CN109516996B - 一种大环内酯类衍生物、其合成及应用 - Google Patents
一种大环内酯类衍生物、其合成及应用 Download PDFInfo
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Abstract
本发明公开了一种大环内酯类衍生物、其合成及应用,属于有机化合物开发和应用领域。本发明的大环内酯类衍生物结构如式(I)所示。本发明的大环内酯类衍生物光稳定性好,这一优势在农业上防治害虫具有非常大的优势。既可防治多种害虫,同时可以抑制真菌生长;兼有抑制病原菌和害虫生长的特性,对于有害生物防治,降低农药用量具有非常重要的现实意义。
Description
技术领域
本发明涉及有机化合物开发和应用领域,特别涉及一种大环内酯类衍生物、其合成及应用。
背景技术
高毒和对环境不安全的农药品种逐渐被各国政府禁用,对于农业病虫害的防治,亟需新农药的研发。但是近年来,新化合物的出现和登记却变的非常困难,这是因为新农药化合物筛选的成功率在下降,研发周期在延长,从而加大了研发成本。其原因主要是起点要求高,新品种必须在通过了活性和功能筛选程序后,还要通过生态环境筛选,以致成功率降低。
通过对具有活性的母体进行结构改造来获得活性更优、安全性更高的新品种,已经成为当今新农药创制的重要手段。并且已有很多成功的案例。
具有16元大环内酯结构的化合物是从土壤微生物-链霉菌的发酵物中提取而得到的,已被成功应用于农药和兽药等领域,带来了巨大的经济价值,为社会的健康发展做出了巨大的贡献。目前开发成杀虫剂比较成功的品种是阿维菌素和弥拜菌素,但它们还存在一些缺点,如:对高等动物的毒性比较高毒,对水生生物中的鱼类、大型溞、藻类、虾类和蟹类都是高毒,以及容易降解等缺点。研究者针对这两种化合物进行了大量的结构衍生研究(已有许多的研究型论文和专利报道),取得了许多突破性的进展。其中商品化的阿维菌素衍生物有伊维菌素(ivermectin)、埃玛菌素(emamectin)、道拉菌素(doramectin)、埃珀利诺菌素(eprinomectin)和色拉菌素(selamectin)等。派生的新化合物克服了阿维菌素的某些不足,在防治范围、杀虫活性和对人畜及环境毒性等方面有所改善,但这些新化合物光稳定性差,施用到植物叶面后容易降解,因而不能长期有效控制农业害虫。
发明内容
为了弥补现有技术的不足,本发明提供了一种大环内酯类衍生物、其合成及应用。
本发明的技术方案为:
一种大环内酯类衍生物,如式(Ⅰ)所示:
其中,
X-Y为CH2-CH2、CH=CH、CH2-CH-OR1或CH2-O;
R为氢、卤素、硝基、羟基、烷基或取代烷基、烷氧基或取代烷氧基、烷基羰基或取代烷基羰基、烷氧基羰基或取代烷氧基羰基、芳基或取代芳基中的任意一种;
其中,R3为烷基或取代烷基、烷氧基或取代烷氧基、烷基羰基或取代烷基羰基、烷氧基羰基或取代烷氧基羰基、芳基或取代芳基。
作为优选方案,所述芳基为单环芳香烃基、多环芳香烃基、稠环芳香烃基或芳杂环基。如苯基、萘基、蒽基、菲基、苊基、吡咯基、咪唑基、噻唑基、吡啶基、吡嗪基、吡唑基、吲哚基、喹啉基等等。
作为优选方案,所述取代烷基为卤素、氰基、硝基、羟基、磺酰基取代的烷基;所述取代芳基为卤素、烷基或取代烷基、烷氧基、氰基、硝基、羟基、磺酰基取代的芳基;所述取代烷氧基为烷氧基中任意一个或多个氢被卤素、氰基、硝基、羟基、磺酰基取代的烷氧基;所述取代烷基羰基为烷基羰基中任意一个或多个氢被卤素、氰基、硝基、羟基、磺酰基取代的烷基羰基;所述取代烷氧基羰基为烷氧基羰基中任意一个或多个氢被卤素、氰基、硝基、羟基、磺酰基取代的烷氧基羰基。
作为优选方案,所述烷基为C1~C8直链、支链或环状烷基(如甲基、乙基、正丙基、异丙基、丁基、正丁基、环戊基、环己基等等);所述烷氧基为C1~C6烷氧基(如甲氧基、乙氧基等等);所述烷基羰基为C1~C6的烷基羰基(如甲酰基、乙酰基、丙酰基、异丙酰基、丁酰基、异丁酰基、叔丁酰基等等);所述烷氧基羰基为C1~C6的烷氧基羰基(如甲氧羰基、乙氧羰基、异丙氧羰基、丁氧羰基、异丁氧羰基、叔丁氧羰基等等)。
作为优选方案,所述芳杂环基为嘧啶基、吡唑基、噻吩基、噁唑基、异噻唑基。
所述大环内酯类衍生物的合成方法,将化合物A于10℃~100℃下溶解到溶剂中,加入催化剂,搅拌并通入氮气保护,滴加化合物B;反应完毕后,经纯化,得到式(Ⅰ)所述大环内酯类衍生物;
化合物A的通式为:
X-Y为CH2-CH2、CH=CH、CH2-CH-OH或CH2-O;
R为氢、卤素、硝基、羟基、烷基或取代烷基、烷氧基或取代烷氧基、烷基羰基或取代烷基羰基、烷氧基羰基或取代烷氧基羰基、芳基或取代芳基中的任意一种;
R’为-OH或
化合物B的结构为:O=C=N-R3或S=C=N-R3。
其中,R3为烷基或取代烷基、烷氧基或取代烷氧基、烷基羰基或取代烷基羰基、烷氧基羰基或取代烷氧基羰基、芳基或取代芳基。
作为优选方案,所述化合物A与化合物B的摩尔比为1:0.5~1:10;催化剂为氯化亚锡、四丁基锡、醋酸三丁基锡、三氯正丁基锡、三甲基锡氢氧化物、二氯二甲基锡、二月桂酸二丁基锡中的任意一种。
更优选的,所述化合物A与化合物B的摩尔比为1:1~1:3;化合物A与催化剂的摩尔比为1:0.05~1:0.2。
所述溶剂为苯、甲苯、二甲苯、二氯甲烷、戊烷、己烷、环己烷、环己酮、丙酮、乙腈中的一种或几种。
