CN110746363B - 一种含酰肼的喹唑啉酮类衍生物、制备方法及应用 - Google Patents
一种含酰肼的喹唑啉酮类衍生物、制备方法及应用 Download PDFInfo
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Abstract
本发明属于农药领域,公开了一种含酰肼的喹唑啉酮类衍生物、制备方法及应用,该类衍生物的结构如式(I)所示:
Description
技术领域
本发明涉及农药领域,具体来说涉及一种含酰肼的喹唑啉酮类衍生物,同时涉及该类衍生物的制备方法,还涉及该类衍生物在防治植物真菌病害方面的应用。
背景技术
植物病原真菌具有侵染范围广、发病迅速和防治困难的特点,给农业生产造成了巨大的经济损失。当前,化学防治依旧是防止植物病原真菌在农业上流行爆发的主要办法。但现有药剂的持续性使用以及作用靶点相对单一使植物病原真菌的抗性问题逐渐显现。与此同时,现有药剂中存在的对非靶标生物毒性较大和对环境污染严重的问题也使其在生产应用中受到了极大的限制。因此,研制具有高效、对靶标生物专一性好和环境友好型的新型杀菌剂对保障农业增产稳产和粮食安全具有重要的作用和意义。
喹唑啉酮作为一种重要的天然活性亚结构片段被广泛应用在药物的创制工作中。当前,药物创制工作者已发现喹唑啉酮衍生物具有抑细菌、抗炎、抑真菌、抗肿瘤、抗痉挛、杀虫、抗痢疾、抗结核和抗病毒等生物活性。值得注意的是,喹唑啉酮衍生物除具有良好的医用活性外,其在农药创制领域具有的潜在应用价值亦被发现和开发。近年来的研究表明,在喹唑啉酮结构的3位引入希夫碱(Molecules 2007,12:2621-2642.)、1,4-戊二烯-3-酮(J.Agric.Food Chem.2014,62:8928-8934.)、查儿酮(Bioorg.Med.Chem.Lett.2016,26:168-173.)和阿魏酸(Pest Manag.Sci.2017,73:2079-2089.)等活性结构,发现所得化合物对植物病毒具有良好的抑制效果。与此同时,鲍小平课题组在喹唑啉酮结构的3位引入1,2,4-三唑(Chem.Pap.2016,70:983-993.)、1,2,4-三唑并[1,5-a]嘧啶(Mol.Divers.2018,22:1-10.)和1,2,4-三唑并[3,4-b][1,3,4]噻二唑(J.Saudi.Chem.Soc.2018,22:101-109.)等杂环结构后,亦发现所得化合物对植物病原细菌具有良好的抑制作用。
另一方面,酰肼结构广泛存在于具有抑细菌、抗肿瘤、抗炎、抑真菌、抗痢疾、抗病毒、杀虫和除草等生物活性的活性化合物中。近年来,虫酰肼、环虫酰肼和甲氧虫酰肼等诸多酰肼类化合物被相继开发为商品农药。此外,药物创制工作者将酰肼结构引入到吡唑(Chin.J.Chem.2012,30:919-923.)和1,2,3-三唑(Eur.J.Med.Chem.2017,126:171-182.)的结构中,发现所得吡唑酰肼和1,2,3-三唑酰肼类化合物对植物病原真菌具有良好的体外抑制效果。
综上,喹唑啉酮类化合物和酰肼类化合物具有广谱的生物活性,在新型农药先导化合物的发现过程中发挥着重要作用。鉴于此,本发明将喹唑啉酮与酰肼结构进行有机结合,设计了一种含酰肼的喹唑啉酮类衍生物,以创制具有高效广谱活性的抑制植物病原真菌的新化合物。
发明内容
本发明的目的在于,提供一种含酰肼的喹唑啉酮类衍生物。
本发明的另一目的在于提供含一种含酰肼的喹唑啉酮类衍生物的制备方法。
本发明的第3个目的在于提供上述衍生物的用途。
本发明的第一方面提供了一种具有通式(I)所示结构的一种含酰肼的喹唑啉酮类衍生物,
在式(I)中,所述各个基团具有如下所述的定义:
R1选自下列1-4个基团:氢原子、卤素原子、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、硝基;
R2选自下列1-5个基团:卤素原子、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、硝基;
以上基团的定义中提及的卤素选自F、Cl、Br、I,卤代是指被1-6个卤素原子取代。
在式(I)中,所述各个基团具有如下所述的优选定义:
R1选自下列1-2个基团:氢原子、卤素原子、C1-C6烷基、C1-C6烷氧基;
R2选自下列1-2个基团:卤素原子;
以上基团的定义中提及的卤素选自F、Cl、Br、I。
在式(I)中,所述各个基团具有如下所述的进一步优选定义:
R1选自下列1-2个基团:氢原子、F、Cl、Br、甲基、甲氧基;
R2选自下列1-2个基团:F、Cl、Br。
在式(I)中,所述各个基团具有如下所述的更进一步优选定义:
R1选自氢原子、6-Cl、8-甲基、6,7-二甲氧基;
R2选自2-F、2-Cl、3-Cl、4-F、4-Cl、4-Br、2,4-(Cl)2。
在式(I)中,所述各个基团具有如表1中所述的特别优选定义:
表1 化合物I1-I21的名称及结构
本发明的第二个方面提供了如通式(A)所示的一种含酰肼的喹唑啉酮类衍生物(I)的制备方法,在O-苯并三氮唑-N,N,N′,N′-四甲基脲鎓四氟硼酸盐(TBTU)和三乙胺(Et3N)存在下,含取代基的2-(4-氧代喹唑啉-3(4H)-基)乙酸(II)与取代苯肼(III)反应生成一种含酰肼的喹唑啉酮类衍生物(I):
其中在上述各结构式中:
R1、R2均具有如前所述的相应基团的定义。
本发明的第三个方面提供了式(I)所示的一种含酰肼的喹唑啉酮类衍生物的应用,该类衍生物对植物病原真菌具有显著的抑制活性,可应用于抑制植物病原真菌、防治植物真菌病害。
本发明的一种含酰肼的喹唑啉酮类衍生物适合于抑制水稻纹枯病菌和小麦赤霉病菌,适合用于防治水稻纹枯病和小麦赤霉病。
有益效果:
本发明与现有技术相比,具有明显的有益效果,从以上技术方案可知:本发明将属于优良活性基团的酰肼结构引入喹唑啉酮的结构中,设计合成了一系列含酰肼的喹唑啉酮类衍生物(I),该类化合物的结构具有新颖性;将该类化合物应用于抗植物病原真菌方面的研究,发现此类化合物在抗植物病原真菌方面拥有突出的抑制活性,体现出本技术方案的显著进步;其中部分化合物对水稻纹枯病菌和小麦赤霉病菌的抑制活性超过对照药剂恶霉灵或多菌灵,具有明显的应用价值。
具体实施方式
本发明的实质性特点可从下述实施例得以体现,但它不应视为是对本发明的任何限制。
制备实施例
实施例一:2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼(I1)的合成
将2-(4-氧代喹唑啉-3(4H)-基)乙酸(II-1)(2.50mmol)、4-氟苯肼(III-1)(2.50mmol)、三乙胺(7.50mmol)、O-苯并三氮唑-N,N,N′,N′-四甲基脲鎓四氟硼酸盐(TBTU)(2.50mmol)和乙腈(30mL)加入到50mL三口瓶中,室温下搅拌4小时后,停止反应。将反应液过滤,滤饼先后用乙醇、二氯甲烷淋洗,干燥,即得化合物2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼(I1)。
