CN108017607B - 一类n-取代胺基香豆素及其除草与杀菌用途 - Google Patents

一类n-取代胺基香豆素及其除草与杀菌用途 Download PDF

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CN108017607B
CN108017607B CN201711303401.4A CN201711303401A CN108017607B CN 108017607 B CN108017607 B CN 108017607B CN 201711303401 A CN201711303401 A CN 201711303401A CN 108017607 B CN108017607 B CN 108017607B
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魏艳
郝双红
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Qingdao Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
    • 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
    • A01N43/14—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 six-membered rings
    • A01N43/16—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 six-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
    • A01N43/34—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
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Organic Chemistry (AREA)
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Abstract

本发明涉及25种N‑取代氨基香豆素衍生物及其制备方法，以及在抑菌、除草方面的用途。25种N‑取代氨基香豆素衍生物，通过6‑氨基香豆素与间氟苯甲醛缩合并用NaBH4还原得中间体，再将其与不用酰氯在三乙胺存在下缩合得系列目标化合物。这些化合物可作为除草剂防治杂草马唐及反枝苋，也可作为杀菌剂防治番茄灰霉病菌及苹果腐烂病菌。

Description

一类N-取代胺基香豆素及其除草与杀菌用途
技术领域
本发明涉及一类新型N-取代胺基香豆素类化合物及其除草与杀菌用途，具体的涉及农用除草剂及杀菌剂领域。
背景技术
香豆素类化合物具有广谱生物活性和广泛用途。该类化合物的农药活性涉及杀虫、杀螨、杀鼠、除草及杀菌作用。酰基芳胺类化合物也具有广泛生物活性，如杀菌剂甲霜灵、萎锈灵，除草剂乙草胺、氟吡草胺等。该专利基于活性亚结构拼接思想，以香豆素为骨架，在其6-位引入氨基，然后在氨基上接上间氟苄基，最后将氨基用不同酰基酰化，合成了一类新型N-取代胺基香豆素类化合物，并评价了该类化合物的除草活性及抑菌活性。
发明内容
本发明的目的在于提供一类新型N-取代胺基香豆素类化合物及其制备方法，它可应用于农业上以防治田间杂草及农作物病害。
本发明的技术方案如下：
本发明提供的新型N-取代胺基香豆素类化合物，其结构通式如下：
R选自：乙烯基、甲基乙烯基、1-甲基丁基、2-甲基丙烯基、1-氯乙基、1-氯丙基、1-溴乙基、1-溴戊基、4-甲基苯基、4-乙基苯基、3-氯丙氧基、4-甲氧苯基、苯氧基、3-溴苯基、萘-1-基、萘-2-基、噻吩-2-基、噻吩-2-甲基、噻吩-3-基、呋喃-2-基、吡啶-4-基、2-氯吡啶-5-基、2-氯吡啶-3-基、3-氟吡啶-5-基、4-叔丁基苯基；
新型N-取代胺基香豆素类化合物合成反应式：
c d e
e1 - e25，R依次同上；
目标化合物参考文献方法合成。6-氨基香豆素c首先与间氟苯甲醛缩合得西弗碱，再用NaBH4还原得中间体d，其与不用酰氯在三乙胺存在下缩合得系列目标化合物e。目标化合物e1- e25的Mp、ESI-MS及1H NMR数据列于表1。
表1. 目标化合物的Mp、MS及1H NMR数据
（续表1）
具体实施方式
实例1 除草活性评价
先将目标化合物用丙酮溶解配制成3000 mg/L的母液，取上述母液1 mL加入到30mL 0.5%的琼脂溶液中，充分混匀，得100 mg/L带毒培养基，然后将其分匀倒入3个10 mL小烧杯中。取1 mL丙酮加入培养基中做空白对照（CK)，每处理重复3次。
把催芽露白的马唐和反枝苋种子分别接到培养基上培养，每个小杯接种10粒，将接种后的小杯放入培养箱（28 ℃，相对湿度90%，L/D=12h:12h）中培养，当空白对照根长到合适长度时测量种子根、茎长度。按照下式计算根茎生长抑制率：
抑制率/ % = [对照根（茎）长-处理根（茎）长]/ 对照根（茎）长×100
化合物e1-e25的除草活性数据列于表2中。
表2. 目标化合物的除草活性评价数据（抑制率，%，100 mg/L）
实例2 抑菌活性测定
待测化合物加丙酮溶解，配制成合适浓度的药液。无菌条件下，分别移取1 mL加入到100 mL 60 ℃左右灭菌的PDA培养基中， 混匀后，快速倒入灭菌的培养皿中，凝固后将供试菌菌饼移接至培养基上。每个处理重复三次，以含等量丙酮的灭菌培养基作对照。置于27℃恒温培养箱中培养， 待对照组菌落长至培养皿直径的3/4时，采用十字交叉法测量菌落直径，以其平均值作为菌落大小，并计算抑制率。目标化合物除草活性数据列于表3中。
表3. 目标化合物的抑菌活性评价数据（抑制率，%，100 mg/L）

Claims (2)

1.一种N-取代氨基香豆素衍生物结构如通式所示：
R选自甲基乙烯基、2-甲基丙烯基、4-乙基苯基、苯氧基、3-溴苯基、噻吩-3-基、4-叔丁基苯基。
2.权利要求1所述化合物在防治植物病害方面的用途，所述的植物病害为番茄灰霉病菌、苹果腐烂病菌。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775373A (zh) * 2012-08-10 2012-11-14 青岛农业大学 一种n-取代氨基香豆素类化合物及其制备与应用
CN104592183A (zh) * 2015-01-15 2015-05-06 青岛农业大学 N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775373A (zh) * 2012-08-10 2012-11-14 青岛农业大学 一种n-取代氨基香豆素类化合物及其制备与应用
CN104592183A (zh) * 2015-01-15 2015-05-06 青岛农业大学 N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
N-酰基-N-间氟苄基-6-氨基香豆素的合成及除草活性;王栋，等;《有机化学》;20151231;第35卷(第8期);第1692-1693页、第1698页 *

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