CN110156723B - Synthesis method of 1, 2-epoxy compound - Google Patents
Synthesis method of 1, 2-epoxy compound Download PDFInfo
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- CN110156723B CN110156723B CN201810151202.4A CN201810151202A CN110156723B CN 110156723 B CN110156723 B CN 110156723B CN 201810151202 A CN201810151202 A CN 201810151202A CN 110156723 B CN110156723 B CN 110156723B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
A process for synthesizing 1, 2-epoxy compound features that 1, 2-cyclic carbonate is used as substrate and under the action of catalyst, the 1, 2-epoxy compound is generated by decomposing. The synthesis method of the 1, 2-epoxy compound has the advantages of simple process flow, high product yield, lower cost, safe process and industrial prospect.
Description
Technical Field
The invention belongs to the technical field of epoxy compound synthesis, and particularly relates to a synthesis method of a 1, 2-epoxy compound.
Background
Epoxy compounds, also known as olefin oxides, are important organic chemical raw materials and have wide application. In addition to the formation of polyethers, they can be reacted with compounds containing active hydrogen atoms. The reactant of epoxy compound and boric acid can be used for producing surfactant such as nonionic emulsifier, demulsifier, etc. from mineral oil and epoxy compound copolymer. The epoxy compound can be used as a specific acid scavenger for chlorinated hydrocarbon solvents such as trichloroethylene, and has wide application in the aspects of medicines, agricultural chemicals and the like.
Currently, the production routes of epoxy compounds include chlorohydrin processes, direct oxidation processes, and indirect oxidation processes. The production of epoxy compounds by a chlorohydrination method mainly comprises two steps: the first step is chlorohydrination, which requires a large amount of fresh water; the second step is saponification, i.e. the chlorohydrin produced in the first step is reacted with slaked lime. The process for producing epoxy compounds by the chlorohydrination method has the characteristics of short flow, mature process, good selectivity, higher yield, low requirement on the specification of olefin, less investment and relatively safe production. But the chlorohydrin method production process has the defects of large waste water generation amount, serious equipment corrosion, poor environmental friendliness and the like. The direct oxidation method is classified into a cumene oxidation method and a direct oxidation of hydrogen peroxide. The cumene oxidation process employs a fixed bed reactor with a titanium-based catalyst, and cumene hydroperoxide is used as an oxidant to epoxidize olefins to obtain epoxy compounds. The hydrogen peroxide is directly oxidized by taking hydrogen peroxide as an oxidant and oxidizing olefin by using a tungsten-containing catalyst, and the tungsten-containing catalyst and the hydrogen peroxide are in a soluble state when used together. When the hydrogen peroxide is used up, tungsten is precipitated and is easy to separate out, and the catalyst can be recycled. The direct oxidation method has complex process control and hydrogen peroxide is easy to explode. Since the development of the indirect oxidation process in the 70 s, people have attracted great attention and developed rapidly, but the requirement on the purity of raw olefin is higher.
In view of the foregoing, there is a need for a novel method for synthesizing 1, 2-epoxy compounds to solve the problems of the prior art.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a method for synthesizing a 1, 2-epoxy compound that solves at least one of the above problems.
The invention is realized by the following technical scheme:
the invention provides a method for synthesizing a 1, 2-epoxy compound, which comprises the following steps:
adding 1, 2-cyclic carbonate, a solvent and a catalyst into a reaction vessel, and heating to generate a 1, 2-epoxy compound, wherein the reaction formula is as follows:
wherein: r is C1-C10Alkyl group of (1).
Preferably, the catalyst structure is as follows:
or
Wherein R is1Is C1-C10Alkyl of (A), R2, R3Is methyl, X is bromide ion, chloride ion, iodide ion, tetrafluoroborate ion, hexafluorophosphateOne of the ions.
Preferably, the mass ratio of the 1, 2-cyclic carbonate to the catalyst is 5-1000: 1.
Preferably, the solvent is one or a combination of more than two of liquid paraffin, n-dodecane, n-tetradecane, n-octadecane and pine oil.
