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阿维菌素B2a肟醚类衍生物及其在农药上的应用

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专利汇可以提供阿维菌素B2a肟醚类衍生物及其在农药上的应用专利检索,专利查询,专利分析的服务。并且本 发明 涉及阿维菌素B2a肟醚类衍 生物 ,结构通式为(I)。以阿维菌素B2a为原料,通过保护反应、 氧 化反应、肟化反应和脱保护,合成得到阿维菌素B2a肟醚类化合物,并且对该类化合物进行杀虫、杀螨、杀 线虫 活性测试,其生物活性测试结果显示该类化合物具有良好的杀虫、杀螨、杀线虫活性,是一类结构新颖、未见文献报道、应用前景广阔的 杀虫剂 、 杀螨剂 和 杀线虫剂 。,下面是阿维菌素B2a肟醚类衍生物及其在农药上的应用专利的具体信息内容。

1.一种阿维菌素B2a肟醚类衍生物,其特征在于其结构通式为(I)。
其中:R1代表氢、甲基、乙基、苄基、三苯基甲基、 R2代表4-腈
基、4-F、4-Br、4-CH3、4-C(CH3)3、4-O-CH3、4-CF3、2-Cl-6-Cl、2-F-6-F、2-F-6-Cl。
2.权利要求1所述的阿维菌素B2a肟醚类衍生物及其可以接受的盐在农业上用作杀虫剂
3.权利要求1所述的阿维菌素B2a肟醚类衍生物及其可以接受的盐在农业上用作杀螨剂
4.权利要求1所述的阿维菌素B2a肟醚类衍生物及其可以接受的盐在农业上用作线虫剂。
5.权利要求1所述的阿维菌素B2a肟醚类衍生物及其可以接受的盐与其他成分混合作为农药复合物用作杀虫剂、杀螨剂和杀线虫剂

说明书全文

阿维菌素B2a肟醚类衍生物及其在农药上的应用

技术领域

[0001] 本发明涉及阿维菌素B2a肟醚类衍生物的合成方法及应用,特别是阿维菌素B2a肟醚类衍生物在杀虫、杀螨、杀线虫方面的用途。

背景技术

[0002] 阿维菌素(Avermectin,简称AVM)作为农药和兽药应用在农业和畜牧业领域,是世界范围内用量最大的生物农药品种。AVM属于大环内酯类化合物,主要包括8个同系物。阿维菌素结构如式(II)所示:
[0003]
[0004] 阿维菌素B1(AVM B1)作为杀虫剂杀螨剂被先正达公司引入农药市场,其衍生物,甲基阿维菌素苯甲酸盐(简称甲维盐)也被广泛用于防治农田鳞翅目害虫。AVM B1在工业生产过程中,会产生废渣,废渣的产生增加能源消耗、造成环境污染,其主要成分是阿维菌素B2a(AVM B2a)。2012年,我国禁止在阿维菌素乳油中混合使用阿维菌素油膏。由于阿维菌素油膏毒性较高需要特殊处理且成本过高,成为限制阿维菌素行业发展的重要问题。
[0005] AVM B2a单独使用价值有限,采用化学转化方法,变成更有用的农用化学品对于阿维产业的健康发展是十分必要的。AVM B2a中存在4个羟基,其活性顺序依次为C5-OH、C23-OH、C4″-OH、C7-OH,关于AVM B2a的研究主要集中在5位和4″位,暂没有发现具有应用价值的新化合物。因此将衍生化位点聚焦在没有修饰改造过的C23-OH。参考AVM B1的结构改造规律,对其进行化学结构修饰,期待提高其生物活性。

发明内容

[0006] 本发明的目的是提供了16种阿维菌素B2a肟醚类衍生物的合成方法以及在杀虫、杀螨、杀线虫方面的用途。以阿维菌素B2a为原料,使用羟基保护基试剂保护阿维菌素B2a的5位和4″位羟基,通过化反应、肟化反应和脱保护,合成得到阿维菌素B2a肟醚类化合物,并且对该类化合物进行杀虫、杀螨、杀线虫活性测试,其生物活性测试结果显示该类化合物具有良好的杀虫、杀螨、杀线虫活性,是一类结构新颖、未见文献报道、应用前景广阔的杀虫剂、杀螨剂和杀线虫剂
[0007] 本发明提供阿维菌素B2a肟醚类化合物的结构通式为(I)。
[0008]
[0009] 其中:R1代表氢、甲基、乙基、苄基、三苯基甲基、
[0010] R2代表4-腈基、4-F、4-Br、4-CH3、4-C(CH3)3、4-O-CH3、4-CF3、2-Cl-6-Cl、2-F-6-F、2-F-6-Cl。
[0011] 本发明设计的化合物的制备方法是先使用羟基保护基试剂保护阿维菌素B2a的5位和4″位羟基,通过氧化反应、肟化反应和脱保护,合成得到阿维菌素B2a肟醚类化合物。
[0012] 本发明涉及的化合物及其可以接受的盐在农业上用作杀虫剂、杀螨剂和杀线虫剂。
[0013] 本发明涉及的化合物及其在农业上可以接受的盐还可以作为有效成分与其他成分混合作为农药复合物,用作杀虫剂、杀螨剂和杀线虫剂。
[0014] 本发明提供了阿维菌素B2a肟醚类化合物,并且对该类化合物进行杀虫、杀螨、杀线虫活性测试,其生物活性测试结果显示该类化合物具有良好的杀虫、杀螨、杀线虫活性,是一类结构新颖、未见文献报道、应用前景广阔的杀虫剂、杀螨剂和杀线虫剂。具体实施方案:
[0015] 实施例1:
[0016]
[0017] 取15.00g AVM B2a和120mL二氯甲烷于250mL四口圆底烧瓶中,降温至0℃,分别将3.25g氯甲酸烯丙酯和3.95g四甲基乙二胺溶于5mL二氯甲烷,并将其缓慢滴加到反应体系中,0℃温度下反应8-12h,再缓慢滴加4.53gTMEDA的二氯甲烷稀释液,控温反应2h,反应完全后,加入50mL饱和酸氢钠溶液,再用3×20mL二氯甲烷萃取,收集二氯甲烷层,有机相用无硫酸镁干燥后,减压浓缩,胶色谱柱纯化得到14.80g白色晶体状固体2,质谱分析结果TOF-MS:1081.320[M+Na]+,熔点107-116℃,产率83%。
