CN1117055C - 农药化合物、组合物及其制备方法 - Google Patents
农药化合物、组合物及其制备方法 Download PDFInfo
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- CN1117055C CN1117055C CN96199336A CN96199336A CN1117055C CN 1117055 C CN1117055 C CN 1117055C CN 96199336 A CN96199336 A CN 96199336A CN 96199336 A CN96199336 A CN 96199336A CN 1117055 C CN1117055 C CN 1117055C
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- 230000008569 process Effects 0.000 title description 2
- -1 methylenedioxy- Chemical class 0.000 claims abstract description 54
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
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- 230000000694 effects Effects 0.000 claims description 43
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- 238000006243 chemical reaction Methods 0.000 claims description 25
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
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- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 5
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- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical compound CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 claims description 5
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- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 claims description 4
- BQAMTBVLQALJGB-UHFFFAOYSA-N CC(C1=CC=CC2=CC=CC=C12)C#CC Chemical compound CC(C1=CC=CC2=CC=CC=C12)C#CC BQAMTBVLQALJGB-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005950 Oxamyl Substances 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
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- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 4
- QBSJMKIUCUGGNG-UHFFFAOYSA-N isoprocarb Chemical compound CNC(=O)OC1=CC=CC=C1C(C)C QBSJMKIUCUGGNG-UHFFFAOYSA-N 0.000 claims description 4
- KZAUOCCYDRDERY-UHFFFAOYSA-N oxamyl Chemical compound CNC(=O)ON=C(SC)C(=O)N(C)C KZAUOCCYDRDERY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- SMKRKQBMYOFFMU-UHFFFAOYSA-N prallethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OC1C(C)=C(CC#C)C(=O)C1 SMKRKQBMYOFFMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002728 pyrethroid Substances 0.000 claims description 4
- CXBMCYHAMVGWJQ-CABCVRRESA-N (1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)methyl (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-CABCVRRESA-N 0.000 claims description 3
- XIIHIHJIEDXAJC-UHFFFAOYSA-N 1-nitro-4,5-dihydroimidazole Chemical compound [O-][N+](=O)N1CCN=C1 XIIHIHJIEDXAJC-UHFFFAOYSA-N 0.000 claims description 3
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 claims description 3
- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical compound OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 claims description 3
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- 241001597008 Nomeidae Species 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
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- 150000003869 acetamides Chemical class 0.000 claims description 3
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- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 3
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- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- FOANIXZHAMJWOI-UHFFFAOYSA-N bromopropylate Chemical compound C=1C=C(Br)C=CC=1C(O)(C(=O)OC(C)C)C1=CC=C(Br)C=C1 FOANIXZHAMJWOI-UHFFFAOYSA-N 0.000 claims description 3
- KVSLPQXJQYNHIK-UHFFFAOYSA-N c1ccc2ncncc2c1.Cc1ccc(cc1)S(O)(=O)=O.Cc1ccc(cc1)S(O)(=O)=O Chemical compound c1ccc2ncncc2c1.Cc1ccc(cc1)S(O)(=O)=O.Cc1ccc(cc1)S(O)(=O)=O KVSLPQXJQYNHIK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 claims description 3
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 3
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- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 3
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- 150000003217 pyrazoles Chemical class 0.000 claims description 3
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- IAKOZHOLGAGEJT-UHFFFAOYSA-N 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)-Ethane Chemical compound C1=CC(OC)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(OC)C=C1 IAKOZHOLGAGEJT-UHFFFAOYSA-N 0.000 claims description 2
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- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 claims description 2
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- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 claims description 2
- FRCCEHPWNOQAEU-UHFFFAOYSA-N heptachlor Chemical compound ClC1=C(Cl)C2(Cl)C3C=CC(Cl)C3C1(Cl)C2(Cl)Cl FRCCEHPWNOQAEU-UHFFFAOYSA-N 0.000 claims description 2
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- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 claims description 2
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- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000361 pesticidal effect Effects 0.000 claims description 2
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Classifications
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- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
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- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
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Abstract
