二氢吡喃环中取代的异色满类化合物的合成研究简

二氢吡喃环中取代的异色满类化合物大多具药理活性,本文主要就此类化合物的合成方法进行简要综述.     

卤盐离子液体/氧气催化芳硫酚与异色满反应

以1-羧乙基-3-甲基咪唑氯（[COOH-EtMIm][Cl]）/O2体系催化异色满与取代苯硫酚发生脱氢偶联反应,合成了1-(取代苯硫酚)异色满。通过单因素实验对反应影响因素进行筛选,得到最佳反应条件为：4-甲基苯硫酚（128 mg, 0.5 mmol）、异色满（134 mg, 1.0 mmol）、[COOH-EtMIm][Cl]（95 mg, 0.5 mmol）、氧气（0.1 MPa）、反应温度120 ℃、反应时间12 h。在该条件下,催化剂可重复使用4次,实现了1-(4-甲基苯硫酚)异色满克级合成,底物拓展后得到12种1-(取代苯硫酚)异色满,产率为52%~96%。并提出了[COOH-EtMIm][Cl]阴阳离子通过氢键分别活化苯硫酚与异色满,经O2氧化,脱氢得到1-(取代苯硫酚)异色满的反应机理。     

卤盐离子液体/氧气催化芳硫酚与异色满反应

以1-羧乙基-3-甲基咪唑氯（[COOH-EtMIm][Cl]）/O2体系催化异色满与取代苯硫酚发生脱氢偶联反应,合成了1-(取代苯硫酚)异色满。通过单因素实验对反应影响因素进行筛选,得到最佳反应条件为：4-甲基苯硫酚（128 mg, 0.5 mmol）、异色满（134 mg, 1.0 mmol）、[COOH-EtMIm][Cl]（95 mg, 0.5 mmol）、氧气（0.1 MPa）、反应温度120 ℃、反应时间12 h。在该条件下,催化剂可重复使用4次,实现了1-(4-甲基苯硫酚)异色满克级合成,底物拓展后得到12种1-(取代苯硫酚)异色满,产率为52%~96%。并提出了[COOH-EtMIm][Cl]阴阳离子通过氢键分别活化苯硫酚与异色满,经O2氧化,脱氢得到1-(取代苯硫酚)异色满的反应机理。     

Friedlaender反应合成异喹啉并喹啉和异色满并喹啉

利用异喹啉酮和异色满酮与邻氨基苯甲醛的Ｆｒｉｅｄｌａｅｎｄｅｒ反应合成了４种新的异喹啉并喹啉和异色满并喹啉化合物。通过元素分析、红外光谱和核磁共振氢谱表征了新化合物的结构。     

多环麝香的分子结构和香气关系的研究

本文论述了多环麝香的近期进展,提出了分类的原则和系统的分类方法。研究和总结了茚满型、萘满型、色满酮型、异色满型、氢化引达省型、苊型等各种多环麝香化合物的分子结构与香气的关系。     

异色满并杂环化合物的合成

通过3-乙氧甲酰基异色满-4-酮合成异色满并吡唑和异色满并嘧啶类化合物得到了5个新的异色满衍生物.其结构均经红外光谱、核磁共振谱及元素分析证实。     

异香豆素类衍生物的卤化烷氧基化反应

以N-溴代丁二酰亚胺(NBS)、N-氯代丁二酰亚胺(NCS)分别为溴代、氯代试剂,醇类化合物作为反应原料及溶剂,实现了异香豆素类衍生物3,4-位的卤化烷氧基化反应.室温(25℃)下即可在3,4-位之间发生加成反应,合成具有潜在药理活性的异色满-1-酮类衍生物.对4-溴-3-甲氧基-3-苯基异色满-1-酮(Ⅳa)的合成反...     

