Carbon monoxide chloride effect

The reaction of chloroamine 214 with carbon monoxide is effectively catalyzed by palladium metal, palladium(II) chloride, or rhodium(III) chloride to produce carbamoyl chloride 215. 

These processes have supplanted the condensation reaction of ethanol, carbon monoxide, and acetylene as the principal method of generating ethyl acrylate [140-88-5] (333). Acidic catalysts, particularly sulfuric acid (334—338), are generally effective in increasing the rates of the esterification reactions. Care is taken to avoid excessive polymerisation losses of both acryflc acid and the esters, which are accentuated by the presence of strong acid catalysts. A synthesis for acryflc esters from vinyl chloride (339) has also been examined. 

As noted above, there is experimental evidence to indicate that the carbonyl groups of (vinyl chloride)-(carbon monoxide) copolymers are effective sensitizers for the photodegradation of these materials (9,10,11). A reasonable sensitization mechanism can be formulated for this system on the basis of the information now on hand. 

The analogous hydroxylation of alkynes to produce ketones is enhanced by the co-catalytic effect of Aliquat and platinum(IV) chloride-carbon monoxide [3] it is assumed that HPtCI(CO) is the active hydration species. C-S and C-Br bonds are cleaved under the reaction conditions. 

Finally, manganese carbonyl complexes also show potential for effecting interesting phase transfer catalyzed carbonylation reactions. Alkynes react with carbon monoxide and methyl iodide in methylene chloride, using 5N NaOH as the aqueous phase, benzyl-triethylammonium chloride as the phase transfer catalyst, and either bromopentacarbonylmanganese or dimanganese decacarbonyl to afford... 

An attempt was also made to produce 0-iodo acyl iodides by the reaction of iodine, carbon monoxide and olefins in the presence of palladium or platinum chloride. This is, in effect, an attempt to make Dr. Tsuji s reaction catalytic rather than stoichiometric. No carbonyl insertion occurred at 1 atm. of carbon monoxide. However, it was found that iodination of the olefin was catalyzed by platinum olefin complexes and that an additional increase in catalytic activity accompanied the presence of carbon monoxide. There has been much speculation at this conference concerning the possibility of affecting catalytic activity by changing the ligands in the coordination sphere of the catalyst. This would appear to be such a case. 

The previous extension of solvent mixtures involved solvent interfaces. This organic-water interfacial technique has been successfully extended to the synthesis of phenylacetic and phenylenediacetic acids based on the use of surface-active palla-dium-(4-dimethylaminophenyl)diphenylphosphine complex in conjunction with dode-cyl sodium sulfate to effect the carbonylation of benzyl chloride and dichloro-p-xylene in a toluene-aqueous sodium hydroxide mixture. The product yields at 60°C and 1 atm are essentially quantitative based on the substrate conversions, although carbon monoxide also undergoes a slow hydrolysis reaction along with the carbonylation reactions. The side reaction produces formic acid and is catalyzed by aqueous base but not by palladium. The phosphine ligand is stable to the carbonylation reactions and the palladium can be recovered quantitatively as a compact emulsion between the organic and aqueous phases after the reaction, but the catalytic activity of the recovered palladium is about a third of its initial activity due to product inhibition (Zhong et al., 1996). 

Putz, V.R., Johnson, B.L. Setzer, J.V (1976) A comparative study of the effects of carbon monoxide and methylene chloride on human performance. J. environ. Pathol. Toxicol., 2,97-112... 

A mixture of palladium chloride and triphenylphosphine effectively catalyzes carboxylation of linoleic and linolenic acids and their methyl esters with water at 110°-140°C and carbon monoxide at 4000 psig. The main products are 1,3-and 1,4-dicarboxy acids from dienes and tricarboxy acids from trienes. Other products include unsaturated monocar-boxy and dicarboxy acids, carbomethoxy esters, and substituted a,J3-unsaturated cyclic ketones. The mechanism postulated for dicarboxylation involves cyclic unsaturated acylr-PdCl-PhsP complexes. These intermediates control double bond isomerization and the position of the second carboxyl group. This mechanism is consistent with our finding of double bond isomerization in polyenes and not in monoenes. A 1,3-hydrogen shift process for double bond isomerization in polyenes is also consistent with the data. 

Fauveau and Le Paire 23 studied the anti-flash effect of potassium chloride and of other salts and concluded that the lowering of the temperature of the gas which undoubtedly results from their volatilization and dissociation is insufficient to account for the extinction of the flash. Prettre24 found that the chlorides of sodium and of lithium, and other alkali metal salts which are volatile, had the same effect as potassium chloride. He found that small amounts of potassium chloride, volatilized in mixtures of carbon monoxide and air, had a powerful anti-oxidant action and a correspondingly large effect in raising the temperature of inflammation of the gas. Some of his results are shown in the table below. He found that potassium chloride was without effect... 

Recently, it has been discovered that catalysis by rhodium compounds is more effective than by the older cobalt catalyst when tris(triphenylphosphine)rhodium chloride is treated with carbon monoxide, the catalyst bis(triphenylphosphine)rhodium carbonyl chloride is formed. This catalyst is very effective under very mild conditions (49-51). It is believed that the tr-ir rearrangement is also important with this catalyst and operates in a manner analogous to that in the cobalt-catalyzed process, since stablization of the cr complex has been shown to lead to olefin isomerization and lower linear selectivity (52). 

As Table 2-1 shows, the treatment of the mustard agent (HD) resulted in stack concentrations, DRE, operating temperatures, carbon monoxide concentrations, stack particulate concentrations, and hydrogen chloride emissions that were all within required limits for all four test mns. At the time the trial bum report was prepared, no limits had been established for metals. However, the report notes that the measured concentrations were very close to the detection limits in all cases (U.S. Army, 1992). It is not clear whether the low concentrations were due to low metals content in the agent stream or to the effective removal of metals during processing. 

The application of surface-enhanced Raman spectroscopy (SERS) for monitoring redox and other processes at metal-solution interfaces is illustrated by means of some recent results obtained in our laboratory. The detection of adsorbed species present at outer- as well as inner-sphere reaction sites is noted. The influence of surface interaction effects on the SER spectra of adsorbed redox couples is discussed with a view towards utilizing the frequency-potential dependence of oxidation-state sensitive vibrational modes as a criterion of reactant-surface electronic coupling effects. Illustrative data are presented for Ru(NH3)63+/2+ adsorbed electrostatically to chloride-coated silver, and Fe(CN)63 /" bound to gold electrodes the latter couple appears to be valence delocalized under some conditions. The use of coupled SERS-rotating disk voltammetry measurements to examine the kinetics and mechanisms of irreversible and multistep electrochemical reactions is also discussed. Examples given are the outer- and inner-sphere one-electron reductions of Co(III) and Cr(III) complexes at silver, and the oxidation of carbon monoxide and iodide at gold electrodes. 

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