JP7229028B2 - Method for producing N-mono(hydrocarbon) isocyanuric acid - Google Patents

Description

The present invention relates to a novel method for producing N-mono(hydrocarbon)isocyanuric acid.

Isocyanuric acid derivatives have been used in various fields including the semiconductor field (for example, Patent Documents 1 and 2), and various reports have been made on their synthesis methods for a long time (for example, Non-Patent Documents 1-3).
Under these circumstances, the present inventors have so far reported a method for producing an isocyanuric acid derivative having one hydrocarbon group (Patent Document 3).

WO 02/086624 WO2013/035787 WO2017/208910

Journal of American Chemical Society, 75, pp. 3617-3618 (1953) Tetrahedron Letters, 44, pp. 4399-4402 (2003) Journal of Organic Chemistry, 80, pp. 11200-11205 (2015)

A conventionally known method for producing an isocyanuric acid derivative having one alkyl group requires heating at a high temperature of 150° C. or higher for a long time because the solubility of isocyanuric acid in an organic solvent is low. However, the high-temperature reaction causes a decrease in yield due to decomposition of raw materials and products, and a decrease in yield and selectivity due to successive reactions, and is not industrially useful. There is also a problem that a closed high-pressure reactor is required when using a high-temperature, low-boiling reagent. On the other hand, in the low-temperature reaction, a large excess of organic solvent is required to dissolve isocyanuric acid.
The method described in Patent Document 3, which aims to solve these problems, needs to undergo a multi-step reaction process, and there is room for improvement when factors such as cost reduction and time reduction are considered.

The present invention aims to provide a method for producing an isocyanuric acid derivative suitable for industrial production, that is, it enables selective production of the desired derivative in one pot without requiring multi-step processes or complicated treatments. The purpose is to provide a new manufacturing method.

The present inventors have made intensive studies to solve the above problems. As a result, an alkylating agent for introducing a hydrocarbon group and a base are added to a supersaturated solution of isocyanuric acid dissolved in a small amount of solvent. Thus, the present inventors have found that a mono-substituted N-mono(hydrocarbon)isocyanuric acid can be selectively obtained in one pot, and have completed the present invention.

That is, the present invention provides, as a first aspect, a method for producing N-mono(hydrocarbon)isocyanuric acid using isocyanuric acid as a starting material, comprising the steps of preparing a supersaturated solution of isocyanuric acid, and adding halogen to the supersaturated solution. It relates to a process comprising adding a hydrocarbyl compound or a pseudohalogenated hydrocarbon compound and a base.
As a second aspect, the supersaturated solution contains isocyanuric acid and an amide solvent,
It relates to the manufacturing method according to the first aspect.
As a third aspect, the production method according to the first aspect or the second aspect, wherein the addition step includes adding a phase transfer catalyst in addition to the halogenated hydrocarbon compound or the pseudohalogenated hydrocarbon compound and the base. Regarding.

According to the production method of the present invention, it is possible to selectively produce N-mono(hydrocarbon)isocyanuric acid in one pot without the need for multi-step processes or complicated treatments, and it is expected to be mass-produced. An industrially useful production method can be provided.

The present invention comprises the steps of (1) preparing a supersaturated solution of isocyanuric acid, and (2) adding a halogenated hydrocarbon compound or a pseudohalogenated hydrocarbon compound and a base to the supersaturated solution. A method for producing N-mono(hydrocarbon)isocyanuric acid is of interest.

上記式（１）において、Ｒは、例えば炭素原子数１乃至１０の炭化水素基を表す。当該炭化水素基は、直鎖状、分岐鎖状、環状いずれでもよく、二重結合又は三重結合を少なくとも１つ有してもよい。前記炭化水素基がアルキル基である場合、当該アルキル基として、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ペンチル基、ｎ－ノニル基、ｎ－デシル基、シクロヘキシルメチル基、及びシクロペンチルメチル基が挙げられる。アルキル基を除く前記炭化水素基として、例えば、ベンジル基、アリル基、及びプロパルギル基が挙げられる。 The N-mono (hydrocarbon) isocyanuric acid according to the present invention refers to an isocyanuric acid derivative having one hydrocarbon group, and the following formula in which one hydrocarbon group is introduced as a substituent bonded to the nitrogen atom of isocyanuric acid It refers to a compound represented by (1).

In formula (1) above, R represents, for example, a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be linear, branched or cyclic, and may have at least one double bond or triple bond. When the hydrocarbon group is an alkyl group, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl, n-octyl, n-pentyl, n-nonyl, n-decyl, cyclohexylmethyl, and cyclopentylmethyl groups. Examples of the hydrocarbon groups other than alkyl groups include benzyl, allyl, and propargyl groups.

Each step according to the present invention will be described below.

