Science of Synthesis

Phillips, A. J.; Love, C. E., Science of Synthesis, (2007) 20, 241.

The Favorskii rearrangement of α-halogenated ketones in the presence of a base has been known since 1892 and has been reviewed several times.[‌1‌,‌2‌] In its simplest form the rearrangement allows for the conversion of an α-halo carbonyl compound into a carboxylic acid by the action of a base (‌Scheme 1‌). In a more general sense, variation of reaction conditions allows for the synthesis of other carboxylic acid derivatives such as esters and amides from α-halo carbonyl compounds (‌Scheme 2‌). Examples of the rearrangement to produce esters can be found in Section ‌20.5.1.6.9‌

‌Meeeee 8‌ Meeeeeeee Meeeeeeeeeeee

‌Meeeee 8‌ Meeeeeeee Meeeeeeeeeeeee Meeeeee ee Meeeee eee Meeeee

Mee eeeeeeee ee eeeeeee eeeeeeee ee eeeeee eeeee eeeeeeeeee, eeeeeeee e eeee eeeeeee ee eeeee eeeeeeeeee eeee eeee eeeeeeee eeeeeeeee eeeeeeeeeeeeeee[‌8‌–‌8‌] eee eeeeeeeeeeeee[‌8‌] eeeeeeeeee, eee eeeeeeee eeeee eeeeeeeeee eeee ee eeeeee eeeeeeeee.[‌8‌] Mee eeeeeeeeee eeeeeeeeee e eee-eeee eeeeeeee eeeeeeeee eeeeee eeeeeeeeeeeeeee ee eeeeee eeeeeee eeeeeeee ee eeeee eeeeeeeeee eeeeee ee eeeeeeeeee.[‌8‌]

Mee eeeeeee ee eee eeeeeeee eee ee eeeeeeeee eee eeeeeeeee eeeeeeeee; eeeeeeeee, eeeee ee ee eeeeee eeeeee eeeeeeeeeeee eeeeeeeee. Meeeeee, eee eeeeeeee ee eeeeeeee eeeeeee eee ee eeeeeeeee ee e eeeeeeee ee eee α-eeee eeeeeeee eeeeeeee ee eeeee, ee eeeeeeeee eeeeeee, ee eeeee, eeee e eeeeeeee ee eee eeee. Meeeeeee eeeeeeeeeeee eee eeee eeeeeeeee eeeeeeeee eee eeeee eeee eeeeeeeeeeeee 8 ee 888°M. Meeeee eeee eeeeeeeee eeeeeee eee eeeeeeeee ee eeeeee eeeeeeee, eeeeeeeeeee ee eeee α,β-eeeeeeeeeee eeeeeee, eee eeeeee eeeeeeeeeeee ee eee α-eeeeeee ee eee eeee. Mee eeee eeeeeeee eee eeeeeee eeeeeeeee eee ee eeeeee eeeeeeeeeee eeeeeeeeeeeeee.

Mee eeeeeeeee ee eee eeeeeeee eee eeee eeeeeee ee eeeeeeeeeee eeeeee, eee eee eeeee eeeeeeeeee eeee eeee eeeeeeee ee eeeeeee eee eee eeeeeeee eeeeeeee: eee eee eeeeeeeeeeee ee e eeeeeeeeeeeeee, eee/ee eee e eeee-eeeeeeee eeee eeeeeee (‌Meeeee 8‌).[‌8‌] Mee eeeee eeeeeeeee eeeeeee ee eee eeeeeeeee ee eeeeeee eeeeeeeeeeeee eeee ee eee eeeeeeeeeeeeee ee eee eeeeeeee eeeeee. Mee eeeeeeeeeeee ee eeeeeeee eeeeeee ee eeee eeeee eee eeee eeeeeeeeeeee ee eeeeeeee eeee eeeeeeeee eeee ee eeeee ee eeee eee [8+8] eeeeeeeeeeee.[‌88‌] Mee eeeeeee eeeee eee eeeeeeeee ee eee eeeeeeeeeeeeee ee eeeeeeeeee ee eeeeee ee eee eeeeeee ee eeeeee α-eeeeeee, eee eeee-eeeeeeee eeeeeee ee eeeeeeeee (e.e., ‌8‌ → ‌8‌, ‌Meeeee 8‌).[‌88‌] Meeeeeeee eeee eeeeeee eee eeee eeeeeeeee eee eeeee eeeeeeee ee ee eeeee-Meeeeeeee eeeeeeeeeeeeee.

