trimethylsilyl fluorosulfonate | 3167-56-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trimethylsilyl fluorosulfonate
• 英文别名: Me3SiOSO2F；Trimethylsilyl fluorosul-fonate；[fluorosulfonyloxy(dimethyl)silyl]methane
• CAS: 3167-56-4
• 化学式: C₃H₉FO₃SSi
• 分子量: 172.253
• InChiKey: NVDGINOUYJGSHJ-UHFFFAOYSA-N

物化性质

• 沸点：
  125.3±9.0 °C(Predicted)
• 密度：
  1.174±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.05
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  trimethylsilyl fluorosulfonate 生成 三甲基氟硅烷
  参考文献：
  名称：

  Reaction of 10,10-dimethyl-9-trimethylsiloxy-9,10-dihydrophenanthrene-9-carbonitrile with acids

  摘要：

  The behavior of 10,10-dimethyl-9-trimethylsiloxy-9,10-dihydrophenanthrene-9-carbonitrile in trifluoromethanesulfonic acid and acid systems CF(3)SO(3)H-CD(2)Cl(2), HSO(3)F-SO(2)ClF-CD(2)Cl(3), and CF(3)COOH-CD(2)Cl(2) were studied by NMR spectroscopy. Principal reaction schemes were determined; the first step in these schemes is protonation of the initial compound at the oxygen or nitrogen atom.

  DOI：

  10.1134/s1070428011070141
• 作为产物：
  描述：

  四甲基硅烷 在 氟磺酸 作用下， 生成 trimethylsilyl fluorosulfonate
  参考文献：
  名称：

  用强酸裂解烷基硅烷II。甲磺酰氟的形成

  摘要：

  已经发现，通过氟磺酸从氟代三烷基甲硅烷基氟代磺酸酯裂解甲基，除了形成甲烷以外，还产生相当数量的甲磺酰氟。动力学数据表明，这种新的裂解方式发生在氟磺酸甲硅烷基酸被质子初质子化之后。提出了形成甲磺酰氟的机制，其中在质子化的氟代甲硅烷基磺酸盐的硅上发生酸分子的亲核攻击，然后甲基从硅重排为硫。

  DOI：

  10.1016/s0022-328x(00)80271-5
• 作为试剂：
  描述：

  甲氧基三甲基硅烷 、 苯乙醛 在 trimethylsilyl fluorosulfonate 作用下， 反应 1.5h， 以89%的产率得到1,1-二甲氧基-2-苯基乙烷
  参考文献：
  名称：

  Trimethylsilylfluorosulfonate (TMSOFs): An alternative to TMS triflate as a source of Me3Si+

  摘要：

  Generation of trimethylsilylfluorosulfonate in situ provides a useful source of TMS+, the reactivity of which is essentially equivalent to that of TMS triflate. Its precursors, in particular FSO3H, are less costly than those of TMSOTf or the reagent itself

  DOI：

  10.1016/s0040-4039(00)77474-0

文献信息

• Cleavage of alkylsilanes by strong acids
  作者：David D. Hopf、Daniel H. O'Brien

  DOI：10.1016/s0022-328x(00)87129-6

  日期：1976.5

  The kinetics of cleavage of alkyl groups and fluorine from five alkyldimethylfluorosilanes by fluorosulfonic acid dissolved in methylene chloride has been studied with proton magnetic resonance. Competitive cleavage of alkyl, methyl and fluoro occurs to form three products. A mechanism is proposed based on the third order kinetics which involves the formation of a pentacoordinate intermediate through

  利用质子磁共振研究了氟磺酸溶解在二氯甲烷中从五个烷基二甲基氟硅烷中裂解烷基和氟的动力学。发生烷基，甲基和氟的竞争裂解，形成三种产物。提出了一种基于三阶动力学的机理，该机理涉及通过氟磺酸对硅的亲核进攻，然后对硅的亲电进攻，形成五配位中间体。
• Further reactions of chlorine(I) and bromine(I) trifluoromethanesulfonate and bromine(I)fluorosulfate
  作者：Kamalesh K. Johri、Yutaka Katsuhara、Darryl D. DesMarteau

