CN113429300B - 对䓝烷-7-基仲胺类化合物及其制备方法与除草应用 - Google Patents

对䓝烷-7-基仲胺类化合物及其制备方法与除草应用 Download PDF

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CN113429300B
CN113429300B CN202110556303.1A CN202110556303A CN113429300B CN 113429300 B CN113429300 B CN 113429300B CN 202110556303 A CN202110556303 A CN 202110556303A CN 113429300 B CN113429300 B CN 113429300B
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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 DDA0003077360730000011
烷‑7‑基仲胺类化合物及其制备方法与除草应用。该方法以对
Figure DDA0003077360730000012
烷‑7‑醛和伯胺为原料，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 DDA0003077360730000013
烷‑7‑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 DDA0003077360730000014
烷‑7‑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

对䓝烷-7-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 BDA0003077360710000012
烷-7-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 BDA0003077360710000013
烷-7-醛和伯胺为原料，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 BDA0003077360710000014
烷-7-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，促进了病虫害的发生，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。截止2021年3月，全球有263种杂草(双子叶152种，单子叶111种)的521个生物型对167种除草剂产生抗性，对已知的26个除草剂活性位点中的23个产生抗性。植物源除草剂的开发和应用为解决这一问题提供了一条有效的策略，具有活性突出、来源广泛、化学改性衍生物种类丰富、易降解、对环境友好等优点。松节油是我国重要的天然精油之一，松节油制品及其衍生物广泛应用于香料、医药、农药、高分子等领域，在除草方面也颇具优势。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，将这些化合物进行化学改性得到了一系列衍生物，结构包括：席夫碱、仲胺、酰胺、酯、硫脲等，均具有良好的除草活性，有望发展成为新型环境友好型除草剂。
前期研究表明，由松节油衍生的对
Figure BDA0003077360710000015
烯骨架及对
Figure BDA0003077360710000016
烷骨架衍生物具有优异的除草活性，包括3-对
Figure BDA0003077360710000017
烯-1-胺席夫碱衍生物、3-对
Figure BDA00030773607100000110
烯-1-仲胺衍生物、顺-1,8-对
Figure BDA0003077360710000018
烷二胺席夫碱衍生物、顺-1,8-对
Figure BDA0003077360710000019
烷二仲胺衍生物、紫苏基仲胺衍生物等均具有较好的除草活性，如N-(2,6-二氯-苯亚甲基)-4-异丙基-1-甲基环己胺-3-烯胺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 BDA00030773607100000111
烯-1-胺对稗草根的IC50值为0.03mmol/L(相当于7mg/L)；N-己基紫苏胺对稗草茎的IC50值为0.07mmol/L，对根的IC50值为0.09mmol/L，大部分化合物除草效果优于市售除草剂草甘膦，而且这些化合物对人体正常细胞毒性非常小，对
Figure BDA00030773607100000112
烷(烯)骨架衍生物具有开发为植物源除草剂的前景。
为了探究对
Figure BDA00030773607100000113
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，本发明将紫苏醛经加氢反应制得对
Figure BDA00030773607100000114
烷-7-醛(即四氢紫苏醛)，再与伯胺在极性有机溶剂中进行醛胺缩合反应，后直接由氢化物还原，制备得到一系列新型对
Figure BDA00030773607100000115
烷-7-基仲胺类化合物，采用培养皿种子萌发法测定不同浓度对
Figure BDA00030773607100000116
烷-7-基仲胺类化合物培养下稗草和油菜根和茎的生长受害情况，评价其除草活性。将得到的除草活性数据与3-对
Figure BDA0003077360710000022
烯-1-胺衍生物、顺-1,8-对
Figure BDA0003077360710000023
烷二胺衍生物的除草活性数据进行对比，分析除草效果差异性和构效关系，探究对
Figure BDA0003077360710000024
烷骨架结构与对
Figure BDA0003077360710000025
烯骨架结构、氨基及醛基在对
Figure BDA0003077360710000026
烷骨架上的取代位置、席夫碱衍生物与仲胺衍生物等不同化合物类型对于除草活性的影响，找出发挥除草活性的关键基团，以此为切入点，设计合成更新颖、活性更好的化合物。本发明方法工艺简单、条件温和、速率快、收率高、除草活性优异，在新型植物源除草剂领域展示出良好的开发利用前景。
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 BDA0003077360710000027
烷-7-基仲胺类化合物的制备及除草应用。本发明以对
Figure BDA0003077360710000028
烷-7-醛和伯胺为原料，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 BDA0003077360710000029
烷-7-基仲胺类化合物。
本发明的技术方案为：对
