3,4-di-1-adamantylthiophene 1,1-dioxide | 127973-13-1

• 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: 3,4-di-1-adamantylthiophene 1,1-dioxide
• 英文别名: 3,4-Di-(1-adamantyl)thiophene 1,1-dioxide；3,4-bis(1-adamantyl)thiophene 1,1-dioxide
• CAS: 127973-13-1
• 化学式: C₂₄H₃₂O₂S
• 分子量: 384.583
• InChiKey: DXWJLVPTHIBMHP-UHFFFAOYSA-N

物化性质

• 密度：
  1.309±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  4-苯基-1,2,4-三唑啉-3,5-二酮 、 3,4-di-1-adamantylthiophene 1,1-dioxide 以 甲苯 为溶剂， 以72%的产率得到13,14-bis(1-adamantyl)-4,10-diphenyl-2,4,6,8,10,12-hexazatetracyclo[5.5.2.02,6.08,12]tetradec-13-ene-3,5,9,11-tetrone
  参考文献：
  名称：

  The first synthesis of aromatic compounds carrying two 1-adamantyls on adjacent positions. 3,4-Di-1-adamantylthiophene, o-di-1-adamantylbenzene, and 4,5-di-1-adamantylpyridazine

  摘要：

  DOI：

  10.1021/ja00170a048
• 作为产物：
  描述：

  3,4-di-tert-butylthiophene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以79%的产率得到3,4-di-1-adamantylthiophene 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

• Oxidation of congested thiophene 1,1-dioxides with m-chloroperbenzoic acid. Formation of epoxides vs. ring-contracted thiete 1,1-dioxides
  作者：Juzo Nakayama、Hiroaki Kamiyama

  DOI：10.1016/s0040-4039(00)60818-3

  日期：——

  Highly congested thiophene 1,1-dioxides, which carry two bulky substituents at 3- and 4-positions, afford the corresponding epoxides in high yields on oxidation with m-chloroperbenzoic acid in the presence of sodium carbonate, while the oxidation in the absence of sodium carbonate gives the ring-contracted thiete 1,1-dioxides as the principal product.

  高度拥塞噻吩1,1-二氧化物，其携带在3-两个大体积的取代基和4-位，得到在氧化高产率与相应的环氧化物米在碳酸钠的存在下氯过苯甲酸，同时在不存在的氧化碳酸钠得到的主要产物是缩环的1,1-二氧化物。
• Nakayama, Juzo; Hasemi, Ryuji; Iwasaki, Fujiko, Phosphorus, Sulfur and Silicon and the Related Elements, 1991, vol. 59, # 1-4, p. 243 - 246
  作者：Nakayama, Juzo、Hasemi, Ryuji、Iwasaki, Fujiko

  DOI：——

  日期：——
• NAKAYAMA, JUZO;HASEMI, RYUJI;IWASAKI, FUJIKO, PHOSPH., SULFUR AND SILICON AND RELAT. ELEM., 58-59,(1991) N-4, C. 243-24+
  作者：NAKAYAMA, JUZO、HASEMI, RYUJI、IWASAKI, FUJIKO

  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.
• The first synthesis of aromatic compounds carrying two 1-adamantyls on adjacent positions. 3,4-Di-1-adamantylthiophene, o-di-1-adamantylbenzene, and 4,5-di-1-adamantylpyridazine
  作者：Juzo Nakayama、Ryuji Hasemi

  DOI：10.1021/ja00170a048

  日期：1990.7