CH307797A - Process for the preparation of a new carbamic acid ester. - Google Patents
Process for the preparation of a new carbamic acid ester.Info
- Publication number
- CH307797A CH307797A CH307797DA CH307797A CH 307797 A CH307797 A CH 307797A CH 307797D A CH307797D A CH 307797DA CH 307797 A CH307797 A CH 307797A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid ester
- methyl
- carbamic acid
- new
- preparation
- Prior art date
Links
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000932 sedative agent Substances 0.000 claims description 4
- 230000001624 sedative effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- UFEJKYYYVXYMMS-UHFFFAOYSA-N methylcarbamic acid Chemical compound CNC(O)=O UFEJKYYYVXYMMS-UHFFFAOYSA-N 0.000 claims description 2
- 230000003533 narcotic effect Effects 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- -1 hydrazine-activated sodium azide Chemical class 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GWVCIJWBGGVDJJ-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyl-n-(3-methoxypyrazin-2-yl)acetamide Chemical compound COC1=NC=CN=C1N(C(C)=O)S(=O)(=O)C1=CC=C(N)C=C1 GWVCIJWBGGVDJJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung eines neuen Carbamins¯ureesters.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung eines Carbaminsäureesters, welches dadurch gekennzeich- net ist, dass man ¯thinyl-¯thyl-methyl-carbinol mit Methylisocyanat umsetzt.
Der so erhaltene N-Methyl-carbamnis¯ure ester des Äthinyl-äthyl-methyl-earbinols der Formel
EMI1.1
vom Kp. 103 bei 11 mm/Hg und vom F. = 54-55 ist neu.
Der neue Carbaminsäureester besitzt sedative und narkotische Wirkung und kann als Beruhigungs-oder Schlafmittel Verwendung finden.
Beispiel 1 :
12, 7 Gewichtsteile Methylisoeyanat werden unter Feuchtigkeitsausschluss tropfenweise zu 31, 5 Gewiehtsteilen Äthinyl-äthyl-methyl-car- binol getropft und mit 1, 5 Gewichtsteilen wasserfreiem Kaliumaeetat vermischt. Die Temperatur steigt dabei auf 26 . Nach 24stündigem Stehen bei Raumtemperatur werden 4 Volumteile Triäthylamin zugegeben, wobei die Temperatur wiederum kurz von 20 auf 26 ansteigt. Nach 16tägigem Stehen bei Raumtem- peratur ist der Geruch nach Isocyanat verschwunden.
Das Reaktionsprodukt wird dann in , ¯ther aufgenommen, zweimal mit wenig Wasser, dreimal mit verdünnter Salzsäure und noch- mals mit Wasser gewaschen, mit Natriumsulfat getrocknet und der Äther abdestilliert.
Im Wasserstrahlvakuum wird nun das über- schüssige ¯thinyl-carbinol abdestilliert und der Rüekstand im Hochvakuum destilliert. Der N-Methylcarbamins¯ureester des Äthinyl-äthyl methyl-carbinols der Formel
EMI1.2
siedet bei 1030'lllmm Hg und schmilzt aus Methyleyelohexan umkristallisiert bei 54-55 .
Beispiel 2 :
69 Gewichtsteile mit Hydrazin aktiviertes Natrinmazid werden in einem Rührkolben unter Feuchtigkeitsausschluss in 400 Volumteilen absolutem Benzol suspendiert und bei 20-25 78, 5 Gewichtsteile Acetylchlorid in 1 Stunde zugetropft. Nach weiteren 4 Stunden Rühren bei 25 reagiert das Gemisch nur noch schwach sauer. Es werden 112 Gewichts- teile Äthinyl-methyl-äthyl-carbinol und 5 Volumteile Triäthylamin zugesetzt und die Mi sehung während 4 Tagen auf 40 bis 80 erwärmt, wobei die Temperatur während 2 Tagen auf 40-45 gehalten und dann langsam auf die Endtemperatur von 80 gesteigert wird.
Dabei zerfällt das vorhandene Acetyl- azid in Stickstoff und Methylisocyanat, nnd bildet letzteres mit dem Carbinol das ge wünschte Urethan.
Die Mischung wird mit Wasser versetzt, die Benzollösung abgetrennt, das Lösungsmittel im Vakuum abdestilliert und der kristalline Rückstand im Vakuum fraktioniert. Der Me thyl-carbaminsäureester des Äthinyl-methyl- äthvl-carbinols der Formel
EMI2.1
destilliert bei 118-119¯/17 mm Hg und kristallisiert sofort. Er ist mit dem in Beispiel 1 beschriebenen Produkt identisch.
Process for the production of a new carbamic acid ester.
The subject of the present patent is a process for the production of a carbamic acid ester which is characterized in that ¯thynyl-¯thyl-methyl-carbinol is reacted with methyl isocyanate.
The N-methyl-carbamnis¯ate thus obtained of ethynyl-ethyl-methyl-earbinol of the formula
EMI1.1
from Bp. 103 at 11 mm / Hg and from F. = 54-55 is new.
The new carbamic acid ester has sedative and narcotic effects and can be used as a sedative or sleeping aid.
Example 1 :
12.7 parts by weight of methyl isoyanate are added dropwise with exclusion of moisture to 31.5 parts by weight of ethynyl-ethyl-methyl-carbinol and mixed with 1.5 parts by weight of anhydrous potassium acetate. The temperature rises to 26. After standing at room temperature for 24 hours, 4 parts by volume of triethylamine are added, the temperature again rising briefly from 20 to 26. After 16 days of standing at room temperature, the odor of isocyanate has disappeared.
The reaction product is then taken up in ether, washed twice with a little water, three times with dilute hydrochloric acid and again with water, dried with sodium sulfate and the ether is distilled off.
The excess ¯thynyl-carbinol is now distilled off in a water jet vacuum and the residue is distilled in a high vacuum. The N-Methylcarbamins¯ureester des Äthinyl-ethyl methyl-carbinols of the formula
EMI1.2
boils at 1030'lllmm Hg and melts from methyleyelohexane recrystallized at 54-55.
Example 2:
69 parts by weight of hydrazine-activated sodium azide are suspended in 400 parts by volume of absolute benzene in a stirred flask with exclusion of moisture and, at 20-25, 78.5 parts by weight of acetyl chloride are added dropwise over 1 hour. After a further 4 hours of stirring at 25, the mixture only reacts slightly acidic. 112 parts by weight of ethynyl-methyl-ethyl-carbinol and 5 parts by volume of triethylamine are added and the Mi sehung is heated to 40 to 80 for 4 days, the temperature being maintained at 40-45 for 2 days and then slowly to the final temperature of 80 is increased.
The acetyl azide present breaks down into nitrogen and methyl isocyanate, and the latter forms the desired urethane with the carbinol.
Water is added to the mixture, the benzene solution is separated off, the solvent is distilled off in vacuo and the crystalline residue is fractionated in vacuo. The methyl carbamic acid ester of ethynyl methyl äthvl-carbinols of the formula
EMI2.1
distilled at 118-119¯ / 17 mm Hg and crystallized immediately. It is identical to the product described in Example 1.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH307797T | 1955-06-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH307797A true CH307797A (en) | 1955-06-15 |
Family
ID=4493279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH307797D CH307797A (en) | 1955-06-15 | 1952-02-22 | Process for the preparation of a new carbamic acid ester. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH307797A (en) |
-
1952
- 1952-02-22 CH CH307797D patent/CH307797A/en unknown
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