杀虫植物苦皮藤毒杀成分的研究

从苦皮藤Celastrus angulatus Max.根皮中分离出5个对粘虫Mythimna separata (walker)具有毒杀活性的新化合物。经高分辨质谱和核磁共振谱鉴定其 结构为1α，2α,6β-三乙酰氧基－4β－羟基－8α－异丁酰氧基9β－呋喃甲酰氧 基－13－异戊酰氧基－β－二氢沉香呋喃（1），1α，2α，6β－二乙酰氧基－4 β－羟基8α，13－二异丁酰氧基－9β－苯甲酰氧基－β－二氢沉香呋喃（2）， 1α，2α，6β－三乙酰氧基－4β－羟基－8α－β异丁酰氧基－9β－苯甲酰氧基 －13－异戊酰氧基－β-二氢沉香呋喃（3），1α，6β，8α，13－四乙酰氧基－ 2α－羟基－9α－苯甲酰氧基－β－二氢沉香呋喃（4），1α，2α－二乙酰氧基 －4β，6β－二羟基－8β－异丁酰氧基9α－苯甲酰氧基－13－异戊酰氧基－β－ 二氢沉香呋喃（5）。它们对5龄粘虫的致死中量LD50分别为91.4,271.5，168.8, 388.0和135.5μg/g。     

聚(N-对丙烯酰氧苯甲酰氧基)丁二酰亚胺的合成及其共聚物与血清蛋白的固定化

新的丙烯酸活性酯,N-(对甲基丙烯酰氧苯甲酰氧基)丁二酰亚胺(MBOSu)及N-(对丙烯酰氧苯甲酰氧基)丁二酰亚胺(ABOSu)单体分别由对甲基丙烯酰氧基苯甲酸(MBA)、对丙烯酰氧基苯甲酸(ABA)与N-羟基丁二酰亚胺(HOSu)在环已基羰二亚胺存在下经偶联反应合成。MBOSu及 ABOSu 容易进行均聚合及与MBA或ABA进行共聚合而得到相应的反应性聚合物。P(MBOSu-MBA)共聚物是一个较好的固定化蛋白质的载体。它极易与抗血清(驴抗人A·B·O混合血清)或正常人 A·B·O混合血清反应,形成一种具有较高免疫活性的固定化免疫吸附剂。     

聚丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]及聚甲基丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]的合成

周其凤等曾报道聚丙烯酸［２,５－双（对甲氧基苯甲酰氧基）节酯］［１］和聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］［２］的合成．但后来的研究发现,在合成单体的条件下出现的一种未见报道的异常反应［３］使产物成分复杂化,因此当时报道的聚合物可能不是聚丙烯酸［２,５－双－（对甲氧基苯甲酰氧基）苄酯］或聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］,而可能是共聚物．针对这一问题,我们重新设计了合成路线以避免发生上述副反应,成功地合成了丙烯酸或ａ－甲基丙烯酸［２,５－双－（对甲氧基苯甲酰氧基…     

氢键诱导聚马来酸单酯液晶复合物的合成及表征

合成了聚马来酸６－（４－辛氧基偶氮苯氧基）－１－己酯（ＰＭＡＮ－ＯＡＢ），并以其为质子给体，４－（４－庚氧基苯甲酰氧基）－苯乙烯基吡啶（７ＳＺ）为质子受体，研究了两者复合前后的液晶行为，结果表明，ＰＭＡＮ－ＯＡＢ在液晶态时是以羧酸二聚体形式存在的，其倾角为３９．３°，７ＳＺ含量在４０％～９０％范围内的复合物液晶范围比７ＳＺ和ＰＭＡＮ－ＯＡＢ的宽。     

