CN113683529A - 一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用 - Google Patents

一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用 Download PDF

Info

Publication number
CN113683529A
CN113683529A CN202111105564.8A CN202111105564A CN113683529A CN 113683529 A CN113683529 A CN 113683529A CN 202111105564 A CN202111105564 A CN 202111105564A CN 113683529 A CN113683529 A CN 113683529A
Authority
CN
China
Prior art keywords
schiff base
tetrahydrolinalyl
tetrahydrolinalool
base compound
aldehyde
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.)
Granted
Application number
CN202111105564.8A
Other languages
English (en)
Other versions
CN113683529B (zh
Inventor
赵振东
张红梅
陈玉湘
王婧
徐士超
董欢欢
卢言菊
古研
毕良武
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.)
Institute of Chemical Industry of Forest Products of CAF
Original Assignee
Institute of Chemical Industry of Forest Products of CAF
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 Institute of Chemical Industry of Forest Products of CAF filed Critical Institute of Chemical Industry of Forest Products of CAF
Priority to CN202111105564.8A priority Critical patent/CN113683529B/zh
Publication of CN113683529A publication Critical patent/CN113683529A/zh
Application granted granted Critical
Publication of CN113683529B publication Critical patent/CN113683529B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • 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
    • A01N43/08—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 with oxygen as the ring hetero atom
    • 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
    • A01N43/10—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 with sulfur as the ring hetero atom
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

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

Abstract

本发明公开了一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用。该方法以四氢芳樟胺和醛为原料，于0～100℃在极性有机溶剂中进行缩合反应，待原料充分反应后，经无水硫酸钠干燥、过滤、减压蒸馏得到四氢芳樟基席夫碱类化合物，重结晶或硅胶柱层析得到目标产物纯品。采用培养皿种子萌发法测定不同浓度四氢芳樟基席夫碱类化合物培养下黑麦草根和茎的生长受害情况，评价其除草活性。本发明方法工艺简单、条件温和、速率快、收率高、底物适用性广，产物对黑麦草的根和茎的生长具有很好的抑制作用。

