CN111269237B - 偕二氟化螺-γ-内酰胺吲哚啉化合物及其制备方法和在防治植物病虫害中的应用 - Google Patents
偕二氟化螺-γ-内酰胺吲哚啉化合物及其制备方法和在防治植物病虫害中的应用 Download PDFInfo
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- CN111269237B CN111269237B CN201811477904.8A CN201811477904A CN111269237B CN 111269237 B CN111269237 B CN 111269237B CN 201811477904 A CN201811477904 A CN 201811477904A CN 111269237 B CN111269237 B CN 111269237B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
- C07F9/65615—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings containing a spiro condensed ring system of the formula where at least one of the atoms X or Y is a hetero atom, e.g. S
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
本发明涉及偕二氟化螺‑γ‑内酰胺吲哚啉化合物及其制备方法和在防治植物病虫害中的应用,式中各基团的意义见说明书。本专利中偕二氟化螺‑γ‑内酰胺吲哚啉化合物表现出良好的抗TMV、杀菌和杀虫活性。
Description
技术领域
本发明涉及偕二氟化螺-γ-内酰胺吲哚啉化合物及其制备方法和在防治植物病虫害中的应用,属于农业防护技术领域。
背景技术
3,3-螺环吲哚啉是自然界中无处不在的一种骨架结构,它代表了包括白坚木属、马钱子属、蕊木属等生物碱家族的核心骨架。同时,该类化合物及其衍生物具有广泛的药理活性,如抗肿瘤、抗菌、抗血小板、抗血栓等。2005年Cassayre等以“具有杀虫效果的螺吲哚衍生物”为标题,公开了具有杀虫性能的含吲哚啉环结构的螺环化合物的专利,详细介绍了近千种该类化合物的合成及杀虫活性,表明该类化合物也可以应用在农药领域(WO2005058035 A1.2005-06-30)。但目前还没有文献报道该类化合物在抗植物病毒、病菌方面的应用。又由于氟原子、含膦官能团以及含氮杂环等在农药领域应用十分广泛,因此我们设计合成了同时含氟、含膦以及同时含氟、含吲哚结构的两类螺-γ-内酰胺吲哚啉化合物,并研究了其在抗植物病毒、病菌和杀虫活性方面的应用。
发明内容
本发明目的是提供偕二氟化螺-γ-内酰胺吲哚啉化合物及其制备方法和在抗植物病毒、杀菌以及杀虫方面的应用。本发明的偕二氟化螺-γ-内酰胺吲哚啉化合物具有很好的抗植物病毒、杀菌以及杀虫活性。
本发明的偕二氟化螺-γ-内酰胺吲哚啉化合物是如下通式I所示的化合物,具体包括Ia和Ib。
结构式一
Ia按照反应式一所示的方法制备:通式II化合物首先在光催化条件下发生去芳构化羟基化得到通式III化合物。III无需分离,直接加入当量通式IV膦氧化物以及当量浓盐酸进行反应,最终得到通式Ia产物。
反应式一
Ib按照反应式二所示的方法制备:通式II化合物首先在光催化条件下发生去芳构化羟基化得到通式III化合物。III无需分离,直接加入当量通式V吲哚化合物以及当量浓盐酸进行反应,最终得到通式Ib产物。
反应式二
以上各通式中,
其中,X为磷氧基、吲哚基;
R1分别为一到四个C1-C12的烷基、C3-C6的环烷基、卤素、氰基、硝基、酯基、三氟甲基、三氟甲氧基、酰胺基、C1-C6的烃基、C1-C6的烷氧基、C1-C4的烷基取代的羰氧基和C1-C4的烷氧基取代的羰氧基;
R2为C1-C12的烷基、C3-C6的环烷基、取代的或未取代的苯基、取代的或未取代的萘基、取代的或未取代的苄基、取代的或未取代的苯乙基、取代的或未取代的苯丙基、取代的或未取代的苯丁基、含有1-10个碳原子的含氮杂环、含有1-10个碳原子的含氧杂环、含有1-10个碳原子的含硫杂环;所述取代的苯基、取代的萘基、取代的苄基、取代的苯乙基、取代的苯丙基和取代的苯丁基的取代基各自独立地选自羟基、卤素、氰基、硝基、酯基、三氟甲基、三氟甲氧基、酰胺基、C1-C6的烃基、C1-C6的烷氧基、C1-C4的烷基取代的羰氧基和C1-C4的烷氧基取代的羰氧基;
R3分别为C1-C12的烷基、C3-C6的环烷基、取代的或未取代的苯基、取代的或未取代的萘基、取代的或未取代的苄基、取代的或未取代的苯乙基、取代的或未取代的苯丙基、取代的或未取代的苯丁基;所述取代的苯基、取代的萘基、取代的苄基、取代的苯乙基、取代的苯丙基和取代的苯丁基的取代基各自独立地选自羟基、卤素、氰基、硝基、酯基、三氟甲基、三氟甲氧基、酰胺基、C1-C6的烃基、C1-C6的烷氧基、C1-C4的烷基取代的羰氧基和C1-C4的烷氧基取代的羰氧基;
R4为C1-C12的烷基、取代的或未取代的苯基、取代的或未取代的萘基、取代的或未取代的苄基、取代的或未取代的苯乙基、取代的或未取代的苯丙基、取代的或未取代的苯丁基、含有1-10个碳原子的含氮杂环、含有1-10个碳原子的含氧杂环、含有1-10个碳原子的含硫杂环、C1-C6的烷氧基;所述取代的苯基、取代的萘基、取代的苄基、取代的苯乙基、取代的苯丙基和取代的苯丁基的取代基各自独立地选自羟基、卤素、氰基、硝基、酯基、三氟甲基、三氟甲氧基、酰胺基、C1-C6的烃基、C1-C6的烷氧基、C1-C4的烷基取代的羰氧基和C1-C4的烷氧基取代的羰氧基;
