CN103539768A - 一种苯并呋喃取代肟醚类化合物及其制备方法与应用 - Google Patents

一种苯并呋喃取代肟醚类化合物及其制备方法与应用 Download PDF

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CN103539768A
CN103539768A CN201310517838.3A CN201310517838A CN103539768A CN 103539768 A CN103539768 A CN 103539768A CN 201310517838 A CN201310517838 A CN 201310517838A CN 103539768 A CN103539768 A CN 103539768A
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吐松
谢亚强
卢英华
叶李艺
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Abstract

一种苯并呋喃取代肟醚类化合物及其制备方法与应用，涉及农药杀菌剂。苯并呋喃取代肟醚类化合物是有效的杀菌剂，这些化合物具有内吸活性并可用作叶面和土壤杀菌剂，能有效地防治多种植物病害，包括植物叶面杀菌剂、土壤杀菌剂等。所述作物病害包括但不限于玉米锈病、稻瘟病、大麦白粉病、小麦白粉病、黄瓜白粉病、葡萄白粉病、苹果白粉病、黄瓜霜霉病、黄瓜炭疽病、葡萄霜霉病。所述苯并呋喃取代肟醚类化合物作为活性组分可与其它载体、稀释剂、其它杀菌剂组成复合杀菌剂。所述苯并呋喃取代肟醚类化合物具有很高的生物活性，即使在很低的剂量下仍可以获得很好的杀菌效果，因此所述苯并呋喃取代肟醚类化合物可用于制备杀菌剂。

Description

一种苯并呋喃取代肟醚类化合物及其制备方法与应用
技术领域
本发明涉及农药杀菌剂，尤其是涉及一种苯并呋喃取代肟醚类化合物及其制备方法与应用。
背景技术
1999年，美国罗门哈斯（ROHM AND HASS）公司报道了苯基亚丙烯基肟醚类杀菌、杀虫剂，专利号为：EP936213，其结构式如下：
Figure BDA0000403323060000011
2000年，美国陶氏益农（DOW AGROSCIENCES）公司也报道了一类芳基环丙烷基取代肟醚类杀菌剂，专利号为：US6063956，其结构式如下：
Figure BDA0000403323060000012
2002年，美国陶氏益农（DOW AGROSCIENCES）公司又报道了另一类芳基环丙烷基取代肟醚类杀菌剂，专利号为：WO2002046142，其结构式如下：
Figure BDA0000403323060000013
据报道，这些不饱和肟醚结构的化合物具有广谱活性，可用于防止在各种作物上的由藻菌纲、卵菌纲、子囊菌纲和半知菌纲等多种真菌引起的病害。后两类杀菌剂以芳基环丙烷基代替了EP936213中所公开化合物的芳基亚丙烯基，据报道该类化合物同样具有广谱杀菌活性，对小麦叶锈病、小麦白粉病、番茄晚疫病、稻瘟病及其他多种植物病害都具有很好的防效。
2006年，吐松等人报道了一类茚取代肟醚类杀菌剂，公开号为：CN1824648，其结构式如下：
Figure BDA0000403323060000021
该类化合物同样具有广谱杀菌活性，部分化合物对稻瘟病、小麦白粉病及其他多种植物病害的防效作用优于部分已经商品化的杀菌剂，例如，BAS490F和SYP-Z071，其结构式如下：
Figure BDA0000403323060000022
发明内容
本发明的第一目的在于提供苯并呋喃取代肟醚类化合物。
本发明的第二目的在于提供苯并呋喃取代肟醚类化合物的制备方法。
本发明的第三目的在于提供苯并呋喃取代肟醚类化合物在制备杀菌剂中的应用。
所述苯并呋喃取代肟醚类化合物的通式I为：排除化合物I-1和I-19：
Figure BDA0000403323060000023
其中：
R1为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R2为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R3为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R4为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R5为氢、C1-C4烷基、C3-C6环烷基、苯基或取代苯基；
Q选自如下所示基团之一：
Figure BDA0000403323060000031
化合物I-1和I-19：
Figure BDA0000403323060000032
所述通式I中，优选：
R1为氢；
R2为氢、氟、氯、C1-C4烷基或C1-C4烷氧基；
R3为氢或C1-C4烷氧基；
R4为氢；
R5为甲基；
Q选自如下所示基团之一：
Figure BDA0000403323060000033
所述苯并呋喃取代肟醚类化合物的制备方法如下：
反应式1：
Figure BDA0000403323060000034
反应式2：
Figure BDA0000403323060000041
反应式3：
Figure BDA0000403323060000042
反应式1中，在溶剂丙酮中，在碱碳酸钾存在下，于25～60℃条件下，用通式Ⅱ所示的化合物和α-氯丙酮反应得通式Ⅲ所示的化合物；通式Ⅲ所示的化合物与盐酸羟胺，在碱乙酸钠存在下，在乙醇/水（V/V=2/1）中，于25～80℃条件下，反应得通式Ⅳ所示的化合物；
反应式2中，在溶剂乙腈中，在碱碳酸钾存在下，于25～80℃条件下，用通式Ⅳ所示的化合物分别和3个不同的中间体A、B或C反应得相对应的通式I-Q1、I-Q2和I-Q3所示的化合物；
反应式3中，在溶剂甲醇中，于25～80℃条件下，用通式I-Q2或I-Q3所示的化合物分别与甲胺水溶液（25wt%）反应得相对应的通式I-Q4和I-Q5所示的化合物。
所述苯并呋喃取代肟醚类化合物可用于制备防治作物病害制剂中应用。
所述苯并呋喃取代肟醚类化合物的通式I为：
Figure BDA0000403323060000043
其中R1为氢；
R2为氢、氟、氯、C1-C4烷基或C1-C4烷氧基；
R3为氢或C1-C4烷氧基；
R4为氢；
R5为甲基；
Q选自如下所示基团之一：
Figure BDA0000403323060000051
本发明的通式I的苯并呋喃取代肟醚类化合物是有效的杀菌剂，这些化合物具有内吸活性并可用作叶面和土壤杀菌剂，能有效地防治多种植物病害，包括植物叶面杀菌剂、土壤杀菌剂等。所述作物病害包括但不限于玉米锈病、稻瘟病、大麦白粉病、小麦白粉病、黄瓜白粉病、葡萄白粉病、苹果白粉病、黄瓜霜霉病、黄瓜炭疽病、葡萄霜霉病，特别适合于防治小麦白粉病、玉米锈病、黄瓜炭疽病和稻瘟病。
所述苯并呋喃取代肟醚类化合物作为活性组分可与其它载体或稀释剂一起组成杀菌剂组合物，杀菌剂组合物中苯并呋喃取代肟醚类化合物的质量百分比含量可为1%～99%。
所述苯并呋喃取代肟醚类化合物作为活性组分可与其它杀菌剂组成复合杀菌剂，复合杀菌剂中苯并呋喃取代肟醚类化合物的质量百分比含量可为1%～99%。
所述苯并呋喃取代肟醚类化合物具有很高的生物活性，即使在很低的剂量下仍可以获得很好的杀菌效果，因此所述苯并呋喃取代肟醚类化合物可用于制备杀菌剂。
具体合成方法如下：
在溶剂丙酮中，在碱碳酸钾存在下，于25～60℃条件下，用通式Ⅱ所示的化合物和α-氯丙酮反应得通式Ⅲ所示的化合物，所述通式Ⅱ所示的化合物为：
Figure BDA0000403323060000052
通式Ⅳ的化合物可由如下方法制备：
在乙醇/水溶液（V/V=2/1）中，在碱乙酸钠存在下，于25～80℃条件下，用通式Ⅲ所示的化合物和盐酸羟胺反应得通式Ⅳ所示的化合物。
通式I-Q1、I-Q2和I-Q3的化合物可由如下方法制备：
在溶剂乙腈中，在碱碳酸钾存在下，于25℃-80℃条件下，用通式Ⅳ所示的化合物分别和三个不同的中间体A、B或C反应得相对应的通式I-Q1、I-Q2和I-Q3所示的化合物。
通式I-Q4和I-Q5的化合物可由如下方法制备：
在溶剂甲醇中，于25℃-80℃条件下，用通式I-Q2或I-Q3所示的化合物分别与甲胺水溶液（25wt%）反应得相对应的通式I-Q4和I-Q5所示的化合物。
本发明具有通式Ⅲ结构的部分化合物的具体结构式、化合物物理性质、1H NMR(CDCl3,400MHz)、13C NMR(CDCl3,100MHz)数据如下，用来进一步说明本发明，但不意味着限制本发明。
Figure BDA0000403323060000061
化合物Ⅲ-1:淡黄色固体Mp:69.7-70.2℃
1H NMR(CDCl3,400MHz)δ:2.61(s,3H,C-CH3),7.29-7.33(m,1H,ArH),7.45-7.50(m,1H,ArH),7.50(d,J=1.2Hz,1H,C=CH),7.56-7.59(m,1H,ArH),7.69-7.72(m,1H,ArH)ppm.13CNMR(CDCl3,100MHz)δ:26.78,112.79,113.37,123.62,124.23,127.38,128.70,152.98,156.00,188.97ppm.
