CN113200871A - 一种对䓝烷-1-基仲胺类化合物及其制备方法与除草应用 - Google Patents

一种对䓝烷-1-基仲胺类化合物及其制备方法与除草应用 Download PDF

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CN113200871A
CN113200871A CN202110556572.8A CN202110556572A CN113200871A CN 113200871 A CN113200871 A CN 113200871A CN 202110556572 A CN202110556572 A CN 202110556572A CN 113200871 A CN113200871 A CN 113200871A
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赵振东
张红梅
徐士超
陈玉湘
王婧
卢言菊
古研
毕良武
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Abstract

本发明公开了一种对
Figure DDA0003077466840000011
烷‑1‑基仲胺类化合物及其制备方法与除草应用。该方法以对
Figure DDA0003077466840000012
烷‑1‑胺和醛为原料，于0～100℃在极性有机溶剂中进行缩合反应，待原料充分反应后将反应液温度降至‑20～60℃，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、减压蒸馏得到对
Figure DDA0003077466840000013
烷‑1‑基仲胺类化合物，重结晶或硅胶柱层析得到目标产物纯品。采用培养皿种子萌发法测定不同浓度对
Figure DDA0003077466840000014
烷‑1‑基仲胺类化合物培养下稗草根和茎、油菜根和茎的生长受害情况，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，产物对稗草及油菜的根和茎的生长具有很好的抑制作用。

Description

一种对䓝烷-1-基仲胺类化合物及其制备方法与除草应用
技术领域：
本发明涉及一种对
Figure BDA0003077466820000012
烷-1-基仲胺类化合物及其制备方法与除草应用，具体涉及一种以对
Figure BDA0003077466820000013
烷-1-胺和醛为原料，在极性有机溶剂中反应后不经分离纯化直接经氢化物还原，制备得到对
Figure BDA0003077466820000014
烷-1-基仲胺类化合物，并将其用作稗草、油菜等的除草活性成分。
背景技术
杂草不仅会与作物争夺水分、养分和阳光，有些甚至是病虫中间寄主，导致了病虫害的发生，使粮食品质下降、产量降低。施用化学合成除草剂是目前农业最主要的除草方式之一，但化学除草剂的长期大量使用会产生环境污染、生物毒害、生态破坏等影响，还易使杂草产生抗性，继而需要施用更大量的除草剂。因此，急需开发绿色、环境友好的高性能除草剂来替代传统化学合成除草剂。
植物源农药是指有效成分来源于植物体的农药，通常以植物提取物为原料加工、用于防控农业有害生物的农药制剂。和传统的化学合成农药相比，植物源农药具有以下特点：大多数植物源农药对哺乳动物毒性较低，对非靶标生物安全；防治谱窄，有明显的选择性；容易降解，对环境影响小；多种成分协同发挥作用；延缓有害生物的抗性。目前常用的开发植物源农药途径有两条：一是开发利用植物资源，将其加工成农药制剂，直接用于防治病害，二是以植物源农药活性成分为模板或灵感，创制新农药。许多天然精油如α-蒎烯、β-蒎烯、3-蒈烯、柠檬烯、紫苏醛、香芹酚和百里香酚等都具有良好的除草活性。含对
Figure BDA0003077466820000015
烷(1)或对
Figure BDA0003077466820000016
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 BDA0003077466820000017
烷和对
Figure BDA0003077466820000018
烯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，并显示出良好的开发利用前景。其中，1983年壳牌公司以1,4-桉叶素为模板合成的含氧杂环类对
Figure BDA0003077466820000019
烷型衍生物环庚草醚(cinmethylin,3)，是目前已知商业化应用效果最好的植物源除草剂之一，其为分生组织抑制剂，具有施药期宽、用量少(1～2g a.i/亩)的优点，用于稻田防除禾本科杂草。
在已完成的前期研究工作中，由松节油衍生的对
Figure BDA00030774668200000110
烯骨架及对
Figure BDA00030774668200000111
烷骨架衍生物具有优异的除草活性，包括3-对
Figure BDA00030774668200000112
烯-1-胺席夫碱衍生物、3-对
Figure BDA00030774668200000113
烯-1-仲胺衍生物、顺-1,8-对
Figure BDA00030774668200000114
烷二胺席夫碱衍生物、顺-1,8-对
Figure BDA00030774668200000115
烷二仲胺衍生物、对
Figure BDA00030774668200000116
烷7-基仲胺衍生物、紫苏基仲胺衍生物等均具有较好的除草活性，优于除草剂草甘膦及敌草隆(Journal ofAgricultural and Food Chemistry,2016,64(51):9702-9707；Industrial Crops&Products,2018,115:111-116；Journal of Agricultural and Food Chemistry,2020,68:11829-11838；New Journal of Chemistry,2020,44:8280-8288.)。如N-(2,6-二氯-苯亚甲基)-3-对
