Tri(propan-2-yl)silyl benzoate | 197312-72-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Tri(propan-2-yl)silyl benzoate
• CAS: 197312-72-4
• 化学式: C₁₆H₂₆O₂Si
• 分子量: 278.467
• InChiKey: LSYSDNLPRJFOGH-UHFFFAOYSA-N

物化性质

• 沸点：
  299.2±13.0 °C(Predicted)
• 密度：
  0.939±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Tri(propan-2-yl)silyl benzoate 在 水 、 N,N-二甲基甲酰胺 作用下， 反应 4.0h， 以94%的产率得到苯甲酸
  参考文献：
  名称：

  DMF-mediated deprotection of bulky silyl esters under neutral and fluoride-free conditions

  摘要：

  Bulky TBDPS and TIPS carboxylic esters were efficiently cleaved by a green and mild protocol using only DMF-H2O (20:1) at 70 degrees C. The neutral conditions tolerate various common acid- and base-labile functionalities, including alkyl and aryl silyl ethers. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.11.048
• 作为产物：
  描述：

  三异丙基硅烷 在 咪唑 、 4-二甲氨基吡啶 、 三溴乙酸乙酯 、 palladium dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 1.25h， 生成 Tri(propan-2-yl)silyl benzoate
  参考文献：
  名称：

  A new and efficient method for the synthesis of bromosilanes from hydrosilanes using Br3CCOOEt/PdCl2 as the catalyst

  摘要：

  Bromosilanes were prepared conveniently and efficiently via the reaction of hydrosilanes and Br3CCOOEt in the presence of a catalytic amount of PdCl2 in refluxing THE over 15 min in high yields. The developed methodology was further applied for the one-pot synthesis of silyl ethers and silyl esters in excellent yields. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.03.028

文献信息

• Two New Catalysts for the Dehydrogenative Coupling Reaction of Carboxylic Acids with Silanes—Convenient Methods for an Atom‐Economical Preparation of Silyl Esters
  作者：Guo‐Bin Liu、Hong‐Yun Zhao、Thies Thiemann

  DOI：10.1080/00397910701465669

  日期：2007.8

  Abstract Tris(triphenylphosphine)cuprous chloride [Cu(PPh3)3Cl] has been found to be an efficient catalyst for the dehydrosilylation of carboxylic acids with silanes. In the presence of 4 mol% Cu(PPh3)3Cl, dehydrosilylation reactions in acetonitrile afforded the corresponding silyl esters at 80°C in good yields. It was noted that triphenylphosphine itself also functions as an adequate catalyst for

  摘要 三（三苯基膦）氯化亚铜 [Cu(PPh3)3Cl] 已被发现是羧酸与硅烷脱氢硅烷化的有效催化剂。在 4 mol% Cu(PPh3)3Cl 存在下，乙腈中的脱氢硅烷化反应在 80°C 下以良好的产率得到相应的甲硅烷基酯。注意到三苯基膦本身也用作反应的适当催化剂。
• Triphenylphosphine-Catalyzed Dehydrogenative Coupling Reaction of Carboxylic Acids with Silanes – A Convenient Method for the Preparation of Silyl Esters
  作者：Guo-Bin Liu、Hong-Yun Zhao、Thies Thiemann

  DOI：10.1002/adsc.200600338

  日期：2007.4.2

  Triphenylphosphine has been found to be an efficient catalyst for the dehydrosilylation of carboxylic acids with silanes. In the presence of 4 mol % of triphenylphosphine (PPh3), dehydrosilylation reactions in DMF afforded the corresponding silyl esters at 120 °C in good yield.

  已经发现三苯膦是羧酸与硅烷的脱氢硅烷化的有效催化剂。在4mol％的三苯基膦（PPh 3）的存在下，在DMF中的脱氢甲硅烷基化反应在120℃下以良好的产率提供了相应的甲硅烷基酯。
• Visible-Light-Induced <i>In Situ</i> Generation of Fischer-Type Copper Carbene Complexes from Acylsilanes and Its Application to Catalytic [4 + 1] Cycloaddition with Siloxydienes
  作者：Taiichi Takeuchi、Tsukasa Aoyama、Kurumi Orihara、Kento Ishida、Hiroyuki Kusama

  DOI：10.1021/acs.orglett.1c03683

  日期：2021.12.17

  A novel methodology for in situ generation of Fischer-type metal–carbene complexes was developed. Photoirradiation to a mixture of an acylsilane and a cationic copper complex cleanly gave a Fischer-type copper–siloxycarbene complex, which was detected by spectroscopic methods. This carbene complex reacted with siloxydienes in a [4 + 1] cycloaddition manner to give cyclopentene derivatives. It is noteworthy

  开发了一种原位生成 Fischer 型金属-卡宾配合物的新方法。对酰基硅烷和阳离子铜配合物的混合物进行光照射，干净地得到了 Fischer 型铜 - 硅氧卡宾配合物，可通过光谱方法检测到。这种卡宾配合物与甲硅烷氧基二烯以 [4 + 1] 环加成的方式反应得到环戊烯衍生物。值得注意的是，该反应通过原位生成 Fischer 型铜 - 硅氧卡宾配合物中间体，在催化量的铜下进行。
• REACTION OF STABLE TRIALKYLSILYL ESTERS WITH Ph₃P(SCN)₂: A NOVEL METHOD FOR THE PREPARATION OF ACYL AND AROYL ISOTHIOCYANATES UNDER NEUTRAL CONDITION
  作者：N. Iranpoor、H. Firouzabadi、H. R. Shaterian

  DOI：10.1081/scc-120014983

  日期：2002.1

  one-pot conversion of stable triisopropylsilyl- and tert-butyldimethylsilyl carboxylates to their corresponding acyl- or aroyl isothiocyanates using in-situ generation of Ph3P(SCN)2 at room temperature under neutral condition. This method has also been applied for the high yield preparation of 2-thioxo-3,4-dihydro-2H-1,3-benzoxazine-4-one, which has fungicidal and bactericidal activities.

  摘要描述了一种高效、温和且新颖的方法，可在中性条件下在室温下原位生成 Ph3P(SCN)2，将稳定的三异丙基甲硅烷基和叔丁基二甲基甲硅烷基羧酸酯一锅法转化为相应的酰基或芳酰基异硫氰酸酯。该方法还用于高产率制备具有杀菌和杀菌活性的2-thioxo-3,4-dihydro-2H-1,3-benzoxazine-4-one。
• EFFECTIVE SILYLATION OF CARBOXYLIC ACIDS UNDER SOLVENT-FREE CONDITIONS WITH <i>tert</i>-BUTYLDIMETHYLSILYL CHLORIDE (TBDMSCL) AND TRIISOPROPYLSILYL CHLORIDE (TIPSCL)
  作者：Habib Firouzabadi、Naser Iranpoor、Hamid Reza Shaterian

  DOI：10.1080/10426500008076532

  日期：2000.1.1

  Various types of carboxylic acids can be converted effectively to their corresponding TBDMS and TIPS esters using TBDMSCI and TIPSCI in the presence of imidazole under solvent-free conditions. The advantage of this modified method in comparison with that reported by Corey is the elimination of DMF, which eliminates aqueous work-up. The method is not a time-consuming process and the reactions proceed spontaneously. By this method, absolute chemoselectivity for the protection of carboxylic acid functions in the presence of 2 degrees, 3 degrees hydroxyl groups are observed.