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DOI: 10.1055/sos-SD-234-00262

Bietti, M.; Dénès, F.Science of Synthesis: Free Radicals: Fundamentals and Applications in Organic Synthesis, (20211537.

Bromination at benzylic positions can be achieved with molecular bromine upon irradiation.[‌139‌] For instance, upon irradiation using a sunlamp 4-nitrotoluene (73-mmol scale) leads to 4-nitrobenzyl bromide (36) in 71% yield in refluxing carbon tetrachloride in the presence of molecular bromine and traces of molecular iodine as catalyst (Scheme 59).

Meeeee 88 Meeeeeeeeee ee 8-Meeeeeeeeeee eeee Meeeeeeee Meeeeee[‌888‌]

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Mee eeeee ee eeeeeeeeee eee eeeeeeee ee eee M=M eeee eee ee eeeeee ee eeeee M-eeeeeeeeeeeeeeee ee e eeeeee ee eeeeeeeee eeeeeee, eeeee ee eeee eeeeeeeee ee e eee, eeeeee-eeeee eeeeeeeeeeeee ee eee eeeee eeeeeeee eeeeeee M-eeeeeeeeeeeeeeee eee eeeeeeee eeeeeee.[‌888‌] Mee eeeeeee eeeeeeeeeee ee eeeeeee eee eeeeeeee eeeeeeeee eeeee M-eeeeeeeeeeeeeeee (eeeee ee eee Meee–Meeeeee eeeeeeee)[‌888‌‌888‌] ee eeeeeee eeeeeee eee ee e eeeeeeee eeeeeee, eeeeeeeee eeeeee eeeeeeeeeeeee, e eeeeeee ee eeeee M-eeeeeeeeeeeeeeee ee eeeeee eeeeeeeee, eee ee eee eeeeeeee ee e eeeeeee eeeeeeeee (e.e., 8,8′-eeeeeeeeeeeeeeeeeeeeee, ee-eeee-eeeee eeeeeeee, eeeeeeeee eeeeeeee), ee eeee eeeeeeeeeee eeee MM eeeee, eeeeeeee eeeee eeee eeeeeeeeee eeee eeeeeeeeeee eeee eeeeeeeee eeeeeee eeeeeeeeeee eeeee (MMM).[‌888‌] Meeeeeee eeeeee eeeeeeeeeeeee ee eee eeeeeeee eeeeeee ee eeeeee ee eeeee eee eeeeeeeeeeee ee eeeeeeeeeee eeeeeeeee, eee eee ee ee eeeeeeeeeee eeee ee (eeeeeeeeeeeeeee)eeeeeee ee eeeeeeee.[‌888‌] Meeeeeee-eeeeeeeee eeeeeeee eeeeeee eee ee eeeeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee ee eeeee eeeeeee eeee ee 8-eeeee-8-eeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeee ([eeee]MM8);[‌888‌] eeeeeee, eeeee eeeeeeeeee eeeee eee eeeee eeeeeeeeeee ee eee eeee eee eeeeeeee-eeee eeeeee. Me eeee eeee, eeeeeee-eeee eeeeeeeeee eeee ee eeee.[‌888‌]

Mee eeeeeeeee ee eee eeeeeee eee eeeeeeee eeeeeeeeeeee eee eeee eee eeeeeee ee eeeeee. Mee eeeeeeeee eeeeeeee eeeeeeeeee eeee eeee eeeeeeeee eeeeeeee, eeeeee eee Meeeeeeeee eeeeeeeee,[‌888‌] eeeee eeeeeeee MM eeeeeeeeeee ee e eeeeeeee-eeeeeeee eeeeeee (eeeeeeeeeeee eeeeeee), ee e eeeeeee eeeeeeeee ee Meeeeeeeeeʼe eeeeeeeee (eeeeeeeee eeeeeeeee eee eeeeeeeeeeee eeee M-eeeeeeeeeeeeeeeee),[‌888‌,‌888‌] ee eeeee M-eeeeeeeeeeeeeeee eeeee eeeee ee e eeeeee ee eeeeeeeee eeeeeee. Me eee eeeeee eeee, e eeeeeee eeeeeee eeeee ee eee eeeeeee eeeeeeeeeee eee MMM eeee eee eeeeeee (ee eeeeeeee) MM eeee.

M eeeeeeeeeeee eeeeee ee eeee eee eeee eeee ee eeeeeeeee eee eeeeeeee eeeeeeeee ee eee eeeeeeeeeee eeee M-eeeeeeeeeeeeeeee. Meeeeee, eee eeeeee ee eee eeeeeee eeee eeeeeeeee eee eeeeeeee eeee eeee eeeeeeeee eeeeeee (ee eeeeeeee) MM eeeee eee eeeeeeeee ee eeeeeee eeeeeee. Meeeee eeee eeee ee eeee e eeeeee ee eeeeee eeeeeeee eeeeeee eeeeeeeeeee eeeeeee eeeeeeeee eeeeeee eee M-eeeeeeeeeeeeeeee,[‌888‌‌888‌] eee eeee eeeeeee ee eee eeeeeeeee ee eee M-eeeeeeeeee eee ee eeeeee ee eee eeeeeeeeeee ee eee eeeeeeee[‌888‌,‌888‌] ee eeeeeee eeeeeeeeeee.[‌888‌] Mee eeeee eeeeeee eeeee eeeeee e eeeeeee eeeeeee ee eee eeeeeeeeeee eeeeeee ee eee eeee ee eee eeeeeee eee eeeeeeee eeeeeeeeeee ee eeeeeeee eeeeeeee (Meeeeeeeeeʼe eeeeeeeee). Me e eeeeee ee eee eeee eeee eeeeeeeeee ee eee eeeeeee ee eeeeee eeeeeeeeeeeee, eee eeeeee ee eee eeeeeee eeee ee eee eeeeeeeee ee eee MMe eeee ee eeeeeeeeee, ee eeee eeee, ee eeeeeeeee eeeeeee eee eee ee M-eeeeeeeeeeeeeeee.[‌888‌,‌888‌] Mee eee ee eeee eeeee eeeeeeee eee eeeeeeeeeeee eeeeee eee eeeeee ee eee eeeeeeee eee eeee eeeeee eee eeeeeee ee eeeeee ee e Meeeeeeeee eeeeeeeee, eeee eeeeeeeee eeeeeeeeeeee eee eee eeeeeeeeeee ee eee eeeeeeeeeee ee eeeeeeeeeeee (eee Meeeeee[‌888‌]

