl bromide, be heated to 50 DEG C of reactions 8 hours.Be cooled to room temperature, remove solvent under reduced pressure, add water, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains yellow solid 6.013g, yield 65%. 1H NMR(400MHz,DMSO-d 6)δ8.28(d,J＝7.6Hz,1H),8.24(d,J＝8.4Hz,1H),8.13(t,J＝7.6Hz,1H),7.97(t,J＝7.6Hz,1H),5.21(d,J＝2.4Hz,2H),3.43(t,J＝2.5Hz,1H)； 13C NMR(100MHz,DMSO-d 6)δ154.1,143.6,135.7,133.3,128.2,124.6,119.3,78.1,75.6,38.8.
11.2 preparation 3-((1-(4-p-methoxy-phenyl)-1H-1,2,3-triazole-4-yl) methyl) benzo [d] [1,2,3] triazine-4 (3H)-one
0.295g (2.4mmol) 4-anisidine is added in 5ml acetonitrile, be down to 0 DEG C, add 0.371g (3.6mmol) nitrous acid special butyl ester and 0.331g (2.88mmol) TMSA successively, stir 10 minutes at 0 DEG C, reaction is continued 1 hour under being placed on room temperature, add 0.296g (1.6mmol) 3-(2-propine-1-base) benzo [d] [1 more successively, 2, 3] triazine-4 (3H)-one, 0.036g (0.192mmol) cuprous iodide and 0.34ml (2.4mmol) triethylamine, add 5ml acetonitrile, react 2 hours under room temperature.In reaction solution, add proper silica gel, remove solvent under reduced pressure, post is separated, and obtains yellow solid 0.278g, yield 52%. 1h NMR (400MHz, CDCl 3) δ 8.34 (dd, J 1=8.0Hz, J 2=0.8Hz, 1H), 8.16 (d, J=8.0Hz, 1H), 8.09 (s, 1H), 7.98-7.92 (m, 1H), 7.84-7.77 (m, 1H), 7.63-7.56 (m, 2H), 7.02-6.96 (m, 2H), 5.85 (s, 2H), 3.85 (s, 3H); 13c NMR (100MHz, CDCl 3) δ 159.9,155.4,144.4,142.8,135.0,132.5,130.4,128.5,125.0,122.3,122.1,119.9,114.7,55.6,45.4.HRMS (ES+) C 17h 15n 6o 2(M+H) +, calculated value: 335.1256, measured value: 335.1251.
Embodiment 12 3-(2-(1-(the 4-tertiary butyl) phenyl-1H-1,2,3-triazole-4-yl) ethyl)-7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one
The synthesis of target compound and the step 11.2 of embodiment 11 similar, difference is, 4-anisidine is replaced with 4-tertiary butyl aniline, with 3-(3-butine-1-base)-7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(2-propine-1-base) benzo [d] [1,2,3] triazine-4 (3H)-one.Light yellow solid, yield 45%.HRMS (ES-) C 21h 20n 7o 3(M-H) –, calculated value: 418.1628, measured value: 418.1631.
Embodiment 13 3-(3-((5-cyclopropyl-1,3,4-thiadiazoles-2-base) sulphur) propyl group)-7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one
3-(3-bromopropyl)-7-nitro benzo [d] [1,2,3] in the preparation method of triazine-4 (3H)-one and embodiment 1, the preparation of 3-(3-bromopropyl)-7-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one is similar, difference is, 7-chlorobenzene also [d] [1 is replaced by 7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one, 2,3] triazine-4 (3H)-one.
By 0.626g (2mmol) 3-(3-bromopropyl)-7-nitro benzo [d] [1,2,3] triazine-4 (3H)-one, 0.474g (3mmol) 5-cyclopropyl-2-dimercaptothiodiazole and 0.331g (2.4mmol) salt of wormwood, add in 30ml acetone, stirring makes it, in suspension, to be heated to back flow reaction 8 hours.Be cooled to room temperature, remove solvent under reduced pressure, add water, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains yellow solid 0.624g, yield 80%.HRMS (ES-) C 15h 13n 6o 3s 2(M-H) –, calculated value: 389.0491, measured value: 389.0496.
Embodiment 14 3-(3-((6-methoxyl group benzo [d] oxazole-2-base) sulphur) propyl group)-4-oxygen-3,4-dihydrobenzo [d] [1,2,3] triazine-6-sulphonamide
The synthesis of target compound and the step of embodiment 13 similar, difference is, with 3-(3-bromopropyl)-6-amino-sulfonyl benzo [d] [1, 2, 3] triazine-4 (3H)-one replaces 7-chlorobenzene also [d] [1, 2, 3] triazine-4 (3H)-one, difference is, with 6-amino-sulfonyl benzo [d] [1, 2, 3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-nitro benzo [d] [1, 2, 3] triazine-4 (3H)-one, 5-cyclopropyl-2-dimercaptothiodiazole is replaced with 6-methoxyl group benzo [d] oxazole-2-mercaptan.Yellow solid, yield 71%.HRMS (ES+) C 18h 18n 5o 5s 2(M+H) +, calculated value: 448.0749, measured value: 448.0755.
