3,3-dimethyl-1,3-thiasilinane 1-oxide | 209158-56-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 亚砜
• 英文名称: 3,3-dimethyl-1,3-thiasilinane 1-oxide
• 英文别名: 3,3-dimethyl-3-sila-1-thiacyclohexane S-oxide；3,3-dimethyl-1λ⁴,3-thiasilinane 1-oxide；3,3-dimethyl-1,3-thiasilinane S-oxide
• CAS: 209158-56-5
• 化学式: C₆H₁₄OSSi
• 分子量: 162.328
• InChiKey: GPPHRDRQFOJYRV-UHFFFAOYSA-N

物化性质

• 熔点：
  54-55 °C
• 沸点：
  281.9±29.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.39
• 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：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3-dimethyl-1,3-thiasilinane 1-oxide 以 四氢呋喃 为溶剂， 反应 2.0h， 以97%的产率得到2,2-Dimethyl-[1,6,2]oxathiasilepane
  参考文献：
  名称：

  3,3-二甲基-3-silathiane S-氧化物的sila-Pummerer重排

  摘要：

  亚砜1到O-甲硅烷基化的环状O，S-乙缩醛（2）的热转化是环状有机硅亚砜的sila-Pummerer重排导致环膨胀的第一个例子。研究了重排动力学，并确定了热力学参数。结果符合涉及五配位硅原子的机理。

  DOI：

  10.1016/s0040-4039(98)80054-3
• 作为产物：
  描述：

  3,3-Dimethyl-3-sila-1-thiacyclohexan 在 sodium periodate 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 以44%的产率得到3,3-dimethyl-1,3-thiasilinane 1-oxide
  参考文献：
  名称：

  1,3-硫代硅烷基环烷烃的五元和六元S-官能衍生物的合成及相对稳定性

  摘要：

  已经在各种条件下检查了五元和六元1,3-硫代硅烷基环烷烃的氧化，酰亚胺化和S-甲基化反应。在小号的1,3- thiasilacycloalkanes官能化衍生物进行溶剂化SiC（S）键断裂在质子介质。开环的难易程度取决于S功能和环的大小。

  DOI：

  10.1016/s0022-328x(03)00348-6

文献信息

• Kirpichenko; Suslova; Tolstikova, Russian Journal of General Chemistry, 1997, vol. 67, # 9, p. 1449 - 1454
  作者：Kirpichenko、Suslova、Tolstikova、Albanov、Shainyan

  DOI：——

  日期：——
• Lithiation-methylation of thiasilinane 1-oxides
  作者：E. N. Suslova、A. I. Albanov、B. A. Shainyan

  DOI：10.1134/s1070363206010191

  日期：2006.1

  Lithiation-methylation of 3,3-dimethyl-1 lambda(4),3-thiasilinane 1-oxide and 4,4-dimethyl-1 lambda(4),4-thiasilinane I-oxide under the action of butyllithium or lithium diisopropylamide and methyl iodide was studied. In both cases, monomethylation proceeds selectively alpha to the sulfoxide group to form 2,3,3-trimethyl-1 lambda(4),3-thiasilinane 1-oxide and 2,4,4-trimethyl-1 lambda(4),4-thiasilinane 1-oxide, respectively. Subsequently, 2,3,3,3-trimethyl-1 lambda(4),3-thiasilinane 1-oxide undergoes monomethylation into the same alpha position to give 2,2,3,3-tetramethyl-1 lambda(4),3-thiasilinane 1-oxide, while 4,4-dimethyl-1 lambda(4),4-thiasilinane 1-oxide is dimethylated into the neighboring alpha' position to form two stereoisomers of 2,4,4,6-tetramethyl-1 lambda(4),4-thiasilinane 1-oxide with axial-equatorial or equatorial-equatorial methyl groups in the 2 and 6 positions.
• Comparative reactivity of substituted 1,3-and 1,4-thiasilinane S-oxides in the sila-Pummerer rearrangement and inversion of the thiocarbonyl group
  作者：E. N. Suslova、I. A. Ushakov、B. A. Shainyan