[0018] 核磁共振氢谱:1H NMR(CDCl3,δ/ppm,400MHz):5.83-5.93(m,2H,-CH2-CH=CH2),5.77(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.65(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.50(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.30-5.32(m,4H,-CH=CH2),5.30(d,J=2.8Hz,1H,-C=C-CH-OH),5.20(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),4.90(d,J=
4.4Hz,1H,-CH-CH-O-),4.70(d,J=4.0Hz,1H,-CH=C-),4.61(s,2H,-CH2-),4.60-4.63(m,
1H,-CH-O-C=O-),4.59(s,2H,-CH2-),4.56(t,J=3.2Hz,2H,-O-CH-CH2-),4.40(d,J=
16.0Hz,1H,-CH-),4.04(d,J=12.0Hz,1H,-CH-),3.88(s,1H,-OH),3.80-3.85(m,1H,CH3-CH-),3.70(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.59-3.61(m,1H,-(CH2)2-CH-OH),3.54-3.57(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.37(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.36(s,3H,-O-CH3),3.32(s,3H,-O-CH3),3.30-3.31(m,
1H,-CH-CH-CH2-),3.30(d,J=8.0Hz,1H,-C-CH-CH-),3.29(d,J=14.4Hz,1H,-C=O-CH-CH=C-),3.16(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.46(d,J=3.6Hz,1H,-CH-CH-),2.16-
2.23(m,2H,-C=CH-CH2-CH-),1.90-2.23(m,2H,-CH-CH2-),1.75-2.15(m,4H,-CH-CH2-CH-),1.75-1.93(m,2H,-CH-CH2-CH-),1.68-1.72(m,1H,-CH-CH3),1.61-1.62(m,2H,-CH2-CH-OH),1.49-1.52(m,1H,CH3-CH-CH-),1.47-1.49(m,2H,-CH-CH2-CH3),1.19-1.34(m,6H,-CH3),0.88-1.19(m,12H,-CH3),0.76-0.85(m,6H,-CH3).
[0019] 取10.00g中间体2和50mL二氯甲烷于150mL四口圆底烧瓶中,在氮气保护下,加入8.10g戴斯氧化剂,室温下反应2h,反应完成后,用50mL混合液(饱和碳酸氢钠溶液:饱和硫代硫酸钠溶液体积比为1∶2)终止反应,再用二氯甲烷萃取、分液,有机相用无水硫酸镁干燥,减压浓缩,硅胶色谱柱纯化得到7.62g淡黄色固体3,质谱分析结果TOF-MS:1079.286[M+Na]+,熔点102-110℃,产率76%。
[0020] 核磁共振氢谱:1H NMR(CDCl3,δ/ppm,400MHz):5.85-5.91(m,2H,-CH2-CH=CH2),5.75(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.66(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.50(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.29-5.33(m,4H,-CH=CH2),5.22(d,J=2.8Hz,1H,-C=C-CH-OH),5.19(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),4.85(d,J=
4.4Hz,1H,-CH-CH-O-),4.68(d,J=4.0Hz,1H,-CH=C-),4.60-4.63(m,3H),4.59(s,2H,-CH2-),4.56(t,J=3.2Hz,2H,-O-CH-CH2-),4.40(d,J=16.0Hz,1H,-CH-),4.05(d,J=
12.0Hz,1H,-CH-),3.86(s,1H,-OH),3.73-3.84(m,2H),3.44-3.57(m,5H),3.36(s,3H,-O-CH3),3.32(s,3H,-O-CH3),3.29-3.31(m,3H),3.15(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),
2.45(d,J=3.6Hz,1H,-CH-CH-),2.13-2.41(m,7H),1.18-1.75(m,14H),0.92-1.18(m,
12H,-CH3),0.90-0.92(m,6H,-CH3).
