JPS5993064A - Preparation of acetonyl isocyanurate - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a raw material of synthetic resin and biochemical drug, etc., by oxidizing 2-hydroxypropyl isocyanurate having the structure of hydrated triallyl isocyanurate, in a polar solvent at 0-120 deg.C. CONSTITUTION:The objective compound of formula IV-IX can be prepared in high yield, suppressing the polymerization and decomposition of allyl group, decomposition of 2-hydroxypropyl group, and scission of triazine ring, by the liquid-phase oxidation of a 2-hydroxypropyl isocyanurate having the structure of hydrated triallyl isocyanurate and selected from 2-hydroxypropyl diallyl isocyanurate, bis(2-hydroxypropyl)allyl isocyanurate and tris(2-hydroxypropyl) isocyanurate, in a polar solvent at 0-120 deg.C, especially 10-100 deg.C, using an oxidizing agent, especially chromium trioxide, nitric acid, or hydrogen peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION The acetonyl isocyanurate obtained by the method of the present invention has a wide range of uses such as synthetic resins, biochemical drugs, synthetic raw materials, and reagents.

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.

Here, the present inventors oxidized 2-hydroxypropylisocyanurate having a hydrate structure of triallylisocyanurate at O - 120°C in a polar solvent to obtain various desired acetonyl isocyanurates. They succeeded in synthesizing it with good yield. The acetonyl isocyanurate referred to in the present invention is acetonyl diallyl isocyanurate, acetonyl hydroxypropyl allyl isocyanurate, diacetonyl allyl isocyanurate, acetonyl bis(2-hydroxypropy/1/) isocyanurate, cyacetonyl lv2- It refers to either hydroxypropyl isocyanurate or tri-7-di-μ isocyanurate, or a mixture of two or more thereof.

2- with triallylisocyanurate aquarium ladle
What is hydroxypropyl isocyanurate (1), (1)
), (1).

CH2CH(OR)CH5 CI(2-CHCH2CCI(2CH=CH,-to1 CH2CH(OH)CH.

] 1 ○ CH2CH(OH)CH3 1 The compounds of the above formulas (I), (1), and (1) are produced by hydrating triallylisocyanurate as a raw material and 1 to 1 in the presence of an acidic substance such as sulfuric acid. It can be obtained as a mixture by the method described in Japanese Patent Application No. 56-97951.

In the above water utilization method, which of (1), (1), or (1) is obtained as the main component depends on reaction conditions such as ■sulfuric acid concentration, ■sulfuric acid usage amount, θ reaction temperature, and ■reaction time. - Although it cannot be said generally, if the reaction conditions are mild (1
) becomes the main component, but if the reaction conditions are harsh, the main components become the main components. To isolate each compound from a mixture of (1), (1), and (1), distillation or recrystallization may be used.
The mixture of (■), (1), and (1) does not necessarily have to be separated and purified before being used as a starting material for the present invention. This is because the target compound of the present invention can be obtained in the form of a mixture through the reaction, and if necessary, a specific target compound can be subsequently separated and collected.

(1) The common properties of the compounds (1) and (1) are that they have a strong tendency to dehydrate and decompose when ignited, and are relatively stable against oxidation h1. 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 (1), (M), and (1) by overcoming their oxidation resistance, a rather strong liquid phase oxidation must be performed, and the desired acetonyl isocyanurate cannot be obtained with a weak oxidizing agent. It is difficult. If oxidation with an oxidizing agent is too strong, polymerization and decomposition of the allylic group, decomposition of the 2-hydroxypropyl μ group, and splitting of the triazine ring will occur. In order to prevent such unexpected reactions, it is necessary to select the oxidation conditions, especially in polar solvents with 0 to 1
Liquid phase oxidation using an oxidizing agent at 20°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. The oxidation reaction temperature is D~12
It is carried out at 0"C, particularly preferably between 10 and 100"C. At temperatures below 0''C, due to the oxidation resistance of 2-hydroxypropyl isocyanurate, even if a strong oxidizing agent is used, it will not be easily oxidized and will take a long time, which is economically disadvantageous. Fission of the triazine ring and oxidative decomposition of the allyl group occur together, resulting in a markedly poor yield of the target product.

Next, what kind of oxide can be obtained as a target object from 0), (1), and (1) will be illustrated using a chemical formula.

CHCo positive.