(1) Step of preparing a supersaturated solution of isocyanuric acid This step is a step of preparing a supersaturated solution of isocyanuric acid as a starting material.
As the solvent used for preparing the supersaturated solution, an amide-based solvent is particularly suitable.
Examples of amide solvents include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methyl -2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone and the like, but these include Not limited. These solvents may be used singly or in combination of two or more.
In addition to the amide-based solvent, other solvents than the amide-based solvent may be used in combination within a range that does not impair the effects of the present invention.

To prepare the supersaturated solution, after adding an amount of isocyanuric acid that becomes supersaturated at the time of cooling, which will be described later, to the amide solvent, the system is heated to completely dissolve the isocyanuric acid, and then cooled. Just do it.
The heating temperature at this time can be a temperature below the boiling point of the amide solvent used, for example , 80°C to 150°C.

After confirming that the isocyanuric acid has completely dissolved and becomes a uniform solution, the system is gradually cooled so as not to precipitate the isocyanuric acid to obtain a supersaturated solution of isocyanuric acid.
The final cooling temperature at this time can be a temperature above the melting point and below the boiling point of the halogenated hydrocarbon compound or pseudohalogenated hydrocarbon compound used in step (2) described later. Depending on the selection of the halogenated or pseudohalogenated hydrocarbon compound, the final cooling temperature can be, for example, about 30°C to 60°C. The final cooling temperature is preferably lower in consideration of the selectivity related to the production of the desired N-mono (hydrocarbon) isocyanuric acid, but considering the occurrence of isocyanuric acid precipitation at low temperatures, It can be selected as appropriate.

(2) A step of adding a halogenated hydrocarbon compound or a pseudohalogenated hydrocarbon compound and a base to the supersaturated solution. Alternatively, it is a step of adding a pseudohalogenated hydrocarbon compound and a base.

Examples of the halogenated hydrocarbon compound or the pseudohalogenated hydrocarbon compound include compounds used for the purpose of introducing a hydrocarbon group called an alkylating agent.

Examples of halogenated hydrocarbon compounds or pseudo-halogenated hydrocarbon compounds include compounds represented by the following formula (2).
RX (2)
In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms as exemplified in formula (1), and the hydrocarbon group may be linear, branched, or cyclic, and has a double bond. Alternatively, it may have at least one triple bond.
Also, X represents a halogen atom or a pseudohalogen group.

The halogen atom can be selected from an iodine atom, a bromine atom, a basic atom and a fluorine atom.
When X represents a halogen atom, the compound represented by formula (2) is a halogenated hydrocarbon compound, such as methyl iodide, ethyl bromide, propyl bromide, allyl bromide, and propargyl bromide. However, it is not limited to these.

Examples of the pseudohalogen group include alkylsulfonyloxy groups such as methanesulfonyloxy group; fluoroalkylsulfonyloxy groups such as trifluoromethanesulfonyloxy group and nonafluorobutanesulfonyloxy group; benzenesulfonyloxy group, toluenesulfonyloxy group and the like. and aromatic sulfonyloxy groups.
When X represents a pseudohalogen group, the compound represented by formula (2) is a pseudohalogenated hydrocarbon compound, and examples thereof include methyl p-toluenesulfonate and ethyl p-toluenesulfonate methanesulfonate. can be used, but is not limited to these.

The halogenated hydrocarbon compound or the pseudohalogenated hydrocarbon compound can be used in an amount of 0.3 to 1.5 molar equivalents with respect to 1 molar equivalent of isocyanuric acid in the supersaturated solution of isocyanuric acid.

An inorganic base can be preferably used as the base.
Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; and alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. is mentioned. Among these, alkali metal carbonates are preferred, and sodium carbonate can be preferably used. These inorganic bases may be used alone or in combination of two or more. Moreover, an anhydride may be used and a hydrate may be used.
The inorganic base can be used in an amount of 0.3 to 1.5 molar equivalents with respect to 1 molar equivalent of isocyanuric acid in the supersaturated solution.

Moreover, in the step (2), a phase transfer catalyst may be added.
Examples of phase transfer catalysts include quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetra-n-butylammonium bromide, and tetra-n-butylammonium hydrogensulfate; quaternary phosphonium salts; crown ethers such as 12-crown-4, 18-crown-6 and the like. Among these, quaternary ammonium salts can be mentioned as preferable phase transfer catalysts. These phase transfer catalysts may be used alone or in combination of two or more.
When the phase transfer catalyst is used, it can be used in an amount of 0.01 to 1.5 molar equivalents with respect to 1 molar equivalent of isocyanuric acid in the supersaturated solution.

