3,3-Dimethyl-thietan | 13188-85-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环丁烷
• 英文名称: 3,3-Dimethyl-thietan
• 英文别名: 3,3-dimethylthiethane；3,3-dimethylthietane；3,3-dimethylthietan；3,3-dimethyl-thietane；3,3-Dimethyl-trimethylensulfid
• CAS: 13188-85-7
• 化学式: C₅H₁₀S
• 分子量: 102.2
• InChiKey: RPRIYERFOHERFT-UHFFFAOYSA-N

物化性质

• 保留指数：
  739

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3-Dimethyl-thietan 在 双氧水 、 溶剂黄146 作用下， 生成 3,3-Dimethyl-thietan-1,1-dioxid
  参考文献：
  名称：

  Backer; Keuning, Recueil des Travaux Chimiques des Pays-Bas, 1934, vol. 53, p. 798,805

  摘要：

  DOI：
• 作为产物：
  描述：

  二溴新戊烷 在 sodium sulfide 作用下， 以 二甲基亚砜 为溶剂， 反应 0.25h， 以88.6%的产率得到3,3-Dimethyl-thietan
  参考文献：
  名称：

  Nagasawa, Kazuo; Yoneta, Akemi, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 11, p. 5048 - 5052

  摘要：

  DOI：

文献信息

• The Catalytic Cyclooligomerization of Thietane by Trirhenium Cluster Complexes. A New Route to Polythiaether Macrocycles
  作者：Richard D. Adams、Stephen B. Falloon

  DOI：10.1021/ja00102a022

  日期：1994.11

  complex Re[sub 3](CO)[sub 10] [[mu]-SCH[sub 2]CH[sub 2]]([mu]-H)[sub 3] (1) reacts with dimethyl sulfide by a ring opening addition to the bridging thietane ligand to yield the zwitterionic complex Re[sub 3](CO)[sub 10][[mu]-SCH[sub 2]CH[sub 2]CH[sub 2]SMe[sub 2]]([mu]-H)[sub 3] (2) in 48% yield that contains a sulfonium-substituted thiolate ligand bridging an edge of the cluster. The structure of 2 was established

  三铼配合物 Re[sub 3](CO)[sub 10] [μ-SCH[sub 2]CH[sub 2]](μ-H)[sub 3] (1) 与二甲硫反应对桥接硫杂环丁烷配体开环加成以产生两性离子复合物 Re[sub 3](CO)[sub 10][μ-SCH[sub 2]CH[sub 2]CH[sub 2]SMe[sub 2] ]](μ-H)[sub 3] (2)，产率为 48%，其中包含桥接簇边缘的锍取代的硫醇盐配体。通过单晶X射线衍射分析确定了2的结构。在本报告中，描述了我们对 1 与硫醚 Me[sub 2]S 和硫杂环丁烷本身反应的研究结果。已证明这些硫醚也使 1 中的桥接硫杂环丁烷配体开环，但在硫杂环丁烷的情况下，发生一系列开环偶联反应，通过产生聚硫醚大环的环化过程结束。事实上，开环环化可以在合适的条件下催化进行，以产生大量游离态的大环。13 个参考文献，2 个图，6 个标签。
• Effect of variation in ligand ring size upon the inversion barrier at sulphur in complexes of palladium(II) and platinum(II). A dynamic hydrogen-1 nuclear magnetic resonance study
  作者：Edward W. Abel、Martin Booth、Keith G. Orrell

  DOI：10.1039/dt9790001994

  日期：——

  the iodo-complexes. The pyramidal inversion energies are very dependent upon ligand ring size; those for five- and six-membered rings are comparable with complexes of linear sulphides, but the complexes of four-membered rings show a considerable heightening of the pyramidal sulphur inversion barrier. For the complexes of the three-membered ring sulphides no inversion was detectable up to the temperature

  该系列复合物的反式- [MX 2 [图形省略] R 2）Ñ } 2 ]（M =钯II或Pt II ; X =氯，溴，或I; R = H和/或Me; ñ = 2 –5）已合成，并且已通过带形拟合方法对它们的可变温度nmr光谱进行了精确分析，以确定在硫原子处发生金字塔倒置的势垒。氯配合物中的势垒能比相应的溴化物高2–3 kJ mol –1，而溴化物则为4–5 kJ mol –1高于碘复合物。金字塔形反转能量非常依赖于配体环的大小。五元环和六元环的那些与线性硫化物的配合物相当，但是四元环的配合物显示出金字塔形硫转化阻挡层的显着提高。对于三元环硫化物的络合物，直到分解开始的温度都没有检测到反转，这是在二烷基硫化物金属络合物中这种刚性的第一个报道实例。
• Catalytic Macrocyclization of 3,3-Dimethylthietane by Re₂(CO)₉(SCH₂CMe₂CH₂)
  作者：Richard D. Adams、Joseph L. Perrin、Joachim A. Queisser、Judy B. Wolfe

