CN106905157B - 2,4-二乙酰基间苯三酚酯类化合物的杀菌应用 - Google Patents

2,4-二乙酰基间苯三酚酯类化合物的杀菌应用 Download PDF

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CN106905157B
CN106905157B CN201710015720.9A CN201710015720A CN106905157B CN 106905157 B CN106905157 B CN 106905157B CN 201710015720 A CN201710015720 A CN 201710015720A CN 106905157 B CN106905157 B CN 106905157B
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高锦明
师伟
邓杉
张鞍灵
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Abstract

本发明涉及2,4‑二乙酰基间苯三酚酯类化合物及其杀菌的应用，所涉及的化合物结构式如Ⅰ所示。本发明的2,4‑二乙酰基间苯三酚酯类化合物对水稻稻瘟病、番茄灰霉病、番茄早疫病、苹果腐烂病、苹果炭疽病和马铃薯干腐病六种植物病原菌有很强的抑制作用。

Description

2,4-二乙酰基间苯三酚酯类化合物的杀菌应用
技术领域
本发明涉及一种2,4-二乙酰基间苯三酚(2,4-diacetylphloroglucinol,DAPG)的合成，特别是利用2,4-二乙酰基间苯三酚为原料，经过DCC缩合制备2,4- 二乙酰基间苯三酚酯类化合物与应用，属于生物抗生素2,4-二乙酰基间苯三酚酯基衍生物技术领域。
背景技术
2,4-二乙酰基间苯三酚(2,4-diacetylphloroglucinol,DAPG)，也称2,4-二乙酰基藤黄酚，是一种由生防荧光假单胞杆菌(Pseuodomonas fluorescens)产生的酚类抗生素，该化合物具有广泛的生物活性，如抗植物病原真菌、细菌和对线虫、蠕虫的强烈杀伤作用等，在农业上多用于植物病虫害的生物防治。在赤背蝾螈(redback salamanders)皮肤上的溶杆菌gummosus也能代谢生成2,4-二乙酰基间苯三酚。
发明内容
针对现有技术的不足，本发明的目的是，提供一种2,4-二乙酰基间苯三酚酯类化合物，该化合物是以2,4-二乙酰基间苯三酚为原料加以结构改造而制成，并将得到的2,4-二乙酰基间苯三酚酯类化合物作为一种新型生物抗生素。
本发明的2,4-二乙酰基间苯三酚酯类化合物结构式为：
Figure BDA0001206472490000011
其中，R＝乙基、正丙基、正丁基、异丁基、正戊基、特戊基、正己基、正庚基、甲基丙烯基、丙烯基或环丙甲基。
本发明2,4-二乙酰基间苯三酚酯类化合物的制备方法包括：冰浴条件下将反应量的脂肪酸加入2,4-二乙酰基间苯三酚和4-二甲氨基吡啶的无水二氯甲烷溶液中反应后，加入反应量的二环己基碳二亚胺，冰浴条件下反应后反应物经洗涤、干燥、纯化得2,4-二乙酰基间苯三酚酯类化合物。
本发明还涉及2,4-二乙酰基间苯三酚酯类化合物用于水稻稻瘟病、番茄灰霉病、番茄早疫病、苹果腐烂病、苹果炭疽病和马铃薯干腐病防治的应用。
本发明对2,4-二乙酰基间苯三酚及其酯类化合物进行NMR(核磁共振)分析，生物活性等测试。根据NMR数据，对所制备的2,4-二乙酰基间苯三酚酯类化合物进行结构鉴定，确定化合物的结构。
