CN116239500A - 一种高活性脱落酸功能类似物(i)及其制备方法 - Google Patents
一种高活性脱落酸功能类似物(i)及其制备方法 Download PDFInfo
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Abstract
一类高活性脱落酸功能类似物(I)，其结构式为：
Description
技术领域
本发明属于植物化学和生物技术领域，具体来说，是涉及一种能够模拟天然脱落酸在植物体内生理作用的化合物N-[2-(4-氰基-3,5-二环丙基苯基)乙酰基]-D/L-缬氨酸，这种高活性脱落酸功能类似物及其制备方法和应用。
背景技术
脱落酸(Abscisic acid,S-(+)-ABA)是一种广泛存在于植物体内的倍半萜类植物内源性激素。已经有大量研究表明ABA在植物生长发育的许多生理过程中都发挥着重要的作用，包括控制气孔关闭、诱导种子休眠和促进果实的着色和成熟等。同时，最近研究也发现ABA在诱导植物抵抗多种逆境胁迫，比如干旱、低温、盐碱和病虫害等，ABA也因此被誉为“植物抗逆诱导因子”。由于ABA的这些重要生理活性，使其在农业生产中具有广阔的应用价值，如提高盐碱地作物的产量，提高作物的抗干旱能力，保持种子的储藏和果实的着色等。
由于天然ABA固有的结构缺陷和复杂性使得其很难大规模地应用到农业生产中。为了解决这些问题，已经有许多的非ABA骨架的ABA功能类似物被筛选和合成出来。Opabactin(OP)是2021年开发出来的新型广谱ABA受体激动剂，其可以有效地模拟ABA的生理活性，包括诱导种子的休眠和提高小麦的抗干旱胁迫能力。相比磺酰胺类ABA功能类似物，OP具有更加优异和广谱的生理活性，如能够显著水稻、番茄和小麦的抗干旱胁迫能力。由于OP的环己烷环处于受体结合腔的疏水区域。因此，本发明在专利WO2020006508的基础上，通过引入不同类型的天然和非天然氨基酸，以改进化合物的生理活性。
发明内容
本发明的目的在于提供一种新型的廉价且兼并ABA生理活性的天然脱落酸替代物，其合成及用途，主要用于调节植物生长发育或用于制备新型植物抗逆性的农用制剂。
具体的说，本发明的第一方面，是提供了一种I式化合物：
I为对映异构体，即R-体和S-体。
这里的包括I末端羧基衍生的酯衍生物及盐。
本发明的第二方面是提供本发明第一方面化合物的合成方法，包括如下步骤：
本发明的第三方面，是将本发明的第一和第二方面所述的高活性脱落酸功能类似物(I)，用于调节植物生长发育或用于制备新型植物抗逆性的农用制剂的用途。
本发明取得下述优异的技术效果：
1、化合物I所表现出的生物活性为ABA在植物体内参与的生理作用。
2、化合物I所诱导的ABA参与的生理调节包括但不限于：种子萌发抑制、气孔关闭和幼苗生长抑制等。
3、化合物I诱导的ABA参与的非生物胁迫包括但不限于：耐寒性、耐旱性、耐盐碱或耐渗透压等。
4、化合物I表现出比ABA更好的生物活性。
5、本发明中所述的植物包括但不限于：十字花科植物(如油菜，拟南芥，白菜)、茄科植物(如烟草，番茄，大豆)、禾本科植物(水稻，小麦，大麦)等。
本发明的化合物可以以常规剂型施用，所述常规剂型的形式有可湿性粉剂、乳油、颗粒剂或悬乳浓缩剂。
附图说明
图1为化合物I和对照药剂对拟南芥种子萌发抑制活性的结果照片。
图2为化合物I和对照药剂对拟南芥幼苗生长抑制实验结果的照片。
图3为化合物I和对照药剂对提高小麦的抗旱活性的照片。
图4为化合物I和对照药剂对小麦离体叶片的失水速率的影响的曲线图。
图5为化合物I能够显著提高干旱胁迫下小麦体内的含水量的柱形示意图。
具体实施方式
下面结合实施例对本发明做进一步介绍。
下述实施例中所使用的方法如无特殊说明，均为常规方法。
下述实例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实例1：化合物I的合成
第一步：对氰基苯乙酸甲酯(III)的合成
用适当的二氯甲烷溶解1当量的对氰基苯乙酸于500mL的圆底烧瓶中，小心向混合液中加入1.2当量的草酰氯并回流过夜，TLC检测反应进程，反应完毕，直接至真空脱溶剂，进行下一步反应；将上一步所得中间体置于500mL圆底烧瓶中，用适当无水甲醇溶解，并于冰浴条件下反应30min，TLC检测反应进程，反应完毕。脱溶剂，加入乙酸乙酯溶解粗产物，适当饱和Na2CO3水溶液洗涤三次，分液得有机相，干燥，脱溶剂，得无色针状固体，收率95％。1HNMR(500MHz,CDCl3)δ7.71–7.48(m,2H),7.40–7.27(m,2H),3.64(s,3H),3.62(s,2H).
