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CN114105806A - 新型炔酸酯类和炔酰胺类植物抗菌剂 - Google Patents

新型炔酸酯类和炔酰胺类植物抗菌剂 Download PDF

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CN114105806A
CN114105806A CN202111548419.7A CN202111548419A CN114105806A CN 114105806 A CN114105806 A CN 114105806A CN 202111548419 A CN202111548419 A CN 202111548419A CN 114105806 A CN114105806 A CN 114105806A
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propiolate
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周乐
杨珊珊
张育浩
吕晴云
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Northwest A&F University
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Abstract

本发明涉及一类丙炔酸酯类和丙炔酰胺类化合物及其合成方法、以及含有该化合物的药物及应用。两类化合物对十多种植物病原真菌具有高效广谱的抑制活性，同时具有结构简单、易于规模化制备和对动植物安全性高的特点，可作为有效成分用于高效低毒的新型植物抗菌剂的开发。

Description

新型炔酸酯类和炔酰胺类植物抗菌剂
技术领域
本发明涉及植物抗菌药物，具体涉及一类丙炔酸酯类和丙炔酰胺类化合物及其合成方法、以及含有该化合物的药物及应用。
背景技术
植物真菌病不仅能降低农作物的产量和质量，有的还会影响人类和动物的健康。化学杀菌剂的应用一直是植物真菌病防治的主要手段。为了应对病原菌日益严重的抗药性，人们就必须不断开发出具有新颖结构或新作用机制的新型杀菌剂，或者对现有化学杀菌剂进行必要的更新换代。
丙炔酸酯和丙炔酰胺是α,β-不饱和羰基类迈克尔受体化合物，可与半胱氨酸、谷胱甘肽及蛋白质中的巯基通过迈克尔加成反应，生成相应的共价结合物。因此，丙炔酸酯和丙炔酰胺单元是设计和开发靶向共价结合药物最常用的化学“弹头”。
Yamazoe H等人(Yakugaku Zasshi,1982,102(3),278-84)采用三氯化磷和三乙胺为催化剂，由丙炔酸和苯胺类化合物合成了一系列丙炔酰苯胺化合物，并报道了其对人皮肤病原真菌、念珠菌和病原细菌的抑制活性。到目前为止，未见同类化合物抑制植物病原真菌的相关报道。
到目前为止，未见同类化合物抑制植物病原真菌的相关报道。Fujinami A等人(Ger.Offen.1971,DE 2117431 A19711209)采用对甲苯磺酸为催化剂，由丙炔酸和醇合成了一系列丙炔酸酯，并报道了后者对黑根霉(R.nigricans)、球毛壳菌(C.globosum)、疣孢漆斑菌(M.verrucaria)、桔青霉菌(P.citrinum)、腊叶芽枝霉(C.herbarum)、烟曲霉(A.fumigatus)、土曲霉(A.terreus)、黄曲霉菌(A.flavus)的抑制活性。Shuto,A等人(Eur.Pat.Appl.1995,EP 637582 A119950208)采用类似的方法合成了一系列丙炔酸芳香酯，并报道了其杀螨活性。除此而外，未见其他有关丙炔酸酯类生物活性的报道。
发明内容
本发明旨在提供一类丙炔酸酯类和丙炔酰胺类化合物及其合成方法、以及含有该化合物的药物及应用，此类化合物对多种植物病原菌具有高效广谱的抑制活性。
