Amino compounds Nomenclature alkylamine dialkylamine trialkylamine primry secondary tertiary methylamine ethylamine aniline ethylmethylamine triethylamine N-methylaniline N,N-dimethylaniline p-aminobenzoic acid. kys. sulfanilic acid p-toluidine p-anisidine o-phenylenediamine p-phenylenediamine Amino compounds amonium salts quarternary amonium salts butylamonium bromide ethylmethylamonium hydrogensulfate triethylamonium pikrate anilinium perchlorate triethylmethylamonium bromid butylethylphenylmethylamonium chloride Amino compound Reactivity 1.basic and nucleophilic properties – reactions with proton and elektrophiles 2.exceptional reaction with nitrous acid 3.hydrogen atoms at nitrogen are acidic 4.hydrogen bonds with nitrogen atom (weaker than at alcoholes) 5. characteristic vibration in infrared spectrum: valence vibration N-H prim. amine – two bands (region 3300 – 3500 cm-1) sek. amine - only one band tert. amine - without any band vibration C-N alifatic amines 1020 – 1220 cm-1 aromatic 1250 – 1350 cm-1 Fil036 Amino compounds Fil037 nN-H = 3300-3500 cm-1 Amino compounds Fil038 nC-N = 1250 – 1350 cm-1 Amino compounds Amino compounds 1.basic and nucleophilic properties – reactions with proton and elektrophiles 2.exceptional reaction with nitrous acid 3.hydrogen atoms at nitrogen are acidic 4.hydrogen bonds with nitrogen atom (weaker than at alcoholes) 5. Amino compounds Amino compounds Amino compounds 4-(N,N-dimethylamino)-4’-nitroazobenzene Amino compounds diazoaminocompounds diazoaminobenzene returning back Aminosloučeniny the strong base is searching the most acidic proton (Hofmann rule for eliminations) and the least substituted alkene is produced Amino compounds OXIDATION Amino compounds Amines as nucleophiles Amino compounds „isonitril test“ a proof of amino group in biological material Amino compounds ENAMINES tautomerism application in synthesis: they are used as propriate reagents with electrophiles b-carbon has nucleophilic character (but not the nitrogen atom) tautomerization is impossible at t-derivatives Amino compounds iminium salts can be easily hydrolysed SN AdE Amino compounds PREPARATION 1.Alkylation of ammonia by the reaction of ammonia with alkyl halogenides is formed a mixture of primary, secondary and tertiary amino derivatives, which must be resolved: Hinsberg method: prim. a sec. react with p-toluene sulfochloride (tert. do not react) and are separated primary are soluble in alkaline solution - they are dissolved in water and are separated from secondary, which are water nonsoluble no reaction soluble in water Amino compounds 2. Gabriel method 3. Alkylation of cyanamide (sec.amines) 4. Reduction of nitro compounds (mainly aromatic) reduction agents: Zn, Sn, SnCl2, TiCl3, CrCl2, Pd/ H2 Amino compounds 5. Reduction of oximes 6. Reduction of nitriles and amides Amino compounds 7. Hofmann’s amides decomposition