CN111377844B - 一种二氧吡咯烷乙酸的衍生物、制备方法及其应用 - Google Patents
一种二氧吡咯烷乙酸的衍生物、制备方法及其应用 Download PDFInfo
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Abstract
本发明属于杀菌剂领域,公开了一种二氧吡咯烷乙酸的衍生物、制备方法及其应用,该化合物的结构如式(I)所示:
Description
技术领域
本发明涉及一种二氧吡咯烷乙酸的衍生物、制备方法及其在防治植物真菌病害方面的应用,具有作为农药杀菌剂的用途。
背景技术
吡咯烷二酮是一种含氮五元杂环,常出现在一些天然化合物的结构中,含吡咯烷二酮的化合物常常表现出抗肿瘤、杀菌、除草等各种生物活性,人们常常将其作为研发新型药物尤其是农药的先导化合物。如专利ZL201210524110.9和ZL201510204812.2公开的吡咯烷二酮类化合物,具有良好的抑制植物病原真菌的活性。肼基团是一种重要的活性基团,人们经常将其引入到农药的分子结构中,如环虫酰肼(chromafenozide)、氯虫酰肼(halofenozide)均属于含有肼基团的杀虫剂,在农业害虫的防治方面被广泛应用。专利ZL201110453110.X公开了一类含有苯肼基团的吡咯烷二酮类化合物,对植物病原真菌具有显著的抑制活性。专利WO9962335A1则公开了一类具有抗真菌活性的酰肼类化合物。此外,含有酰胺基团的化合物也常常具有良好的生物活性。如,啶酰菌胺(boscalid)、氟唑菌酰胺(fluxapyroxad)均属于典型的酰胺类杀菌剂。
本发明在二氧吡咯烷乙酸的4位引入取代苯肼基团,同时在2位通过乙酰基与苯胺或苯肼基团链接,设计并合成了一种二氧吡咯烷乙酸的衍生物,生物活性测定结果表明,这类化合物具有显著抑制植物病原真菌的活性。
发明内容
本发明的目的在于提供一种二氧吡咯烷乙酸的衍生物。
本发明的第二个目的在于提供一种二氧吡咯烷乙酸的衍生物的制备方法。
本发明的第三个目的在于提供上述衍生物的应用。
本发明的第一方面提供了一种具有通式(I)所示结构的一种二氧吡咯烷乙酸的衍生物,
在式(I)中,所述各个基团具有如下所述的定义:
Y(m)中,m=1-5取代,Y(m)选自下列1-5个基团:X、R,其中X表示卤素;R表示氢、未取代或被1-6个卤素取代的C1-6烷基;
Z(n)中,n=1-5取代,Z(n)选自下列1-5个基团:X、R,其中X表示卤素;R表示氢、未取代或被1-6个卤素取代的C1-6烷基;
k选自0、1。
在式(I)中,所述各个基团具有如下所述的优选定义:
Y(m)中,m=1-2取代,Y(m)选自下列1-2个基团:X、R,其中X表示卤素;R表示C1-3烷基;
Z(n)中,n=1-2取代,Z(n)选自1-2个卤素;
k选自0、1。
在式(I)中,所述各个基团具有如下所述的进一步优选定义:
Y(m)中,m=1取代,Y(m)选自下列1个基团:4-X、4-CH3,其中X表示F、Cl、Br;
Z(n)中,n=1-2取代,Z(n)选自1-2个F、Cl、Br;
k选自0、1。
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:
Y(m)选自4-Cl、4-CH3;
Z(n)选自2-Cl、4-Cl、2,4-(Cl)2、4-Br;
k选自0、1。
在式(I)中,所述各个基团具有如下所述的特别优选定义:
N-(4-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-a)、
N-(4-溴苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-b)、
N-(4-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-c)、
N-(4-溴苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-d)、
N′-(2-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-e)、
N′-(4-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-f)、
N′-(2,4-二氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-g)、
N′-(4-溴苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-h)、
N′-(2-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-i)、
N′-(4-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-j)、
N′-(2,4-二氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-k)、
N′-(4-溴苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-l)。
本发明的第二个方面提供了制备式(I)的一种二氧吡咯烷乙酸的衍生物的制备方法,该方法以式(II)的化合物与式(III)的化合物反应,制备式(I)的一种二氧吡咯烷乙酸的衍生物,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:
Y(m)、Z(n)、k均具有如前所述的相应基团的定义。
本发明的第三个方面涉及式(I)的一种二氧吡咯烷乙酸的衍生物在抑制植物病原真菌、防治植物真菌病害方面的应用,适合作为杀菌剂,应用于农药领域。
本发明的化合物适合应用于抑制植物病原真菌,如水稻纹枯病菌、小麦赤霉病菌、草莓灰霉病菌。
本发明的化合物适合应用于防治植物真菌病害,如水稻纹枯病、小麦赤霉病、草莓灰霉病。
有益效果:
1、本发明专利所述的式(I)的一种二氧吡咯烷乙酸的衍生物的化学结构具有新颖性,该类化合物的结构式含有一个吡咯烷二酮核心杂环,其4位上的亚乙基与取代苯肼基团链接,2位上的乙酰基与取代苯胺或取代苯肼链接。
2、本发明专利所述的式(I)的一种二氧吡咯烷乙酸的衍生物的制备方法简便、易行、原料易得。
3、本发明专利所述的式(I)的一种二氧吡咯烷乙酸的衍生物具有实用性,具有显著的抑制植物病原真菌的活性,可应用于防治由真菌引起的植物病害,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:本发明的一种二氧吡咯烷乙酸的衍生物I-a的制备
在50mL单口瓶中加入化合物II-a(3mmol)、对氯苯胺III-a(3mmol)、TBTU(3mmol)、三乙胺(3mmol)和20mL二氯甲烷,常温下搅拌反应10h,有固体析出,抽滤,用石油醚洗涤,得黄色粉末状固体,即二氧吡咯烷乙酸的衍生物I-a,其反应方程式如下:
