CH595351A5 - Orotic acid prodn. - Google Patents
Orotic acid prodn.Info
- Publication number
- CH595351A5 CH595351A5 CH587275A CH587275A CH595351A5 CH 595351 A5 CH595351 A5 CH 595351A5 CH 587275 A CH587275 A CH 587275A CH 587275 A CH587275 A CH 587275A CH 595351 A5 CH595351 A5 CH 595351A5
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- reaction
- bromo
- added
- bromine
- Prior art date
Links
- PXQPEWDEAKTCGB-UHFFFAOYSA-N orotic acid Chemical compound OC(=O)C1=CC(=O)NC(=O)N1 PXQPEWDEAKTCGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229960005010 orotic acid Drugs 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011976 maleic acid Substances 0.000 claims abstract description 21
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 24
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- RAJPFQIQPQVRAJ-UHFFFAOYSA-N OC(=O)C1=NC(=O)NC(=O)C1Br Chemical compound OC(=O)C1=NC(=O)NC(=O)C1Br RAJPFQIQPQVRAJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000375 suspending agent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000001419 dependent effect Effects 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- SOWPGKJPEXNMCS-OWOJBTEDSA-N (e)-2-bromobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Br)C(O)=O SOWPGKJPEXNMCS-OWOJBTEDSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- FPNCYXWKYIKGDF-UHFFFAOYSA-N COC(=O)C1=NC(=O)NC(=O)C1Br Chemical compound COC(=O)C1=NC(=O)NC(=O)C1Br FPNCYXWKYIKGDF-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- -1 maleic acid ureide Chemical class 0.000 abstract 2
- TWHXMCSPQHQVFV-UHFFFAOYSA-N 5-bromo-2,6-dioxo-1,3-diazinane-4-carboxylic acid Chemical compound OC(=O)C1NC(=O)NC(=O)C1Br TWHXMCSPQHQVFV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
- C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/557—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. orotic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Prodn. of orotic acid (I) comprises reacting maleic acid ureide (II) or its salt or ester with Br2 at 0-50 degrees C to give 5-bromo-4,6-dihydroorotic acid (III). This is isolated and converted to (I) in aq. soln. with alkali metal hydroxide, pref. KOH or NaOH.Pref. 0.9-1.1 mole, esp. 1.0 mole Br2 are used/mole (II). The reaction is pref. carried out at 10-25 degrees C and in the presence of a dispersing agent.In an example, 16g Br2 were added to a suspension of 15.8g (II) in 120 ml H2O and stirred 9 hrs. at 15 degrees C. After filtration and drying 93% yield of (III) was obtd.23.7g (III) were added over 15 mins. to 20.0g NaOH in 170.0g H2O. After 3 hours the reaction mixt. was acidified with HCl to give 11.0g pure (I) (70%).
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Orotsäure aus Maleinsäureureid.
Aus Journal of the American Chemical Society 63, 995 (1941) ist es bekannt, Maleinsäureureid mit Bromwasser umzusetzen. Als Endprodukt resultierte das 3-Brom-maleinsäureureid.
Es wurde auch versucht, Maleinsäureureid durch Bromierung in Wasser und anschliessender Zugabe von KOH Orotsäure herzustellen. Es resultierten Ausbeuten von nur rund 14% (Chemical Abstracts 64, 2084 f).
Es wurde nun gefunden, dass bei geeigneten Reaktionsbedingungen die Umsetzung von Maleinsäureureid mit Brom nicht zum 3-Brom-maleinsäureureid führt, sondern dass sich weit wertvollere Verbindungen herstellen lassen und diese Zwischenprodukte in hoher Ausbeute zur Orotsäure umgesetzt werden können.
Erfindungsgemäss wird das dadurch erreicht, dass man Maleinsäureureid oder dessen Ester oder Salze mit Brom bei Temperaturen von 0 bis 500C zu 5-Brom-5,6-dihydroorotsäure oder den entsprechenden Estern oder Salzen umsetzt, die erhaltenen Verbindungen isoliert und anschliessend zu einer wässrigen Lösung eines Alkalihydroxids zufügt und zur Orotsäure umsetzt.
Ausser dem Maleinsäureureid können auch dessen Ester, beispielsweise Methyl- oder Äthylester oder dessen Salze, beispielsweise Natrium- oder Kaliumsalz, verwendet werden.
Pro Mol Maleinsäureureid werden zweckmässig 0,9 bis 1,1 Mol, vorzugsweise 1,0 Mol, Brom angewendet.
Der vorzugsweise Temperaturbereich für die Ausführung der Reaktion liegt bei 10 bis 250C.