Embodiment 15 3-(4-oxygen benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group benzo [d] [1,2,3] thiadiazoles-7-carboxylicesters
15.1 preparation 3-(3-hydroxypropyl) benzo [d] [1,2,3] triazine-4 (3H)-one
7-fluorobenzene also the preparation method of [d] [1,2,3] triazine-4 (3H)-one and the step 1.1 of embodiment 1 similar, difference is, replaces 2-amino-4-chloro-benzoic acid with 2-amino-4-fluorobenzoic acid.
By 0.330g (2mmol) 7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one and 0.552g (4mmol) salt of wormwood, add in 30ml acetone, stirring makes it in suspension, add 0.417g (3mmol) 3-bromopropyl alcohol, be heated to back flow reaction 6 hours.Be cooled to room temperature, remove solvent under reduced pressure, add water, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains buff white solid 0.317g, yield 71%.HRMS (ES+) C 10h 11n 3o 2f (M+H) +, calculated value: 224.0835, measured value: 224.0841.
15.2 prepare benzo [d] [1,2,3] thiadiazoles-7-carbonyl chlorine
3.780g (21mmol) benzo [d] [1,2,3] thiadiazoles-7-carboxylic acid is added in 40ml sulfur oxychloride, is heated to back flow reaction 8 hours.Be cooled to room temperature, remove the sulfur oxychloride that unreacted is complete under reduced pressure, obtain light yellow solid 3.552g, be unprocessedly directly used in next step.
15.3 preparation 3-(4-oxygen-7-fluorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group benzo [d] [1,2,3] thiadiazoles-7-carboxylicesterss
By 0.446g (2mmol) 3-(3-hydroxypropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one dissolves in 20ml methylene dichloride, add 0.31ml (2.2mol) triethylamine, 0.478g (2.4mmol) benzo [d] [1 is added under room temperature, 2,3] the 20ml dichloromethane solution of thiadiazoles-7-carbonyl chlorine.Finish, continue reaction under room temperature 4 hours, in reaction solution, add saturated sodium bicarbonate aqueous solution, fully stir, separate organic phase, aqueous phase uses dichloromethane extraction again, merges all organic phases, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains white solid 0.246g, yield 32%. 1h NMR (400MHz, DMSO-d 6) δ 8.98 (d, J=8.4Hz, 1H), 8.23-8.14 (m, 2H), 7.91 (dd, J 1=8.8Hz, J 2=2.0Hz, 1H), 7.80 (t, J=8.0Hz, 1H), 7.69 (td, J 1=8.8Hz, J 2=2.4Hz, 1H), 4.63 (t, J=6.0Hz, 2H), 4.55 (t, J=5.6Hz, 2H), 2.46-2.35 (m, 2H); 19f NMR (376MHz, DMSO-d 6) δ-102.0 (td, J 1=8.6Hz, J 2=5.6Hz) .HRMS (ES+) C 17h 13n 5o 3fS (M+H) +, calculated value: 386.0723, measured value: 386.0724.
Embodiment 16 3-(4-oxygen-5-bromobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group benzo [d] [1,2,3] thiadiazoles-7-carboxylicesters
The synthesis of target compound and the step 15.3 of embodiment 15 similar, difference is, with 3-(3-hydroxypropyl)-5-bromobenzene also [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-hydroxypropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one.White solid, yield 26%. 1h NMR (400MHz, DMSO-d 6) δ 8.99 (d, J=8.4Hz, 1H), 8.27 (s, 1H), 8.20 (d, J=7.2Hz, 1H), 8.01 (d, J=8.4Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.81 (t, J=8.0Hz, 1H), 4.63 (t, J=6.4Hz, 2H), 4.56 (t, J=5.6Hz, 2H), 2.47-2.36 (m, 2H); 13c NMR (100MHz, DMSO-d 6) δ 164.0,158.3,154.5,144.4,139.2,135.6,130.7,129.9,128.6,128.1,126.5,122.3,118.3,64.4,47.1,27.0.HRMS (ES+) C 17h 12n 5o 3naS 79br (M+Na) +, calculated value: 467.9742, measured value: 467.9744; C 17h 12n 5o 3naS 81br (M+Na) +, calculated value: 469.9721, measured value: 469.9716.
