WO2013104170A1 - 一种含吡啶的三氟丁烯类杀虫剂 - Google Patents
一种含吡啶的三氟丁烯类杀虫剂 Download PDFInfo
- Publication number
- WO2013104170A1 WO2013104170A1 PCT/CN2012/076560 CN2012076560W WO2013104170A1 WO 2013104170 A1 WO2013104170 A1 WO 2013104170A1 CN 2012076560 W CN2012076560 W CN 2012076560W WO 2013104170 A1 WO2013104170 A1 WO 2013104170A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pyridine
- insecticide
- acetone
- trifluorobutene
- inert solvent
- Prior art date
Links
- 0 *Cc(cn1)ccc1Cl Chemical compound *Cc(cn1)ccc1Cl 0.000 description 1
- GEFTYZNPHWZAIY-UHFFFAOYSA-N C=[O]CCC(F)=C(F)F Chemical compound C=[O]CCC(F)=C(F)F GEFTYZNPHWZAIY-UHFFFAOYSA-N 0.000 description 1
- QYYXDUKOSUSIFB-UHFFFAOYSA-N FC(CCCCc(cn1)ccc1Cl)=C(F)F Chemical compound FC(CCCCc(cn1)ccc1Cl)=C(F)F QYYXDUKOSUSIFB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention relates to a pesticide, which is a pyridine-containing trifluorobutene insecticide.
- the activity of the trifluorobutene compound having nematicidal activity was first disclosed in the United States, and thereafter, Japan, China and other countries also disclosed various nematicidal compounds different from the US patent structure. These different compounds have different characteristics when they are killed by nematodes. For example; the compound disclosed in the 00809783. 6 patent, although having nematicidal properties, is expensive to produce and high in use.
- An object of the present invention is to provide a pyridinium-containing trifluorobutene insecticide which is specialized for nematicidal action and which has a remarkable nematicidal effect, and has advantages in production cost and low use cost.
- An olefinic insecticide the structural formula of the insecticide is:
- the preparation method of the pyridine-containing trifluorobutene insecticide is acetone, hydrazine, hydrazine-dimethylformamide (Li F) or dimethyl miscellaneous (MS0).
- the insecticide of the present invention has extremely high activity and is specialized for nematicidal, and its nematicidal effect is remarkable. It has good compatibility with various crops. It can be used to prevent the genus of the genus Nematode; the genus Heterodera: the genus of the genus Helicover; the genus Heterodera: the genus Soybean; the root-knot nematode: the dried rice worm, the perforated nematode, the stalk of the genus Semi-puncture nematode; long-necked nematode; S. cerevisiae; Trichinella genus; Umbrella nematode: pine wood nematode.
- the insecticide of the present invention can be prepared into a conventional dosage form: an emulsion, a water-dispersible granule, a wettable powder, a microcapsule or the like.
- the preparation method of the insecticide of the invention has no special equipment and requirements, has low preparation cost, and can reduce the use cost due to the extremely high insecticidal activity.
- the invention is obtained by measuring the efficacy of nematicidal, and the control effect is remarkable.
- This reagent is used to kill tomato root knot nematodes. Before the treatment, the average number of root-knot nematodes per plant is 50, and the reagent dosage is 3 liters per acre.
- the reagent is placed in the root-knot nematode soil, and the root-knot nematode is detected after 30 days.
- Article, the insecticidal effect was 99%. After 60 days of treatment, 1.8 rods per root of nematode were detected, and the insecticidal effect was 97%.
- the above insecticidal effect was given by repeating the reagent use and detection 10 times.
- a pyridinium-containing trifluorobutene insecticide according to the present invention, the structural formula of the insecticide is (1), where 0, 1, 2.
- 6-chloro-3- 3-mercaptopyridine (4) a method for preparing a pyridine-containing trifluorobutene insecticide according to the present invention in the presence of an inert solvent,
- n 0, which is obtained by reacting with an oxidizing agent in a solvent.
- the inert solvent is acetone, hydrazine, hydrazine-dimethylformamide (DMF) or dimethyl sulfoxide (DMS0).
- Example 1 Preparation of the following pesticides: The procedure is as follows: 0.01 mol of 6-chloro-3-methylpyridylpyridine (3) is dissolved in 10 ml of acetone, 0.05 mol of potassium carbonate previously added, and 4 -bromo-1,1 is added dropwise at normal temperature. 2-trifluoro-1-butene (4) 0.01 mol, after completion of the dropwise addition, reflux for 8 hours.
