THEORETICAL STUDIES OF ORGANIC REACTION MECHANISMS USING MNDO AND MINDO/3 (SULFUR, CYCLOBUTYL CATION, CYCLOPROPYL CARBINYL).

摘要

MINDO/3 calculations are presented for a series of theoretically interesting cations. These studies include a MINDO/3 study of the rearrangement of protonated anisole, and a MINDO/3 study of the biomimetic cyclization of cis- and trans-2-undeca-6,10-dienyl cations. Other species investigated are the cyclopropylcarbinyl and bicyclobutyl cations. Many of these cations have bridged (nonclassical) structures, and are discussed in terms of (pi)-complex theory. MNDO calculations for the o-, m- and p-didehydrobenzenes were also carried out. These studies indicated that the ortho and meta isomers may have very similar stabilities. Improved MNDO parameters for sulfur are presented, along with calculations for a large number of sulfur compounds. In addition, a new method for calculating the properties of high-valent sulfur components is outlined.