Embodiment 17 3-(4-oxygen-6-trifluoromethyl benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group benzo [d] [1,2,3] thiadiazoles-7-carboxylicesters
The synthesis of target compound and the step 15.3 of embodiment 15 similar, difference is, with 3-(3-hydroxypropyl)-6-trifluoromethyl benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-hydroxypropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one.White solid, yield 16%. 1h NMR (400MHz, DMSO-d 6) δ 9.19 (t, J=5.2Hz, 1H), 8.88 (d, J=8.4Hz, 1H), 8.53-8.42 (m, 2H), 8.42-8.31 (m, 2H), 7.90 (t, J=7.6Hz, 1H), 4.48 (t, J=6.8Hz, 2H), 3.48-3.40 (m, 2H), 2.00-1.90 (m, 2H), 1.78-1.65 (m, 2H); 19f NMR (376MHz, DMSO-d 6) δ-61.5 (s) .HRMS (ES+) C 19h 16n 6o 2f 3s (M+H) +, calculated value: 449.1008, measured value: 449.1006.
Embodiment 18 N-(3-(4-oxygen-7-fluorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group) benzo [d] [1,2,3] thiadiazoles-7-acid amides
18.1 preparation 2-(3-(4-oxygen-7-fluorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group) isoindoline-1,3-diketone
By 0.572g (2mmol) 3-(3-bromopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one, 0.353g (2.4mmol) phthalic imidine and 0.331g (2.4mmol), add in 10ml DMF, stirring makes it in suspension, is heated to 60 DEG C of reactions 3 hours.Be cooled to room temperature, remove solvent under reduced pressure, add water, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, concentrated, post is separated, and obtains beige solid 0.598g, yield 85%.HRMS (ES+) C 18h 14n 4o 3f (M+Na) +, calculated value: 353.1050, measured value: 353.1053.
18.2 preparation 3-(3-aminopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one
By 0.352g (1mmol) 2-(4-(4-oxygen benzo [d] [1,2,3] triazine-3 (4H)-Ji) butyl) isoindoline-1,3-diketone, add in the mixed solvent of 10ml methylene dichloride and 10ml ethanol, be heated to back flow reaction 12 hours.Be cooled to room temperature, remove solvent under reduced pressure, in residue, add saturated aqueous sodium carbonate, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, removes solvent under reduced pressure, obtains yellow oily liquid 0.191g, is directly used in next step without purification.
18.3 preparation N-(3-(4-oxygen-7-fluorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group) benzo [d] [1,2,3] thiadiazoles-7-acid amides
By 0.222g (1mmol) 3-(3-aminopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one is dissolved in 10ml methylene dichloride, add 0.15ml (1.1mmol) triethylamine, 0.259g (1.3mmol) benzo [d] [1 is added under room temperature, 2,3] the 10ml dichloromethane solution of thiadiazoles-7-carbonyl chlorine.Finish, continue reaction under room temperature 5 hours, in reaction solution, add saturated sodium bicarbonate aqueous solution, fully stir, separate organic phase, aqueous phase uses dichloromethane extraction again, merges all organic phases, through anhydrous sodium sulfate drying, concentrated, post is separated, and obtains beige solid 0.131g, yield 34%. 1h NMR (400MHz, DMSO-d 6) δ 9.24 (t, J=5.2Hz, 1H), 8.88 (d, J=8.4Hz, 1H), 8.42 (d, J=7.2Hz, 1H), 8.26 (dd, J 1=8.8Hz, J 2=5.6Hz, 1H), 7.97 (dd, J 1=8.8Hz, J 2=2.0Hz, 1H), 7.90 (t, J=7.6Hz, 1H), 7.74 (td, J 1=8.8Hz, J 2=2.0Hz, 1H), 4.50 (t, J=7.2Hz, 2H), 3.58-3.48 (m, 2H), 2.27-2.16 (m, 2H); 19f NMR (376MHz, DMSO-d 6) δ-102.0 (td, J 1=8.6Hz, J 2=5.6Hz) .HRMS (ES+) C 17h 14n 6o 2fS (M+H) +, calculated value: 385.0883, measured value: 385.0885.
