CN118221547A - 一种肉桂醛苯腙类化合物以及其合成方法、以及含有该化合物的药物及应用 - Google Patents
一种肉桂醛苯腙类化合物以及其合成方法、以及含有该化合物的药物及应用 Download PDFInfo
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Abstract
本发明涉及一种肉桂醛苯腙类化合物以及其合成方法、以及含有该化合物的药物及应用,属于植物抗真菌药物技术领域。本发明涉及的肉桂醛苯腙类化合物对十多种致病性植物病原真菌有显著的抑制活性,且具有广谱抗菌性。除此之外,该类化合物还具有成本低、易于规模化制备、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
技术领域
本发明涉及一种肉桂醛苯腙类化合物以及其合成方法、以及含有该化合物的药物及应用,属于植物抗真菌药物技术领域。
背景技术
植物病原真菌不仅会降低农作物的产量,还会导致农作物质量下降,每年引起全球农作物遭受灾难性损失。除此之外,植物病原真菌也会引起食品安全问题,因为其代谢产生的真菌毒素会影响人和哺乳动物的健康。化学杀菌剂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(J. Agric. Food. Chem.,2022,70,4256-4266; J. Agric. Food. Chem.,2023,71,3681-3693)。
苯腙类化合物是杂环化学中重要的中间体,通常通过肼与羰基化合物(醛或酮)作用形成。一些天然的苯腙衍生物具有抗惊厥、镇痛、抗炎、降压、抗菌、抗结核、抗肿瘤等多种生物活性(ChemistrySelect,2021,6,1366-1371)。在农药方面,人们也成功开发了一些腙类抗真菌剂,如嘧菌腙、敌菌酮等。
到目前为止,本专利涉及的肉桂醛苯腙类化合物的抗植物真菌活性鲜有报道。Achagar R等人曾报道了肉桂醛苯腙对金黄色葡萄球菌(Staphylococcus aureus)、大肠埃希氏杆菌(Escherichia coli)及绿脓杆菌(Pseudomonas aeruginosa)的抑制活性。除此之外,关于上述化合物对植物病原真菌的抑制活性未见报道,也未见其他该类化合物抗植物真菌活性的报道。
发明内容
为解决现有技术存在的技术问题,本发明提供了一种肉桂醛苯腙类化合物以及其合成方法、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真菌具有高效广谱的抑制活性,可作为有效成分或增效成分用于新型农用抗真菌剂的研究开发。
为实现上述目的,本发明所采用的技术方案为一种肉桂醛苯腙类化合物,其特征在于:具有如下分子结构特征,其中:R1、R2是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子或三氟甲基;R1、R2的位置为苯环的邻位、间位和对位。
一种肉桂醛苯腙类化合物的合成方法,具有以下合成路线,其中:R1、R2是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子或三氟甲基;R1、R2的位置为苯环的邻位、间位和对位。
优选的,具有以下反应条件,取代肉桂醛和取代苯肼盐酸盐的摩尔比为:1.0:1.0~1.0:1.5;优选为:1.0:1.1;反应温度为:0~35 ℃。
一种肉桂醛苯腙类化合物的应用,该肉桂醛苯腙类化合物作为在制备植物抗真菌药物中的应用。
优选的,该肉桂醛苯腙类化合物作为单一有效成分或增效成分与其他药物共同作为植物抗真菌剂使用。
优选的,该肉桂醛苯腙类化合物对以下植物病原真菌都有显著的抑制活性:高粱炭疽病原菌、苹果轮纹病原菌、水稻稻瘟病原菌、苹果腐烂病原菌、南瓜枯萎病原菌、苹果炭疽病原菌、玉米弯孢病原菌、烟草赤星病原菌、白菜黑斑病原菌、番茄早疫病原菌、小麦赤霉病原菌、番茄灰霉病原菌、马铃薯干腐病原菌、西瓜枯萎病原菌、棉花枯萎病原菌。
一种肉桂醛苯腙类化合物的药物的应用,该药物对以下植物病具有显著的预防和治疗效果:高粱炭疽病、苹果轮纹病、水稻稻瘟病、苹果腐烂病、南瓜枯萎病、苹果炭疽病、玉米弯孢病、烟草赤星病、白菜黑斑病、番茄早疫病、小麦赤霉病、番茄灰霉病、马铃薯干腐病、西瓜枯萎病、棉花枯萎病、葡萄霜霉病、甜瓜白粉病。
与现有技术相比,本发明具有以下技术效果:1)本发明所涉及的肉桂醛苯腙类化合物很多都是未见文献报道的新化合物;
