methyl ester of/the/ L(-)-2-bromo-caproic acid | 5445-19-2

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物 - 羧酸酯及其衍生物
• 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: methyl ester of/the/ L(-)-2-bromo-caproic acid
• 英文别名: Methylester der L(-)-2-Brom-capronsaeure；methyl (2S)-2-bromohexanoate
• CAS: 5445-19-2；70288-61-8；114438-79-8；114438-64-1
• 化学式: C₇H₁₃BrO₂
• 分子量: 209.083
• InChiKey: YGLPDRIMFIXNBI-LURJTMIESA-N

物化性质

• 沸点：
  94°C/15mmHg(lit.)
• 密度：
  1.289 g/mL at 20 °C (lit.)
• 闪点：
  69 °C
• LogP：
  2.61 at 25℃

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• TSCA：
  Yes
• 危险品标志：
  Xi
• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38,R36/38
• WGK Germany：
  3
• 海关编码：
  2915900090
• 危险品运输编号：
  1993

制备方法与用途

用途：用于制备农药和医药中间体。

反应信息

• 作为产物：
  描述：

  反式-2-己烯甲酯 在 葡萄糖 、 enoate reductase old yellow enzyme 3 from S_. cerevisiae 、 GDH from B_. megaterium 、 溴 、 nicotinamide adenine dinucleotide phosphate 作用下， 以 正庚烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.0h， 生成 methyl ester of/the/ L(-)-2-bromo-caproic acid
  参考文献：
  名称：

  Enoate Reductase-Mediated Preparation of Methyl (S)-2-Bromobutanoate, a Useful Key Intermediate for the Synthesis of Chiral Active Pharmaceutical Ingredients

  摘要：

  Enoate reductases belonging to the Old Yellow Enzyme (OYE) family were employed to develop a biocatalysed approach to methyl (S)-2-bromobutanoate, a key intermediate for the introduction of a particular stereogenic unit into the molecular skeleton of a certain class of chiral drugs. Methyl (Z)-2-bromocrotonate afforded, respectively, (S)-2-bromobutanoic acid (ee = 97%) and methyl (S)-2-bromobutanoate (ee = 97%) by baker's yeast fermentation and by OYE1-3 biotransformations. The bioreductions of other methyl 2-haloalkenoates were also considered. It was observed that the (Z)- and (E)-diastereoisomers of alpha-bromo unsaturated esters afforded the same enantiomer of the corresponding reduced product.

  DOI：

  10.1021/op200086t

文献信息

• Enantioselective synthesis of α-bromo acid derivatives and bromohydrins † from tartrate derived bromoacetals
  作者：Scott A. Boyes、Alan T. Hewson

  DOI：10.1039/b002106g

  日期：——

  Bromination of the acetals 4 derived from aryl alkyl ketones, ArCOR, and (2R,3R)-tartaric acid results in bromoacetals 5 with 78–90% de. Hydrolysis of those compounds with Ar = 4-methoxyphenyl or 3-bromo-4-methoxyphenyl results, after recrystallisation, in α-bromoketones 8 with 66–98% ee which are shown to undergo the Baeyer–Villiger oxidation to α-bromoesters 9 with minimal racemisation. α-Bromoketone

  溴化 的 缩醛 4衍生自芳基烷基酮，ArCOR和（2 R，3 R）-酒石酸产生溴缩醛5的de-含量为78-90％。水解 取Ar = 4-甲氧基苯基或3-溴-4-甲氧基苯基的那些化合物 重结晶，在ee含量为66-98％的α-溴代酮8中，已显示出其经过Baeyer-Villiger氧化成α-溴代酸酯9的消旋作用极小。α-溴酮8d被证明经历了羰 减少到苏式-溴代醇15并保留立体化学。
• GC Separation of Enantiomers of Alkyl Esters of 2-Bromo Substituted Carboxylic Acids Enantiomers on 6-TBDMS-2,3-di-alkyl- β- and γ-Cyclodextrin Stationary Phases
  作者：Ivan Špánik、Darina Kačeriaková、Jan Krupčík、Daniel Wayne Armstrong

  DOI：10.1002/chir.22310

  日期：2014.6

  The gas chromatographic separation of enantiomers of 2‐Br carboxylic acid derivatives was studied on four different 6‐TBDMS‐2,3‐di‐O‐alkyl‐ β‐ and ‐γ‐CD stationary phases. The differences in thermodynamic data ΔH and –ΔS} for the 15 structurally related racemates were evaluated. The influence of structure differences in the alkyl substituents covalently attached to the stereogenic carbon atom, as

  在4种不同的6-TBDMS-2,3-di-O-烷基-β-和γ-CD固定相上研究了2-Br羧酸衍生物对映体的气相色谱分离。热力学数据的差异 ΔH和–ΔS}对15个与结构相关的外消旋体进行了评估。详细研究了共价连接到立体碳原子上的烷基取代基以及同源分析物的酯基中结构差异的影响，以及改性β-和γ-环糊精衍生物的选择性。环糊精空腔的大小，以及6-TBDMS-β-CD的2和3位的烷基取代基的延伸，也影响了它们的选择性。对映体分离的质量主要受分子酯基团的烷基链影响，这似乎与所用的CD固定相无关。在某些情况下，分离是由于外部吸附而不是与手性选择剂形成包合物而发生的。手性26：279–285，2014。©2014 Wiley Periodicals，Inc.
• Levene; Kuna, Journal of Biological Chemistry, 1941, vol. 141, p. 404
  作者：Levene、Kuna

  DOI：——

  日期：——
• Enoate Reductase-Mediated Preparation of Methyl (<i>S</i>)-2-Bromobutanoate, a Useful Key Intermediate for the Synthesis of Chiral Active Pharmaceutical Ingredients
  作者：Elisabetta Brenna、Francesco G. Gatti、Alessia Manfredi、Daniela Monti、Fabio Parmeggiani

  DOI：10.1021/op200086t

  日期：2012.2.17

  Enoate reductases belonging to the Old Yellow Enzyme (OYE) family were employed to develop a biocatalysed approach to methyl (S)-2-bromobutanoate, a key intermediate for the introduction of a particular stereogenic unit into the molecular skeleton of a certain class of chiral drugs. Methyl (Z)-2-bromocrotonate afforded, respectively, (S)-2-bromobutanoic acid (ee = 97%) and methyl (S)-2-bromobutanoate (ee = 97%) by baker's yeast fermentation and by OYE1-3 biotransformations. The bioreductions of other methyl 2-haloalkenoates were also considered. It was observed that the (Z)- and (E)-diastereoisomers of alpha-bromo unsaturated esters afforded the same enantiomer of the corresponding reduced product.