Embodiment 19 N-(4-(4-oxygen-7-bromobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) butyl) benzo [d] [1,2,3] thiadiazoles-7-acid amides
The synthesis of target compound and the step 18.2 of embodiment 18 similar, difference is, with 3-(4-aminobutyl)-7-bromobenzene also [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-aminopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one.Beige solid, yield 25%. 1h NMR (400MHz, DMSO-d 6) δ 9.18 (t, J=4.8Hz, 1H), 8.88 (d, J=8.0Hz, 1H), 8.44 (d, J=7.2Hz, 1H), 8.39 (s, 1H), 8.10 (d, J=8.4Hz, 1H), 8.03 (d, J=8.8Hz, 1H), 7.89 (t, J=8.0Hz, 1H), 4.42 (t, J=6.8Hz, 2H), 3.48-3.39 (m, 2H), 1.98-1.87 (m, 2H), 1.73-1.62 (m, 2H); 13c NMR (100MHz, DMSO-d 6) δ 163.5,158.1,154.3,144.5,138.3,135.7,130.1,128.6,127.8,126.7,126.6,126.3,118.3,49.0,25.8,25.6.HRMS (ES+) C 18h 16n 6o 2s 79br (M+H) +, calculated value: 459.0239, measured value: 459.0241; C 18h 16n 6o 2s 81br (M+H) +, calculated value: 461.0218, measured value: 461.0221.
Embodiment 20 N-(3-(5-chloro-4-oxygen benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group)-5-methyl isophthalic acid, 2,3-thiadiazoles-4-acid amides
The synthesis of target compound and the step 18.2 of embodiment 18 similar, difference is, with 3-(3-aminopropyl)-5-chlorobenzene also [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-aminopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one, uses 5-methyl isophthalic acid, 2,3-thiadiazoles-4-carbonyl chloro is for benzo [d] [1,2,3] thiadiazoles-7-carbonyl chlorine.White solid, yield 41%.HRMS (ES+) C 14h 13n 6o 2naS 35cl (M+Na) +, calculated value: 387.0407, measured value: 387.0411; C 14h 13n 6o 2naS 37cl (M+Na) +, calculated value: 389.0377, measured value: 389.0380.
Embodiment 21 1-(6-methoxyl group benzo [d] thiazol-2-yl)-3-(3-(4-oxygen-7-trifluoromethyl benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group) thiocarbamide
3-(3-aminopropyl)-7-trifluoromethyl benzo [d] [1,2,3] 3-(3-aminopropyl)-7-fluorobenzene also [d] [1 in the preparation method of triazine-4 (3H)-one and embodiment 18,2,3] preparation of triazine-4 (3H)-one is similar, difference is, with 3-(3-bromopropyl)-7-trifluoromethyl benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one.The preparation method of 2-isothiocyanate group-6-methoxyl group benzo [d] thiazole as described in " WO2014117677 ", can be obtained by 2-amino-6-methoxyl group benzo [d] thiazole.
By 0.136g (0.5mmol) 3-(3-aminopropyl)-7-trifluoromethyl benzo [d] [1,2,3] triazine-4 (3H)-one is dissolved in 2ml acetonitrile, add 0.111g (0.5mmol) 2-isothiocyanate group-6-methoxyl group benzo [d] thiazole, stirred at ambient temperature, TLC follows the tracks of reaction process.After reaction terminates, suction filtration, filter cake ethyl alcohol recrystallization, obtains brownish-yellow powder shape solid 0.191g, yield 77%.HRMS (ES+) C 20h 18n 6o 2f 3s 2(M+H) +, calculated value: 495.0885, measured value: 495.0882.
Embodiment 22 1-(benzo [d] isoxazole-3-base)-3-(3-(4-oxygen-8-methoxyl group benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group) thiocarbamide
The synthesis of target compound and the step of embodiment 21 similar, difference is, with 3-(3-aminopropyl)-8-methoxyl group benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-aminopropyl)-7-trifluoromethyl benzo [d] [1,2,3] triazine-4 (3H)-one, 3-(3-aminopropyl)-7-trifluoromethyl benzo [d] [1 is replaced with 3-isothiocyanate group benzo [d] isoxazole, 2,3] triazine-4 (3H)-one.Yellow powdery solid, yield 71%.HRMS (ES+) C 19h 18n 6o 3naS (M+Na) +, calculated value: 433.1059, measured value: 433.1062.
Embodiment 23 N-((3-(4-oxygen-8-chlorobenzene is [d] [1,2,3] triazine-3 (4H)-Ji also) propyl group) thiocarbamoyl)-2-(trifluoromethoxy) benzamide
23.1 preparation 2-(trifluoromethoxy) benzoyl isothiocyanate
The preparation method of 2-(trifluoromethoxy) Benzoyl chloride and the step 15.2 of embodiment 15 similar, difference is, with 2-(trifluoromethoxy) phenylformic acid replace benzo [d] [1,2,3] thiadiazoles-7-carboxylic acid.
1.8g (8mmol) 2-(trifluoromethoxy) Benzoyl chloride is dissolved in 20ml methylene dichloride, add 0.912g (12mmol) ammonium thiocyanate, add 0.144g PEG-400, stirred at ambient temperature 1 hour, suction filtration, concentrates filtrate, through dodging column purification, obtain yellow oily liquid 1.581g, be directly used in next step reaction.
