The Mechanism of the Alkylation of Paraffins. II. Alkylation of Isobutane with Propene, 1-Butene and 2-Butene

Abstract

ALKYLATION OF ISOBUTANE WITH PROPENE, BUTENE AND %BUTENE 275Treatment of the lactone with methyl-alcoholic ammonia at room temperature furnished the crystalline amide of 2,3,5-trimethyl-Z-arabonic acid in good yield and established the furanose structure of the original pentosid:; m. p. 136' (from acetone); specific rotation +Zoo (18 , c 2, water).Anal. Calcd. for CsH1706N: OCHI, 44.9; N, 6.7. Found: OCHB, 44.9; N, 6.8.Identification of 2,4-Dimethyl-d-galactose.-Fraction VII, Table 11, crystallized spontaneously and was dissolved in methyl alcohol. Partial crystallization took place upon standing and recrystallization from methanol gave ~-methyl-2,4-dimethyl-d-galactoside; m. p. 165' : specific rotation not measurable (ZOO, G 5, water). The residual sirup freed from methyl alcohol, partially crystallized from acetone solution and after recrystallization from the same solvent furnished cr-methyl-2,4-dimethyl-d-galactoside; m. p. 105°,8 specific rotation +145O (ZOO, c 2, water). Hydrolysis of both isomers, and the residual sirup (2 g.) with 25 cc. of .N sulfuric acid on a boiling water-bath for ten hours gave 2,4-dimethyl-galactose and this, upon treatment with aniline (1 cc.) in ethanol solution under reflux for three hours, gave the anilide upon removal of solvent. Recrystallization from methanol furnished the anilide of 2,4-dimethyl-d-galactose in good yield; m. p. 215 O.9Summary 1. The methyl ether of mesquite gum has been prepared by treatment of the polysaccharide with dimethyl sulfate and alkali.Methanolysis of mesquite gum methyl ether using methanol-hydrogen chloride yields a sirup which is shown to contain 2,3,5-trimethyl-methylarabinoside, 3,5-dimethyl-methyl~arabinoside, 2,4-dimethyl-methyl-galactoside and 2,3,4-trimethyl-methyl-glucuronoside.3. The ratio of the above components was found to be as 1:3:2:1, respectively. The ratio of arabinose t o galactose t o methoxy-glucuronic acid in mesquite gum is therefore 4:2:1. (3) J. P. N o d s and B. M. Sturgis, ibid., 61, 1413 (1939).

Stability, Deactivation, and Regeneration of Chloroaluminate Ionic Liquid as Catalyst for Industrial C4 Alkylation

“…In a previous study on isobutane/butene alkylation catalyzed by solid aluminum chloride, the complex of AlCl 3 •CH 3 OH was a good catalyst and the catalytic performance was better than with AlCl 3 itself. However, the product of the complexation of aluminum chloride with two molecular proportions of methanol, i.e., AlCl 3 •2CH 3 OH, was not catalytically active for alkylation [21,22]. This conclusion was consistent with the result in this work.…”

On the mechanism of catalyzed isobutane/butene alkylation by zeolites

“…Fig. 13 displays the basic alkylation mechanism as adapted from Schmerling [22,23]. The product distribution is governed by the relative rates of the three individual steps, i.e., alkene addition, isomerization, and hydride transfer.…”

Liquid-phase isobutane alkylation with butenes over aluminum chloride complexes synthesized in situ from activated aluminum and tert-butyl chloride

“…All spectra were obtained on a NICOLET 5700 spec trometer (Thermo Fisher Scientific). Table 1 lists parameters of the liquid phase alkyla tion of isobutane with butenes in the presence of alu minum chloride complexes formed in situ in liquid isobutane at different TBC : Al* molar ratios and a temperature of 353 K. Table 1 includes the results of isobutane alkylation with 2 but 2 ene over AlCl 3 from two other studies [10,11]. Both of these studies were carried out in a well stirred reactor, with the difference that an equimolar amount of HCl was additionally used in one of them [10] according to the presumed reaction mechanism [12].…”