SU843742A3 - Method of preparing triacetoamine - Google Patents

Description

This invention relates to an improved process for the preparation of triacetonammins (2.2.6 g of 6-tetramethyl-4-oxopiperiline, which can be used as an intermediate in the chemical industry.  Known methods for the preparation of triacetonamine consist in the condensation of acetone with aglmiac or phorone with antimyac, or in the disproportionation of 2,2,4,4,6-pentamethyl-2,3,4,5-tetrahydropyrimidine and water in the presence of calcium chloride, the catalytic condensation of diacetone alcohol with ammonia G11.  However, in these methods a low yield of the target product, which does not allow them to be used on an industrial scale.  The closest to the present invention is a method for producing triacetonamine by reacting acetonine with water in the presence of Lewis Acid 2.  A disadvantage of the known method is also a relatively low yield of the target product, not exceeding 60% of the theoretical, and large quantities of resinous by-products.  The purpose of the invention is to increase the yield of the target product.  This goal is achieved due to the fact that acetonin is reacted with water in the presence of an acid catalyst, which is a mineral or carboxylic acid, or sulfonic acid, or a salt of this acid: ammonia, or a nitrogen-containing organic base, which is used in an amount of 12,100 mole. . % in the calculation of the taken, and it is better to conduct the process in an organic solvent medium, it is possible to conduct the process in the presence of a cocatalyst, taken in an amount of 0.010.5 mol. % based on acetonine taken, and potassium iodide, or sodium or lithium, or lithium bromide, or ammonium thiocanate, or lithium cyanide, or lithium nitrate, or ammonium sulfide, or bromine, or iodine, or salts are used as cocatalysis as cocatalysis. ammonium, or triethylamine, or urea, or thiourea with methyl bromide or hydrogen iodide, or nitric, or sulfuric or p-toluenesulfonic acid.  A distinctive feature of the proposed method is the use of a mineral or carboxylic acid, or sulfonic acid, or a salt of this acid with ammonia, or a nitrogen-containing organic base, as an acid catalyst. 12.5-400 mol. % based on acetonine taken.  According to the proposed method, triacetonamine can be obtained with a significantly higher yield than by a known method, and only with an insignificant number of easily removed by-products.  The process can be conducted in an organic solvent, and the group of acceptable solvents includes aliphatic and aromatic hydrocarbons, which can be halogenated or non-halogenated, for example, hexane, heptane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride. , trichlorethylene or chlorobenzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, substituted or unsubstituted aliphatic monohydric or polyhydric alcohols, in particular methanol, ethane ol, propanol, isopropanol, butanol, octanol, cyclohexanol, benzyl alcohol, ethylene glycol monomethyl ether and ethylene glycol, ethers, in particular dioxane, tetrahydrofuran and diethyl ether, esters, in particular ethyl acetate, aprotic polar solvents, in particular dimethylformamyl forms, in particular dimethylformamyl forms, and dimethylformamyl forms, ethers, in ethyl acetate, aprotic polar solvents; dimethyl sulfoxide, tetramethyl urea and hexamethylamide phosphoric acid, sulfolane, acetonitrile and nitromethane. Mixtures of such solvents can also be used.  It is especially advisable to use acetone or diacetone alcohol, or mesityl oxide, or phorone, or diacetonamine, or triacetone diamine, or alcohols with 1-4 carbon atoms, or ethylene glycol monomethyl ether, or mixtures thereof.  Especially preferred as solvents are methanol and acetone, as well as mixtures of these two compounds.  The reaction temperature does not have a pemateiiiero value, and usually a good yield can be achieved with anepat pe from -15 to.  Particularly good results are obtained at a temperature of from 0 to, with the most preferred temperature being in the range of from 0 to.  When using an organic solvent that is a ketone other than acetone, the preferred reaction temperature should not exceed 40 ° C, in which case the optimum reaction temperature is in the range from -15 to.  The reaction can be carried out at atmospheric pressure, but it can also be carried out, if necessary, at a pressure greater than atmospheric.  