本发明涉及通式(I)化合物、其光学活性异构体及其盐,其中Ar=脂环、芳族或含有一或多个杂原子的杂环部分,任选由一或多个烷氧基、亚甲二氧基、烷基、卤素、卤代烷基或硝基基团取代,和/或与苯环稠合;R1、R2=独立的氢、烷基、链烯基、卤代烷基、苯基、取代的苯基、环烷基,R3、R4=独立的氢、烷基、链烯基、卤代烷基、苯基、取代的苯基、环烷基,或R3、R4一起是=O;Y=C;PO,或YR3R4一起形成基团(a);X=-O-;-NR10-;R9=氢、烷基、苯基、取代的苯基;R10=氢、烷基;R5、R6、R7、R8独立地是氢、烷基、链烯基、卤代烷基,或Ar-(CR1R2)m-(YR3R4)n-X-一起形成羧酰亚胺基团;E=氢、卤素、甲基;m=0、1、2;n=0、1;o=0、1、2;p=0、1、2;其条件是,桥链-(CR1R2)m-(CR3R4)n-X-(CR5R6)o-(CR7R8)p的原子或基团之总和是3,且-C≡C-E链与该桥的原子形成由6个原子组成的、优选以甲基基团结尾的直链,另一条件是,如果Ar是萘基基团,则Y是C原子,X是O原子,R3和R4一起不可以是=O。本发明的通式(I)化合物可以用作农药,优选杀节肢动物剂组合物的活性成分,以及作为其它杀节肢动物剂活性成分的增效剂。
Description
本发明涉及通式I的炔基农药化合物、含有通式I活性成分的农药组合物,还涉及通式I的农药增效剂和带有已知农药活性成分的增效农药组合物,以及涉及其制备方法。
通式I中,
Ar-(CR1R2)m-(YR3R4)n-X-(CR5R6)o-(CR7R8)p-C≡C-E
I.
取代基具有下列含意:Ar=脂环-、芳族-、或含有一或多个杂原子的杂环部分,任选由一或多个烷氧基、亚甲二氧基、烷基、卤素、卤代烷基或硝基基团取代,和/或与苯环稠合,R1、R2=独立的氢、烷基、链烯基、卤代烷基、苯基、取代的苯基、环烷基,R3、R4=独立的氢、烷基、链烯基、卤代烷基、苯基、取代的苯基、环烷基,或R3、R4一起是=O;Y=C、=PO,或YR3R4一起形成基团-C(R9)=N-;X=-O-;-NR10-;R9=氢、烷基、苯基、取代的苯基;R10=氢、烷基;R5、R6、R7、R8独立地是氢、烷基、链烯基、卤代烷基,或Ar-(CR1R2)m-(YR3R4)n-X-一起形成羧酰亚胺基团;E=氢、卤素、甲基;m=0、1、2;n=0、1;o=0、1、2;p=0、1、2;其条件是,桥-(CR1R2)m-(CR3R4)n-X-(CR5R6)o-(CR7R8)p的原子或基团之总和是3,且-C≡C-E链与该桥的原子形成由6个原子组成的直链,最好以甲基基团结尾。另一条件是,如果Ar是萘基基团,则Y是C-原子,X是O原子,R3和R4一起不可以是=O。
本发明还包括通式I化合物的盐及其光学活性异构体。
通式I化合物中的范围更窄的组由通式IA、IB、IC、ID、IE、IF,其盐和光学活性异构体代表,Ar-(CR1R2)m-(CR3R4)n-O-(CR5R6)o-(CR7R8)p-C≡C-E
其中取代基的含意与上面定义的相同。
优选的代表性通式I化合物是
1-萘基-甲基2-丁炔基醚,
2-丙炔基-1,3-苯并间二氧杂环戊烯(benzodioxol)-5-羧酸酯,
1-[(2-丁炔氧基)-乙基]-3,4-二甲氧基苯,
2,6-二氯-1-(2-丁炔氧基甲基)苯,
1-[1-(2-丁炔氧基)丙基]萘,
R-(+)-2-[1-(2-丁炔氧基)乙基]萘,
5-[(丁-2-炔基氧基)甲基]-1,3-苯并间二氧杂环戊烯,
5-[2-甲基-1-(2-丁炔氧基)丙基]-1,3-苯并间二氧杂环戊烯,
5-[(丁-2-炔基氧基)苯基甲基]-1,3-苯并间二氧杂环戊烯,
2-[(2-丁炔氧基)甲基]-1,4-苯并二噁烷,
2,3-二氢-2,2-二甲基-7-(3-戊炔氧基)苯并呋喃。
在术语Ar中,芳族基团优选是苯基或萘基基团。Ar为杂环部分时可以含有一或多个O、S、N杂原子,它优选代表苯并间二氧杂环戊烯-、苯并二噁烷-、2-苯并呋喃-、7-苯并呋喃-部分。
脂环基团可以优选与苯环稠合,因此例如可以代表1,2-二氢化茚基团或1,2,3,4-四氢萘基基团。羧酰亚胺基团可以优选代表邻苯二甲酰亚胺部分。
芳族、杂环族和脂环族Ar基团任选由C1-4烷氧基、亚甲二氧基、C1-4烷基、卤素、C1-4卤代烷基或硝基基团取代。
增效剂是无毒或只稍微有点毒性,但与农药,优选与杀节肢动物剂一起时,可以显著增加农药的效力。这些物质原则上可以以几种方式作用,但它们是通过阻断活性物质的代谢来发挥其决定性的作用。代谢可经氧化、水解、共轭和吸附反应来进行,且也可以通过其变异型反应来进行。目前,对在受体水平作用的增效剂尚无明确例证,且它们在实践上也未起重要的作用。
SR50值越偏离1,则增效效力越高。在杀节肢动物制剂中使用增效剂是非常有吸引力的,因为增效剂提供产生新制剂的可能性,而此新制剂可以包含本领域实际上所有代表性化合物。与现有技术的相比,这些新制剂有希望是低成本、低毒、更有选择性、环境危害更小、抑制抗性发生以及对已经产生抗性种类也有活性。
自发现增效剂和揭示其作用方式之后,从60年代中期开始直至70年代后期,作了广泛的研究和开发工作,以开发出新的增效剂。然而,这些研究只产生了少数几个获得应用的分子(目前,登记的杀虫剂增效剂数目少于10个)。这些化合物在抗性研究上有基础科学重要性(K.F.Raffa和T.M.Priester,J.Agric.Entomol.[农业昆虫学杂志],2(1),27-45,(1985))。然而在[Pesticide Manual]《农药手册》中只有2-3个分子作为产品列出,且只有二种物质(PBO,MGK264)实际上市。大田应用受到几种因素的限制:很难找到一种可以有选择性且安全地使用的化学工具,较之活性成分的费用/效益比有竞争力的费用/效益比。为了经济地施用,增效剂必须是高效的,且它必须在低剂量下作用(不超过活性成分的原有剂量)。
就其化学结构而言,目前已知的杀节肢动物剂的增效化合物可以分成下列几组:###1,3-亚甲二氧基苯基(MDP)衍生物###O-2-丙炔基和丙炔基同系物及其衍生物(醚类、肟醚类、酯类)###N-烷基衍生物###磷酯类###其它衍生物例如硫氰酸酯类、多卤代醚等。
这些化合物还可以根据其作用靶体分成几组[K.F.Raifa和T.M.Priester,J.Agric.Entomol.[农业昆虫学杂志],2(1),27-45,(1985)],但是这样分组,只是理论上的,并不准确,主要是因为实际代谢过程尚不完全清楚。多数化合物的代谢是顺序进行的,但也可以同时进行,且可能沿几种机理,因此,这样分组是不清晰的,虽然,我们认为阶式降解的第一步是关键步骤。
对于多数杀节肢动物剂的代谢而言,首先起作用是的加氧酶(Oxigenaze)***。文献中称,这组化合物基本上是通过阻断微粒体氧化***的细胞色素P-450酶来发挥其活性[John E.Cassida,J.Agr.Food Chem.[农业食品化学杂志],18(5),753-772,(1970),R.M.Sacher,R.L.Metcalf和T.R.Fukuto:J.Agr.Food Chem.[农业食品化学杂志],16(5),779-786,(1968)]。结构上类似的一组酶称作同工酶,这些酶构成有机体解毒***的主要部分[Ortiz deMontellano,P.R.编,Cytochrome P-450:Structure Mech.and Biochem[细胞色素P-450:结构机理与生物化学],Plenum,纽约(1986)]。它们经底物的单加氧作用来解毒,产生多个极性产物,可能在进一步的转化后,这些产物可以被有机体***。此***通过相同的方式降解非常不同的结构体。因此,它们也被称作多功能加氧酶(MFO)和多底物单加氧酶(PSMO)。
以此为基础,人们可以预料到,酶的表面对增效剂也是非特异性的。与此完全相反,我们却发现,这些化合物或许可以最优化。
昆虫细胞色素P-450酶的分离和试验已有标准的方法可循[J.G.Scott和S.S.T.Lee;Arch.Insect Biochem.and Phys.[昆虫生物化学与生理学文献],24,1-19,(1993)]。不同种类的酶会显示出极大的相似性,但它们相互间也可能有明显的差异。由文献已知的并且我们作了研究的增效剂属于O-2-丙炔基、丙炔基同系物及其衍生物(醚类、肟醚类、酯类)这一组群。如文献所示,它们对不同的种类表现出不同的效力,这表明,不同种类的氧化能力有一定程度的不同。这便是为何这组化合物有着高的昆虫/哺乳动物选择性和增效剂选择性的特征。这些选择性是增效剂开发和安全应用的基础,尽管对选择性尚不能用上述作用方式作直接的解释。另一方面,这便是为何这些化合物未能商业化的原因。就所制备和评价的所有的这组化合物而言,迄今我们所能肯定的是,一般而言,其效果主要集中于其丙炔基侧链上,此链在烯丙基的位置上,主要经氧原子,由不同的芳环取代。这些目前已知的化合物可以分成下列几组:###苯基 炔丙基 醚类[Fellig等,J.Agr.Food.Chem.[农业食品化学杂志],18(5),78,(1970)]### 苄基 炔丙基 醚类[Ciba Geigy,德国专利公开2 235 005(1972)]### 苯甲醛肟 炔丙基 醚类[Ciba Geigy,德国专利公开2 016190(1970)]### 萘甲酸 炔丙基 酯类[Hoffman-La Roche,比利时专利867849(1978)]### 炔基邻苯二甲酰亚胺类[FMC,德国专利1 217 693(1966)]### 苯基膦酸 炔丙基 酯类[Niagara Chem.Div.,FMC Corp.,Technical Data Sheet on NIA 16824,(1968)]。
由于芳族基团及其取代基的高度可变性,将前二组又细分成另外的几组。因此,已知有萘基 炔丙基 醚类[Hoffman-La Roche,US 3 362871(1968);Ciba Geigy,德国专利公开2 100 325(1971)],4-羟基喹啉 炔丙基 醚类[Alkaloida,HU210 557,(1992)],亚甲二氧基苄基 炔丙基 醚类[Sumitomo,JP 03 01177,(1973)]和α-取代的亚甲二氧基苄基 炔丙基 醚类[Sumitomo,JP 61 24585,61 24586(1986)]。
对萘基 炔丙基 醚类的研究得出这样的结论,丁炔基醚,首先是3-丁炔基醚比类似的炔丙基和戊炔基醚的效力强[R.M.Sacher等,J.Agr.Food.Chem.[农业食品化学杂志],16,779-786,(1968)]。有趣的是,未继续做工作,且此发现也未申请专利。对文献数据的详细分析表明,丙炔基侧链不能用同系的链代替,因为上述文献与专利均未涉及炔丙基衍生物。为了澄清这一相反结论,我们制备出所讨论的化合物,结果发现,与文献公开的内容相反,2-丁炔基衍生物(以甲基基团封端)比3-丁炔基衍生物的效力强;α-异构体比类似的β-异构体的效力强;且3-戊炔基衍生物比2-丁炔基衍生物的效力强。这些数据与我们的理论能很好地吻合,且在文献中给出的数据或许是为何此研究方向没有被其它研究者深入的缘由。类似的是,关于4-戊炔基邻苯二甲酰亚胺衍生物的活性,也得出相反结论,虽然此类衍生物是烯丙菊酯的强增效剂,但它们拮抗除虫菊酯[H.Jaffe,J.L.Neumeyer,J.Med.Chem.[医学化学杂志]13,901,(1970)]。同样在这些结构物中,炔基链的叁键在末端。这些结构物的杂化变型,即N-烷氧基-O-炔丙基-邻苯二甲酰亚胺也已被制备出来,其中,叁键是在末端位置[Sumitomo,NL,6 600 916(1966)]。
综上所述,虽然在一些试验中表现出突出的活性,且有着优越的增效剂/活性成分比[D.J.Henessy,Biochemical Toxicology of Insecticides[昆虫的生化毒理学],R.D.O’Brian & I.Yamamoto编,Academic Press,105-114,(1970)],但此组的最有活性的代表未曾实际应用过。这其中有几点原因:其活性未达到早先开发已定形的衍生物的效力,它们只在狭窄范围内表现出活性,其效力是高度种类依赖的,且在一种种类中,它在很大程度上取决于个体的“强度”。因此不能确保其安全性和广泛的应用。
US-A-3,718,686公开了炔基醚和酯,例如炔丙基酯,它是被氧或硫脂族链取代的环。这些醚和酯通过干扰昆虫的激素平衡来杀灭和防止昆虫的繁殖。所述专利的申请人未能意识到所公开化合物的杀昆虫增效活性,因而其中也未公开相关的生物学数据。
列于上文的炔基化合物是一般性优化结构的所有衍生物,但作者尚未认清其间的相互关系,且还未制备出最有活性的代表,熔合和改进这组化合物的优点。
我们进行了实验测试,比较和分析已知化合物以及我们制备出的新衍生物的生物效果,并揭示出对效果起作用的结构要素。以此为基础,我们制备出新化合物,其活性明显超出早先的化合物的活性,且综合了确保对更多的种类有效果和能用于更多已知活性成分的那些性能。
