CN110105224B - 3-对䓝烯-1-仲胺类化合物及其制备方法与除草应用 - Google Patents

3-对䓝烯-1-仲胺类化合物及其制备方法与除草应用 Download PDF

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CN110105224B
CN110105224B CN201910490475.6A CN201910490475A CN110105224B CN 110105224 B CN110105224 B CN 110105224B CN 201910490475 A CN201910490475 A CN 201910490475A CN 110105224 B CN110105224 B CN 110105224B
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secondary amine
amine compound
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赵振东
董欢欢
徐士超
曾小静
陈玉湘
毕良武
王婧
张红梅
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Abstract

本发明公开了3‑对
Figure DDA0002086833180000011
烯‑1‑仲胺类化合物及其制备方法与除草应用。该方法以3‑对
Figure DDA0002086833180000012
烯‑1‑席夫碱类化合物为原料，在极性有机溶剂中，在‑10～50℃条件下分批次投入还原剂，反应1～24h，反应结束后反应液经蒸馏水淬灭、二氯甲烷萃取、无水硫酸钠干燥、过滤、减压蒸馏得3‑对
Figure DDA0002086833180000013
烯‑1‑仲胺类化合物粗品，硅胶柱层析得纯品。采用培养皿种子萌发法测定不同浓度3‑对
Figure DDA0002086833180000014
烯‑1‑仲胺类化合物培养下，水稻稗草根和茎的生长受害症状，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3‑对
Figure DDA0002086833180000015
烯‑1‑仲胺类化合物对水稻稗草根及茎的生长具有很好的抑制作用。

Description

3-对䓝烯-1-仲胺类化合物及其制备方法与除草应用
技术领域：
本发明涉及3-对
Figure BDA0002086833160000012
烯-1-仲胺类化合物及其制备方法与除草应用，具体涉及一种以3-对
Figure BDA0002086833160000013
烯-1-席夫碱类化合物为原料，与选择性还原剂在极性有机溶剂中发生选择性还原反应，制备3-对
Figure BDA0002086833160000014
烯-1-仲胺类化合物，以及相关产物对水稻稗草的除草应用。
背景技术
杂草是农业生产最主要的影响因素之一，不仅与农作物争夺养料、水分、阳光和空间，有些甚至是病虫中间寄主，促进病虫害发生，降低了作物的产量和品质。自20世纪中叶起，合成农药逐渐成为农业生产中最主要的除草方式之一，对全球粮食产量的提高起到举足轻重的作用。然而，合成农药具有毒性大、难以生物降解等缺陷，过量的农药应用对环境的危害日益严重，严重影响了食品和生态安全，新型环境友好型农药的开发和应用日益受到重视。
植物源除草剂是利用植物资源开发的农药，由于具有毒性低、可生物降解等特性，植物源除草剂是近年来研究最广泛的新型农药。含对
Figure BDA0002086833160000015
烷(1)或对
Figure BDA0002086833160000016
烯(2)骨架的单萜类化合物是自然界中分布最广的萜类化合物，由于具有良好的环境相容性和生物活性，含对
Figure BDA0002086833160000017
烷(1)或对
Figure BDA0002086833160000018
烯(2)骨架的植物源除草剂的研究和应用日益受到各国科研工作者的重视，并展示出良好的开发利用前景，其中，含氧杂环类对
Figure BDA0002086833160000019
烷型衍生物环庚草醚(2)是目前已知商业化应用效果最好的植物源除草剂之一，可以有效抑制植物分生组织的生长，具有施药期宽，用量少等优点(农药,1996，35(3):34-34；林产化学与工业，2019，39(2):1-8)。
Figure BDA00020868331600000110
在已完成前期研究中，以松节油或蒎烯为原料合成的一系列3-对
Figure BDA00020868331600000111
烯-1-席夫碱类植物源除草活性物质，其大多数对一年生黑麦草根茎生长的抑制作用都好于市售除草剂敌草隆或草甘膦(ZL 201610947955.7；Journal of Agricultural and Food Chemistry,2016,64(51):9702–9707)。但是，席夫碱类化合物含有不饱和的亚胺基(-C＝N-)，化学性质不够稳定，不仅容易被空气中的氧气氧化，在酸性条件下也极易发生水解等反应，限制了其进一步开发和应用。通过选择性氢化还原反应，可以在保留对