化合物I2-I21按照实施例一的方法依次合成,所合成的含酰肼的喹唑啉酮类衍生物(I1-I21)的结构均采用红外光谱(IR)、核磁共振谱(NMR)和高分辨质谱(HRMS)进行了确证,目标化合物的理化参数和光谱数据如下所示:
2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼(I1):白色固体,熔点276-278℃,产率80%;IR(KBr,cm-1):3221,3123,1699,1667,1613,1508,1477,1370,1328,1222,1173,821,776;1H NMR(400MHz,DMSO-d6)δA:10.15(d,J=2.4Hz,1H,CONH),8.37(s,1H,Qu-2-H),8.20-8.13(m,1H,Qu-5-H),7.89-7.82(m,2H,Qu-7,8-2H),7.71(d,J=8.1Hz,1H,Ar-NH),7.57(t,J=7.6Hz,1H,Qu-6-H),7.00(t,J=8.9Hz,2H,Ar-3,5-2H),6.81-6.74(m,2H,Ar-2,6-2H),4.77(s,2H,CH2);B:9.58(s,1H,OH),8.34(s,1H,Qu-2-H),8.20-8.13(m,1H,Qu-5-H),8.08(s,1H,Ar-NH),7.89-7.82(m,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.57(t,J=7.6Hz,1H,Qu-6-H),7.12(t,J=8.8Hz,2H,Ar-3,5-2H),6.95-6.89(m,2H,Ar-2,6-2H),4.88(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.38,160.76,148.96,148.55,145.95,134.96,127.70,127.59,126.46,121.96,115.72,115.50,113.90,113.83,47.67;B:171.61,160.72,149.27,148.59,145.40,134.87,127.67,127.51,126.46,121.93,116.11,115.88,114.61,114.54,46.82;HRMS calcd for C16H14FN4O2[M+H]+313.1095,found 313.1089.
2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼(I2):白色固体,熔点281-283℃,产率55%;IR(KBr,cm-1):3229,3095,1701,1668,1615,1491,1477,1371,1328,1227,1173,775;1H NMR(400MHz,DMSO-d6)δA:10.18(d,J=2.0Hz,1H,CONH),8.37(s,1H,Qu-2-H),8.20-8.14(m,1H,Qu-5-H),8.07(d,J=1.9Hz,1H,Ar-NH),7.86(t,J=7.8Hz,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.58(t,J=8.3Hz,1H,Qu-6-H),7.19(d,J=8.8Hz,2H,Ar-3,5-2H),6.78(t,J=5.9Hz,2H,Ar-2,6-2H),4.78(s,2H,CH2);B:9.61(s,1H,OH),8.33(s,1H,Qu-2-H),8.28(s,1H,Ar-NH),8.20-8.14(m,1H,Qu-5-H),7.86(t,J=7.8Hz,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.58(t,J=8.3Hz,1H,Qu-6-H),7.31(d,J=8.3Hz,2H,Ar-3,5-2H),6.91(t,J=8.8Hz,2H,Ar-2,6-2H),4.85(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.41,160.76,148.93,148.55,148.41,134.97,128.94,127.71,127.60,126.46,122.38,121.96,114.15,47.67;B:171.63,160.70,149.23,148.57,147.85,134.89,129.32,127.67,127.52,126.46,123.61,121.92,114.74,46.75;HRMS calcd forC16H14ClN4O2[M+H]+329.0800,found 329.0794.
2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼(I3):白色固体,熔点275-277℃,产率51%;IR(KBr,cm-1):3227,3095,1701,1668,1613,1488,1477,1371,1227,1173,774;1H NMR(400MHz,DMSO-d6)δA:10.18(d,J=1.9Hz,1H,CONH),8.37(s,1H,Qu-2-H),8.19-8.14(m,1H,Qu-5-H),8.08(d,J=1.8Hz,1H,Ar-NH),7.85(t,J=7.6Hz,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.57(t,J=7.1Hz,1H,Qu-6-H),7.30(d,J=8.8Hz,2H,Ar-3,5-2H),6.73(d,J=8.8Hz,2H,Ar-2,6-2H),4.78(s,2H,CH2);B:9.61(s,1H,OH),8.32(s,1H,Qu-2-H),8.29(s,1H,Ar-NH),8.19-8.14(m,1H,Qu-5-H),7.85(t,J=7.6Hz,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.57(t,J=7.1Hz,1H,Qu-6-H),7.43(d,J=8.8Hz,2H,Ar-3,5-2H),6.86(d,J=8.8Hz,2H,Ar-2,6-2H),4.85(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.41,160.76,148.92,148.81,148.55,134.96,131.78,127.71,127.60,126.46,121.96,114.68,109.91,47.68;B:171.64,160.71,149.22,148.57,148.25,134.88,132.16,127.68,127.52,126.46,121.92,115.21,111.19,46.74;HRMS calcd forC16H14BrN4O2[M+H]+373.0295,found 373.0291.
