Abstract
Abstract Friedel–Crafts acylation, bromination, deuteration, and nitration of acetylpentamethylbenzene (APMB), 1-acetyl-2,3,4,6-tetramethylbenzene (ATMB), and 1-benzoyl-2,3,4,6-tetramethylbenzene (BTMB) and the resulting product distributions were investigated. Friedel–Crafts acylation, bromination, and deuteration of APMB and Friedel–Crafts acylation of ATMB gave deacetylation-substitution products. On the other hand, bromination and deuteration of ATMB (or BTMB) and Friedel–Crafts acylation of BTMB gave 5-substituted products. In both cases, the positional reactivities were in accordance with the relative σ-complex stability. Conversely, except for Friedel–Crafts-type nitration, the positional reactivities in the nitration of these substrates were strikingly different from those of the above three reactions. Thus, side-chain functionalization at the 6-methyl group occurred in nitration with fuming nitric acid, depending on the solvents in use. The MNDO calculations and the reaction of APMB with single-electron transfer reagents such as tetranitromethane-hν or cerium(IV) ammonium nitrate suggest that the product distribution in nitration can be explained in terms of a single-electron transfer mechanism.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
