CA2299364A1 - Process for the preparation of l-ascorbic acid - Google Patents
Process for the preparation of l-ascorbic acid Download PDFInfo
- Publication number
- CA2299364A1 CA2299364A1 CA002299364A CA2299364A CA2299364A1 CA 2299364 A1 CA2299364 A1 CA 2299364A1 CA 002299364 A CA002299364 A CA 002299364A CA 2299364 A CA2299364 A CA 2299364A CA 2299364 A1 CA2299364 A1 CA 2299364A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- keto
- gulonic
- ascorbic acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/62—Three oxygen atoms, e.g. ascorbic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process is disclosed for preparing L-ascorbic acid by reaction of 2-keto-L-gulonic acid with concentrated mineral acid at temperatures of between 40 and 80 ~C.
Description
Process for the preparation of L-ascorbic acid The invention relates to a process for the preparation of L-ascorbic acid by reaction of 2-keto-L-gulonic acid with concentrated mineral acid at temperatures between 40 and 80°C.
The invention relates in particular to a process for the preparation of L-ascorbic acid, characterized in that the reaction is carried out at temperatures between 50 and 70°C.
Processes for the preparation of ascorbic acid in one step by reaction of 2-keto-L-gulonic acid with an acid are known. US 2,185,383 describes the reaction of 2-keto-L-gulonic acid with concentrated hydrochloric acid and acetic acid as a solvent . Japanese Unexamined Application 58-177986 describes a process for the preparation of L-ascorbic acid in which a solution of sodium 2-keto-L-gulonate in ethanol and acetone is first neutralized with hydrochloric acid. Japanese Examined Application 48-15931 describes the reaction of 2-keto-L-gulonic acid with a mineral acid in an inert solvent and in the presence of a surface-active substance. Likewise, the preparation of L-ascorbic acid starting from 2-keto-L-gulonic anhydride in the presence of a surface-active substance is described in WO 87/00839. EP 0 324 261 and GB 2,205,567 describe the reaction of 2-keto-L-gulonic acid with an acid in a mixture of inert solvents in the presence of a surface-active substance.
The reaction of 2-keto-L-gulonic acid with 36%
hydrochloric acid is described in DE 2939052. Here, the L-ascorbic acid is obtained in a yield of 87o after a reaction at 100°C and after distilling off the hydrochloric acid.
Surprisingly, investigations in the context of L-ascorbic acid synthesis showed that high yields are obtained if the reaction is carried out at temperatures between 40 and 80°, in particular between 50 and 70°C.
A temperature range from 57 to 63°C has proven particularly preferable for carrying out the reaction.
The novel process according to the invention enables L-ascorbic acid to be obtained in high yields by lactonization of 2-keto-L-gulonic acid with concentrated mineral acid.
It has proven particularly advantageous that at the lower temperatures the decomposition of the ascorbic acid obtained takes place significantly more slowly than in the processes known from the prior art (e.g. DE
2939052; process at 100°C).
A further advantage proves to be the lower energy consumption associated therewith and thus lower environmental pollution.
Moreover, it proves advantageous in comparison with the prior art that the reaction can be carried out without organic solvents.
The process according to the invention proves to be advantageous if the 2-keto-L-gulonic acid and the hydrochloric acid are employed in a quantitative ratio of 1:3.
The invention thus also relates to a process in which the 2-keto-L-gulonic acid and the mineral acid are employed in the ratio 1:3.
However, the concentration can be varied within wide ranges. A more concentrated and also a more dilute procedure can be carried out.
The weight ratio 2-keto-L-gulonic acid/concentrated mineral acid can be, for example, between 10:1 and 1:10. The range is particularly preferably between 1:2 and 1:4, and a ratio of 1:3 is very particularly advantageous.
Mineral acid means, for example, hydrochloric acid, phosphoric acid or sulfuric acid. The concentrated mineral acids are preferably employed.
The invention also relates to a process, as described, characterized in that the mineral acid used is concentrated hydrochloric acid.
The invention relates in particular to a process for the preparation of L-ascorbic acid, characterized in that the reaction is carried out at temperatures between 50 and 70°C.
Processes for the preparation of ascorbic acid in one step by reaction of 2-keto-L-gulonic acid with an acid are known. US 2,185,383 describes the reaction of 2-keto-L-gulonic acid with concentrated hydrochloric acid and acetic acid as a solvent . Japanese Unexamined Application 58-177986 describes a process for the preparation of L-ascorbic acid in which a solution of sodium 2-keto-L-gulonate in ethanol and acetone is first neutralized with hydrochloric acid. Japanese Examined Application 48-15931 describes the reaction of 2-keto-L-gulonic acid with a mineral acid in an inert solvent and in the presence of a surface-active substance. Likewise, the preparation of L-ascorbic acid starting from 2-keto-L-gulonic anhydride in the presence of a surface-active substance is described in WO 87/00839. EP 0 324 261 and GB 2,205,567 describe the reaction of 2-keto-L-gulonic acid with an acid in a mixture of inert solvents in the presence of a surface-active substance.