Figure BDA00030773607100000210
烷-7-基仲胺类化合物，结构通式如下：
Figure BDA0003077360710000021
通式I中，R是含有4～10个碳的直链烷烃、支链烷烃、羟基或卤代直链烷烃、羟基或卤代支链烷烃，含有5～7个碳的环烷烃、羟基或卤代环烷烃，含有4～10个碳的直链烯烃、支链烯烃、羟基或卤代直链烯烃、羟基或卤代支链烯烃，含有4～10个碳的直链炔烃、支链炔烃、羟基或卤代直链炔烃、羟基或卤代支链炔烃，含有4～6个碳的芳烃、羟基或卤代芳烃中的任意一种。
通式I的化合物以对
Figure BDA00030773607100000211
烷-7-醛和伯胺为原料，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。
对
Figure BDA00030773607100000212
烷-7-醛和伯胺的摩尔比在1∶1～5之间，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，以对
Figure BDA00030773607100000213
烷-7-醛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。
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 BDA0003077360710000031
烷-7-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 BDA0003077360710000032
烷-7-基仲胺类化合物作为除草剂活性成分的应用。
所述的对
Figure BDA0003077360710000033
烷-7-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 BDA0003077360710000034
烷-7-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 BDA0003077360710000035
烷-7-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-己基-对
Figure BDA0003077360710000036
烷-7-胺的1H NMR图；
图2为N-异丁基-对
Figure BDA0003077360710000037
烷-7-胺的1H NMR图；
图3为N-环己基-对
Figure BDA0003077360710000038
烷-7-胺的1H NMR图；
图4为N-(3-对
Figure BDA0003077360710000039
烯-1-基)-对
Figure BDA00030773607100000310
烷-7-胺的1HNMR图；
图5为N,N'-双(对
Figure BDA00030773607100000311
烷-7-基)-1,4-丁二胺的1H NMR图；
图6为N-(间甲基苯基)-对
Figure BDA00030773607100000312
烷-7-胺的1HNMR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 BDA00030773607100000313
烷-7-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 BDA00030773607100000314
烷-7-醛和伯胺为原料，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 BDA00030773607100000315
烷-7-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 BDA00030773607100000316
烷-7-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 BDA00030773607100000317
烷-7-基仲胺类化合物的结构通式如下：
Figure BDA0003077360710000041
通式I中，R是含有4～10个碳的直链烷烃、支链烷烃、羟基或卤代直链烷烃、羟基或卤代支链烷烃，含有5～7个碳的环烷烃、羟基或卤代环烷烃，含有4～10个碳的直链烯烃、支链烯烃、羟基或卤代直链烯烃、羟基或卤代支链烯烃，含有4～10个碳的直链炔烃、支链炔烃、羟基或卤代直链炔烃、羟基或卤代支链炔烃，含有4～6个碳的芳烃、羟基或卤代芳烃中的任意一种。
第一步：
将对
Figure BDA0003077360710000042
烷-7-醛加入含有极性有机溶剂的三口烧瓶中，磁力搅拌下加入伯胺，待原料充分反应后将烧瓶转移至冰水浴中，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 BDA0003077360710000043
烷-7-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 BDA0003077360710000044
烷-7-醛和伯胺的摩尔比在1∶1～5之间；对
Figure BDA0003077360710000045
烷-7-醛和伯胺的缩合反应温度在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 BDA0003077360710000046
烷-7-醛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 BDA0003077360710000047
烷-7-基仲胺类化合物，分别用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，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 BDA0003077360710000048
烷-7-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 BDA0003077360710000051
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3.08g(20mmol)对
Figure BDA0003077360710000052
烷-7-醛加入含有20mL甲醇的三口烧瓶中，磁力搅拌下加入1.46g(20mmol)己胺，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-己基-对
Figure BDA0003077360710000053
烷-7-胺，产率93％。
实施例2
除原料伯胺为异丁胺，其它操作过程同实施例1，得N-异丁基-对
Figure BDA0003077360710000054
烷-7-胺，产率72％
实施例3