R5分别为一到四个C1-C12的烷基、C3-C6的环烷基、卤素、氰基、硝基、酯基、三氟甲基、三氟甲氧基、酰胺基、C1-C6的烃基、C1-C6的烷氧基、C1-C4的烷基取代的羰氧基和C1-C4的烷氧基取代的羰氧基。
在本发明中,C1-C12的烷基的具体实例例如可以为:甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基等。
C1-C6的烃基、C1-C4的烷基可以从上述的烷基的具体实例进行选择并进行满足相应限定即可。
C1-C6的烷氧基可以是上述的满足1-6个碳原子限定的烷基的具体实例形成的烷氧基。
含有1-10个碳原子的含氮杂环可以是不饱和氮杂环,也可以是饱和氮杂环,只要其杂环的环结构中以氮为结构原子且该杂环具有的碳原子个数为1-10个,例如可以是未取代的或者C1-C6的烷基取代的吡咯、未取代的或者C1-C6的烷基取代的氢化吡咯、未取代的或者C1-C7的烷基取代的咪唑、未取代的或者C1-C7的烷基取代的氢化咪唑、未取代的或者C1-C5的烷基取代的吡啶、未取代的或者C1-C5的烷基取代的氢化吡啶、未取代的或者C1-C7的烷基取代的吡唑、未取代的或者C1-C7的烷基取代的氢化吡唑、未取代的或者C1-C7的烷基取代的噻唑、未取代的或者C1-C7的烷基取代的氢化噻唑、未取代的或者C1-C7的烷基取代的噁唑、未取代的或者C1-C7的烷基取代的氢化噁唑等。其中,作为取代基的烷基可以从上文中所描述的烷基具体实例中进行相应的选择,这些烷基的取代可以是单点的,也可以是多点的取代,本发明对此并无特别的限定。
含有1-10个碳原子的含氧杂环可以是不饱和氧杂环,也可以是饱和氧杂环,只要其杂环的环结构中以氧为结构原子且该杂环具有的碳原子个数为1-10个,例如可以是未取代的或者C1-C6的烷基取代的呋喃、未取代的或者C1-C6的烷基取代的氢化呋喃、未取代的或者C1-C7的烷基取代的噁唑、未取代的或者C1-C7的烷基取代的氢化噁唑、未取代的或者C1-C3的烷基取代的1,3-苯并二噁茂、未取代的或者C1-C2的烷基取代的1,4-苯并二噁等。
含有1-10个碳原子的含硫杂环可以是不饱和硫杂环,也可以是饱和硫杂环,只要其杂环的环结构中以硫为结构原子且该杂环具有的碳原子个数为1-10个,例如可以是未取代的或者C1-C6的烷基取代的噻吩、未取代的或者C1-C6的烷基取代的氢化噻吩、未取代的或者C1-C7的烷基取代的噻唑、未取代的或者C1-C7的烷基取代的氢化噻唑等。
本发明优选化合物如结构式二所示:
结构式二
本发明的偕二氟化螺-γ-内酰胺吲哚啉化合物I表现出很好的抗植物病毒、杀菌以及杀虫活性。
具体实施方式
下述的实施例和生测试验结果可用来进一步说明本发明,但不意味着限制本发明。
实施例1:偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-1~Ia-10的合成
Ia-1:向5mL小玻璃瓶中加入化合物II-1(74.4mg,0.2mmol),Ir(ppy)3(1.3mg,0.002mmol),K2HPO4(52.2mg,0.3mmol),甲基叔丁基醚1.8mL和水0.2mL。然后在Ar保护下置换气体。之后将玻璃瓶封口并在3瓦LED蓝光灯照射下室温搅拌反应10小时。反应完毕,向III-1的混合物体系中加入二苯基氧膦IV-1(30.3mg,0.3mmol)和浓盐酸(0.6mmol),于室温搅拌反应2小时。完毕,加入乙酸乙酯10mL,用饱和碳酸氢钠和饱和食盐水依次洗涤。有机相用无水硫酸钠干燥,减压脱溶,以石油醚(60-90℃)/乙酸乙酯体系柱层析分离得到白色固体Ia-1 82mg,收率83%,熔点76-77℃。1H NMR(400MHz,CDCl3)δ8.00-7.87(m,4H),7.62-7.43(m,4H),7.37(td,J=7.6,2.7Hz,2H),7.01(d,J=8.0Hz,1H),6.60(d,J=8.1Hz,1H),6.57(s,1H),4.47-4.34(m,2H),4.27(d,J=10.4Hz,1H),3.11(d,J=10.3Hz,1H),2.29(s,3H),2.15(s,3H),1.16(d,J=6.7Hz,3H),1.08(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.5(dd,J=31.2,29.7Hz),150.8(d,J=4.0Hz),132.39(d,J=2.9Hz),132.36(d,J=8.5Hz),132.34(d,J=2.9Hz),132.04(d,J=87.8Hz),131.6(d,J=8.7Hz),130.9,130.6,129.8(d,J=95.3Hz),128.9(d,J=11.4Hz),128.6(t,J=3.1Hz),128.5(d,J=11.3Hz),122.7,116.0(ddd,J=261.0,251.1,10.1Hz),112.3,66.4(dd,J=91.2,4.1Hz),54.7(td,J=21.0,1.2Hz),45.5(dd,J=8.1,2.0Hz),44.3,41.2(d,J=3.2Hz),20.9,19.3,19.2.19FNMR(376MHz,CDCl3)δ-106.43(d,J=253.2Hz,1F),-123.07(d,J=253.2Hz,1F).31P NMR(162MHz,CDCl3)δ24.5.HRMS(ESI)calcd for C28H30F2N2O2P[M+H]+495.2007,found495.2001.
