二烯丙基硫醚化合物的合成

二烯丙基一硫醚（DS）,二烯丙基二硫醚（DDS）,二烯丙基三硫醚（DTS）和二烯丙基四硫醚（DTTS）等是大蒜提取液中的主要有效成分,具有十分广泛独特的生理药理活性。作者以甲酸、丙三醇为超始原料合成了这些化合物,烯丙基硫醚化合物总含量达83%,其中DDS,DTS含量分别达30%。产物均GC-MS鉴定确证。合成方法简单,原料易得,反应步骤少,实用性较强。     

PVC有机锡热稳定剂的研究

双（β－烷氧羰烷基）二氯化锡与二酸、二酚、二醇、二醇通过界面缩聚反应，合成了一系列新的有机锡聚酯、聚醚、聚硫醚。新合成的聚合物可作为ＰＶＣ制品的热稳定剂使用。     

新型含硫高折光指数光学树脂单体MPSDMA的合成及其共聚树脂的性能研究

通过氯磺化反应,还原反应和低温相转移仙化反应合成了一种新型光学树脂单体合成 4,4′-二巯基二苯硫醚双甲基丙烯酸酯（MPSDMA）,。成功地将苯环、含硫基团和双键引入光学树脂单体结构中,将MPSDMA分别与甲基丙烯酸甲酯（MMA）和苯乙烯（St)通过自由基共聚制成透明树脂,共聚树脂性能的研究表明该类新型光学树脂具有高折光指数,高表面硬度等特点。     

碘催化芳基磺酰氯与富电子化合物的硫醚化反应

报道了在单质碘的催化下,以三苯基膦作为还原剂,通过芳基磺酰氯与各类富电子化合物的硫醚化反应,合成多种含硫化合物的方法.该方法具有较广的底物普适性,原料来源广泛、易得,操作简便以及反应高效等优点.     

有机化合物PDBP的合成及其在催人反应中的应用

用量子化学AM1方法优化了1－苯基二苯并膦（PDBP）和三苯基膦（TPP）的几何构型,比较了两种化合物的电子结构和空间结构,发现PDBP作为羧基合成铑膦催化剂的配体要优于三苯基膦（TPP）;系统研究了PDBP的合成方法,其最佳合成条件为：在无水无氧的条件下,采用二乙胺锂与溴化四苯基膦摩尔比为3,反应温度为22℃,反应5h,反应后酸化,pH值为1－2,产物收率可达到85％－88％,采用元素分析、红外、核磁等方法,对其结果进行了表征,并将PDBP用于丙烯氢甲酰化反应的催化剂配体。实验证明,在相同的反应条件下,以其为配体的催化剂活性约是目前工业上使用的以三苯基膦为配体的催化剂的1．2倍,选择性约为其1．7倍。     

超声波作用下固－液相转移催化合成芳香族和脂肪族α，ω－二羧基硫醚

超声波作用下固－液相转移催化合成芳香族和脂肪族α，ω－二羧基硫醚王建华，沈维珉（淮北煤师院化学系淮北２３５０００）近年来，有机硫醚酸类化合物广泛应用于含硫大环化合物的合成中间体￣［１］、电化学分析￣［２］和配位化学领域￣［３］。早期，硫醚酸的合成是通...     

η6-苯乙烯二羰基(三苯基膦)铬配合物的合成与聚合

以η＾６－苯乙烯三羰基铬为原料,通过多步配体取代反应,合成了金属有机单体η＾６－苯乙烯二羰基（三苯基膦）铬配合物,经元素分析,ＩＲ和＾１Ｈ－ＮＭＲ进行了结构分析。研究了它在自由基引发下的聚合反应,结果表明强电子给体三苯基膦取代羰基配体可以改善配合物的聚合活性。     

镍基催化剂上硫醇与异戊二烯硫醚化反应的研究

在上流式气-液-固三相固定床微型反应装置上，对Ni／Al2O3催化剂上硫醇与异戊二烯硫醚化反应进行了研究，并考察了反应温度、压力、空速、临氢条件对催化剂二烯硫醚化反应性能的影响。结果表明，异戊二烯与硫醇在镍基催化剂的作用下，可以发生反应生成高沸点的硫醚化合物，反应温度和空速对催化剂二烯硫醚化活性有明显的影响，提高反应温度和降低空速有利于提高硫醇在二烯硫醚化反应过程中的转化率，在临氢反应条下，可以提高催化剂二烯硫醚化反应的活性和稳定性。     

