DE1518649C3 - Process for the production of 1,4d-sugar acid lactone - Google Patents
Process for the production of 1,4d-sugar acid lactoneInfo
- Publication number
- DE1518649C3 DE1518649C3 DE1965C0035835 DEC0035835A DE1518649C3 DE 1518649 C3 DE1518649 C3 DE 1518649C3 DE 1965C0035835 DE1965C0035835 DE 1965C0035835 DE C0035835 A DEC0035835 A DE C0035835A DE 1518649 C3 DE1518649 C3 DE 1518649C3
- Authority
- DE
- Germany
- Prior art keywords
- sugar acid
- acid lactone
- lactone
- sugar
- aqueous solution
- 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
Links
- 150000002596 lactones Chemical class 0.000 title claims description 38
- 239000002253 acid Substances 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 239000013078 crystal Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 aliphatic alcohols Chemical class 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 2
- 239000006188 syrup Substances 0.000 claims 2
- 235000020357 syrup Nutrition 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 238000011081 inoculation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UBYZGUWQNIEQMH-SBBOJQDXSA-M potassium;(2s,3s,4s,5r)-2,3,4,5,6-pentahydroxy-6-oxohexanoate Chemical compound [K+].OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UBYZGUWQNIEQMH-SBBOJQDXSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004816 paper chromatography Methods 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
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/01—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Der Gehalt an den beiden Lactonen in der wäßrigen Lösung wurde durch papierchromatographische Fraktionierung bestimmt
(das Entwicklungs-Lösungsmittel bestand aus n-Butanol: Äthanol: Ameisensäure : Wasser im Verhältnis von 4:1:1 :5). Der
Grund dafür, daß die Summe des Gehaltes an beiden Lactonen weniger als 100% ausmacht, besteht darin, daß die wäßrige
Lösung freie zweibasische d-Zuckersäure u. dgl. neben diesen beiden Lactonen enthält.
Die Ausbeute ist bezogen auf die eingesetzte freie d-Zuckersäure.The content of the two lactones in the aqueous solution was determined by paper chromatographic fractionation (the developing solvent consisted of n-butanol: ethanol: formic acid: water in a ratio of 4: 1: 1: 5). The reason why the sum of the two lactones is less than 100% is that the aqueous solution contains free dibasic α-sugar acid and the like in addition to these two lactones.
The yield is based on the free d-saccharic acid used.
Das Verhältnis wurde wie unter ') beschrieben durch Fraktionierung bestimmt. Infolge der Meßfehlergrenze bei der Bestimmung beträgt die Summe der beiden Lactonen nicht genau 100%.The ratio was determined as described under ') by fractionation. As a result of the measurement error limit in the determination the sum of the two lactones is not exactly 100%.
Das Verteilungsverhältnis zwischen dem 1,4-d-Zuckersäurelacton und dem 3,6-d-Zuckersäurelacton in den aus der Mutterlauge erhaltenen Kristallen war das gleiche wie das in der ersten Kristallfraktion.The distribution ratio between the 1,4-d-sugar acid lactone and the 3,6-d-sugar acid lactone in the mother liquor obtained crystals was the same as that in the first fraction of crystals.
Man erkennt aus den Proben Nr. 1 und 2, daß man aus einer verdünnten Lösung, die eine geringe spezifische Dichte hat, zwar Kristalle mit hoher Reinheit, aber in geringer Ausbeute erzielen kann. Dagegen erkennt man aus den Versuchen Nr. 6 bis 8, daß die konzentrierte Lösung, die eine hohe spezifische Dichte aufweist, eine It can be seen from Samples Nos. 1 and 2 that although crystals of high purity can be obtained from a dilute solution which has a low specific density , the yield is low. In contrast, it can be seen from the experiments No. 6 to 8 that the concentrated solution, which has a high specific density, a
Man erkennt aus den Proben Nr. 1 und 2, daß man aus einer verdünnten Lösung, die eine geringe spezifische Dichte hat, zwar Kristalle mit hoher Reinheit, aber in geringer Ausbeute erzielen kann. Dagegen erkennt man aus den Versuchen Nr. 6 bis 8, daß die konzentrierte Lösung, die eine hohe spezifische Dichte aufweist, eine ausreichende Ausbeute an Kristallen ergibt, diese aber sehr wenig rein sind. Demgegenüber läßt sich aus den Versuchen Nr. 3 bis 5 erkennen, daß man 1,4-d-Zuckersäurelacton mit einer guten Ausbeute und einer hohen Reinheit dann erhalten kann, wenn man sie aus wäßrigen Lösungen gewinnt, deren spezifische Dichte im Bereich von 1,300 bis 1,360 liegt.It can be seen from Samples Nos. 1 and 2 that a dilute solution results in a low has specific density, although crystals with high purity, but can achieve in low yield. Against it It can be seen from experiments No. 6 to 8 that the concentrated solution has a high specific density has a sufficient yield of crystals, but these are very poorly pure. In contrast It can be seen from experiments No. 3 to 5 that 1,4-d-sugar acid lactone is obtained with a good Yield and high purity can then be obtained when they are obtained from aqueous solutions, the specific gravity of which is in the range from 1.300 to 1.360.