Acid catalyst used in the implementation of the proposed method, you can choose from the following classes: mineral acids, carboxylic acids, sulfonic acids.  Examples of sulfonic acids are alkylsulfuric acids, in particular methylsulfuric acid, sulfinic acids. .  in particular, benzenesulfinic acids and preferably sulfonic acids, for example aliphatic sulfonic acids, c. in particular, methanesulfonic acid, and aromatic sulfonic acids, whose aromatic ring may be substituted or unsubstituted, in particular benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid and naphthalene-1,5-disulfonic acid.  Examples of mineral acids that can be used as catalysts in the implementation of the proposed method are hydrogen halides (e.g., hydrochloric, hydrobromic or hydroiodic acid), or nitrogen. on, or sulfuric, or phosphoric acid.  Examples of carboxylic acids that can be used are mono-, di-, and tribasic aliphatic and aromatic carboxylic acids.  They include saturated and unsaturated monobasic aliphatic acids, preferably those whose molecules contain from 1 to 18 carbon atoms, in particular formic, acetic, propionic, butyric, lauric, palmitic, stearic, acrylic, and methacrylic acids; in particular, chloroacetic, dichloroacetic, trichloroacetic and trifluoroacetic acids, saturated and unsaturated dibasic aliphatic carboxylic acids, preferably those whose molecules contain from 2 to 12 carbon atoms, in particular malonic, succinic, adipic, sebacic, tartaric, block, fumaric and maleic acids, tribasic aliphatic carboxylic acids, in particular citric acid, monobasic carboxylic acids, whose aromatic ring can be substituted or unsubstituted, in particular benzoic , toluic and naphthoic acids, dibasic aromatic carboxylic acids, in particular phthalic and terephthalic acids, and tribasic aromatic carboxylic acids, in particular trimell tovuyu acid.  The pKd value of the acids used should preferably be less than 5, more preferably 1.5 or less.  The group of particularly preferred acids includes hydrochloric, hydrobromic, hydroiodic, sulfuric, nitric, benolesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, dichloro acetic acid and trichloroacetic acid.  Instead of the acid itself, it is possible to use the salt of one of these acids with ammonia or nitrogen containing an organic base as the acid catalyst.  As an acid catalyst, it is also possible to use a mixture of several acids, several such salts, or one or more such acids with one or several such salts. The acids used to form the salts include mineral acids, carboxylic acids, organic sulfur-containing acids, preferably carboxylic acids, mineral acids and sulfonic acids, it is particularly convenient to use mineral acids and sulfonic acids.  The ammonium salts or salts of the nitrogen-containing organic bases of hydrochloric, hydrobromic, hydroiodic acid, hydrogen sulfide, nitric acid, organic sulfonic acids, in particular benzenesulfonic acid, p-toluenesulfonic acid or methanesulfonic acid, and haloacetic acid, in particular, I have a reason and I have a reason and I have a reason to use a simple, non-volatile interface.  Examples of nitrogen-containing organic bases include the following classes: aliphatic, alicyclic and aromatic primary, secondary and tertiary amines; saturated and unsaturated nitrogen-containing heterocyclic bases; urea, thiourea and cation exchange resins.  For example, aliphatic primary amines, preferably those whose molecules contain from 1 to 18 carbon atoms, in particular methylamine, ethylamine, n-butylamine, octylamine, dodecylamine and hexamethylenediamine} aliphatic secondary amines, preferably those whose molecules contain from 2 to 16 carbon atoms, in particular dimethylamine, diethylamine / di-n-propylamine and di-iso-butylamine, aliphatic tertiary amines, in particular triethylamine alicyclic primary amines, in particular cyclohexy amine, alicyclic secondary amines, per hour dicyclohexylamine 7 aromatic primary clmines whose aromatic ring can be egimized or unsubstituted, in particular aniline, toluidine, naphtha lamin and benzidine aromatic secondary amines, in particular N-methylaniline and diphenylamine, aromatic tertiary amines, in particular N, N-diethyllylline, unsaturated nitrogen-containing heterocyclic bases, in particular, pyrrolidone, piperidine, M-methyl-2-pyrrolidone, priazolidine, piperazine, pyridine picoline, indoline, quinuclidine, morpholine, N-methylmorpholine, l, 4-diazadic klo {2, 2,2) oktan, atsetonin and triacetonamine; thiourea and strongly alkaline and weakly alkaline ion exchange resins.  