- Example 3 preparing the following insecticidal:
- Example 2 0.01 mol was dissolved in 10 ml of methanol, 0.03 mol of hydrogen peroxide was added, refluxed for 8 hours, sodium sulfite was added to destroy residual oxidant, extracted with ethyl acetate, and the solvent was distilled off, and purified by chromatography to obtain a yellow liquid.
- the liquid separation was n-hexane: ethyl acetate in a weight ratio of 2:8, elemental analysis: C: 40.08%, H: 3.03%, Cl: 11.83%, F: 19.02% 5 N: 4.67 o AO: 10.68%, S : 10.70%.
Landscapes
- 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
本发明提供了一种含吡啶的三氟丁烯类杀虫剂,该杀虫剂的结构式为:(1),其中n=0,1,2。其制备方法:(1),其中n=1或2,将(1),其中n=0时,与氧化剂在惰性溶剂下进行反应制得。本发明专用于杀线虫,并使其具有显著的杀线虫的效果,制备成本和使用成本低的优点。
Description
一种含吡啶的三氟丁烯类杀虫剂
技术领域
本发明涉及农药, 是一种含吡啶的三氟丁烯类杀虫剂。
背景技术
三氟丁烯化合物具有杀线虫的活性最早在美国公开, 之后, 日本、 中国等 国也公开了多种不同于美国专利结构的杀线虫化合物。 这些不同的化合物在 杀线虫时, 各自有不同的特点。 例如; 00809783. 6专利中公开的化合物, 虽 然具有杀线虫的性能, 但是, 它的制备成本高, 并且使用量较高。
发明内容
本发明的目的是提供一种含比啶的三氟丁烯类杀虫剂, 它专用于杀线虫, 并使其具有显著的杀线虫的效果, 制备成本和使用成本低的优点。
本发明为实现上述目的, 通过以下技术方案实现: 一种含吡啶的三氟丁
中 n:0, 1,2。
所述的一种含吡啶的三氟丁烯类杀虫剂的制备方法,
( 1 ) , 其中 n=0时, 6 -氯- 3 甲巯基吡定
(3)和卤化剂 (4)在惰性溶剂存在下 所述的一种含吡啶的
或
(1), 其中 n=0时, 与氧化剂在惰性溶剂下进 行反应制得。
步骤如下: 将 6氯- 3 甲巯基吡啶(3) 0.01摩尔溶解在 10毫升的丙酮 中,加入预先千燥过的碳酸钾 0.05摩尔,在常温下滴加 4-溴 -1, 1, 2-三氟 -1- 丁烯 (4 ) 0.01 摩尔, 滴加完毕后, 回流 48小时, 过滤, 得到含
-5次,
4:6。
所述的一种含吡啶的三氟丁烯类杀虫剂的制备方法, 惰性溶剂为丙酮、 Ν, Ν-二甲基甲酰胺 (丽 F)或二甲基亚雜(MS0)。
所述的一种含吡啶的三氟丁烯类杀虫剂的应用,该杀虫剂作用于线虫或其 栖息地。
本发明所述的杀虫剂具有极高的活性, 专用于杀线虫, 其杀线虫的效果显 著。 它与各种农作物有良好的兼容性。 它可用于防止短体线虫属; 球异皮线 虫属: 马铃翦全线虫; 异皮线虫属: 大豆异皮线虫; 根结线虫属: 水稻干尖 线虫, 穿孔线虫, 起绒草茎线虫, 半穿刺线虫; 长针线虫属; 剑线虫属; 毛 刺线虫属; 伞滑刃线虫属: 松材线虫等。
本发明所述杀虫剂可以制成常规剂型: 乳液、 水分散颗料剂、 可湿粉剂、 微胶囊等。
本发明所述的杀虫剂制备方法无特殊设备及要求, 制备成本低, 由于具有 极高的杀虫活性, 可降低使用成本。 本发明经过測定杀线虫药效得出, 防治 效果显著。 测试制剂: 1份活性化合物 (结构式 1 , 其中, n=2), 9份高岭土, 制备得到含活性化合物 (结构式 1, 其中 n=2 ) 的 10%精细颗粒。 该试剂用于 杀番茄根结线虫。用药前,测得种植番茄保护用地每亩根结线虫平均为 50条, 试剂用量为每亩 3公升, 将试剂置入含根结线虫土壤中, 30天后检出每亩根 结线虫 0. 9条, 杀虫效果为 99%, 用药 60天后检出每亩根结线虫 1. 8条, 杀 虫效果为 97%, 上述杀虫效果是在试剂使用和检测重复 10次给出的结论。 具体实施方式
本发明所述的一种含吡锭的三氟丁烯类杀虫剂, 该杀虫剂的结构式为
(1), 其中 0,1,2。 本发明所述的一种含吡啶的三 丁烯类杀虫剂的制备方法
本发明所述的一种含 啶的三氟丁烯类杀虫剂的制备方法,惰性溶剂为 丙酮、 Ν,Ν-二甲基甲酰胺 (DMF)或二甲基亚砜 (DMS0)。
本发明所述的一种含吡啶的三氟丁烯类杀虫剂的应用, 该杀虫剂作用于 线虫或其栖息地。
例 1: 制备下述杀虫剂:
步骤如下:将 6-氯- 3-甲巯基吡啶(3) 0.01 摩尔溶解在 10毫升的丙酮中, 加入预先千燥过的碳酸钾 0.05摩尔, 在常温 下滴加 4 -溴- 1, 1, 2-三氟 -1-丁烯 (4) 0.01摩尔,滴加完毕后, 回流 8小时,
过滤, 得到含
用丙酮淋洗 固体 3-5 次 , 合并得到 的丙酮溶液 , 蒸馏去丙酮 , 得到
(2), 用层析法提纯得到淡黄色的液体, 其中 层析液为正己烷: 乙酸乙酯的重量比为 4:6, 元素分析: C :44.87%H: 3.39%
