CN104530037B - Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof - Google Patents

Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof Download PDF

Info

Publication number
CN104530037B
CN104530037B CN201510031222.4A CN201510031222A CN104530037B CN 104530037 B CN104530037 B CN 104530037B CN 201510031222 A CN201510031222 A CN 201510031222A CN 104530037 B CN104530037 B CN 104530037B
Authority
CN
China
Prior art keywords
compound
formula
substituted
unsubstituted
inert solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201510031222.4A
Other languages
Chinese (zh)
Other versions
CN104530037A (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN201510031222.4A priority Critical patent/CN104530037B/en
Publication of CN104530037A publication Critical patent/CN104530037A/en
Priority to PCT/CN2016/071608 priority patent/WO2016116058A1/en
Application granted granted Critical
Publication of CN104530037B publication Critical patent/CN104530037B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • A01N43/90—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
    • 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<
    • A01N47/36—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
    • 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
    • A01N47/40—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
    • C07D417/12—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • 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, a preparation method and application thereof. Specifically, the invention discloses a compound with a formula (I) or an optical isomer, a cis-trans isomer or an agriculturally and pharmaceutically acceptable salt thereof, and a preparation method thereof. The invention also discloses a compound containing the compoundAgricultural compositions and uses thereof. The above compounds have excellent nematicidal activity.

Description

Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticides. In particular to a triazine heterocyclic compound with nematicidal activity, a preparation method and application thereof.
Background
Plant parasitic nematodes are pathogenic microorganisms with great harm, have wide distribution range, various varieties and strong environment adaptability, can be parasitic in roots, stems, leaves, seeds, buds and fruits of plants, can cause mechanical damage to the host plants through feeding activities, and graze the nutrition of the host plants, particularly the secretion of esophageal glands of the plants can cause a series of pathological changes of the host plants, and can infect the host plants together with other pathogenic microorganisms to cause compound diseases and yield loss. The agricultural loss caused by plant parasitic nematodes is over 1000 billion dollars each year in the world, and the development of agricultural economy is severely restricted.
There are many agricultural means for preventing and controlling nematodes, and chemical prevention is the main point at present. The widely used chemical nematocides are mainly high-toxicity and high-residue organophosphorus or carbamate pesticides, such as cadusafos, ethoprophos, fenamiphos, fosthiazate, aldicarb, oxamyl, carbofuran and the like, have low safety to human beings and other non-target organisms, and can cause pollution to soil, water sources and agricultural products to different degrees. In addition, because of single variety, the nematicide is used excessively and frequently, so that serious drug resistance is caused, and the control difficulty of the nematodes is increased day by day. Therefore, the search for a chemical nematicide with novel structure, high efficiency, low toxicity and good environmental compatibility is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
One of the purposes of the invention is to provide a chemical nematicide with high efficiency, low toxicity and good environmental compatibility and a novel structure, and a preparation method and application thereof.
In a first aspect of the present invention, there is provided a compound having a structure represented by general formula (I), or an optical isomer, cis-trans isomer, or agriculturally pharmaceutically acceptable salt of said compound:
Figure BDA0000659782670000011
in the formula:
x is O or S;
y is O, S, S (═ O)
Figure BDA0000659782670000012
S(＝O)2
Figure BDA0000659782670000013
NH or a covalent bond;
q is carbonyl
Figure BDA0000659782670000021
Thiocarbonyl-amino group
Figure BDA0000659782670000022
Thiocarbonyl-amino-carbonyl
Figure BDA0000659782670000023
Or a covalent bond;
when L is substituted or unsubstituted C1-6Alkylene, substituted or unsubstituted C1-6Haloalkylene, substituted or unsubstituted C2-6Alkenylene, substituted or unsubstituted C2-6Haloalkenylene, substituted or unsubstituted C2-6Alkynylene, substituted or unsubstituted C2-6Haloalkynylene, substituted or unsubstituted C3-7Cycloalkylene, substituted or unsubstituted C5-7Cycloalkenylene, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted 5-or 6-membered heterocyclylene, or substituted or unsubstituted 8-to 14-membered heteroarylene bicyclic or tricyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR ', Si (R ')3、NR'R"、C(O)R'、C(O)OR'、C(O)NR'R"、SR'、S(O)mR1、S(O)2NR'R"、OC(O)R1、OC(O)NR'R"、OS(O)2R1、OS(O)2NR'R"、N(R2)C(O)R1、N(R2)C(O)NR'R"、N(R2)S(O)2R1Or N (R)2)S(O)2NR 'R'; m is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, substituted or unsubstituted C2-6Alkynyl, C2-6Haloalkynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 14-membered heteroaromatic bicyclic or tricyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR ', Si (R ')3、NR'R"、C(O)R'、C(O)OR'、C(O)NR'R"、SR'、S(O)mR1、S(O)2NR'R"、OC(O)R1、OC(O)NR'R"、OS(O)2R1、OS(O)2NR'R"、N(R2)C(O)R1、N(R2)C(O)NR'R"、N(R2)S(O)2R1Or N (R)2)S(O)2NR' R "; or
When L is substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C1-6Haloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Haloalkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C2-6Haloalkynyl, substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 14-membered heteroaromatic bicyclic or tricyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR ', Si (R ')3、NR'R"、C(O)R'、C(O)OR'、C(O)NR'R"、SR'、S(O)mR1、S(O)2NR'R"、OC(O)R1、OC(O)NR'R"、OS(O)2R1、OS(O)2NR'R"、N(R2)C(O)R1、N(R2)C(O)NR'R"、N(R2)S(O)2R1Or N (R)2)S(O)2NR 'R'; m is nothing;
and a is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-or 6-membered heterocyclyl, or substituted or unsubstituted 8-to 14-membered heteroaromatic bicyclic or tricyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR ', Si (R ')3、NR'R"、C(O)R'、C(O)OR'、C(O)NR'R"、SR'、S(O)mR1、S(O)2NR'R"、OC(O)R1、OC(O)NR'R"、OS(O)2R1、OS(O)2NR'R"、N(R2)C(O)R1、N(R2)C(O)NR'R"、N(R2)S(O)2R1Or N (R)2)S(O)2NR'R"；
G represents a substituent at any one or more positions of A, and G is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, substituted or unsubstituted C2-6Alkynyl, C2-6Haloalkynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR ', Si (R ')3、NR'R"、C(O)R'、C(O)OR'、C(O)NR'R"、SR'、S(O)mR1、S(O)2NR'R"、OC(O)R1、OC(O)NR'R"、OS(O)2R1、OS(O)2NR'R"、N(R2)C(O)R1、N(R2)C(O)NR'R"、N(R2)S(O)2R1Or N (R)2)S(O)2NR'R"；
Wherein R 'and R' are each independently H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Haloalkynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Halogenated alkynyl, hydroxy C1-4Alkyl, OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5Or N (R)6)S(O)2NR3R4；
R1Is C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Haloalkynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Halogenated alkynyl, OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5Or N (R)6)S(O)2NR3R4；
R2Is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl or C2-6Haloalkynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-or 6-membered heterocyclyl, or substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ringA ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Halogenated alkynyl, OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5Or N (R)6)S(O)2NR3R4；
Wherein R is3、R4、R6Each independently is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl or C2-6A haloalkynyl group;
R5is C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl or C2-6A haloalkynyl group;
m is 1 or 2;
n is 0, 1,2,3, 4 or 5.
In another preferred embodiment, the compound is selected from the group consisting of:
Figure BDA0000659782670000031
Figure BDA0000659782670000041
in each of the above formulae, X, L, G, A, M and n are as defined above, and Y is O, S, S (═ O), S (═ O)2Or a covalent bond.
In another preferred embodiment, X is O or S.
In another preferred embodiment, L is substituted or unsubstituted C1-6Alkylene, substituted or unsubstituted C1-6Haloalkylene, substituted or unsubstituted C2-6Alkenylene, substituted or unsubstituted C2-6Haloalkenylene, substituted or unsubstituted C2-6Alkynylene, substituted or unsubstituted C3-7Cycloalkylene, substituted or unsubstituted C5-7A cycloalkenylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted 5-or 6-membered heterocyclylene group, or a substituted or unsubstituted 8-to 12-membered heteroarylbicyclic ring system, the substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy radical, C1-4Alkyl-carbonyl, C1-4Alkoxy-carbonyl, C1-4Alkylamino-carbonyl or phenylamino-carbonyl; or
L is substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C1-6Haloalkyl, substituted or unsubstituted C2-6Alkenyl, substituted or unsubstituted C2-6Haloalkenyl, substituted or unsubstituted C2-6Alkynyl, substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy radical, C1-4Alkyl-carbonyl, C1-4Alkoxy-carbonyl, C1-4Alkylamino-carbonyl or phenylamino-carbonyl.
In another preferred embodiment, L is any of the groups shown in columns L in tables 2 to 6 in examples.
In another preferred embodiment, M is absent; or M is H, C1-6Alkyl radical, C1-6Haloalkyl group、C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, trimethylsilylethynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7A cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-or 6-membered heterocyclyl group, or a substituted or unsubstituted 8-to 14-membered heteroaromatic bicyclic or tricyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy radical, C1-4Alkyl-carbonyl, C1-4Alkoxy-carbonyl, C1-4Alkylamino-carbonyl or phenylamino-carbonyl.
In another preferred embodiment, M is any of the groups shown in the columns of M in tables 2 to 6 in the examples.
In another preferred embodiment, a is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-or 6-membered heterocyclyl, or substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy radical, C1-4Haloalkoxy, phenoxy, aminosulphonic, amino-carbonyl, C1-4Alkyl-carbonyl, C1-4Alkoxy-carbonyl, C1-4Alkylamino-carbonyl or phenylamino-carbonyl.
In another preferred embodiment, G is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, trimethylsilylethynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-or 6-membered heterocyclyl or substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring systems, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy radical, C1-4Alkyl-carbonyl, C1-4Alkoxy-carbonyl, C1-4Alkylamino-carbonyl or phenylamino-carbonyl.
In a further preferred embodiment of the method,
Figure BDA0000659782670000051
in examples, tables 2 to 6
Figure BDA0000659782670000052
Any of the groups shown in the columns.
In another preferred embodiment, the compounds are those listed in tables 2 to 6 of the examples.
In a second aspect the present invention provides an agricultural composition comprising:
(1)0.001 to 99.99% by weight of a compound of the first aspect of the invention, or an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt of said compound, or a combination thereof; and
(2) an agriculturally pharmaceutically acceptable carrier and/or excipient.
In a third aspect, the present invention provides the use of a compound according to the first aspect of the present invention, or an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt of said compound or an agricultural composition according to the second aspect of the present invention, for killing or preventing nematodes or for the preparation of a nematicide composition.