2)本发明所涉及的肉桂醛苯腙类化合物具有分子量小,结构简单;合成方法简单,工艺条件简单、环保,适宜于规模化生产;收率高,纯化方法简单易行等优点;
3)本发明涉及的肉桂醛苯腙类化合物抗菌活性强,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。
综上所述,本发明所涉及的肉桂醛苯腙类化合物具有作为植物抗菌剂的巨大开发潜力。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明基于活性基团拼接的原理,设计并合成出一系列肉桂醛苯腙类化合物,并发现这类化合物对十多种植物病原真菌有显著的抑制活性,并且对植物及哺乳动物的毒性较低。该类化合物可作为有效成分或增效成分用于新型农用抗真菌剂的研究开发。
上述肉桂醛苯腙类化合物,其分子结构式为:其中:
R1、R2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、R2的位置为苯环的邻位、间位和对位。具有以下合成路线:取代肉桂醛和取代苯肼盐酸盐的摩尔比为:1.0:1.0~1.0:1.5;优选为:1.0:1.1;
反应温度为:0~35 ℃。
一类肉桂醛苯腙类化合物作为单一有效成分或者与其他抗菌药物合用,用于制备植物抗真菌药物。
一类肉桂醛苯腙类化合物对以下植物病原真菌具有显著的抑制活性,由其作为单一有效成分制成的药物可有效预防和治疗由以下病菌引起的植物病害:
高粱炭疽病原菌、苹果轮纹病原菌、水稻稻瘟病原菌、苹果腐烂病原菌、南瓜枯萎病原菌、苹果炭疽病原菌、玉米弯孢病原菌、烟草赤星病原菌、白菜黑斑病原菌、番茄早疫病原菌、小麦赤霉病原菌、番茄灰霉病原菌、马铃薯干腐病原菌、西瓜枯萎病原菌、棉花枯萎病原菌。
对于上述肉桂醛苯腙类化合物的合成,本发明提供如下的具体方法和工艺:
一、肉桂醛苯腙类化合物的制备
向反应瓶中加入30 mL的95%乙醇和取代苯肼盐酸盐(5 mmol),搅拌至固体全部溶解,之后向体系中缓慢滴加取代肉桂醛(5.5 mmol)的乙醇溶液,将体系置于室温反应。当反应完全后,向反应体系中加入100 mL水,用乙酸乙酯萃取(50 mL×3),之后合并有机相,用饱和食盐水洗涤,无水硫酸钠干燥。过滤后,将滤液真空浓缩除去溶剂,即得固体粗产物。用石油醚和乙酸乙酯对粗产物进行重结晶,可得到纯度较高的肉桂醛苯腙类化合物。
以下是采用上述方法合成的肉桂醛苯腙类化合物的名称、理化性质和核磁共振谱数据:4-甲基肉桂醛苯腙(1):黄色粉末;产率85.6%;mp 145.2~146.1 ℃;1H NMR (400MHz, DMSO-d 6) δ 10.27 (s, 1H), 7.72 (dd, J = 9.3, 1.0 Hz, 1H), 7.43 (d, J =8.1 Hz, 2H), 7.24 – 7.15 (m, 4H), 7.04 – 6.92 (m, 3H), 6.78 – 6.70 (m, 2H),2.30 (s, 3H);13C NMR (101 MHz, DMSO-d 6) δ 145.50, 139.96, 137.65, 134.49,133.35, 129.83, 129.56, 126.81, 126.03, 119.13, 112.35, 21.34。
4-氯肉桂醛苯腙(2)(新化合物):黄色粉末;产率88.3%;mp 135.1~136.0 ℃;1HNMR (400 MHz, DMSO-d 6) δ 10.37 (s, 1H), 7.72 (dd, J = 9.3, 1.1 Hz, 1H), 7.57(d, J = 8.6 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 7.22 (dd, J = 8.6, 7.3 Hz,2H), 7.08 – 6.99 (m, 3H), 6.81 – 6.72 (m, 2H);13C NMR (101 MHz, DMSO-d 6) δ145.32, 139.46, 136.25, 132.37, 131.75, 129.59, 129.17, 128.48, 127.87,119.36, 112.44。