Ia-2~Ia-10的合成过程与Ia-1相同,数据如下:
Ia-2:白色固体,收率95%,熔点201-202℃。1H NMR(400MHz,CDCl3)δ8.01-7.86(m,4H),7.63-7.45(m,4H),7.37(td,J=7.6,3.0Hz,2H),6.65(d,J=7.7Hz,1H),6.53(d,J=8.1Hz,1H),6.51(s,1H),4.45(d,J=3.2Hz,1H),4.43-4.31(m,1H),4.23(d,J=10.3Hz,1H),3.13(d,J=10.3Hz,1H),2.29(s,3H),2.28(s,3H),1.14(d,J=6.8Hz,3H),1.06(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.8-161.0(m),153.0(d,J=3.6Hz),140.5,132.41(d,J=2.8Hz),132.34(d,J=2.8Hz),132.32(d,J=8.5Hz),132.03(d,J=92.7Hz),131.5(d,J=8.7Hz),129.9(d,J=95.8Hz),128.9(d,J=11.2Hz),128.5(d,J=11.2Hz),125.5(t,J=3.4Hz),121.8,121.8,116.0(ddd,J=260.7,250.9,9.9Hz),112.82,66.3(dd,J=90.4,4.0Hz),54.5(t,J=20.8Hz),45.5(d,J=6.4Hz),44.2,40.5(d,J=2.5Hz),21.6,19.3,19.2.19F NMR(376MHz,CDCl3)δ-106.94(d,J=252.6Hz,1F),-123.42(d,J=252.5Hz,1F).31P NMR(162MHz,CDCl3)δ24.4.HRMS(ESI)calcd for C28H30F2N2O2P[M+H]+495.2007,found 495.2007.
Ia-3:白色固体,收率87%,熔点191-192℃。1H NMR(400MHz,CDCl3)δ8.07-8.00(m,2H),7.86-7.75(m,2H),7.64-7.51(m,3H),7.41(td,J=7.4,1.3Hz,1H),7.33-7.24(m,2H),6.98(d,J=7.4Hz,1H),6.74(t,J=7.5Hz,1H),6.64(d,J=7.4Hz,1H),4.45-4.30(m,3H),3.21(d,J=10.5Hz,1H),2.47(s,3H),2.25(s,3H),1.20(d,J=6.8Hz,3H),1.12(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.4(dd,J=31.6,29.6Hz),151.6(d,J=2.4Hz),132.29(d,J=2.7Hz),132.25,132.18(d,J=8.5Hz),132.12(d,J=2.5Hz),132.03(d,J=97.3Hz),131.5(d,J=8.5Hz),130.8(t,J=3.6Hz),129.7(d,J=96.8Hz),128.8(d,J=11.3Hz),128.1(d,J=11.3Hz),125.1,123.3,119.6,118.70-113.38(m),67.5(dd,J=91.0,4.2Hz),54.5(td,J=21.4,3.1Hz),44.8(dd,J=6.7,2.7Hz),44.3,42.6(d,J=6.4Hz),19.4,19.2,18.4.19F NMR(376MHz,CDCl3)δ-105.44(d,J=252.7Hz,1F),-121.25(d,J=252.7Hz,1F).31P NMR(162MHz,CDCl3)δ25.4.HRMS(ESI)calcd for C28H30F2N2O2P[M+H]+495.2007,found 495.2010.
