Carbon monoxide preparation

Yuguchi, M., Tokuda, M., Qrito, K. Pd(0)-Catalyzed conjugate addition of benzylzinc chlorides to a,p-enones in an atmosphere of carbon monoxide Preparation of 1,4-diketones. J. Org. Chem. 2004, 69, 908-914. 

The halotricarbonyliridium(I) compounds Ir(CO)3X (X = Cl, Br, I), unlike other Ir(I) compounds, are insoluble in organic solvents but may be purified by sublimation in a stream of carbon monoxide Preparation is by the following route ... 

The apparatus and the general experimental technique employed were the same as those described earlier 8). Experiments were conducted by the static method in the gas phase. The products of the reaction were released from the bomb at the reaction temperature. Commercial ethylene (99.2% pure), carbon monoxide (prepared in the laboratory by the action of formic acid on concentrated sulfuric acid), distilled water, A.E.. grade n-propyl, and n-butyl alcohols were the reactants used. The ethylene gas contained a small amount of sulfur, which, however, was found to have no deleterious effect on the synthesis. 

CO Carbon monoxide Preparation of methanol and other organic chemicals... 

The issue of yields was closely investigated in a series of palladium-catalyzed carbonylations of aryl/heteroaryl halides and triflates with [ C]carbon monoxide, prepared through treatment of well-defined quantities of lithium [ C]formate with concentrated sulfuric acid. The experiments were carried out in a dual-chamber reaction vessel, one section for the generation of CO, the other for the carbonylation reaction. This arrangement eliminated the need to manipulate the CO released but instead relied on its being drawn from the first chamber into the second as it was consumed. The reaction sequence was typically performed with two equivalents of Ba COj, which corresponded... 

Carbon monoxide is formed by the incomplete combustion of carbon. It is prepared in the laboratory by dropping methanoic (formic) acid into warm concentrated sulphuric acid the latter dehydrates the methanoic acid ... 

Carbon monoxide is very poisonous all operations involving its preparation and use must be carried out in an efficient fume cupboard. 

In some instances the use of sulphuric acid leads to unsatisfactory results. Thus with formic acid carbon monoxide would be evolved. Esters of formic acid are most simply prepared from the alcohol and excess of formic acid, for example ... 

The reaction of trivalent carbocations with carbon monoxide giving acyl cations is the key step in the well-known and industrially used Koch-Haaf reaction of preparing branched carboxylic acids from al-kenes or alcohols. For example, in this way, isobutylene or tert-hutyi alcohol is converted into pivalic acid. In contrast, based on the superacidic activation of electrophiles leading the superelectrophiles (see Chapter 12), we found it possible to formylate isoalkanes to aldehydes, which subsequently rearrange to their corresponding branched ketones. 

Until the 1920s the major source of methanol was as a byproduct m the production of charcoal from wood—hence the name wood alcohol Now most of the more than 10 billion lb of methanol used annually m the United States is synthetic prepared by reduc tion of carbon monoxide with hydrogen... 

A mixture of the two reactants carbon monoxide and hydrogen is called synthesis gas and IS prepared by several processes The most widely used route to synthesis gas employs methane (from natural gas) and gives a 3 1 hydrogen to carbon monoxide ratio... 

The linear a olefins described m Section 14 15 are starting materials for the preparation of a variety of aldehydes by reaction with carbon monoxide The process is called hydroformylation... 

Although these humble origins make interesting historical notes m most cases the large scale preparation of carboxylic acids relies on chemical synthesis Virtually none of the 3 X 10 lb of acetic acid produced m the United States each year is obtained from vinegar Instead most industrial acetic acid comes from the reaction of methanol with carbon monoxide... 

Formic acid [64-18-6] (methanoic acid) is the first member of the homologous series of alkyl carboxyHc acids. It occurs naturally ia the defensive secretions of a number of insects, particularly of ants. Although the acid nature of the vapors above ants nests had been known since at least 1488, the pure acid was not isolated until 1671, when the British chemist John Ray described the isolation of the pure acid by distillation of ants (1). This remained the main preparative method for more than a century until a convenient laboratory method was discovered by Gay-Lussac (2). The preparation of formates using carbon monoxide was described by Berthelot in 1856. 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

Other possible chemical synthesis routes for lactic acid include base-cataly2ed degradation of sugars oxidation of propylene glycol reaction of acetaldehyde, carbon monoxide, and water at elevated temperatures and pressures hydrolysis of chloropropionic acid (prepared by chlorination of propionic acid) nitric acid oxidation of propylene etc. None of these routes has led to a technically and economically viable process (6). 

