CH310985A - Process for the preparation of a sulfur-containing pyridone. - Google Patents
Process for the preparation of a sulfur-containing pyridone.Info
- Publication number
- CH310985A CH310985A CH310985DA CH310985A CH 310985 A CH310985 A CH 310985A CH 310985D A CH310985D A CH 310985DA CH 310985 A CH310985 A CH 310985A
- Authority
- CH
- Switzerland
- Prior art keywords
- compound
- parts
- sulfur
- ethyl
- methyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 4
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 title claims description 4
- 229910052717 sulfur Inorganic materials 0.000 title claims description 4
- 239000011593 sulfur Substances 0.000 title claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- -1 formic acid ester Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VSWICNJIUPRZIK-UHFFFAOYSA-N 2-piperideine Chemical compound C1CNC=CC1 VSWICNJIUPRZIK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000000517 effect on sleep Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000725 suspension Substances 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Hydrogenated Pyridines (AREA)
Description
verfahren zur Herstellung eines schwefelhaltigen Pyridons. Es wurde gefunden, dass die Verbindungen der alleemeinen Formel
EMI0001.0004
worin R.1 und R2 niedere Alkyl- oder Alkenyl- reste mit 1 bis 4 Kohlenstoffatomen darstellen, sich durch tiefe, kurz dauernde Schlafwirkung auszeiehnen.
Gemäss der vorliegenden Erfindung wer den die bisher unbekannten 2-Thio-3,3-dialkyl- 4-oxo-1,2,3,4-tetrahydropyridine dadurch ge ,vonnen, da.ss man ein a,a-Dialkyl-acetaceto- nit.ril mit. einem Ameisensäureester in Gegen wart eines alkalischen Kondensationsmittels in die y-Oxymethylenverbindung und diese mit Ammoniak in die y-Aminomethylenverbin- dung umwandelt, diese mit einem alkalischen Kondensationsmittel cyclisiert und mit Schwe felwasserstoff oder einem Schwefelwasser stoff abspaltenden Mittel behandelt.
Die a,a <I>-</I> Dialkylacetacetonitrile werden durch Alkylierung der von E. Mohr (Journal für praktische Chemie (2), Band 75 [1907], Seite 749, und (2), Band 90 [1914], Seite <B>189)</B> dargestellten a-Alkyl-acetacetonitrile er halten, Die Alkylierung kann mit Alkenyl- oder Alkylhalogeniden mit den für a-Alkyl- acetessigester üblichen Methoden ausgeführt werden.
Die a,a-Dialkyl-y-oxymethylen-acet- acetonitrile werden vorteilhaft durch Umset zen der entsprechenden Nitrile mit einem Ameisensäureester in einem indifferenten or ganischen Lösungsmittel, wie z. B. Benzol, To luol oder Diäthylkohlensäureester, in Gegen wart eines alkalischen Kondensationsmittels, wie z. B. Natrium, Kalium oder Natriumalko- holat, dargestellt.
Die in Wasser schwer löslichen a,a-Dialkyl- acetacetonitrile bilden mit wässerigen Laugen keine Salze und sind leicht von den in wäs serigen Alkalilaugen gut löslichen a,a-Dialkyl- y-oxymethylen-acetacetonitrilen zu trennen. Diese Alkalisalzlösungen können mit Ammo niak und Ammoniumchlorid in die in wässeri ger Lösung schwer löslichen a,a-Dialkyl-y- aminomethylen - Verbindungen übergeführt werden.
Mit alkalischen Kondensationsmitteln, wie z. B. Alkalialkoholate, vorteilhaft in einem or ganischen Lösungsmittel, wie z. B. Methanol, lassen sich die a,a-Dialkyl-y-aminomethylen- acetacetonitrile cyclisieren. Durch Umsetzen des Kondensationsproduktes mit Schwefelwas serstoff oder mit Schwefelwasserstoff abgeben den Mitteln, wie z. B. Phosphorpentasulfid, entstehen die 2-Thio-3,3-dialkyl-4-oxo-1,2,3,4- tetrahydropyridine.
Die neuen Verbindungen sind gelblich, in Wasser schwer und in den gebräuchlichen or ganischen Lösungsmitteln leicht löslich. In Laugen lösen sie sich unter Farbvertiefung und fallen auf Zusatz von Säuren unter Farb- aufhellung unverändert wieder aus. Sie, sollen als Schlafmittel Verwendung finden.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung eines schwefel haltigen Pyridons, das dadurch gekennzeich- riet ist, dass man a-Äthyl-a-methyl-acetaceto- nitril mit einem Ameisensäureester in Gegen wart eines alkalischen Kondensationsmittels in die y-Oxymethylenverbindung und diese mit Ammoniak in die y-Aminomethylenverbindung umwandelt, diese mit einem alkalischen Kon densationsmittel cyclisiert und mit Schwefel wasserstoff oder einem Schwefelwasserstoff abgebenden Mittel behandelt.
