15597ch21.373-38811/7/0514:44Page382 EQA 382.chapter 21 AMINES AND THEIR DERIVATIVES:FUNCTIONAL GROUPS CONTAINING NITROGEN H.CCH NHCH HCH.CCH H COH, 46. 2.NaOHL.H.O CHaN(CH)go..A Mannich reaction Hofmann elimination The Mannich reaction-Hofmann elimination sequence isa useful synthesis of B-unsaturated ketones CHCH' CH CHCI CH.CHOH 丝达o】 CH,C电9 NO46. The Mannich reaction–Hofmann elimination sequence is a useful synthesis of
, -unsaturated ketones. 47. (a) All possible products of And, after hydride shift to (d) N NO CH OH CH3CH2 CH3CH2 Cl 3CH2 CH3CH2 CH3CHCl CH3CHOH CH3CH So, CH2 CH CH3CH ! O 1. CH2 O, (CH3)2NH, HCl, CH3CH2OH 2. NaOH, H2O Mannich reaction O 1. CH3I, 2. Ag2O, H2O,  Hofmann elimination CH2N(CH3)2 O CH2 Second Mannich H H H CH2 OH CH2 C NCH3 tropinone After enolization NHCH3 CH2CCH3 O H Proton transfers H H H OH2 H2O O CH2CCH3 NCH3 O 382 • Chapter 21 AMINES AND THEIR DERIVATIVES: FUNCTIONAL GROUPS CONTAINING NITROGEN 1559T_ch21_373-388 11/7/05 14:44 Page 382