JPS5830308B2 - Triacetone amino acid - Google Patents

Description

[Detailed description of the invention] The present invention The present invention relates to a novel method for producing triacetonamine having the following properties.

More particularly, the present invention relates to an improved process for producing triacetonamine from acetonin having the formula:

Conventionally, the best method for producing triacetonamine was known to be by reacting acetonin and water in the presence of a Lewis acid (Japanese Patent Publication No. 44-1
2141).

However, even in this method, the yield is up to 60
%, and as a by-product in the reaction, a large amount of resinous substances containing Lewis acids such as calcium chloride and zinc chloride used in the reaction are produced, and the treatment should include treatment of pollution problems. There were several problems that needed to be solved, such as the need to take complicated measures.

As a result of intensive research to solve these problems, the present inventors solved the above problems and completed the present invention by adopting means completely different from conventional methods.

That is, the method of the present invention comprises reacting acetonin with acetone and/or diacetone alcohol under anhydrous conditions in the presence of an acid catalyst of at least 12.5 mol % or more based on acetonin.

Preferably, in the method of the invention acetonin is reacted with acetone in the presence of an acid catalyst.

Acid catalysts used in the method of the present invention include salts of protic acids and ammonia or nitrogen-containing organic bases.

Protic acids used to form such salts include mineral acids or organic acids such as organic phosphorus-oxygen acids, organic sulfur-oxygen acids, preferably sulfonic acids or carboxylic acids.

Mineral acids include hydrohalic acids such as hydrochloric acid, hydrobromic acid or hydriodic acid; nitric acid and phosphoric acid.

Carboxylic acids include -basic, dibasic and tribasic aliphatic and aromatic carboxylic acids.

For example, preferably a saturated or unsaturated monobasic aliphatic carboxylic acid having 1 to 18 carbon atoms, such as formic acid,
acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid, stearic acid, acrylic acid and meccrylic acid; halogen-containing carboxylic acids such as chloroacetic acid, dichloroacetic acid or trichloroacetic acid and trifluoroacetic acid; preferably saturated with 2 to 12 carbon atoms or unsaturated dibasic aliphatic carboxylic acids such as malonic acid, succinic acid, adipic acid, cepatic acid, tartaric acid, malic acid, fumaric acid,
maleic acid; tribasic aliphatic carboxylic acids, such as citric acid; optionally substituted monobasic aromatic carboxylic acids;
Examples are benzoic acid, toluic acid, cinnamic acid, naphthoic acid; dibasic aromatic carboxylic acids such as fucuric acid and terephthalic acid; and tribasic aromatic carboxylic acids such as trimellitic acid.

Examples of organic sulfur-oxygen acids include alkyl sulfuric acids such as methyl sulfuric acid and sulfinic acids such as benzenesulfinic acid, but sulfonic acids are preferred.

Examples of sulfonic acids include aliphatic and optionally substituted aromatic sulfonic acids, such as methanesulfonic acid, benzenesulfonic acid, p-4 luenesulfonic acid, naphthalenesulfonic acid and naphculene-1,5-disulfonic acid. can give.

Organic phosphorus-oxyacids include aliphatic or aromatic phosphonic or phosphinic acids, such as methyl-, benzyl- or phenylphosphonic acid or dimethyl- or diethylphosphonic acid or diethyl- or benzenephosphinic acid.

Examples of nitrogen-containing organic bases include aliphatic and aromatic primary bases,
Mention may be made of secondary and tertiary amines, saturated and unsaturated nitrogen-containing heterocyclic bases, urea, thiourea and basic ion exchange resins.

Examples of the bases used are preferably aliphatic amines having 1 to 18 carbon atoms, such as methylamine, ethylamine, n-butylamine, octylamine, dodecylamine and hexamethylene diamine; 2 to 16 aliphatic secondary amines, such as dimethylamine, diethylamine, di-n-propylamine and diisobutylamine; aliphatic tertiary amines, such as triethylamine; cycloaliphatic-class amines, such as cyclohexylamine; optionally substituted aromatic-grade amines such as aniline, toluidine, naphthylamine and benzidine; aromatic secondary amines such as N-methylaniline,
Diphenylamine; aromatic tertiary amine, e.g. N, N-
Diethylaniline; saturated and unsaturated nitrogen-containing heterocyclic bases, such as pyrrolidine, piperidine, N-methyl-2-
Pyrrolidone, pyrazolidine, piperazine, pyridine, picoline, indoline, quinuclidine, morpholine, N-
Methylmorpholine, 1,4-diazabicyclo(2,2,
2) octane, acetonin and triacetonamine;
Urea; thiourea and strong to weakly basic ion exchange resins such as Amberlite IR-45 and IRP-5
8 (manufactured by Rohm and Haas).