实施例2:本发明的一种二氧吡咯烷乙酸的衍生物I-i的制备
在50mL单口瓶中加入化合物II-i(3mmol)、2-氯苯肼III-i(3mmol)、TBTU(3mmol)、三乙胺(3mmol)和20mL二氯甲烷,常温下搅拌反应10h,有固体析出,抽滤,用石油醚洗涤,得白色粉末状固体,即二氧吡咯烷乙酸的衍生物I-i,其反应方程式如下:
采用实施例1、实施例2的方法,制备了二氧吡咯烷乙酸的衍生物(I)中的I-a~I-l化合物:
N-(4-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-a)
黄色粉末;收率53.3%;m.p.:229.6-230.9℃;IR(KBr):v=3280,3195,3116,1676,1641,1605,1569,1533,1491,1399,1356,1312,1248,1093,1012,950,901cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.49(s,1H,CH3CNHNH),10.17(s,1H,NHC=O),8.49(s,1H,CH3CNHNH),7.93(s,1H,CHNH),7.65-7.62(m,2H,ArH),7.38-7.36(m,2H,ArH),7.31-7.29(m,2H,ArH),6.75-6.73(m,2H,ArH),4.06-4.03(m,1H,CH),2.74-2.73(m,1H,CH2),2.46(s,3H,CH3),2.43-2.41(m,1H,CH2)ppm;trans-isomer:δ=11.56(s,1H,CH3CNHNH),10.17(s,1H,NHC=O),8.53(s,1H,CH3CNHNH),7.65-7.62(m,3H,CHNH and ArH),7.38-7.36(m,2H,ArH),7.31-7.29(m,2H,ArH),6.75-6.73(m,2H,ArH),4.12-4.09(m,1H,CH),2.78-2.77(m,1H,CH2),2.49(s,3H,CH3),2.43-2.41(m,1H,CH2)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.59(s,pyrrolidine-5-C),174.51(s,pyrrolidine-3-C),169.99(s,CONH),169.04(s,=CNH),146.79(s,ArC),138.50(s,ArC),129.55(s,ArC),129.00(s,ArC),127.18(s,ArC),124.29(s,ArC),121.21(s,ArC),114.58(s,ArC),94.17(s,pyrrolidine-4-C),58.45(s,CH),40.04(s,CH2),13.03(s,CH3)ppm;trans-isomer:δ=198.41(s,pyrrolidine-5-C),171.37(s,pyrrolidine-3-C),170.32(s,CONH),168.84(s,=CNH),146.79(s,ArC),138.50(s,ArC),129.55(s,ArC),129.00(s,ArC),127.18(s,ArC),124.29(s,ArC),121.21(s,ArC),114.58(s,ArC),95.90(s,pyrrolidine-4-C),56.16(s,CH),40.04(s,CH2),12.32(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C20H18Cl2N4NaO3([M+Na]+)455.0648,found 455.0642.
N-(4-溴苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-b)
白色粉末;收率56.3%;m.p.:223.1-224.9℃;IR(KBr):v=3649,3527,34340,3285,3207,1676,1646,1599,1573,1532,1489,1396,1307,1241,1008,893cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.48(s,1H,CH3CNHNH),10.16(s,1H,NHC=O),8.49(s,1H,CH3CNHNH),7.93(s,1H,CHNH),7.60-7.57(m,2H,ArH),7.50-7.48(m,2H,ArH),7.31-7.28(m,2H,ArH),6.75-6.73(m,2H,ArH),4.05-4.02(m,1H,CH),2.74-2.73(m,1H,CH2),2.46(s,3H,CH3),2.43-2.41(m,1H,CH2)ppm;trans-isomer:δ=11.56(s,1H,CH3CNHNH),10.16(s,1H,NHC=O),8.52(s,1H,CH3CNHNH),7.61(s,1H,CHNH),7.60-7.57(m,2H,ArH),7.50-7.48(m,2H,ArH),7.31-7.28(m,2H,ArH),6.75-6.73(m,2H,ArH),4.11-4.08(m,1H,CH),2.77-2.76(m,1H,CH2),2.49(s,3H,CH3),2.43-2.41(m,1H,CH2)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.59(s,pyrrolidine-5-C),174.51(s,pyrrolidine-3-C),169.99(s,CONH),169.07(s,=CNH),146.67(s,ArC),138.91(s,ArC),131.91(s,ArC),129.56(s,ArC),124.30(s,ArC),121.60(s,ArC),115.20(s,ArC),114.58(s,ArC),94.18(s,pyrrolidine-4-C),58.44(s,CH),39.80(s,CH2),13.04(s,CH3)ppm;trans-isomer:δ=198.42(s,pyrrolidine-5-C),171.37(s,pyrrolidine-3-C),170.32(s,CONH),168.89(s,=CNH),146.67(s,ArC),138.91(s,ArC),131.92(s,ArC),129.56(s,ArC),124.30(s,ArC),121.60(s,ArC),115.20(s,ArC),114.58(s,ArC),95.90(s,pyrrolidine-4-C),56.17(s,CH),39.80(s,CH2),12.33(s,CH3)ppm;HRMS(ESI+):m/z calcd for C20H18BrClN4NaO3([M+Na]+)501.0122,found 501.0125.