一种新型芳基硫鎓盐光引发剂的合成及应用

将二苯二硫醚作为硫源与1-甲基-2-苯基吲哚反应合成了含杂原子环的硫醚类化合物,然后再与二芳基碘三氟甲磺酸鎓盐反应,合成了一种新的芳基硫鎓盐。采用1 HNMR、MS等技术对目标化合物进行了表征,并确定了最佳反应条件。在硫醚类化合物与二芳基碘三氟甲磺酸鎓盐的摩尔比为1∶1.2,催化剂为CuI/Cu,溶剂为1,1,2,2-四氯乙烷的反应条件下,目标化合物的产率达到了62.0%。同时,对这类结构的芳基硫鎓盐进行了紫外光固化性能测试,发现其能够在紫外光固化体系中作为阳离子光引发剂得到应用。     

醋酸酮催化二硫醚与四氢呋喃的氧化偶联反应

研究了醋酸酮催化二硫醚与四氢呋喃以氧化偶联反应构建C—S键。 结果表明,在醋酸酮(10%摩尔分数)、二硫醚(0.5 mmol)、四氢呋喃(2 mL)和双氧水(35%,2倍化学计量),反应温度120 ℃条件下,二硫醚与四氢呋喃能够顺利地发生氧化偶联反应,生成相应的C—S键化合物,合成硫醚类化合物产率中等到良好。 该反应以双氧水为氧化剂,具有环境友好等特性。     

Synthesis of aromatic polyesters by direct polycondensation with triphenylphosphine dichloride

Aromatic polyesters of high molecular weights were prepared by the direct polycondensation reaction of dicarboxylic acids and bisphenols or hydroxybenzoic acids with triphenylphosphine dichloride as a new condensing agent. Reaction conditions, including the amount of reagents and the concentration of monomer, solvent, and acid acceptor, were investigated. The aromatic polyester with the solution viscosity of 1.66 dL/g was obtained from bisphenol. A and terephthalic and isophthalic acid in quantitative yield under the optimum condition. The principal advantage of this condensing agent is that, based on the recycling system, recovered triphenylphosphine oxide can be reconverted to the reactive triphenylphosphine dichloride by treating with phosgene or oxalyl chloride.     

Palladium-Catalyzed Carbonylative Lactonization of Propargyl Alcohols with Organic Dichalcogenides and Carbon Monoxide

The reaction of propargylic alcohols with diaryl disulfides and carbon monoxide in the presence of tetrakis(triphenylphosphine)palladium leads to a novel thiolative lactonization to afford beta-(arylthio)-alpha,beta-unsaturated lactones in moderate to good yields. Similar conditions can be employed with homopropargylic alcohols, giving the corresponding delta-lactones with a beta-arylthio group successfully. The reaction using diaryl diselenides in lieu of diaryl disulfides also attains a similar one-pot thiolation/lactonization sequence to provide the corresponding beta-selenobutenolides (7).     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Stereochemical and mechanistic aspects of the nickel complex catalysed formation of olefins from allylic alcohols and Grignard reagents

The reaction of (+)-S-but-1-en-3-ol with phenylmagnesium bromide in the presence of bis(triphenylphosphine)nickel dichloride has been shown to proceed with inversion of configuration to yield (?)-R-3-phenylbut-1-ene.     

用异戊二烯的催化调聚反应合成梨圆蚧性信息素组份

梨圆蚧Quadraspidiotus perniciosus是世界性的农业害虫,主要危害苹果、梨树等果树.Gieselmann和Anderson等分离并鉴定出梨圆蚧性信息素为3,7-二甲基-2,7-辛二烯-1-醇丙酸酯(1)和7-甲基-3-亚甲基-7-辛二烯-1-醇丙酸酯(2).1的Z体和E体的比例约为10:1.田间生测发现.1的Z体、E体对雄性蚧虫均有强烈的引诱活性,两者以不同比例混合使用,活性并无明显的降低.     