本发明对2,4-二乙酰基间苯三酚酯类化合物的生物活性测定，利用生长速率抑制法(参见文献:Shi Wei et al.,Bioorganic&Medicinal Chemistry Letters, 2016,26(9):2156-2158.)测定化合物的抗植物病原真菌活性，发现2,4-二乙酰基间苯三酚酯类化合物对水稻稻瘟病、番茄灰霉病、番茄早疫病、苹果腐烂病、苹果炭疽病和马铃薯干腐病六种植物病原菌有很强的抑制作用，且IC50值较低。
具体实施方式
本发明所用的2,4-二乙酰基间苯三酚(1)，其结构通式为：
Figure BDA0001206472490000021
其可采用现有的方法制备或在市场上购买所得，其中一种制备方法是：
称取1.26g(10mmol)间苯三酚于装有搅拌子和冷凝回流的50mL三口瓶中，加入15mL三氟化硼乙醚溶液，置于冰浴中，缓慢滴加2.4mL(25mmol) 乙酸酐，滴加完毕，逐步升温至100℃，反应4h，TLC检测原料点基本消失。反应液冷却至室温，倒入20mL冰水混合液中，搅拌15min，用乙酸乙酯(15 mL)萃取三次。收集有机相，乙酸乙酯层依次用饱和碳酸钠溶液，饱和氯化钠溶液洗涤，无水硫酸钠干燥，减压蒸馏除去溶剂，得白色固体，经硅胶柱(200～300,石油醚：乙酸乙酯＝5:1,V/V)柱层析得到淡黄色固体1.72g，产率82％，熔点：163.2～164.1℃。
本发明的2,4-二乙酰基间苯三酚酯类化合物，其结构通式为：
式中，R＝乙基、正丙基、正丁基、异丁基、正戊基、特戊基、正己基、正庚基、甲基丙烯基、丙烯基或环丙甲基。
其制备方法是：
在冰浴条件下将反应量的脂肪酸加入2,4-二乙酰基间苯三酚和4-二甲氨基吡啶(DMAP)的无水二氯甲烷溶液中反应一定时间后，加入反应量的二环己基碳二亚胺(DCC)，冰浴条件下反应一定时间后反应物经洗涤、干燥、纯化得2,4-二乙酰基间苯三酚酯类化合物。
本发明可采用TLC检测原料点基本消失，以确定反应的终点。
本发明的洗涤、干燥和纯化可采用减压蒸馏除去溶剂，得白色固体，经硅胶柱(200～300,石油醚：乙酸乙酯＝5:1,V/V)柱层析得到淡黄色固体232 mg，产率92％，熔点：111.7～113.1℃。
本发明的洗涤、干燥和纯化还可采用反应液依次用饱和碳酸钠溶液，饱和氯化钠溶液洗涤，无水硫酸镁干燥，减压浓缩，其残余物以石油醚和乙酸乙酯(体积比5:1)的混合溶液为洗脱剂，通过硅胶柱层析分离纯化。
以下是发明人给出的实施例，以对本发明的技术方案作进一步解释。
实施例1：2,4-二乙酰基间苯三酚的制备(1)
1.26g(10mmol)间苯三酚于装有搅拌子和冷凝回流的50mL三口瓶中，加入15mL三氟化硼乙醚溶液，置于冰浴中，缓慢滴加2.4mL(25mmol)乙酸酐滴加完毕，逐步升温至100℃，反应4h，TLC检测原料点基本消失。反应液冷却至室温，倒入20mL冰水混合液中，搅拌15min，用乙酸乙酯(15mL) 萃取三次。收集有机相，乙酸乙酯层依次用饱和碳酸钠溶液，饱和氯化钠溶液洗涤，无水硫酸钠干燥，减压蒸馏除去溶剂，得白色固体，经硅胶柱(200～300, 石油醚：乙酸乙酯＝5:1,V/V)柱层析得到淡黄色固体1.72g，产率82％，熔点： 163.2～164.1℃。
Figure BDA0001206472490000041
分子式：C10H10O5,1H NMR(400MHz,Acetone-d6)δ5.94(s,1arom.H),2.64 (s,6H,2CH3).
13C NMR(100MHz,Acetone-d6)δ204.7,172.1,172.0,104.6,95.6,33.0. ESI-MS:m/z[M+H]+211.05.