23.2 preparation N-((3-(4-oxygen benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group) thiocarbamoyl)-2-(trifluoromethoxy) benzamide
3-(3-aminopropyl) benzo [d] [1,2,3] 3-(3-aminopropyl)-7-fluorobenzene also [d] [1 in the preparation method of triazine-4 (3H)-one and embodiment 18,2,3] preparation of triazine-4 (3H)-one is similar, difference is, with benzo [d] [1,2,3] triazine-4 (3H)-one replaces 3-(3-bromopropyl)-7-fluorobenzene also [d] [1,2,3] triazine-4 (3H)-one.
By 0.102g (0.5mmol) 3-(3-aminopropyl) benzo [d] [1; 2; 3] triazine-4 (3H)-one is dissolved in 2ml acetonitrile; add 0.124g (0.5mmol) 2-(trifluoromethoxy) benzoyl isothiocyanate; stirred at ambient temperature, TLC follows the tracks of reaction process.After reaction terminates, suction filtration, concentrates filtrate, and post is separated, and obtains light yellow solid 0.153g, yield 68%. 1h NMR (400Mz, CDCl 3) δ 10.77 (br, 1H), 9.57 (br, 1H), 8.32 (d, J=7.6Hz, 1H), 7.92-7.88 (m, 3H), 7.82 (t, J=7.2Hz, 1H), 7.64 (t, J=7.2Hz, 1H), 7.46 (t, J=7.2Hz, 1H), 7.36 (d, J=7.2Hz, 1H), 4.81 (t, J=6.0Hz, 2H), 3.92-3.91 (m, 2H), 2.73-2.59 (m, 2H); 13c NMR (100Mz, CDCl 3) δ 180.2,167.8,163.9,146.3,146.0,134.5,134.3,133.5,131.6,127.5,126.4,125.4,125.3,124.0,120.2 (q, 1j cF=260.0Hz), 117.8,67.1,42.27,27.9.HRMS (ES+) C 19h 17f 3n 5o 3s (M+H) +, calculated value: 452.1004, measured value: 452.1004.
Embodiment 24 3-(5-methyl isophthalic acid, 2,4-oxadiazole-3-base)-N-((3-(3-oxygen-7-nitro benzo [d] [1,2,3] triazine-3 (4H)-Ji) propyl group) thiocarbamoyl) benzamide
The preparation of target compound and the step 23.2 of embodiment 23 similar; difference is; with 3-(3-aminopropyl)-7-nitro benzo [d] [1; 2; 3] triazine-4 (3H)-one replaces 3-(3-aminopropyl) benzo [d] [1; 2; 3] triazine-4 (3H)-one; with 3-(5-ethyl-1; 2,4-oxadiazole-3-base) benzoyl isothiocyanate replacement 2-(trifluoromethoxy) benzoyl isothiocyanate.Light yellow solid, yield 65%.HRMS (ES –) C 22h 19n 8o 5s (M – H) –, calculated value: 507.1199, measured value: 507.1194.
The eelworm-killing activity test of embodiment 25 the compounds of this invention
Root knot nematode belongs to Nematoda, Tylenchida (Tylenchida), pad sword suborder, different skin Superfamily, Heteroderidae (Heteroderidea), root knot nematode subfamily (Meloidogyninae), Meloidogyne, is a kind ofly to endanger serious plant nematode.
With Meloidogyne incognita (Meloidogyne incognita) for tested object, be for examination host with cucumber seedling, adopt the test of test tube planting method.
Operating process: will treat that test agent is made into liquid by desired concn stand-by, and get out enough root knot nematode second instar larvaes.The cucumber seedling in one week age is planted after in test tube, in test tube, adds the liquid prepared in right amount, and access about 2000 larvas to often propping up in test tube.Test tube is placed in 20 ~ 25 DEG C, cultivates under 10 h light, 20 days " Invest, Then Investigate " results, counts the root knot number on every strain plant root.Each sample revision test 3 times, each sample of each test does 4 re-treatments.
Take distilled water as blank, it is negative control that distilled water adds root knot nematode, with fenamiphos and abamectin solution for positive control.
Classification (see table 1) is carried out, statistics inhibiting rate by root knot quantity.Statistics is in table 2 ~ 6.
Inhibiting rate (%)=(negative control goals for-test group goals for)/negative control goals for × 100%
Table 1
grade scale:
0:0-5 root knot;
5:6-10 root knot;
10:11-20 root knot;
20: more than 20 root knots.
