Consecutive Menschutkin Reaction of Cyclic Amines with Dichloromethane under High Pressure: Synthesis of Methylenebisamines

New dithiazinanes and bis‐dithiazinanes‐bearing pendant ethylamines: Structure and reactivity

“…15 N spectra were obtained with single pulse experiments. IR spectra were taken in KBr disk using a FT Spectrum GX Perkin Elmer spectrometer.…”

“…Each molecule presented two 15 N NMR signals for two different tertiary nitrogen atoms (δ = −346.9 ppm exocyclic, −349.9 ppm endocyclic for 7, and −335.4 ppm exocyclic −349.9 ppm endocyclic for 8, the assignment was performed by comparison with N-ethanoldithiazinane δ = −352.9 ppm [8]). 15 N NMR data indicated that the exo-nitrogen atoms have been alkylated. IR showed a small band at ν = 640 cm −1 , which could be attributed to the S S bond.…”

“…The amine quaternization by methylene chloride is not a common reaction. We have only found the reports of the formation of 1,1 -bis(pyrrolidine)-methane from pyrrolidine and methylene chloride [14], and the reaction of secondary amines with methylene chloride that requires 5 days under high pressure (6-9 kbar) to produce the corresponding R 2 HNCH 2 Cl + Cl − derivatives in 50-70% yield [15]. The extreme conditions for the reported reactions of CH 2 Cl 2 with secondary amines in contrast with the soft conditions reported here.…”

Bis[4-(2-methyl-2-propenyl)piperazin-1-yl]methane

“…It is known that dichloromethane undergoes double nucleophilic substitution. The first reaction of this type was performed with dimethylamine (Jones & Whalen, 1925) and later with diethylamine (Souquet et al, 1993;Matsumoto et al, 1984). All these reactions were conducted at high temperature; in our case the double nucleophilic substitution occurs at room temperature with a reaction time of 2-3 months.…”

Interaction of an imidazolium-2-amidinate (NHC-CDI) zwitterion with zinc dichloride in dichloromethane: role as ligands and C–Cl activation promoters

“…As mentioned before, formation of cation 2 is a very unusual reaction. It is known that some secondary aliphatic, 16 alicyclic 17 or heteroaromatic 18 amines perform similar substitution reactions but these usually requires using special conditions (e. g., very high pressures, or highly polar solvent mixtures under phase transfer conditions). Since few mechanistic studies have been reported for such reactions, 19 we built a DFT model of the reaction using a slightly simplified version of the betaine (L, see SI for details).…”