O-trimethylsilylacetol | 26205-43-6

• 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: O-trimethylsilylacetol
• 英文别名: 1-Trimethylsilyloxypropan-2-one
• CAS: 26205-43-6
• 化学式: C₆H₁₄O₂Si
• 分子量: 146.261
• InChiKey: AYRKUIXYSPQXJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.43
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  O-trimethylsilylacetol 在 sodium 、 zinc(II) chloride 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 3.0h， 生成 4,4-dimethyl-3-<(trimethylsilyl)oxy>pentan-2-one
  参考文献：
  名称：

  Reetz, Manfred T.; Heimbach, Horst, Chemische Berichte, 1983, vol. 116, # 11, p. 3702 - 3707

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(三甲基硅氧基)丙烯 在 间氯过氧苯甲酸 作用下， 生成 O-trimethylsilylacetol
  参考文献：
  名称：

  Macrae,D.M.; Brook,A.G., Journal of Organometallic Chemistry, 1974, vol. 77, p. C19 - C21

  摘要：

  DOI：

文献信息

• Total synthesis of dl-asparenomycins A, B and C, novel carbapenem antibiotics
  作者：Hisao Ona、Shoichiro Uyeo

  DOI：10.1016/s0040-4039(01)80220-3

  日期：1984.1

  Total synthesis of dl-asparenomycins was accomplished with direct conversion of carbonates 13a, 13b and 14a, 14b to asparenomycin esters 15 and 16 and carboxy deprotection by the AlCl3-anisole method.

  通过将碳酸盐13a，13b和14a，14b直接转化为天冬酰胺酯15和16并通过AlCl 3-茴香醚方法使羧基脱保护，从而完成dl-阿斯巴霉素的全合成。
• Identification and Quantification of Aerosol Polar Oxygenated Compounds Bearing Carboxylic or Hydroxyl Groups. 1. Method Development
  作者：M. Jaoui、T. E. Kleindienst、M. Lewandowski、E. O. Edney

  DOI：10.1021/ac049919h

  日期：2004.8.1

  In this study, a new analytical technique was developed for the identification and quantification of multifunctional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) of the multifunctional compound using an alcohol (e.g., methanol, 1-butanol) in the presence of a relatively strong Lewis acid (BF3) as a catalyst. This esterification reaction quickly and quantitatively converts carboxylic acids to their ester forms. The second step is based on silylation of the ester compounds using bis(trimethylsilyl) trifluoroacetamide (BSTFA) as the derivatizing agent. For compounds bearing ketone groups in addition to carboxylic and hydroxyl groups, a third step was used based on PFBHA derivatization of the carbonyls. Different parameters including temperature, reaction time, and effect due to artifacts were optimized. A GC/MS in EI and in methane-CI mode was used for the analysis of these compounds. The new approach was tested on a number of multifunctional compounds. The interpretation of their EI (70 eV) and CI mass spectra shows that critical information is gained leading to unambiguous identification of unknown compounds. For example, when derivatized only with BF3−methanol, their mass spectra comprise primary ions at m/z M•+ + 1, M•+ + 29, and M•+ − 31 for compounds bearing only carboxylic groups and M•+ + 1, M•+ + 29, M•+ − 31, and M+. − 17 for those bearing hydroxyl and carboxylic groups. However, when a second derivatization (BSTFA) was used, compounds bearing hydroxyl and carboxylic groups simultaneously show, in addition to the ions observed before, ions at m/z M•+ + 73, M•+ − 15, M•+ − 59, M•+ − 75, M•+ − 89, and 73. To the best of our knowledge, this technique describes systematically for the first time a method for identifying multifunctional oxygenated compounds containing simultaneously one or more hydroxyl and carboxylic acid groups.

