CN110003077B - 一种含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物、制备方法及应用 - Google Patents
一种含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物、制备方法及应用 Download PDFInfo
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- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
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- JFSPBVWPKOEZCB-UHFFFAOYSA-N fenfuram Chemical compound O1C=CC(C(=O)NC=2C=CC=CC=2)=C1C JFSPBVWPKOEZCB-UHFFFAOYSA-N 0.000 description 1
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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Abstract
本发明属于杀菌剂领域,公开了一种含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物、制备方法及应用,该化合物的结构如式(I)所示:
Description
技术领域
本发明涉及一种含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物、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
酰肼类化合物常常表现出显著的生物活性,在农药领域具有广泛的应用,如环虫酰肼 (chromafenozide)、甲氧虫酰肼(methoxyfenozide)及氯虫酰肼(halofenozide)等均为含有酰肼基团的杀虫剂,可有效防治农业害虫。苯胺基团是农用杀菌剂分子结构中常见的活性基团,如杀菌剂嘧霉胺 (pyrimethanil)、甲呋酰苯胺(fenfuram)及敌菌灵(anilazine)等。此外,一些含有吡咯烷二酮基团的化合物可表现出显著的杀菌活性,如专利ZL201110453110.X与ZL201210524110.9公开的不同类型的吡咯烷二酮类化合物,均具有良好的抑制植物病原真菌的活性。
本专利根据活性基团拼接原理,将酰肼、苯胺及吡咯烷二酮基团引入到同一个分子结构中,设计并合成了一系列结构新颖的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物,经杀菌活性测定,发现该类化合物对植物病原真菌具有显著的抑制活性。
发明内容
本发明的目的在于提供一种含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物。
本发明的另一目的在于提供一种含吡咯烷二酮和苯胺基团的丁酰苯肼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)所示结构的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物,
在式(I)中,所述各个基团具有如下所述的定义:
X(m)中,m=1-5取代,X(m)选自下列1-5个基团:X、R’、OR”、NO2,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;R”表示氢、未取代或被1-6卤素取代的C1-6烷基;
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’表示氢、未取代或被1-6个卤素取代的C1-6烷基;R”表示氢、未取代或被1-6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:
X(m)中,m=1-3取代,X(m)选自下列1-3个基团:X、R’、OR”,其中X表示卤素;R’表示氢、未取代或被1-3个卤素取代的C1-3烷基;R”表示未取代或被1-3卤素取代的C1-3烷基;
Y(n)中,n=1-3取代,Y(n)选自下列1-3个基团:X、R’、OR”,其中X表示卤素;R’表示氢、未取代或被1-3个卤素取代的C1-3烷基;R”表示未取代或被1-3卤素取代的C1-3烷基。
在式(I)中,所述各个基团具有如下所述的进一步优选定义:
X(m)中,m=1取代,X(m)选自下列1个基团:X、R’、OR”,其中X表示卤素;R’表示氢、未取代或被1-3个卤素取代的甲基;R”表示未取代或被1-3卤素取代的甲基;
Y(n)中,n=1-2取代,Y(n)选自下列1-2个基团:X、R’、OR”,其中X表示卤素;R’表示氢、甲基; R”表示甲基。
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:
X(m)选自下列基团:H、4-F、2-Cl、3-Cl、4-Cl、4-Br、2-CH3、3-CH3、4-CH3、3-OCH3、3-CF3、3-OCF3;
Y(n)选自下列基团:H、2-F、4-F、2-Cl、3-Cl、4-Cl、4-Br、2,4-Cl2、4-CH3、3,4-(CH3)2、4-OCH3。
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)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Ia)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((4-氟苯基)氨基)丁酰肼(Ib)、
N′-(4-氯苯基)-4-((2-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Ic)、
N′-(4-氯苯基)-4-((3-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Id)、
N′-(4-氯苯基)-4-((4-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Ie)、
4-((4-溴苯基)氨基)-N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(If)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((邻甲苯基)氨基)丁酰肼(Ig)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((间甲苯基)氨基)丁酰肼(Ih)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((对甲苯基)氨基)丁酰肼(Ii)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-甲氧基苯基)氨基)丁酰肼(Ij)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-(三氟甲基)苯基)氨基)丁酰肼(Ik)、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-(三氟甲氧基)苯基)氨基)丁酰肼(Il)、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-苯基-4-(苯基氨基)丁酰肼(Im)、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(2-氟苯基)-4-(苯基氨基)丁酰肼(In)、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(4-氟苯基)-4-(苯基氨基)丁酰肼(Io)、
N′-(2-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Ip)、
N′-(3-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Iq)、
N′-(4-溴苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Ir)、
N′-(2,4-二氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Is)、
4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)-N′-(对甲苯基)丁酰肼(It)、
N′-(3,4-二甲基苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Iu)、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(4-甲氧基苯基)-4-(苯基氨基)丁酰肼(Iv)、
N′-(2-氯苯基)-4-((3-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Iw)、