α—位取代的异色满—4—酮衍生物的合成

利用缩合反应合成出8种尚未见报道的α-位取代的异色满-4-酮衍生物,其结构均已经红外光谱、核磁共振谱及元素分析证实。     

3—氯—1—(2-吡啶基)-3,5-二甲基-吡唑-4-乙酰胺基-5-三氟甲基-苯基-1,3,4-噻二唑的合成研究

<正>许多杂环化合物具有非常好的生物活性,尤其是含N杂环化合物,因其具有较高的生物活性和广谱性而被广泛应用于农药。含N杂环化合物一直都是科研界的研究热点,以其生理活性高而倍受青睐,尤其是含N五元杂环化合物在实际应用中有着非常重要的意义。吡唑类化合物中,四大取代位点和取代基的不同,赋予了广泛     

异色满类化合物合成方法综述

1前言 异色满类化合物的合成方法有一步法、两步法和三步法。最具代表性的异色满类化合物为三环异色满麝香(Tricyclic isochromans),俗称佳乐麝香,化学名称为1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基-环戊基-γ-2-苯并吡喃(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyrane)。由于其官能团是醚基,故它对光、碱的稳定性非常好,是良好的麝香香料。它具有异香豆酮类的三环结构,为无色透明的粘稠液体。沸点129℃(0.8mmHg),密度d_4~201.005,折光率nd201.5432。     

Synthesis and Quantitative Structure–Activity Relationships of Selective BCRP Inhibitors

The breast cancer resistance protein (BCRP/ABCG2) is a member of the ABC transporter superfamily. This protein has a number of physiological functions, including protection of the human body from xenobiotics. The overexpression of BCRP in certain tumor cell lines causes cross‐resistance against various drugs used in chemotherapeutic treatment. In a previous work we showed that a new class of compounds derived from XR9576 (tariquidar) selectively inhibits BCRP. In this work we synthesized more members of this class, with modification on the second and third aromatic rings. The inhibitory activities against BCRP and P‐gp were assayed using a Hoechst 33342 assay for BCRP and a calcein AM assay for P‐gp. Finally, quantitative structure–activity relationships for both aromatic rings were established. The results obtained show the importance of the electron density on the third aromatic ring, influenced by substituents, pointing to interactions with aromatic residues of the protein binding site. In the second aromatic ring the activity of compounds is influenced by the steric volume of the substituents.     

Experimental measurement of noncovalent interactions between halogens and aromatic rings

Chemical double mutant cycles have been used to quantify the interactions of halogens with the faces of aromatic rings in chloroform. The halogens are forced over the face of an aromatic ring by an array of hydrogen-bonding interactions that lock the complexes in a single, well-defined conformation. These interactions can also be engineered into the crystal structures of simpler model compounds, but experiments in solution show that the halogen-aromatic interactions observed in the solid state are all unfavourable, regardless of whether the aromatic rings contain electron-withdrawing or electron-donating substituents. The halogen-aromatic interactions are repulsive by 1-3 kJ mol(-1). The interactions with fluorine are slightly less favourable than with chlorine and bromine.     

Group structure characteristics of the liquid thermolysis products of vitrinites of different ranks

The results of the group structure analysis of asphaltenes, resins, and hydrocarbons in the liquid products obtained upon the thermolysis of vitrinites of different ranks are presented. The molecular weights of components decreased with the degree of vitrinite conversion: aromatic structures were predominant among ring compounds, and the lengths of alkyl substituents decreased. The molecules of asphaltenes predominantly consisted of two-block structures, whereas tars and oils mainly exhibited a single-block organization; in all cases, the alkyl substituents of aromatic rings had a length of C₁–C₄.     

Aufklärung der Molekülstruktur von Rohölinhaltsstoffen durch NMR-Spektroskopie. II. Struktur der Alkylsubstituenten in den Aromaten des Rohöls

Elucidation of the Molecular Structure of Petroleum Constituents by N.M.R. -Spectroscopy. II. Structure of Alkyl Substituents in Aromatic Hydrocarbons in Petroleum Crude The structure of alkyl chains of aromatic hydrocarbons of heavier petroleum fractions is studied by ¹H and ¹³C-n.m.r. spectroscopy An average aromatic molecule is found with an average degree of substitution of 40–50%, the substituents representing short paraffinic chains or naphthenic rings.     