Das so erhältliche, neue 2-Thio-3-äthyl-3- methyl-4-oxo-1,2,3,4-tetrahydropyridin bildet gelbe Kristalle mit einem Schmelzpunkt von 113-114 C. Die Verbindung ist schwer lös lich in Wasser, in den gebräuchlichen organi schen Lösungsmitteln dagegen leicht löslich. <I>Beispiel:</I> Eine Lösung von 23 Gewichtsteilen Na trium in 500 Raumteilen trockenem Alkohol wird mit einem Gemisch von 97 Gewichtsteilen 2-Cyanobutanon-3 (E.
Mohr, Journal für praktische Chemie (2), Band 90 [1914], Seite 189 [Kp.19 n,. 78 C]) und 109 Gewichtsteilen Äthylbromid versetzt und 16 Stunden bei 50 C verrührt. Nachdem die Hauptmenge des Alkohols im Vakuum abdestilliert worden ist, wird der Rückstand mit Wasser versetzt und das oben schwimmende a-Äthyl-a-methyl-acet- acetonitril abgetrennt. Das in Alkalien unlös liche Öl siedet uniersetzt zwischen 80 und 82 C unter 1.4 mm Druck.
125 Gewiehtsteile des a-Äthyl-a-methyl- acetacetonitrils werden mit 90 Gewichtstei len Ameisensäure-methylester in eine Su spension von 24 Gewichtsteilen Natrium in 800 Raumteilen Toluol zugegeben und 16 Stunden bei 20 C verrührt.
Das ent stehende a-Äthyl-a-methyl-y-oxymethylen-aeet- acetonitril wird mit Wasser als Natriumsalz gelöst, abgetrennt und direkt mit Ammonium- ehlorid und Ammoniak in die Aminomet.hy - lenv erbindung übergeführt. Das in verdünn ter Ammoniaklösung schwer lösliehe a-Äthyl- a.-methyl-y-aminometh@-len-acetacetonitril wird mit Benzol ausgezogen, getrocknet und im Va kuum eingeengt.
Das verbleibende Öl kann im Hochvakuum rektifiziert werden (Kp.0,05 Inn" 106 C).
152 Gewichtsteile a-Äthyl-a-methyl-y-amino- methylen-acetacetonitrilwerden mit einer aus 3<B><I>'0</I></B> Gewichtsteilen Natrium in 500 Raumteilen Alkohol zubereiteten Natriumalkoholatlösung umgesetzt und 12 Stunden stehengelassen. Dann werden 80 Gewiehtsteile Schwefelwas serstoff eingeleitet, wobei sich die Lösung er wärmt. Nach dem Abklingen der Reaktion wird mit 125 Raumteilen 37o/oiger Salzsäure tropfenweise versetzt, wobei Schwefelwasser stoff entweicht.
Das dunkel gefärbte Reak tionsgut wird durch Tierkohle filtriert und mit 500 Raumteilen Wasser tropfenweise ver setzt, wobei das 2-Thio-3-äthyl-3-methyl-4-oxo. 1,2,3,4-tetrahydropyridin in gelben Kristallen ausfällt. Nach Umlösen aus Methanol schmel zen die Kristalle bei 113-11.4 C.
process for the production of a sulfur-containing pyridone. It has been found that the compounds of the general formula
EMI0001.0004
in which R.1 and R2 represent lower alkyl or alkenyl radicals with 1 to 4 carbon atoms, are drawn out by deep, short-lasting sleep effect.
According to the present invention, the hitherto unknown 2-thio-3,3-dialkyl-4-oxo-1,2,3,4-tetrahydropyridines are given that an a, a-dialkyl-acetaceto- nit.ril with. a formic acid ester in the presence of an alkaline condensing agent into the γ-oxymethylene compound and converting this with ammonia into the γ-aminomethylene compound, cyclizing this with an alkaline condensing agent and treating it with hydrogen sulfide or a hydrogen sulfide-releasing agent.
The a, a <I> - </I> Dialkylacetacetonitrile are by alkylation of E. Mohr (Journal for practical chemistry (2), volume 75 [1907], page 749, and (2), volume 90 [1914], Page 189) shown a-alkyl-acetacetonitrile, the alkylation can be carried out with alkenyl or alkyl halides using the methods customary for a-alkyl acetic esters.
The a, a-dialkyl-y-oxymethylene-acet-acetonitrile are advantageous by converting the corresponding nitriles with a formic acid ester in an inert or ganic solvent, such as. B. benzene, To luene or diethyl carbonate, in the presence of an alkaline condensing agent such. B. sodium, potassium or sodium alcoholate shown.
The a, a-dialkyl acetacetonitriles, which are sparingly soluble in water, do not form any salts with aqueous alkaline solutions and can be easily separated from the a, a-dialkyl y-oxymethylene acetacetonitriles, which are readily soluble in aqueous alkaline solutions. These alkali salt solutions can be converted with ammonia and ammonium chloride into the a, a-dialkyl-y-aminomethylene compounds, which are sparingly soluble in aqueous solution.
