Amines carbon monoxide

Synthesis of ureas. Ureas can be synthesized by the reaction of aliphatic amines, carbon monoxide, and oxygen with selenium as a catalyst. For example, n-butylamine (0.1 mole) is dissolved in THF (100 ml.) amorphous selenium (0.005 g.-atom) is added and carbon monoxide is blown through the solution. Then oxygen (or air) is blown through. 1,3-Di-n-butylurea is obtained in stoichiometric yield. The reaction proceeds in two steps as formulated. 

Catalytic formylation of aryl, heteroaryl, and vinylic halides in the presence of an amine, carbon monoxide, and hydrogen using a palladium complex such as PdCljfPPh.O provides a convenient route to conjugated aldehydes in good to excellent yields (Eq. 59). The use of iodo substrates secures excellent yields. 

Products of degradation CO, HCN, caprolactam, amines, carbon monoxide, hydrogen, hydrocarbons, crosslinks, carbon dioxide, acids, aldehydes, ketones, water, ammonia, hydroperoxides, pyrrole, ethylene ... 

Olefins react with secondjuy amines, carbon monoxide, and water in the presence of rhodium and iron catalysts to give alkylamines by a process of aminomethylation (Scheme 116). ... 

Aminomethylation of olefins can be attained in good yields by reaction of alkenes with secondary amines, carbon monoxide, and water in the presence of Rh203 and/or Fe(CO)5. Rhodium oxide is superior to Fe(CO)5 but highest yields can be realized when they are used together. This reaction has been applied to the synthesis of long-chain alkylamines (Iqbal, 1975). 

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 ). 

Both dimethyl carbonate [616-38-6] and diphenyl carbonate [102-09-0] have been used, in place of carbon monoxide, as reagents for the conversion of amines into isocyanates via this route (28,29). Alternatively, aniline [62-53-3] toluene diamines (I JJA), and methylene dianilines (MDA) have also been used as starting materials in the carbonylations to provide a wide variety of isocyanate monomers. 

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. 

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). 

An equimolar mixture of carbon monoxide and chlorine reacts at 500 K under a slight positive pressure. The reaction is extremely exothermic (Ai/gQQp. = —109.7 kJ or —26.22 kcal), and heat removal is the limiting factor in reactor design. Phosgene (qv) is often produced on-site for use in the manufacture of toluene diisocyanate (see Amines, aromatic-diaminotoluenes Isocyanates, organic). 

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 nature of the hazard considering its degree of toxicity and its warning properties. A release of carbon monoxide provides no warning while a release of some amine nornuilly provides a strong odor at concentrations well below hanuful levels. 

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. 

Direct measurements on metals such as iron, nickel and stainless steel have shown that adsorption occurs from acid solutions of inhibitors such as iodide ions, carbon monoxide and organic compounds such as amines , thioureas , sulphoxides , sulphidesand mer-captans. These studies have shown that the efficiency of inhibition (expressed as the relative reduction in corrosion rate) can be qualitatively related to the amount of adsorbed inhibitor on the metal surface. However, no detailed quantitative correlation has yet been achieved between these parameters. There is some evidence that adsorption of inhibitor species at low surface coverage d (for complete surface coverage 0=1) may be more effective in producing inhibition than adsorption at high surface coverage. In particular, the adsorption of polyvinyl pyridine on iron in hydrochloric acid at 0 < 0 -1 monolayer has been found to produce an 80% reduction in corrosion rate . 

Borane, 1-methylbenzylaminocyanohydropyrrolyl-, 3, 84 Borane, thiocyanato-halogenohydro-, 3,88 Borane, trialkoxy-amine complexes, 3, 88 Borane, triaryl-guanidine complexes, 2,283 Borane, trifluoro-complexes Lewis acids, 3,87 van der Waals complexes, 3, 84 Borane complexes aminecarboxy-, 3,84 aminehalogeno-, 3, 84 amines, 3, 82, 101 B-N bond polarity, 3, 82 preparation, 3, 83 reactions, 3, 83 bonds B-N, 3, 88 B-O, 3, 88 B-S, 3, 88 Jt bonds, 3, 82 carbon monoxide, 3, 84 chiral boron, 3, 84 dimethyl sulfide, 3, 84 enthalpy of dissociation, 3, 82... 

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]. 

The reaction of CDI with primary phosphines was expected to lead first to an azolide ImCOPHR, analogous to imidazole-N-carboxamide as the reaction product of primary amines and CDI. In fact, reaction of phenylphosphine with CDI leads directly to imidazole, carbonmonoxide, and tetraphenylcyclotetraphosphine (THF, reflux, 5h). In analogy to the dissociation of imidazole-AT-carboxamide into isocyanates and imidazole, this can be explained by the assumption that the first-formed ImCOPHC6H5 dissociates into an isocyanate analogue, C6H5P=C=0, which is unstable and decomposes into carbon monoxide and phenylphosphene (C6H5P) which tetramerizes. However, the intermediate formation of phenylphosphene has not yet been definitely proved. 

Lehn and Ziessel166 have also developed systems for the photochemical reduction of C02. These systems are similar to those represented by Fig. 18. Visible-light irradiation of C02-saturated aqueous acetonitrile solutions containing Ru(bpy)2+ as a photosensitizer, cobalt(II) chloride as an electron acceptor, and triethyl-amine as a sacrificial electron donor gave carbon monoxide and... 

During the vacuum fractional distillation of bulked residues (7.2 t containing 30-40% of the bis(hydroxyethyl) derivative, and up to 900 ppm of iron) at 210-225°C/445-55 mbar in a mild steel still, a runaway decomposition set in and accelerated to explosion. Laboratory work on the material charged showed that exothermic decomposition on the large scale would be expected to set in around 210-230°C, and that the induction time at 215°C of 12-19 h fell to 6-9 h in presence of mild steel. Quantitative work in sealed tubes showed a maximum rate of pressure rise of 45 bar/s, to a maximum developed pressure of 200 bar. The thermally induced decomposition produced primary amine, hydrogen chloride, ethylene, methane, carbon monoxide and carbon dioxide. 

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