CN100404531C - 苯二甲酰亚胺类除草剂 - Google Patents
苯二甲酰亚胺类除草剂 Download PDFInfo
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 7
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/32—Cyclic imides of polybasic carboxylic acids or 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
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- Indole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明合成了苯二甲酰亚胺类六只高效新结构除草剂，它与以往国内外专利不同之处，在保留部分分子结构中2-位氟、4-位氯原子和1-位的苯二甲酰亚胺具有的生物活性外，改变了苯环上5-位取代基团。此变化不影响苯环当杂环之间的夹角及长度，使本发明得到的新化合物具有超高效、低毒等药效。
Description
【技术领域】
本发明属于精细化工农药除草剂。
【背景技术】
近年来，苯二甲酰亚胺类化合物具有除草活性已屡见报道，举数例如下：
此类除草剂的分子结构中，在苯环上的第1、2、4、5位均有取代基，2、4位为卤素，1-位与杂环相连。
由于人类对环保问题的重视，对农药的毒性及对环境的影响，提出了更高的要求。因此，化学农药将进入“超高效、无毒、无污染”的新时期。
【发明内容】
本发明的目的就是开发研制一种高效农药除草剂。
本发明为苯二甲酰亚胺类除草剂，其结构上最大的特点在于：
1.苯环上的1-位与杂环相连。
2.苯环上的2-位由氟取代。
3.苯环上的3-位由氯取代。
4.苯环上5位烷氧基分别由2-甲基烯丙氧基、烯丙氧基、呋喃、环戊烷氧基、硫代乙酸甲酯、2-氯丙酸乙酯基取代。
本发明共合成六个新结构的高效除草剂，他们的结构为：
上述六个新化合物属原卟啉原氧化酶抑制剂类除草剂。他们具有以下特点：
1.脱色的除草作用；
2.抑制叶绿素生化合成；
3.抑制原卟啉原氧化酶及引起原卟啉IX的积累；
4.破环类囊体膜的光氧化作用。
本发明化合物的合成方法如下：
(1)苯并呋喃的合成：
由2-氟-4-氯-5-甲代烯丙氧基苯胺经转位、闭环制得相应的苯并呋喃化合物，即：
该反应分两步进行：
(a)甲代烯丙基转移到羟基的邻位，生成中间产品(B)。
(b)羟基加成到碳-碳双键上，生成产品(C)。反应在N，N-二乙基苯胺存在下经回流反应进行，闭环时间用三氟甲基磺酸作催化剂。
(2)2-氯丙酸甲酯基苯胺的合成：
将2-氟-4-氯-5-氨基酰替苯胺与丙烯酸、亚硝酸、叔丁酯在氯化铜催化剂存在下反应而制得，即：
原料酰替苯胺与丙烯酸甲酯的配比为1∶20，反应在氯化铜存在下，在乙腈中进行，得到的产品(B’)在酸性条件下水解制得产品(C’)。
(3)硫代乙酸甲酯基苯胺的合成：
2-氟-4-氯-5-氨基酰替苯胺经重氮化后，与巯基乙酸反应制得相应的巯基乙酸化合物，再经甲酯化及水解制得产品，即：
本步反应分三步进行：
(a)氨基化合物(A’)和亚硝酸钠水溶液，在酸性条件下重氮化反应生成中间体(B”)；
(b)重氮化合物在碱式碳酸铜存在下和巯基乙酸反应生成产物(c”)；
(c)产物(C”)经水解、酯化得到产品(D”)。
(4)原药的合成：
由相应的胺和苯酐在乙酸中回流反应制得，即：
其中R＝硫代乙酸甲酯、环戊烷氧基、烯丙氧基、甲代烯丙氧基、2-氯丙酸乙酯、呋喃。
由于苯二甲酰亚胺类化合物以植物细胞的叶绿素为作用点，因此，确保动植物之间的选择毒性，具有高效、低毒特点。与国外已发表的相关专利品种相比，具有相同或更高的除草效果。经盆栽实验，结果如下：
试验的植物：
稗草(Echinochloa crusgalli) 马唐(Digitaria sanguinolis)
苘麻(Abutilon thephrasti) 苋菜(Acalypha australis)
初筛结果：
I～VI六种药剂茎叶处理对阔叶草的活性均高于对禾本科草的活性。其各种剂量的茎叶处理数据见下表。
六种药剂不同用量茎叶处理对不同杂草的抑制率
【具体实施方式】
以下给出四个实施例来进一步说明本发明。
实施例1
5.2克芳胺A溶于10毫升N，N-二乙基苯胺中，回流12小时，冷却至室温后，溶于乙酸乙酯中，用10％盐酸洗三次，脱去二乙基苯胺的反应液，经干燥、浓缩，用己烷∶乙酸乙酯＝4∶1柱层析提纯，得到3.8克产品B，其状态为黄色油，收率为73％。
取上述产品B 3.8克，溶于16毫升氯仿中，5℃滴加CF3SO3H 3.6克，5分钟滴加完毕，然后在室温下反应5小时，反应完全后，将反应液倾入20毫升5％氢氧化钠溶液中，用乙酸乙酯萃取、干燥、浓缩，得苯并呋喃胺C3.2克，收率84％。产品经H-NMR确认结构。
实施例2
14.0克2-氟-4-氯-5-胺基酰替苯胺悬浮于18毫升浓盐酸和80毫升水及120克冰的混合液中，在0～5℃下滴加5.0克亚硝酸钠和8毫升水配成的溶液，在此温度下反应1小时，制得的重氮化液加入0.4克氨基磺酸、8.2克巯基乙酸和46克碱式碳酸铜及68毫升水溶液，在室温下反应30分钟。滴加16.8毫升50％氢氧化钠溶液调节pH值为7～8，再在95～100℃下反应1小时；反应液趁热过滤出铜盐，用浓盐酸24毫升酸化母液，再用乙酸乙酯萃取，萃取液经常规处理后，得到9.6克产品D”，收率50％。产品经H-NMR确认结构。
实施例3
17.2丙烯酸甲酯，3.1克亚硝酸叔丁酯在100毫升乙腈中，加氯化铜3.8克，搅拌下加入4.1克2-氟-4-氯-5-胺基酰替苯胺，室温反应1小时，用50毫升3摩尔/升的盐酸洗，乙酸乙酯萃取。有机层经水洗，饱和食盐水洗，用无水硫酸镁干燥，减压浓缩。在乙醇中重结晶得到4.7克产品B’，收率77％。产品B’经H-NMR确认结构。
实施例4
向5.5克2-氟-4-氯-5-烯丙氧基苯胺中加入85毫升冰醋酸、苯二甲酸酐8.0克，室温下反应12小时，将反应液倾入200毫升冷水中，过滤出固体，经乙醚-己烷洗，干燥得产品I 7.0克，重量收率为81.0％，熔点134～137℃，产品经H-NMR确认结构。