本发明的完整部分是这样一个发现,在最佳化合物中,活性的载体是带有富电子Ar环的炔基结构的叁键,而所述Ar环通过由三个原子组成的流动桥与叁键相连。桥的几个原子是可变的,且可以具有取代基,且环也是如此。为提高活性,有利的是引入亲脂与富电子原子和取代基。因此,除了碳原子外,桥上的原子可以是氧、硫、氮和磷杂原子。这些原子可以通过单或多键相互连接且任选带有另外的含有上述杂原子的取代基,这些取代基可以被取代而成另外的官能基团或衍生物。这些原子可以相互替代。桥的第一个单元可以与其取代基形成环,该环可以连接在芳环上,且因此可以是富电子部分的一部分。如上面所列的杂原子也可以掺入连接到桥上的环中,且可以通过引入烷氧基、卤素、烷基、卤代烷基或硝基取代基而另外增强效果。该环可以是5-、6-或7元的且可以与另外的环(它根据上述原则构建)稠合且可以掺入桥的第一单元。与带有末端叁键的类似物相比,其中炔基侧链的炔属氢被甲基基团替代的化合物的活性更高。根据这一规律,按照应用领域的需要(亲脂性、translaminarity、对称性等),我们可以实现新的取代,并由此我们可以对化合物的特性作修饰。
对于光学活性化合物异构体(例如,α-甲基取代的苄基衍生物)而言,R(+)对映体比S(-)对映体的效力强。异构体活性间的差异随着外消旋混合物的活性提高而增加。
由我们开发出的化合物是新的,其特征在于,在相对于活性成分为低剂量的情况下,它们产生突出的哺乳动物/昆虫选择性和高的效力。这是由于我们的化合物具有突出的高受体亲合性。在对比实验中,我们的化合物与活性成分比的指数远远超过早先的已知增效剂与活性成分比的指数。那些已知增效剂的代谢是以微粒体氧化作用为基础的。在小区范围的大田研究中,此高活性和选择也得到证实。本发明化合物未显示出fito毒性,它们不会与活性成分分离,其物理化学参数与活性成分的参数十分匹配。因为有了这些特点,从前妨碍应用的剂量/效力/价格值可以得到改善,且因此使得应用成为可能。
使用通式I的活性物质,可以有利地使下列已知的杀节肢动物活性成分的效果增效:乙酰胺衍生物:例如杀线威;苯甲酰脲化合物:例如氟螨脲、氟铃脲、伏虫隆、杀虫隆;类苯甲酰脲IGR化合物;双环庚二烯化合物:例如庚烯磷;交联桥接的二苯基化合物:例如醚菊酯、溴螨酯、甲氧滴滴涕、双硫磷、三氯杀螨砜;氨基甲酸酯类:例如灭害威、涕灭威、氧涕灭威、磺草灵、噁虫威、丙硫克百威、甲萘威、卡草胺、克百威、丁硫克百威、乙霉威、二氧威、乙硫苯威、仲丁威、双氧威、呋线威、叶蝉散、灭多威、杀线威、抗蚜威(pirimor)、残杀威、硫双威、久效威、灭杀威;氨基甲酰基肟衍生物:例如棉铃威、丁酮威;环二烯类:例如艾氏剂、氯丹、硫丹、七氯;二唑类:锐劲特(fipronil);酰肼类:RH 5992、RH 5849、CGA 215′944;沙蚕毒(Nereistoxin)类似物:杀虫磺(pl.bensultap);硝基亚咪唑烷基烷基胺(Nitroimidazolidynylenamines):例如吡虫啉;有机磷化合物:例如喹硫磷、二嗪磷、伏杀硫磷、乐果、保棉磷;有机锡化合物:例如***锡、三环锡、苯丁锡、SSI-121;苯氧基化合物:例如杀螨隆;吡唑类:例如吡嘧磷;拟除虫菊酯:例如烯丙菊酯、生物烯丙菊酯(esbol)、氟酯菊酯、氰戊菊酯、烯炔菊酯、炔酮菊酯、苄呋菊酯、MTI-800、氟醚菊酯(flufenprox)、氯菊酯、胺菊酯、氯氰菊酯及其异构体和异构体组合体;哒嗪酮类:例如哒螨酮;吡啶衍生物:例如毒死蜱;嘧啶衍生物:例如嘧啶磷、甲基嘧啶磷;吡咯类:例如AC 303-t.630;喹唑啉类:例如喹螨醚;萜类衍生物:例如烯虫酯;四嗪类:例如四螨嗪,SzI-121(flufenzin);噻二嗪类:例如噻嗪酮;噻唑烷类:例如噻螨酮;***类:例如氯唑磷、RH 7988;氯化烃类:林丹;大环内酯类:吡螨胺(tebufenpyrad);唑螨酯;Triazamate;
上述已知活性成分分别描述于[Pesticide Manual][农药手册]第8版和第10版,欧洲专利申请0635499(SZI-121),A.G.Chem.New Compoundreview第11卷(1993)和ACS Symposium Series 504,第272页。
通式I化合物可以最优选用于使氨基甲酸酯类优选是克百威的效果增效。
我们发现,这些化合物具有双重作用,它们不仅是杀节肢动物剂活性成分的优越增效剂,而且它们还通过阻止蜕皮素(ecdison)(一种在节肢动物生长中起关键作用的物质)的生物合成来阻碍节肢动物个体生长。因此增效与阻碍个体生长活性间存在着明确的关系。除了这些化合物的突出的阻断代谢活性外,后一种效果同样是这一事实的必然结果,即,与其它的早先已知的一类化合物物质相反,这些物质在节肢动物有机体中实际上不降解,或降解极其缓慢。因此,当单独使用时,在一段长时期内(取决于蜕皮素调节的时间长短),它们能够阻断激素的合成且妨碍生物内和外(endo andexo-biotica)的降解。由于毒素在有机体内累积,则节肢动物个体变得不能生存,它们不吃、不产卵和不繁殖。
除了这些增高的活性外,化合物对哺乳动物的毒性值并未增加。这点是因为哺乳动物与节肢动物的微粒体氧化***的电极电势值的差异。由于高等动物有机体的氧化电势值高,因此它们能够克服配位的增效剂的电子屏障,而节肢动物的氧化***电势低,它不能够氧化和通过氧化将配位的分子从酶表面去除掉,因而造成该***的麻痹。这就是为何这些化合物可以安全和有选择性地使用的原因。与节肢动物相反,由于哺乳动物酶活性高和酶结合迅速,哺乳动物对这些化合物具有超过平均水平的快速降解和***,确保了这些物质不提高对哺乳动物有机体所发现的和采取的生物效果,因此它们是安全的。在各种节肢动物种类上我们证实了这些效果。单独使用,或作为增效剂,这些化合物对昆虫、植食寄生虫和螨有活性。由上文可知,这一事实再次涉及到哺乳动物的有量的差异的解毒***。
我们的这些化合物的非常有价值的优点是,当将它们施用于已产生抗性的种类时,毒性剂量可以降到已知活性成分原有剂量之下(用敏感植株测定)。用其它增效剂则看不到这种现象。这使得对抗性种群的安全有效治理成为可能,且符合现代的有关条例的要求。
除了上面提到的预期优点之外(它们使得开发出更低廉、对哺乳动物更低毒、有选择性和可以抑制抗性的工具成为可能),借助于这些化合物,许多老品种活性成分可以焕发新的生机,这些品种(克百威、喹硫磷、杀螟丹、灭多威)在过去许多年中,因为抗性的原因从市场上撤出。我们的这些化合物创造出新的应用和市场可能性,因为它们提高活性较低的物质(苄呋菊酯、生物烯丙菊酯、抗蚜威等)的效力,使其达到最有活性的化合物的水平,且不增加其毒性。PBO在市场上占有很大的份额,但随着自然资源正在耗尽,价格在不断地攀升,且因其有刺激肿瘤产生的效果之嫌,目前市场正逐渐萎缩,或许借助于我们的这些化合物能替代它。
通式I化合物的制备根据不同的化合物组会有所不同,且可以用以制备下列几组的化合物为特点的化学方法来制备。a)制备通式IA化合物,式中,Ar、R1、R2、R5、R6、R7、R8、Y、E、m、o和p具有与上面定义相同的含意,使通式II与III化合物反应,其中Ar、R1、R2、R5、R6、R7、R8、Y、E、m、o和p具有与上面定义相同的含意,A和B是适合于形成酯键的基团,B-(CR5R6)o-(CR7R8)p-C≡C-E III.b)制备通式IB化合物,式中,Ar、R1、R2、R5、R6、R7、R8、R10、Y、E、m、o和p具有与上面定义相同的含意,使通式IV和V的化合物反应,式中,Ar、R1、R2、R5、R6、R7、R8、Y、E、m、o和p具有与上面定义相同的含意,且C和D代表适合于形成酰胺键的基团,D-(CR5R6)o-(CR7R8)p-C≡C-E V.c)制备通式IC化合物,式中,Ar、R1、R2、R5、R6、R7、R8、E、m、n、o和p具有与上面定义相同的含意,R3和R4相互独立地代表H、烷基、链烯基、卤代烷基、苯基、取代的苯基,使通式VI和VII的化合物反应,式中,Ar、R1、R2、R5、R6、R7、R8、E、m、n、o和p具有与上面定义相同的含意,R3和R4相互独立地代表H、烷基、链烯基、卤代烷基、苯基、取代的苯基,且F和G代表适合于形成醚键的基团,Ar-(CR1R2)m-(CR3R4)n-F VI.G-(CR5R6)o-(CR7R8)p-C≡C-E VII.d)制备通式ID化合物,式中,Ar-(CR1R2)m-(CR2R4)n-N-代表羧酰亚胺基团,R5、R6、R7、R8、E、o和p具有与上面定义相同的含意,使通式VIII的羧酰亚胺与通式IX的化合物反应,式中,R5、R6、R7、R8、E、o和p具有与上面定义相同的含意,且Lg代表离去基团,Lg-(CR5R6)o-(CR7R8)p-C≡C-E IX.e)制备通式IE化合物,式中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、R10、E、m、n、o和p具有与上面定义相同的含意,使通式X和XI的化合物反应,式中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、E、m、n、o和p具有与上面定义相同的含意,且H和I代表适合于形成-N(R10)-基团的基团,其中R10具有与上面定义相同的含意,Ar-(CR1R2)m-(CR3R4)n-H X.I-(CR5R6)o-(CR7R8)p-C≡C-E XI.f)制备通式IF化合物,式中,Ar、R1、R2、R5、R6、R7、R8、R9、E、m、o和p具有与上面定义相同的含意,使通式XII和IX的化合物反应,式中,Ar、R1、R2、R5、R6、R7、R8、R9、E、m、n、o和p具有与上面定义相同的含意,且Lg代表离去基团,
Lg-(CR5R6)o-(CR7R8)p-C≡C-E IX.且如果需要,通式I化合物可以转化成其盐,或可以从其盐释放,如果需要,可以分离其光学活性异构体。
制备通式I化合物时,有利地是:a)在酸结合剂存在下,使通式II的酰基卤与通式III的炔醇反应,或通式II的羧酸与通式III的炔基卤反应,或在活化剂,优选偶氮二羧酸二乙酯和三苯基膦或二环己基碳化二亚胺和酸性催化剂存在下,使通式II的羧酸与通式III的炔醇反应,b)任选在酸结合剂存在下,使通式II的酰基卤与通式V的伯或仲炔基胺反应,或是使通式IV的羧酰胺与通式V的炔基卤反应,c)在碱存在下,使通式VI的醇与通式VII的炔基卤反应,或使通式VI的卤化物与通式VII的炔醇反应,或在活化剂,优选偶氮二羧酸二乙酯和三苯基膦或二环己基碳化二亚胺和酸性催化剂存在下,使通式VI的醇与通式VII的炔醇反应,d)使通式VIII的羧酰亚胺在碱存在下与通式IX的炔基卤化物或-甲磺酸酯、-甲苯磺酸酯、-三氟乙酸酯反应,或e)在碱存在下,使通式X的仲胺与通式XI的炔基卤反应,或通式X的卤化物与通式XI的仲胺反应,或f)使通式XII的醛肟或酮肟在碱存在下与通式IX的炔基卤化物或-甲磺酸酯、-甲苯磺酸酯、-三氟乙酸酯反应。
我们制备出并要求保护的化合物是新的,它们未被文献公开。其结构在纯化后已作出阐明,纯度用TLC和GC方法检测。这些化合物的分子式用元素分析证实,且结构得到IR、1H-和13C-NMR测定的明确支持。
这些物质可以加工成单独的组合物或与其它已知杀节肢动物剂活性成分混合,根据施用的目的,可以使用已知的载体和其它辅助材料。因此,用本身已知的方法,可以制备出乳油、微乳剂、粉剂、气雾剂、熏蒸剂和烟剂[Rhone Poulenc-Geronazzo:Surfactant and Specialities for PlantProtection,Application Manual[植物保护用表面活性剂与特殊产品——应用手册](1994),ICI:Surfactants,Application Manual[表面活性剂——应用手册](1992)]。
因此本发明还涉及一种农药组合物,它包含按重量计0.0001-99.9%的作为活性成分的通式I化合物。另外,本发明还涉及一种杀节肢动物剂组合物,它包含按重量计0.0001-99.9%的作为活性成分的通式I化合物,和任选的其它杀节肢动物剂活性成分,以及载体和其它辅助材料。在一优选实施方案中,所述杀节肢动物剂活性成分是氨基甲酸酯,优选克百威。
在施用过程中,含有通式I的制剂和含有一或多个已知活性成分的制剂,可以依次使用或将之制成桶混物后使用。
因此本发明还涉及一种消灭害虫的方法,包含用适当量的上述组合物,如果需要,以这样的方式处理害虫,即将含有通式I化合物的组合物和含有已知活性成分的组合物以桶混物形式使用或依次使用。
为证实本发明的范围,我们给出下列实施例,但并非旨在将本发明范围限定于这些实施例。制备实施例:
化合物的纯化用TLC和GC方法检测(CP9000,CP-SIL-5CB,60m x0.53μm,5ml/minN2、FID·220℃)。如这些方法所示,所有的化合物纯度均超过95%。这些物质的结构得到IR、1H和C13-NMR谱测定的支持,分子式得到元素分析的证实。1.炔基酯类
一般方法A.)
将适宜的炔基醇溶解于无水苯中,加入吡啶,并将混合物冷却至0-5℃。向此混合物中加入酰基氯,加入的速率应使内部温度不超过5℃。将反应混合物在室温下过夜,滤出沉淀出的吡啶鎓盐酸盐。滤液用盐酸溶液中和,随后用水和饱和氯化钠溶液洗涤,用MgSO4干燥,并蒸发。粗产物用色谱纯化。B.)
