CN110128277A - cis-对*烷-1,8-二仲胺类化合物及其制备方法与除草应用 - Google Patents

cis-对*烷-1,8-二仲胺类化合物及其制备方法与除草应用 Download PDF

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CN110128277A
CN110128277A CN201910490796.6A CN201910490796A CN110128277A CN 110128277 A CN110128277 A CN 110128277A CN 201910490796 A CN201910490796 A CN 201910490796A CN 110128277 A CN110128277 A CN 110128277A
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alkane
cis
pairs
amine compound
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CN110128277B (zh
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徐士超
赵振东
曾小静
王婧
董欢欢
张红梅
陈玉湘
毕良武
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Institute of Chemical Industry of Forest Products of CAF
Research Institute of Forestry New Technology of Chinese Academy of Forestry
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Abstract

本发明公开了cis‑对烷‑1,8‑二仲胺类化合物的制备方法与除草应用。该方法以cis‑对烷‑1,8‑二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cis‑对烷‑1,8‑二仲胺类化合物，重结晶或硅胶柱层析得纯品。采用培养皿种子萌发法测定cis‑对烷‑1,8‑二仲胺类化合物，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cis‑对烷‑1,8‑二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

cis-对*烷-1,8-二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cis-对烷-1,8-二仲胺类化合物及其制备方法与除草活性应用，具体涉及一种以cis-对烷-1,8-二席夫碱类化合物为原料，与还原剂在极性有机溶剂中发生还原反应，制备得到cis-对烷-1,8-二仲胺类化合物，并将其用作水稻稗草等的除草活性成分。
背景技术
自20世纪中叶起，除草剂的施用对于全球粮食产量的提高具有十分重要的意义，但传统除草剂以有机合成化合物为主，毒性大、化学稳定性强、难生物降解，因此，积极开发绿色、环境友好型的高性能除草剂来代替传统化学合成除草剂是近年来世界各国农药开发领域的研究热点。
植物源除草剂是利用天然植物资源开发的农药，来源丰富、高效低毒、可生物降解，是近年来研究最广泛的新型环境友好型农药之一。含对烷(1)或对烯(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，含对烷(1)或对烯(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，含氧杂环类对烷型衍生物环庚草醚(3)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)。
在已完成前期研究工作中，以松节油或蒎烯为原料合成的一系列cis-对烷-1,8-二席夫碱类植物源除草活性物质，其大多数化合物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 201610942979.3；Chinese Chemical Letters,2017,28(7),1509–1513；Industrial Crops&Products,2018,115:111–116)。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。通过氢化还原反应，可以将亚胺基还原成化学性质稳定的仲胺基，而所得到的仲胺基也是多种医药、农药类化合物的活性中心，可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cis-对烷-1,8-二席夫碱类化合物的相关研究还尚未见报道。本发明申请提供一类新型植物源除草剂cis-对烷-1,8-二仲胺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。
发明内容
为解决合成农药毒性大、难以生物降解等缺陷，本专利公开了一类新型植物源除草剂——cis-对烷-1,8-二仲胺类化合物及其制备方法与除草活性应用。本发明以cis-对烷-1,8-二席夫碱类化合物为原料，通过氢化还原反应将亚胺基还原成化学性质稳定的仲胺基，制得cis-对烷-1,8-二仲胺类化合物，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：cis-对烷-1,8-二仲胺类化合物，结构通式如下：
通式I中，R是中的任意一种，R’是氢、烷基、取代烷基或卤素中的任意一种。
所述的cis-对烷-1,8-二仲胺类化合物的制备方法，以cis-对烷-1,8-二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、氢化锂铝中的任意一种。
cis-对烷-1,8-二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。
所述的后处理具体指，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cis-对烷-1,8-二仲胺类化合物粗品，重结晶或硅胶柱层析得纯品。
所述的cis-对烷-1,8-二仲胺类化合物作为除草剂活性成分的应用。
所述的cis-对烷-1,8-二仲胺类化合物作为针对水稻稗草的除草剂活性成分的应用。
有益效果
1.本发明公开的cis-对烷-1,8-二仲胺类化合物为天然产物衍生物，属于单萜类植物源除草活性物质，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cis-对烷-1,8-二仲胺类化合物对水稻稗草的根长具有优异的除草活性，活性皆高于相应cis-对烷-1,8-二席夫碱类化合物。
附图说明
图1为cis-对烷-1,8-二-(4-氯苄基)胺的1H核磁共振(1H NMR)图；
