JPH08176119A - Method for producing guanamines - Google Patents

Abstract

(57) [Summary] [Structure] Formula (1) in the presence of a basic catalyst. (In the formula, the bonding position of the cyano group represents the 2,5- or 2,6-position), by reacting dicyandiamide in the range of 1.1 to 1.9 mol with respect to 1 mol of the dinitrile, monoguanamine is obtained. It is characterized in that it co-produces diguanamines. [Effect] According to this method, both the raw materials dinitrile and dicyandiamide can be completely reacted, and both guanamines can be obtained in high purity and high yield.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polymerizable monomer, a coating resin, an adhesive resin, a paper processing resin, a fiber processing resin, a powder coating resin, a building material, a molding material, a foam molding material, etc. Resin raw material, rubber material modifier, organic material flame retardant, guanamine compound derivative raw material, epoxy resin,
Curing agent such as urethane resin, stabilizer, compatibilizer, medicine,
Further, the present invention relates to a method for producing monoguanamines and diguanamines which are industrially useful compounds as agricultural chemicals.

[0002]

2. Description of the Related Art Heretofore, a method of reacting a corresponding dinitrile compound with dicyandiamide has been known as a method for producing diguanamines and the like. In this method, when the reaction of the dinitrile compound and dicyandiamide is carried out at a reaction molar ratio of 1: 2 or more, the reaction molar ratio is as large as 2 or more. It is difficult to control, and the reaction system becomes extremely high in temperature, the production of by-products rapidly increases to a non-negligible level, and the purity of the product is remarkably reduced. When the reaction is carried out at a large excess molar ratio of dicyandiamide, There was a defect that the recovery and purification steps such as removal and separation of reaction dicyandiamide became complicated, and there were significant technical and economic restrictions.

When the reaction is carried out at a reaction ratio of less than 2, the reaction mixture contains an unreacted dinitrile compound together with monoguanamines and diguanamines. In such a reaction mixture, unreacted raw materials are recovered from monoguanamines and diguanamines,
The steps of removing and the step of purifying such guanamines are remarkably complicated, and further, there is a defect that a target compound having a practically sufficient purity cannot be obtained, which is a serious limitation in practical use.

[0004]

Means for Solving the Problems As a result of intensive investigations on the production of guanamines, the inventors of the present invention have made it extremely industrially possible by reacting dinitrile having a specific structure with dicyandiamide under specific conditions. We have found that useful novel monoguanamines are selectively produced in high yield. The present inventors have conducted extensive studies in view of the above defects in the production method of diguanamines, etc., based on the above findings, dinitrile and dicyandiamide having a specific structure, under a condition such as a specific reaction molar ratio. By reacting, it can be produced without significant exotherm, the production of by-products is extremely small, and the reaction mixture contains no unreacted components of the raw materials dinitrile and dicyandiamide. It is practically unnecessary to recover and separate raw materials, the purification and separation process is extremely simple, it is easy to obtain high-purity guanamines, and it is possible to simultaneously obtain industrially extremely useful monoguanamines and diguanamines. The present invention has been reached by finding a manufacturing method having the technically and economically excellent characteristics of

That is, the present invention provides (a) a compound of formula (1) (formula 4) in the presence of a basic catalyst.

[Chemical 4] (Wherein the bonding position of the cyano group indicates the 2,5- or 2,6-position), dicyandiamide is reacted in the range of 1.1 to 1.9 mol per mol of the dinitrile. , Formula (2) (Formula 5)

Embedded image [In the formula, (4,6-diamino-1,3,5-triazin-2-yl)
The bonding position of the group represents 5- or 6-position], and monoguanamines represented by the formula (3)

[Chemical 6] [In the formula, (4,6-diamino-1,3,5-triazin-2-yl)
The bonding position of the group is 2,5- or 2,6-position] represented by the method for producing guanamines co-producing diguanamines,
(B) The basic catalyst comprises an alkali metal, an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alcoholate, an alkali metal salt of dicyandiamide, an alkaline earth metal salt of dicyandiamide, an amine, and ammonia. The production method according to (a) above, wherein the reaction is at least one selected from the group, and (c) the reaction using at least one selected from the group consisting of a non-aqueous protic solvent and an aprotic polar solvent as a reaction solvent. The production method described in (a) or (b) above, characterized in that the reaction is carried out at a temperature of 60 to 200 ° C. (a), (b) or The manufacturing method according to (C) is provided.

