8-[1-Chloro-1-(4-methylphenyl)sulfinylethyl]-7-methyl-1,4-dioxaspiro[4.5]decan-8-ol | 912539-62-9

• 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: 8-[1-Chloro-1-(4-methylphenyl)sulfinylethyl]-7-methyl-1,4-dioxaspiro[4.5]decan-8-ol
• CAS: 912539-62-9
• 化学式: C₁₈H₂₅ClO₄S
• 分子量: 372.913
• InChiKey: NDEFYYXNTQKKGM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  75
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  8-[1-Chloro-1-(4-methylphenyl)sulfinylethyl]-7-methyl-1,4-dioxaspiro[4.5]decan-8-ol 、 氘代甲醇-d 在 叔丁基氯化镁 、 异丙基氯化镁 作用下， 以 四氢呋喃 为溶剂， 反应 0.58h， 以82%的产率得到9-deuterio-7,9-dimethyl-1,4-dioxaspiro[4.6]undecan-8-one
  参考文献：
  名称：

  One-carbon ring-expansion of 2-substituted cyclohexanones via lithium- and magnesium β-oxido carbenoid rearrangement: a new synthesis of 2,7-disubstituted and 2,2,7-trisubstituted cycloheptanones

  摘要：

  Lithium alpha-sulfinyl carbanion of 1-chloroethyl p-tolyl sulfoxide was reacted with 2-substituted cyclohexanones to afford adducts in good yields. The adducts were treated with LDA or t-BuMgCl to give lithium or magnesium alkoxides, which were treated with t-BuLi or i-PrMgCl to afford one-carbon ring-expanded 2,7-disubstituted cycloheptanones through beta-oxido carbenoids. Interestingly, 2,3-disubstituted cycloheptanones were obtained in a trace amount or were not obtained at all. The enolate intermediates of this reaction were found to be able to get trapped with electrophiles to give 2,2,7-trisubstituted cycloheptanones in moderate to good yields. This method is very useful for the synthesis of 2,7-disubstituted cycloheptanones and 2,2,7-trisubstituted cycloheptanones from 2-substituted cyclohexanones in only two steps. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.07.082
• 作为产物：
  描述：

  1-chloroethyl p-tolyl sulfoxide, lithium α-sulfinyl carbanion 、 7-甲基-1,4-二氧杂-螺[4.5]癸烷-8-酮 以95%的产率得到8-[1-Chloro-1-(4-methylphenyl)sulfinylethyl]-7-methyl-1,4-dioxaspiro[4.5]decan-8-ol
  参考文献：
  名称：

  One-carbon ring-expansion of 2-substituted cyclohexanones via lithium- and magnesium β-oxido carbenoid rearrangement: a new synthesis of 2,7-disubstituted and 2,2,7-trisubstituted cycloheptanones

  摘要：

  Lithium alpha-sulfinyl carbanion of 1-chloroethyl p-tolyl sulfoxide was reacted with 2-substituted cyclohexanones to afford adducts in good yields. The adducts were treated with LDA or t-BuMgCl to give lithium or magnesium alkoxides, which were treated with t-BuLi or i-PrMgCl to afford one-carbon ring-expanded 2,7-disubstituted cycloheptanones through beta-oxido carbenoids. Interestingly, 2,3-disubstituted cycloheptanones were obtained in a trace amount or were not obtained at all. The enolate intermediates of this reaction were found to be able to get trapped with electrophiles to give 2,2,7-trisubstituted cycloheptanones in moderate to good yields. This method is very useful for the synthesis of 2,7-disubstituted cycloheptanones and 2,2,7-trisubstituted cycloheptanones from 2-substituted cyclohexanones in only two steps. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.07.082