2-(4-氧代喹唑啉-3(4H)-基)-N’-(2-氟苯基)乙酰肼(I4):白色固体,熔点270-272℃,产率57%;IR(KBr,cm-1):3239,1698,1664,1626,1613,1504,1488,1477,1383,1329,1251,1174,739;1H NMR(400MHz,DMSO-d6)δA:10.20(s,1H,CONH),8.38(s,1H,Qu-2-H),8.17(t,J=8.8Hz,1H,Qu-5-H),7.85(dd,J=10.5,4.8Hz,2H,Ar-NH,Qu-7-H),7.71(d,J=8.0Hz,1H,Qu-8-H),7.57(t,J=7.5Hz,1H,Qu-6-H),7.20-6.89(m,3H,Ar-3,5,6-3H),6.73(q,J=9.4Hz,1H,Ar-4-H),4.80(s,2H,CH2);B:9.59(s,1H,OH),8.32(s,1H,Qu-2-H),8.22(s,1H,Ar-NH),8.17(t,J=8.8Hz,1H,Qu-5-H),7.85(dd,J=10.5,4.8Hz,1H,Qu-7-H),7.71(d,J=8.0Hz,1H,Qu-8-H),7.57(t,J=7.5Hz,1H,Qu-6-H),7.20-6.89(m,3H,Ar-3,5,6-3H),6.86(q,J=10.2Hz,1H,Ar-4-H),4.88(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.45,160.75,148.95,148.54,136.98,136.87,134.97,127.71,127.61,125.34,121.95,119.30,115.38,115.20,114.17,47.58;B:171.59,160.69,149.35,149.22,136.98,136.87,134.89,127.67,127.52,124.98,121.93,119.23,115.62,115.44,114.14,46.80;HRMS calcd for C16H14FN4O2[M+H]+313.1095,found 313.1091.
2-(4-氧代喹唑啉-3(4H)-基)-N’-(3-氯苯基)乙酰肼(I5):白色固体,熔点278-280℃,产率79%;IR(KBr,cm-1):3275,3036,1682,1661,1612,1593,1475,1370,1323,1219,1174,975,774;1H NMR(400MHz,DMSO-d6)δA:10.21(s,1H,CONH),8.39(s,1H,Qu-2-H),8.20-8.13(m,2H,Qu-5-H,Ar-NH),7.86(t,J=7.6Hz,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.58(t,J=7.5Hz,1H,Qu-6-H),7.16(t,J=8.0Hz,1H,Ar-5-H),6.80(s,1H,Ar-2-H),6.72(t,J=6.9Hz,2H,Ar-4,6-2H),4.79(s,2H,CH2);B:9.64(s,1H,OH),8.39(s,1H,Qu-2-H),8.35(s,1H,Ar-NH),8.20-8.13(m,1H,Qu-5-H),7.86(t,J=7.6Hz,1H,Qu-7-H),7.71(d,J=8.1Hz,1H,Qu-8-H),7.58(t,J=7.5Hz,1H,Qu-6-H),7.28(t,J=8.0Hz,1H,Ar-5-H),6.92(s,1H,Ar-2-H),6.86(t,J=9.2Hz,2H,Ar-4,6-2H),4.86(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.50,160.78,151.02,148.92,148.56,134.95,134.06,130.80,127.71,127.59,126.44,121.97,118.53,111.97,111.35,47.79;B:171.64,160.73,150.52,149.23,148.56,134.88,134.28,131.19,127.67,127.51,126.44,121.92,119.74,112.65,111.91,46.75;HRMS calcd for C16H14ClN4O2[M+H]+329.0800,found 329.0797.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氯苯基)乙酰肼(I6):白色固体,熔点269-271℃,产率61%;IR(KBr,cm-1):3271,1683,1661,1613,1493,1475,1368,1326,1176,978,776,751,698,534;1H NMR(400MHz,DMSO-d6)δA:10.30(s,1H,CONH),8.38(s,1H,Qu-2-H),8.17(dt,J=12.0,6.0Hz,1H,Qu-5-H),7.89-7.82(m,1H,Qu-7-H),7.71(dd,J=7.9,3.9Hz,1H,Qu-8-H),7.62(s,1H,Ar-NH),7.60-7.54(m,1H,Qu-6-H),7.28(dd,J=7.9,1.1Hz,1H,Ar-3-H),7.19(t,J=7.7Hz,1H,Ar-5-H),6.94(d,J=7.4Hz,1H,Ar-4-H),6.76(td,J=7.8,1.3Hz,1H,Ar-6-H),4.82(s,2H,CH2);B:9.63(s,1H,OH),8.29(s,1H,Qu-2-H),8.17(dt,J=12.0,6.0Hz,1H,Qu-5-H),8.08(s,1H,Ar-NH),7.89-7.82(m,1H,Qu-7-H),7.71(dd,J=7.9,3.9Hz,1H,Qu-8-H),7.60-7.54(m,1H,Qu-6-H),7.37(d,J=8.0Hz,1H,Ar-3-H),7.35-7.30(m,1H,Ar-5-H),7.08(d,J=7.2Hz,1H,Ar-4-H),6.86(t,J=7.8Hz,1H,Ar-6-H),4.86(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.40,160.77,148.93,148.54,144.79,134.98,129.63,128.20,127.72,127.62,126.48,121.95,120.06,117.57,113.55,47.58;B:171.55,160.69,149.16,148.54,144.37,134.89,129.86,128.58,127.67,127.52,126.48,121.95,120.93,117.87,113.92,46.78;HRMS calcd for C16H14ClN4O2[M+H]+329.0800,found 329.0795.