肉桂醛苯腙(3):浅黄色粉末;产率93.3%;mp 174.4~175.3 ℃;1H NMR (400 MHz,DMSO-d 6) δ 10.32 (s, 1H), 7.73 (d, J = 9.3 Hz, 1H), 7.55 (d, J = 7.2 Hz, 2H),7.36 (t, J = 7.5 Hz, 2H), 7.28 – 7.18 (m, 3H), 7.06 – 6.98 (m, 3H), 6.82 –6.71 (m, 2H);13C NMR (101 MHz, DMSO-d 6) δ 145.43, 139.77, 137.23, 133.28,129.58, 129.21, 128.18, 127.00, 126.86, 119.25, 112.40。
肉桂醛-2-氟苯腙(4):黄色粉末;产率87.9%;mp 157.8~158.3 ℃;1H NMR (400MHz, DMSO-d 6) δ 10.25 (d, J = 2.0 Hz, 1H), 8.02 (d, J = 9.3 Hz, 1H), 7.57 (d,J = 7.2 Hz, 2H), 7.46 – 7.40 (m, 1H), 7.36 (dd, J = 8.3, 6.8 Hz, 2H), 7.30 –7.24 (m, 1H), 7.17 – 7.00 (m, 3H), 6.84 – 6.73 (m, 2H); 13C NMR (101 MHz,DMSO-d 6) δ 149.58 (d, J = 240.38 Hz), 142.52, 137.05, 134.41, 133.64 (d, J =9.09 Hz), 129.21, 128.40, 127.00, 126.87, 125.43 (d, J = 4.04 Hz), 119.06 (d,J = 7.07 Hz), 115.48 (d, J = 17.17 Hz), 114.14 (d, J = 3.03 Hz)。
肉桂醛-3-氟苯腙(5):黄色粉末;产率90.6%;mp 163.5~164.6 ℃;1H NMR (400MHz, DMSO-d 6) δ 10.52 (s, 1H), 7.75 (d, J = 9.2 Hz, 1H), 7.56 (d, J = 7.6 Hz,2H), 7.36 (t, J = 7.5 Hz, 2H), 7.24 (dt, J = 23.2, 7.4 Hz, 2H), 7.02 (dd, J =16.0, 9.2 Hz, 1H), 6.87 – 6.76 (m, 3H), 6.52 (td, J = 8.4, 2.4 Hz, 1H); 13CNMR (101 MHz, DMSO-d 6) δ 163.82 (d, J = 241.4 Hz), 147.44 (d, J = 11.11 Hz),140.98, 137.06, 134.38, 131.16 (d, J = 10.1 Hz), 129.22, 128.39, 126.97,126.69, 108.57 (d, J = 2.02 Hz), 105.29 (d, J = 21.218 Hz), 98.85 (d, J =26.26 Hz)。
肉桂醛-4-氟苯腙(6):黄色粉末;产率89.6%;mp 156.0~156.9 ℃;1H NMR (400MHz, DMSO-d 6) δ 10.32 (s, 1H), 7.72 (dd, J = 9.3, 1.0 Hz, 1H), 7.57 – 7.51(m, 2H), 7.38 – 7.32 (m, 2H), 7.28 – 7.23 (m, 1H), 7.08 – 6.97 (m, 5H), 6.78(d, J = 16.1 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 156.35 (d, J = 235.3 Hz),142.14, 142.13, 139.81, 137.21, 133.34, 129.21, 128.19, 126.93, 126.85,116.09 (d, J = 22.2 Hz), 113.32 (d, J = 8.08 Hz)。
肉桂醛-2-氯苯腙(7):浅黄色粉末;产率83.7%;mp 170.2~171.3 ℃;1H NMR (400MHz, DMSO-d 6) δ 9.87 (s, 1H), 8.16 (d, J = 9.3 Hz, 1H), 7.60 – 7.55 (m, 2H),7.48 (dd, J = 8.3, 1.5 Hz, 1H), 7.39 – 7.22 (m, 5H), 7.04 (dd, J = 16.1, 9.3Hz, 1H), 6.87 – 6.76 (m, 2H);13C NMR (101 MHz, DMSO-d 6) δ 143.49, 141.58,136.96, 134.99, 129.84, 129.22, 128.51, 128.47, 127.07, 126.82, 120.08,116.68, 114.35。
