A nitrogen-15 NMR study of hydrogen bonding in 1-alkyl-4-imino-1,4-dihydro-3-quinolinecarboxylic acids and related compounds.
The title compounds contain groups (amine, amide, imine, carboxylic acid) that are capable of forming intramolecular hydrogen bonds involving a six-membered ring. In compounds where the two interacting functional groups are imine and carboxylic acid, the imine is protonated to give a zwitterion; where the two groups are imine and amide, the amide remains intact and forms a hydrogen bond to the imine nitrogen. The former is confirmed by the iminium 15N signal, which shows the coupling of 1J(15N,1H) -85 to -86.8 Hz and 3J(1H,1H) 3.7-4.2 Hz between the iminium proton and the methine proton of a cyclopropyl substituent on the iminium nitrogen. Hydrogen bonding of the amide is confirmed by its high 1H chemical shift and by coupling of the amide hydrogen to (amide) nitrogen [(1J(15N,1H) -84.7 to -90.7 Hz)] and to ortho carbons of a phenyl substituent. Data obtained from N,N-dimethylanthranilic acid show 15N-1H coupling of (-)8.2 Hz at 223 K (increasing to (-)5.3 Hz at 243 K) consistent with the presence of a N... H-O hydrogen bond.
Carlton
Laurence
L
Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, P.O. Wits, 2050, South Africa. carlton@aurum.chem.wits.ac.za
Staskun
Benjamin
B
van Es
Theodorus
T
D002264:Carboxylic Acids / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D009587:Nitrogen Isotopes / Q000032:analysis; D011804:Quinolines / Q000737:chemistry*
D002264:Carboxylic Acids; D009587:Nitrogen Isotopes; D011804:Quinolines; C037219:quinoline