Suitable examples of ammonium salts of mineral acids are ammonium halides such as ammonium chloride, ammonium bromide or ammonium iodide, ammonium nitrate and ammonium borate.

Suitable examples of ammonium salts of organic acids are - ammonium salts of basic and dibasic lower aliphatic carboxylic acids, as well as ammonium salts of monobasic aromatic sulfonic acids, such as ammonium formate, ammonium acetate, and ammonium trichloroacetate, ammonium trifluoroacetate, ammonium malonate, ammonium benzoate and ammonium p-toluenesulfonate.

Suitable examples of salts of mineral acids and nitrogen-containing organic bases include methylamine hydrochloride, cyclohexylamine hydrochloride, hexamethylenediamine dihydrochloride, aniline hydrochloride, p-nitroaniline hydrochloride, dimethylamine hydrochloride, diphenylamine hydrochloride. salt, diisobutylamine hydrochloride, triethylamine hydrochloride, triethylamine hydrobromide, 1,4-diazabicyclo(2,2,2)octane hydrochloride, triacetonamine hydrochloride, triacetonamine sulfate, urea nitrate, thio It is a basic ion exchange resin treated with urea hydrochloride and hydrochloric acid.

Suitable examples of salts of organic acids and nitrogen-containing organic bases include cyclohexylamine formate, pyridine formate, and pyridine.I)-
Toluene sulfonate, di-n-butylamine acetate,
Di-n-butylamine benzoate, morpholine succinate, morpholine maleate, triethylamine acetate, triethylamine succinate, triethylamine maleate, aniline acetate and triacetonamine p-toluenesulfonic acid It's salt.

Particularly preferred nitrogen-containing organic bases that form such salts include triacetonamine, triethylamine,
Hexamethylene diamine, 1,4-diazabicyclo(2
,2,2) octane, urea or thiourea.

Particularly preferred acids that form such salts are:
Hydrochloric acid, hydrobromic acid, hydriodic acid, nitric acid, halogenoacetic acid or organic sulfonic acid.

Using ammonium salts of hydrochloric acid, hydrobromic acid, hydriodic acid, nitric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, dichloroacetic acid or trichloroacetic acid or salts with particularly preferred nitrogen-containing organic bases as mentioned above. Particularly good results are obtained when

Ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium p-toluenesulfonate, triacetonamine hydrochloride, urea nitrate, urea p-t-toluenesulfonate, thiourea hydrochloride and hexamethylene diamine diamine Hydrochloride salts are most preferably used as catalysts.

Furthermore, acids can also be used as acid catalysts in the method of the invention.

Acids include Lewis acids such as aluminum chloride, tin chloride, zinc chloride and calcium chloride, iodine, bromine, preferably boron trifluoride.

Protonic acids can also be used as acids.

As the protic acid, the aforementioned mineral acids or organic acids, such as organic phosphorus-oxygen acids, organic sulfur-oxygen acids, preferably sulfonic acids or carboxylic acids, can be used.

Suitable examples of organic acids are monobasic and dibasic aliphatic and aromatic carboxylic acids and monobasic aromatic sulfonic acids.

The most preferred examples of protic acids are hydrochloric acid, formic acid, acetic acid, malonic acid, succinic acid, maleic acid, benbroic acid or cinnamic acid and benzenesulfonic acid or p-toluenesulfonic acid.

A preferred embodiment of the invention is to use stoichiometric amounts of acid to acetonin.

The invention therefore consists of reacting an acid addition salt of acetonin with diacetone alcohol and/or preferably acetone under anhydrous conditions.

As the acid addition salt of acetonin, an addition salt with a protonic acid can be used, and mineral and organic acid salts of acetonin, such as carboxylates and sulfonates, are preferably used.

As mineral acids, carboxylic acids and sulfonic acids, the same acids as mentioned above can be used.

Suitable examples of acid addition salts of acetonin are monobasic and dibasic aliphatic acid salts of acetonin and monobasic aromatic sulfonate salts of acetonin.

The most preferred example of an acid addition salt of acetonin is acetonin.
Hydrochloride, acetonin/formate, acetonin/acetate, acetonin/malonate, acetonin/succinate, acetonin/maleate, acetonin/benzoate, acetonin/cinnamate, acetonin/benzenesulfonate, and Contains acetonin/p-toluenesulfonate.

The present inventors have demonstrated that an acid addition salt of acetonin is formed quantitatively by reacting a stoichiometric amount of acid with acetonin (I) under low temperature conditions in the presence of an organic solvent; It was also found that this acid addition salt itself is relatively stable.