With alkaline condensing agents, such as. B. alkali metal, advantageously in an or ganic solvent, such as. B. methanol, the a, a-dialkyl-y-aminomethylene acetacetonitrile can be cyclized. By reacting the condensation product with hydrogen sulfide or hydrogen sulfide give off the means such. B. phosphorus pentasulfide, the 2-thio-3,3-dialkyl-4-oxo-1,2,3,4-tetrahydropyridines arise.
The new compounds are yellowish, heavy in water and easily soluble in the common organic solvents. In alkaline solutions they dissolve with a deepening of the color, and when acids are added they precipitate again with a lightening of the color. They should be used as a sleeping aid.
The subject of the present patent is a process for the production of a sulfur-containing pyridone, which is characterized by converting α-ethyl-α-methyl-acetacetonitrile with a formic acid ester in the presence of an alkaline condensing agent into the γ-oxymethylene compound and this converted with ammonia into the γ-aminomethylene compound, cyclized this with an alkaline condensation agent and treated with hydrogen sulfide or a hydrogen sulfide releasing agent.
The new 2-thio-3-ethyl-3-methyl-4-oxo-1,2,3,4-tetrahydropyridine obtainable in this way forms yellow crystals with a melting point of 113-114 C. The compound is sparingly soluble in water , however, easily soluble in common organic solvents. <I> Example: </I> A solution of 23 parts by weight of sodium in 500 parts by volume of dry alcohol is mixed with a mixture of 97 parts by weight of 2-cyanobutanone-3 (E.
Mohr, Journal for practical chemistry (2), Volume 90 [1914], page 189 [Kp.19 n ,. 78 C]) and 109 parts by weight of ethyl bromide are added and the mixture is stirred at 50 C for 16 hours. After the bulk of the alcohol has been distilled off in vacuo, the residue is mixed with water and the floating α-ethyl-α-methyl-acet-acetonitrile is separated off. The oil, which is insoluble in alkalis, boils between 80 and 82 C under 1.4 mm pressure.
125 parts by weight of the a-ethyl-a-methyl-acetacetonitrile are added with 90 parts by weight of methyl formate in a suspension of 24 parts by weight of sodium in 800 parts by volume of toluene and the mixture is stirred at 20 ° C. for 16 hours.
The resulting α-ethyl-α-methyl-γ-oxymethylene-aeet-acetonitrile is dissolved as the sodium salt with water, separated off and converted directly into the aminometric hydrogen compound with ammonium chloride and ammonia. The a-ethyl- a.-methyl-y-aminometh@-len-acetacetonitrile, which is poorly soluble in dilute ammonia solution, is extracted with benzene, dried and concentrated in vacuo.
The remaining oil can be rectified in a high vacuum (boiling point 0.05 Inn "106 C).
152 parts by weight of a-ethyl-a-methyl-y-aminomethylene acetacetonitrile are reacted with a sodium alcoholate solution prepared from 3 parts by weight of sodium in 500 parts by volume of alcohol and left to stand for 12 hours . Then 80 parts by weight of hydrogen sulfide are introduced, whereby the solution warms up. After the reaction has subsided, 125 parts by volume of 37% hydrochloric acid are added dropwise, with hydrogen sulphide escaping.
The dark-colored reac tion material is filtered through animal charcoal and added dropwise ver with 500 parts by volume of water, the 2-thio-3-ethyl-3-methyl-4-oxo. 1,2,3,4-tetrahydropyridine precipitates in yellow crystals. After redissolving from methanol, the crystals melt at 113-11.4 C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH310985T | 1952-12-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH310985A true CH310985A (en) | 1955-11-15 |
Family
ID=4494383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH310985D CH310985A (en) | 1952-12-04 | 1952-12-04 | Process for the preparation of a sulfur-containing pyridone. |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE524609A (en) |
| CH (1) | CH310985A (en) |
| DE (1) | DE1000381C2 (en) |
| GB (1) | GB735686A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE634284C (en) * | 1935-06-18 | 1936-08-25 | Hoffmann La Roche & Co Akt Ges | Process for the preparation of 2, 4-dioxo-3, 3-dialkyltetrahydropyridines |
-
0
- BE BE524609D patent/BE524609A/fr unknown
-
1952
- 1952-12-04 CH CH310985D patent/CH310985A/en unknown
-
1953
- 1953-11-02 DE DE1953H0018193 patent/DE1000381C2/en not_active Expired
- 1953-11-18 GB GB31959/53A patent/GB735686A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BE524609A (en) | |
| GB735686A (en) | 1955-08-24 |
| DE1000381B (en) | 1957-01-10 |
| DE1000381C2 (en) | 1957-06-19 |
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