CN101870688A - Synthesis method of 4-methyl ethyl sulfate - Google Patents
Synthesis method of 4-methyl ethyl sulfate Download PDFInfo
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- CN101870688A CN101870688A CN200910111558A CN200910111558A CN101870688A CN 101870688 A CN101870688 A CN 101870688A CN 200910111558 A CN200910111558 A CN 200910111558A CN 200910111558 A CN200910111558 A CN 200910111558A CN 101870688 A CN101870688 A CN 101870688A
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- methyl ethyl
- ethyl sulfate
- methyl
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- potassium permanganate
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Abstract
The invention relates to a synthesis method of 4-methyl ethyl sulfate, which adopts two steps that: 4-methyl ethylene sulfite is firstly catalyzed and oxidized by sodium hypochlorite solution under the effect of the catalyst, and then the rest 4-methyl ethylene sulfite is oxidized by potassium permanganate and the manganese dioxide therein is removed by a reducing agent. The method has the advantages of high yield, simple post-treatment, no organic solvent and the like.
Description
Technical field
The present invention is the synthetic method of relevant 4-methyl ethyl sulfate, is the two-step synthetic method about the 4-methyl ethyl sulfate in detail.
Background technology
4-methyl ethyl sulfate among the present invention is the compound with following structure:
The 4-methyl ethyl sulfate synthetic method of reporting in the document mainly contains:
1) method of catalyzed oxidation
Be 4-methyl glycol sulfite under the katalysis of ruthenium compound, in the presence of organic solvent, use chlorine bleach liquor's oxidation, then, carry out layering, washing, drying, underpressure distillation, obtain the 4-methyl ethyl sulfate.The shortcoming of this method is to use deleterious organic solvent, and reaction is incomplete, purifies for the underpressure distillation of back and brings difficulty; If thoroughly reaction, will time expand, and owing to be under alkaline condition, hydrolysis reaction will take place in the 4-methyl ethyl sulfate, certainly will influence yield like this.
2) method of potassium permanganate direct oxidation
Be that 4-methyl glycol sulfite is dissolved in the organic solvent, under acidic conditions, use the potassium permanganate direct oxidation, after oxidation finishes, layering, the alkali neutralization, dry, removal solvent is after the method purification of underpressure distillation or recrystallization.This method uses potassium permanganate as oxygenant, produces a large amount of Manganse Dioxide solids, the carrying out that influence is reacted, and aftertreatment is brought unfavorable, be not suitable for suitability for industrialized production.
Summary of the invention
The invention provides the operational path that an advantages of simplicity and high efficiency is suitable for suitability for industrialized production 4-methyl glycol sulfite.
The two-step synthetic method of 4-methyl ethyl sulfate: 4-methyl glycol sulfite carries out catalyzed oxidation with the chlorine bleach liquor earlier under the effect of catalyzer, then remaining 4-methyl glycol sulfite is with the two-step synthetic method of potassium permanganate oxidation, and this method has characteristics such as productive rate height, aftertreatment are simple.
Find by test, the catalytic oxidation of 4-methyl glycol sulfite can carry out in the aqueous solution, promptly under the katalysis of ruthenium compound, make solvent with water, under suitable stirring velocity, make 4-methyl glycol sulfite to be scattered in well in the water, add the chlorine bleach liquor and carry out oxidation, generate the 4-methyl ethyl sulfate.With water is reaction medium, make production process environmental protection more, and cost is lower.
Reaction times can be controlled at 20～50 minutes, temperature of reaction is controlled between 0～10 ℃, because reaction is to carry out under alkaline condition, may cause 4-methyl ethyl sulfate generation hydrolysis reaction, so high temperature or prolongation reaction times are all unfavorable to the yield of 4-methyl ethyl sulfate.
Above-mentioned reacted product is told organic phase, uses efficient liquid phase chromatographic analysis, finds except product 4-methyl ethyl sulfate, also has the intact raw material 4-methyl glycol sulfite of unreacted, and its content is about 5%.
The organic phase of telling is used potassium permanganate oxidation, makes 4-methyl glycol sulfite all be converted into the 4-methyl ethyl sulfate.
Potassium permanganate oxidation is reaction medium with water.
Potassium permanganate oxidation carries out under the tart condition, and potassium permanganate adopts the solid mode, adds in batches.Potassium permanganate is excessive slightly, i.e. it is constant that reaction finishes the color of back system.
The Manganse Dioxide solid that potassium permanganate oxidation generates adopts to add alkali metal sulfite or the removal of basic metal bisulfite reaction.Alkali metal sulfite comprises S-WAT and potassium sulfite, and the basic metal hydrosulphite comprises sodium bisulfite and Potassium hydrogen sulfite.
The method that Manganse Dioxide is taked to react removal can be exempted production upward owing to filter the trouble that Manganse Dioxide brings.
Product layering, alkali neutralization, drying, decompression dewater, and get product 4-methyl ethyl sulfate, use efficient liquid phase chromatographic analysis, and the 4-methyl ethyl sulfate gets content more than 99.5%.
Embodiment
The invention will be further described below by specific embodiment, but the present invention not only is defined in these examples.
Embodiment 1:
4-methyl glycol sulfite 366 (3mol) gram, 500 milliliters of distilled water, ruthenium trichloride 0.1 gram, stir, be cooled to 5 ℃, begin to add the chlorine bleach liquor, the reaction times is 30 minutes, reaction finishes the back standing demix, tell organic layer, organic layer distilled water wash twice, product is through liquid-phase chromatographic analysis, the result shows: 4-methyl ethyl sulfate content 93.7743%, 4-methyl glycol sulfite content 6.1683%.