N′-(4-溴苯基)-4-((4-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Ix)。
本发明的第二个方面提供了制备式(I)的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物的方法,该方法以式(II)的化合物与式(III)的取代苯肼反应,制备式(I)的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物,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:
X(m)、Y(n)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)的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物在防治植物病原真菌方面的应用,可应用于农药领域,作为杀菌剂。
本发明的式(I)的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物可以在植物保护中用于防治下列病原菌引起的作物真菌病害,但它不应视为是对本发明的任何限制:
防治麦类作物真菌病害:
镰孢属,如禾谷镰孢菌Fusarium graminearum,引起小麦赤霉病;
丝核菌属,如禾谷丝核菌Rhizoctonia cereadis,引起小麦纹枯病;
防治水稻作物真菌病害:
梨孢属,如灰梨孢菌Pyricularia grisea,引起稻瘟病;
丝核菌属,如茄丝核菌Rhizoctonia solani,引起水稻纹枯病;
防治水果作物真菌病害:
葡萄孢属,如灰葡萄孢菌Botrytis cinerea,引起草莓灰霉病、葡萄灰霉病;
防治蔬菜作物真菌病害:
葡萄孢属,如灰葡萄孢菌Botrytis cinerea,引起茄科蔬菜灰霉病,如辣椒灰霉病、茄子灰霉病;
炭疽菌属,如辣椒刺盘孢Colletotrichum capsici,引起辣椒炭疽病。
本发明的化合物特别适合于用于防治麦类作物真菌病害,如小麦赤霉病;防治蔬菜作物真菌病害,如辣椒炭疽病;防治水稻作物真菌病害,如水稻纹枯病;防治水果作物真菌病害,如草莓灰霉病。
有益效果:
1、本发明专利所述的式(I)的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物的分子结构新颖,该结构式含有一个丁酰肼主链,在其肼基的N′上连有一个取代苯基,在4位C原子上同时连接取代苯胺和吡咯烷二酮两个基团。
2、本发明专利所述的式(I)的含吡咯烷二酮和苯胺基团的丁酰苯肼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)的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物表现出显著的抑制植物病原真菌的活性,可应用于由真菌引起的作物病害,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:含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物Ia的制备
在50mL三口瓶中加入10mL乙醇、1mmol的中间体IIa、1mmol的4-氯苯肼(IIIa),搅拌,在室温下反应,用TLC监测反应进程,约30min后,反应完成,有固体析出,抽滤,用乙醇洗涤,干燥,得含吡咯烷二酮和苯胺基团的丁酰肼类化合物Ia,其反应方程式如下:
采用实施例1的方法,制备了含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物(I)中的Ia-Ix化合物:
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Ia):
白色粉末,收率87.8%;m.p.181.0℃,分解;IR(KBr,cm-1)v:3347,3314,3269,3194,3039,2911,1678, 1667,1648,1544,1442,1336,1249,1090,818,751.1H NMR(400MHz,DMSO-dd)δ:E-isomer:11.62(s,1H,C=CNH),9.95(s,1H,PhNHNH),8.53(s,1H,PhNHNH),7.54(d,J=7.8Hz,2H,PhH),7.49(s,1H, CH2NH),7.29(dd,J=12.4,5.3Hz,4H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.77(d,J=8.8Hz,2H,PhH), 3.67(s,2H,CH2NH),3.28-3.22(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);Z-isomer:11.46(s, 1H,C=CNH),9.93(s,1H,PhNHNH),8.47(s,1H,PhNHNH),7.76(s,1H,CH2NH),7.54(d,J=7.8Hz, 2H,PhH),7.29(dd,J=12.4,5.3Hz,4H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.77(d,J=8.8Hz,2H, PhH),3.62(s,2H,CH2NH),3.21-3.12(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);EI-MS(m/z)398.1[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((4-氟苯基)氨基)丁酰肼(Ib):
白色粉末,收率92.1%;m.p.266.2℃,分解;IR(KBr,cm-1)v:3345,3313,3187,3076,2911,1679,1667, 1647,1548,1489,1222,1091,816,778.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H, C=CNH),10.01(s,1H,PhNHNH),8.52(s,1H,PhNHNH),7.55(dd,J=9.0,5.0Hz,2H,PhH),7.48(s,1H, CH2NH),7.29(d,J=8.8Hz,2H,PhH),7.12(t,J=8.9Hz,2H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.67 (s,2H,CH2NH),3.28-3.21(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);Z-isomer:11.46(s,1H,C=CNH),9.99(s,1H,PhNHNH),8.46(s,1H,PhNHNH),7.76(s,1H,CH2NH),7.55(dd,J=9.0,5.0Hz, 2H,PhH),7.29(d,J=8.8Hz,2H,PhH),7.12(t,J=8.9Hz,2H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.62 (s,2H,CH2NH),3.21-3.12(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2); EI-MS(m/z)416.1[M]+.
N′-(4-氯苯基)-4-((2-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Ic):
白色粉末,收率80.5%;m.p.172.4-173.4℃;IR(KBr,cm-1)v:3322,3267,3181,3032,2917,1650,1580,1437,1246,1091,824,745.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H,C=CNH),9.52(s, 1H,PhNHNH),8.53(s,1H,PhNHNH),7.67(d,J=6.8Hz,1H,PhH),7.51-7.44(m,1H,PhH and CH2NH),7.30(t,J=7.4Hz,3H,PhH),7.17(t,J=7.7Hz,1H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.68 (s,2H,CH2NH),3.29-3.22(m,2H,C=CCH2),2.72-2.58(m,2H,C=CCH2CH2);Z-isomer:11.46(s,1H, C=CNH),9.52(s,1H,PhNHNH),8.47(s,1H,PhNHNH),7.76(s,1H,CH2NH),7.67(d,J=6.8Hz,1H, PhH),7.51-7.44(m,1H,PhH),7.30(t,J=7.4Hz,3H,PhH),7.17(t,J=7.7Hz,1H,PhH),6.77(d,J= 8.8Hz,2H,PhH),3.63(s,2H,CH2NH),3.22-3.12(m,2H,C=CCH2),2.72-2.58(m,2H,C=CCH2CH2); EI-MS(m/z)432.1[M]+.
