CN109897001B - 一种含二取代肼基的酯类化合物、制备方法及应用 - Google Patents
一种含二取代肼基的酯类化合物、制备方法及应用 Download PDFInfo
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Abstract
本发明属于杀菌剂领域,公开了一种含二取代肼基的酯类化合物、制备方法及应用,该类化合物的结构如式(I)所示:
Description
技术领域
本发明涉及一种含二取代肼基的酯类化合物、制备方法及其在防治植物病原真菌方面的应用,具有制备农药杀菌剂的用途。
背景技术
肼与酯基团均为农药分子结构中常见的活性基团。消螨通(dinobuton)和消螨多(meptyldinocap)均含碳酸酯基团,具有良好的杀螨活性,并能有效防治作物白粉病。氨基甲酸酯类杀虫剂,如西维因(carbaryl)等被广泛应用于害虫的防治;乙霉威(diethofencarb)属于氨基甲酸酯类杀菌剂,用于作物灰霉病的防治。专利CN1692099介绍了含酯基团的螺环吡咯啉酮类化合物,该类化合物具有优异的杀虫活性。专利CN103183628A介绍了一种含取代肼基的吡咯烷二酮类化合物的制备方法及应用,该类化合物具有良好的抑制真菌活性。
发明内容
本发明的目的在于,提供一种含二取代肼基的酯类化合物。
本发明的另一目的在于提供含二取代肼基的酯类化合物的制备方法。
本发明的另一个目的在于提供上述化合物的用途。
本发明的第一方面提供了一种具有通式(I)所示结构的含二取代肼基的酯类化合物,
在式(I)中,所述各个基团具有如下所述的定义:
R1选自氢、C1-12烷基;
R2选自氢、C1-12烷基;
R3选自C1-12烷基、苯甲基、取代苯甲基,所述的取代基团选自1-3个卤素、1-2个C1-6烷基;
Z选自N-R4、CH-R5、O、S,所述的R4、R5各自独立地选自氢、C1-12烷基、C3-8环烷基、C1-12烷酰基、苯基、取代苯基、苯甲基、取代苯甲基,所述的取代基团选自1-3个卤素、1-2个C1-6烷基、1-2个C1-6烷氧基、1-3个NO2;
Y(n)中,n=1-5取代,Y(n)选自下列1-5个基团:X、R’、OR”、NO2,其中X表示卤素;R’表示未取代或被1个或多个卤素取代的C1-6烷基;R”表示氢、未取代或被1个或多个卤素取代的C1-6烷基。
在式(I)中,所述各个基团具有如下所述的优选定义:
R1选自氢、C1-6烷基;
R2选自氢、C1-6烷基;
R3选自C1-6烷基、苯甲基;
Z选自N-R4、CH-R5,所述的R4、R5各自独立地选自氢、C1-6烷基、C3-6环烷基、C1-6烷酰基、苄基,R5选自氢;
Y(n)中,n=1-3取代,Y(n)选自下列1-3个基团:卤素、C1-6烷基、C1-6烷氧基。
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选自氢、甲基;
R2选自氢;
R3选自甲基、乙基、丙基、异丙基、丁基、异丁基、苯甲基;
Z选自N-R4,所述的R4选自氢、甲基、乙基、环丙基、环己基、乙酰基、苯甲基;
Y(n)选自2-氟、4-氟、2-氯、3-氯、4-氯、4-溴、2,4-二氯、4-甲基、3,4-二甲基、4-甲氧基;
或者,
R1选自氢;
R2选自氢;
R3选自甲基、乙基、丙基、异丙基、丁基、异丁基、苄基;
Z选自CH-R5,所述的R5选自氢;
Y(n)选自2-氟、4-氟、2-氯、3-氯、4-氯、4-溴、4-甲基、4-甲氧基。
在式(I)中,所述各个基团具有如下所述的特别优选定义:
1-(1-(4-((甲氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸甲酯、
1-(1-(4-((乙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸乙酯、
1-(1-(4-((丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((丁氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丁酯、
1-(1-(4-((异丁氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丁酯、
1-(1-(4-((苄氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸苄酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-甲基苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-甲氧基苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(3,4-二甲基苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2-氟苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氟苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(3-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2,4-二氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-溴苯基)肼基-1-甲酸异丙酯、
1-(1-(1-甲基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-乙基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-乙酰基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-环丙基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-环己基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-苄基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-5-甲基-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(2-((甲氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸甲酯、
1-(1-(2-((乙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸乙酯、
1-(1-(2-((丙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丙酯、
1-(1-(2-((异丙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丁酯、
1-(1-(2-((异丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丁酯、