Ia-4:白色固体,收率70%,熔点220-221℃。1H NMR(400MHz,CDCl3)δ8.00-7.81(m,4H),7.66-7.47(m,4H),7.41(td,J=7.6,3.0Hz,2H),6.69(dd,J=8.3,5.4Hz,1H),6.41-6.30(m,2H),4.55(d,J=1.7Hz,1H),4.43-4.32(m,1H),4.20(d,J=10.5Hz,1H),3.22(d,J=10.4Hz,1H),2.29(s,3H),1.16(d,J=6.8Hz,3H),1.05(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ164.8(d,J=245.7Hz),161.2(dd,J=31.4,29.4Hz),154.4(dd,J=11.7,3.3Hz),132.62(d,J=2.7Hz),132.56(d,J=2.8Hz),132.3(d,J=8.7Hz),131.7(d,J=95.4Hz),131.4(d,J=8.9Hz),129.5(d,J=96.0Hz),129.0(d,J=11.4Hz),128.6(d,J=11.3Hz),123.66-123.50(m),123.1(d,J=10.8Hz),115.9(ddd,J=262.4,251.5,10.7Hz),107.0(d,J=23.3Hz),99.2(d,J=26.6Hz),66.2(dd,J=88.3,4.8Hz),54.2(td,J=20.9,1.6Hz),45.1(dd,J=7.8,2.3Hz),44.3(s),39.5(d,J=1.9Hz),19.3,19.2.19F NMR(376MHz,CDCl3)δ-107.50(d,J=252.6Hz,1F),-110.72--111.29(m,1F),-123.76(d,J=252.7Hz,1F).31P NMR(162MHz,CDCl3)δ24.3.HRMS(ESI)calcd for C27H27F3N2O2P[M+H]+499.1757,found 499.1760.
Ia-5:无色油状物,收率79%。1H NMR(400MHz,CDCl3)δ8.00-7.83(m,4H),7.64-7.50(m,4H),7.40(td,J=7.6,3.1Hz,2H),7.15(dd,J=8.5,2.0Hz,1H),6.72(d,J=1.9Hz,1H),6.58(d,J=8.5Hz,1H),4.52(d,J=2.2Hz,1H),4.44-4.31(m,1H),4.20(d,J=10.6Hz,1H),3.21(d,J=10.3Hz,1H),2.29(s,3H),1.17(d,J=6.8Hz,3H),1.05(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.43-160.61(m),151.5(d,J=3.3Hz),132.64(d,J=2.3Hz),132.61(d,J=2.6Hz),132.3(d,J=8.7Hz),131.6(d,J=95.6Hz),131.4(d,J=8.8Hz),130.3,129.90-129.70(m),129.4(d,J=96.4Hz),129.0(d,J=11.6Hz),128.6(d,J=11.2Hz),125.3,122.5,118.41-113.01(m),112.6,66.1(dd,J=89.0,4.3Hz),54.6(t,J=21.3Hz),45.0(d,J=7.3Hz),44.4,40.1(d,J=1.9Hz),19.20,19.17.19F NMR(376MHz,CDCl3)δ-107.07(d,J=253.9Hz,1F),-123.06(d,J=253.9Hz,1F).31P NMR(162MHz,CDCl3)δ24.5.HRMS(ESI)calcd for C27H27ClF2N2O2P[M+H]+515.1461,found 515.1464.
Ia-6:白色固体,收率76%,熔点229-230℃。1H NMR(400MHz,CDCl3)δ7.95(dd,J=10.1,7.9Hz,2H),7.91-7.83(m,2H),7.64-7.48(m,4H),7.41(td,J=7.6,2.7Hz,2H),6.81(d,J=8.0Hz,1H),6.77(s,1H),6.61(d,J=8.0Hz,1H),4.54(s,1H),4.42-4.30(m,1H),4.16(d,J=10.5Hz,1H),3.24(d,J=10.5Hz,1H),2.29(s,3H),1.15(d,J=6.7Hz,3H),1.03(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.1(dd,J=31.2,29.5Hz),154.0(d,J=3.2Hz),132.7(d,J=2.7Hz),132.6(d,J=2.8Hz),132.2(d,J=8.7Hz),131.6(d,J=95.0Hz),131.4(d,J=8.8Hz),129.5(d,J=96.2Hz),129.1(d,J=11.4Hz),128.6(d,J=11.3Hz),127.27-127.11(m),124.1,123.31,123.3,118.46-112.96(m),114.5,65.9(dd,J=88.1,4.7Hz),54.4(td,J=21.0,1.6Hz),45.0(dd,J=7.9,2.2Hz),44.3,39.4(d,J=1.8Hz),19.23,19.17.19F NMR(376MHz,CDCl3)δ-107.21(d,J=253.1Hz,1F),-123.46(d,J=252.9Hz,1F).31P NMR(162MHz,CDCl3)δ24.3.HRMS(ESI)calcd for C27H27BrF2N2O2P[M+H]+559.0954,found 559.0953 and 561.0938.