Description

一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用
技术领域：
本发明涉及一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用，具体涉及一种以四氢芳樟胺和醛为原料，在极性有机溶剂中反应后，经无水硫酸钠干燥、过滤、减压蒸馏制备得到四氢芳樟基席夫碱类化合物，并将其用作黑麦草等的除草活性成分。
背景技术
随着人口的增长，人们对于粮食的需求也随之增加，这就要求生产出更多更优质的粮食以保障国计民生。杂草是造成粮食产量下降的最主要原因，它不仅会与作物争夺水分、养分和阳光，还会带来病虫害，使粮食品质下降、产量降低。自20世纪中叶起，施用化学合成除草剂是目前农业生产中最主要的除草方式，但化学除草剂的长期大量使用会产生环境污染、生物毒害、生态破坏等影响，还易使杂草产生抗性，继而需要施用更大量的除草剂。因此，开发绿色、环境友好的高性能除草剂来替代传统化学合成除草剂，是解决这些问题的核心，植物源除草剂的开发和应用为此提供了一条有效的策略。
植物源除草剂是利用天然植物资源开发的农药，具有来源丰富、高效低毒、可生物降解的优点，是近年来研究最广泛的新型环境友好型农药之一。许多天然精油如α-蒎烯、β-蒎烯、3-蒈烯、柠檬烯、紫苏醛、香芹酚和百里香酚等都具有良好的除草活性。含对
Figure BDA0003272163410000011
烷(1)或对
Figure BDA0003272163410000012
烯(2)骨架的单萜类化合物是自然界中分布最广泛的萜类化合物，由于具有良好的环境相容性和生物活性，其在植物源除草剂开发和研究领域受到了重视，展现出了良好的前景。1983年壳牌公司以1,4-桉叶素为前体合成的含氧杂环类对
Figure BDA0003272163410000013
烷型衍生物环庚草醚(cinmethylin,3)，是目前已知商业化应用效果最好的植物源除草剂之一，其为分生组织抑制剂，用于稻田防除禾本科杂草，具有施药期宽、用量少(1～2g a.i/亩)的优点。
前期研究成果表明，由松节油衍生的3-对
Figure BDA0003272163410000014
烯-1-胺席夫碱和仲胺衍生物、cis-1,8-对
Figure BDA0003272163410000015
烷二胺席夫碱和仲胺衍生物以及紫苏基仲胺衍生物等均具有较好的除草活性，部分化合物活性优于除草剂草甘膦及敌草隆(Zhu,Journal of Agricultural and FoodChemistry,2016,64(51),9702-9707；Zhu,Industrial Crops&Products,2018,115,111-116；Xu,Journal ofAgricultural and Food Chemistry,2020,68,11829-11838；Dong,NewJournal of Chemistry,2020,44,8280-8288.)。例如N-(4-氟苄基)-3-对
Figure BDA0003272163410000016
烯-1-胺(4)对稗草根生长的IC50值约为7mg/L。
Figure BDA0003272163410000021
此前的研究主要集中在以对
Figure BDA0003272163410000024
烯和对
Figure BDA0003272163410000025
烷为母体结构的衍生化反应，对于开环的单萜胺及其衍生物的除草活性尚未涉及。芳樟醇(5)是一种链状单萜烯醇，具有铃兰香气，常用于香精香料行业，同时由于其具有除臭、杀虫、抑菌、镇静等作用，还被用于医药和农药行业。四氢芳樟胺是一类链状单萜胺类化合物，可由芳樟醇经加氢、Ritter反应以及碱水解制得，是一类有机反应中间体(Zhu,Industrial Crops&Products,2018,115,111-116；王,林产化学与工艺,2018,38(6),59-66.)。
本发明申请提供一类新型植物源除草活性物质四氢芳樟基席夫碱类化合物及其制备方法以及相关化合物在除草领域的应用，通过与前期研究成果对比，以期探明含对
Figure BDA0003272163410000026
烷骨架与不含对
Figure BDA0003272163410000027
烷骨架结构对于除草活性的影响情况，并以此为基础，设计合成结构更新颖、活性更好的除草活性物质。
发明内容
为解决合成除草剂毒性大、难以生物降解等缺陷，本发明公开了一类新型植物源除草活性物质—四氢芳樟基席夫碱类化合物的制备及除草应用。本发明以对四氢芳樟胺和醛为原料，在极性有机溶剂中充分反应后，经干燥、减压蒸馏制得相关四氢芳樟基席夫碱类化合物。
本发明的技术方案为：一种四氢芳樟基席夫碱类化合物，结构通式如下：
Figure BDA0003272163410000022
通式I中，R是
Figure BDA0003272163410000023
中的任意一种，R’是氢、甲基、三氟甲基、甲氧基、巯甲基或卤素中的任意一种。
所述的通式I的化合物以四氢芳樟胺和醛为原料，在一定温度下在极性有机溶剂中充分反应后，反应液经后处理而得，所述醛为苯甲醛、2-氟苯甲醛、4-氟苯甲醛、2-氯苯甲醛、4-氯苯甲醛、2,6-二氯苯甲醛、4-溴苯甲醛、对甲基苯甲醛、对甲氧基苯甲醛、对巯甲基苯甲醛、2-三氟甲基苯甲醛、吡啶-2-甲醛、噻吩-2-甲醛、呋喃-2-甲醛。
所述的四氢芳樟胺和醛的摩尔比在1∶1～5之间。
所述的四氢芳樟胺和醛的反应温度在0～100℃之间。
所述的极性有机溶剂为甲醇、乙醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜中的一种或任意几种的混合物。
反应时间为1～72h。
所述的后处理具体指，反应液经无水硫酸钠干燥、过滤、减压蒸馏得四氢芳樟基席夫碱类化合物粗品，重结晶或硅胶柱层析得纯品。
所述的四氢芳樟基席夫碱类化合物作为除草剂活性成分的应用。
所述的四氢芳樟基席夫碱类化合物作为针对黑麦草的除草剂活性成分应用。
有益效果
1.本发明公开的四氢芳樟基席夫碱类化合物为新型天然产物衍生物，具有毒性低、安全性高、环境友好等特点；
2.本发明的合成工艺简单、条件温和、反应速率快、产物收率高、底物适用性广，易于规模化生产。
3.本发明公开的四氢芳樟基席夫碱类化合物对黑麦草茎和根生长具有优异的除草活性。
附图说明
图1为N-苯亚甲基四氢芳樟胺的1H NMR图；
图2为N-(2-氟苯亚甲基)四氢芳樟胺的1H NMR图；
图3为N-(4-氟苯亚甲基)四氢芳樟胺的1H NMR图；
图4为N-(2-氯苯亚甲基)四氢芳樟胺的1H NMR图；
图5为N-(4-氯苯亚甲基)四氢芳樟胺的1H NMR图；
图6为N-(2,6-二氯苯亚甲基)四氢芳樟胺的1H NMR图；
图7为N-(4-溴苯亚甲基)四氢芳樟胺的1H NMR图；
图8为N-(对甲基苯亚甲基)四氢芳樟胺的1H NMR图；
图9为N-(对甲氧基苯亚甲基)四氢芳樟胺的1H NMR图；
图10为N-(对巯甲基苯亚甲基)四氢芳樟胺的1H NMR图；
图11为N-(2-三氟甲基苯亚甲基)四氢芳樟胺的1H NMR图；
图12为N-(2-吡啶亚甲基)四氢芳樟胺的1H NMR图；
图13为N-(2-噻吩亚甲基)四氢芳樟胺的1H NMR图；
图14为N-(2-呋喃亚甲基)四氢芳樟胺的1H NMR图。
具体实施方式
分析方法