1-(1-(2-((苄氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸苄酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(2-氟苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氟苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(2-氯苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(3-氯苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-溴苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-甲苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-甲氧基苯基)肼基-1-甲酸丁酯。
本发明的第二个方面提供了制备式(I)的含二取代肼基的酯类化合物的方法,该方法以式(II)的化合物与氯甲酸酯反应,制备式(I)的含二取代肼基的酯类化合物,其反应方程式可用下述通式(A)表示:
其中在上述各结构式中:
R1、R2、R3、Z、Y(n)均具有如前所述的相应基团的定义。
构式中含五元杂环、苯肼、甲酸酯三种特征基团;五元杂环是饱和的吡唑烷的二元酮;甲酸酯基团连接在肼基的1位N原子上;五元环和肼基之间通过一个含双键的亚烃基连接。
2、本发明专利所述的式(I)的含吡唑烷二酮和苯肼基团的甲酸酯类化合物的制备方法简便、原料易得、产率高。
3、本发明专利所述的式(I)的含吡唑烷二酮和苯肼基团的甲酸酯类化合物表现出显著的抑制植物病原真菌的活性,具有作为农药杀菌剂的用途。
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1:含吡唑烷二酮和苯肼基团的甲酸酯类化合物A1的制备
在冰浴条件下,在50mL三口瓶中加入20mL二氯甲烷、1.9mmol化合物(II-A1)和5mL三乙胺,搅拌,缓慢滴加2.1mmol氯甲酸甲酯,用TLC监控反应进程,反应完成后,用水洗涤,干燥,蒸除溶剂,经重结晶提纯(溶剂为乙醚与石油醚按照体积比10∶1配制的混合溶液),得含吡唑烷二酮和苯肼基团的甲酸酯类化合物A1,其反应方程式如下:
采用实施例1的方法,制备了含吡唑烷二酮和苯肼基团的甲酸酯类化合物(I)中的A、B、C、D、E系列化合物:
1-(1-(3,5-二氧吡唑烷-4-基亚基)乙基)-2-(4-氯苯基)肼基甲酸甲酯(A1)
Yellow powder,yield 40.3%;m.p.141.5-142.8℃;IR(KBr,cm-1)v:3220,2919,1716,1598,1533,1489,1436,1276,1240,1031,830,610;1H NMR(400MHz,DMSO-d6)δ:10.66(s,1H,ArNHN),9.13(s,1H,CONH),7.23(s,1H,CONH),7.17(d,J=8.6Hz,2H,ArH),6.67(d,J=8.2Hz,2H,ArH),3.77(s,3H,COOCH3),2.21(s,3H,C=CCH3);MS(EI)m/z:296[M-30]+.
1-(1-(3,5-二氧吡唑烷-4-基亚基)乙基)-2-(4-氯苯基)肼基甲酸乙酯(A2)
Yellow powder,yield 44.1%;m.p.120.9-122.1℃;IR(KBr,cm-1)v:3271,2981,1717,1686,1598,1544,1464,1368,1231,1010,897,611;1H NMR(400MHz,DMSO-d6)δ:9.05(s,1H,ArNHN),8.54(s,2H,CONH),7.17(d,J=8.4Hz,2H,ArH),6.66(d,J=8.2Hz,2H,ArH),4.26(q,J=6.7Hz,2H,COOCH2),2.40(s,3H,C=CCH3),1.26(t,J=6.9Hz,3H,COOCH2CH3);MS(EI)m/z:296[M-44]+.
1-(1-(3,5-二氧吡唑烷-4-基亚基)乙基)-2-(4-氯苯基)肼基甲酸正丙酯(A3)
白色粉末,收率73.5%,m.p.175.7-177.4℃;IR(KBr,cm-1)v:3291,3216,3098,2950,2921,1764,1718,1693,1678,1599,1491,1439,1392;1H NMR(400MHz,DMSO)δ:8.24(s,1H,PhNH),8.20(s,1H,CH2NH),7.17(d,J=8.8Hz,2H,PhH),6.89(d,J=8.9Hz,2H,PhH),5.34(s,1H,C=CH2),5.28(s,1H,C=CH2),4.26(s,2H,CH2NH),3.84(s,3H,OCH3),3.57(s,3H,OCH3);MS(EI)m/z:382[M]+.
1-(1-(4-((乙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸乙酯(A2)
白色粉末,收率58.3%,m.p.141.5-146.2℃;IR(KBr,cm-1)v:3350,3219,3090,2999,2974,1781,1687,1633,1598,1515,1489,1439,1370;1H NMR(400MHz,DMSO)δ:8.27(s,1H,PhNH),8.18(s,1H,CH2NH),7.17(d,J=8.8Hz,2H,PhH),6.90(d,J=8.8Hz,2H,PhH),5.29(s,1H,C=CH2),5.14(s,1H,C=CH2),4.30-4.22(m,4H,CH2NH+OCH2),4.00(q,J=7.1Hz,2H,OCH2),1.27(t,J=7.1Hz,3H,CH3),1.08(t,J=7.1Hz,3H,CH3);MS(EI)m/z:410[M]+.
1-(1-(4-((丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丙酯(A3)
白色粉末,收率50.7%,m.p.115.6-116.3℃;IR(KBr,cm-1)v:3314,3188,3082,2970,2881,1777,1688,1603,1508,1491,1473,1410,1344;1H NMR(400MHz,DMSO)δ:8.26(s,1H,PhNH),8.19(s,1H,CH2NH),7.17(d,J=8.8Hz,2H,PhH),6.90(d,J=8.8Hz,2H,PhH),5.31(s,1H,C=CH2),5.16(s,1H,C=CH2),4.25(s,2H,CH2NH),4.18(t,J=6.6Hz,2H,OCH2),3.91(t,J=6.4Hz,2H,OCH2),1.74-1.60(m,2H,CH3CH2),1.54-1.39(m,2H,CH3CH2),0.91(t,J=7.4Hz,3H,CH3),0.74(t,J=7.4Hz,3H,CH3);MS(EI)m/z:437[M-H]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A4)
白色粉末,收率80.3%,m.p.162.3-166.4℃;IR(KBr,cm-1)v:3335,3180,3074,2990,2878,1779,1722,1697,1630,1596,1489,1495,1376;1H NMR(400MHz,DMSO)δ:8.28(s,1H,PhNH),8.18(s,1H,CH2NH),7.17(d,J=8.8Hz,2H,PhH),6.91(d,J=8.8Hz,2H,PhH),5.25(s,1H,C=CH2),5.00(s,1H,C=CH2),4.93-4.84(m,1H,CH),4.76-4.64(m,1H,CH),4.25(s,2H,CH2NH),1.29(d,J=6.2Hz,6H,CH(CH3)2),1.08(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:351[M-87]+.