第二步：(3,5-二溴-4-氰基苯基)乙酸甲酯(IV)的合成
用适当的1,2-二氯乙烷溶解1当量的对氰基苯乙酸甲酯于50mL的圆底烧瓶中，依次加入3当量的NBS、0.5当量的TsOH和5％的醋酸钯于70℃下反应过夜，TLC检测反应进程，待反应结束。过滤，饱和食盐水洗涤滤液，无水Na2SO4干燥有机相，脱去溶剂，柱层析(PE:EA＝6:1)得白色固体，收率70％。1H NMR(500MHz,CDCl3)δ7.51(s,2H),3.67(s,2H),3.57(s,2H).
第三步：(4-氰基-3,5-二环丙基苯基)乙酸甲酯(V)的合成
用适当的甲苯溶解1当量的二溴取代的对氰基苯乙酸甲酯和3当量的环丙基硼酸于100mL的克莱瓶中，氩气置换空气三次，然后向混合液加入0.1当量的P(Cy)3和1mL的水并用氩气置换空气10min，最后向反应液中加入5％的醋酸钯于100℃下反应过夜，TLC检测反应进程，反应完毕，饱和食盐水洗涤溶液，乙酸乙酯萃取水相，合并有机相，饱和NaHCO3溶液洗涤有机相三次，分液，无水Na2SO4干燥有机相，脱去溶剂，柱层析(PE:EA＝10:1)得白色固体，收率97％。1H NMR(500MHz,CDCl3)δ6.57(s,2H),3.60(s,3H),3.47(s,2H),2.19(m,2H),1.09–0.99(m,4H),0.67-0.70(m,4H).
第四步：(4-氰基-3,5-二环丙基苯基)乙酸(VI)的合成
在50mL的圆底烧瓶中，用10mL的甲醇和水的混合溶液溶解1当量的上步产物，混合液处于0℃下搅拌10min，再加入3当量的LiOH·H2O，反应处于0℃下搅拌过夜，TLC检测反应进程，待反应结束，1N的HCl水溶液调节反应液至pH至2～3，乙酸乙酯萃取水相三次，合并有机相，无水Na2SO4干燥有机相，脱去溶剂，柱层析(PE:EA＝1:1)得白色固体，收率94％。1HNMR(500MHz,CDCl3)δ6.57(s,2H),3.60(s,3H),3.47(s,2H),2.19(m,2H),1.09–0.99(m,4H),0.67-0.70(m,4H).
第五步：N-[2-(4-氰基-3,5-二环丙基苯基)乙酰基]-D/L-缬氨酸(Ia/Ib)的合成
用适当的二氯甲烷溶解1当量的酸于50mL的圆底烧瓶中，依次加入1.2当量的氨基酸甲酯盐酸盐、2.6当量的DMAP和1.2当量的DCC于室温下反应1h，TLC检测反应进程，待反应结束，过滤得滤液用饱和Na2CO3水溶液洗涤三次，乙酸乙酯萃取水相三次，合并有机相，无水Na2SO4干燥，脱去溶剂，柱层析(PE:EA＝6:1)得白色固体，收率97％。1H NMR(500MHz,CDCl3)δ6.64(s,2H),5.93(d,J＝8.5Hz,1H),4.52(dd,J＝8.5,5.0Hz,1H),3.72(s,3H),3.51(s,2H),2.28(tt,J＝8.5,5.0Hz,2H),2.11–2.07(m,1H),1.17–1.05(m,4H),0.86(d,J＝7.0Hz,3H),0.80(d,J＝7.0Hz,3H),0.78–0.74(m,4H).
在50mL的圆底烧瓶中，用10mL的甲醇和水的混合溶液溶解1当量的化合物酯，混合液处于0℃下搅拌10min，再加入3当量的LiOH·H2O，反应处于0℃下搅拌过夜，TLC检测反应进程，待反应结束，1N的HCl水溶液调节反应液至pH至2～3，乙酸乙酯萃取水相三次，合并有机相，无水Na2SO4干燥有机相，脱去溶剂，柱层析(PE:EA＝1:1)得目标化合物，为白色固体，收率98％。1H NMR(500MHz,DMSO-d6)δ12.61(s,1H),8.29(d,J＝8.5Hz,1H),6.79(s,2H),4.13(dd,J＝8.5,5.5Hz,2H),3.49(s,2H),2.16(tt,J＝8.5,5.0Hz,2H),2.06(dq,J＝13.5,6.5Hz,1H),1.13–1.05(m,4H),0.87(d,J＝6.5Hz,3H),0.83(d,J＝6.5Hz,3H),0.80–0.70(m,4H).13C NMR(126MHz,DMSO-d6)δ173.04,169.54,147.23,142.31,122.04,117.41,110.64,57.14,42.20,29.85,26.36,19.12,17.87,13.95,9.32,9.21.