Figure BDA0000403323060000062
化合物Ⅲ-2:淡黄色固体Mp:84.1-85.7℃
1H NMR(CDCl3,400MHz)δ:2.61(s,3H,C-CH3),7.19-7.24(m,1H,ArH),7.36(dd,J=8.4,2.8Hz,1H,ArH),7.47(d,J=0.8Hz,1H,C=CH),7.53(dd,J=8.8,4.0Hz,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:26.78,108.42,108.66,113.70,113.79,116.77,117.04,162.20,164.41,188.82ppm.
Figure BDA0000403323060000063
化合物Ⅲ-3:淡黄色固体Mp:97.0-98.0℃
1H NMR(CDCl3,400MHz)δ:2.62(s,3H,C-CH3),7.42-7.45(m,2H,ArH),7.52(d,J=8.8Hz,1H,ArH),7.69(d,J=1.6Hz,1H,C=CH)ppm.13C NMR(CDCl3,100MHz)δ:36.82,112.36,113.87,122.93,128.61,128.90,129.87,154.03,154.20,188.76ppm.
Figure BDA0000403323060000064
化合物Ⅲ-4:淡黄色固体Mp:80.7-81.0℃
1H NMR(CDCl3,400MHz)δ:2.46(s,3H,C-CH3),2.60(s,3H,Ar-CH3),7.28-7.31(m,1H,ArH),7.43(d,J=1.2Hz,1H,ArH),7.45-7.48(m,1H,ArH),7.48(d,J=0.8Hz,1H,C=CH)ppm.13CNMR(CDCl3,100MHz)δ:21.61,26.73,112.28,113.18,123.05,127.48,130.21,133.85,155.12,154.54,188.98ppm.
Figure BDA0000403323060000071
化合物Ⅲ-5:白色粉末Mp:84.8-85.1℃
1H NMR(CDCl3,400MHz)δ:2.59(s,3H,C-CH3),3.85(s,3H,Ar-OCH3),7.08-7.11(m,2H,ArH),7.43(d,J=0.8Hz,1H,C=CH),7.45-7.47(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:26.48,55.93,104.03,113.09,113.21,118.54,127.66,150.93,153.46,156.69,188.68ppm.
Figure BDA0000403323060000072
化合物Ⅲ-6:淡黄色固体Mp:100.8-101.2℃
1H NMR(CDCl3,400MHz)δ:2.57(s,3H,C-CH3),3.88(s,3H,Ar-OCH3),6.95(dd,J=8.8,2.4Hz,1H,ArH),7.04(d,J=2.0Hz,1H,ArH),7.45(d,J=0.8Hz,1H,C=CH),7.56(d,J=8.8Hz,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:26.53,56.05,96.93,114.08,114.73,120.67,123.92,152.65,157.62,161.47,188.21ppm.
本发明具有通式Ⅳ结构的部分化合物的具体结构式、化合物物理性质、1H NMR(CDCl3,400MHz)、13C NMR(CDCl3,100MHz)数据如下，用来进一步说明本发明，但不意味着限制本发明。
化合物Ⅳ-1:白色晶体Mp:153.9-154.4℃
1H NMR(CDCl3,400MHz)δ:2.32(s,3H,C-CH3),7.00(s,1H,C=CH),7.22-7.26(m,1H,ArH),7.31-7.36(m,1H,ArH),7.52(d,J=9.2Hz,1H,ArH),7.59(d,J=7.6Hz,1H,ArH),8.53(s,1H,N-OH)ppm.13C NMR(CDCl3,100MHz)δ:11.61,107.07,111.93,121.73,123.51,126.02,128.21,148.18,152.15,155.48ppm.
Figure BDA0000403323060000074
化合物Ⅳ-2:黄色粉末Mp:155.6-155.8℃
1H NMR(CDCl3,400MHz)δ:2.30(s,3H,C-CH3),6.96(s,1H,C=CH),6.96-7.08(m,1H,ArH),7.36(dd,J=8.4,2.8Hz,1H,ArH),7.44(dd,J=8.8,4.0Hz,1H,ArH),8.50(s,1H,N-OH)ppm.13CNMR(CDCl3,100MHz)δ:11.54,107.01,107.26,112.58,112.67,113.71,113.98,148.22,151.70,153.84ppm.
Figure BDA0000403323060000081
化合物Ⅳ-3:白色晶体Mp:165.1-166.9℃
1H NMR(CDCl3,400MHz)δ:2.30(s,3H,C-CH3),6.94(s,1H,C=CH),7.29(dd,J=8.8,1.6Hz,1H,ArH),7.44(d,J=8.8Hz,1H,ArH),7.56(d,J=1.6Hz,1H,ArH),8.55(s,1H,N-OH)ppm.13CNMR(CDCl3,100MHz)δ:11.65,106.40,112.92,121.28,126.26,129.17,129.55,148.22,153.56,153.82ppm.
Figure BDA0000403323060000082
化合物Ⅳ-4:白色晶体Mp:189.9-190.2℃
1H NMR(CDCl3,400MHz)δ:2.30(s,3H,C-CH3),2.44(s,3H,Ar-CH3),6.92(s,1H,C=CH),7.14(dd,J=8.4,1.2Hz,1H,ArH),7.36(dd,apparent t,J=1.6,0.8Hz,1H,ArH),7.39(d,J=8.4Hz,1H,ArH),8.46(s,1H,N-OH)ppm.13C NMR(CDCl3,100MHz)δ:11.53,21.64,106.94,111.43,121.48,127.40,128.30,133.01,148.58,152.22,153.97ppm.