The eelworm-killing activity of table 2 formula (II) compound
The eelworm-killing activity of table 3 formula (III) compound
The eelworm-killing activity of table 4 formula (IV) compound
The eelworm-killing activity of table 5 formula (V) compound
The eelworm-killing activity of table 6 formula (VI) compound
In above table, for "-", Y represents that Y is covalent linkage, M is that "/" represents that M is nothing.
The composition of embodiment 26 containing the compounds of this invention nematocides
(a) microemulsion
Prepare following component in proportion: any one compound (table 2 ~ 6) in 5.0% (weight percent, lower same) Compound II per-1 ~ VI-36; 30.0% PVP-VA multipolymer; 30.0% alkyl polyglycoside; 15.0% olein; 20.0% water.
(b) wettable powder
Prepare following component in proportion: any one compound (table 2 ~ 6) in 65.0% Compound II per-1 ~ VI-36; 2.0% dodecyl phenol polyglycol ether; 4.0% sodium lignosulfonate; 6.0% lagoriolite; 23.0% montmorillonite (burnt).
(c) seed treatment agent
Prepare following component in proportion: any one compound (table 2 ~ 6) in 20.00% Compound II per-1 ~ VI-36; 5.00% PVP-VA multipolymer; 5.00% montanic acid wax; 1.00% calcium lignin sulphonate; 1.00% polyoxyethylene/polyoxypropylene block copolymers; 2.00% stearyl alcohol (POE 20); 0.20% poly organic silicon; 0.05% tinting material orchil; 65.75% water.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (10)

1. there is a compound for structure shown in general formula (I), or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science:
In formula:
X is O or S;
Y is O, S, S (=O), S (=O) 2, NH or covalent linkage;
Q is carbonyl, thiocarbonyl group-amino, thiocarbonyl group-amino-carbonyl or covalent linkage;
When L is substituted or unsubstituted C 1-6alkylidene group, substituted or unsubstituted C 1-6halogeno alkylen, substituted or unsubstituted C 2-6alkenylene, substituted or unsubstituted C 2-6haloalkenediyl, substituted or unsubstituted C 2-6alkynylene, substituted or unsubstituted C 2-6halo alkynylene, substituted or unsubstituted C 3-7cycloalkylidene, substituted or unsubstituted C 5-7mix fragrant two rings or three ring ring systems in sub-cycloalkenyl group, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylidene, substituted or unsubstituted 5 yuan or 6 yuan of sub-heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan Asias, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R " time; M is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R "; Or
When L is substituted or unsubstituted C 1-6alkyl, substituted or unsubstituted C 1-6haloalkyl, substituted or unsubstituted C 2-6thiazolinyl, substituted or unsubstituted C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, substituted or unsubstituted C 2-6halo alkynyl, substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R " time; M is nothing;
And A is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R ";
G represents the substituting group on any one or more positions of A, and G is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, R', OR', Si (R') 3, NR'R ", C (O) R', C (O) OR', C (O) NR'R ", SR', S (O) mr 1, S (O) 2nR'R ", OC (O) R 1, OC (O) NR'R ", OS (O) 2r 1, OS (O) 2nR'R ", N (R 2) C (O) R 1, N (R 2) C (O) NR'R ", N (R 2) S (O) 2r 1or N (R 2) S (O) 2nR'R ";
Wherein, R', R " is H, C independently of one another 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, hydroxyl, hydroxyl C 1-4alkyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4;
R 1for C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4;
R 2for H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl or C 2-6halo alkynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, C 2-6halo alkynyl, OR 3, NR 3r 4, C (O) R 3, C (O) OR 3, C (O) NR 3r 4, SR 3, S (O) mr 5, S (O) 2nR 3r 4, OC (O) R 5, OC (O) NR 3r 4, OS (O) 2r 5, OS (O) 2nR 3r 4, N (R 6) C (O) R 5, N (R 6) C (O) NR 3r 4, N (R 6) S (O) 2r 5or N (R 6) S (O) 2nR 3r 4;
Wherein, R 3, R 4, R 6be H, C independently of one another 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl or C 2-6halo alkynyl;
R 5for C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl or C 2-6halo alkynyl;
M is 1 or 2;
N is 0,1,2,3,4 or 5.
2. compound as claimed in claim 1, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, it is characterized in that, described compound is selected from lower group:
Above-mentioned various in, as described in the appended claim 1, Y is O, S, S (=O), S (=O) in the definition of X, L, G, A, M and n 2or covalent linkage.
3. compound as claimed in claim 1 or 2, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, it is characterized in that, X is O or S.
