Method for producing N-(hydrocarbon)isocyanuric acid

Abstract

A novel production method enables selective production of an isocyanuric acid N-substituted product of interest in one pot, requiring neither multiple steps nor cumbersome treatment, the method producing an N-(hydrocarbon)isocyanuric acid which includes a step N for reacting, in a solvent, a dihalogenated isocyanuric acid derivative with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound.

Claims

1. A method for producing an N-(hydrocarbon)isocyanuric acid, the method comprising: a step N of reacting, in a solvent, at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound.

2. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 1, wherein: the step N comprises a step X of providing a solution or dispersion of at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate, and a step Y of mixing the solution or dispersion of the dihalogenated isocyanuric acid derivative with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound; or comprises a step S of providing a solution or dispersion of at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and a step T of mixing the solution or dispersion of the hydrocarbonization agent with at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate.

3. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 2, wherein the solution or dispersion of the dihalogenated isocyanuric acid derivative is an aqueous solution or an aqueous dispersion.

4. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 3, wherein the aqueous solution or aqueous dispersion of the dihalogenated isocyanuric acid derivative contains water at a mixing ratio (by mass) of the water to the solvent of 0.1:99.9 to 99.9:0.1.

5. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 2, wherein the step Y is a step of mixing the solution or dispersion of the dihalogenated isocyanuric acid derivative with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and with a surfactant.

6. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 5, wherein the surfactant contains at least one selected from the group consisting of a quaternary ammonium salt, a crown ether, and an alkylbenzenesulfonic acid salt.

7. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 2, wherein the step X is a step of providing a solution or dispersion containing at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate, and a base.

8. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 7, wherein the base contains an inorganic base.

9. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 2, wherein the solution or dispersion of the hydrocarbonization agent is an aqueous solution or an aqueous dispersion.

10. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 9, wherein the aqueous solution or aqueous dispersion of the hydrocarbonization agent contains water at a mixing ratio (by mass) of the water to the solvent of 0.1:99.9 to 99.9:0.1.

11. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 2, wherein the step S is a step of providing a solution or dispersion containing at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and a surfactant.

12. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 11, wherein the surfactant contains at least one selected from the group consisting of a quaternary ammonium salt, a crown ether, and an alkylbenzenesulfonic acid salt.

13. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 2, wherein the step S is a step of providing a solution or dispersion containing at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and a base.

14. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 13, wherein the base contains an inorganic base.

15. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 1, wherein the hydrocarbonization agent contains at least one selected from the group consisting of methyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, dimethyl sulfate, and diethyl sulfate.

16. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 15, wherein the hydrocarbonization agent contains at least one selected from the group consisting of dimethyl sulfate and diethyl sulfate.

17. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 1, wherein the dihalogenated isocyanuric acid derivative contains at least one selected from the group consisting of dichloroisocyanuric acid, sodium dichloroisocyanurate, and sodium dichloroisocyanurate dihydrate.

18. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 17, wherein the dihalogenated isocyanuric acid derivative contains sodium dichloroisocyanurate.

19. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 1, wherein the amount of the hydrocarbonization agent is 0.3 mole equivalent to 4.0 mole equivalent relative to 1 mole equivalent of the dihalogenated isocyanuric acid derivative.

20. The method for producing an N-(hydrocarbon)isocyanuric acid according to claim 1, wherein the amount of the dihalogenated isocyanuric acid derivative is 0.03 to 0.3 times by mass that of the solvent used.

Description

EXAMPLES

(1) The present invention will next be described in more detail by way of Examples, but the present invention should not be construed as being limited to the following Examples.

(2) In the Examples, the following apparatuses and conditions were used for preparation of samples and analysis of physical properties.

(3) (1) HPLC: LC-2010A HT System, available from SHIMADZU CORPORATION

(4) Column: HyperCarb (Thermo), 5 μm, 4.6×100 mm

(5) Oven: 40° C.

