Carbon monoxide with amines

Reaction of carbon monoxide with amines N- Formylation... 

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. 

The shift towards the monoaminocarbonylation, obtained under these conditions, as compared with the dialkoxycarbonylation observed in alcoholic solvents, is due to the basicity of the amine, which favors the formation of an alkynylpalladium complex (Scheme 37). This species then inserts carbon monoxide with formation of an alkynoylpalladium intermediate, which undergoes nucleophilic displacement by R2NH to give the final 2-ynamide. 

Volume 17 covers gas-phase combustion, which includes probably the most complex processes investigated by chemists. Chapter 1, about half the book, deals with the oxidation of hydrogen and carbon monoxide, with extensive consideration of all the individual reactions occurring. In Chapter 2, the combustion of hydrocarbons is discussed, with emphasis on the general mechanisms which have been suggested to account for the numerous products of partial oxidation. In Chapter 3, the oxidation of aldehydes, which are important intermediates in combustion of other compounds, is considered, and in Chapter 4, the oxidation of alcohols, ketones, oxirans, ethers, esters, peroxides, amines and halocarbons. 

It does not react with ammonia, but the basic amines, like pyridine, react to produce carbon monoxide. With hydrazine it reacts vigorously, forming a syrupy substance with an intense red colour for each molecule of hydrazine, four molecules of carbon monoxide are set free. ... 

Despite the presence of a formally divalent carbon atom, CO is not in fact a particularly reactive molecule and much of its chemistry depends on the use of either extreme conditions, energetic reagents or some form of catalysis. Perhaps the simplest examples of such catalysis are found in the reactions of carbon monoxide with protic reagents such as alcohols or secondary amines, affording esters or amides of formic acid. These reactions are catalyzed by alkoxide or amide anions, respectively, and, as shown in Scheme 1, the key step is nucleophilic attack on CO by the catalyst to give a strongly basic alkoxyacyl or aminoacyl anion which is immediately trapped by proton transfer from the alcohol or amine, so generating the catalytic species. 

McGhee and co-workers at Monsanto have studied the preparation of isocyanates using nontoxic carbon dioxide (instead of the poisonous carbon monoxide) with the amine (2.17).47... 

A large variety of carbon-containing gas species have been employed to synthesize diamond by CVD, These include methane, aliphatic and aromatic hydrocarbons, alcohols, ketones, amines, ethers, and carbon monoxide, with methane being the most frequently used reagent. In... 

Thiocarbamates. Thiocarbamates can be prepared in fair to high yield by reaction of amines and disulfides with carbon monoxide with selenium as catalyst. If triethylamine is added as cocatalyst, aromatic amines can also be used. ... 

Carbon monoxide is purified and used as a feedstock for several primary petrochemicals The largest quantity is used for carbonylation of methanol to produce acetic acid. Acetic acid is used in the production of vinyl acetate, acetic anhydride and cellulose acetates. Phosgene, formed by the reaction of carbon monoxide with chlorine, is reacted with amines to form polyurethane intermediates. Phosgene is also reacted with bisphenol A to form polycarbonate resins, used for engineering plastics. 

Polyfunctional isocyanates can be formed in many ways. Commercially, the most important way is through reactions of phosgene with amines or amine salts. Other reactions, however, like that of carbon monoxide with nitro compounds, are now also becoming important. Addition of isocyanic acid to olefins is also gaining prominence. 

Further studies revealed that there are two courses leading to amide from the carbony-lation of benzylpalladium complexes depending on the amount of secondary amine employed. One involves the formation of benzyl(carbamoyl)palladium intermediate, from which amide is produced on reductive elimination when neat amine is used. The other is composed of the CO insertion into benzyl-palladium bond to give phenylacetylpalladium intermediate, which may further react with amine to liberate the single carbonylation product. The latter process takes place when a limited amount of amine is employed. The a-keto amides were found to be produced in the reaction of carbon monoxide with trans- and di-methylpalladium carbamate complexes, PdMe(OCONRR )L2, accompanied by formation of amides (Eq. 20). The process was assumed to involve decarboxylation of the carbamate ligand associated with CO insertion and attack of the amide entity on the coordinated CO. 

