5-Methyl-4-oxo-3-tosylhexanoic acid | 143766-57-8

• 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: 5-Methyl-4-oxo-3-tosylhexanoic acid
• 英文别名: 5-Methyl-3-(4-methylphenyl)sulfonyl-4-oxohexanoic acid；5-methyl-3-(4-methylphenyl)sulfonyl-4-oxohexanoic acid
• CAS: 143766-57-8
• 化学式: C₁₄H₁₈O₅S
• 分子量: 298.36
• InChiKey: FZOSMXKGGKANRK-UHFFFAOYSA-N

物化性质

• 沸点：
  505.9±50.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  96.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-Methyl-4-oxo-3-tosylhexanoic acid 在 盐酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 生成 Methyl 5-methyl-4-oxohex-2-enoate
  参考文献：
  名称：

  Lithium 3-Lithio-3-tosylalkanoates: .beta.-Acylvinyl Anion Equivalents of .beta.-Lithiated .alpha.,.beta.-Unsaturated Carboxylic Acids

  摘要：

  The dilithiation of beta-tosylated propanoic, 2-methylpropanoic, and butanoic acid 10 with n-butyllithium at -78 degrees C leads to the corresponding lithium 3-lithio-3-tosylalkanoates 11. They react with different electrophilic reagents (deuterium oxide, iodine, trimethylchlorosilane, alkyl halides, and acyl chlorides) to give the corresponding 3-substituted tosylated alkanoic acids 12. When carbonyl compounds are allowed to react with intermediates 11 followed by in situ lactonization with trifluoracetic anhydride and base-promoted elimination alpha,beta-butenolides are obtained. This methodology is applied to the direct synthesis of the rosefuran lactone precursor 14cg, the O-benzyl derivative of (+/-)-umbelactone (14ch), and (+/-)-andirolactone (14ci). The alkylation and acylation reactions of organolithium compounds 11 followed by esterification with hydrogen chloride in methanol and treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afford alpha,beta- and/or beta,gamma-unsaturated esters 17 and/or 18 and unsaturated 4-keto esters 19, respectively. The last methodology has been applied to the synthesis of the unsaturated 4-keto ester 19ae precursor of the seco acid of (+/-)-pyrenophorin (22).

  DOI：

  10.1021/jo00090a043
• 作为产物：
  描述：

  sodium 4-methylbenzenesulfinate 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 为溶剂， 反应 25.0h， 生成 5-Methyl-4-oxo-3-tosylhexanoic acid
  参考文献：
  名称：

  Lithium 3-Lithio-3-tosylalkanoates: .beta.-Acylvinyl Anion Equivalents of .beta.-Lithiated .alpha.,.beta.-Unsaturated Carboxylic Acids

  摘要：

  The dilithiation of beta-tosylated propanoic, 2-methylpropanoic, and butanoic acid 10 with n-butyllithium at -78 degrees C leads to the corresponding lithium 3-lithio-3-tosylalkanoates 11. They react with different electrophilic reagents (deuterium oxide, iodine, trimethylchlorosilane, alkyl halides, and acyl chlorides) to give the corresponding 3-substituted tosylated alkanoic acids 12. When carbonyl compounds are allowed to react with intermediates 11 followed by in situ lactonization with trifluoracetic anhydride and base-promoted elimination alpha,beta-butenolides are obtained. This methodology is applied to the direct synthesis of the rosefuran lactone precursor 14cg, the O-benzyl derivative of (+/-)-umbelactone (14ch), and (+/-)-andirolactone (14ci). The alkylation and acylation reactions of organolithium compounds 11 followed by esterification with hydrogen chloride in methanol and treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afford alpha,beta- and/or beta,gamma-unsaturated esters 17 and/or 18 and unsaturated 4-keto esters 19, respectively. The last methodology has been applied to the synthesis of the unsaturated 4-keto ester 19ae precursor of the seco acid of (+/-)-pyrenophorin (22).

  DOI：

  10.1021/jo00090a043

文献信息

• Lithium 3-lithio-3-tosylpropanoate: A useful α-tosylated homoenolate anion
  作者：Pedro Bonete、Carmen Nájera

  DOI：10.1016/0040-4039(92)88101-a

  日期：1992.7

  Lithium 3-lithio-3-tosylpropanoate (7), prepared by dilithiation of 3-tosylpropanoic acid (6) with n-butyllithium at −78°C, reacts with different elctrophiles yielding the expected 3-functionalized tosylated propanoic acids 8. When carbonyl compounds are used as electrophiles the corresponding α,β-butenolides are prepared directly.

  通过在-78°C下将3-甲苯基丙酸（6）与正丁基锂二锂化制备的3-lithio-3-甲苯基丙酸锂（7）与不同的亲电子试剂反应生成预期的3-官能化甲苯磺酸丙酸8。当羰基化合物用作亲电试剂时，可以直接制备相应的α，β-丁烯内酯。