化合物Ⅳ-5:白色晶体Mp:157.1-157.6℃
1H NMR(CDCl3,400MHz)δ:2.30(s,3H,C-CH3),3.85(s,3H,O-CH3),6.93(s,1H,C=CH),6.95(d,J=2.4Hz,1H,ArH),7.03(d,J=2.4Hz,1H,ArH),7.41(d,J=8.8Hz,1H,ArH),8.45(s,1H,N-OH)ppm.13C NMR(CDCl3,100MHz)δ:11.63,56.24,103.83,112.43,115.02,128.75,148.46,150.54,152.88,156.52ppm.
Figure BDA0000403323060000084
化合物Ⅳ-6:白色晶体Mp:165.3-165.9℃
1H NMR(CDCl3,400MHz)δ:2.28(s,3H,C-CH3),3.86(s,3H,O-CH3),6.88(dd,J=8.4,2.0Hz,1H,ArH),6.92(d,J=0.8Hz,1H,C=CH),7.04(d,J=2.0Hz,1H,ArH),7.44(d,J=8.4Hz,1H,ArH),8.22(br,1H,N-OH)ppm.13C NMR(CDCl3,100MHz)δ:11.47,56.05,77.56,96.23,107.33,112.90,121.51,121.90,151.36,156.71,159.48ppm.
本发明具有通式I结构的部分化合物的具体结构式、化合物物理性质、1H NMR(CDCl3,400MHz)、13C NMR(CDCl3,100MHz)数据如下，用来进一步说明本发明，但不意味着限制本发明。
Figure BDA0000403323060000091
化合物I-1:淡黄色油状
1H NMR(CDCl3,400MHz)δ:2.26(s,3H,N=C-CH3),3.69(s,3H,C=C-OCH3),3.83(s,3H,O=C-OCH3),5.25(s,2H,O-CH2),6.97(d,J=0.4Hz,1H,O-C=CH),7.16-7.19(m,1H,ArH),7.20-7.25(m,1H,ArH),7.29-7.38(m,3H,ArH),7.52-7.59(m,4H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.50,51.96,62.28,75.32,107.11,110.58,112.03,121.63,123.46,125.88,127.96,128.24,128.27,128.65,131.26,132.10,136.61,147.66,152.22,155.51,160.29,168.26ppm.
Figure BDA0000403323060000092
化合物I-2:淡黄色油状物
1H NMR(CDCl3,400MHz)δ:2.25(s,3H,N=C-CH3),3.69(s,3H,C=C-OCH3),3.82(s,3H,O=C-OCH3),5.24(s,2H,O-CH2),6.94(s,1H,O-C=CH),7.01-7.05(m,1H,ArH),7.16-7.19(m,1H,ArH),7.22(dd,J=6.8,2.0Hz,1H,ArH),7.33-7.36(m,2H,ArH),7.45(dd,J=7.2,3.2Hz,1H,ArH),7.51-7.54(m,1H,ArH),7.58(s,1H,O-CH=C)ppm.13C NMR(CDCl3,100MHz)δ:12.41,51.95,62.28,75.43,106.87,107.12,110.59,112.63,112.73,113.49,113.75,128.02,128.25,128.66,129.12,131.30,132.13,136.52,147.48,153.97,160.28,168.24ppm.
Figure BDA0000403323060000093
化合物I-3:淡黄色晶体Mp:111.9-113.8℃
1H NMR(CDCl3,400MHz)δ:2.25(s,3H,N=C-CH3),3.69(s,3H,C=C-OCH3),3.82(s,3H,O=C-OCH3),5.24(s,2H,O-CH2),6.91(s,1H,O-C=CH),7.16-7.19(m,1H,ArH),7.25-7.28(m,1H,ArH),7.32-7.38(m,2H,ArH),7.44(d,J=8.8Hz,1H,ArH),7.51-7.54(m,2H,ArH),7.59(s,1H,O-CH=C)ppm.13C NMR(CDCl3,100MHz)δ:12.44,51.97,62.29,76.48,106.24,110.61,113.00,121.14,126.05,128.05,128.26,128.68,129.08,129.66,131.32,132.15,136.50,147.40,153.69,153.83,160.28,168.25ppm.
化合物I-4:淡黄色固体Mp:96.7-101.3℃
1H NMR(CDCl3,400MHz)δ:2.24(s,3H,N=C-CH3),2.42(s,3H,Ar-CH3),3.68(s,3H,C=C-OCH3),3.80(s,3H,O=C-OCH3),5.24(s,2H,O-CH2),6.89(d,J=0.8Hz,1H,O-C=CH),7.11(dd,J=8.8,1.6Hz,1H,ArH),7.15-7.19(m,1H,ArH),7.29-7.37(m,3H,ArH),7.40(d,J=8.4Hz,1H,ArH),7.52-7.55(m,1H,ArH),7.58(s,1H,O=CC=H)ppm.13C NMR(CDCl3,100MHz)δ:12.23,21.37,51.69,62.01,76.04,106.69,110.34,111.27,121.13,127.00,127.69,127.99,128.13,128.39,131.02,131.86,132.66,136.41,147.61,152.02,153.73,160.04,168.00ppm.
Figure BDA0000403323060000102
化合物I-5:淡红色晶体Mp:89.0-91.8℃
1H NMR(CDCl3,400MHz)δ:2.24(s,3H,N=C-CH3),3.69(s,3H,C=C-OCH3),3.82(s,3H,Ar-OCH3),3.84(s,3H,O=C-OCH3),5.24(s,2H,O-CH2),6.91(d,J=0.8Hz,1H,O-C=CH),6.90-6.94(m,1H,ArH),7.01(d,J=2.4Hz,1H,ArH),7.16-7.19(m,1H,ArH),7.30-7.38(m,2H,ArH),7.42(d,J=8.8Hz,1H,ArH),7.52-7.55(m,1H,ArH),7.58(s,1H,O=CC=H)ppm.13C NMR(CDCl3,100MHz)δ:12.47,51.97,56.21,62.29,75.32,103.73,107.14,110.61,112.53,114.86,127.97,128.249,128.66,128.84,131.27,132.11,136.64,147.73,150.57,152.97,156.48,160.29,168.27ppm.
Figure BDA0000403323060000103
化合物I-6:淡黄色固体Mp:94.4-95.1℃
1H NMR(CDCl3,400MHz)δ:2.23(s,3H,N=C-CH3),3.69(s,3H,Ar-OCH3),3.82(s,3H,C=C-OCH3),3.84(s,3H,O=C-OCH3),5.23(s,2H,O-CH2),6.86(dd,J=8.8,2.4Hz,1H,ArH),6.89(d,J=0.4Hz,1H,O-C=CH),7.07(d,J=1.6Hz,1H,ArH),7.17(dd,J=6.4,2.4Hz,1H,ArH),7.20-7.38(m,2H,ArH),7.42(d,J=8.4Hz,1H,ArH),7.529-7.55(m,1H,ArH),7.580(s,1H,O=CC=H)ppm.13C NMR(CDCl3,100MHz)δ:12.45,51.95,56.00,62.27,75.21,96.41,107.28,110.62,112.74,121.61,121.77,127.92,128.23,128.62,131.247,132.08,136.71,147.60,151.43,156.71,159.33,160.27,168.27ppm.
