CH302905A - Process for the preparation of methyl isonicotinate. - Google Patents
Process for the preparation of methyl isonicotinate.Info
- Publication number
- CH302905A CH302905A CH302905DA CH302905A CH 302905 A CH302905 A CH 302905A CH 302905D A CH302905D A CH 302905DA CH 302905 A CH302905 A CH 302905A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- isonicotinic acid
- ester
- hydrogen
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 4
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 title description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- SQSYNRCXIZHKAI-UHFFFAOYSA-N 2,6-dichloroisonicotinic acid Chemical compound OC(=O)C1=CC(Cl)=NC(Cl)=C1 SQSYNRCXIZHKAI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XSKGHSUHOYEBTK-UHFFFAOYSA-N methyl 2,6-dichloropyridine-4-carboxylate Chemical compound COC(=O)C1=CC(Cl)=NC(Cl)=C1 XSKGHSUHOYEBTK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QLRUROKTVFUQIV-UHFFFAOYSA-N 2,6-dichloropyridine-4-carbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=NC(Cl)=C1 QLRUROKTVFUQIV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- -1 isopropyl ester Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung des Isonicotinsänremethylesters. Es wurde gefunden, dass man Isonicotin- säureester dadurch herstellen kann, dass man auf einen in einem Alkohol gelösten niederen Alkylester der 2,6-Dichlor-isonicotinsäure in Gegenwart eines Hydrierungskatalysators und eines chlorwasserstoffbindenden Mittels unter solchen Bedingungen, dass keine Verseifung des Esters eintritt, Wasserstoff einwirken lässt.
Als chlorwasserstoffbindende Mittel haben sich besonders Alkaliacetate und tertiäre Ba sen bewährt. Bei der Verwendung von Alkali- acetat empfiehlt es sich, als Lösungsmittel Methanol oder Äthanol, dem man zweckmässig etwas Wasser zusetzt, zu verwenden. Dagegen ist die Verwendung von absoluten Alkoholen als Lösungsmittel empfehlenswert, wenn mit organischen Basen gearbeitet wird.
Bei der Herstellung des Methylesters wer den besonders gute Resultate erzielt, wenn man den 2,6-Dichlor-isonicotinsäure-methyl- ester in etwa 95o/oigem Methanol in Gegen wart der doppelt molaren Menge Kaliumacetat und eines Palladiiim-Kohle-Katalysators bei etwa 50 hydriert.
Nach einer weiteren vorteilhaften Arbeits weise hydriert man den niederen 2,6-Dichlor- isonicotinsäurealkylester in absolut alkoholi scher Lösung in Gegenwart von Triäthylamin mittels eines Palladium-Kohle-Katalysators oder mit Raney-Nickel bei erhöhter Tempera tur und, falls Raney-Nickel verwendet wird, unter einem Wasserstoffdruck von etwa 40 Atmosphären.
Da der Isonicotinsäure-methylester und in geringerem Masse auch die nächst höheren Ester recht flüchtig und leicht verseifbar sind, empfiehlt es sich bei der Aufarbeitung, die bei der Behandlung von Stoffen mit sol chen Eigenschaften übliche Vorsicht walten zu lassen.
Die niederen 2,6-Dichlor-isonicotinsäure- alkylester können z. B. aus dem bekannten 2,6 Dichlor-isonicotinsäurechlorid durch Erwär men des letzteren mit dem gewünschten Alko hol (z. B. Methanol, Äthanol, Isopropanol, n- Butanol) und Fällung des gebildeten Esters aus dem Reaktionsgemisch durch Zusatz von Eiswasser gewonnen werden.
In der folgenden Tabelle sind charakte ristische physikalische Daten einiger 2,6-Di- chlor-isonicotinsäureester sowie der daraus er hältlichen Isonicotinsäureester angeführt:
EMI0002.0001
Dichlorisonicotin- <SEP> Isonicotinsäure säure-alkylester <SEP> alkylester
<tb> Methylester <SEP> Smp. <SEP> : <SEP> 83 C <SEP> Smp. <SEP> : <SEP> 12-140C
<tb> Kpl4: <SEP> 96-97<B>0</B>C
<tb> nD <SEP> <SEP> = <SEP> 1,5124
<tb> <B><I>U.</I></B><I> <SEP> V.-Absorption <SEP> U.V.-Absorption</I>
<tb> Äthylester <SEP> Smp. <SEP> : <SEP> 67 C <SEP> max. <SEP> 394 <SEP> m,u <SEP> Kpo <SEP> :
<SEP> 89-90 C <SEP> max. <SEP> 274 <SEP> mss
<tb> s <SEP> - <SEP> 4350 <SEP> n,250'= <SEP> 1,5002 <SEP> s <SEP> = <SEP> 2700
<tb> Isopropylester <SEP> smp. <SEP> : <SEP> 58 <SEP> C <SEP> min. <SEP> 243 <SEP> mu <SEP> Kpo <SEP> : <SEP> 89-90 C <SEP> min. <SEP> 236 <SEP> mA
<tb> s <SEP> = <SEP> 450 <SEP> n,"" <SEP> = <SEP> 1,4884 <SEP> s <SEP> = <SEP> 460
<tb> n-Butylester <SEP> Kplo: <SEP> 157 C <SEP> Kpo: <SEP> 113 C
<tb> nD <SEP> <SEP> = <SEP> 1,5188 <SEP> nD <SEP> <SEP> = <SEP> 1,4900 Die nach dem erfindungsgemässen Verfah ren erhältlichen niederen Isonicotinsäure-alkyl- ester sind als Zwischenprodukte für die Syn these pharmakologisch wirksamer Verbindun gen verwendbar.
