Carbon dioxide synthesis

Isse, A.A., Ferlin, M.G. and Gennaro, A. (2005a) Electrocatalytic reduction of arylethyl chlorides at silver cathodes in the presence of carbon dioxide Synthesis of 2-arylpropanoic acids. J. Electroanal. Chem. 581, 38 15. 

Casadei MA, Inesi A, Micheletti Moracci F, Rossi L (1996) Electrochemical activation of carbon dioxide synthesis of carbamates. Chem Commun 22 2575-2576... 

Oxytocin Neurohypophysis planar by layer. Inhibits carbon dioxide synthesis. Oxytocin analog antagonizes oxytocin... 

Takimoto M, Kawamura M, Mori M (2004) Nickel-mediated regio-and stereoselective carboxylation of trimethylsilylallene under an atmosphere of carbon dioxide. Synthesis 2004 791-795... 

Methanol is typicaUy synthesized in the gas phase over a heterogeneous catalyst from a gas containing a combination of hydrogen, carbon monoxide, and carbon dioxide. Synthesis can be from either of the foUowing chemical reactions... 

As an example of the application of a fixed-bed tubular reactor, consider the production of methanol. Synthesis gas (a mixture of hydrogen, carbon monoxide, and carbon dioxide) is reacted over a copper-based cat dyst. The main reactions are... 

Carbon dioxide, COj. Sublimes — 78 5 C. A colourless gas at room temperature, occurs naturally and plays an important part in animal and plant respiration. Produced by the complete combustion of carbon-containing materials (industrially from flue gases and from synthesis gas used in ammonia production) and by heating metal carbonates or by... 

Carboxyl and nitrile groups are usually introduced in synthesis with commercial carboxylic acid derivatives, nitriles, or cyanide anion. Carbanions can be carboxylated with carbon dioxide (H.F. Ebel, 1970) or dialkyl carbonate (J. Schmidlin, 1957). 

The /-butoxycarbonyl group (Boc, "t-box ) has been eMens vely used in peptide synthesis, and Boc derivatives of many amino acids are commercially available. The customary reagent for the preparation from the amine is t-butyl azidoformate in water, dioxane/water, DMSO, or DMF. The cleavage by acids of medium strength proceeds with concomitant loss of isobutene and carbon dioxide (L.A. Carpino, 1957, 1973 see section 4.1.2.2). 

To illustrate the specific operations involved, the scheme below shows the first steps and the final detachment reaction of a peptide synthesis starting from the carboxyl terminal. N-Boc-glycine is attached to chloromethylated styrene-divinylbenzene copolymer resin. This polymer swells in organic solvents but is completely insoluble. ) Treatment with HCl in acetic acid removes the fert-butoxycarbonyl (Boc) group as isobutene and carbon dioxide. The resulting amine hydrochloride is neutralized with triethylamine in DMF. 

A similar reaction in which ammonia and carbon dioxide are heated under pres sure IS the basis of the industrial synthesis of urea Here the reactants first combine yielding a salt called ammonium carbamate... 

The carbon-carbon bond forming potential inherent m the Claisen and Dieckmann reac tions has been extensively exploited m organic synthesis Subsequent transformations of the p keto ester products permit the synthesis of other functional groups One of these transformations converts p keto esters to ketones it is based on the fact that p keto acids (not esters ) undergo decarboxylation readily (Section 19 17) Indeed p keto acids and their corresponding carboxylate anions as well lose carbon dioxide so easily that they tend to decarboxylate under the conditions of their formation... 

The key compound m the synthesis of aspirin salicylic acid is prepared from phe nol by a process discovered m the nineteenth century by the German chemist Hermann Kolbe In the Kolbe synthesis also known as the Kolbe—Schmitt reaction, sodium phen oxide IS heated with carbon dioxide under pressure and the reaction mixture is subse quently acidified to yield salicylic acid... 

Section 24 10 The Kolbe-Schmitt synthesis of salicylic acid is a vital step m the preparation of aspirin Phenols as their sodium salts undergo highly regioselective ortho carboxylation on treatment with carbon dioxide at elevated temperature and pressure... 

Kolbe-Schmitt reaction (Section 24 10) The high pressure re action of the sodium salt of a phenol with carbon dioxide to give an o hydroxybenzoic acid The Kolbe-Schmitt reac tion IS used to prepare salicylic acid in the synthesis of as pinn... 

Uses, cx-Aminonitriles may be hydrolyzed to aminoacids, such as is done in producing ethylenediaminetetracetate (EDTA) or nittilotriacetate (NTA). In these cases, formaldehyde is utilized in place of a ketone in the synthesis. The principal use of the ketone-based aminonitriles described above is in the production of azobisnittile radical initiators (see below). AN-64 is also used as an intermediate in the synthesis of the herbicide Bladex. Aminonitriles are also excellent intermediates for the synthesis of substituted hydantoins by reaction with carbon dioxide however, this is not currently commercially practiced. 

The technology of urea production is highly advanced. The raw materials requited ate ammonia and carbon dioxide. Invariably, urea plants ate located adjacent to ammonia production faciUties which conveniently furnish not only the ammonia but also the carbon dioxide, because carbon dioxide is a by-product of synthesis gas production and purification. The ammonia and carbon dioxide ate fed to a high pressure (up to 30 MPa (300 atm)) reactor at temperatures of about 200°C where ammonium carbamate [111-78-0] CH N202, urea, and water ate formed. 

