Ipatieff alkylation

Ipatieff Alkylation of paraffins with superacid catalysts (commercialized for the production of kerosene in 1942)... 

Through the 19.30s, Ipatieff led UOP in its effort to develop two catalytic processes for the production of high-octane fuel alkylation and polymerization— the first, a reaction of a hydrocarbon with an olefin (double-bonded compound) the second, the formation of long molecules from smaller ones. Both processes produce high-octane blending compounds that increase the quality of cracked gasoline. 

The Heterogeneity of Catalyst Surfaces for Chemisorption Hugh S. Taylor Alkylation of Isoparaffins V. N. Ipatieff and Louis Schmerling Surface Area Measurements. A New Tool for Studying Contact Catalysts P. H. Emmett... 

Pines, H., W. D. Huntsman and V. N. Ipatieff Isomerization Accompanying Alkylation. VII. Reaction of Benzene with Methylcyclopropane, Ethylcyclopropane and with Dimethylcyclopropanes. J. Amer. chem. Soc. 73, 4343 (1951). 

The competition of the alkyl groups in p-dialkylbenzenes for ethylene provides information about the rate-controlling step in base alkylation. Early work by Pines, Vesely, and Ipatieff (19) showed that p-cymene reacted with ethylene to yield predominantly ferf-pentyltoluene. It is well known that p-cymene is almost exclusively metalated on the methyl group... 

Ipatieff and Grosse4 showed in 1936 that n-butane is isomerized to isobutane by properly promoted aluminum chloride. The importance of isobutane in the alkylation of alkenes and the possibility of converting n-alkanes of low octane values into branched high-octane alkanes for gasoline quickly resulted in much research that furnished information of both theoretical and industrial importance.5-11... 

Ipatieff and coworkers observed first that A1C13 catalyzes the destructive alkylation of aromatics with branched alkanes.179 For example, rm-butylbenzene (35%), p-di-rm-butylbenzene (25%), and considerable isobutane are the main products when benzene is reacted at 20-50°C with 2,2,4-trimethylpentane. Toluene and biphenyl are alkylated at 100°C in a similar way.180 Straight-chain alkanes required more severe reaction conditions. n-Pentane reacted at 175°C to yield 8% propylbenzene, 25% ethylbenzene, and 20% toluene.181 Phosphoric acid afforded similar products at higher temperature (450°C).182 Pentasil zeolites and dealumi-nated pentasils have been found to promote alkylation of benzene with C2—C4 alkanes to form toluene and xylenes.183,184... 

Hydrocarbons with easily abstractable hydride ion such as 1,4-cyclohexa-diene,227 cycloheptatriene,223 or compounds possessing tertiary or benzylic hydro-gen217,218,223 230 231 are suitable substitutes for silanes. In fact, this was the case in the first ionic hydrogenation observed by Ipatieff and coworkers. In an attempt to carry out alkylation of p-cymene with 3-methylcyclohexene, hydrogenation of the latter occurred, where p-cymene was the hydride ion source ... 

Ipatieff was, first of all, a brilliant and able teacher who preferred the title of Professor to any other. His research activity of a purely scientific nature brought with it unusual industrial success, and many plants, operating all over the world, are based on catalytic reactions discovered by him. Among the most important of his contributions are the introduction of high-pressure techniques in chemistry and chemical industry, destructive hydrogenation, the production of acetone from propyl alcohol, and the production of high-octane aviation fuel by the reactions of polymerization, alkylation, and isomerization. He was the first to demonstrate the specificity of catalysts and the use of mixed catalysts and promotors. 

The oldest method of alkylation with ethylene is the liquid phase reaction using anhydrous aluminum chloride as the catalyst. This reaction is a form of the classic Friedel-Crafts reaction and was discovered in 1879 by Balsohn. Most Lewis and Bronsted acids are known to be active for olefin alkylations. Alkylation by H2SO1, and H3PO1, was first shown by Ipatieff, et al, in 1936 who extended the reaction to isoparaffins. For the liquid phase alkylation of benzene with ethylene, however, aluminum chloride is preferred over the other acids, although a co-catalyst or promoter is usually needed to obtain efficient alkylation. AICI3 when dissolved in benzene containing some HCl forms a complex which can be simply described as ... 

