JPH0138787B2 - - Google Patents

Description

Detailed Description of the Invention The present invention relates to a method for producing acetonyl isocyanurate, and the acetonyl isocyanurate obtained by the method of the present invention can be used as a synthetic resin, a biochemical drug, a synthetic raw material, a reagent, etc. It is versatile.

The present inventors have tried various methods using monochloroacetone or acetol as raw materials in an attempt to synthesize acetonyl isocyanurate, but the yield of the target product was not sufficient, and it was difficult to synthesize various acetonyl isocyanurates. I couldn't do it.

Here, the present inventors prepared 2-hydroxypropylisocyanurate having a hydrate structure of triallylisocyanurate in a polar solvent at 0-120
They succeeded in synthesizing various desired acetonyl isocyanurates in good yields by oxidizing them at ℃. The acetonyl isocyanurate referred to in the present invention is acetonyl diallyl isocyanurate, acetonyl hydroxypropyl allyl isocyanurate, diacetonyl allyl isocyanurate, acetonyl bis(2-hydroxypropyl) isocyanurate, diacetonyl 2
- Refers to either hydroxypropyl isocyanurate, triacetonyl isocyanurate, or a mixture of two or more thereof.

2-hydroxypropylisocyanurate having a hydrate structure of triallylisocyanurate is a compound represented by any one of (), (), and ().

The compounds of the above formulas (), (), and () can be obtained as a mixture by using triallylisocyanurate as a raw material and hydrating it in the presence of an acidic substance such as sulfuric acid (patent application). Akira
56-97951, Japanese Patent Application Laid-open No. 57-212173).

In the above hydration method, whether (), (), or () is obtained as the main component depends on the reaction conditions such as ○ concentration of sulfuric acid, ○ amount of sulfuric acid used, ○ C reaction temperature, and ○ D reaction time. Although it is difficult to make a general statement because the conditions are different, if the reaction conditions are mild, then () will be the main component, and if the reaction conditions are severe, () will be the main component. (), (),
Distillation or recrystallization can be used to isolate each compound from a mixture of (), (),
The mixture () does not necessarily have to be separated and purified before being used as a starting material for the present invention. This is because even in this case, the target compound of the present invention can be obtained in the form of a mixture by the reaction of the present invention described later, and if necessary, a specific target compound can be separated and collected thereafter.

The common properties of the compounds (), (), and () are that they have a strong tendency to undergo dehydration and decomposition when ignited, and are relatively stable against oxidizing agents. This is a result of the molecules of these compounds interacting with each other through strong hydrogen bonds, which makes more sense than the very low vapor pressure.

In order to oxidize the compounds (), (), and () to overcome their oxidation resistance, a rather strong liquid phase oxidation must be performed, and it is difficult to obtain the desired acetonyl isocyanurate with a weak oxidizing agent. . If oxidation with an oxidizing agent is too strong, polymerization and decomposition of the allyl group, decomposition of the 2-hydroxypropyl group, and splitting of the triazine ring will occur. To prevent such unexpected reactions, it is necessary to select oxidation conditions, especially in polar solvents.
Liquid phase oxidation using an oxidizing agent at 120°C is required.

The polar solvent used in the present invention includes water, sulfuric acid, nitric acid, phosphoric acid, hydrohalic acid, acetic acid, methylene dichloride, chloroform, acetone, tertiary alcohol, pyridine, etc. alone or in mixtures. Water, sulfuric acid aqueous solution, acetic acid, acetic acid aqueous solution, alkali hydroxide aqueous solution, acetone, and pyridine are economical. Oxidation reaction temperature is 0-120
It is preferably carried out at a temperature of 10 to 100°C.
If the temperature is below 0.degree. C., 2-hydroxypropyl isocyanurate is not easily oxidized even if a strong oxidizing agent is used due to its oxidation resistance, and it takes a long time to oxidize, which is economically disadvantageous. Furthermore, at temperatures above 120°C, splitting of the triazine ring and oxidative decomposition of allyl groups occur simultaneously, resulting in a markedly poor yield of the target product.

Next, what kind of oxide can be obtained as a target object from (), (), and () will be illustrated using a chemical formula.

The above () to () are the oxides according to the present invention, and among these, (), (), and () are the complete oxides from (), (), and (), respectively, and () and (), (). is an incomplete oxide from () and (). The method of the present invention can conveniently produce either complete oxides or incomplete oxides by selecting the oxidation conditions, the amount of oxidizing agent used, etc. The above formula shows that a complete oxide is generated sequentially through an incomplete oxide, but in reality, by selecting the oxidation method, () or () can be synthesized from () or () in one step. can do.