1-(1-(4-((丁氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丁酯(A5)
白色粉末,收率58.8%,m.p.104.6-105.7℃;IR(KBr,cm-1)v:3326,3187,3080,2962,2929,1784,1744,1688,1600,1490,1439,1399;1H NMR(400MHz,DMSO)δ:8.25(s,1H,PhNH),8.19(s,1H,CH2NH),7.17(d,J=8.8Hz,2H,PhH),6.90(d,J=8.8Hz,2H,PhH),5.31(s,1H,C=CH2),5.15(s,1H,C=CH2),4.25(s,2H,CH2NH),4.22(t,J=6.6Hz,2H,OCH2),3.95(t,J=6.4Hz,2H,OCH2),1.69-1.57,1.48-1.29,1.24-1.09(m,8H,2×(CH2)2CH3),0.90(t,J=7.4Hz,3H,CH3),0.78(t,J=7.4Hz,3H,CH3);MS(EI)m/z:465[M-H]+.
1-(1-(4-((异丁氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丁酯(A6)
白色粉末,收率68.2%,m.p.102.1-105.5℃;IR(KBr,cm-1)v:3327,3227,3096,2960,2874,1782,1694,1601,1489,1401,1380;1H NMR(400MHz,DMSO)δ:8.24(s,1H,PhNH),8.20(s,1H,CH2NH),7.17(d,J=8.8Hz,2H,PhH),6.91(d,J=8.9Hz,2H,PhH),5.33(s,1H,C=CH2),5.19(s,1H,C=CH2),4.25(s,2H,CH2NH),4.01(d,J=6.6Hz,2H,OCH2),3.74(d,J=6.4Hz,2H,OCH2),2.03-1.88(m,1H,CH),1.79-1.65(m,1H,CH),0.91(d,J=6.7Hz,6H,CH(CH3)2),0.73(d,J=6.7Hz,6H,CH(CH3)2);MS(EI)m/z:465[M-H]+.
1-(1-(4-((苄氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸苄酯(A7)
白色粉末,收率56.4%,m.p.166.3-167.2℃;IR(KBr,cm-1)v:3295,3212,3094,2961,2901,1764,1715,1694,1599,1491,1457,1375;1H NMR(400MHz,DMSO)δ:8.36(s,1H,PhNH),8.19(s,1H,CH2NH),7.47-7.35(m,5H,PhH),7.31-7.23(m,3H,PhH),7.20-7.10(m,4H,PhH),6.95-6.86(m,2H,PhH),5.33(s,1H,C=CH2),5.26(s,2H,CH2Ph),5.19(s,1H,C=CH2),5.00(s,2H,CH2Ph),4.20(s,2H,CH2NH);MS(EI)m/z:534[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-甲基苯基)肼基-1-甲酸异丙酯(A8)
白色粉末,收率77.9%,m.p.155.2-156.0℃;IR(KBr,cm-1)v:3328,3178,3069,2994,2876,1778,1719,1690,1629,1515,1465,1378;1H NMR(400MHz,DMSO)δ:8.15(s,1H,PhNH),7.84(s,1H,CH2NH),6.95(d,J=8.1Hz,2H,PhH),6.76(d,J=8.1Hz,2H,PhH),5.24(s,1H,C=CH2),5.02(s,1H,C=CH2),4.94-4.83(m,1H,OCH),4.75-4.63(m,1H,OCH),2.17(s,3H,PhCH3),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.07(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:314[M-103]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-甲氧基苯基)肼基-1-甲酸异丙酯(A9)
白色粉末,收率53.0%,m.p.150.3-151.9℃;IR(KBr,cm-1)v:3330,3179,3075,2989,2979,1772,1716,1693,1629,1508,1469,1374;1H NMR(400MHz,DMSO)δ:8.15(s,1H,PhNH),7.68(s,1H,CH2NH),6.83(d,J=8.9Hz,2H,PhH),6.75(d,J=8.9Hz,2H,PhH),5.26(s,1H,C=CH2),5.03(s,1H,C=CH2),4.95-4.82(m,1H,OCH),4.75-4.62(m,1H,OCH),4.23(s,2H,CH2NH),3.66(s,3H,OCH3),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.07(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:330[M-103]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(3,4-二甲基苯基)肼基-1-甲酸异丙酯(A10)
白色粉末,收率59.7%,m.p.152.6-153.7℃;IR(KBr,cm-1)v:3328,3227,3033,2987,2934,1769,1691,1636,1525,1501,1440,1374;1H NMR(400MHz,DMSO)δ:8.15(s,1H,PhNH),7.76(s,1H,CH2NH),6.88(d,J=8.1Hz,1H,PhH),6.68(s,1H,PhH),6.61-6.55(m,1H,PhH),5.24(s,1H,C=CH2),5.01(s,1H,C=CH2),4.95-4.82(m,1H,OCH),4.75-4.63(m,1H,OCH),4.23(s,2H,CH2NH),2.10(d,J=13.9Hz,6H,2×PhCH3),1.29(d,J=6.2Hz,6H,CH(CH3)2),1.08(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:210[M-221]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2-氟苯基)肼基-1-甲酸异丙酯(A11)
