TY - JOUR
T1 - A nitrogen-15 NMR study of hydrogen bonding in 1-alkyl-4-imino-1,4-dihydro- 3-quinolinecarboxylic acids and related compounds
AU - Carlton, Laurence
AU - Staskun, Benjamin
AU - Van Es, Theodorus
PY - 2006/5
Y1 - 2006/5
N2 - 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 13N-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.
AB - 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 13N-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.
UR - http://www.scopus.com/inward/record.url?scp=33646364058&partnerID=8YFLogxK
U2 - 10.1002/mrc.1760
DO - 10.1002/mrc.1760
M3 - Article
C2 - 16489550
AN - SCOPUS:33646364058
SN - 0749-1581
VL - 44
SP - 510
EP - 514
JO - Magnetic Resonance in Chemistry
JF - Magnetic Resonance in Chemistry
IS - 5
ER -