Preferred examples of salts of nitrogen-containing organic bases and mineral acids are metilamiigidrohlorid, tsiklogeksils1mingidrohlorid, geksametilendiamindigidrohlorid, anilingidrohlorid, p-nitroanilingidrohlorid, dimethylamine hydrochloride, difenilamingidrohlorid, dizobutilamingidrohlorid, triethylamine hydrochloride, trietilaMinsulfat, 1,4-diazoditsiklo (2,2,2) octane hydrochloride, triacetyl Nain hydrochloride, triacetonamine sulfate, urea nitrate, thiourea hydrochloride and alkali hydroxide treated with hydrochloric acid but exchange resin.  Preferred examples of the salts of the nitrogen-containing organic bases and organic acids are cyclohexylamine formate, pyridine for mates, pyridine p-toluenesulfonate, di-n-butylamine acetate, di-n-butylamine benzoate, triethylglylsuccinate, triethylamine maleate, acetyl acetate, mats, mats, macerates, triethyl hyglycine succinate, triethylamine maleate, anilane acetate, mats, mats, macerates, triethylglylsuccinate, triethylamine maleate, aniline acetate, mats, mats, trimethylamine maleate, aniline acetates, maras, triethyl hyglycine succinate, triethylamine maleate, anylacane acetate, mats, mats, trimethylamine maleate, aniline acetamine, mate, triethylglymethylsuccinate, triethylamine maleate, aniline acetate and mary acetate.  Particular preference should be given to salts of triacetonamine, triethylamine, urea and thiourea.  Preferred examples of ammonia and mineral acid salts are ammonium halides, such as ammonium chloride, ammonium bromide and ammonium iodide, ammonium nitrate and ammonium borate. Preferable examples of the ammonium salts of organic acids are salts al edonievye monobasic and dibasic lower aliphatic carboxylic acids and monobasic ammonium salts of aromatic sulfonic acids, in particular ammonium formate, ammonium acetate, ammoniydihloratsetat, ammonium trichloroacetate, ammonium trifluoroacetate, ammonium malonate, ammonium benzoate and ammonium p-toluensulfonate.  In a preferred embodiment of the process according to the invention, the ratio between the acid used as the catalyst and acetonine is stochimetric.  This can be achieved by preparing an acetonine salt with an acid in the preparatory stage.  An organic solvent used in the preparation of acidic acetone acetic acid should be inert with respect to the reaction and, therefore, practically should not contain water.  Examples of such solvents are aromatic hydrocarbons, in particular benzene, toluene and xylene, ketones, in particular acetone, and alcohols, in particular methanol and ethanol.  One such solvent can be used as well as mixtures of two or more such solvents.  The reaction is preferably carried out at a temperature of from 0 to 10 ° C (preferably from O to 5 ° C).  The acid used to prepare the acid adduct is introduced in stools with a metric amount relative to acetonine.  Preferred acids are mineral acids, carboxylic acids and sulfonic acids, preferably hydrogen halide, sulfuric, nitric, phosphoric, ants on, acetic, chloroacetic, dichloroacetic, trichloroacetic, trifluoroacetic, maleic, succinic, benzoic, shades, syndromatic, trifluoroacetic, maleic, succinic, hydrochloroacetic, hydrochloric, hydrochloric, hydroxyacetate, hydrochloric, hydrochloric, hydroxyacetate, hydrochloric acid  It is best to use hydrochloric, sulfuric, nitric, methanesulfonic acid, p-toluene sulfonic acid and benzenesulfonic acid.  It is most advantageous to use gaseous hydrogen chloride, sulfuric acid or p-toluenesulfonic acid. The acidic acetonine adduct is usually obtained either in the form of crystals precipitated from the organic solvent used in the reaction, or in the form of a solution in the solvent.  The resulting acetonine acid adduct is used to react with water to obtain the triaceto amine (the acidic adduct can be removed by the reaction solution or it can be left in this reaction solution).  This acid adduct can be used in the form of a solution or suspension in an organic liquid.  