为实现上述目的，本发明所采用的技术方案为：
一种丙炔酰胺类化合物A，其特征在于：分子式为：
Figure BDA0003416355970000021
其中：
R1是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子、三氟甲基等；R2是氢、甲基等；R3是氢、甲基等；n＝0,1,2,3；R1的位置为苯环的邻位、间位或对位。
一种丙炔酸酯类化合物B，其特征在于：分子式为：
Figure BDA0003416355970000022
其中：
R′是相同或不同的氢、甲基、乙基、烷氧基、苯氧基、卤素原子、三氟甲基、硝基、氰基、等；R″是氢、甲基等；n＝1,2,3；R′的位置为苯环的邻位、间位或对位。
丙炔酰胺类化合物A的合成方法，其特征在于：
具有以下合成路线：
Figure BDA0003416355970000031
其中：
R1是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子、三氟甲基等；R1的位置为苯环的邻位、间位或对位；R2是氢、甲基等；R3是氢、甲基等；n＝0,1,2,3；催化剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)和1-羟基苯并三唑。
丙炔酸酯类化合物B的合成方法，其特征在于：
具有以下合成路线：
Figure BDA0003416355970000032
其中：
R′是相同或不同的氢、甲基、乙基、烷氧基、苯氧基、卤素原子、三氟甲基、硝基、氰基、等；R′的位置为苯环的邻位、间位或对位；R″是氢、甲基等；n＝1,2,3；催化剂为过渡金属硫酸氢盐。
丙炔酰胺类化合物A或丙炔酸酯类化合物B作为有效成分或增效成分在制备植物抗菌药物的应用。
丙炔酰胺类化合物A或丙炔酸酯类化合物B对以下植物病原菌具有显著的抑制活性：
棉花枯萎病原菌；西瓜枯萎病原菌；马铃薯干腐病原菌；小麦赤霉病原菌；番茄早疫病原菌；白菜黑斑病原菌；烟草赤星病原菌；玉米弯孢病原菌；苹果炭疽病原菌；南瓜枯萎病原菌；苹果腐烂病原菌；水稻稻瘟病原菌；苹果轮纹病原菌；甜瓜白粉病菌；葡萄霜霉病菌。
含有丙炔酰胺类化合物A或丙炔酸酯类化合物B的药物。
该药物作为植物抗菌药物的应用。
该药物对以下病原菌引起的植物病具有显著的抑制活性：
棉花枯萎病原菌；西瓜枯萎病原菌；马铃薯干腐病原菌；小麦赤霉病原菌；番茄早疫病原菌；白菜黑斑病原菌；烟草赤星病原菌；玉米弯孢病原菌；苹果炭疽病原菌；南瓜枯萎病原菌；苹果腐烂病原菌；水稻稻瘟病原菌；苹果轮纹病原菌；甜瓜白粉病菌；葡萄霜霉病菌。
与现有技术相比，本发明具有以下优点：
1)本发明丙炔酸酯类和丙炔酰胺类化合物分子量小，结构简单；合成方法简单，步骤少，工艺条件简单、环保，适宜于规模化生产；收率高，纯化方法简单易行；
2)本发明丙炔酸酯类和丙炔酰胺类化合物制备植物抗菌药物抗菌活性强，抗菌谱广且不易产生抗药性，对十多种常见植物病原菌均具有良好的防治效果；对动植物的安全性高。
具体实施方式
下面结合具体实施方式对本发明进行详细的说明。
本发明基于靶向共价结合原理，设计并合成出一系列丙炔酰胺类化合物A和丙炔酸酯类B，并发现化合物A和B对多种植物病均具有高效的抑制活性，及对动植物的低毒性。二者均具有作为有效成分或增效成分用于新型高效低毒植物抗菌剂开发的潜力。
一种丙炔酰胺类化合物A，具有如下分子结构特征：
Figure BDA0003416355970000051
其中：
R1是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子、三氟甲基等；R1的位置为苯环的邻位、间位或对位；R2是氢、甲基等；R3是氢、甲基等；n＝0,1,2,3；
具有以下合成路线：
Figure BDA0003416355970000052
其中：