The oxidizing agent used in the method of the present invention is liquid phase oxidation using a polar solvent, and since the raw materials and reaction temperature are limited, a strong oxidizing agent is required. Typical oxidizing agents include chromium trioxide (chromic acid) and its salts, dichromate, chromyl chloride, manganese dioxide, permanganate,
Halogen acids and their salts, perhalogen acids and their salts, persulfates, perborates, hydrogen peroxide, nitric acid, N-halogen organic acid amides, chromic acid-t-
These include butyl, vanadium pentoxide, organic peroxides, etc., but industrially advantageous oxidizing agents are chromium trioxide (chromic acid), nitric acid, and hydrogen peroxide.

When using chromium trioxide (chromic acid), water, acetic acid, chloroform, hydrohalic acid, etc. are advantageous as the solvent, and in some cases, acetone, pyridine, etc. are used.

When using dichromate, water, sulfuric acid, acetic acid, etc. are used as a solvent. water in the case of nitric acid,
Dilute sulfuric acid or the like is used as a solvent, and in the case of hydrogen peroxide, water, t-butanol, etc. are used as a solvent, and manganese dioxide may be used as a catalyst as a reaction accelerator. Potassium permanganate is used as an aqueous solution. Water is also an excellent polar solvent when using halogen acids, perhalogen acids, and their salts.

The present inventors conducted a large number of experiments regarding the method of the present invention described above and clarified the superiority of the present invention.Next, several representative examples will be shown as examples.

Synthesis example of raw material compound 1 Triallylisocyanurate 100g (0.40mol)
While stirring at about 40℃, add 100g of 98% sulfuric acid to this.
(1.02 mol) was gradually added dropwise until the reaction temperature reached
Complete this without exceeding 50°C. This mixture was heated at approximately 35°C for 3 hours, then at 45°C.
After stirring at 50℃ for 1 hour, 200ml of water was gradually added.
Stir for an additional 30 minutes at 60-70°C. After cooling the reaction mixture to room temperature, 200 ml of water was added, and this was extracted with benzene. The extract was washed with a saturated aqueous solution of sodium bicarbonate, then water, and dried over anhydrous sodium sulfate, and then the benzene was distilled off. , and then distilled under reduced pressure to obtain 2-, which is a colorless viscous liquid.
Hydroxypropyl diallyl isocyanurate 88
g (yield 82%) is obtained. The properties and analytical values of this substance are as follows.

bp., 154-155℃/0.5mgHg, elemental analysis value C ₁₂ H ₁₇ N ₃ O ₄ Calculated value C53.92%, H6.41%, N15.72% Actual value C53.77%, H6.35% , N15.91% IR spectrum (neat) cm ^-1 : 3500, 1680, 765 nmr spectrum ( _CDCl3 ) δ: 6.2-5.5 (2H, m, _CH2 - CH = _CH2 ),
5.4-5.1 (4H, m, _CH2 -CH= CH2 ), _4.5
~4.4 (4H, d, CH2 _- CH= _CH2 ), 4.2
(1H, m, _CH3 - CH - _CH2OH ), Synthesis example of raw material compound 2 Triallyl isocyanurate 100g (0.4 mol)
Add 200g of 95% sulfuric acid to this while stirring at below 40℃.
(2.0 mol) was added dropwise over a period of 2 hours, the reaction was allowed to stand for 8 hours at 30-35°C, and then 400 ml of water was added and boiled for 7 hours. The reaction mixture is then neutralized by adding sodium hydroxide, the neutralized solution is extracted repeatedly with benzene, the extracts are collected, dried over anhydrous sodium sulfate, and then distilled to recover the solvent. The residue is distilled under reduced pressure at 160℃/0.5mmHg.
Hydroxypropyl diallyl isocyanurate is first separated. Further vacuum distillation of this residue yields bis2-hydroxypropyl)allylisocyanurate, bp 140°C/0.05mmHg. Yield 77.5g
(yield approximately 68%).

In this method, the sulfuric acid concentration is less than 98%, i.e. 80-98%.
%, but if the sulfuric acid concentration is lowered, it is necessary to raise the reaction temperature or make the reaction time longer than under the above conditions. Bis(2-hydroxypropyl)allylisocyanurate can be purified by distillation or adsorption using activated clay, but the extract must be free of any sulfate radicals before carrying out the distillation or adsorption operation. It is advisable to check that. If there is a small amount of sulfate radicals, it is necessary to remove them in advance with barium hydroxide in order to improve the yield.