In another preferred embodiment, the nematicide composition is used for killing or preventing the parasitic nematodes of the agricultural and forest plants or is used for preparing the nematicide composition for killing or preventing the parasitic nematodes of the agricultural and forest plants.
In a fourth aspect, the invention provides a process for the preparation of a compound according to the first aspect of the invention, or an optical isomer, a cis-trans isomer or an agriculturally pharmaceutically acceptable salt of said compound,
(A) the method comprises the following steps:
(1) subjecting a compound of formula (a) to a ring closure reaction with bis (trichloromethyl) carbonate (BTC) in an inert solvent to give a compound of formula (b):
(2) subjecting the compound of formula (b) to a ring-opening reaction with ammonium carbonate in an inert solvent to give a compound of formula (c):
(3) in an inert solvent, carrying out diazotization reaction and ring closing reaction on the compound shown in the formula (c) to obtain a compound shown in the formula (d):
Figure BDA0000659782670000053
(4) reacting a compound of formula (d) with BrCH in an inert solvent in the presence of a base2(CH2)nBr reaction to obtain the compound of formula (e);
(5) reacting a compound of formula (e) with a compound of formula (f) or a compound of formula (p) (H-Y-Q-L-M) in an inert solvent to obtain a compound of formula (I):
Figure BDA0000659782670000054
or (B) the method comprises the steps of:
(4') reacting a compound of formula (d) with BrCH in an inert solvent in the presence of a base2(CH2)nC ≡ CH reaction to give a compound of formula (g):
(5') reacting a compound of formula (g) with a compound of formula (h) in an inert solvent to obtain a compound of formula (I):
Figure BDA0000659782670000061
or (C) the method comprises the steps of:
(4') reacting a compound of formula (d) with BrCH in an inert solvent in the presence of a base2(CH2)nYH reaction to obtain the compound of formula (i):
(5 ") reacting the compound of formula (I) with a compound of formula (k) in an inert solvent to obtain a compound of formula (I):
Figure BDA0000659782670000062
or (D) the method comprises the steps of:
(5') reacting the compound of formula (e) with the compound of formula (m) in an inert solvent in the presence of a base, followed by deprotection to provide the compound of formula (n):
(6) reacting a compound of formula (n) with a compound of formula (o) in an inert solvent to obtain a compound of formula (I):
Figure BDA0000659782670000063
or (E) the method comprises the steps of:
(6') reacting the compound of formula (n) with the compound of formula (o') in an inert solvent to give the compound of formula (I):
Figure BDA0000659782670000064
or (F) the method comprises the steps of:
(5') reacting a compound of formula (e) with a compound of formula (p) in an inert solvent in the presence of a base to provide a compound of formula (I):
Figure BDA0000659782670000071
in the above formulae, X, Y, Q, L, M, A, G and n are as defined above.
In a fifth aspect of the invention there is provided a nematicidal and/or nematicidal method comprising the steps of: applying the compound of the first aspect of the invention or the agricultural composition of the second aspect to a plant suffering from, or likely to suffer from, nematode damage, the soil or environment surrounding it.
In a sixth aspect of the present invention there is provided a process for the preparation of an agricultural composition according to the second aspect of the present invention, the process comprising the steps of: combining (1) a compound described in the first aspect of the present invention, an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof, or a combination thereof; mixing with (2) an agriculturally pharmaceutically acceptable carrier and/or excipient to form said agricultural composition.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The inventor has conducted long-term and intensive research and unexpectedly found and synthesized a series of triazine heterocyclic compounds with novel structures and remarkable insecticidal activity. On this basis, the inventors have completed the present invention.
Radical definition
The term "C1-6Alkyl "means a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The term "C2-6Alkenyl "means a straight or branched chain alkenyl group having 2 to 6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or the like.
The term "C2-6Alkynyl "means a straight or branched chain alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl, or the like.
The term "C3-7Cycloalkyl "refers to a cyclic alkyl group having 3 to 7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.
The term "C5-7Cycloalkenyl "refers to a cyclic alkenyl group having 5 to 7 carbon atoms with one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1, 3-cyclohexadienyl, 1, 4-cyclohexadienyl, or the like.
As used herein, the term "C1-4Alkoxy "means having 1-4 carbonsAn atomic straight-chain or branched alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.
The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted with one or more of the above halogen atoms, which may be the same or different, such as trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or the like.
The term "ring" or "ring system" refers to a carbocyclic or heterocyclic ring.
The term "heterocycle" means that at least one of the atoms forming the skeleton of the heterocycle is not carbon, and is nitrogen, oxygen or sulfur. Typically, the heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens, and/or no more than 2 sulfurs. Unless otherwise indicated, the heterocyclic ring may be a saturated, partially unsaturated, or fully unsaturated ring.
The term "ring system" refers to fused rings where two or more rings are joined together.
As used herein, the term "5-or 6-membered heterocyclyl" refers to a five-or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, for example, pyridyl, thiazolyl, isothiazolyl, thienyl, furyl, pyrrolyl, pyrazolyl, pyrimidinyl, tetrahydrofuryl, 4, 5-dihydrothiazol-2-yl, 2-cyanoimino-4-oxo-1, 3-thiazolidin-3-yl, 2-cyanoimino-4-oxo-1, 3-thiazinan-3-yl, oxazolyl, isoxazolyl, 1H-tetrazolyl, 1H-1,2, 3-triazolyl, 4H-1,2, 4-triazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, tetrazolyl, or the like.
The term "heterocyclic ring system" refers to a ring system in which at least one ring in the ring system is heterocyclic.
The term "heteroaromatic ring system" refers to systems in which at least one ring in the ring system is aromatic.
As used herein, the term "8-to 12-membered heteroaromatic bicyclic ring system" or "8-to 14-membered heteroaromatic bicyclic or tricyclic ring system" may be selected from the group consisting of: benzofuran, benzo [ b ] thiophene, indole, quinoline, isoquinoline, 1H-indazole, 1H-benzo [ d ] imidazole, benzo [ d ] thiazole, benzo [ d ] oxazole, benzo [ d ] isoxazole, benzo [ d ] [1,2,3] thiadiazole, 2, 3-dihydroimidazo [1,2-a ] pyridine, quinazoline, quinoxaline, cinnoline, phthalazine, 1, 8-naphthyridine, 4,5,6, 7-tetrahydrobenzo [ b ] thiophene, benzo [ b ] thiophene-1, 1-dioxane, 8H-indeno [2,1-b ] thiophene, 7, 8-dihydro-6H-cyclopenta [4,5] thieno [2,3-d ] pyrimidine, 3,5,6, 7-tetrahydro-4H-cyclopenta [4,5] thieno [2,3-d ] pyrimidin-4-one, spiro [ indoline-3, 2'- [1,3] dioxolane ] -2-one, spiro [ indoline-3, 2' - [1,3] dioxane ] -2-one, indoline-2, 3-dione, or the like.
The term "alkyl" refers to a group derived from an alkane molecule by the removal of one hydrogen atom; the term "alkylene" refers to a group of an alkane molecule lacking two hydrogen atoms. Similarly, "alkenylene", "alkynylene", "cycloalkylene", "cycloalkenylene", "phenylene", "naphthylene", "heterocyclylene" or "heteroarylene bicyclic or tricyclic ring system" are defined analogously.
Unless specifically stated to be "substituted or unsubstituted", the groups of the present invention may be substituted with a substituent selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Halogenated alkynyl, hydroxy C1-4Alkyl, OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5Or N (R)6)S(O)2NR3R4Etc., wherein R is3、R4、R5、R6As defined above, m is 1 or 2.
The inert solvent refers to various solvents which do not react with the raw materials, including various straight chain, branched chain or cyclic alcohols, ethers or ketones, alkyl halides, 1, 4-dioxane, acetonitrile, tetrahydrofuran, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like.
The compounds of the present invention may contain one or more asymmetric centers and thus occur as racemates, racemic mixtures, single enantiomers, diastereomeric compounds and individual diastereomers. Asymmetric centers that may be present depend on the nature of the various substituents on the molecule. Each such asymmetric center will independently produce two optical isomers and all possible optical isomers and diastereomeric mixtures and pure or partially pure compounds are included within the scope of the invention. The present invention includes all isomeric forms of the compounds.
In the compounds of formula I of the present invention, when Y or Q is a covalent bond, it means that the groups on both sides of Y or Q are linked by a covalent bond.
Nematicidal Activity of the active substances of the invention
The term "active substance of the present invention" or "active compound of the present invention" refers to a compound having a structure represented by the general formula (I), an optical isomer, a cis-trans isomer, or an agriculturally pharmaceutically acceptable salt thereof. The compound contains N, S heterocyclic structure, has obvious nematocidal activity, wide nematocidal spectrum and high stability.
The term "agriculturally pharmaceutically acceptable salt" means that the anion of the salt is known and acceptable in forming a pharmaceutically acceptable salt of the nematicide. Preferably, the salt is water soluble. Suitably, the acid addition salts formed by the compounds of formula (I) include salts formed with inorganic acids, such as hydrochlorides, phosphates, sulphates, nitrates; and salts formed with organic acids, such as acetates, benzoates, and the like.
The active substance of the invention can be used for controlling and killing a wide range of parasitic nematodes of agricultural and forestry plants. In the present specification, "nematicide" is a collective term for substances having an effect of controlling all of the plant-parasitic nematodes mentioned herein.
