CN110590725B - 一类东莨菪素磺酸酯化合物及其制备与杀螨用途 - Google Patents

一类东莨菪素磺酸酯化合物及其制备与杀螨用途 Download PDF

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CN110590725B
CN110590725B CN201911044773.9A CN201911044773A CN110590725B CN 110590725 B CN110590725 B CN 110590725B CN 201911044773 A CN201911044773 A CN 201911044773A CN 110590725 B CN110590725 B CN 110590725B
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郝双红
郑攀元
魏艳
李宁
余鑫平
张渝婉
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Qingdao Agricultural University
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    • 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
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    • 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
    • C07D311/16—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 7
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    • 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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Abstract

本发明（名称为：一类东莨菪素磺酸酯化合物及其制备与杀螨用途）涉及11种东莨菪素磺酸酯化合物及其制备方法，以及在杀螨方面的用途。11种东莨菪素磺酸酯化合物，通过3‑取代东莨菪素与磺酰氯，在碱性条件下缩合而得。这些化合物可作为杀螨剂防治植物害螨二斑叶螨等。

Description

一类东莨菪素磺酸酯化合物及其制备与杀螨用途
技术领域
本发明涉及一类东莨菪素磺酸酯化合物及其制备与杀螨用途，具体的涉及农用杀螨剂领域。
背景技术
东莨菪素（scopoletin）又称东莨菪内酯、莨菪亭、莨菪酚，是一种重要的香豆素类化合物，其化学名为7-羟基- 6-甲氧基香豆素。东莨菪素是植物体内的一种重要植物毒素，当植物受到病原菌、害虫侵扰或其它环境因素变化干扰时，能够大量合成和累积东莨菪素，用于防御不良因素的干扰。东莨菪素具有良好杀螨活性，2012年，全国农药标准化技术委员会正式将其通用名定为甲氧香螨酯（农标字2012第005号）。
苯磺酸苯酯类化合物曾被开发为商品杀螨剂使用，如1947年Allied公司开发的格螨酯（Genite）、1952年Murphy公司开发的分螨酯（Fenson），这两个品种均为低毒非内吸杀螨剂。1949年Dow公司开发的杀螨酯（Chlorfenson），又称螨卵酯或K-6451，是一种磺酸酯类有机氯杀螨剂，化学名为4-氯苯基-4-氯苯磺酸酯。该物质化学性质稳定，具有很好的杀卵活性，可防治多种作物螨类的卵、若螨和成螨，残效期较长，对人畜毒害较低。
本专利基于活性结构拼接思想，拟设计合成系列新型东莨菪素磺酸酯类衍生物，同时对其杀螨活性进行评价，以期发现新杀螨活性化合物。
发明内容
本发明的目的在于提供一类新型东莨菪素磺酸酯化合物及制备方法，它可应用于农业上以防治植物害螨。
本发明的技术方案如下：
本发明提供的东莨菪素磺酸酯化合物，结构通式如下：
Figure 450630DEST_PATH_IMAGE001
Ⅰ
R1选自：H、对氟苯基，或对溴苯胺基甲酰基；
R2选自：萘-2-基、对甲氧基苯基、噻吩-3-基、苯基、对硝基苯基、对溴苯基、对氯苯基、对氟苯基；
该东莨菪素苯磺酸酯化合物合成反应式如下：