Furthermore, the present inventors have discovered that the acid addition salt of acetonin can be mixed with acetone and/or diacetone alcohol, optionally in the presence of an organic solvent, i.e., as a solution or suspension in an organic solvent, without or without being removed from the reaction solution. It has been found that triacetonamine can be obtained in a completely unexpectedly high yield by reacting the compound under the conditions described above.

The most preferred reagent in this case is acetone.

Therefore, in the present invention, it is particularly important to use an acid addition salt of acetonin as a raw material.

The organic solvent used in the production of the acid addition salt of acetonin is one that is inert to the reaction and does not contain water.

Such solvents are aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone; alcohols such as methanol and ethanol.

The reaction is carried out at a temperature kept in the range from 0 to 10°C, preferably from 0 to 5°C.

The acid is used in stoichiometric amounts with acetonin, and the acid used is a protic acid.

Suitable protic acids are mineral acids or organic acids such as carboxylic acids and sulfonic acids.

In particular hydrohalic acids, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, maleic acid, succinic acid, malonic acid, benzoic acid, cinnamic acid and aromatic and aliphatic sulfonic acids. It is.

Most preferably, hydrochloric acid, formic acid, acetic acid, maleic acid, succinic acid, malonic acid, benzoic acid, cinnamic acid, p-toluenesulfonic acid and benzenesulfonic acid are used.

Acid addition salts of acetonin generally precipitate out as crystals in the solvent used or are formed as a solution in the solvent.

The method of the invention can be carried out at various temperatures.

For example, 0~150℃, 30~150℃, 50~100℃
°C and preferably 10 to 110 °C, particularly preferably 20 to 6 °C
The temperature is 5°C.

In some cases, the reaction is carried out under pressure in a closed system or with external pressure applied.

A pressure range of 1 to 30 atmospheres, preferably 1 to 10 atmospheres, most preferably 1 to 3 atmospheres may be provided.

When carrying out the method of the present invention, the use of a solvent is not particularly essential, but it is advantageous to carry out the reaction in the presence of an organic solvent.

Examples of organic solvents used include aliphatic or aromatic optionally chlorinated hydrocarbons, such as hexane, heptane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, trichloride. ethylene or chlorobenzene; saturated or unsaturated aliphatic mono- or polyhydric alcohols such as methanol, ethanol, propatool, impropatol, butanol, octatool, cyclohexanol;
benzyl alcohol, ethylene glycol monomethyl ether or glycol; ethers such as dioxane, tetrahydrofuran or diethyl ether; esters such as ethyl acetate; aprotic polar solvents such as dimethylformamide, diethylacetamide, dimethylsulfoxide, tetramethylurea, Mention may be made of hexamethylphosphoramide, sulfolane, acetonitrile or nitromethane, or mixtures of these solvents.

Lower alcohols having 1 to 4 carbon atoms or ethylene glycol monomethyl ether are preferably used.

Most preferably methanol or ethanol or mixtures thereof are used as solvent.

Although the reaction must be carried out under anhydrous conditions, the presence of water contained in solvents, raw materials, and reagents, as well as water contained in the atmosphere, which are usually referred to as anhydrous, does not have a significant effect; Anhydrous solvents and reagents can be used without special dehydration treatment.

Triacetonamine is usually obtained in a yield of 85% or more, particularly when an excess ammonium salt of 1 molar ratio or more to acetonin is used in the presence of acetone.

In addition to the acid catalyst, the yield of the method of the present invention is bromine, iodine, sodium iodide, potassium iodide, lithium iodide, lithium bromide, lithium thiocyanate, ammonium thiocyanate,
Lithium cyanide, lithium nitrate or ammonium sulfide or other catalysts selected from bromides, iodides, nitrates, methanesulfonates, benzenesulfonates or p-toluenesulfonates of ammonia, triethylamine, urea or thiourea The yield is improved and the reaction time is shortened by using 0.01 to 0.5 mol % of acetonin in combination.

Although the reaction time varies depending on the reaction conditions and the type of catalyst used, the reaction is usually completed in several hours to more than ten hours.

After the reaction is complete, the desired product, triacetonamine, is collected from the reaction mixture by a conventional method.

For example, after the reaction is complete, excess acetone and/or diacetone alcohol and the solvent are distilled off under reduced pressure, water is added to the residue, the mixture is made alkaline, extracted with an appropriate solvent, and the solvent is distilled from the extract. By removing the residue and vacuum distilling the residue, the desired product can be obtained as a pure product.

Therefore, the by-products of the reaction are very small, and the purification of the final product and the removal of the by-products are easy.

Therefore, the method of the present invention is extremely superior as an industrial method for producing triacetonamine compared to conventional methods, and triacetonamine is used in large quantities as a light stabilizer for polymeric materials and as a synthetic raw material for pharmaceuticals. , its industrial value is extremely large.