The analytical values of the purified product obtained by this sulfation hydration method are as follows.

Elemental analysis value C ₁₂ H ₁₉ O ₅ N ₃ (molecular weight 285.30) N calculated value 14.73%, N actual value 14.81% IR spectrum (neat); cm ^-1 3500 (O-H), 3090
(C-H of olefin), 1680 (C=O), 760 (N
-C) nmr spectrum ( _CDCl3 ); δ1.10-1.30 (d,
6H), 3.55-4.25 (m, 8H), 4.35-4.55 (d,
2H), 5.05-5.45 (m, 2H), 5.55-6.20 (m,
1H), Example 1 10 g of 2-hydroxypropyl diallyl isocyanurate was dissolved in 20 ml of acetone, cooled on ice, and mixed with chromic acid solution (2.5 g of chromic anhydride, sulfuric acid) while stirring.
After dropping 3.1 g of water (mixture of 15 ml of water) at 25℃,
Stir for an hour and destroy excess chromic acid with acidic sodium sulfite. The reaction mixture is extracted with ether, the extract is washed with water, dried, and then distilled to obtain acetonyl diallylisocyanurate with a yield of about 70%. This product was a colorless liquid with a boiling point of 146°C/0.3mmHg, and the analysis results were as follows.

ir: 1710 cm ^-1 (C=O); nmr. (CCl ₄ ): δ2.20 (S,
3H) indicates the proton of H ₃ of CH ₃ COCH ₂ groups,
4.55 (S, 2H) indicates a pronaton of H ₂ with CH ₃ COCH ₂ groups. Elemental analysis showed N actual value 15.90%, (N
The calculated value was 15.84%).

Example 2 30 g of 2-hydroxypropyl diallyl isocyanurate, 20 ml of water, 10 ml of 50% hydrofluoric acid, acetic acid
A chromic acid solution (mixture of 8 g of chromic acid anhydride and 10 ml of water) was added dropwise to the mixture with stirring. After the reaction was carried out at 30° C. for 3 hours, the mixture was cooled and the solids were separated. If the liquid is extracted with toluene, the extract is washed with water, dried, and distilled, acetonyl diallylisocyanurate can be obtained with a yield of about 82%. The properties of this product were compared with those obtained in Example 1, and it was confirmed that they were the same.

Example 3 A mixture of 3 g of 2-hydroxypropyl diallylisocyanurate, 10 g of 40% nitric acid, and 10 g of 40% sulfuric acid was placed in a sealed tube and reacted at 750°C for 7 hours with vigorous shaking, then cooled and the reaction mixture was diluted with an aqueous alkaline solution. and extract it with ether. When the extract was separated, washed with water, dried, and then distilled, acetonyl diallyl isocyanurate was obtained with a yield of about 66%. The properties of this product were compared with those obtained in Example 1, and it was confirmed that they were the same.

Example 4 3 g of 2-hydroxypropyl diallyl isocyanurate, 0.01 g of emulsifier, 5 g of 30% hydrogen peroxide,
20 ml of water and 0.1 g of activated manganese dioxide are placed in a sealed tube and reacted at 50-60°C with vigorous shaking for 10 hours, then cooled and the reaction mixture is poured into cold water for benzene extraction. When the extract was separated, washed with water, dried, and then distilled, acetonyl diallyl isocyanurate was obtained in a yield of about 44%. The properties of this product were compared with those obtained in Example 1, and it was confirmed that they were the same.

Example 5 10 g of 2-hydroxypropyl diallyl isocyanurate, 100 g of 50% sulfuric acid, 10 g of manganese dioxide
After reacting for 4 hours at room temperature with vigorous stirring, extracting with ether, washing the extract with water, drying and distilling, acetonyl diallylisocyanurate is obtained at about 68%
% yield. This product was compared with the product obtained in Example 1 and was confirmed to be the same product.

Example 6 Tris (2-hydroxypropyl) isocyanurate was synthesized by the sulfation hydration method, fractionated and purified, and then oxidized using three times the amount of chromic acid solution in the same manner as in Example 1. However, if the sulfation hydration method is used, tris(2-hydroxypropyl) isocyanurate, which is a synthetic intermediate, is not separated by extraction, distillation, and recrystallization. Triacetonyl isocyanurate can be made continuously as follows.