N-(4-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-c)
白色粉末;收率56.3%;m.p.:228.3-229.9℃;IR(KBr):v=3441,3324,3269,1668,1635,1599,1574,1531,1511,1491,1357,1250,1082,947,813cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.50(s,1H,CH3CNHNH),10.30(s,1H,NHNHC=O),9.67(s,1H,CH3CNHNH),8.27(s,1H,NHNHC=O),7.85(s,1H,CHNH),7.69-7.65(m,1H,ArH),7.36-7.64(m,1H,ArH),7.07-7.05(m,2H,ArH),6.94-6.93(m,1H,ArH),6.68-6.64(m,3H,ArH),4.02-3.95(m,1H,CH),2.78-2.69(m,1H,CH2),2.47(s,3H,CH3),2.36-2.31(m,1H,CH2),2.21(s,3H,ArCH3)ppm;trans-isomer:δ=11.62(s,1H,CH3CNHNH),10.30(s,1H,NHNHC=O),9.67(s,1H,CH3CNHNH),8.33(s,1H,NHNHC=O),7.53(s,1H,CHNH),7.69-7.65(m,1H,ArH),7.36-7.64(m,1H,ArH),7.07-7.05(m,2H,ArH),6.94-6.93(m,1H,ArH),6.68-6.64(m,3H,ArH),4.11-4.07(m,1H,CH),2.78-2.69(m,1H,CH2),2.47(s,3H,CH3),2.36-2.31(m,1H,CH2),2.17(s,3H,ArCH3)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.45(s,pyrrolidine-5-C),174.82(s,pyrrolidine-3-C),169.83(s,CONH),169.20(s,=CNH),147.38(s,ArC),145.38(s,ArC),138.67(s,ArC),130.17(s,ArC),128.94(s,ArC),127.13(s,ArC),121.28(s,ArC),113.34(s,ArC),93.78(s,pyrrolidine-4-C),58.42(s,CH),36.89(s,CH2),20.64(s,ArCH3),13.10(s,CH3)ppm;trans-isomer:δ=198.37(s,pyrrolidine-5-C),171.57(s,pyrrolidine-3-C),170.21(s,CONH),169.02(s,=CNH),147.38(s,ArC),145.28(s,ArC),138.67(s,ArC),129.72(s,ArC),129.52(s,ArC),127.55(s,ArC),121.28(s,ArC),113.09(s,ArC),95.58(s,pyrrolidine-4-C),56.19(s,CH),36.89(s,CH2),20.64(s,ArCH3),12.41(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C21H22ClN4O3([M+H]+)413.1375,found413.1374.
N-(4-溴苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺(I-d)
黄色粉末;收率60.1%;m.p.:229.9-231.9℃;IR(KBr):v=3442,3292,1677,1639,1581,1532,1509,1488,1396,1357,1305,1246,1214,1073,1008,951,901,812cm-1;1HNMR(400MHz,DMSO-d6):cis-isomer:δ=11.50(s,1H,CH3CNHNH),10.47(s,1H,NHC=O),8.40(s,1H,CH3CNHNH),7.86(s,1H,CHNH),7.65-7.63(m,2H,ArH),7.49-7.46(m,2H,ArH),7.07-7.05(m,2H,ArH),6.67-6.65(m,2H,ArH),4.04-4.01(m,1H,CH),2.79-2.75(m,1H,CH2),2.47(s,3H,CH3),2.34-2.30(m,1H,CH2),2.21(s,3H,ArCH3)ppm;trans-isomer:δ=11.63(s,1H,CH3CNHNH),10.47(s,1H,NHC=O),8.45(s,1H,CH3CNHNH),7.53(s,1H,CHNH),7.65-7.63(m,2H,ArH),7.49-7.46(m,2H,ArH),7.07-7.05(m,2H,ArH),6.67-6.65(m,2H,ArH),4.11-4.08(m,1H,CH),2.79-2.75(m,1H,CH2),2.47(s,3H,CH3),2.34-2.30(m,1H,CH2),2.21(s,3H,ArCH3)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.44(s,pyrrolidine-5-C),174.80(s,pyrrolidine-3-C),169.84(s,CONH),169.19(s,=CNH),145.35(s,ArC),139.08(s,ArC),131.85(s,ArC),130.17(s,ArC),129.72(s,ArC),121.65(s,ArC),115.11(s,ArC),113.32(s,ArC),93.76(s,pyrrolidine-4-C),58.36(s,CH),45.79(s,CH2),20.64(s,ArCH3),13.09(s,CH3)ppm;trans-isomer:δ=198.26(s,pyrrolidine-5-C),171.48(s,pyrrolidine-3-C),170.21(s,CONH),169.01(s,=CNH),145.35(s,ArC),139.08(s,ArC),131.85(s,ArC),130.17(s,ArC),129.72(s,ArC),121.65(s,ArC),115.11(s,ArC),113.32(s,ArC),93.76(s,pyrrolidine-4-C),56.12(s,CH),45.79(s,CH2),20.64(s,ArCH3),12.40(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C21H21BrN4NaO3([M+Na]+)479.0689,found479.0689.
