Nitrogen compounds.pptVIP

Nitrogen compounds (Chapter 37) Nitrogen containing compound T.N.T. Proteins Enzymes Drugs Amines Aliphatic 1o amine 2o amine 3o amine 4o ammonium cpds Aromatic IUPAC names CH3NH2 Methanamine (CH3)2NH N-methylmethanamine (CH3)3N N,N-dimethylmethanamine C6H5NH2 Phenylamine (aniline) Formation of amines Alkylation of NH3 RX + NH3 ? R-NH2 + R2-NH + R3N + R4N+X- (NH3 in large excess, 1o amine as main product) 1o Amine from Amides and Nitriles R-C?N ? RCH2NH2 (H2/Ni or LiAlH4) RCONH2 ? RCH2NH2(LiAlH4 /ether than H+) Formation of Amines C6H5-NO2 ? C6H5-NH2 Reducing agent: H2/Ni or HCl,Fe (or Zn, Sn, SnCl2) then OH- Basicity of Amines Basicity of Amines Explanation Solvation of protonated amine in water by hydrogen bonding (more H, better solvation) NH31o2o3o Explanation Effect of the inductive electron push of the R groups Increase the basicity Stabilize the alkylammonium ion 3o2o1oNH3 Explanation Lone pair e- partly incorporated into benzene ring Less ready for protonation Reactions Salt Formation Reactions Amide Formation Reaction with Nitrous acid HNO2 prepared by NaNO2 + HCl 1o aliphatic amines Reaction with Nitrous acid 1o aromatic amine Mechanism Stability of Ar-N+?N Benzenediazonium salt C6H5-N2+ Cl- C-N bond heavily polarized away from benzene ring C atom accept Nu: (against the norm of aromatic chemistry) Has considerable synthetic value Benzenediazonium salt Can be replaced by a variety of function groups High yield No multiple substitution Coupling reaction * * CH3 NO2 NO2 NO2 R-NH2 R-N-H R’ R-N-R” R’ R + R-N-R” Br- R’ NH2 9.4 C6H5NH2 4.30 (CH3)3N 3.28 (CH3)2NH 3.33 CH3CH2CH2NH2 3.25 CH3CH2NH2 3.36 CH3NH2 pKb = 4.74 NH3 R H H N: H O H R H H N H + OH- Order of basicity: 2o 1o 3o NH3 C6H5NH2 Why? R H H N H + H2O H2O H2O R R R N: R R R N H + NH2 .. NH2 ..- + NH2 + HCl NH3+ Cl- NaOH ? NH2 + H2O + NaCl O O R-NH2 + CH3CCl ? CH3CNHR + HCl O O R-NH2 + C6H