In the case when the acid adduct is not removed from the reaction solution, this solution can be used to prepare the reaction mixture. The acid adduct can be removed from the pea; solution, and then dilute or suspend in another organic solvent. . An aromatic hydrocarbon can be used as an organic solvent, in particular benzene, toluene or xylene, ketone, in particular acetone or alcohol, in particular methanol or ethanol.  Preferred liquids are acetone or methanol.  When carrying out the reaction of the acidic adduct of acetonine with water, water diluted with an organic solvent or their mixture or without dilution, is added with stirring to a solution or suspension of the acidic adduct of aceto Nin.  The preferred amount of water is stoichiometric, t. e.  1 mol.  eq in terms of acid adduct acetonine. in the case of using water in significantly larger quantities, the yield of the final product may be reduced. The amount of water required may be the crystallization moisture of the starting material. In this embodiment of the inventive method, the reaction is preferably carried out at a temperature of from 5 to 40 ° C, more preferably from 10 to 25 ° C. Usually, at least 1 mol of water is used for each mole of acetonine, and water is preferably used in a molar ratio of acetonine: water in the range from 1: 1 to 1:. five.  However, in the case when diacetone alcohol is used as the solvent for carrying out the reaction, or better than acetone, the amount of water used may be less than 1 mole per mole of acetonine.  However, it is necessary to indicate that the reaction cannot proceed under anhydrous or substantially anhydrous conditions.  The appropriate amount of water can be successfully introduced into the reaction system in the form of acetonine hydrate.  In addition, water can be introduced into the reaction system in the form of salt hydrates.  A particularly high yield of the final product can be achieved if a molar excess of ammonium salt is used as catalyst in terms of the amount of acetonine or by carrying out the reaction in acetone used as a solvent.  This reaction can usually be completed within 1 to 20 hours, in particular from.  2 to 10 am  The yield of the final product in the implementation of the proposed method can be increased, and the reaction time can be shortened by using, besides an acid catalyst, from 0.01 to 0.5 mol. % based on the amount of acetonine catalyst other than the acid catalyst. A group of suitable other catalysts includes potassium iodide, sodium iodide, lithium bromide, lithium iodide, lithium thiocyanate, ammonium thiocyanate, lithium cyanide, lithium nitrate, ammonium sulfide, bromine, ammonium iodine, ammonium bromide, ammonium iodide, ammonium nitrate, ammonium methanesulfonate, ammonium benzenesulfonate, ammonium p-toluenesulfonate, triethylammonium bromide, triethylamine iodide, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzenesulfate, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzenesulfate, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzenesulfate, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzenesulfate, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzenesulfate, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzenesulfate, triethylamine nitrate, triethylamine methanesulfonate, triethylaminebenzene, and t, trietilaminbenzolsulfonat, triethylamine-p-toluenesulfonate, geksametilendiaminbromid, geksametilendiaminiodid, hexamethylenediamine rat, geksametilendiaminmetan. Sulphate thiourea toluene sulfonate.  Typically, triacetonamine can be obtained by the proposed method with a yield that exceeds 85% of theoretical (based on acetone), and in the case when the reaction is carried out using acetone as a solvent, the yield exceeds even 100% acet nin.  Triacetonamine is isolated by conventional methods, for example, by distillation and isolation of salts or hydrates.  Example 1  A solution of 8.1 g of chloro-acetic acid in 15 ml of sulfuric ether is added dropwise at 5-1 ° to a solution of 7.7 g of acetonine in 15 ml of sulfuric ether with stirring.  According to this, the reaction mixture is stirred for 1-2 hours  The crystalline precipitate is filtered off, washed with ether and dried under reduced pressure.  15.5 g (97.9%) of acetonine trichloroacetate are obtained in the form of colorless crystals with m. square  113-114 ° Examples 2-10.  Analogously to example 1, receive salts of acetonine, are given in table. one.  Table of Reference  80 ml of acetonine are added to 34.4 g of acetonin mono-p-toluenesulfonate (decomposition temperature 115-117 ° C).  