Crystal and molecular structures of isomeric 2-morpholino-2-thiono-4-methyl-1,3,2-dioxaphosphinane and 2-morpholino-2-oxo-4-methyl-1,3,2-dioxaphosphinane |
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Authors: | Micha W Wieczorek Wiesaw R Majzner Renata Kaczmarek Janina Baraniak Wojciech J Stec |
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Abstract: | Two isomeric pairs of compounds, cis- and trans-2-morpholino-2-thiono-4-methyl-1,3,2-dioxaphosphinane ( 1A + 1B ) and 2-morpholino-2-oxo-4-methyl-1,3,2-dioxaphosphinane ( 2A + 2B ) were obtained and separated into the pure compounds by silica gel chromatography. Attempts at crystallization afforded 1A , 1B , and 2B . Each crystalline isomer was studied by the X-ray technique, and each crystal and molecular structures assigned. These studies revealed that 1B and 2B have exocyclic 4-CH3 and sulfur (for 1B ) or 4-CH3 and oxygen (for 2B ) in the diequatorial position (cis-geometry), while compound 1A possesses the 4-CH3 group in equatorial position while sulfur is in an axial position (trans-geometry). For all the examined compounds, all the basic geometrical parameters, such as bond lengths, bond and torsion angles, and the deformation of a chair conformation of the six-membered heterocyclic rings, have been established. Such unambiguous assignment of cis-trans geometry in both pairs of 1 and 2 allowed us to confirm the stereoretentive PS → PO conversion by means of OXONE® and the stereoinvertive mechanism of formic-acid catalyzed hydrolysis of phosphorothiomorpholidates. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:271–279, 1998 |
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