Examples of the basic catalyst in the method for producing guanamines according to the present invention include alkali metals such as potassium and sodium, alkali metals such as potassium hydroxide, sodium hydroxide, calcium hydroxide and barium hydroxide, and alkali metals. Earth metal hydroxides, alkali metals such as potassium carbonate and barium carbonate, alkali earth metal carbonates, alkali metal alcoholates such as potassium ethylate, sodium methylate and sodium ethylate, dicyandiamide alkali metal, alkaline earth Examples thereof include metal salts, amines such as piperidine, ethylenediamine and pyrrolidone, and ammonia. These may be used alone or in combination of two or more. In the method of the present invention, among the above, alkali metal, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal alcoholate, alkali metal salt or alkaline earth metal salt of dicyandiamide, amines, and ammonia It is more preferred to use one or more selected from the group.

The amount of the basic catalyst used is not particularly limited, but is usually 0.001 to 500 relative to norbornane dicarbonitrile in view of production conditions and economy.
It is in the range of mol%, more preferably in the range of 0.1 to 300 mol%.

In the process of the present invention, the reaction is carried out with dicyandiamide per mol of norbornanedicarbonitrile.
Carry out at a ratio of 1.1 to 1.9 mol. That is, when the amount of this dicyandiamide is less than 1.1 mol, it is not only difficult to produce both the target monoguanamines and diguanamines efficiently, but also unreacted dinitrile may remain in the reaction mixture. Therefore, the purification and separation process becomes complicated, and it is difficult to achieve the object of the present invention.

Furthermore, this dicyandiamide is 1.9
If the ratio exceeds the molar amount, unreacted dicyandiamide will remain in the reaction mixture, and a complicated purification and separation step will still be required.
Outside the range of 1.9 mol, it is difficult to attain the object of the present invention.

Further, in such a production method, a method of using various solvents as a reaction solvent in order to carry out the reaction more smoothly is extremely useful, but it causes the formation of compounds other than the initial target compound and the inhibition of the reaction. Solvents such as fatty acids, the acid anhydrides, trifluoroacetic acid, liquid sulfur dioxide, sulfuryl chloride, mineral acids, water are not preferred.

Examples of the reaction solvent include methanol, ethanol, n-propanol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol,
Diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, alcohols such as 1-methoxy-2-propanol and 1-ethoxy-2-propanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, diethyl ether , Ethers such as dioxane and tetrahydrofuran, carboxylic acid amides such as N, N-dimethylformamide and N, N-diethylformamide, sulfoxides such as dimethylsulfoxide, sulfolanes such as sulfolane, methylamine, dimethylamine, trimethylamine, aniline , Amines such as piperidine, pyridine, and triethanolamine, and ammonia, but especially non-water such as alcohols, amines, and ammonia. Proton solvent, carboxylic acid amides, sulfolanes, aprotic polar solvents such as sulfoxides are preferable. Incidentally, these solvents may be used alone, or ammonia and alcohol,
It may be used in a mixed system of two or more kinds such as a mixed solvent of dimethyl sulfoxide and cellosolves, etc., and can be appropriately selected according to need.

In the method of the present invention, the reaction temperature is 60 to 20.
It is carried out in the range of 0 ° C, more preferably 80 to 180 ° C, and even more preferably 110 to 180 ° C. If the reaction temperature is lower than 60 ° C., the progress of the reaction is slow, and it not only takes a long time for the production, but also the yield is lowered and the unreacted raw materials remain, which is not preferable. Also, at reaction temperatures above 200 ° C, the amount of reaction by-products other than the target product increases rapidly to a non-negligible level, significantly reducing the product purity or performing complicated purification and separation steps. Is required, which is not preferable. The reaction system is not particularly limited, but it may be carried out under normal pressure, or under a naturally occurring pressure in a closed container, and further under pressure, and it may be appropriately selected as necessary.