N′-(2-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-e)
白色粉末;收率48.8%;m.p.:231.9-232.9℃;IR(KBr):v=3551,3477,3415,3275,3035,1680,1635,158,1521,1492,1383,1357,1223,1095,1036,1008,819cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.46(s,1H,CH3CNHNH),9.89(s,1H,NHNHC=O),8.48(s,1H,CH3CNHNH),7.79(s,1H,CHNH),7.30-7.25(m,4H,NHNHC=O and ArH),7.17-7.13(m,1H,ArH),6.92-6.88(m,1H,ArH),6.77-6.72(m,3H,ArH),4.00-3.97(m,1H,CH),2.66-2.59(m,1H,CH2),2.46(s,3H,CH3),2.40-2.29(m,1H,CH2)ppm;trans-isomer:δ=11.56(s,1H,CH3CNHNH),9.89(s,1H,NHNHC=O),8.53(s,1H,CH3CNHNH),7.48(s,1H,CHNH),7.30-7.25(m,4H,NHNHC=O and ArH),7.17-7.13(m,1H,ArH),6.92-6.88(m,1H,ArH),6.77-6.72(m,3H,ArH),4.06-4.03(m,1H,CH),2.66-2.59(m,1H,CH2),2.48(s,3H,CH3),2.40-2.29(m,1H,CH2)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.38(s,pyrrolidine-5-C),174.43(s,pyrrolidine-3-C),170.02(s,CONH),169.98(s,=CNH),146.80(s,ArC),144.97(s,ArC),129.56(s,ArC),128.24(s,ArC),124.28(s,ArC),119.97(s,ArC),117.50(s,ArC),114.60(s,ArC),113.76(s,ArC),94.12(s,pyrrolidine-4-C),58.43(s,CH),37.02(s,CH2),13.04(s,CH3)ppm;trans-isomer:δ=198.21(s,pyrrolidine-5-C),171.25(s,pyrrolidine-3-C),170.36(s,CONH),169.86(s,=CNH),146.80(s,ArC),144.97(s,ArC),129.45(s,ArC),128.24(s,ArC),124.28(s,ArC),119.97(s,ArC),117.50(s,ArC),114.55(s,ArC),113.76(s,ArC),95.85(s,pyrrolidine-4-C),56.19(s,CH),37.02(s,CH2),12.31(s,CH3)ppm;HRMS(ESI+):m/z calcd for C20H20Cl2N5O3([M+H]+)448.0938,found 448.0934.
N′-(4-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-f)
Yield 70.0%;yellow solid;m.p.:234.2-235.1℃;IR(KBr):v=3551,3475,3414,3283,1678,1635,1580,1516,1401,1359,1251,1224,1172,1096,823cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.45(s,1H,CH3CNHNH),9.72(s,1H,NHNHC=O),8.47(s,1H,CH3CNHNH),7.85(s,1H,NHNHC=O),7.79(s,1H,CHNH),7.30-7.28(m,2H,ArH),7.23-7.14(m,2H,ArH),6.78-6.72(m,4H,ArH),3.98-3.95(m,1H,CH),2.64-2.57(m,1H,CH2),2.45(s,3H,CH3),2.40-2.33(m,1H,CH2)ppm;trans-isomer:δ=11.56(s,1H,CH3CNHNH),9.72(s,1H,NHNHC=O),8.53(s,1H,CH3CNHNH),7.85(s,1H,NHNHC=O),7.47(s,1H,CHNH),7.30-7.28(m,2H,ArH),7.23-7.14(m,2H,ArH),6.78-6.72(m,4H,ArH),4.05-4.02(m,1H,CH),2.64-2.57(m,1H,CH2),2.48(s,3H,CH3),2.40-2.33(m,1H,CH2)ppm;13C NMR(400MHz,DMSO-d6):cis-isomer:δ=195.59(s,pyrrolidine-5-C),174.55(s,pyrrolidine-3-C),169.91(s,CONH),169.73(s,=CNH),148.60(s,ArC),146.82(s,ArC),129.56(s,ArC),128.86(s,ArC),124.26(s,ArC),122.18(s,ArC),114.58(s,ArC),114.24(s,ArC),94.25(s,pyrrolidine-4-C),58.17(s,CH),36.76(s,CH2),13.01(s,CH3)ppm;trans-isomer:δ=198.43(s,pyrrolidine-5-C),171.41(s,pyrrolidine-3-C),170.24(s,CONH),169.60(s,=CNH),148.60(s,ArC),146.82(s,ArC),129.56(s,ArC),128.86(s,ArC),124.26(s,ArC),122.18(s,ArC),114.58(s,ArC),114.24(s,ArC),94.25(s,pyrrolidine-4-C),55.91(s,CH),36.76(s,CH2),12.31(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C20H20Cl2N5O3([M+H]+)448.0938,found 448.0939.