R1是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子、三氟甲基等；R′的位置为苯环的邻位、间位或对位；R2是氢、甲基等；R3是氢、甲基等；n＝0,1,2,3；催化剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)和1-羟基苯并三唑。
一种丙炔酸酯类化合物B，具有如下分子结构特征：
Figure BDA0003416355970000053
其中：
R′是相同或不同的氢、甲基、乙基、烷氧基、苯氧基、卤素原子、三氟甲基、硝基、氰基、等；R′的位置为苯环的邻位、间位或对位；R″是氢、甲基等；n＝1,2,3；
具有以下合成路线：
Figure BDA0003416355970000061
其中：
R′是相同或不同的氢、甲基、乙基、烷氧基、苯氧基、卤素原子、三氟甲基、硝基、氰基、等；R′的位置为苯环的邻位、间位或对位；R″是氢、甲基等；n＝1,2,3；催化剂为过渡金属硫酸氢盐。
化合物A或B作为有效成分或增效成分在制备植物抗菌药物中的应用。
两类化合物对以下植物病原菌均具有显著的抑制活性：
棉花枯萎病原菌；西瓜枯萎病原菌；马铃薯干腐病原菌；小麦赤霉病原菌；番茄早疫病原菌；白菜黑斑病原菌；烟草赤星病原菌；玉米弯孢病原菌；苹果炭疽病原菌、南瓜枯萎病原菌；苹果腐烂病原菌；水稻稻瘟病原菌；苹果轮纹病原菌、甜瓜白粉病菌、葡萄霜霉病菌。
化合物的体外抗菌活性采用菌丝生长速率法进行测定，防治效果采用盆栽法进行测定。结果证明本发明所涉及的丙炔酰胺类化合物A或丙炔酸酯类化合物B对棉花枯萎病原菌；西瓜枯萎病原菌、马铃薯干腐病原菌、小麦赤霉病原菌、番茄早疫病原菌、白菜黑斑病原菌、烟草赤星病原菌、玉米弯孢病原菌、苹果炭疽病原菌、南瓜枯萎病原菌、苹果腐烂病原菌、水稻稻瘟病原菌、苹果轮纹病原菌、甜瓜白粉病菌、葡萄霜霉病菌等多种植物病原菌普遍具有强的抑制活性，具有作为抗菌活性成分或增效成分用于制备植物抗菌剂的巨大潜力。
以下结合附表和合成方法及其活性测定对本发明作进一步详细说明：
一、酰胺类化合物A的制备
通用方法：向反应瓶(100mL)中加入苯胺或取代苯胺(5mmol)和N,N-二甲基甲酰胺(30mL)，搅拌至固体全溶。将反应体系冷却至0℃，在搅拌下，向其中依次加入1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)(6mmol)、1-羟基苯并三唑(0.5mmol)和丙炔酸(6mmol)。随后，撤去冷浴，让反应液自然升至室温，并继续搅拌。当TLC检测到反应完成后，将反应液转移至分液漏斗，加入水(100mL)稀释，用乙酸乙酯萃取(50mL×3)，饱和食盐水洗涤，无水硫酸钠。过滤后，将滤液减压蒸除溶剂，得粗产物。使用石油醚和乙酸乙酯的混合液进行重结晶，得到纯的酰胺类化合物A，以下简称化合物A。
以下是采用上述方法合成的化合物A的名称、理化性质和核磁共振谱数据。
N-苯基丙炔酰胺(A1)：白色粉末；产率85.5％；mp 79.3-79.7℃；1H NMR(400MHz,DMSO-d6):δ10.79(s,1H),7.66–7.54(m,2H),7.37–7.29(m,2H),7.13–7.06(m,1H),4.41(s,1H).
N-苯基-2-丁炔酰胺(A2)：白色粉末；产率95.0％；mp 99.3-100.1℃；1H NMR(400MHz,DMSO-d6):δ10.60(s,1H),7.63–7.57(m,2H),7.31(t,J＝7.9Hz,2H),7.07(t,J＝7.3Hz,1H),2.05(s,3H).
N-(2-氯苯基)丙炔酰胺(A2)：棕色固体；产率60.0％；mp 86.2-86.9℃；1H NMR(400MHz,DMSO-d6):δ10.51(s,1H),7.51(ddd,J＝16.1,7.9,1.6Hz,2H),7.39–7.32(m,1H),7.32–7.25(m,1H),4.42(s,1H).