用上述同样方法制得化合物II，熔点150～151℃，经H-NMR确认结构。
用上述同样方法制得化合物III，熔点128～135℃，经H-NMR确认结构。
用上述同样方法制得化合物IV，熔点154～155℃，经H-NMR确认结构。
用上述同样方法制得化合物V，熔点101～104℃，经H-NMR确认结构。
用上述同样方法制得化合物VI，熔点139～140℃，经H-NMR确认结构。
Claims (1)
1.一种苯二甲酰亚胺类除草剂，其特征在于本除草剂的分子结构为：
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101048809A CN100404531C (zh) | 2003-10-21 | 2003-10-21 | 苯二甲酰亚胺类除草剂 |
| PCT/CN2004/001177 WO2005037789A1 (fr) | 2003-10-21 | 2004-10-18 | Herbicides a base de phtalimide |
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| CNB2003101048809A CN100404531C (zh) | 2003-10-21 | 2003-10-21 | 苯二甲酰亚胺类除草剂 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4881967A (en) * | 1986-12-10 | 1989-11-21 | E. I. Du Pont De Nemours And Company | Heterocyclic 2,3-dihydrobenzofuran herbicides |
| US5424277A (en) * | 1990-07-17 | 1995-06-13 | Sagami Chemical Research Center | Benzene derivatives substituted with heterocyclic ring, and herbicides containing same as active ingredients |
| WO2000003985A1 (fr) * | 1998-07-16 | 2000-01-27 | Mitsubishi Chemical Corporation | Phtalimides et herbicide contenant ceux-ci comme principe actif |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63156787A (ja) * | 1986-12-10 | 1988-06-29 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 除草用置換ベンゾフランおよびベンゾピラン |
| JPH08335497A (ja) * | 1995-06-08 | 1996-12-17 | Tama Electric Co Ltd | 放電管点灯回路 |
| JPH11222472A (ja) * | 1998-02-03 | 1999-08-17 | Mitsubishi Chemical Corp | フタル酸誘導体類、およびこれを有効成分とする除草剤 |
-
2003
- 2003-10-21 CN CNB2003101048809A patent/CN100404531C/zh not_active Expired - Lifetime
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2004
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4881967A (en) * | 1986-12-10 | 1989-11-21 | E. I. Du Pont De Nemours And Company | Heterocyclic 2,3-dihydrobenzofuran herbicides |
| US5424277A (en) * | 1990-07-17 | 1995-06-13 | Sagami Chemical Research Center | Benzene derivatives substituted with heterocyclic ring, and herbicides containing same as active ingredients |
| US6365753B1 (en) * | 1998-06-17 | 2002-04-02 | Mitsubishi Chemical Corporation | Phthalimides and herbicide containing the same as active component |
| WO2000003985A1 (fr) * | 1998-07-16 | 2000-01-27 | Mitsubishi Chemical Corporation | Phtalimides et herbicide contenant ceux-ci comme principe actif |
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| Publication number | Publication date |
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| WO2005037789A1 (fr) | 2005-04-28 |
| CN1608466A (zh) | 2005-04-27 |
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