CH202368A - Process for the preparation of the dimethylcarbamic acid ester of m-diethylaminophenol. - Google Patents
Process for the preparation of the dimethylcarbamic acid ester of m-diethylaminophenol.Info
- Publication number
- CH202368A CH202368A CH202368DA CH202368A CH 202368 A CH202368 A CH 202368A CH 202368D A CH202368D A CH 202368DA CH 202368 A CH202368 A CH 202368A
- Authority
- CH
- Switzerland
- Prior art keywords
- diethylaminophenol
- acid ester
- preparation
- water
- dimethylcarbamic acid
- Prior art date
Links
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 title claims description 7
- -1 dimethylcarbamic acid ester Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- PIJVFDBKTWXHHD-UHFFFAOYSA-N Physostigmine Natural products C12=CC(OC(=O)NC)=CC=C2N(C)C2C1(C)CCN2C PIJVFDBKTWXHHD-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- PIJVFDBKTWXHHD-HIFRSBDPSA-N physostigmine Chemical compound C12=CC(OC(=O)NC)=CC=C2N(C)[C@@H]2[C@@]1(C)CCN2C PIJVFDBKTWXHHD-HIFRSBDPSA-N 0.000 claims 1
- 229960001697 physostigmine Drugs 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung des Dimethylearbaminsäureesters des m-Diäthylaminophenols. Nach dem Verfahren des Hauptpatentes Nr. 152IM und seiner Zusätze werden di- substituierte Carbaminsäureester dadurch ge wonnen, dass mau Dialkyl-, Arylalkyl- oder Diarylcarbaminsäurehalogenide auf Alkali salze :
der basisch substituierten Phenole ein- wirken: lässt.
Es wurde nun gefunden, dass man an Stelle,der Alkalisalze,der basisch substituier- ten Phenole vorteilhaft die freien Phenole verwenden kann.
Die Darstellung der Alkalisalze der ba sisch substituierten Phenole, die in den meisten Fällen leicht vom Luftsauerstoff an- gegriffen werden und begierig Wasser auf nehmen, ist wegen diesen unangenehmen Eigenschaften oft mit Schwierigkeiten ver bunden.
Bei -der Verwendung der freien Phenole können diese Schwierigkeiten. um gangen werden. Die Einwirkung der disub- stituierten Carbaminsäurechloride auf die basisch substituierten Phenole kann in An oder Abwesenheit eines Lösungsmittels er folgen.
Meist ist es zweckmässig, ein Molekül Carbaminsäurechlorid auf 2 Holeküle des basisch substituierten Phenols zu verwenden. Die Reaktion findet nach folgender Gleichung statt: 2;
ROH + R' R" N CO Cl > R 0 CO NR' R" + ROH, HC1 In dieser Gleichung bedeuten R einen basisch substituierten Phenolrest, R' und R" Alkyl oder Aryl oder Aralkyl oder beide zusam- men. die Kohlenstoffkette eines Piperidin- ringe.
Es ist indessen nicht notwendig, an diesen Mengen festzuhalten. Man kann auch andere Mengenverhältnisse der Ausgangs- verbindungen verwenden:, z. B. äquimoleku- lare Mengen, was besonders vorteilhaft ist, wenn man Arylallzylcarbaminsäurechloride auf Phenole, die eine quartäre basische Gruppe enthalten, einwirken lässt.
Hier dient die freiwerdende Halogenwasserstoffsä.ure zum Neutralisieren des quartären Ainmo- niumhydroxydes, und es bildet sich unmittel- bar das ITalogenid des disubstituierten Carbaminsä-uremters der quartären Phenol- verbindung. Die Reaktionsbedingungen, z. B. die Temperatur, können in weiten Grenzen verändert werden.
Gegenstand des vorliegenden Patentes ist .ein Verfahren zur Darstellung des Dimethyl- carbaminsäureesters des m-Diäthylamino- phenols. welches dadurch gekennzeiehnet ist. dass man Dimethylcarbaminsäurehalogenid auf m-Diäthylaminophenol einwirken lässt.