[0021] 取23.75g中间体3于1000mL三口圆底烧瓶中,将其用400mL无水乙醇溶解,水降温至0℃,加入25mL吡啶和10.38g盐酸羟胺,0℃下反应2h,用摩尔浓度为3mol/L的HCl调pH至3~4时析出大量白色固体,减压抽滤得到粗产物,自然晾干后用硅胶色谱柱纯化得到18.3g白色中间体4a,质谱分析结果TOF-MS:1094.520[M+Na]+,熔点108-112℃,产率76%。
[0022] 核磁共振氢谱:1H NMR(DMSO-d6δ/ppm,400MHz):10.46(s,1H,-OH),5.88-5.98(m,2H,-CH2-CH=CH2),5.78(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.66(dd,J=16.0,
12.0Hz,1H,-CH-CH=C-C=C-),5.54(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.30-5.36(m,
4H,-CH=CH2),5.27(d,J=2.8Hz,1H,-C=C-CH-OH),5.24(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),4.80(d,J=4.4Hz,1H,-CH-CH-O-),4.71(d,J=4.0Hz,1H,-CH=C-),4.62-4.63(m,
3H),4.57(s,2H,-CH2-),4.47(t,J=3.2Hz,2H,-O-CH-CH2-),4.29(d,J=16.0Hz,1H,-CH-),
3.89(d,J=12.0Hz,1H,-CH-),3.78(s,1H,-OH),3.56-3.76(m,2H),3.33-3.56(m,5H),3.31(s,3H,-O-CH3),3.26(s,3H,-O-CH3),3.16-3.19(m,3H),3.14(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.46(d,J=3.6Hz,1H,-CH-CH-),1.80-2.50(m,7H),1.24-1.70(m,14H),0.95-
1.18(m,12H,-CH3),0.89-0.94(m,6H,-CH3).
[0023] 取0.97g中间体4a于100mL单口瓶中,用30mL的醋酸异丙酯和乙醇的混合溶液(体积比为7∶3)溶解,降温至0℃,加入0.01g四(三苯基膦)钯,之后缓慢加入0.07g氢化钠,室温下敞口反应,反应完全后,加入10mL饱和碳酸氢钠溶液,用3×10mL二氯甲烷萃取产物,合并二氯甲烷层后用无水硫酸镁干燥,减压浓缩,硅胶柱色谱纯化得到0.51g淡黄色中间体5a,高分辨质谱分析结果HRMS:926.4878[M+Na]+,熔点136-144℃,产率62%。
[0024] 核磁共振氢谱:1H NMR(DMSO-d6,δ/ppm,400MHz):10.46(s,1H,-OH),5.87(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.75(dd,J=16.0,12.0Hz,1.H,-CH-CH=C-C=C-),5.61(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.34(s,1H,-OH),5.24(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.10(br,1H,-OH),5.04(d,J=4.0Hz,1H,-CH=C-),4.73-4.84(m,1H,-CH-O-C=O-),4.70(t,J=3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.45(d,J=
12.0Hz,1H,-CH-),4.07(s,1H,-OH),4.00-4.06(m,1H,CH3-CH-),3.90(d,J=2.8Hz,1H,-C=C-CH-OH),3.75(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.61(d,J=4.4Hz,1H,-CH-CH-O-),
3.54-3.57(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),
3.37(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.32(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.23-
3.27(m,1H,-CH-CH-CH2-),3.17(d,J=8.0Hz,1H,-C-CH-CH-),3.08(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.89(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),
2.50(d,J=3.6Hz,1H,-CH-CH-),2.34-2.61(m,2H,-CH2-C=N-),2.21-2.32(m,2H,-C=CH-CH2-CH-),1.86-2.21(m,2H,-CH-CH2-),1.72-2.18(m,4H,-CH-CH2-CH-),1.72-1.99(m,2H,-CH-CH2-CH-),1.60-1.63(m,1H,CH3-CH-CH-),1.51-1.54(m,2H,-CH-CH2-CH3),1.30-1.47(m,6H,-CH3),1.02-1.30(m,12H,-CH3),0.89-0.95(m,6H,-CH3).
[0025] 化合物5b~5p按照与5a相似的方法合成,相关理化数据列于表1中。
[0026] 表1 目标化合物5b~5p的理化参数及质谱数据
[0027]
[0028]
[0029] 核磁共振氢谱:
[0030] 化合物5b:1H NMR(DMSO-d6,δ/ppm,400MHz):5.87(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.74(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.62(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.33(s,1H,-OH),5.23(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.10(br,
1H,-OH),5.03(d,J=4.0Hz,1H,-CH=C-),4.73-4.85(m,1H,-CH-O-C=O-),4.70(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.46(d,J=12.0Hz,1H,-CH-),4.05(s,1H,-OH),4.01-4.04(m,1H,CH3-CH-),3.90(d,J=2.8Hz,1H,-C=C-CH-OH),3.78(s,
3H,-CH3),3.74(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.61(d,J=4.4Hz,1H,-CH-CH-O-),3.54-
3.58(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.38(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.23-3.27(m,1H,-CH-CH-CH2-),3.12(d,J=8.0Hz,1H,-C-CH-CH-),3.06(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.89(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.70(m,1H,-CH-CH3),2.51(d,J=3.6Hz,1H,-CH-CH-),2.32-2.61(m,2H,-CH2-C=N-),2.18-2.32(m,2H,-C=CH-CH2-CH-),1.86-2.15(m,2H,-CH-CH2-),1.72-2.18(m,4H,-CH-CH2-CH-),1.72-1.99(m,2H,-CH-CH2-CH-),1.61-1.63(m,1H,CH3-CH-CH-),1.51-1.54(m,2H,-CH-CH2-CH3),1.29-1.48(m,
6H,-CH3),1.02-1.28(m,12H,-CH3),0.89-0.93(m,6H,-CH3).