Examples of plant parasitic nematodes include, but are not limited to: root-knot nematodes, such as peanut root-knot nematodes (melodogyne arenaria), Meloidogyne chia (melodogyne chilo di), Meloidogyne pumila (melodogyne exigua), Meloidogyne hapla (melodogyne hapla), Meloidogyne incognita (melodogyne incognita), Meloidogyne javanica (melodogyne japonica), and other Meloidogyne species (melodogyne); cyst nematodes, such as potato gold nematode (Globodera rostochiensis), potato white nematode (Globodera pallida), tobacco cyst nematode (Globodera tabacum), and other cyst nematodes (Globodera); heterodera species, such as Heterodera graminicola (Heterodera avenae), Heterodera glycines (Heterodera glycines), Heterodera betacellularis (Heterodera schachtii), Heterodera trifolii (Heterodera trifolii), and other Heterodera species (Heterodera); nodorworms, such as pratylenchus glumae (Anguina funesta), Triticum tritici (Anguina tritici) and other Ditylenchus (Anguina); stem and leaf bud nematodes, such as Aphelenchoides besseyi (Aphelenchoides besseyi), Aphelenchoides fragaria (Aphelenchoides fragaria), Chrysanthemum Aphelenchoides (Aphelenchoides ritzemabosi), and other Aphelenchoides (Aphelenchoides); nematoda, such as weed nematoda (Belololaimus longicaudatus) and other nematoda (Belololaimus); pine nematodes, such as pine wood nematodes (Bursaphelenchus xylophilus) and other species of Gliocladium spp (Bursaphelenchus); ring nematodes, such as Trichinella circinata (Criconema), Trichinella ringgola (Criconema), Trichinella (Criconemoides) and Mesocronium (Mesocroniema); corm nematodes, such as the rot-stalk nematode (Ditylenchus destructor), Ditylenchus dipsaci (Ditylenchus dipsaci), Agaricus campestris (Ditylenchus myceliophagus), and other phylogens (Ditylenchus); conus nematodes, such as the genus Conidiobolus (Dolichodorus); helicopters, such as helicoptera palaestis (Helicotylenchus dihystera), helicoptera plecoglosa (Helicotylenchus multicinctus), and other Helicotylenchus (Helicotylenchus); sheath nematodes, such as coleoptera (Hemiclilophora) and Hemicconemoides (Hemicconomodes); coronaries, such as Nematoda Columbus (Hoploaimus columbus) and other Nematoda species (Hoploaimus); pseudorhizomatoid nematodes, such as the species Heterophyllus heterocycas (Nacobbus aberrans) and other species of Phyllanthus nacanthus (Nacobbus); nematodes such as the nematode longerongatus (longidrorus) and other longerongatus (longidrorus); stapled nematodes, such as the genus nematode (Paratylenchus); root-rot nematodes, such as Pratylenchus brachyurus, Pratylenchus coffei (Pratylenchus coffei), Pratylenchus zea (Pratylenchus zeae), Pratylenchus penetrans (Pratylenchus penatrans), and other bretylenchus species (Pratylenchus); perforactidae, such as Radopholus similis (Radopholus simlis) and other species of Periporia (Radopholus); reniform nematodes, such as reniform nematodes (Rotylenchus robustus) and other reniform nematodes (Rotylenchus); residual root nematodes, such as primitive Bursaphelenchus (Trichoderma primaivus) and other Bursaphelenchus (Trichoderma); dwarf nematodes, such as Kleinhovia dwarfis (Tylenochlornchus clavytoni), Amylophilus dwalus (Tylenochlornchus dubius), and other species of dwarfing nematodes (Tylenochlornchus); citrus nematodes, such as citrus hemiptera (Tylenchulus semipenenetrans) and other species of Tylenchulus tenuis (Tylenchulus); sword nematodes, such as American sword nematode (Xiphilinema americanum), standard sword nematode (Xiphilinema index), cleft tail sword nematode (Xiphilinema diversicaudate), and other Sword nematodes (Xiphilinema).
The compound provided by the invention has a good control effect on Meloidogyne incognita.
Nematicide compositions comprising an active substance according to the invention
The active substances according to the invention can be prepared in a customary manner to form nematicide compositions. These active compounds can be formulated in the customary formulations, for example as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substance, microcapsules in polymers, coating compositions for seeds, and formulations for use with combustion devices, for example smoking cartridges, smoking pots and smoking trays, and ULV Cold mist (Cold mist) and hot mist (Warm mist) formulations.
These formulations can be produced by known methods, for example by mixing the active compounds with extenders, that is, liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, that is, emulsifiers and/or dispersants and/or foam formers. Organic solvents may also be used as adjuvants, for example when water is used as extender.
When a liquid solvent is used as the diluent or carrier, it is basically suitable, for example: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less commonly polar solvents such as dimethylformamide and dimethylsulfoxide, and water.
Liquid gas diluents or carriers refer to liquids that will become gases at normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
The solid carrier may be a finely divided natural mineral such as kaolin, clay, talc, quartz, attapulgite, montmorillonite or diatomaceous earth; and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates. Solid carriers for granules are crushed and classified natural zircon, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic coarse powders, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stalks, and the like.
Nonionic and anionic emulsifying trains may be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. The dispersant comprises lignin sulfite waste liquor and methyl cellulose.
Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
Colorants such as inorganic dyes, e.g., iron oxide, cobalt oxide, and prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and with trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, and the like.
The active compounds according to the invention can be present in their commercial preparations in a mixture with other active compounds, such as insecticides, fungicides, herbicides, growth control agents, etc., or in the use forms prepared from these preparations. Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as avermectins, etc., and fungicides include strobilurins, amides, triazoles, etc.
Furthermore, the active compounds according to the invention can also be present in their commercial preparations in a mixture with synergists, which are compounds which increase the action of the active compounds, or in the use forms prepared from these preparations, it being possible for no synergists to be added, since the active compounds themselves are active.
These formulations generally contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight, of the active compound according to the invention, based on the total weight of the nematicide composition. The concentration of the active compound in the commercial preparations or dosage forms to be used can vary within wide limits. The concentration of active compound in the dosage form to be used may be from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1% (g/v).
Process for the preparation of the compounds of the invention
The compound represented by the general formula (I) of the present invention can be produced by the following method, however, the conditions of the method, such as reactants, solvent, base, amount of the compound used, reaction temperature, time required for the reaction, etc., are not limited to the following explanation. The compounds of the present invention may also be conveniently prepared by optionally combining various synthetic methods described in the present specification or known in the art, and such combinations may be readily carried out by those skilled in the art to which the present invention pertains.
In the preparation method of the invention, each reaction is usually carried out in an inert solvent at a reaction temperature of-20 ℃ to 120 ℃ (preferably-10 ℃ to 0 ℃, or 20 ℃ to 30 ℃, or 80 ℃ to 100 ℃). The reaction time is usually 2 to 24 hours, preferably 4 to 18 hours.
Bases used in the reaction include (but are not limited to): triethylamine, diisopropylethylamine, diethylamine, piperidine, piperazine, morpholine, N-methylmorpholine, triethylenediamine (DABCO), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, or a combination thereof.
In a preferred embodiment, the starting compound of formula (d) of the present invention may be synthesized by a method comprising the steps of:
Figure BDA0000659782670000121
x, A, G is as defined above in each of the above formulae;
(1) reacting the compound of formula (a) with BTC in an inert solvent at a temperature (e.g., -10 to-5 ℃) to obtain the compound of formula (b).
(2) And (c) reacting the compound of the formula (b) with ammonium carbonate in an inert solvent at a certain temperature (such as 55-60 ℃) to obtain the compound of the formula (c).
(3) In an inert solvent, at a certain temperature (such as-5-0 ℃), the compound of the formula (c) and NaNO are mixed2To obtain the compound of formula (d).
Preferably, the method comprises the steps of:
(1) adding the compound of the formula (a) into a proper amount of tetrahydrofuran, and cooling to-10 ℃. Controlling the temperature to be minus 10 to minus 5 ℃, slowly dripping a tetrahydrofuran solution of BTC, reacting at room temperature after adding, tracking the reaction process by TLC, removing the solvent under reduced pressure after the reaction is finished, adding anhydrous ether into the residual solid, fully stirring, filtering, and drying to obtain the compound of the formula (b).
(2) Adding a compound shown in the formula (b) into a proper amount of 1, 4-dioxane, adding ammonium carbonate, heating to 55-60 ℃ for reaction, tracking the reaction process by TLC, cooling to room temperature after the reaction is finished, removing the solvent under reduced pressure, adding a proper amount of saturated sodium bicarbonate aqueous solution, extracting with ethyl acetate, drying an organic phase with anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a compound shown in the formula (c).
(3) Adding NaNO2Adding into 0.5M dilute hydrochloric acid, and cooling to-5 deg.C. And (3) slowly dropwise adding a DMF (dimethyl formamide) solution of the compound of the formula (c) at the temperature of-5-0 ℃, after adding, reacting at room temperature, tracking the reaction process by TLC (thin layer chromatography), adjusting the pH value to 8-10 by using ammonia water after the reaction of the compound of the formula (c) is completed, adjusting the pH value to 2-5 by using hydrochloric acid, performing suction filtration, washing a filter cake by using a large amount of water, and drying to obtain the compound of the formula (d).
In another preferred embodiment, the compound represented by the general formula (II) of the present invention can be synthesized by the following method:
Figure BDA0000659782670000122
in each of the above formulae, X, Y, L, M, G and A are as defined above, and n is an integer of 0 to 5;
(1) the compound of formula (d) is reacted with BrCH in the presence of a base (e.g., potassium carbonate, etc.) in an inert solvent (e.g., acetone)2(CH2)nAnd (3) reacting Br at a certain temperature (such as reflux) for a period of time (such as 5-10 hours), cooling to room temperature after the reaction is finished, evaporating the solvent under reduced pressure, adding water into the residue, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and performing column separation to obtain the compound shown in the formula (e).
(2) Reacting the compound of the formula (e) with the compound of the formula (f1) at a certain temperature (such as 80-90 ℃) for a period of time (such as 10-15 hours) in the presence of potassium iodide by using an inert solvent (such as DMF) as a solvent, cooling to room temperature after the reaction is finished, evaporating the solvent under reduced pressure, adding dilute hydrochloric acid into the residue, extracting with dichloromethane, washing an organic phase with saturated saline solution, drying with anhydrous sodium sulfate, concentrating, and carrying out column separation to obtain a compound of the formula (II);
or, in the presence of alkali (such as potassium carbonate, etc.), using an inert solvent (such as DMF or acetone) as a solvent, reacting the compound of the formula (e) with the compound of the formula (p1) at a certain temperature (such as 80-90 ℃ or reflux) for a period of time (such as 8-12 hours), cooling to room temperature after the reaction is finished, evaporating the solvent under reduced pressure, adding water to the residue, extracting with dichloromethane, washing the organic phase with saturated saline, drying with anhydrous sodium sulfate, concentrating, and performing column separation to obtain the compound of the formula (II).
Alternatively, the compound represented by the general formula (II) is synthesized by the following method:
Figure BDA0000659782670000131
in each of the above formulae, X, Y, L, M, G and A are as defined above, and n is an integer of 0 to 5;
(1) the compound of formula (d) is reacted with BrCH in the presence of a base (e.g., potassium carbonate, etc.) in an inert solvent (e.g., acetone)2(CH2)nC ≡ CH is reacted for a period of time (such as 5-8 hours) at a certain temperature (such as reflux), after the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed by evaporation under reduced pressure, water is added into residues, dichloromethane is used for extraction, an organic phase is dried by anhydrous sodium sulfate, concentration and column separation are carried out, and the compound of the formula (g) is obtained.
(2) In the presence of alkali (such as triethylamine and the like), taking an inert solvent (such as acetonitrile) as a solvent, taking CuI as a catalyst, reacting the compound of the formula (g) with the compound of the formula (h1) at room temperature for a period of time (such as 2-4 hours), after the reaction is finished, evaporating the solvent under reduced pressure, and separating a residue column to obtain the compound of the formula (II).