所述大环内酯类衍生物在防治害虫中的用途;所述害虫包括蛛形纲、双壳纲、腹足纲、线虫纲、唇足目、弹尾目、虱目、双翅目、鞘翅目、直翅目、异翅亚目、同翅目、膜翅目、等翅目、鳞翅目、食毛目、啮虫目、蚤目、缨翅目、缨尾目、植物寄生线虫。
所述大环内酯类衍生物在抑制真菌生长中的用途。
所述大环内酯类衍生物与成分C的混合物在防治害虫中的用途;所述害虫包括蛛形纲、双壳纲、腹足纲、线虫纲、唇足目、弹尾目、虱目、双翅目、鞘翅目、直翅目、异翅亚目、同翅目、膜翅目、等翅目、鳞翅目、食毛目、啮虫目、蚤目、缨翅目、缨尾目、植物寄生线虫;所述成分C选自哒螨灵、稻瘟灵、氰氟虫腙、杀螨素、苯螨特、溴螨酯、三氯杀螨醇、三氯杀螨砜、噻螨酮、三唑锡、三环锡、苯丁锡、炔螨特、苯氟磺胺、唑螨酯、嘧螨胺、阿维菌素、甲氨基阿维菌素苯甲酸盐、伊维菌素、雷皮菌素、弥拜菌素、多杀菌素、乙基多杀菌素、苏云金素、印楝素、鱼藤酮、藜芦碱、杀螟丹、杀虫环、杀虫单、杀虫双、氟吡菌酰胺、氯虫酰胺、氯虫苯甲酰胺、溴氰虫酰胺、虫脲、噻嗪酮、氟啶脲、氟啶胺、灭蝇胺、环虫腈、除虫脲、氟螨脲、氟虫脲、氟铃脲、虱螨脲、氟酰脲、氟幼脲、氟苯脲、杀铃脲、灭幼脲、苯氧威、烯虫乙酯、烯虫酯炔、烯虫酯、吡丙醚、啶虫丙醚、环虫酰肼、氯虫酰肼、甲氧虫酰肼、虫酰肼、呋喃虫酰肼、氟啶虫酰胺、噻虫胺、噻虫嗪、噻虫啉、吡虫啉、啶虫脒、烯啶虫胺、呋虫胺、吡蚜酮、氟啶虫胺腈、哌虫胺、茚虫威、氟虫腈、丁烯氟虫腈、唑虫酰胺、溴虫腈、螺螨酯、螺虫乙酯、丁醚脲、联苯菊酯、氟氯氰菊酯、高效氯氟氰菊酯、高效氟氯氰菊酯、高效氯氰菊酯、氰戊菊酯、噁虫威、灭多威、杀线威、残杀威、毒死蜱、甲基毒死蜱、二嗪磷、辛硫磷、甲基嘧啶磷、噻唑膦、杀朴磷中的一种或几种。
现已发现本发明所述大环内酯类衍生物与成分C的混合物,具有协同活性,并可用于防治有害生物,这不但扩大了本发明所述大环内酯类衍生物和成分C的作用范围,而且也有助于降低农药用量,延缓有害生物的抗药性。其中本发明所述大环内酯类衍生物与成分C的重量比为1000:1至1:1000,其中优选100:1至1:80,更优选30:1至1:9。
本发明所述大环内酯类衍生物或者其与成分C的组合物可以用于防治(抑制或消灭)以上出现在农业、园艺、林业和卫生中的害虫。
本发明所述大环内酯类衍生物或者其与成分C的组合物的用量取决于防治对象和预期效果,通常用量范围为1-2000g活性成分/公顷。
本发明所述大环内酯类衍生物或者其与成分C的组合物可以制成任何剂型或者药物类型;例如可以制成种子处理干粉剂,种子处理乳剂,种子处理悬浮剂,种子处理液剂,种子处理可分散粉剂,种子处理微囊悬浮剂,种子处理凝胶,乳油,悬浮剂,悬乳剂,微囊悬浮剂,水分散粒剂,乳粒剂,水乳剂,微乳剂,油分散体,油悬浮剂,油剂,可溶液剂,超低容量液剂,超低容量微囊悬浮剂,母药,可分散液剂,可湿性粉剂或结合农业上可接受的助剂的任何技术上可行的制剂。通常,制剂含有0.01至90t%的活性成分,0-20%农业上可接受的表面活性剂和10-90%固体或液体制剂惰性物质和助剂。
本发明的有益效果为:
1、本发明所得新化合物,即,式(Ⅰ)所示的大环内酯类衍生物,光稳定性好,这一优势在农业上防治害虫具有非常大的优势。
2、本发明大环内酯类衍生物的合成方法操作简单,收率较高,合成成本低,适于产业化应用。
3、本发明所得式(Ⅰ)所示的大环内酯类衍生物既可防治多种害虫,同时可以抑制真菌生长;兼有抑制病原菌和害虫生长的特性,对于有害生物防治,降低农药用量具有非常重要的现实意义。
4、本发明所得式(Ⅰ)所示的大环内酯类衍生物与成分C的组合物,可降低农药用量,并可延缓有害生物的抗药性。
具体实施方式
衍生物制备实施例
在50℃条件下,将1.00mol化合物A溶解到二氯甲烷中,加入催化剂0.005mol,形成反应液;将反应液移至50℃温下搅拌反应,并通入氮气,按照化合物A与化合物B的摩尔比为1:3缓慢滴加化合物B,反应完成后,有机相经蒸馏、干燥、纯化后得到目标化合物。
各实施例中化合物A、化合物B以及生产的新的大环内酯类衍生物的结构如表1所示。
表1各实施例中反应物与产物结构汇总表
表1中各化合物A的结构式如下:
一、化合物结构或特性研究
1.1化合物结构测定谱数据:
化合物1:1H NMR(400MHz,DMSO-d6)δ8.97(d,J=34.7Hz,3H),8.23(s,1H),7.13(t,J=7.8Hz,1H),6.94(t,J=7.4Hz,9H),6.62-6.30(m,7H),5.60(d,J=4.7Hz,1H),5.37-5.23(s,1H),4.71(d,J=8.0Hz,1H),4.49(d,J=23.7Hz,2H),3.89(d,J=5.4Hz,1H),3.79(dd,J=18.9,7.4Hz,1H),2.11-1.87(m,2H),1.64-1.49(m,9H),1.18(d,J=9.2Hz,2H),1.11-0.97(m,2H),0.85(m,3H).13C NMR(126MHz,DMSO-d6)δ156.7,152.94,146.9,139.5,138.6,130.17,129.7,127.5,126.08,124.8,122.66,118.2,117.5,101.4,96.4,87.3,77.9,73.6,70.5,68.2,65.2,56.8,45.9,39.8,39.7,38.6,34.3,30.7,22.3,18.1,16.1,13.6,11.7.
