(2E)-5-[[(1,1-dimethylethyl)di-methylsilyl]oxy]-2-fluoro-2-pentenoic acid ethyl ester | 120632-27-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2E)-5-[[(1,1-dimethylethyl)di-methylsilyl]oxy]-2-fluoro-2-pentenoic acid ethyl ester
• 英文别名: ethyl (2E)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-fluoropent-2-enoate；ethyl (2E)-{[4-t-butyl(dimethyl)silyl]oxy}-2-fluoropent-2-enoate；ethyl (E)-2-fluoro-5-(tert-butyldimethylsilyloxy)-2-pentenoate；(2E)-5-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-fluoro-2-pentenoic acid ethyl ester；(2E)-5-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-fluoro-pentenoic acid ethyl ester；ethyl (E)-2-fluoro-5-(tertbutyldimethylsilyloxy)-2-pentenoate；ethyl (E)-5-[tert-butyl(dimethyl)silyl]oxy-2-fluoropent-2-enoate
• CAS: 120632-27-1
• 化学式: C₁₃H₂₅FO₃Si
• 分子量: 276.424
• InChiKey: JINVTOCRUUCTMW-PKNBQFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2E)-5-[[(1,1-dimethylethyl)di-methylsilyl]oxy]-2-fluoro-2-pentenoic acid ethyl ester 在 盐酸 、 三乙胺 、 红铝 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 0.5h， 生成 (2E)-2-fluoro-5-[(methylsulfonyl)oxy]pent-2-enyl methanesulfonate
  参考文献：
  名称：

  3-Methyl-4H-[1,2,4]-oxadiazol-5-one: a versatile synthon for protecting monosubstituted acetamidines

  摘要：

  The utilization of 3-methyl-4H-[1,2,4]-oxadiazol-5-one as a versatile protected acetamidine is demonstrated through employment in a variety of synthetic sequences. The potassium salt (2a) or the neutral form (2b) is alternatively shown to be superior for various synthetic reactions (i.e., alkylation, Michael addition, Mitsunobu) to incorporate side chains for further synthesis. The 3-methyl-4H-[1,2,4]-oxadiazol-5-one moiety was found to be stable to acid or base under non-aqueous conditions. It was also found to be stable to many reagents commonly used for organic synthesis. Despite this stability, the free acetamidine may be released by mild reduction including Lindlar hydrogenation or dissolving metal reductions. Alternatively, the hydroxyl amidine may be formed via alkaline hydrolysis. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.09.030
• 作为产物：
  描述：

  2-氟-2-磷酰基乙酸三乙酯 、 3-(叔丁基-二甲基-硅烷基OXY)-丙醛 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以80%的产率得到(2E)-5-[[(1,1-dimethylethyl)di-methylsilyl]oxy]-2-fluoro-2-pentenoic acid ethyl ester
  参考文献：
  名称：

  Asymmetric Photodeconjugation: Highly Stereoselective Synthesis of α-Fluorocarboxylic Derivatives

  摘要：

  α-氟代-α,β-不饱和酯的辐照导致相应的α-氟代-β,γ-不饱和异构体，产率良好。反应需要使用非手性碱（通常是胺）来促进光二烯醇中间体的质子化。通过用二丙酮-d-葡萄糖部分替换乙基，反应可以以对映选择性方式进行，以提供去共轭酯，产率和选择性高达95%。产物经氧化条件处理，一步生成α-氟代-β-羟基丁内酯。

  DOI：

  10.1055/s-2002-20028

文献信息

• Novel carboxylic acid esters, method for their production and
  申请人：Sumitomo Chemical Company, Limited

  公开号：US05004753A1

  公开（公告）日：1991-04-02

  This invention relates to novel carboxylic acid esters represented by the formula (I) below, methods for their production and insecticides containing them as an active ingredient, and an alcohol compound useful as an intermediate for manufacturing carboxylic acid esters represented by the formula (I), ##STR1## wherein R.sup.1 represents a halogenated lower alkyl group, R.sup.2 represents a fluorine atom or a methyl group, R.sup.3 represents a hydrogen atom or a methyl group, R.sup.4 represents a hydrogen atom or a methyl group, and when R.sup.4 is a hydrogen atom, R.sup.5 represents a group of the formula, ##STR2## in which X and Y are the same or different and represent a hydrogen atom, a methyl group, a halogen atom or a halogenated lower alkyl group, and when R.sup.4 is a methyl group, R.sup.5 represents a methyl group.