(6) Detector: UV 210 nm

(7) Flow rate: 1.0 mL/minute

(8) Eluent and Conditions: liquid A=acetonitrile for HPLC, liquid B=0.1% by mass aqueous phosphoric acid solution

(9) 0 min to 8 min liquid B 90%.fwdarw.20 min liquid B 5% (gradation)

(10) 20 min to 25 min liquid B 5% (continuation)

(11) 25 min liquid B 5%.fwdarw.25.1 min liquid B 90% (gradation)

(12) 25.1 min to 30 min liquid B 90% (continuation)

(13) Internal standard substance for quantitative analysis: p-xylene

(14) Preparation of calibration curve of monomethylisocyanuric acid: Firstly, 100 mg of standard monomethylisocyanuric acid was placed in a 50 mL measuring flask, and the flask was charged with acetonitrile to a predetermined volume. Subsequently, the resultant solution was removed from the flask with 5 mL, 10 mL, and 15 mL transfer pipettes, and each portion of the solution was added to a 50 mL measuring flask.

(15) Separately, 0.50 g of p-xylene was placed in a 500 mL measuring flask, and the flask was charged with acetonitrile to a predetermined volume, to thereby prepare an internal standard solution. The resultant solution was removed from the flask with a 5 mL transfer pipette, and then added to each 50 mL measuring flask containing the above-prepared standard monomethylisocyanuric acid solution. The flask was charged with acetonitrile to a predetermined volume.

(16) The thus-prepared three standard solutions were analyzed by HPLC, to thereby prepare a three-point internal standard calibration curve. The calibration curve was used for quantification of monomethylisocyanuric acid.

(17) Quantification of dimethylisocyanuric acid: The molar sensitivity ratio of standard dimethylisocyanuric acid to standard monomethylisocyanuric acid was determined to be 1.93 under the present analytical conditions. Dimethylisocyanuric acid was quantified by the following formula using the internal standard quantitative value of monomethylisocyanuric acid and the molar sensitivity ratio of dimethylisocyanuric acid.
Quantitative value of dimethylisocyanuric acid=(the peak area of dimethylisocyanuric acid/the peak area of monomethylisocyanuric acid)×the internal standard quantitative value of monomethylisocyanuric acid/the molar sensitivity ratio (1.93)

(18) Quantification of trimethylisocyanuric acid: The molar sensitivity ratio of standard trimethylisocyanuric acid to standard monomethylisocyanuric acid was determined to be 2.97 under the present analytical conditions. Trimethylisocyanuric acid was quantified by the following formula using the internal standard quantitative value of monomethylisocyanuric acid and the molar sensitivity ratio of trimethylisocyanuric acid.
Quantitative value of trimethylisocyanuric acid=(the peak area of trimethylisocyanuric acid/the peak area of monomethylisocyanuric acid)×the internal standard quantitative value of monomethylisocyanuric acid/the molar sensitivity ratio (2.97)

(19) Retention time: trichloroisocyanuric acid: 1.5 min, sodium dichloroisocyanurate: 2.3 min, isocyanuric acid: 2.3 min, monomethylisocyanuric acid: 3.5 min, dimethylisocyanuric acid: 7.0 min, trimethylisocyanuric acid: 12.2 min, p-xylene: 16.0 min, monoethylisocyanuric acid: 3.7 min, diethylisocyanuric acid: 7.4 min, triethylisocyanuric acid: 12.3 min

(20) (2) .sup.1H-NMR: JNM-ECA500, available from JEOL Ltd.

(21) Monomethylisocyanuric acid .sup.1H-HMR (500 MHz, DMSO-d.sub.6, δ ppm): 11.4 (2H, d, J=4.0 Hz) 3.04 (3H, s).

(22) Dimethylisocyanuric acid .sup.1H-HMR (500 MHz, DMSO-d.sub.6, δ ppm): 11.6 (1H, s), 3.10 (6H, s).

(23) Trimethylisocyanuric acid .sup.1H-HMR (500 MHz, DMSO-d.sub.6, δ ppm): 3.16 (9H, s).

[Example 1] Reaction in Water

(24) A glass-made reaction container was charged with 5.23 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for six hours.

(25) The reaction product was diluted with acetonitrile for HPLC (available from KANTO CHEMICAL CO., INC.) and pure water in a measuring flask, and the diluted product was sampled. p-Xylene (internal standard substance) was added to the sample, and quantitative analysis was performed by HPLC.

(26) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 87.0%, 3.7%, and 0.0%, respectively. The results are shown in Table 1.