Figure BDA0000403323060000111
化合物I-7:淡黄色固体Mp:83.3-85.4℃
1H NMR(CDCl3,400MHz)δ:2.30(s,3H,N=C-CH3),3.78(s,3H,N-OCH3),3.80(s,3H,O=C-OCH3),5.38(s,2H,O-CH2),6.99(s,1H,O-C=CH),7.21-7.25(m,1H,ArH),7.30-7.34(m,1H,ArH),7.37-7.38(m,3H,ArH),7.51-7.53(m,1H,ArH),7.56-7.59(m,2H,ArH)ppm.13CNMR(CDCl3,100MHz)δ:12.58,53.85,62.48,72.87,107.14,112.00,121.67,123.49,125.94,127.23,128.25,128.80,129.02,129.34,135.66,137.81,148.05,152.09,155.51,156.11ppm.
Figure BDA0000403323060000112
化合物I-8:淡黄色晶体Mp:89.0-90.3℃
1H NMR(CDCl3,400MHz)δ:2.29(s,3H,N=C-CH3),3.78(s,3H,N-OCH3),3.80(s,3H,O=C-OCH3),5.37(s,2H,O-CH2),6.95(s,1H,C=CH),7.01-7.06(m,1H,ArH),7.22(dd,J=8.4,2.8Hz,1H,ArH),7.36-7.42(m,3H,ArH),7.44(dd,J=8.8,4.0Hz,1H,ArH),7.56-7.58(m,H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.51,53.86,62.48,73.00,106.92,107.16,112.64,112.73,113.68,113.84,127.30,128.87,129.05,129.37,135.59,137.82,147.88,151.73,153.85,156.11ppm.
Figure BDA0000403323060000121
化合物I-9:淡黄色晶体Mp:93.3-94.6℃
1H NMR(CDCl3,400MHz)δ:2.29(s,3H,N=C-CH3),3.77(s,3H,N-OCH3),3.79(s,3H,O=C-OCH3),5.37(s,2H,O-CH2),6.92(s,1H,O-C=CH),7.22-7.29(m,1H,ArH),7.37-7.40(m,3H,ArH),7.43(d,J=8.8Hz,1H,ArH),7.53-7.57(m,2H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.53,53.86,62.48,73.03,106.30,112.98,121.19,126.12,127.31,128.87,129.06,129.12,129.37,129.63,135.52,137.83,147.79,153.56,153.84,156.10ppm.
Figure BDA0000403323060000122
化合物I-10:淡黄色固体Mp:76.4-78.0℃
1H NMR(CDCl3,400MHz)δ:2.29(s,3H,N=C-CH3),2.43(s,3H,Ar-CH3),3.78(s,3H,N-OCH3),3.79(s,3H,O=C-OCH3),5.37(s,2H,O-CH2),6.91(d,J=1.2Hz,1H,O-C=CH),7.12(d,J=8.4,1.6Hz,1H,ArH),7.34-7.35(m,1H,ArH),7.36-7.41(m,4H,ArH),7.56-7.60(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.57,21.61,53.84,62.48,72.83,106.98,111.49,121.40,127.20,127.30,128.33,128.78,129.010,129.33,132.96,136.68,137.80,148.14,152.13,153.98,156.09ppm.
化合物I-11:棕黄色油状物
1H NMR(CDCl3,400MHz)δ:2.28(s,3H,N=C-CH3),3.78(s,3H,N-OCH3),3.79(s,3H,C-OCH3),3.84(s,3H,Ar-OCH3),5.37(s,2H,O-CH2),6.92(d,J=0.8Hz,1H,O-C=CH),6.92(dd,J=8.8,2.4Hz,1H,ArH),7.36-7.42(m,4H,ArH),7.56-7.59(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.53,53.84,56.20,62.48,72.85,103.72,107.17,112.49,114.93,124.03,127.23,128.79,129.02,129.33,135.66,137.79,148.11,150.56,152.79,156.09,156.49ppm.
Figure BDA0000403323060000131
化合物I-12:棕黄色油状物
1H NMR(CDCl3,400MHz)δ:2.27(s,3H,N=C-CH3),3.78(s,3H,N-OCH3),3.79(s,3H,C-OCH3),3.84(s,3H,Ar-OCH3),5.36(s,2H,O-CH2),6.87(dd,J=8.4,2.0Hz,1H,ArH),6.91(d,J=0.8Hz,1H,C=CH),7.05(d,J=2.0Hz,1H,ArH),7.36-7.40(m,3H,ArH),7.43(d,J=7.6Hz,1H,ArH),7.57-7.60(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.53,53.83,55.99,62.49,72.75,96.31,107.37,112.82,121.54,121.80,127.21,128.74,129.01,129.30,135.74,137.75,147.96,151.24,156.09,156.71,159.37ppm.
Figure BDA0000403323060000132
化合物I-13:棕色油状物
1H NMR(CDCl3,400MHz)δ:2.29(s,3H,N=C-CH3),2.89(d,J=4.8Hz,3H,N-CH3),3.71(s,3H,N-OCH3),5.43(s,2H,O-CH2),5.95-5.96(m,1H,NH),6.96(d,J=0.8Hz,1H,C=CH),7.20-7.24(m,1H,ArH),7.28-7.31(m,1H,ArH),7.32-7.38(m,3H,ArH),7.48-7.52(m,1H,ArH),7.55-7.57(m,2H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.58,27.09,62.18,72.99,106.89,111.93,121.64,123.45,125.83,126.21,128.29,128.40,128.66,129.11,136.43,139.00,147.81,147.81,152.28,155.47,158.44ppm.
Figure BDA0000403323060000133
化合物I-14:棕色油状物
1H NMR(CDCl3,400MHz)δ:2.28(s,3H,N=C-CH3),2.89(d,J=5.2Hz,3H,N-CH3),3.71(s,3H,-OCH3),5.42(s,2H,O-CH2),5.94-5.96(m,1H,NH),6.93(d,J=0.8Hz,1H,C=CH),7.00-7.05(m,1H,ArH),7.21(dd,J=8.4,2.4Hz,1H,ArH),7.31-7.38(m,3H,ArH),7.42(d,J=8.8,4.0Hz,1H,ArH),7.52-7.56(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.49,27.09,62.19,73.10,106.66,106.87,107.12,112.64,112.64,113.44,113.70,126.16,128.69,129.05,136.31,139.01,147.64,151.66,154.02,158.42ppm.
Figure BDA0000403323060000141
化合物I-15:棕色油状物
1H NMR(CDCl3,400MHz)δ:2.28(s,3H,N=C-CH3),2.89(d,J=4.8Hz,3H,N-CH3),3.71(s,3H,OCH3),5.42(s,2H,O-CH2),5.95-5.97(m,1H,NH),6.90(d,J=0.8Hz,1H,C=CH),7.26(dd,J=8.8,2.4Hz,1H,ArH),7.32-7.36(m,3H,ArH),7.41(d,J=8.8Hz,1H,ArH),7.52-7.56(m,2H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.51,27.09,62.17,73.14,106.05,112.90,121.15,125.98,126.14,128.38,128.70,129.05,129.66,136.28,139.03,147.54,153.74,153.79,158.41ppm.