Lead sesquioxide is used as an oxidation catalyst for carbon monoxide ia exhaust gases (44,45) (see Exhaust control), as a catalyst for the preparation of lactams (46) (see Antibiotics, P-lactams), ia the manufacture of high purity diamonds (47) (see Carbon, diamond-natural), ia fireproofing compositions for poly(ethylene terephthalate) plastics (48), ia radiation detectors for x-rays and nuclear particles (49), and ia vulcanization accelerators for neoprene mbber (50). 

The reaction of methyl propionate and formaldehyde in the gas phase proceeds with reasonable selectivity to MMA and MAA (ca 90%), but with conversions of only 30%. A variety of catalysts such as V—Sb on siUca-alumina (109), P—Zr, Al, boron oxide (110), and supported Fe—P (111) have been used. Methjial (dimethoxymethane) or methanol itself may be used in place of formaldehyde and often result in improved yields. Methyl propionate may be prepared in excellent yield by the reaction of ethylene and carbon monoxide in methanol over a mthenium acetylacetonate catalyst or by utilizing a palladium—phosphine ligand catalyst (112,113). 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Most chromium-based catalysts are activated in the beginning of a polymerization reaction through exposure to ethylene at high temperature. The activation step can be accelerated with carbon monoxide. Phillips catalysts operate at 85—110°C (38,40), and exhibit very high activity, from 3 to 10 kg HDPE per g of catalyst (300—1000 kg HDPE/g Cr). Molecular weights and MWDs of the resins are controlled primarily by two factors, the reaction temperature and the composition and preparation procedure of the catalyst (38,39). Phillips catalysts produce HDPE with a MJM ratio of about 6—12 and MFR values of 90—120. 

Fluoroformyl peroxide [692-74-0] (20, R = R = F), has been prepared by the reaction of carbon monoxide, fluorine, and oxygen or by the photolytic reaction of oxalyl fluoride with oxygen (187). 

Semiconductors. Phosphine is commonly used in the electronics industry as an -type dopant for siUcon semiconductors (6), and to a lesser extent for the preparation of gaUium—indium—phosphide devices (7). For these end uses, high purity, electronic-grade phosphine is required normally >99.999% pure. The main impurities that occur in phosphine manufactured by the acid process are nitrogen [7727-37-9] hydrogen [1333-74-0] arsine [7784-42-17, carbon dioxide [124-38-9], oxygen [7782-44-7], methane [74-82-8], carbon monoxide [630-08-0], and water [7732-42-1]. Phosphine is purified by distillation under pressure to reduce the level of these compounds to <1 ppm by volume. The final product is sold as CYPURE (Cytec Canada Inc.) phosphine. 

StUl another ore preparation is the nodulizing process where the ore is heated in a rotary kiln to incipient fusion. The tumbling action in the kiln causes the phosphate ore to cohere and form spheroidal agglomerates. Combustion of carbon monoxide from the furnaces is used along with supplemental fuel to supply heat to 1300—1500°C. A boring bar is used near the kiln discharge to aid in breaking up the fused ore. The material is then cooled, cmshed, and screened to the appropriate size for furnace feed. 

The oldest method of preparation of ben2enehexol involves the reaction of molten potassium with carbon monoxide to give the potassium salt of the hexol the free phenol is obtained by neutrali2ation of the salt with dilute acid (263). This reaction has been reinvestigated and improved (264). 

Synthesis gas preparation consists of three steps ( /) feedstock conversion, (2) carbon monoxide conversion, and (2) gas purification. Table 4 gives the main processes for each of the feedstocks (qv) used. In each case, except for water electrolysis, concommitant to the reactions shown, the water-gas shift reaction occurs. 

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