[Example 2] Reaction in Water Using Surfactant (Phase Transfer Catalyst)

(27) A glass-made reaction container was charged with 5.23 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 0.09 g of tetramethylammonium chloride (available from Tokyo Chemical Industry Co., Ltd.) was added to the resultant solution, and then 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for two hours.

(28) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 80.4%, 3.4%, and 0.0%, respectively. The results are shown in Table 1.

[Example 3] Reaction in Water

(29) The reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the amount of dimethyl sulfate was changed to 1.48 g, and the stirring time was changed from six hours to four hours.

(30) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 42.5%, 2.1%, and 0.0%, respectively. The results are shown in Table 1.

[Example 4] Reaction in Water

(31) The reaction and the quantitative analysis were performed in the same manner as in Example 3, except that the amount of dimethyl sulfate was changed to 2.97 g.

(32) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 77.8%, 4.0%, and 0.0%, respectively. The results are shown in Table 1.

[Example 5] Reaction in Water

(33) The reaction and the quantitative analysis were performed in the same manner as in Example 3, except that the amount of dimethyl sulfate was changed to 4.45 g.

(34) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MNIe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 80.8%, 3.8%, and 0.0%, respectively. The results are shown in Table 1.

[Example 6] Reaction in Water (Containing Base)

(35) A glass-made reaction container was charged with 5.23 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation), 0.94 g of sodium hydroxide (special grade, available from KANTO CHEMICAL CO., INC.), and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for two hours.

(36) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 43.7%, 32.3%, and 0.3%, respectively. The results are shown in Table 1.

[Example 7] Reaction in Water (Containing Base)

(37) The reaction and the quantitative analysis were performed in the same manner as in Example 6, except that the amount of sodium hydroxide was changed to 1.88 g.

(38) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 14.1%, 41.3%, and 5.8%, respectively. The results are shown in Table 1.

[Example 8] Reaction in Water (Use of Sodium Dichloroisocyanurate Hydrate)

(39) A glass-made reaction container was charged with 6.10 g of sodium dichloroisocyanurate dihydrate (trade name: HILITE 55G, available from Nissan Chemical Corporation) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 4.51 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for six hours.

(40) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to sodium dichloroisocyanurate dihydrate) of monomethylisocyanuric acid (MIVIe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 82.8%, 3.2%, and 0.0%, respectively. The results are shown in Table 1.

[Example 9] Reaction in Water (Use of Sodium Dichloroisocyanurate Hydrate)

(41) The reaction and the quantitative analysis were performed in the same manner as in Example 8, except that the amount of dimethyl sulfate was changed to 6.01 g.

(42) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate dihydrate) of monomethylisocyanuric acid (MIVIe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 79.4%, 2.9%, and 0.0%, respectively. The results are shown in Table 1.

(43) TABLE-US-00001 TABLE 1 Quantitative yield with reference to sodium dichloroisocyanurate or sodium dichloroisocyanurate dihydrate MMe-ICA DMe-ICA TMe-ICA Example 1 87.0% 3.7% 0.0% Example 2 80.4% 3.4% 0.0% Example 3 42.5% 2.1% 0.0% Example 4 77.8% 4.0% 0.0% Example 5 80.8% 3.8% 0.0% Example 6 43.7% 32.3%  0.3% Example 7 14.1% 41.3%  5.8% Example 8 82.8% 3.2% 0.0% Example 9 79.4% 2.9% 0.0%

(44) The results shown in Table 1 indicated that the production method of the present invention can selectively produce an N-mono(hydrocarbon)isocyanuric acid of interest (i.e., mono-substituted product of isocyanuric acid) in one pot at high production efficiency (Examples 1 to 5 and Examples 8 and 9).

(45) The results also indicated that the presence of a base enables production of an N-di(hydrocarbon)isocyanuric acid (i.e., di-substituted product) at high yield, and adjustment of the amount of a base leads to more selective production of the di-substituted product (Examples 6 and 7).

[Example 10] Reaction in Buffer (Control of pH During Reaction)

(46) The reaction and the quantitative analysis were performed in the same manner as in Example 1, except that water was replaced with 10 mM buffer having a pH adjusted to 7.0 (ammonium acetate (special grade, available from KANTO CHEMICAL CO., INC., ammonium formate (Cica first grade, available from KANTO CHEMICAL CO., INC.), aqueous solution).

