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United States Patent Office Patented Feb 2,736,752 United States Patent Office Patented Feb. 28, 1956 g 2 dizonic acid, triquinoyl, croconic acid and leuconic acid 2,736,752 can be obtained, but also in that upon hydrogenation, iPROCESS FOR THE PREPARATION OF inositol can be obtained, HEXAHYDROXYBENZENE In practice of the process according to the invention, the sodium or sodium with additions of other alkali metals Ullrich Hoffmann, Bad Homburg (Taunus), Otto. Schweit or alkaline earth, metals is, for example, introduced into zer, Frankfurt am Main, and Karl Rinn, Darmstadt, Germany, assignors to Deutsche Gold- und Silber-Scheir a rotary steel autoclave and carbon monoxide, is intro deanstalt, vormals Roessler, Frankfurt am Main, Ger duced until the desired starting pressure is obtained. many Thereafter the autoclave is heated to the desired reaction 0: temperature. As the surface of the alkali metal quickly No Drawing. :Application November 24, 1952, acquires a hard crust of the reaction: product, it was : Serial No. 322,348 found advantageous:to introduce grinding: bodies: espe cially those with sharp edges into the autoclave-to-grind Claims priority, application Germany December 1, 1951 off the crusts as they are formed. In view of the increase 9. Claims. (CI. 260-621) 5 of the temperature, the beginning pressure increases sub stantially and then after the reaction proceeds gradually, The present invention. relates to the production of decreases to that engendered by the excess of the carbon hexahydroxybenzene by hydrolyzing alkali metal. salts. of imonoxide: employed. thexahydroxybenzene with water, alcohols, or, acids. The main reaction proceeds according to the following It is already known that potassium, carbonyl (KCO)6 20: equation: sis: obtained as a by-product in the preparation of metallic 6Na-I-6COs (NaCO)6 potassium. from carbon, and potassium carbonate, which :-carbonyl' upon hydrolysis yields hexahydroxybenzene. A smaller quantity of carbonate' can also be formed The same product is obtained when carbon monoxide is according to the following equation: ... passed over metallic potassium. An-analogous, reaction 25 2Na-3CO=Na2CO3-2C with other alkali metals has hitherto. been unknown. Al - A certain portion of unreacted alkali metal may remain though, a reaction between carbon monoxide, and other in the reaction mixture in view-of insufficient freeing of alkali metals is known, the product obtained with a di the surfaces thereof. The relative proportion of the un ..meric carbonyl of the formula (MeCO)2. which upon ": reacted alkali metal, however, decreases: with an increase hydrolysis yields glyoxal rather than hexahydroxybenzene. 30 inithe: quantity of metal originally charged. :It has now been unexpectedly discovered that.the:hexa iIt is also possible to introduce the alkali-metal into the carbonyls. of alkali metals other than potassium,prefer : autoclave in a highly disperse form such as; for example, ably of sodium, can be produced in a relatively. Smooth in the form of a suspension or a colloidal solution. :Pref reaction from the metals and carbon monoxide if the erably relatively non-volatile dispersing mediums are em reaction is "permitted to proceed in a closed, system at ployed for this purpose. elevated temperatures and pressures. The results obtained It is possible according to the invention. to convert up were even more surprising, as according to previous ex :-to-80% of the alkali metal charged into the-corresponding periences under these conditions, metallic potassium re hexacarbonyl. The remainder of the quantity of alkali acts with carbon monoxide to produce potassium carbon metal charged is either converted to the carbonate or is ate and carbon exclusively. It was also found that in 40 occluded in the reaction product and remains unchanged. the production of the sodium hexahydroxybenzene cer The addition of small amounts of alkali metal salts to tain temperature limits must be observed in connection the reaction mixture is advantageous as facilitating the with the pressure employed, over these limits, the forma grinding off of formed crusts and a more complete re tion of sodium carbonate is favored. For example, this action of the alkali metal originally charged. limit is about 380° C. at a pressure of about 70 atmos 45 The reaction for the production of the hexacarbonyl pheres and 340 C. at a pressure of about 140 atmos compounds can be carried out at temperatures between pheres. Under the critical limit the alkali metal carbonate 250° C. and 380° C., preferably at 340° C., and at pres is only formed in relatively small quantities as a by-prod sures between 30 atmospheres and 180 atmospheres, pref. uct. The sodium employed for the reaction can with erably between 70 and 90 atmospheres. advantage be alloyed or mechanically mixed with up to 50 The hexacarbonyl compounds obtained are easily con 10% of other alkali metals such as lithium or potassium verted to hexahydroxy benzene by conventional hydrol or alkaline earth metals such as calcium as a better sub ysis with compounds having a mobile hydrogen atom such division of the sodium and a more complete conversion as water and acids, for example, acetic acid. Whilst the of the sodium is obtained. Sodium can also advanta hexahydroxy benzene can very easily be oxydized under geously be employed in the form of its amalgam. 