Studies on certain new polymaleamidehydrazides

Three polymaleamidehydrazides have been synthesised by the ring-opening polyaddition of N,N′-bisisomaleimide with aromatic diamines (having methyl or methoxy ring substituents or flexible SO₂ groups between benzene rings) at room temperature. Thermogravimetry and mass spectrometry have been used in conjunction with infrared spectroscopy, inherent viscosity measurements, NMR and UV-visible spectroscopy to characterise these polymers.     

The effect of bisphenol monomer structure on the gas permeability of aromatic polycarbonates

Permeability measurements for oxygen and, to a lesser extent, carbon dioxide were carried out on a series of 24 structurally different aromatic polycarbonates. Polymers were prepared from bisphenols bearing substituents on the aromatic rings and/or the central aliphatic carbon atom. A strong correlation between monomer structure and polymer permeability was found, with gas transport rates varying by over two orders of magnitude between the most and the least permeable materials. In addition, a semilogarithmic relationship was found between oxygen transmission rates and monomer composition for two series of copolycarbonates. Of several methods explored, an excess free volume model was found best able to relate the experimental permeability values to the polymer molecular structure.     

霍林河褐煤化学结构特性的13C NMR与FTIR对比分析

采用¹³C NMR及FTIR对霍林河褐煤的化学结构特性进行深入分析,通过¹³C NMR计算得到霍林河褐煤包含34.32%的脂肪族碳、61.25%的芳香族碳以及4.43%的羰基碳。平均每个芳环团簇包含1~2个芳香环,每个芳香环中平均碳原子取代数为3~4。平均亚甲基碳链数为1.4,烷链支化度为25.47%,说明脂肪族多以短链分支形式存在。通过对霍林河褐煤红外光谱进行分峰拟合,计算得到煤的FTIR结构参数（平均亚甲基碳链数、芳香环取代度、烷链支化度）与¹³C NMR计算结果相吻合。虽然芳碳率（f_ar-F=55.37%）与¹³C NMR计算结果存在一定的偏差,但是FTIR很大程度上仍然可以反映煤的碳骨架结构特性。     

Reactions of methylene and ether bridges

The reactions of model compounds containing methylene and ether bridges were examined, in the temperature range 350–400 °C. Aromatic displacement reactions, in which atomic hydrogen displaced the bridges, and homolysis via a keto-enol intermediate were the dominant modes of bridge decomposition. The aromatic displacement reactions of methylene-bridge compounds occurred with activation energies of ≈10 kcal mol^?1 and with A factors of 10^10.5–12 Is^?1 m^?1. The A factors vary with the size of the rings and the substituents on the rings connected by the methylene bridges. The activation energy is relatively independent of these effects. When phenolic substituents are present, methylene bridges can unimolecularly decompose via a keto-enol tautomerism, and the rate of product formation is solvent-dependent. Reactions for ether bridge decomposition were more complex and the rate parameters encompassed a much larger range of values.     

Heterocyclic polyimides containing siloxane groups in the main chain

BACKGROUND: Among the polymers widely studied for applications in advanced techniques, aromatic polyimides have received considerable attention due to their outstanding thermal stability associated with good electrical and mechanical properties. However, these polymers are usually difficult to process, being insoluble and without a glass transition. To improve the processing characteristics of polyimides, modification of their structure is often achieved by the introduction of flexible linkages in the macromolecular chain or various substituents on the aromatic rings. RESULTS: A series of polyimides and intermediate polyamidic acids were synthesized from aromatic oxadiazole‐diamines and a dianhydride containing a siloxane bridge (? R₂Si? O? SiR₂? ). These polymers exhibit good solubility in certain organic solvents and can be cast into thin and very thin films from their solutions. They exhibit high thermal stability with decomposition being above 440 °C and relatively low glass transition temperatures in the range 160–190 °C. These polymers show strong photoluminescence in the blue spectral region. CONCLUSION: The introduction of oxadiazole rings together with siloxane groups into the chains of aromatic polyimides gives highly thermostable polymers with remarkable solubility and film‐forming ability and that emit blue light, being attractive for applications in micro‐ and nanoelectronics and other related advanced fields. Copyright © 2009 Society of Chemical Industry