TLC Separation of Isomeric Diazinodithiins and Diazinyl Sulfides as the Smiles Rearrangement Products

Abstract

The reactions of diazinodithiins 1, 5, and 9 with sodium methanethiolate in DMSO, followed by methylation with methyl iodide, proceed with or without the Smiles rearrangement to give isomeric diazinodithiins 4, 8, and 12 and diazinyl sulfides 2, 3, 6, 7, 10, and 11. The aim of this was to find TLC conditions to follow the rearrangement, to separate and identify thioazines 1–12. The retention parameter R_F was measured and next calculated as separation factors ΔR_F, R_S, and α. The R_F values were correlated with the dipole moments of thioazines 1–12 and the symmetry (C_2h and C_2v) of diazinodithiins 1, 4, 5, 8, 9, and 12.

Keywords:

• Dipyridodithiins
• Diquinodithiins
• Diquinolinyl sulfides
• Dipyridinyl sulfides
• Retention and separation factors
• The Smiles Rearrangement

Keywords:

• Part CVIII in the series of Azinyl sulfides

ACKNOWLEDGMENT

Part of this work has been supported by the Nebraska Research Initiative.

Notes

A1 = CH₂Cl₂/Al₂O₃, A2 = C₆H₆-CHCl₃ 1:1/Al₂O₃, B1 = CHCl₃-C₂H₅OH 10:1/SiO₂, B2 = CHCl₃/SiO₂