Ia-7:白色固体,收率80%,熔点203-204℃。1H NMR(400MHz,CDCl3)δ7.87-7.70(m,4H),7.33(d,J=6.4Hz,2H),7.23-7.17(m,1H),7.16(d,J=8.4Hz,2H),6.77(d,J=7.4Hz,1H),6.70(t,J=7.5Hz,1H),6.66(d,J=8.0Hz,1H),4.43(d,J=3.1Hz,1H),4.43-4.34(m,1H),4.31(d,J=10.6Hz,1H),3.17(d,J=10.4Hz,1H),2.41(s,3H),2.34(s,3H),2.32(s,3H),1.17(d,J=6.7Hz,3H),1.09(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.92-160.97(m),152.9(d,J=3.7Hz),143.0(d,J=2.5Hz),142.9(d,J=2.5Hz),132.3(d,J=8.9Hz),131.5(d,J=9.2Hz),130.3,129.6(d,J=11.8Hz),129.2(d,J=11.6Hz),128.8(d,J=98.8Hz),128.3(t,J=3.3Hz),126.4(d,J=98.2Hz),122.2,120.7,116.0(ddd,J=261.9,251.4,10.2Hz),111.8,66.0(dd,J=90.1,3.6Hz),54.6(t,J=20.6Hz),45.4(d,J=6.7Hz),44.3,40.3(d,J=2.0Hz),21.61,21.56,19.3,19.2.19F NMR(376MHz,CDCl3)δ-106.89(d,J=252.8Hz,1F),-123.18(d,J=252.8Hz,1F).31P NMR(162MHz,CDCl3)δ25.0.HRMS(ESI)calcd for C29H32F2N2O2P[M+H]+509.2164,found 509.2166.
Ia-8:白色固体,收率88%,熔点250-251℃。1H NMR(400MHz,CDCl3)δ8.03-7.84(m,4H),7.33-7.19(m,3H),7.05(t,J=7.8Hz,2H),6.84-6.68(m,3H),4.46-4.37(m,2H),4.34(d,J=10.3Hz,1H),3.13(d,J=10.3Hz,1H),2.38(s,3H),1.19(d,J=6.7Hz,3H),1.14(d,J=6.7Hz,3H).13C NMR(100MHz,CDCl3)δ165.3(d,J=255.0Hz),161.67-160.64(m),152.7(d,J=3.8Hz),135.0(t,J=9.2Hz),134.1(t,J=9.5Hz),130.5,128.2(t,J=3.0Hz),127.7(dd,J=101.3,3.0Hz),125.2(dd,J=98.6,3.0Hz),122.3,121.4,118.50-113.17(m),116.4(dd,J=21.4,12.5Hz),116.0(dd,J=21.2,12.0Hz),112.4,66.1(dd,J=92.3,4.2Hz),54.7(t,J=20.5Hz),45.0(d,J=7.6Hz),44.4,40.8(d,J=2.7Hz),19.3,19.2.19FNMR(376MHz,CDCl3)δ-105.13(s,1F),-105.21(s,1F),-107.14(d,J=252.9Hz,1F),-123.16(d,J=252.8Hz,1F).31P NMR(162MHz,CDCl3)δ23.4.HRMS(ESI)calcd forC27H26F4N2O2P[M+H]+517.1663,found 517.1658.
Ia-9:白色固体,收率84%,熔点261-262℃。1H NMR(400MHz,CDCl3)δ7.94-7.73(m,4H),7.52(dd,J=8.2,1.7Hz,2H),7.32(dd,J=8.3,1.9Hz,2H),7.22(t,J=7.2Hz,1H),6.83-6.67(m,3H),4.46-4.35(m,2H),4.30(d,J=10.3Hz,1H),3.16(d,J=10.3Hz,1H),2.38(s,3H),1.19(d,J=6.7Hz,3H),1.13(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.2(dd,J=31.3,29.5Hz),152.7(d,J=3.7Hz),139.39,139.35,133.7(d,J=9.3Hz),132.9(d,J=9.7Hz),130.6,130.1(d,J=100.0Hz),129.4(d,J=12.0Hz),129.0(d,J=11.7Hz),128.25-128.09(m),127.7(d,J=96.8Hz),122.4,121.6,118.47-112.99(m),112.5,66.0(dd,J=92.2,4.6Hz),54.7(td,J=21.0,2.2Hz),45.1(dd,J=8.0,2.0Hz),44.5,41.0(d,J=3.3Hz),19.4,19.3.19F NMR(376MHz,CDCl3)δ-107.20(d,J=253.0Hz,1F),-123.01(d,J=252.9Hz,1F).31P NMR(162MHz,CDCl3)δ23.5.HRMS(ESI)calcd for C27H26Cl2F2N2O2P[M+H]+549.1072,found 549.1061.
Ia-10:无色油状物,收率72%。1H NMR(400MHz,CDCl3)δ7.67(dd,J=11.4,7.7Hz,1H),7.47(t,J=7.5Hz,1H),7.39(t,J=7.4Hz,1H),7.35-7.23(m,4H),7.20(t,J=7.6Hz,1H),7.08(t,J=6.6Hz,1H),6.93(d,J=7.5Hz,1H),6.77(t,J=7.5Hz,1H),6.62(d,J=7.9Hz,1H),4.73(d,J=2.8Hz,1H),4.51-4.38(m,1H),4.16(d,J=10.9Hz,1H),3.83(d,J=10.8Hz,1H),2.59(s,3H),2.48(s,3H),2.18(s,3H),1.24(d,J=6.8Hz,3H),0.99(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ161.76-160.80(m),152.7(d,J=3.1Hz),144.8(d,J=6.7Hz),143.2(d,J=6.7Hz),132.7(d,J=9.7Hz),132.27(d,J=10.8Hz),132.26(d,J=9.1Hz),132.04(d,J=14.3Hz),131.95(d,J=87.3Hz),130.3,129.6(d,J=98.0Hz),128.9(t,J=3.4Hz),125.4(d,J=6.5Hz),125.3(d,J=7.8Hz),122.0,120.6,119.31-113.87(m),111.4,65.3(dd,J=89.3,3.9Hz),54.7(t,J=20.6Hz),47.0(d,J=5.2Hz),44.3,39.6(d,J=1.5Hz),21.6(d,J=2.5Hz),21.3(d,J=3.8Hz),19.2,19.1.19F NMR(376MHz,CDCl3)δ-103.73(d,J=254.0Hz,1F),-122.54(d,J=254.2Hz,1F).31P NMR(162MHz,CDCl3)δ35.3.HRMS(ESI)calcd for C29H32F2N2O2P[M+H]+509.2164,found 509.2163.
