CN1059891C - 酒石酸的制备方法 - Google Patents
酒石酸的制备方法 Download PDFInfo
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- CN1059891C CN1059891C CN95196138A CN95196138A CN1059891C CN 1059891 C CN1059891 C CN 1059891C CN 95196138 A CN95196138 A CN 95196138A CN 95196138 A CN95196138 A CN 95196138A CN 1059891 C CN1059891 C CN 1059891C
- Authority
- CN
- China
- Prior art keywords
- tartaric
- ketogluconate
- tartrate
- preparation
- tartaric acid
- 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.)
- Expired - Fee Related
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 title abstract 4
- 235000002906 tartaric acid Nutrition 0.000 title abstract 4
- 239000011975 tartaric acid Substances 0.000 title abstract 4
- IZSRJDGCGRAUAR-MROZADKFSA-M 5-dehydro-D-gluconate Chemical compound OCC(=O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IZSRJDGCGRAUAR-MROZADKFSA-M 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 18
- 229940095064 tartrate Drugs 0.000 claims description 17
- 239000007853 buffer solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000872 buffer Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 description 8
- IZSRJDGCGRAUAR-MROZADKFSA-N 5-dehydro-D-gluconic acid Chemical compound OCC(=O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O IZSRJDGCGRAUAR-MROZADKFSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 241000589220 Acetobacter Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241000589236 Gluconobacter Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000006481 glucose medium Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
- Fodder In General (AREA)
Abstract
本发明涉及由5-酮葡糖酸盐制备酒石酸的方法。本发明的目的是，提供由5-酮葡糖酸盐转化成酒石酸的转化率尽可能高的简单方法。为此使5-酮葡糖酸盐在碳酸盐缓冲液中，在碱性pH值下，氧化转化成酒石酸。尤其与钒酸盐进行转化反应，优选在pH值范围为8-10的情况下进行。
Description
本发明涉及酒石酸的制备方法。
酒石酸主要用于食品工业和纺织工业。这样，酒石酸例如用作食品添加剂，尤其是用作抗氧剂和酸化剂。此外，酒石酸还用作建筑材料添加剂以改进水泥的凝固性能，并用作许多化学反应的原料，特别用于手性合成。
制备酒石酸的一条路线是从酒石得到，酒石是制酒时产生的一种物质。然而，制酒时产生的酒石粗品通常被有机物质污染，因此，为了从酒石获得酒石酸，需进行昂贵的处理。
基于此缺点，又开发了制备酒石酸的其他方法。例如在USP 1425605中，描述了在硝酸盐存在下通过氧化碳水化合物而制备酒石酸的方法。然而这种方法导致生成酒石酸的不同立体异构体，因此选择性较差。
此外，采用化学路线时，所加入的原料转化成酒石酸的转化率相当小：例如用硝酸作为氧化剂时，由5-酮葡糖酸盐或其他碳水化合物转化成酒石酸的转化率在约10％(美国专利USP 2380196)至最多约40％(W.E.Barch，J.Am.Chem.Soc.55，3653，1933)之间变化。在含有1M氢氧化钙溶液或苛性钠溶液的碱性介质中，由5-酮葡糖酸转化成酒石酸时，酒石酸产率约达10％(H.Isbell和N.Holt，J.Res.Bur.Stand.35，433，1945)。
制备酒石酸的另一个方法是，在以痕量元素形式的钒酸盐存在下，通过微生物，例如醋杆菌或葡糖杆菌使葡萄糖转化成酒石酸(参看USP3585109)。已表明在此方法中，酒石酸的制备用二个步骤实现：在第一步中，在葡萄糖介质中培养的微生物将5-酮葡糖酸盐析出于介质中，在第二步中，5-酮葡糖酸盐与在介质中含有的作为痕量元素的钒盐纯化学地，即不依赖于微生物地反应生成酒石酸(R.Klasen，S.Bringer-Meyer和H.Sahm，Biotechn and Bioengin.40，183，1992)。此制备方法尤其具有以下优点，就是只生成酒石酸的一种异构体，即所希望的L-(+)-酒石酸。不过至今通过此方法所达到的由5-酮葡糖酸盐转化成酒石酸的转化率尚不令人满意。
本发明的任务是，实现一种制备酒石酸的简单方法，通过此方法使5-酮葡糖酸盐转化为酒石酸的过程能达到尽量高的转化率。
根据本发明此任务是这样解决的，即使5-酮葡糖酸盐在碳酸盐缓冲液中，于碱性pH值条件，氧化转化成酒石酸。意外地表明，在此反应条件下，即使不加入钒酸盐或其他催化剂，5-酮葡糖酸盐也能转化为酒石酸，其中5-酮葡糖酸盐转化为酒石酸的转化率最高可达55％。
如果向反应混合物还加入钒酸盐，那么所加入的5-酮葡糖酸盐转化成酒石酸的转化率甚至最多达75％。在其他缓冲剂存在下，例如像碱式硼酸盐缓冲液存在下，酒石酸的形成相反完全会被抑制。
优选进行反应的pH范围包括pH 8至PH 10。
实施例：
向20mL量瓶中加入2.0mL浓度为0.50M的5-酮葡糖酸的钾盐溶液。此外加入0.40mL浓度为50mM的钒酸铵溶液，并用0.50M碳酸盐-或磷酸盐缓冲剂(pH 10.0)充满至20ml。相似地用0.40mL水代替钒酸铵制备溶液。将这些组分混合后调节此溶液的pH值，并随后将反应混合物无菌过滤到事先压热处理过的50ml锥形瓶中。用软木塞将烧瓶无菌封闭，并在培育振摇器中于27℃和每分种180转摇动8天。
随后借助HPLC测定5-酮葡糖酸的消耗和形成的酒石酸量。由此可确定产率和反应的选择性。结果表示于图1中。
在图1中：
C：碳酸盐缓冲剂， P：磷酸盐缓冲剂，
V：钒酸盐 TA：酒石酸，
5-KGA： 5-酮葡糖酸盐
产率：加入的5-酮葡糖酸盐转化成酒石酸的转化率，其中由1 mol
5-酮葡糖酸转化成1 mol酒石酸时等于100％。
选择性：分解的5-酮葡糖酸盐转化成酒石酸的转化率。
由图1可知，在磷酸盐缓冲液中，以钒酸盐为催化剂并在碱性pH值下，由5-酮葡糖酸转化时酒石酸的产率最高为约25％，与此相反在碳酸盐缓冲液中，最高为约75％。无催化剂时，5-酮葡糖酸盐也可转化为酒石酸，其中在碳酸盐缓冲液中，于pH 10的情况下，酒石酸产率可达约55％。此外，5-酮葡糖酸盐在碳酸盐缓冲液中转化时的选择性约为65-80％，相当高，这意味着副产物少。因此在所选择的反应条件下，分解的5-酮葡糖酸的最大部分转化成为酒石酸。
