Preparation method of trioxetane

Abstract

The invention relates to the technical field of trioxetane, and discloses a preparation method of trioxetane, which is characterized in that acetone, 1, 1-dimethyl-3-hydroxybutyl hydroperoxide and a sulfuric acid aqueous solution are reacted to obtain trioxetane. According to the method, methyl-2, 4-pentanediol is used as a solvent, acetone and 1, 1-dimethyl-3-hydroxybutyl hydroperoxide are used as reactants, the sulfuric acid aqueous solution is used as a catalyst, and the yield and purity of the prepared trioxetane are high by optimizing reaction conditions. A brand-new and efficient synthesis strategy is provided for preparing the trioxetane compound.

Description

Technical Field

[0001] The present invention relates to the technical field of trioxepanes, and particularly to a preparation method of trioxepanes. Background Art

[0002] Trioxepane is a novel oxygen-containing heterocyclic compound and has wide applications in initiators, ignition-improved fuels, etc. Patent CN1204136C discloses novel trioxepane compounds, reporting that compounds such as 1,2,4-trioxepane ( CAS Registry Number 215877-64-8) etc. have broad application prospects in aspects such as the controlled degradation of polypropylene and the polymerization method of high-solid acrylate polymers. Patent CN1234818C discloses the use of trioxepane in ignition-improved fuels, reporting that trioxepanes containing substituents such as isopropyl, isobutyl, pentyl, isopentyl, etc. have good practical applications in ignition-improved fuels and reducing the ignition time of liquefied gas fuels. Currently, there are few reports on patents and literature related to the preparation methods of trioxepane compounds. The present invention aims to use acetone and 1,1-dimethyl-3-hydroxybutyl hydroperoxide as raw materials to prepare trioxepane compounds with high yield and purity. Summary of the Invention

[0003] (1) Technical problems to be solved: The present invention provides a preparation method of trioxepane with high purity and high yield.

[0004] (2) Technical solution: A preparation method of trioxepane: Add 2-methyl-2,4-pentanediol solvent, acetone, and 1,1-dimethyl-3-hydroxybutyl hydroperoxide into a reaction vessel, set the reaction temperature, then dropwise add an aqueous sulfuric acid solution, stir the reaction, and perform extraction after the reaction to obtain trioxepane.

[0005] Preferably, the molar ratio of acetone to 1,1-dimethyl-3-hydroxybutyl hydroperoxide is 1:(1 - 1.2).

[0006] Preferably, the reaction temperature is 0 - 10°C and the reaction time is 0.5 - 3 h.

[0007] Preferably, the mass fraction of the aqueous sulfuric acid solution is 15 - 30%.

[0008] Preferably, during the extraction process, add petroleum ether and water, shake and then let it stand for layering, remove the aqueous phase, extract 3 times, combine the petroleum ether organic phases, dry the petroleum ether organic phases with anhydrous sodium sulfate, filter, then distill the filtrate under reduced pressure, and then separate by silica gel column chromatography, elute with petroleum ether and ethyl acetate solution to obtain trioxepane. The reaction formula is as follows:

[0009]

[0010] Technical effects of the present invention: Using 2-methyl-2,4-pentanediol as a solvent, acetone and 1,1-dimethyl-3-hydroxybutyl hydroperoxide as reactants, and sulfuric acid aqueous solution as a catalyst, by optimizing the reaction conditions, the yield of the prepared trioxepane reaches up to 86.74%, and the purity is relatively high. It provides a new and efficient synthesis strategy for the preparation of trioxepane compounds. Specific embodiments