图2为cis-对烷-1,8-二-(4-氟苄基)胺的1H核磁共振(1H NMR)图；
图3为cis-对烷-1,8-二-(4-溴苄基)胺的1H核磁共振(1H NMR)图；
图4为cis-对烷-1,8-二-(4-甲基苄基)胺的1H核磁共振(1H NMR)图；
图5为cis-对烷-1,8-二-(4-甲氧基苄基)胺的1H核磁共振(1H NMR)图；
图6为cis-对烷-1,8-二-(4-三氟甲基苄基)胺的1H核磁共振(1H NMR)图；
图7为cis-对烷-1,8-二-(4-二甲氨基苄基)胺的1H核磁共振(1H NMR)图；
图8为cis-对烷-1,8-二-(4-甲硫基苄基)胺的1H核磁共振(1H NMR)图；
图9为cis-对烷-1,8-二-(2-三氟甲基苄基)胺的1H核磁共振(1H NMR)图；
图10为cis-对烷-1,8-二-(5-溴呋喃-2-甲基)胺的1H核磁共振(1H NMR)图；
图11为cis-对烷-1,8-二-(5-甲基呋喃-2-甲基)胺的1H核磁共振(1H NMR)图；
图12为cis-对烷-1,8-二(呋喃-2-甲基)胺的1H核磁共振(1H NMR)图；
图13为cis-对烷-1,8-二-(吡啶-2-甲基)胺的1H核磁共振(1H NMR)图；
图14为cis-对烷-1,8-二-(吡啶-3-甲基)胺的1H核磁共振(1H NMR)图；
图15为cis-对烷-1,8-二-(吡啶-4-甲基)胺的1H核磁共振(1H NMR)图；
图16为cis-对烷-1,8-二-(噻吩-2-甲基)胺的1H核磁共振(1H NMR)图；
图17为cis-对烷-1,8-二-(吡咯-2-甲基)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)。
cis-对烷-1,8-二仲胺类化合物及其制备方法与除草活性应用。该方法以cis-对烷-1,8-二席夫碱类化合物为原料，通过氢化还原反应将亚胺基还原成化学性质稳定的仲胺基，制得cis-对烷-1,8-二仲胺类化合物，并采用培养皿种子萌发法测定不同浓度cis-对烷-1,8-二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。cis-对烷-1,8-二仲胺类化合物的结构通式如下：
通式I中，R是中的任意一种，R’是氢、烷基、取代烷基或卤素的任意一种。
第一步：将cis-对烷-1,8-二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cis-对烷-1,8-二仲胺类化合物粗品，重结晶或硅胶柱层析得纯品。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；cis-对烷-1,8-二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，反应时间为1～24h，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 cis-对烷-1,8-二席夫碱类化合物以及cis-对烷-1,8-二仲胺类化合物，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cis-对烷-1,8-二仲胺类化合物对稗草种子根长或茎长的抑制率(y)。
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4.14g(10mmol)cis-对烷-1,8-二-(4-氯苯基)席夫碱(自制。制备方法参见ZL201610942979.3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，用乙醇重结晶得cis-对烷-1,8-二-(4-氯苄基)仲胺纯品，产率85％。
准确称取1mmol cis-对烷-1,8-二-(4-氯苯基)席夫碱以及cis-对烷-1,8-二-(4-氯苄基)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(5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.1563mmol/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5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(4-氯苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：20.9％、22.8％、23.9％、4.6％以及1.4％，对根长的抑制率分别为：92.4％、49.9％、76.7％、24.3％以及-5.0％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-氯苄基)胺溶液对水稻稗草种子茎的生长抑制率分别为：75.1％、68.0％、63.4％、65.8％、41.6％以及35.7％，对根的生长抑制率分别为：96.7％、91.6％、90.8％、87.3％、57.1％以及31.4％。
实施例2
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-氟苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-氟苄基)胺，产率98％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(4-氟苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：32.3％、20.1％、23.9％、2.7％和-13.7％，对根长的抑制率分别为：79.7％、82.9％、85.7％、72.8％以及15.7％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-氟苄基)胺溶液对稗草种子茎的生长抑制率分别为：100.0％、85.9％、75.1％、58.3％、10.5％以及7.2％，对根的生长抑制率分别为：100.0％、98.6％、78.6％、78.6％、48.3％以及38.2％。
实施例3
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-溴苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-溴苄基)胺产率96％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(4-溴苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：55.9％、39.3％、42.3％、19.6％以及6.5％，对根长的抑制率分别为：69.4％、72.6％、46.8％、28.5％以及-3.2％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-溴苄基)胺溶液对稗草种子茎的生长抑制率分别为：92.3％、88.2％、58.5％、51.7％、35.4％以及25.2％，对根的生长抑制率分别为：100.0％、97.4％、89.6％、83.4％、57.6％以及30.7％。