实施例2：乙酰2,4-二乙酰基间苯三酚酯化合物制备(2)
于装有搅拌子的50mL梨形瓶中加入210mg(1.0mmol)2,4-二乙酰基间苯三酚和DMAP(0.1mmol)，置于冰浴下，加入10mL无水二氯甲烷，搅拌条件下加入0.15mL(1.5mmol)乙酸，滴加完毕，继续搅拌15min，然后加入412mg DCC(2mmol)。反应4h，TLC检测原料点基本消失。减压蒸馏除去溶剂，得白色固体，经硅胶柱(200～300,石油醚：乙酸乙酯＝5:1,V/V)柱层析得到淡黄色固体232mg，产率92％，熔点：111.7～113.1℃。
Figure BDA0001206472490000042
分子式：C12H12O6，1H NMR(500MHz,CDCl3)δ15.59(s,1H,OH),14.46(s, 1H,OH),6.20(s,1arom.H),2.75(s,3H,CH3),2.59(s,3H,CH3),2.38(s,3H, CH3).
13C NMR(125MHz,CDCl3)δ205.3,202.0,170.8,170.5,167.7,157.3,108.6,106.9,104.6,33.5,31.8,21.8.,ESI-MS:m/z[M+H]+252.22.
实施例3：丙酰2,4-二乙酰基间苯三酚酯化合物制备(3)
合成方法同实施例2，所用酸是丙酸；得白色固体，熔点：96.9–98.3℃，产率90％。
分子式：C13H14O6,.1H NMR(500MHz,CDCl3)δ15.59(s,1H,OH),14.44(s, 1H,OH),6.18(s,1arom.H),2.74(s,3H,CH3),2.65(q,J＝7.5Hz,2H,CH2 CH3), 2.56(s,3H,CH3),1.28(t,J＝7.5Hz,3H,CH2 CH3 ).
13C NMR(125MHz,CDCl3)δ205.3,202.1,171.4,170.8,170.5,157.6,108.55,106.94,104.44,33.52,31.83,28.44,8.85.ESI-MS:m/z[M+H]+266.24.
实施例4：正丁酰2,4-二乙酰基间苯三酚酯化合物制备(4)
合成方法同实施例2，所用酸是正丁酸；得白色固体，熔点：76.7–78.6℃，产率91％。
Figure BDA0001206472490000052
分子式：C14H16O6,1H NMR(500MHz,CDCl3)δ15.59(s,1H,OH),14.45(s, 1H,OH),6.17(s,1arom.H),2.74(s,3H,CH3),2.60(t,J＝7.4Hz,2H,COCH2), 2.57(s,3H,CH3),1.80(dd,J＝14.8,7.4Hz,2H,CH2 CH3),1.05(t,J＝7.4Hz,3H, CH2 CH3 ).
13C NMR(125MHz,CDCl3)δ205.3,202.1,170.7,170.6,170.5,157.6,108.6,107.0,104.5,36.8,33.5,31.9,18.2,13.7.ESI-MS:m/z[M+H]+280.27.
实施例5：异丁酰2,4-二乙酰基间苯三酚酯化合物制备(5)
合成方法同实施例2，所用酸是异丁酸；得白色固体，熔点：72.5–73.9℃，产率80％。
Figure BDA0001206472490000061
分子式：C14H16O6,1H NMR(500MHz,CDCl3)δ15.61(s,1H,OH),14.46(s, 1H,OH),6.12(s,1arom.H),2.81(dt,1H,CH(Me)2),2.73(s,3H,CH3),2.54(s, 3H,CH3),1.33(s,3H,CH(Me)2),1.31(s,3H,CH(Me)2).
13C NMR(125MHz,CDCl3)δ205.3,202.1,174.4,170.8,170.6,158.1,108.6,107.2,104.3,34.9,33.6,31.9,18.8(2CH3).ESI-MS:m/z[M+H]+280.24.