In another preferred embodiment, the compound of formula (III) of the present invention can be synthesized by the following method:
Figure BDA0000659782670000132
in each of the above formulae, X, L, M, G and A are as defined above, and n is an integer of 0 to 5;
(1) the compound of formula (d) is reacted with BrCH in the presence of a base (e.g., potassium carbonate, etc.) in an inert solvent (e.g., acetone)2(CH2)nAnd (3) reacting OH at a certain temperature (such as reflux) for a period of time (such as 5-8 hours), cooling to room temperature after the reaction is finished, evaporating the solvent under reduced pressure, adding water into the residue, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and carrying out column separation to obtain the compound shown as the formula (i 1).
(2) Dissolving the compound of the formula (i1) in an inert solvent (such as dichloromethane) in the presence of a base (such as triethylamine and the like), dropwise adding the compound of the formula (k1) at room temperature, continuously reacting for a period of time (such as 2-4 hours), adding a saturated sodium bicarbonate aqueous solution after the reaction is finished, fully stirring, separating an organic phase, extracting a water phase for 2 times by using dichloromethane, combining all the organic phases, drying by using anhydrous sodium sulfate, concentrating, and carrying out column separation to obtain the compound of the formula (III).
In another preferred embodiment, the compound of formula (IV) of the present invention can be synthesized by the following method:
Figure BDA0000659782670000133
in each of the above formulae, X, L, M, G and A are as defined above, and n is an integer of 0 to 5;
(1) reacting the compound of formula (e) with the compound of formula (m1) at a certain temperature (e.g. 50-60 ℃) for a certain time (e.g. 8-12 hours) in the presence of alkali (e.g. potassium carbonate) and an inert solvent (e.g. DMF), adding water into the residue after the reaction is finished, extracting with dichloromethane, drying an organic phase with anhydrous sodium sulfate, concentrating, and carrying out column separation to obtain the compound of formula (q).
(2) Reacting the compound of the formula (q) with hydrazine hydrate in an inert solvent (such as ethanol) at a certain temperature (such as reflux) for a period of time (such as 6-10 hours), after the reaction is finished, performing suction filtration, filtering off insoluble substances, removing the solvent in the filtrate by vacuum evaporation, adding a saturated sodium bicarbonate aqueous solution into the residue, extracting with dichloromethane, drying an organic phase with anhydrous sodium sulfate, and removing the solvent by vacuum evaporation to obtain the compound of the formula (n1) as a yellow oily liquid.
(3) Dissolving the compound of the formula (n1) in an inert solvent (such as dichloromethane) in the presence of alkali (such as triethylamine and the like), dropwise adding the compound of the formula (o1) at room temperature, continuously reacting for a period of time (such as 2-4 hours), adding a saturated sodium bicarbonate aqueous solution after the reaction is finished, fully stirring, separating an organic phase, extracting a water phase for 2 times by using dichloromethane, combining all the organic phases, drying by using anhydrous sodium sulfate, concentrating, and carrying out column separation to obtain the compound of the formula (IV).
In another preferred embodiment, the compounds of the general formulae (V-VI) according to the invention can be synthesized by the following method:
Figure BDA0000659782670000141
in each of the above formulae, X, L, M, G and A are as defined above, and n is an integer of 0 to 5;
reacting the compound of the formula (n1) with the compound of the formula (o'1) in an inert solvent (such as acetonitrile) at room temperature for a period of time (such as 8-12 hours), filtering after the reaction is finished, and recrystallizing a filter cake by using absolute ethyl alcohol to obtain the compound of the formula (V).
And (3) reacting the compound of the formula (n1) with the compound of the formula (o'2) in an inert solvent (such as dichloromethane) at room temperature for a period of time (such as 8-12 hours), after the reaction is finished, performing suction filtration, concentrating the filtrate, and performing column separation to obtain the compound of the formula (VI).
Preferably, the content of said intermediate product in said reaction mixture is from 10 to 99.99% by weight; preferably 20 to 90 wt%; more preferably 50 to 80 wt%.
Therefore, the inventor can purify the intermediate product and then carry out the next reaction; it is of course also possible to subject the reaction mixture containing the compound directly to the next reaction.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Example 12-Cyanoimino-3- (N-3- (4-oxo-7-chlorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl)) -1, 3-thiazolidin-4-one
1.1 preparation of 7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one
1.1.1 preparation of 7-Chloroindigylic anhydride
Figure BDA0000659782670000151
6.864g (40mmol) of 2-amino-4-chlorobenzoic acid is added into 100ml of tetrahydrofuran, stirred to form a suspension, cooled to-10 ℃, controlled at the temperature of-10 ℃ to-5 ℃, 11.88g (40mmol) of BTC solution in 20ml of tetrahydrofuran is slowly dropped into the suspension, and after the addition is finished, the mixture is placed at room temperature for reaction, and the progress of the reaction is tracked by TLC. After the reaction, the solvent was distilled off under reduced pressure, 150ml of anhydrous ether was added to the residual solid, followed by stirring thoroughly, filtration, washing of the filter cake with anhydrous ether and drying to obtain 6.718g of a white solid with a yield of 85%.1H NMR(400MHz,DMSO-d6)11.84(s,1H),7.92(d,J＝8.4Hz,1H),7.30(dd,J1＝8.4Hz,J2＝1.6Hz,1H),7.14(d,J＝1.6Hz,1H)；13CNMR(100MHz,DMSO-d6)159.1,146.9,142.5,141.1,130.9,123.6,114.7,109.5.
1.1.2 preparation of 2-amino-4-chlorobenzamide
Figure BDA0000659782670000152
5.928g (30mmol) of 7-chloroisatoic anhydride was added to 120ml of 1, 4-dioxane, 14.40g (150mol) of ammonium carbonate was added thereto, and stirred to form a suspension, which was heated to 60 ℃ for reaction, and the progress of the reaction was followed by TLC. After completion of the reaction, the solvent was distilled off under reduced pressure, 120ml of a saturated aqueous sodium hydrogencarbonate solution was added to the residue, extraction was performed with ethyl acetate (60 ml. times.3), the organic phase was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 4.197g of a pale brown solid, which was obtained in 82% yield.1H NMR(400MHz,DMSO-d6)7.78(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,J1＝8.4Hz,J2＝2.0Hz,1H)；13C NMR(100MHz,DMSO-d6)170.4,151.5,136.3,130.6,115.1,114.0,112.4.
1.1.3 preparation of 7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000153
3.450g (50mmol) NaNO2Dissolving in 200ml of 0.5M diluted hydrochloric acid, cooling to-5 ℃, controlling the temperature to be-5-0 ℃, slowly dripping 4.265g (25mmol) of 2-amino-4-chlorobenzamide in 15ml of DMF solution, reacting at room temperature after the addition is finished, and tracking the reaction process by TLC. After the reaction was completed, the pH was adjusted to 10 with ammonia water, and the mixture was stirred thoroughly for 15 minutes, then adjusted to 2 with hydrochloric acid, and stirred thoroughly for 15 minutes, followed by suction filtration, washing the filter cake with a large amount of water, and drying to obtain 3.860g of a white solid with a yield of 85%.1H NMR(400MHz,DMSO-d6)15.10(s,1H),8.29(d,J＝2.0Hz,1H),8.21(dd,J1＝8.4Hz,J2＝1.6Hz,1H),7.94(dd,J1＝8.4Hz,J2＝2.0Hz,1H)；13C NMR(100MHz,DMSO-d6)155.0,145.0,139.9,132.7,127.1,126.6,119.1.
1.2 preparation of 3- (3-bromopropyl) -7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000154
3.632g (20mmol) of 7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one was added to 120ml of acetone, and 24.24g (120mmol) of 1, 3-dibromopropane and 5.520g (40mmol) of potassium carbonate were added thereto, and stirred to form a suspension, which was heated to reflux, followed by TLC. After completion of the reaction, the solvent was distilled off under reduced pressure, 200ml of water was added to the residue, extraction was performed with methylene chloride (80 ml. times.2), the organic phase was dried over anhydrous sodium sulfate, concentration and column separation were performed to obtain 3.150g of a pale yellow solid, yield 52%.1H NMR(400MHz,DMSO-d6)8.35–8.30(m,1H),8.25(d,J＝8.4Hz,1H),7.96(ddd,J1＝8.4Hz,J2＝2.0Hz,J3＝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-d6)154.4,144.5,139.7,132.9,127.1,126.8,118.3,48.0,31.6,31.2.
1.3 preparation of 2-cyanoimino-4-oxo-1, 3-thiazolidin-3-potassium salt
Figure BDA0000659782670000161
11.68g (80mmol) of dimethyl N-cyanodithioiminocarbonate and 4.220g (44mmol) of ammonium carbonate were added to 120ml of ethanol, stirred to form a suspension, heated to 60 ℃ for reaction, and the progress of the reaction was followed by TLC. When the reaction of N-cyano dithioimine dimethyl carbonate is completed, 7.15ml (80mmol) of methyl thioglycolate and 8.960g (80mmol) of 50% KOH aqueous solution are added, the mixture is heated to reflux reaction for 8 hours, the mixture is cooled to room temperature and is filtered, a filter cake is washed by absolute ethyl alcohol and is dried, and light yellow solid 10.12g is obtained, and the yield is 71%.