N-(3-氯苯基)丙炔酰胺(A3)：浅黄色粉末；产率72.8％；mp 130.3-131.0℃；1HNMR(400MHz,DMSO-d6):δ11.00(s,1H),7.75(t,J＝2.1Hz,1H),7.49(ddd,J＝8.3,2.1,1.0Hz,1H),7.36(t,J＝8.1Hz,1H),7.17(ddd,J＝8.0,2.1,1.0Hz,1H),4.49(s,1H).
N-(4-氯苯基)丙炔酰胺(A4)：棕色絮状结晶；产率74.0％；mp 169.7-170.9℃；1HNMR(400MHz,DMSO-d6):δ10.94(s,1H),7.69–7.58(m,2H),7.45–7.35(m,2H),4.46(s,1H).
N-(4-氟苯基)丙炔酰胺(A5)：浅黄色固体；产率88.2％；mp 157.4-158.2℃；1HNMR(400MHz,DMSO-d6):δ10.86(s,1H),7.66–7.57(m,2H),7.23–7.14(m,2H),4.43(s,1H).
N-(4-溴苯基)丙炔酰胺(A6)：黄色固体；产率88.9％；mp 186.7-187.4℃；1HNMR(400MHz,DMSO-d6):δ10.94(s,1H),7.62–7.45(m,4H),4.46(s,1H).
N-(4-碘苯基)丙炔酰胺(A7)：白色固体；产率61.3％；mp 202.5-203.0℃；1HNMR(400MHz,DMSO-d6):δ10.91(s,1H),7.75–7.62(m,2H),7.49–7.37(m,2H),4.46(s,1H).
N-(4-三氟甲基苯基)丙炔酰胺(A8)：浅黄色针状结晶；产率64.8％；mp171.5-171.8℃；1H NMR:(400MHz,DMSO-d6)δ11.18(s,1H),7.82(d,J＝8.5Hz,2H),7.71(d,J＝8.6Hz,2H),4.53(s,1H).
N-(2-甲基苯基)丙炔酰胺(A9)：白色固体；产率86.6％；mp 133.4-134.2℃；1HNMR(400MHz,DMSO-d6):δ10.24(s,1H),7.29–7.13(m,4H),4.35(s,1H),2.18(s,3H).
N-(3-甲基苯基)丙炔酰胺(A10)：棕色油状液体；产率88.8％；1H NMR(400MHz,DMSO-d6):δ10.72(s,1H),7.44(d,J＝2.0Hz,1H),7.38(dd,J＝8.2,2.1Hz,1H),7.20(t,J＝7.8Hz,1H),6.92(d,J＝7.5Hz,1H),4.39(s,1H),2.28(s,3H).
N-(4-甲基苯基)丙炔酰胺(A11)：浅黄色固体；产率91.3％；mp 122.5-123.2℃；1HNMR(400MHz,DMSO-d6):δ10.71(s,1H),7.54–7.42(m,2H),7.12(d,J＝8.3Hz,2H),4.37(s,1H),2.25(s,3H).
N-(4-异丙基苯基)丙炔酰胺(A12)：棕色油状液体；产率88.4％；1H NMR(400MHz,DMSO-d6):δ10.72(s,1H),7.57–7.45(m,2H),7.25–7.14(m,2H),4.37(s,1H),2.84(hept,J＝7.0Hz,1H),1.17(d,J＝6.9Hz,6H,).
N-(4-叔丁基苯基)丙炔酰胺(A13)：棕色油状液体；产率85.4％；1H NMR(400MHz,DMSO-d6):δ10.72(s,1H),7.55–7.46(m,2H),7.37–7.30(m,2H),4.37(s,1H),1.25(s,9H).
N-(4-甲氧基苯基)丙炔酰胺(A14)：浅紫色粉末；产率83.6％；mp 88.8-90.1℃；1HNMR(400MHz,DMSO-d6):δ10.65(s,1H),7.53–7.48(m,2H),6.92–6.87(m,2H),4.35(s,1H),3.72(s,3H).
N-(4-苯氧基苯基)丙炔酰胺(A15)：灰色粉末；产率70.0％；mp 128.4-129.3℃；1HNMR(400MHz,DMSO-d6):δ10.91(s,1H),7.73–7.62(m,6H),7.45(t,J＝7.7Hz,2H),7.37–7.31(m,1H),4.45(s,1H).