N′-(4-氯苯基)-4-((3-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Id):
白色粉末,收率85.0%;m.p.244.5-246.3℃;IR(KBr,cm-1)v:3330,3185,3076,2903,1667,1645,1534, 1423,1250,1197,1089,820,774.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H,C=CNH), 10.15(s,1H,PhNHNH),8.51(s,1H,PhNHNH),7.79-7.73(m,1H,PhH),7.49(s,1H,CH2NH),7.39(d,J =8.1Hz,1H,PhH),7.34-7.26(m,3H,PhH),7.08(dd,J=7.9,1.1Hz,1H,PhH),6.77(d,J=8.9Hz,2H, PhH),3.67(s,2H,CH2NH),3.29-3.22(m,2H,C=CCH2),2.65-2.54(m,2H,C=CCH2CH2);Z-isomer: 11.46(s,1H,C=CNH),10.13(s,1H,PhNHNH),8.46(s,1H,PhNHNH),7.79-7.73(m,2H,PhH and CH2NH),7.39(d,J=8.1Hz,1H,PhH),7.34-7.26(m,3H,PhH),7.08(dd,J=7.9,1.1Hz,1H,PhH), 6.77(d,J=8.9Hz,2H,PhH),3.62(s,2H,CH2NH),3.21-3.14(m,2H,C=CCH2),2.65-2.54(m,2H, C=CCH2CH2);EI-MS(m/z)432.1[M]+.
N′-(4-氯苯基)-4-((4-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Ie):
白色粉末,收率96.2%;m.p.273.8-275.2℃,分解;IR(KBr,cm-1)v:3345,3309,3192,3072,2906,1679, 1669,1647,1538,1489,1335,1247,1091,816,775.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s, 1H,C=CNH),10.10(s,1H,PhNHNH),8.52(s,1H,PhNHNH),7.57(d,J=8.8Hz,2H,PhH),7.49(s,1H, CH2NH),7.33(d,J=8.9Hz,2H,PhH),7.29(d,J=8.8Hz,2H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.67 (s,2H,CH2NH),3.29-3.21(m,2H,C=CCH2),2.65-2.54(m,2H,C=CCH2CH2);Z-isomer:11.46(s,1H, C=CNH),10.08(s,1H,PhNHNH),8.46(s,1H,PhNHNH),7.77(s,1H,CH2NH),7.57(d,J=8.8Hz,2H, PhH),7.33(d,J=8.9Hz,2H,PhH),7.29(d,J=8.8Hz,2H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.62(s, 2H,CH2NH),3.21-3.12(m,2H,C=CCH2),2.65-2.54(m,2H,C=CCH2CH2);EI-MS(m/z)432.1[M]+.
4-((4-溴苯基)氨基)-N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(If):
白色粉末,收率93.2%;m.p.278.9℃,分解;IR(KBr,cm-1)v:3343,3307,3191,3067,2905,1669,1647, 1537,1487,1335,1246,1092,815,776.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H,C=CNH),10.09(s,1H,PhNHNH),8.51(s,1H,PhNHNH),7.52(d,J=9.0Hz,2H,PhH),7.49(s,1H, CH2NH),7.46(d,J=8.9Hz,2H,PhH),7.28(d,J=8.8Hz,2H,PhH),6.76(d,J=8.8Hz,2H,PhH),3.67 (s,2H,CH2NH),3.28-3.21(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);Z-isomer:11.45(s,1H, C=CNH),10.08(s,1H,PhNHNH),8.46(s,1H,PhNHNH),7.76(s,1H,CH2NH),7.52(d,J=9.0Hz,2H, PhH),7.46(d,J=8.9Hz,2H,PhH),7.28(d,J=8.8Hz,2H,PhH),6.76(d,J=8.8Hz,2H,PhH),3.61(s, 2H,CH2NH),3.21-3.12(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);EI-MS(m/z)476.0[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((邻甲苯基)氨基)丁酰肼(Ig):
白色粉末,收率76.3%;m.p.239.9-242.2℃,分解;IR(KBr,cm-1)v:3254,3190,3035,2906,1683,1663, 1644,1604,1571,1530,1489,1454,1292,1059,745.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.63 (s,1H,C=CNH),9.30(s,1H,PhNHNH),8.54(s,1H,PhNHNH),7.49(s,1H,CH2NH),7.38(t,J=7.5Hz, 1H,PhH),7.29(d,J=8.7Hz,2H,PhH),7.19(d,J=7.5Hz,1H,PhH),7.13(t,J=7.1Hz,1H,PhH),7.06 (t,J=6.9Hz,1H,PhH),6.78(d,J=8.7Hz,2H,PhH),3.68(s,2H,CH2NH),3.30-3.22(m,2H, C=CCH2),2.68-2.54(m,2H,C=CCH2CH2),2.16(s,3H,CH3);Z-isomer:11.47(s,1H,C=CNH),9.29(s, 1H,PhNHNH),8.48(s,1H,PhNHNH),7.76(s,1H,CH2NH),7.38(t,J=7.5Hz,1H,PhH),7.29(d,J= 8.7Hz,2H,PhH),7.19(d,J=7.5Hz,1H,PhH),7.13(t,J=7.1Hz,1H,PhH),7.06(t,J=6.9Hz,1H,PhH),6.78(d,J=8.7Hz,2H,PhH),3.63(s,2H,CH2NH),3.22-3.12(m,2H,C=CCH2),2.68-2.54(m, 2H,C=CCH2CH2),2.16(s,3H,CH3);EI-MS(m/z)412.1[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((间甲苯基)氨基)丁酰肼(Ih):
