title: Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.
abstract: Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.
authors.affiliation: NamiTek Specialty Materials Corporation, 13 Milldam Road, Acton, Massachusetts 01720, USA. chenghong_li@outlook.com
authors.forename: Chenghong
authors.initials: C
authors.lastname: Li
mesh_terms: D000478:Alkylation; D000588:Amines / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry
chemical_list: D000588:Amines; D009569:Nitric Oxide