4,6-dimethyltrimethylene (cis,trans) sulphite | 29882-38-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧硫杂环戊烷
• 英文名称: 4,6-dimethyltrimethylene (cis,trans) sulphite
• 英文别名: cis-4, trans-6-dimethyl-r-2-oxo-1,3,2-dioxathiane；(4RS,6RS)-4,6-dimethyl-1,3,2-dioxathiane-2-oxide；trans-4,6-Dimethyl-2-oxo-1,3,2-dioxathian；dl-4.6-Dimethyl-trimethylensulfit；dl-4cis,6trans-Dimethyl-1,3-dioxa-2-thiacyclohexan-2ref-oxid；4r,6t-dimethyl-[1,3,2]dioxathiane 2-oxide；(4R,6R)-4,6-dimethyl-1,3,2-dioxathiane 2-oxide
• CAS: 29882-38-0
• 化学式: C₅H₁₀O₃S
• 分子量: 150.199
• InChiKey: USNQMYYMYHSTGH-RFZPGFLSSA-N

物化性质

• 沸点：
  198.8±9.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  9
• 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：
  54.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,6-dimethyltrimethylene (cis,trans) sulphite 在 ruthenium trichloride 、 sodium periodate 作用下， 以 水 、 乙腈 为溶剂， 反应 1.0h， 以96%的产率得到(4R,6R)-4,6-dimethyl-1,3,2-dioxathiane-2,2-dioxide
  参考文献：
  名称：

  Schmidt反应使双环[3.3.0]辛烷-3,7-二酮不对称化：容易合成tecomanine

  摘要：

  顺式-双环[3.3.0]辛烷-3,7-二酮1的C 2v对称性通过选择性施密特反应改变，得到了3-氮杂双环[4.3.0] noanmine结构单元3b，可在短时间内使用（±）-tecomanine的合成4。上AsymmetricSchmidt反应1，采用（2S，4R）-2-叠氮基-4- hydroxypentane 14作为手性诱导剂，显示出令人鼓舞的对映亚甲基立体声分化的水平。

  DOI：

  10.1016/s0957-4166(97)00308-x
• 作为产物：
  描述：

  乙酰丙酮 生成 4,6-dimethyltrimethylene (cis,trans) sulphite
  参考文献：
  名称：

  Conformational analysis. XVIII. 1,3-Dithianes. Conformational preferences of alkyl substituents and the chair-boat energy difference

  摘要：

  DOI：

  10.1021/ja01038a050

文献信息

• Application of a lanthanide shift reagent in 17O n.m.r. spectroscopy to determine the stereochemical course of oxidation of cyclic sulphite diesters to cyclic sulphate diesters with ruthenium tetroxide
  作者：Gordon Lowe、Salvatore J. Salamone

  DOI：10.1039/c39830001392

  日期：——

  Cyclic sulphite diesters are rapidly oxidized to cyclic sulphate diesters with ruthenium tetroside in good yield; diastereotopically labelled cyclic [17O] sulphate diesters obtained by oxidation of diastereoisomeric cyclic sulphite diesters with ruthenium [17O] tetroxide are shown, by the effect of a lanthanide shift reagent on their 17O n.m.r. signals, to be formed with retention of configuration

  环式亚硫酸二酯与四溴化钌可快速氧化为环式硫酸二酯，收率良好。通过镧系元素转移试剂对其17 O nmr信号的影响，显示了通过用钌[ 17 O]四氧化物氧化非对映异构环状亚硫酸二酯而得到的非对位标记的环状[ 17 O]硫酸二酯。硫。
• Desymmetrization of bicyclo[3.3.0]octane-3,7-dione by the Schmidt reaction: am easy synthesis of tecomanine
  作者：Giovanni Vidari、Marco Tripolini、Pietro Novella、Patrizio Allegrucci、Luigi Garlaschelli

  DOI：10.1016/s0957-4166(97)00308-x

  日期：1997.9

  selective Schmidt reaction to give the the 3-azabicyclo[4.3.0]noanmine building block 3b which was employed in a short synthesis of (±)-tecomanine 4. AsymmetricSchmidt reaction on 1, employing (2S,4R)-2-azido-4-hydroxypentane 14 as a chiral inducer, showed encouraging levels of enantiotopic methylene group stereo differentiation.

  顺式-双环[3.3.0]辛烷-3,7-二酮1的C 2v对称性通过选择性施密特反应改变，得到了3-氮杂双环[4.3.0] noanmine结构单元3b，可在短时间内使用（±）-tecomanine的合成4。上AsymmetricSchmidt反应1，采用（2S，4R）-2-叠氮基-4- hydroxypentane 14作为手性诱导剂，显示出令人鼓舞的对映亚甲基立体声分化的水平。
• Synthesis of sulfated mono- and ditertiary phosphines, complex chemistry and catalysis
  作者：H Gulyás、A Dobó、J Bakos

  DOI：10.1139/v01-040

  日期：2001.5.1

  have been prepared from commonly available alcohols. Nucleophilic cleavage of the cyclic sulfates affords a new type of water-soluble mono- and ditertiary phophines bearing -OSO3Li groups in distinguished positions in the molecular framework. Both phosphines have amphiphilic character. Reactions of the chiral 2 and the dppp analogue 5 with [Rh(COD)Cl]2 and Pt(PhCN)2Cl2 provide novel zwitterionic complexes

  环状和双环硫酸盐已由常用醇制备。环硫酸盐的亲核裂解提供了一种新型的水溶性单和二叔膦，在分子框架的不同位置带有 -OSO3Li 基团。两种膦都具有两亲性。手性 2 和 dppp 类似物 5 与 [Rh(COD)Cl]2 和 Pt(PhCN)2Cl2 的反应提供了新的两性离子配合物。2 和 5 的铑配合物已成功应用于苯乙烯和辛烯-1 的液体双相加氢甲酰化。当5的铑配合物用作苯乙烯加氢甲酰化的催化剂时，有机相中可以检测到小于4ppm的铑。关键词：环状硫酸盐，水溶性膦，两亲性，Rh配合物，Pt配合物，加氢甲酰化。
• A general route to enantiomerically pure sulfoxides from a chiral sulfite
  作者：F. Rebiere、O. Samuel、L. Ricard、H. B. Kagan

  DOI：10.1021/jo00021a008

  日期：1991.10

  Enantiomerically pure cyclic chiral sulfite (S)-7 (trans stereochemistry) has been easily obtained in two steps from (S)-ethyl lactate. This compound was found to react cleanly with many organometallics to give crystalline sulfinates with high regioselectivity (> 90:10). Addition of a second organometallic transforms the purified sulfinate in excellent yield into a chiral sulfoxide (100% ee) of predictable absolute configuration. The mechanism and scope of this approach are discussed. This method completes the various other methods of preparation of chiral sulfoxides and is especially convenient for the preparation of tert-butyl sulfoxides. Examples for the synthesis of many chiral tert-butyl sulfoxides are given. The case of chiral sulfites derived from a C2 diol or of a chiral monoalcohol is also proposed as a route to chiral sulfinates, and some promising preliminary results have been obtained. The general main routes to obtain chiral sulfoxides from sulfites are also discussed.
• Conformational analysis. XVIII. 1,3-Dithianes. Conformational preferences of alkyl substituents and the chair-boat energy difference
  作者：Ernest L. Eliel、Robert O. Hutchins

  DOI：10.1021/ja01038a050

  日期：1969.5