实施例4
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-甲基苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-甲基苄基)胺产率97％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-甲基苄基)胺溶液对稗草种子茎的生长抑制率分别为：93.3％、87.1％、74.7％、65.9％、64.6％以及42.1％，对根的生长抑制率分别为：100.0％、95.2％、91.9％、89.6％、86.6％以及42.5％。
实施例5
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-甲氧基苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-甲氧基苄基)胺产率94％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(4-甲氧基苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：2.1％、8.0％、4％、6.9％以及15.4％，对根长的抑制率分别为：7.6％、28.1％、55.3％、66.7％以及70.7％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-甲氧基苄基)胺溶液对稗草种子茎的生长抑制率分别为：84.3％、84.4％、70.6％、72.5％、27.9％以及9.9％，对根的生长抑制率分别为：100.0％、96.5％、95.1％、88.7％、42.2％以及37.8％。
实施例6
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-三氟甲基苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-三氟甲基苄基)胺产率96％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(4-三氟甲基苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：31.1％、19.5％、14.6％、30.9％以及20.6％，对根长的抑制率分别为：48.4％、7.1％、17.5％、0.8％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-三氟甲基苄基)胺溶液对稗草种子茎的生长抑制率分别为：78.5％、83.4％、67.0％、55.1％、42.2％以及11.6％，对根的生长抑制率分别为：100.0％、100.0％、86.1％、82.3％、62.8％以及1.0％。
实施例7
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-二甲氨基苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-二甲氨基苄基)胺产率92％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(4-二甲氨基苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：13.2％、1.9％、6.9％、9.5％以及-12.2％，对根长的抑制率分别为：67.1％、59.3％、49.8％、45.4％以及9.7％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-二甲氨基苄基)胺溶液对稗草种子茎的生长抑制率分别为：56.6％、34.3％、22.3％、24.9％、19.6％以及19.1％，对根的生长抑制率分别为：89.3％、70.3％、48.1％、21.0％、31.0％以及14.4％。
实施例8
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(4-甲硫基苯基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(4-甲硫基苄基)胺产率89％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(4-甲硫基苄基)胺溶液对稗草种子茎的生长抑制率分别为：85.1％、77.5％、83.4％、66.2％、66.0％以及22.8％，对根的生长抑制率分别为：98.5％、96.0％、90.8％、77.2％、58.1％以及32.0％。
实施例9
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(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cis-对烷-1,8-二-(2-三氟甲基苄基)胺产率83％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L以及0.3125mmol/L的cis-对烷-1,8-二-(2-三氟甲基苯基)席夫碱溶液对稗草种子茎长的抑制率分别为：21.2％、12.1％、17.7％、13.2％以及9％，对根长的抑制率分别为：34.8％、20.6％、2.7％、15.4％以及20.9％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(2-三氟甲基苄基)胺溶液对稗草种子茎的生长抑制率分别为：90.3％、87.4％、59.6％、49.0％、43.6％以及36.9％，对根的生长抑制率分别为：100％、100％、93.％、68.0％、57.0％以及51.9％。
实施例10
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(5-溴呋喃基-2)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(5-溴呋喃-2-甲基)胺产率88％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(5-溴呋喃-2-甲基)胺溶液对稗草种子茎的生长抑制率分别为：71.8％、50.5％、30.3％、11.6％、5.6％以及10.1％，对根的生长抑制率分别为：90.7％、84.4％、61.5％、54.8％、39.6％以及42.2％。
实施例11
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二-(5-甲基呋喃基)席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二-(5-甲基呋喃-2-甲基)胺产率87％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二-(5-甲基呋喃-2-甲基)胺溶液对稗草种子茎的生长抑制率分别为：79.8％、36.5％、17.1％、6.8％、12.5％以及7.2％，对根的生长抑制率分别为：95.5％、64.4％、50.3％、24.7％、41.3％以及23.1％。
