Mechanism of hydrolysis and alcoholysis of 2-ethoxy-N-vinylpyrrolidiniminium tetrafluoroborate

Abstract

iV-Vinyl-2-ethoxypyrrolidiniminium tetrafluoroborate, 1, undergoes rapid hydrolysis to give acetaldehyde and ethyl 2-aminobutyrate, 2. Imidate 1 reacts with methanol or ethanol, however, to give the N-(l-alkoxyethyl)-2-alkoxypyrrolidiniminium tetrafluoroborate 7 or 9, respectively. Both hydrolysis and alcoholysis appear to be pseudo first order and the mechanism of each can be explained by initial formation of an "enamine-like" intermediate. The mechanism of both reactions is presented.

Five-, Six-, and Seven-membered Lactim Ethers. Methods of Synthesis and Chemical Properties. (Review)

“…The heating of lactams with dimethyl sulfate [2][3][4][5][6][7][8][9][10][11][12][13][14][15], or more rarely diethyl sulfate [4,5,[15][16][17], is the most widely used method for the synthesis of lactim ethers (Table 1).…”

“…The second method in frequency of use for the production of lactim ethers is the treatment of lactams with trialkyloxonium fluoroborates 4 at 20-25°C [3,4,[16][17][18][19][20][21] (Table 2).…”

“…The salts of the lactim ether 24, formed with high yields by the action of gaseous hydrogen chloride (diethyl ether, 25) or hydrofluoroboric acid (methylene chloride, 5°C) on the corresponding lactim ethers, are converted by the action of water at room temperature into the salts of the esters of ω-amino carboxylic acids 25 [16,17]. The reaction of valerolactim methyl ether with methyl fluorosulfonate (9) gives an 80% yield of the fluorosulfate 26 [24,39] …”