Triallylisocyanurate 15g, 80% sulfuric acid 50
ml was mixed and kept at 80℃ for 10 hours, then 40ml of water was added and kept at 100℃ for 2 hours. After cooling, add chromic acid solution (mixture of chromium trioxide 13g and water 15ml).
It is added dropwise at 40-50°C and kept at this temperature for 2 hours before being cooled. The reaction mixture is extracted with benzene, the extract is washed with water, and after drying, the benzene is distilled off. If the residue is recrystallized from methanol, triacetonyl isocyanurate can be obtained with a yield of about 50%. This thing is
The analysis results for white crystals with a temperature of mp.138-139°C are as follows.

ir. (nujol): 1730~1680cm ^-1 (C=O), 760cm ^-1
(NC); nmr. (DMSO-d ⁶ ): δ1.86 (S,
9H), 4.28 (S, 6H); Elemental analysis: N actual value
14.08%, (N calculated value 14.14%) Example 7 When the same operation as in Example 6 was carried out using 45 g of triallyl isocyanurate, the amount of acetonyl diallyl isocyanurate was approximately 77%.
was obtained in a yield of . This product was found to be the same as that obtained in Example 1.

Example 8 10 g of bis(2-hydroxypropyl)allylisocyanurate and 40 ml of acetone were cooled on ice and stirred, and chromium mixed acid (5.7 g of chromium trioxide, 5.7 g of chromium trioxide,
Add 6.1 g of sulfuric acid). Then at room temperature 3
After stirring for an hour, the reaction mixture was poured into cold water and extracted with toluene. The extract is washed with water, dried, and then distilled to remove toluene, and the residue is recrystallized from methanol to obtain acetonyl 2-hydroxypropyl allyl isocyanurate in a yield of about 55%. This is a compound in which the three N substituents on the isocyanuric ring are all different, and each of the three functional groups has a unique reactivity. Pure product is white crystal and MP.132~
The temperature was 133°C, and the properties and analytical values were as follows.

Elemental analysis value (as C ₁₂ H ₁₇ O ₅ N ₃ ) N: Actual value 14.79%, (N: Calculated value 14.84%) ir (nujol): cm ^-1 3500 (O-H), 1720 and 1680 (C =
O), 760 (N-C).

nmr ( _CDCl3 ): δ1.15-1.25 (d, 3H), 2.20 (S,
3H), 2.40 (S, 1H), 3.60-4.25 (m, 3H),
4.40-4.50 (d, 2H), 4.70 (S, 2H), 4.70 (S,
2H), 5.05-5.45 (m, 2H), 5.60-6.15 (m,
1H).

Example 9 10 g of bis(2-hydroxypropyl)allylisocyanurate was dissolved in 100 ml of water, and while stirring under ice cooling, 50 g of sulfuric acid and 20 g of sodium sulfate were added.
Add. 50 g of artificial brownstone powder was added to this solution at room temperature, and the reaction was continued for 5 hours with vigorous stirring at 50 to 60°C. After cooling, the reaction mixture was extracted with benzene, the extract was washed with water, and dried to distill off the benzene. leave If the residue is recrystallized from methanol, white crystals of diacetonylallylisocyanurate (mp. 139-140°C) are obtained in a yield of 56%. The results of this analysis are as follows.

Elemental analysis value (as C ₁₂ H ₁₅ O ₅ N ₃ ) N: Actual value 14.99%, (N: Calculated value 14.95%) ir (nujol): cm ^-1 1720 and 1680 (C=O), 760 (N-
C) nmr ( _CDCl3 ): δ2.20 (S, 6H), 4.35-4.50 (d,
2H), 4.65 (S, 4H), 5.05-5.45 (m, 2H),
5.55-6.15 (m, 1H) Example 10 In Example 9, tris(2-hydroxypropyl)allylisocyanurate was replaced with tris(2-hydroxypropyl)allylisocyanurate.
-Hydroxypropyl) isocyanurate was used, and triacetonyl isocyanurate was obtained in a yield of about 50%. This product is the same as that obtained in Example 6. The aldol condensate or dehydrated product of this product, in which one or two of the three acetonyl groups are reacted with aldehyde, is an asymmetric isocyanurate with high condensability or polymerizability and is used as a modifier for various polymeric materials. be able to.

Claims (1)

[Scope of Claims] 1. A method for producing acetonyl isocyanurate, which comprises oxidizing 2-hydroxypropyl isocyanurate having a hydrate structure of triallyl isocyanurate in a polar solvent at 0 to 120°C. 2 2-hydroxypropyl isocyanurate is at least one compound selected from the group consisting of 2-hydroxypropyl diallyl isocyanurate, bis(2-hydroxypropyl)allyl isocyanurate and tris(2-hydroxypropyl)isocyanurate. A method for producing acetonyl isocyanurate according to claim 1.