CN101045701B - Preparation method of thioacetic acid potassium - Google Patents
Preparation method of thioacetic acid potassium Download PDFInfo
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- CN101045701B CN101045701B CN200610050064A CN200610050064A CN101045701B CN 101045701 B CN101045701 B CN 101045701B CN 200610050064 A CN200610050064 A CN 200610050064A CN 200610050064 A CN200610050064 A CN 200610050064A CN 101045701 B CN101045701 B CN 101045701B
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- thioacetic acid
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Abstract
This invention relates to a preparation method of thioacetic acid kalium. In existing method, hydrogen sulfide does not has plenary reaction, so utilization ratio is low, result in hydrogen sulfide dosage is large, cost high and three waste are too many, especially in exhaust gas, has serious pollution to environment. This invention uses ketene dimer and sodium polysulfide to inlet hydrogen sulfide gas to absolute alcohol solvent, add antioxidant, after completeness thio reaction, rectify to gain thioacetic acid and absolute alcohol solvent; add thioacetic acid or its hybrid with absolute alcohol solvent by distribution droplets to absolute alcohol solvent of potassium hydroxide, whipping, decompress and reclaim absolute alcohol solvent, and the precipitable white crystal is thioacetic acid kalium.
Description
Technical field
The invention belongs to organic chemistry filed, specifically a kind of preparation method of thioacetic acid potassium.
Background technology
Thioacetic acid potassium is an important sulfo-reagent in the organic compound reaction, and purposes is very extensive, Organic.Syntheses, and CV4,928 have set forth the usefulness acetic anhydride feeds needed H under the condition of small amounts of sodium hydroxide
2S, flash distillation then, thioacetic acid and acetate are separated with sodium salt, rectifying separation goes out thioacetic acid again, productive rate is 72～76%, also useful acetate and five phosphorus oxide in the document, Acetyl Chloride 98Min. and potassium thiocyanate sulphur, the hydrolysis of diacetyl sulphur, acetic anhydride and hydrogen sulfide react at acidic medium or under triethylamine and pyridine, and Acetyl Chloride 98Min. and hydrogen sulfide reacts in the presence of aluminum chloride, and acetic anhydride and hydrogen sulfide join simultaneously in the ammonia and prepares U.S.BUR.Mines.Rept.Intest.No.6519 with 80% yield based on acetic anhydride, 6pp (1964) etc., all the other mass yields are all not high except that acetic anhydride-hydrogen sulfide method.
WO2004/078706 mentions with 1-butanols and triethylamine and mixes feeding hydrogen sulfide recently, after adding ketene dimer again, distillation makes thioacetic acid with 65% yield, or do not distill, directly add 45% potassium hydroxide solution, return and separate out thioacetic acid potassium, cold filtration after heating up in a steamer, with 1-butanols washing, oven dry yield only 63%.In above-mentioned reaction, because its used 1-butanols is aqueous alcoholic solvent (being generally 70% concentration), the yield of thioacetic acid potassium is low and repetitive operation is difficult, and because hydrogen sulfide does not obtain reacting more fully in this reaction, utilization ratio is lower, causes the hydrogen sulfide consumption big, the cost height, the three wastes are also a lot, and particularly waste gas causes more serious pollution to environment.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes above-mentioned prior art, and the preparation method of a kind of yield height, cost is low, exhaust emission is few thioacetic acid potassium is provided.
For this reason, the present invention adopts following technical scheme: airtight feeding hydrogen sulfide, adding antioxidant in the absolute alcohol kind solvent with ketene dimer and sodium polysulphide, and after sulfo-was complete, rectifying made thioacetic acid and absolute alcohol kind solvent; The mixture of thioacetic acid or itself and absolute alcohol kind solvent is added drop-wise in the absolute alcohol kind solvent of potassium hydroxide, drips and finish, stir, reclaim under reduced pressure absolute alcohol kind solvent, the white crystal of separating out are thioacetic acid potassium.Key of the present invention is using of antioxidant and to the control of moisture content in the solvent, require anhydrous, so adopted the absolute alcohol kind solvent in the reaction.Sodium polysulphide among the present invention had been the basic catalyst of this reaction both, and thio reaction is carried out fully, simultaneously also for reaction provides sulfonium ion, had reduced the consumption of hydrogen sulfide significantly, and the utilization ratio height of hydrogen sulfide in the reaction; Antioxidant is the stablizer of reaction.Yield height of the present invention (reaching more than 90%), exhaust emission is few, and production cost is low.
