Ruthenium-catalyzed one-pot hydroformylation of alkenes using carbon dioxide as a reactant

A new hydroformylation of alkenes using carbon dioxide as a reactant is shown to take place in the presence of ruthenium cluster complexes and halide salts. Similar or even better yields of alcohols were formed as compared to the conventional hydroformylation with CO under the same reaction conditions. The reaction proceeded in three steps: CO₂ is first converted to CO; then it is used as a reagent for hydroformylation to give aldehyde; subsequently, it is hydrogenated to alcohol. ESI-mass spectrometric analyses of the reaction solutions indicated formation of four kinds of ruthenium anionic complexes including tetra-, tri-, and mononuclear species. On the basis of experimental findings, possible roles of these complexes are discussed.     

Synthesis of phthalide derivatives using nickel-catalyzed cyclization of o-haloesters with aldehydes

The reaction of o-bromobenzoate (1 b) with benzaldehyde (2 a) in the presence of [NiBr(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) and zinc powder in THF (24 hours, reflux temperature), afforded 3-phenyl-3H-isobenzofuran-1-one (3 a) in an 86 % yield. Similarly, o-iodobenzoate reacts with 2 a to give 3 a, but in a lower yield (50 %). A series of substituted aromatic and aliphatic aldehydes (2 b, 4-MeC(6)H(4)CHO; 2 c, 4-MeOC(6)H(4)CHO; 2 d, 3-MeOC(6)H(4)CHO; 2 e, 2-MeOC(6)H(4)CHO; 2 f, 4-CNC(6)H(4)CHO; 2 g, 4-(Me)(3)CC(6)H(4)CHO; 2 h, 4-C(6)H(5)C(6)H(4)CHO; 2 i, 4-ClC(6)H(4)CHO; 2 j, 4-CF(3)C(6)H(4)CHO; 2 k, CH(3)(CH(2))(5)CHO; 2 l, CH(3)(CH(2))(2)CHO) also underwent cyclization with o-bromobenzoate (1 b) producing the corresponding phthalide derivatives in moderate to excellent yields and with high chemoselectivity. Like 1 b, methyl 2-bromo-4,5-dimethoxybenzoate (1 c) reacts with tolualdehyde (2 b) to give the corresponding substituted phthalide 3 m in a 71 % yield. The methodology can be further applied to the synthesis of six-membered lactones. The reaction of methyl 2-(2-bromophenyl)acetate (1 d) with benzaldehyde under similar reaction conditions afforded six-membered lactone 3 o in a 68 % yield. A possible catalytic mechanism for this cyclization is also proposed.     

Rhodium-catalyzed CH activation/cyclization of enaminones with sulfoxonium ylides toward polysubstituted naphthalenes

A rhodium-catalyzed ortho-CH functionalization and annulation between enaminones and sulfoxonium ylides was developed, affording a series of multi-substituted naphthalenes in good to moderate yields with excellent functional group compatibility. The procedure featured with enaminone acting as both a directing and cyclization bifunctional group, and the application of sulfoxonium ylide in CH functionalization.     

Synthesis and catalytic activity of a fluorous-tagged TEMPO radical

A fluorous-tagged TEMPO radical has been prepared and its catalytic activity in the chemoselective oxidation of alcohols to carbonyl compounds has been investigated. The new fluorous radical proved to be an efficient, selective and easily recoverable catalyst, which can be conveniently used in standard organic solvents and then isolated and recycled by fluorous liquid-liquid extraction.     

硫酸氢钠催化合成己酸异戊酯的研究

己酸异戊酯是应用最广泛的食用香料之一。通常它是在硫酸催化下由己酸和异戊醇酯化反应而得[1] ,硫酸虽然活性高 ,价廉 ,但选择性差 ,产品质量不好 ,设备腐蚀严重 ,同时产生大量废液 ,污染环境。已发现对甲苯磺酸、磺酸树脂、固体超酸、杂多酸、氯化铁以及过渡金属硫酸盐等均可作为酯化反应的优良催化剂[2～ 7] 。本文探讨了硫酸氢钠催化羧酸的酯化反应 ,结果发现它具有良好的催化性能 ,且后处理方便 ,无污染。1　实验部分在装有分水器、温度计和回流冷凝器的四颈烧瓶中 ,加入一定量分析纯的己酸、异戊醇、甲苯和催化剂硫酸氢钠 (ＮａＨＳＯ…     

NdOx作为助催化剂对PtRu/C电催化氧化甲醇活性的影响

采用沉积-还原法制备了PtRu-NdOx/C催化剂, 借助TEM、EDS和XRD等测试手段对其进行了微结构和组成的表征. 结果表明, 催化剂中Pt与Ru以合金形式存在, 而Nd的氧化物则以无定形形态存在. 催化剂粒子的平均粒径在2 nm左右, 晶胞参数为0.3896 nm, Nd氧化物的加入对PtRu合金的晶体结构影响不明显. 采用循环伏安法和计时电流法, 比较了PtRu-NdOx/C催化剂和PtRu /C催化剂对甲醇氧化的电催化活性, 结果表明, 加入Nd的氧化物作为助催化剂能明显提高PtRu /C催化剂对甲醇氧化的电催化性能.     

Reactions of esters of tetracoordinated phosphorus acids with nucleophilic reagents in highly organized media

Characteristic features of reactions involving esters of phosphorus-containing acids in highly organized media (micelles, liquid crystals, vesicles, and emulsions) are surveyed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 298–312, February, 1996.     

Solvothermale Synthese und Bestimmung der Kristallstrukturen von AgBiI4 und Ag3BiI6

Solvothermal Synthesis and Crystal Structure Determination of AgBiI₄ and Ag₃BiI₆ AgBiI₄ and Ag₃BiI₆ were synthesized by solvothermal reaction from AgI and BiI₃ in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI₄) or hexagonal/trigonal platelets (Ag₃BiI₆). AgBiI₄ crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag₃BiI₆ shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI₄ is explored. AgBiI₄ and Ag₃BiI₆ show close structural relationship, with AgBiI₄ as a variant with a higher degree of order.     

相转移催化合成增塑剂BBP和水杨醛的研究

相转移催化合成增塑剂ＢＢＰ和水杨醛的研究郭锡坤，高文华，曾东宇（汕头大学化学系，汕头５１５０６３）关键词相转移催化，季铵盐，聚乙二醇，邻苯二甲酸丁苄酯，水杨醛，增塑剂邻苯二甲酸丁苄酯（增塑剂ＢＢＰ）是一种优良的增塑剂．邻羟基苯甲醛（水杨醛）不仅是重要...     

Aerobic alcohol oxidation catalyzed by a new, oxygen-bridged heterometallic compound [PPh4][Ru(N)Me2(μ2-O)2Pd((−)-sparteine)]

The reaction between the new hydroxy compound [PPh₄][Ru(N)(OH)₂Me₂] and Pd(OSiMe₃)₂((−)-sparteine) produces (Me₃Si)₂O, H₂O and a new heterobimetallic compound [PPh₄][Ru(N)Me₂(μ₂-O)₂Pd((−)-sparteine)] in good yield. The Ru/Pd bimetallic compound catalyzes the oxidation of aryl and allyl alcohols to the corresponding carbonyl compound in air and the rearrangement of allylic alcohols unsaturated aldehydes. It also oxidizes PPh₃ to O-PPh₃ under O₂.