(47) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 80.3%, 3.6%, and 0.0%, respectively. The results are shown in Table 2.

[Example 11] Reaction in Water (Reaction Temperature)

(48) The reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the reaction temperature was changed to 10° C., and the reaction time was changed to seven hours.

(49) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 85.2%, 2.8%, and 0.1%, respectively. The results are shown in Table 2.

[Example 12] Reaction in Water (Reaction Temperature)

(50) The reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the reaction temperature was changed to 30° C., and the reaction time was changed to three hours.

(51) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 78.4%, 2.6%, and 0.1%, respectively. The results are shown in Table 2.

[Example 13] Reaction in Water (Reaction Temperature)

(52) The reaction and the quantitative analysis were performed in the same manner as in Example 12, except that the reaction temperature was changed to 40° C.

(53) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 77.3%, 2.5%, and 0.1%, respectively. The results are shown in Table 2.

[Example 14] Reaction in Water (Amount of Water, Reaction Temperature)

(54) The reaction and the quantitative analysis were performed in the same manner as in Example 13, except that the amount of water was changed to 60.6 g.

(55) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 68.4%, 1.7%, and 0.1%, respectively. The results are shown in Table 2.

[Example 15] Reaction in Water (Amount of Water)

(56) The reaction and the quantitative analysis were performed in the same manner as in Example 14, except that the reaction temperature was changed to 20° C.

(57) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 76.7%, 1.9%, and 0.1%, respectively. The results are shown in Table 2.

[Example 16] Reaction in Water (Amount of Water)

(58) The reaction and the quantitative analysis were performed in the same manner as in Example 15, except that the amount of water was changed to 45.5 g.

(59) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 78.2%, 2.2%, and 0.1%, respectively. The results are shown in Table 2.

[Example 17] Reaction in Water (Dropwise Addition Time)

(60) The reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the dropwise addition time of dimethyl sulfate was prolonged to one hour, and the reaction time was changed to 2.5 hours.

(61) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 78.2%, 3.1%, and 0.1%, respectively. The results are shown in Table 2.

[Example 18] Reaction in Water (Dropwise Addition Time)

(62) The reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the dropwise addition time of dimethyl sulfate was prolonged to two hours, and the reaction time was changed to 1.5 hours.

(63) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 76.7%, 3.2%, and 0.1%, respectively. The results are shown in Table 2.

[Example 19] Reaction in Water (Addition of Sodium Dichloroisocyanurate)

(64) A glass-made reaction container was charged with 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for dispersion. Thereafter, 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) was added in a divided manner to the resultant dispersion over one hour. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for 2.5 hours.

(65) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 78.4%, 1.6%, and 0.1%, respectively. The results are shown in Table 2.

[Example 20] Reaction in Water (Addition of Sodium Dichloroisocyanurate)

(66) The reaction and the quantitative analysis were performed in the same manner as in Example 19, except that the addition time of sodium dichloroisocyanurate was changed to two hours, and the reaction time was changed to 1.5 hours.

(67) As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 77.3%, 1.3%, and 0.1%, respectively. The results are shown in Table 2.

(68) TABLE-US-00002 TABLE 2 Quantitative yield with reference to sodium dichloroisocyanurate MMe-ICA DMe-ICA TMe-ICA Example 10 80.3% 3.6% 0.0% Example 11 85.2% 2.8% 0.1% Example 12 78.4% 2.6% 0.1% Example 13 77.3% 2.5% 0.1% Example 14 68.4% 1.7% 0.1% Example 15 76.7% 1.9% 0.1% Example 16 78.2% 2.2% 0.1% Example 17 78.2% 3.1% 0.1% Example 18 76.7% 3.2% 0.1% Example 19 78.4% 1.6% 0.1% Example 20 77.3% 1.3% 0.1%

(69) The results shown in Table 2 indicated that the production method of the present invention can selectively produce an N-mono(hydrocarbon)isocyanuric acid of interest (i.e., mono-substituted product of isocyanuric acid) in one pot at high production efficiency (Examples 10 to 20).