化合物2:1H NMR(400MHz,DMSO-d6)δ10.01(s,1H),8.84(s,20H),7.51-7.44(m,31H),6.68-6.40(m,3H),5.64(dd,J=15.6,9.8Hz,1H),5.13(s,1H),4.72(d,J=16.5Hz,1H),4.09(d,J=14.5Hz,1H),3.89-3.79(m,1H),2.52-2.47(m,12H),2.20(d,J=7.8Hz,3H),1.52(dd,J=13.1,8.1Hz,1H),1.19(d,J=5.1Hz,2H),0.81(d,J=20.7Hz,5H).13C NMR(126MHz,DMSO-d6)δ158.2,149.2,139.5,131.51,128.3,119.5,113.36,101.5,95.6,77.6,70.9,68.5,67.1,57.8,56.4,45.6,39.3,30.5,29.4,21.5,19.8,16.5,15.2,13.5,11.8.
化合物3:1H NMR(400MHz,DMSO-d6)δ10.00(s,1H),8.84(s,24H),7.38-7.29(m,20H),6.52-6.20(m,3H),5.67-5.51(m,1H),4.42(s,2H),3.89(d,J=5.1Hz,1H),3.27-3.12(m,1H),2.50(p,J=1.9Hz,11H),2.21(s,3H),2.08(d,J=8.8Hz,1H),1.73(s,2H),1.41-1.25(m,1H),1.21(s,4H),1.18(d,J=6.0Hz,1H),0.96(dd,J=16.3,6.5Hz,2H),0.88(dt,J=20.7,7.1Hz,5H).13C NMR(126MHz,DMSO-d6)δ152.5,140.5,139.0,138.7,134.7,128.7,123.8,121.1,119.3,113.79,98.6,85.6,81.3,79.2,78.8,72.6,70.6,68.7,67.2,57.1,56.2,44.2,42.6,39.1,34.3,33.9,30.0,27.2,21.0,19.7,14.0,13.1,11.8.
化合物4:1H NMR(400MHz,DMSO-d6)δ9.76(s,1H),8.55(s,9H),7.28(d,J=8.1Hz,22H),6.62-6.26(m,9H),5.74-5.51(m,2H),5.39(d,J=5.1Hz,1H),5.14(t,J=7.7Hz,1H),4.79-4.45(m,1H),3.47-3.30(m,11H),2.64(dt,J=9.2,4.6Hz,1H),2.21(d,J=9.0Hz,5H),1.74(s,3H),1.41-1.30(m,1H),1.25(d,J=7.6Hz,1H),0.90(dt,J=19.8,7.7Hz,9H),0.80(d,J=11.7Hz,2H).13C NMR(126MHz,DMSO-d6)δ152.9,140.1,138.4,129.8,128.0,123.1,121.0,119.3,115.9,98.6,81.9,79.3,78.0,70.4,68.9,67.2,57.1,56.2,45.82,41.6,35.3,34.9,30.0,27.2,21.0,20.9,19.7,18.67,15.0,12.8.
化合物5:1H NMR(400MHz,DMSO-d6)δ8.68(s,13H),7.75-7.36(m,29H),7.21(t,J=9.7Hz,28H),6.61-6.20(m,2H),5.87-5.56(m,1H),4.77-4.34(m,2H),3.92-3.81(m,2H),3.25-3.03(m,9H),2.98-2.64(m,2H),1.76(s,3H),1.61-1.44(m,2H),0.92(d,J=15.6Hz,1H),0.81(d,J=21.1Hz,3H).13C NMR(126MHz,DMSO-d6)δ173.7,156.1,145.8,138.3,127.9,128.4,121.8,116.1,110.9,92.5,87.4,82.8,76.7,72.1,70.3,68.1,66.7,57.4,56.4,39.3,33.4,30.5,29.9,22.1,19.5,18.7,16.3,12.6,11.4.
化合物6:1H NMR(400MHz,DMSO-d6)δ11.05(s,2H),7.51(s,4H),7.18(d,J=8.1Hz,10H),6.59-6.34(m,6H),4.22-4.15(m,2H),3.63-3.50(m,2H),3.41(d,J=9.2Hz,12H),3.18-3.01(m,8H),2.82-2.60(s,1H),2.48-2.20(m,4H),2.13(dd,J=10.2,7.3Hz,1H),1.90-1.84(m,1H),1.44-1.25(m,1H),1.21(s,1H),1.19-1.07(m,6H),0.95(dd,J=20.36,9.5Hz,2H),0.80(d,J=12.1Hz,3H).13C NMR(126MHz,DMSO-d6)δ173.7,157.1,153.8,152.3,138.3,136.4,136.5,131.1,127.9,117.7,128.4,121.3,121.3,118.9,106.4,92.5,83.4,79.8,75.9,74.1,70.6,68.3,67.9,57.4,45.6,39.9,34.2,29.9,28.2,20.3,18.7,15.9,13.2,11.9.
化合物7:1H NMR(400MHz,DMSO-d6)δ12.84(s,2H),7.92(s,12H),7.55(d,J=8.5Hz,16H),6.57-6.25(m,2H),5.79-5.42(m,2H),4.71-4.43(m,1H),4.19(t,J=16.8,9.1Hz),3.57-3.34(m,2H),3.31-3.02(m,2H),2.90-2.60(m,1H),2.40-2.20(m,2H),2.10(dd,J=11.2,7.1Hz,1H),1.52-1.42(m,3H),1.15-1.09(m,6H),0.96(d,J=26.5Hz,6H),0.82(d,J=15.6Hz,3H).13C NMR(126MHz,DMSO-d6)δ169.7,145.5,138.3,127.9,126.6,125.6,118.1,111.9,106.7,96.7,86.5,81.3,79.4,74.4,68.3,57.4,45.9,39.9,36.2,29.9,29.6,25.3,20.3,19.1,16.3,15.5,13.2,11.8.化合物8:1H NMR(400MHz,DMSO-d6)δ11.0(s,2H),8.88(s,1H),7.16(d,J=8.5Hz,20H),6.19(d,J=7.3Hz,2H),5.89-5.60(m,1H),4.60(t,J=10.6Hz,1H),4.54-4.44(m,2H),3.86-3.60(m,3H),2.74(d,J=4.0Hz,2H),2.14-2.01(m,J=11.2,7.1Hz,1H),1.74-1.56(m,4H),1.52(s,2H),0.91(t,J=11.2Hz,12H),0.82(d,J=16.7Hz,6H).13C NMR(126MHz,DMSO-d6)δ173.7,156.2,139.7,138.3,135.5,127.9,124.8,121.4,111.9,106.4,86.5,83.4,79.8,78.3,75.9,74.1,70.6,68.3,67.9,57.4,45.6,34.2,30.9,25.3,20.3,18.7,16.3,15.9,12.1.
