CN102304133A - Method for preparing (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate and salt of (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid - Google Patents
Method for preparing (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate and salt of (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid Download PDFInfo
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Abstract
The invention discloses a method for preparing (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate and salt of (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid and relates to the field of chemical synthesis. In the method, acetone and 2-keto-l-gulonic acid are taken as initial raw materials and fuming sulphuric acid is taken as a catalyst; and the method comprises the following steps of: cooling the acetone, dripping the fuming sulphuric acid, controlling the dripping speed of the fuming sulphuric acid, adding the 2-keto-l-gulonic acid, and heating until complete dissolution; performing cooling conversion on (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid-containing reaction liquid, dripping the reaction liquid into 10 to 20 percent aqueous alkali for neutralization, cooling the alkali neutralized liquid, filtering to remove salt, washing with acetone, and mixing filtrate; cooling residual liquid obtained after the acetone is recycled, dripping hydrochloric acid with stirring, filtering, and washing with cold water to obtain a wet product of (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate for later use; dissolving the obtained (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate in which the molar ratio of acid to alkali is 1 to 1 in an alkaline solution, evaporating water, performing vacuum drying to obtain the salt of the (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid. In the preparation method, only one organic solvent, namely the acetone is used, the operation and solvent recycling are simplified, the cost is reduced, and the industrial feasibility is high.
Description
Technical field
The present invention relates to the preparation method of ancient imperial sour monohydrate of diketone in the field of chemical synthesis and the ancient imperial hydrochlorate of diketone thereof.
Background technology
Ancient imperial acid of diketone and salt thereof are because its particular structure is widely used in industry and agroforestry field.Be applied in the production of vitamin C as ascorbic intermediate at first; Use as resolving agent in recent years, can resolving chiral aminated compounds and some DL type amino acid; Be applied on the other hand chirality synthetic in, induce the generation of a corresponding body; Especially application is more extensive in the agroforestry field, can improve the quality and the output of vegetables, fruit and strengthen the vitality of planting grass planting as plant-growth regulator.
Ancient imperial acid of diketone and salt preparation method thereof are found by the Reichstein (U.S.Pat.No.2301811) of Germany at first; With the L-sorbose is the synthesis method of raw material; At first use the acetone ketonize; The ketonize after product is with oxidations such as clorox/single nickel salts; Acidifying obtains product acid again, can obtain corresponding salt with alkali reaction.Diacetone-l-sorbose in preparation needs 60 ℃ benzene continuous extraction just can obtain high-quality product five times; It is thus clear that this method has not all met working condition from environmental protection, energy-saving and emission-reduction, raw materials cost etc.
Ancient imperial acid can be generated by biological fermentation process in view of 2-ketone group-L-, and exploitation 2-ketone group-L-Gu dragon acid is a kind of megatrend for the synthesis method of raw material, but reports seldom with the synthesis method that the ancient imperial acid of 2-ketone group-L-is raw material; Kwiatkotski has reported a kind of method (US6239293 of the ancient dragon acid of synthetic diacetone under sulfuric acid catalysis; US5688971) use in the reaction a large amount of 2,2-Propanal dimethyl acetal, product extracted in toluene.Because 2, the higher and large usage quantity of 2-Propanal dimethyl acetal price causes cost higher and operation is loaded down with trivial details.Therefore, the preparation method who develops ancient imperial sour monohydrate of a kind of diketone and the ancient imperial hydrochlorate of diketone thereof is the new problem that needs to be resolved hurrily always.
Summary of the invention:
The object of the present invention is to provide a kind of is the preparation method of ancient imperial sour monohydrate of the synthetic diketone of raw material and the ancient imperial hydrochlorate of diketone thereof with the ancient imperial acid of 2-ketone group-L-; This method is in acetone solvent; Through oleum catalysis and the ancient imperial sour monohydrate of the synthetic diketone of dehydration; Again the reaction in the alkaline aqueous solution of this compound dissolution is obtained the ancient imperial hydrochlorate of diketone; In preparation method of the present invention, only use a kind of organic solvent-acetone; Simplified the recovery of operation and solvent; Reduced cost, the industrialization feasibility is strong.