实例2：化合物I的生物活性
本发明的和已知的最接近的现有技术的化合物用于对照实施例：
性能实验例1-3
1、拟南芥种子萌发实验和幼苗生长
样品制备：用十万分之一天平精确称取一定量的I化合物和对照，分别溶于100μL的DMSO中，得到10mM的母液，避光保存于-20℃下。使用时用移液枪准确量取一定量的母液，用蒸馏水稀释到所需的浓度。
MS培养基的制备：0.44g MS519，3.0g蔗糖和0.67g琼脂溶于100mL蒸馏水中。盖上封口膜并用橡皮筋密封。放入高温灭菌锅120℃下灭菌20min。冷却到室温，加入定量的母液，然后倒入培养皿，得到含有不同浓度药剂的MS培养基。
拟南芥种子萌发实验：用70％的乙醇对拟南芥种子进行消毒10min，然后用无菌水漂洗6-10次，吸走多余的水分，将50粒拟南芥种子点播到含有待测药剂的MS培养基上。吹干后，封口膜密封放于4℃冰箱春化3天，春化完后将培养皿转移到培养箱中，温度为22℃，光照周期16h光照\8h黑暗。48小时后统计萌发率。每组实验三次。
抑制率＝((DMSO种子萌发数-药剂处理种子萌发数)/DMSO种子萌发数)×100％
水稻种子萌发实验：首先用70％乙醇对水稻种子进行消毒10min，然后用无菌水漂洗6-10次。吸走多余的水分，将30粒水稻种子点播到铺有两张滤纸的培养皿中，每个皿中加入2ml待测药剂，封口后将培养皿转移至培养箱中培养，温度为22℃，光周期为24光照\0h黑暗，3天后，统计萌发率，每组实验重复三次。
2、拟南芥幼苗生长实验
将拟南芥种子用70％的乙醇消毒灭菌10min，无菌水漂洗6-10次，然后将种子点播到MS培养基上。封口膜密封后转移到4℃冰箱春化3天，接着转移到光照培养箱中培养之萌发。将萌发后的幼苗点播到含有待测药剂的培养基中，封口膜密封，转移至培养箱垂直生长，温度为22℃，光周期为24h光照，7天后测量根长以及鲜重。
3、小麦抗旱实验
干旱处理：选取均匀一致，大小饱满的小麦种子用70％乙醇灭菌10min，再用无菌水漂洗6-10次。将消毒过的种子用蒸馏水浸泡，致其充分吸收水分并露白，将露白的种子种于培养土中，放入光照培养箱中，光周期为温度25℃，14h光照\10h黑暗，在水分充足的条件下生长两周。待小麦长出第三片叶片时，开始断水处理，同时每盆小麦喷施10mL15μM的测试化合物溶液。
离体叶片失水率：喷洒药物7h后，分别取喷洒不同药剂的植株的地上部分，称其鲜重，在室温下放置，每隔1h再分别称量重量。失水率＝(鲜重-干重)/鲜重×100
叶片相对含水量测定：将喷洒药剂的小麦干旱处理一周后，拍照记录叶片枯萎状况，并进行取样，每组取3颗。三次重复，放入10mL EP管中，称量鲜重。在取样管中加满水，吸水过夜，称量叶片吸水饱和后的重量。将水到干净后放入80℃烘箱中烘干，并测量干重。
表1.化合物I与对照药物的种子萌发抑制活性(IC50，μM/L)
表2.化合物I和对照药剂对拟南芥根部生长抑制实验(cm)
表3.化合物I和对照药剂对拟南芥生长抑制实验(mg)
化合物I和对照药剂对拟南芥种子萌发抑制活性的结果见图1；化合物I和对照药剂对拟南芥幼苗生长抑制实验结果见图2；化合物I和对照药剂对提高小麦的抗旱活性见图3；化合物I和对照药剂对小麦离体叶片的失水速率的影响见图4；化合物I能够显著提高干旱胁迫下小麦体内的含水量见图5。
由上述实施例和实验例的结果可以看到，本发明取得了下述优异的检索效果：化合物I对模式植物拟南芥的种子萌发具有优异的抑制效应，其在最低浓度小于0.1μM时，仍具有明显的抑制效应；在对拟南芥幼苗生长抑制实验中，化合物I能够显著的抑制拟南芥侧根生长，使得被施药植株根系单一，不发达；在对提高小麦抗干旱实验中，化合物I能够达到和ABA类似的调节效应，如图3，4所示，喷药6小时后，离体叶片的失水速率明显慢于未喷药测试植株，干旱7天后，测量叶片含水量发现喷洒I化合物植株的叶片含水量明显高于对照药剂DMSO，这些数据都说明了化合物I在提高作物的抗干旱性能方面具有巨大的应用前景。
本领域技术人员在考虑说明书及实践这里公开的公开后，将容易想到本公开的其它实施方案。本申请旨在涵盖本公开的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本公开的一般性原理并包括本公开未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本公开的真正范围和精神由本申请的权利要求书指出。
Claims (3)
1.一种高活性脱落酸功能类似物(I)，其结构式为：
I为对映异构体，即R-体和S-体。
2.一种权利要求1所示化合物的合成方法，其合成路线为:
3.权利要求1所示化合物，以其为活性成分制成的任何制剂或混剂作为植物生长调节剂的应用。
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