Synthesis of Some New Benzo[b][1,4]diazepine Based Heterocycles

Preparation of 4‐chloro‐3H‐benzo[b][1,4]diazepine‐2‐carbaldehyde 5 , which is used as a key intermediate in the synthesis of chalcones derivatives, via its condensation with some aromatic acetophenone derivatives under ethanol piperidine condition was described. Also illustrated was the reaction of such chalcones with available nucleophilics and reagents of active methylene group to afford new series of fused and isolated pyrazoles, isoxazolines pyrimidines, pyridines, triazolo[1,5‐a]pyrimidines, benzo[1,4]oxa(thia)zepines, and pyrido[1,2‐a]benzimidazoles incorporating 4‐chloro‐3H‐benzo[b][1,4]diazepine moiety, which have a potential pharmaceutical interest. Furthermore, condensation reaction of 4‐chloro‐3H‐benzo[b][1,4]diazepine‐2‐carbaldehyde with aromatic amine derivatives to afford the Schiff's bases was described. The C═N double bond of the latter compounds has been reacted with chloroketene to give β‐lactams and with sulfanylacetic acid to give the 2‐(4‐oxo‐1,3‐thiazolidinyl)‐substituted derivative. The structures of the newly prepared compounds were established by elemental analysis, IR, MS, and ¹H NMR spectral analysis.     

1-Butyl-3-methylimidazolium Hydrogen Sulfate [bmim]HSO4: An Efficient Reusable Acidic Ionic Liquid for the Formylation of Alcohols

1-Butyl-3-methylimidazolium hydrogen sulfate [bmim]HSO4 as an acidic ionic liquid was prepared and used as a catalyst for the formylation of alcohols with ethyl formate at room temperature with good to excellent yields. A good selectivity was observed for the formylation of primary alcohols in the presence of tertiary alcohols.     

Ring-contraction from benzo[b][1,4]thiazines to benzo[d]thiazolines induced by oxygen

An unexpected ring-contraction from benzo[b]pyrazino[1,2-d][1,4]thiazine-1,4-diones (6) to benzo[4,5]thiazolo[3,2-a]pyrazine-1,4-diones (7) has been developed. The preliminary mechanistic studies showed the transformation contained two independent steps: the first step is the formation of a Michael adduct upon the addition of the protic solvent, in the presence of base, to the C-2-C-3 double bond of compound 6, and the second step is a ring-contraction induced by oxygen via the migration of sulfur atom from C-2 to C-3 position. And its scope is also studied.     

Facile,One-Pot,Three-Component Synthesis of Benzo[a]naphthacene-8,13-diones

One-pot synthesis of 14-aryl-14H-7-oxa-benzo[a]naphthacene-8,13-diones was developed by the reaction of 2-hydroxynaphthalene-1,4-dione, aromatic aldehydes, and 2-naphthol in the presence of acetic acid. The structures of these compounds were identified by elemental analyses, infrared, ¹H NMR, and mass.     

碱性离子液体催化“一锅法”合成1,4-二氢吡喃并[2,3-c]吡唑

在碱性离子液体氢氧化1-丁基-3-甲基咪唑([bmim]OH)催化作用下,由芳香醛、丙二腈、苯甲酰乙酸乙酯和肼或苯肼"一锅法"合成了一系列1,4-二氢吡喃并[2,3-c]吡唑化合物.实验中考察了催化剂、反应温度、催化剂用量、溶剂对反应的影响,确定了最优反应条件,给出了可能的反应机理.此外催化剂可以方便地收回,且循环使用四次其催化活性并没有显著降低.目标产物经过了1H NMR,IR,MS和元素分析确证.合成方法条件温和、反应时间短、产率高且对环境友好.     

Studien zur Chemie von thienoanellierten O,N-und S,N-haltigen Heterocyclen, 5. Mitt.: Ein Zugang zum Thieno[2,3-b][1,4]oxazin-Ringsystem

Summary The reactivity of 5-acetyl-2-chloro-3-nitrothiophene with -hydroxyesters is described. The influence of the solvent (DMF, tetrahydrofurane, toluene) and of the used base is discussed. These reactions provide an access to substituted thiophene derivatives, which were cyclized after reduction by iron powder/glacial acetic acid to give thieno [2,3-b][1,4]oxazine derivatives.

     

One-Pot Synthesis of N2-Substituted 2-Amino-4-aryl-5,6,7,8-tetrahydroquinoline-3-carbonitrile in Basic Ionic Liquid [bmim]OH

N2-Methyl- or aryl-substituted 2-amino-4-aryl-5,6,7,8-tetrahydroquinoline-3-carbonitriles were synthesized via a four-component, one-pot reaction of aromatic aldehyde, cyclohexanone, malononitrile, and amines in basic ionic liquid [bmim]OH with good to excellent yields. During this transformation, at least 11 bonds were cleaved and 7 new bonds were constructed.      