55 the conditions of hydrolysis, it is advisable to exclude The addition of inert gases, such as nitrogen or meth the presence of oxygen during this part of the process; ane, to the carbon monoxide employed is without influence otherwise it may be undertaken in the presence of re on the course of the reaction, but can be of advantage in ducing agents, as for instance stannous chloride acidified preventing local overheating caused by a too rapid re by hydrogen chloride. action. 60 The following examples will serve to illustrate the man The reaction product which, depending upon the re ner in which the process according to the invention can action conditions employed, can contain a greater or lesser be carried out. quantity of unconverted alkali metal, is then hydrolyzed Example 1 to form hexahydroxybenzene. The latter can be isolated A rotary autoclave containing iron balls for grinding or can be directly converted into other products by appro 65 reaction products was charged with 25 grams of sodium priate chemical reactions. In contrast to the correspond and sufficient carbon monoxide to provide a pressure of ing potassium compound, the sodium hexahydroxyben 90 atmospheres and heated to 340 C. After 4 hours zene is easily hydrolyzed without the known difficulties rotation at this temperature, the pressure amounted to 76 of handling of the potassium hexahydroxybenzene caused atmospheres and an analysis of the reaction product indi by the extraordinarily labile character of such compound. 70 cated that 38% of the sodium had been converted to the The hexahydroxybenzene obtained is not only of in sodium salt of hexa hydroxy benzene, 32% to sodium terest in that upon oxidation tetrahydroxy quinone, rho carbonate and 30% remained unchanged. 2,786,752 3 4. Example 2 We claim: 1. In a process for the production of hexa hydroxy 25 grams of sodium containing 1.5% of lithium were benzene by reacting an alkali metal and carbon monoxide treated with carbon monoxide at a starting pressure of to form an alkali metal carbonyl and hydrolyzing such 70 atmospheres at 340 C. for 4 hours in a rotary auto carbonyl the step which comprises reacting sodium with clave provided with angular grinding bodies. The carbon carbon monoxide at an elevated temperature up to 380 monoxide taken up amounted to 8 atmospheres and an C. and an elevated pressure up to 180 atmospheres to form analysis of the reaction mixture indicated that 41% of the alkali metal carbonyl. the sodium had been converted to the sodium hexacar 2. In a process for the production of hexa hydroxy bonyl, 26% to the carbonate and 33% remained un 10 benzene by reacting an alkali metal and carbon monoxide reacted. to form an alkali metal carbonyl and hydrolyzing such Example 3 carbonyl the step which comprises reacting sodium with 25 grams of sodium with a 1% potassium content were carbon monoxide at an elevated temperature between 250 treated in an autoclave as in Example 2 for 72 hours. C. and 380° C. and an elevated pressure between 180 The carbon monoxide taken up amounted to 14 atmos 15 and 30 atmospheres to form the alkali metal carbonyl. pheres and 77.5% of the alkali metal was converted to 3. A process according to claim 2, in which the reac the hexacarbonyl, 22.5% to the carbonate. tion between the sodium and the carbon monoxide is car ried out at a temperature between 250 and 380 C. and Example 4 at pressures between 180 and 70 atmospheres. 25 grams of sodium were treated with carbon monoxide 20 4. A process according to claim 2, in which the re at starting pressure of 70 atmospheres at 340 C. for 8.8 action between the sodium and the carbon monoxide is hours in a rotary autoclave provided with iron cubes as carried out at a temperature of about 340 C. and at grinding bodies. 72% of the sodium was converted to the pressures between about 70 and 90 atmospheres. hexacarbonyl, 15.4% to the carbonate and about 12.6% 5. A process according to claim 2, in which said sodium 25 is admixed with up to 10% of another metal selected remained unreacted. from the group consisting of the alkali and alkaline earth Example 5 metals. 25 grams of sodium are treated with carbon monoxide 6. A process according to claim 2, in which said sodium in the presence of 1 gram of sodium carbonate at a is admixed with up to 10% of a sodium salt, starting pressure of 70 atmospheres at 340 C.
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