N-甲基-N-苯基丙炔酰胺(A16)：白色晶体；产率89.1％；mp 73.2-74.0℃；1H NMR(400MHz,DMSO-d6):δ7.48–7.43(m,2H),7.42–7.37(m,3H),4.19(s,1H),3.21(s,3H).
N-苄基丙炔酰胺(A17)：白色晶体；产率91.9％；mp 87.3-87.6℃；1H NMR(400MHz,DMSO-d6):δ9.26(t,J＝6.2Hz,1H),7.33(dd,J＝8.3,6.5Hz,2H),7.25(td,J＝6.3,1.6Hz,3H),4.29(d,J＝6.1Hz,2H),4.17(s,1H).
N-(2-苯基乙基)丙炔酰胺(A18)：浅黄色固体；产率93.6％；mp 66.2-66.7℃；1HNMR(400MHz,DMSO-d6):δ8.82(t,J＝5.8Hz,1H),7.33–7.26(m,2H),7.24–7.17(m,3H),4.10(s,1H),3.35–3.28(m,2H),2.74(t,J＝7.4Hz,2H).
N-(3-苯基丙基)丙炔酰胺(A19)：白色晶体；产率86.0％；mp 45.9-47.0℃；1H NMR(400MHz,DMSO-d6):δ8.78(t,J＝5.7Hz,1H),7.28(t,J＝7.5Hz,2H),7.22–7.16(m,3H),4.12(s,1H),3.09(td,J＝7.0,5.6Hz,2H),2.59–2.53(m,2H),1.71(m,2H).
N-(联苯-4-基)丙炔酰胺(A20)：白色粉末；产率61.8％；mp 124.6-125.3℃；1HNMR(400MHz,DMSO-d6)δ10.92(s,1H),7.71(d,J＝8.8Hz,2H),7.67–7.62(m,4H),7.45(dd,J＝8.4,7.0Hz,2H),7.37–7.31(m,1H),4.45(s,1H).
二、丙炔酸酯类化合物B的制备
通用方法：向反应瓶(100mL)中加入丙炔酸或2-丁炔酸(0.12mol)、苄醇或取代苄醇(0.1mol)和过渡金属硫酸氢盐(5mmol)。将反应液在65℃搅拌2h，然后在40-65℃对反应液进行旋蒸，直至不再有液体蒸出为止。将反应液冷却至室温，向其中加入300毫升乙酸乙酯，过滤，除去不溶物。将所得溶液转入分液漏斗，依次用水、5％碳酸钠和饱和食盐水洗涤，最后用无水硫酸钠干燥。过滤后，减压蒸除溶剂。将所得残留物进行硅胶闪柱层析，洗脱剂为石油醚/乙酸乙酯(10:1，v/v)，得纯净的炔酸酯B。
以下是采用上述方法合成的丙炔酸酯类化合物B的名称、理化性质和核磁共振谱数据。
丙炔酸苄酯(B1)：产率87％；无色透明液体；1H NMR(500MHz,CH3D)δ7.39–7.35(m,5H),5.22(s,2H),2.89(s,1H).
丙炔酸-2-氟苄酯(B2)：产率85％；无色透明液体；1H NMR(400MHz,CH3D)δ7.43–7.33(m,2H),7.18–7.07(m,2H),5.29(s,2H),2.90(s,1H).
丙炔酸-3-氟苄酯(B3)：产率80％；无色透明液体；1H NMR(400MHz,CH3D)δ7.35(td,J＝7.9,5.7Hz,1H),7.16–7.03(m,3H),5.21(s,2H),2.92(s,1H).
丙炔酸-4-氟苄酯(B4)：产率84％；无色透明液体；1H NMR(500MHz,CH3D)δ7.37(dd,J＝8.4,5.3Hz,2H),7.06(t,J＝8.6Hz,2H),5.18(s,2H),2.90(s,1H).
