含1,6-二氢-6-哒嗪酮的1,3,4-噁二唑啉和噻唑烷-4-酮类化合物的合成

以1,6-二氢-6-哒嗪酮-3-甲酰肼(1)与芳香醛反应得到相应的1,6-二氢-6-哒嗪酮-3-羰基芳香醛腙(2a～2e). 再将2a～2e与乙酸酐作用, 合环得到一系列含有1,3,4-噁二唑啉环的衍生物3a～3e; 在DMF中用HSCH₂COOH合环, 得到含有4-噻唑烷酮的衍生物4a～4e. 所有化合物的结构均经元素分析, IR, ¹H NMR 和MS谱得以证实.     

4-(色酮-3-基)-3-乙氧羰基-1,4,5,6,7,8-六氢-5-氧代-2,7,7-三甲基喹啉的一步合成

报道了用3-甲酰基色酮、5,5-二甲基-1,3-环己二酮、乙酰乙酸乙酯与醋酸铵一步法合成4-(色酮-3-基)-3-乙氧羰基-1,4,5,6,7,8-六氢-5-氧代-2,7,7-三甲基喹啉类化合物, 对其结构进行了表征, 并分析了代表性化合物2f的晶体结构. 2f晶体属于单斜晶系, P2/c空间群, 所得晶胞参数为: a＝2.0255(4) nm, b＝0.9132(2) nm, c＝1.4066(3) nm, β＝121.60(3)°, V＝2.2159(8) nm³, Z＝4, D_c＝1.335 g/cm³, μ＝0.209 mm^－1, F(000)＝736, R₁＝0.0556, wR₂＝0.1248.     

用铝-镍合金还原1-萘酚反应的再研究

文献曾报道以铝-镍合金为还原剂, 在稀碱水溶液中, 可以将1-萘酚(1)以高收率还原为5,6,7,8-四氢-1-萘酚(2). 本研究工作发现, 在相同的条件下该反应除了生成少量2外, 3,4-二氢-2H-萘-1-酮(3)和1,2,3,4-四氢-1-萘酚(4)为主要产物, 该结果明显不同于文献报道, 对反应产物分布及其可能机理进行了探讨. 该还原反应体系为3,4-二氢-1(2H)-萘酮(3)和1,2,3,4-四氢-1-萘酚(4)的合成提供了一条新途径.     

哒嗪并[3,2-c]1,2,4-三唑类化合物的合成

以取代苯和丁二酸酐为起始原料, 经Friedel-Crafts反应, 肼合环, Br₂/HOAc氧化脱氢后得到一系列1,6-二氢-3-芳基-6-哒嗪酮(2a～2d). 然后将2a～2d与PCl₅在POCl₃中回流, 得到相应的氯代产物3a～3d, 将其与酰肼作用, 合环后得到一系列未见报道的哒嗪并[3,2-c]1,2,4-三唑类化合物. 所有化合物结构均经元素分析, IR, ¹H NMR 和MS谱得以证实, 并对其波谱性质进行了讨论.     

两个基于呋喃-3-酮配体的钯(Ⅱ)化合物的合成、晶体结构和光谱性质

合成了2个钯（Ⅱ）化合物Pd（L¹）₂（1）和Pd（L²）₂（2）,（L¹=（Z）-4-（（对甲苯胺基）亚甲基）-2,2,5,5-四甲基二氢呋喃-3（2H）-酮,L²=（Z）-4-（（邻甲苯胺基）亚甲基）-2,2,5,5-四甲基二氢呋喃-3（2H）-酮）,并利用元素分析,红外光谱,核磁共振氢谱,紫外光谱和X射线单晶衍射等手段对其结构进行了表征。X射线单晶衍射表明,化合物1和2中包含多种弱相互作用。在化合物1中,呋喃环上氧原子和苯环上的甲基氢原子之间形成氢键,氢键桥联分子形成了一条平行于c轴方向的一维链结构,一维链之间通过C-H…H-C和C-H…C弱相互作用形成了三维超分子结构。在化合物2中,分子之间通过C-H…H-C和C-H…C弱相互作用形成了一个二维层状结构。     

