Ring conformations of 2-substituted 2-oxo-4-methyl-1,3,2-dioxaphosphorinanes. Evidence for a boat conformation in equilibrium with two interconverting chairs

✍ Scribed by John A. Mosbo

• Publisher: John Wiley and Sons
• Year: 1978
• Tongue: English
• Weight: 611 KB
• Volume: 11
• Category: Article
• ISSN: 0749-1581
• DOI: 10.1002/mrc.1270110604

✦ Synopsis

Abstract

The 220 MHz proton NMR spectra of three isomeric pairs of 2‐R‐2‐oxo‐4‐methyl‐1,3,2‐dioxaphosphorinanes, where R = methoxy (1a, b), methyl (2a, b) and dimethylamino (3a, b) (a represents the trans and b the cis arrangement of R and the 4‐methyl group) were analyzed by iterative computer techniques. Ten ring conformations, two chairs, two half‐chairs and six boats were initially considered as being possible contributors to the overall solution conformations. Compounds 1a, 2a, 2b and 3b were all concluded to exist as single chair conformations with the 4‐methyl group equatorially oriented (eqch). In addition to 68% of compound 3a being in that eqch conformation, however, significant concentrations of the chair form containing an axially oriented 4‐methyl group (axch, 16%) and a boat conformation containing an equatorially oriented 4‐methyl group with phosphorus and C‐5 serving as the bow and stern (eq25, 16%) were also postulated. Similarly, it was suggested that 1b contained 60% eqch, 20% axch and 20% of the boat eq25. From the data for compounds 2a and b it was concluded that in the chair conformations of 2‐oxo species the phosphorus substituent orientation has little effect upon the ^3^J(POCH) coupling constants.