肉桂醛-3-氯苯腙(8):黄色针状结晶;产率80.8%;mp 140.5~141.3 ℃;1H NMR(400 MHz, DMSO-d6) δ 10.52 (s, 1H), 7.75 (d, J = 9.3 Hz, 1H), 7.60 – 7.53 (m,2H), 7.36 (t, J = 7.5 Hz, 2H), 7.31 – 7.19 (m, 2H), 7.09 – 6.99 (m, 2H), 6.94– 6.74 (m, 3H);13C NMR (101 MHz, DMSO-d6) δ 146.90, 141.20, 137.05, 134.47,134.35, 131.18, 129.22, 128.40, 126.99, 126.69, 118.58, 111.66, 111.13。
肉桂醛-4-氯苯腙(9):黄色粉末;产率85.3%;mp 143.7~144.8 ℃;1H NMR (400MHz, DMSO-d 6) δ 10.45 (s, 1H), 7.74 (d, J = 9.2 Hz, 1H), 7.58 – 7.52 (m, 2H),7.36 (t, J = 7.5 Hz, 2H), 7.26 (dd, J = 10.4, 8.0 Hz, 3H), 7.06 – 6.97 (m,3H), 6.81 (d, J = 16.0 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 144.37, 140.59,137.11, 133.98, 129.38, 129.22, 128.31, 126.92, 126.76, 122.46, 113.81。
肉桂醛-2-溴苯腙(10)(新化合物):黄色粉末;产率83.2%;mp 107.0~107.6℃;肉桂醛-2-溴苯腙(10)(新化合物):黄色粉末;产率83.2%;mp 107.0~107.6℃;肉桂醛-2-溴苯腙(10)(新化合物):黄色粉末;产率83.2%;mp 107.0~107.6℃;肉桂醛-2-溴苯腙(10)(新化合物):黄色粉末;产率83.2%;mp 107.0~107.6℃;肉桂醛-2-溴苯腙(10)(新化合物):黄色粉末;产率83.2%;mp 107.0~107.6℃;1H NMR(400 MHz,DMSO-d 6)δ9.63(s,1H),8.17(dd,J=9.3,0.9 Hz,1H),7.61–7.55(m,2H),7.46(ddd,J=17.7,8.1,1.5 Hz,2H),7.37(t,J=7.6Hz,2H),7.32–7.25(m,2H),7.04(dd,J=16.1,9.3Hz,1H),6.83(d,J=16.1Hz,1H),6.74(td,J=7.5,1.6Hz,1H);13CNMR(101MHz,DMSO-d 6)δ143.67,142.61,136.94,135.09,133.07,129.23,129.02,128.54,127.09,126.80,120.81,114.85,106.57.HRMS(positive ESI)m/z:calcd forC15H14BrN2 +[M+H+],301.0335(79Br),303.0314(81Br),found301.0314(79Br),303.0297(81Br)。
肉桂醛-3-溴苯腙(11)(新化合物):黄色粉末;产率79.6%;mp 119.1~119.9 ℃;1HNMR (400 MHz, DMSO-d 6) δ 10.49 (s, 1H), 7.74 (dd, J = 9.3, 1.0 Hz, 1H), 7.59– 7.53 (m, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.30 – 7.24 (m, 1H), 7.21 (t, J =2.0 Hz, 1H), 7.15 (t, J = 8.0 Hz, 1H), 7.04 (dd, J = 16.0, 9.3 Hz, 1H), 6.95– 6.81 (m, 3H);13C NMR (101 MHz, DMSO-d 6) δ 147.01, 141.25, 137.05, 134.51,131.51, 129.23, 128.41, 127.00, 126.68, 122.93, 121.46, 114.52, 111.49。