两个基于苯并噻唑-2-硫酮的银(Ⅰ)配合物的合成、晶体结构和光谱性质

合成了2个含有杂环硫酮的银(Ⅰ)配合物,[AgCl(PPh₃)₂(BTZT)]₂ (1),[Ag(PPh₃)₂(BTZT)₂](NO₃)CH₃OH (2)(PPh₃=三苯基膦; BTZT=苯并噻唑-2-硫酮),并通过红外光谱、X射线单晶衍射、荧光光谱和核磁共振氢谱进行表征和分析。杂环硫酮存在化学活性基团-N(H)-C(=S)-,在平衡中与其硫醇形式可以相互转化。2个配合物是在含有2-巯基苯并噻唑(MBT)的甲醇与二氯甲烷混合溶液中,AgCl或AgNO₃与三苯基膦反应得到的。配合物1的每个不对称单元中包含2个相同的分子结构,但是它们具有不同的键长和键角。配合物2是一个简单的单核杂配配合物,它的主体结构通过氢键作用连接游离的CH₃OH和NO₃^-离子。配合物1和2发射峰的红移源于配体中的π-π^*跃迁。     

两个基于呋喃-3-酮配体的钯(Ⅱ)化合物的合成、晶体结构和光谱性质

合成了2个钯（Ⅱ）化合物Pd（L¹）₂（1）和Pd（L²）₂（2）,（L¹=（Z）-4-（（对甲苯胺基）亚甲基）-2,2,5,5-四甲基二氢呋喃-3（2H）-酮,L²=（Z）-4-（（对甲苯胺基）亚甲基）-2,2,5,5-四甲基二氢呋喃-3（2H）-酮）,并利用元素分析,红外光谱,核磁共振氢谱,紫外光谱和X射线单晶衍射等手段对其结构进行了表征。X射线单晶衍射表明,化合物1和2中包含多种弱相互作用。在化合物1中,呋喃环上氧原子和苯环上的甲基氢原子之间形成氢键,氢键桥联分子形成了一条平行于c轴方向的一维链结构,一维链之间通过C-H…H-C和C-H…C弱相互作用形成了三维超分子结构。在化合物2中,分子之间通过C-H…H-C和C-H…C弱相互作用形成了一个二维层状结构。     

(±)-6,7-丙酮缩二醇-3-酮-庚酸乙酯合成研究

用对甲苯磺酸-2,3-丙酮缩甘油酯(2)与乙酰乙酸乙酯盐、碳酸二乙酯反应, 制备β-酮酯类衍生物1. 以(±)-1,2-丙酮缩甘油为起始物, 经对甲苯磺酰化、亲核取代、脱羧等反应, 方便、高产率地合成了6,7-丙酮缩二醇-3-酮-庚酸乙酯(1). 试图通过对甲苯磺酸-2,3-丙酮缩甘油酯(2)和乙酰乙酸乙酯双阴离子反应制备6,7-丙酮缩二醇-3-酮-庚酸乙酯(1)未获成功. 所合成的化合物经元素分析, IR, ¹H NMR, ¹³C NMR和MS光谱表征.     

4-取代-3-烷基-4,5-二氢-1-(3-氯-4-氟苯基)-1,2,4-三唑-5-酮的合成及生物活性

为寻找活性强、作用时间长的新型非肽类血管紧张素II AT₁受体拮抗剂, 从易得原料3-烷基-4,5-二氢-1-(3-氯-4-氟苯基)-1,2,4-三唑-5-酮出发, 经过N-烃化反应、1,3-偶极反应、氢解、水解和酰化等反应, 合成得到一系列4-取代-3-烷基-4,5-二氢-1-(3-氯-4-氟苯基)-1,2,4-三唑-5-酮类衍生物, 总收率为58%～87%, 其结构经IR, ¹H NMR, MS和元素分析确证. 初步药理试验结果表明: 所有目标化合物均有一定的AT₁受体拮抗活性, 其中化合物12d抑制AII诱导的兔主动脉环收缩的IC₅₀值为4.0×10^－9 mol/L, 与阳性药坎地沙坦(candesartan)相当, 具有进一步的研究意义.     

3-(4-取代-哌嗪-1-甲基)-1,2,3,9-四氢咔唑-4-酮衍生物的合成与止吐活性研究

以1,3-环己二酮(1)为起始原料, 一个羰基与盐酸苯肼发生缩合反应生成1,3-环己二酮单苯腙(2), 2在ZnCl₂催化下通过分子内环合、重排反应得到1,2,3,9-四氢咔唑-4-酮(3), 3的甲基化物4在冰醋酸中经Mannich反应获得其3-二甲胺甲基物5, 5与哌嗪类化合物通过亲核取代反应合成了9个未见文献报道的3-(4-取代-哌嗪-1-甲基)-1,2,3,9-四氢咔唑-4-酮衍生物6a～6i. 所有合成的新化合物均经元素分析、红外光谱、质谱和核磁共振光谱证明其结构; 初步药理试验采用顺铂诱导的大鼠干呕模型研究了新化合物的止吐活性, 结果表明部分新化合物活性与昂丹司琼相当.     