4. compound as claimed in claim 1 or 2, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, is characterized in that,
L is substituted or unsubstituted C 1-6alkylidene group, substituted or unsubstituted C 1-6halogeno alkylen, substituted or unsubstituted C 2-6alkenylene, substituted or unsubstituted C 2-6haloalkenediyl, substituted or unsubstituted C 2-6alkynylene, substituted or unsubstituted C 3-7cycloalkylidene, substituted or unsubstituted C 5-7mix fragrant bicyclic ring system for sub-cycloalkenyl group, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylidene, substituted or unsubstituted 5 yuan or 6 yuan of sub-heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan Asias, and described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl; Or
L is substituted or unsubstituted C 1-6alkyl, substituted or unsubstituted C 1-6haloalkyl, substituted or unsubstituted C 2-6thiazolinyl, substituted or unsubstituted C 2-6haloalkenyl group, substituted or unsubstituted C 2-6alkynyl, substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
5. compound as claimed in claim 1 or 2, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, it is characterized in that, M is nothing; Or M is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, Trimethylsilanylethynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 14 yuan assorted fragrant two rings or three ring ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
6. compound as claimed in claim 1 or 2, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, it is characterized in that, A is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, and described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4halogenated alkoxy, phenoxy group, amidosulfonic acid base, amido-carbonyl, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
7. compound as claimed in claim 1 or 2, or acceptable salt in the optical isomer of described compound, cis-trans-isomer or Pesticide Science, it is characterized in that, G is H, C 1-6alkyl, C 1-6haloalkyl, C 2-6thiazolinyl, C 2-6haloalkenyl group, C 2-6alkynyl, Trimethylsilanylethynyl, or substituted or unsubstituted C 3-7cycloalkyl, substituted or unsubstituted C 5-7cycloalkenyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 yuan or 6 yuan of heterocyclic radicals or substituted or unsubstituted 8 yuan to 12 yuan assorted fragrant bicyclic ring systems, described replacement refers to that the one or more groups being selected from lower group replaced: halogen, cyano group, nitro, C 1-4alkyl, C 1-4haloalkyl, C 1-4alkoxyl group, C 1-4alkyl-carbonyl, C 1-4alkoxy-carbonyl, C 1-4alkyl amine group-carbonyl or phenyl amido-carbonyl.
8. an agricultural composition, is characterized in that, it comprises:
(1) acceptable salt or their combination in the optical isomer of the compound according to any one of claim 1-7 of 0.001-99.99 % by weight or described compound, cis-trans-isomer or Pesticide Science; And
(2) acceptable carrier and/or vehicle in Pesticide Science.
9. the purposes of acceptable salt or agricultural composition as claimed in claim 8 in the optical isomer of compound as claimed in claim 1 or described compound, cis-trans-isomer or Pesticide Science, it is characterized in that, for killing or prevent nematode or for the preparation of nematicidal agent composition.
10. the preparation method of acceptable salt in the optical isomer of compound as claimed in claim 1 or described compound, cis-trans-isomer or Pesticide Science, is characterized in that,
(A) described method comprises step:
(1) in inert solvent, formula (a) compound and two (trichloromethyl) carbonic ether (BTC) are carried out ring closure reaction, obtain formula (b) compound:
(2) in inert solvent, formula (b) compound and volatile salt are carried out ring-opening reaction, obtain formula (c) compound:
(3) in inert solvent, by formula (c) compound through diazotization reaction, ring closure reaction, formula (d) compound is obtained:
(4) in inert solvent, in the presence of a base, formula (d) compound and BrCH 2(CH 2) nbr reacts, and obtains formula (e) compound;
(5) in inert solvent, formula (e) compound and formula (f) compound or formula (p) compound (H-Y-Q-L-M) are reacted, thus obtain formula (I) compound:
Or (B) described method comprises step:
(4') in inert solvent, in the presence of a base, formula (d) compound and BrCH 2(CH 2) nc ≡ CH reacts, and obtains formula (g) compound:
(5') in inert solvent, formula (g) compound and formula (h) compound are reacted, thus obtain formula (I) compound:
Or (C) described method comprises step:
(4 ") in inert solvent, in the presence of a base, formula (d) compound and BrCH 2(CH 2) nyH reacts, and obtains formula (i) compound:
(formula (i) compound and formula (k) compound, in inert solvent, react by 5 "), thus obtain formula (I) compound:
