r-5-tert-Butyl-c-2-(trimethylsilyl)cyclohexan-t-ol | 66228-04-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: r-5-tert-Butyl-c-2-(trimethylsilyl)cyclohexan-t-ol
• 英文别名: (1S,2S,5R)-5-tert-butyl-2-trimethylsilylcyclohexan-1-ol
• CAS: 66228-04-4；66228-05-5；111324-98-2；142744-05-6；142744-07-8；142744-08-9
• 化学式: C₁₃H₂₈OSi
• 分子量: 228.45
• InChiKey: UNPIWWPINOKEAY-WOPDTQHZSA-N

物化性质

• 熔点：
  71 °C
• 沸点：
  276.8±33.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  r-5-tert-Butyl-c-2-(trimethylsilyl)cyclohexan-t-ol 在 吡啶 、 间氯过氧苯甲酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 3-(2-甲基-2-丙基)-7-氧杂双环[4.1.0]庚烷
  参考文献：
  名称：

  Stabilization of positive charge by .beta.-silicon

  摘要：

  DOI：

  10.1021/ja00259a036
• 作为产物：
  描述：

  反式-1,2-环氧-4-叔丁基环己烷 在 potassium methanolate 、 potassium carbonate 作用下， 以 甲醇 、 六甲基磷酰三胺 为溶剂， 反应 20.0h， 生成 r-5-tert-Butyl-c-2-(trimethylsilyl)cyclohexan-t-ol
  参考文献：
  名称：

  Stereoelectronic effect of the trimethylsilyl substituent upon carbon-oxygen bond lengths at the .beta. position: some structural studies

  摘要：

  Results of low-temperature (130 K) crystal structure analyses for seven beta-trimethylsilyl-substituted cyclo-hexylnitrobenzoate esters are reported. For those molecules (three) with the Si-C and C-O bonds antiperiplanar the C-O bond lengths are increased by 0.014 angstrom av (DELTA/sigma min = 2.9) compared with that in the silicon-free For those molecules (four) with the Si-C and C-O bonds gauche no such systematic lengthening of the C-O bonds is observed. The result is in qualitative agreement with that [DELTA-l is-proportional-to cos2 (Si-C-C-O)] predicted from semiempirical MO calculations on a simple model complex and is attributed to the effects of interactions between the Si-C sigma and C-O sigma* orbitals. It is suggested that existence of the observed ground-state effect constitutes persuasive, if circumstantial, evidence that the major kinetic effects known to result from the presence of a beta silicon substituent also have their genesis in the same sigma-sigma* interactions.

  DOI：

  10.1021/jo00043a020

文献信息

• Gauging the Donor Ability of the C-Si Bond. Results from Low-Temperature Structural Studies of gauche and Antiperiplanar β-Trimethylsilyl-cyclohexyl Esters and Ethers by Use of the Variable Oxygen Probe.
  作者：Alison J. Green、Josie Giordano、Jonathan M. White

  DOI：10.1071/ch99138

  日期：——

  A plot of C–OR bond distance against pKa(ROH) for esters and ether derivatives of the antiperiplanar β-silyl alcohol (4) has a slope of –5.310–3. This represents a stronger response of the C–OR distance than was observed for the corresponding gauche β-silyl alcohol (5) and its derivatives. This result is consistent with the greater donor ability of a C–Si bond compared with a C–C bond. Comparison of these plots with those previously reported for derivatives (3) of tetrahydropyran-2-ol reveals that a C–Si bond is a weaker donor than an oxygen non-bonded pair of electrons. An estimate of the pKa value for 2,4-dinitrobenzenesulfenic acid (14) was derived from these plots.

  C–OR键距离与酯和醚类衍生物的pKa(ROH)之间的关系图，对于反平面β-硅醇(4)具有-5.310-3的斜率。这代表了C–OR距离的更强响应，这种响应比对应的反式β-硅醇(5)及其衍生物观察到的要强。这一结果与C–Si键的更强给体能力相一致，相比之下，C–C键的给体能力较小。将这些图与先前报道的四氢吡喃-2-醇衍生物(3)的图进行比较，发现C–Si键是一个比氧的非成键电子对更弱的给体。从这些图中推导出了2,4-二硝基苯硫酸(14)的pKa值估计。
• Ground State Stereoelectronic Effects of Silicon: A Comparison of the Effects of Synperiplanar and Antiperiplanar Silicon on C-O Bond Lengths at the .beta. Position
  作者：Alison J. Green、Yew-leong Kuan、Jonathan M. White

  DOI：10.1021/jo00114a021

  日期：1995.5

  Results from low-temperature crystal structure analyses of beta-trimethylsilyl esters with synperiplanar and antiperiplanar geometry are reported. These studies reveal a significant response of the C(alkyl)-O(ester) bond length to the electron demand of the ester function when the beta-trimethylsilyl substituent is antiperiplanar to the ester. However, when the geometry is synperiplanar, the C-O bond lengths are not significantly different from those of the corresponding nonsilylated derivatives. This is interpreted in terms of more effective overlap between the sigma(C-Si) orbital and the sigma*(C-O) antibonding orbital in the antiperiplanar geometry than in the synperiplanar geometry.