肉桂醛-4-溴苯腙(12):黄色粉末;产率80.7%;mp 140.9~141.6 ℃;1H NMR (400MHz, DMSO-d 6) δ 10.45 (s, 1H), 7.73 (dd, J = 9.3, 1.0 Hz, 1H), 7.58 – 7.52(m, 2H), 7.40 – 7.34 (m, 4H), 7.30 – 7.24 (m, 1H), 7.04 – 6.93 (m, 3H), 6.82(d, J = 16.1 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 144.73, 140.70, 137.10,134.08, 132.21, 129.23, 128.34, 126.94, 126.74, 114.32, 110.02。
肉桂醛-4-碘苯腙(13):黄色针状结晶;产率83.7%;mp 156.3~157.8 ℃;1H NMR(400 MHz, DMSO-d 6) δ 10.44 (s, 1H), 7.73 (d, J = 9.2 Hz, 1H), 7.57 – 7.48 (m,4H), 7.36 (dd, J = 8.4, 6.9 Hz, 2H), 7.26 (td, J = 7.1, 1.4 Hz, 1H), 7.01(dd, J = 16.0, 9.3 Hz, 1H), 6.89 – 6.77 (m, 3H);13C NMR (101 MHz, DMSO-d 6) δ145.17, 140.73, 137.95, 137.10, 134.09, 129.23, 128.34, 126.95, 126.73,114.93, 80.56。
肉桂醛-4-异丙基苯腙(14)(新化合物):黄色粉末;产率81.9%;mp 134.9~136.0℃;1H NMR (400 MHz, DMSO-d 6) δ 10.23 (s, 1H), 7.70 (dd, J = 9.3, 1.1 Hz, 1H),7.57 – 7.51 (m, 2H), 7.35 (t, J = 7.6 Hz, 2H), 7.28 – 7.22 (m, 1H), 7.10 –6.92 (m, 5H), 6.75 (d, J = 16.0 Hz, 1H), 2.79 (p, J = 6.9 Hz, 1H), 1.17 (d, J= 6.9 Hz, 6H);13C NMR (101 MHz, DMSO-d 6) δ 143.46, 139.23, 139.14, 137.31,132.76, 129.19, 128.06, 127.30, 127.10, 126.79, 112.39, 33.13, 24.64。
肉桂醛-4-苄氧基苯腙(15)(新化合物):黄色粉末;产率78.6%;mp 129.8~130.7℃;1H NMR (400 MHz, DMSO-d 6) δ 10.15 (s, 1H), 7.68 (dd, J = 9.3, 1.1 Hz, 1H),7.56 – 7.51 (m, 2H), 7.45 – 7.32 (m, 7H), 7.27 – 7.22 (m, 1H), 7.03 – 6.92(m, 5H), 6.73 (d, J = 16.0 Hz, 1H), 5.02 (s, 2H);13C NMR (101 MHz, DMSO-d 6) δ152.18, 139.71, 138.73, 137.98, 137.37, 132.38, 129.19, 128.83, 128.15,128.10, 128.00, 127.16, 126.74, 116.23, 113.38, 70.12。
肉桂醛-4-甲氧基苯腙(16):黄色粉末;产率80.3%;mp 134.5~135.8 ℃;1H NMR(400 MHz, DMSO-d 6) δ 10.12 (s, 1H), 7.68 (d, J = 9.3 Hz, 1H), 7.52 (d, J =7.3 Hz, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.24 (t, J = 7.3 Hz, 1H), 7.05 – 6.93(m, 3H), 6.84 (d, J = 9.0 Hz, 2H), 6.72 (d, J = 16.0 Hz, 1H), 3.69 (s, 3H);13CNMR (101 MHz, DMSO-d 6) δ 153.12, 139.47, 138.63, 137.38, 132.30, 129.18,127.97, 127.17, 126.73, 115.10, 113.42, 55.72, 55.69。
