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CN113973824A - 环己烷-1,3-二酮类化合物作为除草剂的用途 - Google Patents

环己烷-1,3-二酮类化合物作为除草剂的用途 Download PDF

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CN113973824A
CN113973824A CN202111332014.XA CN202111332014A CN113973824A CN 113973824 A CN113973824 A CN 113973824A CN 202111332014 A CN202111332014 A CN 202111332014A CN 113973824 A CN113973824 A CN 113973824A
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cyclohexane
herbicide
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邓照西
胡合伟
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Zhengzhou Hengcheng Instrument Consumables Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • 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
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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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
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Abstract

本发明提供了一种环己烷‑1,3‑二酮类化合物作为除草剂的用途，该环己烷‑1,3‑二酮类化合物的结构式为

Description

环己烷-1,3-二酮类化合物作为除草剂的用途
技术领域
本发明涉及除草剂领域，尤其涉及一种环己烷-1,3-二酮类化合物的新用途。
背景技术
环己烷-1,3-二酮类除草剂是除草剂中非常重要的一类，此类除草剂最早开发于20世纪60年代，通过抑制乙酰辅酶A羧化酶(ACCase)，破坏脂肪酸的生物合成，来除掉杂草。此类除草剂是一种高效安全、高选择性的ACCase抑制剂，仅对于大多数一年生和多年生的禾本科杂草有特效，对双子叶作物安全，为此，不少人致力于此类除草剂的研发。
发明内容
有鉴于此，确有必要提供一种环己烷-1,3-二酮类化合物作为除草剂的用途。
具体地，本发明提供一种环己烷-1,3-二酮类化合物作为除草剂的用途，所述环己烷-1,3-二酮类化合物的结构式为
Figure BDA0003349244160000011
所述除草剂用于防治大豆田杂草。
其中，所述大豆田杂草包括稗草、野燕麦、马唐、狗尾草、早熟禾、看麦娘或硬草等。
具体实施方式
下面通过具体实施方式，对本发明的技术方案做进一步的详细描述。
实施例1
本实施例提供一种化合物e1：2-{1-[2-(4-氯-苯氧基)-丙氧基亚氨基]-丙基}-5-(2-乙硫基-丙基)-3-羟基-环己-2-烯酮，其结构式为：
Figure BDA0003349244160000021
该化合物的合成方法包括以下步骤：
第一步，合成2-(甲苯-4-磺酸基)-丙酸甲酯：
Figure BDA0003349244160000022
向反应器中加入10.4g乳酸甲酯、0.36g DMAP和19g对甲苯磺酰氯，用甲苯溶解，维持温度0℃，然后向反应体系中滴入10.1g三乙胺，滴加完毕后升温至50℃保温1h；反应结束后过滤除去不溶物，并向滤液中加入酸水进行萃取，取有机层除去溶剂得到24.5g 2-(甲苯-4-磺酸基)-丙酸甲酯。
第二步，合成2-(4-氯-苯氧基)-丙酸甲酯：
Figure BDA0003349244160000023
向反应器中加入24.5g 2-(甲苯-4-磺酸基)-丙酸甲酯、14.7g对氯苯酚和8.5g碳酸氢钠，用甲苯溶解，在60℃下减压反应3h，反应结束后离心除去不溶物，并向滤液中加入酸水进行萃取，取有机层除去溶剂得到18.6g 2-(4-氯-苯氧基)-丙酸甲酯。
第三步，合成2-(4-氯苯氧基)-丙醇：
