Patent GB-446013-A (GB)
Title: Improvements in or relating to the reduction of hydrocarbons
IPC: C07C5/10
Filed: 1934-10-22
Abstract: Hydrogenated acenaphthene, naphthalene and homologues thereof, and polymers of the said hydrogenated products are obtained by treating the hydrocarbon with alkali metal in the ethers specified in Specifications 443,361 and 445,417, i.e. certain dialkyl mono-ethers and polyethers alone or mixed with other inert compounds, as solvents, to form the alkali metal addition p  products, and hydrolyzing the said products either (1) to produce the monomeric hydrogenated hydrocarbon by hydrolysis with customary agents at specified low temperatures, or by continuous hydrolysis at higher temperatures so that free unreacted alkali-hydrocarbon compound does not remain in the solution, (which condition is determined by the green colour of the solution), or (2) to produce one or more polymerized hydrogenated hydrocarbons (which may also be obtained by treating an alkali-hydrocarbon compound in solution with one of the hydrogenated hydrocarbons) by hydrolysis at specified higher temperatures.  Complex polymers may be obtained by the above-mentioned method, or by starting with a mixture of hydrocarbons in solution.  According to examples: (1) naphthalene is reacted with finely divided sodium in liquid dimethyl ether in an atmosphere of nitrogen to convert it to the green sodium-naphthalene compound which is hydrolyzed at the same low temperature by excess of methanol, removal of solvent, &c. to give a mixture of dihydronaphthalenes chiefly 1 : 4-dihydronaphthalene; (2) naphthalene is treated with sodium in dimethyl glycol ether followed by substantially instantaneous hydrolysis by means of a mixture of water and solvent or addition of water to give an equimolecular mixture of naphthalene and dihydronaphthalene or dihydronaphthalene alone; (3) the method of hydrolysis of example 1 is replaced by hydrolysis with methanol at a rate insufficient to discharge the green colour, to give naphthalene and dihydronaphthalene; (4) the mixture obtained by hydrolyzing with water the partially formed sodium-naphthalene addition product is reacted with a further quantity of sodium at room temperature and hydrolyzed and distilled to give a colourless condensation product; (5) a product similar to the above mixed with a dimer of dihydronaphthalene and by-products is obtained by treating an equimolecular mixture of dihydronaphthalene and naphthalene with sodium and completely hydrolyzing; (6) the above-mentioned dimer of naphthalene is treated with the sodium-naphthalene compound, and hydrolyzed completely with water to give a resinous condensation product; (7) a -methyl and b -methylnaphthalene are partially converted to their respective sodium compounds, the products hydrolyzed, the remainder of the hydrocarbons treated with sodium, and the products from the reaction between the first-formed dihydro-compound and the remainder of the sodium-hydrocarbon compound after hydrolysis with water, distilled, giving mixtures of viscous dimeric dihydromethylnaphthalenes, and resinous trimeric compounds; (8) acenaphthene is converted to the dihydro-body by reaction with sodium and instantaneous hydrolysis; (9) dihydroacenaphthene is reacted with sodium-acenaphthene to give on hydrolysis, a resinous trimeric compound, containing the dimeric compound.  Further specified hydrolyzing agents which may be used are organic hydroxy compounds, amines, ketones which will react with alkali metals, organic acids, inorganic acids and unsaturated aliphatic hydrocarbons, especially tertiary butyl alcohol, aniline, acetic acid and acetylene.  The sodium hydroxide formed when water is used as hydrolytic agent is preferably removed as sodium bicarbonate.  Other water - soluble hydrolysis products with the sodium may be removed by washing with water.