白色粉末,收率64.7%,m.p.146.5-147.8℃;IR(KBr,cm-1)v:3342,3175,3072,2990,2883,1766,1720,1691,1631,1501,1497,1450,1378;1H NMR(400MHz,DMSO)δ:8.24(s,1H,PhNH),7.95(s,1H,CH2NH),7.30(t,J=8.0Hz,1H,PhH),7.17-7.05(m,1H,PhH),7.00(t,J=7.6Hz,1H,PhH),6.83-6.69(m,1H,PhH),5.35(s,1H,C=CH2),5.08(s,1H,C=CH2),4.96-4.84(m,1H,OCH),4.78-4.65(m,1H,OCH),4.28(s,2H,CH2NH),1.31(d,J=6.2Hz,6H,CH(CH3)2),1.09(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:421[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氟苯基)肼基-1-甲酸异丙酯(A12)
白色粉末,收率67.0%,m.p.142.5-143.3℃;IR(KBr,cm-1)v:3338,3177,3073,2990,2883,1778,1718,1698,1631,1505,1466,1376;1H NMR(400MHz,DMSO)δ:8.17(s,1H,PhNH),8.04(s,1H,CH2NH),6.98(t,J=8.8Hz,2H,PhH),6.94-6.88(m,2H,PhH),5.28(s,1H,C=CH2),5.02(s,1H,C=CH2),4.95-4.83(m,1H,OCH),4.77-4.65(m,1H,OCH),4.25(s,2H,CH2NH),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.08(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:421[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2-氯苯基)肼基-1-甲酸异丙酯(A13)
黄色粉末,收率53.2%,m.p.136.5-138.1℃;IR(KBr,cm-1)v:3331,3187,3078,2988,2868,1779,1716,1689,1633,1592,1490,1462,1386;1H NMR(400MHz,DMSO)δ:8.27(s,1H,PhNH),7.70(s,1H,CH2NH),7.29(t,J=8.7Hz,2H,PhH),7.16(t,J=7.7Hz,1H,PhH),6.79(t,J=7.6Hz,1H,PhH),5.40(s,1H,C=CH2),5.21(s,1H,C=CH2),4.95-4.85(m,1H,OCH),4.77-4.66(m,1H,OCH),4.25(s,2H,CH2NH),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.08(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:438[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(3-氯苯基)肼基-1-甲酸异丙酯(A14)
黄色粉末;收率65.8%;m.p.178.2-178.5℃;IR(KBr,cm-1)v:3349,3218,3097,2985,2936,1779,1772,1688,1634,1594,1479,1375;1H NMR(400MHz,DMSO)δ:8.46(s,1H,PhNH),8.21(s,1H,CH2NH),7.15(t,J=8.0Hz,1H,PhH),7.01(s,1H,PhH),6.86-6.80(m,1H,PhH),6.78-6.71(m,1H,PhH),5.23(s,1H,C=CH2),4.97(s,1H,C=CH2),4.95-4.83(m,1H,OCH),4.77-4.65(m,1H,OCH),4.25(s,2H,CH2NH),1.29(d,J=6.2Hz,6H,CH(CH3)2),1.09(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:438[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2,4-二氯苯基)肼基-1-甲酸异丙酯(A15)
黄色粉末,收率61.5%,m.p.128.4-130.4℃;IR(KBr,cm-1)v:3332,3209,3089,2981,2872,1775,1724,1694,1628,1592,1488,1466,1392;1H NMR(400MHz,DMSO)δ:8.28(s,1H,PhNH),7.97(s,1H,CH2NH),7.46(d,J=2.1Hz,1H,PhH),7.38(d,J=8.8Hz,1H,PhH),7.25-7.18(m,1H,PhH),5.36(s,1H,C=CH2),5.14(s,1H,C=CH2),4.96-4.85(m,1H,OCH),4.78-4.67(m,1H,OCH),4.30(s,2H,CH2NH),1.31(d,J=6.2Hz,6H,CH(CH3)2),1.10(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:472[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-溴苯基)肼基-1-甲酸异丙酯(A16)
白色粉末,收率53.6%,m.p.148.0-149.3℃;IR(KBr,cm-1)v:3334,3183,3076,2992,2877,1779,1724,1696,1630,1594,1490,1462,1386;1H NMR(400MHz,DMSO)δ:8.33(s,1H,PhNH),8.20(s,1H,CH2NH),7.29(d,J=8.7Hz,2H,PhH),6.86(d,J=8.7Hz,2H,PhH),5.24(s,1H,C=CH2),5.00(s,1H,C=CH2),4.94-4.82(m,1H,OCH),4.76-4.64(m,1H,OCH),4.25(s,2H,CH2NH),1.29(d,J=6.2Hz,6H,CH(CH3)2),1.08(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:482[M]+.
1-(1-(1-甲基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A17)
白色粉末,收率61.3%,m.p.133.6-135.2℃;IR(KBr,cm-1)v:3249,3099,2981,2934,1777,1715,1689,1668,1598,1490,1464,1375;1H NMR(400MHz,DMSO)δ:8.30(s,1H,NH),7.17(d,J=8.8Hz,2H,PhH),6.93(d,J=8.9Hz,2H,PhH),5.25(s,1H,C=CH2),4.99(s,1H,C=CH2),4.95-4.83(m,1H,OCH),4.76-4.64(m,1H,OCH),4.36(s,2H,CH2NH),2.92(s,3H,CH3N),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.06(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:452[M]+.