The concentration of is determined by measurement of the specific P-activity. Usually, the carbon from the sample is converted into a gas, eg, carbon dioxide, methane, or acetylene, and introduced into a gas-proportional counter. Alternatively, Hquid-scintiHation counting is used after a benzene synthesis. The limit of the technique, ca 50,000 yr, is determined largely by the signal to background ratio and counting statistics. 

In addition to the processes mentioned above, there are also ongoing efforts to synthesize formamide direcdy from carbon dioxide [124-38-9J, hydrogen [1333-74-0] and ammonia [7664-41-7] (29—32). Catalysts that have been proposed are Group VIII transition-metal coordination compounds. Under moderate reaction conditions, ie, 100—180°C, 1—10 MPa (10—100 bar), turnovers of up to 1000 mole formamide per mole catalyst have been achieved. However, since expensive noble metal catalysts are needed, further work is required prior to the technical realization of an industrial process for formamide synthesis based on carbon dioxide. 

Cmde gas leaves from the top of the gasifier at 288—593°C depending on the type of coal used. The composition of gas also depends on the type of coal and is notable for the relatively high methane content when contrasted to gases produced at lower pressures or higher temperatures. These gas products can be used as produced for electric power production or can be treated to remove carbon dioxide and hydrocarbons to provide synthesis gas for ammonia, methanol, and synthetic oil production. The gas is made suitable for methanation, to produce synthetic natural gas, by a partial shift and carbon dioxide and sulfur removal. 

Hydrazine as Nucleophile. Reaction of hydrazine and carbon dioxide or carbon disulfide gives, respectively, hydrazinecarboxyhc acid [471-31-8], NH2NHCOOH, and hydrazinecarbodithioic acid [471-32-9], NH2NHCSSH, in the form of the hydrazinium salts. These compounds are useful starting materials for further synthesis. For example, if carbon disulfide reacts with hydrazine in basic medium with an alkyl haUde, an alkyl dithiocarbazate ester is obtained in a one-step reaction ... 

Resorcinol carboxylation with carbon dioxide leads to a mixture of 2,4-dihydroxyben2oic acid [89-86-1] (26) and 2,6-dihydroxyben2oic acid [303-07-1] (27) (116). The condensation of resorcinol with chloroform under basic conditions, in the presence of cyclodextrins, leads exclusively to 2,4-dihydroxyben2aldehyde [95-01-2] (28) (117). Finally, the synthesis of l,3-bis(2-hydroxyethoxy)ben2ene [102-40-9] (29) has been described with ethylene glycol carbonate in basic medium (118), in the presence of phosphines (119). Ethylene oxide, instead of ethyl glycol carbonate, can also be used (120). 

A simpler nonphosgene process for the manufacture of isocyanates consists of the reaction of amines with carbon dioxide in the presence of an aprotic organic solvent and a nitrogeneous base. The corresponding ammonium carbamate is treated with a dehydrating agent. This concept has been apphed to the synthesis of aromatic and aUphatic isocyanates. The process rehes on the facile formation of amine—carbon dioxide salts using acid haUdes such as phosphoryl chloride [10025-87-3] and thionyl chloride [7719-09-7] (30). 

In 1974 a 1000 t/d ammonia plant went into operation near Johaimesburg, South Africa. The lignitic (subbituminous) coal used there contains about 14% ash, 36% volatile matter, and 1% sulfur. The plant has six Koppers-Totzek low pressure, high temperature gasifiers. Refrigerated methanol (—38° C, 3.0 MPa (30 atm)) is used to remove H2S. A 58% CO mixture reacts with steam over an iron catalyst to produce H2. The carbon dioxide is removed with methanol (at —58° C and 5.2 MPa (51 atm)). Ammonia synthesis is carried out at ca 22 MPa (220 atm) (53) (see Ammonia). 

In the chloride shift, Ck plays an important role in the transport of carbon dioxide (qv). In the plasma, CO2 is present as HCO, produced in the erythrocytes from CO2. The diffusion of HCO requires the counterdiffusion of another anion to maintain electrical neutraUty. This function is performed by Ck which readily diffuses into and out of the erythrocytes (see Fig. 5). The carbonic anhydrase-mediated Ck—HCO exchange is also important for cellular de novo fatty acid synthesis and myelination in the brain (62). 

New Synthesis. Many attempts have been made to synthesize oxaUc acid by electrochemical reduction of carbon dioxide in either aqueous or nonaqueous electrolytes (53—57). For instance, oxaUc acid is prepared from CO2 as its Zn salt in an undivided ceU with Zn anodes and stainless steel cathodes ia acetonitrile containing (C4H2)4NC104 and current efficiency of >90% (53). Micropilot experiments and a process design were also made. 

Synthesis gas, a mixture of CO and o known as syngas, is produced for the oxo process by partial oxidation (eq. 2) or steam reforming (eq. 3) of a carbonaceous feedstock, typically methane or naphtha. The ratio of CO to may be adjusted by cofeeding carbon dioxide (qv), CO2, as illustrated in equation 4, the water gas shift reaction. 

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