The reaction of 2-keto-L-gulonic acid with 36%
hydrochloric acid is described in DE 2939052. Here, the L-ascorbic acid is obtained in a yield of 87o after a reaction at 100°C and after distilling off the hydrochloric acid.
Surprisingly, investigations in the context of L-ascorbic acid synthesis showed that high yields are obtained if the reaction is carried out at temperatures between 40 and 80°, in particular between 50 and 70°C.
A temperature range from 57 to 63°C has proven particularly preferable for carrying out the reaction.
The novel process according to the invention enables L-ascorbic acid to be obtained in high yields by lactonization of 2-keto-L-gulonic acid with concentrated mineral acid.
It has proven particularly advantageous that at the lower temperatures the decomposition of the ascorbic acid obtained takes place significantly more slowly than in the processes known from the prior art (e.g. DE
2939052; process at 100°C).
A further advantage proves to be the lower energy consumption associated therewith and thus lower environmental pollution.
Moreover, it proves advantageous in comparison with the prior art that the reaction can be carried out without organic solvents.
The process according to the invention proves to be advantageous if the 2-keto-L-gulonic acid and the hydrochloric acid are employed in a quantitative ratio of 1:3.
The invention thus also relates to a process in which the 2-keto-L-gulonic acid and the mineral acid are employed in the ratio 1:3.
However, the concentration can be varied within wide ranges. A more concentrated and also a more dilute procedure can be carried out.
The weight ratio 2-keto-L-gulonic acid/concentrated mineral acid can be, for example, between 10:1 and 1:10. The range is particularly preferably between 1:2 and 1:4, and a ratio of 1:3 is very particularly advantageous.
Mineral acid means, for example, hydrochloric acid, phosphoric acid or sulfuric acid. The concentrated mineral acids are preferably employed.
The invention also relates to a process, as described, characterized in that the mineral acid used is concentrated hydrochloric acid.
The invention also relates to a process, as described, characterized in that a mixture consisting of 2-keto-L-gulonic acid and concentrated mineral acid is heated to the desired reaction temperature.
The reaction time is customarily between 1 and 5 hours, in particular between 2 and 4 hours, and a reaction time of approximately 3 hours is particularly preferred.
Working up is carried out by methods known per se, e.g. by active carbon treatment, filtration, removal of the solvent and crystallization. In accordance with the process according to the invention, the yields of L-ascorbic acid are, as a rule, over 90%, such that complicated purification steps can be dispensed with.
Above and below, all temperatures are indicated in °C.
The reaction time is customarily between 1 and 5 hours, in particular between 2 and 4 hours, and a reaction time of approximately 3 hours is particularly preferred.
Working up is carried out by methods known per se, e.g. by active carbon treatment, filtration, removal of the solvent and crystallization. In accordance with the process according to the invention, the yields of L-ascorbic acid are, as a rule, over 90%, such that complicated purification steps can be dispensed with.
Above and below, all temperatures are indicated in °C.
Example 1 100 g of 2-keto-L-gulonic acid are introduced into 300 g of 37% hydrochloric acid. The batch is then heated to 58° and kept at this temperature for 3 hours.
After removal of the hydrochloric acid and work-up, a yield of L-ascorbic acid of 91.4% of theory is obtained.
Example 2 100 g of 2-keto-L-gulonic acid are introduced into 300 g of 37 o hydrochloric acid. The batch is then heated to 59-60° and kept at this temperature for 3 hours.
After removal of the hydrochloric acid and work-up, a yield of L-ascorbic acid of 90.2% of theory is obtained.
Example 3 100 g of 2-keto-L-gulonic acid are introduced into 300 g of 37% hydrochloric acid. The batch is then heated to 59-60° and kept at this temperature for about 1.5 hours.
After removal of the hydrochloric acid and work-up, a yield of L-ascorbic acid of 88.4% of theory is obtained.
After removal of the hydrochloric acid and work-up, a yield of L-ascorbic acid of 91.4% of theory is obtained.
Example 2 100 g of 2-keto-L-gulonic acid are introduced into 300 g of 37 o hydrochloric acid. The batch is then heated to 59-60° and kept at this temperature for 3 hours.