The objective of the invention is to realize like this: the preparation method of the ancient imperial sour monohydrate of diketone is a starting raw material with acetone, the ancient imperial acid of 2-ketone group-L-, and oleum is a catalyzer, comprises the steps:
(1) with acetone cooling, drip oleum, control oleum rate of addition, solution temperature be-10-5 ℃, solution optimum temps-5-0 ℃;
(2) add the ancient dragon acid of 2-ketone group-L-, be warming up to dissolving fully, the temperature during the ancient dragon acid of dissolving 2-ketone group-L-is controlled at 10-15 ℃, dissolution time 1-3 hour;
(3) the cooling transformation stage is the reaction solution that contains the ancient dragon acid of diketone, and the temperature of transformation stage is-20 ℃-0 ℃, and optimum temps-15--8 ℃, the time of transformation stage is 3-6 hour, and Best Times is 4-5 hour;
(4) reaction solution be added drop-wise in the 10-20% alkaline solution neutralize, in the alkaline solution with the time temperature be controlled at 10-20 ℃, be 8-10 with pH value in the alkaline solution, in the alkaline solution and optimal ph be 9;
(5) alkali neutralizer cooling is filtered desalination, washing with acetone, merging filtrate, the temperature 0-10 of filter salts ℃, optimum temps 5-8 ℃;
(6) method with decompression reclaims acetone, and the temperature that reclaims acetone is 30-50 ℃, and optimum temps is 35-40 ℃;
(7) cool to reclaiming residual solution behind the acetone-5-5 ℃, optimum temps-3-0 ℃, dripping hydrochloric acid makes pH value of solution to 2-3 while stirring; It is subsequent use that the filtration cold water washing gets the wet article of the ancient imperial sour monohydrate of diketone, hot blast dry air, 40-50 ℃ of control hot blast temperature, optimum temps 44-46 ℃, 2-4 hour time of drying, Best Times 2.5-3.5 hour;
Acetone is 8-15 with the weight or meausurement ratio of the ancient dragon acid of 2-ketone group-L-: 1, and best weight or meausurement is than being 10-12: 1; The weight ratio of the ancient dragon acid of oleum and 2-ketone group-L-is 1-3: 2, and the concentration of oleum is 100-110%; Alkaline solution is sodium hydroxide or potassium hydroxide strong base solution; The ancient imperial sour monohydrate of the diacetone that above-mentioned steps (7) is obtained is dissolved in the basic solution by the amount of soda acid equal proportion, steams moisture, after the vacuum-drying, can obtain the ancient imperial hydrochlorate of diketone; The ancient imperial hydrochlorate of diketone is sodium salt or sylvite; Basic solution is a kind of in salt of wormwood, saleratus, potassium hydroxide, yellow soda ash, sodium hydrogencarbonate, the sodium hydroxide solution.
Main points of the present invention are chemical synthesis and preparation method.Its principle is: the present invention is to be raw material with the ancient imperial acid of 2-ketone group-L-, and in advance to the acetone cooling, control oleum rate of addition adds the ancient dragon acid of 2-ketone group-L-then, rising temperature for dissolving, and the dissolving back gets into the transformation stage fully, and cooling is converted into the diacetone product again.Solution colour is shallow, and by product is few; At best controlled temperature of transformation stage, can satisfy fully transforming, and help energy-conservation.In the alkaline solution that reaction solution is added drop-wise to, definitely can not become acid; If become acidity should in time add alkali lye,, neutralization is strong basicity if finishing solution.Desalination is filtered in the cooling of alkali neutralizer then, small amount of acetone washing, merging filtrate.Method with decompression reclaims acetone, and recovery set is used after the acetone rectifying of recovery.The residual solution cooling behind the recovery acetone, dripping hydrochloric acid while stirring; Filter cold water washing and get the wet article of the ancient imperial sour monohydrate of diketone.The hot blast dry air.
The preparation of the ancient imperial hydrochlorate of diketone: the amount by the soda acid equal proportion is dissolved into the ancient imperial sour monohydrate of diacetone in the basic solution, steams water through decompression, after the vacuum-drying, can obtain its salt; Wherein alkali is sodium hydroxide and potassium hydroxide or its salt of weak acid like carbonate or supercarbonate.
The preparation method of ancient imperial sour monohydrate of diketone and the ancient imperial hydrochlorate of diketone thereof compared with prior art; Only a kind of organic solvent-acetone has been simplified the recovery of operation and solvent among this preparation method, has reduced cost; The industrialization feasibility is strong, can be widely used in the field of chemical synthesis.
