CN102696609B - Trifluoro butene pesticide containing pyridine - Google Patents

Trifluoro butene pesticide containing pyridine Download PDF

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Publication number
CN102696609B
CN102696609B CN 201210151694 CN201210151694A CN102696609B CN 102696609 B CN102696609 B CN 102696609B CN 201210151694 CN201210151694 CN 201210151694 CN 201210151694 A CN201210151694 A CN 201210151694A CN 102696609 B CN102696609 B CN 102696609B
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Prior art keywords
pyridine
insecticides
acetone
butylene
trifluoro
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CN102696609A (en
Inventor
许辉
唐剑峰
吴雪
刘杰
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Shandong intermediate peasant union biological Polytron Technologies Inc
Weifang Zhongnong United Chemical Co.,Ltd.
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WEIFANG ZHONGNONG UNITED CHEMICAL CO Ltd
SHANDONG SINO-AGRI UNITED BIOTECHNOLOGY Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a trifluoro butene pesticide containing pyridine. The structural formula of the pesticide is represented as formula (1), wherein n=0, 1 and 2. A preparation method of the pesticide is that in the formula (1), n=1 or 2; and when n=0, the pesticide is prepared by undergoing a reaction with an oxidant in inert solvents. The trifluoro butene pesticide containing pyridine is specially used for killing nematode and has the advantages of being remarkable in nematode-killing effect and low in preparation cost and using cost.