Figure BDA0000403323060000142
化合物I-16:棕色油状物
1H NMR(CDCl3,400MHz)δ:2.28(s,3H,N=C-CH3),2.42(s,3H,Ar-CH3),2.88(d,J=4.8Hz,3H,N-CH3),3.71(s,3H,-OCH3),5.42(s,2H,O-CH2),5.94-5.96(m,1H,NH),6.89(d,J=0.8Hz,1H,C=CH),7.11(dd,J=8.4,1.6Hz,1H,ArH),7.31-7.39(m,5H,ArH),7.54-7.57(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.57,21.61,27.09,62.18,72.95,106.73,111.43,121.43,126.54,127.19,128.41,128.64,129.12,132.91,136.45,138.99,147.91,152.31,153.93,158.44ppm.
Figure BDA0000403323060000143
化合物I-17:棕色油状物
1H NMR(CDCl3,400MHz)δ:2.28(s,3H,N=C-CH3),2.89(d,J=4.8,3H,N-CH3),3.71(s,3H,-OCH3),3.83(s,3H,Ar-OCH3),5.42(s,2H,O-CH2),5.92-5.96(m,1H,NH),6.90-6.93(m,2H,ArH),7.00(d,J=2.4Hz,1H,ArH),7.30-7.37(m,3H,ArH),7.39(d,J=9.2Hz,1H,ArH),7.53-7.57(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.54,27.10,56.21,62.19,73.00,103.72,106.92,112.44,114.82,126.21,128.40,128.65,128.85,129.12,136.44,139.02,147.90,150.53,153.01,156.48,158.45ppm.
Figure BDA0000403323060000151
化合物I-18:棕色油状物
1H NMR(CDCl3,400MHz)δ:2.26(s,3H,C-CH3),2.89(d,J=4.8Hz,3H,N-CH3),3.71(s,3H,N-OCH3),3.84(s,3H,Ar-OCH3),5.41(s,2H,O-CH2),5.93-5.96(m,1H,NH),6.86(dd,J=8.8,2.4Hz,1H,C=CH),6.89(d,J=0.8Hz,1H,ArH),7.03(d,J=2.0Hz,1H,ArH),7.31-7.38(m,3H,ArH),7.42(d,J=8.4Hz,1H,ArH),7.54-7.57(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.540,27.09,56.01,62.17,72.904,96.33,107.10,112.73,126.27,128.41,128.62,129.12,136.51,129.12,136.51,138.99,147.74,151.47,156.67,158.43,159.30ppm.
Figure BDA0000403323060000152
化合物I-19:淡黄色油状物
1H NMR(CDCl3,400MHz)δ:2.23(s,3H,N=C-CH3),3.84(s,3H,O=C-OCH3),4.05(s,3H,N-OCH3),5.22(s,2H,O-CH2),6.98(d,J=0.8Hz,1H,C=CH),7.19-7.25(m,2H,ArH),7.29-7.34(m,1H,ArH),7.37-7.47(m,2H,ArH),7.52-7.58(m,3H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.43,53.25,64.17,75.61,107.20,112.04,121.04,123.49,125.94,128.19,128.25,128.83,129.13,129.78,130.20,135.87,148.10,149.79,152.05,155.52,163.65ppm.
Figure BDA0000403323060000153
化合物I-20:淡黄色晶体Mp:109.7-110.6℃
1H NMR(CDCl3,400MHz)δ:2.22(s,3H,N=C-CH3),3.84(s,3H,O=C-OCH3),4.04(s,3H,N-OCH3),5.21(s,2H,O-CH2),6.94(d,J=0.8Hz,1H,C=CH),7.01-7.06(m,1H,ArH),7.19-7.23(m,2H,ArH),7.39-7.47(m,3H,ArH),7.50-7.53(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.33,53.24,64.16,75.70,106.93,107.14,112.65,112.74,113.55,113.82,128.24,128.90,129.15,129.78,130.22,135.77,147.91,149.77,151.71,153.78,163.63ppm.
Figure BDA0000403323060000161
化合物I-21:白色固体Mp:129.5-130.1℃
1H NMR(CDCl3,400MHz)δ:2.21(s,3H,N=C-CH3),3.84(s,3H,O=C-OCH3),4.04(s,3H,N-OCH3),5.21(s,2H,O-CH2),6.91(d,J=0.8Hz,1H,C=CH),7.20(dd,J=7.2,1.2Hz,1H,ArH),7.27(dd,J=8.8,2.0Hz,1H,ArH),7.39-7.46(m,3H,ArH),7.50-7.54(m,2H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.36,53.25,64.17,76.73,106.34,113.00,121.17,128.26,128.90,129.10,129.16,129.60,129.80,130.22,135.73,147.82,149.76,153.49,153.83,163.62ppm.
Figure BDA0000403323060000162
化合物I-22:白色固体Mp:125.8-126.1℃
1H NMR(CDCl3,400MHz)δ:2.22(s,3H,N=C-CH3),2.42(s,3H,Ar-CH3),3.84(s,3H,O=C-OCH3),4.04(s,3H,N-OCH3),5.21(s,2H,O-CH2),6.90(d,J=0.8Hz,1H,C=CH),7.12(dd,J=8.4,1.2Hz,1H,ArH),7.20(dd,J=7.6,1.2Hz,1H,ArH),7.33-7.35(m,1H,ArH),7.36-7.46(m,3H,ArH),7.53(dd,J=7.6,0.8Hz,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.43,21.62,53.25,64.17,75.57,107.05,111.54,121.40,127.31,128.16,128.34,128.87,129.12,129.78,130.19,132.96,135.89,148.19,149.79,152.09,153.99,163.64ppm.
Figure BDA0000403323060000163
化合物I-23:淡黄色固体Mp:102.2-102.6℃
1H NMR(CDCl3,400MHz)δ:2.21(s,3H,N=C-CH3),3.84(s,3H,O=C-OCH3),3.84(s,3H,N-OCH3),4.04(s,3H,Ar-OCH3),5.21(s,2H,O-CH2),6.90-6.94(m,2H,ArH),7.00(d,J=2.8Hz,1H,ArH),7.22(dd,J=7.6,1.2Hz,1H,ArH),7.38-7.44(m,3H,ArH),7.52(d,J=7.6Hz,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.39,53.25,56.21,64.17,76.59,103.83,107.24,112.54,114.94,128.18,128.80,12.880,129.13,129.78,130.20,135.88,148.15,149.79,150.58,152.76,156.49,163.64ppm.
化合物I-24:白色粉末Mp:131.3-131.4℃
1H NMR(CDCl3,400MHz)δ:2.20(s,3H,N=C-CH3),3.84(s,3H,O=C-OCH3),3.84(s,3H,Ar-OCH3),4.04(s,3H,N-OCH3),5.20(s,2H,O-CH2),6.86(dd,J=8.8,2.4Hz,1H,ArH),6.89(d,J=0.8Hz,1H,O-C=CH),7.06(d,J=2.0Hz,1H,ArH),7.20(dd,J=7.6,1.2Hz,1H,ArH),7.36-7.46(m,3H,ArH),7.53(dd,J=7.6,1.2Hz,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.40,53.25,56.02,75.51,96.38,107.43,112.83,121.57,121.81,128.15,128.88,129.11,129.78,130.18,135.96,148.01,149.82,151.23,156.74,159.39,163.65ppm.