1-(1-(1-乙基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A18)
白色粉末,收率55.4%,m.p.120.2-121.6℃;1R(KBr,cm-1)v:3249,3099,2981,2934,1777,1715,1689,1668,1598,1490,1464,1375;1H NMR(400MHz,DMSO)δ:8.25(s,1H,NH),7.17(d,J=8.7Hz,2H,PhH),6.93(d,J=8.8Hz,2H,PhH),5.26(s,1H,C=CH2),5.00(s,1H,C=CH2),4.95-4.83(m,1H,OCH),4.76-4.64(m,1H,OCH),4.36(s,2H,CH2NH),3.40(q,J=7.1Hz,2H,CH3CH2N),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.15-1.01(m,9H,CH(CH3)2+CH3CH2N);MS(EI)m/z:362[M-104]+.
1-(1-(1-乙酰基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A19)
白色粉末,收率68.7%,m.p.127.3-128.5℃;IR(KBr,cm-1)v:3298,3091,2988,2938,1783,1720,1689,1620,1595,1489,1442,1352;1H NMR(400MHz,DMSO)δ:8.38(s,1H,NH),7.19(d,J=8.8Hz,2H,PhH),6.87(d,J=8.9Hz,2H,PhH),5.34(s,1H,C=CH2),4.99(s,1H,C=CH2),4.97-4.86(m,1H,OCH),4.79-4.67(m,3H,OCH+CH2NH),2.45(s,3H,CH3CO),1.31(d,J=6.2Hz,6H,CH(CH3)2),1.08(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:480[M]+.
1-(1-(1-环丙基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A20)
白色粉末,收率49.2%,m.p.147.9-149.1℃;IR(KBr,cm-1)v:3249,3098,2987,2935,1773,1715,1697,1682,1593,1490,1466,1364;1H NMR(400MHz,DMSO)δ:8.27(s,1H,NH),7.17(d,J=8.8Hz,2H,PhH),6.92(d,J=8.8Hz,2H,PhH),5.25(s,1H,C=CH2),4.97(s,1H,C=CH2),4.93-4.83(m,1H,OCH),4.75-4.64(m,1H,OCH),4.29(s,2H,CH2NH),2.77-2.68(m,1H,NCH),1.29(d,J=6.2Hz,6H,CH(CH3)2),1.07(d,J=6.2Hz,6H,CH(CH3)2),0.77-0.68(m,4H,C2H4);MS(EI)m/z:478[M]+.
1-(1-(1-环己基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A21)
白色粉末,收率58.9%,m.p.151.0-152.0℃;IR(KBr,cm-1)v:3255,3098,2985,2939,2857,1771,1712,1691,1667,1597,1488,1466,1385;1H NMR(400MHz,DMSO)δ:8.26(s,1H,NH),7.17(d,J=8.8Hz,2H,PhH),6.94(d,J=8.8Hz,2H,PhH),5.26(s,1H,C=CH2),4.99(s,1H,C=CH2),4.94-4.83(m,1H,OCH),4.75-4.64(m,1H,OCH),4.31(s,2H,CH2NH),3.94-3.81(m,1H,NCH),1.83-1.56,1.49-1.32,1.18-1.09(m,10H,C5H10),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.07(d,J=6.2Hz,6H,CH(CH3)2);MS(EI)m/z:329[M-191]+.
1-(1-(1-苄基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A22)
白色粉末,收率48.8%,m.p.117.0-118.9℃;IR(KBr,cm-1)v:3260,3033,2981,2920,1769,1714,1685,1597,1491,1412,1390;1H NMR(400MHz,DMSO)δ:8.31(s,1H,PhNH),7.36(t,J=7.2Hz,2H,PhH),7.28(dd,J=14.2,7.2Hz,3H,PhH),7.18(d,J=8.7Hz,2H,PhH),6.93(d,J=8.7Hz,2H,PhH),5.30(s,1H,C=CH2),5.06(s,1H,C=CH2),4.92-4.78(m,1H,OCH),4.77-4.65(m,1H,OCH),4.59(s,2H,CH2NH),4.30(s,2H,PhCH2),1.27(d,J=6.2Hz,6H,CH(CH3)2),1.05(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:528[M]+.
1-(1-(4-((异丙氧基甲酰基)氧基)-5-甲基-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(A23)
棕色油状物,收率41.2%,IR(KBr,cm-1)v:3275,2981,2935,2877,1768,1697,1645,1596,1490,1466,1373;1H NMR(400MHz,DMSO)δ:8.35(s,1H,PhNH),8.33(s,1H,CHNH),7.17(d,J=8.8Hz,2H,PhH),6.92(d,J=8.9Hz,2H,PhH),5.20(s,1H,C=CH2),4.97-4.87(m,1H,C=CH2),4.86(s,1H,CHNH),4.77-4.68(m,1H,OCH),4.49-4.40(m,1H,OCH),1.30(t,J=5.9Hz,6H,CH(CH3)2),1.23(d,J=6.7Hz,3H,CH3CH),1.09(d,J=6.3Hz,6H,CH(CH3)2);MS(EI)m/z:452[M]+.
1-(1-(2-((甲氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸甲酯(B1)
土黄色粉末,收率46.0%,m.p.122.1-122.5℃;IR(KBr,cm-1)v:3247,3221,2988,2980,2952,2900,1784,1662,1621,1439;1H NMR(400MHz,DMSO)δ:8.35(s,1H,NH),7.18(d,J=8.8Hz,2H,PhH),6.84(d,J=8.8Hz,2H,PhH),5.27(s,1H,C=CH2),4.94(s,1H,C=CH2),3.86(s,3H,OCH3),3.56(s,3H,OCH3),3.04-2.98(m,2H,CH2CH2),2.56-2.52(m,2H,CH2CH2);MS(EI)m/z:380[M]+.