Yoshi (Ma) (■) @
(IX) Above (IV) ~ ([)
are the oxides according to the present invention, among which (ff), (V
l) and (2) are perfect oxides from 0), (1), and (11), (ma) and (匍, and (2) are (1) and (11), respectively.
The method of the present invention, which is an incomplete oxide from 1), can conveniently produce either a complete oxide or an incomplete oxide by selecting the oxidation conditions, the amount of oxidizing agent used, etc. In the above equation, it is shown that a complete oxide is generated sequentially through an incomplete oxide, but in reality, depending on the selection of the oxidation method, (1) t or (1) to ( W) or ([
) can be synthesized.

As the oxidizing agent used in the method of the present invention, a strong oxidizing agent is required because liquid phase oxidation is performed using a polar solvent, and the raw materials and reaction temperature are limited. Typical oxidizing agents include chromium trioxide (chromic acid) and its salts, dichromate, chromyl chloride, manganese dioxide, permanganate, halogen acid and its salts, perhalogen acid and its salts, and persulfuric acid. Salts, perborates, hydrogen peroxide, nitric acid, N-halogen organic acid amides, L-butyl chromate, vanadium pentoxide, organic peroxides, etc., but the industrially advantageous oxidizing agent is chromium dioxide. (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 acetone, pyridine, etc. are used in some cases.

When using dichromate, water, sulfuric acid, acetic acid, etc. are used as a solvent. In the case of nitric acid, water, dilute sulfuric acid, etc. are used as a solvent, and in the case of hydrogen peroxide, water, t-butano-p, 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 numerous 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゜triallyl in cyanuride-1-10 (1 (0.4o mot
While stirring v) at about 40°C, add 98 sulfuric acid + oo
9 (ts..02 mol) was gradually added dropwise to complete the reaction while ensuring that the reaction temperature did not exceed 5°C.

This mixture was heated at about 35°C for 3 hours, then heated at 45-50°C.
After stirring at 0° C. for 1 hour, 200 g of water was added to the mixture, and the mixture was further stirred at 60 to 70° C. for 60 minutes. After the reaction mixture was cooled to room temperature, 200 M of water was added, and this was extracted with benzene. The extract was washed with a saturated aqueous solution of sodium bicarbonate, then with water, and dried over anhydrous sodium sulfate, and then the benzene was distilled off. Then, by subsequent distillation under reduced pressure, 2-human p-xypropyl sialyl isocyanurate (yield 82%) is obtained as a colorless viscous liquid. The properties and analytical values of this substance are as follows.

bp. , 154-155°C10・5mHg, elemental analysis value C12"17N5"4 Calculated value C5
3.92chi, H6.41%, Ni5.72 coefficient actual measurement value C
56・77chi, H6・65chi, N15・91%j, Spect/Shoku50ru) ctIL': 3500, 1680, 765pn-
rr shuek) l (CDCex, )f:6・2
~5・5 (2H, Qi, CH2-Wish=positive,), 5・
4-5・1(, aH, ~, CH2-CH = ca
2), 4.5-4.4 (4H, Kou, Nozomi 2-CH=
CH2), 4・2(1■, Chiku, CH5-CH-1, OR
), 2・9 (IH, S, -CH2-OH
), 1・s (3H, flower, CH3- CH
- ), Synthesis Example 2 of raw material compound.

While stirring 100 g (0.4 mol) of triallylisocyanurate at a temperature below 40°C, add 200 g (200 g) of 95-thiosulfuric acid (
2.0 μ) was added dropwise over 2 hours, and heated to 60-35°C.
After the reaction was allowed to stand for 8 hours, 40t3Mt of water was added and boiled for 7 hours.Next, sodium hydroxide was added to the reaction mixture to neutralize it, the neutralized solution was extracted 9 times with benzene, and the extracts were collected. After drying with anhydrous sodium sulfate, distill it to recover the solvent. Distill the residue under reduced pressure at 160°C.
First, 2-hydroxypropyl μ diallyl isocyanurate distilled out at 0.5 mH9 is fractionated. Further vacuum distillation of this residue yields bis(2-hydroxypropyl)allyl isocyanurate, bP140°C10.051u
The yield of lHg is 77% σ (1% rate of about 68%).