C113.24% F:21.29% N:5.23% S:11.98%。
步骤如下:
(2) 0.01摩尔溶解在 10毫升 的甲醇中, 加入 0.01摩尔的双氧水, 在 30-4CTC反应 10小时, 加亚硫酸钠破 坏残余氧化剂, 加乙酸乙酯萃取, 蒸馏去溶剂, 用层析法提纯, 得到黄色的
液体, 其中层析液为正己烷: 乙酸乙酯重量比为 3:7, 元素分析: C:42.34% H:3.20%,C1: 12.50%5F;20.09%5N:4.94%,O:5.64%5S :11.30% 。
Claims
1、一种含吡啶的三氟丁烯类杀虫剂, 其特征在于: 该杀虫剂的结
构式为: l
2、 权利要求 1所述的- 种含吡啶的三氟丁烯类杀虫剂的制备方 法, 其特
征在于: - '3-
3、 权利要求 1所述的一种含吡啶的三氟丁烯类杀虫剂的制备方 法, 其特
步骤如下: 将 6-氯- 3-甲巯基吡啶 (3 ) 0. 01摩尔溶解在 10毫 升的丙酮中, 加入预先千燥过的碳酸钾 0. 05摩尔, 在常温下滴加 4- 溴 1, 1,2 三氟- 1 丁烯 (4) 0. 01摩尔, 滴加完毕后, 回流 48小时,
5、权利要求 2所述的一种含吡啶的三氟丁烯类杀虫剂的制备方 法, 其特征在于: 惰性溶剂为丙酮、 N,N™二甲基甲酰胺(DMF)或二甲 基亚砜(DMS0)。
6、 权利要求 1所述的一种含吡啶的三氟丁歸类杀虫剂的应用,其 特征在于: 该杀虫剂作用于线虫或其栖息地。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210005777.8 | 2012-01-10 | ||
CN201210005777 | 2012-01-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013104170A1 true WO2013104170A1 (zh) | 2013-07-18 |
Family
ID=46889897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2012/076560 WO2013104170A1 (zh) | 2012-01-10 | 2012-06-07 | 一种含吡啶的三氟丁烯类杀虫剂 |
Country Status (2)
Country | Link |
---|---|
CN (2) | CN102696609B (zh) |
WO (1) | WO2013104170A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106554335B (zh) * | 2015-09-30 | 2017-09-19 | 山东省联合农药工业有限公司 | 一种反式结构的含内酯环的杀线虫剂及其制备方法和用途 |
CN109845741A (zh) * | 2018-11-26 | 2019-06-07 | 刘西芳 | 含糠醛的杀线虫组合物 |
CN114075300B (zh) * | 2020-08-21 | 2023-02-28 | 佛山市海力盈生物科技有限公司 | 一类壳寡糖衍生物杀线剂及其制备方法和应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3654293A (en) * | 1969-11-20 | 1972-04-04 | Stauffer Chemical Co | 2- and 4-(3 4 4-trifluoro-3-butenyl-thio)pyridines |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0228447A4 (en) * | 1985-06-20 | 1990-12-27 | Fmc Corporation | Pesticidal polyhaloalkene derivatives |
US4748186A (en) * | 1986-06-30 | 1988-05-31 | Fmc Corporation | S-trifluorobutenyl derivatives and pesticidal uses thereof |
DE69227527T2 (de) * | 1991-03-01 | 1999-06-24 | Monsanto Co | Fluoroalkenyl verbindungen und ihre verwendung als schädlingsbekämpfungsmittel |
IL112721A0 (en) * | 1994-03-10 | 1995-05-26 | Zeneca Ltd | Azole derivatives |
JP2001019685A (ja) * | 1999-07-06 | 2001-01-23 | Nippon Bayer Agrochem Co Ltd | 殺センチュウ性トリフルオロブテン類 |
JP2001322988A (ja) * | 2000-03-09 | 2001-11-20 | Nippon Bayer Agrochem Co Ltd | 殺センチュウ性トリフルオロブテン類 |
CN101516878A (zh) * | 2006-09-13 | 2009-08-26 | 住友化学株式会社 | 噻二唑化合物及其用途 |
-
2012
- 2012-05-16 CN CN 201210151694 patent/CN102696609B/zh active Active
