Organic Chemistry City University of New York纽约市有机化学城市大学.pptVIP

Preparation via Azides Alkylation of azide ion. Overall Alkyl Halide ? Alkyl amine Example: Preparation via Azides Alkylation of azide ion. Note retention of configuration, trans ? trans Reaction with HNO2 Nitrous acid, a weak acid, is most commonly prepared by treating NaNO2 with aqueous H2SO4 or HCl. In its reactions with amines, nitrous acid: Participates in proton-transfer reactions. A source of the nitrosyl cation, NO+, a weak electrophile. Reaction with HNO2 NO+ is formed in the following way. Step 1: Protonation of HONO. Step 2: Loss of H2O. We study the reactions of HNO2 with 1°, 2°, and 3° aliphatic and aromatic amines. Tertiary Amines with HNO2 3° Aliphatic amines, whether water-soluble or water-insoluble, are protonated to form water-soluble salts. 3° Aromatic amines: NO+ is a weak electrophile and participates in Electrophilic Aromatic Substitution. Secondary Amines with HNO2 2° Aliphatic and aromatic amines react with NO+ to give N-nitrosamines. carcinogens Mechanism: RNH2 with HNO2 1° aliphatic amines give a mixture of unrearranged and rearranged substitution and elimination products, all of which are produced by way of a diazonium ion and its loss of N2 to give a carbocation. Diazonium ion: An RN2+ or ArN2+ ion 1° RNH2 with HNO2 Formation of a diazonium ion. Step 1: Reaction of a 1° amine with the nitrosyl cation. Step 2: Protonation followed by loss of water. 1° RNH2 with HNO2 (Aliphatic) Aliphatic diazonium ions are unstable and lose N2 to give a carbocation which may: 1. Lose a proton to give an alkene. 2. React with a nucleophile to give a substitution product. 3. Rearrange and then react by Steps 1 and/or 2. 1° RNH2 with HNO2 Tiffeneau-Demjanov reaction: Treatment of a ?-aminoalcohol with HNO2 gives a ketone and N2. Mechanism of Tiffeneau-Demjanov Reaction with NO+ gives a diazonium ion. Concerted loss of N2 and rearrangement followed by proton transfer gives the ketone. Similar to pinacol rearrangement Pinacol Rearra