白色粉末,收率94.6%;m.p.192.3℃,分解;IR(KBr,cm-1)v:3345,3297,3185,3036,2918,1680,1647,1546,1440,1334,1249,1090,819,775.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H, C=CNH),9.87(s,1H,PhNHNH),8.52(s,1H,PhNHNH),7.49(s,1H,CH2NH),7.37(s,1H,PhH),7.30(t, J=10.1Hz,3H,PhH),7.15(t,J=7.8Hz,1H,PhH),6.84(d,J=7.5Hz,1H,PhH),6.77(d,J=8.8Hz, 2H,PhH),3.67(s,2H,CH2NH),3.27-3.21(m,2H,C=CCH2),2.63-2.53(m,2H,C=CCH2CH2),2.25(s, 3H,CH3);Z-isomer:11.46(s,1H,C=CNH),9.85(s,1H,PhNHNH),8.47(s,1H,PhNHNH),7.76(s,1H, CH2NH),7.37(s,1H,PhH),7.30(t,J=10.1Hz,3H,PhH),7.15(t,J=7.8Hz,1H,PhH),6.84(d,J=7.5 Hz,1H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.62(s,2H,CH2NH),3.20-3.12(m,2H,C=CCH2),2.63- 2.53(m,2H,C=CCH2CH2),2.25(s,3H,CH3);EI-MS(m/z)412.1[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((对甲苯基)氨基)丁酰肼(Ii):
白色粉末,收率95.0%;m.p.248.8℃,分解;IR(KBr,cm-1)v:3346,3303,3195,3042,2914,1679,1665, 1651,1560,1490,1335,1248,1141,1091,813,777.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s, 1H,C=CNH),9.86(s,1H,PhNHNH),8.52(s,1H,PhNHNH),7.48(s,1H,CH2NH),7.42(d,J=8.3Hz, 2H,PhH),7.29(d,J=8.8Hz,2H,PhH),7.08(d,J=8.3Hz,2H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.67 (s,2H,CH2NH),3.26-3.21(m,2H,C=CCH2),2.61-2.52(m,2H,C=CCH2CH2),2.23(s,3H,CH3);Z-isomer:11.45(s,1H,C=CNH),9.84(s,1H,PhNHNH),8.47(s,1H,PhNHNH),7.76(s,1H,CH2NH), 7.42(d,J=8.3Hz,2H,PhH),7.29(d,J=8.8Hz,2H,PhH),7.08(d,J=8.3Hz,2H,PhH),6.77(d,J=8.8 Hz,2H,PhH),3.61(s,2H,CH2NH),3.19-3.12(m,2H,C=CCH2),2.61-2.52(m,2H,C=CCH2CH2),2.23(s,3H,CH3);EI-MS(m/z)412.1[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-甲氧基苯基)氨基)丁酰肼(Ij):
白色粉末,收率84.4%;m.p.166.0-166.9℃;IR(KBr,cm-1)v:3344,3306,3190,3093,2900,1679,1648, 1549,1456,1334,1230,1156,1045,818,777.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H, C=CNH),9.94(s,1H,PhNHNH),8.52(s,1H,PhNHNH),7.49(s,1H,CH2NH),7.29(d,J=8.8Hz,2H, PhH),7.25(s,1H,PhH),7.18(t,J=8.1Hz,1H,PhH),7.06(d,J=8.2Hz,1H,PhH),6.77(d,J=8.8Hz, 2H,PhH),6.61(dd,J=8.0,2.1Hz,1H,PhH),3.71(s,3H,OCH3),3.67(s,2H,CH2NH),3.27-3.20(m, 2H,C=CCH2),2.63-2.53(m,2H,C=CCH2CH2);Z-isomer:11.45(s,1H,C=CNH),9.92(s,1H, PhNHNH),8.46(s,1H,PhNHNH),7.76(s,1H,CH2NH),7.29(d,J=8.8Hz,2H,PhH),7.25(s,1H,PhH), 7.18(t,J=8.1Hz,1H,PhH),7.06(d,J=8.2Hz,1H,PhH),6.77(d,J=8.8Hz,2H,PhH),6.61(dd,J=8.0,2.1Hz,1H,PhH),3.71(s,3H,OCH3),3.62(s,2H,CH2NH),3.19-3.12(m,2H,C=CCH2),2.63-2.53 (m,2H,C=CCH2CH2);EI-MS(m/z)428.1[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-(三氟甲基)苯基)氨基)丁酰肼(Ik):
白色粉末,收率55.6%;m.p.180.6℃,分解;IR(KBr,cm-1)v:3342,3296,3186,3032,2903,1679,1667, 1647,1556,1445,1331,1248,1117,823,792.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H, C=CNH),10.38(s,1H,PhNHNH),8.60(s,1H,PhNHNH),7.74(d,J=8.1Hz,1H,PhH),7.58-7.47(m, 2H,PhH),7.37(d,J=7.7Hz,2H,PhH andCH2NH),7.27(d,J=8.7Hz,2H,PhH),6.77(d,J=8.8Hz, 2H,PhH),3.67(s,2H,CH2NH),3.31-3.23(m,2H,C=CCH2),2.68-2.58(m,2H,C=CCH2CH2); Z-isomer:11.46(s,1H,C=CNH),10.37(s,1H,PhNHNH),8.55(s,1H,PhNHNH),7.77(s,1H,CH2NH), 7.74(d,J=8.1Hz,1H,PhH),7.58-7.47(m,2H,PhH),7.37(d,J=7.7Hz,1H,PhH),7.27(d,J=8.7Hz, 2H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.62(s,2H,CH2NH),3.23-3.15(m,2H,C=CCH2),2.68-2.58 (m,2H,C=CCH2CH2);EI-MS(m/z)466.1[M]+.
