DEB0027506MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: September 17, 1953 BekaiMitgeimadht on August 23, 1956

GERMAN PATENT OFFICE

It is known that monoalkynols which contain a free methine hydrogen atom can be treated with oxygen or oxygen-hooked, gases; in the presence of cuprous chloride and ammonium chloride in predominantly aqueous solution, optionally under excess pressure (German Patent 875 649), in the can convert corresponding diacetylene glycols. However, this method has the disadvantage that corrosion damage is caused when the conventional vessels made of steel are used and pitting can occur.

Attempts have already been made to avoid these disadvantages by using as catalysts for the oxidation of acetylene alcohols, with oxygen, air or other oxygen-containing gases basic in solutions containing halogen ions Salts of divalent copper are used (cf. the documents of patent application E 4362 IVb / 120 = Patent 890796). This well-known way of working has the disadvantage 'that basic copper salts are only slightly soluble in water and that Settling of the catalyst can only be avoided by constant stirring. Besides, it is required, the undissolved catalyst after the oxidation in a separate operation to separate. According to another known method (See. German Patent 870 845) the acetylene compounds are oxidized to form dioders Polyacetylene compounds using copper (II) salts. This procedure has though the advantage that you can do without air or oxygen in the implementation. In practice it could However, this process does not prevail because, despite the use of considerable amounts of catalyst the yields of dimerization products are unsatisfactory. Since the copper (II) salts also are consumed during implementation,

609 580/481

Claims (1)

B 27506 IVb / 12 ο it is necessary to re-oxidize them in a separate work step before they can be reused, This also makes it possible to dispense with the use of, which initially appears to be advantageous Oxygen and air or other gases containing oxygen are largely eliminated during the oxidation will. It has now been found that this disadvantage can be avoided with good conversion rates can and very good yields of diacetylene glycols if you get the one free Methine hydrogen atom containing monoalkynols with oxygen or oxygen-containing gases in predominantly aqueous solution, optionally under excess pressure, in the presence of Cuproehlorid ■ and quaternary salts of. Elements of the V group of the periodic. System treated. The quaternary ammonium, phosphonium, arsonium or stibonium salts that come into question can be identical or different aliphatic, araliphatic, cycloaliphatic, heterocyclic or contain aromatic residues. The halides, especially the quaternary ones, are particularly suitable Ammonium halides. Examples of the compounds mentioned include tetramethylammonium chloride, Dimethylpyrrolidinium chloride, triphenylmethylphosphonium chloride, tetramethylammoiiium bromide, Tetraethylarsonium chloride and tetramethylstibonium iodide. The diacetylene glycols obtained can, as Saver pickling or electroplating additives can be used, and are valuable intermediate products for the manufacture of plastics and plasticizers. The monoalkynols, such as propargyl alcohol, butyn- (i) -ol- (3) or 3-methylbutyn- (i) -ol- (3), are generally used in aqueous solution, but you can also use water-soluble organic solvents such as methanol or acetone. The amount of cuprochloride can vary within wide limits, it is advantageous to use it Cuprochloride, based on the alkynol, in a ratio of about 1: 1 to 1: 7, expediently in a ratio from ι: 4, on. The amount of additional +5 th quaternary salt can be varied within wide limits with respect to the cuprous chloride, a ratio of about ι: ι having proven to be most expedient.
Depending on the type of used. Alkinols works. one, at normal or elevated temperature, for example at 25 to 70 °, if desired under elevated pressure. Working under pressure, for example 1 to 30 atmospheres or above, when using air as the oxidizing agent has proven particularly advantageous. The process can be carried out continuously in cocurrent or in countercurrent or also batchwise, for example by using gases containing oxygen or gases such. B. air, from below, the reaction chamber filled with catalyst liquid and alkynol can flow through for several hours. When working continuously. it is appropriate, from time to time or continuously, from the catalyst solution freed from the reaction product, with an adsorbent, for. B .. to remove active charcoal, disruptive impurities. . Are the products of oxidation, the diacetylene glycols, sparingly soluble or insoluble in water, then they can be removed from the reaction product, e.g. B .. by filtering, centrifuging or extracting, advantageously also continuously during the implementation. The water-soluble end products can with ether or others; suitable extraction agents are extracted, The parts given in the examples are parts by weight. Example ι i 230 parts of 3-methylpentine- (i) -ol- (3), 100 parts of tetraethylammonium chloride, 55 parts of cuprous chloride and 900 parts of water are placed in a stirred pressure vessel made of steel; it is 20 at air pressed and heated to 40 ⁰ '. After 6 hours, the pressure has dropped to 18 atm. It relaxes and breathes out again. 20 at pressed on. After a further 10 hours, the pressure is released, the contents of the reaction vessel are filtered and the 3,8-dimethyldecadiyne- (4,6) -diol- (3,8), which is sparingly soluble in water, is washed with water. After recrystallization from petroleum ether, it has a melting point of.89 ⁰ . Based on the methylpentynol used, the yield is 91%. Example "^ 230 parts of 3-methylpentin-i-ol-3, 100 parts of tri-95 'phenylmethylphosphonium chloride, 55 parts of cuprous chloride and 1000 parts of water are poured into a stirred pressure vessel made of steel. Man. presses 20 atm of air and warms to 40 ⁰ '. The pressure drops to 18 atm within .10 hours. The pressure is released and again 20 atm of air are pressed in and stirring is continued. After a further 12 hours, the pressure has fallen again to 18, Sat. The pressure in the reaction vessel is released. 52 parts of crude 3,8-dimethyldecadiyne- (4, 6) -diol- (3, 8) with a melting point of 83 ° to 86 ° are obtained. The yield is 75% _s based on methylpentynol. ^r ATENTANSPP, UCH: . Process for the preparation of diacetylene glycols by treating monoalkynols containing a free methine hydrogen atom with oxygen or oxygen-containing gases in the presence of catalysts and. in predominantly aqueous solution, optionally under excess pressure, characterized in that the treatment in the presence of cuprous chloride ^ and quaternary. Salts of - elements, the * V group of the periodic table takes place. , - ·. ' ISO. Documents considered:. German Patent Nos. 875649, 870845; German patent application E 4362 IVb / 120 '(Patent 890 796. © 609 580/481 8.96