TMS is Superior to Residual C H Cl3 for Use as the Internal Reference for Routine 1H NMR Spectra Recorded in CDCl3

J Org Chem. 2022 Jan 21;87(2):905-909. doi: 10.1021/acs.joc.1c02590. Epub 2022 Jan 2.

Abstract

Tetramethylsilane was recommended for use as an internal reference compound in proton NMR spectroscopy over 60 years ago. However, it is a common practice that researchers reference the analyte chemical shifts to the residual proton resonance in the deuterated solvent in which the spectrum is recorded. Because CDCl3 is the most commonly used NMR solvent for routine analysis of organic compounds, the effect of various functional groups on the CHCl3 resonance is important. Described here are results that show why referencing spectra to TMS rather than CHCl3 in CDCl3 results in more accurate chemical shifts and should be the recommended practice. Simultaneous measurement of separate compartments of unperturbed CDCl3/TMS vis-à-vis CDCl3/TMS/solute solutions using a concentric tube arrangement was key. This study is reported in this venue because the audience/readership is quite appropriate and is, hopefully, both receptive to and appreciative of the guidance provided.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Magnetic Resonance Imaging*
  • Magnetic Resonance Spectroscopy
  • Proton Magnetic Resonance Spectroscopy
  • Protons*
  • Solvents

Substances

  • Protons
  • Solvents