Gegenstand des Patentes ist ein Verfah ren zur Herstellung des bekannten Isonicotin- säuremethylesters, welches dadurch gekenn zeichnet ist, dass man auf den 2,6-Dichloriso- nicotinsäuremethylester, der in einem Alkohol gelöst ist, in Gegenwart eines Hydrierimgs- katalysatörs und eines chlorwasserstoffbinden- den Mittels unter solchen Bedingungen,
dass keine Verseifung des Esters eintritt, Wasser stoff einwirken lässt.
<I>Beispiel 1:</I> 206 Gewichtsteile 2,6-Dichlor-isonicotin- säuremethylester, 60 Gewichtsteile feuchte Palladiumkohle (enthaltend 1,5 Gewichtsteile Palladiiun), 200 Gewichtsteile Kaliumacetat, 560 Gewichtsteile Methanol und 30 Gewichts teile - Wasser werden in einem Hydrierkolben bei 50 -unter einem Druck von etwa 0,1 Atü unter Wasserstoff geschüttelt;
nach Aufnahme von 2_ Mol Wasserstoff kommt die Hydrie rung zum Stillstand. Man nutseht vom Kata lysator und vom ausgefallenen Kaliumchlorid ab und verdampft darauf das Methanol mög lichst vollständig. Den Rückstand versetzt man unter Kühlung allmählich mit konzentriertem Ammoniak (25a4), bis Lackmus eben gebläut wird. Man extrahiert erschöpfend mit Äther, trocknet und dampft den Äther wieder ab. Beim Destillieren des Rückstandes unter einem Druck von 74 mm Hg geht bei 96 bis 97 reiner Isonicotinsäuremethylester über.
Ausbeute 89"/o.
Beispiel <I>2:</I> 41,2 Gewichtsteile 2,6-Dichlor-isonicotin- säure-methylester (0,2 Mol), 40 Gewichtsteile Triäthylamin, 12 Gewichtsteile feuchte Palla- diumkohle (enthaltend 0,3 Gewichtsteile Pal ladium) und 200 Raumteile absoluter Metha nol werden in einem Hydrierkolben bei 40 unter Wasserstoff geschüttelt. Nach Auf nahme von 0,4 112o1 Wasserstoff kommt die Hydrierung zum Stillstand. Man nutscht vom Katalysator ab und engt vorsichtig ein.
Man versetzt den Rückstand mit 200 em3 ab solutem Äther, lässt den Kristallbrei 1-2 Stunden bei 0 stehen -und nutscht hierauf ab. Den Niederschlag wäscht man sorgfältig mit mehreren Portionen absolutem Äther aus. Die Ätherauszüge werden mit gesättigter Koch- salzlösung gewaschen, getrocknet und hierauf eingedampft. Beim Destillieren des Rückstan des unter vermindertem Druck erhält man Isonicotinsäure-methylester (KP-14 96-97 ). Ausbeute: etwa 900/9.
Process for the preparation of the isonicotinic remethyl ester. It has been found that isonicotinic acid esters can be prepared by reacting on a lower alkyl ester of 2,6-dichloro-isonicotinic acid dissolved in an alcohol in the presence of a hydrogenation catalyst and a hydrogen chloride-binding agent under conditions such that no saponification of the ester occurs, Allows hydrogen to act.
Alkali acetates and tertiary bases have proven particularly useful as agents that bind hydrogen chloride. When using alkali acetate, it is advisable to use methanol or ethanol as the solvent, to which a little water is expediently added. In contrast, the use of absolute alcohols as solvents is recommended when working with organic bases.
In the preparation of the methyl ester who achieved particularly good results if the 2,6-dichloro-isonicotinic acid methyl ester in about 95% methanol in the presence of twice the molar amount of potassium acetate and a palladium-carbon catalyst at about 50% hydrogenated.
According to a further advantageous operation, the lower 2,6-dichloro-isonicotinic acid alkyl ester is hydrogenated in an absolutely alcoholic solution in the presence of triethylamine using a palladium-carbon catalyst or with Raney nickel at an elevated temperature and, if Raney nickel is used , under a hydrogen pressure of about 40 atmospheres.
Since the methyl isonicotinate and, to a lesser extent, the next higher esters are quite volatile and easily saponifiable, it is advisable to exercise the usual caution when treating substances with such properties.
