* a-Halogenation of Ketones (22-5) This reaction if possible for any halogens (Cl,, Br, I,) under acidic conditions (acetic acid is often used). Therefore, the mechanism will proceed via the enol intermediate. oO t CH. t CH,Bi — —CH,Br o~ : cucoon FS @ + Br, > IC) + HBr SS a acetophenone ‘e-bromoxcetophenone (70%) Siey 1: The enol stacks the halogen Step 2: Deprotorstion BHO HO, HO, fc a + Hox Z ema baloger Copyright @®20"0 Pearson Prentice Hall, ne. ¢ Under basic conditions it also possible carry out this reaction. However, if more than one a-hydrogens are present, they will all be substituted. 9 x “ex, AS ts x enohwvion = + HO. Coartight © 2010 Pearson Prentice Hal, Ine ° ° 9 9 cl cl cl cl cl cl ~H Sh “cl “cl Ch “Cl OH, HO —_— —_—¢ This polyhalogenation under basic conditions is the basis of the haloform reaction producing carboxylic acid. Because the CX; group on the carbonyl is a good leaving group, acyl substitution with the hydroxide ion takes place leading to the formation of carboxylate anions. 6 6 © I | ou | R-C-cH, > [r-dox,} ro + nex, Pp e i i elie, 70H ed ot & oH suceopic uel susition sombonylte ion 4 haloorm ¢ The aldol condensation of aldehydes and ketones can also be catalyzed by acid. The enol tautomer is acting as the nucleophile in these cases. M H F . no HO on > DeacK + Ho I . FH + Thos 4 to form ne ROH resonance-stabilized intermediate aldol product¢ Dehydration of the Aldol Product (22-8) ° Aldol products, B-hydroxycarbonyls are very easy to dehydrate because the resulting product is very stable (unsaturated carbonyls). Since the aldol addition is at equilibrium, this step is usually necessary to complete the reaction. These two steps together (aldol addition + dehydration) will generate o,f-unsaturated carbonyl. ° on R-¢ocn—k heat Wor-OH ¢ The dehydration of the aldol addition product can be done under acidic or basic conditions. new double bond —= gece + [HOH dizcetone alcohol (mesityl oxide) ‘Copyignt ©2006 Pearson Prenice Hal Ie i t 9 NaOH i HySO, Z a a H O A A HoaMecha m_of the Michael Ad fo ON be ‘on ° H PoON yoy % HL $e! Loe “cH, = due cf oH FE Nie HES, Nae ce cH wey eo ? rae ana feton pon tte emanate [conyight ©2010 Pearson Preis Hal ne Example of Michael Addition ° ol Ie 1) CH;O” 2)H,0*, heat ‘OCHy och, Mechanism of Robinson Annulation Sep f Michel wditon s cay See A, Step 2° Cys silo frm sit-members ig. i) voteRMX: BLE RRC&: RRCUL 2) a Réactions d’addition nucléophile (AN) (Ennien basique) En miliew acide ) oe [D2 ROW, Dil I 1) Composts azote ceaOy 2)440 eo oN etal: Cétal mines; Enamines, (Cyanhidrine) (@cyclique \Oximes: Hydrazones) =O: desire = Oxydants classiques: KMnO4; KyCr30-; CrOy; INOS Aldéhydes Cétones Acie m-shloroperony-benzoique (m-CPBA) + Onidaatssélectfs: Réactf de Tollens; Reactif de Febiing| (Oxydationspécifique dela fonction aldehyde) Fae TSéactions de réduction Réaction de réduction IR] + NaBH, récnctenr moins réactif plus sélectf(carbonyle) Réduction - LiAIH, réducteur plus réactif moins sélectif Clemens - (OiPr),Al ou Na ou Mg Zug HC - H/Pa de Réactions liées a la mobilitée des hydro genes ena du carbonyle ‘Réactions Lées & la motilité de Hajphs du carbonyle Liaison: C-C, CN, C-0, C8) EN a GEENESICS saauon 4 E> Addition 2 eT Eames ba ‘Halogénation jusqu' quilaya plus dBen alpha Tate ae] saetiyles (3H Views Ialoorme R.COO'+ CHX:Mechanism. We show the mechanism of a Michael addition reaction in Figure 18.82 using a general example. Figure 18.82 pseu! 4 goa | vee Lust F RP, Relate Enttawaiatiy YF No Pe me SE (Head Malu)