* conc. H2 SO4 , KMnO 4 , H + , heat * KOH, ethanol, heat + CO2 + H2O + O=CH2 (ALKENE) 1 CH3CH=CH2 CH3CH2CH2Br CH3CH2CH3 (oxidative cleavage) (halogenation) OXIDATION CH3CHCH2 Br Br CH3CHCH2 OHBr CH3CHCH2 OHOH CH3CHCH3 Cl CH3CHCH3 OH CH3CHCH3 OH O CH3C OH O CH3C H CH3CHCH3 Br Markovnikov’s rule Anti-Markovnikov’s rule * Saytzeff’s rule
Cl 2 ,FeCl 3 Conc HNO 3 , Conc H 2SO 4 50 -55 o C CH 3Cl,AlCl 3 NO 2+ H 2 O H 3 C CO Cl , AlCl 3 + HCl CO C H 3 + HCl C H 3 Br 2 , uv KMnO 4 , H + Δ C H 2 Br + HBr COOH Cl+ HCl Benzene Alkylbenzene H Cl CH 3 + Cl H 3 C CH 3Cl,AlCl 3 NO 2 Cl Cl 2 ,FeCl 3
Nucleophilic Substitution Reactions of R−X With aqueous solution of NaOH R–X + NaOH(aq) R−OH + NaX R–X + excessNH3 (1ᵒamine) R–NH2 +HX With alcohol (ROH) R–X + ROH R−OR + HX With H2O R–X + 2H2O R−OH +X− +H3O+ With KCN in alcohol, reflux R– X + KCN R−CN + KX ROH R–X + −OR R−OR + X− R–X + CH3COO− CH3COOR + X − With CH3COO− With excess NH3 With RO− 3
USES OF RMgX 1° alcohol alkane 2° alcohol methanal aldehyde Preparation of Alkane Preparation of 1° Alcohol Preparation of 2° Alcohol 4
USES OF RMgX 3° alcohol Preparation of 3° Alcohol carboxylic acid Preparation of Carboxylic Acid ketone carbon dioxide 5
H3 CCH2 Cl H3 CCH2 OCH3 H3 CCH2 CN H3 CCH2 NH2 H3 CCH2 OH H3 CCH2 OH H3 CCH2 OCH3 H3 C CH2 OCCH3 O + Mg NaOH(aq) CH3 OH CH3 O - CH3 COOdry ether H3 CCH2MgCl H3 CCH3 H3 CCH2 CH2 OMgCl H3 CCH2 CH2 OH KCN, ethanol NH3 excess H3 O + H C H O H3 O + CO2 H3 CCH2 C O OMgCl H3 O + H3 CCH2 C O OH H3 CCH O H3 CCCH3 O H3 C CHCH2 CH3 OMgCl H3 CC CH3 OMgCl CH2 CH3 H3 O + H3 O + H3 C CHCH2 CH3 HO H3 CC CH3 OH CH2 CH3 2H2O