Figure BDA00020868331600000112
烯环内不饱和键的同时，选择性还原亚胺基生成相应的仲胺类化合物，所生成的仲胺基不仅可以有效提高相关化合物的化学稳定性，同时也是多种医药、农药等生物活性物的活性中心，可望有效提高相关化合物的除草活性。
目前，席夫碱类化合物-C＝N-键的氢化还原主要通过化学还原剂还原氢化法实现(Journal of Environmental Science and Health,Part B,2009,44,344–349)，但相关研究还比较少，采用化学还原剂还原氢化3-对
Figure BDA0002086833160000021
烯-1-席夫碱类合物的相关研究还尚未见报道。本发明申请公开一类新型植物源除草剂3-对
Figure BDA0002086833160000022
烯-1-仲胺类化合物及其制备方法，并公开相关化合物在除草剂领域的应用。
发明内容
为解决合成农药毒性大、难以生物降解等缺陷，本发明公开了一类新型植物源除草剂——3-对
Figure BDA0002086833160000023
烯-1-仲胺类化合物及其制备方法与除草应用。该方法以3-对
Figure BDA0002086833160000024
烯-1-席夫碱类化合物为原料，通过还原剂选择性作用，在保留对
Figure BDA0002086833160000025
烯环内双键的同时选择性还原环外亚胺基(-C＝N-)，制得3-对
Figure BDA0002086833160000026
烯-1-仲胺类化合物，并采用培养皿种子萌发法测定其对水稻稗草的除草活性。
本发明的技术方案为：3-对
Figure BDA0002086833160000027
烯-1-仲胺类化合物，结构通式为：
Figure BDA0002086833160000028
通式I中，R是
Figure BDA0002086833160000029
中的任意一种，R’是氢、烷基、取代烷基或卤素的任意一种。
所述的3-对
Figure BDA00020868331600000210
烯-1-仲胺类化合物的制备方法，以3-对
Figure BDA00020868331600000211
烯-1-席夫碱类化合物为原料，在极性有机溶剂中，分批次投入还原剂反应，反应结束后反应液经后处理得纯品。
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。
所述的还原剂为硼氢化钠、硼氢化钾、氢化铝锂中的任意一种。
3-对
Figure BDA00020868331600000212
烯-1-席夫碱类化合物与还原剂的摩尔比在1∶1～5之间。
反应温度在-10～50℃之间。
反应时间为1～24h。
所述的后处理是指反应液经蒸馏水淬灭、二氯甲烷萃取、无水硫酸钠干燥、过滤、减压蒸馏得3-对
Figure BDA00020868331600000213
烯-1-仲胺类化合物粗品，硅胶柱层析得纯品。
所述的3-对
Figure BDA00020868331600000214
烯-1-仲胺类化合物作为除草剂活性成分应用。
所述的3-对
Figure BDA00020868331600000215
烯-1-仲胺类化合物作为针对水稻稗草的除草剂活性成分应用。
有益效果
1.本发明公开的3-对
Figure BDA0002086833160000031
烯-1-仲胺类化合物为天然产物的衍生物，属于单萜烯类植物源除草活性物，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3-对
Figure BDA0002086833160000032
烯-1-仲胺类化合物对水稻稗草的根长抑制率LD50均小于0.63mmol/L，具有非常优异的除草活性。
附图说明
图1为3-对
Figure BDA0002086833160000033
烯-1-(4-甲硫基苄基)仲胺的1H核磁共振(1H NMR)图；
图2为3-对
Figure BDA0002086833160000034
烯-1-(4-氟苄基)仲胺的1H核磁共振(1H NMR)图；
图3为3-对
Figure BDA0002086833160000035
烯-1-(4-氯苄基)仲胺的1H核磁共振(1H NMR)图；
图4为3-对
Figure BDA0002086833160000036
烯-1-(4-溴苄基)仲胺的1H核磁共振(1H NMR)图；
图5为3-对
Figure BDA0002086833160000037
烯-1-(4-甲基苄基)仲胺的1H核磁共振(1H NMR)图；
图6为3-对
Figure BDA0002086833160000038
烯-1-(2-氯苄基)仲胺的1H核磁共振(1H NMR)图；
图7为3-对
Figure BDA0002086833160000039
烯-1-(2,4-二氯苄基)仲胺的1H核磁共振(1H NMR)图；