将6毫摩尔该酸溶解于20毫升无水THF中,并加入1.0克(6毫摩尔)偶氮二羧酸二乙酯(DEAD)。混合物于冰-水浴中冷却,并加入10毫摩尔炔醇和1.6克(6毫摩尔)三苯基膦的10毫升THF溶液。DEAD特征橙色逐渐消失。将此溶液在室温下搅拌过夜,之后用50毫升乙酸乙酯稀释,用饱和氯化钠溶液洗涤,干燥并蒸发。加入己烷-乙酸乙酯混合物,使三苯基膦氧化物由残留物中结晶出来。滤液用柱色谱纯化。
2.炔基酰胺类一般方法
化合物 | Mp(℃) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
1.1501 | 2-丙炔基1,3-苯并间二氧杂环戊烯-5-羧酸酯 | 69-70 | 3270,3010,2922,2853,2124,1726,1625,1606,1501,1445,1373,1279,1263,1157,1103,1076,1039,762. | 2.51(1H,t,J=2.4Hz,≡C-H),4.88(2H,d,J=2.4Hz,OCH2-C≡).6.03(2H,s,OCH2O).6.83(1H,d,J=8.2Hz).7.47(1H,d,J=1.6Hz),7.66(1H,dd,J=8.2,1.6Hz | 52.34(OCH2-C≡),74.92(≡CH),77.81(OCH2-C≡),101.85(OCH2O),107.99.109.59(C-4,C-7),123.29(C-5),125.71(C-6),147.74(C-3a),151.91(C-7a),165.07(CO酯) |
1.2502 | 2-丁炔基1,3-苯并间二氧杂环戊烯-5-羧酸酯 | 63-64 | 3016,2959,2920,2244,1714,1626,1606,1508,1450,1372,1276,1240,1163,1117,1078,1036,970,925,758. | 1.86(3H,t,J=2.3Hz,≡C-CH3),4.84(2H,q,J=2.3Hz,OCH2-C≡),6.03(2H,s,OCH2O),6.83(1H,d,J=8.2Hz),7.47(1H,d,J=1.6Hz),7.67(1H,dd,J=8.2,1.6Hz). | 3.65(≡C-CH3),53.19(OCH2-C≡),73.33(OCH2-C≡),83.17(≡C-CH3),101.81(OCH2O),107.95,109.62(C-4,C-7),123.69(C-5),125.62(C-6),147.72(C-3a),151.78(C-7a),165.33(CO酯) |
在吡啶存在下,在室温下,将酰基氯溶液与炔基胺溶液反应。稀释悬浮液,依次用水、稀盐酸溶液和碳酸氢钠溶液洗涤,干燥,蒸发并色谱纯化和结晶。
3.炔基酰亚胺类一般方法
化合物 | Mp(℃) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
2.1523 | N-(2-丁炔基)3,4-亚甲基二氧基-苯甲酰胺 | 143-144 | 3334,3075,2918,1641,1620,1605,1546,1500,1485,1313,1264,1239,1042. | 1.82(3H,t,J=2.4Hz,CH3-C≡),4.16(2H,m,NH-CH2-C≡),6.02(2H,s,(CH2O)2),6.23(NH),6.81(1H,dd,J=0.6,7.8Hz,H-4),7.28-7.34(2H,m,H-6,H-7) | 3.54(CH3-C≡),30.37(NH-CH2-C≡),74.72和79.77(C≡C),101.73(OCH2O),107.72.108.02(C-4,C-7),121.70(C-6),128.26(C-5),148.01(C-3a),150.49(C-7a),166.37(CONH) |
2.2535 | N-(2-丁炔基)-2-萘甲酰胺 | 133-134 | 3295(NH),3055,2922,2913,2850,1641,1629,1602,1541,1414,1309,776,756 | 1.08(3H,t,J=2.1Hz,CH3-C≡),3,38(1H,s,NH),4.10(2H,m,CH2-C≡),7.60(2H,m),8.0(3H,m),8.49(1H,s,H-1),9.03(1H,t,J=5.3Hz) | 3.27(CH3-C≡),29.11(-CH2-C≡),76.77和78.07(C≡C),124.29(C-3),126.90,127.82(三个信号叠加).128.08,129.07,131.51(C-4a),132.32(C-2),134.37(C-8a),166.07(CO) |
2.3541 | N-(2-丙炔基)-1-萘甲酰胺 | 105-106 | 3229(NH),3046,2963,2927,2118,,1635,1618,1590,1576,1531,1415,1301,1245,1033,788,773,759,519 | 2.27(3H,t,J=2.4Hz,H-C≡),4.24(2H,q,J=2.4,CH2-C≡),6.52(1H,broads,NH),7.35(1H,t,J=8.1Hz),7.50(3H,m),7.84(2H,m),8.26(1H,m) | 29.62(-CH2-C≡),71.80(H-C≡C),79.43(H-C≡C),124.59,125.19,125.29,126.41,127.14,128.28,130.06(C-8a),130.85(C-2),133.34(C-1),133.59(C-4a),169.14(CO) |
2.4542 | N-(2-丁炔基)-1-萘甲酰胺 | 120-122 | 3276(NH),3046,3011,2917,2856,1632,1618,1591,1577,1522,1444,1432,1287,1258,783 | 1.83(3H,t,J=2.1Hz,CH3-C≡),4.25(2H,q,J=2.1Hz,CH2-C≡),6.25(1H,s,NH),7.31-7.60(3H,m),7.85(2H,m),8.32(1H,m) | 3.50(CH3-C≡),30.24(-CH2-C≡),74.47和79.81(C≡C),124.59,125.19,124.62,125.09,125.37,126.39,127.10,128.26,130.11(C-8a),130.75(C-2),133.64和133.75(C-1,C-4a),169.03(CO) |
向邻苯二甲酰亚胺的无水DMF溶液中加入1摩尔当量的无水碳酸钾,并向此悬浮液中滴加入1摩尔当量炔基溴的甲苯溶液。将此悬浮液在80℃下搅拌3小时,之后倒入冰-水中,收集晶体,并用96%的乙醇重结晶。
4.(芳烷基)-、烷基-炔基醚类4.0制备1-[(2-丁炔氧基)-乙基]-3,4-二甲氧基苯(化合物599)
化合物 | Mp(℃) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
3.1537 | N-(丁-2-炔基)-邻苯二甲酰亚胺 | 216-218 | 3090,3040(H-C芳族),2957,2920(CH脂族),2234(C≡C)1768,1718(CO),1609(C=C芳族),1468,1431,1397,1354,1333,1126,1090,952,775,732,712,629,560,532. | 1.76(3H,t,J=2.3Hz,CH3-C≡),4.32(2H,q,J=2.3Hz,N-CH2-C=),7.86-7.91(4H,m,芳族) | 3.12(CH3-C≡),27.16(N-CH2-C≡),73.82(CH3-C≡),79.06(CH2-C≡),123.48(C-3,C-6),131.64(C-1,C-2),134.87(C-4,C-5),167.01(CO) |
在备有温度计、磁力搅拌器、加料漏斗并与惰性气体***连接的50毫升烧瓶中制备出30毫升无水THF和1.5克(0.063摩尔)NaH(cca.90%)的悬浮液。在室温下,向此悬浮液中滴加入4.0克(0.021摩尔)α-甲基-藜芦醇的21毫升无水THF溶液。将混合物在回流条件下加热1小时,冷却至室温,加入4.1克(0.0315摩尔)1-溴-2-丁炔,之后继续加热。反应用TLC(洗脱液:己烷∶乙酸乙酯4∶1)监测。约3-4小时后反应完毕。
向冷却的稠悬浮液中加入50毫升***,混合物经Celite过滤,滤液用蒸馏水洗涤,用硫酸镁干燥并蒸发。残留的油状物用柱色谱(洗脱液:己烷∶乙酸乙酯4∶1,Rf=0.37)纯化。
产量:2.3克(9.8毫摩尔),46.9%。
此产物的纯度用GC分析:(CP9000,CP-SIL-5CB,60m×0.53μm,5ml/minN2,FID,250℃)tR=12.0min,>99%。
结构证实:
元素分析:(C14H17O3,233.29):
计算值:C%72.08,H%7.35
实测值:C%69.70,H%7.21
IR(CHCl3)νcm-1:2976,2855,2837,1605,1595,1514,1465,1419,1371,
1353,1311,1260,1164,1141,1086,1027,864
1H-NMR(200MHz,CDCl3)δ:
1.46(3H,d,J=6.5Hz,CH-CH3),1.85(3H,t,J=2.3Hz,≡C-CH3),
3.83和4.01(2H,ABX3 JAB=15.0Hz,JAX=JBX=2.3Hz,=C-CH2O),
3.87和3.89(summa 6H,s各OCH3)
4.55(2H,q,J=6.5Hz,Ar-CHO),
6.80-6.89(3H,m,芳族).
13C-NMR(50MHz,CDCl3)δ:
3.61(≡C-CH3),23.76(CH-CH3),55.87(OCH3),55.95(≡C-CH2O),
75.36(≡C-CH2),76.40(Ar-CH-CH3),81.91(≡C-CH3),109.06(C-2),
110.86(C-5),118.94(C-6),135.30(C-1),148.52(C-3),149.19(C-4),
类似于实施例4.0中描述的方式,制备出下列化合物:
5.芳族的烷基-烷基-炔基胺衍生物一般方法
化合物 | Mp(℃) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
4.1279 | 1-萘基-甲基2-丁炔基醚 | 油状物 | 3044,3001,2945,2920,2854,1598,1509,1356,1166,1086,1067 | 1.93(3H,t,J=2.3Hz,C≡C-CH3),4.22(2H,q,J=2.1Hz,O-CH2-C≡C),5.06(2H,s,C10H7-CH2-O),7.45(1H,t,J=8Hz),7.53(3H,m),7.84(1H,d,J=8.1Hz),7.88(3H,m),7.88(1H,d,J=7.7Hz),8.19(1H,d,J=8.2Hz) | 3.6(C≡C-CH3),57.71(O-CH2-C≡C),69.72C10H7-CH2-O),75.10(O-CH2-C≡C),82.76(O-CH2-C≡C),124.03,125.10.125.72,126.19,126.85,128.43,128.72,131.79(C-8a),133.06,133.70 |
4.2292 | 1-{1-(2-丁炔氧基)-乙基}-萘 | 油状物 | 3052,2977,2921,2856,1596,1509,1444,1371,1095,1078 | 1.67(3H,d,J=6.5Hz,CH3-CH),1.87(3H,t,J=2.3Hz,≡C-CH3),2.96和4.15(summa2H,ABX,JAB=15.0Hz,JAX=JBX=2.3Hz,OCH2-CvC),5.40(1H,q,J=6.5Hz,C10H7-CH-O),7.51(3H,m),7.61(1H,d,J=6.8Hz),7.79(1H,d,J=8.1Hz),7.89(1H,dd,J=7.9,1.8Hz),8.22(1H,d,J=8.1Hz) | 3.64(C≡C-CH3),22.96(CH3-CH),56.37(O-CH2-C≡C),74.29(CH3-CH),75.36和82.14(C≡C),123.26(C-8),123.52,125.50,125.85,127.92,128.83,130.78(C-8a),133.88(C-4a),138.42(C-1) |
4.3454 | 1-[1-(2-丁炔氧基)-丙基]-萘 | 油状物 | 3058,3048,3000,2962,2932,2923,2876,2856,1598,1509,1460,1105,1062, | 1.02(3H,t,J=7.4Hz,CH3-CH2),1.89(3H,t,J=2.3Hz,C≡C-CH3),2.03(2H,m,CH3-CH2),3.95和4.17(summa2H,ABX,JAB=15.0Hz,JAX=JBX=2.3Hz,OCH2-C≡C),5.15(1H,t,J=6.4Hz,C10H7-CH-O),7.53(3H,m),7.59(1H,d),7.81(1H,d),7.89(3H,m),8.27(1H,d) | 3.59(C≡C-CH3),10.62,(CH3-CH2)30.27(CH3-CH2),56.54(O-CH3-C=C),75.50(O-CH2-C≡C),80.08和81.96(OCH-萘基和O-CH2-C≡C),123.43(C-8),124.40,125.31,125.36,125.73,127.91,128.79,131.19(C-8a),133.88(C-4a),137.12(C-1) |
化合物 | Mp(℃) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
4.4472 | 1-[2-甲基-1-(2-丁炔氧基)-丙基]-萘 | 油状物 | 3051,2959,2922,2871,1598,1509,1466,1064, | 0.87和1.16(summa6H,d各,J=6Hz,CH(CH3)2),1.88(3H,t,J=2.3Hz,C≡C-CH3),2.31(1H,m,CH(CH3)2),3.89和4.14(2H summa ABX3,JAB=15Hz,JAX=JBX=2.3Hz,OCH2),4.92(1H,d,J=6Hz,CH-O),7.53(4H,m),7.83(1H,d,J=8Hz),7.91(1H,dd,J=7.2Hz),8.30(1H,d,J=7.6Hz) | 3.57(C≡C-CH3),19.87和18.77(CH(CH3)2),34.20(CH(CH3)2),56.71(OCH2),75.67(C≡C-CH3),81.77(C≡C-CH3),123.84(C-8),125.15,125.31,125.39,125.60,127.91(C-4),128.76(C-5),131.74(C-8a),133.87(C-4a),136.56(C-1), |
4.5389 | 1-[(1-甲基-2-丙炔氧基)-甲基]-萘 | 油状物 | 3306,3049,2990,2935,2866,1599,1510,1447,1374,1327,1099,1064 | 1.51(3H,d,J=6Hz),CH3:2.56(1H,d,J=2Hz),CH:4.30(H,qxdJ=6.2Hz)OCH:4.91和15.34(2H,AB,JAB=15Hz)OCH2:7.46(11H,dd,J=7.8Hz),7.54(3H,m),7.86(2H,m),8.18(1H,mxd,J=6Hz)芳族 | 22.1,CH3,64.25,OCH:68.99,CH:73.34,aryl-CH2:83.71,CH-C.124.11,C-8:125.17,C-2:125.74,C-3:126.18,C-6,126.92,C-7:128.47,C-4:128.75,C-5:131.88,C-8a,133.20,C-4a,133.77,C-1 |