N′-(2,4-二氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-g)
Yield 40.4%;yellow solid;m.p.:229.0-231.0℃;IR(KBr):v=3564,3473,3415,3270,3165,1682,1633,1580,1522,1492,1405,1357,1258,1222,1097,996,816cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.46(s,1H,CH3CNHNH),9.94(s,1H,NHNHC=O),8.49(s,1H,CH3CNHNH),7.85(s,1H,NHNHC=O),7.81(s,1H,CHNH),7.51(s,1H,ArH),7.42(s,1H,ArH),7.30-7.28(m,2H,ArH),7.20-7.18(m,1H,ArH),6.94-6.90(m,1H,ArH),6.75-6.72(m,ArH,2H),4.00-3.97(m,1H,CH),2.63-2.59(m,1H,CH2),2.46(s,3H,CH3),2.41-2.30(m,1H,CH2)ppm;trans-isomer:δ=11.56(s,1H,CH3CNHNH),9.94(s,1H,NHNHC=O),8.54(s,1H,CH3CNHNH),7.85(s,1H,NHNHC=O),7.81(s,1H,CHNH),7.52(s,1H,ArH),7.42(s,1H,ArH),7.30-7.28(m,2H,ArH),7.20-7.18(m,1H,ArH),6.94-6.90(m,1H,ArH),6.75-6.72(m,ArH,2H),4.07-4.04(m,1H,CH),2.63-2.59(m,1H,CH2),2.49(s,3H,CH3),2.41-2.30(m,1H,CH2)ppm;13C NMR(400MHz,DMSO-d6):cis-isomer:δ=195.38(s pyrrolidine-5-C),174.44(s,pyrrolidine-3-C),170.03(s,CONH),170.01(s,=CNH),146.80(s,ArC),144.21(s,ArC),129.57(s,ArC),128.73(s,ArC),128.14(s,ArC),124.27(s,ArC),122.40(s,ArC),117.89(s,ArC),114.86(s,ArC),114.60(s,ArC),94.10(s,pyrrolidine-4-C),58.37(s,CH),36.99(s,CH2),13.04(s,CH3)ppm;trans-isomer:δ=198.19(s,pyrrolidine-5-C),171.26(s,pyrrolidine-3-C),170.36(s,CONH),169.89(s,=CNH),146.80(s,ArC),144.21(s,ArC),129.57(s,ArC),128.73(s,ArC),128.14(s,ArC),124.27(s,ArC),122.40(s,ArC),117.89(s,ArC),114.86(s,ArC),114,53(s,ArC),95.74(s,pyrrolidine-4-C),56.12(s,CH),36.99(s,CH2),12.32(s,CH3)ppm;HRMS(ESI+):m/z calcd for C20H18Cl3N5NaO3([M+Na]+)504.0367,found 504.0371.
N′-(4-溴苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-h)
黄色粉末;产率75.4%;m.p.:231.1-230.0℃;IR(KBr):v=3282,3184,1686,1623,1606,1573,1515,1486,1384,1358,1223,1100,1005,820cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.45(s,1H,CH3CNHNH),9.73(s,1H,NHNHC=O),8.47(s,1H,CH3CNHNH),7.88(s,1H,NHNHC=O),7.80(s,1H,CHNH),7.30-7.26(m,4H,ArH),6.74-6.71(m,4H,ArH),3.98-3.95(m,1H,CH),2.58-2.57(m,1H,CH2),2.45(s,3H,CH3),2.40-2.33(m,1H,CH2)ppm;trans-isomer.:δ=11.55(s,1H,CH3CNHNH),9.73(s,1H,NHNHC=O),8.58(s,1H,CH3CNHNH),7.88(s,1H,NHNHC=O),7.48(s,1H,CHNH),7.30-7.26(m,4H,ArH),6.74-6.71(m,4H,ArH),4.05-4.03(m,1H,CH),2.62-2.61(m,1H,CH2),2.48(s,3H,CH3),2.40-2.33(m,1H,CH2)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.88(s,pyrrolidine-5-C),174.56(s,pyrrolidine-3-C),169.93(s,CONH),169.77(s,=CNH),148.99(s,ArC),146.81(s,ArC),131.69(s,ArC),129.55(s,ArC),124.29(s,ArC),114.77(s,ArC),114.57(s,ArC),109.73(s,ArC),94.27(s,pyrrolidine-4-C),58.18(s,CH),36.77(s,CH2),13.03(s,CH3)ppm;trans-isomer:δ=195.58(s,pyrrolidine-5-C),171.42(s,pyrrolidine-3-C),170.27(s,CONH),169.61(s,=CNH),148.99(s,ArC),146.81(s,ArC),131.69(s,ArC),129.55(s,ArC),124.29(s,ArC),114.77(s,ArC),114.57(s,ArC),109.73(s,ArC),95.99(s,pyrrolidine-4-C),55.91(s,CH),36.77(s,CH2),12.31(s,CH3)ppm;HRMS(ESI+):m/zcalcd for C20H19BrClN5NaO3([M+Na]+)516.0231,found 516.0231.