Figure 558263DEST_PATH_IMAGE002
Figure 953472DEST_PATH_IMAGE003
Figure 299003DEST_PATH_IMAGE004
Ⅱ Ⅲ Ⅰ
式中R1及R2定义如上；
通式化合物制备方法：在适当溶剂中，适当温度下，加入适当催化剂，东莨菪素或其衍生物Ⅱ和芳基磺酰氯Ⅲ发生缩合，反应一定时间后，处理即得目标产物Ⅰ；
适当溶剂可选自甲苯、二氯甲烷、1,2-二氯乙烷、丙酮、乙腈等；
适当温度指20 ℃至溶剂的沸点温度；
适当催化剂指无水碳酸钾、无水碳酸钠、碳酸氢钠、氢氧化钠、哌啶、吡啶、三乙胺等；
反应时间为2小时至8小时。
具体实施方式
实例1. 化合物Ⅰ-9的制备
Figure 387045DEST_PATH_IMAGE005
Figure 654078DEST_PATH_IMAGE006
Figure 180874DEST_PATH_IMAGE007
将0.57 g（2 mmol）3-对氟苯基-东莨菪素，5 mL吡啶，0.48 g（2.5 mmol）4-氟苯磺酰氯，加入到25 mL三口瓶中，升温搅拌回流，TLC跟踪反应。反应完毕，反应液用盐酸调至pH为3~4，抽滤，干燥得浅黄色固体，通过柱层析[流动相为V（石油醚）：V（乙酸乙酯）= 3:1分离，获得化合物Ⅰ-9，即3-对氟苯基-7-对氟苯磺酸酯基-东莨菪素；
化合物Ⅰ-1~Ⅰ-8及Ⅰ-10~Ⅰ-11，按照与化合物Ⅰ-9相似的方法合成，合成化合物MS及1H NMR数据列于表1；
表1 目标化合物MS及1H NMR数据
Figure 849753DEST_PATH_IMAGE008
Figure 374275DEST_PATH_IMAGE009
Figure 128605DEST_PATH_IMAGE010
Figure 131196DEST_PATH_IMAGE011
Figure 654581DEST_PATH_IMAGE012
。
实例2. 杀螨活性测试
称取0.01 g上述目标化合物，加入2 mL丙酮配置成5000 mg/L的母液，溶解，从中取出0.1 mL加入5 mL吐温80水溶液，配制成100 mg/L浓度的药液；从5000 mg/L的母液取0.6 mL的溶液，加入5 mL吐温-80水溶液，溶匀配制成600 mg/L浓度的药液。每个浓度重复3次；
把150~200头朱砂叶螨接到盆栽的两叶期蚕豆苗叶片上，培养8 h。利用微型喷雾装置喷施上述药液，施药量约40 mL/m2。对照喷施等量吐温-80水溶液。每处理重复3次。然后放入温室（光照周期16L：8D，湿度60%-80%，温度26±1℃），培养72 h。显微镜下观察、计算朱砂叶螨的死亡率。计算公式如下：
死亡率（%）=（施药前活螨数-施药后活螨数）/ 施药前活螨数 × 100%
化合物Ⅰ-1~Ⅰ-11的杀螨活性数据列于表2中；
表2 目标化合物杀螨活性
Figure 615584DEST_PATH_IMAGE013

Claims (2)

1.一种东莨菪素磺酸酯化合物，其特征在于，结构如通式所示：
Figure DEST_PATH_IMAGE001
R1为H时，R2为萘-2-基；
R1为对氟苯基时，R2为萘-2-基、噻吩-3-基、苯基、对硝基苯基、对溴苯基、对氯苯基、对氟苯基；
R1为对溴苯胺基甲酰基时，R2为苯基或对氯苯基。
2.权利要求1所述化合物在防治植物害螨方面的用途，其特征在于，所述的植物害螨为朱砂叶螨。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946828A (zh) * 2017-03-21 2017-07-14 西南大学 东莨菪内酯酚醚衍生物及其制备方法和应用
CN107011306A (zh) * 2017-05-26 2017-08-04 青岛农业大学 一类新型酰胺基羟甲基香豆素类化合物及其制备与杀螨用途

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946828A (zh) * 2017-03-21 2017-07-14 西南大学 东莨菪内酯酚醚衍生物及其制备方法和应用
CN107011306A (zh) * 2017-05-26 2017-08-04 青岛农业大学 一类新型酰胺基羟甲基香豆素类化合物及其制备与杀螨用途

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