图8为3-对
Figure BDA00020868331600000310
烯-1-(2,6-二氯苄基)仲胺的1H核磁共振(1H NMR)图；
图9为3-对
Figure BDA00020868331600000311
烯-1-(4-甲氧基苄基)仲胺的1H核磁共振(1H NMR)图；
图10为3-对
Figure BDA00020868331600000312
烯-1-(2-三氟甲基苄基)仲胺的1H核磁共振(1H NMR)图；
图11为3-对
Figure BDA00020868331600000313
烯-1-(吡啶-3-甲基)仲胺的1H核磁共振(1H NMR)图；
图12为3-对
Figure BDA00020868331600000314
烯-1-(吡啶-4-甲基)仲胺的1H核磁共振(1H NMR)图；
图13为3-对
Figure BDA00020868331600000315
烯-1-(噻吩-2-甲基)仲胺的1H核磁共振(1H NMR)图；
图14为3-对
Figure BDA00020868331600000316
烯-1-(5-溴呋喃-2-甲基)仲胺的1H核磁共振(1H NMR)图。
具体实施方案
分析方法
采取气相峰面积归一化法对产物进行分析，气相条件：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)。
3-对
Figure BDA00020868331600000317
烯-1-仲胺类化合物及其制备方法与在除草活性方面的应用。该方法以3-对
Figure BDA00020868331600000318
烯-1-席夫碱类化合物为原料，通过还原剂选择性作用，在保留对
Figure BDA00020868331600000319
烯环内双键的同时选择性还原环外亚胺基(-C＝N-)，制得3-对
Figure BDA00020868331600000320
烯-1-仲胺类化合物，并采用培养皿种子萌发法测定其对水稻稗草的除草活性。3-对
Figure BDA00020868331600000321
烯-1-仲胺类化合物的结构通式如下：
Figure BDA0002086833160000041
通式I中，R是
Figure BDA0002086833160000042
中的任意一种，R’是氢、烷基、取代烷基或卤素的任意一种。
第一步：将3-对
Figure BDA0002086833160000043
烯-1-胺席夫碱类化合物溶于甲醇，冰浴条件下分次加入还原剂，每次投料间隔半小时，投料完毕继续反应一定时间，反应结束后反应液经蒸馏水淬灭、二氯甲烷萃取、无水硫酸钠干燥、过滤、减压蒸馏得3-对
Figure BDA0002086833160000044
烯-1-仲胺类化合物粗品，硅胶柱层析得纯品。其中极性有机溶剂为甲醇、乙醇、四氢呋喃、二甲基甲酰胺、二甲基亚砜中的任意一种；还原剂为硼氢化钠、硼氢化钾、氢化铝锂等的任意一种；3-对
Figure BDA0002086833160000045
烯-1-席夫碱类化合物与还原剂的摩尔比在1∶1到1∶5之间；反应温度在-10～50℃之间，优化反应温度在0～25℃之间，反应时间为1～24h，优化反应时间为1～3h，所合成化合物对正常细胞的抑制作用皆在-10％～10％之间，证明相关化合物皆没有细胞毒性。
第二步：
准确称取1mmol 3-对
Figure BDA0002086833160000046
烯-1-胺席夫碱类化合物以及3-对
Figure BDA0002086833160000047
烯-1-仲胺类化合物，分别用0.25mL DMF溶解，滴加一滴吐温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(稀释液中DMF和吐温80的浓度和母液一致)。
将稗草种子置于28℃恒温箱中用适量蒸馏水浸泡12h，清水滤出后，置于28℃恒温箱中催芽24h。在培养皿内铺2张滤纸，各皿内摆放大小一致的稗草种子10粒，每处理重复三次；加入10mL该类化合物对应浓度的样品溶液，加等量的水、DMF与吐温80的混合液作为空白对照。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℃、光照5000lx、光照周期为昼∶夜＝16∶8、相对湿度70～80％的条件下培养96h。实验数据由DPS软件进行处理分析，计算3-对
Figure BDA0002086833160000048
烯-1-仲胺类化合物对稗草种子根长或茎长的抑制率(y)。
Figure BDA0002086833160000049
式中：y为根长或茎长的抑制率(％)，x0为对照样品的根长或茎长，x1为样品的根长或茎长。
实施例1
将5.50g(20mmol)3-对
Figure BDA0002086833160000051
烯-1-(4-氯苯基)席夫碱(自制。制备方法参见：ZL201610947955.7实施例部分)加入含有20mL甲醇的三口烧瓶中，冰水浴条件下，磁力搅拌下分3次加入1.513g(40mmol)硼氢化钠，每次间隔30min，加料完毕后室温反应2h，反应完全后，加入20mL水淬灭，二氯甲烷萃取，收集有机相，饱和食盐水洗涤，无水硫酸钠干燥，过滤，减压除去溶剂，再用硅胶柱色谱提纯得3-对