化合物9:1H NMR(400MHz,DMSO-d6)δ15.84(s,2H),7.65(s,20H),7.12(d,J=20.3Hz,11H),6.65(d,J=15.3Hz,1H),6.09(d,J=10.3Hz,1H),5.79-5.58(m,1H),4.71(s,1H),4.54-4.35(m,1H),4.11-3.96(m,3H),3.84-3.74(m,1H),3.57(dd,J=10.2,5.2Hz,2H),3.33-3.20(m,1H),2.70(dt,J=11.6,4.4Hz,8H),2.13(dd,J=11.2,7.1Hz,3H),1.99-1.80(m,11H),1.48(s,1H),1.20(d,J=6.4Hz,6H),0.74(dd,J=12.8,7.6Hz,9H).13C NMR(126MHz,DMSO-d6)δ189.8,173.7,139.7,124.8,127.9,111.9,103.3,93.6,86.7,79.4,72.3,68.3,62.5,57.4,45.9,39.9,36.8,36.2,30.3,27.5,20.3,18.6,16.3,15.9,13.2,11.9.
化合物10:1H NMR(400MHz,DMSO-d6)δ9.88(s,2H),7.88(s,22H),7.41(t,J=7.33Hz,10H),6.83-6.68(m,1H),6.32(d,J=7.5Hz,1H),5.75-5.51(m,3H),5.40-5.21(m,1H),4.82(t,J=10.6,2H),1H),4.10-3.86(m,3H),3.77-3.65(dd,J=10.2,5.2Hz,1H),3.22-3.07(m,1H),2.60(d,J=16.2,1H),1.74(s,9H),1.05-0.91(m,12H),0.81(t,J=12.8Hz,6H).13C NMR(126MHz,DMSO-d6)δ173.7,153.8,142.3,139.7,129.2,118.1,106.4,93.3,81.3,70.6,68.3,67.9,57.4,57.1,45.6,40.5,39.9,36.8,33.3,29.9,20.3,18.7,17.3,15.9,13.2,12.9.
化合物11:1H NMR(400MHz,DMSO-d6)δ9.61(s,1H),8.15(s,1H),7.73(dd,J=19.3,9.2Hz,2H),6.94-6.87(m,2H),6.12-6.08(m,2H),6.05(d,J=7.3Hz,1H),5.82-5.61(m,3H),4.58(t,J=26.4Hz,1H),4.53-4.33(m,1H),4.11(t,J=18.4Hz,2H),3.88-3.72(m,1H),2.54-2.34(m,1H),2.11-1.84(m,4H),1.68-1.51(m,4H),1.15-0.95(m,1H),0.80(d,J=17.4Hz,3H).13C NMR(126MHz,DMSO-d6)δ173.7,163.1,153.8,142.1,139.7,127.9,121.4,118.1,117.7,103.3,95.5,79.8,74.1,68.3,67.9,57.1,45.6,40.5,36.2,36.1,33.4,30.6,25.3,20.3,15.9,12.5.
化合物12:1H NMR(400MHz,DMSO-d6)δ10.5(s,2H),7.62(s,8H),7.41(d,J=16.2Hz,2H),6.97-6.62(m,2H),6.52(s,2H),5.83-5.64(m,3H),4.92-4.78(m,1H),4.33-4.02(m,1H),3.93-3.76(m,5H),3.44-3.22(m,1H),2.46-2.15(m,6H),2.06-1.74(m,5H),1.58-1.35(m,6H),0.91(d,J=16.8Hz,2H),0.77(t,J=15.4Hz,9H).13C NMR(126MHz,DMSO-d6)δ156.3,140.7,138.6,137.3,128.8,125.4,121.1,118.6,106.4,103.3,86.5,81.3,79.8,72.6,70.6,68.3,57.4,57.1,40.5,39.9,34.4,34.3,31.5,29.9,21.3,20.3,18.7,17.3,17.2,16.3,15.9,12.0.
化合物13:1H NMR(400MHz,DMSO-d6)δ9.65(s,2H),7.72-7.51(m,10H),6.97-6.62(m,2H),5.62-5.44(t,J=19.3Hz,2H),5.02(m,2H),4.97-4.62(m,2H),3.95(t,J=18.4Hz,2H),3.02(s,1H),2.61-2.42(m,6H),2.25(dd,J=12.4,6.1Hz,2H),1.19-0.9 8(m,3H),0.66(t,J=18.4Hz,3H).13C NMR(126MHz,DMSO-d6)δ173.7,153.8,139.7,128.8,121.4,106.4,79.8,78.3,68.3,57.1,45.6,40.5,39.9,35.2,34.5,23.1,23.1,20.3,18.7,16.3,15.9,14.5,13.2,10.8.
化合物14:1H NMR(400MHz,DMSO-d6)δ13.86(s,2H),9.82(d,J=5.6Hz,2H),7.63(s,1H),6.82-6.52(m,2H),5.98(d,J=7.3Hz,1H),5.50-5.34(t,J=22.4Hz,2H),4.89-4.50(m,1H),3.94-3.65(m,6H),2.84(d,J=22.1 1H),1.80-1.63(m,5H),1.22(d,J=9.4Hz,6H),0.92(s,1H),0.89(t,J=10.4Hz,6H).13C NMR(126MHz,DMSO-d6)δ188.5,154.4,139.7,127.9,118.1,102.9,95.9,92.9,81.3,79.4,74.4,72.3,68.3,60.8,60.8,57.4,45.9,40.5,34.6,30.2,25.3,20.3,19.1,16.3,15.9,13.2,11.9.
化合物15:1H NMR(400MHz,DMSO-d6)δ13.3(s,2H),7.82(s,6H),7.62(dt,J=19.3Hz,8.32Hz,12H),6.92(t,J=11.3Hz,2H),5.78-5.64(m,3H),5.51-5.30(t,J=19.3Hz,2H),4.83-4.63(m,1H),4.56(t,J=26.4Hz,2H),4.10(d,J=18.4Hz,2H),4.05–3.98(m,5H),3.85(dd,J=10.2,5.2Hz,2H),3.02(s,2H),2.46-2.25(m,1H),1.90-1.74(m,5H),1.23(d,J=6.4Hz,6H),1.05-0.96(m,3H),0.91(t,J=16.7Hz,9H).13C NMR(126MHz,DMSO-d6)δ188.5,173.7,150.7,141.2,136.0,129.7,121.4,118.1,113.9,106.7,103.3,86.5,85.5,81.3,79.4,71.3,68.3,62.5,57.6,57.2,39.9,31.5,29.9,29.6,17.6,17.3,16.3,15.9,13.2,11.1.