除原料伯胺为环己胺，其它操作过程同实施例1，得N-环己基-对
Figure BDA0003077360710000055
烷-7-胺，产率91％。
实施例4
除原料伯胺为3-对
Figure BDA0003077360710000056
烯-1-胺，其它操作过程同实施例1，得N-(3-对
Figure BDA0003077360710000057
烯-1-基)-对
Figure BDA0003077360710000058
烷-7-胺，产率90％。
实施例5
除原料伯胺为1,4-二氨基丁烷，其它操作过程同实施例1，得N,N'-双(对
Figure BDA0003077360710000059
烷-7-基)-1,4-丁二胺，产率80％。
实施例6
除原料伯胺为间甲基苯胺，其它操作过程同实施例1，得N-(间甲基苯基)-对
Figure BDA00030773607100000510
烷-7-胺，产率73％。
实施例7
除原料伯胺为4-氨基-1-丁醇，其它操作过程同实施例1，得N-(1-羟基丁基)-对
Figure BDA0003077360710000061
烷-7-胺，产率70％。
实施例8
除原料伯胺为3-氨基环己醇，其它操作过程同实施例1，得N-(3-羟基环己基)-对
Figure BDA0003077360710000062
烷-7-胺，产率60％。
实施例9
除对
Figure BDA0003077360710000063
烷-7-醛与己胺的摩尔比为1∶3，其它操作过程同实施例1，产率88％。
实施例10
除对
Figure BDA0003077360710000064
烷-7-醛与己胺的反应温度为0℃，其它操作过程同实施例1，产率80％。
实施例11
除对
Figure BDA0003077360710000065
烷-7-醛与己胺的反应温度为70℃，其它操作过程同实施例1，产率90％。
实施例12
除对
Figure BDA0003077360710000066
烷-7-醛与己胺的反应溶剂为N,N-二甲基甲酰胺，其它操作过程同实施例1。
实施例13
除还原剂为硼氢化钾，其它操作过程同实施例1。
实施例14
除还原剂为氢化铝锂，其它操作过程同实施例1。
实施例15
除对
Figure BDA0003077360710000067
烷-7-醛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16
除对
Figure BDA0003077360710000068
烷-7-醛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17
除还原反应温度为-10℃，其它操作过程同实施例1，产率80％。
实施例18
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19
准确称取1mmol N-己基-对
Figure BDA0003077360710000071
烷-7-胺，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，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-己基-对
Figure BDA0003077360710000072
烷-7-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、96.6％、72.5％、56.1％、46.1％、29.5％、9.8％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、97.2％、88.5％、79.1％、68.7％、60.8％、55.0％、46.0％。(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20
准确称取1mmol N-异丁基-对
Figure BDA0003077360710000073
烷-7-胺，其它操作过程同实施例19。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-异丁基-对
Figure BDA0003077360710000074
烷-7-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、97.5％、72.4％、45.9％、30.4％、21.2％、15.2％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、99.7％、91.7％、74.0％、67.3％、58.4％、53.2％、47.8％、22.4％。
实施例21
准确称取1mmol N-环己基-对
Figure BDA0003077360710000081
烷-7-胺，其它操作过程同实施例19。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-环己基-对
Figure BDA0003077360710000082
烷-7-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、95.5％、76.4％、54.1％、50.3％、35.5％、26.2％、19.3％、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、95.4％、81.5％、72.6％、66.5％、60.3％、53.6％、46.9％。
实施例22
准确称取1mmol N-(3-对
Figure BDA0003077360710000083
烯-1-基)-对
Figure BDA0003077360710000084
烷-7-胺，其它操作过程同实施例19。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-(3-对
Figure BDA0003077360710000085
烯-1-基)-对
Figure BDA0003077360710000086
烷-7-胺溶液对稗草种子茎长的抑制率分别为：100.0％、100.0％、91.5％、68.4％、58.7％、52.0％、39.9％、26.9％、19.0％、15.6％，对根长的抑制率分别为：100.0％、100.0％、99.8％、96.1％、87.7％、82.0％、73.1％、62.2％、52.6％、33.5％。
实施例23
准确称取1mmol N,N'-双(对
Figure BDA0003077360710000087
烷-7-基)-1,4-丁二胺，其它操作过程同实施例19。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,N'-双(对
Figure BDA0003077360710000088
烷-7-基)-1,4-丁二胺溶液对稗草种子茎长的抑制率分别为：100.0％、81.4％、43.2％、26.7％、15.6％、无抑制、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％、100.0％、95.9％、88.8％、57.1％、34.8％、16.4％、无抑制、无抑制。