  DOI：10.1134/s1070363207020119

  日期：2007.2

  The thermal sila-Pummerer rearrangement of diastereomeric 2,3,3-trimethyl-1,3-thiasilinane S-oxides was studied. Introduction of the methyl group in the 2 position of 3,3-trimethyl-3-thiasilinane S-oxide slows down the rearrangement. When heated in CCl4, the trans isomer (2-Me-eq, SOeq) converts into the cis isomer (2-Me-eq, SOax) which rapidly rearranges into 2,2,7-trimethyl-1,6,2-oxathiasilepane. On the contrary, the isomeric 2,4,4-trimethyl-1,4-thiasilinane S-oxide is thermally stable up to 160 degrees C in DMSO. The inversion at the sulfur atom in 2,3,3-trimethyl-1,3-thiasilinane S-oxides and 2,4,4-trimethyl-1,4-thiasilinane S-oxides under the action of triethyloxonium tetrafluoroborate was studied. The trans isomer of 2,3,3-trimethyl-1.3-thiasilinane S-oxide (2-Me-eq, SOeq) forms with Et3O+BF4- a salt which decomposes in two ways. The first involves recovery of the starting sulfoxide due to SN2 substitution at the carbon atom of the ethoxy group, and the second, convertion into the cis isomer (2-Meeq, SOax) which rearranges into 2,2,7-trimethyl-1,6,2-oxathiasilepane. Under the same conditions, the cis isomer of 2,3,3-trimethyl-1,3-thiasilinane S-oxide (2-Me-eq: SOeq) decomposes to form siloxanes. traiis-2,4,4-Trimethyl-4-thiasilinane S-oxide (2-Me-eq, SOeq) under the action of Et3O+BF4- convers into the cis isomer (2-Me-eq, SOax). The B3LYP/6-311G(d,p) theoretical analysis showed that the thermal inversion at the sulfur atom in the compounds studied has a high energy barrier.
• Synthesis and relative stability of five- and six-membered S-functional derivatives of 1,3-thiasilacycloalkanes
  作者：Elena N Suslova、Aleksandr I Albanov、Bagrat A Shainyan

  DOI：10.1016/s0022-328x(03)00348-6

  日期：2003.7

  Oxidation, imidation, and S-methylation reactions of five- and six-membered 1,3-thiasilacycloalkanes have been examined under various conditions. The S-functional derivatives of 1,3-thiasilacycloalkanes undergo solvolytic SiC(S) bond cleavage in protic media. The ease of the ring opening depends on the S-functionality and on the ring size.

  已经在各种条件下检查了五元和六元1,3-硫代硅烷基环烷烃的氧化，酰亚胺化和S-甲基化反应。在小号的1,3- thiasilacycloalkanes官能化衍生物进行溶剂化SiC（S）键断裂在质子介质。开环的难易程度取决于S功能和环的大小。
• The sila-Pummerer rearrangement of 3,3-dimethyl-3-silathiane S-oxide
  作者：Svetlana V. Kirpichenko、Elena N. Suslova、Alexandr I. Albanov、Bagrat A. Shainyan

  DOI：10.1016/s0040-4039(98)80054-3

  日期：1999.1

  The thermal conversion of sulfoxide 1 into the O-silylated cyclic O,S-acetal (2) is the first example of the sila-Pummerer rearrangement of cyclic organosilicon sulfoxides leading to ring expansion. The kinetics of the rearrangement are studied and thermodynamic parameters are determined. The results are in compliance with mechanism involving a pentacoordinated silicon atom.

  亚砜1到O-甲硅烷基化的环状O，S-乙缩醛（2）的热转化是环状有机硅亚砜的sila-Pummerer重排导致环膨胀的第一个例子。研究了重排动力学，并确定了热力学参数。结果符合涉及五配位硅原子的机理。