Zweckmässig wird die Reaktion in Gegenwart eines Suspensionsmittels ausgeführt. Die Wahl des Suspensionsmittels ist nicht kritisch und beeinflusst den Reaktionsablauf nicht.
Geeignete Suspensionsmittel sind Wasser, verdünnte Schwefelsäure, Essigsäure, Methanol, Tetrachlorkohlenstoff, Chloroform, Methylenchlorid usw.
Vorzugsweise wird Wasser als Suspensionsmittel angewendet.
Die 5-Brom-5,6-dihydroorotsäure oder deren Ester oder Salze wird zweckmässig zu einer wässrigen Lösung von Natriumhydroxid oder Kaliumhydroxid zugefügt und zur Orotsäure umgesetzt.
Die Reaktionszeit liegt bei 0,5 bis 50 Stunden, bei optimalen Reaktionsbedingungen dauert der Ablauf der Reaktion 5 bis 20 Stunden.
Das erfindungsgemässe Verfahren führt bei fast quantitativen Umsätzen zu hohen Ausbeuten.
Beispiele 1. Zu einer Suspension von 15,8 g Maleinsäureureid in 120 ml
Wasser gibt man 16 g Brom und rührt während 9 Stunden bei einer Temperatur von 15ob. Nach Filtration und Trock nung erhielt man 5-Brom-5,6-dihydroorotsäure in einer
Ausbeute von rund 93%.
2. Zu einer Suspension von 18 g Maleinsäureureid-Natrium salz in 100 ml Wasser fügt man 16 g Brom bei und rührt während 10 Stunden bei 15ob. Man erhielt nach Filtration und Trocknung 5-Brom-5,6-dihydroortosäure in einer
Ausbeute von rund 90%.
3. 17,2 g Maleinsäureureid-methylester wurden in 100 ml
Wasser suspendiert und mit 16,0 g Brom vermischt. Nach
10 Stunden Rühren bei 18"C erhielt man 5-Brom-5,6 dihydroorotsäure-methylester in einer Ausbeute von 95%.
4. Zu 20,0 g Natriumhydroxid in 170,0 g Wasser werden bei einer Temperatur von 750C innerhalb von 15 Minuten
23,7 g 5-Brom-5,6-dihydroorotsäure, hergestellt nach Bei spiel 1 oder 2, zugefügt. Nach 3 Stunden wird das Reak tionsgemisch mit Salzsäure angesäuert und man erhält 11,0 g reine Orotsäure (70%).
PATENTANSPRUCH
Verfahren zur Herstellung von Orotsäure, dadurch gekennzeichnet, dass man Maleinsäureureid oder dessen Ester oder Salze mit Brom bei Temperaturen von 0 bis 50"C zu 5-Brom5,6-dihydroorotsäure oder den entsprechenden Estern oder Salzen umsetzt, die erhaltenen Verbindungen isoliert und anschliessend zu einer wässrigen Lösung eines Alkalihydroxids zufügt und zur Orotsäure umsetzt.
UNTERANSPRÜCHE
1. Verfahren gemäss Patentanspruch, dadurch gekennzeichnet, dass pro Mol Maleinsäureureid 0,9 bis 1,1 Mol, vorzugsweise 1,0 Mol, Brom angewendet wird.
2. Verfahren gemäss Patentanspruch und Unteranspruch 1, dadurch gekennzeichnet, dass die Reaktion vorzugsweise bei Temperaturen von 10 bis 250C ausgeführt wird.
3. Verfahren gemäss Patentanspruch und Unteransprüchen 1 und 2, dadurch gekennzeichnet, dass die Reaktion in Gegenwart eines Suspensionsmittels ausgeführt wird.
4. Verfahren gemäss Patentanspruch und Unteransprüchen 1 bis 3, dadurch gekennzeichnet, dass die Reaktion in Gegenwart von Wasser ausgeführt wird.
5. Verfahren gemäss Patentanspruch und Unteransprüchen 1 bis 3, dadurch gekennzeichnet, dass die 5-Brom-5,6-dihydroorotsäure oder deren Ester oder Salze zu einer wässrigen Lösung von Natriumhydroxid oder Kaliumhydroxid zugefügt und zur Orotsäure umgesetzt wird.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
The invention relates to a process for the production of orotic acid from maleic acid acid.
From Journal of the American Chemical Society 63, 995 (1941) it is known to react maleic acid acid with bromine water. The end product was 3-bromo maleic acid acid.
Attempts have also been made to produce maleic acid acid by bromination in water and subsequent addition of KOH orotic acid. This resulted in yields of only around 14% (Chemical Abstracts 64, 2084 f).