In this method, the sulfuric acid concentration is 80-98% or less than 98%.
However, if the sulfuric acid concentration is decreased, it is necessary to raise the reaction temperature or lengthen the reaction time even under the above conditions. Bis(2-hydroxypropy)V)allylisocyanurate can be purified by distillation as well as by 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 CI2H1905N3 @ molecular weight 285.60)
As a result, N calculated value is 14.75 inches, N actual value is 14.81 inches.
r Nuvecto/1/ (neat) H cm”
3500 (0-H), 6o9o (olefin C-
H), 1680 (C=O), Fzngui'':nmr7pect)V(CDCI,);J'1・1o
-1-30 (a, 6H), 3-55-4・25 (ml
8H), 4-3.5 to 4-55 (d.2H), 5-0
5 ~ 5-45 (ml 2H), 5-55 ~ 6-20
(m, IH), Example 1.

2-Hydroxypropyl) V sialyl isocyanurate) 1
(Dissolve l in 20 ytl of acetone, cool on ice, and stir while stirring to remove chromic acid solution (2.5 g of chromic anhydride, 3.1 g of sulfuric acid.
, water 15s? After dropping a mixture of (mixed liquid of), the mixture was stirred at 25°C for 6 hours, and excess chromic acid was decomposed with acidic sodium sulfite. The reaction mixture was extracted with ether, and the extract was washed with water, dried, and then distilled to reveal that acetonyl diallylisocyanurate was a colorless liquid with a boiling point of 146°C and 10·5 tytHq, with the following analysis results.

ir. : 1710cm ” (C = O) H n
mr. (CCd4): J'2・20(S, 6H)
indicates the H5 proton of CH, COCH2 group, and 4.5
5 (S, zH) indicates the H2 proton of the CH3CoCH2 group. The elemental analysis showed that the actual N value was 15.90 inches, (the calculated N value was 15.84 inches).

Example 2゜2-Hydroxypropyl diallylisocyanuride) 30
g, 20 liters of water, 1 ozl of SO% hydrofluoric acid, 1 oz of acetic acid
mt was mixed, and while stirring, a chromic acid solution (mixture of 8 g of chromic acid anhydride and 1 aml of water) was added dropwise to the mixture for 3 hours and 30 minutes.
After the reaction is carried out at °C, it is cooled and the solids are separated. Extract the furnace liquor with toluene, wash the extract with water, dry it, and distill it to obtain acetonyl diallylisocyanurate in a yield of about 82%.The properties of this product were compared with those obtained in Example 1. Example 3 3 g of 2-hydroxypropyl diallyl isocyanurate
A mixture of 40φ nitric acid, 109.40% sulfuric acid, and 10 g was placed in a sealed tube, shaken vigorously, and reacted at 750° C. for 7 hours, cooled, and the reaction mixture was poured into an alkaline aqueous solution and extracted with ether. When the extract was separated, washed with water, dried, and then distilled, acetonyl sifsononanurate was obtained at a yield of about 66%. This thing realizes its properties.
15 Colors It was confirmed that they were the same as those obtained in Example 1.

Example 4 3g of 2-hydroxypropyl diallyl isocyanurate
, emulsifier 0.Olg, 50 hydrogen peroxide solution 5g, water 20
Place 0.1 g of Mls activated manganese dioxide in a sealed tube 5
After reacting at 0 to 60°C for 10 hours with vigorous shaking, the mixture is cooled, and the reaction mixture is poured into cold water and extracted with benzene. When the extract was separated, washed with water, dried, and distilled, acetonyl diallylisocyanurate was obtained in a yield of about 44 cm.The properties of this product were compared with those obtained in Example 1, and it was found to be the same product. It was confirmed that

Example 5 2-hydroxypropyl diallylisocyanurate) 10
After reacting 100g of 50 sulfuric acid and 10g of manganese dioxide at room temperature for 4 hours with vigorous stirring, extracting with ether, washing the extract with water, drying and distilling, acetonyl diallylisocyanurate can be obtained with a yield of about 681. This product was compared with the product obtained in Example 1 and was confirmed to be the same product.