[0031] 化合物5c:1H NMR(DMSO-d6,δ/ppm,400MHz):5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.74(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.60(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.34(s,1H,-OH),5.23(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.10(br,
1H,-OH),5.08(d,J=4.0Hz,1H,-CH=C-),4.77-4.80(m,1H,-CH-O-C=O-),4.71(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.45(d,J=12.0Hz,1H,-CH-),4.08(s,1H,-OH),3.95-4.03(m,1H,CH3-CH-),3.90(d,J=2.8Hz,1H,-C=C-CH-OH),3.75(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.61(d,J=4.4Hz,1H,-CH-CH-O-),3.51-3.60(m,2H,-O-CH2-CH3),3.54-3.57(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.38(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.23-3.27(m,1H,-CH-CH-CH2-),3.13(d,J=8.0Hz,1H,-C-CH-CH-),3.05(d,J=
14.4Hz,1H,-C=O-CH-CH=C-),2.89(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,
1H,-CH-CH3),2.51(d,J=3.6Hz,1H,-CH-CH-),2.35-2.61(m,2H,-CH2-C=N-),2.21-2.32(m,2H,-C=CH-CH2-CH-),1.84-2.14(m,2H,-CH-CH2-),1.72-2.18(m,4H,-CH-CH2-CH-),
1.72-1.99(m,2H,-CH-CH2-CH-),1.60-1.63(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.30-1.48(m,6H,-CH3),1.10-1.30(m,12H,-CH3),0.81-0.96(m,6H,-CH3).[0032] 化合物5d:1H NMR(DMSO-d6,δ/ppm,400MHz):7.27-1.38(m,5H,Ph-H),5.88(dd,J=
14.8,12.4Hz,1H,-C=CH-C=C),5.76(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.63(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.34(s,1H,-OH),5.24(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.13(br,1H,-OH),5.04(d,J=4.0Hz,1H,-CH=C-),5.01-5.09(m,2H,-O-CH2-CH3),4.80-4.87(m,1H,-CH-O-C=O-),4.73(t,J=3.2Hz,2H,-O-CH-CH2-),4.59(d,J=
16.0Hz,1H,-CH-),4.45(d,J=12.0Hz,1H,-CH-),4.09(s,1H,-OH),4.01-4.04(m,1H,CH3-CH-),3.91(d,J=2.8Hz,1H,-C=C-CH-OH),3.77(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.62(d,J=4.4Hz,1H,-CH-CH-O-),3.55-3.57(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-
3.54(m,1H,-CH-CH-CH2-),3.39(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),
3.31(s,3H,-O-CH3),3.22-3.24(m,1H,-CH-CH-CH2-),3.17(d,J=8.0Hz,1H,-C-CH-CH-),
3.06(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.90(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),
2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,1H,-CH-CH-),2.35-2.62(m,2H,-CH2-C=N-),2.23-2.33(m,2H,-C=CH-CH2-CH-),1.86-2.18(m,2H,-CH-CH2-),1.72-2.15(m,4H,-CH-CH2-CH-),1.72-1.99(m,2H,-CH-CH2-CH-),1.61-1.62(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.29-1.48(m,6H,-CH3),0.98-1.26(m,12H,-CH3),0.89-0.96(m,6H,-CH3).
[0033] 化合物5e:1H NMR(DMSO-d6,δ/ppm,400MHz):5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.76(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.61(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.37(s,1H,-OH),5.24(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.22-
5.24(t,J=3.2Hz,1H,-CH-CH2-),5.16(d,J=4.0Hz,1H,-CH=C-),5.10(br,1H,-OH),
4.73-4.86(m,1H,-CH-O-C=O-),4.70(t,J=3.2Hz,2H,-O-CH-CH2-),4.57(d,J=16.0Hz,
1H,-CH-),4.45(d,J=12Hz,1H,-CH-),4.07(s,1H,-OH),4.00-4.06(m,1H,CH3-CH-),3.89(d,J=2.8Hz,1H,-C=C-CH-OH),3.75(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.67-3.74(m,2H,-CH2-CH3-),3.62(d,J=4.4Hz,1H,-CH-CH-O-),3.56-3.57(m,1H,CH3-CH-),3.53-3.56(m,
1H,CH3-CH-O-),3.45-3.53(m,1H,-CH-CH-CH2-),3.40(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.32(s,3H,-O-CH3),3.30(s,3H,-O-CH3),3.22-3.27(m,1H,-CH-CH-CH2-),3.12(d,J=8.0Hz,1H,-C-CH-CH-),3.07(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.89(dd,J=14.8,
8.8Hz,1H,-CH-CH-CH-),2.63-2.68(m,1H,-CH-CH3),2.50(d,J=3.6Hz,1H,-CH-CH-),
2.36-2.63(m,2H,-CH2-C=N-),2.26-2.34(m,2H,-C=CH-CH2-CH-),1.84-2.09(m,2H,-CH-CH2-),1.72-2.17(m,4H,-CH-CH2-CH-),1.66-1.99(m,2H,-CH-CH2-CH-),1.63-1.82(m,2H,-CH-CH2-CH2-),1.29-1.63(m,13H),1.09-1.29(m,12H,-CH3),0.89-0.94(m,6H,-CH3).[0034] 化合物5f:1H NMR(DMSO-d6,δ/ppm,400MHz):7.07-7.49(m,15H,Ph-H),5.89(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.79(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.64(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.33(s,1H,-OH),5.27(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.10(br,1H,-OH),5.05(d,J=4.0Hz,1H,-CH=C-),4.75-4.84(m,1H,-CH-O-C=O-),4.68(t,J=3.2Hz,2H,-O-CH-CH2-),4.59(d,J=16.0Hz,1H,-CH-),4.49(d,J=
12Hz,1H,-CH-),4.12(s,1H,-OH),4.01-4.10(m,1H,CH3-CH-),3.93(d,J=2.8Hz,1H,-C=C-CH-OH),3.79(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.67(d,J=4.4Hz,1H,-CH-CH-O-),3.59-
3.61(m,1H,CH3-CH-),3.57-3.59(m,1H,CH3-CH-O-),3.45-3.48(m,1H,-CH-CH-CH2-),3.36(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.19-3.22(m,1H,-CH-CH-CH2-),3.16(d,J=8.0Hz,1H,-C-CH-CH-),3.10(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.93(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.64-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,1H,-CH-CH-),2.43-2.57(m,2H,-CH2-C=N-),2.33-2.42(m,2H,-C=CH-CH2-CH-),1.85-2.12(m,2H,-CH-CH2-),1.74-2.15(m,4H,-CH-CH2-CH-),1.64-1.99(m,2H,-CH-CH2-CH-),1.61-1.67(m,1H,CH3-CH-CH-),1.50-1.59(m,2H,-CH-CH2-CH3),1.27-1.48(m,
6H,-CH3),1.08-1.27(m,12H,-CH3),0.69-0.90(m,6H,-CH3).