Figure BDA00020868331600000512
烯-1-(4-氯苄基)仲胺，产率92％。
准确称取1mmol 3-对
Figure BDA0002086833160000052
烯-1-(4-氯苯基)席夫碱以及3-对
Figure BDA0002086833160000053
烯-1-(4-甲硫基苄基)仲胺，分别用0.25mL DMF溶解，滴加一滴吐温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(10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L，稀释液中DMF和吐温80的浓度和母液一致)。
将稗草种子置于28℃恒温箱中用适量蒸馏水浸泡12h，清水滤出后，置于30℃恒温箱中催芽24h。在培养皿内铺2张滤纸，各皿内摆放大小一致的稗草种子10粒，每处理重复三次；加入10mL上述对应浓度的样品溶液，加等量的水、DMF与吐温80的混合液作为空白对照。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℃、光照5000lx、光照周期为昼∶夜＝16∶8、相对湿度70％～80％的条件下培养96h。实验数据由DPS软件进行处理分析，得10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000054
烯-1-(4-氯苄基)仲胺溶液对水稻稗草种子根长的抑制率分别为：100.0％、100.0％、71.0％、70.9％、67.4％以及59.7％，对茎长的抑制率分别为：100.0％、100.0％、88.2％、85.7％、76.7％以及54.6％。
实施例2
除原料3-对
Figure BDA0002086833160000055
烯-1-胺席夫碱类化合物为3-对
Figure BDA0002086833160000056
烯-1-(4-氟苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000057
烯-1-(4-氟苄基)仲胺产率76.0％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000058
烯-1-(4-氟苯基)席夫碱溶液对稗草种子根长的抑制率分别为：88.6％、87.9％、86.1％、65.8％、41.0％以及26.8％，对茎长的抑制率分别为：97.5％、94.7％、74.3％、56.4％、44.5％以及40.0％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000059
烯-1-(4-氟苄基)仲胺溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、100.0％、68.0％、84.2％以及67.0％，对茎长的抑制率分别为：100.0％、100.0％、100.0％、85.6％、65.4％以及56.0％。
实施例3
除加入的3-对
Figure BDA00020868331600000510
烯-1-胺席夫碱衍生物为3-对
Figure BDA00020868331600000511
烯-1-(4-甲硫基苯基)席夫碱，其它操作过程同实施例1，目标产物产率73％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000061
烯-1-(4-甲硫基苄基)仲胺溶液对稗草种子根长的抑制率分别为：71.8％、71.4％、69.5％、64.9％、63.9％以及53.1％，对茎长的抑制率分别为：86.9％、67.0％、49.4％、45.0％、35.2％以及21.0％。
实施例4
除加入的3-对
Figure BDA0002086833160000062
烯-1-胺席夫碱衍生物为3-对
Figure BDA0002086833160000063
烯-1-(4-溴苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000064
烯-1-(4-溴苄基)仲胺产率64％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000065
烯-1-(4-溴苯基)席夫碱溶液对稗草种子根长的抑制率分别为：92.2％、72.8％、21.5％、2.8％、5.8％以及1.4％，对茎长的抑制率分别为：98.2％、95.1％、93.8％、72.0％、4.0％以及-9.7％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000066
烯-1-(4-溴苄基)仲胺溶液对稗草种子根长的抑制率分别为：96.4％、86.2％、85.5％、85.7％、81.6％以及67.0％，对茎长的抑制率分别为：98.1％、86.3％、89.9％、87.4％、83.7％以及72.8％。
