A direct comparison of azide and nitrile vibrational probes

Phys Chem Chem Phys. 2011 Apr 7;13(13):5926-30. doi: 10.1039/c0cp02774j. Epub 2011 Feb 18.

Abstract

The synthesis of 2'-azido-5-cyano-2'-deoxyuridine, N(3)CNdU (1), from trityl-protected 2'-amino-2'-deoxyuridine was accomplished in four steps with a 12.5% overall yield. The IR absorption positions and profiles of the azide and nitrile group of N(3)CNdU were investigated in 14 different solvents and water/DMSO solvent mixtures. The azide probe was superior to the nitrile probe in terms of its extinction coefficient, which is 2-4 times larger. However, the nitrile IR absorbance profile is generally less complicated by accidental Fermi resonance. The IR frequencies of both probes undergo a substantial red shift upon going from water to aprotic solvents such as THF or DMSO. DFT calculations supported the hypothesis that the molecular origin of the higher observed frequency in water is primarily due to hydrogen bonds between the probes and water molecules.

Publication types

  • Comparative Study
  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Azides / chemistry*
  • Deoxyuridine / analogs & derivatives*
  • Deoxyuridine / chemical synthesis
  • Deoxyuridine / chemistry
  • Dimethyl Sulfoxide / chemistry
  • Infrared Rays
  • Molecular Structure
  • Nitriles / chemistry*
  • Solvents / chemistry
  • Spectroscopy, Fourier Transform Infrared
  • Vibration
  • Water / chemistry

Substances

  • 2'-azido-5-cyano-2'-deoxyuridine
  • Azides
  • Nitriles
  • Solvents
  • Water
  • Deoxyuridine
  • Dimethyl Sulfoxide