Figure BDA0003077466820000025
烯-1-胺(4)对稗草根的抑制作用比草甘膦高出355.6％，N-(4-氟苄基)-3-对
Figure BDA0003077466820000026
烯-1-胺(5)对稗草根的IC50值约为7mg/L。
Figure BDA0003077466820000021
此前的研究主要集中在以3-对
Figure BDA0003077466820000027
烯-1-胺和1,8-对
Figure BDA0003077466820000028
烷二胺为母体结构的衍生化反应，对于对
Figure BDA0003077466820000029
烷-1-胺及其衍生物的除草活性未见报道，因此，本发明申请提供一类新型植物源除草活性物质对
Figure BDA00030774668200000210
烷-1-基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，通过与前期研究成果对比，以期探明对
Figure BDA00030774668200000211
烷骨架结构上不同部位不同取代基对于除草活性的影响情况，并以此为灵感，设计合成结构更新颖、活性更好的除草活性物质。
发明内容
为解决合成除草剂毒性大、难以生物降解等缺陷，本发明公开了一类新型植物源除草活性物质—对
Figure BDA00030774668200000212
烷-1-基仲胺类化合物的制备及除草应用。本发明以对
Figure BDA00030774668200000213
烷-1-胺和醛为原料，在极性有机溶剂中充分反应后不经分离纯化直接由氢化物还原，制得相关对
Figure BDA00030774668200000214
烷-1-基仲胺类化合物。
本发明的技术方案为：对
Figure BDA00030774668200000215
烷-1-基仲胺类化合物，结构通式如下：
Figure BDA0003077466820000022
通式I中，R是
Figure BDA0003077466820000023
Figure BDA0003077466820000024
中的任意一种，R’是氢、烷基、取代烷基、羟基或卤素中的任意一种。
所述的对
Figure BDA00030774668200000216
烷-1-基仲胺类化合物的制备方法，以对
Figure BDA00030774668200000217
烷-1-胺和醛为原料，在一定温度下在极性有机溶剂中充分反应后，分批次投入氢化物类还原剂还原，反应结束后反应液经后处理而得。
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。
对
Figure BDA00030774668200000218
烷-1-胺和醛的摩尔比在1∶1～5之间，反应温度在0～100℃之间。
原料与还原剂的摩尔比，以对
Figure BDA0003077466820000031
烷-1-胺和还原剂摩尔量之比计算在1∶1～10之间。
还原反应的反应温度在-20～60℃之间，还原反应的反应时间为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、减压蒸馏得对
Figure BDA0003077466820000032
烷-1-基仲胺类化合物粗品，重结晶或硅胶柱层析得纯品。
所述的对
Figure BDA0003077466820000033
烷-1-基仲胺类化合物作为除草剂活性成分的应用。
所述的对
Figure BDA0003077466820000034
烷-1-基仲胺类化合物作为针对稗草、油菜的除草剂活性成分的应用。
有益效果
1.本发明公开的对
Figure BDA0003077466820000035
烷-1-基仲胺类化合物为新型天然产物衍生物，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.本发明公开的对
Figure BDA0003077466820000036
烷-1-基仲胺类化合物对稗草根长和油菜根长具有优异的除草活性，对稗草茎长和油菜茎长具有较好的除草活性。
附图说明
图1为N-(4-氟苄基)-对
Figure BDA0003077466820000037
烷-1-胺的1H NMR图；
图2为N-(2-氯苄基)-对
Figure BDA0003077466820000038
烷-1-胺的1H NMR图；
图3为N-(2,6-二氯苄基)-对
Figure BDA0003077466820000039
烷-1-胺的1H NMR图；
图4为N-(2-三氟甲基苄基)-对
Figure BDA00030774668200000310
烷-1-胺的1H NMR图；
图5为N-(吡啶-4-甲基)-对
Figure BDA00030774668200000311
烷-1-胺的1HNMR图；
图6为N-(呋喃-2-甲基)-对
Figure BDA00030774668200000312
烷-1-胺的1HNMR图；
图7为N-(紫苏基)-对
Figure BDA00030774668200000313
烷-1-胺的1H NMR图；
图8为N-(四氢紫苏基)-对
Figure BDA00030774668200000314
烷-1-胺的1H NMR图。
具体实施方式
分析方法
采取气相色谱峰面积归一化法对产物进行分析，分析条件：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)。
对
Figure BDA00030774668200000315
烷-1-基仲胺类化合物及其制备方法及除草活性应用。该方法以对
Figure BDA00030774668200000316
