Tri-isopropylfluorsilan | 426-67-5

• 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: Tri-isopropylfluorsilan
• 英文别名: Tri-isopropylfluorosilane；fluoro-tri(propan-2-yl)silane
• CAS: 426-67-5
• 化学式: C₉H₂₁FSi
• 分子量: 176.35
• InChiKey: QDQTZCVWLBTXKP-UHFFFAOYSA-N

物化性质

• 沸点：
  169 °C(Press: 742 Torr)
• 密度：
  0.803±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.13
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Tri-isopropylfluorsilan 在 sodium ethanolate 作用下， 生成 ethoxytriisopropylsilane
  参考文献：
  名称：

  Malignant Peripheral Nerve Sheath Tumors with t(X;18). A Pathologic and Molecular Genetic Study

  摘要：

  Spindle cell sarcomas often present the surgical pathologist with a considerable diagnostic challenge. Malignant peripheral nerve sheath tumor, leiomyosarcoma, fibrosarcoma, and monophasic synovial sarcoma may all appear similar histologically. The application of ancillary diagnostic modalities, such as immunohistochemistry and electron microscopy, may be helpful in the differentiation of these tumors, but in cases in which these adjunctive: techniques fail to demonstrate any more definitive evidence of differentiation, tumor categorization may remain difficult. Cytogenetic and molecular genetic characterization of tumors have provided the basis for the application of molecular assays as the newest components of the diagnostic armamentarium. Because the chromosomal translocation t(X;18) has been observed repeatedly in many synovial sarcomas, it has been heralded as a diagnostic hallmark of synovial sarcoma To formally test the specificity of this translocation for the diagnosis of synovial sarcoma, RNA extracted from formalin-fixed, parrafin-embedded tissue from a variety of soft tissue and spindle cell tumors was evaluated fbr the presence of t(X;18) by reverse transcriptase-polymerase chain reaction. Although 85% of the synovial sarcomas studied demonstrated t(X;18), 75% of the malignant peripheral nerve sheath tumors in our cohort also demonstrated this translocation. We conclude that the translocation t(X;18) is not specific to synovial sarcoma and discuss the implications of the demonstration of t(X;18) in a majority of malignant peripheral nerve sheath tumors.

  DOI：

  10.1038/modpathol.3880230
• 作为产物：
  描述：

  三异丙基硅烷 在 吡啶 、 氢氟酸 作用下， 反应 24.0h， 生成 Tri-isopropylfluorsilan
  参考文献：
  名称：

  Olah, George A.; Heiliger, Ludger; Li, Xing-Ya, Journal of the American Chemical Society, 1990, vol. 112, # 16, p. 5991 - 5995

  摘要：

  DOI：

文献信息

• Anion-Initiated Trifluoromethylation by TMSCF₃: Deconvolution of the Siliconate–Carbanion Dichotomy by Stopped-Flow NMR/IR
  作者：Craig P. Johnston、Thomas H. West、Ruth E. Dooley、Marc Reid、Ariana B. Jones、Edward J. King、Andrew G. Leach、Guy C. Lloyd-Jones

  DOI：10.1021/jacs.8b06777

  日期：2018.9.5

  suppliers, also affect the kinetics. Some reactions are complete in milliseconds, others take hours, and others stall before completion. Despite these differences, a general mechanism has been elucidated in which the product alkoxide and CF3– anion act as chain carriers in an anionic chain reaction. Silyl enol ether generation competes with 1,2-addition and involves protonation of CF3– by the α-C–H of the

  由 M+X–（<0.004 至 10 mol%）引发的 CF3 从 R3SiCF3（R = Me、Et、iPr）转移到酮和醛的机制已通过动力学分析进行了研究（可变比率停止） -flow NMR 和 IR）、13C/2H KIE、LFER、添加配体（18-c-6、crypt-222）以及密度泛函理论计算。动力学、反应级数和选择性随试剂 (R3SiCF3) 和引发剂 (M+X–) 的不同而有很大差异。 R3SiCF3 试剂中存在的微量外源抑制剂（批次和供应商之间的比例和特性差异很大）也会影响动力学。有些反应在几毫秒内完成，有些反应需要几个小时，还有一些反应在完成之前就停止了。尽管存在这些差异，但一般机制已被阐明，其中产物醇盐和CF3-阴离子在阴离子链式反应中充当链载体。甲硅烷基烯醇醚的生成与 1,2-加成竞争，并涉及通过酮的 α-C-H 和烯醇的 OH 使 CF3– 质子化。 R3SiCF3
• Thiols, unsymmetrical sulfides and thioacetals from the new reagent: Triisopropylsilanethiol
  作者：Edgar I. Miranda、Michael J. Díaz、Izander Rosado、John A. Soderquist

  DOI：10.1016/s0040-4039(00)76869-9

  日期：1994.5

  Triisopropylsilanethiol (HSTIPS, 1), easily prepared in 98% yield from H2S and TIPSCl, is efficiently alkylated in a selective manner with 1° and 2° alkyl halides or tosylates through its potassium thiolate (2c) to provide RSTIPS (3) in excellent yields. Compound 3 provides a convenient source of alkanethiols (4), unsymmetrical dialkyl sulfides (5) and thioacetals (6).

