1-Decene benzene alkylation with

Table 1 Benzene alkylation with 1-dodecene and 1-decene, using fluorided-moidenite catalyst.

Non-chloroaluminate ILs for alkylation reactions were first investigated by Wassercheid et al., where imidazolium Bronsted acidic AILs containing the HSO4 anion were used as additives to sulfuric acid for benzene alkylation with 1-decene. The yields obtained were between 3.5 and 68%, with selectivities from 35 to 41%, and while fairly low, these showed the potential of this type of IL for alkylation reactions. 

In continuous-flow, liquid phase runs, high conversions of 1-decene to mixtures of decylbenzene isomers occurred in reaction with benzene over REX catalyst (Fig. 25). In analogous benzene alkylation attempts with 1-decene or 1-decanol at atmospheric pressure, side reactions of... 

Keim and co-workers have carried out various alkylation reactions of aromatic compounds in ionic liquids substantially free of Lewis acidity [84]. An example is the reaction between benzene and decene in [BMIM][HS04], which was used together with sulfuric acid as the catalyst (Scheme 5.1-54). These authors have also claimed that these acid-ionic liquids systems can be used for esterification reactions. 

Another recent patent (22) and related patent application (31) cover incorporation and use of many active metals into Si-TUD-1. Some active materials were incorporated simultaneously (e.g., NiW, NiMo, and Ga/Zn/Sn). The various catalysts have been used for many organic reactions [TUD-1 variants are shown in brackets] Alkylation of naphthalene with 1-hexadecene [Al-Si] Friedel-Crafts benzylation of benzene [Fe-Si, Ga-Si, Sn-Si and Ti-Si, see apphcation 2 above] oligomerization of 1-decene [Al-Si] selective oxidation of ethylbenzene to acetophenone [Cr-Si, Mo-Si] and selective oxidation of cyclohexanol to cyclohexanone [Mo-Si], A dehydrogenation process (32) has been described using an immobilized pincer catalyst on a TUD-1 substrate. Previously these catalysts were homogeneous, which often caused problems in separation and recycle. Several other reactions were described, including acylation, hydrogenation, and ammoxidation. 

The synthesis of several hydrogensulphate and tetrakis(hydrogensulphato)borate ionic liquids has been described by our group [29]. Mixtures of these ionic liquids with sulphuric acid were used as non-volatile acidic phases with tuneable solubility properties for catalytic applications such as e.g. the alkylation of benzene with 1-decene. 

The yttrium silanolate complex 11 shows good catalytic activity with high anti-Markovnikov regioselectivity in the hydrosilylation of 1-decene (Tablet) [59]. Cationic silanolate rare-earth metal alkyl species derived from 11 were either inactive or exhibited significantly diminished activity, possibly as a result of tight binding of the benzene solvent as well as decomposition of the cationic metal hydride intermediate. 

Fio. 26. Activity of BEX catalyst vs time for the alkylation of benzene with 1-decene in the liquid phase (43). 

BP Chemicals studied the use of chloroaluminates as acidic catalysts and solvents for aromatic alkylation [43]. At present, the AICI3 existing technology (based on red oil catalyst) is still used industrially, but continues to suffer from poor catalyst separation and recycle [44]. The aim of the work was to evaluate the AlCls-based ionic liquids, with the emphasis placed on the development of a clean and recyclable system for the production of ethylbenzene (benzene/ethene alkylation) and synthetic lubricants (alkylation of benzene with 1-decene). The production of linear alkyl benzene (LAB) has also been developed by Akzo [45]. The eth)4benzene experiments were run by BP in a pilot loop reactor similar to that described for the dimerization (Fig. 5.4-8). 

As described previously, protic ionic liquids that are free of Lewis acidity, such as [BMIM][HS04]/H2S04, have also been used as catalysts-solvents. Alkylation of benzene with 1-decene has been described. The difficulty is probably to adjust the acidity of the IL to have the right balance between olefin double bond isomerization and aromatic alkylation [16]. 

Wasserscheid et al. (2002) have described a highly Brpnstedt-acidic IL consisting of tetrakis(hydrogensulfato)borate as anion (G in Figure 29.2) and [BMIM]+ or [OMIM]+ as cation. In a two-phase system of sulfuric acid and benzene, the ILs promoted the electrophilic alkylation of benzene with 1-decene, by increasing the contents of acidic Friedel-Crafts catalyst in the organic phase. 

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