In the production method of the present invention, since the content of the unreacted components of the raw materials dinitrile and dicyandiamide is not contained in the reaction mixture obtained, it is practically unnecessary to collect and separate the unreacted raw materials, and the purification separation step is performed. Is extremely simple. Furthermore, the reaction mixture of the above reaction is
The production of by-products is negligibly small or does not remain at all, and the initial target compounds monoguanamines and diguanamines can be obtained almost quantitatively. Such monoguanamines and diguanamines can be easily obtained by cooling the reaction solution and separating the crystallized diguanamines by filtration. Further, depending on the purpose of use, when further purification separation is required, the above-mentioned reaction solvents such as alcohols, cellosolves, carboxylic acid amides, sulfolanes, sulfoxides, etc., mixed solvents of these solvents and water, heat Recrystallization with water, etc.,
It can be performed by a method of dissolving and separating, a method of separating by sublimation, or the like.

[0014]

EXAMPLES The production method of the present invention will be described in more detail below with reference to examples. In the following analysis of dinitrile compounds by gas chromatography, dicyandiamide, diguanamines, monoguanamines,
The reaction by-product is a numerical value as a result of quantification by liquid chromatography.

Reference Example 1 Production of dinitriles: In a 500 ml flask equipped with a stirrer, a thermometer, a liquid introducing tube, and a condenser, bicyclo [2.2.1] hept-5-ene-2-carbonitrile 297.92 g (2.50) Mol), Ni [P (OC ₆ H ₅ ) ₃ ] ₄ 8.77 g (6.75 mmol),
ZnCl ₂ 4.80 g (35.22 mmol), P (OC ₆ H ₅ ) ₃ 32.27
After g (0.104 mol) was charged and the inside of the system was sufficiently replaced with nitrogen gas, the reaction mixture was kept at 65 ° C. with stirring. Next, 94.59 g (3.50 mol) of ice-cold liquid hydrocyanic acid was added at a flow rate of
After supplying to the reactor at ~ 55 ml / hr for 3 hours, the reaction was further performed for 1 hour. Next, after replacing the inside of the system with nitrogen gas, deionized water was added to separate and remove the water layer part,
A semi-solid oil was obtained. This oily substance was filtered and distilled under reduced pressure to obtain 362.20 g (yield 99.1%) of bicyclo [2.2.1] heptane-2,5-dicarbonitrile and bicyclo [2.2.1] heptane-2,6-dicarbonitrile. Mixture (boiling point 129-13
7 ° C./1 mmHg) was obtained. The results of elemental analysis of the target product are shown below. Elemental analysis CHN Measured value: 73.9% 6.9% 19.2% Calculated value: 73.94% 6.90% 19.16%

Reference Example 2 Preparation of bicyclo [2.2.1] heptane-2,5-dicarbonitrile: In a 2 liter flask equipped with a stirrer, thermometer, reflux condenser, 5-cyano-bicyclo [2.2.1]. Hepta-2
-Carbaldehyde 179.0 g (1.2 mol), N, O-bis (trifluoroacetyl) hydroxylamine 292.6 g (
1.3 mol), pyridine 197.8 g (2.5 mol), benzene 6
I charged 00 ml. The mixture was stirred and heated for 3 hours while gradually heating and refluxing. Next, 500 ml of deionized water was added to this reaction mixture, and the aqueous layer portion was separated and removed to obtain an oily substance. This oily substance was distilled under reduced pressure to obtain 128.0 g (yield 73%) of bicyclo [2.2.1] heptane-2,5-dicarbonitrile (boiling point 131-136 ° C / 1 mmHg). The results of elemental analysis of the target product are shown below. Elemental analysis CHN Measured value: 74.0% 6.9% 19.1% Calculated value: 73.94% 6.90% 19.16%