To this mixture is added dropwise a solution of 2 ml of water in 20 ml of acetone with stirring, and the temperature is kept at 5-1 (C.  After that, the reaction mixture is stirred at room temperature (20-25 C) for 8 hours.  The ammonium p-toluenesulfonate crystals are filtered, washed with cold acetone.  The acetone wash was combined with the filtrate and evaporated.  The residue is dissolved in benzene, washed with a 10% aqueous solution of potassium carbonate and dried over anhydrous potassium carbonate.  The benzene is distilled off and the residue is distilled under reduced pressure.  . 14.1 g (91.0%) of triacetonamine are obtained in the form of a pale yellow liquid with m. kip  75-76С with a residual pressure of 4 mm Hg. Art.  Upon cooling, the liquid crystallizes, resulting in crystals with m. square  35-36s.  Found,%: C 69.60; H 11.03; N 9.06.  C, Hj7 No.  Calculated,%: C 69.63; H 11.04; N 9.02.  IR spectrum (liquid film) 3320 cm, 1707.  The NMR and IR spectra of the product coincide with the corresponding spectra of a reliable sample of the product.  Example 12  60 ml of methanol is added to 20.3 g of diacetonin sulfate (decomposition temperature 166-168 Ci) To this mixture is added dropwise an aqueous solution of methanol containing 15 ml of methanol and 2 ml of water, with stirring and at a temperature. The reaction mixture is stirred at 20250 s for 7, then it is neutralized by the addition of potassium carbonate, and then methanol is distilled off.  The residue is extracted with benzene, and the benzene solution is dried over anhydrous potassium carbonate.  The benzene is distilled off and the residue is distilled under reduced pressure.  Get it. 13.7 g (88.3%) of triacetonamine as a icy yellow liquid with m. kip  78790s at 6 mm Hg. Art.  When cooled, the liquid crystallizes, resulting in crystals with m. square  35-3b0s.  The IR spectrum and NMR spectrum of this product are identical to the corresponding spectra of a reliable sample of the product.  Example 13  A solution of 19 g of p-toluenesulfonic acid monohydrate in 40 ml of acetone with stirring is added dropwise to a solution of 15.5 g of acetonine in 30 ml of acetone while the mixture is cooled to maintain its temperature in the range from 0 to toluenesulfonate, then this mixture is stirred for 10 hours at a temperature of 25 in order to carry out the reaction of acetonin-p-toluenesulfonate with water, which is introduced together with p-toluenesulfonic acid monohydrate.  This reaction mixture is cooled with ice, the crystals are filtered and washed with cold acetone.  The percussion was combined with the filtrate and evaporated.  The residue is extracted with benzene.  The benzene extract is washed with 20% aqueous sodium hydrogen carbonate and dried over anhydrous potassium carbonate.  The benzene is distilled off and the residue is distilled under reduced pressure.  13.5 g (86.7%) of triacetonamine are obtained in the form of a pale yellow liquid with m. kip   at b rt. Art.  Example 14  A solution obtained by blowing 8.4 g of dry chlorine hydrogen through 40 ml of acetone was added dropwise to a solution of 30.8 acetonine in 90 ml of acetone.  After adding a solution of hydrogen chloride, the mixture is stirred at 5-10 ° C for 50 minutes.  Acetonin monohydrochloride precipitates.  At the same temperature, acetone monohydrate is added dropwise with aqueous acetone (4 ml of water and 30 ml of acetone).  This mixture is stirred at 20-25 ° C for 6 hours and evaporated.  An aqueous solution of potassium carbonate is added to the residue and extracted with benzene.  The benzene solution is dried over anhydrous potassium carbonate, evaporated, and the residue is distilled under reduced pressure.  This gives 28.6 g (92.3%) of triacetonamine as a pale yellow liquid with m. kip  787 9 at 6 mm Hg. Art.  Example 15  A mixture of 5 g of acetonine hydrate with 1.7 g of acetic acid and 40.0 ml of acetone is heated for 10 hours in a hermetically sealed vessel.  The solvent was then distilled off, a saturated aqueous solution of potassium carbonate was added to the residue, and extracted with benzene.  The extra is dried over anhydrous potassium carbonate and evaporated, the residue is distilled under reduced pressure.  They get trioncio onamin with a yield of 95.9%.  C p and me r 16.  The process described in example 15 is repeated except that. instead of vinegar. .  