Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ⁵-phosphane

Abstract

The symmetric hydrido-spiro-λ ⁵-phosphane derived from anhydroerythritol (meso-oxolane-3,4-diol, AnEryt), HP(AnErytH_{− 2})₂(3), was prepared by two different synthetic protocols. One route involves a three step synthesis starting from phosphorus trichloride via 2-chloro-tetrahydro-furo[3,4-d][1,3,2]dioxaphosphole (1) and diethyl-(tetrahydro-furo[3,4-d][1,3,2]dioxaphosphol-2-yl)-amine (2) as intermediates. The first intermediate, P(AnErytH_{− 2})Cl (1), was isolated as a crystalline solid and its structure was determined by single crystal X-ray diffraction. 1 is the first example of a halogeno substituted phosphane derived from an aliphatic diol whose molecular structure in the solid state was determined by X-ray diffraction studies. Alternatively, the title compound can also be obtained in a one-pot procedure starting from tris(N,N-dimethylamino)phosphane. All new compounds were characterized by their physical constants (melting point, refractory index), NMR, IR, Raman, UV/VIS, mass spectrometry, as well as elemental analysis. Some spectroscopic proofs for the spiro nature of the title compound are given.

Keywords:

• Alkylenedioxyphosphane
• crystal structure
• phosphorus
• spiro compounds

Acknowledgments

The authors thank Dr. Peter Mayer for professional help during crystal structure analysis and Prof. T. M. Klapötke for generous allocation of measurement time on the Raman spectrometer. Tobias Kerscher, M. Sc., is thanked for keen and swift assistance during the preparation and performance of DFT calculations.