JPS60146876A - Production of hydantoin - Google Patents

Abstract

PURPOSE:To produce the titled compound economically from inexpensive raw materials, preventing the discoloration, without using a high-pressure equipment, etc., by using glycinonitrile as a raw material, reacting with ammonium bicarbonate, ammonium carbonate or ammonia and carbon dioxide, and treating the reaction product with an acid. CONSTITUTION:Glycinonitrile is made to react with ammonium bicarbonate, ammonium carbonate, a combination of ammonia and carbon dioxide, or their mixture, in water or an aqueous solvent such as hydrated methanol, etc. at 45- 80 deg.C for about 2-10hr. After the reaction, 3-5 equivalent (based on the used glycinonitrile) of concentrated sulfuric acid or concentrated hydrochloric acid is added to the reaction mixture, and the acid-treatment is carried out at 80-110 deg.C for about 1hr to obtain the titled compound. The amount of the ammonium bicarbonate, etc. is preferably 1.0-3.0mol per 1mol of glycinonitrile. The concentration of glycinonitrile in the reaction mixture is preferably about 5-30wt%.

Description

[Detailed description of the invention] The present invention relates to a method for producing hydantoin.

Conventional methods for producing hydantoin include Buc, which involves reacting formaldehyde, ananide, and (bi)ammonium carbonate in water or an aqueous alcoholic solvent under normal pressure.
The herer-Bergs reaction is known. However, this method is extremely difficult, and improved methods have since been reported.

For example, a method in which glycolonitrile and ammonium bicarbonate are reacted under closed pressure and then treated with acid (Japanese Patent Publication Publication No. 39 Sho.
-24807). A method of reacting glycolonitrile and ammonium bicarbonate at normal pressure in the presence of the following diamine or tertiary amine (Japanese Patent Publication No. 5O-671).

There is also a method (Japanese Patent Laid-Open No. 138557/1983) in which glycolonitrile and ammonium bicarbonate are reacted with a water-soluble alkoxyethanol using water as a solvent.

However, in these methods, for example, the coloring of the reaction product is significant, glycolonitrile (IJ) is particularly unstable, and this decomposition is also a cause of coloration, and the reaction is carried out under closed pressure. There were operational and equipment problems, such as the need to use pressure-resistant equipment.

In addition, as another method, the reaction between glycine ethyl ester hydrochloride and cyanate (Chem, Ber, 33 p.
.

3418 (1900)), the combination of glycine and cyanate (J, Chem, Soc, 192679)
, and reaction with urea (Chem, Ber
, 442953 (1908)), etc., but there is a problem that the raw materials such as glycine, glycine ethyl ester hydrochloride, cyanate, etc. are expensive.

The present inventors conducted various studies to overcome these problems, and found that the yield was improved by reacting glycinonitrile and ammonium bicarbonate in water or an aqueous solvent under normal pressure, followed by acid treatment. It has been found that hydantoin can be produced successfully. .

Incidentally, an example of producing hydantoin from gly7nonitrile and ammonium bicarbonate has not yet been found in any conventionally known literature, patents, etc.

The present invention aims to provide a method for producing hydantoin, which comprises reacting glycinonitrile and ammonium bicarbonate in water or an aqueous solvent under normal pressure, followed by adding sulfuric acid or hydrochloric acid and heat-treating the reaction. However, in the present invention, glycinonitrile that can be used as a raw material can be industrially produced, for example, from formaldehyde, hydrocyanic acid, or ammonia, and purified products, crude products, and glycinonitrile sulfate are neutralized with an alkali. and those that have been released.

Also, carbon dioxide gas and ammonia can be used instead of ammonium bicarbonate.

Also, as a hydrophilic organic solvent that can be used in combination with water,
Examples include methanol, ethanol, dioxane, tetrahydrofuran, glycerin, ethylene glycol, isozorono and nor, n-frono and nor.

