Carbon monoxide addition with

At room temperature, Htde reaction occurs between carbon dioxide and sodium, but burning sodium reacts vigorously. Under controUed conditions, sodium formate or oxalate may be obtained (8,16). On impact, sodium is reported to react explosively with soHd carbon dioxide. In addition to the carbide-forrning reaction, carbon monoxide reacts with sodium at 250—340°C to yield sodium carbonyl, (NaCO) (39,40). Above 1100°C, the temperature of the DeviHe process, carbon monoxide and sodium do not react. Sodium reacts with nitrous oxide to form sodium oxide and bums in nitric oxide to form a mixture of nitrite and hyponitrite. At low temperature, Hquid nitrogen pentoxide reacts with sodium to produce nitrogen dioxide and sodium nitrate. 

Commercial production of these acids essentially follows the mechanistic steps given. This is most clearly seen in the Exxon process of Figure 1 (32). In the reactor, catalyst, olefin, and CO react to give the complex. After degassing, hydrolysis of this complex takes place. The acid and catalyst are then separated, and the trialkylacetic acid is purified in the distillation section. The process postulated to be used by Shell (Fig. 2) is similar, with additional steps prior to distillation being used. In 1980, the conditions used were described as ca 40—70°C and 7—10 MPa (70—100 bar) carbon monoxide pressure with H PO —BF —H2O in the ratio 1 1 1 (Shell) or with BF (Enjay) as catalyst (33). 

In the Fischer-Tropsch process, carbon monoxide reacts with hydrogen in the presence of a solid catalyst, with the formation of a mixture of hydrocarbons. The composition of the product varies considerably with the catalyst and the operating conditions. The mixture may include (in addition to hydrocarbons) alcohols, aldehydes, ketones, and acids. 

Labelling studies with 13C-enriched acetic acid, where 13C NMR data are consistent with carbon monoxide addition to the carbonyl carbon of the acid substrate. 

Furthermore, carbon monoxide reacts with water to generate additional hydrogen and carbon dioxide ... 

The soot-free synthesis gas is then charged to a shift converter where the carbon monoxide reacts with steam to form additional hydrogen and carbon dioxide at the stoichiometric rate of 1 mole of hydrogen for every mole of carbon monoxide charged to the converter. 

Reduction of sodium sulphate with charcoal at red heat produces sodium sulphide and carbon monoxide, along with sodium polysulphides and carbon dioxide. Addition of alcohol to a solution of sodium sulphate in aqueous hydrogen peroxide precipitates a complex derivative of the formula Na2SO H O,H202.10... 

Carbon monoxide reacts with Grignard reagents, thongh more slowly than carbon dioxide. The initial reaction is a 1,1-addition to the carbon, resnlting in an acyhnagnesinm halide. Despite potential applications of snch species, the reaction nsnally leads to mixtnres of prodncts, and has not been developed synthetically. ... 

Many reactions afford, in addition to the naphthalene derivatives, mixtures of products. One of the major side reactions is the formation of indene derivatives directly from the metathesis intermediate without insertion of carbon monoxide. Other products frequently isolated as minor components are furans, cyclobutanones, and cyclopentenediones. The product distribution is dependent on numerous factors, including solvent, reaction temperature, concentration of the alkyne, and the nature of the aryl substituent. Molybdenum carbenes give, depending on the alkyne, either naphthols or indenes exclusively. The molybdenum Fischer carbenes can be tuned to give naphthoquinones by replacing one of the carbon monoxide ligands with a phosphine (Scheme 45). 

Nucleophilic substitution and addition reactions of olefins are possible with Pd2 salts. A typical example is the formation of acetaldehyde by the reaction of ethylene with water (Wacker reaction). As nucleophiles, water, alcohols, phenols, carboxylic acids, amines, enamines, carbanions derived from active methylene compounds, and carbon monoxide react with olefins with stoichiometric consumption of Pd2 salts. 

M(C0)5X , and H2 in the presence of a general base to provide anionic metal hydrides. This process was shown to be first-order in both metal complex and dihydrogen and was not inhibited by addition of carbon monoxide. Consistent with the rds in catalysis being formation of the metal hydride intermediate, the metal catalyzed reaction of RX/CO2/H2 to provide HCOOR is not inhibited by CO. The well-established formation of metalloformate, M(C0)s02CH", from M(C0)5H and CO2 is followed by a less facile process involving the reaction of the metalloformate with RX. This latter reaction is first-order in both metal complex and alkyl halide and is inhibited by carbon monoxide. 

There are many methods for the preparation of carbenes. A simple approach is to photolyze ketenes (290) at 270-370 nm (100.5-76.5 kcal moT, 438.8-320.2 kJ mol l) in the presence of oxygen.226 irradiation of 290 at 270 nm gave carbon monoxide (CO, with a quantum yield = 2) and the yield of ethene was independent of the pressure of oxygen. At 370 nm, the quantum yield of CO varies with the pressure of applied oxygen and also with the temperature. The presence of additional oxygen diminishes the yield of ethene by = 3.226 xhe reaction proceeds via formation of excited ketene (291), which fragments to methylene... 

Uranium complexes have also shown imprecedented reactivity with carbon monoxide. Addition of carbon monoxide to [(COT)(Cp )U(THF)j [122] produced a dimeric 0303 debate uranium complex, [ ( j -Cp )( j -COT)U 2... 

Elliott 7) has reported some experiments using wood flour, lignin, and cellulose without any addition of CO. At 350 C final temperature for 1 hr, with 18% substrate slurry, the oil yields were 39, 23, and 30% respectively. The result with cellulose is in agreement with our data. The effect of carbon monoxide addition to an aqueous system with a 30% cellulose slurry was to increase oil yield by only 3-4% in our experiments, up to 500 psig initial CO pressure. This is also in agreement with Elliott s data. The CO-enhancement effect on oil yield is thus barely noticeable with cellulose at CO pressures below 500 psig. 

The reaction of stable N-heterocyclic carbenes (NHCs) with carbon monoxide and the carbonylation of diazo compounds also provide routes to ketene formation. Ketene formation by carbon monoxide addition to a stable carbene (with 55% conversion) has been confirmed by the characteristic IR absorption, and the ketene has been isolated as a purple solid at low temperature with the structure determined by X-ray crystallography (Scheme 7.42). 

In addition, automobile exhaust may contain considerable quantities of carbon monoxide. Even with the most careful attention to engine design, it is impossible under normal driving conditions to reduce the quantity of these pollutants to an acceptable level in the exhaust gases. It is therefore necessary to remove them from the exhaust before they are vented to the air. This removal is accomplished in the catalytic converter. 

In addition, the high operating temperature ensures that the gas product contains no ammonia, tars, phenols, or condensable hydrocarbons. The raw gas can be upgraded to synthesis gas by reacting all or part of the carbon monoxide content with steam to produce additional hydrogen plus carbon dioxide. 

The method has been directed so far, to only the typical syngas carbon monoxide/hydrogen with or without a small content of carbon dioxide, but not yet to BFG with a large carbon dioxide content. In addition, influence of the mixing ratio in the hybrid catalyst has not been well investigated in spite of its importance for the process design and operation. 

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