1.4 preparation of 2-cyanoimino-3- (N- (3- (4-oxo-7-chlorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000162
0.606g (2mmol) of 3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazine-4 (3H) -ketone is added into 10ml DMF, then 0.332g (2mmol) of potassium iodide and 0.358g (2mmol) of 2-cyanoimino-4-oxo-1, 3-thiazolidine-3-potassium salt are added and stirred to form suspension, the suspension is heated to 90 ℃ for reaction for 10 hours, the solvent is evaporated under reduced pressure, diluted hydrochloric acid is added, dichloromethane is used for extraction, the organic phase is washed by saturated saline solution, anhydrous sodium sulfate is used for drying, concentration and column separation are carried out, and light yellow solid 0.305g is obtained, and the yield is 42%.1H NMR(400MHz,DMSO-d6)8.35(d,J＝2.0Hz,1H),8.25(dd,J1＝8.4Hz,J2＝2.0Hz,1H),7.97(dd,J1＝8.4Hz,J2＝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-d6)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+)C14H11N6O2NaS35Cl(M+Na)+Calculating the value: 385.0250, found: 385.0258, respectively; c14H11N6O2NaS37Cl(M+Na)+Calculating the value: 387.0221, found: 387.0232.
example 22-Cyanoimino-3- (N- (4- (4-oxo-7-fluorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000171
The synthesis of the title compound was performed in analogy to example 1, step 1.4, except using 3- (4-bromobutyl) -7-fluorobenzo [ d ]][1,2,3]Triazin-4 (3H) -one in place of 3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one. Yellow solid, yield 53%.1H NMR(400MHz,DMSO-d6)8.33(dd,J1＝8.8Hz,J2＝5.6Hz,1H),8.07(dd,J1＝8.8Hz,J2＝2.4Hz,1H),7.81(td,J1＝8.8Hz,J2＝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-d6)-101.9(td,J1＝8.6Hz,J2＝5.6Hz).HRMS(ES-)C15H12N6O2FS(M-H)–Calculating the value: 359.0726, found: 359.0723.
example 32-Cyanoimino-3- (N- (5- (4-oxo-6-methylbenzo [ d ] [1,2,3] triazin-3 (4H) -yl) pentyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000172
The synthesis of the title compound was performed in analogy to example 1, step 1.4, except using 3- (5-bromopentyl) -6-methylbenzo [ d ]][1,2,3]Triazin-4 (3H) -one in place of 3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one. Pale yellow solid, yield 65%.1H NMR(400MHz,DMSO-d6)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-d6)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-)C17H17N6O2S(M-H)–Calculating the value: 369.1134, found: 369.1137.
example 42-Cyanoimino-3- (N- (6- (4-oxo-7-methoxybenzo [ d ] [1,2,3] triazin-3 (4H) -yl) hexyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000173
The synthesis of the title compound was performed in analogy to example 1, step 1.4, except using 3- (6-bromohexyl) -7-methoxybenzo [ d][1,2,3]Triazin-4 (3H) -one in place of 3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one. Pale yellow solid, yield 41%.1H NMR(400MHz,DMSO-d6)8.15(d,J＝8.8Hz,1H),7.62(d,J＝2.4Hz,1H),7.47(dd,J1＝8.8Hz,J2＝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-d6)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+)C18H21N6O3S(M+H)+Calculating the value: 401.1396, found: 401.1396.
example 52-Cyanoimino-3- (N- (3- (4-oxo-6-methylthio [3,2-d ] [1,2,3] triazin-3 (4H) -yl) propyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000181
The synthesis of the title compound was performed in analogy to example 1, step 1.4, except using 3- (3-bromopropyl) -6-methylthiophene [3,2-d ]][1,2,3]Triazin-4 (3H) -one substitution3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one. Yellow solid, yield 18%. HRMS (ES +) C13H13N6O2S2(M+H)+Calculating the value: 349.0541, found: 349.0538.
example 62-Cyanoimino-3- (N- (3- (4-oxo-5, 6,7, 8-tetrahydrobenzo [4,5] thiophene [2,3-d ] [1,2,3] triazin-3 (4H) -yl) propyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000182
The synthesis of the title compound was performed in analogy to example 1, step 1.4, except using 3- (3-bromopropyl) -5,6,7, 8-tetrahydrobenzo [4,5] benzo]Thiophene [2,3-d ]][1,2,3]Triazin-4 (3H) -one in place of 3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one. Pale yellow solid, yield 30%. HRMS (ES +) C16H17N6O2S2(M+H)+Calculating the value: 389.0854, found: 389.0858.
example 72-Cyanoimino-3- (N- (3- (4-thio-6-nitrobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl)) -1, 3-thiazolidin-4-one
Figure BDA0000659782670000183
The synthesis of the title compound was analogous to step 1.4 of example 1, except that 6-nitrobenzo [ d ] was used][1,2,3]Triazine-4 (3H) -thiones instead of 3- (3-bromopropyl) -7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -one. Yellow solid, yield 28%. HRMS (ES-) C14H10N7O3S2(M-H)–Calculating the value: 388.0287, found: 388.0291.
example 85-chloro-1- (4- (4-oxo-7-trifluoromethoxybenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl) indoline-2, 3-dione
Figure BDA0000659782670000191
The 3- (4-bromobutyl) -7-trifluoromethoxybenzo [ d ] [1,2,3] triazin-4 (3H) -one was prepared analogously to the preparation of 3- (3-bromopropyl) -7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one in example 1, with the difference that 7-trifluoromethoxybenzo [ d ] [1,2,3] triazin-4 (3H) -one was used instead of 7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one and 1, 4-dibromobutane was used instead of 1, 3-dibromopropane.
0.732g (2mmol) of 3- (4-bromobutyl) -7-trifluoromethoxybenzo [ d][1,2,3]Triazine-4 (3H) -ketone is added into 15ml DMF, then 0.399g (2.2mmol) of 5-chloro isatin and 0.414g (3mmol) of potassium carbonate are added, stirred to form a suspension, heated to 80 ℃ for reaction for 8 hours, the solvent is removed by reduced pressure evaporation, water is added, dichloromethane is used for extraction, an organic phase is washed by saturated saline solution, dried by anhydrous sodium sulfate, concentrated and separated by a column, 0.486g of yellow solid is obtained, and the yield is 52%. HRMS (ES +) C20H15N4O4F3 35Cl(M+H)+Calculating the value: 467.0734, found: 467.0738, respectively; c20H15N4O4F3 37Cl(M+H)+Calculating the value: 469.0704, found: 469.0768.
example 91- (4- (4-oxo-7-nitrobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl) spiro [ indoline-3, 2' - [1,3] dioxolane ] -2-one
9.1 preparation of spiro [ indoline-3, 2' - [1,3] dioxolane ] -2-one
Figure BDA0000659782670000192
2.94g (20mmol) of isatin, 22ml of ethylene glycol and 0.38g (1mmol) of p-toluenesulfonic acid were added to 160ml of toluene and heated to reflux for 12 hours. Cooling to room temperature, removing the solvent by evaporation under reduced pressure, adding saturated aqueous sodium carbonate solution, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and separating with column to obtain light yellow needle crystal 2.636g with yield of 69%.1H NMR(400MHz,DMSO-d6)10.43(s,1H),7.37-7.28(m,2H),7.01(td,J1＝7.6Hz,J2＝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-d6)174.4,142.8,131.6,124.9,124.6,122.3,110.5,101.6,65.4.
9.2 preparation of 1- (4- (4-oxo-7-nitrobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl) spiro [ indoline-3, 2' - [1,3] dioxolane ] -2-one
Figure BDA0000659782670000193
The preparation of 3- (4-bromobutyl) -7-nitrobenzo [ d ] [1,2,3] triazin-4 (3H) -one is analogous to that of 3- (3-bromopropyl) -7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one in example 1, with the exception that 7-nitrobenzo [ d ] [1,2,3] triazin-4 (3H) -one is used instead of 7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one and 1, 4-dibromobutane is used instead of 1, 3-dibromopropane.
0.327g (1mmol) of 3- (4-bromobutyl) -7-nitrobenzo [ d][1,2,3]Triazine-4 (3H) -one was added to 10ml of DMF, and 0.210g (1.1mmol) of spiro [ indoline-3, 2' - [1,3] was added]Dioxolanes]-2-ketone and 0.207g (1.5mmol) of potassium carbonate, stirred to form a suspension, and heated to 80 ℃ for 10 hours. Cooling to room temperature, removing solvent by evaporation under reduced pressure, adding water, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and separating with column to obtain yellow solid 0.323g with yield of 74%.1H NMR(400MHz,DMSO-d6)8.90(d,J＝2.0Hz,1H),8.59(dd,J1＝8.8Hz,J2＝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)；13C NMR(100MHz,DMSO-d6)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-)C21H18N5O6(M-H)–Calculating the value: 436.1257, found: 436.1260.
example 101- (4- (4-oxo-7-vinylbenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl) -6-bromospiro [ indoline-3, 2' - [1,3] dioxan ] -2-one
Figure BDA0000659782670000201
The synthesis of the title compound was performed in analogy to example 9, step 9.2, except using 3- (4-bromobutyl) -7-vinylbenzo [ d ]][1,2,3]Triazin-4 (3H) -one in place of 3- (4-bromobutyl) -7-vinylbenzo [ d][1,2,3]Triazin-4 (3H) -ones from 6-bromospiro [ indoline-3, 2' - [1,3]]Dioxane (dioxane)]-2-one instead of spiro [ indoline-3, 2' - [1,3]]Dioxolanes]-2-ketones. White solid, yield 88%. HRMS (ES +) C24H24N4O4 79Br(M+H)+Calculating the value: 511.0981, found: 511.0985, respectively; c24H24N4O4 81Br(M+H)+Calculating the value: 513.0960, found: 513.0958.
example 113- ((1- (4-methoxyphenyl) -1H-1,2, 3-triazol-4-yl) methyl) benzo [ d ] [1,2,3] triazin-4 (3H) -one
11.1 preparation of 3- (2-propyn-1-yl) benzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000202
7.350g (50mmol) of benzo [ d ]][1,2,3]Triazin-4 (3H) -one and 8.28g (60mmol) of potassium carbonate were added to 200ml of acetone, stirred to give a suspension, 8.925g (75mmol) of 3-bromopropyne was added, and the mixture was heated to 50 ℃ to react for 8 hours. Cooling to room temperature, removing the solvent by evaporation under reduced pressure, adding water, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and separating with a column to obtain 6.013g of yellow solid with a yield of 65%.1H NMR(400MHz,DMSO-d6)8.28(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-d6)154.1,143.6,135.7,133.3,128.2,124.6,119.3,78.1,75.6,38.8.
11.2 preparation of 3- ((1- (4-methoxyphenyl) -1H-1,2, 3-triazol-4-yl) methyl) benzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000211
0.295g (2.4mmol) of 4-methoxyaniline in 5ml of acetonitrile is added, the temperature is reduced to 0 ℃, 0.371g (3.6mmol) of tert-butyl nitrite and 0.331g (2.88mmol) of azidotrimethylsilane are added in succession, stirring is carried out for 10 minutes at 0 ℃, the reaction is continued for 1 hour at room temperature, and 0.296g (1.6mmol) of 3- (2-propyn-1-yl) benzo [ d ] is added in succession][1,2,3]Triazin-4 (3H) -one, 0.036g (0.192mmol) cuprous iodide and 0.34ml (2.4mmol) triethylamine, supplemented with 5ml acetonitrile, were reacted at room temperature for 2 hours. An appropriate amount of silica gel was added to the reaction solution, the solvent was distilled off under reduced pressure, and column separation was carried out to obtain 0.278g of a yellow solid with a yield of 52%.1H NMR(400MHz,CDCl3)8.34(dd,J1＝8.0Hz,J2＝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,CDCl3)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+)C17H15N6O2(M+H)+Calculating the value: 335.1256, found: 335.1251.
example 123- (2- (1- (4-tert-butyl) phenyl-1H-1, 2, 3-triazol-4-yl) ethyl) -7-nitrobenzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000212
The synthesis of the title compound is analogous to step 11.2 of example 11, except that 4-tert-butylaniline is used instead of 4-methoxyaniline and 3- (3-butyn-1-yl) -7-nitrobenzo [ d ] is used][1,2,3]Triazin-4 (3H) -ones in place of 3- (2-propyn-1-yl) benzo [ d][1,2,3]Triazin-4 (3H) -one. Pale yellow solid, yield 45%. HRMS (ES-) C21H20N7O3(M-H)–Calculating the value: 418.1628, found: 418.1631.
example 133- (3- ((5-cyclopropyl-1, 3, 4-thiadiazol-2-yl) thio) propyl) -7-nitrobenzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000213
The preparation of 3- (3-bromopropyl) -7-nitrobenzo [ d ] [1,2,3] triazin-4 (3H) -one is similar to that of 3- (3-bromopropyl) -7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one in example 1, except that 7-nitrobenzo [ d ] [1,2,3] triazin-4 (3H) -one is used instead of 7-chlorobenzo [ d ] [1,2,3] triazin-4 (3H) -one.