1,2-Bis-[(5-methyl/chloro/nitro)-2-1H-benzimidazolyl]-1,2-ethanediols and their PdCl2 complexes

1,2-Bis-[(5-methyl)-2-1H-benzimidazolyl]- (L ¹), 1,2-bis-[(5-chloro)-2-1H-benzimidazolyl]- (L ²), 1,2-bis-[(5-nitro)-2-1H-benzimidazolyl]-1,2-ethanediol (L ³) and their PdCl₂ complexes were synthesized and characterized by elemental analysis, molar conductivity, i.r. and ¹H-n.m.r. spectra. The benzene ring substituents lead to a decrease in melting point. The methyl group reduces the solubility and the acidity of L ¹ and Pd(L ¹)Cl₂, whereas the Cl and NO₂ groups increase the solubility and the acidity of L ², L ³, Pd(L ²)Cl₂ and Pd(L ³)Cl₂. In Pd(L ¹)Cl₂ and Pd(L ²)Cl₂ complexes, the ligands act as a bidentate through two nitrogen atoms. In Pd(L ³)Cl₂, ligand coordination occurs through one OH group oxygen atom and one of the benzimidazole nitrogen atoms.     

Antimicrobial efficiency of diorganotin(IV) bis-[3-(4-chlorophenyl)-2-methylacrylate]

Abstract

Four new diorganotin(IV) carboxylates, [n-Bu₂SnL₂] (1), [Et₂SnL₂] (2), [Me₂SnL₂] (3) and [n-Oct₂SnL₂] (4), where L?=?3-(4-chlorophenyl)-2-methylacrylate, were synthesized and characterized by elemental analysis, FT-IR, multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn) and X-ray single crystal analysis for 1. A chelating bidentate ligand and six-coordinate tin centers were confirmed in the solid state by IR for all complexes and for 1 by X-ray single crystal analysis. The NMR study has shown a decrease in the coordination number of tin in solution. The complexes were screened for their in vitro antibacterial and antifungal activities. A compromised lipo/hydrophilicity and a diffusion controlled antimicrobial activity was shown by the complexes in the order 1?>?2>3?>?4. Molecular docking studies have shown hydrogen bonding and hydrophobic interactions for 1 with the target proteins of the antimicrobial strains.     

3-O-乙酰基熊果酸3-乙酰基-2-[(未)取代苯基]-2,3-二氢-1,3, -噁二唑-5-甲酯的合成及其抗炎活性研究

熊果酸与氯乙酸乙酯反应制得熊果酸乙氧甲酰基甲酯(2), 2与水合肼反应得到熊果酸甲酰肼甲酯(3), 3与羰基化合物反应得到一系列酰腙4a～4g, 再将4a～4g与乙酸酐作用, 环合得到3-O-乙酰基熊果酸3-乙酰基-2-[(未)取代苯基]-2,3-二氢-1,3,4-噁二唑-5-甲酯(5a～5g). 15个新化合物均未见文献报道, 其结构经¹H NMR, IR, MS加以确证, 并进行了药理结果筛选. 结果表明, 部分化合物具有良好的抗炎活性. 其中, 化合物5a (40 mg•kg^－1), 5d (40 mg•kg^－1), 5g (40 mg•kg^－1)与熊果酸相比, 具有更强的疗效.     

Platinum(II) Mono-N1-(2"-Tetrahydrofuranyl)-5-Fluorouracilate Complexes with Ammonia

The reaction between cis-[Pt(NH₃)₂Cl₂], N¹-(2"-tetrahydrofuranyl)-5-fluorouracil (HL), and NaOH (taken in a molar ratio of 1 : 1 : 1) or between cis-[Pt(NH₃)₂Cl₂], HL, and Ag₂O (taken in the molar ratio of 1 : 1 : 0.5) was used to synthesize complexes Ia (in the case of NaOH) or Ib (in the case of Ag₂O) with composition Pt(NH₃)₂LCl. The model complex [Pt(NH₃)₃L]NO₃ (II) was synthesized by the reaction between [Pt(NH₃)₃Cl]Cl, HL, AgNO₃, and Ag₂O (1 : 1 : 1 : 0.5). The obtained compounds were characterized by chemical analysis, chromatography, thermogravimetry, conductometry, potentiometry, IR, electronic, and NMR spectroscopies. Complexes Ia and Ib were found to have both similar and different properties. The structures of the compounds and the type of L^– coordination to platinum(II) were suggested. Cytotoxic properties of Iaand Ib were studied.     