N′-(2-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-i)
白色粉末;产率65.3%;m.p.:231.1-230.0℃;IR(KBr):v=3392,3320,3273,1679,1641,1612,1576,1500,1406,1387,1253,1229,1036,966,815cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.48(s,1H,CH3CNHNH),9.93(s,1H,NHNHC=O),8.25(s,1H,CH3CNHNH),7.74(s,1H,CHNH),7.31-7.25(m,2H,NHNHC=O and ArH),7.17-7.12(m,1H,ArH),7.07-7.03(m,2H,ArH),6.95-6.87(m,1H,ArH),6.78-6.73(m,1H,ArH),6.68-6.62(m,2H,ArH),3.99-3.96(m,1H,CH),2.66-2.59(m,1H,CH2),2.48(s,3H,CH3),2.37-2.29(m,1H,CH2),2.21(s,3H,ArCH3)ppm;trans-isomer:δ=11.63(s,1H,CH3CNHNH),9.93(s,1H,NHNHC=O),8.32(s,1H,CH3CNHNH),7.42(s,1H,CHNH),7.31-7.25(m,2H,NHNHC=O and ArH),7.17-7.12(m,1H,ArH),7.07-7.03(m,2H,ArH),6.95-6.87(m,1H,ArH),6.78-6.73(m,1H,ArH),6.68-6.62(m,2H,ArH),4.06-4.03(m,1H,CH),2.66-2.59(m,1H,CH2),2.48(s,3H,CH3),2.37-2.29(m,1H,CH2),2.21(s,3H,ArCH3)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.21(s,pyrrolidine-5-C),174.72(s,pyrrolidine-3-C),170.11(s,CONH),169.90(s,=CNH),145.36(s,ArC),144.97(s,ArC),145.02(s,ArC),130.17(s,ArC),129.72(s,ArC),129.43(s,ArC),128.25(s,ArC),120.00(s,ArC),113.88(s,ArC),113.29(s,ArC),93.68(s,pyrrolidine-4-C),58.42(s,CH),37.08(s,CH2),20.65(s,ArCH3),13.13(s,CH3)ppm;trans-isomer:δ=198.13(s,pyrrolidine-5-C),171.44(s,pyrrolidine-3-C),170.25(s,CONH),169.96(s,=CNH),145.23(s,ArC),145.02(s,ArC),130.17(s,ArC),129.77(s,ArC),129.51(s,ArC),128.25(s,ArC),120.00(s,ArC),117.57(s,ArC),113.35(s,ArC),113.07(s,ArC),95.48(s,pyrrolidine-4-C),56.19(s,CH),37.08(s,CH2),20.65(s,ArCH3),12.42(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C21H23ClN5O3([M+H]+)428.1484,found 428.1482.
N′-(4-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-j)
白色粉末;产率80.3%;n.p.:231.1-230.0℃;IR(KBr):v=3444,3340,3289,3024,1678,1632,1583,1513,1492,1404,1385,1359,1253,1225,1116,1093,943,904,812cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.48(s,1H,CH3CNHNH),9.75(s,1H,NHNHC=O),8.25(s,1H,CH3CNHNH),7.73(s,1H,NHNHC=O),7.43(s,1H,CHNH),7.23-6.93(m,4H,ArH),6.78-6.63(m,4H,ArH),3.97-3.94(m,1H,CH),2.64-2.58(m,1H,CH2),2.47(s,3H,CH3),2.39-2.33(m,1H,CH2),2.21(s,3H,ArCH3)ppm;trans-isomer:δ=11.63(s,1H,CH3CNHNH),9.66(s,1H,NHNHC=O),8.32(s,1H,CH3CNHNH),7.69(s,1H,NHNHC=O),7.40(s,1H,CHNH),7.23-6.93(m,4H,ArH),6.78-6.63(m,4H,ArH),4.04-4.01(m,1H,CH),2.64-2.58(m,1H,CH2),2.47(s,3H,CH3),2.39-2.33(m,1H,CH2),2.17(s,3H,ArCH3)ppm;13C NMR(400MHz,DMSO-d6):cis-isomer:δ=195.40(s,pyrrolidine-5-C),174.82(s,pyrrolidine-3-C),169.85(s,CONH),169.81(s,=CNH),148.65(s,ArC),145.38(s,ArC),130.18(s,ArC),128.84(s,ArC),122.16(s,ArC),114.29(s,ArC),113.33(s,ArC),113.06(s,ArC),93.81(s,pyrrolidine-4-C),58.16(s,CH),36.85(s,CH2),20.64(s,ArCH3),13.08(s,CH3)ppm;trans-isomer:δ=198.34(s,pyrrolidine-5-C),171.55(s,pyrrolidine-3-C),170.15(s,CONH),169.76(s,=CNH),147.38(s,ArC),145.26(s,ArC),129.72(s,ArC),129.51(s,ArC),127.52(s,ArC),114.29(s,ArC),113.33(s,ArC),113.06(s,ArC),95.61(s,pyrrolidine-4-C),55.95(s,CH),20.64(s,ArCH3),36.85(s,CH2),12.38(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C21H22ClN5NaO3([M+Na]+)450.1303,found 450.1303.