采取气相色谱峰面积归一化法对产物进行分析，分析条件：岛津GC-2014AF，载气N2压力为0.6MPa，空气压力为0.6MPa，H2压力为0.6MPa，采取程序升温，升温程序为：70℃(保持2min，速率3℃/min)→130℃(保持0min，速率10℃/min)→270℃(保持2min)。
该方法以四氢芳樟胺和醛为原料，在极性有机溶剂中进行缩合反应，反应结束后反应液经无水硫酸钠干燥、过滤、减压蒸馏得四氢芳樟基席夫碱类化合物粗品，重结晶或硅胶柱层析得目标产物纯品，并采用培养皿种子萌发法测定不同浓度四氢芳樟基席夫碱类化合物培养下黑麦草的根和茎的生长受害情况，评价其除草活性。四氢芳樟基席夫碱类化合物的结构通式如下：
Figure BDA0003272163410000041
通式I中，R是
Figure BDA0003272163410000042
中的任意一种，R’是氢、甲基、三氟甲基、甲氧基、巯甲基或卤素中的任意一种。
Figure BDA0003272163410000043
四氢芳樟醇购自上海阿拉丁化学试剂有限公司，四氢芳樟胺是以四氢芳樟醇为原料，经Ritter反应和碱水解得到，四氢芳樟胺粗品经蒸馏得到纯度为97％的四氢芳樟胺。
具体合成步骤如下：
将四氢芳樟胺加入含有极性有机溶剂的三口烧瓶中，磁力搅拌下加入醛，待反应结束后，反应液无水硫酸钠干燥、过滤、减压蒸馏得四氢芳樟基席夫碱类化合物粗品，重结晶或硅胶柱层析得纯品。其中四氢芳樟胺和醛的摩尔比在1∶1～5之间，缩合反应温度在0～100℃之间，反应时间为1～72h；极性有机溶剂为甲醇、乙醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜中的一种或任意几种的混合物。
所述的四氢芳樟基席夫碱类化合物作为除草剂活性成分的应用。
所述的四氢芳樟基席夫碱类化合物作为针对黑麦草的除草剂活性成分应用。
除草剂活性测试：
准确称取1mmol四氢芳樟基席夫碱类化合物，分别用1mL DMF溶解，滴加三滴吐温80，充分溶解后转移到100mL容量瓶中，用蒸馏水稀释至刻度，得到浓度为10mmol/L的溶液作为母液。采用二倍稀释法，用稀释液(DMF和吐温80的浓度与母液一致)配置成一系列浓度的供试溶液。
将黑麦草种子分别置于28℃恒温箱中用适量蒸馏水浸泡15h。在培养皿内铺2张滤纸，加入7mL该类化合物对应浓度的样品溶液，加7mL稀释液作为对照，每处理重复三次。每个培养皿中加入10粒种子，置于人工气候培养箱中，在温度28℃、相对湿度70～80％的条件下无光照培养120h。培养结束后，量取黑麦草根长与茎长，计算四氢芳樟基席夫碱化合物对黑麦草种子的根长和茎长抑制率(y)。
Figure BDA0003272163410000051
式中：y为根长或茎长的抑制率(％)，x0为对照的根长或茎长，x1为药液处理的根长或茎长。
实施例1
将2.43g(15mmol，97％)四氢芳樟胺加入含有20mL乙醇的三口烧瓶中，磁力搅拌下加入1.86g(15mmol)苯甲醛，室温反应48h，反应完全后，加入无水硫酸钠干燥，过滤，减压蒸馏除去溶剂，得N-苯亚甲基四氢芳樟胺3.6g，产率89.1％。
准确称取1mmol N-苯亚甲基四氢芳樟胺，用1mLDMF溶解，滴加三滴吐温80，充分溶解后转移到100mL容量瓶中，用蒸馏水稀释至刻度，得到浓度为10mmol/L的溶液作为母液。采用二倍稀释法，配置成一系列浓度(5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L，稀释液中DMF和吐温80的浓度和母液一致)。
将黑麦草种子置于28℃恒温箱中用适量蒸馏水浸泡15h。在培养皿内铺2张滤纸，加入7mL该类化合物对应浓度的样品溶液，加7mL稀释液作为空白对照，每处理重复三次。每个培养皿中加入10粒种子，置于人工气候培养箱中，在温度28℃、相对湿度70～80％的条件下无光照培养120h。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-苯亚甲基四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、98.5％、75.6％、68.9％、55.2％、48.0％、35.2％、29.7％、15.4％，对根长的抑制率分别为：100.0％、100.0％、98.5％、75.6％、68.9％、55.2％、48.0％、35.2％、29.7％、15.4％。(2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的草甘膦溶液对稗草种子茎长的抑制率分别为：100.0％、99.5％、93.6％、82.3％、55.0％、40.2％、37.8％、22.4％、11.5％、9.5％，对根长的抑制率分别为：100.0％、100.0％、95.7％、87.8％、76.1％、68.6％、57.8％、27.2％、19.5％、12.3％)。
实施例2
除原料醛为2-氟苯甲醛，其它操作过程同实施例1，得N-(2-氟苯亚甲基)四氢芳樟胺3.3g，产率84.2％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-氟苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、98.9％、93.9％、76.3％、66.2％、54.8％、43.2％、35.4％、19.9％，对根长的抑制率分别为：100.0％、100.0％、100.0％、95.9％、74.5％、60.3％、44.0％、30.8％、25.0％、18.9％。
实施例3
除原料醛为4-氟苯甲醛，其它操作过程同实施例1，得N-(4-氟苯亚甲基)四氢芳樟胺3.77g，产率89.1％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(4-氟苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、94.2％、73.6％、58.7％、53.0％、45.9％、38.8％、30.5％、27.3％，对根长的抑制率分别为：100.0％、100.0％、99.6％、73.0％、57.7％、50.6％、42.2％、32.0％、22.1％、15.0％。
实施例4
除原料醛为2-氯苯甲醛，其它操作过程同实施例1，得N-(2-氯苯亚甲基)四氢芳樟胺4.0g，产率87.9％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-氯苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、95.1％、88.7％、79.2％、68.5％、53.3％、48.0％、28.7％、20.3％，对根长的抑制率分别为：100.0％、100.0％、100.0％、95.3％、78.5％、67.9％、54.7％、35.5％、21.3％、16.3％。
实施例5
除原料醛为4-氯苯甲醛，其它操作过程同实施例1，得N-(4-氯苯亚甲基)四氢芳樟胺2.87g，产率63.7％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(4-氯苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、100.0％、94.3％、78.0％、58.6％、49.5％、39.1％、31.0％、24.5％，对根长的抑制率分别为：100.0％、100.0％、100.0％、98.3％、82.0％、59.3％、49.2％、38.9％、28.0％、18.3％。
