Published on Web 08/13/2008 Selective Methylative Homologation: An Alternate Route to Alkane Upgrading John E. Bercaw,‡ Nilay Hazari,‡ Jay A. Labinger,*,‡ Valerie J. Scott,‡ and Glenn J. Sunley*,# Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, and BP Chemicals Limited, Hull Research and Technology Centre, Kingston Upon Hull, North Humberside HU12 8DS, England Received April 24, 2008; E-mail: [email protected]; [email protected] Abstract: InI3 catalyzes the reaction of branched alkanes with methanol to produce heavier and more highly branched alkanes, which are more valuable fuels. The reaction of 2,3-dimethylbutane with methanol in the presence of InI3 at 180-200 °C affords the maximally branched C7 alkane, 2,2,3-trimethylbutane (triptane). With the addition of catalytic amounts of adamantane the selectivity of this transformation can be increased up to 60%. The lighter branched alkanes isobutane and isopentane also react with methanol to generate triptane, while 2-methylpentane is converted into 2,3-dimethylpentane and other more highly branched species. Observations implicate a chain mechanism in which InI3 activates branched alkanes to produce tertiary carbocations which are in equilibrium with olefins. The latter react with a methylating species generated from methanol and InI3 to give the next-higher carbocation, which accepts a hydride from the starting alkane to form the homologated alkane and regenerate the original carbocation. Adamantane functions as a hydride transfer agent and thus helps to minimize competing side reactions, such as isomerization and cracking, that are detrimental to selectivity. Introduction upgrading light hydrocarbons such as n-hexane to diesel- range linear alkanes.5,6 The catalytic conversion of abundant but relatively inert alkanes into higher value chemicals has been a longstanding The dehydrative condensation of methanol to hydrocarbons challenge for chemists and the petrochemical industry. While has attracted a good deal of interest over the years. Most often there have been significant advances in our understanding this involves reaction over shape-selective solid acids, as in the of C-H activation reactions over the last three decades, they MTG (methanol-to-gasoline) and MTO (methanol-to-olefins) have not yet led to practical methods for alkane functional- processes.7 In contrast, Kim et al. reported that the reaction of ization, because of limitations imposed by unfavorable MeOH with zinc iodide at 200 °C led to formation of an alkane- 1 thermodynamics, low selectivity, and/or economic factors. rich hydrocarbon mixture, with surprising selectivity to one In principle one could avoid these difficult functionalization particular alkane, 2,2,3-trimethylbutane (triptane), in overall problems by simply converting a given alkane into another yields of up to 20% (based on moles of carbon), corresponding alkane of higher value. Well-known examples, which are to as much as half of the gasoline-range fraction (eq 1).8,9 An extensively utilized by the petrochemical industry, include efficient synthetic route to triptane (research octane number ) isomerization of linear to branched alkanes2 and the alkylation of isobutane with olefins.3 On a research scale, alkanes may be coupled by mercury-photosensitized dehydrodimerization, (5) (a) Vidal, V.; The´olier, A.; Thivolle-Cazat, J.; Basset, J.-M. Science although selectivity is limited by the radical mechanism 1997, 276, 99–102. (b) Basset, J.-M.; Cope´ret, C.; Soulivong, D.; involved.4 More recently the so-called alkane metathesis Taoufik, M.; Thivolle-Cazat, J. Angew. Chem., Int. Ed. Engl. 2006, 45, 6082–6085. reaction has been proposed as a potential method for (6) Goldman, A. S.; Roy, A. H.; Huang, Z.; Ahuja, R.; Schinski, W.; Brookhart, M. Science 2006, 312, 257–261. (7) (a) Chang, C. D. Catal. ReV.sSci. Eng. 1983, 25, 1–118. (b) Olah, ‡ Caltech. G. A.; Molna´r, A´ . Hydrocarbon Chemistry, 2nd ed.; John Wiley & # BP. Sons: Hoboken, NJ, 2003; pp 117-122. (c) Haw, J. F.; Song, W.; (1) See, for example,(a) Crabtree, R. H. J. Chem. Soc., Dalton Trans. Marcus, D. M.; Nicholas, J. B. Acc. Chem. Res. 2003, 36, 317–326. 2001, 17, 2437–2450. (b) Labinger, J. A.; Bercaw, J. E. Nature 2002, (d) Olsbye, U.; Bjørgen, M.; Svelle, S.; Lillerud, K.-P.; Kolboe, S. 417, 507–514. (c) Goldman, A., Goldberg, K. I., Eds. ActiVation and Catal. Today 2005, 106, 108–111. Functionalization of C-H Bonds, American Chemical Society: Wash- (8) Kim, L.; Wald, M. M.; Brandenburger, S. G. J. Org. Chem. 1978, 43, ington, DC, 2004. (d) Fekl, U.; Goldberg, K. I. AdV. Inorg. Chem. 3432–3433. 2003, 54, 259–320. (9) The reaction can also be carried out by reacting methyl iodide with (2) Ono, Y. Catal. Today 2003, 81, 3–16. Zn(OMe)2 (Diaconescu, P. L., unpublished results) or ZnO (Wal- (3) Hommeltoft, S. I. Appl. Catal., A 2001, 221, 421–428. spurger, S.; Prakash, G. K. S.; Olah, G. A. Appl. Catal., A 2008, 336, (4) Brown, S. H.; Crabtree, R. H. J. Am. Chem. Soc. 1989, 111, 2935– 48–53) with similar outcomes, indicating that the various species 2946. readily interconvert under reaction conditions. 