Science of Synthesis

Chiba, S.; Narasaka, K., Science of Synthesis Knowledge Updates, (2011) 4, 475.

Conversion of oximes and O-substituted derivatives into amides (e.g., ‌52‌) and lactams is known as the Beckmann rearrangement (‌Scheme 42‌).[‌39‌,‌273‌,‌435‌,‌436‌] In general, the Beckmann rearrangement requires the use of excess amounts of acid such as sulfonic acid, hydrochloric acid, polyphosphoric acid,[‌437‌] or various Lewis acids. Among the variety of reagents available for this transformation are phosphorus pentachloride,[‌438‌] triphenylphosphine/carbon tetrachloride,[‌439‌] sulfuric acid,[‌440‌,‌441‌] thionyl chloride,[‌442‌] 4-toluenesulfonyl chloride/pyridine,[‌341‌,‌443‌] and phosphorus pentoxide/methanesulfonic acid.[‌444‌,‌445‌] Microwave irradiation[‌446‌] and photoirradiation[‌447‌,‌448‌] have also been reported.

‌Meeeee 88‌ Meeeeeeee ee ee Meeee ee Meeeeeee Meeeeeeeeeeee[‌888‌]

Meeeeeee eeeeeeee (8,8,8-eeeeeeeee-8,8,8-eeeeeeee) (‌Meeeee 88‌),[‌888‌–‌888‌] 8,8,8,8,8,8-eeeeeeeeee-8,8,8,8λ8,8λ8,8λ8-eeeeeeeeeeeeeeeeeeee, eee eeeee(eeeeeeee)eeeeeeeee eeeeeee[‌888‌] eeee ee eeeeeeeee eeeeeeeee eee Meeeeeee eeeeeeeeeeeee ee eee eeeeeeee ee eeeee. 8,8-Meeeeeeeeeeeeeeeeeeee eeeeeeeee ee eeee eeee eeeeeeeeeeeeeee eee eeeeee eeeeeeee eeee ee eeeeeeeee ee eeeeeee eeeeee eeee eeeeee eeeeeee eee eeeeeeeeeee ee eeeeeee eeeeeeeeeee.[‌888‌] Meeeeee eeeeeeeee ee eeeeeeeeee eeeeee eeee ee eeeeeee,[‌888‌] eeeeeee,[‌888‌,‌888‌] eeeeeee,[‌888‌] eeeeeee,[‌888‌] eee eeeeeeeee[‌888‌] eee eeeeeeee ee eeeeeee eee eeeeeeeee Meeeeeee eeeeeeeeeeeee.

‌Meeeee 88‌ Meeeeeeee Meeeeeee Meeeeeeeeeeee[‌888‌]

Me eeeeeeeee M-eeeeeeeeeee eeeeee eeee ee M-eeeeeeeeeeeeee eee M-(8,8,8-eeeeeeeeeeee­ee)eeeeee (eeeee eeeeeeee),[‌888‌] eeeee eeee e eeee eeeeeee eeeee ee eee eeeeeeee eeee, eeeeeeeeeeeeee eee ee eeeeeeee eeeee eeee eeeeeeeeee, eeeeeeeee eeeeee eee/eeeeeeeeee,[‌888‌] eeeeeee,[‌888‌] eeeeeeeeeeeee,[‌888‌] eee eeeeeeeee eeeeeeeee/eeeeeee.[‌888‌] Meeeeee M-eeeeeeee­eeeeee eee ee eeeeee eeee eee eeeeeeeeeeeee eeeee eeeee eeeeeee ee eeee eeeeeeeeeee, ee eee eeee, eee eeeeeee eee eeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee eee Meeeeeee Meeeeeeeeeeee[‌88‌]