实施例5
除加入的3-对
Figure BDA0002086833160000067
烯-1-胺席夫碱衍生物为3-对
Figure BDA0002086833160000068
烯-1-(4-甲基苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000069
烯-1-(4-甲基苄基)仲胺产率67％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000610
烯-1-(4-甲基苯基)席夫碱溶液对稗草种子根长的抑制率分别为：90.3％、89.7％、88.6％、85.1％、75.4％以及53.2％，对茎长的抑制率分别为：93.4％、91.4％、93.3％、66.4％以及56.0％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000611
烯-1-(4-甲基苄基)仲胺溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、100.0％、79.0％、84.2％以及81.4％，对茎长的抑制率分别为：100.0％、100.0％、100.0％、86.0％、66.4％以及56.0％。
实施例6
除加入的3-对
Figure BDA00020868331600000612
烯-1-胺席夫碱衍生物为3-对
Figure BDA00020868331600000613
烯-1-(2-氯苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA00020868331600000614
烯-1-(2-氯苄基)仲胺产率80％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000615
烯-1-(2-氯苯基)席夫碱溶液对稗草种子根长的抑制率分别为：56.3％、60.4％、55.3％、14.4％、0.0％以及0.0％，对茎长的抑制率分别为：85.3％、76.3％、22.6％、54.5％、12.3％以及8.0％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000616
烯-1-(2-氯苄基)仲胺溶液对稗草种子根长的抑制率分别为：84.7％、82.8％、76.0％、76.1％、72.5％以及59.4％，对茎长的抑制率分别为：92.4％、90.3％、64.2％、48.9％、32.0％以及15.3％。
实施例7
除加入的3-对
Figure BDA0002086833160000071
烯-1-胺席夫碱衍生物为3-对
Figure BDA0002086833160000072
烯-1-(2,4-二氯苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000073
烯-1-(2,4-二氯苄基)仲胺产率82％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000074
烯-1-(2,4-二氯苄基)仲胺溶液对稗草种子根长的抑制率分别为：90.2％、88.3％、87.6％、84.7％、77.8％以及65.9％，对茎长的抑制率分别为：91.1％、86.5％、42.6％、44.4％、14.4％以及12.3％。
实施例8
除加入的3-对
Figure BDA0002086833160000075
烯-1-胺席夫碱衍生物为3-对
Figure BDA0002086833160000076
烯-1-(2,6-二氯苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000077
烯-1-(2,6-二氯苄基)仲胺产率82％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000078
烯-1-(2,6-二氯苯基)席夫碱溶液对稗草种子根长的抑制率分别为：63.2％、58.9％、41.7％、58.9％、50.5％以及53.2％，对茎长的抑制率分别为：60.7％、56.4％、60.6％、64.8％、67.8％以及65.4％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000079
烯-1-(2,6-二氯苄基)仲胺溶液对稗草种子根长的抑制率分别为：100％、100％、87.6％、92.5％、92.1％以及87.8％，对茎长的抑制率分别为：91.1％、86.5％、42.6％、96.3％、77.3％以及65.7％。
实施例9
除加入的3-对
Figure BDA00020868331600000710
烯-1-胺席夫碱衍生物为3-对
Figure BDA00020868331600000711
烯-1-(4-甲氧基苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA00020868331600000712