1-(1-(2-((乙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸乙酯(B2)
灰白色粉末,收率35.1%,m.p.121.6-124.3℃;IR(KBr,cm-1)v:3273,3258,2987,2973,2965,2950,1781,1659,1631,1440;1H NMR(400MHz,DMSO)δ:8.35(s,1H,NH),7.18(d,J=8.8Hz,2H,PhH),6.85(d,J=8.8Hz,2H,PhH),5.23(s,1H,C=CH2),4.85(s,1H,C=CH2),4.28(q,J=7.1Hz,2H,OCH2),3.99(q,J=7.1Hz,2H,OCH2),2.99(dd,J=5.1,2.2Hz,2H,CH2CH2),2.55-2.52(m,2H,CH2CH2),1.28(t,J=7.1Hz,3H,CH3),1.06(t,J=7.1Hz,3H,CH3);MS(EI)m/z:408[M]+.
1-(1-(2-((丙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丙酯(B3)
黄色粉末,收率49.1%,m.p.111.3-112.5℃;IR(KBr,cm-1)v:3281,3273,2973,2965,2951,2922,1614,1490,1469,1453;1H NMR(400MHz,DMSO)δ:8.33(s,1H,NH),7.17(d,J=8.8Hz,2H,PhH),6.85(d,J=8.8Hz,2H,PhH),5.25(s,1H,C=CH2),4.85(s,1H,C=CH2),4.19(t,J=6.4Hz,2H,OCH2),3.90(t,J=6.4Hz,2H,OCH2),3.08-2.93(m,2H,CH2CH2),2.56-2.52(m,2H,CH2CH2),1.72-1.63(m,2H,CH3CH2),1.48-1.39(m,2H,CH3CH2),0.91(t,3H,CH3),0.72(t,3H,CH3);MS(EI)m/z:436[M]+.
1-(1-(2-((异丙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯(B4)
白色粉末,收率40.1%,m.p.110.4-112.7℃;IR(KBr,cm-1)v:3282,3269,2981,2967,2949,2932,1615,1487,1472,1458;1H NMR(400MHz,DMSO)δ:8.32(s,1H,NH),7.18(d,J=8.8Hz,2H,PhH),6.85(d,J=8.8Hz,2H,PhH),5.20(s,1H,C=CH2),4.96-4.85(m,1H,OCH),4.75(s,1H,C=CH2),4.69(dt,J=12.4,6.2Hz,1H,OCH),3.01-2.96(m,2H,CH2CH2),2.56-2.52(m,2H,CH2CH2),1.30(d,J=6.2Hz,6H,CH(CH3)2),1.06(d,J=6.1Hz,6H,CH(CH3)2);MS(EI)m/z:436[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丁酯(B5)
粉红色粉末,收率51.1%,m.p.104.2-106.4℃;IR(KBr,cm-1)v:3337,3000,2962,2930,2922,1772,1723,1690,1620,1599,1494,1472;1H NMR(400MHz,DMSO)δ:8.34(s,1H,NH),7.18(d,J=8.8Hz,2H,PhH),6.85(d,J=8.8Hz,2H,PhH),5.25(s,1H,C=CH2),4.84(s,1H,C=CH2),4.23(t,J=6.5Hz,2H,OCH2),3.94(t,J=6.3Hz,2H,OCH2),3.05-2.94(m,2H,CH2CH2),2.53(dd,J=5.0,2.2Hz,2H,CH2CH2),1.69-1.59,1.45-1.34,1.14(m,8H,2×(CH2)2CH3),0.90(t,J=7.4Hz,3H,CH3),0.77(t,J=7.4Hz,3H,CH3);MS(EI)m/z:464[M]+.
1-(1-(2-((异丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丁酯(B6)
棕色粉末,收率49.9%,m.p.111.3-112.2℃;IR(KBr,cm-1)v:3322,2998,2962,2922,1772,1723,1690,1655,1620,1599,1494,1460;1H NMR(400MHz,DMSO)δ:8.32(s,1H,NH),7.18(d,J=8.8Hz,2H,PhH),6.86(d,J=8.9Hz,2H,PhH),5.27(s,1H,C=CH2),4.87(s,1H,C=CH2),4.03(d,J=6.6Hz,2H,OCH2,3.73(d,J=6.3Hz,2H,OCH2),3.03-2.97(m,2H,CH2CH2),2.55-2.52(m,2H,CH2CH2)),2.08-1.87(m,1H,CH(CH3)2),1.82-1.63(m,1H,CH(CH3)2),0.91(d,J=6.7Hz,6H,CH(CH3)2),0.72(d,J=6.7Hz,6H,CH(CH3)2);MS(EI)m/z:464[M]+.
