(+/-)-3-ethynyl-4-methylcyclohex-3-en-1-ol | 32635-27-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-3-ethynyl-4-methylcyclohex-3-en-1-ol
• 英文别名: 1-Ethynyl-5-hydroxy-2-methyl-1-cyclohexene；3-Ethynyl-4-methylcyclohex-3-en-1-ol
• CAS: 32635-27-1
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: PLLPCYXAEHFXRV-UHFFFAOYSA-N

物化性质

• 沸点：
  213.8±40.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-3-ethynyl-4-methylcyclohex-3-en-1-ol 、 (S)-(+)-1-(1-萘基)乙基异氰酸酯 以 苯 为溶剂， 反应 70.0h， 以46%的产率得到(1S,1'S)-3-ethynyl-4-methylcyclohex-3-en-1-yl N-<1'-(1-naphthyl)ethyl>carbamate
  参考文献：
  名称：

  Studies of vitamin D (calciferol) and its analogs. 44. Thermal [1,7]-sigmatropic shift of previtamin D3 to vitamin D3: synthesis and study of pentadeuterio derivatives

  摘要：

  Specifically pentadeuteriated previtamin D3 11 has been synthesized to impart thermal stability to the otherwise labile material. A 12-step synthesis of the trideuteriated A-ring 14b from p-methoxyphenol was developed and employed the addition of (methyl-d3)magnesium iodide to either the keto thiomethylene intermediate 23 or the keto dioxane 27. The enantiomerically pure trideuterio A-ring (-)-14b was then coupled with the deuteriated CD fragment 13b followed by hydrogenation to afford pentadeuteriated previtamin D3 11. A primary deuterium kinetic isotope effect (KIE) study of the [1,7]-sigmatropic hydrogen migration in the conversion of previtamin D3 to vitamin D3 indicated a more ''normal'' primary deuterium isotope effect (as compared to a previously reported literature value of approximately 45). At 80-degrees-C, a k(H)/k(D) for the previtamin D3 to vitamin D3 isomerization was determined to be approximately 6.2. At 25-degrees-C, this [1,7]-sigmatropic hydrogen migration proceeds with a k(H)/k(D) Of approximately 11.4. The reversible, first-order [1,7]-sigmatropic hydrogen shift of previtamin D3 to D3, determined over the temperature range 60.1-85.5-degrees-C is characterized by the following activation parameters: log A(H) = 8.8 and E(a)H = 19.6 kcal/mol. Deuteriated pre-D3, which rearranges over this temperature range, is characterized by the activation parameters log A(D) = 9.5 and E(a)D = 21.9 kcal/mol.

  DOI：

  10.1021/jo00055a011
• 作为产物：
  描述：

  5-Hydroxy-2-methylcyclohex-1-en acrylic acid 在 吡啶 、 氨 、 溴 、 sodium 、 氯化铵 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 生成 (+/-)-3-ethynyl-4-methylcyclohex-3-en-1-ol
  参考文献：
  名称：

  Calciferol及其亲戚。第十二部分。（S）-3-乙炔基-4-甲基环己-3-烯-1-醇

  摘要：

  迄今仅以与其双键异构体之一的混合物形式获得的1-乙炔基-2-甲基环己-1-烯是通过ω-卤代二烯如1-（2-氯乙烯基）-2-甲基环己烯（ 6; X = Cl）。旋光的5-羟基-2-甲基环己-1-烯甲醛（10）与氯亚甲基三苯基磷烷反应，生成混合的顺式和反式-ω-氯二烯[ cf. （11）]，其脱卤化氢得到标题化合物（12），其是合成钙化前醇3所必需的。

  DOI：

  10.1039/j39710002352

文献信息

• Selective Acylation of A-Ring Precursors of Vitamin D Using Enzymes in Organic Solvents
  作者：Susana Fernandez、b Miguel Ferrero、Vicente Gotor、William H. Okamura

  DOI：10.1021/jo00124a014

  日期：1995.9

  Whereas Chromobacterium viscosum lipase (CVL) catalyzes selectively the acylation of the C-5 hydroxyl of the three stereoisomeric vitamin D A-ring precursors 2a, 3a and 3b, only the C-3 hydroxyl of the fourth stereoisomer 2b is acylated under the same conditions in organic solvent. In a convenient application, the racemic vitamin D A-ring precursor 4, possessing only the C-5 hydroxyl, was resolved using suitable conditions identified from the studies of 2 and 3.
• Studies of vitamin D (calciferol) and its analogs. 44. Thermal [1,7]-sigmatropic shift of previtamin D3 to vitamin D3: synthesis and study of pentadeuterio derivatives
  作者：William H. Okamura、Hassan Y. Elnagar、Michael Ruther、Susanne Dobreff

  DOI：10.1021/jo00055a011

  日期：1993.1

  Specifically pentadeuteriated previtamin D3 11 has been synthesized to impart thermal stability to the otherwise labile material. A 12-step synthesis of the trideuteriated A-ring 14b from p-methoxyphenol was developed and employed the addition of (methyl-d3)magnesium iodide to either the keto thiomethylene intermediate 23 or the keto dioxane 27. The enantiomerically pure trideuterio A-ring (-)-14b was then coupled with the deuteriated CD fragment 13b followed by hydrogenation to afford pentadeuteriated previtamin D3 11. A primary deuterium kinetic isotope effect (KIE) study of the [1,7]-sigmatropic hydrogen migration in the conversion of previtamin D3 to vitamin D3 indicated a more ''normal'' primary deuterium isotope effect (as compared to a previously reported literature value of approximately 45). At 80-degrees-C, a k(H)/k(D) for the previtamin D3 to vitamin D3 isomerization was determined to be approximately 6.2. At 25-degrees-C, this [1,7]-sigmatropic hydrogen migration proceeds with a k(H)/k(D) Of approximately 11.4. The reversible, first-order [1,7]-sigmatropic hydrogen shift of previtamin D3 to D3, determined over the temperature range 60.1-85.5-degrees-C is characterized by the following activation parameters: log A(H) = 8.8 and E(a)H = 19.6 kcal/mol. Deuteriated pre-D3, which rearranges over this temperature range, is characterized by the activation parameters log A(D) = 9.5 and E(a)D = 21.9 kcal/mol.
• Calciferol and its relatives. Part XII. (S)-3-ethynyl-4-methylcyclohex-3-en-1-ol
  作者：T. M. Dawson、J. Dixon、P. S. Littlewood、B. Lythgoe

  DOI：10.1039/j39710002352

  日期：——

  1-Ethynyl-2-methylcyclohex-1-ene, hitherto obtained only as a mixture with one of its double-bond isomers, is obtained pure by dehydrohalogenation of ω-halogenodienes such as 1-(2-chlorovinyl)-2-methylcyclohexene (6; X = Cl). The optically active 5-hydroxy-2-methylcyclohex-1-enecarbaldehyde (10) reacts with chloromethylenetriphenylphosphorane giving mixed cis- and trans-ω-chloro-dienes [cf.(11)], dehydrohalogenation

  迄今仅以与其双键异构体之一的混合物形式获得的1-乙炔基-2-甲基环己-1-烯是通过ω-卤代二烯如1-（2-氯乙烯基）-2-甲基环己烯（ 6; X = Cl）。旋光的5-羟基-2-甲基环己-1-烯甲醛（10）与氯亚甲基三苯基磷烷反应，生成混合的顺式和反式-ω-氯二烯[ cf. （11）]，其脱卤化氢得到标题化合物（12），其是合成钙化前醇3所必需的。