54815-12-2Relevant academic research and scientific papers
Nickel-catalyzed direct synthesis of dialkoxymethane ethers
Subaramanian, Murugan,Bera, Abhijit,Prasad, Bhagavatula L V,Balaraman, Ekambaram
, p. 1153 - 1159 (2017/08/26)
221A simple and efficient method for the preparation of dialkoxymethane ethers (oxymethylene ethers) from alcohols and paraformaldehyde in the presence of commercially available nickel(II) salt is described. The reaction proceeds readily under neutral, solvent-free conditions using paraformaldehyde as a C 1 source. The present strategy has a broad substrate scope including aliphatic (both primary and secondary) and aromatic alcohols and provides a benign method for the preparation of symmetrical dialkoxymethanes in good yields (up to 89%). Graphical Abstract: SYNOPSIS A facile nickel-catalyzed synthesis of dialkoxymethane ethers from alcohols and paraformaldehyde using inexpensive, commercially available NiBr 2 is reported. The reaction proceeds readily under mild, neutral and solvent-free conditions. [Figure not available: see fulltext.].
An efficient method for the preparation of dialkoxymethanes from dichloromethane with alcohols catalyzed by a Cu-NHC complex
Zhan, Lewu,Pan, Renming,Xing, Ping,Jiang, Biao
supporting information, p. 4036 - 4038 (2016/08/18)
A facile, rapid and efficient method for the preparation of dialkoxymethanes from dichloromethane with alcohols catalyzed by a Cu-NHC complex is reported. A variety of symmetrical dialkoxymethanes can be prepared under mild condition in excellent yields (up to 98%). The unsymmetrical ether is also obtained in 89% yield from the etherification of p-tolylmethanol and n-butyl chloride catalyzed by ICyCuCl complex at 80?°C. The reaction provides a new method for the preparation of dialkoxymethanes under mild conditions in excellent yields.
Formation of Δ4-oxocenes from Lewis acid promoted cyclizations of 5-hexenyl acetals. Evidence for a concerted ene cyclization mechanism
Blumenkopf, Todd A.,Look, Gary C.,Overman, Larry E.
, p. 4399 - 4403 (2007/10/02)
Both the intermolecular (kinetic) and intramolecular (product) hydrogen-deuterium isotope effects were determined to be 1.65 for the formation of 2-methyl-4-(trimethylsilyl)-Δ4-oxocene (20) from the SnCl4-promoted cyclization of acetals 19, 30, and 31 (eq 6). In other experiments silyl acetal 32 was found to cyclize in the presence of SnCl4 to form the silyl-Δ4-oxocene 34 and the alkylideneoxepane 35 in 2:1 ratio (eq 7). Both results provide strong evidence that the formation of 4-(trimethylsilyl)-Δ4-oxocenes from SnCl4-promoted cyclizations of 5-(trimethylsilyl)-5-hexenyl acetals takes place by a concerted intramolecular ene mechanism. Also reported are SnCl4-promoted exchange reactions of formaldehyde- and aldehyde-derived acetals, which occur readily at -10 to 0 °C and -70 °C, respectively (eqs 2 and 3).