Description of drawings
Below in conjunction with accompanying drawing and instance the present invention is elaborated.
Fig. 1 is the ancient imperial sour monohydrate structural formula figure of diketone of the present invention.
Fig. 2 is the ancient imperial hydrochlorate structural formula figure of diketone of the present invention.
Fig. 3 is that the ancient dragon acid of 2-ketone group of the present invention-L-is starting raw material structural formula figure.
Embodiment
Following examples will help understanding of the present invention, but these embodiment are only in order to illustrate the present invention, and the present invention is not limited to these contents.
Embodiment 1
In the 2000mL four-hole bottle, add 1500mL acetone, under mechanical stirring stirs, cool to-3 ℃, begin to drip 20% oleum 75g, controlled temperature is not higher than 0 ℃ in the dropping process; Dropwise, add 150g 2-ketone group-ancient dragon acid of L-(content 90%), be warmed up to 10 ℃, stirring and dissolving cools to-8 ℃ after the dissolving fully, reacts 4 hours.Reaction finishes, and reaction solution is added drop-wise to (the 143g dissolution of sodium hydroxide cools to 0 ℃ in advance in the 700mL purified water) in the sodium hydroxide solution, and control reaction temperature is not higher than 15 ℃, dropwises, and the pH value should be between 8-9; Dropwise, cool to 5 ℃, filter immediately, filtering sodium sulfate, filter cake is with acetone 60mL washing three times, merging filtrate; Reduce pressure 35 ℃ and reclaim acetone, residual solution drops to-3 ℃, begins to drip the about 75mL of concentrated hydrochloric acid, and congo-red test paper becomes bright blue look (the pH value is about 2); Stirred 5 minutes, and filtered, with 150mL frozen water washing three times; 45 ℃ of vacuum-dryings get crude product 113g, yield 55.7% to constant weight; Nuclear-magnetism structural confirmation behind acetone refining
1H-NMR (600MHZ, DMSO-d
6, 25 ℃) and δ: 1.20 (s, 3H), 1.32 (s, 3H), 1.38 (s, 3H), 1.43 (s, 3H), 3.3 (br, 2H), 3.85 (d, 1H), 4.05 (m, 2H), 4.31 (d, 1H), 4.67 (s, 1H), 13.2 (br, 1H).
Embodiment 2
In the 2000mL four-hole bottle, add 1500mL acetone, under mechanical stirring stirs, cool to-5 ℃, begin to drip 20% oleum 150g, controlled temperature is not higher than 0 ℃ in the dropping process; Dropwise, add 150g 2-ketone group-ancient dragon acid of L-(content 90%), be warmed up to 15 ℃, stirring and dissolving cools to-10 ℃ after the dissolving fully, reacts 4 hours.Reaction finishes, and reaction solution is added drop-wise to (the 175g dissolution of sodium hydroxide cools to 0 ℃ in advance in the 700mL purified water) in the sodium hydroxide solution, and control reaction temperature is not higher than 15 ℃, dropwises, and the pH value should be between 8-9; Dropwise, cool to 5 ℃, filter immediately, filtering sodium sulfate, filter cake is with acetone 60mL washing three times, merging filtrate; Reduce pressure 35 ℃ and reclaim acetone, residual solution drops to-3 ℃, begins to drip the about 75mL of concentrated hydrochloric acid, and congo-red test paper becomes bright blue look (the pH value is about 2); Stirred 5 minutes, and filtered, with 150mL frozen water washing three times; 45 ℃ of vacuum-dryings get crude product 165g, yield 81.3% to constant weight.
165g crude product was dissolved in 330mL of acetone, dissolved in 35 ℃ heating and stirring, and then cooled to 0 ℃ starting water 660mL, until the temperature dropped to -5 ℃, and then stirred for 15 minutes, filtered, 45 ℃ vacuum-dried to constant weight to give diketone cologne acid monohydrate 150g, yield 90.9%; Specific rotation:
melting point: 89.3 ℃.