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-(三氟甲氧基)苯基)氨基)丁酰肼(Il):
白色粉末,收率61.0%,m.p.175.4℃,分解;IR(KBr,cm-1)v:3343,3283,3196,3031,2903,1680, 1668,1648,1547,1441,1371,1272,1092,822,782.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s, 1H,C=CNH),10.26(s,1H,C=CNH),8.52(s,1H,PhNHNH),7.73(s,1H,PhH),7.47-7.39(m,2H,PhH), 7.28(d,J=8.8Hz,2H,PhH),7.01(d,J=7.0Hz,1H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.68(s,2H, CH2NH),3.30-3.23(m,2H,C=CCH2),2.66-2.55(m,2H,C=CCH2CH2);Z-isomer:11.46(s,1H, C=CNH),10.24(s,1H,C=CNH),8.46(s,1H,PhNHNH),7.73(s,1H,PhH),7.47-7.39(m,2H,PhH), 7.28(d,J=8.8Hz,2H,PhH),7.01(d,J=7.0Hz,1H,PhH),6.77(d,J=8.8Hz,2H,PhH),3.62(s,2H, CH2NH),3.23-3.15(m,2H,C=CCH2),2.66-2.55(m,2H,C=CCH2CH2);EI-MS(m/z)482.1[M]+.
4-(2,4-二氧吡咯烷-3-基亚基)-N′-苯基-4-(苯基氨基)丁酰肼(Im):
白色粉末,收率94.8%;m.p.189.6-191.3℃,分解;IR(KBr,cm-1)v:3373,3255,3199,3085,2911,1681, 1660,1633,1555,1440,1234,1085,915,788.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.68(s,1H, C=CNH),9.96(s,1H,PhNHNH),8.39(s,1H,PhNHNH),7.55(d,J=7.8Hz,2H,PhH),7.47(s,1H, CH2NH),7.27(dd,J=15.5,7.3Hz,4H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.89(t,J=7.3Hz,1H,PhH), 6.77(d,J=7.8Hz,2H,PhH),3.68(s,2H,CH2NH),3.31-3.23(m,2H,C=CCH2),2.67-2.55(m,2H, C=CCH2CH2);Z-isomer:11.49(s,1H,C=CNH),9.94(s,1H,PhNHNH),8.34(s,1H,PhNHNH),7.74(s, 1H,CH2NH),7.55(d,J=7.8Hz,2H,PhH),7.27(dd,J=15.5,7.3Hz,4H,PhH),7.02(t,J=7.4Hz,1H, PhH),6.89(t,J=7.3Hz,1H,PhH),6.77(d,J=7.8Hz,2H,PhH),3.62(s,2H,CH2NH),3.23-3.14(m, 2H,C=CCH2),2.67-2.55(m,2H,C=CCH2CH2);EI-MS(m/z)364.2[M]+.
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(2-氟苯基)-4-(苯基氨基)丁酰肼(In):
白色粉末,收率91.1%;m.p.209.0-210.2℃,分解;IR(KBr,cm-1)v:3348,3309,3188,3034,2900,1681, 1668,1649,1597,1549,1444,1253,1092,843,784.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s, 1H,C=CNH),9.96(s,1H,PhNHNH),8.44(s,1H,PhNHNH),7.54(d,J=7.8Hz,2H,PhH),7.49(s,1H, CH2NH),7.28(t,J=7.9Hz,2H,PhH),7.19(dd,J=11.9,8.2Hz,1H,PhH),7.11(t,J=7.7Hz,1H,PhH), 7.02(t,J=7.4Hz,1H,PhH),6.90(dd,J=12.6,7.7Hz,1H,PhH),6.82(t,J=8.4Hz,1H,PhH),3.68(s, 2H,CH2NH),3.30-3.23(m,2H,C=CCH2),2.69-2.57(m,2H,C=CCH2CH2);Z-isomer:11.46(s,1H, C=CNH),9.95(s,1H,PhNHNH),8.40(s,1H,PhNHNH),7.77(s,1H,CH2NH),7.54(d,J=7.8Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.19(dd,J=11.9,8.2Hz,1H,PhH),7.11(t,J=7.7Hz,1H,PhH), 7.02(t,J=7.4Hz,1H,PhH),6.90(dd,J=12.6,7.7Hz,1H,PhH),6.82(t,J=8.4Hz,1H,PhH),3.63(s, 2H,CH2NH),3.23-3.14(m,2H,C=CCH2),2.69-2.57(m,2H,C=CCH2CH2);EI-MS(m/z)382.1[M]+.
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(4-氟苯基)-4-(苯基氨基)丁酰肼(Io):
白色粉末,收率78.4%;m.p.182.8-184.9℃;IR(KBr,cm-1)v:3346,3313,3272,3185,3037,2914,1679, 1667,1650,1544,1447,1226,1095,823,778.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.65(s,1H, C=CNH),9.96(s,1H,PhNHNH),8.34(s,1H,PhNHNH),7.54(d,J=7.8Hz,2H,PhH),7.47(s,1H, CH2NH),7.28(t,J=7.9Hz,2H,PhH),7.10(t,J=8.8Hz,2H,PhH),7.02(t,J=7.3Hz,1H,PhH),6.83- 6.74(m,2H,PhH),3.67(s,2H,CH2NH),3.30-3.24(m,2H,C=CCH2),2.65-2.54(m,2H,C=CCH2CH2); Z-isomer:11.47(s,1H,C=CNH),9.94(s,1H,PhNHNH),8.29(s,1H,PhNHNH),7.74(s,1H,CH2NH), 7.54(d,J=7.8Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.10(t,J=8.8Hz,2H,PhH),7.02(t,J=7.3 Hz,1H,PhH),6.83-6.74(m,2H,PhH),3.61(s,2H,CH2NH),3.23-3.15(m,2H,C=CCH2),2.65-2.54(m,2H,C=CCH2CH2);EI-MS(m/z)382.1[M]+.