Condensation reactions of indole with acetophenones affording mixtures of 3,3-(1-phenylethane-1,1-diyl)bis(1H-indoles) and 1,2,3,4-tetrahydro-3-(1H-indol-3-yl)-1-methyl-1,3-diphenylcyclopent[b]indoles

Condensation of indole 1a with eight acetophenones 8a–h in ethanolic HCl afforded the corresponding mixtures of condensation products: 3,3-(1-phenylethane-1,1-diyl)bis(1H-indoles) 11a–h (2:1 condensation of indole:acetophenone, –H₂O) and diastereomers of substituted 1,2,3,4-tetrahydro-3-(1H-indol-3-yl)-1-methyl-1,3-diphenylcyclopent[b]indoles 12a–h and 13a–h (2:2 condensation of indole:acetophenone, –2H₂O). Each mixture was analyzed by ¹H NMR. The use of substituted electron-withdrawing acetophenones favored formation of 2:1 condensation products, whereas the use of substituted electron-donating acetophenones favored formation of 2:2 condensation products. Increased reaction temperature gave higher 2:2 condensation yields, but temperatures above 40?°C were unfavorable, giving complex, tarry mixtures.     

One-Pot Synthesis and Methylation of 3-[2-(1H-Benzimidazol-2-yl-Sulfanyl)-Acetyl]-Chromen-2-Ones

Abstract

3-(2-Bromoacetyl)coumarins (I), when treated with 2-mercatobenzimidazole (II) in acetone containing K₂CO₃ (mild base) and tetrabutylammonium bromide (TBAB) as a phase transfer catalyst, at room temperature yielded the title compound 3-[2-(1H-benzimidazole-2-yl-sufanyl)-acetyl]-chromen-2-one (III) in a one-pot synthesis. Alternatively, III could also be prepared by treating dithiocarbonic acid O-ethyl ester, S-[2-oxo-2-(2-oxo-2H-chromen3-yl)-ethyl] ester (V), with o-phenylenediamine (VI). The methylation of the title compound III was performed with dimethyl sulfate (DMS), in acetonitrile containing TBAB and K₂CO₃ at room temperature, resulting in 3-[2-(N-methyl-benzimidazol-2-yl-sulfanyl)]-acetyl-chromen-2-ones (VII). Alternatively, methylation of III could also be performed with DMS in acetonitrile containing K₂CO₃ as base and clay as surface catalyst. All the compounds were synthesized in good yields and their structures were confirmed by spectral and analytical data.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: ¹H NMR of IIIB, VB and VIIB]     

Synthesis and DFT calculations of oxido and phenylimido-rhenium(V) complexes incorporating the N,O donor ligand 2-[(2-hydroxyethylimino)methyl]phenol

The reactions of equimolar amounts of trans-[ReOC1₃(PPh₃)₂] or trans-[Re(NPh)(PPh₃)₂Cl₃] with a Schiff base formed by condensation of 2-hydroxy-4-methoxybenzaldehyde and ethanolamine (H₂L) result in the formation of cis-[ReO(HL)PPh₃Cl₂] (1a) and trans-[Re(NPh)(HL)(PPh₃)Cl₂] (2b), respectively, in good yields. 1a and 2b have been characterized by a range of spectroscopic and analytical techniques. The X-ray crystal structures of 1a and 2b reveal that 1a is an octahedral cis-Cl,Cl oxorhenium(V) complex, while 2b is a trans-Cl,Cl phenylimidorhenium(V) complex. The complexes are weakly emissive at room temperature with quantum yields of 10^?4. Density functional theory calculations of the electronic properties of the complexes were performed and are in agreement with the experimental results. The complexes display quasi-reversible Re(V)/Re(VI) redox couples in acetonitrile. There is reasonable agreement between the experimental and calculated redox potentials of 1a and 2b.     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

Detailed studies on the reduction of aliphatic 3-, 4-, 6-, and 13-oximino esters: Synthesis of novel isomeric amino esters,oximino alcohols,and amino alcohols

The preparation of novel 3-, 4-, 6-, and 13-amino-tetradecanoic acid methyl esters (2a–d) obtained by the reduction of 3-, 4-, 6-, and 13-oximino-tetradecanoic acid methyl esters (1a–d), was investigated. Oximino esters were reduced to afford the corresponding amino esters using NaBH₄–ZrCl₄ reducing system with good yields (58–82%). However, the reduction of oximino esters with LiAlH₄ and BH₃. Tetrahydrofuran gave the corresponding novel 3-, 4-, 6-, and 13-oximino alcohols (3a–d), and 3-, 4-, 6-, and 13-amino alcohols (4a–d) respectively with good chemical yields.