DE734402C - Process for the production of ethers - Google Patents

Description

Process for the preparation of ethereal It is known to use vinyl acetylene with alcohols in the presence of mercury oxide and boron trifluoricl or addition compounds to implement the boron fluoride, with the addition of 3 moles of alcohol to the double and triple bond of a mole of vinyl acetylene ether with three ether groups develop.

It has now been found that ethers with several ether groups can be found in more advantageous way if you get alcohols or phenols with hydrocarbons, either the cumulative double bonds or a double and triple bond contained in conjugation, in the presence of mercury sulfate while pausing such Reacts temperatures at which polymerization is avoided. .

Examples of hydrocarbons with accumulated double bonds are Allen and 3Tethylallen; Hydrocarbons that have a double and triple bond contained in conjugation are, for example, _Polymers of acetylene of the type of vinyl acetylene.

The reaction can be carried out in the presence of inert solvents or else an excess of alcohol or phenol, which then acts as a solvent act, make. The hydrocarbons can be liquid or gaseous, if appropriate can also be diluted with inert gases.

The implementation provides warmth. To a polymerization of the unsaturated To avoid hydrocarbons, one preferably only maintains the working temperature little above the temperature at which the reaction starts noticeably. Advantageously sets one of the mercury sulfate serving as a catalyst has an oxidizing effect, such as Vanadates, chromates, manganates, ferric or cupric salts., Too. These extend the Lifetime of the catalyst, increase the yield of ether and also set the tendency of the unsaturated hydrocarbons to polymerize.

The ethers obtained are mostly water-white, easily mobile liquids. They are valuable solvents; they can also be used because of their high octane number use as motor fuels or as additives to motor fuels.

The invention offers the above-mentioned known method the advantage that it is no longer necessary to eat boron fluoride or its addition compounds to be used. In addition, the ethers obtained are consistently purer than when working with dorofluoride, to blame that for the formation of undesirable by-products is.

Although it is known to convert alcohols to acetylene in the presence of mercury compounds. also of mercury sulfate, to-. to store. In this reaction, the starting material contains only a triple bond but no double bond. It's surprising to see that double and triple unsaturated hydrocarbons of the type of vinyl acetylene the 2vierlzurisulfat an addition of alcohols to both causes the double bond as well as the triple bond, since other mercury compounds, z. B. mercury oxide, only favor the addition to the triple bond and when reacting vinyl acetylene with alcohols only by adding boron fluoride, which is able to promote the addition of alcohols to double bonds, to mercury oxide Contains fully saturated ether.

The parts given in the examples below are parts by weight. EXAMPLE i 255 parts of methylallene are introduced into a mixture of 237 parts of methanol and 50 parts of Ierlcurisulfat in the course of one-half hours with stirring. The implementation immediately entering already at about 20 "under excessive heat is tempered by strong cooling the mixture to 2.1`. If no methylallene is more added, the mixture is neutralized with methyl alcoholic potash and stirred for 1 5 minutes ahead long. Coming in from the by neutralizing Colorless products obtained and freed from the catalyst, obtainable in good yield: Uher is purified by fractional distillation. In this way, 3 10 parts of dimethoxybutane (bp7 "o = 104.5 to 105.2'j. ES is an easily mobile, colorless one Liquid with a pleasant, ethereal odor. It is suitable as a solvent for resins, lacquers or rubber the temperature is maintained by cooling at 55 to 60. When no more metal is absorbed, it is neutralized with methyl alcohol he potassium hydroxide. The liquid part of the mixture is made up of solid parts - .. ti-ennt and distilled. At 116- the quantity of the ether obtained passes over as a colorless, easily mobile liquid with a pleasant ethereal odor.

If, all other things being equal, the catalyst is still 5o If you add parts of errisulfate, you can use three times the amount of the starting material realize. Example Into a mixture of 941 parts of 1-ethanol and 50 parts of mercury sulfate and 30 parts of ferric sulphate are passed between in a vessel spared with Rübrer 25 and 3o 'in the course of; Hours .1G # 9 parts @ -inylacety len a-after completion the reaction is neutralized with niethylailkoliolisclier potassium hydroxide solution and filtered. The filtrate is distilled in vacuo. At 55- / 45mm (i55 to i57 /; 6ommi go 6i6 parts of 2, 2, 4-trimethoxybutane about. Example q. To a mixture of 100 parts Phenol with 20 parts llerl #: uristtlfat. 5 parts of ferric sulfate and; oo parts of carbon tetrachloride add vinyl octylene at 60,000 parts. After 5 to 6 hours, the Catalyst off, neutralized with amniotic methanol solution and distilled under reduced pressure. The resulting ether (1p2 "= i25- i is obtained in form an easily agile liquid.

Claims (1)

PATENT CLAIM: Process for the production of _Uhern by the action of hydrotyl-containing organic compounds on polyunsaturated hydrocarbons in the presence of mercury compounds, characterized in that alcohols or phenols with hydrocarbons which contain either cumulative double bonds or a double and triple bond in conjugation are in Reacts the presence of mercury sulfate while maintaining temperatures at which polymerization is avoided.