Friedel-Crafts alkylation reactions olefins

Other catalysts which may be used in the Friedel - Crafts alkylation reaction include ferric chloride, antimony pentachloride, zirconium tetrachloride, boron trifluoride, zinc chloride and hydrogen fluoride but these are generally not so effective in academic laboratories. The alkylating agents include alkyl halides, alcohols and olefines. 

The synthetic detergents industry originated in the 1940s, when it was found that a new anionic surfactant type—alkylbenzene sulfonate—had detergent characteristics superior to those of natural soaps. The first surfactant of this kind was sodium dodecylbenzene sulfonate (SDBS). This material was produced by the Friedel-Crafts alkylation reaction of benzene with propylene tetramer (a mixture of Co olefin isomers), followed by sulfonation with oleum or sulfur trioxide and then neutralization, usually with sodium hydroxide. The alkylation was typically performed using homogenous acid catalysts, such as HF or sulfuric acid. 

This reaction is related to the Friedel-Crafts Alkylation, Darzens Olefin Acylation, Fries Rearrangement, Haworth Phenanthrene Synthesis, and Nencki Reaction. 

ILs may themselves also act as catalyst. For heterogeneous catalysis, the IL has to be immobilized, for example, by covalent bonds on a porous support, as shown by Hoelderich et al. [40] for Friedel-Crafts alkylation reactions. Further examples of reactions tested with grafted ILs are acetylization [41], cycloaddition of CO2 [42, 43], and epoxidation of olefines [44]. 

Ferrocene behaves in many respects like an aromatic electron-rich organic compound which is activated toward electrophilic reactions.In Friedel-Crafts type acylation of aromatic compounds with acyl halides, ferrocene is lO times more reactive than benzene and gives yields over 80%. However, ferrocene is different from benzene in respect to reactivity and yields in the Friedel-Crafts alkylation with alkyl halides or olefins. The yields of ferrocene alkylation are often very low. and the separations of the polysubstituted byproducts are tedious. 

The first systematic investigations of the catalytic Friedel-Crafts-type reaction with alcohols and olefines were performed by Yamamoto and colleagues. After reporting the development of a Pd-catalyzed method for the allylation of different naphthol derivatives [24], the authors used Mo(CO)g for the Friedel-Crafts-type alkylation of electron-rich arenes with allyl acetates [25], The same molybdenum catalyst was additionally used for a Friedel-Crafts-type alkylation of arenes using 1-phenylethanol and styrene as alkylating reagents [26], However, Mo(CO)g is toxic and must be handled under strictly inert conditions. Thus, more stable Lewis acids were necessary. 

As recognized in the pioneering work of Meerwein, Ingold, and Whitmore,10 12 18 19 744 trivalent alkyl cations (C H2 +i+) play important roles in the acid-catalyzed transformations of hydrocarbons as well as various electrophilic and Friedel-Crafts-type reactions. Trivalent alkyl cations can directly be formed by the ionization of lone-pair (nonbonded electron pair) containing precursors (w-bases) such as alkyl halides, alcohols, thiols, and so on, or by protonation of singlet carbenes or olefins. 

These catalytic reactions provide a unique pathway for addition of aromatic C-H bonds across C=C bonds. In contrast with Friedel-Crafts catalysts for olefin hydroarylation, the Ru-catalyzed hydrophenylation reactions of a-olefins selectively produce linear alkyl arenes rather than branched products. Although the selectivity is mild, the formation of anti-Markovnikov products is a unique feature of the Ru(II) and Ir(III) catalysts discussed herein. Typically, the preferred route for incorporation of long-chain linear alkyl groups into aromatic substrates is Friedel-Crafts acylation then Clemmensen reduction, and the catalysts described herein provide a more direct route to linear alkyl arenes. 