4.6256 | 2-[1-(2-丙炔氧基)-乙基]-萘 | 油状物 | 3307,3000,2979,2929,2857,1603,1505,1442,1373,1311,1270,1215,1087,1055,860,821,633 | 1.58(3H,d,J=6.5Hz,CH3-CH),2.44(1H,t,J=2.4Hz)CH,3.92(1H,dd,J=2.4,15.7Hz)OCHa-C≡C,4.13(1H,dd,J=2.4,15.7Hz),OCHb-C≡C,4.84(1H,q,J=6.5Hz,C10H7-CH-O),7.50(3H,m),7.77(1H,s),7.85(3H,m) | 23.66(CH3-CH),55.55(O-CH2-C≡C),74.07和76.80(CH-O,CCH),79.98,(CCH),124.11,(C-6),125.60(C-7),125.90,126.15,127.68,127.85,128.5,133.16,133.21,139.75(C-1) |
4.7293 | 2-[1-(2-丁炔氧基)-乙基]-萘 | 油状物 | 3051,2977,2920,2854,1602,1444,1084 | 1.57(3H,d,J=6.5Hz,CH3-CH),1.87(3H,t,J=2.3Hz,CH3-C),3.90和4.08(1-1H,ABX3,J=15,2.3Hz,OCHa,b-C≡C),4.79(1H,q,J=6.5,C10H7-CH-O),7.49(3H,m),7.77(1H,bs,H-1),7.85(3H,m) | 3.64(C≡C-CH3),23.78(CH3-CH),56.23(O-CH2-C≡C),75.28(C≡C-CH3),76.72(CH-CH3),82.10(C≡C-CH3),124.14,(C-6),125.42,125.78,126.05,127.64,127.80,128.40,133.07(C-4),133.19(C-8),140.14(C-2) |
化合物 | Mp(C°) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
4.8441 | 5-[(丁-2-炔氧基)-甲基]-1,3-苯并间二氧杂环戊烯 | 油状物 | 2997,2946,2921,2888,2376,1609,1503,1491,1445,1251,1099,1070,1042,937,865,810 | 1.87(3H,t,J=2.3Hz,Me),4.10(2H,q,J=2.3Hz,O-CH2-C≡),4.47,(2H,s,O-CH2-Ar),5.94(2H,s O-CH2-O),6.76(1H,d,J=8Hz,H-7),6.81(1H,dd,J=8.15Hz,H-6),6.86(1H,J=1.5Hz,H-4) | 3.52(Me),57.29(O-CH2-C≡),71.15(O-CH2-Ar),82.54(CH3-C≡),100.9C-2,107.95,108.71(C-4,7),121.66(C-6),131.39,(C-5),147.15,147.66(C3a,C-7a) |
4.9484 | 5-[(2-甲基-1-(2-丁炔氧基)-丙基]-1,3-苯并间二氧杂环戊烯 | 油状物 | 2958,2921,2874,1608,1502,1486,1441,1076,1041,940 | 0.63和0.94(summa6H,d各,J=6.8Hz,CH(CH3)2),1.76(3H,t,J=2.3Hz,C≡C-CH3),1.81(1H,m,CH(CH3)2),3.69和3.94 (summa 2H,ABX3,JAB=15.1Hz,JAX=JBX=2.3Hz,OCH2),3.86(1H,d,J=7.8Hz,CH-O),5.87(2H,AB,OCH2O),6.62(1H,dd,J=7.9,1.6Hz,6-H),6.68(1H,d,J=7.9Hz,7-H),6.71(1H,d,J=1.6Hz,4-H) | 3.58(C≡C-CH3),18.93和19.30((CH(CH3)2),34.42(CH(CH3)2),56.20(OCH2),75.48(C≡C-CH3),81.66(C≡C-CH3),86.25(CH-O),100.85(OCH2O),107.44,107.63(C-4,7),121.29(C-6),134.48(C-5),146.88和147.63(C-3a,7a) |
4.10554 | 5-[(丁-2-炔氧基)-环己基-甲基]-1,3-苯并间二氧杂环戊烯 | 油状物 | 2920,2877,2851,1610,1502,1485,1441,1357,1243,1132,1064,1040,942, | 0.84-1.31(6H,m),1.50-1.77(4H,m)1.83(3H,t,J=2.3Hz.≡C-CH3),2.08(1H,m,H-1′),3.76和4.01(ABX3,JAB=15Hz,JAX=JBX=2.3Hz,OCH2),3.98(1H,d,J=8.3Hz,CH-O),5.97(2H,s,OCH2O),6.65-6.78(3H,m), | 3.64(C≡C-CH3),25.93和26.05(C-2′,C-6′),26.52(C-3),29.25和29.86(C-3′,C-5′),43.97(C-1′),56.19(OCH2),75.57(C≡C-CH3),81.64(C≡C-CH3),85.45(CH-O),100.88(OCH2O),107.47和107.64(C-4,C-7),121.31(C-6),134.48(C-5),146.91和147.69(C-3a,C-7a). |
4.11555 | 5-[(丁-2-炔氧基)-苯基-甲基]-1,3-苯并间二氧杂环戊烯 | 油状物 | 2993,2887,2859,1605,1502,1486,1442,1357,1239,1037,937. | 1.89(3H,t,J=2.3Hz,≡C-CH3),4.12(2H,q,J=2.3Hz,OCH2),5.56(1H,s,CH-O),5.93(2H,s,OCH2O),6.74-6.86(3H,m),7.25-7.39(5H,m) | 3.69(C≡C-CH3),56.34(OCH2),75.12(C≡C-CH3),81.23(C≡C-CH3),82.56(CH-O),100.99(OCH2O),107.78和107.95(C-4,C-7),120.98(C-6),127.01(C-2′,C-6′),127.50(C-4′),128.36(C-3′,C-5′),135.54(C-5),141.62(C-1'),147.05和147.83(C-3a,C-7a) |
化合物 | Mp(℃) | IR(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
4.12493 | (2-丁炔氧基-甲基)-3,4-二甲氧基-苯 | 油状物 | 3025,3000,2956,2937,2921,2855,2839,1607,1595,1512,1466,1443,1420,1158,1140,1070,1028 | 1.84(3H,t,J=2.3Hz,C≡C-CH3),3.83和3.85(summa 6H,CH3O),4.08(2H,q,J=2.3Hz,OCH2C≡C-),4.48(2H,s.aryl-CH2),6.77-6.88(3H,m,aryl) | 3.45(C≡C-CH3),55.67和55.71(CH3O),57.31(OCH2C≡C-),71.22(aryl-CH2),75.0(C≡C-CH3),82.42(C≡C-CH3),110.76(C-2),111.23(C-5),120.54(C-6),130.05(C-1),148.58(C-4),148.88(C-3), |
4.13503 | 2-6-二氯-1-(2-丁炔氧基-甲基)-苯 | 油状物 | 2931,2918,2881,2849,2241,1584,1563,1473,1356,1198,1157,1091,1073,787,769 | 1.87(3H,t,J=2.3Hz,≡C-CH3),4.21(2H,q,J=2.3Hz,OCH2-C≡),4.83(2H,s,C6H4Cl2-O-CH2),7.17(1H,dd,J=9.1,6.7Hz),7.31(2H,m) | 3.64(≡C-CH3),58.68(OCH2-C≡),66.15(C6H4Cl2-O-CH2),74.94(OCH2-C≡),82.81(≡C-CH3),128.33(C-3,C-5),129.96(C-4),133.17(C-2,C-6),136.97(C-1) |
4.14498 | 1-(2-丁炔氧基)-1,2,3,4-四氢化萘 | 油状物 | 2998,2941,2860,1604,1489,1440,1070,1044 | 1.84(3H,1,J=2.3Hz,C≡C-CH3),3.83和3.85(summa 6H,CH3O),4.08(2H,q,J=2.3Hz,OCH2C≡C-),4.48(2H,s芳基-CH2),6.77-6.88(3H,m,芳基) | 3.45(C≡C-CH3),55.67和55.71(CH3O),57.31(OCH2C≡C-),71.22(芳基-CH2),75.0(C≡C-CH3),82.42(C≡C-CH3),110.76(C-2),111.23(C-5),120.54(C-6),130.05(C-1),148.58(C-4),148.88(C-3) |
4.15479 | 1-(2-丁炔氧基)二氢化茚 | 油状物 | 3073,3000,2938,2924,2854,2243,1711,1667,1608,1461,1332,1097,1063,1018 | 1.91(3H,t,J=2.3Hz,C≡C-CH3),2.15(1H,dddd,J=13.2,8.4,4.8,3.8Hz,2-H),2.37(1H,dddd,J=15,8.4,6.5,6.5Hz,2-H),2.83(1H,ddd,J=15.8,8.4,4.8Hz,3-H),3.12(1H,ddd,J=15,7.2,8.4,3-H),4.21(2H,q,J=2.3Hz,OCH2),5.14(1H,dd,J=6.5,3.7Hz,1-H),7.23(1H,m),7.28(2H,m),7.45(1H,d,J=7Hz). | 3.52(C≡C-CH3),30.11(C-2),32.25(C-3),56.14(OCH2),75.45(C≡C-CH3),81.68(C-1),82.15(C≡C-CH3),124.80,125.16(C-5.6),126.11,128.36(C-4.7),142.10,144.14(C-3a,7a). |
化合物 | Mp(℃) | IRν(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
4.16510 | 2-[(2-丁炔氧基)-甲基]-1,4-苯并二噁烷 | 油状物 | 2996,2921,2858,2222,1594,1492,1466,1269,1097,1043 | 1.87(3H,t,J=2.4Hz,3.70和3.80(2H,ABX,JAB=10.1Hz,JAX=JBX=5.0Hz,CH-CH2-O),4.08(1H,dd,J=7.6,11.8Hz,H-3β),4.20(2H,d,J=2.3Hz,O-CH2-C≡),4.28-4.41(2H,m,H-3α,H-2α),6.81-6.92(4H,m,C6H4) | 3.57(H3C-C≡),59.43(O-CH2-C≡),65.58(CH-CH2-O),68.12(C-3),71.96(C-2),74.54(CH2-C≡),83.22(H3C-C≡),117.12,117.40(C-5和C-8),121.37,121.56(C-6和C-7),143.07,143.21(C-4a,C-8a) |
4.17539 | 2-(2-丁炔氧基-甲基)-2,3-二氢苯并呋喃 | 油状物 | 3598,3478(宽),3080,3040,2996,2952,2871,1611,1598,1481,1462,1232,1092,1050,1012,1004.954,899,865 | 2.65(1H,t,J=5.4Hz,OH),2.97和3.25(summa 2H,ABX,JAB=15.6Hz,JAX=9.4Hz,JBX=7.5Hz,H-3),3.79(2H,m,CH2-OH),4.90(1H,m,H-2),6.79(1H,d,J=8.0Hz),6.87(1H,td,J=7.5,0.8Hz),7.11(1H,d,J=7.8Hz),7.16(td,J=7.2,0.5Hz) | 31.18(C-3),64.77(CH2-OH),83.02(C-2),109.36(C-7),120.54(C-5),124.97(C-6),126.48(C-3a),127.95(C-4),159.08(C-7a) |
化合物 | Mp(℃) | IR(cm-1) | [α]D 20 | |
4.18330 | S-(-)-1-[1-(2-丁炔氧基)-乙基]-萘 | 油状物 | 似4.2 292 | (-)78°(c=1,MeOH) |
4.19331 | R-(+)-1-[1-(2-丁炔氧基)-乙基]-萘 | 油状物 | 似4.2 292 | (+)155°(c=1,氯仿) |
4.20456 | S-(-)-2-[1-(2-丁炔氧基)-乙基]-萘 | 油状物 | 似4.7 293 | (-)190.8°(c=1.0,氯仿) |
4.21455 | R-(+)-2-[1-(2-丁炔氧基)-乙基]-萘 | 油状物 | 似4.7 293 | (+)199.0°(c=1.17,氯仿) |
4.22474 | S-(-)-2-[1-(2-丙炔氧基)-乙基]萘 | 油状物 | 似4.6 256 | (-)224.4°(c=1.18,氯仿) |
4.23475 | R-(+)-2-[1-(2-丙炔氧基)-乙基]萘 | 28-29 | 似4.6 256 | (+)228°(c=1,氯仿) |
将胺溶解于无水苯中,加入炔基溴,并将混合物在室温下搅拌。之后用水和***稀释,将不同的相分离,水相用***萃取二次,合并的有机相用水洗涤,用硫酸镁干燥。
6.芳基炔基醚类一般方法A.)
化合物 | Mp(℃) | IR(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
5.1251 | N-α-二甲基-N-2-丙炔基-β-萘基-甲胺 | 51-53 | 3173,3053,2970,2941,2837,2788,1600,1444,1433,1371,1334,1295,1227,1123,1074,1011,969,952,935,900,863,827.754,734,713.557.482 | 1.455(3H,d,CH-Me),2.271(1H,s,CCH),2.360(3H,s,NMe),3.253-3.302和3.487-3.530(2H,CH2),3.708-3.757(1H,m,CHMe).7.260-7.834(7H,m,芳族) |
将适宜的苯酚溶解于无水DMF中,向此溶液中加入无水碳酸钾,并加入适宜的炔基卤。将反应混合物加热到60℃,并在该温度下搅拌3-6小时。之后真空蒸馏掉DMF,残留物加入氯仿与蒸馏水的混合物中。将不同的相分离,水相用氯仿萃取二次,合并的有机相依次用水和饱和的氯化钠溶液洗涤,用硫酸镁干燥并蒸发。粗产物用色谱纯化。B.)
