双语化学辞典Chem Lexicon
化合物 · 分析化学 · 核磁共振 Analytical chemistry · NMR

四甲基硅烷Tetramethylsilane

拼音Pinyin sì jiǎ jī guī wán 别名Also TMS;TMS;SiMe₄

定义Definition

四甲基硅烷(TMS)是分子式为 Si(CH₃)₄ 的有机硅化合物,常温下为无色易挥发液体。由于其 12 个等价氢和 4 个等价碳都处于高度屏蔽的环境,它被规定为 ¹H、¹³C 和 ²⁹Si 核磁共振化学位移的零点参比物。

Tetramethylsilane, Si(CH₃)₄, is an organosilicon compound and a colourless, volatile liquid at room temperature. Because its 12 equivalent hydrogens and 4 equivalent carbons are highly shielded, it is defined as the zero of chemical shift for ¹H, ¹³C and ²⁹Si NMR.

作为参比的优点Why it is the reference

硅的电负性(1.90)低于碳(2.55),使甲基上电子云密度高、屏蔽强,信号出现在比绝大多数有机物都更高场的位置,不会与样品峰重叠;12 个氢完全等价,只出一个尖锐单峰,少量即可观察;化学惰性,不与样品反应;沸点仅 26.6 °C,测完易蒸发除去,回收样品方便;能溶于大多数有机溶剂。水溶液中则用 DSS 或 TSP 等水溶性参比物。

Silicon (electronegativity 1.90) is less electronegative than carbon (2.55), so the methyl groups are electron-rich and strongly shielded, and the signal lies upfield of almost all organic compounds without overlapping them; the 12 equivalent hydrogens give a single sharp peak visible in small amounts; it is chemically inert; it boils at only 26.6 °C, so it evaporates easily and the sample can be recovered; and it dissolves in most organic solvents. In water, soluble references such as DSS or TSP are used.

由来Origin

1958 年美国化学家乔治·蒂尔斯提出用 TMS 作 NMR 内标参比,取代此前使用的水、苯、氯仿等参比物,统一了化学位移标度。现代仪器常以氘代溶剂的残余质子峰(如 CDCl₃ 中 CHCl₃ 在 δ 7.26)间接定标。

In 1958 the American chemist George Tiers proposed TMS as the internal NMR reference, replacing water, benzene, chloroform and others and unifying the chemical-shift scale. Modern spectra are often referenced indirectly to the residual proton signal of the deuterated solvent, such as CHCl₃ in CDCl₃ at δ 7.26.

其他用途Other uses

TMS 也是化学气相沉积制备碳化硅和二氧化硅薄膜的前驱体。三甲基硅基(TMS 基,–Si(CH₃)₃)是有机合成中常用的羟基和炔基保护基,也用于气相色谱分析前的硅烷化衍生。

TMS is also a precursor for chemical vapour deposition of silicon carbide and silicon dioxide films. The trimethylsilyl (TMS) group, –Si(CH₃)₃, is a common protecting group for hydroxyl and alkyne groups in synthesis and is used to silylate compounds before GC analysis.

反应Reactions

SiCl4 + 4 CH3MgCl ⟶ Si(CH3)4 + 4 MgCl2

格氏试剂法合成;工业上为甲基氯硅烷生产的副产物。

Grignard synthesis; industrially a by-product of methylchlorosilane manufacture.

化学性质Chemical properties

化学性质稳定,但极易燃。

Chemically inert but extremely flammable.

年表Timeline

  • 1958

    蒂尔斯提出 TMS 作 NMR 参比

    Tiers proposes TMS as the NMR reference

相关公式Formulas

化学位移 Chemical shift→
\[\delta = \frac{\nu - \nu_\text{ref}}{\nu_0}\times10^6\ \text{ppm} = (\sigma_\text{ref} - \sigma)\times10^6\]
例题Worked example

400 MHz 谱中某峰比 TMS 高 2908 Hz:δ = 2908/400 = 7.27 ppm(芳香 H)。

A peak 2908 Hz from TMS at 400 MHz: δ = 7.27 ppm (aromatic H).