实施例6：正戊酰2,4-二乙酰基间苯三酚酯化合物制备(6)
合成方法同实施例2，所用酸是正戊酸；得黄色蜡状物，熔点：57.2– 58.1℃，产率88％。
Figure BDA0001206472490000062
分子式：C15H18O6,1H NMR(500MHz,CDCl3)δ15.60(s,1H,OH),14.46(s, 1H,OH),6.17(s,1arom.H),2.75(s,3H,CH3),2.62(t,J＝7.5Hz,2H,COCH2 ), 2.57(s,3H,CH3),1.75(dt,J＝15.2,7.5Hz,2H,CH2),1.45(dd,J＝15.0,7.5Hz, 2H,CH2),0.97(t,J＝7.4Hz,3H,CH2 CH3 ).
13C NMR(125MHz,CDCl3)δ205.3,202.1,170.8,170.7,170.6,157.6,108.6,107.0,104.5,34.7,33.8,31.9,26.7,22.3,13.8.ESI-MS:m/z[M+H]+294.30.
实施例7：特戊酰2,4-二乙酰基间苯三酚酯化合物制备(7)
合成方法同实施例2，所用酸是特戊酸；得白色固体，熔点：93.6–94.7℃，产率78％。
分子式：C15H18O6,1H NMR(500MHz,CDCl3)δ15.61(s,1H,OH),14.44(s, 1H,OH),6.92(s,1arom.H),2.44(s,6H,2CH3),1.30(s,9H,3CH3).
13C NMR(125MHz,CDCl3)δ205.3,202.2,175.8,175.7,170.7,158.9,109.0,107.9,104.0,39.3,31.4(2CH3),27.1(3CH3).ESI-MS:m/z[M+H]+294.29.
实施例8：己酰2,4-二乙酰基间苯三酚酯化合物制备(8)
合成方法同实施例2，所用酸是己酸；得黄色膏状物，产率86％。
分子式：C16H20O6,1H NMR(500MHz,CDCl3)δ15.60(s,1H,OH),14.46(s, 1H,OH),6.18(s,1arom.H),2.75(s,3H,CH3),2.61(t,J＝7.5Hz,2H,COCH2 ), 2.57(s,3H,CH3),1.79-1.74(m,2H,CH2),1.39-1.36(m,4H,2CH2),0.94-0.92(m, 3H,CH2 CH3 ).
13C NMR(125MHz,CDCl3)δ205.3,202.1,170.8,170.8,157.6,148.6,108.6,107.0,104.5,34.9,33.6,31.9,31.3,24.3,22.4,14.0.ESI-MS:m/z[M+H]+308.32.
实施例9：庚酰2,4-二乙酰基间苯三酚酯化合物制备(9)
合成方法同实施例2，所用酸是庚酸；得黄色膏状物，产率85％。
Figure BDA0001206472490000073
分子式：C17H22O6,1H NMR(500MHz,CDCl3)δ15.60(s,1H,OH),14.46(s, 1H,OH),6.17(s,1arom.H),2.74(s,3H,CH3),2.61(t,J＝7.5Hz,2H,CH2),2.57 (s,3H,CH3),1.75(dt,J＝15.2,7.5Hz,2H,CH2),1.32(dd,J＝8.6,5.5Hz,6H, 3CH2),0.90(d,J＝3.4Hz,3H,CH2 CH3 ).
13C NMR(125MHz,CDCl3)δ205.2,202.1,170.7,170.5,157.6,148.6,108.5,107.0,104.4,35.0,33.5,31.9,31.5,28.8,25.0,22.6,14.1.ESI-MS:m/z[M+H]+ 322.35.
实施例10：甲基丙烯酰2,4-二乙酰基间苯三酚酯化合物制备(10)
合成方法同实施例2；所用酸是甲基丙烯酸；得白色固体，熔点：59.8– 61.7℃，产率83％。
Figure BDA0001206472490000081
分子式：C14H14O6,1H NMR(500MHz,CDCl3)δ15.60(s,1H,OH),14.46(s, 1H,OH),6.40-6.37(m,1H,C＝CH2 ),6.15(s,1arom.H),5.92-5.89(m,1H, C＝CH2 ),2.76(s,3H,CH3),2.53(s,3H,CH3),2.08(s,3H,CH3).