Example 6 Tris(2-hydroxypropy/L/) by sulfation hydration method
When isocyanurate is synthesized, fractionated and purified, and then oxidized using 6 times the amount of chromic acid solution in the same manner as in Example 1, triacetyl-dilysocyanurate is obtained, but sulfated water According to the Japanese method, tris (2-hydroxypropyl) isocyanurate, which is a synthetic intermediate, is extracted,
Even if it is not separated by distillation or recrystallization, it can be continuously converted to tri-7tonyl isocyanurate as shown below. t50
After mixing 40 gl and holding at 80°C for 10 hours, water 40
After cooling at 100°C for 2 hours, add chromic acid solution (mixture of chromium trioxide 13g and water 15m/ml) dropwise at 40-50°C, maintain at this temperature for 2 hours, and then cool. do. The reaction mixture is extracted with benzene, the extract is washed with water, the benzene is distilled off after drying, and the residue is recrystallized from methanol to obtain doria 7 to 2μ isocyanurate in a yield of about 50%. This one is mp・138~16
The analysis result for white crystals at 9°C is 9 as follows.

ir, (nujol) two 1730
~1680m' (C=O), 760cM"
(N-C) Hnmr, (DMSO-d6):♂
1・Ill/l(S, 9H), 4・28(S, 61
() i Elemental analysis 2N Actual value 14.08, (N calculated value 14.14) Example 7 When the same operation as in Example 6 was performed using 45g of triallyl isocyanurate, acetate Nildiallylisocyanurate was obtained in a yield of about 77%. This product was found to be the same as that obtained in Example 1.

Example 8 While cooling 109 g of bis(2-hydroxypropyl/I/)allylisocyanurate and 40 liters of acetone with stirring, add chromium mixed acid (5.7 g of chromium trioxide, 6.0 g of sulfuric acid).
1 g of mixture) is added. After stirring at room temperature for 3 hours, the reaction mixture was poured into cold water and extracted with toluene. The extract was washed with water, dried and then distilled to remove toluene, and the residue was recrystallized from methanol. Each of the five functional groups in a compound has a unique reactivity, and the pure product is a white crystal (Illll), 132-1
At 63°C, the properties and analytical values were as high as those of Aggi.

Elemental analysis value (as C12H1705N6) N: Actual value 14.79chi, (N: Calculated value 14.84chi) ir (nu
jol)Hcm-”!1500(0-H), 172
o and 168.

(c.,,o), 760(N-C).

nmr (CDCl,): Cf1・15-1・25(d,
3H), 2・20(S, 3H), 2-40(S, I
H), 3-60 to 4-25 (m, 3H), 4-40-
4.50 (cl, 2H), 4.70 (S, 2H), 4
・70 (S, 2H), 5.05 to 5.45 (m, 2H)
, 5・60-6-15(m,1)I).

Example 9.

10 g of bis(2-hydroxyproha, I/)allylisocyanurate is dissolved in 100 g of water, and while stirring under water cooling, 50 g of sulfuric acid and 20 g of sodium sulfate are added. 50F of artificial brownstone powder was added to this solution at room temperature, and the reaction was continued for 5 hours with vigorous stirring at SO2 6o°C. After cooling, the reaction mixture was extracted with benzene, and the extract was washed with water and dried to remove benzene. To leave. Recrystallization of the residue from methanol yields white crystals of diacetonyl allyl isocyanurate (mp.

139-140°C) with a yield of 56%. The results of this analysis are as follows.

Elemental analysis value (as C12H1505N3) N: Actual value 14.99chi, (N: Calculated value 14.95chi) ir (nu
jol): ts' 1720 and 168 (1 (
C=O), 76o (N-C) nmr (CD0g3): c/' 2.20 (8,
6H), 4.55 to 4.50 ((1,2H), 4.6
5 (8, 4H), 5.05 ~ 5-45 (m12H),
5-55 to 6.15 (m, IH) Example 10.

The same procedure as in Example 9 was carried out except that trino(2-hydroxypropy) V) isocyanurate was used instead of bis(2-hydroxypropy/V)allyl isocyanurate, and triacetonyl isocyanurate was Obtained in a yield of 50 cm. This product is the same as that obtained in Example 6. 1 out of 6 acetonyl groups in this thing
An aldol condensate obtained by reacting two of these aldols with an aldehyde or a dehydrated product thereof is an asymmetric isocyanurate that is highly condensable or polymerizable and can be used as a modifier for various polymeric materials.

patent applicant Foundation for Production Development Science

Claims (1)

[Claims] ■ Acetoni!, which is characterized by oxidizing 2-hydroxypropylisocyanurate having a hydrate structure of triallylisocyanu V-) in a polar solvent at 0 to 120°C! Method for producing lysocyanurate. ■ 2-hydroxypropyl isocyanurate is 2-hydroxypropyl diallyl isocyanurate, bis(2
acetonyl isocyanurate according to claim 0, which is at least one compound selected from the group consisting of -hydroxypropy/I/) allyl isocyanurate and tris(2-hydroxypropy/V) isocyanurate. Manufacturing method.