Above-mentioned organic phase is scattered in 500 ml distilled waters, stirs, and adds solid potassium permanganate at normal temperatures in batches, is not changing until the color of system, has gray Manganse Dioxide solid to generate.Then add S-WAT, stirring reaction, the Manganse Dioxide solids disappeared, solution is the clarification shape.Standing demix is told organic phase, and organic phase neutralizes with distilled water wash twice, alkali, more once with distilled water wash, drying, decompression further dewaters, and promptly gets 4-methyl ethyl sulfate finished product.Product is through liquid-phase chromatographic analysis, and the result shows: 4-methyl ethyl sulfate content 99.85%, 4-methyl glycol sulfite content 0.12%.
Embodiment 2:
4-methyl glycol sulfite 244 (2mol) gram, 500 milliliters of distilled water, ruthenium trichloride 0.1 gram, stir, be cooled to 5 ℃, begin to add the chlorine bleach liquor, the reaction times is 30 minutes, reaction finishes the back standing demix, tell organic layer, organic layer distilled water wash twice, product is through liquid-phase chromatographic analysis, the result shows: 4-methyl ethyl sulfate content 93.67%, 4-methyl glycol sulfite content 6.28%.
Above-mentioned organic phase is scattered in 500 ml distilled waters, stirs, and adds solid potassium permanganate at normal temperatures in batches, is not changing until the color of system, has gray Manganse Dioxide solid to generate.Then add S-WAT, stirring reaction, the Manganse Dioxide solids disappeared, solution is the clarification shape.Standing demix is told organic phase, and organic phase neutralizes with distilled water wash twice, alkali, more once with distilled water wash, drying, decompression further dewaters, and promptly gets 4-methyl ethyl sulfate finished product.Product is through liquid-phase chromatographic analysis, and the result shows: 4-methyl ethyl sulfate content 99.95%, 4-methyl glycol sulfite content 0.04%.
Embodiment 3:
12.2 kilograms of 4-methyl glycol sulfites, 35 kilograms of distilled water, ruthenium trichloride 10 grams, stir, be cooled to 5 ℃, begin to add the chlorine bleach liquor, the reaction times is 50 minutes, reaction finishes the back standing demix, tell organic layer, organic layer distilled water wash twice, product is through liquid-phase chromatographic analysis, the result shows: 4-methyl ethyl sulfate content 95.28%, 4-methyl glycol sulfite content 4.70%.
Above-mentioned organic phase is scattered in 40 kilograms of distilled water, stirs, and adds solid potassium permanganate at normal temperatures in batches, is not changing until the color of system, has gray Manganse Dioxide solid to generate.Then add sodium bisulfite, stirring reaction, the Manganse Dioxide solids disappeared, solution is the clarification shape.Standing demix is told organic phase, and organic phase neutralizes with distilled water wash twice, alkali, more once with distilled water wash, drying, decompression further dewaters, and promptly gets 4-methyl ethyl sulfate finished product.Product is through liquid-phase chromatographic analysis, and the result shows: 4-methyl ethyl sulfate content 99.92%, 4-methyl glycol sulfite content 0.07%.
Claims (8)
1. the synthetic method of a 4-methyl ethyl sulfate comprises the steps: 4-methyl glycol sulfite elder generation catalyzed oxidation, and then potassium permanganate oxidation, reductive agent are removed Manganse Dioxide.
2. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: the catalyzer that uses in the catalyzed oxidation step of described 4-methyl glycol sulfite is a ruthenium trichloride.
3. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: the reaction medium that uses in the catalyzed oxidation step of described 4-methyl glycol sulfite is water.
4. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: the oxygenant that uses in the catalyzed oxidation step of described 4-methyl glycol sulfite is the chlorine bleach liquor.
5. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: described potassium permanganate is solid-state or the solution form.
6. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: described potassium permanganate is solid-state.
7. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: the reaction medium that uses in the potassium permanganate oxidation step of described 4-methyl glycol sulfite is water.
8. the synthetic method of 4-methyl ethyl sulfate as claimed in claim 1 is characterized in that: described reductive agent is selected from sodium bisulfite, S-WAT, Potassium hydrogen sulfite or potassium sulfite.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910111558A CN101870688A (en) | 2009-04-24 | 2009-04-24 | Synthesis method of 4-methyl ethyl sulfate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910111558A CN101870688A (en) | 2009-04-24 | 2009-04-24 | Synthesis method of 4-methyl ethyl sulfate |
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| CN101870688A true CN101870688A (en) | 2010-10-27 |
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| CN200910111558A Pending CN101870688A (en) | 2009-04-24 | 2009-04-24 | Synthesis method of 4-methyl ethyl sulfate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| CN111825652A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for preparing vinyl sulfate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037510A (en) * | 1988-03-08 | 1989-11-29 | 罗纳-布朗克制药公司 | The preparation method of cyclic sulfates |
-
2009
- 2009-04-24 CN CN200910111558A patent/CN101870688A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037510A (en) * | 1988-03-08 | 1989-11-29 | 罗纳-布朗克制药公司 | The preparation method of cyclic sulfates |
Non-Patent Citations (1)
| Title |
|---|
| DAVID LLPKLN ET AL: "Cyclic Sulfite and Sulfate Esters of Polymethylene Glycols", 《JOURNAL OF CHEMICAL AND ENGINEERING DATA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| CN111825652A (en) * | 2019-04-17 | 2020-10-27 | 江苏长园华盛新能源材料有限公司 | Method for preparing vinyl sulfate |
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Application publication date: 20101027 |