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KMID : 0903520000430010037
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Journal of the Korean Society of Agricultural Chemistry and Biotechnology
2000 Volume.43 No. 1 p.37 ~ p.43
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Structural Determination of cis- and trans-5-Hydroxymethyl -5-methyl-2-thiono-r-2-ethoxy-1 , 3 , 2-dioxaphosphorinane by NMR and X-ray Crystallography
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Kim, Jeong Han
Toia, Robert F ./Craig, Donald C .
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Abstract
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1,3,2-Dioxaphosphorinanes are suitable compounds for studying the stereochemistry of substitution at phosphorus. Cis- and trans-5-hydroxymethyl-5-methyl-2-thiono-2ethoxy-1,3,2-dioxaphosphorinane were prepared, and their structures and stereochemistry unambiguously assigned by NMR and X-ray crystallography with acetoxy and 3,5-dinitrobenzoyloxy derivatives, respectively. Trans isomer gave ^(31)P NMR signal at higher field than cis isomer, and the ring proton spectrum of cis isomer showed characteristic pattern for identifying its geometry In X-ray crystallography they adopted a chair conformation with the ethoxy groups in the axial positions, and the sulfide groups in the equatorial positions. A flattening of the ring around the phosphorus center was noted, the POC bond angles were about 120°, and the C-O bonds in the ring were significantly longer than the C-O bond for the ethoxy group or the C-O bond for hydroxyl group.
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