N′-(2-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Ip):
白色粉末,收率95.3%;m.p.226.3℃,分解;IR(KBr,cm-1)v:3335,3261,3187,3034,2909,1683,1667, 1644,1545,1443,1300,1155,1035,784.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.67(s,1H, C=CNH),9.97(s,1H,PhNHNH),8.32(s,1H,PhNHNH),7.54(d,J=7.8Hz,2H,PhH),7.51(s,1H, CH2NH),7.39(dd,J=7.9,1.2Hz,1H,PhH),7.32-7.23(m,3H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.95 -6.87(m,1H,PhH),6.82-6.76(m,1H,PhH),3.69(s,2H,CH2NH),3.26-3.19(m,2H,C=CCH2),2.71- 2.59(m,2H,C=CCH2CH2);Z-isomer:11.52(s,1H,C=CNH),9.96(s,1H,PhNHNH),8.29(s,1H, PhNHNH),7.79(s,1H,CH2NH),7.54(d,J=7.8Hz,2H,PhH),7.39(dd,J=7.9,1.2Hz,1H,PhH),7.32- 7.23(m,3H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.95-6.87(m,1H,PhH),6.82-6.76(m,1H,PhH),3.64 (s,2H,CH2NH),3.18-3.10(m,2H,C=CCH2),2.71-2.59(m,2H,C=CCH2CH2);EI-MS(m/z)398.1 [M]+.
N′-(3-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Iq):
白色粉末,收率92.5%;m.p.211.2℃,分解;IR(KBr,cm-1)v:3342,3295,3192,3036,2903,1679,1665, 1645,1546,1442,1251,1094,863,776.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.61(s,1H, C=CNH),9.96(s,1H,PhNHNH),8.62(s,1H,PhNHNH),7.54(d,J=7.7Hz,2H,PhH),7.50(s,1H, CH2NH),7.33-7.21(m,3H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.93-6.87(m,1H,PhH),6.76(s,1H, PhH),6.72(d,J=8.2Hz,1H,PhH),3.68(s,2H,CH2NH),3.28-3.21(m,2H,C=CCH2),2.65-2.54(m, 2H,C=CCH2CH2);Z-isomer:11.45(s,1H,C=CNH),9.94(s,1H,PhNHNH),8.57(s,1H,PhNHNH),7.77 (s,1H,CH2NH),7.54(d,J=7.7Hz,2H,PhH),7.33-7.21(m,3H,PhH),7.02(t,J=7.4Hz,1H,PhH), 6.93-6.87(m,1H,PhH),6.76(s,1H,PhH),6.72(d,J=8.2Hz,1H,PhH),3.62(s,2H,CH2NH),3.21- 3.12(m,2H,C=CCH2),2.65-2.54(m,2H,C=CCH2CH2);EI-MS(m/z)398.1[M]+.
N′-(4-溴苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Ir):
白色粉末,收率91.1%;m.p.200.4℃,分解;IR(KBr,cm-1)v:3345,3301,3181,3034,2903,1681,1647, 1544,1442,1368,1072,817,752.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.61(s,1H,C=CNH), 9.95(s,1H,PhNHNH),8.54(s,1H,PhNHNH),7.54(d,J=7.8Hz,2H,PhH),7.49(s,1H,CH2NH),7.41 (d,J=8.8Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.02(t,J=7.3Hz,1H,PhH),6.72(d,J=8.8Hz, 2H,PhH),3.67(s,2H,CH2NH),3.28-3.20(m,2H,C=CCH2),2.63-2.53(m,2H,C=CCH2CH2); Z-isomer:11.45(s,1H,C=CNH),9.93(s,1H,PhNHNH),8.48(s,1H,PhNHNH),7.77(s,1H,CH2NH), 7.54(d,J=7.8Hz,2H,PhH),7.41(d,J=8.8Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.02(t,J=7.3 Hz,1H,PhH),6.72(d,J=8.8Hz,2H,PhH),3.62(s,2H,CH2NH),3.20-3.12(m,2H,C=CCH2),2.63-2.53(m,2H,C=CCH2CH2);EI-MS(m/z)442.1[M]+.
N′-(2,4-二氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Is):
白色粉末,收率95.5%;m.p.230.0℃,分解;IR(KBr,cm-1)v:3339,3303,3196,3036,2904,1668,1645, 1547,1443,1252,1049,852,750.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.62(s,1H,C=CNH), 9.95(s,1H,PhNHNH),8.43(s,1H,PhNHNH),7.53(dd,J=5.0,2.5Hz,4H,PhH and CH2NH),7.34- 7.22(m,3H,PhH),7.02(t,J=7.3Hz,1H,PhH),6.79(dd,J=8.8,3.6Hz,1H,PhH),3.68(s,2H,CH2NH), 3.25-3.17(m,2H,C=CCH2),2.69-2.57(m,2H,C=CCH2CH2);Z-isomer:11.49(s,1H,C=CNH),9.94(s, 1H,PhNHNH),8.40(s,1H,PhNHNH),7.80(s,1H,CH2NH),7.53(dd,J=5.0,2.5Hz,3H,PhH),7.34- 7.22(m,3H,PhH),7.02(t,J=7.3Hz,1H,PhH),6.79(dd,J=8.8,3.6Hz,1H,PhH),3.63(s,2H,CH2NH), 3.16-3.08(m,2H,C=CCH2),2.69-2.57(m,2H,C=CCH2CH2);EI-MS(m/z)432.1[M]+.
4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)-N′-(对甲苯基)丁酰肼(It):
白色粉末,收率95.9%;m.p.196.1-197.1℃;IR(KBr,cm-1)v:3340,3320,3194,3022,2917,1673,1646,1543,1441,1335,1248,1031,810,749.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.67(s,1H, C=CNH),9.95(s,1H,PhNHNH),8.24(s,1H,PhNHNH),7.54(d,J=7.8Hz,2H,PhH),7.45(s,1H, CH2NH),7.28(t,J=7.9Hz,2H,PhH),7.07(d,J=8.2Hz,2H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.68 (d,J=8.3Hz,2H,PhH),3.67(s,2H,CH2NH),3.29-3.23(m,2H,C=CCH2),2.65-2.53(m,2H, C=CCH2CH2),2.21(s,3H,CH3);Z-isomer:11.47(s,1H,C=CNH),9.94(s,1H,PhNHNH),8.18(s,1H, PhNHNH),7.72(s,1H,CH2NH),7.54(d,J=7.8Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.07(d,J=8.2Hz,2H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.68(d,J=8.3Hz,2H,PhH),3.61(s,2H,CH2NH),3.22 -3.14(m,2H,C=CCH2),2.65-2.53(m,2H,C=CCH2CH2),2.21(s,3H,CH3);EI-MS(m/z)378.2[M]+.
