title: Efficient, scalable and economical preparation of tris(deuterium)- and 13C-labelled N-methyl-N-nitroso-p-toluenesulfonamide (Diazald®) and their conversion to labelled diazomethane.
abstract: A method for the preparation of multi-gramme quantities of N-methyl-d3-N-nitroso-p-toluenesulfonamide (Diazald-d3) and N-methyl-(13)C-N-nitroso-p-toluenesulfonamide (Diazald-(13)C) and their conversion to diazomethane-d2 and diazomethane-(13) C, respectively, is presented. This approach uses robust and reliable chemistry, and critically, employs readily commercially available and inexpensive methanol as the label source. Several reactions of labelled diazomethane are also reported, including alkene cyclopropanation, phenol methylation and α-diazoketone formation, as well as deuterium scrambling in the preparation of diazomethane-d2 and subsequent methyl esterification of benzoic acid.
authors.affiliation: Carleton University, Department of Chemistry, 1125 Colonel By Drive, 203 Steacie Building, Ottawa, Ontario, K1S 5B6, Canada.
authors.forename: Samuel W J
authors.initials: SW
authors.lastname: Shields
authors.forename: Jeffrey M
authors.initials: JM
authors.lastname: Manthorpe
mesh_terms: D002247:Carbon Isotopes / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic / Q000379:methods; D003903:Deuterium / Q000737:chemistry*; D003978:Diazomethane / Q000138:chemical synthesis*; D009602:Nitrosamines / Q000138:chemical synthesis*; D019275:Radiopharmaceuticals / Q000138:chemical synthesis*; D014105:Tosyl Compounds / Q000138:chemical synthesis*
chemical_list: D002247:Carbon Isotopes; D009602:Nitrosamines; D019275:Radiopharmaceuticals; D014105:Tosyl Compounds; D003978:Diazomethane; C056772:diazalo; D003903:Deuterium
keywords: Diazald-13C; Diazald-d3; cost-effective isotope sources; deuterium exchange; diazomethane-13C; diazomethane-d2; methanol-13C; methanol-d4