N′-(2,4-二氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-k)
白色粉末;产率66.9%;m.p.:231.1-230.0℃;IR(KBr):v=3390,3317,3275,1682,1640,1613,1580,1498,1407,1390,1356,1253,1228,1105,1047,982,939,814cm-1;1HNMR(400MHz,DMSO-d6):cis-isomer:δ=11.48(s,1H,CH3CNHNH),10.03(s,1H,NHNHC=O),8.35(s,1H,CH3CNHNH),7.75(s,1H,CHNH),7.48-7.41(m,2H,NHNHC=O and ArH),7.20-7.16(m,1H,ArH),7.07-7.05(m,2H,ArH),6.94-6.91(m,1H,ArH),6.67-6.64(m,2H,ArH),3.99-3.96(m,1H,CH),2.66-2.60(m,1H,CH2),2.48(s,3H,CH3),2.39-2.41(m,1H,CH2),2.21(s,3H,ArCH3)ppm;trans-isomer:δ=11.64(s,1H,CH3CNHNH),10.03(s,1H,NHNHC=O),8.44(s,1H,CH3CNHNH),7.45(s,1H,CHNH),7.48-7.41(m,2H,NHNHC=O and ArH),7.20-7.16(m,1H,ArH),7.07-7.05(m,2H,ArH),6.94-6.91(m,1H,ArH),6.67-6.64(m,2H,ArH),4.06-4.03(m,1H,CH),2.66-2.60(m,1H,CH2),2.48(s,3H,CH3),2.39-2.41(m,1H,CH2),2.21(s,3H,ArCH3)ppm;13C NMR(400MHz,DMSO-d6):cis-isomer:δ=195.20(s pyrrolidine-5-C),174.74(s,pyrrolidine-3-C),170.18(s,CONH),169.93(s,=CNH),145.34(s,ArC),144.34(s,ArC),130.16(s,ArC),129.72(s,ArC),128.69(s,ArC),128.14(s,ArC),122.47(s,ArC),117.98(s,ArC),114.97(s,ArC),113.34(s,ArC),93.68(s,pyrrolidine-4-C),58.37(s,CH),37.05(s,CH2),20.64(s,ArCH3),13.13(s,CH3)ppm;trans-isomer:δ=198.10(s,pyrrolidine-5-C),171.49(s,pyrrolidine-3-C),170.26(s,CONH),170.02(s,=CNH),144.97(s,ArC),144.34(s,ArC),130.16(s,ArC),129.78(s,ArC),128.69(s,ArC),128.14(s,ArC),122.47(s,ArC),117.98(s,ArC),114.97(s,ArC),113.29(s,ArC),95.47(s,pyrrolidine-4-C),56.15(s,CH),37.05(s,CH2),20.64(s,ArCH3),12.42(s,CH3)ppm;HR-MS(ESI+):m/z calcdfor C21H21Cl2N5NaO3([M+Na]+)484.0914,found 484.0912.
N′-(4-溴苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼(I-l)
白色粉末;产率66.9%;m.p.:231.1-230.0℃;IR(KBr):v=3442,3336,3293,1678,1632,1583,1512,1468,1404,1384,1359,1224,1171,997,815cm-1;1H NMR(400MHz,DMSO-d6):cis-isomer:δ=11.47(s,1H,CH3CNHNH),9.75(s,1H,NHNHC=O),8.23(s,1H,CH3CNHNH),7.86(s,1H,NHNHC=O),7.73(s,1H,CHNH),7.27-7.24(m,2H,ArH),7.07-7.05(m,2H,ArH),6.73-6.63(m,4H,ArH),3.97-3.94(m,1H,CH),2.63-2.57(m,1H,CH2),2.47(s,3H,CH3),2.39-2.32(m,1H,CH2),2.21(s,3H,ArCH3)ppm;trans-isomer:δ=11.63(s,1H,CH3CNHNH),9.75(s,1H,NHNHC=O),8.31(s,1H,CH3CNHNH),7.86(s,1H,NHNHC=O),7.39(s,1H,CHNH),7.27-7.24(m,2H,ArH),7.07-7.05(m,2H,ArH),6.73-6.63(m,4H,ArH),4.04-4.01(m,1H,CH),2.63-2.57(m,1H,CH2),2.47(s,3H,CH3),2.39-2.32(m,1H,CH2),2.21(s,3H,ArCH3)ppm;13C NMR(100MHz,DMSO-d6):cis-isomer:δ=195.39(s,pyrrolidine-5-C),174.83(s,pyrrolidine-3-C),169.87(s,CONH),169.81(s,=CNH),149.04(s,ArC),145.38(s,ArC),131.67(s,ArC),130.17(s,ArC),129.70(s,ArC),114.82(s,ArC),113.32(s,ArC),109.65(s,ArC),93.79(s,pyrrolidine-4-C),58.16(s,CH),36.83(s,CH2),20.65(s,ArCH3),13.10(s,CH3)ppm;trans-isomer:δ=198.31(s,pyrrolidine-5-C),171.58(s,pyrrolidine-3-C),170.12(s,CONH),169.71(s,=CNH),149.04(s,ArC),145.24(s,ArC),131.67(s,ArC),130.17(s,ArC),129.70(s,ArC),114.82(s,ArC),113.32(s,ArC),109.65(s,ArC),95.59(s,pyrrolidine-4-C),55.94(s,CH),36.83(s,CH2),20.65(s,ArCH3),12.40(s,CH3)ppm;HR-MS(ESI+):m/z calcd for C21H22BrN5NaO3([M+Na]+)494.0798,found494.0798.
