The method of obtainingw-alkalicarbonate acids

 

(57) Abstract:

Usage: as intermediates in the pharmaceutical industry, as well as lubricants. Entity : an improved method of obtaining alkalicarbonate acids f-crystals: A- (COOH)2where C6-C1, - alkyl. Reagent 1: the corresponding cycloalkyl. Reagent 2: ozone. Reaction conditions: reagent 1 and treated with reagent 2 in the lower aliphatic alcohol at a temperature of from -80 to +20C To produce the peroxide solution, at a concentration in solution of 0.1 mol of peroxide with subsequent removal of alcohol from the reaction mixture, dissolving the obtained dialdehyde in an inert nonpolar, aprotic solvent such as chlorobenzene, and oxidation at 50-100C. for 6 h.p. f-crystals.

The invention relates to the field of organic synthesis and concerns a method for obtaining -, -alkalicarbonate acids.

A method of obtaining , -alkalicarbonate acids of the formula: HOOC - (CH2)n-COOH, in which n = 6-10, namely, that the dialdehyde of the formula X-(CH2)n-CHO, where X is SNO, n = 6-10, are oxidized by oxygen or its mixture with an inert gas at 1-10 ATS in polar solvent at 20-80aboutIn the presence of catalysis is an Object of the present invention is a method of obtaining , -alkalicarbonate acids of General formula

A I where a - C6-C12-alkyl, with the use of oxidation-alkalihalide in solvent with oxygen or oxygen-containing gas at elevated temperature and pressure in the presence of a catalyst, characterized in that, to simplify the process of cycloalken General formula

A where a has the above meaning, is subjected to treatment with ozone in the lower aliphatic alcohol at a temperature of from -80 to +20aboutWith receipt of the peroxide solution, which is subjected to catalytic hydrogenation in the presence of a suitable hydrogenation catalyst at a concentration in solution of 0.1 mol of peroxide with subsequent removal of alcohol from the reaction mixture, dissolving the obtained dialdehyde in an inert non-polar, and proton solvent such as chlorobenzene, and oxidation at a temperature of 50-100aboutC.

And means, for example, a butylene radical, pentylene, hexylene, heptylene, octalene, norilana, decylene, undecylenic, modellen,

And, mainly, means a radical of pentylene, hexylene or decylene.

Ozonation and subsequent hydrogenation can be performed in the traditional way. To this end the original Sejny products catalytically hydronaut using hydrogen. As catalysts suitable for hydrogenation process traditionally used catalysts with noble metals that can be applied in the form of powder coating materials of the carrier, or without the latter, for example, Pd-, Pt-, Ru-, Rh - and Ni-catalysts. As material carriers of catalysts can be used, such as activated carbon, silica gel and diatomaceous earth. Mainly used as catalysts Pd/C in caso3.

For the reaction of cycloalken dissolved in an organic solvent in which it is soluble, for example, in a lower aliphatic alcohol, mainly in methanol, and treated then the equivalent amount of ozone. Ozonation is carried out at a temperature of from -80aboutC to +20aboutC.

Following the process of ozonation and catalytic hydrogenation ozonolytic products is carried out in dilute solution, and in the process of hydrogenation support controlled the content of the peroxide is preferably at most 0.1 mol/L. To do this, prepare a suspension of catalyst in solution and hydrogen and produce continuous power solution ozonolysis. The low percentage of peroxide in relistor.

The hydrogenation takes place practically without pressure, i.e. at pressures equal to 1-3 bar, which use is usually to prevent penetration of air into the reactor.

The reaction temperature during the process of hydrogenation is about 20-40aboutC. the pH Value of support in the range of 5-7. Because during the hydrogenation can produce small amounts of acidic products, the pH value if necessary you can store in a small interval using additives reasons, mainly, by the addition of dilute sodium hydroxide solution or sodium hydroxide solution.

The catalyst was then filtered off and the solvent is removed. The residue is dissolved in a suitable for the subsequent oxidation process inert solvent and oxidized using an oxidizing agent.

The solvent can be applied in the conditions of a reaction inert appreticeship organic solvents, for example aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene, etc., as oxidants can adopt the conventional oxidizing agents such as peroxide, i.e., N2ABOUT2the oxygen combined with salts of oreda (preferably oxygen), as the oxidant flows as and when necessary use of metal salts and dicarboxylic acid are formed with a high degree of purity and with excellent outputs. As the solvent used accordingly, oxygen or air, but a particularly preferred oxygen.