0.626g (2mmol) of 3- (3-bromopropyl) -7-nitrobenzo [ d][1,2,3]Triazin-4 (3H) -one, 0.474g (3mmol) of 5-cyclopropyl-2-mercaptothiadiazole and 0.331g (2.4mmol) of potassium carbonate were added to 30ml of acetone, stirred to give a suspension, and heated to reflux for 8 hours. Cooling to room temperature, removing solvent by evaporation under reduced pressure, adding water, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and separating with column to obtain yellow solid 0.624g with yield of 80%. HRMS (ES-) C15H13N6O3S2(M-H)–Calculating the value: 389.0491, found: 389.0496.
example 143- (3- ((6-methoxybenzo [ d ] oxazol-2-yl) thio) propyl) -4-oxo-3, 4-dihydrobenzo [ d ] [1,2,3] triazine-6-sulfonamide
Figure BDA0000659782670000221
The synthesis of the title compound was performed in analogy to the procedure of example 13, except using 3- (3-bromopropyl) -6-aminosulfonylbenzo [ d ]][1,2,3]Triazin-4 (3H) -ones in place of 7-chlorobenzo [ d][1,2,3]Triazin-4 (3H) -ones, except that 6-aminosulfonylbenzo [ d ] is used][1,2,3]Triazin-4 (3H) -one in place of 3- (3-bromopropyl) -7-nitrobenzo [ d][1,2,3]Triazin-4 (3H) -ones with 6-methoxybenzo [ d]Oxazole-2-thiol replaces 5-cyclopropyl-2-mercaptothiadiazole. Yellow solid, yield 71%. HRMS (ES +) C18H18N5O5S2(M+H)+Calculating the value: 448.0749, found: 448.0755.
example 153- (4-Oxobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propylbenzo [ d ] [1,2,3] thiadiazole-7-carboxylate
15.1 preparation of 3- (3-hydroxypropyl) benzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000222
The preparation of 7-fluorobenzo [ d ] [1,2,3] triazin-4 (3H) -one is analogous to example 1, step 1.1, except that 2-amino-4-fluorobenzoic acid is used instead of 2-amino-4-chlorobenzoic acid.
0.330g (2mmol) of 7-fluoro-benzo [ d ]][1,2,3]Triazin-4 (3H) -one and 0.552g (4mmol) of potassium carbonate were added to 30ml of acetone, stirred to give a suspension, 0.417g (3mmol) of 3-bromopropanol was added, and the mixture was heated to reflux for 6 hours. Cooling to room temperature, removing the solvent by evaporation under reduced pressure, adding water, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and separating with column to obtain beige solid 0.317g with yield of 71%. HRMS (ES +) C10H11N3O2F(M+H)+Calculating the value: 224.0835, found: 224.0841.
15.2 preparation of benzo [ d ] [1,2,3] thiadiazole-7-carbonyl chloride
Figure BDA0000659782670000231
3.780g (21mmol) of benzo [ d ] [1,2,3] thiadiazole-7-carboxylic acid was added to 40ml of thionyl chloride, and heated to reflux for 8 hours. After cooling to room temperature, unreacted thionyl chloride was distilled off under reduced pressure to obtain 3.552g of a pale yellow solid, which was used in the next step without treatment.
15.3 preparation of 3- (4-oxo-7-fluorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propylbenzo [ d ] [1,2,3] thiadiazole-7-carboxylate
Figure BDA0000659782670000232
0.446g of (2mmol)3- (3-hydroxypropyl) -7-fluorobenzo [ d][1,2,3]Triazine-4 (3H) -one is dissolved in 20ml of dichloromethane, 0.31ml (2.2mol) of triethylamine is added and 0.478g (2.4mmol) of benzo [ d ] is added dropwise at room temperature][1,2,3]Thiadiazole-7-carbonyl chloride in 20ml dichloromethane. After the addition, the reaction was continued at room temperature for 4 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by stirring, separation of the organic phase, extraction of the aqueous phase with dichloromethane, combination of all the organic phases, drying over anhydrous sodium sulfate, concentration, and column separation to obtain 0.246g of a white solid with a yield of 32%.1H NMR(400MHz,DMSO-d6)8.98(d,J＝8.4Hz,1H),8.23-8.14(m,2H),7.91(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.80(t,J＝8.0Hz,1H),7.69(td,J1＝8.8Hz,J2＝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-d6)-102.0(td,J1＝8.6Hz,J2＝5.6Hz).HRMS(ES+)C17H13N5O3FS(M+H)+Calculating the value: 386.0723, found: 386.0724.
example 163- (4-oxo-5-bromobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propylbenzo [ d ] [1,2,3] thiadiazole-7-carboxylate
Figure BDA0000659782670000233
The synthesis of the title compound was performed in analogy to example 15, step 15.3, except using 3- (3-hydroxypropyl) -5-bromobenzo [ d ]][1,2,3]Triazin-4 (3H) -one instead of 3- (3-hydroxypropyl) -7-fluoro-benzo [ d][1,2,3]Triazin-4 (3H) -one. White solid, yield 26%.1H NMR(400MHz,DMSO-d6)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-d6)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+)C17H12N5O3NaS79Br(M+Na)+Calculating the value: 467.9742, found value: 467.9744, respectively; c17H12N5O3NaS81Br(M+Na)+Calculating the value: 469.9721, found: 469.9716.
example 173- (4-oxo-6-trifluoromethylbenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propylbenzo [ d ] [1,2,3] thiadiazole-7-carboxylate
Figure BDA0000659782670000241
The synthesis of the title compound was performed in analogy to example 15, step 15.3, except using 3- (3-hydroxypropyl) -6-trifluoromethylbenzo [ d ]][1,2,3]Triazin-4 (3H) -one instead of 3- (3-hydroxypropyl) -7-fluoro-benzo [ d][1,2,3]Triazin-4 (3H) -one. White solid, yield 16%.1H NMR(400MHz,DMSO-d6)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-d6)-61.5(s).HRMS(ES+)C19H16N6O2F3S(M+H)+Calculating the value: 449.1008, found: 449.1006.
example 18N- (3- (4-oxo-7-fluorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) benzo [ d ] [1,2,3] thiadiazole-7-amide
18.1 preparation of 2- (3- (4-oxo-7-fluorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) isoindoline-1, 3-dione
Figure BDA0000659782670000242
0.572g (2mmol) of 3- (3-bromopropyl) -7-fluoroph-eno [ d][1,2,3]Triazin-4 (3H) -one, 0.353g (2.4mmol) phthalimide and 0.331g (2.4mmol) were added to 10ml DMF, stirred to give a suspension, and heated to 60 ℃ for reaction for 3 hours. Cooling to room temperature, removing solvent by evaporation under reduced pressure, adding water, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, concentrating, and separating with column to obtain off-white solid 0.598g with yield of 85%. HRMS (ES +) C18H14N4O3F(M+Na)+Calculating the value: 353.1050, found: 353.1053.
18.2 preparation of 3- (3-aminopropyl) -7-fluorobenzo [ d ] [1,2,3] triazin-4 (3H) -one
Figure BDA0000659782670000243
0.352g (1mmol) of 2- (4- (4-oxybenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl) isoindoline-1, 3-dione was added to a mixed solvent of 10ml of methylene chloride and 10ml of ethanol, and the mixture was heated to reflux for 12 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, a saturated aqueous sodium carbonate solution was added to the residue, extraction was performed with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.191g of a yellow oily liquid which was used in the next step without purification.
18.3 preparation of N- (3- (4-oxo-7-fluorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) benzo [ d ] [1,2,3] thiadiazole-7-amide
Figure BDA0000659782670000244
0.222g (1mmol) of 3- (3-aminopropyl) -7-fluorobenzo [ d][1,2,3]Triazine-4 (3H) -one is dissolved in 10ml dichloromethane, 0.15ml (1.1mmol) triethylamine is added and 0.259g (1.3mmol) of benzo [ d ] are added dropwise at room temperature][1,2,3]Thiadiazole-7-carbonyl chloride in 10ml dichloromethane. After the addition, the reaction was continued at room temperature for 5 hours, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by thorough stirring, separation of the organic phase, extraction of the aqueous phase with dichloromethane, combination of all the organic phases, drying over anhydrous sodium sulfate, concentration, and column separation to obtain 0.131g of an off-white solid with a yield of 34%.1H NMR(400MHz,DMSO-d6)9.24(t,J＝5.2Hz,1H),8.88(d,J＝8.4Hz,1H),8.42(d,J＝7.2Hz,1H),8.26(dd,J1＝8.8Hz,J2＝5.6Hz,1H),7.97(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.90(t,J＝7.6Hz,1H),7.74(td,J1＝8.8Hz,J2＝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-d6)-102.0(td,J1＝8.6Hz,J2＝5.6Hz).HRMS(ES+)C17H14N6O2FS(M+H)+Calculating the value: 385.0883, found: 385.0885.
example 19N- (4- (4-oxo-7-bromobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) butyl) benzo [ d ] [1,2,3] thiadiazole-7-amide
Figure BDA0000659782670000251
The synthesis of the title compound was analogous to step 18.2 of example 18, except using 3- (4-aminobutyl) -7-bromobenzo [ d ]][1,2,3]Triazin-4 (3H) -one instead of 3- (3-aminopropyl) -7-fluoro-benzo [ d][1,2,3]Triazin-4 (3H) -one. Off-white solid, yield 25%.1H NMR(400MHz,DMSO-d6)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-d6)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+)C18H16N6O2S79Br(M+H)+Calculating the value: 459.0239, found: 459.0241, respectively; c18H16N6O2S81Br(M+H)+Calculating the value: 461.0218, found: 461.0221.
example 20N- (3- (5-chloro-4-oxybenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) -5-methyl-1, 2, 3-thiadiazole-4-amide
Figure BDA0000659782670000252
The synthesis of the title compound was performed analogously to example 18, step 18.2, with the exception that 3- (3-aminopropyl) -5-chlorobenzo [ d ] was used][1,2,3]Triazin-4 (3H) -one in place of 3- (3-aminopropyl) -7-fluoroBenzo [ d ] carbonyl][1,2,3]Triazin-4 (3H) -one with 5-methyl-1, 2, 3-thiadiazole-4-carbonyl chloride instead of benzo [ d][1,2,3]Thiadiazole-7-carbonyl chloride. White solid, yield 41%. HRMS (ES +) C14H13N6O2NaS35Cl(M+Na)+Calculating the value: 387.0407, found: 387.0411, respectively; c14H13N6O2NaS37Cl(M+Na)+Calculating the value: 389.0377, found: 389.0380.
example 211- (6-Methoxybenzo [ d ] thiazol-2-yl) -3- (3- (4-oxo-7-trifluoromethylbenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) thiourea
Figure BDA0000659782670000261
The 3- (3-aminopropyl) -7-trifluoromethylbenzo [ d ] [1,2,3] triazin-4 (3H) -one was prepared in a similar manner to the preparation of 3- (3-aminopropyl) -7-fluorobenzo [ d ] [1,2,3] triazin-4 (3H) -one in example 18, except that 3- (3-bromopropyl) -7-trifluoromethylbenzo [ d ] [1,2,3] triazin-4 (3H) -one was used in place of 3- (3-bromopropyl) -7-fluorobenzo [ d ] [1,2,3] triazin-4 (3H) -one. 2-isothiocyanato-6-methoxybenzo [ d ] thiazole can be prepared from 2-amino-6-methoxybenzo [ d ] thiazole as described in "WO 2014117677".