‌Meeeee 8‌ Meeeeeeeeeeeee eee Meee-Meeeeeee Meeeeeeeee eee eee Meeeeeeee Meeeeeeeeeeee[‌8‌]

‌Meeeee 8‌ Meeee-Meeeeeeee Meeeeeeeeeeee ee ee Meee Meeeee Meeeeee α-Meeeeeeee[‌88‌]

Mee Meeeeeeee eeeeeeeeeeeee ee eeeeeee α-eeee eeeeeee ee e eeeeee eeeeee eee eee eeeeeeeee ee α-eeeeeeee eeeeee eee eeeee. Meeeee eee eeeeeee ee eee eeeee ee 88–88%, eeeeeeee eeeeeeee eee eeeee eeeee eeeeee eeeeee eeee eeee eeeeeeee. ‌Meeeee 8‌ eeeee eeeee eeeeeeeee eeee ee eeeeeeeeee. Mee eeeeeeeee ee (M)-eee-8-eeeee eeee (‌8‌) eeee 8,8-eeeeeeeeeeee-8-eee (‌8‌) eee e Meeeeeeee eeeeeeeeeeeee, eeeeeeee ee eeeeeeeeeee eee eeee eeeeeeee ee eeeeeee ee 88–88% eeeee.[‌88‌,‌88‌] Mee eeeeeeee ee 8-eeeeeeeeeeeeeeeeeee ‌8‌ ee eeeeeeeee ee ee eeeeeeeee eeeeeee eee eee eeeee eeeeeee ee eeeeeeeeeeee eeeeeeeeee ee eeee eeeeeeeeee eeee ‌8‌ ee 88% eeeee.[‌88‌] Mee eeeeeeee ee eeeeeeee eeeeeeee ‌8‌ ee eeeeeeeee eeeee eeeeeee eeeeeeeeee ee eeee eee eeeeeeeeee eeee ‌8‌ ee 88% eeeee.[‌88‌]

‌Meeeee 8‌ Meeeeeeee Meeeeeeeeeeee ee α-Meee Meeeeee[‌88‌–‌88‌]

Meeeeee eeeeeeeeeeee eeeeeeee ee Meeeeeeee eeeeeeeeeeeeee eeeeeee ee eeeee eee eeeeeeeee ee ‌Meeee 8‌.

‌Meeee 8‌ Meeeeeeeeeeeee Meeeeeeee Meeeeeeeeeeeee[‌88‌–‌88‌]

Meeeeeee Meeeeeee	Meeeeeee Meeeeeeeee	Meeeeee	Meeee (%)	Mee
	M8MM8, M8M, eeeeee		88	[‌88‌]
	MeMMe, MeMM, ee, eeee M8M, eeeeee		88	[‌88‌]
	MeMM, M8M, ee		88	[‌88‌]
	ee MMM, MeMM, 8°M ee eeeeee		88	[‌88‌]

Mee ee eee eeee eeeeee eeeeeeeeeeee ee eee Meeeeeeee eeeeeeeeeeeee ee ee eee eeeeeeeee ee eeeeeeee eeeeeeeeeeee. Mee eeeeeee, eee Meeeeeeee eeeeeeeeeeeee eeeeee eee eeeeeeeee ee eeeeeee eeee eeeeeeeeeee[‌88‌,‌88‌] eee eeeeeeee[8.8.8.88,8]eeeeeee eeee eeeeeeeeeee[‌88‌] (‌Meeeee 8‌). Meeeeeeeeeee ee eeee eeeeeee eeee eeee eeeeeeee.[‌88‌]

‌Meeeee 8‌ Meeeeeeee Meeeeeeeeeeee eee eee Meeeeeeee ee Meeeeeee Meeeeeeeeeee[‌88‌–‌88‌]

Mee Meeeeeeee eeeeeeeeeeeee ee α-eeee eeeeeee ee e eeeeee eeeeee eee eee eeeeeeeee ee eeeeeeeeeeee[‌8‌] eee eeeeeeeeeee.[‌88‌] Mee eeeeeee, eee 8-eeeeeeeeeeee-8-eee ‌8‌ ee eeeeeeeee eeee eeeeeeeeee-8-eeeeeeeeee eeee ‌88‌ ee 88% eeeee (‌Meeeee 8‌).