2-(4-氧代喹唑啉-3(4H)-基)-N’-(2,4-二氯苯基)乙酰肼(I7):白色固体,熔点280-282℃,产率81%;IR(KBr,cm-1):3261,3067,1665,1613,1492,1475,1368,1327,1176,775;1H NMR(400MHz,DMSO-d6)δA:10.35(s,1H,CONH),8.38(s,1H,Qu-2-H),8.16(dd,J=13.1,8.2Hz,1H,Qu-5-H),7.86(d,J=11.4Hz,2H,Ar-NH,Qu-7-H),7.76-7.67(m,1H,Qu-8-H),7.57(t,J=7.4Hz,1H,Qu-6-H),7.41(d,J=2.0Hz,1H,Ar-3-H),7.25(dd,J=8.8,1.9Hz,1H,Ar-5-H),6.93(d,J=8.8Hz,1H,Ar-6-H),4.81(s,2H,CH2);B:9.68(s,1H,OH),8.29(s,1H,Qu-2-H),8.26(s,1H,Ar-NH),8.16(dd,J=13.1,8.2Hz,1H,Qu-5-H),7.86(d,J=11.4Hz,1H,Qu-7-H),7.76-7.67(m,1H,Qu-8-H),7.57(t,J=7.4Hz,1H,Qu-6-H),7.51(d,J=1.9Hz,1H,Ar-5-H),7.38(s,1H,Ar-3-H),7.07(d,J=8.8Hz,1H,Ar-6-H),4.84(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.47,160.79,148.88,148.54,144.05,134.99,128.92,128.11,127.72,127.62,126.48,122.57,121.94,118.05,114.58,47.63;B:171.52,160.69,149.11,148.54,143.58,134.88,129.12,128.52,127.66,127.52,126.48,123.58,121.94,118.45,115.02,46.78;HRMS calcd for C16H13Cl2N4O2[M+H]+363.0410,found 363.0401.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼(I8):白色固体,熔点277-279℃,产率63%;IR(KBr,cm-1):3281,3015,2835,1674,1610,1503,1372,1276,1254,1225,867;1H NMR(400MHz,DMSO-d6)δA:10.13(d,J=2.3Hz,1H,CONH),8.25(s,1H,Qu-2-H),7.81(d,J=2.1Hz,1H,Ar-NH),7.45(s,1H,Qu-5-H),7.16(s,1H,Qu-8-H),7.00(t,J=8.9Hz,2H,Ar-3,5-2H),6.81-6.74(m,2H,Ar-2,6-2H),4.75(s,2H,CH2),3.91(s,3H,CH3),3.88(s,3H,CH3);B:9.53(s,1H,OH),8.22(s,1H,Qu-2-H),8.06(s,1H,Ar-NH),7.45(s,1H,Qu-5-H),7.16(s,1H,Qu-8-H),7.12(t,J=8.9Hz,2H,Ar-3,5-2H),6.95-6.89(m,2H,Ar-2,6-2H),4.85(s,2H,CH2),3.91(s,3H,CH3),3.88(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.52,160.05,155.01,149.22,147.50,145.98,145.97,144.73,115.71,115.49,115.01,113.93,113.86,108.39,105.43,56.44,56.22,47.54;B:171.75,157.52,155.20,149.15,147.79,145.44,145.42,144.73,116.08,115.85,115.03,114.66,114.58,108.34,105.48,56.44,56.19,46.72;HRMS calcd for C18H18FN4O4[M+H]+373.1307,found 373.1301.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼(I9):白色固体,熔点282-284℃,产率52%;IR(KBr,cm-1):3278,3025,1676,1609,1503,1462,1399,1369,1279,1223,862;1H NMR(400MHz,DMSO-d6)δA:10.16(s,1H,CONH),8.25(s,1H,Qu-2-H),8.03(s,1H,Ar-NH),7.46(s,1H,Qu-5-H),7.19(d,J=8.7Hz,2H,Ar-3,5-2H),7.17(s,1H,Qu-8-H),6.78(d,J=8.7Hz,2H,Ar-2,6-2H),4.75(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);B:9.57(s,1H,OH),8.26(s,1H,Qu-2-H),8.21(s,1H,Ar-NH),7.45(s,1H,Qu-5-H),7.31(d,J=8.7Hz,2H,Ar-3,5-2H),7.17(s,1H,Qu-8-H),6.91(d,J=8.7Hz,2H,Ar-2,6-2H),4.83(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.55,160.04,155.01,149.23,148.43,147.48,144.73,128.94,122.39,115.00,114.18,108.40,105.43,56.44,56.23,47.55;B:171.77,160.04,154.95,149.16,147.88,147.75,144.73,129.29,123.62,114.77,114.18,108.35,105.48,56.44,56.19,46.66;HRMS calcdfor C18H18ClN4O4[M+H]+389.1011,found 389.1002.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼(I10):白色固体,熔点280-282℃,产率64%;IR(KBr,cm-1):3275,3023,1677,1609,1503,1488,1463,1399,1130,1017,862;1H NMR(400MHz,DMSO-d6)δA:10.15(s,1H,CONH),8.25(s,1H,Qu-2-H),8.05(s,1H,Ar-NH),7.46(s,1H,Qu-5-H),7.30(d,J=8.7Hz,2H,Ar-3,5-2H),7.16(s,1H,Qu-8-H),6.73(d,J=8.8Hz,2H,Ar-2,6-2H),4.75(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);B:9.57(s,1H,OH),8.27(s,1H,Qu-2-H),8.20(s,1H,Ar-NH),7.45(s,1H,Qu-5-H),7.42(d,J=8.7Hz,2H,Ar-3,5-2H),7.16(s,1H,Qu-8-H),6.86(d,J=8.8Hz,2H,Qu-2,6-2H),4.82(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.54,160.04,155.02,149.23,148.84,147.47,144.73,131.78,115.00,114.69,109.90,108.40,105.48,56.45,56.23,47.55;B:171.77,160.04,154.95,149.16,148.27,147.74,144.73,132.13,115.23,114.69,111.17,108.35,105.43,56.45,56.19,46.65;HRMS calcdfor C18H18BrN4O4[M+H]+433.0506,found 433.0347.