肉桂醛-4-甲基苯腙(17):黄色粉末;产率84.6%;mp 145.2~146.1 ℃;1H NMR(400 MHz, DMSO-d 6) δ 10.22 (s, 1H), 7.70 (d, J = 9.3 Hz, 1H), 7.57 – 7.51 (m,2H), 7.35 (t, J = 7.6 Hz, 2H), 7.27 – 7.22 (m, 1H), 7.06 – 6.97 (m, 3H), 6.92(d, J = 8.4 Hz, 2H), 6.75 (d, J = 16.1 Hz, 1H), 2.21 (s, 3H);13C NMR (101 MHz,DMSO-d 6) δ 143.18, 139.10, 137.32, 132.74, 130.01, 129.19, 128.06, 127.79,127.10, 126.79, 112.44, 20.71。
肉桂醛-4-三氟甲基苯腙(18):浅黄色结晶;产率75.9%;mp 163.5~165.1 ℃;1HNMR (400 MHz, DMSO-d 6) δ 10.75 (s, 1H), 7.82 (d, J = 9.2 Hz, 1H), 7.60 – 7.52(m, 4H), 7.37 (t, J = 7.5 Hz, 2H), 7.31 – 7.26 (m, 1H), 7.14 (d, J = 8.5 Hz,2H), 7.05 (dd, J = 16.0, 9.2 Hz, 1H), 6.89 (d, J = 16.0 Hz, 1H)。
肉桂醛-4-溴-2-氟苯腙(19):浅黄色絮状结晶;产率83.6%;mp 172.5~173.9 ℃;1H NMR (400 MHz, DMSO-d 6) δ 10.37 (s, 1H), 8.00 (d, J = 9.3 Hz, 1H), 7.56 (d,J = 7.3 Hz, 2H), 7.44 – 7.25 (m, 6H), 7.01 (dd, J = 16.1, 9.3 Hz, 1H), 6.83(d, J = 16.1 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 149.25 (d, J = 245.4 Hz),143.34, 136.93, 135.11, 133.25 (d, J = 9.09 Hz), 129.22, 128.55, 128.36 (d, J= 3.03 Hz), 127.07, 126.62, 118.64 (d, J = 21.2 Hz), 115.42 (d, J = 4.04 Hz),108.68 (d, J = 9.09 Hz)。
4-氯肉桂醛-4-氟苯腙(20)(新化合物):黄色粉末;产率79.9%;mp 155.0~156.3℃;1H NMR (400 MHz, DMSO-d 6) δ 10.36 (s, 1H), 7.70 (dd, J = 9.3, 1.1 Hz, 1H),7.56 (d, J = 8.6 Hz, 2H), 7.39 (d, J = 8.6 Hz, 2H), 7.09 – 6.97 (m, 5H), 6.77(d, J = 16.0 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 156.42 (d, J = 234.3 Hz),142.03, 142.02, 139.50, 136.22, 132.40, 131.80, 129.17, 128.47, 127.80,116.11 (d, J = 22.2 Hz), 113.37 (d, J = 8.08 Hz)。
4-氯肉桂醛-4-氯苯腙(21)(新化合物):黄色粉末;产率92.3%;mp 159.3~160.2℃;1H NMR (400 MHz, DMSO-d 6) δ 10.49 (s, 1H), 7.72 (dd, J = 9.3, 1.1 Hz, 1H),7.58 (d, J = 8.6 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.27 – 7.22 (m, 2H), 7.06– 6.97 (m, 3H), 6.81 (d, J = 16.0 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 144.26,140.29, 136.12, 132.54, 132.46, 129.40, 129.18, 128.55, 127.62, 122.58,113.85。