  本发明涉及一种新型的羧酸酯，其化学式如下（I），以及制备它们的方法和含有它们作为活性成分的杀虫剂，还有一种用于制造化学式（I）中所表示的羧酸酯的中间醇化合物，其中R^1代表卤代的低碳基，R^2代表氟原子或甲基基团，R^3代表氢原子或甲基基团，R^4代表氢原子或甲基基团，当R^4为氢原子时，R^5代表公式的基团：（X和Y相同或不同，代表氢原子、甲基基团、卤原子或卤代的低碳基），当R^4为甲基基团时，R^5代表甲基基团。
• [EN] COMBINATION THERAPY WITH INHIBITORS OF INDUCIBLE NITRIC OXIDE SYNTHASE AND ALKYLATING AGENTS<br/>[FR] THERAPIE DE COMBINAISON AVEC DES INHIBITEURS DE LA SYNTHASE DU MONOXYDE D'AZOTE INDUCTIBLE ET DES AGENTS D'ALKYLATION
  申请人：PHARMACIA CORP

  公开号：WO2005025620A3

  公开（公告）日：2007-01-11
• [EN] METHODS FOR TREATMENT AND PREVENTION OF GASTROINTESTINAL CONDITIONS<br/>[FR] PROCEDES DESTINES AU TRAITEMENT ET A LA PREVENTION DE TROUBLES GASTRO-INTESTINAUX
  申请人：PHARMACIA CORP

  公开号：WO2004012726A3

  公开（公告）日：2004-06-03
• Asymmetric Photodeconjugation: Highly Stereoselective Synthesis of α-Fluorocarboxylic Derivatives
  作者：Frédéric Bargiggia、Sylvia Dos Santos、Olivier Piva

  DOI：10.1055/s-2002-20028

  日期：——

  Irradiations of α-fluoro-α,β-unsaturated esters lead to the corresponding α-fluoro-β,γ-unsaturated isomers in good yields. The reaction required the use of an achiral base (typically an amine) to promote the protonation of the photodienolic intermediate. By replacing the ethyl group with a diacetone-d-glucose moiety, the reaction can be carried out in a diastereoselective manner to furnish the deconjugated esters with similar yields and selectivities up to 95%. The adducts were submitted to osmylation conditions to deliver α-fluoro-β-hydroxy-butyrolactones in one single step.

  α-氟代-α,β-不饱和酯的辐照导致相应的α-氟代-β,γ-不饱和异构体，产率良好。反应需要使用非手性碱（通常是胺）来促进光二烯醇中间体的质子化。通过用二丙酮-d-葡萄糖部分替换乙基，反应可以以对映选择性方式进行，以提供去共轭酯，产率和选择性高达95%。产物经氧化条件处理，一步生成α-氟代-β-羟基丁内酯。
• 3-Methyl-4H-[1,2,4]-oxadiazol-5-one: a versatile synthon for protecting monosubstituted acetamidines
  作者：Alan E. Moormann、Jane L. Wang、Katherine E. Palmquist、Michele A. Promo、Jeffery S. Snyder、Jeffrey A. Scholten、Mark A. Massa、James A. Sikorski、R. Keith Webber

  DOI：10.1016/j.tet.2004.09.030

  日期：2004.11

  The utilization of 3-methyl-4H-[1,2,4]-oxadiazol-5-one as a versatile protected acetamidine is demonstrated through employment in a variety of synthetic sequences. The potassium salt (2a) or the neutral form (2b) is alternatively shown to be superior for various synthetic reactions (i.e., alkylation, Michael addition, Mitsunobu) to incorporate side chains for further synthesis. The 3-methyl-4H-[1,2,4]-oxadiazol-5-one moiety was found to be stable to acid or base under non-aqueous conditions. It was also found to be stable to many reagents commonly used for organic synthesis. Despite this stability, the free acetamidine may be released by mild reduction including Lindlar hydrogenation or dissolving metal reductions. Alternatively, the hydroxyl amidine may be formed via alkaline hydrolysis. (C) 2004 Elsevier Ltd. All rights reserved.