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氟苯基)乙酰肼(I11):白色固体,熔点274-276℃,产率66%;IR(KBr,cm-1):3324,3262,1673,1606,1502,1399,1379,1275,1251,1228,1186,1030,739;1H NMR(400MHz,DMSO-d6)δA:10.18(s,1H,CONH),8.25(s,1H,Qu-2-H),7.81(s,1H,Ar-NH),7.46(s,1H,Qu-5-H),7.20-6.89(m,4H,Qu-8-H,Ar-3,5,6-3H),6.73(dd,J=12.2,6.7Hz,1H,Ar-4-H),4.77(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);B:9.53(s,1H,OH),8.19(s,2H,Qu-2-H,Ar-NH),7.45(s,1H,Qu-5-H),7.20-6.89(m,4H,Qu-8-H,Ar-3,5,6-3H),6.86(dd,J=12.0,6.0Hz,1H,Ar-4-H),4.85(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.59,160.04,155.01,149.23,147.49,144.73,137.02,136.92,125.00,119.31,119.24,115.00,114.22,108.40,105.44,56.44,56.22,47.45;B:171.74,160.04,151.76,149.38,147.73,144.73,136.55,136.44,125.32,120.38,120.32,115.19,114.68,108.34,105.50,56.44,56.19,46.70;HRMS calcd for C18H18FN4O4[M+H]+373.1307,found 373.1299.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(3-氯苯基)乙酰肼(I12):白色固体,熔点274-276℃,产率68%;IR(KBr,cm-1):3315,3011,1667,1614,1599,1474,1381,1272,1222,1128,1020,859;1H NMR(400MHz,DMSO-d6)δA:10.19(s,1H,CONH),8.27(s,1H,Qu-2-H),8.16(s,1H,Ar-NH),7.46(s,1H,Qu-5-H),7.20-7.13(m,2H,Ar-5-H,Qu-8-H),6.80(s,1H,Ar-2-H),6.73(dd,J=7.5,4.1Hz,2H,Ar-4,6-2H),4.77(s,2H,CH2),3.92(s,3H,CH3),3.88(s,3H,CH3);B:9.60(s,1H,OH),8.38(s,1H,Qu-2-H),8.23(s,1H,Ar-NH),7.46(s,1H,Qu-5-H),7.28(t,J=8.0Hz,1H,Ar-5-H),7.20-7.13(m,1H,Qu-8-H),6.92(s,1H,Ar-2-H),6.87(t,J=7.6Hz,2H,Ar-4,6-2H),4.84(s,2H,CH2),3.92(s,3H,CH3),3.88(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:171.75,160.06,155.02,151.05,149.23,147.47,144.74,134.04,130.80,118.52,115.01,111.99,111.33,108.40,105.41,56.44,56.20,47.62;B:167.61,160.06,154.94,150.55,149.15,147.76,144.74,134.25,131.17,119.72,115.01,112.64,111.92,108.35,105.48,55.39,49.08,46.65;HRMS calcd for C18H18ClN4O4[M+H]+389.1011,found 389.1001.
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氯苯基)乙酰肼(I13):白色固体,熔点281-283℃,产率80%;IR(KBr,cm-1):3340,3237,1675,1605,1502,1440,1380,1275,1127,1018,744;1H NMR(400MHz,DMSO-d6)δA:10.27(s,1H,CONH),8.26(s,1H,Qu-2-H),7.58(s,1H,Ar-NH),7.47(s,1H,Qu-5-H),7.28(d,J=7.9Hz,1H,Ar-3-H),7.20(d,J=8.2Hz,1H,Ar-5-H),7.17(s,1H,Qu-8-H),6.93(d,J=8.1Hz,1H,Ar-4-H),6.76(t,J=7.8Hz,1H,Ar-6-H),4.79(s,2H,CH2),3.92(s,3H,CH3),3.89(s,3H,CH3);B:9.58(s,1H,OH),8.17(s,1H,Qu-2-H),8.05(s,1H,Ar-NH),7.45(s,1H,Qu-5-H),7.37(d,J=8.1Hz,1H,Ar-3-H),7.32(d,J=8.0Hz,1H,Ar-5-H),7.16(s,1H,Qu-8-H),7.08(d,J=7.1Hz,1H,Ar-4-H),6.88(t,J=10.8Hz,1H,Ar-6-H),4.83(s,2H,CH2),3.92(s,3H,CH3),3.88(s,3H,CH3);13CNMR(100MHz,DMSO-d6)δA:167.59,160.04,155.01,149.23,147.49,144.73,137.02,136.92,125.00,119.31,119.24,115.00,114.22,108.40,105.44,56.44,56.22,47.45;B:171.74,160.04,154.94,149.38,147.73,144.73,136.55,136.44,125.35,120.38,120.32,115.60,114.88,108.34,105.50,56.44,56.19,46.70;HRMS calcd for C18H18ClN4O4[M+H]+389.1011,found 389.1004.
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼(I14):白色固体,熔点241-243℃,产率61%;IR(KBr,cm-1):3320,1670,1614,1508,1394,1329,1223,1207,822,770;1H NMR(400MHz,DMSO-d6)δA:10.15(d,J=2.4Hz,1H,CONH),8.38(s,1H,Qu-2-H),8.00(t,J=6.9Hz,1H,Qu-5-H),7.84(d,J=2.3Hz,1H,Ar-NH),7.71(d,J=7.1Hz,1H,Qu-7-H),7.44(t,J=7.6Hz,1H,Qu-6-H),7.02(t,J=8.8Hz,2H,Ar-3,5-2H),6.81-6.74(m,2H,Ar-2,6-2H),4.77(s,2H,CH2),2.55(s,3H,CH3);B:9.57(s,1H,OH),8.34(s,1H,Qu-2-H),8.08(s,1H,Ar-NH),8.00(t,J=6.9Hz,1H,Qu-5-H),7.71(d,J=7.1Hz,1H,Qu-7-H),7.44(t,J=7.6Hz,1H,Qu-6-H),7.12(t,J=8.8Hz,2H,Ar-3,5-2H),6.94-6.89(m,2H,Ar-2,6-2H),4.88(s,2H,CH2),2.55(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.41,161.00,147.94,147.01,145.96,135.91,135.25,127.07,124.11,121.91,115.71,115.49,113.93,113.86,47.63,17.58;B:171.65,160.98,148.24,147.05,145.39,135.88,135.15,126.98,124.11,121.89,116.11,115.88,114.60,114.53,46.76,17.58;HRMS calcd for C17H16O2N4F[M+H]+327.1252,found 327.1247.