Examples of the method of the present invention are shown below.

Example 1 2.4 g of ammonium chloride was added to a solution of 6.7 g of acetonin in 20 ml of acetone, and the mixture was heated under reflux at 60° C. for 10 hours.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

The extract was dried with anhydrous potassium carbonate.

Benzene is distilled off and the residue is purified by vacuum distillation to a boiling point of 7.
5-76℃/4 mu Hg pale yellow liquid (cold junction melting point 3
Triacetonamine 6.1 (forms crystals at 5-36°C)
I got g.

Yield 91.1%. Example 2 Acetone 10. Add 26rnl of benzene and 1.0g of ammonium chloride to a solution of 10.0g of acetonin dissolved in :l.
was added and the mixture was heated under reflux at 63°C for 21 hours.

Thereafter, the solvent benzene and excess acetone were distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

The extract was dried with anhydrous potassium carbonate. Benzene is distilled off and the residue is purified by vacuum distillation to a boiling point of 75-76℃/4
8.5 g of triacetonamine was obtained as a pale yellow liquid (forms crystals with a cold melting point of 35-36° C.) at 7 nmHg.

Yield 85%. Example 3 6.4 g of ammonium bromide was added to a solution of 10 g of acetonin in 30 TL of acetone, and the mixture was heated under reflux at 60° C. for 12 hours.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

The extract was dried with anhydrous potassium carbonate.

Benzene is distilled off and the residue is purified by vacuum distillation to a boiling point of 7.
Pale yellow liquid (cold junction melting point 35~
9.0 g of triacetonamine (forming crystals at 36° C.) was obtained.

Yield 90%. Example 4 9.5 g of ammonium iodide was added to a solution of 10.9 g of acetonin dissolved in 30 ml of acetone, and the mixture was heated under reflux at 60° C. for 12 hours.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

The extract was dried with anhydrous potassium carbonate.

Benzene is distilled off and the residue is purified by vacuum distillation to a boiling point of 7.
5-76'C/4mrHg pale yellow liquid (cold junction melting point 35
Triacetonamine 8.9i (forms crystals at ~36°C)
Obtained.

Yield 89%. Example 5 6.0 g of ammonium nitrate was added to a solution of acetonin 1 (Bi') dissolved in acetone 30 and heated under reflux at 60° C. for 12 hours.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

The extract was dried with anhydrous potassium carbonate.

Benzene is distilled off and the residue is purified by vacuum distillation to a boiling point of 7.
5-76'C/4mmHg pale yellow liquid (cold junction melting point 35
8.6 g of triacetonamine (forms crystals at ~36°C)
Obtained.

Yield 86%.

Example 6 6.2 g of ammonium borate was added to a solution of 11 acetonin dissolved in 30 ml of acetone, and 12 g of ammonium borate was added under reflux at 60°C.
heated for an hour.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

The extract was dried with anhydrous potassium carbonate.

Benzene is distilled off and the residue is purified by vacuum distillation to a boiling point of 7.
Pale yellow liquid at 5-76℃/4mmHg (cold junction melting point 35~
8.5 g of triacetonamine (forming crystals at 36° C.) was obtained.

Yield 85%. Example 7 40ml of acetone was added to 15.4g of acetonin and 7°Og of ammonium formate, and the mixture was heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. A saturated aqueous potassium carbonate solution was added to the resulting reaction mixture, and the mixture was extracted with benzene.

The extract was dried over anhydrous potassium carbonate, and benzene was distilled off.

The residue was purified by vacuum distillation to a boiling point of 75-76℃/mm
14.9 g of triacetonamine was obtained as a pale yellow liquid of Hg (forms into crystals with a cold melting point of 35 to 36°C).

Yield: 9640 Example 8 40 ml of acetone was added to 15.4 g of acetonin and 8.0.9 g of ammonium acetate, and the mixture was heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 13.
．． 2g was obtained.

Yield 85%.

Example 9 Acetonin 15.4. @ and diammonium malonate7.
40rfLl of acetone was added to 1g, and the mixture was heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain 13.7 g of triacetonamine.

Yield 90%.

Example 10 15.4 g of acetonin and 13.0 g of diammonium malonate.
8. ! Add acetone 45TrLl to i' and heat at 60℃ for 1
Heated under reflux for 3 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 13.552.

Yield 87%.

Example 11 Acetonin 15.4. F and diammonium succinate7.
40 ml of acetone was added to 8 g, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain 13.2 g of triacetonamine.

Yield 85%.

Example 12 15.4 g of acetonin and 14 g of ammonium benzoate:
40 TL of acetone was added to the mixture, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain 13.8 g of triacetonamine.