Although ammonium bicarbonate is not necessarily limited, it is generally desirable to use it in an amount of 1.0 to 3.0 times the molar amount of glycinonitrile. If the molar ratio is increased, the cost will increase and the yield will not improve much. The appropriate concentration of glycinonitrile in the reaction mixture is about 5 to 30 wt%.

There is no strict limit on the reaction temperature, but it is 45-80℃.
The reaction time is preferably about 2 to 10 hours. The lower the reaction temperature, the longer the reaction time. Furthermore, if the reaction temperature is too high, ammonium bicarbonate will scatter, which is undesirable.

In order to cyclize the hydantoin derivative produced as a by-product after the reaction, acid treatment is performed by adding concentrated sulfuric acid or concentrated hydrochloric acid in an equivalent ratio of 3 to 5 to the glycinonitrile used.

There are no special restrictions on the conditions for acid treatment, but the temperature is 80-1
The temperature is 10°C and the time is about 1 hour.

Next, the present invention will be described in more detail by Examples. However, it goes without saying that these are merely illustrative examples and do not limit the present invention in any way.

Note that the yield is based on the starting glyph nitrile.

Example 1 A 500ml seven-paraple flask with a condenser tube and a waterfall
Equipped with a mechanical stirrer.

A flask was charged with 147.9 g of water, 140 g of a 40 wt % glycinonitrile water bath solution, and ammonium bicarbonate [58I], heated to 75° C., and reacted for 3 hours.

Next, 225 g of 95 wt % concentrated sulfuric acid was added to this reaction solution while being careful to prevent foaming and keeping the temperature below 50°C.

This was heated to 105°C and heat treated for 1 hour.

This reaction solution was collected using a high performance liquid chromatograph (column 5hod).
ex Ion r (1kC-811 eluent 0.4wt%
HClO4.

When analyzed using Column 5hodex OHpckkB-804 eluent (0.05 wt% H3P04), 74 units of hydantoin, 2 units of hydantoic acid, and 10 units of glycine were obtained in liquid yield.

Example 2 Into a 500 ml separable flask equipped with the same equipment as in Example 1, 140.9 g of 40 wt% glycinonitrile aqueous solution was added.
, ammonium bicarbonate was charged on May 9, 1977.

The mixture was heated to 75°C and reacted for 3 hours.

Next, 95vt% concentrated sulfuric acid 180. ! 9 was added while keeping the temperature below 50° C. while being careful to prevent foaming. Then, heat treatment was performed at 105° C. for 1 hour. When this liquid was analyzed by high performance liquid chromatography, the yield in the liquid was 74% for hydantoin, 2% hydantoic acid, and 7% for glycino.

Example 3 A 500 ml separable flask equipped with the same equipment as in Example 1 was charged with 140 g of a 40 wt% glycinonitrile aqueous solution and 158 I of ammonium bicarbonate. This was heated to 55°C and reacted for 10 hours.

Next, 354 g of 36 wt% sulfuric acid was added while keeping the temperature below 50°C. Then, heat treatment was performed at 105° C. for 1 hour.

When this reaction solution was analyzed by high performance liquid chromatography, the yield in the solution was 70% for hydantoin, 2% for hydantoic acid, and 6% for glinone.

Patent applicant Showa Denko Co., Ltd. Procedural amendment (voluntary) March 2, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of the case 1981 Patent Application No. 2692 2, Name of the invention Process for producing hydantoin 3, Relationship with the case of the person making the amendment Patent applicant address 13-9 Shiba Daimon-chome, Minato-ku, Tokyo Name (
200) Showa Denko Co., Ltd. 4, Agent Residence: 6, Showa Denko Co., Ltd., 13-9 Shiba Daimon-chome, Minato-ku, Tokyo, Subject of amendment: Full text of the specification 7, Contents of the amendment: The full text of the specification of the application is amended as shown in the attached document. do.

Amended Description 1, Name of the Invention Process for Producing Hydantoin 2, Claims Glycinonitrile and ammonium bicarbonate, ammonium carbonate or ammonia and carbon dioxide or a mixture thereof are reacted in water or an aqueous solvent, and then sulfuric acid The method for producing hydantoin is still characterized by adding hydrochloric acid and heat treatment.