烷-1-胺和醛为原料，在极性有机溶剂中进行缩合反应，待原料充分反应后分批次投入氢化物类还原剂，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、减压蒸馏得对
Figure BDA0003077466820000044
烷-1-基仲胺类化合物粗品，重结晶或硅胶柱层析得目标产物纯品，并采用培养皿种子萌发法测定不同浓度对
Figure BDA0003077466820000045
烷-1-基仲胺类化合物培养下稗草和油菜的根和茎的生长受害情况，评价其除草活性。对
Figure BDA0003077466820000046
烷-1-基仲胺类化合物的结构通式如下：
Figure BDA0003077466820000041
通式I中，R是
Figure BDA0003077466820000042
Figure BDA0003077466820000043
中的任意一种，R’是氢、烷基、取代烷基、羟基或卤素中的任意一种。
第一步：
将对
Figure BDA0003077466820000047
烷-1-胺加入含有极性有机溶剂的三口烧瓶中，磁力搅拌下加入醛，待原料充分反应后将烧瓶转移至冰浴中，分次加入还原剂，投料完毕在一定温度下继续反应一定时间，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、减压蒸馏得对
Figure BDA0003077466820000048
烷-1-基仲胺类化合物粗品，重结晶或硅胶柱层析得纯品。其中对
Figure BDA0003077466820000049
烷-1-胺和醛的摩尔比在1∶1～5之间，缩合反应温度在0～100℃之间；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；氢化物为硼氢化钠、硼氢化钾、氢化铝锂中的任意一种；原料与氢化物的摩尔比在1∶1～10之间(以对
Figure BDA00030774668200000410
烷-1-胺和还原剂摩尔量之比计算)；还原反应的反应温度在-20～60℃之间；还原反应的反应时间为1～24h。
第二步：
准确称取1mmol对
Figure BDA00030774668200000411
烷-1-基仲胺类化合物，分别用1mL DMF溶解，滴加三滴吐温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，用稀释液(DMF和吐温80的浓度和母液一致)配置成一系列浓度。
将稗草种子、油菜种子分别置于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，加入10mL该类化合物对应浓度的样品溶液，加10mL稀释液作为空白对照，每处理重复三次。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，计算对
Figure BDA0003077466820000052
烷-1-基仲胺类化合物对稗草种子、油菜种子的根长和茎长抑制率(y)。
Figure BDA0003077466820000051
式中：y为根长或茎长的抑制率(％)，x0为空白对照的根长或茎长，x1为样品的根长或茎长。
实施例1
将3.10g(20mmol)对
Figure BDA0003077466820000053
烷-1-胺加入含有20mL甲醇的三口烧瓶中，磁力搅拌下加入2.48g(20mmol)4-氟苯甲醛，室温反应24h，反应结束后，将烧瓶转移至冰水浴中，磁力搅拌下分3次加入3.04g(80mmol)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40mL蒸馏水淬灭，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，柱层析得N-(4-氟苄基)-对
Figure BDA0003077466820000054
烷-1-胺，产率56％。
实施例2
除原料醛为2-氯苯甲醛，其它操作过程同实施例1，得N-(2-氯苄基)-对
Figure BDA0003077466820000055
烷-1-胺，产率59％。
实施例3
除原料醛为2,6-二氯苯甲醛，其它操作过程同实施例1，得N-(2,6-二氯苄基)-对
Figure BDA0003077466820000056
烷-1-胺，产率54％。
实施例4
除原料醛为2-三氟甲基苯甲醛，其它操作过程同实施例1，得N-(2-三氟甲基苄基)-对
Figure BDA0003077466820000057
烷-1-胺，产率59％。
实施例5
除原料醛为吡啶-4-甲醛，其它操作过程同实施例1，得N-(吡啶-4-甲基)-对
Figure BDA0003077466820000058
烷-1-胺，产率64％。
实施例6
除原料醛为呋喃-2-甲醛，其它操作过程同实施例1，得N-(呋喃-2-甲基)-对
Figure BDA0003077466820000059
烷-1-胺，产率66％。
实施例7
除原料醛为紫苏醛，其它操作过程同实施例1，得N-紫苏基-对
Figure BDA0003077466820000061
烷-1-胺，产率40％。
实施例8
除原料醛为四氢紫苏醛(即对
Figure BDA0003077466820000062
烷-7-醛)，其它操作过程同实施例1，得N-(四氢紫苏基)-对
Figure BDA0003077466820000063
烷-1-胺，产率56％。
实施例9
除原料醛为对羟基苯甲醛，其它操作过程同实施例1，得N-(对羟基苄基)-对
Figure BDA0003077466820000064
烷-1-胺，产率60％。
实施例10
除对
Figure BDA0003077466820000065
烷-1-胺与4-氟苯甲醛的摩尔比为1∶3，其它操作过程同实施例1，产率62％。
实施例11
除对
Figure BDA0003077466820000066
烷-1-胺与4-氟苯甲醛的反应温度为0℃，其它操作过程同实施例1，产率50％。
实施例12
除对