[0035] 化合物5g:1H NMR(DMSO-d6,δ/ppm,400MHz):7.20(d,J=8.0Hz,2H,Ph-H),7.12(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.76(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.62(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.32(s,1H,-OH),5.25(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.13(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),4.96-5.02(m,2H,-O-CH2-CH3),4.81-4.87(m,1H,-CH-O-C=O-),4.73(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.47(d,J=12.0Hz,1H,-CH-),4.10(s,1H,-OH),4.01-4.06(m,1H,CH3-CH-),3.92(d,J=2.8Hz,1H,-C=C-CH-OH),3.78(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.63(d,J=4.4Hz,1H,-CH-CH-O-),3.56-3.58(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.39(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.34(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.26-3.28(m,1H,-CH-CH-CH2-),3.16(d,J=8.0Hz,1H,-C-CH-CH-),3.07(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.91(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.34-2.62(m,2H,-CH2-C=N-),2.29(s,3H,-O-CH3),2.20-2.30(m,2H,-C=CH-CH2-CH-),1.86-2.20(m,2H,-CH-CH2-),1.74-2.16(m,4H,-CH-CH2-CH-),1.73-1.99(m,
2H,-CH-CH2-CH-),1.60-1.67(m,1H,CH3-CH-CH-),1.50-1.53(m,2H,-CH-CH2-CH3),1.33-
1.49(m,6H,-CH3),1.03-1.30(m,12H,-CH3),0.85-0.94(m,6H,-CH3).
[0036] 化合物5h:1H NMR(DMSO-d6,δ/ppm,400MHz):7.37(d,J=8.0Hz,2H,Ph-H),7.16(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.76(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.62(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.35(s,1H,-OH),5.25(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.12(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),4.99-5.10(m,2H,-O-CH2-CH3),4.79-4.85(m,1H,-CH-O-C=O-),4.73(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.45(d,J=12.0Hz,1H,-CH-),4.08(s,1H,-OH),4.01-4.06(m,1H,CH3-CH-),3.91(d,J=2.8Hz,1H,-C=C-CH-OH),3.77(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.62(d,J=4.4Hz,1H,-CH-CH-O-),3.55-3.59(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.38(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.22-3.28(m,1H,-CH-CH-CH2-),3.13(d,J=8.0Hz,1H,-C-CH-CH-),3.05(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.90(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.34-2.62(m,2H,-CH2-C=N-),2.20-2.32(m,2H,-C=CH-CH2-CH-),1.86-
2.15(m,2H,-CH-CH2-),1.72-2.03(m,4H,-CH-CH2-CH-),1.72-1.99(m,2H,-CH-CH2-CH-),
1.60-1.63(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.28-1.47(m,6H,-CH3),
1.10-1.23(m,12H,-CH3),0.87-0.96(m,6H,-CH3).
[0037] 化合物5i:1H NMR(DMSO-d6,δ/ppm,400MHz):7.47(d,J=8.0Hz,1H,Ph-H),7.39(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.73(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.60(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.33(s,1H,-OH),5.23(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.20(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),5.04-5.09(m,2H,-O-CH2-CH3),4.76-4.81(m,1H,-CH-O-C=O-),4.71(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.45(d,J=12.0Hz,1H,-CH-),4.07(s,1H,-OH),4.00-4.06(m,1H,CH3-CH-),3.90(d,J=2.8Hz,1H,-C=C-CH-OH),3.75(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.60(d,J=4.4Hz,1H,-CH-CH-O-),3.54-3.58(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.34(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.32(s,3H,-O-CH3),3.30(s,3H,-O-CH3),3.24-3.28(m,1H,-CH-CH-CH2-),3.12(d,J=8.0Hz,1H,-C-CH-CH-),3.05(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.89(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.62-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.33-2.58(m,2H,-CH2-C=N-),2.21-2.30(m,2H,-C=CH-CH2-CH-),1.92-
2.16(m,2H,-CH-CH2-),1.71-1.99(m,4H,-CH-CH2-CH-),1.71-1.99(m,2H,-CH-CH2-CH-),
1.61-1.66(m,1H,CH3-CH-CH-),1.50-1.53(m,2H,-CH-CH2-CH3),1.30-1.47(m,6H,-CH3),
1.02-1.30(m,12H,-CH3),0.86-0.93(m,6H,-CH3).