[Example 21] Generation of Sodium Dichloroisocyanurate in Reaction System

(70) A glass-made reaction container was charged with 3.07 g of isocyanuric acid (trade name: CA-P, available from Nissan Chemical Corporation) and 35.90 g of aqueous sodium hypochlorite solution (Cica first grade, available from KANTO CHEMICAL CO., INC.), and the resultant mixture was stirred at 40° C. for homogeneous dissolution, to thereby generate sodium dichloroisocyanurate in the reaction system. Thereafter, the resultant solution was cooled to 20° C., and 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the solution. The resultant mixture was stirred at 20° C. for six hours.

(71) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to isocyanuric acid) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 27.2%, 7.9%, and 0.2%, respectively. The results are shown in Table 3.

(72) TABLE-US-00003 TABLE 3 Quantitative yield with reference to isocyanuric acid MMe-ICA DMe-ICA TMe-ICA Example 21 27.2% 7.9% 0.2%

(73) The results shown in Table 3 indicated that the production method of the present invention can selectively produce an N-mono(hydrocarbon)isocyanuric acid of interest (i.e., mono-substituted product of isocyanuric acid) in one pot.

[Examples 22 to 26] Reaction in Organic Solvent

(74) A glass-made reaction container was charged with 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of an organic solvent or a mixed solvent of an organic solvent and water shown in Table 4, and the resultant mixture was stirred at 20° C. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred for six hours.

(75) The reaction product was diluted with acetonitrile for HPLC (available from KANTO CHEMICAL CO., INC.) and pure water in a measuring flask, and the diluted product was sampled. p-Xylene (internal standard substance) was added to the sample, and quantitative analysis was performed by HPLC.

(76) The results are shown in Table 4.

(77) TABLE-US-00004 TABLE 4 Quantitative yield with reference to sodium dichloroisocyanurate Solvent MMe-ICA DMe-ICA TMe-ICA Example 22 DMF 83.5% 5.7% 5.3% Example 23 DMF/water = 1:1 84.1% 3.7% 0.2% Example 24 Acetonitrile/water = 92.6% 3.5% 0.2% 1:1 Example 25 NMP/water = 1:1 89.4% 4.4% 0.2% Example 26 PGMEA/water = 1:1 86.3% 5.0% 0.2%

(78) The results shown in Table 4 indicated that the production method of the present invention can selectively produce an N-mono(hydrocarbon)isocyanuric acid of interest (i.e., mono-substituted product of isocyanuric acid) by using various solvents in one pot at high production efficiency.

[Example 27] Reaction in Water (Hydrocarbonization Agent)

(79) A glass-made reaction container was charged with 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation), 0.05 g of tetra-n-butylammonium bromide (available from Tokyo Chemical Industry Co., Ltd.), and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 5.32 g of methyl iodide (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for six hours.

(80) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monomethylisocyanuric acid (MIVIe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 9.0%, 0.0%, and 0.0%, respectively. The results are shown in Table 5.

[Example 28] Reaction in Organic Solvent (Hydrocarbonization Agent)

(81) A glass-made reaction container was charged with 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of dimethylformamide, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 7.33 g of diethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C. for six hours.

(82) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to sodium dichloroisocyanurate) of monoethylisocyanuric acid (MEt-ICA), diethylisocyanuric acid (DEt-ICA), and triethylisocyanuric acid (TEt-ICA) were 90.8%, 0.4%, and 0.0%, respectively. The results are shown in Table 5.

(83) TABLE-US-00005 TABLE 5 Quantitative yield with reference to sodium dichloroisocyanurate Hydrocarbonization agent MMe-ICA DMe-ICA TMe-ICA Example 27 MeI  9.0% 0.0% 0.0% Hydrocarbonization agent MEt-ICA DEt-ICA TEt-ICA Example 28 Et.sub.2SO.sub.4 90.8% 0.4% 0.0%

(84) The results shown in Table 5 indicated that the production method of the present invention can selectively produce an N-mono(hydrocarbon)isocyanuric acid of interest (i.e., mono-substituted product of isocyanuric acid) by using various hydrocarbonization agents in one pot.