化合物16:1H NMR(400MHz,DMSO-d6)δ12.8(s,2H),8.12-8.02(m,2H),7.82(dd,J=19.3Hz,8.32Hz,1H),6.89(d,J=9.25,1H),6.12(s,1H),5.85-5.60(m,2H),5.52-5.20(m,1H),4.52(t,J=26.4Hz,2H),3.98(t,J=21.5Hz,2H),3.44-3.30(m,11H),2.78(d,J=16.3Hz,2H),1.19(s,6H),0.97(t,J=18.5,8.5Hz,3H),0.74(t,J=16.4Hz,6H).13C NMR(126MHz,DMSO-d6)δ173.7,166.7,146.4,135.5,135.4,128.6,121.4,119.9,106.7,96.7,79.4,78.8,68.3,57.6,53.6,45.9,40.5,39.9,35.2,31.3,25.3,20.3,19.1,16.3,15.9,13.2,12.0.
化合物17:1H NMR(400MHz,DMSO-d6)δ8.92(s,1H),7.76(s,9H),7.72(d,J=15.7Hz,19H),6.75(s,2H),5.92(d,J=12.0Hz,1H),5.77-5.66(m,3H),4.56-4.35(m,2H),4.01(t,J=18.4Hz,2H),3.38(t,J=25.7Hz,2H),3.02(t,J=5.5Hz,2H),2.60(d,J=16.7Hz,2H),1.93-1.75(m,5H),1.62-1.42(m,3H),0.92(d,J=26.8Hz,3H),0.81(t,J=15.5Hz,9H).13C NMR(126MHz,DMSO-d6)δ163.7,155.9,145.5,139.7,135.5,127.9,117.7,103.3,96.5,81.3,79.8,70.6,68.3,57.4,45.6,40.5,39.9,36.7,34.2,29.9,18.7,17.3,16.3,15.9,13.2,10.9.
化合物18:1H NMR(400MHz,DMSO-d6)δ11.39(s,3H),8.35(s,9H),7.84(d,J=11.6Hz,6H),6.54(s,1H),6.32(d,J=10.5Hz,1H),5.96(d,J=9.6Hz,1H),5.53-5.41(m,3H),4.90(t,J=13.3Hz,1H),3.72-3.54(m,1H),3.41(t,J=13.6Hz,2H),2.83(d,J=13.6Hz,1H),2.08-1.89(m,2H),1.15(t,J=18.4Hz,3H),0.99(t,J=39.2Hz,9H),0.88(t,J=23.5,10.2Hz,9H).13C NMR(126MHz,DMSO-d6)δ173.7,152.6,143.8,131.2,131.0,129.0,127.9,121.4,106.4,96.5,81.3,72.6,70.6,69.7,57.4,57.1,52.7,45.6,40.8,36.4,36.1,31.3,29.2,20.6,18.7,17.2,15.0,13.2,10.9.
化合物19:1H NMR(400MHz,DMSO-d6)δ9.26(s,3H),7.89(s,8H),7.20(d,J=12.5Hz,22H),6.31(s,9H),6.13(d,J=11.5Hz,1H),5.75-5.63(m,1H),4.84-4.71(m,1H),3.92-3.71(m,4H),3.65-3.54(m,3H),3.45(s,1H),2.54(dd,J=8.2,5.2Hz,1H),2.11-1.81(m,8H),1.31-1.19(m,18H),0.98(t,J=11.4Hz,3H),0.81(t,J=31.2Hz,6H).13C NMR(126MHz,DMSO-d6)δ173.7,149.6,139.1,135.1,129.7,106.4,103.3,79.8,72.3,70.6,57.5,45.6,40.8,39.8,36.1,31.6,29.2,25.7,25.1,24.1,23.5,23.1,20.3,18.6,13.3,13.0,12.6,11.4.
化合物20:1H NMR(400MHz,DMSO-d6)δ9.62(s,1H),7.69(s,3H),7.42(s,12H),6.81(s,1H),6.03(d,J=11.5Hz,1H),5.79-5.68(m,1H),4.81-4.67(t,J=11.6Hz,1H),3.99-3.82(m,1H),3.52(t,J=6.33Hz,2H),2.80(d,J=13.6Hz,1H),2.40-2.17(m,1H),2.06-1.83(m,23H),1.18-1.05(m,1H),0.98(t,J=13.5Hz,3H),0.84(t,J=36.2Hz,4H).13CNMR(126MHz,DMSO-d6)δ173.6,155.6,144.2,135.5,128.5,124.8,118.1,106.4,103.3,92.3,86.5,79.8,75.9,74.1,67.9,57.6,57.1,45.6,40.8,32.1,32.0,29.2,23.6,23.4,23.3,20.3,17.3,13.3,13.0,11.7.
化合物21:1H NMR(400MHz,DMSO-d6)δ9.85(s,8H),7.71(s,4H),6.89-6.51(m,2H),6.15(d,J=11.5Hz,1H),5.44-5.31(m,3H),4.82-4.75(m,1H),4.68-4.46(m,2H),4.12-3.79(m,3H),3.69-3.60(m,3H),2.78-2.51(m,1H),2.43-2.12(m,4H),1.75-1.66(m,14H),1.45-1.12(m,10H),1.05(t,J=18.4Hz,3H),0.86(t,J=33.4Hz,9H).13C NMR(126MHz,DMSO-d6)δ171.5,165.7,145.2,135.5,129.9,129.6,121.8,106.4,103.3,95.3,86.5,79.8,78.3,72.6,72.5,70.0,67.9,67.1,57.2,40.8,39.8,35.1,33.1,30.2,20.3,18.7,17.3,17.2,13.1,12.0,11.8.
化合物22:1H NMR(400MHz,DMSO-d6)δ11.86(s,3H),8.52(s,9H),7.79(s,4H),6.40(s,1H),6.21(d,J=10.5Hz,1H),5.98-5.62(m,1H),4.98-4.72(mz,1H),4.12-3.79(m,3H),3.70-3.52(m,2H),3.20-2.98(m,3H),2.77(d,J=11.4Hz,1H),2.08-1.64(m,17H),1.61-1.48(m,3H),1.14(d,J=28.6Hz,6H),0.96(t,J=17.7Hz,3H),0.81(t,J=32.3Hz,6H).13C NMR(126MHz,DMSO-d6)δ160.5,151.8,141.7,139.7,135.2,120.5,117.6,114.7,92.6,91.4,81.3,79.4,75.9,74.1,72.6,72.5,70.6,69.1,67.0,57.5,45.6,40.7,39.6,38.1,35.2,31.5,29.3,25.4,21.5,18.7,17.3,13.1,11.9,11.8.
