CN107266378B - 含有磺酰基结构三嗪酮衍生物及其制备方法和在杀虫、杀菌方面的应用 - Google Patents
含有磺酰基结构三嗪酮衍生物及其制备方法和在杀虫、杀菌方面的应用 Download PDFInfo
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- CN107266378B CN107266378B CN201610213921.5A CN201610213921A CN107266378B CN 107266378 B CN107266378 B CN 107266378B CN 201610213921 A CN201610213921 A CN 201610213921A CN 107266378 B CN107266378 B CN 107266378B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/10—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及含有磺酰基结构三嗪酮衍生物(I)及其制备方法和在杀虫、杀菌方面的应用,式中各基团的意义见说明书。本专利含有磺酰基结构三嗪酮衍生物表现出很好的杀虫活性,同时还具有杀菌活性。
Description
技术领域
本发明涉及含有磺酰基结构三嗪酮衍生物及其制备方法和在杀虫、杀菌方面的应用,属农药技术领域。
背景技术
吡蚜酮(Pymetrozine)是1988年由Ciba-Geigy公司发现的新型杂环杀虫剂,具有作用方式独特、高度的选择性、与传统杀虫剂无交互抗性、对环境安全等特点,它对刺吸式口器害虫特别是蚜虫具有独特的防治效果。因此,吡蚜酮问世以来,被广泛应用于农田作物和观赏植物防治蚜虫、粉虱和黑尾叶蝉的危害。但是由于吡蚜酮独特的作用方式,目前为止,此类杀虫剂商品化的品种仅有三种,分别是吡蚜酮、R-768和Pyrifluquinazon。通过总结文献,发现关于此类杀虫剂的研究主要集中在对三嗪酮环和吡啶环部分,而砜或亚砜作为医药和农药分子设计中常见的活性基团,文献中却没有报道。随着全世界对环境保护越来越重视,对于研发吡蚜酮类的高效、低毒、环境友好杀虫剂,已经是当前农业生产中的当务之急。
发明内容
本发明的目的是提供含有磺酰基结构三嗪酮衍生物及其制备方法和在杀虫、杀菌方面的应用。本专利的含有磺酰基结构三嗪酮衍生物表现出很好的杀虫活性,同时还具有杀菌活性。
本发明的含有磺酰基结构三嗪酮衍生物是具有如下通式(I)所示结构的化合物:
本发明所述的含有磺酰基结构三嗪酮衍生物(I)是具有如下两种通式(Ia,Ib)所示结构的化合物:
本发明的含有单磺酰基结构三嗪酮衍生物Ia-1--Ia-34可以按如下方法制备(路线一):氨基三嗪酮(II)与不同的磺酰氯反应得到化合物Ia;
路线一:
缚酸剂可以是碳酸钠、碳酸钾、碳酸铯,三乙胺,吡啶;溶剂可以是甲醇、乙醇、吡啶、N,N-二甲基甲酰胺、二甲基亚砜;反应温度在20℃至35℃下进行。
本发明的含有双磺酰基结构三嗪酮衍生物Ib-1--Ib-9可以按如下方法制备(路线二):氨基三嗪酮(II)与不同的磺酰氯反应得到化合物Ib;
路线二:
缚酸剂可以是碳酸钠、碳酸钾、碳酸铯,三乙胺,吡啶;溶剂可以是甲醇、乙醇、吡啶、N,N-二甲基甲酰胺、二甲基亚砜;反应温度在20℃至35℃下进行。
以上各通式中,
R1分别代表1-12碳烷基、3-6碳环烷基、苯基、苄基、苯乙基、苯丙基、苯丁基、1-10碳含氮杂环、1-10碳含氧杂环、1-10碳含硫杂环、取代的苯基(其中取代基可以是氢、羟基、卤素原子、氰基、硝基、酯基、氟、三氟甲基、三氟甲氧基、酰胺基、1-5碳烃基、1-6碳烷氧基、1-4碳烷基羰氧基、1-4碳烷氧基羰氧基;以及同时含有2-3个上述所述取代基)。
本发明所述的含有磺酰基结构三嗪酮衍生物(I)优选如下化合物:
2-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-10);
3-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-11);
4-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-12);
2,4,6-三甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-13);
4-甲氧基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-14);
4-叔丁基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-15);
4-溴-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-22)。
本发明通式(I)的化合物表现出很好的杀蚜虫活性,其中,化合物Ia-10,Ia-11,Ia-12,Ia-13,Ia-14,Ia-15在2.5mg/kg浓度下表现出25%,15%,30%,10%,35%,10%的杀虫活性,而吡蚜酮在相同浓度下没有杀虫活性。同时部分化合物对蚊幼虫表现出很好的活性,其中,在1mg/kg时,化合物Ia-19,Ia-23和Ia-26对蚊幼虫分别表现60%、30%、20%的活性,尤其是化合物Ia-22在0.5mg/kg浓度下对蚊幼虫表现出40%的杀虫活性。此外,所有化合物对棉铃虫、玉米螟及粘虫均表现出杀虫活性。
本发明通式(I)的化合物对以下13种病原菌表现出杀菌活性,13种病原菌分别是:番茄早疫、小麦赤霉、马铃薯晚疫、辣椒疫霉、油菜菌核、水稻纹枯、黄瓜枯萎、花生褐斑、苹果轮纹、小麦纹枯、玉米小斑、西瓜炭疽和水稻恶苗,尤其是化合物Ia-4,Ia-12和Ib-5在50mg/kg浓度下对多种病原菌均表现出良好的抑菌活性。
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:N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)甲基磺酰胺(Ia-1)的合成