稠杂环化合物的研究（Ⅹ）—3—芳基—6—苯甲酰氨基均三唑并[3…

本文利用３－芳基－４－氨基－５－巯基－１，２，４－均三唑和苯甲酰异硫氰酸酯在无水丙酮中反应，得到一系列３－芳基－６－苯甲酰氨基均三唑并［３，４－ｂ］－１，３，４－二噻二唑。用元素分析、ＩＲ、＾１Ｈ ＮＭＲ和ＭＳ确定了其结构，提出了可能的反应机制。并对其代表产物２ｈ进行了初步的抗菌和除草实验。     

Abnormal Reaction of 1-(2′-Methoxybenzoyl)-1-(2′-hydroxy-5′-methoxycarbonylbenzoyl)methane Treated with Etyyl Orthoformate and Acetic Anhydride

邻羟基二苯甲酰基甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应通常是ＨＣ（ＯＥｔ）３作为酰化剂，得到３－苯甲酰基色酮。本文报道５－甲氧羰基－２－羟基苯甲酰基－（２′－甲氧苯甲酰基）甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应时，是Ａｃ２Ｏ而不是ＨＣ（ＯＥｔ）３作为酰化剂，生成３－苯甲酰基－２－甲基色酮。其结构经ＮＭＲ、ＭＳ、ＩＲ和ＥＡ证实。并对其反应机理作了讨论。     

3,3′—二苯甲酰基双酚—S及苯甲酰侧基聚芳醚腈的合成

利用双酚－Ｓ与苯甲酰氯形成的二元酚酯在ＡｌＣｌ３作用下进行Ｆｒｉｅｓ重排制备３，３′－二苯甲酰基双酚－Ｓ，以此与二氯苯甲腈进行缩聚反应合成了带苯甲酰基侧基的聚芳醚腈。     

1—（5‘—甲氧羰基—2’—羟基苯甲酰基（—1—（2‘—甲氧苯甲酰基）甲烷与Ac2O和HC...

邻羟基二苯甲酰基甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应通常是ＨＣ（ＯＥｔ）３作为酰化剂，得到３－苯甲酰基色酮。本文报道５－甲氧羰基－２－羟基苯甲酰基－（２＇－甲氧苯甲酰基）甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）ｓ反应时，是Ａｃ２Ｏ而不是ＨＣ（ＯＥｔ）作为酰化剂，生成３－苯甲酰基－２－甲基色酮。其结构经ＮＭＲ、ＭＳ、ＩＲ和ＥＡ证实。并对其反应机理作了讨论。     

稠杂环化合物的研究（X）──3－芳基－6－苯甲酰氨基均三唑并［3，4－b］－1，3，4－噻二唑类化合物的合成及生物活性

本文利用３－芳基－４－氨基－５－巯基－１，２，４－均三唑和苯甲酰异硫氰酸酯在无水丙酮中反应，得到一系列３－芳基－６－苯甲酰氨基均三唑并［３，４－ｂ］－１，３，４－噻二唑，用元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ确定了其结构，提出了可能的反应机制。并对其代表产物２ｈ进行了初步的抗菌和除草实验。     

铝与溴代二甲氨基苯基荧光酮的多元配合物的光度研究

本文研究了在表面活性剂存在性，铝与溴代二甲氨基苯基荧光酮的显色反应。在弱酸性介质中，Ａｌ＾３＋ＢＤＭＡＦ－ＣＴＭＡＢ三元配合物在水浴加热至７０℃－８０℃时形成，其最大吸收波长为５７７ｎｍ，Ａｌ＾３＋：ＢＤＭＡＦ＝１：２，表观摩尔吸光系数为１．３４×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，表观稳定常数为７．４×１０＾５。在ＰＨ９．５－１０．５的氨性缓冲介质中，Ａｌ＾３＋－Ｆ＾－－ＢＤＭＡＦ－非离子表面     