  在本研究中，开发了一种新的分析技术，用于鉴定和定量含有至少一个羟基或一个羧基或两者的多官能团化合物。该技术基于首先使用醇（例如甲醇、1-丁醇）在相对较强的路易斯酸（BF3）催化下对多官能团化合物的羧基进行衍生化。这种酯化反应迅速且定量地将羧酸转化为酯形式。第二步是使用双(三甲基硅基)三氟乙酰胺（BSTFA）作为衍生化剂对酯化合物进行硅烷化。对于除羧基和羟基外还含有酮基的化合物，采用了基于PFBHA对羰基进行衍生化的第三步。优化了包括温度、反应时间和因人工产物引起的影响等多个参数。使用电子轰击源（EI）和甲烷化学电离（CI）模式的气相色谱/质谱法（GC/MS）分析了这些化合物。对多种多官能团化合物测试了新方法。对其EI（70 eV）和CI质谱的解释表明，获得了关键信息，从而能够明确鉴定未知化合物。例如，仅通过BF3−甲醇衍生化时，它们的质谱包含仅含有羧基的化合物的离子m/z M•+ + 1、M•+ + 29和M•+ − 31，以及同时含有羟基和羧基的化合物的离子m/z M•+ + 1、M•+ + 29、M•+ − 31和M•+ − 17。然而，当使用第二步衍生化（BSTFA）时，同时含有羟基和羧基的化合物除了之前观察到的离子外，还显示出m/z M•+ + 73、M•+ − 15、M•+ − 59、M•+ − 75、M•+ − 89和73的离子。据我们所知，这项技术首次系统地描述了一种鉴定同时含有一个或多个羟基和羧酸基团的多官能团含氧化合物的方法。
• Carbapenem and penem antibiotics. III. Synthesis and antibacterial activity of 2-functionalized-methyl penems related to asparenomycins.
  作者：MITSURU IMUTA、SHOICHIRO UYEO、MASAO NAKANO、TADASHI YOSHIDA

  DOI：10.1248/cpb.33.4371

  日期：——

  Racemic and optically active 2-(heteroaromatic) thiomethyl penems having a 1-(hydroxymethyl) ethylidene or cyclic carbonate side-chain at C-6 (24, 51, 63, 65, 37, 40, 69 and 21b, 61b, 26b, 30b, 64b, 35b, 66b, 39b, 68b) were synthesized, and their antibacterial activities are determined.

  合成了具有C-6位1-(羟甲基)亚乙基或环状碳酸酯侧链的R构型和光学活性2-(杂芳基)硫代甲基青霉烯（24、51、63、65、37、40、69以及21b、61b、26b、30b、64b、35b、66b、39b、68b），并测定了它们的抗菌活性。
• Carbapenem and penem antibiotics. I. Total synthesis and antibacterial activity of dl-asparenomycins A, B and C and related carbapenem antibiotics.
  作者：HISAO ONA、SHOICHIRO UYEO、KIYOSHI MOTOKAWA、TADASHI YOSHIDA

  DOI：10.1248/cpb.33.4346

  日期：——

  Racemic carbapenem antibiotics having a 1-(hydroxymethyl) ethylidene side-chain at C-6 [dl-asparenomycins A (54), B (37), C (53) and related compounds, 55, 56, 38, 59 and 45] were synthesized starting from the common intermediates 9a and 9b, and their antibacterial activities were examined. The synthesis involves transformation of a cyclic carbonate group into the 1-(hydroxymethyl) ethylidene moiety with a catalytic amount of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU) in an appropriate solvent, and deblocking of the p-methoxybenzyl ester group by the AlCl3-anisole method.

  具有C-6位1-(羟甲基)乙烯叉侧链的手性碳青霉烯类抗生素[dl-天冬霉素A（54）、B（37）、C（53）及相关化合物，55、56、38、59和45]从共同中间体9a和9b开始合成，并测试了它们的抗菌活性。合成过程包括在适当溶剂中使用少量1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）将环碳酸酯基团转化为1-(羟甲基)乙烯叉基团，以及通过AlCl3-茴香醚方法去保护对甲氧基苄酯基团。
• Total synthesis of (−)- and (±)-frontalin via ring-closing metathesis
  作者：Matthias Scholl、Robert H. Grubbs

  DOI：10.1016/s0040-4039(98)02677-x

  日期：1999.2

  Racemic and enantiopure targets containing the 6,8-dioxabicyclo [3.2.1]octane skeleton, can be conveniently synthesized from monocyclic diene precursors using an intramolecular ruthenium-catalyzed ring-closing metathesis reaction as the key step.

  含有6,8-二氧杂双环[3.2.1]辛烷骨架的外消旋和对映体纯目标，可以使用分子内钌催化的闭环复分解反应作为关键步骤，方便地从单环二烯前体合成。