Sodium, acetylide hydrocarbons

Reaction XXXIV. (c) Action of Carbon Dioxide on Sodium Acetylides in Dry Ether. (B., 12, 853 J. pr., [2], 27, 417 B., 33, 3586.)—This is an example of the great activating influence of a triple bond. When carbon dioxide is passed into a solution of the sodium derivative of an acetylenic hydrocarbon in dry ether, direct addition takes place to give the sodium salt of the next highest acetylenic carboxylic acid. For example, sodium allylene yields sodium tetrolate—... 

This method finds commercial application in the production of acetaldehyde from acetylene. Mercuric salts in the presence of dilute sulfuric acid act as the catalyst. The reaction has been extended to higher alkylacetylenes, which are obtained in about 60% yield from sodium acetylide and alkyl halides. These compounds are readily hydrated in aqueous solutions of acetone, methanol, or acetic acid to give 80-90% yields of the corresponding methyl ketones, fot example, methyl butyl, methyl amyl, and methyl hexyl ketones. Hydration has been accomplished by passing the acetylenic hydrocarbon and steam over a phosphoric acid catalyst at 150-204° and atmospheric pressure. ... 

Acetylene and other compounds which contain the =CH group react with sodium and potassium and form metallic derivatives. When acetylene is passed over gently-heated sodium one-half of the hydrogen in the hydrocarbon is replaced by the metal and a sodium acetylide, C2HNa, is formed. At red heat the disubstituted-product C2Na2 results. 

The sodium acetylide solution thus prepared may be used for a variety of organic syntheses by the addition of alkyl halides, sulfates, sulfonates, ketones, aldehydes, and esters. Where a fine suspension of the dry acetylide is desired in an inert solvent such as ether or a hydrocarbon, the solvent is added to the ammonia solution and the mixture is stirred whde the ammonia is evaporated. Extra solvent must be used to replace that entrained by the ammonia, the last traces of which are removed by a period of refluxing. Such a suspension gives better yields of, for example, propiolic acid (by the reaction with carbon dioxide) than sodium acetylide prepared in any other way. 

Chlorine Ammonia, acetylene, alcohols, alkanes, benzene, butadiene, carbon disulflde, dibutyl phthalate, ethers, fluorine, glycerol, hydrocarbons, hydrogen, sodium carbide, flnely divided metals, metal acetylides and carbides, nitrogen compounds, nonmetals, nonmetal hydrides, phosphorus compounds, polychlorobi-phenyl, silicones, steel, sulfldes, synthetic rubber, turpentine... 

The silver acetylides appear to have substantially covalent carbon-metal bonds and are less ionic than sodium and potassium alkynides. Silver-ammonia solution may be used to precipitate 1-alkynes from mixtures with other hydrocarbons. The 1-alkynes are regenerated easily from the silver precipitates by treatment with strong inorganic acids. It should be noted, however, that silver alkynides may be shock sensitive and can decompose explosively, especially when dry. 

MERCURY(n) NITRATE (10045-94-0, anhydrous 7783-34-8, monohydrate) Hg(N03)2 H,0 Noncombustible solid. Light sensitive. A powerful oxidizer accelerates the burning of combustible materials. Violent reaction, or may form explosive materials, with reducing agents, including hydrides, nitrides, phosphorus, stannous chloride, and sulfides alkyl esters (forms explosive alkyl nitrates) combustible materials (especially if finely divided), phosphinic acid, hypophosphoric acid, metal powders petroleiun hydrocarbons. Forms heat- and/or shock-sensitive compounds with acetylene (forms explosive mercmy acetylide), ethanol and other alcohols (may form explosive mercury fulminates), ferrocene, isobutene, phosphine gas (forms heat- and shock-sensitive precipitate) potassiiun cyanide, sulfur. Incompatible with strong acids, acetic anhydride, ammonia, ammonium hexacyanofenate(II), organic azides, citric acid, hydrazinium perchlorate, isopropyl chlorocarbonate, nitrosyl perchlorate, sodium thiosulfate, sulfamic acid, thiocyanates, hydrozoic acid, methyl isocyanoacetate, sodium peroxyborate, trinitrobenzoic acid, urea nitrate. Aqueous solution corrodes metals. 

BENSULFOID (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry materia forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysis, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium iodate, potassium peroxoferrate, rubidium acetylide, ruthenium tetraoxide, sodium, sodium chlorite, sodium peroxide, tin, uranium, zinc, zinc(II) nitrate, hexahydrate. Forms heat-, friction-, impact-, and shock-sensitive explosive or pyrophoric mixtures with ammonia, ammonium nitrate, barium bromate, bromates, calcium carbide, charcoal, hydrocarbons, iodates, iodine pentafluoride, iodine penloxide, iron, lead chromate, mercurous oxide, mercury nitrate, mercury oxide, nitryl fluoride, nitrogen dioxide, inorganic perchlorates, potassium bromate, potassium nitride, potassium perchlorate, silver nitrate, sodium hydride, sulfur dichloride. Incompatible with barium carbide, calcium, calcium carbide, calcium phosphide, chromates, chromic acid, chromic... 

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