Yield 89%.

Example 13 15.4 g of acetonin, 19.2 g of ammonium p-toluenesulfonate, and 60 ml of acetone! and 60℃
The mixture was heated under reflux for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain 14.6 g of triacetonamine.

Yield 94%. Example 14 Formate salt of acetonin 10.1 and cyclohexylamine 1
40 degrees of acetone was added to 1.0 g, and the mixture was heated under reflux at 70°C for 13 hours.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
The mixture was extracted with benzene.

The extract was dried with anhydrous potassium carbonate. Benzene was distilled off and the residue was purified by vacuum distillation to a boiling point of 75-76°C.
8.5 g of triacetonamine was obtained as a pale yellow liquid (forms crystals with a cold melting point of 35-36° C.) at 4 mmHg.

Yield 85%. Example 15 40 TL of acetone was added to 10.0 g of acetonin and 10.2 g of pyridine formate, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C/
8.9 g of triacetonamine was obtained as a pale yellow liquid (forming into crystals with a cold melting point of 35-36°C) of 4 mvtHg.

Yield 89%. Example 16 Acetonin 10. Add 40 TL of acetone to 14.5 g of acetate of L9 and di-n-butylamine, and heat at 70°C for 1
Heated under reflux for 3 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
6g was obtained.

Yield 86%. Example 17 40 ml of acetone was added to 10.0 g of acetonin and 18.1 g of aniline acetate, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
I got 6,9.

Yield 86%.

Example 18 10.0 g of acetonin and succinate of morpholine 15.
40TLl of acetone was added to 7g, and the mixture was heated under reflux at 60°C for 13 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
5g was obtained.

Yield 85%.

Example 19 45 ml of acetone was added to 10.0 g of acetonin and 10.8.9 succinate of triethylamine, and 1
Heated under reflux for 3 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
6g was obtained.

Yield 86%. Example 20 Maleate salts of acetonin io, o, p and morpholine 1
45 TL of acetone was added to 57 g, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
5g was obtained.

Yield 85%. Example 21 Acetone (45) was added to 10.0 g of acetonin and 16.79 g of maleate of triethylamine, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 9.
3g was obtained.

Yield 93%. Example 22 60 TL of acetone was added to 10.1 g of acetonin and 19.2 g of benzoate of di-n-butylamine, and the mixture was heated at 60°C for 1
Heated under reflux for 3 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
5g was obtained.

Yield 85%. Example 23 Add 60 ml of acetone to 10.0 g of acetonin and 20.6.9 p-toluenesulfonate of pyridine, and heat at 60°C.
The mixture was heated under reflux for 13 hours.

Thereafter, acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 8.
8g was obtained.

Yield 88%. Example 24 11.3 g of acetone and 501 rLl of benzene were added to 10.0 g of acetonin and 20.69 g of p-toluenesulfonate of pyridine, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the solvent benzene was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 8.59.

Yield 85%.

Example 25 10.0 g of acetonin and acetate of triethylamine3.
0g to acetone 11. :1 and benzene 50M were added and heated under reflux at 60° C. for 13 hours.

Thereafter, the solvent benzene was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain 8.5 g of triacetonamine.

Yield 85%. Example 26 9011 L of acetone was added to 15.4 g of acetonin and 32.79 g of p-toluenesulfonate of triacetonamine, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off, and the resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 29.
．． I got 09.

Yield 87%. Example 27 15.4 g of acetonin and 6.8 g of methylamine hydrochloride
40ml of acetone was added to the mixture, and the mixture was heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off.

A saturated aqueous potassium carbonate solution was added to the resulting reaction mixture, and the mixture was extracted with benzene.

The extract was dried over anhydrous potassium carbonate, and benzene was distilled off.

The residue was purified by vacuum distillation to a boiling point of 75-76℃/4m
Triacetonamine 13.4.9 was obtained as a pale yellow liquid (which becomes crystals with a melting point of 35-36° C. after 4 hours) at mHg.

Yield 86%.

Example 28 Add 40ml of acetone to acetonin 16.4.9 and cyclohexylamine hydrochloride 13.8.9, and add 13.8ml of acetone at 60°C.
Heat under reflux for an hour.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain a pale yellow liquid (35
Triacetonamine 13.2 (forms crystals at ~36°C)
I got g.

Yield 85%. Example 29 40 TL of acetone was added to 15.4 g of acetonin and 13.1 g of dihydrochloride of hexamethylene diamine, and the mixture was heated to 15.4 g at 60°C.
Heated under reflux for 3 hours.

After that, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain a pale yellow liquid (4
15.0 g of triacetonamine (which later became crystals with a melting point of 35 to 36°C) was obtained.