在惰性气氛下,将三苯基膦溶解于无水苯中。并向溶液中加入适宜的醇,之后加入苯酚。将此混合物冷却至0-10℃,并缓慢地加入DEAD(偶氮二羧酸二乙酯),每次加入一小份,保持温度低于10℃。将反应混合物搅拌10-24小时。
处理:将沉淀出的Ph3PO滤出,滤液用水洗涤,干燥并蒸发。残留物色谱纯化。C.)
将0.01摩尔苯酚溶解于7毫升无水乙腈中,并在氩气氛下将之冷却至-4℃。向溶液中加入1.968克(0.0129摩尔)DBU,保持温度低于-4℃。向所得的溶液中加入1.8克氯化铜(II)和同时制备出的另一反应剂——三氟乙酸酯。
在氩气氛下,将0.0115摩尔炔基醇溶解于7毫升乙腈中,并将此溶液冷却到-5℃。向此溶液加入1.968克(0.0129摩尔)DBU,与之同时保持溶液低于-5℃。向此混合物中滴加入1.6克(0.0115摩尔)三氟乙酸酐,保持温度低于2℃。将所得的混合物在0℃下搅拌30分钟。
将由此获得的三氟乙酸酯溶液滴加入到上述第一种溶液中,保持温度低于0℃,并将混合物在0℃下搅拌5小时。反应用TLC监测。反应结束后,真空蒸馏掉乙腈。残留物用150毫升苯和50毫升水的混合物震荡。有机层依次用1N盐酸、1N氢氧化钠、水和饱和氯化钠溶液洗涤,之后干燥并蒸发。产物用色谱进行纯化。
7.炔基肟醚类一般方法
化合物 | Mp(℃) | IR(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
6.1547 | 1-(3-丁炔氧基)-4-硝基苯 | 92-94 | 3287,3111,3085,3075,2964,2947,2920,1609,1596,1510,1466,1344,1333,1263,1179,1110,1019,856,846,753,669,653. | 2.07(1H,t,J=2.6Hz,C≡C-H),2.73(2H,tdJ=6.8,2.6Hz,CH2C≡C),4.18(2H,t,J=6.8Hz,OCH2),6.97和8.18(summa 4H,dm,J=9Hz,C6H4) | 19.37(C≡C-CH2),66.60(C≡CH),70.38(OCH2),79.62(C≡CH),114.51(C-2,C-6),125.89(C-3,C-5),141.73(C-4),163.40(C-1) |
6.2540 | 1-(3-戊炔氧基)-4-硝基苯 | 77-78 | 3067,3048,2963,2917,2886,1923,1607,1594,1512,1467,1403,1339,1260,1178,1110,866,856,753,694,648,628,522,506. | 1.78(3H,t,J=2.3Hz,C≡C-CH3),2.66(2H,m,CH2C≡C),4.12(2H,t,J=7.0Hz,OCH2),6.95和8.18(summa4H,dm,J=9Hz,C6H4) | 3.57(C≡C-CH3),19.61(C≡C-CH2),67.26(OCH2),74.27(C≡C-CH3),77.84(C≡C-CH3),114.49(C-2,C-6),125.85(C-3,C-5),141.59(C-4),163.59(C-1). |
6.3377 | 2,3-二氢,2,2-二甲基-7-(3-丁炔氧基)-苯并呋喃 | 78-80 | 3277,3071,3043,2970,2923,2889,2858,2119,2022,1874,1795,1714,1656,1624,1611,1591,1492,1470,1440,1492,1396,1385,1371,1302,1283,1244,1201,1172,1128,1077,999,972,946,887,838,780,753,720,682,663,635,600,546,502,458 | 1.512(6H,s,diMe),2.033(1H,t,CH),2.710(2H,m,-CH2C),3.027(2H,s,CH2-ar),4.206(2H,t,O-CH2),6.739-6.815(3H,m,芳族 | 19.12(CH2-C),27.88(diMe),42.93(C-3),66.79(C-2),69.61(O-CH2),79.96(CCH),87.06(CC),113.31(C-6),117.86(C-5),119.99(C-4),128.36(C-9),142.62(C-7),147.52(C-8) |
6.4418 | 2,3-二氢-2,2-二甲基-7-(3-戊炔氧基)苯并呋喃 | 58-59.5 | 2977,2963,2942,2918,2880,2849,1621,1591,1492,1468,1389,1369,1329,1305,1286,1245,1203,1174,1135,1115,1080,1065,966,947,881,860,841,779,751,718,634,598,532,499. | 1.510(6H,s,diMe),1.800(3H,t,Me),2.627-2.672(2H,m,-CH2C),3.023(2H,s,CH2-ar),4.150(2H,t,O-CH2),6.751-6.784(3H,m,芳族) | 3.471(Me),19.63(CH2-C),28.18(diMe),43.26(C-3),67.54(C-2),74.82(CC-Me),77.32(O-CH2),87.26(CC),113.21(C-6),117.87(C-5),120.25(C-1),128.48(C-9),143.12(C-7),145.00(C-8) |
用典型的方式,在碳酸钾存在下,通过在二甲基甲酰胺中将肟与炔基溴反应,将肟转化成肟醚(参见制备萘基醚的方法A)。粗产物各用柱色谱纯化。
活性结果:实施例1采用局部施用法用家蝇(Musca domestica)研究增效活性
化合物 | Mp(℃) | IR(cm-1) | 1H-NMRδ(ppm) | 13C-NMRδ(ppm) | |
7.1571 | 1-乙酰-萘肟-(2-丁炔基)-醚 | 油状物 | 2990,2919,2853,2230,1604,1591,1459,1436,1363,1353,1309,1252,1034,1017,1002,912 | 1.94(3H,t,J=2.2Hz,CH3-C≡),2.41(3H,s,CH3-C=N),4.84(2H,q,J=2.3Hz,O-CH2),7.46-7.57(4H,m),7.87(2H,m),8.15(1H,m) | 3.80(CH3-C≡),17.51(CH3-C=N),62.25(O-CH2),75.33(CH2-C≡),82.75(CH3-C=),125.15,125.46(C-6,C-7),125.96(C-3),126.01(C-3),126.49(C-2),128.40(C-5),129.10(C-4),130.85(C-1),133.86(C-4a),135.27(C-8a),157.41(CH3-C=N) |
7.2572 | 3,4-二甲氧基-乙酰苯氧基-m-(2-丁炔基)-醚 | 85 | 3080,3003,2963,2929,2869,2840,2237,1595,1577,1518,1447,1417,1337,1311,1278,1249,1234,1176,1153,1030,937,879,804,768,634,621 | 1.87(3H,t,J=2.3Hz,CH3-C≡),2.23(3H,s,CH3-C=N),3.88和3.90(CH3O),4.75(2H,q,J=2.3Hz,O-CH2),6.83(1H,d,J=8.4Hz),7.15(1H,dd,J=8.4,2Hz),7.29(1H,d,J=2Hz) | 3.77(CH3-C≡),12.76(CH3-C=N),55.86(CH3O),62.23(O-CH2),75.27(CH2-C≡),82.53(CH3-C≡),108.8(C-5),110.51(C-2),119.28(C-6),129.18(℃-1),148.78(C-3),150.14(C-4),155.0(CH3-C=N) |
在两组平行实验中,借助于Hamilton MicroLab P微点滴器,10只2-4日龄雌家蝇用0.2微升试验溶液处理其胸部的腹侧。除了1000ng/蝇的增效剂固定剂量外,每只蝇用剂量为20ng/蝇的克百威处理。溶液使用的是溶纤剂。在二氧化碳的作用下进行蝇的选择和计数。处理后,将蝇保持在盖上绢网的塑料杯中。24小时后的死亡率用%表示。结果示于下列表格:
实施例2采用局部施用法用棉铃虫(Helicoverpa armigera)研究增效活性
材料 | 克百威+增效剂(ng/蝇) | |
20+0 20-1000 | ||
死亡率% | ||
炔基酯类、酰胺类、酰亚胺类501502523535541542 | 300300 | 534717274642 |
芳基-烷基-炔基醚类279256441484493599503292293 | 0010110000 | 72329763100100957245 |
454472479330331455456389554555539474510498475 | 011000020000250 | 756858627270472758904850757047 |
芳族烷基-烷基-炔基-胺衍生物251 | 2 | 37 |
芳基炔基醚类547540377418 | 0000 | 47605763 |
芳烷基醛肟、酮肟炔基醚类571572 | 00 | 5355 |
类似于实施例1中描述的方法进行处理,但用L2龄棉铃虫(Helicoverpaarmigera)作试虫进行处理。由24小时剂量-死亡率数据,使用概率分析确定LD50(ng/虫)值。在1000ng/虫的剂量下,增效剂均无作用。克百威单独施用的LD50值与克百威同增效剂一起施用的LD50值之比为增效比。此实验进行2-4次重复,增效比示于下列表格中。
实施例3采用局部施用法用家蝇和棉铃虫研究增效谱
材料 | 增效比 |
炔基酯类、酰胺类501,502,523,535,541,542,537 | >5 |
芳基-烷基 烷基-炔基醚类279,256,441,484,493,503,292,293,454,510,475,498,479,472,331,455,456,389,554,555,539,474,330,599 | >5 |
芳族的烷基-烷基-炔基-胺衍生物251 | >5 |
Ayil-炔基醚类540,377,418 | >5 |
炔基肟醚类571572 | >5 |
类似于生物实施例1和2中描述的处理方法,用家蝇和棉铃虫确定本发明化合物No.279和599对各种活性成分的增效活性。活性成分以ISO通用名给出(参见:Pesticide Manual 1994)。获得的增效比示于下文:
实施例4活性成分:增效剂的比率对增效活性的效果
活性成分 | 279 | 599 | ||
家蝇 | 棉铃虫 | 家蝇 | 棉铃虫 | |
克百威噁虫威叶蝉散仲丁威灭害威硫双威灭多威抗蚜威二氧威残杀威吡虫啉林丹保棉磷毒死蜱生物烯 丙菊酯氯菊酯胺菊酯 | 增效比 | 增效比 | ||
>20>20>40>10>20>10>10>20>20>20>5>5>5>5>5 | >10>10------->10->5>5>5- | >40>40>40>20>20>10>10>20>40>40>5--->10>5>5 | >20>20>20----->20>20----->10- |
使用Hamilton MicroLab P微点滴器,如实施例1中描述的方法进行处理。在两组平行的实验中,10只2-3日龄雌家蝇用0.2微升试验溶液处理其胸部腹侧。除了1000-400-200-80ng/蝇的增效剂固定剂量外,每只蝇用剂量为恒定的20ng/蝇的克百威处理。在二氧化碳的作用下进行蝇的选择和计数。处理后,将蝇保持在盖上绢网的塑料杯中。24小时后的死亡率用%表示。依据实验结果进行2-4次重复。结果示于下列表格:
实施例5用抗性家蝇种群研究增效活性
材料 | 增效剂的剂量(ng/蝇) | ||||
0 | 80 | 200 | 400 | 1000 | |
24小时死亡率(%) | |||||
501441493503454455599 | 0000000 | 60627537402565 | 75678850454890 | 80909465606395 | 8095100937577100 |