The oxidation is carried out mainly under pressure, preferably using a pressure 3-10 bar. The reaction is carried out at temperatures of 70-90aboutC.

After the oxidation process, the reaction solution is cooled, concentrated to a certain volume or remove the solvent. Dicarboxylic acid is formed in crystalline form.

According to the method according to the invention , -dicarboxylic acid get with great clarity and with excellent outputs. As a rule, achieve outputs 65-85%, after treatment of uterine solution the output is 75-95%. Dicarboxylic acid get at least 95% purity, due to which there is no longer any need for further purification of the final product.

P R I m e R 1. Dodekanisa dikelola

Dodecanediol

to 130.1 g (1 mole) of cyclododecene (purity 95%) was dissolved in 1500 ml of methanol, cooled to -20aboutWith and introduced containing 4 wt.%oredom reactor for hydrogenation, which contained 5 g of Pd/C c CaCO3(Lindlar catalyst), was continuously introduced through the metering capacity of the resulting solution ozonation, preventing excess peroxide content equal to 0.02 mol/L. If a strong move and the addition of hydrogen, the hydrogenation was carried out before receiving negative samples peroxide.

The resulting solution hydrogenation contained 72,96% theory dodecanediol (GC).

Dodekanisa dikelola

From a solution of the hydrogenation boiled away the solvent, and the residue was dissolved in 1000 ml of chlorobenzene. The solution was mixed in an autoclave with stirring and the pressure of 5 bar with oxygen and then heated up to 80aboutC. Upon termination of the reaction the pressure in the autoclave is removed, the solution is cooled to room temperature and the solution concentrated to approximately 300 ml of the Resulting crystalline precipitate is filtered off and washed with water. Thus was obtained 151 g (0,655 mol) dodecanol decollate (65% per cyclodecene) with a purity of 96%.

P R I m m e R 2.

Octandiol

110,2 g (1 mol) cyclooctene (purity 95%) solvents in 1500 ml of methanol, cooled to a temperature of -20aboutWith and containing 4 wt.% ozone mixture 02/03was introduced to until in solution bude is 5.0 g of Lindlar catalyst (Pd/C with caso3) the resulting solution ozonation continuously introduced through a metering device, preventing excess peroxide content of 0.02 mol/L. Under vigorous stirring and addition of hydrogen, the hydrogenation led to negative samples peroxide. The pH value decreased from 7 to 5.4. The resulting solution hydrogenation contained 78,75% theory octangula.

Octangula dikelola:

From the solution of hydrogenation of the solvent was removed and the residue was dissolved in 1000 ml of chlorobenzene. This solution was mixed in an autoclave at a pressure of 5 bar when mixed with oxygen and the temperature was maintained at approximately 80aboutC. After completion of the reaction the pressure in the autoclave was removed, the solution was cooled to room temperature and the solvent was removed to approximately 300 ml. Formed upon cooling to a temperature of approximately 7aboutWith precipitate was filtered and washed with water.

Was obtained for 116.2 g (0,702 mol) octane decollate (70,2%) per used 95% of cyclooctene with a purity of 98.5%.

1. The METHOD of OBTAINING , w-ALKALICARBONATE ACIDS of General formula I

< / BR>
where A - C6- C12- alkyl,

using oxidation - alkalihalide in the solvent coloradoite fact, that, to simplify the process, cycloalken General formula II

< / BR>
where A is the specified value,

processed with ozone in the lower aliphatic alcohol at a temperature of -80...+20oWith receipt of the peroxide solution, which is subjected to hydrogenation in the presence of a suitable hydrogenation catalyst at a concentration in solution of 0.1 mole of peroxide with subsequent removal of alcohol from the reaction mixture, dissolving the obtained dialdehyde in an inert non-polar aprotic solvent, such as chlorobenzene, and oxidation at 50 - 100oC.

2. The method according to p. 1, characterized in that the compounds of formula II used cyclohepten, cyclooctene, cyclododecene,

3. The method according to p. 1, characterized in that the use of ozone in equivalent quantity.

4. The method according to p. 1, wherein the catalytic hydrogenation is carried out at pH 5 to 7.

5. The method according to p. 1, characterized in that the catalyst used Pd/C CaCO3.

6. The method according to p. 1, characterized in that the oxidation is carried out at a pressure of 3 to 10 ATM and a temperature of 70 - 90oC.

7. The method according to p. 1, characterized in that the interaction with ozone is carried out in the presence of lower aliphati the

 

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