3-Adamantan-1-yl-4-tert-butyl-thiophene 1,1-dioxide | 211372-59-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 3-Adamantan-1-yl-4-tert-butyl-thiophene 1,1-dioxide
• 英文别名: 3-(1-Adamantyl)-4-tert-butylthiophene 1,1-dioxide
• CAS: 211372-59-7
• 化学式: C₁₈H₂₆O₂S
• 分子量: 306.469
• InChiKey: IAZNREVYLXWJDI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Adamantan-1-yl-4-tert-butyl-thiophene 1,1-dioxide 、 碘甲烷 在 2,2,6,6-四甲基哌啶 、 正丁基锂 作用下， 生成 3-Adamantan-1-yl-4-tert-butyl-2,5-dimethyl-thiophene 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-溴频哪酮 在 盐酸 、 sodium hydrogensulfide 、 18-冠醚-6 、 potassium tert-butylate 、 四氯化钛 、 对甲苯磺酸 、 间氯过氧苯甲酸 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 27.83h， 生成 3-Adamantan-1-yl-4-tert-butyl-thiophene 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

文献信息

• 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.