Cadogan, J. I. G. published the artcileThe production of 1,4-dialkylpiperazines by the thermal decomposition of 1,1,4,4-tetraalkylpiperazinium salts, COA of Formula: C5H13Cl2N, the publication is Journal of the Chemical Society (1955), 2971-3, database is CAplus.
Several 1,1,4,-4-tetraalkylpiperazinium dihalides were prepared and their pyrolysis products studied. All the dichlorides investigated gave the 1,4-dialkylpiperazine and alkyl chloride in 72-88% yield at atm. pressure. The dibromides under comparable conditions gave lower yields. Et2NCH2CH2Cl.HCl (0.5 mole) added to a vigorously stirred ice-cold mixture of 500 ml. H2O and 250 ml. Et2O, treated with solid Na2CO3, and the layers separated yielded from the dried (MgSO4) Et2O layer a yellow oil which, refluxed with 250 ml. EtOH 3 hrs., gave 80% 1,1,4,4-tetraethylpiperazinium dichloride (I), plates, m. above 300° (from MeOH/acetone). Similarly, MeEtNCH2CH2Br.HBr gave 65% 1,4-diethyl-1,4-dimethylpiperazinium dibromide, m. 295° (from aqueous EtOH), and (CH2Br)2 with (CH2NMe2)2 in EtOH gave 83% 1,1,4,4-tetramethylpiperazinium dibromide (II), m. above 330° (from aqueous EtOH). Ethylene oxide (40 g.) passed into 101 g. NHPr2, 20 ml. N H Cl added, and the mixture, which became dark, kept 2 hrs. at 60°, yielded from the organic layer 75% Pr2NCH2CH2OH, b20 90-2° nD25 1.4375, converted into Pr2NCH2CH2Cl.HCl with excess SOCl2 in dry C6H6 at 0°. The free base was isolated and converted as above to 51% 1,1,4,4-tetrapropylpiperazinium dichloride (III), m. 295° (from EtOH/EtOAc). Similarly, ethylene oxide and NHBu2 gave 68% Bu2NCH2CH2OH, b10 104°, nD25 1.4422, converted to 47% 1,1,4,4-tetrabutylpiperazinium dichloride monohydrate (IV), m. 239° (from aqueous EtOH-EtOAc). Me2NCH2CH(OH)Me was converted into Me2NCH2CHMeCl.HCl by the method of C.A. 42, 4934i and the latter converted to 65% hexamethylpiperazinium dichloride (V), m. 275° (from EtOH-C6H6). The tetraalkylpiperazinium salts were warmed with a free flame until decomposition began, with slight suction maintained to draw the alkyl halides into a cold trap, and the bases collected and fractionated from KOH. In this way were prepared the following 1,4-dialkylpiperazines (alkyl, % yield, b.p./mm., nD25 and m.p. of: dimethiodide given): Et, 88, 68°/10, 1.4520, 240°; Pr, 80, 84°/10, 1.4514 228°; Bu, 72, 112°/10, 1.4542, 215°; Me, 10., 130°/760, 1.4448, 310°. V gave 87% tetramethylpiperazine, b10 62, nD25 1.4522; monomethiodide, m. 251°.
Journal of the Chemical Society published new progress about 4584-49-0. 4584-49-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Salt,Amine,Aliphatic hydrocarbon chain, name is 2-Chloro-N,N-dimethylpropan-1-amine hydrochloride, and the molecular formula is C5H13Cl2N, COA of Formula: C5H13Cl2N.
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