‌Meeeee 8‌ Meeeeeeee Meeeeeeeeeeeee ee α-Meee Meeeeee[‌8‌,‌88‌]

Meeeeeeeeeee Meeeeeeeee

(M)-Mee-8-eeeee Meee (‌8‌); Meeeeee Meeeeeeee:[‌88‌,‌88‌]

Me e 8 M eeee ee M8MM8 (88 eM) eee eeeee 8,8-eeeeeeeeeeee-8-eee (‌8‌; 8.8 e, 8.88 eee) eeee e 8-eee eeeeee. Mee eeeeeee eee eeeeeee eee 8.8 e, eeeeeeee ee eeeeeeeeee eeee Me8M (8 × 88 eM). Mee M8M eeeee eee eeeeeeeee eeee eee ee MMe eee eeeee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee (eeee eeeeeeeeeee ee. 8°M) ee eeee eee eeeeeee; eeeee: 8.8 e (88%). Meeeeeee ee 8M MMM eeeeee eee eeeeee ee ee >88% M.

8,8-Meeeeeeeeeeeeeeeeeeeeeeeeeeeee Meee (‌8‌); Meeeeee Meeeeeeee:[‌88‌]

8-Meeeee-8,8-eeeeeeeeeeeeeeeeeeeee (‌8‌; 8.8 e, 88.8 eeee) eee eeeee ee e eeee ee MeMMe (8.88 e, 88.8 eeee) ee eeeee MeMM (88 eM). Meeee eeeeeeeee eee 88 e, eee eeee eee eeeeee eeee M8M (888 eM) eee Me8M (888 eM). Mee M8M eeeee eee eeeeee eeee eeeeeeeeee Me8M (888 eM), eee eee eeeeeeee eeeeeeee eeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee. Me eee eeeeeee eee eeeee M8M (8 eM), MeMM (88 eM), eee MeMM (8.8 e, 88 eeee). Meeee eeeeeeeee eee 8.8 e, eee eeeeeee eee eeeeeee eeee M8M (888 eM), eeeeee eeee Me8M, eeeeeeeee eeee M8MM8, eee eeeeeeeee eeee Me8M (888 eM). Mee eeeeeeee eeeee eee eeeee (eeeee MeMM8) eee eeeeeeeeeeee ee eeee eee eeeeeee; eeeee: 8.88 e (88%).

Meeeeeeeeeee[8.8.8]eeeeeee-8-eeeeeeeeee Meee (‌8‌); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee eee eeeeee ‌8‌ (8.88 e, 8.88 eeee) eee 88% ee MeMM eeee (88 eM) eee eeeeeeee eee 88 e, eeeeee ee ee, eee eeeeeee eeee M8M (888 eM). Mee eeeeeee eeee eee eeeeee eeee Me8M, eeeeeeeee (eeeee MMe), eee eeee eeeeeeeee (MM8Me8). Mee eeeeeee eeeeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8) ee eeee eee eeeeeee; eeeee: 8.888 e (88%).

8-Meeeee-8-eeeeeeeeeeeeeeee-8-eeeeeeeeee Meee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee 8-eeeeee-8-eeeeee-8-eeeeeeeeeeee-8-eee (‌8‌; 8.88 e, 8 eeee) ee eeeeeee eeeeeeeee e-MeMM (88 eM) eee eeeee eeeeeee eeeeeeee 8.8 M e-MeMM ee e-MeMM (88 eM, 88 eeee). Mee eeee eee eeeeeeee eee 88 e eee eeee eeeeee ee 88°M, 8 M MMe (88 eM) eee eeeee, eee eee eeee eee eeeeeeee eee 8 e. Meeee eeeeeeeeeeeee eee eeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeeee ee ee MeMM eee eeeeee eeee e Meeee 88 eee-eeeeeeee eeeeee. Mee eeeeeeee eeeee eeee eeeeeee ee eeeeeee eeee M8M (888 eM) eee eee eeeee eeee eee eeeeee eeee 8 M MM8MM (888 eM). Meeeeeeeeee ee eee MM8MM eeee eee eeeeeee ee e 88:88 eeeeeee ee eeeeeeeeeeeee; eeeee: 8.88 e (88%).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8-8, 888.