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼(I15):白色固体,熔点247-249℃,产率52%;IR(KBr,cm-1):3324,1675,1616,1602,1492,1396,1350,1327,1220,956,819,769,500;1H NMR(400MHz,DMSO-d6)δA:10.18(s,1H,CONH),8.38(s,1H,Qu-2-H),8.06(s,1H,Ar-NH),7.99(t,J=8.0Hz,1H,Qu-5-H),7.71(d,J=7.2Hz,1H,Qu-7-H),7.44(t,J=7.6Hz,1H,Qu-6-H),7.19(d,J=8.8Hz,2H,Ar-3,5-2H),6.78(d,J=8.8Hz,2H,Ar-2,6-2H),4.78(s,2H,CH2),2.55(s,3H,CH3);B:9.60(s,1H,OH),8.33(s,1H,Qu-2-H),8.28(s,1H,Ar-NH),7.99(t,J=8.0Hz,1H,Qu-5-H),7.71(d,J=7.2Hz,1H,Qu-7-H),7.44(t,J=7.6Hz,1H,Qu-6-H),7.31(d,J=8.7Hz,2H,Ar-3,5-2H),6.91(d,J=8.8Hz,2H,Ar-2,6-2H),4.85(s,2H,CH2),2.55(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.44,161.00,148.41,147.91,147.00,135.91,135.26,128.94,127.08,124.11,122.41,121.90,114.17,47.63,17.58;B:171.66,160.96,148.19,147.85,147.03,135.88,135.16,129.31,126.99,123.63,122.41,121.87,114.72,46.70,17.58;HRMS calcd for C17H16O2N4Cl[M+H]+343.0956,found 343.0949.
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼(I16):白色固体,熔点253-255℃,产率64%;IR(KBr,cm-1):3324,1673,1616,1601,1488,1396,1327,1221,956,816,770;1H NMR(400MHz,DMSO-d6)δA:10.18(s,1H,CONH),8.38(s,1H,Qu-2-H),8.08(s,1H,Ar-NH),7.99(t,J=8.2Hz,1H,Qu-6-H),7.71(d,J=7.3Hz,1H,Qu-7-H),7.44(s,1H,Qu-5-H),7.30(d,J=8.7Hz,2H,Ar-3,5-2H),6.74(d,J=8.7Hz,2H,Ar-2,6-2H),4.78(s,2H,CH2),2.55(s,3H,CH3);B:9.60(s,1H,OH),8.33(s,1H,Qu-2-H),8.30(s,1H,Ar-NH),7.99(t,J=8.2Hz,1H,Qu-6-H),7.71(d,J=7.3Hz,1H,Qu-7-H),7.46(s,1H,Qu-5-H),7.42(d,J=2.1Hz,2H,Ar-3,5-2H),6.86(d,J=8.7Hz,2H,Ar-2,6-2H),4.85(s,2H,CH2),2.55(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.42,161.00,148.81,147.91,147.01,135.92,135.26,131.77,127.09,124.12,121.90,114.68,109.91,47.62,17.59;B:171.65,160.95,148.25,148.19,147.03,135.88,135.17,132.16,127.00,124.12,121.87,115.18,111.18,46.69,17.59;HRMS calcd for C17H16O2N4Br[M+H]+387.0451,found 387.0443.
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氟苯基)乙酰肼(I17):白色固体,熔点230-232℃,产率57%;IR(KBr,cm-1):3300,3044,1681,1610,1540,1503,1361,1222,1191,969,742;1H NMR(400MHz,DMSO-d6)δA:10.20(s,1H,CONH),8.39(s,1H,Qu-2-H),8.00(t,J=8.7Hz,1H,Qu-5-H),7.84(s,1H,Ar-NH),7.71(d,J=7.2Hz,1H,Qu-7-H),7.48-7.40(m,1H,Qu-6-H),7.21-7.05(m,1H,Ar-3-H),7.05-6.98(m,1H,Ar-5-H),6.96-6.90(m,1H,Ar-6-H),6.77-6.70(m,1H,Ar-4-H),4.80(s,2H,CH2),2.56(s,3H,CH3);B:9.57(s,1H,OH),8.32(s,1H,Qu-2-H),8.21(s,1H,Ar-NH),8.00(t,J=8.7Hz,1H,Qu-5-H),7.71(d,J=7.2Hz,1H,Qu-7-H),7.48-7.40(m,1H,Qu-6-H),7.21-7.05(m,1H,Ar-3-H),7.05-6.98(m,1H,Ar-5-H),6.96-6.90(m,1H,Ar-6-H),6.89-6.82(m,1H,Ar-4-H),4.88(s,2H,CH2),2.56(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:171.63,161.00,147.93,147.00,136.89,135.92,135.26,127.08,124.13,121.90,119.32,119.25,115.37,115.20,114.22,114.19,47.53,17.58;B:167.48,160.95,149.38,148.18,136.52,135.88,135.16,127.00,124.98,124.95,120.40,120.34,115.62,115.45,114.62,114.59,46.75,17.58;HRMS calcd forC17H16O2N4F[M+H]+327.1252,found 327.1245.