实施例24
准确称取1mmol N-(间甲基苯基)-对
Figure BDA0003077360710000089
烷-7-胺，其它操作过程同实施例19。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-(间甲基苯基)-对
Figure BDA00030773607100000810
烷-7-胺溶液对稗草种子茎长的抑制率分别为：60.7％、58.9％、51.1％、49.2％、39.2％、29.3％、无抑制、无抑制、无抑制、无抑制，对根长的抑制率分别为：26.1％、17.2％、16.2％、19.6％、14.6％、17.9％、无抑制、无抑制、无抑制、无抑制。
实施例25
除除草活性测试种子为油菜种子外，其余操作同实施例19。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-己基-对
Figure BDA0003077360710000091
烷-7-胺溶液对油菜种子茎长的抑制率分别为：100.0％、100.0％、96.1％、72.4％、38.4％、25.0％、13.9％、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、99.8％、97.9％、92.4％、65.5％、50.2％、29.5％、15.8％、无抑制。(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26
准确称取1mmol N-异丁基-对
Figure BDA0003077360710000092
烷-7-胺，其它操作过程同实施例25。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-异丁基-对
Figure BDA0003077360710000093
烷-7-胺溶液对油菜种子茎长的抑制率分别为：100.0％、100.0％、88.9％、62.0％、46.2％、31.5％、21.1％、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、93.8％、89.5％、68.3％、48.9％、35.2％、13.4％、无抑制、无抑制。
实施例27
准确称取1mmol N-环己基-对
Figure BDA0003077360710000094
烷-7-胺，其它操作过程同实施例25。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-环己基-对
Figure BDA0003077360710000095
烷-7-胺溶液对油菜种子茎长的抑制率分别为：100.0％、100.0％、96.1％、76.0％、48.2％、31.3％、22.3％、12.2％、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、99.4％、97.9％、87.2％、63.2％、50.3％、33.4％、15.9％、无抑制。
实施例28
准确称取1mmol N-(3-对
Figure BDA0003077360710000101
烯-1-基)-对
Figure BDA0003077360710000102
烷-7-胺，其它操作过程同实施例25。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-(3-对
Figure BDA0003077360710000103
烯-1-基)-对
Figure BDA0003077360710000104
烷-7-胺溶液对油菜种子茎长的抑制率分别为：98.6％、96.2％、87.7％、73.2％、51.8％、36.3％、30.2％、21.6％、11.9％、无抑制，对根长的抑制率分别为：100.0％、100.0％、99.4％、96.0％、91.0％、74.2％、57.0％、44.5％、34.3％、无抑制。
实施例29
准确称取1mmol N,N'-双(对孟烷-7-基)-1,4-丁二胺，其它操作过程同实施例25。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,N'-双(对
Figure BDA0003077360710000105
烷-7-基)-1,4-丁二胺溶液对油菜种子茎长的抑制率分别为：100.0％、98.5％、93.8％、60.4％、42.9％、22.1％、15.2％、无抑制、无抑制、无抑制，对根长的抑制率分别为：100.0％、100.0％、100.0％、97.2％、92.5％、71.6％、45.4％、34.9％、16.4％、无抑制。

Claims (10)

1.一种对䓝烷-7-基仲胺类化合物，其特征在于，结构通式如下：
Figure DEST_PATH_IMAGE002AA
通式I中，R是己基、环己基、3-对䓝烯-1-基、3-羟基环己基中的任意一种。
2.权利要求1所述的对䓝烷-7-基仲胺类化合物的制备方法，其特征在于，所述的通式I的化合物以对䓝烷-7-醛和伯胺为原料，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进行还原，反应结束后反应液经处理而得。
3. 根据权利要求2所述的对䓝烷-7-基仲胺类化合物的制备方法，其特征在于，所述的对䓝烷-7-醛和伯胺的摩尔比在1∶1～5之间，所述的对䓝烷-7-醛和伯胺的反应温度在0～100 ℃之间。
4.根据权利要求2所述的对䓝烷-7-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所述的对䓝烷-7-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所述的对䓝烷-7-基仲胺类化合物的制备方法，其特征在于对䓝烷-7-醛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所述的对䓝烷-7-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1～24 h。
8.根据权利要求2所述的对䓝烷-7-基仲胺类化合物的制备方法，其特征在于，所述的反应液经处理而得具体指，反应液经蒸馏水淬灭、二氯甲烷萃取、无水硫酸钠干燥、过滤、减压蒸馏得对䓝烷-7-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所述的对䓝烷-7-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所述的对䓝烷-7-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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