ethyl 3-chloro-2-oxotridecanoate | 113524-86-0

• 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: ethyl 3-chloro-2-oxotridecanoate
• CAS: 113524-86-0
• 化学式: C₁₅H₂₇ClO₃
• 分子量: 290.831
• InChiKey: ITLHRVXMYYHDRC-UHFFFAOYSA-N

物化性质

• 沸点：
  356.8±25.0 °C(predicted)
• 密度：
  1.008±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  19
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 3-chloro-2-oxotridecanoate 在 磷酸二氢铵 、 sodium tetrahydroborate 、 potassium dihydrogenphosphate 、 葡萄糖 、 sodium ethanolate 、 magnesium sulfate 、 calcium carbonate 作用下， 以 乙醇 、 水 为溶剂， 反应 87.5h， 生成 [(2R,3R)-3-丙基-2-环氧乙烷基]甲醇
  参考文献：
  名称：

  Highly enantioselective reduction of 3-chloro-2-oxoalkanoates with fermenting bakers' yeast. A new synthesis of optically active 3-chloro-2-hydroxyalkanoates and glycidic esters

  摘要：

  Reduction of 3-chloro-2-oxoalkanoic esters with fermenting bakers' yeast gave optically active 3-chloro-2-hydroxyalkanoic esters 2 (anti(2S,3R)/syn (2S,3S) = 52:48-90:10) in 50-85% yields with >95% ee except for 43% ee of ethy syn-(2S,3S)-3-chloro-2-hydroxy-4 phenylbutanoate (2j). Compounds 2 were treated with NaOEt to give (E)-(2R,3S)-2,3-epoxyalkanoates 3 in 30-66% yields with 44-64% ee. Optically active 2,3-epoxy alcohols (cis-23, trans-23, and trans-25), key intermediates for the syntheses of (-)-disparlure (4), mosquito pheromone (5), and a component of passion fruit flavor (6), were prepared with more than 86% ee in high yields.

  DOI：

  10.1021/jo00054a036
• 作为产物：
  描述：

  十一醛 在 aluminum oxide 、 sodium ethanolate 作用下， 以 xylene 为溶剂， 反应 6.5h， 生成 ethyl 3-chloro-2-oxotridecanoate
  参考文献：
  名称：

  Lipase-catalyzed kinetic resolution of 3-chloro-2-hydroxyalkanoates. Its application for the synthesis of (−)-disparlure

  摘要：

  Reduction of 3-chloro-2-oxoalkanoates 1 with NaBH4 gave predominantly syn-3-chloro-2-hydroxyalkanoates 2 (synlanti=91/9-99/1) in 50-97% yields. Resolution of syn-2 by lipase-catalyzed transesterification gave (2S,3S)-2 and (2R,3R)-2-acetoxy-3-chloroalkanoates (2R,3R)-3. Total synthesis of (-)-disparlure, the pheromone of the gypsy moth was established from (2S,3S)-2g via 4 steps in 34.9% overall yield. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(96)00529-0

文献信息

• Reinvestigation of Base-Catalyzed Condensation of Ethyl α,α-Dichloroacetoacetate with Aldehydes. A New Synthesis of (±)-Disparlure
  作者：Sadao Tsuboi、Hiroyuki Furutani、Akira Takeda、Kayoko Kawazoe、Sadao Sato

  DOI：10.1246/bcsj.60.2475

  日期：1987.7

  The titled reaction gave ethyl 2-chloro-2,3-epoxyalkanoates (2) and ethyl 3-chloro-2-oxoalkanoates in improved yields. The structure of the by-product was revised as 1,5-dichloro-4,8-dialkyltricyclo[5.1.0.03,5]octane-2,6-dione by means of the 13C–1H two-dimensional NMR spectrum and an X-ray crystallographic analysis. Compound 2 was applied to the synthesis of (±)-disparlure, the pheromone of the gypsy

  标题反应以提高的产率得到2-氯-2，3-环氧链烷酸乙酯(2)和3-氯-2-氧代链烷酸乙酯。副产物的结构通过 13C–1H 二维核磁共振谱和 X 射线衍射谱修正为 1,5-二氯-4,8-​​二烷基三环[5.1.0.03,5]辛烷-2,6-二酮-射线晶体学分析。化合物 2 用于合成 (±)-disparlure，吉普赛蛾的信息素，通过 6 个步骤以 49% 的总产率合成。
• A Practical Synthesis of Chiral 3-Chloro-2-hydroxyalkanoates and 2,3-Epoxyalcohols
  作者：Sadao Tsuboi、Hiroyuki Furutani、Masanori Utaka、Akira Takeda

  DOI：10.1016/s0040-4039(00)96187-2

  日期：1987.1
• TSUBOI, SADAO;FURUTANI, HIROYUKI;TAKEDA, AKIRA;KAWAZOE, KAYOKO;SATO, SADA+, BULL. CHEM. SOC. JAP., 60,(1987) N 7, 2475-2479
  作者：TSUBOI, SADAO、FURUTANI, HIROYUKI、TAKEDA, AKIRA、KAWAZOE, KAYOKO、SATO, SADA+

  DOI：——

  日期：——
• Lipase-catalyzed kinetic resolution of 3-chloro-2-hydroxyalkanoates. Its application for the synthesis of (−)-disparlure
  作者：Sadao Tsuboi、Nobuyuki Yamafuji、Masanori Utaka

  DOI：10.1016/s0957-4166(96)00529-0

  日期：1997.2

  Reduction of 3-chloro-2-oxoalkanoates 1 with NaBH4 gave predominantly syn-3-chloro-2-hydroxyalkanoates 2 (synlanti=91/9-99/1) in 50-97% yields. Resolution of syn-2 by lipase-catalyzed transesterification gave (2S,3S)-2 and (2R,3R)-2-acetoxy-3-chloroalkanoates (2R,3R)-3. Total synthesis of (-)-disparlure, the pheromone of the gypsy moth was established from (2S,3S)-2g via 4 steps in 34.9% overall yield. (C) 1997 Elsevier Science Ltd. All rights reserved.
• Highly enantioselective reduction of 3-chloro-2-oxoalkanoates with fermenting bakers' yeast. A new synthesis of optically active 3-chloro-2-hydroxyalkanoates and glycidic esters
  作者：Sadao Tsuboi、Hiroyuki Furutani、Mohammad Hafeez Ansari、Takashi Sakai、Masanori Utaka、Akira Takeda

  DOI：10.1021/jo00054a036

  日期：1993.1

  Reduction of 3-chloro-2-oxoalkanoic esters with fermenting bakers' yeast gave optically active 3-chloro-2-hydroxyalkanoic esters 2 (anti(2S,3R)/syn (2S,3S) = 52:48-90:10) in 50-85% yields with >95% ee except for 43% ee of ethy syn-(2S,3S)-3-chloro-2-hydroxy-4 phenylbutanoate (2j). Compounds 2 were treated with NaOEt to give (E)-(2R,3S)-2,3-epoxyalkanoates 3 in 30-66% yields with 44-64% ee. Optically active 2,3-epoxy alcohols (cis-23, trans-23, and trans-25), key intermediates for the syntheses of (-)-disparlure (4), mosquito pheromone (5), and a component of passion fruit flavor (6), were prepared with more than 86% ee in high yields.