Figure BDA0000403323060000172
化合物I-25:淡黄色油状物
1H NMR(CDCl3,400MHz)δ:2.22(s,3H,N=C-CH3),2.90(d,J=5.2Hz,3H,N-CH3),3.96(s,3H,N-OCH3),5.20(s,2H,O-CH2),6.76-6.77(m,1H,NH),6.97(d,J=0.8Hz,1H,C=CH),7.19-7.25(m,2H,ArH),7.30-7.35(m,1H,ArH),7.38-7.43(m,2H,ArH),7.51-7.59(m,3H,ArH)ppm.13CNMR(CDCl3,100MHz)δ:12.46,26.57,63.66,75.71,107.22,112.01,121.68,123.61,125.95,128.16,128.27,129.03,129.15,129.68,130.03,135.87,148.00,151.47,152.12,155.51,163.27ppm.
Figure BDA0000403323060000173
化合物I-26:白色固体Mp:135.3-135.7℃
1H NMR(CDCl3,400MHz)δ:2.21(s,3H,N=C-CH3),2.90(d,J=4.8Hz,3H,N-CH3),3.96(s,3H,N-OCH3),5.19(s,2H,O-CH2),6.77-6.79(m,1H,NH),6.94(s,1H,ArH),7.01-7.06(m,1H,ArH),7.19-7.23(m,2H,ArH),7.37-7.47(m,3H,ArH),7.50-7.53(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.37,26.56,63.66,75.79,106.91,107.16,112.62,112.72,113.56,113.82,128.19,129.04,129.12,129.68,130.01,135.79,147.83,151.44,151.71,153.87,163.22ppm.
Figure BDA0000403323060000181
化合物I-27:白色固体Mp:137.9-138.7℃
1H NMR(CDCl3,400MHz)δ:2.20(s,3H,N=C-CH3),2.89(d,J=4.8Hz,3H,N-CH3),3.95(s,3H,N-OCH3),5.20(s,2H,O-CH2),6.76-6.78(m,1H,NH),6.90(d,J=0.8Hz,1H,C=CH),7.19-7.22(m,1H,ArH),7.26(dd,J=8.8,2.0Hz,1H,ArH),7.36-7.45(m,3H,ArH),7.50-7.53(m,2H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.16,26.33,63.43,76.58,106.13,112.74,120.95,125.87,127.97,128.81,128.88,128.89,129.40,129.47,129.77,135.53,147.50,151.18,153.33,153.58,162.99ppm.
Figure BDA0000403323060000182
化合物I-28:淡黄色固体Mp:134.9-135.2℃
1H NMR(CDCl3,400MHz)δ:2.21(s,3H,N=C-CH3),2.43(s,3H,Ar-CH3),2.89(d,J=4.8Hz,3H,N-CH3),3.95(s,3H,N-OCH3),5.19(s,2H,O-CH2),6.74-6.76(m,1H,NH),6.89(d,J=0.8Hz,1H,ArH),7.12(dd,J=8.8,1.2Hz,1H,ArH),7.21(dd,J=7.2,1.2Hz,1H,ArH),7.34-7.35(m,1H,ArH),7.36-7.44(m,3H,ArH),7.52(dd,J=7.2,1.2Hz,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.44,21.62,26.56,63.64,76.66,107.05,111.49,121.41,127.31,128.13,128.35,129.01,129.14,129.68,130.03,132.98,135.87,148.07,151.49,152.16,153.97,163.27ppm.
Figure BDA0000403323060000183
化合物I-29:淡红色固体Mp:115.5-121.7℃
1H NMR(CDCl3,400MHz)δ:2.20(s,3H,N=C-CH3),2.89(d,J=5.2Hz,3H,N-CH3),3.84(s,3H,N-OCH3),3.95(s,3H,Ar-OCH3),5.19(s,2H,O-CH2),6.75-6.77(m,1H,NH),6.91(d,J=0.8Hz,1H,C=CH),6.92(dd,J=8.8,2.4Hz,1H,ArH),7.01(d,J=2.4Hz,1H,ArH),7.19-7.22(m,1H,ArH),7.36-7.45(m,3H,ArH),7.50-7.54(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.40,26.56,56.20,63.64,76.66,103.73,107.26,114.93,128.14,128.80,129.01,129.13,129.61,130.01,135.86,148.04,150.55,151.46,152.81,156.50,163.26ppm.
Figure BDA0000403323060000191
化合物I-30:淡红色油状物
1H NMR(CDCl3,400MHz)δ:2.19(s,3H,N=C-CH3),2.89(d,J=4.8Hz,3H,N-CH3),3.84(s,3H,Ar-OCH3),3.95(s,3H,N-OCH3),5.19(s,2H,O-CH2),6.75-6.77(m,1H,NH),6.87(dd,J=8.8,2.4Hz,1H,ArH),6.89(d,J=0.8Hz,1H,C=CH),7.06(d,J=2.0Hz,1H,ArH),7.21(dd,J=7.2,1.2Hz,1H,ArH),7.36-7.45(m,3H,ArH),7.51-7.54(m,1H,ArH)ppm.13C NMR(CDCl3,100MHz)δ:12.39,26.56,56.01,63.63,75.57,96.36,107.41,112.79,121.57,121.79,128.11,128.99,129.11,129.66,130.00,135.93,147.91,151.29,151.49,156.70,159.38,163.27ppm.