烯-1-(4-甲氧基苄基)仲胺产率67％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000713
烯-1-(4-甲氧基苯基)席夫碱溶液对稗草种子根长的抑制率分别为：88.6％、88.1％、89.7％、90.3％、75.4％以及43.2％，对茎长的抑制率分别为：92.2％、92.5％、88.8％、75.2％、41.6％以及41.1％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000714
烯-1-(4-甲氧基苄基)仲胺溶液对稗草种子根长的抑制率分别为：100％、100％、100％、94.5％、89.8％以及77.2％，对茎长的抑制率分别为：100％、100％、100％、96.3％、47.7％以及22.2％。
实施例10
除加入的3-对
Figure BDA00020868331600000715
烯-1-胺席夫碱衍生物为3-对
Figure BDA00020868331600000716
烯-1-(2-三氟甲基苯基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA00020868331600000717
烯-1-(2-三氟甲基苄基)仲胺产率65％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000718
烯-1-(2-三氟甲基苄基)仲胺溶液对稗草种子根长的抑制率分别为：100％、100％、100％、93.1％、87.3％以及83.3％，对茎长的抑制率分别为：100％、100％、100％、95.9％、94.7％以及86.6％。
实施例11
除加入的3-对
Figure BDA0002086833160000081
烯-1-胺席夫碱衍生物为3-对
Figure BDA0002086833160000082
烯-1-(3-吡啶基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000083
烯-1-(3-吡啶基)仲胺产率76％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol的3-对
Figure BDA0002086833160000084
烯-1-(3-吡啶基)仲胺溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、95.6％、78.8％、66.8％以及61.1％，对茎长的抑制率分别为：100.0％、100.0％、88.9％、43.7％、43.4％以及34.1％。
实施例12
除加入的3-对
Figure BDA0002086833160000085
烯-1-胺席夫碱衍生物为3-对
Figure BDA0002086833160000086
烯-1-(4-吡啶基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA0002086833160000087
烯-1-(4-吡啶基)仲胺产率83％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000088
烯-1-(4-吡啶基)席夫碱溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、91.3％、87.0％、69.1％以及51.4％，对茎长的抑制率分别为：100.0％、100.0％、73.8％、37.3％、12.0％以及4.1％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA0002086833160000089
烯-1-(4-吡啶基)仲胺溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、100.0％、85.8％、84.7％以及79.1％，对茎长的抑制率分别为：100.0％、100.0％、100.0％、38.7％、38.2％以及37.9％。
实施例13
除加入的3-对
Figure BDA00020868331600000810
烯-1-胺席夫碱衍生物为3-对
Figure BDA00020868331600000811
烯-1-(2-噻吩基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA00020868331600000812
烯-1-(2-噻吩基)仲胺产率67％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000813
烯-1-(2-噻吩基)席夫碱溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、99.4％、91.5％、57.7％以及7.8％，对茎长的抑制率分别为：100.0％、100.0％、98.0％、64.1％、36.8％以及36.5％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000814
