1,4-二甲氧基-2-(三甲基甲硅烷基)苯 | 72054-75-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,4-二甲氧基-2-(三甲基甲硅烷基)苯
• 英文名称: 1,4-Dimethoxy-2-(trimethylsilyl)benzene
• 英文别名: 1-(trimethylsilyl)-2,5-dimethoxybenzene；2-(trimethylsilyl)-1,4-dimethoxybenzene；(2,5-dimethoxyphenyl)-trimethylsilane；(2,5-dimethoxyphenyl)trimethylsilane
• CAS: 72054-75-2
• 化学式: C₁₁H₁₈O₂Si
• 分子量: 210.348
• InChiKey: FIYZLOOFEZWQIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.25
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-二甲氧基-2-(三甲基甲硅烷基)苯 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 0.58h， 以97%的产率得到2-(Trimethylsilyl)-1,1,4,4-tetramethoxy-1,4-cyclohexadiene
  参考文献：
  名称：

  Chemistry of quinone derivatives. Quinone monoketals via hydrolysis of electrochemically derived quinone bisketals

  摘要：

  DOI：

  10.1021/jo01305a010
• 作为产物：
  描述：

  三甲基氯硅烷 、 对苯二甲醚 在 正丁基锂 、 四甲基乙二胺 作用下， 生成 1,4-二甲氧基-2-(三甲基甲硅烷基)苯
  参考文献：
  名称：

  Dilithiation of aromatic ethers

  摘要：

  DOI：

  10.1021/jo00198a015

文献信息

• A predicative model for certain directed metalations, IV; The dynamic behavior of the organolithio intermediates formed by metalation of p-dimethoxybenzene (p-DMB)
  作者：D.W. Slocum、G. Hayes、N. Kline

  DOI：10.1016/0040-4039(95)01765-a

  日期：1995.11

  Significant disproportionation between the mono- and 2,5-bis-metalaled intermediates resulting from metalation of p-DMB has been observed. The best procedure for the generation of each of these intermediates involves use of an “incremental” amount of TMEDA.1

  已经观察到由p-DMB金属化导致的单金属和2，5-双金属化中间体之间的显着歧化。生成每种中间体的最佳方法是使用“增量”量的TMEDA。1个
• Anodic oxidation of 1,4-dimethoxy aromatic compounds. A facile route to functionalized quinone bisketals
  作者：Daniel R. Henton、Richard A. McCreery、John S. Swenton

  DOI：10.1021/jo01291a001

  日期：1980.2
• The β Effect of Silicon in Phenyl Cations
  作者：Valentina Dichiarante、Andrea Salvaneschi、Stefano Protti、Daniele Dondi、Maurizio Fagnoni、Angelo Albini

  DOI：10.1021/ja074778x

  日期：2007.12.1

  Irradiation of chloroanisoles, phenols, and N,N-dimethylanilines bearing a trimethylsilyl (TMS) group in the ortho position with respect to the chlorine atom caused photoheterolysis of the Ar-Cl bond and formation of the corresponding ortho-trimethylsilylphenyl cations in the triplet state. The beta effect of silicon on these intermediates has been studied by comparing the resulting chemistry in alcoholic solvents with that of the silicon-free analogues and by computational analysis (at the UB3LYP/6-311+G(2d,p) level in MeOH). TMS groups little affect the photophysics and the photocleavage of the starting phenyl chlorides, while stabilizing the phenyl cations, both in the triplet (ca. 4 kcal/mol per group) and, dramatically, in the singlet state (9 kcal/mol). As a result, although triplet phenyl cations are the first formed species, intersystem crossing to the more stable singlets is favored with chloroanisoles and phenols. Indeed, with these compounds, solvent addition to give aryl ethers (from the singlet) competed efficiently with reduction or arylation (from the triplet). In the case of the silylated 4-chloro-NN-dimethylaniline, the triplet cation remained in the ground state and trapping by pi nucleophiles remained efficient, though slowed by the steric bulk of the TMS group. In alcohols, the silyl group was eliminated via a photoinduced protiodesilylation during the irradiation. Thus, the silyl group could be considered as a directing, photoremovable group that allowed shifting to the singlet phenyl cation chemistry and was smoothly eliminated in the same one-pot procedure.
• Synthesis of the Tetracyclic Carbon Core of Menogaril Utilizing the Benzannulation Reaction of a Fischer Carbene Complex and an Alkyne
  作者：Jing Su、William D. Wulff、Richard G. Ball

  DOI：10.1021/jo981481w

  日期：1998.11.1

  The synthesis of the 2-bromoanthracyclinone 3 containing the tetracyclic core of menogaril is achieved with a strategy that is formulated around the benzannulation reaction of a Fischer carbene complex and an alkyne. This benzannulation requires a 2,5-dimethoxyphenyl carbene complex that bears an additional functional group at the 4-position that is the nascent 2-bromo substituent in 3. The evaluation of 4-bromo- and 4-trimethysilyl-substituted complexes with 1-pentyne revealed that the benzannulation was more efficient with the silyl complex. The synthesis of 3 is achieved with methoxy and acetoxy substituents at the C-9 position, which begins with the methoxy- and benzyloxy-substituted alkynes 14 and 30 that contain the A ring of the menogaril core. The closure of the last ring is accomplished by a Friedel-Crafts reaction on an in situ generated acid chloride. Adjustment of the oxidation states of the B and C rings failed according to procedures that had been developed in model studies. This was accomplished in an unexpected fashion with novel bromination reactions that occurred at a benzylic position with the C-9 methoxyl derivative and alpha to a ketone in the C-9 acetoxy derivative.
• HENTON D. R.; CHENARD B. L.; SWENTON J. S., J. CHEM. SOC. CHEM. COMMUN., 1979, NO 7, 326-327
  作者：HENTON D. R.、 CHENARD B. L.、 SWENTON J. S.

  DOI：——

  日期：——