Im einzelnen kann das erfindungsgemäße Verfahren wie folgt veranschaulicht werden:The method according to the invention can be illustrated in detail as follows:
Eine wäßrige Suspension aus beispielsweise Kaliumhydrogensaccharat wird mit einem Kationenaustauscherharz behandelt, und man gewinnt eine reine wäßrige Lösung aus d-Zuckersäure, die dann gegebenenfalls durch Konzentrierung od. dgl. auf eine spezifische Dichte von 1,300 bis 1,360 gebracht wird. Dazu fügt man dann Kristalle von reinem 1,4-d-Zuckersäurelacton hinzu und läßt in einem gekühlten Raum bei vorzugsweise 2 bis 3°C 5 bis 8 Tage lang stehen, wobei 1,4-d-Zuckersäurelacton auskristallisiert. Während der Kristallisation wird 3,6-d-Zuckersäurelacton zum Teil in das 1,4-d-Zuckersäurelacton umgeformt und kristallisiert infolge Verschiebung des Gleichgewichtes. An aqueous suspension of, for example, potassium hydrogen saccharate is treated with a cation exchange resin, and a pure aqueous solution of d-saccharic acid is obtained, which is then optionally by concentration or the like. Is brought to a specific density of 1.300 to 1.360. Crystals of pure 1,4-d-sugar acid lactone are then added to this and leave to stand in a cool room at preferably 2 to 3 ° C for 5 to 8 days, 1,4-d-sugar acid lactone crystallizing out. During crystallization, 3,6-d-sugar acid lactone becomes partly transformed into 1,4-d-sugar acid lactone and crystallized as a result of a shift in the equilibrium.
Die gebildeten Kristalle werden abfiltriert und gesammelt und dann mit einer geringen Menge an Aceton gewaschen. Das so erhaltene 1,4-d-Zuckersäurelacton wurde als vollständig reines Produkt identifiziert. Auf dem Papierchromatogramm (nach der Hydroxansäuremethode oder einer sonstigen Methode ermittelt) zeigte sich nur eine einzige Adsorptionsstelle. Die Ausbeute betrug etwa 15 bis 20%· Die Mutterlauge behandelt man dann wiederholt in der gleichen Weise, und dabei kann man eine Gesamtausbeute von 80 bis 85% erreichen, wenn man die Kristalle aus drei Behandlungsgängen sammelt. Beim erfindungsgemäßen Verfahren ist eine Wärmebehandlung oder ein Zusatz von Säure nicht erforderlich. 5 The crystals formed are filtered off and collected and then washed with a small amount of acetone. The 1,4-d-sugar acid lactone thus obtained was identified as a completely pure product. The paper chromatogram (determined by the hydroxanic acid method or another method) showed only a single adsorption site. The yield was about 15 to 20%. The mother liquor is then treated repeatedly in the same way, and an overall yield of 80 to 85% can be achieved if the crystals from three treatments are collected. In the process according to the invention, heat treatment or the addition of acid is not necessary. 5
Es wurden 100 g Kaliumhydrogensaccharat in 750 ml Wasser suspendiert, und dazu wurde unter100 g of potassium hydrogen saccharate were suspended in 750 ml of water, and was added under
ίο Rühren ein Ionenaustauscherharz mit der Handelsbezeichnung Amberlite IR-120 (Η-Typ) (Handelsbezeichnung eines Handelsproduktes der Firma Röhm & Haas Inc.) zugegeben, wobei das Kaliumsalz gelöst wird. Das Gemisch wird durch eine mit demίο Stirring an ion exchange resin with the trade name Amberlite IR-120 (Η type) (trade name of a commercial product made by the company Rohm & Haas Inc.) was added, the potassium salt being dissolved. The mixture is through a with the