The halogenated hydrocarbon compound or pseudohalogenated hydrocarbon compound, the base, and optionally the addition of the phase transfer catalyst are carried out subsequent to the above step (1) of obtaining a supersaturated solution of isocyanuric acid. That is, at the cooling temperature finally reached in the step (1), the above halogenated hydrocarbon compound or pseudohalogenated hydrocarbon compound, a base, and optionally a phase transfer catalyst are added.
After completion of the addition of these, a reaction to produce N-mono(hydrocarbon)isocyanuric acid proceeds in the system. By stirring the inside of the system after the addition, the production of N-mono(hydrocarbon)isocyanuric acid can be further promoted.
After the addition, the reaction temperature (temperature in the system) may be maintained at the cooling temperature finally reached in the step (1), or may be appropriately selected in consideration of the occurrence of isocyanuric acid precipitation at low temperatures. good.
The reaction time is, for example, 0.1 to 10 hours, depending on the reaction temperature, the halogenated hydrocarbon compound or pseudohalogenated hydrocarbon compound used, the type of base, and the presence or absence and type of phase transfer catalyst. .

When the above halogenated hydrocarbon compound or pseudohalogenated hydrocarbon compound and a base, or a phase transfer catalyst is used, the order of their addition is not particularly limited. Preferably, the liquid component is added first, followed by the solid component, e.g., the halogenated hydrocarbon compound or pseudohalogenated hydrocarbon compound, followed by the base and, if used, interphase By adding a transfer catalyst, precipitation of isocyanuric acid can be made difficult to occur.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
In the examples, the equipment and conditions used for sample preparation and physical property analysis are as follows.
(1) HPLC: Shimadzu Corporation LC-2010A HT system column: HyperCarb (Thermo), 5 μm, 4.6 × 100 mm
・Oven: 40℃
・Detector: UV210nm
・Flow rate: 1.0 mL/min ・Eluent and conditions: A solution = acetonitrile for HPLC, B solution = 0.1 mass% phosphoric acid aqueous solution 0 min B solution 90% → 20 min B solution 5% (gradation)
20min-25min B liquid 5% (continued)
25 min B liquid 5% → 25.1 min B liquid 50% (gradation)
25.1min - 30min B liquid 90% (continued)
・ Internal standard substance for quantitative analysis: p-xylene (The yield of monomethylisocyanuric acid was quantified with an internal standard, and the yields of dimethylisocyanuric acid and trimethylisocyanuric acid were calculated from the peak areas with the sensitivity ratio = 1.)
Retention time: isocyanuric acid: 2.3 minutes, monomethylisocyanuric acid: 3.5 minutes, dimethylisocyanuric acid: 7.0 minutes, trimethylisocyanuric acid: 12.2 minutes, p-xylene: 16.0 minutes (2) ¹ H-NMR : JNM-ECA500 manufactured by JEOL Ltd.

[Example 1] Reaction under supersaturated conditions In a glass reaction vessel, 1.04 g of isocyanuric acid (manufactured by Nissan Chemical Industries, Ltd., trade name CA-P, the same shall apply hereinafter) and N,N-dimethylformamide (Kanto Kagaku ( 20.0 g of special grade manufactured by Kabushiki Kaisha, Ltd. was added, and stirred at 120° C. to dissolve uniformly. The resulting solution was then gradually cooled to 40°C.
After confirming that the solid of isocyanuric acid is not precipitated due to supersaturation, methyl iodide (Tokyo Chemical Industry Co., Ltd., the same applies hereinafter) 1.14 g, sodium carbonate (Kanto Chemical Co., special grade, the same applies hereinafter) .) 0.21 g were added sequentially.
After that, the resulting mixture was stirred at 40° C. for 7 hours, but although there was undissolved sodium carbonate at the bottom of the reaction vessel, the reaction proceeded to reduce the amount of isocyanuric acid with low solubility and dimethylisocyanuric acid with high solubility. Since the solution was changed to an acid (DMe-ICA), no solid isocyanuric acid precipitated from the reaction solution, and remained a pale yellow solution.
The reaction solution was diluted with acetonitrile for HPLC (Kanto Kagaku Co., Ltd.) and pure water in a volumetric flask, sampled, p-xylene added as an internal standard, and quantitatively analyzed by HPLC.
As a result, the quantitative yield based on methyl iodide was 29.1% for the target monomethylisocyanuric acid (MMe-ICA), 7.9% for dimethylisocyanuric acid (DMe-ICA), and 7.9% for trimethylisocyanuric acid ( TMe-ICA) was 0.9%. Table 1 shows the results obtained.