实施例2:偕二氟化螺-γ-内酰胺吲哚啉化合物Ib-1~Ib-6的合成
Ib-1:向5mL小玻璃瓶中加入化合物II-2(74.4mg,0.2mmol),Ir(ppy)3(1.3mg,0.002mmol),K2HPO4(52.2mg,0.3mmol),甲基叔丁基醚1.8mL和水0.2mL。然后在Ar保护下置换气体。之后将玻璃瓶封口并在3瓦LED蓝光灯照射下搅拌反应10小时。反应完毕,向III-2的混合物体系中加入吲哚V-1(17.6mg,0.3mmol)和浓盐酸(0.6mmol),于室温搅拌反应2小时。完毕,加入乙酸乙酯10mL,用饱和碳酸氢钠和饱和食盐水依次洗涤。有机相用无水硫酸钠干燥,减压脱溶,以石油醚(60-90℃)/乙酸乙酯体系柱层析分离得到黄色固体VII-377.7mg,总收率95%,dr=5.9∶1。主要异构体为白色固体,收率81%,熔点252-253℃。1HNMR(400MHz,CDCl3)δ8.38(s,1H),7.65(d,J=8.1Hz,1H),7.38(d,J=8.2Hz,1H),7.24-7.17(m,2H),7.14(dd,J=7.6,1.8Hz,1H),7.08(d,J=5.0Hz,1H),6.63(d,J=7.6Hz,1H),6.50(s,1H),5.02(s,1H),4.10-3.91(m,1H),3.52(d,J=9.4Hz,1H),3.11(d,J=10.3Hz,1H),2.66(s,3H),2.37(s,3H),0.92(d,J=6.7Hz,3H),0.23(s,3H).13C NMR(100MHz,CDCl3)δ162.4(t,J=30.2Hz),152.9,140.1,136.6,126.8,124.7,123.0,122.5,120.6,120.4,119.6,119.5,118.3(t,J=252.5Hz),111.5,109.5,108.9,67.6-67.2(m),54.5(t,J=18.4Hz),47.2,43.6,33.6,21.8,19.2,18.0.19F NMR(376MHz,CDCl3)δ-113.47(d,J=266.1Hz,1F),-119.76(d,J=266.4Hz,1F).HRMS(ESI)calcd for C24H26F2N3O[M+H]+410.2038,found 410.2045.
Ib-2~Ib-6的合成过程与Ib-1相同,数据如下:
Ib-2:总收率58%,dr=13.4∶1。主要异构体为白色固体,收率54%,熔点220-221℃。1H NMR(400MHz,CDCl3)δ8.47(s,1H),7.75(d,J=8.0Hz,1H),7.41(d,J=8.2Hz,1H),7.27(d,J=2.2Hz,1H),7.25-7.19(m,1H),7.16-7.05(m,3H),6.80(t,J=7.6Hz,1H),4.98(s,1H),4.13-3.95(m,1H),3.51(d,J=10.3Hz,1H),3.09(d,J=10.3Hz,1H),2.93(s,3H),2.50(s,3H),0.95(d,J=6.8Hz,3H),0.31(d,J=6.8Hz,3H).13C NMR(100MHz,CDCl3)δ162.5(t,J=30.3Hz),151.1,136.7,133.1,126.8,126.7,124.9,122.8(d,J=5.2Hz),122.5,120.6,120.4,120.3,119.7,118.2(t,J=253.4Hz),111.5,111.0,67.9-67.6,54.4(t,J=18.2Hz),47.4,43.7,37.7,20.0,19.2,18.1.19F NMR(376MHz,CDCl3)δ-114.04(d,J=265.2Hz,1F),-117.82(d,J=269.4Hz,1F).HRMS(ESI)calcd for C24H26F2N3O[M+H]+410.2038,found 410.2037.
Ib-3:黄色固体,收率92%,dr=1.7∶1。主要非对映异构体:1H NMR(400MHz,CDCl3)δ8.85(s,1H),7.54(s,1H),7.41(d,J=7.0Hz,1H),7.31-6.89(m,5H),6.81(d,J=11.6Hz,1H),5.11(s,1H),4.19-3.96(m,1H),3.55(s,1H),3.15(d,J=9.3Hz,1H),2.67(s,3H),0.96(d,J=4.5Hz,3H),0.27(s,3H).19F NMR(376MHz,CDCl3)δ-112.78(d,J=267.5Hz,1F),-119.52(d,J=264.5Hz,1F).HRMS(ESI)calcd for C23H23BrF2N3O[M+H]+474.0987,found474.0984 and 476.0968.
