Elucidation of the structures of 3-alkylthio-, 3-benzylthio-, 2-arylthio- and 2-heteroarylthio-N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamines by one- and two-dimensional NMR spectroscopy.
Nucleophilic addition of alkyl- and benzylthiols to benzoquinone diimine (1) gave the corresponding 3-alkylthio- or 3-benzylthio-1,4-phenylenediamines (2-5). However, addition of aryl- or heteroarylthiols to 1 formed 2-arylthio- or 2-heteroarylthio-1,4-phenylenediamines (6-14). The structures of 2-14, obtained in 55-91% yields, were confirmed in CDCl3 or DMSO-d6 solution using 1D (NOE difference, coupled 13C NMR spectra, APT and DEPT) and 2D NMR techniques [DQCOSY, NOESY, HETCOR and heteronuclear multiple bond coherence (HMBC)] that resulted in unambiguous proton and carbon NMR resonance assignments. The substituent-induced 13C NMR chemical shift differences were calculated in 2-14 relative to carbon atoms in the model compound N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamine (DMBPPD) (15) (a reduced form of benzoquinone diimine).
Katritzky
Alan R
AR
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, USA. katritzky@chem.ufl.edu
Akhmedov
Novruz G
NG
Abdel-Fattah
Ashraf A A
AA
Wang
Mingyi
M
Rostek
Charles J
CJ
Maender
Otto W
OW
D002247:Carbon Isotopes; D006841:Hydrocarbons, Aromatic / Q000032:analysis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular; D008968:Molecular Conformation; D010655:Phenylenediamines / Q000032:analysis* / Q000737:chemistry* / Q000145:classification
D002247:Carbon Isotopes; D006841:Hydrocarbons, Aromatic; D010655:Phenylenediamines