在100mL单口瓶中,加入氨基三嗪酮(0.26g,2mmol),吡啶(20mL)搅拌溶解,加入甲基磺酰氯(0.24g,2.1mmol)室温搅拌过夜,TLC监测反应完毕。将反应液减压脱溶后,加入水,用二氯甲烷萃取,用饱和氯化钠溶液洗两次,硫酸钠干燥,之后用二氯甲烷/甲醇(150∶1-100∶1)进行硅胶柱层析得到白色固体0.32g,产率78%,熔点191-192℃。1H NMR(300MHz,DMSO-d6)δ10.00(s,1H,NH),9.83(s,1H,NH),4.15(s,2H,CH2),3.01(s,3H,CH3),1.86(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.4,146.0,53.9,41.1,20.1.ESI-HRMS(m/z):Calcd.for C5H11N4O3S[M+H]+207.0546;found 207.0548.
化合物Ia-2--Ia-34通过重复Ia-1的步骤完成。
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)乙基磺酰胺(Ia-2)
白色固体,产率76%,熔点206-208℃。1H NMR(300MHz,DMSO-d6)δ9.98(s,1H,NH),9.79(s,1H,NH),4.15(s,2H,CH2),3.10(q,J=7.2Hz,2H,CH2CH3),1.85(s,3H,CH3),1.27(t,J=7.2Hz,3H,CH2CH3);13C NMR(100MHz,DMSO-d6)δ151.2,145.7,53.8,46.7,19.8,7.9.ESI-HRMS(m/z):Calcd.for C6H13N4O3S[M+H]+221.0703;found 221.0701.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)正丙基磺酰胺(Ia-3)
白色固体,产率73%,熔点177-178℃。1H NMR(300MHz,DMSO-d6)δ9.98(s,1H,NH),9.81(s,1H,NH),4.15(s,2H,CH2),3.07(t,J=7.5Hz,2H,CH2CH2CH3),1.85(s,3H,CH3),1.73-1.80(m,2H,CH2CH2CH3),0.95(t,J=7.5Hz,3H,CH2CH2CH3);13C NMR(100MHz,DMSO-d6)δ151.2,145.6,53.8,19.8,16.7,12.8.ESI-HRMS(m/z):Calcd.for C7H15N4O3S[M+H]+235.0859;found 235.0856.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)正丁基磺酰胺(Ia-4)
白色固体,产率71%,熔点167-169℃。1H NMR(300MHz,DMSO-d6)δ9.99(s,1H,NH),9.81(s,1H,NH),4.15(s,2H,CH2),3.10(t,J=7.5Hz,2H,CH2CH2CH2CH3),1.85(s,3H,CH3),1.67-1.77(m,2H,CH2CH2CH2CH3),1.30-1.40(m,2H,CH2CH2CH2CH3),0.87(t,J=7.2Hz,3H,CH2CH2CH2CH3);13C NMR(100MHz,DMSO-d6)δ151.2,145.7,53.8,51.9,24.9,20.9,19.8,13.5.ESI-HRMS(m/z):Calcd.for C8H17N4O3S[M+H]+249.1016;found 249.1018.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)环丙基磺酰胺(Ia-5)
白色固体,产率64%,熔点146-148℃。1H NMR(400MHz,DMSO-d6)δ9.96(s,1H,NH),9.79(s,1H,NH),4.13(s,2H,CH2),2.57-2.63(m,1H,CH(CH2)2),1.86(s,3H,CH3),0.93-0.98(m,4H,CH(CH2)2);13C NMR(100MHz,DMSO-d6)δ151.3,145.6,53.3,29.9,19.8,5.4.ESI-HRMS(m/z):Calcd.for C7H13N4O3S[M+H]+233.0703;found 233.0703.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)环己基磺酰胺(Ia-6)
白色固体,产率43%,熔点166-168℃。1H NMR(400MHz,DMSO-d6)δ9.95(s,1H,NH),9.73(s,1H,NH),4.14(s,2H,CH2),2.99-3.06(m,1H),1.85(s,3H,CH3),1.76-1.79(m,2H),1.28-1.37(m,3H),1.07-1.25(m,5H);13C NMR(100MHz,DMSO-d6)δ151.3,145.6,59.8,53.9,25.8,24.8,24.7,19.8.ESI-HRMS(m/z):Calcd.for C10H18N4O3S[M+H]+275.1172;found275.1170.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯基甲基磺酰胺(Ia-7)
白色固体,产率78%,熔点189-190℃。1H NMR(300MHz,DMSO-d6)δ10.04(s,1H,NH),9.86(s,1H,NH),7.46-7.50(m,2H,Ar-H),7.33-7.40(m,3H,Ar-H),4.46(s,2H,CH2),4.13(s,2H,CH2),1.86(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.3,145.6,131.2,129.4,128.4,128.2,58.7,53.8,19.8.ESI-HRMS(m/z):Calcd.for C11H15N4O3S[M+H]+283.0859;found 283.0860.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)萘-1-磺酰胺(Ia-8)
