Ionic hydrogenation methanol

Rhodium catalyzed carbonylations of olefins and methanol can be operated in the absence of an alkyl iodide or hydrogen iodide if the carbonylation is operated in the presence of iodide-based ionic liquids. In this chapter, we will describe the historical development of these non-alkyl halide containing processes beginning with the carbonylation of ethylene to propionic acid in which the omission of alkyl hahde led to an improvement in the selectivity. We will further describe extension of the nonalkyl halide based carbonylation to the carbonylation of MeOH (producing acetic acid) in both a batch and continuous mode of operation. In the continuous mode, the best ionic liquids for carbonylation of MeOH were based on pyridinium and polyalkylated pyridinium iodide derivatives. Removing the highly toxic alkyl halide represents safer, potentially lower cost, process with less complex product purification. 

Recently, Eastman Chemical Company reported that ionic liquids can be successfully employed in a vapor take-off process for the carbonylation of methanol to acetic acid in the presence of rhodium and methyl iodide (3). While attempting to extend this earlier work to the carbonylation of ethylene to propionic acid, we discovered that, when using ionic liquids as a solvent, acceptable carbonylation rates could be attained in the absence of any added alkyl iodide or hydrogen iodide (4). We subsequently demonstrated that the carbonylation of methanol to acetic acid could also be operated in the absence of methyl iodide when using ionic liquids (5). 

FIGURE 1.10 Comparison of enantiomer separations of DNB-Leu on quinine (QN) based and 0-9-(terf-butylcarbamoyl)quinine (tBuCQN) based CSPs. 1, ionic interaction 2, jt-7T-interaction 3, hydrogen bonding 4, steric interaction. Experimental conditions Eluent, methanol-0.1 M ammonium acetate (80 20 v/v) (pHa = 6.0) flowrate, 1 mLmin temperature, 25°C column dimension, 150 x 4 mm ID detection, UV 250 nm. Selector loadings, 0.37 and 0.30 mmol g l for QN- and tBuCQN-based CSPs, respectively. (Reproduced from A. Mandl et ah, J. Chromatogr. A, 858 1 (1999). With permission.)... 

Further examples of recent attempts to reduce the consumption of electrical energy are the electrolysis of aqueous solutions of methanol (but CO2 is still produced at the anode) [78, 79] and water electrolysis using ionic liquids as electrolytes [80]. In the latter case, the authors claimed the possibility of obtaining high hydrogen production efficiencies using an inexpensive material such as low-carbon steel. 

Organoborane intermediates can also be used to synthesize alkyl halides. Replacement of boron by iodine is rapid in the presence of base.150 The best yields are obtained with sodium methoxide in methanol.151 If less basic conditions are desirable, the use of iodine monochloride and sodium acetate gives good yields.152 As is the case in hydroboration-oxidation, the regioselectivity of hydroboration-halogenation is opposite to that observed for direct ionic addition of hydrogen halides to alkenes. Terminal alkenes give primary halides. 

Liquid polyols are interesting among nonaqueous solvents because, like water and monoalcohols, they are hydrogen-bonded liquids with a high value of relative permittivity (Table 9.2.1), and therefore they are able to dissolve to some extent ionic inorganic compounds. Moreover, reactions can be carried out in such solvents under atmospheric pressure up to 250°C, i.e., at a temperature range higher than in water or monoalcohols such as methanol or ethanol. 

The last of the direct methods for graft initiation in liquid phase presented in this review involves chemical additives. Either free radical or ionic initiators can be chosen. Benzoyl peroxide is reported for grafting styrene on Nylon fibers in methanol media (71,105-107), as well as vinyl acetate (106). Azoisobutyro-nitrile has been employed in systems where the graft monomer is styrene (71,106) or vinyl acetate (106). Redox systems involving hydrogen peroxide and monomers like styrene (106,108,109). vinyl acetate (106), acrylic acid (108,109), methyl... 

---