acids use 0.4 g of formic acid.  Triacetonamine is obtained with a yield of 103% calculated on the initial acetonine.  .  Example 17, 5.0 g of acetonine hydrate and 3.5 g of benzoic acid are added to a mixture of 20.0 ml of acetone with 20.0 g of methanol, the mixture is stirred at room temperature for 24 hours, then purified in analogy to example 11 to obtain Triacetonamine with a yield of 90 3%.  Example.  18.  154 g of acetonine is dissolved in a solvent, which is a mixture of 169.8 g of aceton, an eton with 56.6 g of methanol.  The solution is cooled with ice, 12.9 dichloroacetic acid, and 1.8 g of water are added with stirring.  The reaction mixture is stirred at room temperature for 24 hours and evaporated under reduced pressure.  A 40% aqueous solution of potassium carbonate is added and extracted with ethyl ether.  The ether extract is dried over anhydrous potassium carbonate and evaporated.  The residue is distilled under reduced pressure.  Triacetonamine is obtained with a yield of 136% based on acetonine.  Example 19  5.0 g of acetonine, 0.5 g of water and 3.1 g of methanesulfonic acid are added to a solvent consisting of 35. g of acetone and 35 g of methanol. The reaction mixture is stirred at room temperature for 2 hours and purified in the same way. example 15.  Triacetonamine is obtained with a yield of 130% (based on acetonine).  Example 20 5, O g of acetonine is dissolved in a solvent consisting of 10 g of acetone and 10 g of methanol.  To this solution is added dropwise a solution of 2.1 nitric acid, which contains 0.63 g of water in 10 g of acetone and 10 g of methanol, the temperature is kept in the range from 15 to 20 ° C. The reaction mixture is kept at room temperature for 24 hours and treated analogously to example 15.  Triacetonamine is obtained with a yield of 119% (based on acetonine).  Example 21 .  A mixture of 6.2 g of diacetoninaleate with g of acetone and 0.5 g of water is heated at room temperature for 10 hours and in a hermetically sealed vessel.  After completion of the reaction, the reaction mixture is treated analogously to example 15, to obtain Triacetonamine with a yield of 133%.  Example 22  The process described in Example 21 is completely repeated, except that 8.78 g of acetonin cinnamate is used instead of diacetonine maleate.  Triacetonamine receive with the release of 91.3%.  Example 23  31.8 g of acetonine trisloracetate is added to the solvent, which is a mixture of 190.8 g of acetone with 63.6 g of methanol.  1.8 g of water is added dropwise to this mixture with simultaneous mixing.  The reaction mixture was stirred at room temperature for 8 hours and kept overnight for the reaction to be completed, then it was purified as in Example 18.  Triacetonamine is obtained with a yield of 166%.  Examples 24-29.  Alternately, but each of the catalysts listed in table. 2, is added, in defined amounts, to a solution of 5.0 acetonine hydrate in a solvent, which is a mixture of 8.5 g of methanol with 16.9 g of acetone. The P mixture was stirred at room temperature for 24 hours and treated as in Example 15.  Get triacetonamine with the release, which is shown in the table. 2  Table 24 Urea nitrate 0.9 90.2 25 Hydrochloride thiourea 3.3 146 26 Ammonium acetate, 2.2 91.8 27 Pyridine 1 formula, 8 99.0 28 Triethylamine hydrochloride 4.0 102 29 Ammonium p-toluenesulfonate 6.0 Example 30 and 31.  In turn, each of the catalysts listed in table. 3, in a specified amount is added to a solution of 5.0 g of acetonine hydrate in a solvent, which is a mixture of 16.9 g of acetone with 1.7 g of methanol.  The reaction mixture is heated at b for 7 hours in a hermetically sealed vessel and the analogues are processed in example 15.  Get triacetone with the output specified in the table. 3, the amount of triacetonamine used as catalysis is determined by the yield indicated in Example 31. , Table Example 32.  A mixture of 5.0 g of acetonine hydrate with 5.7 g of ammonium bromides and 38.8 g of acetone are heated at 60 for 10 hours and are worked up as in Example 15.  Triacetonamine is obtained with a yield of 220% (based on acetonine).  Example 33  19, O g of p-toluenesulfonic acid monohydrate is added to a solution of 15.4 g of acetonine in 100 ml of dimethylformamide.  The mixture was stirred at room temperature for 8 hours, after which it was left to stand still overnight to complete the reaction.  