Ipatieff and coworkers carried out the first alkylation with alkenes and branched and normal chain alkanes (except methane and ethane) in the presence of AlCb as the catalyst. The sulfuric acid catalyzed alkylation reaction of arenes and isoalkanes, developed in 1938, is a still widely used industrial process to produce alkylates with high octane numbers. For synthetic applications, however, Friedel-Crafts-type alkylations of alkenes and alkanes have limited value since they tend to give mixtures of products, including oligomers of alkenes. ... 

The reverse reaction converting monocyclic dienes to bicyclic olefins by a ring-forming internal alkylation was unknown before Ipatieff s work on cycloisomerization of limonene (5, 6) to 2,6-dimethylbicyclo-[3.2.1]-2-octene (2) (Fig. 1). We have generalized this reaction to vinyl-... 

Ipatieff, Vladimir N. (18907-1952). Basic research and development of catalytic alkylation and isomerization of hydrocarbons (with Herman Pines). 

The catalytic alkylation of saturated hydrocarbons and olefins was discovered in 1932 by Ipatieff and Pines. They employed conventional Friedel-Crafts catalyst, i.e., promoted aluminum chloride. The use of sulfuric acid as a catalyst was discovered by Birch and Dunstan in 1936. Promptly after the latter discovery, the reaction was commercialized to produce high-octane aviation gasoline from isobutane and butylenes employing not only sulfuric acid but anhydrous hydrofluoric acid. The processes were expanded rapidly during World War II to supply aviation gasoline. By the end of the war, 59 alkylation plants existed in this country with a rated capacity of... 

The catalytic alkylation of saturated hydrocarbons with olefins was discovered and developed by Ipatieff and his co-workers in the laboratories of the Universal Oil Products Company (Ipatieff, 1). Experiments were carried out in June, 1932, by Ipatieff and Pines, using aluminum chloride as the catalyst, hydrogen chloride as a promoter, and hexane and ethylene as the reactants. These experiments having given positive results, they were repeated by Komarewsky, who then also investigated the alkylation of naphthenes. The alkylation of hexane was studied quantitatively by Grosse, who extended the reaction to other paraffins and catalysts, particularly boron fluoride. 

The formation of these by-products is apparently due in part to further reaction of the primary products by dissociation into new paraffins and olefins and the subsequent reaction of these olefins with the original isoparaffin (as well as of the new paraffins with original olefin). Such reactions, which may be termed destructive alkylation, are similar to those which have been suggested to account for the products of the autodestructive alkylation of paraffins (Ipatieff and Grosse, 23). 

Alkylation with ethylene proceeds best at temperatures above room temperature and under superatmospheric pressure. Ethylation of isobutane in batch operation at 25-35 in the presence of aluminum chloride and hydrogen chloride resulted in a product that was 45% hexanes. The hexane fraction was shown to consist of 70-90% 2,3-dimethylbutane, 10-25% 2-methylpentane, and less than 3% 2,2-dimethylbutane (Grosse and Ipatieff, 25). The catalyst was converted into the typical red-brown liquid lower layer complex. 

Alkylation of n-hexane with ethylene takes place under similar conditions (Ipatieff et al., 26). It seems probable that isomerization to isohexane precedes the alkylation. 

Boron fluoride, promoted by a minor amount of hydrogen fluoride or water, seems to catalyze the alkylation of isoparaffins with ethylene at lower temperatures than does aluminum chloride (Grosse and Ipatieff, 25). The reaction of isobutaiie with ethylene to —30 to —40° and 6 atmospheres pressure yielded a liquid produet, 20% of which was hexanes, to the extent of 180% by weight of the ethylene charged. At 0-5° and 10 atmospheres pressure, a 224% yield of alkylate, 45% of which was hexanes, was obtained. Like the aluminum chloride product formed at 25-35°, the hexanes consisted of 70-90% of 2,3-dimethylbutane, l( -25% of 2-methyl-pentane, and 3% of 2,2-dimethylbutane. 

Alkylation of isobutane with isobutylene at 25° in the presence of boron fluoride promoted by water yielded an alkylate which contained 32% octanes and 15% dodecanes (Ipatieff and Grosse, 37). 

Alkylation of isobutane with ethylene in the presence of zirconium chloride took place at 100 under 15 atmospheres pressure (Ipatieff, 1, p. 682). The product was completely paraffinic and consisted chiefly of hexanes, octanes, and decanes. The catalyst was converted to a dark, pasty mass which was still catalytically active as was shown by its re-use in a second experiment with isobutane and ethylene. 

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