  DOI：10.1021/om970162c

  日期：1997.6.1

  The reaction of Re2(CO)9(NCMe), 1, with 3,3-dimethylthietane (SCH2CMe2CH2, 3,3-DMT) yielded the complex Re2(CO)9(SCH2CMe2CH2), 2. Compound 2 has been found to react with 3,3-DMT at 100 °C to yield the polythioether macrocycles 3,3,7,7,11,11-hexamethyl-1,5,9-trithiacyclododecane, 3 (Me612S3), 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetrathiacyclohexadecane, 4 (Me816S4), and 3,3,7,7,11,11,15,15,19,19-decamethyl-1

  RE的反应2（CO）9（NCME），1，与3,3-二甲基硫代（SCH 2 CME 2 CH 2，3,3-DMT），产生复杂的重新2（CO）9（SCH 2 CME 2 CH 2），2。已发现化合物2在100°C下与3,3-DMT反应生成聚硫醚大环3,3,7,7,11,11-六甲基-1,5,9-三硫代环十二烷3（Me 6 12S3） ，3,3,7,7,11,11,15,15-八甲基-1,5,9,13-四硫代环十六烷，4（Me 816S4）和3,3,7,7,11,11,15,15,19,19-十甲基-1,5,9,13,17-pentathiacycloeicosane，5（Me 10 20S5），催化但活性而且大环的产量很低。3,3-DMT的高分子量低聚物是主要产品。提出了一种大环化机理，该机理由金属诱导的3,3-DMT的三个，四个和五个分子的开环环寡聚组成。的反应3与太平洋地磁观测网（CO）3
• Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes
  作者：Richard D. Adams、Jeffrey E. Cortopassi、Stephen B. Falloon

  DOI：10.1021/om00059a049

  日期：1992.11

  The reactions of 3,3-dimethylthietane, SCH2CMe2CH2 (3,3-DMT), and thietane, SCH2CH2CH2, with Re3(CO)10(NCMe)2(mu-H)3, 1, have yielded the new complexes Re3(CO)10[mu-SCH2CMe2CH2](mu-H)3,2a, and Re3(CO)10[mu-SCH2CH2CH2](mu-H)3, 2b. Compound 2a was characterized crystallographically and was found to consist of a trirhenium cluster with three bridging hydride ligands and a bridging thietane ligand coordinated through its sulfur atom. 2a and 2b react with halide ions by ring-opening additions to the 3,3-DMT ligand to yield the complex anions [Re3(CO)10(mu-SCH2CMe2CH2X)(mu-H)3]-, 3a-6A X = F (71%), Cl (71%), Br (84%), I (87%), and (Re3(CO)10(mu-SCH2CH2CH2Cl)(mu-H)3]-, 4b (67%). Similarly, addition of NMes to 2a and 2b yielded the ring-opened zwitterions Res(CO)10(mu-SCH2CMe2CH2NMe3)(mu-H)3, 7a (43%), and Res(CO)10(mu-SCH2CH2CH2NMe3(u-H)3, 7b (44%). Compounds 4a and 7b were characterized crystallographically. They are zwitterions positively charged at the nitrogen atoms and negatively charged on the trirhenium clusters. Complex 7b was also obtained in a 48% yield from the reaction of Re3(CO)12(mu-H)3 with Me3NO in the presence of thietane, but the corresponding reaction using 3,3-DMT yielded only 2a and Re3(CO)11(SCH2CMe2CH2(mu-H)3, 8. Attempts to obtain a ring-opening addition to 2a by reaction with PMe2Ph yielded only Re3(CO)10(PMe2Ph)2(mu-H)3 by ligand substitution. Attempts to obtain ring-opening addition to 8 by reaction with I- yielded only (Re3(CO)11I(mu-H)3]- by ligand substitution. Crystal Data: for 2a, space group = C2/c, a = 15.749 (2) angstrom, b = 9.082 (2) angstrom, c = 31.799 (5) angstrom, beta = 99.17 (1)-degrees, Z = 8, 2325 reflections, R = 0.037; for 4a, space group = P1BAR, a = 13.140 (2) angstrom, b = 17.966 (4) angstrom, c = 12.252 (3) angstrom, alpha = 93.27 (2)-degrees, beta = 101.31 (2)-degrees, gamma = 74.90 (2)-degrees, Z = 2, 4495 reflections, R = 0.034; for 7b.0.5Me2C=O, space group = P2(1)/c, a = 8.475 (1) angstrom, b = 11.740 (5) angstrom, c = 26.085 (3) angstrom, beta = 93.74 (1)-degrees, Z = 4, 2234 reflections, R = 0.032.
• Thiethan-1-N-arylimide und ihre Umlagerung zu N-Aryl-1,2-thiazolidinen
  作者：Peter K. Claus、Emmerich J�ger

  DOI：10.1007/bf00811249

  日期：1985.10