1-(1-(2-((苄氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸苄酯(B7)
棕色粉末,收率31.9%,m.p.113.4-114.8℃;IR(KBr,cm-1)v:3313,2987,2972,2933,2900,1740,1693,1600,1566,1545,1489;1H NMR(400MHz,DMSO)δ;8.44(s,1H,NH),7.42(ddd,J=7.1,6.4,3.4Hz,5H,PhH),7.31-7.24(m,3H,PhH),7.14(dd,J=10.8,6.4Hz,4H,PhH),6.86(d,J=8.8Hz,2H,PhH),5.29(s,2H,C=CH2),5.26(s,1H,C=CH2),4.99(s,2H,OCH2),4.83(s,2H,OCH2),2.90(d,J=3.3Hz,2H,CH2CH2),2.39(s,2H,CH2CH2);MS(EI)m/z:532[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(2-氟苯基)肼基-1-甲酸丁酯(B8)
棕色粉末,收率32.5%,m.p.111.6-111.8℃;IR(KBr,cm-1)v:3319,2960,2934,2890,2874,1706,1651,1583,1502,1455,1423;1H NMR(400MHz,DMSO)δ:8.07(s,1H,NH),7.18(t,J=8.0Hz,1H,PhH),7.13-7.05(m,1H,PhH),6.99(t,J=7.5Hz,1H,PhH),6.76(dd,J=11.4,7.6Hz,1H,PhH),5.29(s,1H,C=CH2),4.83(s,1H,C=CH2),4.24(t,J=6.5Hz,2H,OCH2),3.93(t,J=6.4Hz,OCH2),3.00(d,J=4.8Hz,2H,CH2CH2),2.55(d,J=4.7Hz,12H,CH2CH2),1.71-1.58(m,2H,CH2CH2CH3),1.37(dt,J=15.1,7.5Hz,4H,2×CH2CH3),1.12(dd,J=14.8,7.3Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH3),0.76(t,J=7.4Hz,3H,CH3);MS(EI)m/z:448[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氟苯基)肼基-1-甲酸丁酯(B9)
红棕色粉末,收率31.5%,m.p.110.8-111.2℃;IR(KBr,cm-1)v:3298,2960,2934,2890,2873,1777,1715,1657,1506,1471,1433;1H NMR(400MHz,DMSO)δ:8.10(s,1H,NH),6.98(t,J=8.9Hz,2H,PhH),6.87-6.81(m,2H,PhH),5.26(s,1H,C=CH2),4.84(s,1H,C=CH2),4.24(t,J=6.6Hz,2H,OCH2),3.93(t,J=6.4Hz,2H,OCH2),3.02-2.94(m,2H,CH2CH2),2.55-2.51(m,2H,CH2CH2),1.68-1.58(m,2H,CH2CH2CH3),1.43-1.30(m,4H,2×CH2CH3),1.12(dd,J=15.0,7.5Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH3),0.77(t,J=7.4Hz,3H,CH3);MS(EI)m/z:448[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(2-氯苯基)肼基-1-甲酸丁酯(B10)
黄褐色粉末,收率32.2%,m.p.92.1-93.2℃;IR(KBr,cm-1)v:3352,2971,2966,2928,2900,1767,1713,1620,1595,1501,1450;1H NMR(400MHz,DMSO)δ:7.80(s,1H,NH),7.31(dd,J=7.9,1.1Hz,1H,PhH),7.24-7.13(m,2H,PhH),6.83-6.75(m,1H,PhH),5.31(s,1H,C=CH2),4.93(s,1H,C=CH2),4.25(t,J=6.5Hz,2H,OCH2),3.93(t,J=6.3Hz,2H,OCH2),3.07-2.96(m,2H,CH2CH2),2.61-2.53(m,2H,CH2CH2),1.70-1.59(m,2H,CH2CH2CH3),1.38(ddd,J=17.5,10.9,5.1Hz,4H,2×CH2CH3),1.13(dt,J=14.3,7.3Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH3),0.77(t,J=7.4Hz,3H,CH3);MS(EI)m/z:464[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(3-氯苯基)肼基-1-甲酸丁酯(B11)
红棕色粉末,收率51.1%,m.p.90.1-90.7℃;IR(KBr,cm-1)v:3300,2960,2933,2892,2873,1775,1715,1621,1598,1567,1480;1H NMR(600MHz,DMSO)δ:8.42(s,1H,NH),7.15(t,J=8.0Hz,1H,PhH),6.91(t,J=2.1Hz,1H,PhH),6.81-6.72(m,2H,PhH),5.24(s,1H,C=CH2),4.82(s,1H,C=CH2),4.24(t,J=6.6Hz,2H,OCH2),3.95(t,J=6.4Hz,2H,OCH2),3.01-2.97(m,2H,CH2CH2),2.55-2.52(m,2H,CH2CH2),1.64(dt,J=14.3,6.6Hz,2H,CH2CH2CH3),1.43-1.33(m,4H,2×CH2CH3),1.14(dd,J=15.0,7.4Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH3),0.78(t,J=7.4Hz,3H,CH3);MS(EI)m/z:464[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-溴苯基)肼基-1-甲酸丁酯(B12)
淡红色粉末,收率47.2%,m.p.96.4-97.6℃;IR(KBr,cm-1)v:3374,2971,2966,2921,2900,1771,1722,1655,1594,1490,1473;1H NMR(400MHz,DMSO)δ:8.35(s,1H,NH),7.29(d,J=8.8Hz,2H,PhH),6.80(d,J=8.9Hz,2H,PhH),5.24(s,1H,C=CH2),4.84(s,1H,C=CH2),4.23(t,J=6.6Hz,2H,OCH2),3.94(t,J=6.4Hz,2H,OCH2),3.04-2.94(m,2H,CH2CH2),2.53(dd,J=5.1,2.2Hz,2H,CH2CH2),1.70-1.57(m,2H,CH2CH2CH3),1.44-1.28(m,4H,2×CH2CH3),1.13(dd,J=15.0,7.4Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH3),0.77(t,J=7.4Hz,3H,CH3);MS(EI)m/z:508[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-甲苯基)肼基-1-甲酸丁酯(B13)
棕色粉末,收率32.7%,m.p.80.0-80.8℃;IR(KBr,cm-1)v:3338,2961,2929,2891,2873,1773,1697,1655,1614,1515,1460;1H NMR(400MHz,DMSO)δ:7.93(s,1H,NH),6.95(d,J=8.2Hz,2H,PhH),6.72(d,J=8.3Hz,2H,PhH),5.23(s,1H,C=CH2),4.81(s,1H,C=CH2),4.24(t,J=6.6Hz,2H,OCH2),3.92(t,J=6.4Hz,2H,OCH2),3.07-2.89(m,2H,CH2CH2),2.53(d,J=3.1Hz,2H,CH2CH2),2.17(s,3H,PhCH3),1.73-1.50(m,2H,CH2CH2CH3),1.45-1.23(m,4H,2×CH2CH3),1.12(dd,J=14.9,7.4Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH3),0.76(t,J=7.4Hz,3H,CH3);MS(EI)m/z:444[M]+.