  三异丙基硅烷硫醇（HSTIPS，1）易于从H 2 S和TIPSCl中以98％的收率制备，并通过1°和2°烷基卤化物或甲苯磺酸盐通过其硫醇钾（2c）有效地烷基化以提供RSTIPS（3）高产。化合物3提供了链烷硫醇（4），不对称二烷基硫化物（5）和硫缩醛（6）的方便来源。
• Silyl-substituted diazoacetic esters in superacid media—a stable ion and solvolysis study
  作者：Kenneth K. Laali、Gerhard Maas、Monika Gimmy

  DOI：10.1039/p29930001387

  日期：——

  FSO3H or CF3SO3H, protonation, dediazoniation and gegenion addition occur without concomitant desilylation, whereas with HF, partial desilylation takes place. Upon solvolysis of 2, only desilylated esters are obtained. When 1 is allowed to react with the superacid FSO3H·SbF5(1 : 1)/SO2 at ⩽–75 °C, five major ions are formed, among them the silyl-substituted enoldiazonium ions (Z)- and (E)-9 corresponding

  对于重氮（三异丙基甲硅烷基）乙酸甲酯（1）和重氮（五甲基二甲硅烷基）乙酸甲酯（2）而言，在超酸中的质子化和随后的化学反应，以及与非水酸（FSO 3 H，CF 3 SO 3 H的溶剂分解反应）（HF）已进行了研究。通过FSO 3 H或CF 3 SO 3 H溶剂化1时，质子化，脱重氮和gegeion加成发生而没有伴随的甲硅烷基化，而在HF的情况下，发生了部分甲硅烷基化。溶剂分解2时，仅获得去甲硅烷基化的酯。当1与超酸FSO 3反应时在⩽–75°C下，H·SbF 5（1：1）/ SO 2形成五个主要离子，其中甲硅烷基取代的烯重氮鎓离子（Z）-和（E）-9对应于O-质子化1和质子化的（氟磺酰氧基）乙酸盐4-H +。在较低酸度超强酸FSO 3 H / SO 2的ö -protonated silyldiazoesters [（Ž）-9，（ë）-9]和Ç，Ô -diprotonated（14 -H +
• Synthesis of unsymmetrical polyfluorinated diaryl sulfides by rhodium-catalyzed aryl exchange reaction
  作者：Mieko Arisawa、Takuya Ichikawa、Masahiko Yamaguchi

  DOI：10.1016/j.tetlet.2013.06.021

  日期：2013.8

  RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene (dppBz) catalyze the aryl exchange reaction of polyfluorinated diaryl sulfides. By employing these catalysts, unsymmetrical polyfluorinated diaryl sulfides are synthesized by the reaction of symmetrical polyfluorinated diaryl sulfides and substituted pentafluorobenzenes in the presence of triisopropylsilane.

  RhH（PPh 3）4和1,2-双（二苯基膦基）苯（dppBz）催化多氟化二芳基硫醚的芳基交换反应。通过使用这些催化剂，在三异丙基硅烷存在下，通过对称多氟二芳基硫醚和取代的五氟苯的反应合成不对称多氟二芳基硫醚。
• Catalytic hydrodefluorination of fluoroaromatics with silanes as hydrogen source at a binuclear rhodium complex: Characterization of key intermediates
  作者：Lada Zámostná、Mike Ahrens、Thomas Braun

  DOI：10.1016/j.jfluchem.2013.05.021

  日期：2013.11

  Stoichiometric and catalytic hydrodefluorination reactions of fluorinated aromatic substrates on using [Rh(μ-H)(dippp)]2 (1) (dippp = 1,3-bis(diisopropylphosphino)propane) as catalyst and HSiEt3 as a hydrogen source are reported. Treatment of the hydrido complex 1 with the fluoroarenes gave the fluorido complex [Rh(μ-F)(dippp)]2 (2) and organic hydrodefluorination products. An unusual ortho-selectivity

  报道了使用[Rh（μ- H）（dippp）] 2（1）（dippp = 1,3-双（二异丙基膦基）丙烷）作为催化剂和HSiEt 3作为氢源的氟化芳族底物的化学计量和催化加氢脱氟反应。。用氟代芳烃处理氢化物络合物1，得到了氟化物络合物[Rh（μ- F）（dippp）] 2（2）和有机加氢氟化产物。在2,3,5,6-四氟吡啶和五氟苯的反应中观察到异常的邻位选择性，得到1,2-氢脱氟产物。配合物2的双核结构通过X射线衍射确认为固态。所述fluorido复杂2与HSiEt反应3和HSI我镨3通过消除对应的氟硅烷，得到η 2 -硅烷氢基络合物的[Rh（H）（η 2 -HSiEt 3）（dippp）]（3）和[铑（H）（η 2 -HSi我镨3）（dippp）]（4）表示。配合物3和4的结构由NMR数据和DFT计算得出。在5 mol％的1存在下，五氟吡啶，2,3,5,6-四氟吡啶或2,3,5,6-四氟吡啶，六氟和五氟苯与HSiEt