4-(tert-Butyl-dimethyl-silanyloxy)-3-methyl-butan-2-one | 191546-09-5

• 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: 4-(tert-Butyl-dimethyl-silanyloxy)-3-methyl-butan-2-one
• 英文别名: 3-Methyl-2-butanone, 4-t-butyldimethylsilyloxy-；4-[tert-butyl(dimethyl)silyl]oxy-3-methylbutan-2-one
• CAS: 191546-09-5
• 化学式: C₁₁H₂₄O₂Si
• 分子量: 216.396
• InChiKey: WKUMUSZIWCTOJR-UHFFFAOYSA-N

物化性质

• 沸点：
  233.2±23.0 °C(Predicted)
• 密度：
  0.866±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 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：

  4-(tert-Butyl-dimethyl-silanyloxy)-3-methyl-butan-2-one 在 四丁基氟化铵 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.5h， 生成 1-[(2,4-dimethoxyphenyl)methyl-(4-hydroxy-3-methylbutan-2-yl)carbamoyl]oxyethyl 5-[(3R)-dithiolan-3-yl]pentanoate
  参考文献：
  名称：

  [EN] DITHIOLAN-3-YLPENTANOATE DERIVATIVES, PHARMACEUTICAL COMPOSITIONS AND METHODS FOR THE TREATMENT OF PAIN
  [FR] DÉRIVÉS DE DITHIOLAN-3-YLPENTANOATE, COMPOSITIONS PHARMACEUTIQUES ET MÉTHODES DE TRAITEMENT DE LA DOULEUR

  摘要：

  本公开提供了式I、式II和式III的1-羰胺氧乙基5-(1,2-二硫代环戊烷-3-基)戊酸酯衍生物。本公开还提供了一种合成式I、式II和式III化合物的方法。式I、式II和式III化合物或其药用可接受的盐，以及其多晶型、溶剂合物和水合物，可制成药物组合物。式I、式II和式III化合物的药物组合物或式I、式II或式III的最终化合物可制成用于非侵入性口服、局部（例如经皮）、肠内、经粘膜、靶向递送、持续释放递送、延迟释放、脉冲释放和静脉途径的方法。这种组合物可用于治疗伴随慢性疾病或其相关并发症表现的慢性疼痛。

  公开号：

  WO2015118554A1
• 作为产物：
  描述：

  4-羟基-3-甲基-2-丁酮 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以95%的产率得到4-(tert-Butyl-dimethyl-silanyloxy)-3-methyl-butan-2-one
  参考文献：
  名称：

  在二叔丁基亚甲硅烷基源的存在下，金属催化的均烯丙基醚到甲硅烷基甲基烯丙基硅烷的重排。

  摘要：

  [反应：见正文]在研究将二叔丁基亚甲硅烷基转移到宝石二取代的烯烃以形成硅环丙烷的范围时，我们发现了均空醚的空前反应。当在室温或更高温度下进行亚甲硅烷基转移时，两个二叔丁基亚甲硅烷基单元被引入分子中，并且碳主链发生了完全重排。该报告描述了这种独特反应的范围以及进行了机制研究的机制。

  DOI：

  10.1021/ol052456x

文献信息

• 1,2 asymmetric induction in the TiCl4 mediated alkylation of α-methyl-β-silyloxy ketones with Grignard reagents
  作者：Giuseppe Bartoli、Marcella Bosco、Letizia Sambri、Enrico Marcantoni

  DOI：10.1016/s0040-4039(97)00735-1

  日期：1997.5

  Transmetallation of an α-methyl-β-silyloxy ketone with TiCl4 in toluene affords a cyclic chelation complex which undergoes highly stereoselective alkylation from Grignard reagents at the less hindered side.

  用甲苯中的TiCl 4对α-甲基-β-甲硅烷氧基酮进行金属转移，得到环状螯合配合物，该螯合配合物在较少受阻的一侧从格氏试剂进行高度立体选择性的烷基化反应。
• COMPOUND AND METHOD FOR THE TREATMENT OF PAIN
  申请人：KANDULA MAHESH

  公开号：US20110237658A1

  公开（公告）日：2011-09-29

  The disclosure herein provides a compound of formula 1. The disclosure also provides a method of synthesizing the compound of formula 1. The compound of formula 1 or its pharmaceutical acceptable salts, as well as polymorphs, solvates, and hydrates thereof may be formulated as pharmaceutical composition. The pharmaceutical composition of compound of formula 1 or the final compound may be formulated for non-invasive peroral, topical (example transdermal), enteral, transmucosal, targeted delivery, sustained release delivery, delayed release, pulsed release and parenteral methods. Such compositions may be used to treat chronic pain manifested with chronic diseases or its associated complications.

