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41.
Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO-PM3 method indicate that the C? Si bond is facilitated to cleave in comparison with the C? H (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p-phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation. 相似文献
42.
The reaction of o-, m-, and p-F2CCFC6H4X with SF5Br produces an intermediate adduct, F5SCF2CFBrC6H4X, which, on treatment with AgBF4, affords the first useful, high yield preparation of o-, m-, and p-F5SCF2CF2C6H4X. 相似文献
43.
Jörg Rethmeier Andreas Rabenstein Monika Langer Ulrich Fischer 《Journal of chromatography. A》1997,760(2):637-302
Depending on the sulfur species, picomoles of different inorganic sulfur compounds can be detected and separated by HPLC in one arrangement in a sample volume less than 50 μl. The combination of fluorescence labelling of reduced inorganic sulfur compounds such as sulfide (S2−), sulfite(SO32− and thiosulfate (S2O32−) with monobromobimane followed by an extraction of elemental sulfur (S°) by chloroform treatment enables the detection of all mentioned sulfur compounds as well as sulfate (remaining aqueous phase) in the same sample. While the derivatized sulfur compounds could be detected by their fluorescence emission at 480 nm, elemental sulfur is identified by its UV absorption at 263 nm. Sulfate in the remaining aqueous phase is detected by HPLC with indirect UV detection at 254 nm. Detection ranges for the different sulfur compounds examined are as follows: sulfide (5 μM to 1.5 mM), sulfite (5 μM to 1.0 mM), thiosulfate (1 μM to 1.5 mM), elemental sulfur (2 μM to 32 mM) and sulfate (5 μM to >1 mM). 相似文献
44.
Man-Kit Lau Qian-Feng Zhang Wing-Tak Wong Wa-Hung Leung 《Journal of organometallic chemistry》2004,689(14):2401-2410
Treatment of [M(Buppy)2Cl]2 (M=Ir (1), Rh (2); BuppyH=2-(4′-tert-butylphenyl)pyridine) with Na(Et2NCS2), K[S2P(OMe)2], and K[N(Ph2PS)2]2 afforded monomeric [Ir(Buppy)2(S∧S)] (S∧S=Et2NCS2 (3), S2P(OMe)2 (4), N(PPh2S)2 (5)) and [Rh(Buppy)2(S∧S)] (S∧S=Et2NCS2 (6), S2P(OMe)2 (7), N(PPh2S)2 (8)), respectively. Reaction of 1 with Na[N(PPh2Se)2] gave [Ir(Buppy)2{N(PPh2Se)2}] (9). The crystal structures of 3, 4, 7, and 8 have been determined. Treatment of 1 or 2 with AgOTf (OTf=triflate) followed by reaction with KSCN gave dinuclear [{M(Buppy)2}2(μ-SCN)2] (M=Ir (10), Rh (11)), in which the SCN− ligands bind to the two metal centers in a μ-S,N fashion. Interaction of 1 and 2 with [Et4N]2[WQ4] gave trinuclear heterometallic complexes [{Ir(Buppy)2}2(μ-WQ4)] (Q=S (12), Se (13)) and [{Rh(Buppy)2}2{(μ-WQ)4}] (Q=S (14), Se (15)), respectively. Hydrolysis of 12 led to formation of [{Ir(Buppy)2}2{W(O)(μ-S)2(μ3-S)}] (16) that has been characterized by X-ray diffraction. 相似文献
45.
The cheap and easily available sodium dithionite and thiourea dioxide have been used as the source of sulfonyl group in the synthesis of sulfones and sulfonamides recently.Compared with other methods for the sulfonylation reactions,the strategies using sodium dithionite or thiourea dioxide provide an alternative and complementary route to diverse sulfonyl compounds.During the reaction process,sulfur dioxide anion radical is the key intermediate,which is usually generated from a single electron transfer under suitable conditions.The advantages using sodium dithionite or thiourea dioxide in the sulfonylation reactions include mild conditions and broad substrate scope with excellent functional group compatibility.Further applications by using sodium dithionite and thiourea dioxide in organic transformations will be anticipated. 相似文献
46.
Christian Reichardt Hans-Peter Erfurt Klaus Harms 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1081-1092
Attempts at the oxidation of 3-ethyl-2-methylbenzothiazolium salt 2 with a variety of oxidizing reagents did not lead to the desired isochiral S -oxide 3 or achiral S , S -dioxide 4 , in some cases, however, unexpectedly to the ring-opened dimeric 2,2'-di( N -ethyl-acetamino)substituted diphenyl disulfane 5 , the molecular structure of which was confirmed by x-ray analysis. The synthesis of 2-methylbenzothiazole- S , S -dioxide 14 , reported by Zincke et al. in 1915, turned out to be not reproducible. \centerline{\epsfbox{:art:fig-01.jpg}} 相似文献
47.
48.
硫掺杂橄榄状BiVO4上可见光降解亚甲基蓝和甲醛水溶液性能 总被引:1,自引:0,他引:1
在无和有S源(Na2S或硫脲)存在的条件下,采用十二胺辅助的醇-水热法制备了多孔单斜晶相结构的BiVO4-δ和不同含量S掺杂的BiVO4-δ光催化剂.利用多种手段表征了催化材料的物化性质,评价了它们在可见光照射下催化降解亚甲基蓝或甲醛的反应活性.结果表明,所制光催化剂为单斜白钨矿晶相结构,具有多孔橄榄状形貌,比表面积为8.4-12.5m2/g,带隙能为2.40-2.48eV.在S掺杂BiVO4-δ表面同时含有Bi5+,Bi4+,V5+和V4+物种.S掺杂对BiVO4-δ光催化剂的活性影响很大.在可见光下照射下,BiVO4-δS0.08光催化剂对亚甲基蓝和甲醛降解反应显示出最高的光催化活性,这与其较高的表面氧物种浓度和较低的带隙能相关. 相似文献
49.
The ionic liquid 1‐butyl‐3‐methylimidazolium hydrogensulfate, [bmim]HSO4, turned out to be resistant even to strong oxidizers like SO3. Thus, it should be a suitable solvent for the preparation of polysulfates at low temperatures. As a proof of principle we here present the synthesis and crystal structure of K2(S2O7)(H2SO4), which has been obtained from the reaction of K2SO4 and SO3 in [bmim]HSO4. In the crystal structure of K2(S2O7)(H2SO4) (orthorhombic, Pbca, Z = 8, a = 810.64(2) pm, b = 1047.90(2) pm, c = 2328.86(6) pm, V = 1978.30(8) Å3) two crystallographically unique potassium cations are coordinated by a different number of monodentate and bidentate‐chelating disulfate anions as well as by sulfuric acid molecules. The crystal structure consists of alternating layers of [K2(S2O7)] slabs and H2SO4 molecules. Hydrogen bonds between hydrogen atoms of sulfuric acid molecules and oxygen atoms of the neighboring disulfate anions are observed. 相似文献
50.
作为无机玻璃的替代品,有机光学树脂具有轻质、抗冲击性好、易加工和可调性强等优点。折射率是光学树脂的主要参数之一,折射率的高低可直接影响成品镜片的厚度、美观性和舒适度。在不降低光学树脂综合性能的基础上提升光学树脂折射率一直是该领域的热点和难点,在光学树脂中引入高摩尔折射率的硫元素被认为是最有效和常用的方法之一。本文将含硫光学树脂分为烯烃类、环氧类、环硫类、多环类和聚氨酯类,简要综述了国内外近几年的研究进展,涉及单体合成、单体聚合以及单体结构对光学树脂综合性能影响,系统总结了以上材料的特性及发展。 相似文献