Selenium reacts with carbon monoxide and amines under mild conditions (15 °C, 1 atm) to give ammonium carbamoselenoates 1050, which are then converted to the corresponding ureas 1051 by aminolysis upon oxidation with molecular oxy-... 

Table 42 [465]. Unsaturated carboxylic acid amides by reaction of alkynes with carbon monoxide and amines or amides resp.

Formation of anhydride succeeds with Ni catalysts even at lower temperatures (230 to 250 °C) than the synthesis of propionic acid from ethylene. Thiolcarboxylic acid esters are obtained analogously by addition of thiols instead of carboxylic acids (2). Olefins, carbon monoxide and amines react to give saturated carboxylic acid amides (3) and acid chlorides are formed from hydrogen chloride and carbon monoxide in the presence of noble metal catalysts of the 8th group of the periodic table of the elements (4). 

Table 49. Reaction of olefins and carbon monoxide with carboxylic acids, thiols, amines or hydrogen chloride in the presence of transition metal carbonyls...

Yields up to 80 % are obtained. Instead of halides also sulfates or sulfonates can be used. Esters are formed in the presence of alcohols or amides in the presence of amines (see table 52). Acid chlorides are available by reaction of carbon monoxide with allyl chloride in the absence of solvents [121, 562]. 

B. and Salerno, G. (1999) Sequential reaction of carbon dioxide and carbon monoxide with acetylenic amines in the presence of a palladium catalyst Journal of Molecular Catalysis A Chemical, 143, 297-310. 

CO. Alkynes will react with carbon monoxide in the presence of a metal carbonyl (e.g. Ni(CO)4) and water to give prop>enoic acids (R-CH = CH-C02H), with alcohols (R OH) to give propenoic esters, RCH CHC02R and with amines (R NH2) to give propenoic amides RCHrCHCONHR. Using alternative catalysts, e.g. Fe(CO)5, alkynes and carbon monoxide will produce cyclopentadienones or hydroquinols. A commercially important variation of this reaction is hydroformyiation (the 0x0 reaction ). 

Use of alcohol as a solvent for carbonylation with reduced Pd catalysts gives vinyl esters. A variety of acrylamides can be made through oxidative addition of carbon monoxide [630-08-0] CO, and various amines to vinyl chloride in the presence of phosphine complexes of Pd or other precious metals as catalyst (14). 

Olefins can be aminomethylated with carbon monoxide [630-08-0] (CO) and amines in the presence of rhodium-based catalysts. Eor example, pipera2ine reacts with cyclohexene [110-83-8] to form W,Af-di-(l-cyclohexylmethyl)-pipera2ine [79952-94-6] (55). 

The reaction produces additional hydrogen for ammonia synthesis. The shift reactor effluent is cooled and tlie condensed water is separated. The gas is purified by removing carbon dioxide from the synthesis gas by absorption with hot carbonate, Selexol, or methyl ethyl amine (MEA). After purification, the remaining traces of carbon monoxide and carbon dioxide are removed in the methanation reactions. 

The idea that dichlorocarbene is an intermediate in the basic hydrolysis of chloroform is now one hundred years old. It was first suggested by Geuther in 1862 to explain the formation of carbon monoxide, in addition to formate ions, in the reaction of chloroform (and similarly, bromoform) with alkali. At the end of the last century Nef interpreted several well-known reactions involving chloroform and a base in terms of the intermediate formation of dichlorocarbene. These reactions included the ring expansion of pyrroles to pyridines and of indoles to quinolines, as well as the Hofmann carbylamine test for primary amines and the Reimer-Tiemann formylation of phenols. 

Finally, the term steric stabihzation coifid be used to describe protective transition-metal colloids with traditional ligands or solvents [38]. This stabilization occurs by (i) the strong coordination of various metal nanoparticles with ligands such as phosphines [48-51], thiols [52-55], amines [54,56-58], oxazolines [59] or carbon monoxide [51] (ii) weak interactions with solvents such as tetrahydrofuran or various alcohols. Several examples are known with Ru, Ft and Rh nanoparticles [51,60-63]. In a few cases, it has been estab-hshed that a coordinated solvent such as heptanol is present at the surface and acts as a weakly coordinating ligand [61]. 

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