实施例6
除原料醛为2,6-二氯苯甲醛，其它操作过程同实施例1，得N-(2,6-二氯苯亚甲基)四氢芳樟胺3.8g，产率90.3％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2,6-二氯苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、100.0％、98.9％、81.7％、68.8％、49.4％、41.6％、30.8％、18.9％，对根长的抑制率分别为：100.0％、100.0％、100.0％、98.2％、82.4％、64.5％、53.2％、47.8％、35.2％、22.4％。
实施例7
除原料醛为4-溴苯甲醛，其它操作过程同实施例1，得N-(4-溴苯亚甲基)-四氢芳樟胺4.6g，产率89.0％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(4-溴苯亚甲基)-四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、100.0％、99.0％、81.5％、78.1％、46.3％、40.1％、27.8％、19.1％，对根长的抑制率分别为：100.0％、100.0％、100.0％、98.2％、84.1％、76.2％、54.8％、46.8％、32.6％、23.4％。
实施例8
除原料醛为对甲基苯甲醛，其它操作过程同实施例1，得N-(对甲基苯亚甲基)四氢芳樟胺3.2g，产率86.4％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(对甲基苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、96.5％、88.4％、74.9％、62.5％、46.1％、39.9％、24.7％、18.4％，对根长的抑制率分别为：100.0％、100.0％、100.0％、94.2％、82.1％、68.4％、50.9％、46.8％、33.9％、26.6％。
实施例9
除原料醛为对甲氧基苯甲醛，其它操作过程同实施例1，得N-(对甲氧基苯亚甲基)-四氢芳樟胺3.2g，产率82.8％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(对甲氧基苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、94.8％、58.9％、53.5％、31.8％、25.2％、16.8％、9.7％、无抑制，对根长的抑制率分别为：100.0％、100.0％、98.7％、80.4％、66.0％、54.1％、48.3％、37.0％、28.8％、19.2％。
实施例10
除原料醛为对巯甲基苯甲醛，其它操作过程同实施例1，得N-(对巯甲基苯亚甲基)-四氢芳樟胺3.5g，产率86.4％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(对巯甲基苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、100.0％、93.2％、65.2％、59.7％、54.6％、45.2％、31.0％、20.8％，对根长的抑制率分别为：100.0％、100.0％、98.7％、80.4％、66.0％、54.1％、48.3％、37.0％、28.8％、19.2％。
实施例11
除原料醛为2-三氟甲基苯甲醛，其它操作过程同实施例1，得N-(2-三氟甲基苯亚甲基)四氢芳樟胺4.3g，产率87.0％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-三氟甲基苯亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、97.7％、68.9％、56.9％、47.4％、41.1％、37.3％、26.1％、13.8％，对根长的抑制率分别为：100.0％、100.0％、100.0％、84.1％、72.9％、50.8％、48.7％、37.7％、24.7％、17.7％。
实施例12
除原料醛为吡啶-2-甲醛，其它操作过程同实施例1，得N-(2-吡啶亚甲基)四氢芳樟胺3.7g，产率98.6％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-吡啶亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、98.7％、88.6％、73.4％、42.9％、26.9％、19.4％、8.1％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、97.9％、82.8％、53.0％、34.8％、25.6％、19.8％、9.2％、无抑制。
实施例13
除原料醛为噻吩-2-甲醛，其它操作过程同实施例1，得N-(2-噻吩亚甲基)四氢芳樟胺3.0g，产率81.6％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-噻吩亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、99.2％、84.4％、68.8％、57.2％、31.0％、24.4％、11.0％、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、91.6％、66.0％、51.7％、35.5％、25.1％、16.8％、8.7％。
实施例14
除原料醛为呋喃-2-甲醛，其它操作过程同实施例1，得N-(2-呋喃亚甲基)四氢芳樟胺2.79g，产率88.6％。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-呋喃亚甲基)四氢芳樟胺溶液对黑麦草种子茎长的抑制率分别为：100.0％、100.0％、97.8％、74.6％、69.2％、55.4％、45.5％、33.1％、21.0％、9.2％，对根长的抑制率分别为：100.0％、100.0％、94.8％、72.0％、61.4％、48.6％、33.5％、22.3％、15.3％、8.1％。
实施例15
除四氢芳樟胺与4-氟苯甲醛的摩尔比为1∶2，其它操作过程同实施例1，产率93％。
实施例16
除四氢芳樟胺与4-氟苯甲醛的反应温度为0℃，其它操作过程同实施例1，产率80％。
实施例17
除四氢芳樟胺与4-氟苯甲醛的反应温度为70℃，其它操作过程同实施例1，产率90％。
实施例18
除四氢芳樟胺与4-氟苯甲醛的反应溶剂为丙酮，其它操作过程同实施例1，产率85％。
实施例19
除反应时间为0.5h，，其它操作过程同实施例1，产率70％。
实施例20
除反应时间为72h，，其它操作过程同实施例1，产率90％。
反例1
四氢芳樟胺与戊醛的摩尔比为1∶1.02，得到的席夫碱GC含量为30％，产率为28％，由于席夫碱本身不稳定，在柱层析分离纯化时易分解，且粗产物含量低，所以并未得到产物。
反例2
四氢芳樟胺与丁醛的摩尔比为1∶1.02，不反应。