Figure BDA0003077466820000067
烷-1-胺与4-氟苯甲醛的反应温度为70℃，其它操作过程同实施例1，产率66％。
实施例13
除对
Figure BDA0003077466820000068
烷-1-胺与4-氟苯甲醛的反应溶剂为N,N-二甲基甲酰胺，其它操作过程同实施例1。
实施例14
除还原剂为硼氢化钾，其它操作过程同实施例1。
实施例15
除还原剂为氢化铝锂，其它操作过程同实施例1。
实施例16
除对
Figure BDA0003077466820000071
烷-1-胺与硼氢化钠的摩尔比为1∶1，其它操作过程同实施例1，产率50％。
实施例17
除对
Figure BDA0003077466820000072
烷-1-胺与硼氢化钠的摩尔比为1∶5，其它操作过程同实施例1，产率90％。
实施例18
除还原反应温度为-10℃，其它操作过程同实施例1，产率92％。
实施例19
除还原反应温度为50℃，其它操作过程同实施例1，产率90％。
实施例20
准确称取1mmol N-(4-氟苄基)-对
Figure BDA0003077466820000073
烷-1-胺，用1mLDMF溶解，滴加三滴吐温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、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/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28℃恒温箱中催芽24h。在培养皿内铺2张滤纸，加入10mL该类化合物对应浓度的样品溶液，加10mL稀释液作为空白对照，每处理重复三次。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。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(4-氟苄基)-对
Figure BDA0003077466820000074
烷-1-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、87.6％、59.0％、48.1％、36.8％、32.1％、25.2％、18.3％、9.7％，对根长的抑制率分别为：100.0％、100.0％、98.0％、89.3％、78.1％、72.6％、70.4％、66.5％、59.2％、50.1％。(2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的草甘膦溶液对稗草种子茎长的抑制率分别为：97.5％、91.9％、77.2％、64.0％、54.1％、38.5％、12.2％、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、99.8％、92.3％、83.9％、79.6％、69.5％、43.9％、24.9％、16.6％、12.3％)。
实施例21
准确称取1mmol N-(2-氯苄基)-对
Figure BDA0003077466820000081
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-氯苄基)-对
Figure BDA0003077466820000082
烷-1-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、96.0％、76.7％、50.6％、45.3％、37.4％、17.8％、13.3％、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、95.8％、85.7％、80.9％、75.0％、70.7％，65.7％、51.8％。
实施例22
准确称取1mmol N-(2,6-二氯苄基)-对
Figure BDA0003077466820000083
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2,6-二氯苄基)-对
Figure BDA0003077466820000084
烷-1-胺溶液对稗草种子茎长的抑制率分别为：97.4％、90.0％、88.2％、70.2％、50.9％、32.5％、19.0％、16.6％、9.7％、无抑制，对根长的抑制率分别为：100.0％、99.3％、98.4％、91.2％、82.9％、77.4％、69.5％、61.9％，49.4％、28.6％。
实施例23
准确称取1mmol N-(2-三氟甲基苄基)-对
Figure BDA0003077466820000085
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-三氟甲基苄基)-对
Figure BDA0003077466820000086
烷-1-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、99.2％、91.6％、70.7％、57.3％、49.4％、41.5％、32.5％、18.7％，对根长的抑制率分别为：100.0％、100.0％、100.0％、98.6％、94.0％、85.4％、77.8％、70.6％，64.8％、51.6％。
实施例24
准确称取1mmol N-(吡啶-4-甲基)-对
Figure BDA0003077466820000087
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(吡啶-4-甲基)-对
Figure BDA0003077466820000088
烷-1-胺溶液对稗草种子茎长的抑制率分别为：99.4％、70.8％、37.7％、28.2％、20.7％、17.6％、10.6％、7.5％、无抑制、无抑制，对根长的抑制率分别为：100.0％、98.6％、90.6％、75.8％、63.3％、54.5％、48.3％、39.6％，32.6％、21.9％。