丙炔酸-2-氯苄酯(B5)：产率79％；无色透明液体；1H NMR(500MHz,CH3D)δ7.45–7.40(m,2H),7.31–7.28(m,2H),5.34(s,2H),2.92(s,1H).
丙炔酸-3-氯苄酯(B6)：产率75％；无色透明液体；1H NMR(500MHz,Chloroform-d)δ7.38(d,J＝2.1Hz,1H),7.34–7.29(m,2H),7.25(d,J＝6.0Hz,1H),5.19(s,2H),2.92(s,1H).
丙炔酸-4-氯苄酯(B7)：产率81％；无色透明液体；1H NMR(500MHz,CH3D)δ7.36–7.31(m,4H),5.18(s,2H),2.90(s,1H).
丙炔酸-2-溴苄酯(B8)：产率65％；白色晶体；1H NMR(400MHz,CH3D)δ7.59(dd,J＝7.9,1.2Hz,1H),7.44(dd,J＝7.7,1.7Hz,1H),7.34(td,J＝7.6,1.2Hz,1H),7.24–7.20(m,1H),5.32(s,2H),2.93(s,1H).
丙炔酸-3-溴苄酯(B9)：产率61％；无色透明液体；1H NMR(400MHz,CH3D)δ7.54(d,J＝1.9Hz,1H),7.49(dt,J＝7.8,1.7Hz,1H),7.33–7.29(m,1H),7.26(s,1H),5.18(s,2H),2.93(s,1H).
丙炔酸-4-溴苄酯(B10)：产率79％；浅黄色固体；1H NMR(500MHz,CH3D)δ7.51(d,J＝8.4Hz,2H),7.25(s,2H),5.16(s,2H),2.91(s,1H).
丙炔酸-4-碘苄酯(B11)：产率67％；浅黄色固体；1H NMR(500MHz,Chloroform-d)δ7.72–7.70(m,1H),7.12(d,J＝7.7Hz,3H),5.15(s,2H),2.91(s,1H).
丙炔酸-2-甲基苄酯(B12)：产率72％；无色透明液体；1H NMR(400MHz,CH3D)δ7.35–7.32(m,1H),7.28(d,J＝6.9Hz,1H),7.21(ddd,J＝6.8,3.7,1.4Hz,2H),5.24(s,2H),2.88(s,1H),2.37(s,3H).
丙炔酸-3-甲基苄酯(B13)：产率75％；无色透明液体；1H NMR(400MHz,CH3D)δ7.26(d,J＝4.4Hz,1H),7.20–7.15(m,3H),5.19(s,2H),2.89(s,1H),2.37(s,3H).
丙炔酸-4-甲基苄酯(B14)：产率79％；无色透明液体；1H NMR(500MHz,CH3D)δ7.27(d,J＝7.9Hz,2H),7.18(d,J＝7.7Hz,2H),5.18(s,2H),2.86(s,1H),2.36(s,3H).
丙炔酸-4-乙基苄酯(B15)：产率73％；无色透明液体；1H NMR(500MHz,CH3D)δ7.30(d,J＝7.8Hz,2H),7.21(d,J＝7.8Hz,2H),5.19(s,2H),2.86(s,1H),2.65(q,J＝7.7Hz,2H),1.23(t,J＝7.6Hz,3H).
丙炔酸-4-三氟甲基苄酯(B16)：产率64％；无色透明液体；1H NMR(500MHz,CH3D)δ7.64(d,J＝7.9Hz,2H),7.50(d,J＝7.9Hz,2H),5.27(s,2H),2.93(s,1H).
丙炔酸-4-硝基苄酯(B17)：产率58％；浅黄色晶体；1H NMR(500MHz,Chloroform-d)δ8.25(d,J＝8.6Hz,2H),7.55(d,J＝8.3Hz,2H),5.32(s,2H),2.98(s,1H).
丙炔酸-4-氰基苄酯(B18)：产率64％；浅黄色晶体；1H NMR(400MHz,CH3D)δ7.69(d,J＝8.2Hz,2H),7.49(d,J＝8.0Hz,2H),5.27(s,2H),2.97(s,1H).