Claims (9)

1.一种四氢芳樟基席夫碱类化合物，其特征在于，结构通式如下：
Figure FDA0003272163400000011
通式I中，R是
Figure FDA0003272163400000012
中的任意一种，R’是氢、甲基、三氟甲基、甲氧基、巯甲基或卤素中的任意一种。
2.权利要求1所述的四氢芳樟基席夫碱类化合物的制备方法，其特征在于，所述的通式I的化合物以四氢芳樟胺和醛为原料，在一定温度下在极性有机溶剂中充分反应后，反应液经后处理而得，所述的醛为苯甲醛、2-氟苯甲醛、4-氟苯甲醛、2-氯苯甲醛、4-氯苯甲醛、2,6-二氯苯甲醛、4-溴苯甲醛、对甲基苯甲醛、对甲氧基苯甲醛、对巯甲基苯甲醛、2-三氟甲基苯甲醛、吡啶-2-甲醛、噻吩-2-甲醛、呋喃-2-甲醛。
3.根据权利要求2所述的四氢芳樟基席夫碱类化合物的制备方法，其特征在于，所述的四氢芳樟胺和醛的摩尔比在1∶1～5之间。
4.根据权利要求2所述的四氢芳樟基席夫碱类化合物的制备方法，其特征在于，所述的四氢芳樟胺和醛的反应温度在0～100℃之间。
5.根据权利要求2所述的四氢芳樟基席夫碱类化合物的制备方法，其特征在于，所述的极性有机溶剂为甲醇、乙醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜中的一种或任意几种的混合物。
6.根据权利要求2所述的四氢芳樟基席夫碱类化合物的制备方法，其特征在于，反应时间为1～72h。
7.根据权利要求2所述的四氢芳樟基席夫碱类化合物的制备方法，其特征在于，所述的后处理具体指，反应液经无水硫酸钠干燥、过滤、减压蒸馏得四氢芳樟基席夫碱类化合物粗品，重结晶或硅胶柱层析得纯品。
8.权利要求1所述的四氢芳樟基席夫碱类化合物作为除草剂活性成分的应用。
9.权利要求1所述的四氢芳樟基席夫碱类化合物作为针对黑麦草的除草剂活性成分的应用。
CN202111105564.8A 2021-09-22 2021-09-22 一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用 Active CN113683529B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111105564.8A CN113683529B (zh) 2021-09-22 2021-09-22 一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111105564.8A CN113683529B (zh) 2021-09-22 2021-09-22 一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用