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(3-氯苯基)乙酰肼(I18):白色固体,熔点254-256℃,产率57%;IR(KBr,cm-1):3263,1666,1611,1598,1536,1475,1362,1222,962,775;1H NMR(400MHz,DMSO-d6)δA:10.20(s,1H,CONH),8.39(s,1H,Qu-2-H),8.17(s,1H,Ar-NH),8.00(t,J=7.6Hz,1H,Qu-5-H),7.70(d,J=7.2Hz,1H,Qu-7-H),7.44(td,J=7.6,3.4Hz,1H,Qu-6-H),7.16(t,J=8.0Hz,1H,Ar-5-H),6.80(s,1H,Ar-2-H),6.75-6.69(m,2H,Ar-4,6-2H),4.79(s,2H,CH2),2.55(s,3H,CH3);B:9.63(s,1H,OH),8.39(s,1H,Qu-2-H),8.35(s,1H,Ar-NH),8.00(t,J=7.6Hz,1H,Qu-5-H),7.70(d,J=7.2Hz,1H,Qu-7-H),7.44(td,J=7.6,3.4Hz,1H,Qu-6-H),7.28(t,J=8.0Hz,1H,Ar-5-H),6.92(s,1H,Ar-2-H),6.86(t,J=8.5Hz,2H,Ar-4,6-2H),4.86(s,2H,CH2),2.55(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δA:167.50,161.01,151.02,147.91,147.01,135.92,135.17,134.05,130.79,127.09,124.10,121.91,118.52,111.97,111.34,47.73,17.59;B:171.65,160.96,150.52,148.20,147.01,135.88,135.26,134.27,131.19,126.99,124.10,121.87,119.73,112.62,111.88,46.69,17.59;HRMS calcd for C17H16O2N4Cl[M+H]+343.0956,found 343.0950.
2-(6-氯-4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼(I19):白色固体,熔点246-248℃,产率71%;IR(KBr,cm-1):3261,3220,3112,3038,1697,1674,1606,1510,1474,1366,1329,1223,972,833,820;1H NMR(400MHz,DMSO-d6)δA:10.15(d,J=2.3Hz,1H,CONH),8.41(s,1H,Qu-2-H),8.11(d,J=2.4Hz,1H,Qu-5-H),7.89(dd,J=8.7,2.5Hz,1H,Qu-7-H),7.84(d,J=2.2Hz,1H,Ar-NH),7.74(d,J=8.7Hz,1H,Qu-8-H),7.00(t,J=8.9Hz,2H,Ar-3,5-2H),6.81-6.73(m,2H,Qu-2,6-2H),4.78(s,2H,CH2);B:9.59(s,1H,OH),8.38(s,1H,Qu-2-H),8.09(d,J=2.5Hz,1H,Qu-5-H),8.08(s,1H,Ar-NH),7.89(dd,J=8.7,2.5Hz,1H,Qu-7-H),7.74(d,J=8.7Hz,1H,Qu-8-H),7.11(t,J=8.8Hz,2H,Ar-3,5-2H),6.94-6.88(m,2H,Ar-2,6-2H),4.89(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.16,159.81,149.39,147.26,145.90,135.07,131.89,130.01,125.40,123.17,115.72,115.50,113.94,113.86,47.83;B:171.39,159.76,149.72,147.30,145.35,135.02,131.82,129.98,125.44,123.10,116.10,115.87,114.62,114.55,47.00;HRMS calcd for C16H13O2N4ClF[M+H]+347.0706,found 347.0703.
2-(6-氯-4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼(I20):白色固体,熔点258-260℃,产率62%;IR(KBr,cm-1):3258,3107,3033,1698,1671,1605,1493,1475,1329,1224,1171,834,815;1H NMR(400MHz,DMSO-d6)δA:10.18(d,J=1.6Hz,1H,CONH),8.41(s,1H,Qu-2-H),8.11(d,J=2.5Hz,1H,Qu-5-H),8.06(d,J=1.5Hz,1H,Ar-NH),7.89(dd,J=8.7,2.4Hz,1H,Qu-7-H),7.74(d,J=8.7Hz,1H,Qu-8-H),7.18(d,J=5.9Hz,2H,Ar-3,5-2H),6.78(d,J=8.8Hz,2H,Ar-2,6-2H),4.79(s,2H,CH2);B:9.63(s,1H,OH),8.37(s,1H,Qu-2-H),8.28(s,1H,Ar-NH),8.09(d,J=2.5Hz,1H,Qu-5-H),7.89(dd,J=8.7,2.4Hz,1H,Qu-7-H),7.74(d,J=8.7Hz,1H,Qu-8-H),7.30(d,J=8.8Hz,2H,Ar-3,5-2H),6.90(d,J=8.8Hz,2H,Ar-2,6-2H),4.86(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.19,159.81,149.37,148.36,147.26,135.08,131.91,130.01,128.94,125.41,123.16,122.44,114.17,46.94;B:171.40,159.74,149.68,147.80,147.28,135.03,131.83,129.98,129.30,125.43,123.67,123.08,114.74,47.83;HRMS calcd for C16H13O2N4Cl2[M+H]+363.0410,found 363.0406.
2-(6-氯-4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼(I21):白色固体,熔点262-264℃,产率55%;IR(KBr,cm-1):3255,3089,3024,1698,1674,1605,1490,1474,1366,1329,1223,1171,1076,833,812;1H NMR(400MHz,DMSO-d6)δA:10.18(d,J=1.7Hz,1H,CPNH),8.41(s,1H,Qu-2-H),8.11(d,J=2.5Hz,1H,Qu-5-H),8.09-8.06(m,1H,Ar-NH),7.92-7.86(m,1H,Qu-7-H),7.74(dd,J=8.7,2.2Hz,1H,Qu-8-H),7.30(d,J=8.8Hz,2H,Ar-3,5-2H),6.73(d,J=8.9Hz,2H,Ar-2,6-2H),4.78(s,2H,CH2);B:9.63(s,1H,OH),8.36(s,1H,Qu-2-H),8.29(s,1H,Ar-NH),8.09-8.06(m,1H,Qu-5-H),7.92-7.86(m,1H,Qu-7-H),7.74(dd,J=8.7,2.2Hz,1H,Qu-8-H),7.42(d,J=8.8Hz,2H,Ar-3,5-2H),6.85(d,J=8.8Hz,2H,Ar-2,6-2H),4.86(s,2H,CH2);13C NMR(100MHz,DMSO-d6)δA:167.18,159.80,149.36,148.76,147.26,135.08,131.91,131.78,130.01,125.41,123.16,114.68,109.96,47.83;B:171.40,159.73,149.67,148.19,147.27,135.03,132.15,131.83,129.98,125.41,123.08,115.21,111.23,46.93;HRMS calcd for C16H13O2N4ClBr[M+H]+406.9905,found 406.9741.