下文表格中示出本发明化合物在二种抗性家蝇品系(INSEL.IX)对各种活性成分的增效活性。研究按照描述于生物实施例1中的方法进行。LD50值和增效比如实施例2中给出的方法确定。
实施例6用禾谷缢管蚜(Rhopalosiphum padi)研究增效活性
处理 | INSEL品系 | IX品系 | ||
克百威+279 | LD50(ng/蝇) | SR | LD50(ng/蝇) | SR |
1537529 530 | >10000094 4760 | |||
灭多威+279 | 47546 10 | 851109 5 | ||
抗蚜威+279 | >100000696 145 | >1000003562 115 | ||
涕灭威+279 | 695172 4 | 2104507 4 | ||
噁虫成+279 | 100000150 667 | 100000746 134 | ||
叶蝉散+279 | >100000983 102 | >1000002145 47 | ||
+279烯丙菊酯 | 10653794 13 | -- - |
将播种于塑料杯中的5-8厘米高的燕麦植株用不同虫龄的禾谷缢管蚜(Rhopalosiphum padi aphids)侵害。在处理前计数定居的蚜虫数,之后用手动喷雾器向植株喷雾,除了施用固定剂量(30ppm)的增效剂之外,喷上1毫升喷雾液。用通常用于制剂加工的方法,使用溶剂和表面活性材料,制备出本发明化合物No.279的浓度为100克/升的乳油。通过稀释,由此乳油和由市场上的制剂,制备出用于喷雾的试验溶液。处理24小时后,确定蚜虫的死亡率。结果示于下列:
实施例7用家蝇研究对繁殖的作用
处理 | 死亡率% |
克百威 1ppm克百威 1ppm+279抗蚜威2ppm抗蚜威2ppm+279吡虫啉0.1ppm吡虫啉0.1ppm-279 | <50>95<30>95<50>95 |
由刚孵化的50只雄性和50只雌性家蝇组成的试验组用分别包含500ppm本发明物质No.441和484颗粒状蔗糖饲喂48小时。并培养在接下来的10天中产下的卵。用处理与未处理组中出现的蝇数之比表示繁殖妨碍作用。实验进行4组重复。
实施例8用二点叶螨(Tetranychus urticae)研究杀螨增效作用
处理 | 对繁殖的妨碍作用 |
441484 | 87%90% |
由1周龄的大豆植株的第一对叶片切下225毫米直径的叶盘,将之通过浸渍入(5分钟)由活性成分和增效剂组成的一定浓度的试验溶液中来处理。制备所需浓度的母液时,使用10%的作为助溶剂的丙酮和0.1%的作为洗涤剂的吐温80。将变干的叶盘放置于湿的表面上,将它们用10只成雌螨/叶侵害。使用显微镜和刷子记录48小时后的死亡率。实验进行4组重复。结果的平均值示于下表中。
实施例9防治马铃薯甲虫(Leptinotarsa decemlineata)的大田试验效果
用单独的活性成分处理 | 浓度(ppm) | ||||
31 | 62 | 125 | 250 | 500 | |
死亡率(%) | |||||
279克百成溴螨酯 | 01318 | 63928 | 84490 | 1881- | 3090- |
用组合的活性成分处理 | 浓度(ppm) | ||||
16+16 | 31+31 | 62+62 | 125+125 | 250+250 | |
死亡率% | |||||
279+克百威279+溴螨酯 | 2975 | 8090 | 80100 | 100- | 100- |
用通常用于制剂加工的方法,使用溶剂和表面活性材料,制备出本发明化合物No.279的浓度为100克/升的乳油。Chinufur 40 FW组合物(包含400克/升克百威)与固定剂量的2升/公顷的化合物No.279一起施用,于小区大田试验中研究对马铃薯甲虫(Leptinotarsa decemlineata)防治效果。用机动喷雾器(Maruyama)施用300升/公顷的喷雾液进行喷雾。用25m2的小区进行处理,处理重复4次。处理的效果在第2天通过计数存活于植株上的甲虫数来评价。结果示于下表中:
实施例10化合物Nr.599的增效活性
处理 | 剂量(1/英亩) | 克百威∶279比率 | 马铃薯甲虫数目只/株 | |
处理前 | 处理后 | |||
未处理Chinufur40 FWChinufur40 FWChinufur40 FW+279 | -0.10.20.1+2.0 | -1∶01∶01∶5 | 23.618.432.021.3 | 28.06.16.80.4 |
通过描述于实施例8中的方法,研究化合物599与各种特定的杀螨剂防治二点叶螨的增效活性。由浓度—死亡关系计算出的LC50和LC95值示出下表中
防治二点叶螨的增效活性
实施例11防治豌豆蚜(Acyrthosiphon pisun)的增效活性
处理 | 杀螨剂/增效剂比 | 接触时间(h) | LC50 | LC95 | 增效比 | |
(mg /l) | SR50 | SR95 | ||||
克百威 | 1∶0 | 24 | 163.9 | 799.9 | - | - |
克百威+MB-599 | 1∶1 | 24 | 55.5 | 286.8 | 3.0 | 2.8 |
1∶2 | 24 | 33.5 | 93.7 | 4.9 | 8.5 | |
1∶4 | 24 | 27.5 | 67.0 | 6.0 | 11.9 | |
喹螨醚 | 1∶0 | 3 | >1000 | - | - | - |
1∶0 | 24 | 41.9 | 801.3 | - | - | |
喹螨醚+PBO | 1∶1 | 3 | 326.7 | >1000 | >3.1 | - |
1∶1 | 24 | 20.4 | 371.8 | 2.1 | 22 | |
喹螨醚+MB-599 | 1∶1 | 3 | 68.1 | 280.2 | >15 | - |
1∶1 | 24 | 31.3 | 174.8 | 1.3 | 4.6 | |
吡螨胺 | 1∶0 | 3 | >1000 | - | - | - |
1∶0 | 24 | 63.4 | >1000 | - | - | |
吡螨胺+PBO | 1∶1 | 3 | 115.9 | 1081 | >9 | - |
1∶1 | 24 | 35.7 | 118.0 | 1.8 | >8.5 | |
吡螨胺+MB599 | 1∶1 | 3 | 61.8 | 658.7 | >16 | - |
1∶1 | 24 | 22.3 | 141.8 | 2.8 | >7.0 |
在大田中,在小区(10m2)上,对化合物No.599防治豌豆蚜(Acyrthosiphon pisun)的增效活性进行试验。使用机动喷雾器(Maruyama)喷雾,喷雾体积为300升/公顷。分别用处理前与处理后二天的蚜虫数/叶片平均数表示效力。(Henderson和Tilton:J.Econ.Entomol.[经济昆虫学杂志]48:157,1955)。结果示于下表中。
实施例12与已知参考增效剂的对比研究
处理 | 剂量a.i./ha | E(%) |
抗蚜威 250 93.880 86.3抗蚜威+MB-599 80+80 95.5 | ||
锐劲特 240 94.6锐劲特-MB-599 120+120 95.7 | ||
克百威 160 99.1110 98.0克百威+MB-599 110+110 100.0 | ||
Triazamate 50 96.8Triazamate+MB-599 33+33 97.7 | ||
吡虫啉 120 98.4吡虫啉+MB-599 120+120 100.0 |
设4次重复,用克百威和1000ng的已知增效剂处理家蝇,确定对比化合物的LD50值,并相对于对照克百威计算出SR50值。这些SR50比与由我们制备的新化合物的SR50比相比较。我们的化合物在每种情况下均更具有活性。1.炔基酯类
已知 本发明
2.(芳基-烷基),烷基-炔基醚类
增效比 | 2-丙炔基-1-萘基-羧酸酯 | 502 |
SR50 | 4.11 | 6.28 |
已知 本发明
增效比 | (2,6二氯苯基)甲基2-丙炔基醚 | 503 |
SR50 | 20.92 | 21.16 |
已知 本发明
增效比 | 5-[(2-丙炔基)甲基]-1,3-苯并间二氧杂环戊烯 | 441 |
SR50 | 10.60 | 25.70 |
已知 本发明
增效比 | 1-萘甲基2-丙炔基醚 | 279 |
SR50 | 5.28 | 28.7 |
已知 本发明
增效比 | 2-[(2-丙炔氧基)甲基]-1,4-苯并二噁烷 | 510 |
SR50 | 5.58 | 18.32 |
已知的 本发明的
3.烷基炔基醚
增效比 | (2-丙炔氧基-甲基)-3,4-二甲氧基苯 | 493 |
SR50 | 6.58 | 32.84 |
已知的 本发明的
4.炔基-肟-醚
增效比 | 2,3-二氢-2,2-二甲基-7-(2-丙炔氧基)苯并呋喃 | 418 |
SR50 | 1.8 | 20.5 |
已知的萘基炔基醚 | 增效比 SR50 |
1-萘基2-炔丙基醚 | 6.52 |
1-萘基-3-丁炔基醚 | 7.95 |
2-萘基-2-丁炔基醚 | 7.72 |
2-萘基3-戊炔基醚 | 9.97 |
已知的 本发明的
增效比 | 1-乙酰萘-肟(2-丙炔基)醚 | 571 |
SR50 | 7.79 | 10.02 |
剂型实施例
在引号中给出市场上出售的辅助材料的名称,接下来的是生产厂家的名
称。1.粉剂的制备A)
在均化器中,将158克细粒状的珍珠岩与20克克百威和20克化合物279混合,向此混合物中加入2克脂族醇聚乙二醇醚(“G-3920”ICI),并将混合物均化。将粉状混合物在喷射研磨机中磨成颗粒,且向其中加入5克辛基-苯酚-聚乙二醇-醚(EO=20)(“Triton X-165”Rohm & Haas)和2克烷基磺基琥珀酸盐(“Aerosol-13”Cyanamid)。所得的产物是可湿性粉剂(WP)。B)
将10克化合物279和10克克百威用2克乙醇稀释。将此溶液在粉末均化器中与5克木素磺酸钙(“Borrespeseca”Borregard)、5克壬基-苯酚-聚乙二醇-醚(EO=20)(“Arkopal N-200”Hoechst)和70克碳酸钙混合。所得的产物在alpine-100型研磨机中研磨。平均粒径为1-2微米。此组合物可以用于制备微悬浮剂。C)
在均化器装置中,用1.0克合成硅酸(Aerosil 200)和191克滑石(dmax.=15-30微米)混合物吸收3克二嗪磷、3克化合物441和0.3克脂族醇-聚乙二醇-醚(“G-3920”ICI)混合物,前者的PH值用磷酸钾和磷酸钠缓冲液预先调节至pH=7.0。在进一步搅拌中,加入1克二辛基-磺基-琥珀酸盐(“Aerosol OTB”Cyanamid)和1克脂族醇-聚乙二醇-醚磺酸盐(“Genapol LRD”Hoechst),最后,将混合物研成平均粒径为20微米的细粉。所得的产物为易流动的粉状制剂。2.乳油的制备A)
将5克抗蚜威和5克化合物493溶解于20克二甲苯和40克丙醇的混合物中。向此溶液加入4克乙氧基化的烷基酚+直链烷基-芳基-磺酸钙盐(“Geronol FF/U”Geronazzo)和6克乙氧基化的胺+脂肪酸+直链烷基-芳基-磺酸碱金属盐(“Geronol MS”Geronazzo)。完全溶解后,加入20克水。获得透明溶液,此溶液的特点是,用水稀释时,它形成乳滴直径为0.8-1.5微米的乳液。B)
将5克喹硫磷和10克化合物484的混合物和7克乙氧基化-(EO=13)-丙氧基化-(PO=21)-壬基苯酚、2克直链十二烷基苯磺酸钙盐和12克POE-(20)-失水山梨醇-单油酸酯的混合物溶解于28.6-28.6毫升丙二醇和松脂酸和23.8毫升向日葵油、9.5毫升乙醇和95毫升萘含量为45%的脂族烃的混合物。由此获得的材料可以优选用于制备微乳剂。C)
将0.02-0.02质量份的活性成分和增效剂混合物溶解于10份质量的丙醇中,向所得的溶液加入99.96质量份的无臭石油醚,搅拌此混合物直到获得均质溶液。所得的油状可分散制剂可以用ULV施用法直接使用。D)