3. Detailed explanation of Ming It is.

Conventional methods for producing hydantoin include Buc, in which formaldehyde, cyanide, and ammonium (bi)carbonate are reacted in water or an aqueous alcoholic solvent under normal pressure.
The herer-Bergs reaction is known. However, this method is extremely difficult, and improved methods have since been reported.

For example, a method in which glycolonitrile and ammonium bicarbonate are reacted under closed pressure and then treated with acid (Japanese Patent Publication Publication No. 39 Sho.
-24807). A method of reacting glycolonitrile and ammonium bicarbonate under normal pressure in the presence of a secondary or tertiary amine (Japanese Patent Publication No. 50-671).

There is also a method (Japanese Patent Laid-Open No. 138557/1983) in which glycolonitrile and ammonium bicarbonate are reacted with a water-soluble alkoxyethanol using water as a solvent.

However, these methods require, for example, that the reaction product is markedly colored, that glycolonitrile is particularly unstable, and this decomposition is the cause of the coloration, and that the reaction is carried out under closed pressure. There were operational and equipment problems such as the need to use pressure-resistant equipment.

In addition, as another method, the reaction between glycine ethyl ester hydrochloride and cyanate (Chem. Ber. 3 3
341'8 (1900)), reaction of glycine with cyanate (J. Chem. Soc. 1 9 2 6 7
9), and the reaction between glycine and urea (Chem-
Ber. 2953 (1908)), but there is a problem that the raw materials such as glycine, glycine ethyl ester hydrochloride, cyanate, etc. are expensive.

As a result of various studies to overcome these problems, the present inventors have found that glycinonitrile and ammonium bicarbonate, ammonium carbonate or U ammonia and carbon dioxide, or a mixture thereof, are regularly mixed in water or an aqueous solvent. It has been found that hydantoin can be produced in good yield by reacting under pressure and then treating with acid.

Incidentally, no examples of producing hydantoin by the reaction of glycinonitrile and ammonium bicarbonate, ammonium carbonate, or ammonia and carbon dioxide have been found in conventionally known literature or patents.

The present invention involves reacting glycinonitrile with ammonium bicarbonate, ammonium carbonate, or ammonia and carbon dioxide, or a mixture thereof in water or an aqueous solvent under normal pressure, and then adding sulfuric acid or hydrochloric acid and heat-treating the mixture. In the present invention, the glycinonitrile that can be used as a raw material can be industrially produced from EVA, formaldehyde, hydrocyanic acid, and ammonia. These include products, crude products, and glycinonitrile sulfates that are neutralized with alkali and liberated.

Further, any of ammonium bicarbonate, ammonium carbonate, or carbon dioxide gas and ammonia may be used, and a mixture thereof may also be used.

Also, as a hydrophilic organic solvent that can be used in combination with water,
Examples include methanol, ethanol, nooxane, tetrahydrofuran, glycerin, ethylene glycol, isonoropanol, n-7'rotP/-l, and the like.

Although ammonium bicarbonate and the like are not necessarily limited, it is generally desirable to use them in a molar amount 10 to 30 times that of glycinonitrile. If the molar ratio is increased, the cost will increase and the yield will not improve much. The appropriate concentration of glycinonitrile in the reaction mixture is 5 to 30 wt%, 8 degrees Celsius.

There is no strict limit on the reaction temperature, but it is 45-80℃.
The reaction time is preferably about 2 to 10 hours. The lower the reaction temperature, the longer the reaction time. If the shredding reaction temperature is too high, ammonium bicarbonate will scatter, which is undesirable.

In order to cyclize the hydantoin derivative produced as a by-product after the reaction, acid treatment is performed by adding concentrated sulfuric acid or concentrated hydrochloric acid in an equivalent ratio of 3 to 5 to the glycinonitrile used.