用途实施例
实施例二:本发明式(I)的一种含酰肼的喹唑啉酮类衍生物I1-I21的杀菌活性
采用菌丝生长速度法测定了一种含酰肼结构的喹唑啉酮类衍生物I1-I21对水稻纹枯病菌(Rhizoctonia solani)、小麦赤霉病菌(Fusarium graminearum)的抑制活性,具体操作步骤如下:
1.称取一定量的目标化合物溶于一定体积的二甲基亚砜中,得到一定质量浓度的母液;
2.量取100μL母液加入到45mL已高压灭菌的土豆琼脂培养基中,震荡均匀;
3.将上述培养基均匀倒入3皿直径为9厘米的培养皿中,待其凝固后,将直径为5毫米的菌饼转接至培养皿中心;
4.将上述培养皿在25±1℃条件下,培养至菌落直接约为7.0至7.5厘米后,测定菌落直径,计算各药剂的抑制率。
5.化合物对真菌抑制率计算公式如下:抑菌率=(空白对照菌落直径-测试药剂菌落直径)÷(空白对照菌落直径-5mm)×100%。
化合物I1-I21对水稻纹枯病菌、小麦赤霉病菌的抑制活性测定结果如表2和表3所示:
表2 化合物I1-I21对水稻纹枯病菌的抑制结果
a三次重复,取其平均值;b以商品药剂恶霉灵和多菌灵为对照药剂。
表2显示,在测试浓度为10μg/mL时,化合物I1-I21对水稻纹枯病菌的抑制率为85-100%,优于对照药剂恶霉灵(35%)。在测试浓度为4μg/mL时,化合物I1、I4-I8、I11-I13和I17-I19对水稻纹枯病菌的抑制率(%)分别为91、96、100、99、98、92、98、100、99、95、99和94%。进一步的生测结果表明:化合物I2、I3、I7、I9、I10、I15、I16、I20和I21对水稻纹枯病菌的EC50(μg/mL)分别为0.27、0.20、0.23、0.20、0.17、0.20、0.19、0.15和0.12μg/mL,优于对照药剂多菌灵(0.32μg/mL)。
表3 化合物I1-I21对小麦赤霉病菌的抑制结果
a三次重复,取其平均值;b以商品药剂恶霉灵和多菌灵为对照药剂。
表3显示,在测试浓度为10μg/mL时,化合物I1-I3、I8-I10、I14-I16和I19-I21对小麦赤霉病菌的抑制率(%)分别为87、86、79、86、85、79、90、81、71、89、83和74%,优于对照药剂恶霉灵(43%)。在测试浓度为4μg/mL时,化合物I1-I3、I8-I10、I14-I16和I19-I21对小麦赤霉病菌的抑制率(%)分别为73、71、57、71、70、64、74、72、57、77、73和70%。进一步的生测结果表明:化合物I1-I3、I8-I10、I14-I16和I19-I21对小麦赤霉病菌的EC50(μg/mL)分别为1.52、1.76、2.96、2.05、2.68、3.07、1.68、2.45、4.21、1.23、1.99和2.96μg/mL,优于对照药剂恶霉灵(29.54μg/mL)。
以上所述,仅是本发明的较佳实施案例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化与修饰,均属于本发明技术方案的范畴。
Claims (9)
2.根据权利要求1所述的一种含酰肼的喹唑啉酮类衍生物,其特征在于:
R1选自下列1-2个基团:氢原子、F、Cl、Br、甲基、甲氧基;
R2选自下列1-2个基团:F、Cl、Br。
3.根据权利要求2所述的一种含酰肼的喹唑啉酮类衍生物,其特征在于:
R1选自氢原子、6-Cl、8-甲基、6,7-二甲氧基;
R2选自2-F、2-Cl、3-Cl、4-F、4-Cl、4-Br、2,4-(Cl)2。
4.根据权利要求3所述的一种含酰肼的喹唑啉酮类衍生物,其特征在于其为如下所述化合物之一:
2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼、
2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼、
2-(4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼、
2-(4-氧代喹唑啉-3(4H)-基)-N’-(2-氟苯基)乙酰肼、
2-(4-氧代喹唑啉-3(4H)-基)-N’-(3-氯苯基)乙酰肼、
2-(4-氧代喹唑啉-3(4H)-基)-N’-(2-氯苯基)乙酰肼、
2-(4-氧代喹唑啉-3(4H)-基)-N’-(2,4-二氯苯基)乙酰肼、
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼、
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼、
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼、
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氟苯基)乙酰肼、
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(3-氯苯基)乙酰肼、
2-(6,7-二甲氧基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氯苯基)乙酰肼、
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼、
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼、
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼、
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(2-氟苯基)乙酰肼、
2-(8-甲基-4-氧代喹唑啉-3(4H)-基)-N’-(3-氯苯基)乙酰肼、
2-(6-氯-4-氧代喹唑啉-3(4H)-基)-N’-(4-氟苯基)乙酰肼、
2-(6-氯-4-氧代喹唑啉-3(4H)-基)-N’-(4-氯苯基)乙酰肼、
2-(6-氯-4-氧代喹唑啉-3(4H)-基)-N’-(4-溴苯基)乙酰肼。
6.权利要求1-4中任一项所述的一种含酰肼的喹唑啉酮类衍生物在抑制植物病原真菌方面的应用。
7.根据权利要求6所述的应用,其特征在于权利要求1-4中任一项所述的一种含酰肼的喹唑啉酮类衍生物在抑制水稻纹枯病菌、小麦赤霉病菌方面的应用。
8.权利要求1-4中任一项所述的一种含酰肼的喹唑啉酮类衍生物在防治植物真菌病害方面的应用。
9.根据权利要求8所述的应用,其特征在于权利要求1-4中任一项所述的一种含酰肼的喹唑啉酮类衍生物在防治水稻纹枯病、小麦赤霉病方面的应用。
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