0.136g (0.5mmol) of 3- (3-aminopropyl) -7-trifluoromethylbenzo [ d][1,2,3]Triazin-4 (3H) -one was dissolved in 2ml acetonitrile and 0.111g (0.5mmol) of 2-isothiocyanato-6-methoxybenzo [ d ] was added]Thiazole, stirring at room temperature, and following the progress of the reaction by TLC. After the reaction is finished, the mixture is filtered, and a filter cake is recrystallized by ethanol to obtain 0.191g of brown yellow powdery solid with the yield of 77 percent. HRMS (ES +) C20H18N6O2F3S2(M+H)+Calculating the value: 495.0885, found: 495.0882.
example 221- (benzo [ d ] isoxazol-3-yl) -3- (3- (4-oxo-8-methoxybenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) thiourea
Figure BDA0000659782670000262
The synthesis of the title compound was performed in analogy to the procedure of example 21, except using 3- (3-aminopropyl) -8-methoxybenzo [ d ]][1,2,3]Triazin-4 (3H) -one in place of 3- (3-aminopropyl) -7-trifluoromethylbenzo [ d][1,2,3]Triazin-4 (3H) -ones, benzo [ d ] with 3-isothiocyanato]Isoxazoles instead of 3- (3-aminopropyl) -7-trifluoromethylbenzo [ d][1,2,3]Triazin-4 (3H) -one. Yellow powdery solid, yield 71%. HRMS (ES +) C19H18N6O3NaS(M+Na)+Calculating the value: 433.1059, found: 433.1062.
example 23N- ((3- (4-oxo-8-chlorobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) aminothiocarbonyl) -2- (trifluoromethoxy) benzamide
23.1 preparation of 2- (trifluoromethoxy) benzoyl isothiocyanate
Figure BDA0000659782670000263
The preparation of 2- (trifluoromethoxy) benzoyl chloride was similar to example 15, step 15.2, except that 2- (trifluoromethoxy) benzoic acid was used instead of benzo [ d ] [1,2,3] thiadiazole-7-carboxylic acid.
1.8g (8mmol) of 2- (trifluoromethoxy) benzoyl chloride was dissolved in 20ml dichloromethane, 0.912g (12mmol) of ammonium thiocyanate was added, 0.144g of PEG-400 was added, stirring was carried out at room temperature for 1 hour, suction filtration was carried out, the filtrate was concentrated and purified by flash column to obtain 1.581g of yellow oily liquid, which was directly used in the next reaction.
23.2 preparation of N- ((3- (4-oxybenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) aminothiocarbonyl) -2- (trifluoromethoxy) benzamide
Figure BDA0000659782670000271
The preparation of 3- (3-aminopropyl) benzo [ d ] [1,2,3] triazin-4 (3H) -one is analogous to that of 3- (3-aminopropyl) -7-fluorobenzo [ d ] [1,2,3] triazin-4 (3H) -one in example 18, except that benzo [ d ] [1,2,3] triazin-4 (3H) -one is used instead of 3- (3-bromopropyl) -7-fluorobenzo [ d ] [1,2,3] triazin-4 (3H) -one.
0.102g (0.5mmol) of 3- (3-aminopropyl) benzo [ d][1,2,3]Triazin-4 (3H) -one was dissolved in 2ml acetonitrile, 0.124g (0.5mmol)2- (trifluoromethoxy) benzoyl isothiocyanate was added, stirred at room temperature and the progress of the reaction was followed by TLC. After the reaction is finished, the reaction solution is filtered, the filtrate is concentrated and separated by a column, and light yellow solid 0.153g is obtained with the yield of 68%.1H NMR(400Mz,CDCl3)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,CDCl3)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,1JCF＝260.0Hz),117.8,67.1,42.27,27.9.HRMS(ES+)C19H17F3N5O3S(M+H)+Calculating the value: 452.1004, found: 452.1004.
example 243- (5-methyl-1, 2, 4-oxadiazol-3-yl) -N- ((3- (3-oxo-7-nitrobenzo [ d ] [1,2,3] triazin-3 (4H) -yl) propyl) aminothiocarbonyl) benzamide
Figure BDA0000659782670000272
The title compound was prepared in analogy to example 23, step 23.2, but using 3- (3-aminopropyl) -7-nitrobenzo [ d ]][1,2,3]Triazin-4 (3H) -one in place of 3- (3-aminopropyl) benzo [ d][1,2,3]Triazin-4 (3H) -one, 3- (5-ethyl-1, 2, 4-oxadiazol-3-yl) benzoyl isothiocyanate was used instead of 2- (trifluoromethoxy) benzoyl isothiocyanate. Pale yellow solid, yield 65%. HRMS (ES-) C22H19N8O5S(M–H)–Calculating the value: 507.1199, found: 507.1194.
EXAMPLE 25 nematicidal Activity of Compounds of the invention
The root-knot nematode belongs to phylum nematoda, order of Tylenchida, suborder of Tylenchida, heterodermic superfamily, heterodermic family (Heterodermida), suborder of root-knot nematode (Meloidogyniae) and genus Meloidogyninella, and is a plant parasitic nematode with serious harm.
Southern root-knot nematode (Meloidogyne incognita) is used as a test object, cucumber seedlings are used as test hosts, and a test tube planting method is adopted for testing.
The operation process is as follows: preparing a sample to be tested into liquid medicine according to the required concentration for standby application, and preparing enough root-knot nematode second-instar larvae. After planting cucumber seedlings of one week old in test tubes, adding a proper amount of prepared liquid medicine into the test tubes, and inoculating about 2000 larvae into each test tube. And (3) culturing the test tube at 20-25 ℃ under 10-hour illumination, investigating the result after 20 days, and counting the root knot number on the root system of each plant. The test was repeated 3 times for each sample, with 4 replicates for each sample per test.
Distilled water is used as a blank control, distilled water and root-knot nematode are used as negative controls, and fenamiphos and abamectin solution are used as positive controls.
The inhibition was counted by ranking by number of root knots (see table 1). The statistical results are shown in tables 2-6.
Inhibition (%) was ═ negative control score-test group score)/negative control score × 100%
TABLE 1
Grading standard:
0: 0-5 root knots;
5: 6-10 root knots;
10: 11-20 root knots;
20: more than 20 root knots.
TABLE 2 nematicidal Activity of Compounds of formula (II)
Figure BDA0000659782670000281
Figure BDA0000659782670000291
Figure BDA0000659782670000301
Figure BDA0000659782670000311
Figure BDA0000659782670000321
Figure BDA0000659782670000331
Figure BDA0000659782670000341
Figure BDA0000659782670000351
Figure BDA0000659782670000361
Figure BDA0000659782670000371
Figure BDA0000659782670000381
Figure BDA0000659782670000391
TABLE 3 nematicidal Activity of Compounds of formula (III)
Figure BDA0000659782670000392
Figure BDA0000659782670000401
Figure BDA0000659782670000411
Figure BDA0000659782670000421
TABLE 4 nematicidal Activity of Compounds of formula (IV)
Figure BDA0000659782670000422
Figure BDA0000659782670000431
Figure BDA0000659782670000441
Figure BDA0000659782670000451
TABLE 5 nematicidal Activity of Compounds of formula (V)
Figure BDA0000659782670000452
Figure BDA0000659782670000461
Figure BDA0000659782670000471
Figure BDA0000659782670000481
Figure BDA0000659782670000491
TABLE 6 nematicidal Activity of Compounds of formula (VI)
Figure BDA0000659782670000492
Figure BDA0000659782670000501
Figure BDA0000659782670000511
In the above tables, Y represents a covalent bond and M represents a bond, "/" represents that M is absent.
Example 26 composition containing a nematicide which is a Compound of the present invention
(a) Microemulsion preparation
Preparing the following components in proportion: 5.0% (by weight, the same applies hereinafter) of any one of the compounds II-1 to VI-36 (tables 2 to 6); 30.0% polyvinylpyrrolidone-vinyl acetate copolymer; 30.0% alkylpolyglycoside; 15.0% glyceryl oleate; 20.0% water.
(b) Wettable powder
Preparing the following components in proportion: 65.0% of any one of the compounds II-1 to VI-36 (tables 2 to 6); 2.0% of dodecylphenol polyglycol ether; 4.0% sodium lignosulfonate; 6.0% sodium aluminum silicate; 23.0% montmorillonite (calcined).