Yield 97%.

Example 30 40 ml of acetone was added to 15.4 g of acetonin and 13.2 g of aniline hydrochloride, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1, and the boiling point was 75-76°C.
7'4 mrrt Hg pale yellow liquid (cold junction melting point 35-3
3.2 g of triacetone amine (forms crystals at 6°C)
I got it.

Yield 85%. Example 31 Acetone 407711 was added to 18.1 g of acetonin 15.4.9 and p-nitroaniline hydrochloride, and 1
Heated under reflux for 3 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain 13.5 g of triacetonamine as a pale yellow liquid with a boiling point of 75-76°C/4 mmHg (forms into crystals with a cold melting point of 35-36°C). I got it.

Yield 87%.

Example 32 15.4 g of acetonin and 8.6 g of dimethylamine hydrochloride
40-g of acetone was added to the mixture, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain 13.9 g of triacetonamine as a pale yellow liquid with a boiling point of 75-76° C./miHg.

Yield 90%.

Example 33 Acetonin 15.4g and dimethylamine hydrochloride 16,
50ml of acetone was added to 111 and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 1 as a pale yellow liquid (forms crystals with a cold melting point of 35-36°C) with a boiling point of 75-76°C/mmHg.
3.1 was obtained.

Yield 88%.

Example 34 15.4 g of acetonin and 20 g of diphenylamine hydrochloride
．． 60 mJ of acetone was added to 79 and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain triacetone amine 1 as a pale yellow liquid (forms crystals with a cold melting point of 35-36°C) with a boiling point of 75-76°C/, iiHg.
3.7g was obtained.

Yield 88%.

Example 35 15.4 g of acetonin and diisobutylamine hydrochloride 1
40 ml of acetone was added to 7.0 g, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain 15.2 g of triacetonamine as a pale yellow liquid with a boiling point of 75-76°C/4 tnmHg (forms into crystals with a cold melting point of 35-36°C). I got it.

Yield 98%.

Example 36 Acetonin 15.4.1? Add 40TfLl of acetone to 14.1 and triethylamine hydrochloride, and add 13
Heat under reflux for an hour.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 1 as a pale yellow liquid with a boiling point of 75-76°C/4 mmHg (forms into crystals with a cold melting point of 35-36°C).
5.0g was obtained.

Yield 97%.

Example 37 50 TL of acetone was added to 15.4 g of acetonin and 18.2.9 g of triethylamine hydrobromide, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 1 as a pale yellow liquid with a boiling point of 75-76°C/4 mmHg (forms into crystals with a cold melting point of 35-36°C).
5.0g was obtained.

Yield 97%.

Example 38 15.4 g of acetonin and 1,4-diazabicyclo[2,
2,2] Acetone 4 to 15.2 g of octane monohydrochloride
01111 was added and heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C/,
13.6 g of triacetonamine was obtained as a pale yellow liquid (forming as crystals with a cold melting point of 35-36° C.) at mmHg.

Yield 88%. Example 39 Acetonin 15.4.9 and 1,4-diazabicyclo(2
,2,2) Sulfate of octane21. (60rrLl of acetone was added to Bi' and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a boiling point of 75-76°C/
, mytHg, triacetonamine 13.3.9 was obtained as a pale yellow liquid (forms crystals with a cold melting point of 35-36°C).

Yield 86%. Example 40 Acetonin 15.4 & Pyridine Hydrochloride 12. 40 TL of acetone was added to 1:1 and heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a boiling point of 75-76°C/
Triacetonamine as a pale yellow liquid (after 4 crystals with a melting point of 35-36°C) at 4 mmHg 13. :l was obtained.

Yield 86%. Example 41 Acetonin 15. 40 ml of acetone was added to 14.9 g of nitrate of =l and pyridine, and the mixture was heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C.
/4 mmHg, triacetonamine 13.2.9 was obtained as a pale yellow liquid (becomes crystals with a melting point of 35-36° C. after 4 hours).

Yield 85%. Example 42 15.4 g of acetonin and triacetonamine hydrochloride 1
60 TL of acetone was added to 9.1 g, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 28 as a pale yellow liquid with a boiling point of 75-76°C/4 mrn Hg (after 4 hours it became crystals with a melting point of 35-36°C). .6g was obtained.

Yield 85%.

Example 43 Acetonin 15.4.9 and Thiokenki hydrochloride 12.5g
45 ml of acetone was added to the mixture, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C.
14.79 of triacetonamine was obtained as a pale yellow liquid (which became crystals with a melting point of 35 to 36°C after 4 mmHg).