After removal of the hydrochloric acid and work-up, a yield of L-ascorbic acid of 90.2% of theory is obtained.
Example 3 100 g of 2-keto-L-gulonic acid are introduced into 300 g of 37% hydrochloric acid. The batch is then heated to 59-60° and kept at this temperature for about 1.5 hours.
After removal of the hydrochloric acid and work-up, a yield of L-ascorbic acid of 88.4% of theory is obtained.
Claims (5)
1. Process for the preparation of L-ascorbic acid, characterized in that 2-keto-L-gulonic acid is reacted with concentrated mineral acid at temperatures between 40 and 80°C.
2. Process according to Claim 1, characterized in that the reaction is carried out at temperatures between 50 and 70°C.
3. Process according to Claim 1 or 2, characterized in that the 2-keto-L-gulonic acid and the mineral acid are employed in the ratio 1:3.
4. Process according to one of Claims 1-3, characterized in that the mineral acid used is concentrated hydrochloric acid.
5. Process according to one of Claims 1-4, characterized in that a mixture consisting of 2-keto-L-gulonic acid and concentrated mineral acid is brought to the desired reaction temperature.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19734086.5 | 1997-08-07 | ||
| DE19734086A DE19734086C1 (en) | 1997-08-07 | 1997-08-07 | L-ascorbic acid preparation |
| PCT/EP1998/004649 WO1999007691A2 (en) | 1997-08-07 | 1998-07-24 | Process for preparing l-ascorbic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2299364A1 true CA2299364A1 (en) | 1999-02-18 |
Family
ID=7838185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002299364A Abandoned CA2299364A1 (en) | 1997-08-07 | 1998-07-24 | Process for the preparation of l-ascorbic acid |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1001952A2 (en) |
| JP (1) | JP2001512722A (en) |
| KR (1) | KR20010022595A (en) |
| CN (1) | CN1265655A (en) |
| AR (1) | AR010938A1 (en) |
| AU (1) | AU9156298A (en) |
| BR (1) | BR9811855A (en) |
| CA (1) | CA2299364A1 (en) |
| CO (1) | CO4770883A1 (en) |
| DE (1) | DE19734086C1 (en) |
| ID (1) | ID25547A (en) |
| WO (1) | WO1999007691A2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19904821C1 (en) * | 1999-02-05 | 2000-07-06 | Merck Patent Gmbh | Preparation of L-ascorbic acid from 2-keto- or 2,3-4,6-diacetone-2-keto-L-gulonic acid |
| DE19919203A1 (en) | 1999-04-28 | 2000-11-02 | Basf Ag | Process for the preparation of L-ascorbic acid |
| DE19954511A1 (en) | 1999-11-12 | 2001-05-17 | Basf Ag | Process for the preparation of alkali salts of L-ascorbic acid |
| DE10022518A1 (en) | 2000-05-10 | 2001-11-15 | Basf Ag | Preparation of L-ascorbic acids by reacting 2-keto-L-gulonic acids or melt of 2-keto-L-gulonic acid alkyl esters under acid catalysis using water-miscible solvent(s) |
| WO2002051826A1 (en) | 2000-12-22 | 2002-07-04 | Eastman Chemical Company | Continuous process for producing l-ascorbic acid |
| JP2004516319A (en) | 2000-12-22 | 2004-06-03 | イーストマン ケミカル カンパニー | Method for producing ascorbic acid in the presence of sulfite |
| NZ528677A (en) * | 2001-04-10 | 2006-11-30 | Danisco Usa Inc | Polymerization of mono and disaccharides with monocarboxylic acids and lactones |
| US6740762B2 (en) | 2001-08-24 | 2004-05-25 | Eastman Chemical Company | Process for ascorbic acids using alkaline earth silicate catalysts |
| US6716997B1 (en) | 2001-10-09 | 2004-04-06 | Eastman Chemical Company | Systems and methods for generation of ascorbic acid with reduced color |
| CN111018815A (en) * | 2019-12-29 | 2020-04-17 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing vitamin C by increasing concentration of hydrochloric acid through solvent extraction |
| CN111087373A (en) * | 2019-12-29 | 2020-05-01 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing vitamin C by acid method |
| CN114369075B (en) * | 2022-02-14 | 2023-09-29 | 河北乐开节能科技股份有限公司 | Method for preparing VC crystal by using aqueous solution of 2-keto-L-gulonic acid in one step |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2462251A (en) * | 1945-05-16 | 1949-02-22 | Merck & Co Inc | Process for preparing ascorbic acids |