丙炔酸2-苯基乙酯(B19)：产率78％；无色透明液体；1H NMR(500MHz,CH3D)δ7.32(dd,J＝8.1,6.7Hz,2H),7.23(dd,J＝8.0,6.3Hz,3H),4.40(t,J＝7.2Hz,2H),2.99(t,J＝7.2Hz,2H),2.87(s,1H).
丙炔酸-3-苯基丙酯(B20)：产率76％；无色透明液体；1H NMR(500MHz,CH3D)δ7.29(dd,J＝8.2,6.8Hz,2H),7.22–7.18(m,3H),4.21(t,J＝6.5Hz,2H),2.89(s,1H),2.72(dd,J＝8.5,6.8Hz,2H),2.06–1.98(m,2H).
2-丁炔酸苄酯(B21)：产率82％；无色透明液体；1H NMR(400MHz,CH3D)δ7.41–7.30(m,5H),5.18(s,2H),1.98(s,3H).
三、化合物A和化合物B的抗菌活性
1.体外抗菌活性
抗菌活性采用菌丝线性生长速率法进行测定。供试菌为：棉花枯萎病原菌(MK)；西瓜枯萎病原菌(XK)；马铃薯干腐病原菌(MG)；小麦赤霉病原菌(XC)；番茄早疫病原菌(FZ)；白菜黑斑病原菌(BH)；烟草赤星病原菌(YC)；玉米弯孢病原菌(YW)；苹果炭疽病原菌(PT)；南瓜枯萎病原菌(NK)；苹果腐烂病原菌(PF)；水稻稻瘟病原菌(SD)；苹果轮纹病原菌(PL)。培养基为PDA。化合物的供试溶液采用5％DMSO水溶液(v/v)进行配制。供试化合物的测定浓度均100μg/mL。每个试验设每次设三个平行，并重复三次。测定结果以平均抑制率来表示。
2.抗霜霉病菌的盆栽试验
供试液的配制：将供试化合物用二甲基亚砜(DMSO)配制成160mg/mL的溶液，其中含10％的OP-10。试验前，将其水稀释533倍，然后对供试叶片进行喷雾处理。
供试菌为葡萄霜霉病菌。试验采用叶片上孢子萌发法进行。将葡萄霜霉病菌的孢子配成浓度为105孢子/毫升的悬浮液，通过喷雾法对葡萄树叶背面进行接种。将接种后的植株先在高湿和环境温度的隔离室中放置24h，然后将植株转入环境湿度和温度的温室中放置48h，最后，再将植株转入高湿环境中放置24h。然后，将植株移至自然环境。等植株表面的水分自然挥发完之后，从植株上取下已感染的叶片，用300μg/mL的供试液对其进行喷雾处理。等液面的水分自然挥发完之后，将叶片的叶柄浸入水中，然后将其置于高湿环境中孵育72h。试验效果通过比较试验组和对照组叶面上的孢子覆盖面积的百分率来评价。
3.抗白粉病菌的盆栽试验
供试液的配制与上述霜霉病菌的盆栽抗菌试验相同。供试菌为甜瓜白粉病菌。试验采用叶片上孢子萌发法进行，具体方法与上述霜霉病菌的盆栽抗菌试验基本相同。每个试验采用的甜瓜幼苗数约为30株，甜瓜幼苗生长在含有消毒过的堆肥中。将接种过甜瓜白粉病孢子悬浮液的甜瓜植株在高湿环境中放置24h，然后用300μg/mL的供试液对其进行喷雾处理。5天之后，采用与上述霜霉病菌的盆栽抗菌试验相同的方法进行抗菌效果评价。
表1.化合物A和B对植物病原菌的抑制活性(100μg/mL)
Figure BDA0003416355970000141
Figure BDA0003416355970000151
表2.化合物B对植物病原菌的抑制活性(100μg/mL)
Figure BDA0003416355970000152
表3.化合物对甜瓜白粉病和葡萄霜霉病的防治指数*
Figure BDA0003416355970000153
Figure BDA0003416355970000161
*0表示防效小于50％；1表示防效为50-80％；2表示防效大于80％
