methyl 2-<2-(1-hydroxycyclohexyl)ethynyl>benzoate | 142458-83-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2-<2-(1-hydroxycyclohexyl)ethynyl>benzoate
• 英文别名: Methyl 2-[2-(1-hydroxycyclohexyl)ethynyl]benzoate
• CAS: 142458-83-1
• 化学式: C₁₆H₁₈O₃
• 分子量: 258.317
• InChiKey: HOLLTQGGSVWKET-UHFFFAOYSA-N

物化性质

• 沸点：
  416.7±30.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-<2-(1-hydroxycyclohexyl)ethynyl>benzoate 在 甲酸 、 potassium tert-butylate 、 四丁基氯化铵 、 palladium diacetate 、 三乙胺 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 28.0h， 生成 5-(4-methylphenyl)-1H-spiro[2-benzoxepine-3,1'-cyclohexan]-1-one
  参考文献：
  名称：

  Pd- and Rh-Catalyzed Hydroarylation of γ-(2-Methoxycarbonylphenyl)propargylic Alcohols: Approaches to 4- or 5-Substituted Seven-Membered Benzolactones and 3,3-Disubstituted Phthalides

  摘要：

  A study of the palladium-catalyzed hydroarylation/hydrovinylation reaction of gamma-(2-methoxycarbonylphenyl)propargylic alcohols with aryl iodides/vinyl triflates and of the rhodium-catalyzed one with organoboron derivatives is described. The opposite regiochemical outcome of the two processes allows an easy selective approach to 5- or 4-substituted benzoxepin-1(3H)-ones by combining the hydroarylative/hydrovinylative step with cyclocondensation between -OH and -COOMe groups in the intermediate gamma,gamma-disubstituted or beta,gamma-disubstituted allylic alcohols. A one-flask procedure to give benzo[c]oxepin-1(3H)-ones directly from the starting alkyne has been also developed. Treatment of crude gamma,gamma-disubstituted allylic alcohols with NaOH, followed by acidification, affords 3,3-disubstituted phthalides.

  DOI：

  10.1021/acs.joc.5b00663
• 作为产物：
  描述：

  2-碘苯甲酸甲酯 、 炔环己醇 在 copper(l) iodide 、 三乙胺 、 三苯基膦 、 palladium dichloride 作用下， 反应 10.0h， 以84%的产率得到methyl 2-<2-(1-hydroxycyclohexyl)ethynyl>benzoate
  参考文献：
  名称：

  Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins

  摘要：

  一种范围广泛的磷酰基吲哚化合物通过一锅法从官能化丙炔醇和适当的P(III)前体经过碱介导的反应制备而成。该反应通过亚烯基磷氧化物的中间体进行。类似地，磷酰基异香豆素通过三氟乙酸介导的反应从亚烯基磷氧化物制备而成；后者也充当溶剂。有趣的是，在存在潮湿的三氟乙酸的情况下，除了磷酰基异香豆素外，还获得了无磷异香豆素。关键产品通过单晶X射线衍射进行了表征。

  DOI：

  10.3762/bjoc.10.99

文献信息

• Rhodium carbenoid mediated cyclizations of o-alkynyl-substituted .alpha.-diazoacetophenones
  作者：Albert Padwa、Keith E. Krumpe、Jamal M. Kassir

  DOI：10.1021/jo00044a032

  日期：1992.8

  o-Alkynyl-substituted alpha-diazoacetophenones undergo facile cyclization to indenone derivatives upon treatment with catalytic quantities of Rh(II) carboxylates. A variety of structural influences were encountered by varying the nature of the substituent group attached to the alkyne carbon atom. The cyclization reaction involves addition of a rhodium stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid. The vinyl carbenoid was found to undergo both CH and CC migration as well as delta-CH insertion into the alkyl backbone. Different catalysts were shown to result in significant variation in the product ratios for these reactions. Treatment of o-(5-(allyloxy)-1-pentynyl)-alpha-diazoacetophenone with rhodium(II) mandelate afforded 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran in high yield. The formation of this compound involves initial formation of a vinyl carbenoid which reacts with the neighboring oxygen atom to give an oxonium ylide which subsequently undergoes a 2,3-sigmatropic rearrangement. When 2-ethynyl-alpha-diazoacetophenone is used, only products derived from 6-endo closure are observed. Substituted o-alkynyl alpha-diazoacetophenones give products derived from 5-exo cyclization. The mode of ring closure is controlled by both steric and electronic factors.