Mee eeeeeeeeeee eeeeeeee eeee M-eeeeeeeeeeeeeeee eeeee eeeeeeee eeeeeeeeee (eeeeeeee eeeeeee, eeeeeeeeeeeee eeeeeeeeee) eeeeeeee eeee eeeeeeeeeee eee eeeeeee MM eeeee (Meeeee 88),[‌888‌] eeeee eee ee eeeeeee eeee eeeeeeee eeee eeeee eeeeeeee eeeeeeeeeeee eee eee eeee eeeeeeee eeee eeeeeeeee eeee.[‌888‌] Meeeeeee, eeeeeeeeee eeeeeee eeee eeeeeee MM eeeee (eeee ee eeeeeeeeeeee eee eeeeeeeeeee) eee eeee eeee eeeeeeee eeee eeeeee eeeeeee.[‌888‌] Mee eeeeeeeeeee ee eeee eeeeee ee eeeeeeeeeee eeeeeeeee eeee ee eeeeeee eeeee.[‌888‌]

Meeeee 88 M-Meeeeeeeeeeeeeee-Meeeeeee Meeeeee Meeeeeeeeee ee eee Meeeeeeee ee (+)-Meeeeeeeee[‌888‌]

Meee-eeeeeeeee eeeeeee eeeeeeeeeee ee eeee eeeeeeee ee eeeeeee eeeeeeeeee, ee eeeeeeeeeee ee eee eeeeeeeeeeee ee eee M88-eeeeeee eeeee ee eee eeeeeeee ee (−)-eeeeeeeeeeeee M eee e eeeeee eeeeeeeeeeeeee Meee–Meeeeee eeeeeee eeeeeeeeeee, eeeeeeee ee eee eeeeeeeeeeee ee eee eeeeeee eeee ee eeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee(M) eeeeeeeeeeeeeeeeeeeeeeeee. Meeeeee, eee Meeee eeeee eeeeeeeee ee (−)-eeeeeeeeeeeee M eee eeeeeeeeeeee ee eeee eeee eeeee eeee (+)-eeeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeee Meeeeee Meeeeeeeeee ee eee Meeeeeeee ee (−)-Meeeeeeeeeeee M[‌888‌]

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8-Meeeeeeeeee Meeeeee (88):[‌888‌]

MMMMMMM: Meeeeee ee e eeeeee eeeeeeee ee eee eeee, eeeeee eeeeeeeee, eeeee, eee eeee. Meeeee eeeeeee eeeeee eeeeee eee eeeeeee eeeee ee eeeeeee eeee eeee eee eeee.

8-Meeeeeeeeeee (88 e, 88 eeee) eeeeeeeee ee e eeee-eeeeeeee eeeee eee eeeeeeeee ee MMe8 (888 eM) (MMMMMMM: eeeee) eee e eeeee eeeeeee ee M8 eee eeeee. Mee eeeee, eeeeee ee eeeeee eeeee ee e eeeeee eeeeeeeee, eee eeeeee ee ee eeeeeeee eeeeeeee ee eeeeee eeeeeeee eee eee eeeeeeee eeee eeeeeee ee eeee. M eeee ee Me8 (88.8 e, 88.8 eeee) ee MMe8 (88 eM) eee eeeeeeeeee e eeeee eeeeeeee ee e eeee ee eeeee ee e eeeeeeeeee eeeeee eeeee eeee eee eeeeee eeee eee eeee ee eee eeeee eeee ee eee eeeeeeeee eeee. Meeee eeeeeeeee ee MMe eeeee ee eeee. Meee eee eeeeeeee ee M8M eeeeeeeee ee Meeee eeeee eeeeee ee eee eeeee eee ee eee eeeeeeeee. Meee eee eee Me8 eee eeee eeee ee, eee eeeee eee eeeeeeee eeeee eeeeeee eee MMe8 eee eeeeeeeee eee. Me eeeeeee, eee eeee eeeeeee ee eee eeeeee ee eee eeeee eeeeeeeeeeee ee e eeeee eeee. Meee eee eeeeeeeee ee eeeeeee ee 88% eeeeeee eee eeeeeeee. Mee eeeeeeee eee eeeeeee eeeeee eee eeeeeee ee eeeee eee e eeeee eeee ee 8 °M. Mee eeee eeeeeeee eeee eeeeeeeee ee eeeeeee eeeeeeeeee eee eeeee eeeee eee eeeeeeeee; eeeee: 88.8 e (88%).