11988 9 J. AM. CHEM. SOC. 2008, 130, 11988–11995 10.1021/ja803029s CCC: $40.75 2008 American Chemical Society Selective Methylative Homologation ARTICLES Scheme 1 112) would provide access to a valuable fuel component and Both the isomerization of and initiation by alkanes implies gasoline additive. that they react with InI3 and thus enter the carbocation/olefin pool, even if only in very low concentrations. This conclusion was supported by an isotopic labeling study. Analysis of the products from a reaction of 13C-MeOH, unlabeled 2,3-dimeth- ylbutane (as an initiator) and InI3 by GC/MS showed that the two major triptane isotopologues were singly labeled and fully labeled (with much more of the latter). Fully labeled triptane Our mechanistic studies on this complex reaction10 implicate presumably arose via de noVo synthesis from MeOH, but a a carbocation-based route, wherein hydrocarbon growth proceeds singly labeled triptane molecule must have come from the by successive olefin methylation and deprotonation, always addition of a single methanol-derived CH2 group to the C6 olefin favoring the most highly substituted carbocations and olefins generated by the activation of unlabeled 2,3-dimethylbutane.13 respectively. Direct C-C bond formation from methanol (and/ It should be noted that this methylatiVe homologation does or dimethyl ether; partial dehydration of MeOH to DME is rapid not suffer from the hydrogen deficiency of the original methanol- under reaction conditions) apparently takes place only when to-triptane conversion; there is no requirement for the formation solids are present; for a completely homogeneous reaction of arenes or any unsaturated hydrocarbons, removing one mixture an initiator is required, typically an olefin or a higher limitation on selectivity. If it were possible to convert large alcohol. Alkanes are generated via hydride transfer from an quantities of light alkanes in this manner, using MeOH as a unsaturated hydrocarbon to a carbocation, with the resulting methylating agent, it would constitute a route for the selective multiply unsaturated intermediates eventually resulting in the conversion of relatively low value and abundant alkanes to more formation of arenes, as illustrated in Scheme 1. valuable fuels by reactions such as eq 2. Isobutane and According to this scheme, triptane yields are limited by two 2-methylbutane (isopentane) are produced on a large scale in constraints. First, the aliphatic pool contains both lighter and refinery operations;14 they are also significant byproducts from heavier highly branched alkanes (and some olefins), along with methanol transformations such as MTG.7a While the latter smaller amounts of less branched isomers; the selectivity for compound is used directly as a gasoline component, its triptane within that pool appears to be governed by the relative homologation to a higher octane, less volatile C6 or C7 branched rates of methylation and hydride transfer at the various stages alkane would represent a significant upgrading of value. We of product growth. Second, some fraction of the methanol feed report here on work aimed at exploring this unprecedented and must be diverted to the aromatic pool to satisfy the stoichiometry potentially useful approach. in hydrogen. The latter factor accounts for the observation that the triptane yield is enhanced by additives containing P-H bonds (phosphorus or hypophosphorous acid), which serve as alternate hydride sources.11 More recently we have found that InI3 also functions as a catalyst for this transformation.12,13 While many of the features, Results and Discussion including reaction conditions and typical triptane yields, are quite Homologation of 2,3-Dimethylbutane. The first series of similar for ZnI2 and InI3, suggesting that the mechanism for experiments were performed using reaction mixtures of InI3 the conversion of MeOH to triptane is basically the same for (4.13 mmol), MeOH (12.4 mmol) and varying amounts of 2,3- the two systems, there are some significant differences, espe- dimethylbutane (DMB), which were heated at 200 °Cfor2h. cially in the detailed product distributions. Much of the The control experiment (with no DMB present) contained difference in behavior can be accounted for by the fact that isopropanol as an initiator. The results of analysis by gas InI3sunlike ZnI2sis able to activate (some) alkanes easily at chromatography (GC) are shown in Table 1. In all experiments 200 °C. In particular, alkanes that contain at least one tertiary conversion of DMB was between 20 and 35%, while all the center are readily isomerized by the InI3 system, and are also MeOH/DME was consumed. Both the yield of triptane (in able to function as initiators for triptane synthesis.13 In contrast, milligrams) and the selectivity to triptane (stated as moles of olefins (or olefin precursors such as higher alcohols) are required carbon in triptane per mole of total converted carbon) increase 10 to initiate ZnI2-catalyzed reactions at e200 °C.