Mee eeeeeeeee eeeeeeee eeeeeeeee[‌888‌–‌888‌] ee eee Meeeeeee eeeeeeeeeeeee ee eeeee ee ‌Meeeee 88‌. Mee M-eeeeeee eeeee ee eee eeeee ee eeeeeeee eeee eeeeeeeeeee eeeeee ee eeeeeeeeeee ee eeeeeeeeeeeeee. Meeeeeeeeee ee eee eeeeeeeee eeeeeee eeeee eee 8,8-eeeeeeeee ee eee eeeee eeeee eeeeeee eeee ee eee eeeeeee eeeee eeeee eeeeeeeeeeeeee, ee eeee eeeeee e eeeeeeeee eee eeeeeee ee ee eeeeeee (ee eeeeeeee eeee e eeeeeeeeeee). Meeeeeeeeeeee, ee eee eeee eeeeeeeee eeee eeeeeeeee eeee eee ee eeeeeeee ee eeeeeee eeeee, eeee ee eee eeeeeeeee ee 8-eeee-eeeeeeeeee-8-eee eeeee.[‌888‌–‌888‌]

Me eeeeeeeee eeeee, eeeeeee eeeeee eee eeeeeeee eee eeeeeeeee 8,8-eeeeeeeee ee eeeee eeeeee eeeeeee eeee ee eee eeeeeee eeeee. Meeeeee, eeeee eee eeeeeeeeee eeeee eeeee eeeeeeeeeeeee ee eeeeee, eee eeeeeee eeeeeeeeeeee ee eee eeeeee ee e eeeeee eeeeeeeeeee ee eeeeeee eeeeeeeee eee eeeeeeee eeeeeeeee eeeeeeeee ee eeeeeeeeeeee ee eeee ee eee eeeeeeeeeeeee eeeeeeeee ee eee eeeee eeeeeee. Meeeeeeee, eee eeeee ee eeeeeeee eeeeeeeee eeeeeeeee ee eeeeeeee eeeee > eeeeeeeee eeeee > eeeeee > eeeeeee eeeee > eeeeee.[‌888‌] Me eee eeee ee eeeeeeee eeeee eeeeeeeee, eeeee eee ee eeeeeeeee eeeeeeeee ee eeeeeeeeeeeee eeeeeeee, e.e. eeeeeeee. Meeeeeee eeeeeeeee eeeeeeeee ee eeeeee eeeeeeeeeee ee eeeeeeee eeee eee eeeeeeeeeeeee ee eeeeeee eee eeeee eeee eeeeeeeeee eeeee eee M-eeeeeeeeeeeee, eeeeeeee ee eeee ee eeeeeeeeeeeee ee eee eeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeee Meeee Meeeeeeee eee Meeeeee Meeeeeeee[‌88‌]

Mee eeeeeeeeeeeee ee eee Meeeeeee eeeeeeeeeeeee (eeeeeeeee eeee, eeeeeee eeeee, eeeeeee eeeeeee, eee eeeee eeeeeeeeeee) eee ee eeeeeee eeee eeeee ee eeee eeeeeee eeeee eeeeeeeeeeee (‌Meeeee 88‌). Meeeeeee eeeeeeeee eee eeeeeeeeeeeee eeee eeeeeeeeeee eeeeeeeeeeee eeeeeeee e eeeeeee ee eeeee eeeeeeeeeee, eeeee eee ee eeeeeeee eee eeeeeee eeeeeeeeeeeeeee. Meeeeee eeeee eeeeeeeee eee ee eeeeee ee Meeeeeee eeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeee, eeeeeeeee, ee eeeeeeeeeee, eeeeee eeeee eeeeeeee,[‌888‌] eeeeeeeeeeee,[‌888‌,‌888‌] ee eeeeee­eeeeeeee,[‌888‌] eeeeeeeeeeee. Meeeee eeeeeeeeeeee eeee ee Meeeeeee eeeeeeee,[‌888‌] eeeeeeeeeeeeee eeeeeeee,[‌88‌,‌888‌,‌888‌,‌888‌] eee eeeee eeee eeeeee[‌888‌] eee eeee ee eeee eee eeeeeeee eeeeeeeee eeee ee eeeeeeeeee eeeeeeeeeeeee (e.e., eeeeeeeee ee ‌88‌ eeee eeeee ‌88‌; ‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeeeeeeeeeeeeee Meeeeee Meeeeeee Meeeeeee Meeeeeeeeeeee ee ee Meeee[‌888‌]

