Carbon formation using ionic liquids

Cationic polymerization of alkenes and alkene derivatives has been carried out frequently in aqueous media.107 On the other hand, the reaction of simple olefins with aldehydes in the presence of an acid catalyst is referred to as the Prins reaction.108 The reaction can be carried out by using an aqueous solution of the aldehyde, often resulting in a mixture of carbon-carbon bond formation products.109 Recently, Li and co-workers reported a direct formation of tetrahydropyranol derivatives in water using a cerium-salt catalyzed cyclization in aqueous ionic liquids (Eq. 3.24).110... 

Pitner and Hussey studied the electrochemistry of tin in acidic and basic AICI3/I-ethyl-3-methyl-imidazolium chloride-based ionic liquids by using voltammetry and chronoamperometry at 40 °C [15]. They reported that the Sn(II) reduction process is uncomplicated at a platinum substrate, where in the atidic ionic liquid the reduction wave was observed at +0.46 V on the Pt electrode and the oxidation at +0.56 V. When they used a gold electrode instead of platinum, they observed an underpotential deposition of a tin monolayer and an additional underpotential deposition process that was attributed to the formation of tin-gold alloy at the surface. The deposition of tin on glassy carbon was controlled by nudeation. 

The electrodeposition of Zn-Co and Zn-Fe alloys in an aqueous bath is classified as an anomalous codeposition [44] because the less noble Zn is preferentially deposited with respect to the more noble metal. This anomaly was attributed to the formation of Zn(OH)+ which adsorbs preferentially on the electrode surface and inhibits the effective deposition of the more noble metal. This anomaly was circumvented by using zinc chloride-n-butylpyridinium chloride ([BP]+C1 / ZnCf ) [27] or [EMIMJ+Ch/ZnCh [28] ionic liquids containing Co(II). The Zn-Co deposits can be varied from Co-rich to Zn-rich by decreasing the deposition potential or increasing the deposition current. XRD measurement reveals the presence of CosZ i in the deposited Zn-Co alloys and that the Co-rich alloys are amorphous and the crystalline nature of the electrodeposits increases as the Zn content of the alloys increases. Addition of propylene carbonate cosolvent to the ionic liquid decreases the melting temperature of the solution and allows the electrodeposition to be performed at a lower temperature. The presence of CoZn alloy is evidenced by the XRD patterns shown in Figure 5.2. 

The Suzuki-Miyaura cross-coupling reaction is a standard method for carbon-carbon bond formation between an aryl halide or triflate and a boronic acid derivative, catalyzed by a palladium-metal complex. As with the Mizoroki-Heck reaction, this cross-coupling reaction has been developed in ionic liquids in order to recycle and reuse the catalyst. In 2000, the first cross-coupling of a halide derivative with phenylboronic acid in [bmim] [BF4] was described. As expected, the reaction proceeded much faster with bromobenzene and iodobenzene, whereas almost no biphenyl 91 was obtained using the chloride derivative (Scheme 36). The ionic liquid allowed the reactivity to be increased, with a turnover number between 72 and 78. Furthermore, the catalyst could be reused repeatedly without loss of activity, even when the reaction was performed under air. Cross-coupling with chlorobenzene was later achieved - although with only a moderate yield (42%) - using ultrasound activation. 

Comparison of the results of Tsuji-Trost coupling of ethyl cinnamyl carbonate and ethyl acetoacetate (Scheme 60) in biphasic mixtures either with water or with an ionic liquid showed clear advantage of using the IL solvent (292). The organic reactants are much better soluble in [bmim]Cl than in water which leads to faster reactions and in the absence of water formation of cinnamyl alcohol as by-product is avoided. 

Acid zeolites have also been tested for the racemisation of alcohols under biphasic conditions.Their scope was found, however, to be limited to benzylic alcohols, since electron-rich benzylic alcohols were not suitable substrates because of the formation of dimers. Under optimised conditions, based on the use of H-Beta zeolite, CALB lipase, and an excess of vinyl octanoate at 60 °C, enantiopure (R)-l-phenylethyl octanoate (>99% ee) was obtained in 90% yield from 1-phenylethanol. In addition, Lozano et al. have recently performed the DKR of this alcohol in the presence of acidic zeolite catalysts (CBV400) in an ionic liquid-supercritical carbon dioxide system with a continuous reaction system. Therefore, when Novozym 435 was employed at 50 °C and 100 bars in the presence of vinylpropanoate as the acyl donor, the expected (R)-phenylethylpropionate was produced in excellent yield of 98% with enantioselectivity of 97% ee and without any activity loss during 14 days of operation. 

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