全氟和多氟烷基磺酸的研究 IX. 5-卤-3-氧杂-全氟戊磺酰氟的化学转化

5-Halo-3-oxa-perfluoropentanesulfonic acids 2,4 were obtained in high yields by treating the corresponding sulfonyl fluorides successively with KOH and concentrated H2SO4: Treatment of the acids with P2O5 gave corresponding anhydrides 3, 5. 3 reacted with various alcohols in the presence of pyridine to yield sulfonates 6. 5-Iodo-3-oxa-perfluoropentanesulfonyl fluoride (1) was converted to the acyl fluoride 9 by fuming sulfuric acid. Depending on the reaction temperature 9 can be hydrolyzed to fluorosulfonyl perfluoroalkanoic acid 10 and/or mixed dibasic acid 11. A similar phenomenon was also observed in the case of hydrolysis of fluorocarbonyl-perfluoromethanesulfonyl fluoride(13). Alcohol reacted readily with the acyl fluoride group but not with the sulfonyl group in 9 giving carboxylic esters, which can be further transformed to the corresponding sulfonates. Perfluoroalkoxide ion -O(CF2)2O(CF2)2SO2F prepared from 9 and F- reacted with active alkyl halides yielding the corresponding ethers. The interaction of 5-halo-3-oxa-perfluoroalkane-sulfonyl fluoride with AlCl3 was investigated. Friedel-crafts acylation of aromatic compounds with 9 in the presence of anhydrous AlCl3 is also reported. The yields of the desired ketones can be improved by using CCl4 as a solvent and changing the order of addition of reactants.     

Regioselection and orthogonality of the 1-phenyl-3-butenyl (PBU) protecting group in glucopyranosides

The 1-phenyl-3-butenyl (PBU) protecting group was alternatively introduced in position 4 or 6 by regioselective opening of methyl 2,3-di-O-benzyl-4,6-O-benzylidene-alpha-D-glucopyranose with allyltrimethylsilane in the presence of the Lewis acid promoters TMSOTf or AlCl3. The PBU group was selectively removed, in presence of t-butyldimethylsilyl, trityl or acetyl protecting groups, with acids (TFA) or using Pd(CH3CN)2Cl2.     

Strukturen und reaktionen von methylantimondihalogeniden und versuche zur darstellung von methylantimon

MeSbCl₂ (1) and SbCl₃ give the adduct MeSbCl₂·0.6SbCl₃ (1a). MeSbBr₂ (2) reacts with NaI to form MeSbI₂ (3) and with Cr(CO)₅ THF to give Me(Br)₂SbCr(CO)₅ (4). The crystal structures of 1a, 2 and 4 are reported. Derivatives of methyl antimony are obtained by reaction of 2 or 4 with Mg in tetrahydrofuran.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Regioselective hydrosilylations of propiolate esters with tris(trimethylsilyl)silane

Lewis acid and substituent dependency on the regioselectivity of hydrosilylation of propiolate esters 1a-c with tris(trimethylsilyl)silane (2a) was found. The reaction of methyl and ethyl propiolate esters and 2a without Lewis acid and in the presence of EtAlCl2 and Et2AlCl gave beta-silicon-substituted Z-alkenes 3 selectively. On the other hand, reaction in the presence of AlCl3 in dichloromethane gave alpha-silicon-substituted alkenes 4. In the case of trifluoroethyl propiolate ester 1c, reaction with aluminum chloride-based Lewis acids gave alpha-silicon-substituted alkenes 4 exclusively. Two competitive mechanisms, free-radical and ionic, are proposed as the source of the complementary regioselectivity displayed in these reactions. A transition state of the radical-forming step was obtained computationally. The reaction of various reactive acetylene substrates and 2a without Lewis acid and without solvent at room temperature gave beta-silicon-substituted Z-alkenes 3 selectively.     

(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯和(Z)-2-苯氧(硫)亚甲基-γ-戊内酯的简便合成

以3-苯氧(硫)基丙炔(1)为原料,经5步反应合成(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯(8)和(Z)-2-苯硫亚甲基-γ-戊内酯(9).合成关键步骤为TMSCl/NaI/H2O/CH3CN体系中化合物(3)的碘氢化和去共轭.     