Figure BDA0003349244160000024
向反应器中加入18.6g 2-(4-氯-苯氧基)-丙酸甲酯、7.7g氯化钙和6.6g硼氢化钠，用乙醇溶解，然后升温至30℃保温5h，反应结束后，向反应体系中加入硫酸水溶液，除去溶剂后，加入水和甲苯，收集有机层除去溶剂得到15.8g 2-(4-氯苯氧基)-丙醇。
第四步，合成甲磺酸2-(4-氯-苯氧基)-丙酯：
Figure BDA0003349244160000025
向反应器中加入15.8g 2-(4-氯苯氧基)-丙醇，用甲苯溶解，向反应体系中滴加12.9g三乙胺，然后在10℃下滴加9.7g甲基磺酰氯，滴加完毕后维持10℃保温3h，反应结束后过滤或离心除去不溶物，并向滤液中加入酸水进行萃取，取有机层除去溶剂得到21.9g甲磺酸2-(4-氯-苯氧基)-丙酯。
第五步，合成2-[2-(4-氯-苯氧基)-丙氧基]-异吲哚-1,3-二酮：
Figure BDA0003349244160000031
向反应器中加入21.9g甲磺酸2-(4-氯-苯氧基)-丙酯、20.3g N-羟基邻苯二甲酰亚胺、3.8g碳酸氢钠，用DMF溶解，在90℃下反应4h，除去溶剂后，加入水和甲苯，收集有机层除去溶剂得到24.8g 2-[2-(4-氯-苯氧基)-丙氧基]-异吲哚-1,3-二酮。
第六步，合成O-[2-(4-氯-苯氧基)-丙基]-羟胺：
Figure BDA0003349244160000032
向反应器中加入24.8g 2-[2-(4-氯-苯氧基)-丙氧基]-异吲哚-1,3-二酮，用二氯甲烷溶解，然后滴加8.4g水合肼，滴加完毕后在40℃下反应1h，反应结束后加入水进行萃取，收集有机层除去溶剂得到14.8g O-[2-(4-氯-苯氧基)-丙基]-羟胺。
第七步，合成化合物e1：2-{1-[2-(4-氯-苯氧基)-丙氧基亚氨基]-丙基}-5-(2-乙硫基-丙基)-3-羟基-环己-2-烯酮
向反应器中加入14.8g O-[2-(4-氯-苯氧基)-丙基]-羟胺和19g丙酰三酮，用甲醇溶解，然后加入0.1g乙酸，在80℃下反应2h，反应结束后除去溶剂，水洗干燥后得到31g化合物e1纯品，红棕色粘稠液体，产率为71％。
对该步骤得到的目标产物化合物e1进行核磁检测的结果为：1HNMR(400MHzCDCl3):δ7.2(2H,m),δ6.8(2H,m),δ4.6(1H,q),δ4.1(2H,d),δ2.8(2H,q),δ2.5(2H,q),δ2.2(2H,m),δ2.1(1H,m),δ1.5(2H,m),δ1.2(11H,m),δ1.1(3H,t),δ0.9(1H,m).因此可判断该目标产物化合物e1的结构式如上所示。
应用验证
有效质量为25％的油悬剂：活性物质、10％十二烷基磺酸钠、65％矿物油，其中所述活性物质为实施例1提供的化合物e1。
将大豆、稗草、野燕麦、马唐、狗尾草、早熟禾、看麦娘、硬草的种子播种于塑料盆中的标准土壤里，置于人工气候室中培养(温度：30℃，湿度：30％)，出苗后3～5叶期喷施上述油悬剂，5～7天后评价植物损害情况，评价结果如下表1所示。其中，植物损害情况的评价标准如下：
5＝对植物完全性的损害；
4＝对生长影响大；
3＝对生长影响较大；
2＝轻度抑制或失绿；
1＝微见症状，局部颜色变化；
0＝对植物没有损害。
表1含有化合物e1的除草剂应用效果表
制剂用量 大豆 稗草 野燕麦 马唐 狗尾草 早熟禾 看麦娘 硬草
15g/亩e1 0 2 2 1 2 3 1 2
25g/亩e1 0 4 5 4 5 5 3 4
40g/亩e1 1 5 5 5 5 5 5 5
从表1中可以看出：本发明实施例提供的环己烷-1,3-二酮类化合物普遍具有较好的杂草防治效果，尤其对于大豆田中广泛发生的稗草、野燕麦、马唐、狗尾草、早熟禾、看麦娘、硬草等杂草具有良好的防治效果，具备工商业化应用前景。
最后应当说明的是：以上实施例仅用以说明本发明的技术方案而非对其限制；尽管参照较佳实施例对本发明进行了详细的说明，所属领域的普通技术人员应当理解：依然可以对本发明的具体实施方式进行修改或者对部分技术特征进行等同替换；而不脱离本发明技术方案的精神，其均应涵盖在本发明请求保护的技术方案范围当中。

Claims (2)

1.一种环己烷-1,3-二酮类化合物作为除草剂的用途，其特征在于：所述环己烷-1,3-二酮类化合物的结构式为
Figure FDA0003349244150000011
所述除草剂用于防治大豆田杂草。
2.一种环己烷-1,3-二酮类化合物作为除草剂的用途，其特征在于：所述大豆田杂草为稗草、野燕麦、马唐、狗尾草、早熟禾、看麦娘或硬草。
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