[Example 29] Purification of Monomethylisocyanuric acid (MMe-ICA)

(85) The reaction was performed by the method of Example 11, and then filtration was performed at ambient temperature, to thereby recover 4.65 g of a wet product containing MMe-ICA. The wet product was placed in a glass-made reaction container, and 3.50 g of methanol (special grade, available from KANTO CHEMICAL CO., INC.) and 28.0 g of water were added to the container, followed by heating to 95° C. Subsequently, 5.0 g of toluene (special grade, available from KANTO CHEMICAL CO., INC.) was added to the resultant mixture for phase separation and recovery of the aqueous phase. This operation was repeated twice. Thereafter, the aqueous phase was cooled to 5° C. and stirred for one hour, and 3.08 g of a precipitated wet product containing a large amount of MMe-ICA was recovered through filtration. Subsequently, 2.46 g of the wet product was placed in a glass-made reaction container, and 13.8 g of methanol was added to the container, followed by heating to 65° C. Thereafter, the resultant mixture was cooled to 5° C. and stirred for one hour, and 2.05 g of a precipitated wet product containing a larger amount of MMe-ICA was recovered through filtration. The resultant wet product was dried under reduced pressure, to thereby yield 1.39 g of an MMe-ICA crystal. The MMe-ICA crystal was diluted with acetonitrile for HPLC in a measuring flask, and relative area (%) was analyzed by HPLC. The relative areas (%) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), trimethylisocyanuric acid (TMe-ICA), and others were 98.5%, 0.5%, 0.7%, and 0.3%, respectively.

[Example 30] Purification of Dimethylisocyanuric Acid (DMe-ICA)

(86) The reaction was performed by the method of Example 7, and then the resultant reaction mixture was cooled to 10° C. and subjected to filtration, to thereby recover 5.03 g of a wet product containing DMe-ICA. The wet product was placed in a glass-made reaction container, and 20 g of water was added to the container, followed by heating to 50° C. Thereafter, the resultant product was cooled to 10° C., and 4.76 g of a precipitated wet product containing a larger amount of DMe-ICA was recovered through filtration. The same operation was repeated again, and 4.61 g of a wet product containing a larger amount of DMe-ICA was recovered through filtration. Subsequently, the wet product was placed in a glass-made reaction container, and 15 g of methanol (special grade, available from KANTO CHEMICAL CO., INC.) was added to the container, followed by heating to 60° C. Thereafter, the resultant mixture was cooled to 10° C., and 2.12 g of a precipitated wet product containing a larger amount of DMe-ICA was recovered through filtration. The resultant wet product was dried under reduced pressure, to thereby yield 2.03 g of a DMe-ICA crystal. The DMe-ICA crystal was diluted with acetonitrile for HPLC in a measuring flask, and relative area (%) was analyzed by HPLC. The relative areas (%) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 6.9%, 92.7%, and 0.4%, respectively.

[Comparative Example 1] Reaction in Water Using Isocyanuric Acid (Containing Base)

(87) A glass-made reaction container was charged with 3.07 g of isocyanuric acid (trade name: CA-P, available from Nissan Chemical Corporation), 0.95 g of sodium hydroxide (special grade, available from KANTO CHEMICAL CO., INC.), and 30.0 g of water, and the resultant mixture was stirred at 20° C. However, homogeneous dissolution failed to be achieved. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant slurry. The resultant mixture was stirred at 20° C. for two hours.

(88) The quantitative analysis was performed in the same manner as in Example 1. As a result, the quantitative yields (with reference to isocyanuric acid) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 11.2%, 12.1%, and 0.4%, respectively. The results are shown in Table 6.

[Comparative Example 2] Reaction in Water Using Isocyanuric Acid (Containing Base)

(89) The reaction and the quantitative analysis were performed in the same manner as in Comparative Example 1, except that the amount of sodium hydroxide was changed to 1.90 g.

(90) As a result, the quantitative yields (with reference to isocyanuric acid) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), and trimethylisocyanuric acid (TMe-ICA) were 13.9%, 25.9%, and 0.0%, respectively. The results are shown in Table 6.

(91) TABLE-US-00006 TABLE 6 Quantitative yield with reference to isocyanuric acid MMe-ICA DMe-ICA TMe-ICA Comparative Example 1 11.2% 12.1% 0.4% Comparative Example 2 13.9% 25.9% 0.0%

(92) As shown in Table 6, when isocyanuric acid was used as a starting material, the yield of N-di(hydrocarbon)isocyanuric acid (i.e., di-substituted product) was improved by increasing the amount of the base. However, the selectivity of the target product was impaired as compared with the case of the method of the present invention shown in Table 1.