Or (D) described method comprises step:
(5 " ') in inert solvent, in the presence of a base, formula (e) compound and formula (m) compound are reacted, then obtain formula (n) compound through deprotection:
(6) in inert solvent, formula (n) compound and formula (o) compound are reacted, thus obtain formula (I) compound:
Or (E) described method comprises step:
(6'), in inert solvent, formula (n) compound and formula (o') compound react, and obtain formula (I) compound:
Or (F) described method comprises step:
(5 " ") in inert solvent, in the presence of a base, formula (e) compound and formula (p) compound react, and obtain formula (I) compound:
Above-mentioned various in, the definition of X, Y, Q, L, M, A, G and n is as described in the appended claim 1.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016042435A1 (en) * 2014-09-19 2016-03-24 Isagro S.P.A. 1,3,4-thiadiazoles having a herbicidal activity, their agronomical compositions and relative use
CN106045922A (en) * 2016-06-12 2016-10-26 湘潭大学 2-(Amino) methylquinazolin-4(3H)-one compound and preparation method and application thereof
CN108084104A (en) * 2017-12-27 2018-05-29 温州大学 1,2,3- phentriazine -4（3H）The synthetic method of -one compound
CN108276352A (en) * 2018-03-13 2018-07-13 华东理工大学 A kind of nitrogen-containing heterocycle compound and its preparation method and purposes with eelworm-killing activity
JP2018525440A (en) * 2015-07-28 2018-09-06 アダム ミツキェヴィチ ユニバーシティ ファウンデーション Application of 7-carboxybenzo [1,2,3] thiadiazole amide as plant stimulant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240014948A (en) 2022-07-26 2024-02-02 한국화학연구원 Carboxamide derivative of triazinyl fused ring and nematicidal use thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES350392A1 (en) * 1967-02-14 1969-11-16 Philips Nv A method of preparing new benzotriazinones. (Machine-translation by Google Translate, not legally binding)
FR2094494A5 (en) * 1970-06-23 1972-02-04 Aries Robert Insecticidal chrysanthemic acid esters - with 3-hydroxymethyl -4-oxo-1, 2, 3-benzotriazine
US3709910A (en) * 1966-08-24 1973-01-09 Sumitomo Chemical Co Cyclopropanecarboxylic acid esters
WO2012154760A1 (en) * 2011-05-10 2012-11-15 Gilead Sciences, Inc. Fused heterocyclic compounds as sodium channel modulators
CN103965134A (en) * 2013-01-31 2014-08-06 华东理工大学 N, S-containing heterocyclic compound with nematicidal activity, preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1926075C3 (en) * 1969-05-22 1980-07-31 Cassella Ag, 6000 Frankfurt 3- (3-Amino-2-benzoxy-propyl) -6,7,8trimethoxy-3H-1 ^ 3-benzotriazin-4-one derivatives, their preparation and use

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3709910A (en) * 1966-08-24 1973-01-09 Sumitomo Chemical Co Cyclopropanecarboxylic acid esters
ES350392A1 (en) * 1967-02-14 1969-11-16 Philips Nv A method of preparing new benzotriazinones. (Machine-translation by Google Translate, not legally binding)
FR2094494A5 (en) * 1970-06-23 1972-02-04 Aries Robert Insecticidal chrysanthemic acid esters - with 3-hydroxymethyl -4-oxo-1, 2, 3-benzotriazine
WO2012154760A1 (en) * 2011-05-10 2012-11-15 Gilead Sciences, Inc. Fused heterocyclic compounds as sodium channel modulators
CN103965134A (en) * 2013-01-31 2014-08-06 华东理工大学 N, S-containing heterocyclic compound with nematicidal activity, preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CAROLINA MOURA ET AL.: "Rhenium(V) oxocomplexes with novel pyrazolyl-based N4- and N3S-donor chelators", 《DALTON TRANS.》 *
MACIEJ MASLYK ET AL.: "Multisite-directed inhibitors of protein kinase CK2: new challenges", 《MOL CELL BIOCHEM》 *
MAIK SCHUBERT ET AL.: "Maleimido-Functionalized NOTA Derivatives as Bifunctional Chelators for Site-Specific Radiolabeling", 《MOLECULES》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016042435A1 (en) * 2014-09-19 2016-03-24 Isagro S.P.A. 1,3,4-thiadiazoles having a herbicidal activity, their agronomical compositions and relative use
JP2018525440A (en) * 2015-07-28 2018-09-06 アダム ミツキェヴィチ ユニバーシティ ファウンデーション Application of 7-carboxybenzo [1,2,3] thiadiazole amide as plant stimulant
US11006632B2 (en) 2015-07-28 2021-05-18 Adam Mickiewicz University Foundation Application of 7-carboxybenzo[1,2,3]thiadiazole amides as plant stimulants
CN106045922A (en) * 2016-06-12 2016-10-26 湘潭大学 2-(Amino) methylquinazolin-4(3H)-one compound and preparation method and application thereof
CN108084104A (en) * 2017-12-27 2018-05-29 温州大学 1,2,3- phentriazine -4（3H）The synthetic method of -one compound
CN108276352A (en) * 2018-03-13 2018-07-13 华东理工大学 A kind of nitrogen-containing heterocycle compound and its preparation method and purposes with eelworm-killing activity

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