结果表明，在100μg/mL浓度时，几乎所有的化合物A和B对13种供试植物病原菌都表现出了较高的抑制率。此外，大部分供试的化合物A和B对葡萄霜霉病菌和甜瓜白粉病菌也表现出了优异的防治效果。
由此可见，本发明涉及的化合物A和B对植物病原菌具有高效广谱的抑制活性，具有制备植物抗菌药物的潜在用途，可作为植物抗菌药物的有效成分或增效成分。
本发明的内容不限于实施例所列举，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。

Claims (9)

1.一种丙炔酰胺类化合物A，其特征在于：分子式为：
Figure FDA0003416355960000011
其中：
R1是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子、三氟甲基等；R2是氢、甲基等；R3是氢、甲基等；n＝0,1,2,3；R1的位置为苯环的邻位、间位或对位。
2.一种丙炔酸酯类化合物B，其特征在于：分子式为：
Figure FDA0003416355960000012
其中：
R′是相同或不同的氢、甲基、乙基、烷氧基、苯氧基、卤素原子、三氟甲基、硝基、氰基、等；R″是氢、甲基等；n＝1,2,3；R′的位置为苯环的邻位、间位或对位。
3.如权利要求1所述的丙炔酰胺类化合物A的合成方法，其特征在于：
具有以下合成路线：
Figure FDA0003416355960000013
其中：
R1是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子、三氟甲基等；R1的位置为苯环的邻位、间位或对位；R2是氢、甲基等；R3是氢、甲基等；n＝0,1,2,3；催化剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)和1-羟基苯并三唑。
4.如权利要求2所述的丙炔酸酯类化合物B的合成方法，其特征在于：
具有以下合成路线：
Figure FDA0003416355960000021
其中：
R′是相同或不同的氢、甲基、乙基、烷氧基、苯氧基、卤素原子、三氟甲基、硝基、氰基、等；R′的位置为苯环的邻位、间位或对位；R″是氢、甲基等；n＝1,2,3；催化剂为过渡金属硫酸氢盐。
5.如权利要求1或2所述的丙炔酰胺类化合物A或丙炔酸酯类化合物B的应用，其特征在于：
丙炔酰胺类化合物A或丙炔酸酯类化合物B作为有效成分或增效成分在制备植物抗菌药物的应用。
6.权利要求5所述的丙炔酰胺类化合物A或丙炔酸酯类化合物B的应用，其特征在于：
丙炔酰胺类化合物A或丙炔酸酯类化合物B对以下植物病原菌具有显著的抑制活性：
棉花枯萎病原菌；西瓜枯萎病原菌；马铃薯干腐病原菌；小麦赤霉病原菌；番茄早疫病原菌；白菜黑斑病原菌；烟草赤星病原菌；玉米弯孢病原菌；苹果炭疽病原菌；南瓜枯萎病原菌；苹果腐烂病原菌；水稻稻瘟病原菌；苹果轮纹病原菌；甜瓜白粉病菌；葡萄霜霉病菌。
7.含有权利要求1或2所述的丙炔酰胺类化合物A或丙炔酸酯类化合物B的药物。
8.根据权利要求7所述的含有丙炔酰胺类化合物A或丙炔酸酯类化合物B的药物的应用，其特征在于：该药物作为植物抗菌药物的应用。
9.根据权利要求8所述的含有丙炔酰胺类化合物A或丙炔酸酯类化合物B的药物的应用，其特征在于：该药物对以下病原菌引起的植物病具有显著的抑制活性：
棉花枯萎病原菌；西瓜枯萎病原菌；马铃薯干腐病原菌；小麦赤霉病原菌；番茄早疫病原菌；白菜黑斑病原菌；烟草赤星病原菌；玉米弯孢病原菌；苹果炭疽病原菌；南瓜枯萎病原菌；苹果腐烂病原菌；水稻稻瘟病原菌；苹果轮纹病原菌；甜瓜白粉病菌；葡萄霜霉病菌。
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