Preferably, an auxiliary agent is further added in the reaction, and the auxiliary agent is one or a combination of any two of potassium carbonate, sodium carbonate, magnesium silicate, potassium silicate, sodium carbonate, calcium carbonate, zinc nitrate, barium nitrate, sodium nitrate, potassium nitrate, cobalt chloride, zinc bromide, bismuth nitrate, ferric chloride, zinc acetate, manganese acetate, calcium acetate, copper chloride, sodium chloride and potassium chloride.
Preferably, the molar ratio of the auxiliary agent to the catalyst is 0-50: 1.
Preferably, the reaction pressure is 0.01 to 0.3 MPa.
Preferably, the reaction temperature is 100 to 240 ℃.
According to the technical scheme, the synthesis method of the 1, 2-epoxy compound has the following beneficial effects: the method has the advantages of simple process flow, high product yield, lower cost, safe process and industrial prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The invention discloses a method for synthesizing a 1, 2-epoxy compound, which takes 1, 2-cyclic carbonate as a substrate and decomposes the 1, 2-epoxy compound under the action of a catalyst. The synthesis method of the 1, 2-epoxy compound has the advantages of simple process flow, high product yield, lower cost, safe process and industrial prospect.
The invention specifically provides a method for synthesizing a 1, 2-epoxy compound, which comprises the following steps:
adding 1, 2-cyclic carbonate, a solvent and a catalyst into a reaction vessel, and heating to generate a 1, 2-epoxy compound, wherein the reaction formula is as follows:
wherein: r is C1-C10Alkyl group of (1).
The catalyst structure is as follows:
or
Wherein R is1Is C1-C10Alkyl of R2、R3Is methyl, and X is one of bromide ion, chloride ion, iodide ion, tetrafluoroborate ion and hexafluorophosphate ion.
The mass ratio of the 1, 2-cyclic carbonate to the catalyst is 5-1000: 1.
The solvent is one or the combination of more than two of liquid paraffin, n-dodecane, n-tetradecane, n-octadecane and pine oil.
And an auxiliary agent is also added in the reaction, and the auxiliary agent is one or the combination of any two of potassium carbonate, sodium carbonate, magnesium silicate, potassium silicate, sodium carbonate, calcium carbonate, zinc nitrate, barium nitrate, sodium nitrate, potassium nitrate, cobalt chloride, zinc bromide, bismuth nitrate, ferric chloride, zinc acetate, manganese acetate, calcium acetate, copper chloride, sodium chloride and potassium chloride.
The molar ratio of the auxiliary agent to the catalyst is 0-50: 1.
The reaction pressure is 0.01-0.3 MPa.
The reaction temperature is 100-240 ℃.
The following will explain the synthesis method of the 1, 2-epoxy compound provided by the present invention in detail with reference to the specific examples.
Example 1
A100 ml three-necked flask is filled with 18.4g of butylene carbonate, 30g of liquid paraffin, 2.5g of 1-ethyl-3-vinylimidazole iodide and 0.2g of magnesium silicate, stirred and reacted for 3 hours at the temperature of 120 ℃ under the pressure of 0.05MPa, an appropriate amount of product is taken after cooling, an internal standard substance is added, and a prepared standard solution is analyzed by gas chromatography to obtain the composition.
Example 2
18.8g of butylene carbonate, 30g of liquid paraffin, 2.5g of N-butylpyridine bromide and 0.3g of sodium nitrate are put into a 100ml three-necked bottle, stirred and reacted for 3 hours at the temperature of 120 ℃ under the pressure of 0.03MPa, an appropriate amount of product is taken after cooling, an internal standard substance is added, and a prepared standard solution is analyzed by gas chromatography to obtain the composition.
Example 3
18.3g of butylene carbonate, 30g of pine oil, 2g of 1-aminopropylamine-3-methylimidazole chloride and 0.3g of magnesium silicate are put into a 100ml three-neck flask, stirred and reacted for 2 hours at the temperature of 110 ℃ under the pressure of 0.05MPa, an appropriate amount of product is taken after cooling, an internal standard substance is added, and a prepared standard solution is analyzed by gas chromatography to obtain the composition.
Example 4
18.7g of butylene carbonate, 30g of n-octadecane, 0.15 g of hexadecylpyridine tetrafluoroborate and 0.3g of sodium acetate are put into a 100ml three-necked bottle, stirred and reacted for 2 hours at the temperature of 120 ℃ under the pressure of 0.05MPa, an appropriate amount of product is taken after cooling, an internal standard substance is added, and the prepared standard solution is analyzed by gas chromatography to obtain the composition.