N′-(3,4-二甲基苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼(Iu):
白色粉末,收率97.2%;m.p.202.1-204.2℃;IR(KBr,cm-1)v:3335,3317,3190,3075,2966,1673,1647, 1544,1440,1335,1250,859,748.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.66(s,1H,C=CNH), 9.95(s,1H,PhNHNH),8.17(s,1H,PhNHNH),7.55(d,J=7.8Hz,2H,PhH),7.45(s,1H,CH2NH),7.28 (t,J=7.9Hz,2H,PhH),7.02(t,J=8.1Hz,2H,PhH),6.58(s,1H,PhH),6.49(dd,J=8.0,2.3Hz,1H, PhH),3.67(s,2H,CH2NH),3.30-3.23(m,2H,C=CCH2),2.66-2.54(m,2H,C=CCH2CH2),2.16(s,3H, CH3),2.12(s,3H,CH3);Z-isomer:11.46(s,1H,C=CNH),9.94(s,1H,PhNHNH),8.11(s,1H,PhNHNH), 7.72(s,1H,CH2NH),7.55(d,J=7.8Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.02(t,J=8.1Hz,2H,PhH),6.58(s,1H,PhH),6.49(dd,J=8.0,2.3Hz,1H,PhH),3.61(s,2H,CH2NH),3.23-3.15(m,2H, C=CCH2),2.66-2.54(m,2H,C=CCH2CH2),2.16(s,3H,CH3),2.12(s,3H,CH3);EI-MS(m/z)392.2 [M]+.
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(4-甲氧基苯基)-4-(苯基氨基)丁酰肼(Iv):
白色粉末,收率92.0%;m.p.181.3-183.1℃;IR(KBr,cm-1)v:3343,3313,3199,3070,2911,1671,1647, 1544,1442,1240,1032,817,753.1H NMR(400MHz,DMSO-d6)δ:11.67(s,1H,C=CNH),9.96(s,1H, PhNHNH),8.09(s,1H,PhNHNH),7.55(d,J=7.9Hz,2H,PhH),7.44(s,1H,CH2NH),7.28(t,J=7.9Hz, 2H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.87(d,J=8.9Hz,2H,PhH),6.74(d,J=8.9Hz,2H,PhH),3.69 (s,3H,OCH3),3.66(s,2H,CH2NH),3.32-3.26(m,2H,C=CCH2),2.66-2.55(m,2H,C=CCH2CH2); 11.46(s,1H,C=CNH),9.94(s,1H,PhNHNH),8.03(s,1H,PhNHNH),7.71(s,1H,CH2NH),7.55(d,J= 7.9Hz,2H,PhH),7.28(t,J=7.9Hz,2H,PhH),7.02(t,J=7.4Hz,1H,PhH),6.87(d,J=8.9Hz,2H,PhH),6.74(d,J=8.9Hz,2H,PhH),3.69(s,3H,OCH3),3.61(s,2H,CH2NH),3.25-3.18(m,2H, C=CCH2),2.66-2.55(m,2H,C=CCH2CH2);EI-MS(m/z)394.2[M]+.
N′-(2-氯苯基)-4-((3-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Iw):
白色粉末,收率79.5%;m.p.213.3℃,分解;IR(KBr,cm-1)v:3295,3255,3189,3074,2900,1685,1630, 1590,1477,1303,1239,1038,879,736.1H NMR(400MHz,DMSO-d6)δ:E-isomer:11.65(s,1H,C=CNH),10.17(s,1H,PhNHNH),8.28(s,1H,PhNHNH),7.75(s,1H,PhH),7.52(s,1H,CH2NH),7.39 (d,J=7.8Hz,2H,PhH),7.31(t,J=8.1Hz,1H,PhH),7.26(t,J=7.8Hz,1H,PhH),7.08(d,J=7.9Hz, 1H,PhH),6.91(t,J=7.6Hz,1H,PhH),6.79(d,J=7.8Hz,1H,PhH),3.69(s,2H,CH2NH),3.24(t,J= 7.7Hz,2H,C=CCH2),2.71-2.59(m,2H,C=CCH2CH2);Z-isomer:11.51(s,1H,C=CNH),10.16(s,1H, PhNHNH),8.25(s,1H,PhNHNH),7.80(s,1H,CH2NH),7.75(s,1H,PhH),7.39(d,J=7.8Hz,2H,PhH), 7.31(t,J=8.1Hz,1H,PhH),7.26(t,J=7.8Hz,1H,PhH),7.08(d,J=7.9Hz,1H,PhH),6.91(t,J=7.6 Hz,1H,PhH),6.79(d,J=7.8Hz,1H,PhH),3.63(s,2H,CH2NH),3.16(t,J=7.8Hz,2H,C=CCH2),2.71-2.59(m,2H,C=CCH2CH2);EI-MS(m/z)432.1[M]+.