白色固体,产率72%,熔点174-175℃。1H NMR(400MHz,CDCl3)δ8.71(d,J=8.4Hz,1H),8.27(d,J=7.2Hz,1H),8.11(d,J=8.4Hz,1H),7.93(d,J=8.0Hz,1H),7.68(t,J=7.2Hz,1H),7.60(t,J=8.0Hz,1H),7.54(t,J=7.6Hz,1H),4.24(s,2H,CH2),1.98(s,3H,CH3);13C NMR(100MHz,CDCl3)δ150.9,146.7,135.7,134.1,132.1,131.4,129.4,129.1,128.6,127.0,124.3,124.1,52.5,20.5.ESI-HRMS(m/z):Calcd.for C14H14N4O3S[M+H]+319.0859;found 319.0860.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-9)
白色固体,产率77%,熔点206-208℃。1H NMR(400MHz,DMSO-d6)δ10.23(s,1H,NH),9.81(s,1H,NH),7.80-7.82(m,2H,Ar-H),7.64-7.67(m,1H,Ar-H),7.54-7.58(m,2H,Ar-H),4.05(s,2H,CH2),1.83(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.7,145.6,138.8,133.2,128.9,127.7,52.7,19.9.ESI-HRMS(m/z):Calcd.for C10H13N4O3S[M+H]+269.0703;found269.0704.
2-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-10)
白色固体,产率59%,熔点240-241℃。1H NMR(400MHz,DMSO-d6)δ10.15(s,1H,NH),9.76(s,1H,NH),7.84(d,J=7.6Hz,1H,Ar-H),7.51(t,J=6.8Hz,1H,Ar-H),7.31-7.37(m,2H,Ar-H),4.03(s,2H,CH2),2.65(s,3H,CH3),1.81(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.9,145.6,138.4,136.9,133.2,132.2,129.6,125.8,52.7,20.2,19.8.ESI-HRMS(m/z):Calcd.for C11H15N4O3S[M+H]+283.0859;found 283.0859.
3-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-11)
白色固体,产率82%,熔点150-151℃。1H NMR(400MHz,DMSO-d6)δ10.16(s,1H,NH),9.79(s,1H,NH),7.60-7.63(m,2H,Ar-H),7.42-7.46(m,2H,Ar-H),4.03(s,2H,CH2),2.37(s,3H,CH3),1.82(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.7,145.6,138.8,138.5,133.8,128.7,127.8,124.9,52.7,20.8,19.8.ESI-HRMS(m/z):Calcd.for C11H15N4O3S[M+H]+283.0859;found 283.0858.
4-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-12)
白色固体,产率68%,熔点199-200℃。1H NMR(300MHz,DMSO-d6)δ10.10(s,1H,NH),9.79(s,1H,NH),7.69(d,J=8.4Hz,2H,Ar-H),7.36(d,J=8.1Hz,2H,Ar-H),4.05(s,2H,CH2),2.38(s,3H,CH3),1.83(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.7,145.7,143.5,135.9,129.4,127.8,52.7,21.1,19.9.ESI-HRMS(m/z):Calcd.for C11H15N4O3S[M+H]+283.0859;found 283.0863.
2,4,6-三甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-13)
白色固体,产率67%,熔点224-226℃。1H NMR(400MHz,DMSO-d6)δ9.91(s,1H,NH),9.80(s,1H,NH),6.99(s,2H,Ar-H),4.01(s,2H,CH2),2.54(s,3H,CH3),2.24(s,3H,CH3),1.82(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.2,145.9,142.2,139.8,133.0,131.4,52.3,22.7,20.5,19.9.ESI-HRMS(m/z):Calcd.for C13H19N4O3S[M+H]+311.1172;found311.1172.
4-甲氧基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-14)
白色固体,产率68%,熔点245-246℃。1H NMR(400MHz,DMSO-d6)δ9.99(s,1H,NH),9.78(s,1H,NH),7.73(d,J=8.8Hz,2H,Ar-H),7.06(d,J=8.8Hz,2H,Ar-H),4.04(s,2H,CH2),3.82(s,3H,OCH3),1.83(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ162.8,150.7,145.6,130.1,130.0,114.1,55.7,52.6,19.9.ESI-HRMS(m/z):Calcd.for C11H15N4O4S[M+H]+299.0809;found 299.0807.