  DOI：10.1016/s0022-1139(00)83128-0

  日期：1982.1

  Substitutive electrophilic dehalogenation reactions of CF3SO2OX (X=Cl,Br) are reported with some covalent inorganic chlorides. These reactions result in the formation of XX′(X,X′Cl,Br) and several new trifluoromethanesulfonate derivatives in excellent yields. Chlorine(I) trifluoromethanesulfonate also oxidatively adds to unsaturated inorganic substrates such as CO, SO2 and SF4 forming new compounds

  据报道，CF 3 SO 2 OX（X = Cl，Br）与某些共价无机氯化物的取代亲电脱卤反应。这些反应导致以极高的收率形成XX'（X，X'Cl，Br）和几种新的三氟甲磺酸酯衍生物。氯（I）三氟甲磺酸盐也氧化添加到不饱和无机基质（如CO，SO 2和SF 4）中，形成新化合物。CF 3 SO 2 OCl的反应性与FSO 2 OBr相当，并且给出了两者之间的一些比较。
• Reactions of methyl(pentafluorophenyl)- and methyl(pentafluorophenyl)phenylsilanes with electrophiles. A convenient preparative route to halogeno(methyl)pentafluorophenylsilanes C6F5SiMe2X and C6F5SiMeX2 (X=F, Cl and Br)
  作者：H.-J Frohn、A Lewin、V.V Bardin

  DOI：10.1016/s0022-328x(98)00805-5

  日期：1998.11

  Halogeno(methyl)pentafluorophenylsilanes C6F5SiMenX3-n (n = 1, 2) (X = F, Cl, Br) were prepared in good yields from the corresponding phenylsilanes C6F5SiMenPh3-n by reactions with the electrophiles aHF, HCl-AlCl3, Br-2-AlBr3 or AlX3 (X = Cl, Br) halogenated hydrocarbons. Additionally, reactions of C6F5SiMe3 and (C6F5)(2)SiMe2 with selected electrophiles were studied. (C) 1998 Elsevier Science S.A. All rights reserved.
• Haas, Alois; Wingender, Norbert, Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Haas, Alois、Wingender, Norbert

  DOI：——

  日期：——
• Synthesis of 20-deethylsilicine from a second-generation 2-cyano-.DELTA.3-piperidine synthon
  作者：David S. Grierson、Jean Luc Bettiol、Ildiko Buck、Henri Philippe Husson、Mario Rubiralta、Anna Diez

  DOI：10.1021/jo00050a012

  日期：1992.11

  The Zn2+ ion mediated reaction of the 2-cyano-DELTA3-piperidine 9a (X = SO2C6H5) with the silyl enol ether of Na-methyl-2-acetylindole (24) led to formation of compounds 29a,b (70%) resulting from introduction of the acetylindole moiety at the exocyclic (C-7) carbon center and migration of the phenylsulfonyl group from C-7 to C-4. In contrast, reaction of 2-Cyano-DELTA3-piperidine 9b (X = CN) with 24 gave the desired C-4 acetylindole-substituted products 36a,b (1:1.3 mixture; 72% overall yield). Attempts to cyclize intermediates 36 to the tetracyclic enamine 27 were unsuccessful. Alternatively, the Zn2+-catalyzed reaction of synthons 9a and 9b with indole gave the C-7 indole-substituted aminonitriles 37a,b and 38, respectively. These intermediates were converted to DELTA2-piperidine 40 on reaction with sodium dimethyl malonate and AgBF4. Stereoselective hydrogenation of the enamine double bond in 40 furnished the required cis 3,4-disubstituted piperidine 41, which was cyclized under acidic conditions to the target molecule, 20-deethylsilicine (20).