Synthesis of a novel bifunctional oxyammonium-based ionic liquid: Application for the synthesis of pyrano[4,3-b]pyrans and tetrahydrobenzo[b]pyrans

In the present investigation, a novel bifunctional oxyammonium-based ionic liquid, namely, 2,2′-(ethane-1,2-diylbis[oxy])bis(ethan-1-aminium)-2,2,2-trifluoroacetate, was designed and synthesized. The structure of the titled ionic liquid was characterized using Fourier-transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (¹HNMR), carbon nuclear magnetic resonance (¹³CNMR), fluorine nuclear magnetic resonance (¹⁹FNMR), homonuclear COSY nuclear magnetic resonance (NMR), thermogravimetry (TG), derivative thermogravimetry (DTG) analysis, X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The described ionic liquid demonstrated robust catalytic performance in the synthesis of pyrano[4,3-b]pyrans and tetrahydrobenzo[b]pyran derivatives. The ionic liquid presents a high potential of recycling and reusing capability in both types of model reactions.     

Efficient Synthesis of a Benzo[b]furan Building Block

Unexpected difficulty in the conversion of a bromobenzofuran to the corresponding formylbenzofuran led us to develop a new synthesis for 5-formylbenzo[b]furan-2-carbonitrile (1).     

Facile Synthesis of 2-Substituted Benzo[b]thiophen-3-ols in Water

A facile synthesis of 2-substituted benzo[b]thiophen-3-ols in a simple reaction system is reported with water as the only media. Density functional theory (DFT) investigations suggest two pathways comparable in energetics: A neutral pathway with concerted C-C bond formation and hydrogen transfer and an anionic pathway with anion attack to the carbonyl group. Studies indicate that water plays crucial mechanistic roles in both cases.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

2-取代苯并噻吩类化合物合成研究进展

2-取代苯并噻吩广泛的存在于天然产物中,独特的分子结构使其表现出了较高的药理和生物活性,常被用于药物化学和材料化学中。已有多种具有苯并噻吩骨架药物用于临床,故具有极高的研究价值。本文结合国内外学者对这方面的相关研究,重点对2-苯基苯并噻吩、2-酰基苯并噻吩和2-氨基苯并噻吩类化合物的合成方法进行了综述。     

Efficient One-Pot,Four-Component Synthesis of 1,2,3-Triazole-Linked Tetrahydrobenzo[b]pyrans

A one-pot procedure has been developed for the synthesis of (1,2,3-triazolyl) methoxyphenyl tetrahydro-5-oxo-4H-chromene derivatives by concurrent reaction of aryloxy propargylated aldehydes, various azides, active methylene compounds, and 1,3-cyclohexanediones using catalytic amounts of Cu(OAc)₂ / sodium ascorbate and diammonium hydrogen phosphate in aqueous ethanol media. Excellent conversion of starting materials was achieved to the desired (1,2,3-triazolyl) methoxyphenyl tetrahydro-5-oxo-4H-chromene products.     

离子液体[C2mim][GaCl4]的溶解热研究

在干燥氩气氛下, 用等摩尔的高纯无水GaCl3和[C2mim][Cl](氯化1-甲基-3-乙基咪唑)直接搅拌混合, 制备了淡黄色透明的的离子液体[C2mim][GaCl4] (1-ethyl-3-methylimidazolium chlorogallate) . 在298.15 K下, 利用具有恒温环境的溶解反应热量计, 测定了这种离子液体的不同浓度摩尔溶解焓 . 针对[C2mim][GaCl4]溶解于水后即分解的特点, 在Pitzer电解质溶液理论基础上, 提出了确定这种离子液体标准摩尔溶解焓的新方法, 得到了[C2mim][GaCl4]在水中的标准摩尔溶解焓, ＝－132 kJ•mol－1, 以及Pitzer焓参数组合: ＝－0.1373076和 ＝0.3484209. 借助热力学循环和Glasser离子液体晶格能理论, 用Ga3＋, Cl－和[C2mim]—的离子水化焓数据以及本文得到的[C2mim][GaCl4]标准摩尔溶解焓, 估算了配离子4Cl－(g)解离成Ga3＋(g)和4Cl－(g)的解离焓ΔHdis([GaCl4]-)≈5855 kJ•mol－1. 这个结果揭示了离子液体[C2mim][GaCl4]的标准摩尔溶解焓绝对值并不很大的原因, 即是很大的离子水化焓被很大的[GaCl4]－(g)的解离焓相互抵消了.     