[0011] Add 100 kg of hydrogen peroxide solution with a mass fraction of 38% to the reaction vessel. At 10°C, while stirring, dropwise add 112 kg of sulfuric acid aqueous solution with a mass fraction of 70%, then add 10 kg of p-toluenesulfonic acid, stir for 10 minutes, and dropwise add 102 kg of 2-methyl-2,4-pentanediol Keep the temperature of the reaction system at 20°C. After adding, raise the temperature to 45°C and react for 3 h. Let it stand for 30 minutes, separate and remove the lower layer liquid. Stir the upper layer liquid and add 150 kg of water. Stir and dropwise add 106 kg of sodium hydroxide solution with a mass fraction of 35%, control the temperature of the reaction system at about 28°C, let it stand for 30 minutes, separate and remove the lower layer liquid. Stir and dropwise add 162 kg of sulfuric acid aqueous solution with a mass fraction of 18% to the upper layer liquid, control the temperature of the reaction system at about 28°C. After dropping, stop stirring, let it stand for 35 minutes, separate and remove the lower layer liquid. Dry the upper layer liquid to obtain 1,1-dimethyl-3-hydroxybutyl hydroperoxide. The structural formula is

[0012]

[0013] The specific embodiments are as follows: Add 70 mL of 2-methyl-2,4-pentanediol solvent, 0.1 mol of acetone, and 0.1 - 0.12 mol of 1,1-dimethyl-3-hydroxybutyl hydroperoxide to the reaction vessel. Set the reaction temperature at 0 - 10°C, then dropwise add 40 mL of sulfuric acid aqueous solution with a mass fraction of 15 - 30%. Stir and react for 0.5 - 3 h. Add petroleum ether and water, shake and let it stand for liquid separation. Remove the aqueous phase, extract 3 times, combine the petroleum ether organic phases, dry with anhydrous sodium sulfate, filter, then distill the filtrate under reduced pressure, and then separate by silica gel column chromatography, elute with petroleum ether and ethyl acetate solution to obtain trioxepane. The structural formula is The theoretical yield is 17.42 g (0.1 mol), and the purity of the product is tested by liquid chromatography. The test results of the yield and purity are shown in the following table.

[0014] Table 1

[0015]

[0016] Table 2

[0017]

[0018] Table 3

[0019]

[0020] Table 4

[0021]

[0022] As can be seen from Tables 1-4, in the present invention, methyl-2,4-pentanediol is used as a solvent, acetone and 1,1-dimethyl-3-hydroxybutyl hydroperoxide are used as reactants, and an aqueous sulfuric acid solution is used as a catalyst. By optimizing the reaction conditions, the ratio of the reactants, and the concentration of the sulfuric acid solution, the yield of the prepared trioxepane reaches up to 86.74%, and the purity is relatively high.

Claims

1. A method for preparing trioxepane, characterized in that, The preparation method is as follows: Add a solvent, acetone, and 1,1-dimethyl-3-hydroxybutyl hydroperoxide into a reaction vessel, set the reaction temperature, then dropwise add an aqueous sulfuric acid solution, stir and react, and perform extraction after the reaction to obtain trioxepane.

2. The preparation method of trioxepane according to claim 1, characterized in that, The solvent is 2-methyl-2,4-pentanediol.

3. The preparation method of trioxepane according to claim 1, characterized in that, The molar ratio of acetone to 1,1-dimethyl-3-hydroxybutyl hydroperoxide is 1:(1 - 1.2).

4. The preparation method of trioxepane according to claim 1, characterized in that, The reaction temperature is 0 - 10 °C, and the reaction time is 0.5 - 3 h.

5. The preparation method of trioxepane according to claim 1, characterized in that, The mass fraction of the aqueous sulfuric acid solution is 15 - 30%.

6. The preparation method of trioxepane according to claim 1, characterized in that, During the extraction process, add petroleum ether and water, shake and then let it stand for stratification, remove the aqueous phase, perform extraction 3 times, combine the petroleum ether organic phases, dry the petroleum ether organic phases with anhydrous sodium sulfate, filter, distill the filtrate under reduced pressure, and then separate by silica gel column chromatography, elute with a petroleum ether and ethyl acetate solution to obtain trioxepane.

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