Example 1 In a 500 ml flask equipped with a stirrer, a thermometer and a reflux condenser, 60.3 g (0.41 mol) of norbornanedicarbonitrile obtained by the method of Reference Example 1 and 50.4 g of dicyandiamide were obtained.
(0.60 mol), potassium hydroxide 13.4 as basic catalyst
g and 150 g of methyl cellosolve as a reaction solvent were charged at room temperature, the inside of the reactor was replaced with nitrogen, and the mixture was gradually heated, and the temperature was kept at 120 to 125 ° C., and the reaction was carried out for 3 hours while stirring. When the reaction solution was analyzed, norbornane dicarbonitrile and dicyandiamide, which were the starting materials, were not detected at all. As a result, the yields of the monoguanamines represented by the formula (2) and the diguanamines represented by the formula (3) based on the charged norbornanedicarbonitrile were 53.4 mol% and 45.8 mol%, respectively. Then, when the reaction solution obtained above was cooled to 30 ° C., a white precipitate was deposited. The white precipitate thus deposited was separated by filtration, washed with 200 ml of ion-exchanged water, and further washed with 2
It was washed with 00 ml of methanol and then dried under reduced pressure. As a result, white crystals of diguanamines having a purity of 99.9% were obtained. On the other hand, the filtrate was desolvated, the obtained solid content was recrystallized from methanol, and then dried under reduced pressure to obtain white crystals.
When analyzed, it was a monoguanamine having a purity of 99.9%.

Example 2 The same procedure as in Example 1 was carried out except that the molar ratio of dicyandiamide to the charged norbornanedicarbonitrile was changed as shown in columns 2-1 and 2-2 in Table 1. Operated. Table 1 shows the results.

[0019]

[Table 1] (Note 1): The molar ratio of the charged dicyandiamide to the charged dinitrile is shown.

Example 3 The same operation as in Example 1 was carried out except that the type of reaction solvent used and the reaction temperature were changed as shown in Tables 3-1 to 3-4. . Table 2 shows the results.

[0021]

[Table 2]

Example 4 In Example 1, norbornane dicarbonitrile obtained by the method of Reference Example 2 was used, and the basic catalyst used was replaced with potassium hydroxide, and sodium methylate 25.8 g was used.
Furthermore, 150 g of dimethyl sulfoxide was used instead of methyl cellosolve as the reaction solvent, and the reaction was carried out.
It was performed at a temperature of 140 to 145 ° C. The same operation as in Example 1 was performed except for the above. Even in this case, neither dinitrile or dicyandiamide as a raw material was detected in the reaction solution after the reaction, and both the monoguanamines represented by the formula (2) and the diguanamines represented by the formula (3) were detected. , Both of which were 99.9% pure.

[0023]

INDUSTRIAL APPLICABILITY According to the method of the present invention, both the raw materials dinitrile and dicyandiamide can be completely reacted, and both industrially useful compounds diguanamines and monoguanamines can be reacted together. It is clear that it can be obtained with high purity and high yield. In addition, according to the method of the present invention, it is not necessary to recover the unreacted material after the reaction. Therefore, it can be said that the purification and separation step is extremely simple and is a very useful method in industrial production.

Claims (4)

[Claims] 1. The formula (1) (formula 1) in the presence of a basic catalyst: (Wherein the bonding position of the cyano group indicates the 2,5- or 2,6-position), dicyandiamide is reacted in the range of 1.1 to 1.9 mol per mol of the dinitrile. Formula (2) (Formula 2) [In the formula, (4,6-diamino-1,3,5-triazin-2-yl)
The bonding position of the group represents the 5- or 6-position], and monoguanamines represented by the formula (3) (Chemical Formula 3) [In the formula, (4,6-diamino-1,3,5-triazin-2-yl)
The bonding position of the group represents the 2,5- or 2,6-position]. A method for producing a guanamine compound, which also produces a diguanamine compound. 2. The basic catalyst is an alkali metal, an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alcoholate, an alkali metal salt of dicyandiamide,
The method according to claim 1, which is at least one selected from the group consisting of alkaline earth metal salts of dicyandiamide, amines, and ammonia. 3. The reaction is carried out using at least one selected from the group consisting of non-aqueous protic solvents and aprotic polar solvents as a reaction solvent.
Or the manufacturing method according to 2. 4. The production method according to claim 1, wherein the reaction is carried out at a temperature of 60 to 200 ° C.