It has now been found that, under suitable reaction conditions, the reaction of maleic acid acid with bromine does not lead to 3-bromo-maleic acid acidide, but that far more valuable compounds can be produced and these intermediates can be converted to orotic acid in high yield.
According to the invention, this is achieved by converting maleic acid or its esters or salts with bromine at temperatures from 0 to 50 ° C. to give 5-bromo-5,6-dihydroorotic acid or the corresponding esters or salts, isolating the compounds obtained and then giving them an aqueous solution an alkali hydroxide and converts to orotic acid.
In addition to the maleic acid acid, its esters, for example methyl or ethyl esters, or its salts, for example sodium or potassium salt, can also be used.
0.9 to 1.1 mol, preferably 1.0 mol, of bromine are expediently used per mole of maleic acid acid.
The preferred temperature range for carrying out the reaction is 10 to 250C.
The reaction is expediently carried out in the presence of a suspending agent. The choice of suspending agent is not critical and does not affect the course of the reaction.
Suitable suspending agents are water, dilute sulfuric acid, acetic acid, methanol, carbon tetrachloride, chloroform, methylene chloride, etc.
Preferably, water is used as a suspending agent.
The 5-bromo-5,6-dihydroorotic acid or its esters or salts are expediently added to an aqueous solution of sodium hydroxide or potassium hydroxide and converted to orotic acid.
The reaction time is 0.5 to 50 hours; under optimal reaction conditions, the reaction takes 5 to 20 hours.
The process according to the invention leads to high yields with almost quantitative conversions.
Examples 1. To a suspension of 15.8 g of maleic acid acid in 120 ml
16 g of bromine are added to water and the mixture is stirred for 9 hours at a temperature of 15ob. After filtration and drying, 5-bromo-5,6-dihydroorotic acid was obtained in one
Yield of around 93%.
2. 16 g of bromine are added to a suspension of 18 g of sodium malefic acid salt in 100 ml of water and the mixture is stirred at 15ob for 10 hours. After filtration and drying, 5-bromo-5,6-dihydroorto acid was obtained in one
Yield of around 90%.
3. 17.2 g of maleic acid methyl ester were added to 100 ml
Suspended water and mixed with 16.0 g of bromine. To
Stirring for 10 hours at 18 ° C. gave 5-bromo-5,6 dihydroorotic acid methyl ester in a yield of 95%.
4. To 20.0 g of sodium hydroxide in 170.0 g of water are added at a temperature of 750C within 15 minutes
23.7 g of 5-bromo-5,6-dihydroorotic acid, prepared according to Example 1 or 2, added. After 3 hours, the reaction mixture is acidified with hydrochloric acid and 11.0 g of pure orotic acid (70%) are obtained.
PATENT CLAIM
Process for the preparation of orotic acid, characterized in that maleic acid acid or its esters or salts are reacted with bromine at temperatures from 0 to 50 "C to give 5-brom5,6-dihydroorotic acid or the corresponding esters or salts, the compounds obtained are isolated and then added an aqueous solution of an alkali hydroxide is added and converted to orotic acid.
SUBCLAIMS
1. The method according to claim, characterized in that 0.9 to 1.1 mol, preferably 1.0 mol, of bromine is used per mole of maleic acid acid.
2. The method according to claim and dependent claim 1, characterized in that the reaction is preferably carried out at temperatures of 10 to 250C.
3. The method according to claim and dependent claims 1 and 2, characterized in that the reaction is carried out in the presence of a suspending agent.
4. The method according to claim and dependent claims 1 to 3, characterized in that the reaction is carried out in the presence of water.
5. The method according to claim and dependent claims 1 to 3, characterized in that the 5-bromo-5,6-dihydroorotic acid or its esters or salts are added to an aqueous solution of sodium hydroxide or potassium hydroxide and converted to orotic acid.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH587275A CH595351A5 (en) | 1975-05-07 | 1975-05-07 | Orotic acid prodn. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH587275A CH595351A5 (en) | 1975-05-07 | 1975-05-07 | Orotic acid prodn. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH595351A5 true CH595351A5 (en) | 1978-02-15 |
Family
ID=4300723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH587275A CH595351A5 (en) | 1975-05-07 | 1975-05-07 | Orotic acid prodn. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH595351A5 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200714A (en) * | 2016-03-18 | 2017-09-26 | 苏州长征－欣凯制药有限公司 | A kind of method for preparing orotic acid |
-
1975
- 1975-05-07 CH CH587275A patent/CH595351A5/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200714A (en) * | 2016-03-18 | 2017-09-26 | 苏州长征－欣凯制药有限公司 | A kind of method for preparing orotic acid |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased | ||
| PL | Patent ceased |