实施例25
准确称取1mmol N-(呋喃-2-甲基)-对
Figure BDA0003077466820000091
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(呋喃-2-甲基)-对
Figure BDA0003077466820000092
烷-1-胺溶液对稗草种子茎长的抑制率分别为：100.0％、87.7％、59.3％、40.2％、26.7％、13.0％、9.3％、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、90.9％、91.9％、84.5％、75.0％、65.0％、47.5％、29.8％，19.9％、14.0％。
实施例26
准确称取1mmol N-紫苏基-对
Figure BDA0003077466820000093
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(紫苏基)-对
Figure BDA0003077466820000094
烷-1-胺溶液对稗草种子茎长的抑制率分别为：100.0％、99.0％、93.8％、76.5％、62.8％、43.0％、39.9％、20.8％、5.6％、无抑制，对根长的抑制率分别为：100.0％、99.9％、99.5％、98.5％、91.4％、83.0％、79.3％、69.7％，63.2％、56.7％。
实施例27
准确称取1mmol N-(四氢紫苏基)-对
Figure BDA0003077466820000095
烷-1-胺，其它操作过程同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(四氢紫苏基)-对
Figure BDA0003077466820000096
烷-1-胺溶液对稗草种子茎长的抑制率分别为：100.0％、99.5％、76.4％、54.1％、32.3％、26.0％、14.7％、9.7％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、99.7％、95.1％、88.6％、78.9％、69.9％、56.1％，49.2％、29.9％。
实施例28
准确称取1mmol N-(4-氟苄基)-对
Figure BDA0003077466820000097
烷-1-胺，除除草活性测试种子为油菜种子外，其余操作同实施例20。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(4-氟苄基)-对
Figure BDA0003077466820000098
烷-1-胺溶液对油菜种子茎长的抑制率分别为：100.0％、96.0％、82.7％、47.1％、38.5％、30.2％、26.9％、10.7％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、98.9％、92.7％、84.6％、65.4％、54.4％、46.8％、40.9％、30.4％。(2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的草甘膦溶液对油菜种子茎长的抑制率分别为：79.6％、61.0％、45.8％、37.3％、26.3％、16.0％、无抑制、无抑制、无抑制、无抑制，对根长的抑制率分别为：97.9％、90.9％、88.5％、81.4％、77.7％、69.7％、62.8％、52.0％、28.1％、无抑制)。
实施例29
准确称取1mmol N-(2-氯苄基)-对
Figure BDA0003077466820000101
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-氯苄基)-对
Figure BDA0003077466820000102
烷-1-胺溶液对油菜种子茎长的抑制率分别为：100.0％、100.0％、93.6％、79.1％、43.3％、23.6％、12.2％、4.3％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、97.5％、89.2％、71.6％、52.1％、33.9％、23.4％、14.8％。
实施例30
准确称取1mmol N-(2,6-二氯苄基)-对
Figure BDA0003077466820000103
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2,6-二氯苄基)-对
Figure BDA0003077466820000104
烷-1-胺溶液对油菜种子茎长的抑制率分别为：81.6％、69.3％、49.2％、41.4％、31.4％、27.6％、8.5％、无抑制、无抑制、无抑制，对根长的抑制率分别为：97.7％、96.6％、93.3％、88.8％、71.6％、60.4％、52.0％、43.0％、35.1％、24.5％。
实施例31
准确称取1mmol N-(2-三氟甲基苄基)-对
Figure BDA0003077466820000105
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(2-三氟甲基苄基)-对
Figure BDA0003077466820000106
烷-1-胺溶液对油菜种子茎长的抑制率分别为：100.0％、99.0％、94.4％、84.2％、57.1％、50.0％、44.7％、39.5％、27.5％、14.4％，对根长的抑制率分别为：100.0％、100.0％、99.5％、98.0％、93.1％、79.2％、63.8％、56.6％、45.0％、31.8％。
实施例32
准确称取1mmol N-(吡啶-4-甲基)-对
Figure BDA0003077466820000107
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(吡啶-4-甲基)-对