[0038] 化合物5j:1H NMR(DMSO-d6,δ/ppm,400M Hz):7.34(d,J=12.0Hz,2H,Ph-H),7.26(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.74(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.61(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.32(s,1H,-OH),5.25(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.12(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),4.96-5.04(m,2H,-O-CH2-CH3),4.71-4.76(m,1H,-CH-O-C=O-),4.72(t,J=
3.2Hz,2H,-O-CH-CH2-),4.59(d,J=16.0Hz,1H,-CH-),4.46(d,J=12.0Hz,1H,-CH-),4.10(s,1H,-OH),4.01-4.08(m,1H,CH3-CH-),3.91(d,J=2.8Hz,1H,-C=C-CH-OH),3.77(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.63(d,J=4.4Hz,1H,-CH-CH-O-),3.56-3.58(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.39(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.20-3.25(m,1H,-CH-CH-CH2-),3.14(d,J=8.0Hz,1H,-C-CH-CH-),3.07(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.91(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.35-2.62(m,2H,-CH2-C=N-),2.20-2.33(m,2H,-C=CH-CH2-CH-),1.96-
2.15(m,2H,-CH-CH2-),1.73-2.01(m,4H,-CH-CH2-CH-),1.73-1.99(m,2H,-CH-CH2-CH-),
1.61-1.67(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.38-1.48(m,6H,-CH3),
1.10-1.26(m,21H,-CH3),0.81-0.96(m,6H,-CH3).
[0039] 化合物5k:1H NMR(DMSO-d6,δ/ppm,400MHz):7.27(d,J=12.0Hz,2H,Ph-H),6.88(d,J=12.0Hz,2H,Ph-H),5.89(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.78(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.63(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.36(s,1H,-OH),5.25(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.13(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),4.93-5.06(m,2H,-O-CH2-CH3),4.80-4.84(m,1H,-CH-O-C=O-),4.73(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.47(d,J=12.0Hz,1H,-CH-),4.10(s,1H,-OH),4.02-4.07(m,1H,CH3-CH-),3.92(d,J=2.8Hz,1H,-C=C-CH-OH),3.78(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.74(s,3H,-O-CH3),3.64(d,J=4.4Hz,1H,-CH-CH-O-),3.56-
3.58(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.40(dd,J=14.4,9.6Hz,1H,-CH-CH-CH-),3.34(s,3H,-O-CH3),3.32(s,3H,-O-CH3),3.26-3.28(m,1H,-CH-CH-CH2-),3.14(d,J=8.0Hz,1H,-C-CH-CH-),3.07(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.92(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.64-2.71(m,1H,-CH-CH3),2.52(d,J=3.6Hz,1H,-CH-CH-),2.35-2.62(m,2H,-CH2-C=N-),2.21-2.32(m,2H,-C=CH-CH2-CH-),1.85-2.21(m,2H,-CH-CH2-),1.74-2.16(m,4H,-CH-CH2-CH-),1.74-2.00(m,2H,-CH-CH2-CH-),1.61-1.68(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.29-1.49(m,
6H,-CH3),1.04-1.27(m,12H,-CH3),0.90-0.96(m,6H,-CH3).
[0040] 化合物5l:1H NMR(DMSO-d6,δ/ppm,400MHz):7.78(d,J=12.0Hz,2H,Ph-H),7.49(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.76(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.61(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.35(s,1H,-OH),5.24(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.19(br,1H,-OH),5.14(d,J=4.0Hz,
1H,-CH=C-),5.11-5.15(m,2H,-O-CH2-CH3),4.80-4.85(m,1H,-CH-O-C=O-),4.73(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.46(d,J=12.0Hz,1H,-CH-),4.09(s,1H,-OH),4.00-4.05(m,1H,CH3-CH-),3.91(d,J=2.8Hz,1H,-C=C-CH-OH),3.77(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.63(d,J=4.4Hz,1H,-CH-CH-O-),3.55-3.57(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.37(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.32(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.21-3.28(m,1H,-CH-CH-CH2-),3.12(d,J=8.0Hz,1H,-C-CH-CH-),3.06(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.90(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.37-2.62(m,2H,-CH2-C=N-),2.23-2.35(m,2H,-C=CH-CH2-CH-),1.86-
2.21(m,2H,-CH-CH2-),1.72-2.14(m,4H,-CH-CH2-CH-),1.72-1.98(m,2H,-CH-CH2-CH-),
1.57-1.60(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.30-1.43(m,6H,-CH3),
1.13-1.19(m,12H,-CH3),0.87-0.93(m,6H,-CH3).