is gleichen Harz beladene Säule hindurchgeleitet, und darin wird das Kaliumion vollständig adsorbiert. Dann wird mit Wasser gewaschen. Die Durchlaufflüssigkeit und die Waschflüssigkeit werden miteinander vereinigt, und anschließend wird durch Abdestillieren von Lösungsmittel die spezifische Dichte der Lösung auf 1,356 eingestellt. Die so erhaltene wäßrige Lösung, die 77,5 g an reiner d-Zuckersäure enthielt, wurde mit Impfkristallen aus reinem 1,4-Lacton-Monohydrat versetzt und dann in einem auf 2 bis 3° C gekühltenis passed through the same resin-loaded column, and the potassium ion is completely adsorbed therein. Then it is washed with water. The run-through liquid and the washing liquids are combined with each other, followed by distilling off adjusted the specific gravity of the solution to 1.356 by solvent. The aqueous solution thus obtained, which contained 77.5 g of pure d-saccharic acid, was seeded with pure 1,4-lactone monohydrate added and then in a cooled to 2 to 3 ° C
as Raum 5 Tage lang stehengelassen. Danach wurden die gebildeten Kristalle~^aas 1,4-Lacton-Monohydrat abfiltriert und mit einer geringen Menge an Aceton gewaschen. Die Ausbeute betrug 14,7 g. Das Produkt hatte einen Schmelzpunkt von 90 bis 93 0C. Die papierchromatographische Analyse (wobei als Entwicklungslösungsmittel die obere Schicht einer Mischung aus Butanol: Äthanol: Ameisensäure: Wasser im Verhältnis von 4:1:1:5 eingesetzt wurde) ergab einen Rf-Wert von nur 0,33. Nachdem die spezifische Dichte der Mutterlauge wie zuvor beschrieben eingestellt worden war, wurde die Kristallabscheidung wiederholt, und man erhielt insgesamt 48,3 g an 1,4-d-Zuckersäurelacton, das die gleiche Reinheit hatte wie dies zuvor für die aus der Mutterlauge erhaltenen Kristalle angegeben wurde.Let the room stand for 5 days. The crystals formed were then filtered off as 1,4-lactone monohydrate and washed with a small amount of acetone. The yield was 14.7 g. The product had a melting point of 90 to 93 ° C. Analysis by paper chromatography (using the upper layer of a mixture of butanol: ethanol: formic acid: water in a ratio of 4: 1: 1: 5 as developing solvent) gave an Rf value of only 0.33. After the specific gravity of the mother liquor had been adjusted as described above, the crystal separation was repeated, and a total of 48.3 g of 1,4-d-sugar acid lactone, which had the same purity as that for the crystals obtained from the mother liquor, were obtained was specified.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2786764 | 1964-05-19 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1518649A1 DE1518649A1 (en) | 1969-02-20 |
| DE1518649B2 DE1518649B2 (en) | 1973-04-19 |
| DE1518649C3 true DE1518649C3 (en) | 1978-11-02 |
Family
ID=12232836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1965C0035835 Expired DE1518649C3 (en) | 1964-05-19 | 1965-05-13 | Process for the production of 1,4d-sugar acid lactone |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH448988A (en) |
| DE (1) | DE1518649C3 (en) |
| GB (1) | GB1079434A (en) |
-
1965
- 1965-05-05 GB GB1902365A patent/GB1079434A/en not_active Expired
- 1965-05-13 DE DE1965C0035835 patent/DE1518649C3/en not_active Expired
- 1965-05-14 CH CH675065A patent/CH448988A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1079434A (en) | 1967-08-16 |
| DE1518649A1 (en) | 1969-02-20 |
| DE1518649B2 (en) | 1973-04-19 |
| CH448988A (en) | 1967-12-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| SH | Request for examination between 03.10.1968 and 22.04.1971 | ||
| C3 | Grant after two publication steps (3rd publication) | ||
| 8339 | Ceased/non-payment of the annual fee |