化合物23:1H NMR(400MHz,DMSO-d6)δ12.78(s,3H),8.55(s,3H),7.92(d,J=9.4Hz,3H),6.50(s,1H),6.29(d,J=10.5Hz,1H),5.89-5.68(m,3H),5.42-5.36(m,2H),4.62(t,J=10.4Hz,2H),4.41-4.26(m,1H),3.99-3.60(m,7H),2.78(d,J=10.6Hz,2H),2.50(dd,J=5.9,4.2Hz,1H),2.10-1.85(m,5H),1.79-1.48(m,18H),1.17(d,J=26.7Hz,12H),0.96(t,J=19.7Hz,2H),0.81(t,J=33.4Hz,4H).13C NMR(126MHz,DMSO-d6)δ173.7,155.1,148.2,139.7,132.5,129.9,121.1,119.9,115.2,107.8,103.3,97.6,93.2,86.8,81.4,79.4,78.9,71.8,67.3,57.4,45.9,41.1,39.6,36.2,34.1,33.5,30.6,22.2,20.2,19.7,17.2,16.1,14.0,13.9.
化合物24:1H NMR(400MHz,DMSO-d6)δ12.61(s,3H),9.21(s,3H),7.49(d,J=13.5Hz,6H),7.24(d,J=19.9Hz,6H),6.52(s,1H),6.45(d,J=9.5Hz,1H),5.68-5.52(m,6H),4.89-4.79(m,1H),4.33-4.25(m,1H),4.16-3.77(m,5H),3.47-3.37(m,1H),2.94-2.81(m,1H),2.65(dd,J=5.9,4.2Hz,1H),1.64-1.45(m,5H),1.17(d,J=29.9Hz,18H),0.97(t,J=19.7Hz,3H),0.84(t,J=35.3Hz,6H).13C NMR(126MHz,DMSO-d6)δ171.5,159.6,144.2,144.1,139.7,134.2,129.3,120.3,106.4,103.1,86.5,79.8,78.5,72.6,69.4,67.0,57.4,54.1,40.8,39.9,38.0,35.1,34.6,29.2,27.1,22.3,20.1,18.7,17.3,16.2,14.7,11.8.
化合物25:1H NMR(400MHz,DMSO-d6)δ11.98(s,3H),8.21(s,16H),7.62(s,9H),7.35(d,J=23.6Hz,6H),6.31(d,J=8.4Hz,1H),5.23(d,J=5.5Hz,1H),4.80-4.77(m,1H),4.60(t,J=19.9Hz,2H),4.16-3.98(m,2H),3.45-3.23(m,2H),2.94-2.63(m,4H),2.31-2.18(m,2H),2.04-1.71(m,11H),1.27(d,J=3.2Hz,18H),0.99(t,J=32.4Hz,6H),0.82(d,J=25.6Hz,6H).13C NMR(126MHz,DMSO-d6)δ173.1,159.2,144.2,139.7,138.1,129.5,127.5,121.4,119.1,106.3,92.9,86.7,79.8,70.1,67.5,58.4,57.4,45.1,36.3,35.1,34.3,29.5,20.3,19.2,18.8,17.3,15.4,13.1,12.8.
化合物26:1H NMR(400MHz,DMSO-d6)δ8.97(d,J=34.7Hz,0H),8.23(s,1H),7.80(d,J=8.1Hz,1H),7.18(d,J=7.5Hz,1H),7.13(t,J=7.8Hz,1H),6.94(t,J=7.4Hz,1H),3.34(s,2H),2.50(p,J=1.8Hz,1H),2.26(s,3H),1.64–0.59(m,0H),1.01–0.47(m,0H);13CNMR(126MHz,DMSO-d6)δ152.9,137.4,130.7,144.6,127.2,126.8,122.6,95.6,80.6,76.5,64.8,52.2,44.4,40.0,39.4,39.7,39.0,39.4,39.1,39.0,25.6,18.3,11.8.
化合物27:1H NMR(400MHz,DMSO-d6)δ10.01(s,1H),8.84(s,24H),7.44(d,J=2.1Hz,82H),5.89–5.80(m,1H),5.13(s,1H),4.91–4.87(m,0H),4.49(d,J=14.5Hz,1H),3.89(d,J=5.4Hz,1H),3.29(s,1H),3.27(s,1H),3.14(s,1H),2.52–2.47(m,12H),2.20(q,J=7.8Hz,3H),1.52(dd,J=13.1,8.1Hz,1H),1.47(s,2H),1.39(d,J=8.1Hz,1H),1.15(d,J=16.9Hz,1H),1.12(s,1H),1.09(d,J=15.1Hz,0H),1.09(s,2H),0.93–0.76(m,8H);13CNMR(126MHz,DMSO-d6)δ138.93,131.51,131.49,120.21,119.5,113.36,95.8,88.6,80.2,76.5,71.2,66.4,59.9,55.5,40.00,39.83,39.67,39.50,39.33,36.17,30.00,26.4,20.6,18.,15.,12.6.
化合物28:1H NMR(400MHz,DMSO-d6)δ9.76(s,3H),8.25(s,9H),7.51(s,2H),6.40(s,1H),5.68(dd,J=15.6,9.8Hz,1H),5.60(d,J=4.7Hz,1H),4.71(d,J=8.0Hz,1H),4.59(d,J=14.4Hz,1H),3.79(dd,J=15.9,8.0Hz,1H),3.62-3.53(m,1H),2.11(s,1H),2.07(s,0H),1.73(s,2H),1.14(d,J=28.6Hz,6H),0.96(t,J=17.7Hz,3H),0.81(t,J=32.3Hz,6H).13C NMR(126MHz,DMSO-d6)δ150.6,141.6,139.7,130.2,111.6,85.6,85.1,84.6,79.4,77.9,76.1,73.4,72.5,70.6,66.2,66.1,46.5,46.4,40.7,38.6,38.1,33.1,33.0,28.3,24.4,21.5,19.7,19.3,13.1,12.9,11.8.
化合物29:1H NMR(400MHz,DMSO-d6)δ11.65(s,3H),9.23(s,3H),7.7.6(d,J=11.2Hz,3H),6.29(d,J=10.5Hz,1H),5.79-5.58(m,3H),4.95(t,J=12.4Hz,2H),3.89-3.55(m,8H),2.50(dd,J=5.9,4.2Hz,1H),2.22-1.89(m,1H),1.59-1.35(m,11H),0.96(t,J=23.1Hz,2H),0.81(t,J=36.1Hz,4H).13C NMR(126MHz,DMSO-d6)δ173.7,156.2,139.7,1338.5,121.9,121.1,119.9,107.8,97.6,97.2,86.8,81.4,79.4,78.9,76.2,74.2,71.8,67.3,57.4,45.9,43.2,38.6 36.2,33.2,33.0,30.6,19.7,17.2,17.0,14.0,12.9.