Example 5
20.4g of butylene carbonate, 30g of liquid paraffin, 0.3g of 1-ethyl-3-vinylimidazole iodide and 0.2g of calcium nitrate are put into a 100ml three-neck flask, stirred and reacted for 3 hours at the temperature of 110 ℃ under the pressure of 0.05MPa, an appropriate amount of product is taken after cooling, an internal standard substance is added, and a prepared standard solution is analyzed by gas chromatography to obtain the composition.
Example 6
18g of butylene carbonate, 30g of liquid paraffin, 2.5g of 1-hexyl-3-methylimidazolium tetrafluoroborate and 0.5g of aluminum silicate are put into a 100ml three-neck flask, stirred and reacted for 3 hours at the temperature of 105 ℃ under the pressure of 0.05MPa, an appropriate amount of product is taken after cooling, an internal standard substance is added, and a prepared standard solution is analyzed by gas chromatography to obtain the composition.
Comparative example
Injecting a mixed solution of toluene, tributyl phosphate and 30 mass percent hydrogen peroxide in a molar ratio of 1: 0.5: 0.8 into a water separator, decompressing and dehydrating to obtain a working solution, charging 1-butene into the working solution, reacting for 2 hours at 50 ℃ and 0.1Mpa in the presence of a catalyst of silicotungstic heteropoly acid salt, and catalytically oxidizing the 1-butene to generate the 1, 2-epoxybutane. Wherein, the mol ratio of 1-butene to 30 percent hydrogen peroxide is 2: 1, and the mass concentration of the catalyst is 1 percent (relative to the working solution). The product obtained was chromatographed with a selectivity to 1, 2-epoxybutane of 99.2% and a yield of 1, 2-epoxybutane to hydrogen peroxide of 95.6%.
The test results of examples 1-6 and comparative example are shown in table 1.
TABLE 1
In conclusion, the synthesis method of the 1, 2-epoxy compound has the advantages of simple process flow, lower cost, safe process and industrial prospect, and the selectivity of the 1, 2-epoxy compound is over 99.1 percent.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A method for synthesizing a 1, 2-epoxy compound is characterized by comprising the following steps:
adding 1, 2-cyclic carbonate, a solvent and a catalyst into a reaction vessel, and heating to generate a 1, 2-epoxy compound, wherein the reaction formula is as follows:
wherein: r is C1-C10Alkyl groups of (a);
the catalyst structure is as follows:
wherein R is1Is C1～10Alkyl of R2、R3Is methyl, and X is one of bromide ion, chloride ion, iodide ion, tetrafluoroborate ion and hexafluorophosphate ion;
the solvent is one or the combination of more than two of liquid paraffin, n-dodecane, n-tetradecane, n-octadecane and pine oil;
and an auxiliary agent is also added in the reaction, wherein the auxiliary agent is one or the combination of any two of magnesium silicate, calcium carbonate, sodium nitrate and potassium nitrate.
2. The method for synthesizing the 1, 2-epoxy compound according to claim 1, wherein the mass ratio of the 1, 2-cyclic carbonate to the catalyst is 5 to 1000: 1.
3. the method for synthesizing a 1, 2-epoxy compound according to claim 1, wherein the reaction pressure is 0.01 to 0.3 MPa.
4. The method for synthesizing a 1, 2-epoxy compound according to claim 1, wherein the reaction temperature is 100 to 240 ℃.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108659A (en) * | 1984-10-25 | 1986-07-16 | 哈尔康·斯迪集团公司 | Produce the method for alkylene oxide by alkylene carbonate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108659A (en) * | 1984-10-25 | 1986-07-16 | 哈尔康·斯迪集团公司 | Produce the method for alkylene oxide by alkylene carbonate |
Non-Patent Citations (1)
| Title |
|---|
| Ionic-liquid-catalyzed decarboxylation of glycerol carbonate to glycidol;Ji Sik Choi Et al.,;《Journal of Catalysis》;20121117;第297卷;摘要，第249页 scheme 1和左栏2.2，第250页表3，第253页表5和倒数第1段，第253页表4，第255页左栏第3段，第254页左栏第1段 * |
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