Der neue Dimethylcarbaminsäureester des m-Diathylaminophenols, welcher als Arznei- mittel verwendet werden soll, siedet bei 1210 und 15 mm; er ist in Wasser sehr schwer löslich; leicht lösen ihn organische Lösungs- mittel wie Äther, Alkohol, Benzol. Chloro form;
er bildet ein wasserlösliches Jod- methyla.t vom Schmelzpunkt 139 , welches das Physost7gmin an Wirksamkeit übertrifft. Beispiel:
Ein Gemisch von 165 Teilen m-Diä.thyl- aminophenol und<B>1.10</B> Teilen Dimethyl- carbazninsäurechlorid wird langsam im Gra- phitbad erhitzt. Bei etwa <B>110'</B> findet leb hafte Reaktion statt, und das Gemisch gerät bald ins Kochen.
Nach zweistündigem Er hitzen wird abgekühlt, mit 300 Teilen Äther iuid 204) Teilen Wasser geschüttelt, die Äther sehieht abgetrennt und mit 50 Teilen lb%iger Natronlauge und darauf wieder mit Wasser gewaschen, mit Pottasche getrocknet und im Vakuum destilliert.
Process for the preparation of the dimethylearbamic acid ester of m-diethylaminophenol. According to the process of main patent No. 152IM and its additives, disubstituted carbamic acid esters are obtained by salting dialkyl, arylalkyl or diarylcarbamic acid halides with alkali:
of the basic substituted phenols: lets.
It has now been found that instead of the alkali metal salts, the basic substituted phenols can advantageously be used with the free phenols.
The preparation of the alkali salts of the basic substituted phenols, which in most cases are easily attacked by atmospheric oxygen and eagerly absorb water, is often associated with difficulties because of these unpleasant properties.
These difficulties can arise when using free phenols. to be walked around. The action of the disubstituted carbamic acid chlorides on the basic substituted phenols can follow in the presence or absence of a solvent.
In most cases it is advisable to use one molecule of carbamic acid chloride for every two molecules of the basic substituted phenol. The reaction takes place according to the following equation: 2;
ROH + R 'R "N CO Cl> R 0 CO NR' R" + ROH, HC1 In this equation, R denotes a basic substituted phenol radical, R 'and R "denote alkyl or aryl or aralkyl or both together. The carbon chain of one Piperidine rings.
However, it is not necessary to stick to these amounts. You can also use other proportions of the starting compounds: B. equimolecular amounts, which is particularly advantageous if Arylallzylcarbaminsäurechloride on phenols which contain a quaternary basic group, can act.
Here the released hydrohalic acid serves to neutralize the quaternary ammonium hydroxide, and the halogenide of the disubstituted carbamic acid of the quaternary phenol compound is formed immediately. The reaction conditions, e.g. B. the temperature can be changed within wide limits.
The subject of the present patent is a process for the preparation of the dimethylcarbamic acid ester of m-diethylaminophenol. which is thereby marked. that dimethylcarbamic acid halide is allowed to act on m-diethylaminophenol.
The new dimethylcarbamic acid ester of m-diethylaminophenol, which is to be used as a medicament, boils at 1210 and 15 mm; it is very sparingly soluble in water; Organic solvents such as ether, alcohol and benzene dissolve it easily. Chloro form;
it forms a water-soluble iodine methyl with a melting point of 139, which is more effective than physost7gmin. Example:
A mixture of 165 parts of m-diethylaminophenol and 1.10 parts of dimethylcarbazinic acid chloride is slowly heated in a graphite bath. At about <B> 110 '</B>, a lively reaction takes place and the mixture soon boils.
After two hours of heating, the mixture is cooled, shaken with 300 parts of ether iuid 204 parts of water, the ether is separated and washed with 50 parts of Ib% sodium hydroxide solution and then again with water, dried with potash and distilled in vacuo.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE202368X | 1937-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH202368A true CH202368A (en) | 1939-01-15 |
Family
ID=5771148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH202368D CH202368A (en) | 1937-04-24 | 1938-02-22 | Process for the preparation of the dimethylcarbamic acid ester of m-diethylaminophenol. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH202368A (en) |
-
1938
- 1938-02-22 CH CH202368D patent/CH202368A/en unknown
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