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-甲氧基苯基)肼基-1-甲酸丁酯(B14)
棕色粉末,收率26.3%,m.p.82.8-83.3℃;IR(KBr,cm-1)v:3316,2961,2933,2874,2835,1773,1721,1693,1616,1511,1468;1H NMR(400MHz,DMSO)δ:7.77(s,1H,NH),6.81-6.72(m,4H,PhH),5.25(s,1H,C=CH2),4.83(s,1H,C=CH2),4.24(t,J=6.6Hz,2H,OCH2),3.92(t,J=6.4Hz,2H,OCH2),3.65(s,3H,OCH3),3.01-2.94(m,2H,CH2CH2),2.55-2.51(m,2H,CH2CH2),1.69-1.59(m,2H,CH2CH2CH3),1.37(dt,J=15.0,7.4Hz,4H,2×CH2CH2CH2CH3),1.13(dd,J=15.0,7.4Hz,2H,CH2CH2CH3),0.90(t,J=7.4Hz,3H,CH2CH3),0.77(t,J=7.4Hz,3H,CH2CH3);MS(E1)m/z:460[M]+.
用途实施例
实施例2:本发明的含二取代肼基的酯类化合物(I)对植物病原真菌的杀菌活性测
定
采用菌丝生长速率法(具体测定方法的参考文献:Chem.Res.Chin.Univ.2015,31(2):228-234.)测定了实施例1中所制备的含二取代肼基的酯类化合物(1)中的A、B系列化合物对四种供试植物病原菌小麦赤霉病菌(Fusarium graminearum)、蔬菜灰霉病菌(Botrytis cinerea)、水稻纹枯病菌(Rhizoctonia solani)和辣椒炭疽病菌(Colletotrichum capsici)在10μg/mL浓度下的杀菌活性,以多菌灵、速克灵、嘧菌酯作为对照药剂,测定结果见表1。
表1显示,在10μg/mL浓度下,含二取代肼基的酯类化合物(I)中的A、B系列化合物对四种供试植物病原菌小麦赤霉病菌、蔬菜灰霉病菌、水稻纹枯病菌和辣椒炭疽病菌具有显著的杀菌活性。其中,化合物A1-A8、A10、A12、A16-A23、B1、B2、B4-B7、B9、B11-B13对小麦赤霉病菌的抑制率大于90%;化合物A1-A6、A12、A14、A16-A20、A22、B8、B9、B11、B12对蔬菜灰霉病菌的抑制率大于90%;化合物A1、A3、A4、A9、A11-A16、A18-A20、A22、A23、B1、B2、B4-B11对水稻纹枯病菌的抑制率大于90%;化合物A1-A7、A11-A20、A22、B1、B2、B4-B8、B11、B12对辣椒炭疽病菌的抑制率大于90%。
表1 含二取代肼基的酯类化合物(I)对4种植物病原菌的抑制率(10μg/mL)
Claims (4)
2.根据权利要求1所述的含二取代肼基的酯类化合物,其特征在于其为如下所述化合物之一:
1-(1-(4-((甲氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸甲酯、
1-(1-(4-((乙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸乙酯、
1-(1-(4-((丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((丁氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丁酯、
1-(1-(4-((异丁氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丁酯、
1-(1-(4-((苄氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸苄酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-甲基苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-甲氧基苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(3,4-二甲基苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2-氟苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氟苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(3-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(2,4-二氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-溴苯基)肼基-1-甲酸异丙酯、
1-(1-(1-甲基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-乙基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-乙酰基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-环丙基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-环己基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(1-苄基-4-((异丙氧基甲酰基)氧基)-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(4-((异丙氧基甲酰基)氧基)-5-甲基-2-氧-2,5-二氢-1H-吡咯-3-基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(2-((甲氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸甲酯、
1-(1-(2-((乙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸乙酯、
1-(1-(2-((丙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丙酯、
1-(1-(2-((异丙氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丙酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸丁酯、
1-(1-(2-((异丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸异丁酯、
1-(1-(2-((苄氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氯苯基)肼基-1-甲酸苄酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(2-氟苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-氟苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(2-氯苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(3-氯苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-溴苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-甲苯基)肼基-1-甲酸丁酯、
1-(1-(2-((丁氧基甲酰基)氧基)-5-氧环戊-1-烯基)乙烯基)-2-(4-甲氧基苯基)肼基-1-甲酸丁酯。
4.权利要求1-2中任一项所述的含二取代肼基的酯类化合物在防治小麦赤霉病、蔬菜灰霉病、水稻纹枯病和辣椒炭疽病方面的应用。
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