PubMed2005
Phencyclone, 1, a potent Diels-Alder diene, reacts with a series of N-alkylmaleimides, 2, to form hindered adducts, 3. The 300 MHz 1H and 75 MHz 13C NMR studies of these adducts at ambient temperatures have demonstrated slow rotations on the nuclear magnetic resonance (NMR) timescales for the unsubstituted bridgehead phenyl groups, and have revealed substantial magnetic anisotropic shielding effects in the 1H spectra of the N-alkyl groups of the adducts. The selected N-alkyl groups for the target compounds emphasized smaller branched alkyls, including C3 (isopropyl, a); C4 (isobutyl, b; and t-butyl, c); C5 (n-pentyl, d; isopentyl [isoamyl], e; 1-ethylpropyl, f; t-amyl, g;) and a related C8 isomer (1,1,3,3-tetramethylbutyl ["t-octyl"], h). The straight-chain n-pentyl analog was included as a reference. This present work on the branched N-alkylmaleimide adducts appreciably extends our earlier compilation on the N-n-alkylmaleimide adducts. Key methods for proton assignments included "high-resolution" 1H-1H chemical shift correlation spectroscopy, COSY45. 13C NMR of the adducts, 3, verified the expected number of aryl carbons for slow exchange limit (SEL) spectra of the bridgehead phenyl groups. The synthetic routes involved reaction of the corresponding amines, 4, with maleic anhydride to give the N-alkylmaleamic acids, 5, which underwent cyclodehydration to form the maleimides, 2. Magnetic anisotropic shielding magnitudes for alkyl group protons in the adducts were calculated relative to corresponding proton chemical shifts in the maleimides. Geometry optimizations for the above adducts (and for the N-n-butylmaleimide adduct) were performed at the Hartree-Fock level with the 6-31G* basis set. The existence of different contributing conformers for the adducts is discussed with respect to their calculated energies and implications regarding experimentally observed anisotropic shielding magnitudes.