Ib-4:总收率93%,dr=4.6∶1。主要异构体为白色固体,收率76%,熔点240-241℃。1H NMR(400MHz,CDCl3)δ8.58(s,1H),7.68(s,1H),7.37-7.22(m,4H),7.16(dd,J=8.7,1.7Hz,1H),6.84(t,J=7.5Hz,1H),6.71(d,J=7.8Hz,1H),4.97(s,1H),4.12-3.98(m,1H),3.51(d,J=11.9Hz,1H),3.14(d,J=10.4Hz,1H),2.68(s,3H),0.95(d,J=6.7Hz,3H),0.25(s,3H).13C NMR(100MHz,CDCl3)δ162.4(t,J=30.7Hz),152.6,135.0,130.0,127.8,126.5,126.2,125.8,125.0,124.9,123.0,119.7,119.1,118.3(t,J=252.9Hz),112.6,108.5,67.6-66.9(m),54.6(t,J=18.2Hz),47.2,43.8,34.0,19.2,18.1.19F NMR(376MHz,CDCl3)δ-112.94(d,J=264.3Hz,1F),-118.66(d,J=266.8Hz,1F).HRMS(ESI)calcd forC23H23ClF2N3O[M+H]+430.1492,found 430.1497.
Ib-5:黄色固体,收率68%,dr=9.1∶1。主要非对映异构体:1H NMR(400MHz,CDCl3)δ8.88(s,1H),7.85(s,1H),7.19-6.90(m,5H),6.85(t,J=6.8Hz,1H),6.72(d,J=5.2Hz,1H),4.95(s,1H),4.12-3.95(m,1H),3.55(d,J=7.8Hz,1H),3.15(d,J=10.2Hz,1H),2.68(s,3H),0.95(d,J=5.8Hz,3H),0.22(s,3H).19F NMR(376MHz,CDCl3)δ-112.37(d,J=267.5Hz,1F),-118.47(d,J=267.3Hz,1F).HRMS(ESI)calcd for C23H23BrF2N3O[M+H]+474.0987,found 474.0979 and 476.0966.
Ib-6:总收率85%,dr=4.5∶1。主要异构体为白色固体,收率70%,熔点259-260℃。1H NMR(400MHz,CDCl3)δ8.93(s,1H),8.16(s,1H),7.52-7.42(m,2H),7.38(d,J=2.2Hz,1H),7.33(t,J=7.7Hz,1H),7.27(d,J=7.6Hz,1H),6.87(t,J=7.5Hz,1H),6.75(d,J=7.9Hz,1H),4.99(s,1H),4.14-3.94(m,1H),3.43(d,J=10.3Hz,1H),3.15(d,J=10.4Hz,1H),2.68(s,3H),0.96(d,J=6.8Hz,3H),0.25(s,3H).13C NMR(100MHz,CDCl3)δ162.4(t,J=30.2Hz),152.4,138.2,130.3,126.6,125.8,125.4,124.88,124.85,124.83,120.5,119.6,112.7,111.1,108.9,103.7,67.3-67.1(m),54.6(t,J=18.0Hz),47.2,43.8,34.3,19.2,18.1.19F NMR(376MHz,CDCl3)δ-113.28(d,J=264.8Hz,1F),-118.16(d,J=265.0Hz,1F).HRMS(ESI)calcd for C24H23F2N4O[M+H]+421.1834,found 421.1835.