Embodiment 3
In the 2000mL four-hole bottle, add 1200mL acetone, under mechanical stirring stirs, cool to 0 ℃, begin to drip 20% oleum 150g, controlled temperature is not higher than 0 ℃ in the dropping process; Dropwise, add 150g 2-ketone group-ancient dragon acid of L-(content 90%), be warmed up to 12 ℃, stirring and dissolving cools to-15 ℃ after the dissolving fully, reacts 4 hours.Reaction finishes, and reaction solution is added drop-wise to (the 175g dissolution of sodium hydroxide cools to 0 ℃ in advance in the 700mL purified water) in the sodium hydroxide solution, and 15 ℃ of control reaction temperature dropwise, and the pH value should be between 8-9; Dropwise, cool to 5 ℃, filter immediately, filtering sodium sulfate, filter cake is with acetone 60mL washing three times, merging filtrate; Reduce pressure 35 ℃ and reclaim acetone, residual solution drops to-3 ℃, begins to drip the about 75mL of concentrated hydrochloric acid, and congo-red test paper becomes bright blue look (the pH value is 2); Stirred 5 minutes, and filtered, with 150mL frozen water washing three times; 45 ℃ of vacuum-dryings get crude product 150g, yield 73.9% to constant weight; Specific rotation:
Fusing point: 88.1 ℃, Fourier's infrared spectra IR (KBr) cm
-1: 3414,2997,1955,1724,1651.
Embodiment 4
In the 2000mL four-hole bottle, add 2250mL acetone, under mechanical stirring stirs, cool to-2 ℃, begin to drip 20% oleum 225g, controlled temperature is not higher than 0 ℃ in the dropping process; Dropwise, add 150g 2-ketone group-ancient dragon acid of L-(content 90%), be warmed up to 12 ℃, stirring and dissolving cools to-8 ℃ after the dissolving fully, reacts 4 hours.Reaction finishes, and reaction solution is added drop-wise to (the 207g dissolution of sodium hydroxide cools to 0 ℃ in advance in the 700mL purified water) in the sodium hydroxide solution, and control reaction temperature is not higher than 15 ℃, dropwises, and the pH value should be between 8-9; Dropwise, cool to 5 ℃, filter immediately, filtering sodium sulfate, filter cake is with acetone 60mL washing three times, merging filtrate; Reduce pressure 35 ℃ and reclaim acetone, residual solution drops to-3 ℃, begins to drip the about 75mL of concentrated hydrochloric acid, and congo-red test paper becomes bright blue look (the pH value is about 2); Stirred 5 minutes, and filtered, with 150mL frozen water washing three times; 45 ℃ of vacuum-dryings get crude product 168g, yield 82.8% to constant weight; Specific rotation:
Fusing point: 89.0 ℃, Fourier's infrared spectra IR (KBr) cm
-1: 3416,2997,1955,1724,1651,1381.
Embodiment 5
In reaction flask, add purified water 50mL, sodium hydroxide 2.05g, alkali dissolve the back fully and add the ancient imperial sour monohydrate 15.0g of diketone, stir it is dissolved fully, and 30 ℃ of controlled temperature, the pH value is 8-9; 50 ℃ of its moisture of evaporate to dryness that reduce pressure, vacuum-drying gets its sodium salt 15.3g.
Embodiment 6
In reaction flask, add purified water 50mL, potassium hydroxide 2.87g, the dissolving back adds the ancient imperial acid of diketone-hydrate 15.0g, stirs it is dissolved fully, 30 ℃ of controlled temperature, the pH value is 8-9; 50 ℃ of its moisture of evaporate to dryness that reduce pressure, vacuum-drying gets its sylvite 16.1g.