Yield 95%. Example 44 45 parts of acetone was added to 15.4.9 g of acetonin and 12.7 g of urea nitrate, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C.
13.29 of triacetonamine was obtained as a pale yellow liquid (which became crystals with a melting point of 35-36° C. after 4 hours) at 74 mmHg.

Yield 85%. Example 45 To a solution of 5 g of acetonin dissolved in 150 TIll of acetone, 66.9 g of the hydrochloride of dried Amparite IR-45 (manufactured by Rohm and Haas) was added and heated under reflux at 60° C. for 8 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a pale yellow liquid (4
4.3 g of triacetonamine (which later became crystals with a melting point of 35 to 36°C) was obtained.

Yield 86%.

Example 46 60ml of acetone was added to 21.49ml of acetonin acetate and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off.

Add saturated potassium carbonate aqueous solution to the resulting reaction mixture,
Extracted with benzene.

After drying the extract over anhydrous potassium carbonate and distilling off the benzene, the residue was purified by vacuum distillation to obtain a boiling point of 75-76.
Pale yellow liquid at 7'4mmHg (melting point 35-36℃ after 4℃)
13.3 g of triacetonamine (forming crystals) was obtained.

Yield 86%. Example 47 21.3 g of basic succinate of acetonin synthesized with 2 moles of acetonin and 1 mole of succinic acid was added with 60 g of acetone.
m1 was added and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a boiling point of 75-76°C/
13.3 g of triacetonamine was obtained as a light yellow liquid (which becomes crystals with a melting point of 35 to 36° C. after 4 mmHg).

Yield 86%. Example 48 Neutral succinate of acetonin 27.2.9 to acetone 8
0TLl was added and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a boiling point of 75-76°C/
, mmHg, 13.2 g of triacetonamine was obtained as a pale yellow liquid (which became crystals with a melting point of 35 to 36° C. after 4 hours).

Yield 85%. Example 49 Acetone 657711 was added to the basic maleate salt of acetonin 21.2.9 and heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C.
/, mmHg, triacetonamine 13.2.9 was obtained as a pale yellow liquid (becomes crystals with a melting point of 35-36° C. after 4 hours).

Yield 87%. Example 50 Benzoate of acetonin 27.6,? acetone 80
m1 was added and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a boiling point of 75-76°C/
16.2 g of triacetylene amine was obtained as a light yellow liquid (which becomes crystals with a melting point of 35 to 36° C. after 4 mmHg).

Yield 85%. Example 51 120 TL of acetone was added to 40.2 g of 0-iodobenzoate of ace1henine, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1, and the boiling point was 75-76°C.
Triacetonamine 1.3.2.9 was obtained as a pale yellow liquid at 4 mmHg (becomes crystals with a melting point of 35-36° C. after 4 hours).

Yield 85%. Example 52 Acetone 90% to 29.1% metatoluizate of acetonin
- was added and heated under reflux at 60°C for 13 hours.

Thereafter, the acetone was distilled off. The obtained reaction mixture was purified in the same manner as in Example 1 to obtain a boiling point of 75-76°C/
13.2 g of triacetonamine was obtained as a pale yellow liquid (which became crystals with a melting point of 35 to 36° C. after 4 imH.g).

Yield 85%. Example 53 p-tert-butylbenzoate of acetonin 33.2
100 ml of acetone was added to the mixture, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The resulting reaction mixture was purified in the same manner as in Example 1 to obtain a pale yellow liquid (4
13.2 g of triacetonamine (which later became crystals with a melting point of 35 to 36°C) was obtained.

Yield 85%.

Example 54 100 Tnl of acetone was added to 32.6 g of p-toluenesulfonate of acetonin, and the mixture was heated under reflux at 60° C. for 13 hours.

After that, the acetone was distilled off. The resulting reaction mixture was purified in the same manner as in Example 1, with a boiling point of 75-76°C.
/4 mmHg, 13.9 g of triacetonamine was obtained as a pale yellow liquid (formed into crystals with a melting point of 35-36° C. after 4 hours).

Yield 90%. Example 55 90 ml of acetone was added to 30.2 g of cinnamate of acetonin, and the mixture was heated under reflux at 60° C. for 13 hours.

Thereafter, the acetone was distilled off.

The obtained reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine 1, a pale yellow liquid with a boiling point of 75-76°C and 74 mmHg (after 4 years, it became crystals with a melting point of 35-36°C).
3.2g was obtained.

Yield 85%. Example 56 6.3 g of acetonin hydrochloride was dissolved in a mixed solvent consisting of 35 g of methanol and 35 p of acetone.

The mixture was left to react in a sealed container at room temperature for 24 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 127%.

Example 57 Acetone 70.9 to acetonin 19. 7 g of methanol was added to the solution obtained by dissolving .
9g was absorbed.