Description

A kind of trifluoro butylene insecticides that contains pyridine
Technical field
The present invention relates to agricultural chemicals, is a kind of trifluoro butylene insecticides that contains pyridine.
Background technology
It is the openest as far back as the U.S. that the trifluoro butene compounds has nematicide activity, and afterwards, states such as Japan, China also disclose the multiple nematicidal compound that is different from the United States Patent (USP) structure.These different compounds each have different characteristics when killing nematode.For example: disclosed compound in 00809783.6 patent, though have nematicide performance,, its preparation cost height, and usage amount is higher.
Summary of the invention
The purpose of this invention is to provide a kind of trifluoro butylene insecticides that contains pyridine, it is exclusively used in nematode extremely, and makes it have significant nematicide effect, the advantage that preparation cost and use cost are low.
The present invention is achieved through the following technical solutions for achieving the above object: a kind of trifluoro butylene insecticides that contains pyridine, and the structural formula of this insecticide is:
Figure 201210151694X100002DEST_PATH_IMAGE001
(1), n=0 wherein, 1,2.
Described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine,
(1), wherein during n=0,6-chloro-3-first sulfydryl pyrrole is fixed (3) and halogenating agent
Figure 201210151694X100002DEST_PATH_IMAGE003
(4) in the presence of atent solvent, react and make.
Described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine,
Figure 154006DEST_PATH_IMAGE001
(1), wherein n=1 or 2 incites somebody to action
Figure 695846DEST_PATH_IMAGE001
(1), wherein during n=0, reacts under atent solvent with oxidant and to make.
Described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine prepares following insecticide:
Figure 319594DEST_PATH_IMAGE004
（2），
Step is as follows: (3) 0.01 moles of 6-chloro-3-first mercaptopyridines are dissolved in 10 milliliters the acetone, add in advance 0.05 mole in the dry potash of crossing, drip 4-bromo-1 at normal temperatures, (4) 0.01 moles of 1,2-, three fluoro-1-butylene are after dropwising, refluxed 48 hours, and filtered, contained
Figure 946884DEST_PATH_IMAGE004
Acetone soln and solid, with acetone drip washing solid 3-5 time, merge the acetone soln that obtains, distill and remove acetone, obtain
Figure 799434DEST_PATH_IMAGE004
(2), obtain yellowish liquid with the chromatography purification, wherein chromatographic solution is n-hexane: the weight ratio of ethyl acetate is 4:6.
Described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine, atent solvent is acetone, N, dinethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
Described a kind of application that contains the trifluoro butylene insecticides of pyridine, this insecticide acts on nematode or its habitat.
Insecticide of the present invention has high activity, is exclusively used in nematode extremely, and its nematicide effect is remarkable.It and various crops have favorable compatibility.It can be used for preventing that Pratylenchidae from belonging to; The ball Heterodera: potato is worm completely; Heterodera: soybean cyst nematode; Meloidogyne: aphelenchoides besseyi, similes thorne, fuller's teasel stem eelworm, the nematode of partly puncturing; The minute hand Turbatrix; Xiphinema; The burr Turbatrix; Umbrella Aphelenchoides: pine wood nematode etc.
Insecticide of the present invention can be made regular dosage form: emulsion, an aqueous dispersion material agent, wettable powder, microcapsules etc.
Insecticide preparation method of the present invention does not have special installation and requirement, and preparation cost is low, owing to have high insecticidal activity, can reduce use cost.The present invention draws through measuring the nematicide effect, and control efficiency is remarkable.Test formulation: (structural formula 1, wherein, n=2), 9 parts of kaolin prepare 10% fine granular that contains reactive compound (structural formula 1, wherein n=2) to 1 part of reactive compound.This reagent is used for killing tomato root-knot eelworm.Before the medication; record 50 of every mu of root-knot nematode average out to of plantation tomato protection land used; reagent dosage is 3 liters every mu; reagent inserted contain in the root-knot nematode soil; detect 0.9 of every mu of root-knot nematode after 30 days, insecticidal effect is 99%, and medication detects 1.8 of every mu of root-knot nematodes after 60 days; insecticidal effect is 97%, and above-mentioned insecticidal effect is to use and detect the conclusion that repetition provides for 10 times at reagent.
Embodiment
A kind of trifluoro butylene insecticides that contains pyridine of the present invention, the structural formula of this insecticide is:
Figure 461359DEST_PATH_IMAGE001
(1), n=0 wherein, 1,2.
A kind of preparation method who contains the trifluoro butylene insecticides of pyridine of the present invention,
Figure 256009DEST_PATH_IMAGE001
(1), wherein during n=0,6-chloro-3-first sulfydryl pyrrole is fixed
Figure 370596DEST_PATH_IMAGE002
(3) and halogenating agent
Figure 620311DEST_PATH_IMAGE003
(4) in the presence of atent solvent, react and make.
A kind of preparation method who contains the trifluoro butylene insecticides of pyridine of the present invention, its
Figure 12109DEST_PATH_IMAGE001
(1), wherein n=1 or 2 incites somebody to action
Figure 853027DEST_PATH_IMAGE001
(1), wherein during n=0, reacts under solvent with oxidant and to make.
A kind of preparation method who contains the trifluoro butylene insecticides of pyridine of the present invention, atent solvent is acetone, N, dinethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
A kind of application that contains the trifluoro butylene insecticides of pyridine of the present invention, this insecticide acts on nematode or its habitat.
Example 1: prepare following insecticide:
Figure 579543DEST_PATH_IMAGE004
(2), step is as follows: (3) 0.01 moles of 6-chloro-3-first mercaptopyridines are dissolved in 10 milliliters the acetone, add in advance 0.05 mole in the dry potash of crossing, drip 4-bromo-1,1 at normal temperatures, (4) 0.01 moles of 2-three fluoro-1-butylene, after dropwising, refluxed 48 hours, and filtered, contained
Figure 164108DEST_PATH_IMAGE004
Acetone soln and solid, with acetone drip washing solid 3-5 time, merge the acetone soln that obtains, distill and remove acetone, obtain
Figure 410413DEST_PATH_IMAGE004
(2), obtain flaxen liquid with the chromatography purification, wherein chromatographic solution is n-hexane: the weight ratio of ethyl acetate is 4:6, elementary analysis: C: 44.87% H:3.39% Cl13.24% F:21.29% N:5.23% S:11.98%.
Example 2 prepares following insecticide:
（1），n=1，
Step is as follows: will
Figure 78023DEST_PATH_IMAGE004
(2) 0.01 moles were dissolved in 10 milliliters the methyl alcohol, add 0.01 mole hydrogen peroxide, 30-40 ℃ of reaction 10 hours, add sodium sulphite and destroy remaining oxidant, add ethyl acetate extraction, the distillation desolventizing, purify with chromatography, obtain yellow liquid, wherein chromatographic solution is n-hexane: the ethyl acetate weight ratio is 3:7, elementary analysis: C:42.34% H:3.20%, Cl:12.50%, F:20.09%, N:4.94%, O:5.64%, S:11.30%.
Example 3 prepares following insecticide:
Figure 901623DEST_PATH_IMAGE006
（1），n=2，
Step is as follows: with in the example 2
Figure DEST_PATH_IMAGE007
(1) n=1,0.01 mole is dissolved in 10 milliliters the methyl alcohol, adds 0.03 mole hydrogen peroxide, refluxed 8 hours, and added sodium sulphite and destroy remaining oxidant, add ethyl acetate extraction, the distillation desolventizing is purified with chromatography, obtains yellow liquid, wherein chromatographic solution is n-hexane: the weight ratio of ethyl acetate is 2:8, elementary analysis: C:40.08%, H:3.03%, Cl:11.83%, F:19.02%, N:4.67%, O:10.68%, S:10.70%..