4-叔丁基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-15)
白色固体,产率59%,熔点240-241℃。1H NMR(400MHz,DMSO-d6)δ10.08(s,1H,NH),9.85(s,1H,NH),7.74(d,J=8.0Hz,2H,Ar-H),7.59(d,J=8.0Hz,2H,Ar-H),3.98(s,2H,CH2),1.80(s,3H,CH3),1.29(s,9H,C(CH3)3);13C NMR(100MHz,DMSO-d6)δ156.2,150.9,145.6,136.2,127.6,125.8,52.6,34.9,30.8,19.8.ESI-HRMS(m/z):Calcd.for C14H21N4O3S[M+H]+325.1329;found 325.1329.
2-氟-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-16)
白色固体,产率73%,熔点206-208℃。1H NMR(400MHz,DMSO-d6)δ10.49(s,1H,NH),9.80(s,1H,NH),7.79(t,J=6.8Hz,1H,Ar-H),7.67-7.72(m,1H,Ar-H),7.39(t,J=9.6Hz,1H,Ar-H),7.33(t,J=7.6Hz,1H,Ar-H),4.13(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ159.2(d,J=254.0Hz),150.6,145.5,135.9(d,J=8.7Hz),130.2,127.1(d,J=14Hz),124.3(d,J=3.2Hz),117.0(d,J=20.9Hz),53.2,19.8.ESI-HRMS(m/z):Calcd.for C10H12FN4O3S[M+H]+287.0609;found 287.0609.
3-氟-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-17)
白色固体,产率81%,熔点180-181℃。1H NMR(400MHz,DMSO-d6)δ10.45(s,1H,NH),9.83(s,1H,NH),7.66(d,J=8.0Hz,1H,Ar-H),7.59-7.63(m,2H,Ar-H),7.53(t,J=8.4Hz,1H,Ar-H),4.11(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ161.5(d,J=246.1Hz),150.5,145.6,141.0(d,J=7.0Hz),131.1(d,J=7.7Hz),124.0(d,J=2.7Hz),120.3(d,J=20.9Hz),114.7(d,J=24.3Hz),53.0,19.8.ESI-HRMS(m/z):Calcd.forC10H12FN4O3S[M+H]+287.0609;found 287.0605.
4-氟-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-18)
白色固体,产率65%,熔点216-217℃。1H NMR(400MHz,DMSO-d6)δ10.29(s,1H,NH),9.81(s,1H,NH),7.85-7.89(m,2H,Ar-H),7.40(t,J=8.8Hz,2H,Ar-H),4.11(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ164.7(d,J=249.9Hz),150.6,145.7,135.1(d,J=2.7Hz),130.9(d,J=9.7Hz),116.0(d,J=22.6Hz),52.9,19.9.ESI-HRMS(m/z):Calcd.for C10H12FN4O3S[M+H]+287.0609;found 287.0606.
2,4-二氟-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-19)
白色固体,产率77%,熔点211-213℃。1H NMR(400MHz,DMSO-d6)δ10.59(s,1H,NH),9.82(s,1H,NH),7.81-7.87(m,1H,Ar-H),7.50(t,J=10.0Hz,1H,Ar-H),7.21(t,J=8.4Hz,1H,Ar-H),4.14(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ165.5(dd,J=12.5,12.5Hz),160.2(dd,J=14.1,14.2Hz),150.6,145.5,132.4(d,J=10.8Hz),123.9(dd,J=4.4,4.7Hz),111.7(dd,J=4.1,3.6Hz),105.7(t,J=25.7Hz),53.3,19.8.ESI-HRMS(m/z):Calcd.for C10H11F2N4O3S[M+H]+305.0514;found 305.0511.
2,3,4-三氟-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-20)
白色固体,产率71%,熔点214-216℃。1H NMR(400MHz,DMSO-d6)δ10.88(s,1H,NH),9.89(s,1H,NH),7.66-7.71(m,1H,Ar-H),7.45-7.51(m,1H,Ar-H),4.18(s,2H,CH2),1.87(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ153.6(dd,J=10.6,9.5Hz),150.7,148.9(dd,J=8.5,8.1Hz),145.7,140.8(t,J=15.6Hz),138.3(t,J=15.3Hz),125.3(m),112.6(dd,J=2.6,2.6Hz),53.4,19.8.ESI-HRMS(m/z):Calcd.for C10H10F3N4O3S[M+H]+323.0420;found323.0414.
4-氯-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-21)
白色固体,产率74%,熔点214-215℃。1H NMR(400MHz,DMSO-d6)δ10.38(s,1H,NH),9.82(s,1H,NH),7.80(d,J=8.4Hz,2H,Ar-H),7.63(d,J=8.4Hz,2H,Ar-H),4.12(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.5,145.6,138.1,137.7,129.7,129.0,53.0,19.9.ESI-HRMS(m/z):Calcd.for C10H12ClN4O3S[M+H]+303.0313;found303.0316.