[0041] 化合物5m:1H NMR(DMSO-d6,δ/ppm,400MHz):7.51(d,J=20.0Hz,2H,Ph-H),7.27(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.79(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.63(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.34(s,1H,-OH),5.25(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.13(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),4.98-5.05(m,2H,-O-CH2-CH3),4.81-4.87(m,1H,-CH-O-C=O-),4.73(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.56(d,J=12.0Hz,1H,-CH-),4.11(s,1H,-OH),3.91-4.06(m,1H,CH3-CH-),3.91(d,J=2.8Hz,1H,-C=C-CH-OH),3.77(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.65(d,J=4.4Hz,1H,-CH-CH-O-),3.58-3.60(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.37(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.19-3.22(m,1H,-CH-CH-CH2-),3.13(d,J=8.0Hz,1H,-C-CH-CH-),3.07(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.91(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.33-2.62(m,2H,-CH2-C=N-),2.21-2.33(m,2H,-C=CH-CH2-CH-),1.85-
2.21(m,2H,-CH-CH2-),1.74-2.21(m,4H,-CH-CH2-CH-),1.74-1.99(m,2H,-CH-CH2-CH-),
1.59-1.65(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.39-1.47(m,6H,-CH3),
1.10-1.20(m,12H,-CH3),0.90-0.91(m,6H,-CH3).
[0042] 化合物5n:1H NMR(DMSO-d6,δ/ppm,400MHz):7.42(m,H,Ph-H),7.32(m,1H,Ph-H),7.21(m,1H,Ph-H),5.87(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.75(dd,J=16.0,
12.0Hz,1H,-CH-CH=C-C=C-),5.61(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.35(s,1H,-OH),5.24(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.11(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),5.04-5.06(m,2H,-O-CH2-CH3),4.77-4.89(m,1H,-CH-O-C=O-),4.68(t,J=
3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.45(d,J=12.0Hz,1H,-CH-),4.08(s,1H,-OH),4.00-4.06(m,1H,CH3-CH-),3.90(d,J=2.8Hz,1H,-C=C-CH-OH),3.76(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.62(d,J=4.4Hz,1H,-CH-CH-O-),3.55-3.58(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.37(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.32(s,3H,-O-CH3),3.30(s,3H,-O-CH3),3.24-3.28(m,1H,-CH-CH-CH2-),3.12(d,J=8.0Hz,1H,-C-CH-CH-),3.06(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.90(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=3.6Hz,
1H,-CH-CH-),2.30-2.62(m,2H,-CH2-C=N-),2.21-2.29(m,2H,-C=CH-CH2-CH-),1.96-
2.15(m,2H,-CH-CH2-),1.72-2.15(m,4H,-CH-CH2-CH-),1.72-1.99(m,2H,-CH-CH2-CH-),
1.56-1.59(m,1H,CH3-CH-CH-),1.54-1.57(m,2H,-CH-CH2-CH3),1.30-1.40(m,6H,-CH3),
1.02-1.19(m,12H,-CH3),0.81-0.92(m,6H,-CH3).
[0043] 化合物5o:1H NMR(DMSO-d6,δ/ppm,400MHz):7.43(dd,J=20.0,12.0Hz,1H,Ph-H),7.08(d,J=8.0Hz,2H,Ph-H),5.88(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.78(dd,J=
16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.63(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.31(s,
1H,-OH),5.25(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.09(br,1H,-OH),5.04(d,J=
4.0Hz,1H,-CH=C-),5.01-5.04(m,2H,-O-CH2-CH3),4.72-4.89(m,1H,-CH-O-C=O-),4.72(t,J=3.2Hz,2H,-O-CH-CH2-),4.58(d,J=16.0Hz,1H,-CH-),4.46(d,J=12.0Hz,1H,-CH-),4.10(s,1H,-OH),3.91-4.06(m,1H,CH3-CH-),3.91(d,J=2.8Hz,1H,-C=C-CH-OH),
3.77(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.64(d,J=4.4Hz,1H,-CH-CH-O-),3.56-3.58(m,
1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.37(dd,J=
14.4,9.6Hz,1H,-CH-CH-CH-),3.33(s,3H,-O-CH3),3.31(s,3H,-O-CH3),3.21-3.24(m,1H,-CH-CH-CH2-),3.14(d,J=8.0Hz,1H,-C-CH-CH-),3.08(d,J=14.4Hz,1H,-C=O-CH-CH=C-),2.91(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.63-2.71(m,1H,-CH-CH3),2.51(d,J=
3.6Hz,1H,-CH-CH-),2.31-2.62(m,2H,-CH2-C=N-),2.17-2.30(m,2H,-C=CH-CH2-CH-),
1.96-2.17(m,2H,-CH-CH2-),1.73-2.15(m,4H,-CH-CH2-CH-),1.73-1.99(m,2H,-CH-CH2-CH-),1.60-1.67(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.37-1.48(m,6H,-CH3),1.02-1.24(m,12H,-CH3),0.87-0.92(m,6H,-CH3).