烯-1-(2-噻吩基)仲胺溶液对稗草种子根长的抑制率分别为：100.0％、100.0％、96.2％、78.7％、78.5％以及71.2％，对茎长的抑制率分别为：100.0％、100.0％、100.0％、81.4％、75.6％以及73.2％。
实施例14
除加入的3-对
Figure BDA00020868331600000815
烯-1-胺席夫碱衍生物为3-对
Figure BDA00020868331600000816
烯-1-(5-溴呋喃基)席夫碱，其它操作过程同实施例1，目标产物3-对
Figure BDA00020868331600000817
烯-1-(5-溴呋喃基)仲胺产率67％。10mmol/L、5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的3-对
Figure BDA00020868331600000818
烯-1-(2-溴呋喃基)仲胺溶液对稗草种子根长的抑制率分别为：76.4％、55.7％、55.6％、55.5％、54.5％以及43.4％，对茎长的抑制率分别为：78.4％、68.0％、67.4％、64.9％、62.1％以及46.7％。
实施例15
除3-对
Figure BDA0002086833160000091
烯-1-(4-氯苯基)席夫碱与硼氢化钠摩尔比为1∶1，其它操作过程同实施例1，产率45％。
实施例16
除3-对
Figure BDA0002086833160000092
烯-1-(4-氯苯基)席夫碱与硼氢化钠摩尔比为1∶5，其它操作过程同实施例1，产率76％。
实施例17
除还原剂为硼氢化钾，其它操作过程同实施例1，产率65％。
实施例18
除反应温度为25℃，其它操作过程同实施例1，产率38％。
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55％。
实施例20
除反应时间为3h，其它操作过程同实施例1，产率75％。
实施例21
除反应试剂为氢化铝锂外，其它操作过程同实施例1。

Claims (10)

1.3-对
Figure FDA0003486957580000012
烯-1-仲胺类化合物，其特征在于，结构通式为：
Figure FDA0003486957580000011
通式I中，R是4-氯苯基、4-氟苯基、4-甲硫基苯基、4-溴苯基、4-甲基苯基、2-氯苯基、2,4-二氯苯基、2,6-二氯苯基、4-甲氧基苯基、2-三氟甲基苯基、3-吡啶基、4-吡啶基、2-噻吩基、5-溴呋喃基中的任意一种。
2.权利要求1所述的3-对
Figure FDA0003486957580000013
烯-1-仲胺类化合物的制备方法，其特征在于，以3-对
Figure FDA0003486957580000014
烯-1-席夫碱类化合物为原料，在极性有机溶剂中，分批次投入还原剂反应，反应结束后反应液经后处理得纯品。
3.根据权利要求2所述的3-对
Figure FDA0003486957580000015
烯-1-仲胺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。
4.根据权利要求2所述的3-对
Figure FDA0003486957580000016
烯-1-仲胺类化合物的制备方法，其特征在于，所述的还原剂为硼氢化钠、硼氢化钾、氢化铝锂中的任意一种。
5.根据权利要求2所述的3-对
Figure FDA0003486957580000017
烯-1-仲胺类化合物的制备方法，其特征在于，3-对
Figure FDA0003486957580000018
烯-1-席夫碱类化合物与还原剂的摩尔比在1∶1～5之间。
6.根据权利要求2所述的3-对
Figure FDA0003486957580000019
烯-1-仲胺类化合物的制备方法，其特征在于，反应温度在-10～50℃之间。
7.根据权利要求2所述的3-对
Figure FDA00034869575800000110
烯-1-仲胺类化合物的制备方法，其特征在于，反应时间为1～24h。
8.根据权利要求2所述的3-对
Figure FDA00034869575800000111
烯-1-仲胺类化合物的制备方法，其特征在于，所述的后处理是指反应液经蒸馏水淬灭、二氯甲烷萃取、无水硫酸钠干燥、过滤、减压蒸馏得3-对
Figure FDA00034869575800000112
烯-1-仲胺类化合物粗品，硅胶柱层析得纯品。
9.权利要求1所述的3-对
Figure FDA00034869575800000113
烯-1-仲胺类化合物作为除草剂活性成分应用。
10.权利要求1所述的3-对
Figure FDA00034869575800000114
烯-1-仲胺类化合物作为针对水稻稗草的除草剂活性成分应用。
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