4-溴-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-22)
白色固体,产率75%,熔点230-232℃。1H NMR(400MHz,DMSO-d6)δ10.40(s,1H,NH),9.84(s,1H,NH),7.79(d,J=8.4Hz,2H,Ar-H),7.73(d,J=8.4Hz,2H,Ar-H),4.13(s,2H,CH2),1.86(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.6,145.7,138.1,132.0,129.8,127.2,53.0,19.9.ESI-HRMS(m/z):Calcd.for C10H12BrN4O3S[M+H]+346.9808;found346.9804.
4-碘-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-23)
白色固体,产率81%,熔点241-243℃。1H NMR(400MHz,DMSO-d6)δ10.36(s,1H,NH),9.84(s,1H,NH),7.95(d,J=8.4Hz,2H,Ar-H),7.56(d,J=8.4Hz,2H,Ar-H),4.11(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.5,145.6,138.5,137.7,129.4,101.5,52.9,19.8.ESI-HRMS(m/z):Calcd.for C10H12IN4O3S[M+H]+394.9669;found394.9666.
N-(4-(N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)氨磺酰)苯基)乙酰胺(Ia-24)
白色固体,产率65%,熔点255-257℃。1H NMR(300MHz,DMSO-d6)δ10.32(s,1H,NH),10.02(s,1H,NH),9.77(s,1H,NH),7.72(brs,4H),4.05(s,2H,CH2),2.08(s,3H,CH3),1.83(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ169.1,150.7,145.6,143.5,132.0,129.0,118.2,52.6,24.2,19.9.ESI-HRMS(m/z):Calcd.for C12H16N5O4S[M+H]+326.0918;found326.0921.
4-氰基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)苯磺酰胺(Ia-25)
白色固体,产率65%,熔点256-257℃。1H NMR(400MHz,DMSO-d6)δ10.66(s,1H,NH),9.85(s,1H,NH),8.06(d,J=8.0Hz,2H,Ar-H),7.97(d,J=8.0Hz,2H,Ar-H),4.15(s,2H,CH2),1.86(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.5,145.7,143.2,132.9,128.5,117.7,115.4,53.2,19.8.ESI-HRMS(m/z):Calcd.for C11H12IN5O3S[M+H]+294.0655;found294.0659.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-4-(三氟甲基)-苯磺酰胺(Ia-26)
白色固体,产率74%,熔点243-244℃。1H NMR(400MHz,DMSO-d6)δ10.59(s,1H,NH),9.86(s,1H,NH),8.02(d,J=8.4Hz,2H,Ar-H),7.95(d,J=8.4Hz,2H,Ar-H),4.15(s,2H,CH2),1.86(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.6,145.7,143.0,132.7(q,J=32Hz),128.8,126.0(q,J=4.3Hz),123.6(q,J=271.2Hz),53.2,19.9.ESI-HRMS(m/z):Calcd.forC11H12F3N4O3S[M+H]+337.0577;found 337.0577.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-4-(三氟甲氧基)-苯磺酰胺(Ia-27)
白色固体,产率70%,熔点215-216℃。1H NMR(400MHz,DMSO-d6)δ10.43(s,1H,NH),9.85(s,1H,NH),7.94(d,J=8.4Hz,2H,Ar-H),7.55(d,J=8.4Hz,2H,Ar-H),4.12(s,2H,CH2),1.85(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.4,150.6,145.7,137.9,130.5,120.9,119.9(q,J=257.7Hz),53.1,19.8.ESI-HRMS(m/z):Calcd.for C11H12F3N4O4S[M+H]+353.0526;found 353.0525.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)噻吩-2-磺酰胺(Ia-28)
白色固体,产率69%,熔点191-193℃。1H NMR(400MHz,DMSO-d6)δ10.33(s,1H,NH),9.87(s,1H,NH),7.99(d,J=5.2Hz,1H,Ar-H),7.63(d,J=3.6Hz,1H,Ar-H),7.17(t,J=4.0Hz,1H,Ar-H),4.04(s,2H,CH2),1.84(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.8,145.7,138.7,134.5,133.7,127.7,52.6,20.0.ESI-HRMS(m/z):Calcd.for C8H11N4O3S2[M+H]+275.0267;found 275.0262.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)噻吩-3-磺酰胺(Ia-29)
白色固体,产率42%,熔点214-215℃。1H NMR(400MHz,DMSO-d6)δ10.14(s,1H,NH),9.85(s,1H,NH),8.25(s,1H,Het-H),7.71(d,J=2.4Hz,1H,Het-H),7.31(d,J=4.8Hz,1H,Het-H),4.03(s,2H,CH2),1.83(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.8,145.6,141.0,138.4,132.7,128.5,126.1,52.6,19.9.ESI-HRMS(m/z):Calcd.for C8H10N4O3S2[M+H]+275.0267;found 275.0272.
