15766-66-2Relevant academic research and scientific papers
Formaldehyde Encapsulated in Zeolite: A Long-Lived, Highly Activated One-Carbon Electrophile to Carbonyl-Ene Reactions
Okachi, Takahiro,Onaka, Makoto
, p. 2306 - 2307 (2004)
Gaseous formaldehyde is extremely unstable and readily undergoes self-polymerization to a solid paraformaldehyde or disproportionation to methanol and formic acid in the presence of moisture. We disclose a simple method to stably store such a labile formaldehyde as a monomer in a nanoporous faujasite zeolite at 5 °C for at least 50 days without self-polymerization or disproportionation. The greater stability of formaldehyde encapsulated in zeolite was confirmed by 13C MAS NMR spectroscopy. Formaldehyde was not only stabilized within the zeolite cages but functioned as a powerful electrophile toward various olefins. Zeolite-encapsulated formaldehyde was proved to be a stable but highly reactive C1 reagent. Copyright
Stabilization of reactive aldehydes by complexation with methylaluminum bis(2,6-diphenylphenoxide) and their synthetic application
Maruoka, Keiji,Concepcion, Arnel B.,Murase, Noriaki,Oishi, Masataka,Hirayama, Naoki,Yamamoto, Hisashi
, p. 3943 - 3949 (2007/10/02)
Reactive aldehydes such as formaldehyde and α-chloro aldehydes can be successfully generated by treatment of readily available trioxane and α-chloro aldehyde trimers, respectively, with methylaluminum bis(2,6-diphenylphenoxide) (MAPH), and stabilized as their 1:1 coordination complexes with MAPH. The resulting CH2=O·MAPH complex reacts with a variety of olefins to furnish ene-reaction products with excellent regio- and stereoselectivities. In addition, this complex as well as α-chloro aldehyde-M APH complexes can be utilized as a stable source of gaseous formaldehyde and reactive α-chloro aldehydes, respectively, for the nucleophilic addition of various carbanions (organometallics, enolates, etc.). Formation of reactive aldehyde-MAPH complexes is firmly confirmed by 1H NMR spectroscopy. A space-filling model of aldehyde-M APH complexes implies that formaldehyde and α-chloro aldehydes coordinated with MAPH may be electronically stabilized by two parallel phenyl groups of aluminum ligands.