Condensation Reaction of 5,6-Dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-dione,Ethyl Orthoformate and Substituted Anilines

Piperonyl methyl ketone was obtained by oxidizing isosafrole with hydrogen peroxide and formic acid.Dianion of ethyl acetoacetate reacted with piperonyl methyl ketone and 5,6-dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-dione was prepared,which reacted with substituted anilines in the presence of ethyl orthoformate to obtain 3-anilinomethylene-5,6-dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-diones.Their structure were confirmed by ^1HNMR and elemental analysis.     

Synthèse de l'évernine

Synthesis of Evernin Two syntheses of the depside evernin 6 are described. Condensation of methyl acetoacetate and methyl crotonate followed by aromatization and reduction with Raney-Ni led to methyl orsellinate (3) . The condensation of everninic acid (4) , obtained by partial methylation of 3 and saponification of the methyl ester, with methyl 2, 4-dihydroxy-3, 6-dimethylbenzoate (methyl β-orcin carboxylate) (5) in presence of cyclohexylcarbodiimide gave evernin ( 6 ). In a second syntheis methyl dihydroorsellinate (1) was regiospecifically converted into its 4-methyl enol ether and aromatized via the benzene selenenyl derivative to yield methyl evernate (7) . Benzylation followed by saponification gave the free acid 8 . Methyl β-orcin carboxylate (5) was synthesized in an analogous way from methyl 3,6-dimethyl-2,4-dioxocyclohexanecarboxylate. Condensation of 8 with the methyl ester 5 by treatment with trifluoroacetic anhydride in toluene yielded 9 , which could be converted into evernin ( 6 ) by hydrogenolysis of the benzyl ether.     

新型5-溴嘧啶衍生物的选择性合成

对甲苯磺酰氯与三甘醇单甲酯完成酯化反应,再与对溴苯酚缩合制得对溴苯基三甘醇单甲醚(3);3与硼酸甲酯完成取代反应、酸解后在Pd(PPh3)4催化下与5-溴-2-碘嘧啶(5)在甲苯中通过Suzuki偶联反应选择性地合成了5-溴-2-对(甲基三甘醇基)苯基嘧啶(1a),收率73%。以1-十二烯和5为主要原料,通过Suzuki偶联反应,一锅法选择性地合成了5-溴-2-十二烷基嘧啶(1b),收率82%。1a和1b未见文献报道,其结构经1HNMR,13C NMR和MS表征。     

Synthesis and Antiproliferative Activity of Phosphorus Substituted 4-Cyanooxazolines, 2-Aminocyanooxazolines, 2-Iminocyanooxazolidines and 2-Aminocyanothiazolines by Rearrangement of Cyanoaziridines

Several phosphorus-substituted N-acylated cyanoaziridines 2 and N-carbamoylated cyanoziridines 5 were prepared in good to high yields. N-Acylated cyanoaziridines 2 were used, after ring expansion, in an efficient synthesis of oxazoline derivative 3a and in a completely regio-controlled reaction in the presence of NaI. Conversely, N-carbamoyl cyanoaziridines 5 reacted with NaI to obtain a regioisomeric mixture of 2-aminocyanooxazolines 7. Mild acidic conditions can be used for the isomerization of N-thiocarbamoyl cyanoaziridine 6a into a 2-aminocyanothiazoline derivative 8a by using BF₃·OEt₂ as a Lewis acid. Likewise, a one pot reaction of NH-cyanoaziridines 1 with isocyanates obtained 2-iminocyanooxazolidines 9 regioselectively. This synthetic methodology involves the addition of isocyanates to starting cyanoaziridines to obtain N-carbamoyl cyanoaziridines 5, which after the ring opening, reacts with a second equivalent of isocyanate to give the final 2-imino cyanooxazolidines 9. In addition, the cytotoxic effect on the cell lines derived from human lung adenocarcinoma (A549) was also screened. 2-Iminooxazolidines 9 exhibited moderate activity against the A549 cell line in vitro. Furthermore, a selectivity towards cancer cells (A549) over non-malignant cells (MCR-5) was detected.