3,5-二甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)异恶唑-4-磺酰胺(Ia-30)
无色油状液体,产率35%。1H NMR(400MHz,DMSO-d6)δ10.55(s,1H,NH),9.96(s,1H,NH),4.17(s,2H,CH2),2.53(s,3H,CH3),2.32(s,3H,CH3),1.88(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ173.8,157.9,150.7,146.1,114.7,52.9,19.9,12.2,10.5.ESI-HRMS(m/z):Calcd.for C9H13N5O4S[M+H]+288.0761;found 288.0759.
1-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-1H-咪唑-4-磺酰胺(Ia-31)
黄色固体,产率43%,熔点188-190℃。1H NMR(400MHz,DMSO-d6)δ9.85(s,1H,NH),9.84(s,1H,NH),7.88(s,1H,Het-H),7.85(s,1H,Het-H),3.98(s,2H,CH2),3.75(s,3H,CH3),1.84(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.2,145.3,139.8,137.9,125.9,52.1,33.5,19.7.ESI-HRMS(m/z):Calcd.for C8H12N6O3S[M+H]+273.0764;found 273.0766.
1,2-二甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-1H-咪唑-4-磺酰胺(Ia-32)
黄色固体,产率47%,熔点180-182℃。1H NMR(400MHz,DMSO-d6)δ10.55(s,1H,NH),9.95(s,1H,NH),8.14(s,1H,Het-H),4.08(s,2H,CH2),3.71(s,3H,CH3),3.16(s,3H,CH3),1.84(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.1,147.7,145.7,127.0,120.4,52.9,34.0,19.9,11.4.ESI-HRMS(m/z):Calcd.for C9H14N6O3S[M+H]+287.0921;found 287.0927.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-2,3-苯并二氢呋喃-5-磺酰胺(Ia-33)
白色固体,产率43%,熔点263-264℃。1H NMR(400MHz,DMSO-d6)δ9.95(s,1H,NH),9.80(s,1H,NH),7.65(s,1H,Ar-H),7.56(d,J=8.4Hz,1H,Ar-H),6.88(d,J=8.4Hz,1H,Ar-H),4.64(t,J=8.4Hz,2H),4.04(s,2H,CH2),3.22(t,J=8.8Hz,2H),1.83(s,3H,CH3);13CNMR(100MHz,DMSO-d6)δ163.6,150.8,145.6,130.0,129.4,128.3,125.2,108.8,72.2,52.6,28.4,19.9.ESI-HRMS(m/z):Calcd.for C12H14N4O4S[M+H]+311.0809;found331.0812.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-2,3-二氢苯并[b][1,4]二恶英-6-磺酰胺(Ia-34)
白色固体,产率36%,熔点213-214℃。1H NMR(400MHz,DMSO-d6)δ10.06(s,1H,NH),9.83(s,1H,NH),7.27(q,J=2.0Hz,1H,Ar-H),7.25(d,J=2.0Hz,1H,Ar-H),7.00(d,J=8.4Hz,1H,Ar-H),4.32(d,J=5.2Hz,2H,OCH2),4.29(d,J=5.2Hz,2H,OCH2),4.03(s,2H,CH2),1.83(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ150.7,147.5,145.6,143.0,131.0,121.5,117.3,116.9,64.5,64.0,52.6,19.9.ESI-HRMS(m/z):Calcd.for C12H14N4O5S[M+H]+327.0758;found 327.0760.
实施例2:化合物Ib-1--Ib-9的合成
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-N-(甲磺酰)甲基磺酰胺(Ib-1)的合成
在100mL单口瓶中,加入氨基三嗪酮(0.26g,2mmol),吡啶(30mL)搅拌溶解,加入甲基磺酰氯(0.55g,4.8mmol)室温搅拌过夜,TLC监测反应完毕。将反应液减压脱溶后,加入水,用二氯甲烷萃取,用饱和氯化钠溶液洗两次,硫酸钠干燥,之后用二氯甲烷/甲醇(150∶1-130∶1)进行硅胶柱层析得到白色固体0.48g,产率85%,熔点220-222℃。1H NMR(400MHz,DMSO-d6)δ10.34(s,1H,NH),4.39(s,2H,CH2),3.56(s,6H,CH3),1.89(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ149.9,146.0,54.3,44.8,19.7.ESI-HRMS(m/z):Calcd.for C6H13N4O5S2[M+H]+285.0322;found 285.0323.
化合物Ib-2--Ib-9通过重复Ib-1的步骤完成。
N-(乙基磺酰)-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-乙基磺酰胺(Ib-2)
白色固体,产率74%,熔点183-184℃。1H NMR(300MHz,DMSO-d6)δ10.33(s,1H,NH),4.31(s,2H,CH2),3.64(q,J=7.5Hz,4H,CH2CH3),1.89(s,3H,CH3),1.33(t,J=9.6Hz,6H,CH2CH3);13C NMR(100MHz,DMSO-d6)δ150.1,146.1,54.0,51.3,19.8,7.6.ESI-HRMS(m/z):Calcd.for C8H17N4O5S2[M+H]+313.0635;found 313.0633.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-N-(正丙基磺酰)丙烷-1-磺酰胺(Ib-3)
白色固体,产率84%,熔点177-178℃。1H NMR(300MHz,DMSO-d6)δ10.32(s,1H,NH),4.33(s,2H,CH2),3.54-3.69(m 4H,CH2CH2CH3),1.89(s,3H,CH3),1.77-1.86(m,4H,CH2CH2CH3),1.00(t,J=7.5Hz,6H,CH2CH2CH3);13C NMR(100MHz,DMSO-d6)δ150.1,146.0,58.2,54.1,19.8,16.5,12.5.ESI-HRMS(m/z):Calcd.for C10H21N4O5S2[M+H]+341.0948;found 341.0946.