The preparation method of described thioacetic acid potassium, the mol ratio of thioacetic acid and potassium hydroxide be preferably 1: 1～and 2, the volume ratio of potassium hydroxide and absolute alcohol kind solvent is preferably 1: 3～and 10.
The preparation method of described thioacetic acid potassium, the absolute alcohol kind solvent is preferably Virahol, isopropylcarbinol, propyl carbinol or primary isoamyl alcohol, and it is convenient to reclaim, and reduces solvent cost significantly.
The preparation method of described thioacetic acid potassium, sodium polysulphide is preferably Sodium sulphate anhydrous, 99min or xln sodium sulphite.
The preparation method of described thioacetic acid potassium, antioxidant is butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA) or tertiary butylated hydroquinone (TBHQ), its consumption is the 0.1-1% of ketene dimer weight, if it is almost quantitative to make reaction yield bring up to. do not add, reaction yield is 40-50%. only
The preparation method of described thioacetic acid potassium also is added with antioxidant in the absolute alcohol kind solvent of potassium hydroxide, and its consumption is the 0.1-1% of thioacetic acid weight, further improves reaction yield.
The preparation method of described thioacetic acid potassium, the temperature during dropping are at 0～5 ℃, and the temperature during stirring is controlled at below 60 ℃, the simple and control easily of reaction conditions.
The preparation method of described thioacetic acid potassium, the level of response of sulfo-detects with gas chromatograph-mass spectrometer, and the content of ketene dimer finishes thio reaction when following 1%.
Reaction conditions gentleness of the present invention, easy and simple to handle; React completely, the hydrogen sulfide consumption is few, and is low in the pollution of the environment, yield height (reaching more than 90%), and cost is low.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1 thiacetic preparation
In the withstand voltage still of 1000ml, drop into sodium polysulphide 4.2g, ketene dimer 168.2g (2.0mol), butylated hydroxytoluene (BHT) 1.0g is blended in the isopropylcarbinol 168ml solution, the chilled brine cooling feeds hydrogen sulfide to 0.1Mpa, stirs, pressurize reaction 2 hours, controlled temperature is at 0～5 ℃, and it is complete at the sulfo-of explanation below 1% that sampling GC analyzes ketene dimer, and pressure release is to another isomorphic response still, to normal pressure, forward in the 500ml batch distillation bottle, add dichloro-acetate 0.5ml as stablizer, reclaim under reduced pressure, get the mixture 420g of thioacetic acid and isopropylcarbinol, it is 70% that GC analyzes thioacetic acid content.The cut that the atmospheric distillation collection is 89～92 ℃ gets thioacetic acid 273.6g (3.6mol), and yield is 90%.It is 99% that GC analyzes content.
The preparation of embodiment 2 thioacetic acid potassiums
Add potassium hydroxide 168.2g at the 2000ml flask, butylated hydroxytoluene (BHT) 0.2g and dry isobutanol 1500ml stirring and dissolving, be as cold as about 0 ℃ with chilled brine, drip the thioacetic acid of embodiment 1 recovery and the mixture 260g of isopropylcarbinol, contain sulfo-acetate 182g (2.4mol), the control dropping time is 1.5 hours, drip and finish, stirring at room 1 hour, controlled temperature is below 60 ℃, the reclaim under reduced pressure isopropylcarbinol, to separating out white crystal, freezing to 0 ℃ of filtration, wash with isopropylcarbinol, dry white crystals 251.7g, yield is up to 92%.
The preparation of embodiment 3 thioacetic acid potassiums
Add potassium hydroxide 40g at the 1000ml flask, butylated hydroxy anisole (BHA) 0.5g and anhydrous normal butyl alcohol 500ml stirring and dissolving are as cold as about 5 ℃ with chilled brine, drip the thioacetic acid 50g (0.658mol) of embodiment 1 preparation, the control dropping time is 1 hour, drips and finishes, stirring at room 1 hour, controlled temperature is below 50 ℃, and the reclaim under reduced pressure propyl carbinol is to separating out white crystal, freezing to 0 ℃ of filtration, with propyl carbinol washing, dry white powdery 72g, based on thioacetic acid yield 96%.
The preparation of embodiment 4 thioacetic acid potassiums
Add potassium hydroxide 40g at the 1000ml flask, tertiary butylated hydroquinone (TBHQ) 0.25g and anhydrous isopropyl alcohol 500ml stirring and dissolving are as cold as about 5 ℃ with chilled brine, drip the thioacetic acid 50g (0.658mol) of embodiment 1 preparation, the control dropping time is 1 hour, drips and finishes, stirring at room 1 hour, controlled temperature is below 50 ℃, and the reclaim under reduced pressure Virahol is to separating out white crystal, freezing to 0 ℃ of filtration, use washed with isopropyl alcohol, dry white powdery 70.5g, based on thioacetic acid yield 94%.