(c) Seed treatment agent
Preparing the following components in proportion: 20.00% of any one of the compounds II-1 to VI-36 (tables 2 to 6); 5.00% polyvinylpyrrolidone-vinyl acetate copolymer; 5.00% montanic acid wax; 1.00% calcium lignosulfonate; 1.00% polyoxyethylene/polyoxypropylene block copolymer; 2.00% stearyl alcohol (POE 20); 0.20% of polyorganosiloxane; 0.05% colorant red dye; 65.75% water.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (10)

1. A compound having a structure represented by the general formula (I), or an agriculturally pharmaceutically acceptable salt of the compound:
Figure FDA0002759254180000011
in the formula:
x is O or S;
y is O, S, S (═ O), S (═ O)2NH or a covalent bond;
q is carbonyl, thiocarbonyl-amino-carbonyl or a covalent bond;
l is
Figure FDA0002759254180000012
Figure FDA0002759254180000013
M is nothing;
and a is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-or 6-membered heterocyclyl, or substituted or unsubstituted 8-to 14-membered heteroaromatic bicyclic or tricyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR', C (O) R ', C (O) OR', C (O) NR 'R', S (O)2NR'R"、OC(O)R1、OC(O)NR'R"、N(R2)C(O)R1、N(R2)S(O)2R1；
G represents a substituent at any one or more positions of A, and G is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, substituted or unsubstituted C2-6Alkynyl, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, R ', OR ', Si (R ')3、C(O)R'、C(O)OR'、C(O)NR'R"；
Wherein R' is independently H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6Haloalkynyl, or substituted or unsubstituted C3-7Cycloalkyl, substituted or unsubstituted C5-7Cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6A haloalkyl group;
r "is independently H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, C2-6A haloalkynyl group;
R1is substituted or unsubstitutedSubstituted or unsubstituted naphthyl, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-6Alkyl radical, C1-6A haloalkyl group;
R2is H, C1-6Alkyl radical, C1-6A haloalkyl group;
wherein the content of the first and second substances,
n is 0, 1,2,3, 4 or 5.
2. The compound of claim 1, or an agriculturally pharmaceutically acceptable salt of the compound, selected from the group consisting of:
Figure FDA0002759254180000021
in each of the above formulae, X, L, G, A, M and n are as defined in claim 1, and Y is O, S, S (═ O), S (═ O)2Or a covalent bond.
3. The compound of claim 1 or 2, or an agriculturally pharmaceutically acceptable salt of the compound, wherein X is O or S.
4. The compound of claim 1 or 2, or an agriculturally pharmaceutically acceptable salt of the compound, wherein L is
Figure FDA0002759254180000022
5. A compound according to claim 1 or 2, or an agriculturally pharmaceutically acceptable salt of the compound, wherein a is a substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-or 6-membered heterocyclyl, or substituted or unsubstituted 8-to 12-membered heteroaromatic bicyclic ring system, said substitution being by one or more groups selected from the group consisting of: halogen, cyano, nitro, C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy radical, C1-4Haloalkoxy, phenoxy, aminosulphonic, amino-carbonyl, C1-4Alkyl-carbonyl, C1-4Alkoxy-carbonyl, C1-4Alkylamino-carbonyl or phenylamino-carbonyl.
6. The compound, or an agriculturally pharmaceutically acceptable salt of the compound, of claims 1 or 2, wherein G is H, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Haloalkenyl, C2-6Alkynyl, trimethylsilyl ethynyl.
7. The compound of claim 1 or 2, or an agriculturally pharmaceutically acceptable salt of the compound, selected from the group consisting of:
Figure FDA0002759254180000031
Figure FDA0002759254180000041
Figure FDA0002759254180000051
Figure FDA0002759254180000061
Figure FDA0002759254180000071
Figure FDA0002759254180000081
Figure FDA0002759254180000091
Figure FDA0002759254180000101
Figure FDA0002759254180000102
Figure FDA0002759254180000111
Figure FDA0002759254180000121
Figure FDA0002759254180000131
Figure FDA0002759254180000141
Figure FDA0002759254180000151
wherein Y is "-" indicates that Y is a covalent bond, and M is "/" indicates that M is absent.
8. An agricultural composition, characterized in that it comprises:
(1) 0.001-99.99% by weight of a compound of any one of claims 1-7, or an agriculturally pharmaceutically acceptable salt of the compound, or a combination thereof; and
(2) an agriculturally pharmaceutically acceptable carrier and/or excipient.
9. Use of a compound according to claim 1, or an agriculturally pharmaceutically acceptable salt of said compound or an agricultural composition according to claim 8, for the preparation of a medicament or composition for killing or preventing nematodes.
10. A process for the preparation of a compound according to claim 1, or an agriculturally pharmaceutically acceptable salt of said compound,
(A) the method comprises the following steps:
(1) in an inert solvent, carrying out a ring closing reaction on the compound shown in the formula (a) and bis (trichloromethyl) carbonate to obtain a compound shown in the formula (b);
(2) carrying out ring-opening reaction on the compound of the formula (b) and ammonium carbonate in an inert solvent to obtain a compound of a formula (c);
(3) in an inert solvent, carrying out diazotization reaction and ring closing reaction on the compound of the formula (c) to obtain a compound of a formula (d);
Figure FDA0002759254180000152
(4) reacting a compound of formula (d) with BrCH in an inert solvent in the presence of a base2(CH2)nBr reaction to obtain the compound of formula (e);
(5) reacting a compound of formula (e) with a compound of formula (f) or a compound of formula (p) in an inert solvent to obtain a compound of formula (I);
Figure FDA0002759254180000153
or (B) the method comprises the steps of:
(4') in an inert solvent inIn the presence of a base, a compound of formula (d) is reacted with BrCH2(CH2)nC is equal to CH to obtain a compound shown in a formula (g);
(5') reacting the compound of formula (g) with the compound of formula (h) in an inert solvent to obtain the compound of formula (I);
Figure FDA0002759254180000161
or (C) the method comprises the steps of:
(4') reacting a compound of formula (d) with BrCH in an inert solvent in the presence of a base2(CH2)nYH reaction to obtain a compound of the formula (i);
(5') reacting the compound of formula (I) with the compound of formula (k) in an inert solvent to obtain the compound of formula (I);
Figure FDA0002759254180000162
or (D) the method comprises the steps of:
(5') reacting the compound of formula (e) with the compound of formula (m) in an inert solvent in the presence of a base, and then deprotecting to obtain the compound of formula (n);
(6) reacting a compound of formula (n) with a compound of formula (o) in an inert solvent to obtain a compound of formula (I);
Figure FDA0002759254180000163
or (E) the method comprises the steps of:
(6') reacting the compound of formula (n) with the compound of formula (o') in an inert solvent to obtain a compound of formula (I);
Figure FDA0002759254180000164
or (F) the method comprises the steps of:
(5') reacting a compound of formula (e) with a compound of formula (p) in an inert solvent in the presence of a base to give a compound of formula (I);
Figure FDA0002759254180000165
in each of the above formulae, X, Y, Q, L, M, A, G and n are as defined in claim 1.
CN201510031222.4A 2015-01-21 2015-01-21 Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof Expired - Fee Related CN104530037B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510031222.4A CN104530037B (en) 2015-01-21 2015-01-21 Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof
PCT/CN2016/071608 WO2016116058A1 (en) 2015-01-21 2016-01-21 Triazine heterocyclic compound with nematicidal activity and preparation method therefor and usage thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510031222.4A CN104530037B (en) 2015-01-21 2015-01-21 Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN104530037A CN104530037A (en) 2015-04-22
CN104530037B true CN104530037B (en) 2020-12-18

Family

ID=52845708

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510031222.4A Expired - Fee Related CN104530037B (en) 2015-01-21 2015-01-21 Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN104530037B (en)
WO (1) WO2016116058A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170275261A1 (en) * 2014-09-19 2017-09-28 Isagro S.P.A. 1,3,4-thiadiazoles having a herbicidal activity, their agronomical compositions and relative use
PL232272B1 (en) * 2015-07-28 2019-05-31 Fundacja Univ Im Adama Mickiewicza W Poznaniu Application of 7-carboxybenz[1,2,3]thiadiazole amides as plants stimulators
CN108084104A (en) * 2017-12-27 2018-05-29 温州大学 1,2,3- phentriazine -4（3H）The synthetic method of -one compound
CN108276352B (en) * 2018-03-13 2022-09-20 华东理工大学 Nitrogen-containing heterocyclic compound with nematicidal activity and preparation method and application thereof
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
Maleimido-Functionalized NOTA Derivatives as Bifunctional Chelators for Site-Specific Radiolabeling;Maik Schubert et al.;《Molecules》;第16卷;20110622;第5228-5240页 *
Multisite-directed inhibitors of protein kinase CK2: new challenges;Maciej Maslyk et al.;《Mol Cell Biochem》;20110713;第356卷;第117-119页 *
Rhenium(V) oxocomplexes with novel pyrazolyl-based N4- and N3S-donor chelators;Carolina Moura et al.;《Dalton Trans.》;20061010;第5630-5640页 *

Also Published As

Publication number Publication date
CN104530037A (en) 2015-04-22
WO2016116058A1 (en) 2016-07-28

Similar Documents

Publication Publication Date Title
CN104530037B (en) Triazine heterocyclic compound with nematicidal activity and preparation method and application thereof
US5077401A (en) Benzo-fused cyclic compounds
KR960002556B1 (en) Imidazole compounds and biocidal composition comprising the same for controlling harmful organisms
LV11464B (en) Fungicidal fused bicyclic pyrimidinones
WO1998023155A1 (en) Arthropodicidal and fungicidal cyclic amides
AU2017251616B9 (en) Agricultural chemicals
AU2019345827B2 (en) Triketone compound, preparation method therefor and use thereof, and herbicide
WO2019141980A1 (en) Agricultural chemicals
CN108276352B (en) Nitrogen-containing heterocyclic compound with nematicidal activity and preparation method and application thereof
CZ2000861A3 (en) Substituted 3-(1,2-benzisothiazole or isoxazol-5-yl)- substituted pyrimidines as herbicidal agents
IE921262A1 (en) Fungicidal pyrazoles, pyrazolines and tetrahydropyridazines
BR112019013653A2 (en) thiobenzoimidazole as a fungicide
CN103965134B (en) It is a kind of to contain N, S heterocyclic compound and its preparation method and purposes with eelworm-killing activity
WO2019020981A1 (en) Pyrazole, isothiazole and isoxazole derivatives useful as agricultural fungicides
WO2018116073A1 (en) 1, 2, 3-thiadiazole compounds and their use as crop protecting agent
EP0060426B1 (en) N-(2,2,2-trifluoroethyl)-n-alkyl-azolyloxyacetic-acid amides, their preparation and use as herbicides and intermediates for their preparation
EP0249938A2 (en) Imidazolesulfonamide derivatives, herbicides and a method for inhibiting growth of undesirable plants
HU196773B (en) Herbicides containing as active substance 4,5-disubstituated 1,3-triasole-2-il-oxi-acetamid-derivatives and process for production of the active substances
CZ28796A3 (en) /1,3,4/oxadiazoles and thiadiazoles as well as herbicidal agents based thereon
CA3164362A1 (en) Pyrido[2,3-e]oxazine derivatives as agricultural chemicals
CN115710195A (en) Trifluoroolefin compound with nematicidal activity and preparation method and application thereof
JPH107657A (en) Sulfonamide compound
CN113527129A (en) Trifluoroolefin compound with nematicidal activity and preparation method and application thereof
CN116265444A (en) Nematicidal compounds, process for their preparation and their use
DE3633485A1 (en) Substituted 2-pyri(mi)dyl-2&#39;-pyridyl (thio)ethers

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20201218