N′-(4-溴苯基)-4-((4-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼(Ix):
白色粉末,收率95.4%;m.p.275.5℃,分解;IR(KBr,cm-1)v:3340,3312,3192,3042,2906,1670, 1645,1596,1487,1299,1090,813,774.1H NMR(400MHz,DMSO-d6)δ(ppm):E-isomer:11.61(s,1H, C=CNH),10.11(s,1H,PhNHNH),8.54(s,1H,PhNHNH),7.57(d,J=8.8Hz,2H,PhH),7.50(s,1H, CH2NH),7.40(d,J=8.7Hz,2H,PhH),7.34(d,J=8.8Hz,2H,PhH),6.72(d,J=8.7Hz,2H,PhH),3.67 (s,2H,CH2NH),3.28-3.20(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);Z-isomer:11.45(s,1H, C=CNH),10.09(s,1H,PhNHNH),8.48(s,1H,PhNHNH),7.78(s,1H,CH2NH),7.57(d,J=8.8Hz,2H, PhH),7.40(d,J=8.7Hz,2H,PhH),7.34(d,J=8.8Hz,2H,PhH),6.72(d,J=8.7Hz,2H,PhH),3.62(s, 2H,CH2NH),3.20-3.12(m,2H,C=CCH2),2.64-2.53(m,2H,C=CCH2CH2);EI-MS(m/z)476.0[M]+.
用途实施例
实施例2:本发明的含吡咯烷二酮和苯胺基团的丁酰苯肼类类化合物(I)对植物病
原真菌的杀菌活性测定
采用菌丝生长速率法测定了含吡咯烷二酮和苯胺基团的丁酰苯肼类类化合物(I)中的化合物 Ia-Ix对4种供试植物病原菌小麦赤霉病菌(Fusarium graminearum)、草莓灰霉病菌(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。
测定方法:准确称取4.5mg的待测化合物(包括对照药剂肼菌酮)溶于2.5mL甲醇中,从中吸取 0.5mL加入到89.5mL经灭菌的PSA培养基中,充分摇匀,制成浓度为10μg/mL的含药培养基,将其倒入直径9cm的无菌培养皿中。以加入等量的溶剂制成的培养基为对照。同时以加入杀菌剂肼菌酮制得的浓度为50μg/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℃下于培养箱中倒置培养。待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)。各浓度和三种对照均设三个重复。计算药剂处理后的生长抑制率,计算公式如下:
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%
含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物(I)对4种供试植物病原菌的生长抑制率测定结果列于表1。
表1 含吡咯烷二酮和苯胺基团的丁酰苯肼类类化合物(I)对4种植物病原菌的抑制率(10μg/mL)
表1显示,含吡咯烷二酮和苯胺基团的丁酰苯肼类类化合物(I)中的化合物Ia-Ix在10μg/mL 浓度下对4种供试植物病原菌小麦赤霉病菌、草莓灰霉病菌、水稻纹枯病菌和辣椒炭疽病菌具有显著的抑制活性。各化合物对小麦赤霉病菌的抑制率在21.2%-99.2%之间,多数化合物在80%以上,其中化合物Ia-Il、Io、Ir和Ix达到了90%以上,优于对照药剂肼菌酮的74.1%。各化合物对草莓灰霉病菌的抑制率在35.6%-83.4%之间,其中化合物In和Ip达到了80%以上,其余大部分化合物在 60%-80%之间。各化合物对水稻纹枯病菌的抑制率在58.6%-100%之间,多数化合物在90%以上,其中化合物Ij、In和Iw达到了100%,优于肼菌酮的86.1%。各化合物对辣椒炭疽病菌的抑制率在47.3%-95.9%之间,均优于肼菌酮的38.33%,其中化合物Ia、Ib、Id、Ig、Ii、Ij、In和Ix达到了 90%以上。
Claims (6)
1.式(I)所示结构的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物,
其特征在于其为如下所述化合物之一:
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((4-氟苯基)氨基)丁酰肼、
N′-(4-氯苯基)-4-((2-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼、
N′-(4-氯苯基)-4-((3-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼、
N′-(4-氯苯基)-4-((4-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼、
4-((4-溴苯基)氨基)-N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((邻甲苯基)氨基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((间甲苯基)氨基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((对甲苯基)氨基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-甲氧基苯基)氨基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-(三氟甲基)苯基)氨基)丁酰肼、
N′-(4-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-((3-(三氟甲氧基)苯基)氨基)丁酰肼、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-苯基-4-(苯基氨基)丁酰肼、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(2-氟苯基)-4-(苯基氨基)丁酰肼、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(4-氟苯基)-4-(苯基氨基)丁酰肼、
N′-(2-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼、
N′-(3-氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼、
N′-(4-溴苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼、
N′-(2,4-二氯苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼、
4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)-N′-(对甲苯基)丁酰肼、
N′-(3,4-二甲基苯基)-4-(2,4-二氧吡咯烷-3-基亚基)-4-(苯基氨基)丁酰肼、
4-(2,4-二氧吡咯烷-3-基亚基)-N′-(4-甲氧基苯基)-4-(苯基氨基)丁酰肼、
N′-(2-氯苯基)-4-((3-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼、
N′-(4-溴苯基)-4-((4-氯苯基)氨基)-4-(2,4-二氧吡咯烷-3-基亚基)丁酰肼。
3.权利要求1中所述的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物在防治植物病原真菌方面的应用。
4.根据权利要求3所述的应用,其特征在于权利要求1中所述的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物在防治麦类作物真菌病害、水稻作物真菌病害、水果作物真菌病害、蔬菜作物真菌病害方面的应用。
5.根据权利要求4所述的应用,其特征在于权利要求1中所述的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物在防治麦类作物中由镰孢属真菌引起的病害、水稻作物中由丝核菌属真菌引起的病害、水果作物中由葡萄孢属真菌引起的病害、蔬菜作物中由炭疽菌属真菌引起的病害。
6.根据权利要求5所述的应用,其特征在于权利要求1中所述的含吡咯烷二酮和苯胺基团的丁酰苯肼类化合物在防治小麦赤霉病、草莓灰霉病、水稻纹枯病和辣椒炭疽病方面的应用。
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