3,4-di-t-butylthiophene 1,1-dioxide | 116375-45-2

• 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-t-butylthiophene 1,1-dioxide
• 英文别名: Thiophene, 3,4-bis(1,1-dimethylethyl)-, 1,1-dioxide；3,4-ditert-butylthiophene 1,1-dioxide
• CAS: 116375-45-2
• 化学式: C₁₂H₂₀O₂S
• 分子量: 228.356
• InChiKey: IHZASRLZINFKKT-UHFFFAOYSA-N

物化性质

• 熔点：
  132.5-133 °C
• 沸点：
  348.0±9.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3,4-di-t-butylthiophene 1,1-dioxide 在 selenium 作用下， 以 苯 为溶剂， 反应 13.0h， 生成 1-(p-tolylsulfonyl)-3,4-di-tert-butylpyrrole
  参考文献：
  名称：

  Synthesis and characterization of 3,4-dl-t-butylfuran, pyrrole, and selenophene

  摘要：

  DOI：

  10.1016/s0040-4039(00)97652-4
• 作为产物：
  描述：

  1-bromo-4,4-dimethylpentan-2-one 在 sodium sulfide 、 四氯化钛 、 间氯过氧苯甲酸 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 7.05h， 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

文献信息

• Synthesis and properties of sterically hindered cycloalkenes carrying two tert-butyls in cis-orientation. 2,3-Di-tert-butylbicyclo[2.2.2]oct-2-ene derivatives
  作者：Juzo Nakayama、Atsushi Hirashima

  DOI：10.1021/ja00177a028

  日期：1990.10

  Le 1,1-dioxyde du 3,4-di-t-butylthiophene reagit avec divers composes vinyliques pour donner des composes benzeniques, des heterocycles et un indane, steriquement encombres

  Le 1,1-dioxyde du 3,4-di-t-butylthiophene reagit avec divers composesvinyliques pour donner des composes benzeniques, desheterocycles et un indane, steriquement encombres
• Synthesis of an Octa-<i>tert</i>-butylphthalocyanine: A Low-Aggregating and Photochemically Stable Photosensitizer
  作者：Nicholas R. S. Gobo、Timothy J. Brocksom、Julio Zukerman-Schpector、Kleber T. de Oliveira

  DOI：10.1002/ejoc.201300415

  日期：2013.8

  The synthesis of a new octa-tert-butylphthalocyanine is described. First, the 4,5-di-tert-butylphthalonitrile building block was synthesized in a six-step approach, in which the last step is a three reaction domino sequence. Then, this phthalonitrile was cyclotetramerized to furnish a new phthalocyanine dye, which presented no aggregation in solution and good photophysical properties.

  描述了一种新的八叔丁基酞菁的合成。首先，4,5-二叔丁基邻苯二甲腈结构单元以六步法合成，其中最后一步是三反应多米诺骨牌序列。然后，将该邻苯二甲腈环四聚化得到一种新的酞菁染料，该染料在溶液中不发生聚集，具有良好的光物理性能。
• 3,4-Di-tert-butylthiophene 1,1-dioxide, a convenient precursor of o-Di-tert-butylbenzene and its derivatives
  作者：Juzo. Nakayama、Shoji. Yamaoka、Tomoko. Nakanishi、Masamatsu. Hoshino

  DOI：10.1021/ja00227a069

  日期：1988.9

  Synthese d'o-di-t-butylbenzenes fonctionnalises par addition de Diels Alder du compose du titre avec des composes acetyleniques

  Synthese d'o-di-t-butylbenzos fonctionnalises par added de Diels Alder du compose du titre avec des composes acetyleniques
• Michael Additions of Oxygen and Sulfur Nucleophiles to 3,4-Di-<i>t</i>-butyl-1-[(<i>p</i>-tolyl)sulfonylimino]-1,1-dihydrothiophene. A Comparison Study with 3,4-Di-<i>t</i>-butylthiophene 1-Oxide and 1,1-Dioxide
  作者：Takashi Otani、Yoshiaki Sugihara、Akihiko Ishii、Juzo Nakayama

  DOI：10.1246/cl.2000.744

  日期：2000.7

  respectively, through Michael adduct formation. The reaction of 3,4-di-t-butylthiophene 1-oxide with RSNa gave 1,6-Michael adducts, whereas the corresponding reaction of 3,4-di-t-butylthiophene 1,1-dioxide produced a mixture of 1,4- and 1,6-adducts.

  3,4-二叔丁基-1-[(对甲苯基)磺酰基亚氨基]-1,1-二氢噻吩与RONa和RSNa的反应分别通过Michael提供了2-烷氧基和2-烷硫基取代的噻吩加合物形成。3,4-二叔丁基噻吩 1-氧化物与 RSNa 反应生成 1,6-迈克尔加合物，而 3,4-二叔丁基噻吩 1,1-二氧化物的相应反应生成 1, 4- 和 1,6- 加合物。
• 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。