Conformational and stereoelectronic investigation of chloromethyl methyl sulfide and its sulfinyl and sulfonyl analogs

摘要: Abstract The rotational equilibria of some sulfur-containing model compounds were theoretically determined, and a rationalization the effects responsible for results obtained is given. Experimental approaches, namely NMR infrared, also used to show gauche (Cl C S CH3 fragment) prevalence these allowed us elucidate orbital interactions involved in such systems. rotamer sulfide about 3.2 kcal mol−1 more stable than anti gas phase. For sulfinyl derivative relative energies most rotamers are 0.0, 1.0 1.7 kcal mol−1, corresponding gauche-1 (C Cl antiperiplanar O), gauche-2 lone pair) anti. calculated energy difference (anti-gauche) between sulfonyl 2.6 kcal mol−1. Natural bond analysis indicated that anomeric effect ( n → σ ∗ ) plays main role stabilization compound, other important hyperconjugative occur remaining compounds.