13C NMR(125MHz,CDCl3)δ205.3,202.1,170.8,170.5,164.5,158.0,135.4,129.5,108.7,107.3,104.6,33.6,31.8,18.5.ESI-MS:m/z[M+H]+278.25.
实施例11：丙烯酰2,4-二乙酰基间苯三酚酯化合物制备(11)
合成方法同实施例2，所用酸是丙烯酸；得白色固体，89.1–90.8℃，产率 85％。
分子式：C13H12O6,1H NMR(500MHz,CDCl3)δ15.61(s,1H,OH),14.48(s, 1H,OH),6.69(dd,J＝17.3,0.8Hz,1H,CH＝CH2 ),6.36(dd,J＝17.3,10.5Hz,1H, CH＝CH2 ),6.22(s,1arom.H),6.16(dd,J＝10.5,0.8Hz,1H,CH＝CH2),2.76(s, 3H,CH3),2.55(s,3H,CH3).
13C NMR(125MHz,CDCl3)δ205.3,202.1,170.8,170.6,163.1,157.3,135.2,127.1,108.7,107.1,104.6,33.6,31.9.ESI-MS:m/z[M+H]+264.23.
实施例12：环丙甲酰2,4-二乙酰基间苯三酚酯化合物制备(12)
合成方法同实施例2，所用酸是环丙甲酸；得白色固体，83.1–84.7℃，产率75％。
Figure BDA0001206472490000091
分子式：C14H14O6,1H NMR(400MHz,CDCl3)δ6.18(s,1arom.H),2.74(s, 3H,CH3),2.61(s,3H,CH3),1.89(tt,J＝7.9,4.6Hz,1H,CH),1.23–1.18(m,2H, CH2),1.14–1.08(m,2H,CH2).
13C NMR(100MHz,CDCl3)δ205.0,202.1,172.0,170.6,170.3,157.5,108.4,107.0,104.40,33.3,31.7,13.2,9.9(2CH2).ESI-MS:m/z[M+H]+278.26.
实施例13：抑菌活性的测定
生长速率抑制法对所合成的化合物进行抑菌活性与IC50(μg/mL)的测定。测试的病原菌是从田间常见病害中分离出的六种病原真菌，分别是苹果腐烂病菌、苹果炭疽病菌、水稻稻瘟病菌、番茄灰霉病菌、番茄早疫病菌和马铃薯干腐病菌
实施方法是：在无菌条件下，将配制好的样品丙酮溶液掺入融化的PDA培养基，使培养基中该化合物的浓度达到100μg/mL，冷凝后接种上述病原菌，每个处理重复3次，28℃恒温培养，每隔24h测定一次病原菌菌斑直径，直到空白对照的菌斑长满平板为止。阳性对照为噻菌灵。初筛后对抑制率达到80％以上的化合物进行IC50的测试，将化合物依次配成50、25、12.5、6.25、3.125、 1.5和0.75μg/mL系列的带毒培养基，阳性对照为噻菌灵。最后根据不同浓度的抑制率计算其IC50值。结果见表1及表2。
表1.化合物1-12对六种病原菌的抑制率(100μg/mL)
Figure BDA0001206472490000101
表2.化合物1-12对植物病原菌IC50值(μg/mL)
Figure BDA0001206472490000102
综上所述，本发明的方法制备的化合物2,4-二乙酰基间苯三酚酯化合物对供试植物病原菌有很强的抑制活性，能够用于制备植物病原真菌抗生素的药物的开发。

Claims (1)

1.2,4-二乙酰基间苯三酚酯类化合物用于制备防治苹果腐烂病和苹果炭疽病杀菌剂的应用，所述2,4-二乙酰基间苯三酚酯类化合物的结构式为：
Figure FDA0002234505680000011
其中，R＝甲基、乙基或环丙基。
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