The lower 2,6-dichloro-isonicotinic acid alkyl esters can, for. B. from the known 2,6 dichloro-isonicotinic acid chloride by warming the latter with the desired Alko hol (z. B. methanol, ethanol, isopropanol, n-butanol) and precipitation of the ester formed from the reaction mixture by adding ice water .
The following table lists the characteristic physical data of some 2,6-dichloro-isonicotinic acid esters and the isonicotinic acid esters obtainable from them:
EMI0002.0001
Dichlorisonicotin- <SEP> isonicotinic acid-alkyl ester <SEP> alkyl ester
<tb> methyl ester <SEP> m.p. <SEP>: <SEP> 83 C <SEP> m.p. <SEP>: <SEP> 12-140C
<tb> Kpl4: <SEP> 96-97 <B> 0 </B> C
<tb> nD <SEP> <SEP> = <SEP> 1.5124
<tb> <B><I>U.</I></B> <I> <SEP> V. Absorption <SEP> U.V. Absorption </I>
<tb> ethyl ester <SEP> melting point <SEP>: <SEP> 67 C <SEP> max. <SEP> 394 <SEP> m, u <SEP> Kpo <SEP>:
<SEP> 89-90 C <SEP> max. <SEP> 274 <SEP> mss
<tb> s <SEP> - <SEP> 4350 <SEP> n, 250 '= <SEP> 1,5002 <SEP> s <SEP> = <SEP> 2700
<tb> isopropyl ester <SEP> smp. <SEP>: <SEP> 58 <SEP> C <SEP> min. <SEP> 243 <SEP> mu <SEP> Kpo <SEP>: <SEP> 89-90 C <SEP> min. <SEP> 236 <SEP> mA
<tb> s <SEP> = <SEP> 450 <SEP> n, "" <SEP> = <SEP> 1.4884 <SEP> s <SEP> = <SEP> 460
<tb> n-butyl ester <SEP> Kplo: <SEP> 157 C <SEP> Kpo: <SEP> 113 C
<tb> nD <SEP> <SEP> = <SEP> 1.5188 <SEP> nD <SEP> <SEP> = <SEP> 1.4900 The lower isonicotinic acid alkyl esters obtainable by the process according to the invention are intermediate products can be used for the synthesis of pharmacologically active compounds.
The subject of the patent is a process for the production of the known isonicotinic acid methyl ester, which is characterized in that the 2,6-dichloroisonicotinic acid methyl ester, which is dissolved in an alcohol, is added in the presence of a hydrogenation catalyst and a hydrogen chloride binder. the means under such conditions,
that no saponification of the ester occurs, hydrogen can act.
<I> Example 1: </I> 206 parts by weight of 2,6-dichloro-isonicotinic acid methyl ester, 60 parts by weight of moist palladium carbon (containing 1.5 parts by weight of palladium), 200 parts by weight of potassium acetate, 560 parts by weight of methanol and 30 parts by weight of water are in a hydrogenation flask at 50 - shaken under a pressure of about 0.1 atmospheres under hydrogen;
after uptake of 2 mol of hydrogen, the hydrogenation comes to a standstill. You nutseht from the catalyst and the precipitated potassium chloride and then evaporated the methanol as completely as possible. Concentrated ammonia (25a4) is gradually added to the residue, while cooling, until litmus is just blued. Extract exhaustively with ether, dry and evaporate the ether again. When the residue is distilled under a pressure of 74 mm Hg, pure methyl isonicotinate is transferred at 96 to 97.
Yield 89 "/ o.
Example <I> 2: </I> 41.2 parts by weight of 2,6-dichloro-isonicotinic acid methyl ester (0.2 mol), 40 parts by weight of triethylamine, 12 parts by weight of moist palladium carbon (containing 0.3 part by weight of palladium ) and 200 parts by volume of absolute methanol are shaken in a hydrogenation flask at 40 under hydrogen. After uptake of 0.4 112o1 hydrogen, the hydrogenation stops. The catalyst is filtered off with suction and carefully concentrated.
The residue is mixed with 200 cubic meters of absolute ether, the crystal slurry is left to stand for 1-2 hours at 0 and then suction filtered. The precipitate is carefully washed out with several portions of absolute ether. The ether extracts are washed with saturated sodium chloride solution, dried and then evaporated. When the residue is distilled off under reduced pressure, methyl isonicotinate is obtained (KP-14 96-97). Yield: about 900/9.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH302905T | 1952-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH302905A true CH302905A (en) | 1954-11-15 |
Family
ID=4491528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH302905D CH302905A (en) | 1952-03-07 | 1952-03-07 | Process for the preparation of methyl isonicotinate. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH302905A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268775A1 (en) * | 1986-09-26 | 1988-06-01 | Ciba-Geigy Ag | Method for protecting plants against diseases |
-
1952
- 1952-03-07 CH CH302905D patent/CH302905A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268775A1 (en) * | 1986-09-26 | 1988-06-01 | Ciba-Geigy Ag | Method for protecting plants against diseases |
| US4968344A (en) * | 1986-09-26 | 1990-11-06 | Ciba-Geigy Corporation | Method for protecting plants against diseases |
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