1,5-dineopentyl-3-thiapentane-1,5-dione | 156222-91-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,5-dineopentyl-3-thiapentane-1,5-dione
• 英文别名: 1,1'-Sulfanediylbis(4,4-dimethylpentan-2-one)；1-(4,4-dimethyl-2-oxopentyl)sulfanyl-4,4-dimethylpentan-2-one
• CAS: 156222-91-2
• 化学式: C₁₄H₂₆O₂S
• 分子量: 258.425
• InChiKey: QHJSSEGIQKBMMF-UHFFFAOYSA-N

物化性质

• 熔点：
  22.5-23.0 °C
• 沸点：
  329.1±27.0 °C(Predicted)
• 密度：
  0.964±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  59.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,5-dineopentyl-3-thiapentane-1,5-dione 在 四氯化钛 、 间氯过氧苯甲酸 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.75h， 生成 3,4-di-t-butylthiophene 1,1-dioxide
  参考文献：
  名称：

  Preparation of Congested Thiophenes Carrying Bulky Substituents on the 3- and 4-Positions and Their Conversion to the Benzene Derivatives

  摘要：

  Highly congested thiophenes, 3,4-di-tert-butyl-, 3,4-di(1-adamantyl)-, 3,4-dineopentyl-, and 3-(1-adamantyl)-4-tert-butylthiophenes (4a-d), were prepared in satisfactory overall yields by intramolecular reductive coupling of 3-thiapentane-1,5-diones (1a-d) followed by acid-catalyzed dehydration of the resulting thiolane-3,4-diols (2a-d). Experimental procedures of this; thiophene synthesis are fully described. Oxidation of the thiophenes 4a-d with m-CPBA gave the corresponding thiophene 1,1-dioxides 13a-d in good yields. The Diels-Alder reactions of 13a-d with phenyl vinyl sulfone gave o-di-tert-butyl-, o-di(1-adamantyl)-, o-dineopentyl-, and o-(1-adamantyl)-tert-butylbenzenes (17a-d) directly in high yields with loss of benzenesulfinic acid and sulfur dioxide. The dioxides 13a-d also underwent Diels-Alder reactions with alkynic dienophiles to give the corresponding benzene derivatives carrying two bulky substituents on adjacent positions. Pyridazines 25b,c, carrying bulky substituents on the 4- and 5-positions, were also synthesized through Diels-Alder reaction of 13b,c with PTAD. Dimethylation of the 2- and 5-positions of 13a-d was attained by treatment with strong bases followed by reactions with methyl iodide. The resulting tetrasubstituted thiophene 1,1-dioxides 14a-d reacted with DMAD to give highly congested hexasubstituted benzene derivatives 15a-d in good yields. Finally, structural features of the congested molecules are discussed on the basis of NMR analyses. Typically, the barriers to rotation (Delta H double dagger) about the benzene to the bulky substituents of 15a,c,d were determined to be 8.59, 15.3, and 7.40 kcal/mol, respectively, by NMR total line-shape analysis.

  DOI：

  10.1021/jo971710z
• 作为产物：
  描述：

  1-bromo-4,4-dimethylpentan-2-one 在 sodium sulfide 作用下， 以 水 、 丙酮 为溶剂， 以88%的产率得到1,5-dineopentyl-3-thiapentane-1,5-dione
  参考文献：
  名称：

  在相邻位置带有两个新戊基的芳族化合物的一般合成

  摘要：

  从甲基新戊基酮开始，以良好的总产率合成了3,4-二戊基噻吩（4）。3,4-Dineopentylthiophene-1,1-dioxide（5a）易于通过4的氧化而制得，它与各种炔属二烯亲二烯物或其等价物进行Diels-Alder反应，以提供在相邻位置带有两个新戊基的芳香族化合物。

  DOI：

  10.1016/s0040-4039(00)77012-2

文献信息

• A general synthesis of aromatic compounds carrying two neopentyl groups on adjacent positions
  作者：Juzo Nakayama、Koichi Yoshimura

  DOI：10.1016/s0040-4039(00)77012-2

  日期：1994.4

  synthesized in a good overall yield starting from methyl neopentyl ketone. 3,4-Dineopentylthiophene-1,1-dioxide (5a), easily obtainable by oxidation of 4, undergoes Diels-Alder reactions with a variety of acetylenic dienophiles or their equivalent to furnish aromatic compounds carrying two neopentyl groups on adjacent positions.

  从甲基新戊基酮开始，以良好的总产率合成了3,4-二戊基噻吩（4）。3,4-Dineopentylthiophene-1,1-dioxide（5a）易于通过4的氧化而制得，它与各种炔属二烯亲二烯物或其等价物进行Diels-Alder反应，以提供在相邻位置带有两个新戊基的芳香族化合物。
• Nakayama Juzo, Yoshimura Koichi, Tetrahedron Lett, 35 (1994) N 17, S 2709-2712
  作者：Nakayama Juzo, Yoshimura Koichi

  DOI：——

  日期：——
• Preparation of Congested Thiophenes Carrying Bulky Substituents on the 3- and 4-Positions and Their Conversion to the Benzene Derivatives
  作者：Juzo Nakayama、Ryuji Hasemi、Koichi Yoshimura、Yoshiaki Sugihara、Shoji Yamaoka

  DOI：10.1021/jo971710z

  日期：1998.7.1

  Highly congested thiophenes, 3,4-di-tert-butyl-, 3,4-di(1-adamantyl)-, 3,4-dineopentyl-, and 3-(1-adamantyl)-4-tert-butylthiophenes (4a-d), were prepared in satisfactory overall yields by intramolecular reductive coupling of 3-thiapentane-1,5-diones (1a-d) followed by acid-catalyzed dehydration of the resulting thiolane-3,4-diols (2a-d). Experimental procedures of this; thiophene synthesis are fully described. Oxidation of the thiophenes 4a-d with m-CPBA gave the corresponding thiophene 1,1-dioxides 13a-d in good yields. The Diels-Alder reactions of 13a-d with phenyl vinyl sulfone gave o-di-tert-butyl-, o-di(1-adamantyl)-, o-dineopentyl-, and o-(1-adamantyl)-tert-butylbenzenes (17a-d) directly in high yields with loss of benzenesulfinic acid and sulfur dioxide. The dioxides 13a-d also underwent Diels-Alder reactions with alkynic dienophiles to give the corresponding benzene derivatives carrying two bulky substituents on adjacent positions. Pyridazines 25b,c, carrying bulky substituents on the 4- and 5-positions, were also synthesized through Diels-Alder reaction of 13b,c with PTAD. Dimethylation of the 2- and 5-positions of 13a-d was attained by treatment with strong bases followed by reactions with methyl iodide. The resulting tetrasubstituted thiophene 1,1-dioxides 14a-d reacted with DMAD to give highly congested hexasubstituted benzene derivatives 15a-d in good yields. Finally, structural features of the congested molecules are discussed on the basis of NMR analyses. Typically, the barriers to rotation (Delta H double dagger) about the benzene to the bulky substituents of 15a,c,d were determined to be 8.59, 15.3, and 7.40 kcal/mol, respectively, by NMR total line-shape analysis.