° ° I cugcrcnc=cs — CHSCCHCHAC=CCH, (a) Protection of carbonyl group | CHCCH,CH,C=cii HOCH:CH.OH ae walewoaca st teme S-Hexyn-2-one Acetal of reactant (80%) (b) Alkylation of alkyne b> san (y ou, Lo HyC’ ‘CH,CH,C=CH H,C’ ‘CH,CH,C=C: jC’ CH,CH»C=CCH; Acetal of product (78%) (c) Removal of the protecting group by hydrolysis UP 105 + dO ° HC’ “CH,CH;C=CCH, 22+ CHyCCHjCH;C=CCH Base de Schiff N-substituted = Water imine i CH + CH,NH, —> € \-cr-sers Benzaldehyde Methylamine —_-N-Benzylidenemethylamine (70%) (0 + (CH3)2CHCH2NH, —> (scree Cyclohexanone Isobutylamine N-Cyclohexylideneisobutylamine (79%)i Mex 08 diethyl ether b+ Grignard reagent acts as a nucleophile toward carbon dioxide Hydration of an Aldehyde or Ketone in Basic Solution we Overall reaction: \ =0: + HO: == ‘C—OH é f Aldehyde Water Geminal or ketone diol STEP 1: Nucleophilic addition of hydroxide ion to the carbonyl group. R RR H6r ac) 22 “tor KX ug: Hydroxide Aldehyde Alkoxide ion or ketone intermediate STEP 2: Proton transfer from water to the intermediate formed in step 1. RR RR Ne S-F6u = \t-0-H + 70H HO: HO: ’ .Reaccion aldol 0 I 2CH,CH,CH,CH “ORES, HCH CRACK Butanal Las condensaciones con aldehidos aromaticos se ven favorecidas por el aumento de la conjugacién, estas reacciones se conocen como condensaciones de Claisen-Schmidt i » enol he (CH3);CCCH;CH; _— (CH sOOGH—CHCHCH, CH, 2.2-Dimethyl-3-pentanone Sydroy.224imety a halogenacion de compuestos carbonilicos O° °°Reaccion de Wittig RA Ye’ + HPO R _A bo + Cane x ete lide Aline oxide (0 + (C.H.)P—CH, 2S (ct, + (CH)P—O- phosphorane (86%) oxide Oxidacion de Baeyer-Villiger 7 vo i q RCR’ + R'COOH —> RCOR’ + R'COH Ketone _Peroxy acid Ester__ Carboxylic acid ° I catdoon i con, SS (oben, (Cyclohexy! methy! ketone Cyelohexyl acetate (67%) —CHs —CH.R —CHR2 —CR3 Metiyt Primary Secondary Tertiary alkyl allyl alkyl Reaccion del haloformo La halogenacién de compuestos carbonilicos también puede hacerse en medio basico, en este caso suele usarse exceso de halégeno y el compuesto formado es cloroformo, bromoformo o yodoformo dependiendo de cual halégeno se use. oO Oo RACER = act x Aldehyde or ketone Halo aldehyde or ketoneAdicidn de Michael cit CH, ° LG ° I gy, Row CCC + H.C=CHCCHs Sina? ‘oO O 2-Methyl-13- ‘Methyl vinyl 2-Methyl-2-(3'-oxobutyl)- ‘cyclohexanedione ‘ketone 1,3-cyclohexanedione Este producto puede reaccionar intramolecularmente mediante una condensacién aldolica. Cuando esto sucede, el producto formado es ciclico y hablamos de una reaccién llamada Robinson annulation. Robinson Annula . E cts CH CH ine CO = CB, ‘oO 2-Methyl-2-(3'-oxobutyD- Intramolecular aldol addition 1,3-cyclohexanedione product; not isolated Uplos anc = Reaccion de Hell-Volhard-Zelinsky eS RCCOH + Bh ™% R,CCOH + HBr | | Br HE «Bromo Hydrogen carboxvlic acid ‘bromide 1HyCH,CH,CO3H “> CHLCHIAHOO ne CHLCHRHICO Br on Botanoic 2-Bromobetancic ‘2-Hydronybutancic acid acid 77%), acid (69%) (CHi):CHCHCOnH ex? (CHa) CHEHCORH gh (CHa) CHCHCOat Br NH) 3-Methylbutanoic 2-Bromo-3-methylbutanoic 2-Amino-3-methylbutanoic acid acid (88%) acid (48%)Descarboxilacién RCO > RH + CO; Cloruros de dcido 1 f RCOH + SOCl —> RCCl + SO, + HCl Casborstic Thionyl Acyl Sulfur. Hydrogen chloride chloride dioxide chloride Oo oO I ll (CH3),CHCOH 2s (CH),CHCCL 2-Methylpropanoic acid 2-Methylpropanoyl chloride (90%)Name of reagent ‘Type of product Example 9 NOH H.NOH Hydroxylamine Oxime cnycH.t amt, cHsct.te Heptanal Heptane! oxime (81-93%) NNNHC.Hs hawks atrinin Pitas (don sts 7) i Acetophenone ‘Acetophenone ‘phenyinydrazone (87-91%) 9 nnd (CH2)oCHs 2.Dodecanone. ‘semicarbazone (93%) ° HaNNHENH, ‘Semicarbazide ‘Semicarbazone CHSCICH.ISCHs surnla, 2.badecanone Reacci6n de Horner-Emmons 9° 0° we HR? base / solvent Re Rib re| RY OR I + RB 0-110°C a RoR! RO NaH, KH, KHMDS, NaHMDS Atkene LHMDS, KOFBu R' = aryl, alkyl; R? = alkyl, aryl, COR, COR, CN, SOR ‘= __Homer-Wittig reaction R! = O-aryl, O-alky, NRp; R? = aryl, alkenyl, COR, COZR, CN, SO;R ‘=> Wadsworth-Emmons reaction