按照实施例A)的方法,所不同的是用10克化合物279作为增效活性成分。3.颗粒剂的制备在机械造粒机中将300克克百威、300克化合物418、1500克多元羧酸碱金属盐(“Sorphol”,Toho),500克十二烷基苯磺酸钠盐(“MarlonTP 370”Huels),500克蔗糖和7200克高岭土。用高剪切力(v=10米/秒)的混合机将由此获得的粉末混合物与8300毫升水混合。此混合物最后喷雾干燥。产品的粒径分布为0.1-0.4毫米。4.气雾剂的制备
在100升带有搅拌器的设备中,将1千克生物烯丙菊酯、0.5千克化合物441、0.1千克气雾空气972、0.1千克乙二醇单水杨酸酯、15千克无臭石油醚和50千克丙醇混合。溶解后,将之装入带有33.3千克液化丙烷-丁烷(25-75)气的钢瓶中。5.熏蒸剂的制备在60毫升乙醇中溶解5克S-生物烯丙菊酯、5克化合物279和1克柠檬香料。此溶液在熏蒸器在于50℃的温度下使用。
Claims (20)
1.通式I化合物、其光学活性异构体及其盐,Ar-(CR1R2)m-(YR3R4)n-X-(CR5R6)o-(CR7R8)p-C≡C-E
I其中Ar=任选由一或多个C1-4烷氧基、亚甲二氧基、C1-4烷基、卤素、C1-4卤代烷基或硝基取代的苯基或萘基;脂环-、或含有一或多个杂原子的杂环部分,任选由一或多个C1-4烷氧基、亚甲二氧基、C1-4烷基、卤素、C1-4卤代烷基或硝基基团取代,和/或与苯环稠合,R1、R2=独立的氢、烷基、链烯基、卤代烷基、苯基、环烷基,R3、R4=独立的氢、烷基、链烯基、卤代烷基、苯基、环烷基,或R3、R4一起是=O;Y=C、=PO,或YR3R4一起形成基团-C(R9)=N-;X=-O-;-NR10-;R9=氢、烷基、苯基;R10=氢、烷基;R5、R6、R7、R8独立地是氢、烷基、链烯基、卤代烷基,或Ar-(CR1R2)m-(YR3R4)n-X-一起形成羧酰亚胺基团;E=甲基;m=0、1、2;n=0、1;o=0、1、2;p=0、1、2;其条件是,桥-(CR1R2)m-(CR3R4)n-X-(CR5R6)o-(CR7R8)p的原子或基团之总和是3,另一条件是,如果Ar是萘基基团,Y是C-原子,X是O原子,则R3和R4一起不可以是=O。
3.根据权利要求1的通式I化合物及其光学异构体,它具有通式IB,其中Ar、R1、R2、R5、R6、R7、R8、R10、Y、E、m、o和p与权利要求1中定义的含意相同。
4.根据权利要求1的通式I化合物及其光学异构体,它具有通式IC,Ar-(CR1R2)m-(CR3R4)n-O-(CR5R6)o-(CR7R8)p-C≡C-E
IC其中Ar、R1、R2、R3、R4、R5、R6、R7、R8、E、m、n、o和p与权利要求1中定义的含意相同。
7.根据权利要求1的通式I化合物及其光学异构体,它具有通式IF,其中Ar、R1、R2、R5、R6、R7、R8、R9、E、m、o和p与权利要求1中定义的含意相同。
8.根据权利要求1的化合物
1-萘基-甲基2-丁炔基 醚,
2-丙炔基-1,3-苯并间二氧杂环戊烯-5-羧酸酯,
1-[(2-丁炔氧基)-乙基]-3,4-二甲氧基苯,
2,6-二氯-1-(2-丁炔氧基甲基)苯,
1-[1-(2-丁炔氧基)丙基]萘,
R-(+)-2-[1-(2-丁炔氧基)乙基]萘,
5-[(丁-2-炔基氧基)甲基]-1,3-苯并间二氧杂环戊烯,
5-[2-甲基-1-(2-丁炔氧基)丙基]-1,3-苯并间二氧杂环戊烯,
5-[(丁-2-炔基氧基)苯基甲基]-1,3-苯并间二氧杂环戊烯,
2-[(2-丁炔氧基)甲基]-1,4-苯并二噁烷,
2,3-二氢-2,2-二甲基-7-(3-戊炔氧基)苯并呋喃。
9.制备通式I化合物的方法,式中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、X、Y、E、m、n、o和p与权利要求1中定义的含意相同,其特征在于,a)制备通式IA化合物,式中,Ar、R1、R2、R5、R6、R7、R8、Y、E、m、o和p具有与权利要求1中定义相同的含意,使通式II与III化合物反应,其中Ar、R1、R2、R5、R6、R7、R8、Y、E、m、o和p具有与权利要求1定义相同的含意,A和B是适合于形成酯键的基团,B-(CR5R6)o-(CR7R8)p-C≡C-E III.b)制备通式IB化合物,式中,Ar、R1、R2、R5、R6、R7、R8、R10、Y、E、m、o和p具有与权利要求1定义相同的含意,使通式IV和V的化合物反应,式中,Ar、R1、R2、R5、R6、R7、R8、Y、E、m、o和p具有与权利要求1定义相同的含意,且C和D代表适合于形成酰胺键的基团,D-(CR5R6)o-(CR7R8)p-C≡C-E V.c)制备通式IC化合物,式中,Ar、R1、R2、R5、R6、R7、R8、E、m、n、o和p具有与权利要求1定义相同的含意,R3和R4相互独立地代表H、烷基、链烯基、卤代烷基、苯基、取代的苯基,使通式VI和VII的化合物反应,式中,Ar、R1、R2、R5、R6、R7、R8、E、m、n、o和p具有与权利要求1定义相同的含意,R3和R4相互独立地代表H、烷基、链烯基、卤代烷基、苯基、取代的苯基,且F和G代表适合于形成醚键的基团,Ar-(CR1R2)m-(CR3R4)n-F VI.G-(CR5R6)o-(CR7R8)p-C≡C-E VII.d)制备通式ID化合物,式中,Ar-(CR1R2)m-(CR2R4)n-N-代表羧酰亚胺基团,R5、R6、R7、R8、E、o和p具有与权利要求1定义相同的含意,使通式VIII的羧酰亚胺与通式IX的化合物反应,式中,R5、R6、R7、R8、E、o和p具有与权利要求1定义相同的含意,且Lg代表离去基团,Lg-(CR5R6)o-(CR7R8)p-C≡C-E IX.e)制备通式IE化合物,式中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、R10、E、m、n、o和p具有与权利要求1定义相同的含意,使通式X和XI的化合物反应,式中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、E、m、n、o和p具有与权利要求1定义相同的含意,且H和I代表适合于形成-N(R10)-键的基团,其中R10具有与权利要求1定义相同的含意,Ar-(CR1R2)m-(CR3R4)n-H X.I-(CR5R6)o-(CR7R8)p-C≡C-E XI.f)制备通式IF化合物,式中,Ar、R1、R2、R5、R6、R7、R8、R9、E、m、o和p具有与权利要求1定义相同的含意,使通式XII和IX的化合物反应,式中,Ar、R1、R2、R5、R6、R7、R8、R9、E、m、n、o和p具有与权利要求1定义相同的含意,且Lg代表离去基团,Lg-(CR5R6)o-(CR7R8)p-C≡C-E IX.且如果需要,如此得到的通式I化合物可以转化成其盐,或可以从其盐释放,如果需要,可以分离其光学活性异构体。
10.农药组合物,包含按重量计0.0001-99.9%的作为活性成分的通式I化合物,其中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、m、n、o和p与权利要求1中定义的含意相同,和任选的其它农药活性成分,以及载体和其它辅助材料。
11.杀节肢动物剂组合物,包含按重量计0.0001-99.9%的作为活性成分的通式I化合物,其中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、m、n、o和p与权利要求1中定义的含意相同,和任选的其它杀节肢动物剂活性成分,以及载体和其它辅助材料。
12.根据权利要求11的组合物,其特征在于,它含有的其它活性成分为:乙酰胺衍生物;苯甲酰脲化合物;类苯甲酰脲IGR化合物;双环庚二烯化合物;交联桥接的二苯基化合物;氨基甲酸酯类;氨基甲酰基肟衍生物;环二烯类;二唑类;酰肼类;沙蚕毒类似物;硝基亚咪唑烷基烷基胺;有机磷化合物;有机锡化合物;苯氧基化合物;吡唑类;拟除虫菊酯;哒嗪酮类;吡啶衍生物;嘧啶衍生物;吡咯类;喹唑啉类;萜类衍生物;四嗪类;噻二嗪类;噻唑烷类;***类;氯化烃类;大环内酯类;吡螨胺;唑螨酯;Triazamate。
13.根据权利要求12的组合物,其特征在于,所述乙酰胺衍生物为杀线威;苯甲酰脲化合物为氟螨脲、氟铃脲、伏虫隆、杀虫隆;双环庚二烯化合物为庚烯磷;交联桥接的二苯基化合物为醚菊酯、溴螨酯、甲氧滴滴涕、双硫磷、三氯杀螨砜;氨基甲酸酯类为灭害成、涕灭威、氧涕灭威、磺草灵、噁虫威、丙硫克百威、甲萘成、卡草胺、克百威、丁硫克百威、乙霉威、二氧威、乙硫苯威、仲丁威、双氧威、呋线威、叶蝉散、灭多威、杀线威、抗蚜威、残杀威、硫双威、久效威、灭杀威;氨基甲酰基肟衍生物为棉铃威、丁酮威;环二烯类为艾氏剂、氯丹、硫丹、七氯;二唑类为锐劲特;酰肼类为RH5992、RH5849、CGA215′944;沙蚕毒类似物为杀虫磺;硝基亚咪唑烷基烷基胺为吡虫啉;有机磷化合物为喹硫磷、二嗪磷、伏杀硫磷、乐果、保棉磷;有机锡化合物为***锡、三环锡、苯丁锡、SSI-121;苯氧基化合物为杀螨隆;吡唑类为吡嘧磷;拟除虫菊酯为烯丙菊酯、生物烯丙菊酯、氟酯菊酯、氰戊菊酯、烯炔菊酯、炔酮菊酯、苄呋菊酯、MTI-800、氟醚菊酯、氯菊酯、胺菊酯、氯氰菊酯及其异构体和异构体组合体;哒嗪酮类为哒螨酮;吡啶衍生物为毒死蜱;嘧啶衍生物为嘧啶磷、甲基嘧啶磷;吡咯类为AC303-t.630;喹唑啉类为喹螨醚;萜类衍生物为烯虫酯;四嗪类为四螨嗪,SzI-121;噻二嗪类为噻嗪酮;噻唑烷类为噻螨酮;***类为氯唑磷、RH7988;氯化烃类为林丹。
14.根据权利要求11-13之任一项的组合物,包含作为通式I活性成分的一或多种下列化合物:
1-萘基-甲基2-丁炔基醚,
2-丙炔基-1,3-苯并间二氧杂环戊烯-5-羧酸酯,
1-[(2-丁炔氧基)-乙基]-3,4-二甲氧基苯,
2,6-二氯-1-(2-丁炔氧基甲基)苯,
1-[1-(2-丁炔氧基)丙基]萘,
R-(+)-2-[1-(2-丁炔氧基)乙基]萘,
5-[(丁-2-炔基氧基)甲基]-1,3-苯并间二氧杂环戊烯,
5-[2-甲基-1-(2-丁炔氧基)丙基]-1,3-苯并间二氧杂环戊烯,
5-[(丁-2-炔基氧基)苯基甲基]-1,3-苯并间二氧杂环戊烯,
2-[(2-丁炔氧基)甲基]-1,4-苯并二噁烷,
2,3-二氢-2,2-二甲基-7-(3-戊炔氧基)苯并呋喃。
15.根据权利要求11的组合物,它包含作为活性成分的按重量计0.0001-99.9%的通式I化合物,其中,Ar、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、m、n、o和p与权利要求1中定义的含意相同,和-种适合于消灭节肢动物的氨基甲酸酯类。
16.根据权利要求15的组合物,其中所述的氨基甲酸酯类为克百威。
17.根据权利要求15的组合物,它包含(2-丁炔氧基-甲基)-3,4-二甲氧基苯作为通式I化合物。
18.根据权利要求15的组合物,它包含5-[(丁-2-炔基氧基)甲基]-1,3-苯并间二氧杂环戊烯作为通式I化合物。
19.消灭害虫的方法,包含用适当量的权利要求10或11组合物,如果需要,以这样的方式处理害虫,即,将含有其中Ar、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、m、n、o和p与权利要求1中定义的含意相同的通式I化合物的组合物和含有已知活性成分的组合物以桶混物形式使用或依次使用。
20.根据权利要求19的方法,其中所述的害虫为节肢动物。
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HU9503318A HU220697B1 (hu) | 1995-11-21 | 1995-11-21 | Arthropodicid hatóanyagok, eljárás előállításukra és ezeket a hatóanyagokat tartalmazó készítmények |
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CN103222473A (zh) * | 2013-05-06 | 2013-07-31 | 南通金陵农化有限公司 | 一种吡虫啉与噻嗪酮复配杀虫剂 |
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