Publications (2)

Publication Number Publication Date
CN113683529A true CN113683529A (zh) 2021-11-23
CN113683529B CN113683529B (zh) 2023-08-11

Family

ID=78586902

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111105564.8A Active CN113683529B (zh) 2021-09-22 2021-09-22 一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用

Country Status (1)

Country Link
CN (1) CN113683529B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115043737A (zh) * 2022-06-10 2022-09-13 中国林业科学研究院林产化学工业研究所 一种四氢芳樟基仲胺类化合物及其制备方法与除草应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105481715A (zh) * 2015-12-24 2016-04-13 陕西师范大学 一种樟脑席夫碱及其制备方法和应用
CN106518725A (zh) * 2016-10-26 2017-03-22 中国林业科学研究院林产化学工业研究所 一种1,8‑对孟烷二席夫碱衍生物及其制备方法与应用
CN110105224A (zh) * 2019-06-06 2019-08-09 中国林业科学研究院林产化学工业研究所 3-对*烯-1-仲胺类化合物及其制备方法与除草应用
CN110128277A (zh) * 2019-06-06 2019-08-16 中国林业科学研究院林业新技术研究所 cis-对*烷-1,8-二仲胺类化合物及其制备方法与除草应用
CN113200871A (zh) * 2021-05-21 2021-08-03 中国林业科学研究院林产化学工业研究所 一种对䓝烷-1-基仲胺类化合物及其制备方法与除草应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105481715A (zh) * 2015-12-24 2016-04-13 陕西师范大学 一种樟脑席夫碱及其制备方法和应用
CN106518725A (zh) * 2016-10-26 2017-03-22 中国林业科学研究院林产化学工业研究所 一种1,8‑对孟烷二席夫碱衍生物及其制备方法与应用
CN110105224A (zh) * 2019-06-06 2019-08-09 中国林业科学研究院林产化学工业研究所 3-对*烯-1-仲胺类化合物及其制备方法与除草应用
CN110128277A (zh) * 2019-06-06 2019-08-16 中国林业科学研究院林业新技术研究所 cis-对*烷-1,8-二仲胺类化合物及其制备方法与除草应用
CN113200871A (zh) * 2021-05-21 2021-08-03 中国林业科学研究院林产化学工业研究所 一种对䓝烷-1-基仲胺类化合物及其制备方法与除草应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115043737A (zh) * 2022-06-10 2022-09-13 中国林业科学研究院林产化学工业研究所 一种四氢芳樟基仲胺类化合物及其制备方法与除草应用
CN115043737B (zh) * 2022-06-10 2024-03-15 中国林业科学研究院林产化学工业研究所 一种四氢芳樟基仲胺类化合物及其制备方法与除草应用