4-氯肉桂醛-4-溴苯腙(22)(新化合物):黄色粉末;产率88.1%;mp 171.8~172.5℃;1H NMR (400 MHz, DMSO-d 6) δ 10.50 (s, 1H), 7.72 (dd, J = 9.3, 1.1 Hz, 1H),7.57 (d, J = 8.6 Hz, 2H), 7.42 – 7.33 (m, 4H), 7.06 – 6.93 (m, 3H), 6.80 (d,J = 16.0 Hz, 1H);13C NMR (101 MHz, DMSO-d 6) δ 144.63, 140.39, 136.11, 132.55,132.22, 129.19, 128.56, 127.61, 114.37, 110.16。
二、肉桂醛苯腙类化合物的抗真菌活性
化合物的抗真菌活性采用菌丝线性生长速率法测定。化合物采用5% DMSO(v/v)进行配制,供试化合物在PDA培养基中的最终浓度为100 μg/mL,每组设3个平行,并重复3次,最终结果以平均抑制率表示。阳性对照为嘧菌酯。供试真菌如下:苹果轮纹病原菌(PL);水稻稻瘟病原菌(SD);苹果腐烂病原菌(PF);南瓜枯萎病原菌(NK);苹果炭疽病原菌(PT);玉米弯孢病原菌(YW);烟草赤星病原菌(YC);白菜黑斑病原菌(BH);番茄早疫病原菌(FZ);小麦赤霉病原菌(XC);马铃薯干腐病原菌(MG);西瓜枯萎病原菌(XK);棉花枯萎病原菌(MK)。
结果表明,在100 μg/mL的浓度时,几乎所有的肉桂醛苯腙类化合物对13种供试植物病原真菌都表现出了较高的的抑制率,且与原料肉桂醛相比,本发明涉及的化合物具有更高的抗真菌活性和更宽的抗菌谱。说明本发明涉及的肉桂醛苯腙类化合物具有制备植物抗真菌药物的潜在用途,可作为植物抗菌药物的有效成分或增效成分。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包在本发明范围内。
Claims (7)
1.一种肉桂醛苯腙类化合物,其特征在于:具有如下分子结构特征,其中:R1、R2是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子或三氟甲基;R1、R2的位置为苯环的邻位、间位和对位。
2.如权利要求1所述的一种肉桂醛苯腙类化合物的合成方法,其特征在于:具有以下合成路线,
其中:R1、R2是相同或不同的氢、烷基、烷氧基、苯氧基、卤素原子或三氟甲基;R1、R2的位置为苯环的邻位、间位和对位。
3. 根据权利要求2所述的一种肉桂醛苯腙类化合物的合成方法,其特征在于:具有以下反应条件,取代肉桂醛和取代苯肼盐酸盐的摩尔比为:1.0:1.0~1.0:1.5;优选为:1.0:1.1;反应温度为:0~35 ℃。
4.如权利要求1所述的一种肉桂醛苯腙类化合物的应用,其特征在于:该肉桂醛苯腙类化合物作为在制备植物抗真菌药物中的应用。
5.根据权利要求4所述的一种肉桂醛苯腙类化合物的应用,其特征在于:该肉桂醛苯腙类化合物作为单一有效成分或增效成分与其他药物共同作为植物抗真菌剂使用。
6.根据权利要求4所述的一种肉桂醛苯腙类化合物的应用,其特征在于:
该肉桂醛苯腙类化合物对以下植物病原真菌都有显著的抑制活性:高粱炭疽病原菌、苹果轮纹病原菌、水稻稻瘟病原菌、苹果腐烂病原菌、南瓜枯萎病原菌、苹果炭疽病原菌、玉米弯孢病原菌、烟草赤星病原菌、白菜黑斑病原菌、番茄早疫病原菌、小麦赤霉病原菌、番茄灰霉病原菌、马铃薯干腐病原菌、西瓜枯萎病原菌、棉花枯萎病原菌。
7.含有权利要求1所述的一种肉桂醛苯腙类化合物的药物的应用,其特征在于:该药物对以下植物病具有显著的预防和治疗效果:高粱炭疽病、苹果轮纹病、水稻稻瘟病、苹果腐烂病、南瓜枯萎病、苹果炭疽病、玉米弯孢病、烟草赤星病、白菜黑斑病、番茄早疫病、小麦赤霉病、番茄灰霉病、马铃薯干腐病、西瓜枯萎病、棉花枯萎病、葡萄霜霉病、甜瓜白粉病。
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