Claims (7)
1. the preparation method of the ancient imperial sour monohydrate of a diketone, it is characterized in that: with acetone, the ancient imperial acid of 2-ketone group-L-is starting raw material, and oleum is a catalyzer, comprises the steps:
(1) with acetone cooling, drip oleum, control oleum rate of addition, solution temperature be-10-5 ℃, solution optimum temps-5-0 ℃;
(2) add the ancient dragon acid of 2-ketone group-L-, be warming up to dissolving fully, the temperature during the ancient dragon acid of dissolving 2-ketone group-L-is controlled at 10-15 ℃, dissolution time 1-3 hour;
(3) the cooling transformation stage is the reaction solution that contains the ancient dragon acid of diketone, and the temperature of transformation stage is-20 ℃-0 ℃, and optimum temps-15--8 ℃, the time of transformation stage is 3-6 hour, and Best Times is 4-5 hour;
(4) reaction solution be added drop-wise in the 10-20% alkaline solution neutralize, in the alkaline solution with the time temperature be controlled at 10-20 ℃, be 8-10 with pH value in the alkaline solution, in the alkaline solution and optimal ph be 9;
(5) alkali neutralizer cooling is filtered desalination, washing with acetone, merging filtrate, the temperature 0-10 of filter salts ℃, optimum temps 5-8 ℃;
(6) method with decompression reclaims acetone, and the temperature that reclaims acetone is 30-50 ℃, and optimum temps is 35-40 ℃;
(7) cool to reclaiming residual solution behind the acetone-5-5 ℃, optimum temps-3-0 ℃, dripping hydrochloric acid makes pH value of solution to 2-3 while stirring; It is subsequent use that the filtration cold water washing gets the wet article of the ancient imperial sour monohydrate of diketone, hot blast dry air, 40-50 ℃ of control hot blast temperature, optimum temps 44-46 ℃, 2-4 hour time of drying, Best Times 2.5-3.5 hour.
2. the preparation method of the ancient imperial sour monohydrate of diketone according to claim 1 is characterized in that: acetone is 8-15 with the weight or meausurement ratio of the ancient dragon acid of 2-ketone group-L-: 1, and best weight or meausurement is than being 10-12: 1.
3. the preparation method of the ancient imperial sour monohydrate of diketone according to claim 1 is characterized in that: the weight ratio of the ancient dragon acid of oleum and 2-ketone group-L-is 1-3: 2, and the concentration of oleum is 100-110%.
4. the preparation method of the ancient imperial sour monohydrate of diketone according to claim 1, it is characterized in that: alkaline solution is sodium hydroxide or potassium hydroxide strong base solution.
5. the preparation method of the ancient imperial hydrochlorate of a diketone is characterized in that: the ancient imperial sour monohydrate of diacetone that above-mentioned steps (7) is obtained is dissolved in the basic solution by the amount of soda acid equal proportion, steams moisture, after the vacuum-drying, can obtain the ancient imperial hydrochlorate of diketone.
6. the preparation method of the ancient imperial hydrochlorate of diketone according to claim 5 is characterized in that: the ancient imperial hydrochlorate of diketone is sodium salt or sylvite.
7. the preparation method of the ancient imperial hydrochlorate of diketone according to claim 5 is characterized in that: basic solution is a kind of in salt of wormwood, saleratus, potassium hydroxide, yellow soda ash, sodium hydrogencarbonate, the sodium hydroxide solution.
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| CN201110171823A CN102304133A (en) | 2011-06-23 | 2011-06-23 | Method for preparing (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate and salt of (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2301811A (en) * | 1933-10-25 | 1942-11-10 | Hoffmann La Roche | 2-keto-levo-gulonic acid and process for the manufacture of same |
| EP0138436A2 (en) * | 1983-09-28 | 1985-04-24 | Takeda Chemical Industries, Ltd. | Process for producing ketals of 2-Ketogulonic acid or its esters |
| US5688971A (en) * | 1996-08-09 | 1997-11-18 | Ptrl East, Inc. | Process for producing dikegulac, its salts and derivatives |
-
2011
- 2011-06-23 CN CN201110171823A patent/CN102304133A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2301811A (en) * | 1933-10-25 | 1942-11-10 | Hoffmann La Roche | 2-keto-levo-gulonic acid and process for the manufacture of same |
| EP0138436A2 (en) * | 1983-09-28 | 1985-04-24 | Takeda Chemical Industries, Ltd. | Process for producing ketals of 2-Ketogulonic acid or its esters |
| US5688971A (en) * | 1996-08-09 | 1997-11-18 | Ptrl East, Inc. | Process for producing dikegulac, its salts and derivatives |
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Inventor after: Wang Yujun Inventor after: Yu Hezhou Inventor after: Liu Jiuzhi Inventor after: Cui Zhenqiang Inventor after: Yan Yan Inventor before: Wang Yujun Inventor before: Yu Hezhou Inventor before: Liu Jiuzhi Inventor before: Cui Zhenqiang Inventor before: Yan Yan |
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Application publication date: 20120104 |