3-(2,2-dimethyl-6-oxo-cyclohexyl)-propionic acid ethyl ester | 35319-19-8

• 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: 3-(2,2-dimethyl-6-oxo-cyclohexyl)-propionic acid ethyl ester
• 英文别名: 3-(2,2-Dimethyl-6-oxo-cyclohexyl)-propionsaeure-aethylester；ethyl 3-(2,2-dimethyl-6-oxocyclohexyl)propanoate
• CAS: 35319-19-8
• 化学式: C₁₃H₂₂O₃
• 分子量: 226.316
• InChiKey: RQKNLJRTDXNRKI-UHFFFAOYSA-N

物化性质

• 沸点：
  85-86 °C(Press: 0.01 Torr)
• 密度：
  1.0125 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-(2,2-dimethyl-6-oxo-cyclohexyl)-propionic acid ethyl ester 在 lithium aluminium tetrahydride 、 草酰氯 、 四氯化钛 、 二甲基亚砜 、 三乙胺 、 锌 作用下， 生成 3-(6',6'-dimethyl-2'-methylenecyclohexyl)propan-1-al
  参考文献：
  名称：

  Studies on the Synthesis of Acanthodoral and Nanaimoal:  Evaluation of Cationic Cyclization Routes

  摘要：

  Intramolecular Lewis acid-promoted reactions of alpha,beta-unsaturated ketone 6 and aldehydes 7 and 8 were examined as potential routes to acanthodoral (1), a structurally interesting natural product. Ketone 6 afforded ene product 22 exclusively, and both 7 and 8 gave mixtures of bicyclic aldehydes 3 and 26 and tricyclic aldehyde 25. The latter most likely results from 7 by intramolecular cyclization of the alkene onto the Lewis acid-activated carbonyl moiety affording carbocation 31 followed by a 1,2-hydride shift and ring closure. Starting from 8, tricyclic aldehyde 25 apparently forms by cyclization to cation 35 and ring closure to cyclobutane 36, followed by ring opening to 31, the same cation as formed in reactions of 7. Nanaimoal (3) results from loss of H+ from 31, and bicyclic aldehyde 26 may be formed in a similar manner or by a concerted ene reaction. The configuration of 25 establishes that the stereochemistry of the initial cyclization to 31 precludes the possible use of this strategy for the synthesis of acanthodoral. However, acid-promoted cyclization of allylic alcohol 23 efficiently gives diene 29 which undergoes selective hydroboration/oxidation to afford nanaimoal.

  DOI：

  10.1021/jo9610568
• 作为产物：
  描述：

  Ethyl 2-(benzenesulfinyl)-3-(2,2-dimethyl-6-oxocyclohexyl)propanoate 在 RaNi 作用下， 以 水 为溶剂， 以98%的产率得到3-(2,2-dimethyl-6-oxo-cyclohexyl)-propionic acid ethyl ester
  参考文献：
  名称：

  Studies on the Synthesis of Acanthodoral and Nanaimoal:  Evaluation of Cationic Cyclization Routes

  摘要：

  Intramolecular Lewis acid-promoted reactions of alpha,beta-unsaturated ketone 6 and aldehydes 7 and 8 were examined as potential routes to acanthodoral (1), a structurally interesting natural product. Ketone 6 afforded ene product 22 exclusively, and both 7 and 8 gave mixtures of bicyclic aldehydes 3 and 26 and tricyclic aldehyde 25. The latter most likely results from 7 by intramolecular cyclization of the alkene onto the Lewis acid-activated carbonyl moiety affording carbocation 31 followed by a 1,2-hydride shift and ring closure. Starting from 8, tricyclic aldehyde 25 apparently forms by cyclization to cation 35 and ring closure to cyclobutane 36, followed by ring opening to 31, the same cation as formed in reactions of 7. Nanaimoal (3) results from loss of H+ from 31, and bicyclic aldehyde 26 may be formed in a similar manner or by a concerted ene reaction. The configuration of 25 establishes that the stereochemistry of the initial cyclization to 31 precludes the possible use of this strategy for the synthesis of acanthodoral. However, acid-promoted cyclization of allylic alcohol 23 efficiently gives diene 29 which undergoes selective hydroboration/oxidation to afford nanaimoal.

  DOI：

  10.1021/jo9610568

文献信息

• Synthese von isomerenfreiem (�)-Dihydro-?-jonon
  作者：D. Stauffacher、H. Schinz

  DOI：10.1002/hlca.19540370426

  日期：——

  Aus 1,1-Dimethyl-2-oxymethyl-cyclohexanon-(3) wird das leicht dimerisierbare 1,1-Dimethyl-2-methylen-cyclohexanon-(3) in Verdünnung hergestellt und mit Acetessigester nach Michael kondensiert, wobei je nach Versuchsbedingungen ein mono- oder ein bicyclisches Kondensationsprodukt entstcht. Beide ergeben bei der Säure-spaltung 1,1-Dimethyl-2-(β-carboxy-äthyl)-3-oxy-3-carboxy-methylcyclohexan. Diese Oxy-dicarbonsäure

  1,1-二甲基-2-氧甲基环己酮（3）是容易二聚1,1-二甲基-2-亚甲基-环己酮（3）在稀释制备和缩合根据与乙酰乙酸酯迈克尔，根据测试条件出现单或双环缩合产物。在酸裂解中，两者均得到1，1-二甲基-2-（β-羧基-乙基）-3-氧-3-羧基-甲基环己烷。该氧二羧酸被内酯化，并且将获得的内酯进行热解。定量地形成1，1-二甲基-2-（β-羧基-乙基）-3-亚甲基-环己烷。通过使该化合物与甲基锂反应，获得了无异构体的二氢-γ-紫罗兰酮。