A 30% aqueous solution of sodium hydroxide was added to the reaction mixture and extracted with ether.  The ether extract is dried over anhydrous potassium carbonate and the sulfuric ether is evaporated.  The residue is distilled under reduced pressure.  Triacetonamine is obtained with a yield of 88.8%.  Example 34  6.2 g of p-toluenesulfonic acid monohydrate is added in.  a solution of 5.0 g of acetonine in 33.8 g of methyl ethyl ketone with stirring.  The reaction mixture was stirred at room temperature for 8 hours and treated in the same manner as in Example 18.  Triacetonamine is obtained with a yield of 91.7%.  P r and m e s 35-38.  5.0 g of acetonine and 3.2 g of ammonium bromide are heated at 44 seconds for 15 hours in a solvent, which is a mixture of acetone and water in various proportions as shown in the table below. four.  The reaction mixture is treated analogously to example 15.  Poluigot triacetonamine with the output specified in the table, and this output is determined in terms of the amount of acetonine consumed.  Table 4

Triethylamine p-toluene sulfo 4, 0 nat

Triacetonamine hydro1.4 chloride

60 Examples 39-42. Alternately

Each of the catchers listed in Table 5 is added in the indicated amount to a mixture of 3.0 g of acetonine hydrate, 9.0 g of acetone and

65 0,60 g of ammonium chloride (catalysis

Claims (15)

Claim 1. The method of obtaining triacetonamine by the interaction of acetonin with. Water in the presence of an acid catalyst, characterized in that, in order to increase the yield of the target product, mineral or carboxylic acid, or sulfonic acid, or a salt of this acid with ammonia or nitrogen-containing organic is used as an acid catalyst the base, which is used in an amount of 12.5-400 mol.% calculated on the taken acetonin. 2. The method according to claim 1, with the fact that the process is conducted in an environment of an organic solvent. 3. The method according to claim 2, characterized in that the solvent used is acetone or diacetone alcohol, or mesityl oxide, or diacetononamine, or triacetone diamine, or phoron, or alcohol with 1-4 C atoms, or ethylene glycol monomethyl ether, or methyl ethyl ketone. 4. The method of pop.Z, characterized in that when using _h as a solvent, mesityl oxide, or diacetononamine, or triacetone diamine, or methyl ethyl ketone, · or foron, the process is carried out at a temperature of from -15 to + 40 ° C. 51 The method according to claim 1, characterized in that the process is conducted in a mixture of organic solvents. 5 or trichloroacetic or p-toluenesulfonic acid. 6. The method according to claim 5, characterized in that a mixture of acetone and methanol is used. 7. The method according to PP. 1-6, characterized in that as the acid catalyst using hydrochloric, or hydrobromic, or hydroiodic, or sulfuric, or nitric, or dichloroacetic, 8. The method according to PP. 1-7, about t and l, characterized in that as the acid catalyst is used Yu 'acid salt, with triacetonamine, hjjh triethylamine, or urea, or thiourea, or ammonia. 9. The method according to claim 1, characterized in that the water is used 15 yut in an amount of 1-5 per mole of acetonin. 10. The method according to PP. 1-3, 5-9 ,. o characterized by the fact that the process is conducted at a temperature from 0 to 20 ^b5 ° ^s - 11. The method according to claim 1, with the fact that as the acid catalyst, a salt of acetonin with mineral or carboxylic acid or sulfonic acid is used. 12. The method according to claim 11, which includes the fact that the catalyst used is a salt of acetonin with hydrogen halide or sulfuric, or 30 nitric acid, or p-toluenesulfonic acid. 13. The method according to claims 1 and 11, 12, characterized in that the reaction with water is carried out at a temperature 35 Ρθ from 5 to 40 ° С. 14. The method according to claims 1 to 13, characterized in that the process is conducted in the presence of a cocatalyst, taken in an amount of 0.01-0.5 mol.% 40 based on acetonin. 15. The method of claim 14, wherein the cocatalyst is potassium iodide or sodium, or lithium, or lithium bromide, or ammonium thiocyanate, or lithium cyanide, or lithium nitrate, or ammonium sulfide or bromine, or iodine, or a salt of ammonium, or triethylamine, or urea, or thiourea and hydrogen bromide or iodide 50, or nitric or sulfuric acid, or p-toluenesulfonic acid.