1-[2-(2-methyl-1,3-dithianyl)]-2-cyclohexen-1-ol | 15040-92-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 1-[2-(2-methyl-1,3-dithianyl)]-2-cyclohexen-1-ol
• 英文别名: 1-(2-methyl-[1,3]dithian-2-yl)-cyclohex-2-enol；1-(2-Methyl-1,3-dithian-2-yl)-2-cyclohexen-1-ol；1-(2-methyl-1,3-dithian-2-yl)cyclohex-2-en-1-ol
• CAS: 15040-92-3
• 化学式: C₁₁H₁₈OS₂
• 分子量: 230.395
• InChiKey: WOHADKSRZVNGHS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  70.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-[2-(2-methyl-1,3-dithianyl)]-2-cyclohexen-1-ol 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 以30%的产率得到3-[2-(2-methyl-1,3-dithianyl)]-cyclohexanone
  参考文献：
  名称：

  Alkoxide-promoted [1,3] rearrangements of 1,3-dithianes

  摘要：

  DOI：

  10.1021/jo01300a040
• 作为产物：
  描述：

  2-甲基-1,3-二噻烷 、 2-环己烯-1-酮 在 正丁基锂 作用下， 生成 1-[2-(2-methyl-1,3-dithianyl)]-2-cyclohexen-1-ol
  参考文献：
  名称：

  Oxidative rearrangement of sulfur-containing tertiary allylic alcohols: synthesis of 2-cycloalkenones bearing 3-[(phenylthio)methyl] and 3-[2-alkyl-1,3-dithian-2-yl] substituents

  摘要：

  Substrate 1-[(phenylthio)methyl]-2-cycloalkenols 3a-d and 1-[2-alkyl-1,3-dithian-2-yl]cyclohexenols 1a-d were prepared by adding [(phenylthio)methyl]lithium and 2-lithio-2-alkyl-1,3-dithianes, respectively, in the 1,2-mode to various 2-cycloalkenones. The ranges of yields for the additions were 86-95% in the (phenylthio)methyl series and 69-88% in the dithiane series. A representative compound from each range of substrate tertiary allylic alcohols was then treated with a series of oxochromium(VI)-amine reagents such as pyridinium chlorochromate (PCC), pyridinium dichromate (PDC), the Collins reagent (CrO3.Pyr2), and 2,2'-bipyridinium chlorochromate (BPCC). The oxochromium(VI)-amine reagents effected conversions of the representative substrates to the corresponding 3-[(phenylthio)methyl]- and 3-[2-alkyl-1,3-dithian-2-yl]-2-cycloalkenones 4a-d and 2a-d which were measured by gas chromatographic-mass spectral analysis. When comparing the efficiency of the range of oxochromium(VI)-amine reagents, PCC was found to give the best conversions to the corresponding transposed alpha,beta-unsaturated carbonyl compounds in both series of substrates while the Jones reagent gave only decomposed material and no recovery of substrate. Distinct improvements on the initial PCC protocol using silica gel as an in situ adsorbent and promotion by ultrasound were then established with a range of substrate tertiary allylic alcohols while comparing sonicated versus nonsonicated experiments. The isolated yields of transposed products were found to be increased as much as 60 % in the dithiane series and 9 % in the (phenylthio)methyl series with the application of high-intensity ultrasound. Prolonged exposure of the substrate (3a) in the (phenylthio)methyl series to the PCC/silica reagent system resulted in the recovery of the corresponding sulfone (5), the identity of which was confirmed by selective oxidation of the transposed enone (4a) with m-chloroperbenzoic acid.

  DOI：

  10.1021/jo00063a011

文献信息

• Nucleophile Acylierung mit 2-Lithium-1,3-dithianen bzw. -1,3,5-trithianen^1,2,3
  作者：D SEEBACH

  DOI：10.1055/s-1969-34190

  日期：——

  Preparative aspects of the chemistry of 2-lithium-1,3-dithianes and 2-lithium-1,3,5-trithianes are surveyed. In particular, nucleophillic acylation reactions using the mentioned lithium derivatives are discussed.

  2-锂-1,3-二硫杂环戊烷和2-锂-1,3,5-三硫杂环庚烷的化学准备性方面被综述。特别地，使用这些锂衍生物的亲核酰基化反应被讨论。
• The Regioselectivity of Addition of Organolithium Reagents to Enones and Enals:  The Role of HMPA
  作者：William H. Sikorski、Hans J. Reich

  DOI：10.1021/ja010053w

  日期：2001.7.1

  addition of sulfur-substituted organolithium reagents to cyclohexenones and hexenal was studied. Low-temperature, multinuclear NMR studies provided quantitative information about the ratio of contact (CIP) and solvent-separated (SIP) ion pairs in solutions of dithianyllithiums and phenylthiobenzyllithiums in THF-HMPA solutions. The ratio of contact and separated ion pairs was manipulated by changes in

  研究了极性溶剂（特别是 HMPA）在控制硫取代的有机锂试剂与环己烯酮和己烯醛的 1,2 到 1,4 添加比例中的作用。低温、多核 NMR 研究提供了有关 THF-HMPA 溶液中二噻吩基锂和苯硫基苄基锂溶液中接触 (CIP) 和溶剂分离 (SIP) 离子对比率的定量信息。接触和分离离子对的比例通过溶剂化强度的变化（通常通过添加 HMPA）来控制。尽管结果与 CIP/SIP 分布是决定这些添加的区域选择性的重要因素一致（Curtin-Hammett 限制阻止了直接相关），但它不能是唯一的。添加 HMPA 后非对映体产物比率的变化表明 HMPA 与锂的络合有两个作用。首先，它会导致离子对分离，从而增强 1,4 加成。其次，它降低了锂阳离子的路易斯酸度和催化效率，这也有利于 1,4 加成。对于大多数硫稳定的锂试剂，2 当量的 HMPA 足以实现 >95% 的 1,4 添加，而需要 4 当量的 DMPU
• Brown, Charles Allan; Chapa, O.; Yamaichi, A., Heterocycles, 1982, vol. 18, p. 187 - 189
  作者：Brown, Charles Allan、Chapa, O.、Yamaichi, A.

  DOI：——

  日期：——
• Regioselectivity of Addition of Organolithium Reagents to Enones:  The Role of HMPA
  作者：Hans J. Reich、William H. Sikorski

  DOI：10.1021/jo981765g

  日期：1999.1.1
• BROWN, C. A.;CHAPA, O.;YAMAICHI, A., HETEROCYCLES, 1982, 18, N ISSUE, 187-189
  作者：BROWN, C. A.、CHAPA, O.、YAMAICHI, A.

  DOI：——

  日期：——