化合物30:1H NMR(400MHz,DMSO-d6)10.00(s,1H),9.45(s,24H),7.38-7.29(m,20H),6.52-6.20(m,3H),5.37(d,J=4.5Hz,1H),5.23(d,J=3.8Hz,1H),4.42(s,2H),3.89(d,J=5.1Hz,1H),3.39-3.30(m,2H),3.27-3.12(m,1H),2.50(p,J=1.9Hz,11H),2.08(d,J=8.8Hz,1H),1.73(s,2H),1.60(s,1H),1.47(s,2H),1.41-1.25(m,1H),1.21(s,4H),1.16-1.09(m,6H),0.96(dd,J=16.3,6.5Hz,2H),0.88(dt,J=20.7,7.1Hz,5H).13C NMR(126MHz,DMSO-d6)δ152.5,140.5,139.0,138.7,134.7,119.3,117.3,113.79,98.6,85.6,81.3,79.2,78.8,75.4,72.6,70.6,69.5,68.7,67.2,57.1,44.2,42.6,41.6,39.1,36.5,34.3,33.9,32.4,31.8,27.2,25.6,21.0,20.9,19.7,18.7,17.1,14.0,13.1,12.0
化合物31:1H NMR(400MHz,DMSO-d6)δ8.84(d,J=37.6Hz,3H),8.20(s,1H),7.56(d,J=10.6Hz,10H),6.94(t,J=7.4Hz,9H),6.62-6.30(m,7H),5.60(d,J=4.7Hz,1H),5.56-5.40(m,3H),4.71(d,J=8.0Hz,1H),4.59(d,J=25.7Hz,1H),3.89(d,J=5.4Hz,1H),3.75-3.63(m,1H),3.51-3.40(m,1H),3.34(s,2H),2.50(d,J=1.8Hz,1H),2.26(s,3H),2.11-1.87(m,2H),1.18(d,J=9.2Hz,2H),1.11-0.97(m,2H).13C NMR(126MHz,DMSO-d6)δ156.7,139.5,138.6,135.2,130.17,129.7,124.8,122.66,119.8,98.2,77.5,77.4,76.4,70.5,68.9,68.2,65.2,56.8,45.9,40.0,36.8,36.7,35.6,35.5,31.3,30.7,18.3,17.1,13.6,11.7.
化合物32:1H NMR(400MHz,DMSO-d6)δ9.54(s,20H),7.86-7.65(m,23H),6.54-6.41(m,2H),5.89-5.80(m,1H),5.13(s,1H),4.51(d,J=16.5Hz,1H),4.09(d,J=13.5Hz,1H),3.92-3.71(m,1H),3.41(d,J=10.1Hz,1H),3.33-3.28(m,1H),2.74-2.50(m,12H),2.23(d,J=9.6Hz,3H),1.78(dd,J=14.2,9.6Hz,1H),1.49-1.52(m,1H),1.15-1.09(m,6H),0.81(d,J=20.7Hz,5H).13C NMR(126MHz,DMSO-d6)δ158.2,135.9,135.1,134.6,131.51,129.4,119.5,118.5,101.5,95.6,83.6,79.5,77.6,77.1,74.2,70.9,67.5,67.1,69.5,58.2,57.6,45.6,44.2,43.6,38.6,38.5,34.5,30.5,29.2,29.1,27.5,26.4,21.5,20.6,19.8,18.4,17.5,16.5,12.5.
1.2利用HPLC分析表1中多种化合物
色谱柱:C18反相柱,150mm×4.6mm
流动相:乙腈:水=80:2 0
吸收波长:250nm
流速:1mL/min
柱温:25℃.
结果如表2所示。
表2表1中多种化合物HPLC分析结果
化合物 | 保留时间 | 化合物 | 保留时间 | 化合物 | 保留时间 |
化合物10 | 4.06 | 化合物11 | 5.52 | 化合物12 | 4.20 |
化合物13 | 5.01 | 化合物14 | 4.80 | 化合物15 | 5.26 |
化合物16 | 5.15 | 化合物17 | 4.35 | 化合物18 | 4.55 |
化合物19 | 4.40 | 化合物20 | 4.76 | 化合物21 | 3.95 |
化合物22 | 4.30 | 化合物23 | 5.01 | 化合物24 | 4.60 |
化合物25 | 6.65 | 化合物26 | 4.55 | 化合物27 | 6.78 |
化合物28 | 3.56 | 化合物29 | 6.59 | 化合物30 | 4.05 |
化合物31 | 4.65 | 化合物32 | 4.75 | 化合物33 | 4.10 |
1.3研究发现本发明公开的新化合物相比于其母体结构,对光的稳定性显著增强
具体结果如表3所示。
表3表1中多个新化合物的光稳定性研究结果
由表3可知,相比于母体结构,新化合物的抗光解能力明显增强,这一特性能延长药物在叶面的持效期,减少施药次数,非常有利于对虫害的防治。
二、农药制剂实施例
实施例34
以质量百分含量计,本实施例可湿性粉剂由下述组分组成:
实施例35
以质量百分含量计,本实施例悬浮剂由下述组分组成:
实施例36
以质量百分含量计,本实施例水分散粒剂由下述组分组成:
实施例37
以质量百分含量计,本实施例乳油由下述组分组成:
三、生物活性实施例
将表1中所示化合物1-33分别进行生物活性试验。将化合物用N,N-二甲基甲酰胺溶解后,用0.1%T-80水溶液稀释成5个梯度浓度,以每个浓度的对数值为横坐标,对应死亡率的机率值为纵坐标建立毒力回归方程,计算EC50值,结果见表4、表5、表6和表7。
表4
表5
表6
表7
四、田间试验实施例
4.1对二斑叶螨的防治
按照实施例35、2)的方法将化合物1、化合物2、化合物14、化合物21、化合物23、化合物30制成制剂,和母体结构阿维菌素B1a进行田间试验,比较其对二斑叶螨的防治效果。结果如表8所示。