本发明的有益效果是：
载体为满足下述条件的物质：它与活性成分配制后便于施用于待处理位点，例如可以是植物、种子或土壤；或者有利于贮存、运输或操作。载体可以是固体或液体，包括通常为气体但已压缩成液体的物质，可使用任何通常在配置杀菌组合物中所用的载体。
适合的固体载体包括天然和合成的粘土和硅酸盐，例如硅藻土、滑石、硅镁土、硅酸铝（高岭土）、蒙脱石和云母；碳酸钙、硫酸钙、硫酸铵、合成的氧化硅和合成硅酸钙或硅酸铝；元素如碳和硫；天然的或合成的树脂如苯并呋喃树脂、聚氯乙烯和苯乙烯聚合物和共聚物；固体多氯苯酚；沥青；蜡如蜂蜡、石蜡。
适合的液体载体包括水、醇、酮、醚、石油馏分、氯化烃；醇如异丙醇和乙醇；酮如丙酮、甲基乙基酮、甲基异丙基酮、环己基酮；醚；芳烃如苯、甲苯、二甲苯；石油馏分如煤油和矿物油；氯代烃如四氯化碳、全氯乙烯和三氯乙烯，通常，这些液体的混合物也是适合的。
杀菌组合物通常加工成浓缩的形式并以此用于运输，在施用之前由施用者将其稀释。组合物中含有少量的表面活性剂有助于稀释过程。这样按照本发明的组合物中至少有一种载体优选是表面活性剂。例如组合物至少有两种载体，其中至少一种是表面活性剂。表面活性剂可以是乳化剂、分散剂或润湿剂；它可以是非离子的或离子的表面活性剂。适合的表面活性剂的例子包括聚丙烯酸和木质素硫酸的钠盐或钙盐；分子中含至少12个碳原子的脂肪酸或酰胺与环氧乙烷和／或环氧丙烷的缩合物。甘醇、山梨酸、蔗糖或季戊四醇脂肪酸酯及这些酯与环氧乙烷和／或环氧丙烷的缩合物；脂肪醇或烷基苯酚如对辛基苯酚或或对辛基甲苯酚与环氧乙烷和／或环氧丙烷的缩合物；这些缩合物的硫酸盐和磺酸盐；在分子中至少含有10个碳原子的硫酸或磺酸酯的碱土金属盐，优选钠盐，例如硫酸月桂酯钠，硫酸仲烷酯钠，磺化蓖麻油钠盐，磺酸烷基芳基酯钠，磺酸烷基芳基酯钠，如十二烷基苯酸钠盐。
本发明的杀菌组合物可以根据需要加工成多种剂型，例如可湿性粉剂、粉剂、颗粒剂和溶液，可乳化的浓缩剂、乳剂、悬浮浓缩剂、气雾剂和烟雾剂。可湿性粉剂通常含有25％，50％或75％重量的活性成分，且通常除固体惰性载体之外，还含有3％～10％重量的分散剂，且若需要可加入0％～10％重量的稳定剂和／或其他添加剂如渗透剂或粘着剂。粉剂通常可成型为具有可湿性粉剂相似的组成但没有分散剂的粉剂浓缩剂，再进一步用固体载体稀释，得到通常含有0.5％～10％重活性组分的组合物。粉剂通常制备成具有10和100目（1.676～0.152mm）大小，且可用成团或注入技术制备，通常，粒剂含0.5％～75％重量的活性成分和0％～10％重量添加剂如稳定剂、表面活性剂、缓释改良剂。所谓的“可流动干粉”又具有相对高浓度活性成分的相对小的颗粒组成。可乳化浓缩剂除溶剂外，当需要时通常含有共溶剂，1％～50％W/V活性成分，2％～20％W/V乳化剂和2％～20％W/V其它添加剂如稳定剂、渗透剂和腐蚀抑制剂。悬浮浓缩机通常含有10％～75％重量的活性成分。0.5％～15％重量的分散剂、0.1％～10％重量的其他添加剂如消泡剂、腐蚀抑制剂、稳定剂、渗透剂和粘着剂。
通过在组合物中加入其它的一种或多种杀菌剂，使其能比单独的通式I化合物具有更广谱的活性。此外，其它杀菌剂可对通式I化合物的杀菌活性具有增效作用。也可以将通式I化合物与其它杀虫剂混用，或同时与另一种杀菌剂以及其它杀虫剂混用。可以包含在本发明组合物中的杀菌化合物的实例有：氰菌唑、粉锈宁、苯菌灵、多菌灵、百菌灵、王酮、波尔多液、麦穗宁、双胍辛盐、土菌消、富士一号、春雷霉素、代森锰锌、代森锰、代森锌、多氧霉素、甲基代森锌、甲基托布津、福美双、十三吗啉、稀酰吗啉等。
具体实施方式
以下实施例和生物活性测定结果可用来进一步说明本发明，但不意味着限制本发明。
实例1通式Ⅲ的化合物的制备：
1-(5-甲基苯并呋喃-2-基)乙酮（Ⅲ-4）的制备
向50mL三口瓶中分别加入1-羟基-5-甲基苯甲醛（1.37g，12mmol），氯丙酮（1.2mL，15mmol），碳酸钾（2.08g，15mmol），丙酮（18mL），加热，电磁搅拌，温度升至60℃回流，TLC检测反应，1.5h后停止反应。向反应液中加入60mL水，用3×60mL乙酸乙酯萃取，无水硫酸钠干燥，减压脱溶，经硅胶柱层析分离（乙酸乙酯/石油醚=1/6），得淡黄色固体1.63g，收率82.3%。
实例2通式Ⅳ的化合物的制备：
1-(5-甲基苯并呋喃-2-基)乙酮肟（Ⅳ-4）的制备
向50mL的三口瓶中分别加入1-(5-甲基苯并呋喃-2-基)乙酮（Ⅲ-4,1.74g,12mmol），盐酸羟胺（1.08g,15mmol），乙酸钠（2.10g,15mmol），乙醇/水（V/V=2/1）溶液18mL，加热，电磁搅拌，温度升至77℃回流，TLC检测反应，1.5h后停止反应。向反应液中加入50mL0.5mol/L的盐酸，用2×50mL乙酸乙酯萃取。用无水硫酸钠干燥，减压脱溶，经重结晶得白色晶体1.54g，收率88.7%。
实例3通式I的化合物的制备：
3-甲氧基-2-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基］丙烯酸甲酯（I-4）的制备
向25mL的三口瓶中，分别加入1-(5-甲基苯并呋喃-2-基)乙酮肟（Ⅳ-4,0.19g,1.0mmol），(E)-甲基-2-(2-(氯甲基)苯基)-3-甲氧基丙烯酸甲酯（中间体A,0.32g,1.3mmol），碳酸钾（0.36g,1.6mmol），乙腈6mL，加热，电磁搅拌，温度升至80℃回流，TLC检测反应，7h后停止反应。向反应液中加入20mL水，用3×20mL乙酸乙酯萃取。用无水硫酸钠干燥，减压脱溶，经硅胶柱层析分离（乙酸乙酯/石油醚=1/12）得产物0.41g，收率96.4%。
N-甲氧基-N-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基]氨基甲酸甲酯（I-10）的制备
向25mL的三口瓶中，分别加入1-(5-甲基苯并呋喃-2-基)乙酮肟（Ⅳ-4,0.28g,1.5mmol），N-2-溴甲基苯基-N-甲氧基氨基甲酸甲酯（中间体B,0.55g,2.0mmol），碳酸钾（0.63g,4.5mmol），乙腈6mL，加热，电磁搅拌，温度升至82℃回流，TLC检测反应，17h后停止反应。向反应液中加入20mL水，用3×20mL乙酸乙酯萃取。用无水硫酸镁干燥，减压脱溶，经硅胶柱层析分离（乙酸乙酯/石油醚=1/12）得产物0.57g，收率99%。
N-甲氧基-N-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基]氨基甲酰甲胺（I-16）的制备
向25mL的三口瓶中，分别加入N-甲氧基-N-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基]氨基甲酸甲酯（I-10,0.33g,0.85mmol），甲醇6mL，甲胺（0.5mL25wt%水溶液，4mmol），加热，电磁搅拌，温度升至80℃回流，TLC检测反应，经11h后停止反应。向反应液中加入20mL水，用3×20mL乙酸乙酯萃取。用无水硫酸镁干燥，减压脱溶，经硅胶柱层析分离（乙酸乙酯/石油醚=1/3）得产物0.17g，收率53.4％。
N-甲氧基-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基]亚胺基乙酸甲酯（I-22）的制备
向25mL的三口瓶中，分别加入1-(5-甲基苯并呋喃-2-基)乙酮肟（Ⅳ-4,0.28g,1.5mmol），(E)-甲基-2-(2–(溴甲基)苯基)-2-甲氧基亚氨基乙酸甲酯（中间体C,0.57g,2.0mmol），碳酸钾（0.63g,4.5mmol），加热，电磁搅拌，温度升至82℃回流，TLC检测反应，经17h后停止反应。向反应液中加入20mL水，用3×20mL乙酸乙酯萃取。用无水硫酸镁干燥，减压脱溶，经硅胶柱层析分离（乙酸乙酯/石油醚=1/12）得产物0.58g，收率98.5%。