[0044] 化合物5p:1H NMR(DMSO-d6,δ/ppm,400MHz):7.45(d,J=8.0Hz,2H,Ph-H),7.28(d,J=8.0Hz,2H,Ph-H),5.89(dd,J=14.8,12.4Hz,1H,-C=CH-C=C),5.78(dd,J=16.0,12.0Hz,1H,-CH-CH=C-C=C-),5.65(dd,J=14.4,9.6Hz,1H,-C=CH-C=C),5.37(s,1H,-OH),5.26(dd,J=12.0,9.2Hz,1H,-C=CH-CH2-),5.13(br,1H,-OH),5.04(d,J=4.0Hz,
1H,-CH=C-),5.05-5.09(m,2H,-O-CH2-CH3),4.81-4.87(m,1H,-CH-O-C=O-),4.73(t,J=
3.2Hz,2H,-O-CH-CH2-),4.60(d,J=16.0Hz,1H,-CH-),4.47(d,J=12.0Hz,1H,-CH-),4.11(s,1H,-OH),4.01-4.06(m,1H,CH3-CH-),3.92(d,J=2.8Hz,1H,-C=C-CH-OH),3.78(dd,J=9.2,6.4Hz,1H,-CH-CH-),3.64(d,J=4.4Hz,1H,-CH-CH-O-),3.57-3.59(m,1H,CH3-CH-),3.54-3.55(m,1H,CH3-CH-O-),3.47-3.54(m,1H,-CH-CH-CH2-),3.39(dd,J=14.4,
9.6Hz,1H,-CH-CH-CH-),3.34(s,3H,-O-CH3),3.32(s,3H,-O-CH3),3.21-3.26(m,1H,-CH-CH-CH2-),3.14(d,J=8.0Hz,1H,-C-CH-CH-),3.09(d,J=14.4Hz,1H,-C=O-CH-CH=C-),
2.91(dd,J=14.8,8.8Hz,1H,-CH-CH-CH-),2.64-2.71(m,1H,-CH-CH3),2.52(d,J=3.6Hz,
1H,-CH-CH-),2.36-2.63(m,2H,-CH2-C=N-),2.21-2.34(m,2H,-C=CH-CH2-CH-),1.87-
2.21(m,2H,-CH-CH2-),1.74-2.16(m,4H,-CH-CH2-CH-),1.74-1.99(m,2H,-CH-CH2-CH-),
1.60-1.67(m,1H,CH3-CH-CH-),1.50-1.54(m,2H,-CH-CH2-CH3),1.47-1.49(m,6H,-CH3),
1.11-1.20(m,12H,-CH3),0.83-0.92(m,6H,-CH3).
[0045] 实施例2
[0046] 用浸叶法测试目标化合物对小菜蛾的杀小菜蛾活性。
[0047] 浸叶法:挑选大小基本一致、健康的3龄小菜蛾供试,用镊子夹住3龄小菜蛾幼虫,在配好的各个浓度的药液中,将试虫浸泡5秒,之后再放置在铺有滤纸的直径9厘米的培养皿中,在每个直径为9cm的培养皿中加入新鲜的等量的甘蓝叶片。一次试验用10头供试粘虫。处理后将培养皿移入温度为27℃、湿度为75%的养虫室内培养。分别在24h、48h后记录供试小菜蛾的死亡数,通过计算校正死亡率来检测化合物的杀小菜蛾活性。
[0048] 化合物5a~5p的杀虫活性列于表2中。
[0049] 表2 化合物5a~5p的杀小菜蛾活性
[0050]
[0051]
[0052] 从表2可以看出化合物5b、5d、5e、5g、5k、5m、5p的杀小菜蛾活性均超过了AVM B2a,尤其是化合物5b和5p,在施药浓度1mg/kg浓度下,杀小菜蛾活性高达100%。
[0053] 实施例3
[0054] 用叶螨叶碟喷雾法测试目标化合物对朱砂叶螨成螨、幼螨及螨卵的活性。
[0055] 叶螨叶碟喷雾法:选取生长一致的蚕豆叶片,用打孔器做成叶碟,每皿2个叶碟,在培养皿内放置湿海绵,其上放滤纸,滤纸放叶碟。将室内饲养的叶螨成螨(幼螨)接种到准备好的其中1个叶碟上,每叶碟5~10头,让其产卵24h后剔除成螨;次日在另一叶片上接种成螨15~20头,让其产卵24h,这样可以得到成螨、48h幼螨、螨卵三种供试螨态。药剂处理前记录基数,采用POTTER喷雾塔进行处理,每处理喷药液量为1mL。定时进行调查,分别记载各处理的死活螨数,通过计算校正死亡率来检测化合物的杀螨活性。
[0056] 化合物5a~5p的杀螨活性列于表3中。
[0057] 表3 化合物5a~5p的杀朱砂叶螨活性
[0058]
[0059]
[0060] 从表3可以看出化合物5b、5e、5g、5k、5l和5m的杀成螨活性优于AVMB2a;化合物5b、5e、5g、5h、5j、5k、5l、5m、5n、5o和5p的杀幼螨活性优于AVM B2a;化合物5b、5e、5g、5h、5k、5l、
5m、5n、5o和5p的杀螨卵活性优于AVM B2a,特别是超过了成药AVM。
[0061] 实施例4
[0062] 采用触杀法测试目标化合物对松材线虫的杀线虫活性。
[0063] 触杀法:采用触杀法,把各种待测化合物配制成一定的质量浓度,同时将10μL不同质量浓度的待测化合物和90μL线虫悬浮液(1000条/mL)加入试管,震动混合均匀以后,放置到25℃条件下培养,24、48h后,在显微镜下检查线虫的存活情况,统计线虫死亡率。
[0064] 化合物5a~5e的杀线虫活性列于表4中。
[0065] 表4 化合物5a~5e在10mg/L浓度下的杀线虫活性
[0066]
[0067] 从表4可以看出在10mg/L浓度下,化合物5b、5c、5d、5e的杀线虫活性均超过60%,尤其是产物5b的杀线虫活性达到75%,超过了AVM B2a。
[0068] 以上所述活性化合物仅为本发明可行实施的穷举。对于本领域一般技术人员而言,对其所做出的任何显而易见的改动,都应当被认为包含在本发明的权利要求保护范围之内。
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