表8对二斑叶螨的防治效果
由表8的结果可以看出,在新化合物对二斑叶螨的田间试验中,新化合物在持效性上明显优于母体结构,这与新化合物的抗光解能力增强有关。
4.2对柑桔全爪螨的防治
以质量百分含量计,可湿性粉剂由下述组分组成:
选择5%化合物2+10%哒螨灵可湿性粉剂,2%化合物12+8%哒螨灵可湿性粉剂、2%化合物21+8%哒螨灵可湿性粉剂分别进行防治柑桔全爪螨的田间试验,分别于施药后1、3、7天调查防效,结果如表9所示。
表9对柑桔全爪螨的防治效果
由表9可知,在新化合物对柑桔全爪螨的田间试验中,新化合物与哒螨灵复配使用后对害虫的防治效果明显高于阿维菌素和哒螨灵单独使用,说明新化合物与哒螨灵混合使用对螨类害虫存在一定的增效作用。
4.3对斑潜蝇的防治
以质量百分含量计,本实施例悬浮剂由下述组分组成:
选择2%化合物4+4%高效氯氰菊酯悬浮剂,3%化合物21+9%高效氯氰菊酯悬浮剂、2%化合物33+4%高效氯氰菊酯悬浮剂分别进行防治斑潜蝇的田间试验,分别与施药后3、7、15天调查防效,结果如表10所示。
表10对斑潜蝇的防治效果
由表10可知,在新化合物对斑潜蝇的田间试验中,新化合物与高效氯氰菊酯复配使用后对害虫的防治效果明显高于阿维菌素和高效氯氰菊酯单独使用,说明新化合物与高效氯氰菊酯混合使用对潜蝇科害虫存在一定的增效作用。
4.4对根结线虫的防治
以质量百分含量计,本实施例悬浮剂由下述组分组成:
选择1%化合物16+3%氟吡菌酰胺悬浮剂,1%化合物21+3%氟吡菌酰胺悬浮剂、2%化合物30+10%氟吡菌酰胺悬浮剂分别进行防治根结线虫的田间试验,分别于施药后60、90天调查防效,结果如表11所示。
表11对根结线虫的防治效果
由表11可知在新化合物对根结线虫的田间试验中,新化合物与氟吡菌酰胺复配使用后对害虫的防治效果明显高于阿维菌素和氟吡菌酰胺单独使用,说明新化合物与氟吡菌酰胺混合使用对线虫存在一定的增效作用。
4.5对棉铃虫的防治
以质量百分含量计,本实施例悬浮剂由下述组分组成:
选择3%化合物15悬浮剂,3%化合物30悬浮剂、3%化合物32悬浮剂分别进行防治棉花棉铃虫的田间试验,分别于施药后3、9天调查防效,结果如表12所示。
表12对棉铃虫的防治效果
由表12可知在新化合物对棉铃虫的田间试验中,药后3天时新化合物对害虫的防治效果与阿维菌素的防效差别不大,药后9天时,新化合物对害虫的防效在61-77%范围内,而1.8%阿维菌素乳油的防效仅为42%,说明新化合物对棉铃虫的防效明显优于阿维菌素。
4.6对棉花烟粉虱的防治
以质量百分含量计,本实施例悬浮剂由下述组分组成:
选择3%化合物17悬浮剂,3%化合物20悬浮剂、3%化合物23悬浮剂、3%化合物24悬浮剂分别进行防治棉花烟粉虱的田间试验,分别于施药后3、5天调查防效,结果如表13所示。
表13对烟粉虱的防治效果
由表13可知在新化合物对烟粉虱的田间试验中,药后3天时新化合物对害虫的防治效果比阿维菌素的防效高出4-7个百分点,药后5天时,新化合物对害虫的防效比1.8%阿维菌素乳油的防效高出7-18个百分点,说明新化合物对烟粉虱的防效明显优于阿维菌素。
4.6本发明大环内酯类衍生物对真菌的抑制作用研究
采用菌丝生长速率法测定了化合物对禾谷镰刀菌(Fusariumgraminearum Schw.)的室内活性,结果如表14所示。
表14本发明大环内酯类衍生物对禾谷镰刀菌的抑制作用结果
采用菌丝生长速率法测定了化合物对立枯丝核菌(Rhixoctonia solani.)的室内活性,结果如表15所示。
表15本发明大环内酯类衍生物对立枯丝核菌的抑制作用结果
采用菌丝生长速率法测定了化合物对番茄灰霉病菌(Botrytis cinerea Pers.)的室内活性,结果如表16所示。
表16本发明大环内酯类衍生物对番茄灰霉病菌的抑制作用结果
由表14、15、16可知,本发明新发现的化合物,对真菌的生长具有一定的抑制作用。在农业生长中,作物上的病虫害往往是同时发生,所以,兼有抑制病原菌和害虫生长的特性,对于有害生物防治,降低农药用量具有非常重要的现实意义。本发明发现的化合物具有巨大的应用价值和开发潜力,具有广阔的市场前景。
Claims (6)
3.如权利要求2所述大环内酯类衍生物的合成方法,其特征在于:所述化合物A与化合物B的摩尔比为1:0.5~1:10;催化剂为氯化亚锡、四丁基锡、醋酸三丁基锡、三氯正丁基锡、三甲基锡氢氧化物、二氯二甲基锡、二月桂酸二丁基锡中的任意一种。
4.如权利要求1所述大环内酯类衍生物在防治害虫中的用途;所述害虫包括蛛形纲、双壳纲、腹足纲、线虫纲、唇足目、弹尾目、虱目、双翅目、鞘翅目、直翅目、异翅亚目、同翅目、膜翅目、等翅目、鳞翅目、食毛目、啮虫目、蚤目、缨翅目、缨尾目。
5.如权利要求1所述大环内酯类衍生物在制备抑制真菌生长的药物中的用途。
6.如权利要求1所述大环内酯类衍生物与成分C的混合物在防治害虫中的用途;所述害虫包括蛛形纲、双壳纲、腹足纲、线虫纲、唇足目、弹尾目、虱目、双翅目、鞘翅目、直翅目、异翅亚目、同翅目、膜翅目、等翅目、鳞翅目、食毛目、啮虫目、蚤目、缨翅目、缨尾目;所述成分C选自哒螨灵、稻瘟灵、氰氟虫腙、杀螨素、溴螨酯、噻螨酮、三唑锡、三环锡、苯丁锡、炔螨特、苯氟磺胺、唑螨酯、嘧螨胺、阿维菌素、甲氨基阿维菌素苯甲酸盐、伊维菌素、雷皮菌素、弥拜菌素、多杀菌素、乙基多杀菌素、苏云金素、印楝素、鱼藤酮、藜芦碱、杀虫单、杀虫双、氯虫酰胺、氯虫苯甲酰胺、溴氰虫酰胺、虫脲、噻嗪酮、氟啶脲、氟啶胺、灭蝇胺、环虫腈、除虫脲、氟螨脲、氟虫脲、氟铃脲、虱螨脲、氟酰脲、氟幼脲、氟苯脲、杀铃脲、灭幼脲、苯氧威、烯虫乙酯、烯虫酯炔、烯虫酯、吡丙醚、啶虫丙醚、环虫酰肼、氯虫酰肼、甲氧虫酰肼、虫酰肼、呋喃虫酰肼、氟啶虫酰胺、噻虫胺、噻虫嗪、噻虫啉、吡虫啉、啶虫脒、烯啶虫胺、呋虫胺、吡蚜酮、氟啶虫胺腈、哌虫胺、茚虫威、丁烯氟虫腈、唑虫酰胺、溴虫腈、螺螨酯、螺虫乙酯、丁醚脲、联苯菊酯、氟氯氰菊酯、高效氯氟氰菊酯、高效氟氯氰菊酯、高效氯氰菊酯、二嗪磷、辛硫磷、甲基嘧啶磷、噻唑膦中的一种或几种。
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