用途实施例
实施例3:本发明的一种二氧吡咯烷乙酸的衍生物(I)对植物病原真菌的杀菌活性
测定
采用菌丝生长速率法测定了一种二氧吡咯烷乙酸的衍生物(I)中的化合物I-a~I-l对3种供试植物病原菌水稻纹枯病菌(Rhizoctonia solani)、小麦赤霉病菌(Fusariumgraminearum)、草莓灰霉病菌(Botrytis cinerea)在10μg/mL浓度下的杀菌活性。
测定方法:将9mg的待测化合物(包括对照药剂恶霉灵、多菌灵、啶酰菌胺)溶解于0.4mL的DMSO中,从中吸取0.1mL溶液,加入0.4mL的DMSO,混合均匀,再从中吸取0.1mL溶液,加入到44.9mL经灭菌的马铃薯葡萄糖琼脂培养基(PDA培养基)中,充分摇匀,制成浓度为10μg/mL的含药培养基,将其平均倒入3只直径9cm的无菌培养皿中。以加入等量的溶剂制成的培养基为空白对照。同时以加入杀菌剂恶霉灵、多菌灵、啶酰菌胺制得的浓度为10μg/mL的培养基为药剂对照。用打孔器(内径0.5cm)将生长正常的菌落打孔制取菌饼,用接种针将菌饼接入上述培养基平板中央,在25℃下于生化培养箱中倒置培养。待空白对照培养基上的菌落直径长至平板的2/3时测量其直径,每个菌落直径按十字交叉法测量2次,计算其平均值(单位:cm)。各浓度处理和各类对照均设三个重复。计算药剂处理后的生长抑制率,计算公式如下:
计算方法:抑制率(%)=(溶剂对照菌落直径-处理菌落直径)÷(溶剂对照菌落直径-0.5)×100%。
测定结果:一种二氧吡咯烷乙酸的衍生物(I)对3种供试植物病原菌的生长抑制率测定结果列于表1。
表1表明,一种二氧吡咯烷乙酸的衍生物(I)对3种供试植物病原菌具有显著的杀菌活性。其中,化合物I-a~I-l对的水稻纹枯病菌的生长抑制率为54.75%~92.58%,均高于对照药剂恶霉灵的7.80%,化合物I-e、I-f、I-g、I-i、I-k的抑制率达到87.33%~92.58%,高于对照药剂啶酰菌胺的82.51%。化合物I-a~I-l对小麦赤霉病菌的生长抑制率为19.85%~89.70%,均高于对照药剂恶霉灵的12.18%,除化合物I-g、I-k之外的其他化合物的抑制率均高于对照药剂啶酰菌胺的38.02%,化合物I-f、I-h的抑制率达到80%以上。化合物I-a~I-l对草莓灰霉病菌的生长抑制率为41.58%~66.00%,均高于对照药剂恶霉灵的39.53%和多菌灵的28.91%,化合物I-e、I-f、I-g、I-h的抑制率达到60%以上。
表1 一种二氧吡咯烷乙酸的衍生物(I)对3种植物病原菌的抑制率(%,10μg/mL)
Claims (9)
2.根据权利要求1所述的一种二氧吡咯烷乙酸的衍生物,其特征在于:
Y(m)中,m=1-2取代,Y(m)选自下列1-2个基团:X、R,其中X表示卤素;R表示C1-3烷基;
Z(n)中,n=1-2取代,Z(n)选自1-2个卤素;
k选自0、1。
3.根据权利要求2所述的一种二氧吡咯烷乙酸的衍生物,其特征在于:
Y(m)中,m=1取代,Y(m)选自下列1个基团:4-X、4-CH3,其中X表示F、Cl、Br;
Z(n)中,n=1-2取代,Z(n)选自1-2个F、Cl、Br;
k选自0、1。
4.根据权利要求3所述的一种二氧吡咯烷乙酸的衍生物,其特征在于:
Y(m)选自4-Cl、4-CH3;
Z(n)选自2-Cl、4-Cl、2,4-(Cl)2、4-Br;
k选自0、1。
5.根据权利要求4所述的一种二氧吡咯烷乙酸的衍生物,其特征在于其为如下所述化合物之一:
N-(4-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺、
N-(4-溴苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺、
N-(4-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺、
N-(4-溴苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰胺、
N′-(2-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(4-氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(2,4-二氯苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(4-溴苯基)-2-(4-(1-(2-(4-氯苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(2-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(4-氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(2,4-二氯苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼、
N′-(4-溴苯基)-2-(4-(1-(2-(4-甲基苯基)肼基)亚乙基)-3,5-二氧吡咯烷-2-基)乙酰肼。
7.权利要求1-5中任一项所述的一种二氧吡咯烷乙酸的衍生物在防治植物真菌病害方面的应用。
8.根据权利要求7所述的应用,其特征在于权利要求1-5中任一项所述的一种二氧吡咯烷乙酸的衍生物在抑制水稻纹枯病菌、小麦赤霉病菌、草莓灰霉病菌方面的应用。
9.根据权利要求7所述的应用,其特征在于权利要求1-5中任一项所述的一种二氧吡咯烷乙酸的衍生物在防治水稻纹枯病、小麦赤霉病、草莓灰霉病方面的应用。
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