There are no special restrictions on the conditions for acid treatment, but the temperature is 80-1
The temperature is 10°C and the time is about 1 hour.

Next, the present invention will be explained in detail with reference to examples. However, this is just an example for illustration purposes only, and does not limit the present invention in any way.

Note that the yield is based on the charged glycinonitrile.

Example 1 A 500-me separable flask was equipped with a ball cooling tube, a thermometer, and a mechanical stirrer.

A flask was charged with 147 g of water, 140 I of a 40'wt% aqueous solution of dalicinonitrile, and 158 g of ammonium bicarbonate, heated to 75° C., and reacted for 3 hours.

Next, 225 g of 95 wt % concentrated sulfuric acid was added to this reaction solution while being careful to prevent foaming and keeping the temperature below 50°C.

This was heated to 105°C and heat treated for 1 hour.

This reaction solution was collected using a high performance liquid chromatograph (column 5hod).
ex Ion pak C-811 eluent o, 4w
t% HClO4+ column 5hodex OHpak
When analyzed using B-804 eluent (0.05 wt% H3P04), a yield of 74% hydantoin, dihydantoic acid, and 10% glycine was obtained.

Example 2 A 40 wt% glycinonitrile aqueous solution was added at 140 wt% in a 500-meter portable flask equipped with the same equipment as in Example 1.
g. Charge 197.5 g of ammonium bicarbonate.

The mixture was heated to 75°C and reacted for 3 hours.

Next, add 180 g of 95 wt% concentrated sulfuric acid to
The mixture was added while keeping the temperature below 0°C. Then, heat treatment was performed at 105° C. for 1 hour. When this liquid was analyzed by high performance liquid chromatography, the yield in the liquid was 774% of hydantoic acid, 2% of hydantoic acid, and 7% of glycine.

Example 3 In a 500 ml separable flask equipped with the same equipment as in Example 1, a 40 wt% glycinonitrile aqueous solution 140 &
, 158 g of M ammonium carbonate was charged. This is 55℃
The mixture was heated to a temperature of 100.degree. C. and reacted for 10 hours.

Next, 354 g of 36 wt% sulfuric acid was added while keeping the temperature below 50°C. Then, heat treatment was performed at 105° C. for 1 hour.

When this reaction solution was analyzed by high performance liquid chromatography, the yield in the solution was 70% of hydantoin, 2% of hydantoic acid, and 6% of glycine.

Example 4 154 g of 22 wt% ammonia water and 56 g of glycinonitrile (IJ) were placed in a 500 ml gable flask equipped with the same equipment as in Example 1, and 451 g of carbon dioxide gas was blown into the flask at a temperature below 50°C. Thereafter, the mixture was heated to 80°C and reacted for 2 hours.

Next, add 225 g of 95 wt% concentrated sulfuric acid to 50 g, being careful not to foam.
The mixture was added while keeping the temperature below ℃. Heat this to 105℃,
Heat treatment was performed for 1 hour. When this reaction solution was analyzed by high performance liquid chromatography, the yield of hydantoin in the solution was 72%.
, 3% hydantoic acid, and 8% glycine were obtained.

Example 5 A 40 wt% glycinonitrile aqueous solution was placed in a 5 () Oml separable flask equipped with the same equipment as in Example 1.
0g, and 188g of ammonium carbonate.

It was heated to 70°C and reacted for 4 hours.

Next, add 95 wt% concentrated sulfuric acid 2259 for 5 minutes to avoid foaming.
The mixture was added while keeping the temperature below 0°C. This was heated to 105°C and heat treated for 1 hour. When this reaction solution was analyzed by high performance liquid chromatography, the yield in the solution was 2.
4% of hydantoic acid and 8% of glycine were obtained.

Patent applicant: Showa Denko Co., Ltd.

Claims (1)

[Claims] A method for producing hydantoin, which comprises reacting glycinonitrile and ammonium carbonate in water or an aqueous solvent, followed by adding sulfuric acid or hydrochloric acid and heat-treating.