- 2012-06-07 WO PCT/CN2012/076560 patent/WO2013104170A1/zh active Application Filing
- 2012-06-15 CN CN201210198040.2A patent/CN102696593B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3654293A (en) * | 1969-11-20 | 1972-04-04 | Stauffer Chemical Co | 2- and 4-(3 4 4-trifluoro-3-butenyl-thio)pyridines |
Non-Patent Citations (1)
Title |
---|
SHEN DE-LONG ET AL.: "Progress in Nematicidal Trifluorobutenes Researches", ZHEJIANG CHEMICAL INDUSTRY, vol. 36, no. 2, 28 February 2005 (2005-02-28), pages 22 - 24, 33 * |
Also Published As
Publication number | Publication date |
---|---|
CN102696609B (zh) | 2013-09-11 |
CN102696609A (zh) | 2012-10-03 |
CN102696593B (zh) | 2014-07-02 |
CN102696593A (zh) | 2012-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
UA121319C2 (uk) | Пестицидно активні поліциклічні похідні з сірковмісними замісниками | |
CN108697087A (zh) | 杀微生物的喹啉(硫代)羧酰胺衍生物 | |
CN110669016B (zh) | 三酮类化合物及其制备方法和应用以及一种除草剂 | |
WO2012034472A1 (zh) | 一种含氰基的邻苯二甲酰胺类化合物、制备方法和作为农用化学品杀虫剂的用途 | |
CN111961041A (zh) | 硫代三嗪酮异恶唑啉类化合物及其制备方法和应用、原卟啉原氧化酶抑制剂和除草剂 | |
EP0635499A2 (en) | Novel acaricidally active tetrazine derivatives | |
CN103214461B (zh) | 一种喹啉衍生物及其用途 | |
WO2013104170A1 (zh) | 一种含吡啶的三氟丁烯类杀虫剂 | |
CN106117064B (zh) | 一种含茉莉酸基团的(反)-β-法尼烯类似物及其制备与应用 | |
WO2013104171A1 (zh) | 一种含噻唑的三氟丁烯类杀虫剂 | |
CN107474021B (zh) | 噁二嗪衍生物及其制备方法和应用 | |
CN110963973B (zh) | 含喹唑啉二酮片段的三酮类化合物及其制备方法和应用以及一种除草剂 | |
JPH04128275A (ja) | N―ベンジルアミド類およびこれを有効成分とする殺虫、殺ダニ剤 | |
ES2202488T3 (es) | Compuestos pesticidas, composiciones que los contienen y su procedimiento de preparacion. | |
KR900008839B1 (ko) | 1,3-디티안류의 제조방법 | |
CN109516956B (zh) | 5-吡唑甲酮类化合物及其应用 | |
CN106946794B (zh) | 一种2-嘧啶氧基苯甲酸衍生物及其制备方法和一种水面杂草除草剂 | |
CN105254621A (zh) | 含噻唑环的三嗪酮类化合物及其制备方法和应用 | |
DE2656289C2 (de) | 1-Cyano-3-isopropyl-2,1,3--benzothiadiazin-4-on-2,2-dioxid-Verbindungen | |
CN114853748A (zh) | 一种含三氟甲烷异噁唑啉类衍生物、其制备方法和应用 | |
CN105646359A (zh) | 芳基吡唑多磺酰胺化衍生物及其超声波辐射合成方法和应用 | |
WO1999020610A1 (fr) | Derives de la pyrazolidine-3,5-dione a substitution 4-aryl-4- | |
JPH09505320A (ja) | ピリミジニルアリールケトンオキシム | |
CN113149913A (zh) | α-C位置修饰苄基取代的喹唑啉二酮类化合物及其制备方法和应用、HPPD除草剂 | |
US4584318A (en) | Nematicidal salicylaldehyde derivatives |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12865160 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12865160 Country of ref document: EP Kind code of ref document: A1 |