实施例3:抗烟草花叶病毒活性的测定,测定程序如下
1.病毒提纯及浓度测定:
病毒提纯及浓度测定参照南开大学元素所生测室编制烟草花叶病毒SOP规范执行。病毒粗提液经2次聚乙二醇离心处理后,测定浓度,4℃冷藏备用。
2.化合物溶液配制:
称量后,原药加入DMF溶解,制得1×105mg/L母液,后用含1‰吐温80水溶液稀释至所需浓度;宁南霉素制剂直接兑水稀释。
3.活体保护作用:
选长势均匀一致的3-5叶期珊西烟,全株喷雾施药,每处理3次重复,并设1‰吐温80水溶液对照。24h后,叶面撒布金刚砂(500目),用毛笔蘸取病毒液,在全叶面沿支脉方向轻擦2次,叶片下方用手掌支撑,病毒浓度10mg/L,接种后用流水冲洗。3d后记录病斑数,计算防效。
4.活体治疗作用:
选长势均匀一致的3-5叶期珊西烟,用毛笔全叶接种病毒,病毒浓度为10mg/L,接种后用流水冲洗。叶面收干后,全株喷雾施药,每处理3次重复,并设1‰吐温80水溶液对照。3d后记录病斑数,计算防效。
5.活体钝化作用:
选长势均匀一致的3-5叶期珊西烟,将药剂与等体积的病毒汁液混合钝化30min后,摩擦接种,病毒浓度20mg/L,接种后即用流水冲洗,重复3次,设1‰吐温80水溶液对照。3d后数病斑数,计算结果。
抑制率(%)=[(对照枯斑数-处理枯斑数)/对照枯斑数]×100%
表1偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-1~Ia-10、Ib-1~Ib-3和Ib-5的抗烟草花叶病毒(TMV)活性测试结果:
表1(续)
从表1中可见偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-1~Ia-10、Ib-1~Ib-3和Ib-5表现出良好的抗烟草花叶病毒活性,其中化合物Ia-2、Ia-8、Ia-9和Ib-3的抗TMV活性非常好,均超过了病毒唑,具备极大的开发价值。
实施例4:抗菌活性测试,测定程序如下:
离体杀菌测试,菌体生长速率测定法(平皿法):
将一定量药剂溶解在适量丙酮内,然后用含有200mg/L乳化剂水溶液稀释至所需浓度,然后各吸取1mL药液注入培养皿内,再分别加入9mL培养基,摇匀后制成50mg/L的含药平板,以添加1mL灭菌水的平板做空白对照。用直径4mm的打孔器沿菌丝外缘切取菌盘,移至含药平板上。每处理重复三次。将培养皿放在24+1℃恒温培养箱内培养。48小时后调查各处理菌盘扩展直径,求平均值,与空白对照比较计算相对抑菌率。
相对抑制率(%)=[(对照组菌盘扩展平均直径-处理组菌盘扩展平均直径)/对照组菌盘扩展平均直径-菌饼直径]×100%
表2偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-3、Ia-6、Ia-7、Ib-2、Ib-4和Ib-6的抗植物病菌离体活性测试结果:
从表2中可以看出,偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-3、Ia-6、Ia-7、Ib-2、Ib-4和Ib-6表现出很好的、广谱的杀菌活性。对于油菜菌核,化合物Ia-3、Ia-6、Ia-7、Ib-2、Ib-4和Ib-6在50mg/L的浓度下抑制率均超过50.0%,其中化合物Ia-6,其抑制率得到68.2%。另外,化合物Ib-2、Ib-4和Ib-6在50mg/L的浓度下对小麦纹枯抑制率也都超过了50%。最后,化合物Ib-2对水稻纹枯抑制率达到65.7%
实施例4:杀粘虫、棉铃虫、玉米螟和蚊幼虫活性的测定,测定程序如下:
棉铃虫、粘虫和玉米螟的活性测试
实验方法:采用国际抗性行动委员会(IRAC)提出的浸叶法。药剂配置所需浓度(600mg/L)后,把直径约为5-6cm的叶片浸入药液中5-6秒,取出,放在吸水纸上晾干,放在指定的培养皿中,接入10头3龄幼虫,放入27+1℃的养虫室中观察3-4天后检查结果。
死亡率(%)=(死虫数/总虫数)×100%
校正死亡率(%)=[(处理死亡率-对照死亡率)/(1-对照死亡率)]×100%
蚊幼虫的活性测试
实验方法:尖音库蚊淡色亚种,室内饲养的正常群体。称取供试化合物约5mg于盘尼西林药瓶中,加5mL丙酮(或适宜溶剂),振荡溶解,即为1000mg/L母液。移取0.5mL母液,加入盛有89.9mL水的100mL烧杯中,选取10头4龄初蚊子幼虫,连同10mL饲养液一并倒入烧杯中,其药液的浓度即为5mg/L。放入标准处理室内,24小时检查结果。以含有0.5mL实验溶剂的水溶液为空白对照。
死亡率(%)=(死虫数/总虫数)×100%
校正死亡率(%)=[(处理死亡率-对照死亡率)/(1-对照死亡率)]×100%
表3偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-1~Ia-4、Ia-6~Ia-9、Ib-3和Ib-4的杀虫活性测试结果:
从表3中可以看出,偕二氟化螺-γ-内酰胺吲哚啉化合物Ia-1~Ia-4、Ia-6~Ia-9、Ib-3和Ib-4表现出了广谱的杀虫活性。其中化合物Ia-1、Ia-7和Ia-8在600mg/L浓度下对粘虫致死率都达到100%。进一步降低浓度到200mg/L,化合物Ia-1对粘虫仍表现出100%的杀虫活性。另外,化合物Ia-1在600mg/L浓度下对棉铃虫和玉米螟也都表现出100%的致死率。
Claims (6)
4.权利要求1中化合物Ia-1~Ia-10和Ib-1~Ib-6在防治烟草花叶病毒中的应用。
5.权利要求1中化合物Ia-1~Ia-10和Ib-1~Ib-6在防治植物病菌病中的应用,其特征在于所述植物病菌为黄瓜枯萎病菌,花生褐斑病菌,苹果轮纹病菌,小麦纹枯病菌,玉米小斑病菌,西瓜炭疽病菌,番茄早疫病菌,小麦赤霉病菌,马铃薯晚疫病菌,辣椒疫霉病菌,油菜菌核病菌,黄瓜灰霉病菌和水稻纹枯病菌。
6.权利要求1中化合物Ia-1~Ia-10和Ib-1~Ib-6在杀灭粘虫、棉铃虫、玉米螟和蚊幼虫方面的应用。
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