N-甲氧基-N-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基]亚胺基乙酰甲胺（I-28）的制备
向25mL的三口瓶中，分别加入N-甲氧基-N-[2-（（1-(5-甲基苯并呋喃-2-基)亚乙基）氨基氧甲基）苯基]亚胺基乙酸甲酯（I-22,0.35g,0.9mmol），甲醇6mL，甲胺（0.5mL25wt%水溶液，4mmol），加热，电磁搅拌，温度升至80℃回流，TLC检测反应，经11h后停止反应。向反应液中加入20mL水，用3×20mL乙酸乙酯萃取。用无水硫酸镁干燥，减压脱溶，经硅胶柱层析分离（乙酸乙酯/石油醚=1/3）得产物0.23g，收率63.5％。
其它化合物可参照上述方法制备。
以下给出配方实例：
实例410％乳油
将10份重的化合物I-5溶解在90份重的下述混合物中：该混合物含90份重二甲苯、6份重的壬基酚聚氧乙烯醚、2份重的十二烷基苯磺酸钙和2份重的环氧乙烷与蓖麻油的加成物（摩尔比40／1），制备乳油（活性化合物含量为10％）。
实例580％液剂
将80份（重量）化合物I-7与20份（重量）的N-甲基吡咯烷酮混合，得到适合以很小液滴形式应用的溶液（活性化合物含量为80％）。
生物活性测定
实例6杀菌活性测定
用本发明的通式I的化合物对植物的各种真菌病害进行了试验。试验的程序如下：将植物试材进行盆栽。待测化合物原药用少量N,N-二甲基甲酰胺溶解，用水稀释至所需的浓度，制剂用水稀释至所需的浓度。喷雾施药到植物试材上，24h后进行病害接种。接种后，将植物放在恒温恒湿培养箱中，使感染继续，待对照充分发病后进行评估调查。“0”代表最严重的发病程度（通常以此值作为基础调查标准），“100”代表无任何病斑。苯并呋喃取代肟醚类甲氧基丙烯酸甲酯类strobilurin化合物的杀菌生物活性见表1。
Figure BDA0000403323060000231
表1
Figure BDA0000403323060000232
注：“／”表示未测试。
苯并呋喃取代肟醚类N-甲氧基-氨基甲酸甲酯类strobilurin化合物的杀菌活性见表2。
Figure BDA0000403323060000233
表2
Figure BDA0000403323060000234
苯并呋喃取代肟醚类N-甲氧基-氨基甲酰甲胺类strobilurin化合物的杀菌活性见表3。
Figure BDA0000403323060000241
表3
Figure BDA0000403323060000242
注：“／”表示未测试。
苯并呋喃取代肟醚类N-甲氧基-亚氨基乙酸甲酯类strobilurin化合物的杀菌活性见表4。
Figure BDA0000403323060000243
表4
Figure BDA0000403323060000244
注：“／”表示未测试。
苯并呋喃取代肟醚类N-甲氧基-亚氨基乙酰甲胺类strobilurin化合物的杀菌活性见表5。
表5
Figure BDA0000403323060000252

Claims (10)

1.苯并呋喃取代肟醚类化合物，其特征在于其通式I为：排除化合物I-1和I-19：
其中：
R1为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R2为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R3为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R4为氢、卤素、三卤甲基、C1-C4烷基、C1-C4烷氧基、硝基或氰基；
R5为氢、C1-C4烷基、C3-C6环烷基、苯基或取代苯基；
Q选自如下所示基团之一：
Figure FDA0000403323050000012
化合物I-1和I-19：
Figure FDA0000403323050000013
2.如权利要求1所述苯并呋喃取代肟醚类化合物，其特征在于：
R1为氢；
R2为氢、氟、氯、C1-C4烷基或C1-C4烷氧基；
R3为氢或C1-C4烷氧基；
R4为氢；
R5为甲基；
Q选自如下所示基团之一：
3.如权利要求1所述苯并呋喃取代肟醚类化合物的制备方法如下：
反应式1：
Figure FDA0000403323050000022
反应式2：
反应式3：
Figure FDA0000403323050000024
反应式1中，在溶剂丙酮中，在碱碳酸钾存在下，于25～60℃条件下，用通式Ⅱ所示的化合物和α-氯丙酮反应得通式Ⅲ所示的化合物；通式Ⅲ所示的化合物与盐酸羟胺，在碱乙酸钠存在下，在乙醇/水中，于25～80℃条件下，反应得通式Ⅳ所示的化合物；
反应式2中，在溶剂乙腈中，在碱碳酸钾存在下，于25～80℃条件下，用通式Ⅳ所示的化合物分别和3个不同的中间体A、B或C反应得相对应的通式I-Q1、I-Q2和I-Q3所示的化合物；
反应式3中，在溶剂甲醇中，于25～80℃条件下，用通式I-Q2或I-Q3所示的化合物分别与甲胺水溶液反应得相对应的通式I-Q4和I-Q5所示的化合物。
4.如权利要求1所述苯并呋喃取代肟醚类化合物在制备杀菌剂中的应用。
5.如权利要求4所述的应用，其特征在于所述杀菌剂为植物叶面杀菌剂或土壤杀菌剂。
6.如权利要求5所述的应用，其特征在于所述植物叶面杀菌剂包括但不限于玉米锈病、稻瘟病、大麦白粉病、小麦白粉病、黄瓜白粉病、葡萄白粉病、苹果白粉病、黄瓜霜霉病、黄瓜炭疽病、葡萄霜霉病杀菌剂。
7.如权利要求4所述的应用，其特征在于所述苯并呋喃取代肟醚类化合物作为活性组分与其它载体或稀释剂一起组成杀菌剂组合物，杀菌剂组合物中苯并呋喃取代肟醚类化合物的质量百分比含量为1%～99%。
8.如权利要求4所述的应用，其特征在于所述苯并呋喃取代肟醚类化合物作为活性组分与其它杀菌剂组成复合杀菌剂，复合杀菌剂中苯并呋喃取代肟醚类化合物的质量百分比含量为1%～99%。
9.如权利要求7所述的应用，其特征在于所述载体为植物、种子或土壤；载体是固体载体、液体载体或通常为气体但已压缩成液体的物质。
10.如权利要求9所述的应用，其特征在于所述固体载体包括天然粘土、合成粘土、硅酸盐，所述固体载体可选自硅藻土、滑石、硅镁土、硅酸铝、蒙脱石、云母、碳酸钙、硫酸钙、硫酸铵、合成氧化硅、合成硅酸钙、合成硅酸铝、天然树脂、合成树脂、固体多氯苯酚、沥青或蜡；
所述液体载体可选自水、醇、酮、醚、石油馏分、氯化烃或芳烃。
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Publication number Priority date Publication date Assignee Title
CN103980179A (zh) * 2014-05-29 2014-08-13 厦门大学 一种吲哚取代肟醚类化合物及其制备方法与应用
CN105340896A (zh) * 2015-11-06 2016-02-24 曹龙巧 一种生殖医学检查室用消毒剂
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CN112661732A (zh) * 2020-12-23 2021-04-16 湖南加法检测有限公司 呋喃酚衍生物及其制备方法与应用
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