Acetylene chlorination/condensation

Figure 8.3 Scheme for global acetylene chlorination/condensation mechanism leading to hexachlorobenzene. (From A. Wehrmeier et al., Environ. Sci. Technol, 1998.)... 

More recently, direct catalytic oxidative condensation of methane to ethane (with metal oxides),57,82-84 as well as to ethylene and acetylene (via high-temperature chlorinative conversion) was explored.76 In all these processes, however, a significant portion of methane is lost by further oxidation and soot formation. The selectivity in obtaining ethane and ethylene (or acetylene), respectively, the first C2 products, is low. There has, however, been much progress in metal-oxide-catalyzed oxidative condensation to ethane. 

Addition of carbenes. Aryl acetylenes condense with the chlorinated oxocarbene 202 (35 hours at 100°) and give, through 1,3-cycloaddition, 3-substituted 4,5,6,7-tetrachloro-2-phenylbenzofurans (203).459 Compound 203 is readily dechlorinated (hydrogenation on Raney nickel in... 

In the first example, nitration of the benzoate (140) with nitric acid affords the nitro derivative. Hydrogenation converts this to the anthranilate (141). In one of the standard conditions for forming quinazolones, that intermediate is then treated with ammonium formate to yield the heterocycle (142). Reaction of 142 with phosphorus oxychloride leads to the corresponding enol chloride (143). Condensation of 143 with m-iodoaniline (144) leads to displacement of chlorine and consequent formation of the aminoquinazoline (145). Reaction with the trimethylsilyl derivative of acetylene in the presence of tetrakis-triphenylphosphine palladium leads to replacement of iodine by the acetylide. Tributylammonium fluoride then removes the silyl protecting group to afford the kinase inhibitor erlotinib (146). ... 

The process is fed with three streams ethane, ethylene, and chlorine. The ethane and ethylene streams have the same molar flow rate, and the ratio of chlorine to ethane plus ethylene is 1.5. The ethane/ethylene stream also contains 1.5 percent acetylene and carbon dioxide. (For this problem, just use 1.5 percent carbon dioxide.) The feed streams are mixed with an ethylene recycle stream and go to the first reactor (chlorination reactor) where the ethane reacts with chlorine with a 95 percent conversion per pass. The product stream is cooled and ethyl chloride is condensed and separated. Assume that all the ethane and ethyl chloride go out in the condensate stream. The gases go to another reactor (hydrochlorination reactor) where the reaction with ethylene takes place with a 50 percent conversion per pass. The product stream is cooled to condense the ethyl chloride, and the gases (predominately ethylene and chlorine) are recycled. A purge or bleed stream takes off a fraction of the recycle stream (use 1 percent). Complete the mass balance for this process. 

Figure 5.3 illustrates a process to manufacture acetylene from calcium carbide. The carbide is introduced by a screw conveyor into a perforated horizontal cylinder housed in a concentric envelope. Water is sprayed inside the internal shell. The acetylene formed passes upstream through the screw conveyor to a scrubbing tower, where, a new water spray carries off most, of the solids conveyed by the gas. The residual lime and carbide impurities are removed by a screw conveyor to a sludge receiver. The acetylene is cooled to — 10°C to condense most of the water. It is then purified by contact with dilute sulfuric acid in a liquid liquid absorber, and then with sodium hypochlorite prepared by the action of chlorine on caustic soda, to. remove impurities. The acetylene is then cooled to 0°C for the more complete separation of moisture. The final product nevertheless still contains 0.4 per cent by weight of water, which is suitable for most uses. More intensive dehydratation can be achieved by passage over silicagel. 

The condensation of aldehydes with thiocyanoacetic esters, catalysed by potassium fluoride or potassium carbonate, gave as minor products yV-carbamoyl-2-imino-5-alkyl(or aryl)-l, 3-oxathiolan-4-carboxylic esters, in which the 4,5-c/j-isomers predominated according to n.m.r. spectroscopy. l,3-Oxathiolan-2-thione was converted into dimethyl 1,3-dithiol-2-one-4,5-dicarboxylate and ethylene on treatment with dimethyl acetylene-dicarboxylate, and the transformation of methyl 2-methoxycarbonyl-methyl-1,3-oxathiolan-2-carboxylate into dimethyl-5,6-dihydro-l, 4-oxa-thiin-2,3-dicarboxylate by chlorination at low temperatures found analogy in the reactions of 2,2-dialkyl-l,3-oxathiolans. Thiomethoxymethyl hexachloroantimonate reacted with potassium t-butoxide to give mainly 3,5,5-trimethyl-l,3-oxathiolanium hexachloroantimonate the mechanism of this remarkable reaction was not settled. ... 

The acetylenic and polyacetylenic monoalcohols are generally simple molecules, with an average of 20 carbon atoms. More condensed molecules with 46 and 47 carbon atoms are frequent and are probably formed by coupling. A dozen original acetylenic alcohols with 16 carbon atoms and a vinylic chlorine atom were recently isolated from the species Haliclona lunisimilis harvested in San Diego (De Jesus and Faulkner, 2003). Acetylenic derivatives are numerous and only a few of the most recent examples are presented in Figures 19.69 (diols) and 19.70 (triols and polyols). 

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