实施例12
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二(呋喃基-2)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二(呋喃-2-甲基)胺产率88％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二(呋喃-2-甲基)胺溶液对稗草种子茎的生长抑制率分别为：65.3％、41.1％、19.3％、16.1％、8.6％以及0％，对根的生长抑制率分别为：92.7％、72.7％、48.8％、39.0％、36.3％以及0％。
实施例13
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二(吡啶基-2)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二(吡啶-2-甲基)胺产率90％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二(吡啶-2-甲基)胺溶液对稗草种子茎的生长抑制率分别为：88.0％、65.3％、46.6％、30.1％、26.4％以及23.8％，对根的生长抑制率分别为：100.0％、95.8％、61.0％、33.8％、20.5％以及18.9％。
实施例14
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二(吡啶基-3)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二(吡啶-3-甲基)胺产率81％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二(吡啶-3-甲基)胺溶液对稗草种子茎的生长抑制率分别为：84.9％、65.3％、44.6％、41.5％、30.6％以及38.0％，对根的生长抑制率分别为：95.2％、86.1％、41.4％、19.2％、10.2％以及5.7％。
实施例15
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二(吡啶基-4)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二(吡啶-4-甲基)胺产率91％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二(吡啶-4-甲基)胺溶液对稗草种子茎的生长抑制率分别为：86.7％、71.3％、53.5％、32.7％、34.5％以及28.6％，对根的生长抑制率分别为：96.5％、91.2％、71.5％、40.6％、37.9％以及19.0％。
实施例16
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二(噻吩基-2)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二(噻吩-2-甲基)胺产率86％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二(噻吩-2-甲基)胺溶液对稗草种子茎的生长抑制率分别为：59.1％、51.0％、45.3％、39.2％、28.9％以及13.3％，对根的生长抑制率分别为：86.0％、75.1％、50.0％、5.8％、1.5％以及0.8％。
实施例17
除原料cis-对烷-1,8-二席夫碱类化合物为cis-对烷-1,8-二(吡咯基-2)-席夫碱，其它操作过程同实施例1，目标产物cis-对烷-1,8-二(吡咯-2-甲基)胺产率65％。5mmol/L、2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L以及0.15625mmol/L的cis-对烷-1,8-二(吡咯-2-甲基)胺溶液对稗草种子茎的生长抑制率分别为：78.3％、71.5％、48.2％、28.6％、26.5％以及15.4％，对根的生长抑制率分别为：94.4％、91.9％、93.1％、87.7％、60.5％以及1.7％。
实施例18
除cis-对烷-1,8-二-(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77％。
实施例19
除cis-对烷-1,8-二-(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85％。
实施例20
除反应温度为25℃，其它操作过程同实施例1，产率82％。
实施例21
除反应时间为0.5h，其它操作过程同实施例1，产率80％。
实施例22
除反应时间为3h，其它操作过程同实施例1，产率85％。
实施例23
除还原剂为硼氢化钾，其它操作过程同实施例1。
实施例24
除还原剂为氢化铝锂，其它操作过程同实施例1。

Claims (10)

1.cis-对烷-1,8-二仲胺类化合物，其特征在于，结构通式如下：
通式I中，R是中的任意一种，R’是氢、烷基、取代烷基或卤素中的任意一种。
2.权利要求1所述的cis-对烷-1,8-二仲胺类化合物的制备方法，其特征在于，以cis-对烷-1,8-二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cis-对烷-1,8-二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cis-对烷-1,8-二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、氢化锂铝中的任意一种。
5.根据权利要求2所述的cis-对烷-1,8-二仲胺类化合物的制备方法，其特征在于，cis-对烷-1,8-二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cis-对烷-1,8-二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cis-对烷-1,8-二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cis-对烷-1,8-二仲胺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cis-对烷-1,8-二仲胺类化合物粗品，重结晶或硅胶柱层析得纯品。
9.权利要求1所述的cis-对烷-1,8-二仲胺类化合物作为除草剂活性成分的应用。
10.权利要求1所述的cis-对烷-1,8-二仲胺类化合物作为针对水稻稗草的除草剂活性成分的应用。
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