Claims (6)

1. trifluoro butylene insecticides that contains pyridine, it is characterized in that: the structural formula of this insecticide is:
Figure DEST_PATH_IMAGE001
(1), n=0 wherein, 1,2.
2. the described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine of claim 1, its spy
Levy and be:
Figure 136135DEST_PATH_IMAGE001
(1), wherein during n=0,6-chloro-3-thiopurine methyltransferase pyridine
Figure DEST_PATH_IMAGE002
(3) and halogenating agent
Figure DEST_PATH_IMAGE003
(4) in the presence of atent solvent, react and make.
3. the described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine of claim 1, its spy
Levy and be:
Figure 741691DEST_PATH_IMAGE001
(1), wherein n=1 or 2 incites somebody to action
Figure 583745DEST_PATH_IMAGE001
(1), wherein during n=0, reacts under atent solvent with oxidant and to make.
4. the described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine of claim 2 is characterized in that: prepare following insecticide:
（2），
Step is as follows: (3) 0.01 moles of 6-chloro-3-thiopurine methyltransferase pyridines are dissolved in 10 milliliters the acetone, add in advance 0.05 mole in the dry potash of crossing, drip 4-bromo-1 at normal temperatures, (4) 0.01 moles of 1,2-, three fluoro-1-butylene are after dropwising, refluxed 48 hours, and filtered, contained Acetone soln and solid, with acetone drip washing solid 3-5 time, merge the acetone soln that obtains, distill and remove acetone, obtain
Figure 478813DEST_PATH_IMAGE004
(2), obtain yellowish liquid with the chromatography purification, wherein chromatographic solution is n-hexane: the weight ratio of ethyl acetate is 4:6.
5. the described a kind of preparation method who contains the trifluoro butylene insecticides of pyridine of claim 2, it is characterized in that: atent solvent is acetone, N, dinethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
6. the described a kind of application that contains the trifluoro butylene insecticides of pyridine of claim 1, it is characterized in that: this insecticide acts on nematode or its habitat.
CN 201210151694 2012-01-10 2012-05-16 Trifluoro butene pesticide containing pyridine Active CN102696609B (en)

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CN106554335B (en) * 2015-09-30 2017-09-19 山东省联合农药工业有限公司 A kind of nematicide containing lactonic ring of transconfiguration and its production and use
CN109845741A (en) * 2018-11-26 2019-06-07 刘西芳 Nematicidal composition containing furfural
CN114075300B (en) * 2020-08-21 2023-02-28 佛山市海力盈生物科技有限公司 Chitosan oligosaccharide derivative nematicide and preparation method and application thereof

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CN87104606A (en) * 1986-06-30 1988-01-13 Fmc有限公司 S-trifluoro butenyl derivative and pesticidal use
CN1143958A (en) * 1994-03-10 1997-02-26 曾尼卡有限公司 (4,4-difluorobut-3-enylthio-)-substituted heterocyclic or carbocyclic ring compounds
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CN1476437A (en) * 2000-03-09 2004-02-18 �ձ��ݶ�ũҩ��ʽ���� Nematicidal trifluorobutenes

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CN86104207A (en) * 1985-06-20 1987-04-01 Fmc有限公司 The pesticidal use of many halogen alkene derivatives
CN87104606A (en) * 1986-06-30 1988-01-13 Fmc有限公司 S-trifluoro butenyl derivative and pesticidal use
CN1143958A (en) * 1994-03-10 1997-02-26 曾尼卡有限公司 (4,4-difluorobut-3-enylthio-)-substituted heterocyclic or carbocyclic ring compounds
CN1359379A (en) * 1999-07-06 2002-07-17 日本拜耳农药株式会社 Nematicidal trifluorobutenes
CN1476437A (en) * 2000-03-09 2004-02-18 �ձ��ݶ�ũҩ��ʽ���� Nematicidal trifluorobutenes

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崔永梅等.生物电子等排原理在药物先导化合物优化中的应用.《生命科学》.2006,第18卷(第02期),161-167.
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Owner name: SHANDONG SINO-AGRI UNITED BIOTECHNOLOGY CO., LTD.

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Address after: Mulberry road Licheng District 250100 in Shandong city of Ji'nan province No. 28

Patentee after: Shandong intermediate peasant union biological Polytron Technologies Inc

Patentee after: Weifang Zhongnong United Chemical Co.,Ltd.

Address before: Mulberry road Licheng District 250100 in Shandong city of Ji'nan province No. 28

Patentee before: Shandong Sino-Agri United Biotechnology Co., Ltd.

Patentee before: Weifang Zhongnong United Chemical Co.,Ltd.