The preparation of embodiment 5 thioacetic acid potassiums
Add potassium hydroxide 150g, tertiary butylated hydroquinone (TBHQ) 1.8g and anhydrous primary isoamyl alcohol 1500ml, stirring and dissolving at the 2000ml flask, be as cold as about 5 ℃ with chilled brine, drip the thioacetic acid 184g (2.42mol) of embodiment 1 preparation, the control dropping time is 1.5 hours, drip and finish, stirring at room 1 hour, controlled temperature is below 60 ℃, the reclaim under reduced pressure primary isoamyl alcohol, to separating out white crystal, freezing to 0 ℃ of filtration, wash with primary isoamyl alcohol, dry white crystals 205g, yield is up to 90%.
The invention is not restricted to the foregoing description, the foregoing description is a preferred embodiment.
Claims (7)
1. the preparation method of thioacetic acid potassium, its step is as follows: with ketene dimer and sodium polysulphide in the absolute alcohol kind solvent airtight feeding hydrogen sulfide, add antioxidant, sulfo-fully after, rectifying makes thioacetic acid and absolute alcohol kind solvent; The mixture of thioacetic acid or itself and absolute alcohol kind solvent is added drop-wise in the absolute alcohol kind solvent of potassium hydroxide, drips and finish, stir, reclaim under reduced pressure absolute alcohol kind solvent, the white crystal of separating out are thioacetic acid potassium; Described antioxidant is butylated hydroxytoluene, butylated hydroxy anisole or tertiary butylated hydroquinone.
2. the preparation method of thioacetic acid potassium according to claim 1, the mol ratio that it is characterized in that thioacetic acid and potassium hydroxide is 1: 1～2, the volume ratio of potassium hydroxide and absolute alcohol kind solvent is 1: 3～10.
3. the preparation method of thioacetic acid potassium according to claim 1 and 2 is characterized in that described absolute alcohol kind solvent is Virahol, isopropylcarbinol, propyl carbinol or primary isoamyl alcohol.
4. the preparation method of thioacetic acid potassium according to claim 3, the consumption that it is characterized in that described antioxidant is the 0.1-1% of ketene dimer weight.
5. the preparation method of thioacetic acid potassium according to claim 4 is characterized in that also being added with antioxidant in the absolute alcohol kind solvent of potassium hydroxide, and its consumption is the 0.1-1% of thioacetic acid weight.
6. the preparation method of thioacetic acid potassium according to claim 5, the temperature when it is characterized in that dripping is at 0～5 ℃, and the temperature during stirring is controlled at below 60 ℃.
7. the preparation method of thioacetic acid potassium according to claim 6 is characterized in that the level of response of sulfo-detects with gas chromatograph-mass spectrometer, and the content of ketene dimer finishes thio reaction when following 1%.
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| CN200610050064A CN101045701B (en) | 2006-03-27 | 2006-03-27 | Preparation method of thioacetic acid potassium |
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| CN200610050064A CN101045701B (en) | 2006-03-27 | 2006-03-27 | Preparation method of thioacetic acid potassium |
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| CN101045701B true CN101045701B (en) | 2010-05-12 |
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| CN106831513A (en) * | 2017-01-06 | 2017-06-13 | 绍兴市上虞区耕创化工技术服务部 | The preparation method of thioacetic acid potassium |
| CN111302994A (en) * | 2020-04-14 | 2020-06-19 | 陶陈丁 | Novel preparation method of potassium thioacetate |
| CN111960979A (en) * | 2020-08-14 | 2020-11-20 | 江西天新药业股份有限公司 | Preparation method of sodium thioacetate and method for preparing thiolactone by using sodium thioacetate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078706A1 (en) * | 2003-03-03 | 2004-09-16 | Lonza Ag | Method for the production of a thioacetic acid and salts thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078706A1 (en) * | 2003-03-03 | 2004-09-16 | Lonza Ag | Method for the production of a thioacetic acid and salts thereof |
Non-Patent Citations (2)
| Title |
|---|
| 邓燕青等.硫代乙酸的合成.湖北化工 6.1998,(6),全文. |
| 邓燕青等.硫代乙酸的合成.湖北化工 6.1998,(6),全文. * |
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