N-(正丁基磺酰)-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)丁烷-1-磺酰胺(Ib-4)
白色固体,产率85%,熔点157-158℃。1H NMR(300MHz,DMSO-d6)δ10.33(s,1H,NH),4.33(s,2H,CH2),3.56-3.72(m,4H,CH2CH2CH2H3),1.90(s,3H,CH3),1.71-1.83(m,4H,CH2CH2CH2H3),1.38-1.46(m,4H,CH2CH2CH2H3),0.9(t,J=7.2Hz,6H,CH2CH2CH2CH3);13C NMR(100MHz,DMSO-d6)δ150.1,146.0,56.4,54.1,24.5,20.7,19.8,13.3.ESI-HRMS(m/z):Calcd.for C12H25N4O5S2[M+H]+369.1261;found 369.1263.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-N-(苯磺酰)苯磺酰胺(Ib-5)
白色固体,产率83%,熔点227-228℃。1H NMR(400MHz,DMSO-d6)δ10.25(s,1H,NH),7.90(d,J=7.5Hz,4H,Ar-H),7.83(t,J=7.5Hz,2H,Ar-H),7.68(t,J=7.8Hz,4H,Ar-H),4.22(s,2H,CH2),1.87(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ149.5,146.3,137.6,135.1,129.5,128.6,53.1,19.9.ESI-HRMS(m/z):Calcd.for C16H17N4O5S2[M+H]+409.0635;found409.0639.
4-甲基-N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-N-对甲基苯磺酰胺(Ib-6)
淡黄色固体,产率81%,熔点219-220℃。1H NMR(300MHz,DMSO-d6)δ10.22(s,1H,NH),7.77(d,J=8.1Hz,4H,Ar-H),7.47(d,J=8.1Hz,4H,Ar-H),4.20(s,2H,CH2),2.44(s,6H,CH3),1.87(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ149.5,146.3,145.9,134.8,129.8,128.7,53.0,21.2,19.9.ESI-HRMS(m/z):Calcd.for C18H21N4O5S2[M+H]+437.0948;found437.0947.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-4-硝基-N-(4-硝基苯磺酰)苯磺酰胺(Ib-7)
淡黄色固体,产率79%,熔点239-240℃。1H NMR(300MHz,DMSO-d6)δ10.37(s,1H,NH),8.49(d,J=9.0Hz,4H,Ar-H),8.20(d,J=9.0Hz,4H,Ar-H),4.41(s,2H,CH2),1.93(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ151.1,149.1,146.4,142.3,130.6,124.8,53.6,19.9.ESI-HRMS(m/z):Calcd.for C16H15N6O9S2[M+H]+499.0336;found 499.0329.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-4-乙酰氨基-N-(4-乙酰氨基苯磺酰)苯磺酰胺(Ib-8)
淡黄色固体,产率78%,熔点188-190℃。1H NMR(300MHz,DMSO-d6)δ10.51(s,2H,NH),10.18(s,1H,NH),7.80(s,8H,Ar-H),4.20(s,2H,CH2),2.12(s,6H,CH3),1.87(s,3H,CH3);13C NMR(100MHz,DMSO-d6)δ169.4,149.5,146.2,144.9,130.6,130.1,118.3,53.1,24.3,19.9.ESI-HRMS(m/z):Calcd.for C20H23N6O7S2[M+H]+540.1330;found 540.1332.
N-(6-甲基-3-酮-2,3-二氢-1,2,4-三嗪-4(5H)-基)-N-(吡啶-3-磺酰基)吡啶-3-磺酰胺(Ib-9)
白色固体,产率42%,熔点213-214℃。1H NMR(400MHz,CDCl3)δ9.05(s,2H,Py-H),8.90(d,J=4Hz,2H,Py-H),8.18-8.21(m,2H,Py-H),7.51(s,1H,NH),7.49(d,J=3Hz,2H,Py-H),4.47(s,2H,CH23),2.03(s,3H,CH3);13C NMR(100MHz,CDCl3)δ155.2,149.9,149.4,146.5,137.1,134.5,123.8,54.8,20.4.ESI-HRMS(m/z):Calcd.for C14H14N6O5S2[M+H]+411.0540;found 411.0534.