Rhodium-catalyzed interconversion between acid fluorides and thioesters controlled using heteroatom acceptors

A rhodium complex catalyzed the equilibrium acyl transfer reaction between acid fluorides and thioesters. In the presence of fluoride or thiolate acceptors, the reaction could be shifted to either product. RhH(PPh₃)₄-dppe catalyzed the reaction of acid fluorides and diorgano disulfides in the presence of triphenylphosphine giving thioesters, which was accompanied by triphenylphosphine difluoride. The same complex catalyzed the reaction of aryl thioesters and hexafluorobenzene giving acid fluorides, which was accompanied by 1,4-di(arylthio)-2,3,5,6-tetrafluorobenzenes.     

Electroreduction of triphenylphosphine dichloride and the efficient one-pot reductive conversion of phosphine oxide to triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode. Further, the one-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide in acetonitrile with oxalyl chloride and subsequent electrochemical reduction.     

Molecular diversity of triphenylphosphine promoted reaction of electron-deficient alkynes and arylidene Meldrum acid (N,N'-dimethylbarbituric acid)

The three-component reaction of triphenylphosphine, dimethyl hex-2-en-4-ynedioate and arylidene N,N'-dimethylbarbituric acids in dry methylene dichloride at room temperature afforded trans-1,3-disubstituted 7,9-diazaspiro[4.5]dec-1-enes in good yields and with high diastereoselectivity. However, the similar three-component reaction with arylidene Meldrum acids resulted in a mixtures of cis/trans-1,2-disubstituted 7,9-dioxaspiro[4.5]dec-1-enes. Additionally, the three-component reaction of triphenylphosphine, dimethyl but-2-ynedioate and arylidene Meldrum acids gave polysubstituted 5-(triphenyl-λ⁵-phosphanylidene)cyclopenta-1,3-dienes. A plausible reaction mechanism was proposed for the formation of various products with different regioselectivity and diastereoselectivity.     

Three-component reaction of triphenylphosphine,dialkyl but-2-ynedioate and arylidene pivaloylacetonitrile for diastereoselective synthesis of densely substituted 2,3-dihydrofurans

The three-component reaction of triphenylphosphine,dialkyl but-2-ynedioate and arylidene pivaloylacetonitrile in dry methylene dichloride at room temperature resulted in unexpected densely substituted 1-(triphenyl-λ~5-phosphanylidene)ethyl)-2,3-dihydrofurans in satisfactory yields with high diastereoselectivity.The relative configuration of the 2,3-dihydrofurans was elucidated by determination of single crystal structures.     

Thermal Functional Polymeric “Iniferters” Based on Phosphorus-Containing Poly(Thiuram Disulfides); Synthesis and Characterization

Secondary amine end-terminated oligomeric poly(phosphonamides) and poly(phosphorylamides) were synthesized by the condensation reaction of phenylphosphonic dichloride, ethyl dichlorophosphate, 2,2,2-tribromoethyl dichlorophosphate, and 2,2,2-trichloroethyl dichlorophosphate with an excess of piperazine or N,N′-dimethyl-1,6-hexanediamine. The macrodiamines were chain extended by reaction with CS₂ to the macrobis(dithiocarbamates) followed by oxidative coupling to the corresponding poly(thiuram disulfides) bearing the phosphorus functions. The diamine precursors and their polythiuram disuffides were characterized by elemental analysis, spectral analysis, thermal analysis, and viscosity measurements. The thermal stabilities of the prepolymers were correlated with their structures. The composition of the thiuram disulfide functions could be determined by TGA, whereas the kinetics of their thermal decomposition in the solid state was studied by DSC analysis. The activation energy varied with the chemical structure of the backbone but was quite independent of the chain length. Alternatively, oligomeric polythiuram disulfides containing phenyl phosphonate groups were synthesized by the condensation reaction of phenylphosphonic dichloride with N,N′-diethyl-N,N′-bis(2-hydroxyethyl)thiuram disulfide.