The solution was sealed and heated at 60° C. for 10 hours to react.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 14.0%.

Example 58 6.2 g of methanol containing 5% by weight of hydrogen chloride was added dropwise to a solution of 76.3 g of acetic acid 1-2 dissolved in 24 g of acetone.

The solution was sealed and heated at 60° C. for 10 hours to react.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 147%.

1 night of implementation] 59 1.6 g of methanesulfonic acid was added to a solution of 6.3 g of acetonin dissolved in a mixed solvent consisting of 30 g of acetone and 30 g of methanol.

The mixture was left to react in a sealed container at room temperature for 24 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 95.3%.

Example 60 0.5 g of acetic acid was added to a solution of 6.3 g of acetonin dissolved in a mixed solvent consisting of 20 g of acetone and 2 g of ethanol.

The mixture was reacted by heating at 60° C. for 10 hours in a sealed container.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 89.5%.

Example 61 0.63 g of maleic acid instead of acetic acid in Example 60
Triacetonamine was obtained in a yield of 102% in substantially the same manner except that .

Example 62 0.5 g of malonic acid was added to a solution of 6.3 g of acetonin in 40 g of acetone, and the mixture was heated to 6.3 g in a sealed container.
The reaction was heated at 0° C. for 10 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 115%.

Example 63 19 g of acetone and 4.0 g of urea nitrate were added to a solution of 5.0 g of acetonin dissolved in 21.9 g of methanol.

The mixture was left to react at room temperature for 24 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 125%.

Example 64 Urea p-t- instead of urea nitrate in Example 63
Triacetonamine was obtained in a yield of 110% in substantially the same manner except that 7.5 g of luenesulfonic acid was used.

Examples 65-67 19 g of acetone and 9.5 g of other solvents listed in the table below! 5.0 g of acetonin was dissolved in a mixed solvent consisting of fl.

The catalyst listed in the table below was added to this solution, and the mixture was reacted by heating at 60° C. for 10 hours in a sealed container.

The reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine in the yield shown in the table below.

Example 68 To a solution of 50 g of acetonin dissolved in a mixed solvent consisting of 19 g of acetone and 1.9 g of methanol, 15 g of hydrochloride of 1-lyacetonamine was added.

The mixture was reacted by heating at 60° C. for 10 hours in a sealed container.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine in a yield of 115% except for the amount of triacetonamine used as a catalyst.

Example 69 Acetone 19! ! and 5.5 g of acetonin in a mixed solvent consisting of 9.5 g of methanol. 1.3 g of ammonium acetate was added to the solution containing Og.

The mixture was left to react in a sealed container at room temperature for 24 hours.

After the reaction was completed, the reaction mixture was diluted with nl in the same manner as in Example 1.
Triacetonamine was obtained with a yield of 91.1%.

Example 70 1.6 g of acetonin formate was added to a solution containing 5.1 g of acetonin in 40 g of acetone.

The mixture was heated and reacted in a sealed container at 60'C for 10 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 95.8%.

Example 71 Ethylate 6.5.9 of boron trifluoride was added dropwise to a solution of 15.4 g of acetonin dissolved in 60 g of acetone at room temperature.

After the addition, the mixture was reacted by heating at 48 to 50°C for 3 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 116%.

Example 72 5 g of acetonin and 1 ammonium bromide in 30 g of acetone
2.4 g was added and the mixture was left to react at room temperature for 38 hours.

After the reaction was completed, the reaction mixture was purified in the same manner as in Example 1 to obtain triacetonamine with a yield of 239%.

Examples 73-75 Other catalysts listed in the table below were added to a mixture of 1.1 acetonin, 4.1 acetone and 0.31 ammonium bromide as catalyst.

The mixture was stirred at 40°G in a tightly capped flask, and the yield of triacetonamine was measured at regular intervals.

The time required to obtain triacetonamine with a yield of 90% is shown in the table below.

Example 76 A solution containing 8.1 g of trichloroacetic acid in 15 ml of ether was added dropwise to a solution of 7.7 g of acetonin in 157711 ether while stirring at 5 to 10°C.

After dropping, the mixture was stirred for 1 to 2 hours.

The precipitated crystals were filtered, washed with ether and dried under reduced pressure to yield 15.5 g of trichloroacetate of acetonin as colorless crystals, mp 113-114°C.

Yield 97.9%.

Examples 77-85 Following a method substantially similar to that shown in Example 76,
The following acetonin salt was obtained.

Claims (1)

[Claims] 1 Under anhydrous conditions, at least 12.5 for acetonin
A method for producing triacetonamine, which comprises reacting acetonin with acetone and/or diacetone alcohol in the presence of an acid catalyst of mol % or more.