Study of the reactivity of aromatic C-H bonds in the presence of transition metal compounds began in the 1960s despite the quite early discovery of Friedel-Crafts alkylation and acylation reactions with Lewis acid catalysts. In 1967, we reported Pd(II)-mediated coupling of arenes with olefins in acetic acid under reflux [1], The reaction involves the electrophilic substitution of aromatic C-H bonds by a Pd(II) species, as shown in Scheme 2, and this is one of the earliest examples of aromatic C-H bond activation by transition metal compounds. Al-... 

The use of immobilised ILs as catalysts would result in the easy separation of the catalyst from the reaction mixture, allowing its fast reuse and avoiding the generation of contaminated waste and its subsequent treatment. Ionic liquids have already been proposed as catalysts for Friedel-Crafts alkylation of benzene with olefins in order to produce LABs32-35. They show Lewis acidic properties when a Lewis acid (e.g. 

The third case shows the immobilisation of Lewis-acidic ionic liquids. The resulting catalysts, named Novel Lewis-Acidic Catalysts (NLACs), are highly active in the Friedel-Crafts alkylation of aromatic compounds with dodecene. Conversions and selectivities to the desired monoalkylated products were excellent. No leaching of the catalytically active component could be observed. The isomer distribution of the monoalkyated products is very similar to that obtained over pure aluminum(III)chloride. The main drawback of the NLACs is that thy are very sensitive towards water, which leads to irreversible deactivation. A second problem is the deactivation after long reaction times. The most likely cause is olefin oligomerisation. 

Another catalytic methodology that is widely used for C-C bond formation is the Heck and related coupling reactions [86, 87]. The Heck reaction [88] involves the palladium-catalysed arylation of olefinic double bonds (Fig. 1.31) and provides an alternative to Friedel-Crafts alkylations or acylations for attaching carbon fragments to aromatic rings. The reaction has broad scope and is currently being widely applied in the pharmaceutical and fine chemical industries. For example, Albemarle has developed a new process for the synthesis of the anti-in-... 

HPAs, however, is their solubility in polar solvents or reactants, such as water or ethanol, which severely limits their application as recyclable solid acid catalysts in the liquid phase. Nonetheless, they exhibit high thermal stability and have been applied in a variety of vapor phase processes for the production of petrochemicals, e.g. olefin hydration and reaction of acetic acid with ethylene [100, 101]. In order to overcome the problem of solubility in polar media, HPAs have been immobilized by occlusion in a silica matrix using the sol-gel technique [101]. For example, silica-occluded H3PW1204o was used as an insoluble solid acid catalyst in several liquid phase reactions such as ester hydrolysis, esterification, hydration and Friedel-Crafts alkylations [101]. HPAs have also been widely applied as catalysts in organic synthesis [102]. 

Friedel Crafts type alkylations of benzene by alkenes involve the initial formation of a lattice associated carbenium ion, formed by protonation of the sorbed olefin. The chemisorbed alkene is covalently bound to the zeolite in the form of an alkoxy group and the carbenium ion formed exists only in the transition state. As would be expected fixjm conventional Friedel Crafts alkylation, the reaction rate over acidic molecular sieves also increases with the degree of substitution of the aromatic ring (tetramethyl > trimethyl > dimethyl > methyl > unsubstituted benzene). The spatial restrictions induced by the pore size and geometry frequently inhibit the formation of large multisubstituted products (see also the section on shape selectivity). 

The lowest cost (di)alkyl benzenes are by-products from linear monoalkylate manufacture used extensively in detergent manufacture. Synthesis is usually by a Friedel-Crafts-type reaction, either by reaction of the alkyl chloride and benzene with anhydrous aluminium chloride as catalyst, or by the catalysed reaction of the appropriate length a-olefin and benzene. 

Propyidiethylsilane, the alkylated Table 1 Alkylation of E2 by Olefinic product, was found to be an n-propyl form Hydrocarbons and not iso form which was confirmed by NMR analysis. This clearly shows that the addition of propene to a Si atom undergoes at the terminal position of propene molecule. If propene activation by acid is an important process, secondary carbocation may produce and iso product could be produced. Hence the reaction mechanism is different from a typical Friedel-Crafts type reaction. 

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