氯化钽在离子液体1-丁基-3-甲基咪唑六氟磷酸盐中电化学行为

采用循环伏安法,研究了0.25 mol/L TaCl₅在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF₆)中的电化学行为。 实验结果表明,电沉积钽是受扩散控制、两步骤的不可逆电极反应过程,首先是Ta(Ⅴ)还原为Ta(Ⅲ),其次是Ta(Ⅲ)还原为金属钽和形成其它低价钽氯化物。 Ta(Ⅴ)/Ta(Ⅲ)和Ta(Ⅲ)/Ta在离子液体[Bmim]PF₆中的阴极传递系数分别为0.155和0.406。 Ta(Ⅴ)在离子液体[Bmim]PF₆中的扩散系数为1.629×10^-9 cm²/s。 在100 ℃和-1.25 V条件下,采用恒电势法在铂片上电沉积钽,扫描电子显微镜照片和EDS分析表明,沉积物为钽和钽的低价氯化物。     

水介质中碱性离子液体[bmim][OH]催化下一锅三组分合成螺杂环衍生物

在水相中碱性离子液体[bmim][OH]催化作用下,由苊醌、丙二腈/氰乙酸乙酯和β-二酮三组分“一锅法”合成了一系列螺杂环化合物,产物的结构通过1H NMR,IR和MS表征.该方法条件温和,操作简单,后处理方便,反应时间短,对环境友好,且催化剂廉价易得.     

飞秒光学外差光学克尔效应和低频拉曼光谱技术研究离子液体[bmim][PF6]的低频光谱

利用飞秒光学外差光学克尔效应技术获得了咪唑类离子液体1-丁基-3-甲基咪唑六氟磷酸盐([bmim][PF6])体系中反映分子间相互作用的低频光谱. 结果分析中, 利用Brownian振子时间相关函数的精确表达式对光学克尔效应动力学数据中的核振动部分进行模拟, 在时域上获得各个振动组分的时间演化行为, 并进而通过快速Fourier变换获得各个振动组分的频域光谱和总加和光谱. 此外还利用低频拉曼光谱技术测量了离子液体[bmim][PF6]的低频光谱, 并和飞秒光学外差光学克尔效应实验的结果进行对比, 发现两种方法获得的低频光谱相近. 实验结果表明Brownian振子时间相关函数的精确表达式可用来解析离子液体体系中低频振动的时间演化行为.     

Synthesis and Characterization of [1,2,4,6]Thiatriazino[2,3-a][1,3]benzimidazol-1(2H)-one and [1,3,5]Thiadiazino[3,4-a][1,3]benzimidazol-2-imine

Abstract

The reaction of thionyl chloride with amidines 2, derived from N-benzimidazol-2-yl imidates 1, leads to [1,2,4,6]thiatriazino[2,3-a][1,3]benzimidazol-1(2H)-one 3 in good yields. [1,3,5]Thiadiazino[3,4-a][1,3]benzimidazol-2-imine 4 was prepared by condensation of NaSCN with benzimidazol-2-yl imidate 1. The isolated compounds 3 and 4 were identified by spectroscopic methods including IR, ¹H NMR, and ¹³C NMR as well as elemental analyses and MS of 3d and 4b.

GRAPHICAL ABSTRACT      

Solvent-free Synthesis, Crystal Structure and Thermal Stability of Ionic Liquid 1-Hexadecyl-3-methylimidazolium Bromide

Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate （[C16mim]Br·H2O）, 4 mm in length, was firstly obtained in the water-trichloromethane-toluene growth system （Vwater＇Vtrichloromethane＇Vtoluene = 0.1：1：2）. The crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P1, with a = 5.4962（15）, b = 7.839（2）, c = 27.279（8） A, α = 94.375, β = 91.500, γ = 101.999°, Z = 2, V = 1145.2（5） A3, C20H41BrN2O, Mr = 405.46, Dc = 1.176 Mg/m3, μ = 1.804 mm^-1, F（000） = 436, the final R = 0.0523 and wR = 0.1345. The 3D supramolecular structure is constructed through weak interactions between imidazolium cations, Br- anions and lattice water molecules. The long alkyl chain to the imidazolium ring and lattice water molecules play an important role in the self-assembly process. Moreover, it is proposed that [C16mim]Br in water has aggregation behavior and the possible self-assembled structure is the interdigitated pattern. Finally, thermal stability of [C16mim][Br]·H2O was also studied by DSC and TGA analysis.     

Ionic liquid promoted one-pot synthesis of 3-aminoimidazo[1,2-a]pyridines

3-Aminoimidazo[1,2-a]pyridines have been synthesized in good to excellent yields in the presence of the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]Br, the reaction workup is simple and the ionic liquid can be easily separated from the product and reused.     

1‐Butyl‐3‐methylimidazolium Hydrogen Sulfate [Bmim]HSO4: An Efficient Reusable Acidic Ionic Liquid for the Synthesis of 1,8‐Dioxo‐Octahydroxanthenes

1‐Butyl‐3‐methylimidazolium hydrogen sulfate [bmim]HSO₄ as an acidic ionic liquid was prepared and used as a catalyst for the synthesis of 1,8‐dioxo‐octahydroxanthenes in excellent yields and short reaction times at 80 °C. The ionic liquid was easily separated from the reaction mixture by water extraction and was recycled four times without any loss in activity.