Also Published As

Publication number Publication date
CN113683529B (zh) 2023-08-11

Similar Documents

Publication Publication Date Title
CN110105224B (zh) 3-对䓝烯-1-仲胺类化合物及其制备方法与除草应用
CN113200871B (zh) 一种对䓝烷-1-基仲胺类化合物及其制备方法与除草应用
JP7149343B2 (ja) ｃｉｓ－ｐ－メンタン－１，８－第二級アミン類化合物の製造方法と除草応用
CN113683529A (zh) 一种四氢芳樟基席夫碱类化合物及其制备方法与除草应用
CN108191629B (zh) 一种阿魏酸衍生物及其应用
WO2024125489A1 (zh) 一种有机联三硫化合物及其应用
US10674723B2 (en) 1,8-bis(Schiff base)-p-menthane derivatives as well as preparation method and applications thereof
CN113429300B (zh) 对䓝烷-7-基仲胺类化合物及其制备方法与除草应用
CN115043737B (zh) 一种四氢芳樟基仲胺类化合物及其制备方法与除草应用
CN116082240A (zh) 一种琥珀酸脱氢酶抑制剂及其合成方法与应用
CN111217708B (zh) 一种烃基紫苏胺衍生物的制备方法与除草应用
SU1316557A3 (ru) Способ получени производных 2(3-пиридил)-2-фениламиноуксусной кислоты (его варианты)
RU2327686C1 (ru) 4-метил-2-хлор-6-{[1-алкил-2-(нитробензилиден)]гидразино}-никотинонитрилы в качестве регулятора роста сахарной свеклы
CN110963931B (zh) 2-(2-甲氧基-5-硝基-苯氧基)乙基三乙基卤化胺及其制备方法和应用
CN108569973A (zh) 一种双氢茉莉酸（二烷基氨基）酯化合物或其盐
CN117720433A (zh) 一种碳酸肟酯类化合物的制备方法及其应用
CN110698354B (zh) 2-(3,4-二氯-苯氧基)乙基三乙基卤化胺及其制备方法和应用
CN110642777B (zh) N-[2-(3,4-二氯-苯氧基)乙基]卤化吡啶及其制备方法和应用
CN110698389B (zh) N-[2-(2-甲氧基-5-硝基-苯氧基)乙基]卤化吡啶及其制备方法和应用
RU2195457C1 (ru) Замещенные 4,4-дифенил-1,2-дигидро-4н-3,1-бензоксазины, проявляющие росторегулирующую и антистрессовую активность
CN110669010B (zh) 1-[2-(2-甲氧基-5-硝基-苯氧基)]-乙基3-甲基咪唑盐及其制备方法
CN102219707A (zh) 一种丙烯海松双肟酯衍生物及其制备方法和应用
KR0126545B1 (ko) 신규한 불소치환 아브시스산 유도체 및 그를 포함하는 식물생장조절제
RU2316211C1 (ru) Замещенные 4,4-дифенил-3,1-бензоксазино(1,2-с)(1,3)бензоксазины - антидоты гербицида гормонального действия 2,4-дихлорфеноксиуксусной кислоты
JPH0613533B2 (ja) 水素化アルミニウムリチウム系不斉還元剤

Legal Events

Date Code Title Description
PB01 Publication
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