  本公开提供了一种化合物的化学式1。本公开还提供了一种合成该化合物的方法。化学式1的化合物或其药用可接受的盐，以及其多晶型、溶剂合物和水合物可以制成药物组合物。化学式1的药物组合物或最终化合物可以制成用于非侵入性口服、局部（例如经皮）、肠内、经粘膜、靶向递送、持续释放递送、延迟释放、脉冲释放和静脉途径的方法。这些组合物可用于治疗伴随慢性疾病或其相关并发症表现的慢性疼痛。
• Internal Lewis Acid Coordination as a Powerful Tool To Promote Highly Stereoselective Alkylation ofα-Alkyl-β-Hydroxy Ketones with Grignard Reagents
  作者：Giuseppe Bartoli、M. Cristina Bellucci、Marcella Bosco、Enrico Marcantoni、Letizia Sambri

  DOI：10.1002/(sici)1521-3765(19981102)4:11<2154::aid-chem2154>3.0.co;2-o

  日期：1998.11.2

  An efficient and highly diastereoselective protocol is described for the alkylation of beta-hydroxy ketones that contain an a-stereocenter. This method is based on the preliminary transformation of the beta-hydroxy group into a titanium alcoholate by means of the facile transmetalation of the corresponding beta-silyloxy derivative with TiCl4 (Method A) or by reaction of the lithium alcoholate with TiCl4 (Method B). On account of the strong internal coordinating action of the Lewis acid, this intermediate assumes a rigid half-chair conformation with the alpha-alkyl substituent in a pseudoaxial position, This geometrical arrangement facilitates the attack of the entering carbanion on the carbonylic function apposite to the alpha-substituent. The method uses simple Grignard reagents as the alkylating agents and allows the addition of a wide variety of carbon frameworks to the carbonyl function. including primary and secondary alkyl chains, arylic, alkynylic, vinylic, and benzylic moieties, with high efficiency and stereoselectivity.
• [EN] DITHIOLAN-3-YLPENTANOATE DERIVATIVES, PHARMACEUTICAL COMPOSITIONS AND METHODS FOR THE TREATMENT OF PAIN<br/>[FR] DÉRIVÉS DE DITHIOLAN-3-YLPENTANOATE, COMPOSITIONS PHARMACEUTIQUES ET MÉTHODES DE TRAITEMENT DE LA DOULEUR
  申请人：KRISANI BIOSCIENCES P LTD

  公开号：WO2015118554A1

  公开（公告）日：2015-08-13

  The disclosure herein provides 1-carbamoyloxyethyl 5-(1,2-dithiolan-3-yl)pentanoate derivatives of formula I, formula II and formula III. The disclosure also provides a method of synthesizing the compound of formula I, formula II and formula III. The compound of formula I, formula II and formula III or its pharmaceutical acceptable salts, as well as polymorphs, solvates, and hydrates, thereof may be formulated as pharmaceutical composition. The pharmaceutical composition of compound of formula I, formula II and formula III or the final compound of formula I, formula II or formula III may be formulated for non-invasive peroral, topical (example transdermal), enteral, transmucosal, targeted delivery, sustained release delivery, delayed release, pulsed release and parenteral methods. Such compositions may be used to treat chronic pain manifested with chronic diseases or its associated complications.

  本公开提供了式I、式II和式III的1-羰胺氧乙基5-(1,2-二硫代环戊烷-3-基)戊酸酯衍生物。本公开还提供了一种合成式I、式II和式III化合物的方法。式I、式II和式III化合物或其药用可接受的盐，以及其多晶型、溶剂合物和水合物，可制成药物组合物。式I、式II和式III化合物的药物组合物或式I、式II或式III的最终化合物可制成用于非侵入性口服、局部（例如经皮）、肠内、经粘膜、靶向递送、持续释放递送、延迟释放、脉冲释放和静脉途径的方法。这种组合物可用于治疗伴随慢性疾病或其相关并发症表现的慢性疼痛。
• Metal-Catalyzed Rearrangement of Homoallylic Ethers to Silylmethyl Allylic Silanes in the Presence of a Di-<i>tert</i>-butylsilylene Source
  作者：Pamela A. Cleary、K. A. Woerpel

  DOI：10.1021/ol052456x

  日期：2005.11.1

  transfer to gem-disubstituted alkenes to form silacyclopropanes, we discovered an unprecedented reaction of homoallylic ethers. When silylene transfer was performed at room temperature or above, two di-tert-butylsilylene units were incorporated into the molecule, and complete rearrangement of the carbon backbone occurred. This report describes the scope of this unique reaction as well as the mechanistic

  [反应：见正文]在研究将二叔丁基亚甲硅烷基转移到宝石二取代的烯烃以形成硅环丙烷的范围时，我们发现了均空醚的空前反应。当在室温或更高温度下进行亚甲硅烷基转移时，两个二叔丁基亚甲硅烷基单元被引入分子中，并且碳主链发生了完全重排。该报告描述了这种独特反应的范围以及进行了机制研究的机制。