Figure BDA0003077466820000111
烷-1-胺溶液对油菜种子茎长的抑制率分别为：98.4％、88.0％、31.5％、27.6％、19.7％、10.0％、无抑制、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、99.1％、87.6％、77.8％、59.4％、45.3％、32.8％、23.4％、15.5％、无抑制。
实施例33
准确称取1mmol N-(呋喃-2-甲基)-对
Figure BDA0003077466820000112
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(呋喃-2-甲基)-对
Figure BDA0003077466820000113
烷-1-胺溶液对油菜种子茎长的抑制率分别为：100.0％、95.1％、56.7％、40.0％、24.8％、15.7％、无抑制、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、92.7％、89.2％、69.7％、59.8％、46.2％、33.6％、17.9％、无抑制。
实施例34
准确称取1mmol N-紫苏基-对
Figure BDA0003077466820000114
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(紫苏基)-对
Figure BDA0003077466820000115
烷-1-胺溶液对油菜种子茎长的抑制率分别为：100.0％、100.0％、97.4％、89.3％、74.9％、44.6％、34.5％、26.1％、11.3％、无抑制，对根长的抑制率分别为：100.0％、100.0％、99.7％、98.4％、97.4％、89.2％、72.4％、57.0％、38.4％、21.4％。
实施例35
准确称取1mmol N-(四氢紫苏基)-对
Figure BDA0003077466820000116
烷-1-胺，其它操作过程同实施例28。2.5mmol/L、1.25mmol/L、0.625mmol/L、0.3125mmol/L、0.1563mmol/L、0.0781mmol/L、0.0391mmol/L、0.0195mmol/L、0.0098mmol/L、0.0049mmol/L的N-(四氢紫苏基)-对
Figure BDA0003077466820000117
烷-1-胺溶液对油菜种子茎长的抑制率分别为：100.0％、97.3％、93.0％、74.0％、51.1％、41.4％、38.2％、26.1％、5.1％、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、98.5％、91.2％、78.3％、66.2％、46.5％、35.2％、27.2％。

Claims (10)

1.一种对
Figure FDA0003077466810000011
烷-1-基仲胺类化合物，其特征在于，结构通式如下：
Figure FDA0003077466810000012
通式I中，R是
Figure FDA0003077466810000013
Figure FDA0003077466810000014
中的任意一种，R’是氢、烷基、取代烷基、羟基或卤素中的任意一种。
2.权利要求1所述的对
Figure FDA0003077466810000015
烷-1-基仲胺类化合物的制备方法，其特征在于，所述的通式I的化合物以对
Figure FDA0003077466810000016
烷-1-胺和醛为原料，在一定温度下在极性有机溶剂中充分反应后，分批次投入氢化物类还原剂还原，反应结束后反应液经后处理而得。
3.根据权利要求2所述的对
Figure FDA0003077466810000017
烷-1-基仲胺类化合物的制备方法，其特征在于，所述的对
Figure FDA0003077466810000018
烷-1-胺和醛的摩尔比在1∶1～5之间，所述的对
Figure FDA0003077466810000019
烷-1-胺和醛的反应温度在0～100℃之间。
4.根据权利要求2所述的对
Figure FDA00030774668100000110
烷-1-基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。
5.根据权利要求2所述的对
Figure FDA00030774668100000111
烷-1-基仲胺类化合物的制备方法，其特征在于，所述的氢化物类还原剂为硼氢化钠、硼氢化钾、氢化铝锂中的任意一种。
6.根据权利要求2所述的对
Figure FDA00030774668100000112
烷-1-基仲胺类化合物的制备方法，其特征在于对
Figure FDA00030774668100000113
烷-1-胺和还原剂摩尔量之比计算在1∶1～10之间。
7.根据权利要求2所述的对
Figure FDA00030774668100000114
烷-1-基仲胺类化合物的制备方法，其特征在于，所述的还原反应的反应温度在-20～60℃之间，所述的还原反应的反应时间为1～24h。
8.根据权利要求2所述的对
Figure FDA00030774668100000115
烷-1-基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、减压蒸馏得对
Figure FDA00030774668100000116
烷-1-基仲胺类化合物粗品，重结晶或硅胶柱层析得纯品。
9.权利要求1所述的对
Figure FDA00030774668100000117
烷-1-基仲胺类化合物作为除草剂活性成分的应用。
10.权利要求1所述的对
Figure FDA00030774668100000118
烷-1-基仲胺类化合物作为针对稗草和油菜的除草剂活性成分的应用。
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