Meee eeeee ee eeeeee eeeeeeeee eee ee eeeeeeee ee Meeeeeee eeeeeeeeeeeee ee eeeeee eeee ee eeeeeeeeeeeeee eeeeeeeeeeee eeeeee. Mee eeeee eee eeeeeeee: eeee eee eeeeeeeeeee ee eeeeeee ee eee eeee-eeeeeeeeeee ee eee eeeee M-eeeee eeeee, eee eeeeeeeeeee eeeeeeee ee eeee-eeee, eee eeeeeeeeeeeeee ‌88‌ ee eeeeeeee, eeeee ee eee eeeee eeee, e eeeeeeeeeeeeeee(eeeee)eeeee ‌88‌ ee eeeeee ee eee-eeee eeeeeeeeeee (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeeeeeeeee eee Meeeeeeeeee ee Meeeee[‌88‌]

Meeeeeeeeeeeee,[‌888‌,‌888‌] eeeeeeeeee,[‌888‌] eeeeeeeeeeeeeee,[‌888‌] eee eeeeeeeee eeeeeeeeeee[‌888‌] eee eeeeeeee ee eeeeeeeeeeeeee eeeeeee ee eee eeeeeeeee eee ee eeeeeee ee e eeeeeeeeee eeeeeeeeeee. Meeeeeee eeeee ee eeeeee eeeeeeee eee eeee eeeeee ee eeeeeee eeeeeeeeeeee. Meeeeeeeeeeee,[‌888‌] eeeeeeeeeeeeeee,[‌888‌,‌888‌] eeeeeeeeeee,[‌888‌] eee eeeeeeeee[‌888‌] eee eee ee eeeeeee eeee eeeee eeeeeeeeeee eeeeee eeeeeeee eeeee ee eeeeee eeeeeeee ee eeeeeeeeeee eeeeeeeee.

Meeeeeeeeeee Meeeeeeee

M-Meeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee eeeeeeeeeeee eeeee (8.88 e, 88 eeee) ee eeeeee (88 eM) eee eeeee ee e eeeeeee eeeeeeeeee ee MMM (8 e) ee eeeeee ee 888°M. Meeee eeeeeee ee 888°M eee 8 e, eee eeeeeeee eee eeeeeeee eeee M8M. Mee eeeeeee eeeee eee eeeeeeeee eee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeeeee; eeeee: eeeee; ee 888°M.

8,8,8,8-Meeeeeeeee-8,8-eeeeeeeeeeeeeee (‌88‌):[‌888‌]

Me e eeeeeee eeee ee eeeee ‌88‌ (8.88 e, 8.88 eeee) ee MM8Me8 (88.8 eM) eee eeeee e 8.88 M eeee ee MMMMM-M ee eeeeee (88.8 eM, 88.8 eeee) eeee 88 eee ee 8–8°M (eeeeeeee eeeeeeeeeee) eeeee eeeee. Meeeeeee eee eeeeeeeee eee 8 eee ee 8°M eee eee 8 e ee ee. MeM eeeeee (8.88 e, 888 eeee) eee M8M (8.8 eM) eeee eeeee ee 8°M, eee eee eeeeeeeee eeeeeee eee eeeeeee eee 88 eee ee eee eeee eeeeeeeeeee. Meee, eee eeeeeee eee eeeeeeee eeeeeee e Meeeee eee. Mee eeeeee eeee eee eeeeee eeee MeMMe, eee eee eeeeeee eee eeeeeee eeee eee eeeeeeee eeeeeee eeeee ee eeee eee eeeee eeeeeee. Meeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeee 8:8) eeeeeee eee eeeeeee; eeeee: 888 ee (88%).

References