Claims (3)
1.制备酒石酸的方法，其中使5-酮葡糖酸盐在碳酸盐缓冲液中于碱性pH值条件氧化转化为酒石酸。
2.根据权利要求1的方法，其特征在于，使用钒酸盐进行转化反应。
3.根据权利要求1或2的方法，其特征在于，转化反应优选在8-10的pH范围内进行。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4440191A DE4440191C1 (de) | 1994-11-10 | 1994-11-10 | Verfahren zur Herstellung von Weinsäure |
| DEP4440191.4 | 1994-11-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1164850A CN1164850A (zh) | 1997-11-12 |
| CN1059891C true CN1059891C (zh) | 2000-12-27 |
Family
ID=6532992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95196138A Expired - Fee Related CN1059891C (zh) | 1994-11-10 | 1995-11-08 | 酒石酸的制备方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5763656A (zh) |
| EP (1) | EP0790973B1 (zh) |
| CN (1) | CN1059891C (zh) |
| AT (1) | ATE188204T1 (zh) |
| DE (2) | DE4440191C1 (zh) |
| WO (1) | WO1996015095A1 (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003038105A2 (en) * | 2001-11-02 | 2003-05-08 | Danisco A/S | Sequences for the preparation of 5-ketogluconic acid from gluconic acid |
| GB2388368A (en) * | 2002-05-07 | 2003-11-12 | Danisco | Production of tartaric acid |
| FR2941377B1 (fr) * | 2009-01-29 | 2013-02-15 | Soliance | Compositions cosmetiques comprenant des derives d'acide cetogluconique |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2197021A (en) * | 1938-12-13 | 1940-04-16 | Pfizer Charles & Co | Preparation of d-tartaric acid |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1425605A (en) * | 1915-12-14 | 1922-08-15 | Allan F Odell | Process of producing organic acids |
| US2380196A (en) * | 1942-05-20 | 1945-07-10 | Atlas Powder Co | Process for the preparation of tartaric acid values |
| US2419038A (en) * | 1943-02-16 | 1947-04-15 | Atlas Powder Co | Method for the preparation of tartaric acid values |
| US2419019A (en) * | 1944-10-23 | 1947-04-15 | Atlas Powder Co | Continuous process for oxidizing carbohydrates to tartaric acid |
| US3585109A (en) * | 1969-03-03 | 1971-06-15 | Us Agriculture | Novel process of producing l(+)-tartaric acid |
| DE2600589C2 (de) * | 1975-01-31 | 1987-04-23 | Takeda Chemical Industries, Ltd., Osaka | Verfahren zur Herstellung von L(+)-Weinsäure durch mikrobiologische Hydrolyse von Calcium-cis-epoxysuccinat |
| JPS51121593A (en) * | 1975-04-16 | 1976-10-23 | Mitsubishi Gas Chem Co Inc | Process for preparing l(+)-tartaric acid or its salts |
-
1994
- 1994-11-10 DE DE4440191A patent/DE4440191C1/de not_active Expired - Fee Related
-
1995
- 1995-11-08 CN CN95196138A patent/CN1059891C/zh not_active Expired - Fee Related
- 1995-11-08 DE DE59507540T patent/DE59507540D1/de not_active Expired - Fee Related
- 1995-11-08 US US08/849,006 patent/US5763656A/en not_active Expired - Fee Related
- 1995-11-08 AT AT95936435T patent/ATE188204T1/de not_active IP Right Cessation
- 1995-11-08 WO PCT/DE1995/001568 patent/WO1996015095A1/de active IP Right Grant
- 1995-11-08 EP EP95936435A patent/EP0790973B1/de not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2197021A (en) * | 1938-12-13 | 1940-04-16 | Pfizer Charles & Co | Preparation of d-tartaric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE188204T1 (de) | 2000-01-15 |
| WO1996015095A1 (de) | 1996-05-23 |
| CN1164850A (zh) | 1997-11-12 |
| DE4440191C1 (de) | 1996-03-14 |
| EP0790973A1 (de) | 1997-08-27 |
| DE59507540D1 (de) | 2000-02-03 |
| US5763656A (en) | 1998-06-09 |
| EP0790973B1 (de) | 1999-12-29 |
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