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 PDFInfo
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Abstract
Description
技术领域:
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,由松节油衍生的对烯骨架及对烷骨架衍生物具有优异的除草活性,包括3-对烯-1-胺席夫碱衍生物、3-对烯-1-仲胺衍生物、顺-1,8-对烷二胺席夫碱衍生物、顺-1,8-对烷二仲胺衍生物、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-对烯-1-胺衍生物、顺-1,8-对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,探究对烷骨架结构与对烯骨架结构、氨基及醛基在对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—对烷-7-基仲胺类化合物的制备及除草应用。本发明以对烷-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,制得相关对烷-7-基仲胺类化合物。
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。
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。
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。
有益效果
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。
附图说明
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。对烷-7-基仲胺类化合物的结构通式如下:
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。其中对烷-7-醛和伯胺的摩尔比在1∶1~5之间;对烷-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)。
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-对烷-7-胺,产率93%。
实施例2
实施例3
实施例4
实施例5
实施例6
实施例7
实施例8
实施例9
实施例10
实施例11
实施例12
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
实施例16
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-对烯-1-基)-对烷-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-对烯-1-基)-对烷-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-对烯-1-基)-对烷-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-对烯-1-基)-对烷-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)
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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