[Example 2] Reaction under supersaturation conditions using a phase transfer catalyst 1.04 g of isocyanuric acid and 20.0 g of N,N-dimethylformamide were placed in a glass reaction vessel and stirred at 120°C to dissolve uniformly. . The resulting solution was then gradually cooled to 40°C.
After confirming that the mixture became supersaturated and no solid isocyanuric acid was precipitated, 1.14 g of methyl iodide was added. Thereafter, 0.23 g of tetramethylammonium chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter the same) and 0.21 g of sodium carbonate were sequentially added.
After that, the resulting mixture was stirred at 40° C. for 7 hours, but although there was undissolved sodium carbonate at the bottom of the reaction vessel, the reaction proceeded to reduce the amount of isocyanuric acid with low solubility and dimethylisocyanuric acid with high solubility. Since the solution was changed to an acid (DMe-ICA), no solid isocyanuric acid precipitated from the reaction solution, and the solution remained as a pale yellow solution with slight turbidity thought to be derived from tetramethylammonium chloride.
The reaction solution was diluted with acetonitrile for HPLC (Kanto Kagaku Co., Ltd.) and pure water in a volumetric flask, sampled, p-xylene added as an internal standard, and quantitatively analyzed by HPLC.
As a result, the quantitative yield based on methyl iodide was 33.7% for the target monomethylisocyanuric acid (MMe-ICA), 8.0% for dimethylisocyanuric acid (DMe-ICA), and 8.0% for trimethylisocyanuric acid ( TMe-ICA) was 0.8%. Table 1 shows the results obtained.

[Example 3] Reaction under supersaturated conditions Reaction and quantitative analysis were performed in the same manner as in Example 1, except that the stirring time was changed from 7 hours to 1.5 hours. At this time, similarly, no deposition of solid isocyanuric acid was confirmed.
As a result, the quantitative yield based on methyl iodide was 21.4% for monomethylisocyanuric acid, 1.7% for dimethylisocyanuric acid, and 0.1% for trimethylisocyanuric acid. Table 1 shows the results obtained.

[Example 4] Reaction under supersaturated conditions Reaction and quantitative analysis were performed in the same manner as in Example 1, except that the stirring time was changed from 7 hours to 0.5 hours. At this time, similarly, no deposition of solid isocyanuric acid was confirmed.
As a result, the quantitative yield based on methyl iodide was 12.4% for monomethylisocyanuric acid, 1.8% for dimethylisocyanuric acid, and 0.1% for trimethylisocyanuric acid. Table 1 shows the results obtained.

[Example 5] Reaction with an excessive amount of isocyanuric acid Reaction and quantification were carried out in the same manner as in Example 1, except that the amount of methyl iodide was changed to 0.57 g and the stirring time was changed to 4 hours instead of 7 hours. Analysis was carried out. At this time, similarly, no deposition of solid isocyanuric acid was confirmed.
As a result, the quantitative yield based on methyl iodide was 52.5% for monomethylisocyanuric acid, 10.5% for dimethylisocyanuric acid, and 1.0% for trimethylisocyanuric acid. Table 1 shows the results obtained.

[Example 6] Reaction with excessive amount of isocyanuric acid Reaction and quantitative analysis were performed in the same manner as in Example 1, except that the amount of methyl iodide was changed to 0.57 g. At this time, similarly, no deposition of solid isocyanuric acid was confirmed.
As a result, the quantitative yield based on methyl iodide was 49.5% for monomethylisocyanuric acid, 7.5% for dimethylisocyanuric acid, and 0.8% for trimethylisocyanuric acid. Table 1 shows the results obtained.

[Example 7] Reaction with reduced amount of solvent Reaction and quantitative analysis were performed in the same manner as in Example 1, except that the amount of N,N-dimethylformamide was changed to 15.0 g. At this time, similarly, no deposition of solid isocyanuric acid was confirmed.
As a result, the quantitative yields based on methyl iodide were 22.7% for monomethylisocyanuric acid, 5.6% for dimethylisocyanuric acid, and 0.7% for trimethylisocyanuric acid. Table 1 shows the results obtained.

As described above, according to the production method of the present invention, it was confirmed that N-mono(hydrocarbon)isocyanuric acid, which is the desired mono-substituted isocyanuric acid, can be selectively obtained in one pot with high production efficiency. was done.

Claims (3)

A method for producing N-mono(hydrocarbon)isocyanuric acid using isocyanuric acid as a starting material,
A process of preparing a supersaturated solution of isocyanuric acid, comprising the steps of adding isocyanuric acid to a solvent, heating and dissolving it at 80° C. or higher to form a uniform solution, and then cooling to 60° C. or lower, containing isocyanuric acid. preparing a solution, and adding a halogenated hydrocarbon compound or a pseudohalogenated hydrocarbon compound and a base to the supersaturated solution;
Manufacturing method including. The supersaturated solution contains isocyanuric acid and an amide solvent,
The manufacturing method according to claim 1. wherein the adding step comprises addition of a halogenated hydrocarbon compound or a pseudohalogenated hydrocarbon compound and a base, as well as a phase transfer catalyst;
The manufacturing method according to claim 1 or 2.