实施例3:杀蚜虫的测定,测定程序如下:
蚜虫的活性测试
杀蚜虫活性测定步骤如下:试虫为豆蚜(Aphis laburni Kaltenbach),实验室蚕豆叶饲养的正常群体。称取药品,加1mL DMF溶解,加两滴吐温-20乳化剂,加入一定量的蒸馏水,搅拌均匀,配成所需浓度的药液。将带蚜虫(约60只)蚕豆叶片浸入药剂中5秒钟,拿出轻轻甩干,用滤纸吸干多余药剂,然后将蚕豆枝插入吸水海绵中,并用玻璃罩罩住枝条,用纱布封口,96小时检查结果,每个化合物重复3次。对照只向蒸馏水中加入乳化剂和溶剂,搅拌均匀。
表1 吡蚜酮及磺酰基结构三嗪酮衍生物(I)的杀蚜虫活性测试结果:
a-未测.
从表1中可见,在10mg/kg浓度时,部分磺酰基结构三嗪酮衍生物表现出很好的100%杀蚜虫活性。在5mg/kg浓度时,Ia-1,Ia-9,Ia-16,Ia-17,Ia-18,Ia-19,Ia-21,Ia-22,Ia-23,Ia-25,Ia-26,Ia-27,Ib-1表现出和吡蚜酮相当的活性。尤其是化合物Ia-10,Ia-11,Ia-12,Ia-13,Ia-14,Ia-15在2.5mg/kg浓度时仍表现出25%,15%,30%,10%,35%,10%的杀虫活性,而吡蚜酮在相同浓度下没有杀虫活性。
实施例4:杀蚊幼虫活性的测定,测定程序如下:
蚊幼虫的活性测试
蚊幼虫的实验方法: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1000ppm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5ppm。放入标准处理室内,24h检查结果。以含有0.5mL试验溶剂的水溶液为空白对照。
表2 吡蚜酮及磺酰基结构三嗪酮衍生物(I)的杀蚊幼虫活性测试结果:
a-未测.
从表2中可见,大多数磺酰基结构三嗪酮衍生物对蚊幼虫均表现出杀虫活性。尤其是化合物Ia-19,Ia-22,Ia-23和Ia-26对蚊幼虫表现出较高的活性。在1mg/kg浓度下,化合物Ia-19,Ia-23和Ia-26对蚊幼虫分别表现出60%、30%、20%的杀虫活性。尤其是化合物Ia-22在0.5mg/kg浓度下对蚊幼虫表现出40%的杀虫活性。
实施例5:杀棉铃虫、玉米螟、粘虫活性的测定,测定程序如下:
棉铃虫的活性测试
棉铃虫的实验方法:饲料混药法,从配置好的溶液中移取3mL加入约27g的刚配置好的饲料中,从而得到稀释十倍的所需浓度。药剂混匀后均匀地倒入干净的24孔板中,晾凉后接入24头三龄棉铃虫,观察3-4天后检查结果。
玉米螟的活性测试
玉米螟的试验方法:浸叶法,配置后所需浓度后,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。
粘虫的活性测试
粘虫的实验方法:浸叶法,配置后所需浓度后,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。
表3 吡蚜酮及磺酰基结构三嗪酮结构衍生物(I)的杀棉铃虫、玉米螟、粘虫活性测试结果
a200mg/kg下死亡率,
从表3中可见,大多数磺酰基结构三嗪酮衍生物对棉铃虫、玉米螟和粘虫均表现出杀虫活性。尤其是化合物Ia-22,在200mg/kg时,对棉铃虫、玉米螟和粘虫分别表现出80%、65%和70%的杀虫活性。
实施例6:杀真菌活性的测定,测定程序如下:
以番茄早疫病菌为例,可以换成其他菌
离体测试方法:将番茄早疫病菌接到PDA培养基上培养7天,用打孔器在菌落边缘制取直径4cm的菌碟接种到含有50μg/ml和不含药剂的PDA培养基上培养4天,量取菌落直径,与对照比较计算出药剂的抑制百分率。
表4 含有磺酰基结构三嗪酮衍衍生物(I)的杀菌活性测试结果:
从表4中可见,大多数含有磺酰基结构三嗪酮衍生物对13种病原菌表现出较好的杀菌活性,尤其是化合物Ia-4,Ia-12和Ib-5在50mg/kg浓度下对多种病原菌均表现出良好的抑菌活性。
Claims (5)
2.权利要求1所述的含有磺酰基结构三嗪酮衍生物杀植物害虫方面的应用。
3.根据权利要求2的应用,其中植物害虫是蚜虫、蚊幼虫、棉铃虫、玉米螟和粘虫。
4.权利要求1所述的含有磺酰基结构三嗪酮衍生物杀植物病菌方面的应用。
5.根据权利要求4的应用,其中植物病菌是番茄早疫、小麦赤霉、马铃薯晚疫、辣椒疫霉、油菜菌核、黄瓜灰霉、水稻纹枯、黄瓜枯萎、花生褐斑、苹果轮纹、小麦纹枯、玉米小斑、西瓜炭疽和水稻恶苗。
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