| DD141832A1 (en) * | 1978-10-31 | 1980-05-21 | Joachim Schmidt | METHOD AND DEVICE FOR PREPARING L-ASCORBIN ACID |
| CN86105960A (en) * | 1985-08-09 | 1987-05-13 | 鲁布里佐尔公司 | Under substantially anhydrous conditions, prepare the L-xitix from 2-ketone-L-gulonic acid |
| DE3819045C2 (en) * | 1987-06-08 | 1997-06-19 | Takeda Chemical Industries Ltd | Production of L-ascorbic acid |
-
1997
- 1997-08-07 DE DE19734086A patent/DE19734086C1/en not_active Expired - Fee Related
-
1998
- 1998-07-24 CN CN98807955A patent/CN1265655A/en active Pending
- 1998-07-24 CA CA002299364A patent/CA2299364A1/en not_active Abandoned
- 1998-07-24 ID IDW20000174A patent/ID25547A/en unknown
- 1998-07-24 WO PCT/EP1998/004649 patent/WO1999007691A2/en not_active Application Discontinuation
- 1998-07-24 JP JP2000506195A patent/JP2001512722A/en active Pending
- 1998-07-24 AU AU91562/98A patent/AU9156298A/en not_active Abandoned
- 1998-07-24 EP EP98943779A patent/EP1001952A2/en not_active Withdrawn
- 1998-07-24 KR KR1020007001187A patent/KR20010022595A/en not_active Application Discontinuation
- 1998-07-24 BR BR9811855-2A patent/BR9811855A/en not_active Application Discontinuation
- 1998-08-06 CO CO98045322A patent/CO4770883A1/en unknown
- 1998-08-07 AR ARP980103913A patent/AR010938A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001512722A (en) | 2001-08-28 |
| BR9811855A (en) | 2000-08-15 |
| ID25547A (en) | 2000-10-12 |
| KR20010022595A (en) | 2001-03-26 |
| WO1999007691A2 (en) | 1999-02-18 |
| DE19734086C1 (en) | 1998-08-13 |
| AR010938A1 (en) | 2000-07-12 |
| AU9156298A (en) | 1999-03-01 |
| EP1001952A2 (en) | 2000-05-24 |
| WO1999007691A3 (en) | 1999-04-08 |
| CO4770883A1 (en) | 1999-04-30 |
| CN1265655A (en) | 2000-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2299364A1 (en) | Process for the preparation of l-ascorbic acid | |
| CZ350596A3 (en) | PROCESS FOR PREPARING N-£3-(CYANOPYRAZOLO£1,5-a|PYRIMIDIN-7-YL)PHENYL|-N-ETHYLACETAMIDE | |
| EP0227829A1 (en) | Production of l-ascorbic acid from 2-keto-l-gulonic acid. | |
| KR100483775B1 (en) | Process for the preparation of ascorbic acid | |
| HUT63404A (en) | Process for producing cyclic sulfate derivatives | |
| KR20180116371A (en) | Process for producing 4-alkoxy-3-hydroxypicolic acid | |
| EP0252353B1 (en) | 4-benzyloxy-3-pyrrolin-2-one-1-yl-acetamide, preparation and use | |
| JP5276241B2 (en) | Method for preparing L-ascorbic acid | |
| RU1779243C (en) | Process for producing 3-fluoro-4-aminophenol | |
| MXPA00001339A (en) | Process for preparing l-ascorbic acid | |
| KR100401284B1 (en) | Method for preparing 1-bromoethyl acetate | |
| US3960884A (en) | Method of preparing racemic biotin | |
| Kubrakova et al. | Facile hydrolytic cleavage of a sulfonamide bond under microwave irradiation | |
| KR840000115B1 (en) | Process for the preparation of a carbazole derivative | |
| IL96149A (en) | Proceses for the preparation of n-(2-hydroxyethyl)-2-hydroxymethyl-3, 4, 5-trihydroxypiperidines | |
| CN115572231B (en) | Synthesis method of salt of bicyclo [1.1.1] pentane-1, 3-diamine | |
| KR100203233B1 (en) | Process of preparation for astaxanthin | |
| JP2950948B2 (en) | Method for producing 3-methylquinoline-8-carboxylic acid | |
| KR850000242B1 (en) | Process for preparing vincristine | |
| KR19990087905A (en) | A process for the preparation of 4-(des-dimethylamino)-tetracyclines | |
| RU2069656C1 (en) | Method for production of 4-nitro-1,3-diaminobenzene | |
| HU176218B (en) | Process for preparing apovincamine from vincamine or epivincamine | |
| CN117658866A (en) | Synthesis method of azido amino acid derivative | |
| JPS58103379A (en) | Preparation of alpha-acetyl lactone | |
| CN114867728A (en) | Novel method for synthesizing decursin derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |