DE188571C - - Google Patents
Info
- Publication number
- DE188571C DE188571C DENDAT188571D DE188571DA DE188571C DE 188571 C DE188571 C DE 188571C DE NDAT188571 D DENDAT188571 D DE NDAT188571D DE 188571D A DE188571D A DE 188571DA DE 188571 C DE188571 C DE 188571C
- Authority
- DE
- Germany
- Prior art keywords
- salicylic acid
- ether
- ester
- esters
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 20
- 229960004889 salicylic acid Drugs 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- 150000003945 chlorohydrins Chemical class 0.000 claims description 2
- 150000003902 salicylic acid esters Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N Diethylethanolamine Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- -1 salicylic acid glycol chlorohydrin ester Chemical class 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-Chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 102000006835 Lamins Human genes 0.000 description 1
- 108010047294 Lamins Proteins 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003444 anaesthetic Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 230000001225 therapeutic Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
- C07C69/88—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with esterified carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Es wurde gefunden, daß sich aus Salicylsäure und Alkaminen Ester herstellen lassen, die durch ihre wertvollen therapeutischen Eigenschaften von Bedeutung sind. Diese Ester lassen sich erhalten:It has been found that esters can be prepared from salicylic acid and alkamines, which are important because of their valuable therapeutic properties. These Esters can be obtained:
1. durch Veresterung der Salicylsäure mit Alkaminen,1. by esterification of salicylic acid with alkamines,
2. durch Einwirkung von Alk)rlaminen auf die Salicylsäureester der Chlorhydrine,2 by the action of Alk) r lamins to the salicylic acid esters of chlorohydrins,
ίο 3. durch Einwirkung von Alkaminen auf die unter dem Namen »Salicylidea bekannten Polyanhydride der Salicylsäure.ίο 3. by exposure to alkamines the polyanhydrides of salicylic acid known under the name »Salicylidea.
Die neuen Ester sind dadurch wertvoll, daß ihnen einerseits die Salicylsäurewirkung, andererseits zugleich eine anästhesierende Wirkung innewohnt.The new esters are valuable because on the one hand the salicylic acid effect, on the other hand, an anesthetic effect is inherent at the same time.
Ein Gemisch von 120 g Salicylsäure und 70 g Diäthylaminoäthanol wird mit trockenem Salzsäuregas gesättigt und dann bei 115 bis 120° während 50 Stunden Salzsäuregas eingeleitet. Nach Erkalten wird in Wasser gelöst, mit Soda alkalisch gemacht, mit Äther ausgeschüttelt und der Äther abdestilliert, wobei der Ester als fast farbloses öl zurückbleibt. A mixture of 120 g of salicylic acid and 70 g of diethylaminoethanol is dried with Saturated hydrochloric acid gas and then introduced hydrochloric acid gas at 115 to 120 ° for 50 hours. After cooling, it is dissolved in water, made alkaline with soda, shaken out with ether and the ether is distilled off, the ester remains as an almost colorless oil.
Zur völligen Reinigung kann der Ester in sein Chlorhydrat verwandelt werden, welches durch Einleiten von Salzsäuregas in die ätherische Lösung erhalten wird und sich durch Umkristallisieren a,us Aceton als weiße Kristallmasse vom Schmelzpunkt 1460 gewinnen läßt.For complete purification of the ester may be obtained by passing hydrogen chloride gas into the ether solution and can be purified by recrystallization A, US acetone gain as white crystal mass of melting point 146 0 are transformed into its hydrochloride.
Das stearinsaure Salz, erhalten durch Zusammenschmelzen äquivalenter Mengen des Esters mit Stearinsäure, bildet eine stearinähnliche halbfeste Kristallmasse, die bei 30 bis 40° zu einer Masse von salbenartiger Konsistenz zusammensintert.The stearic acid salt obtained by melting it together equivalent amounts of the ester with stearic acid, forms a stearin-like semi-solid crystal mass, which at 30 sintered to 40 ° to a mass of ointment-like consistency.
40 Teile des durch längeres Erhitzen von Salicylsäure mit Glykolchlorhydrin und wenig Schwefelsäure erhaltenen Salicylsäureglykolchlorhydrinesters werden mit 50 Teilen Diäthylamin ιJ Stunden gelinde gekocht, dann mit Wasser verdünnt, mit 15 Teilen calc. Soda versetzt und mit Äther ausgeschüttelt. Nach Abdestillieren des Äthers bleibt ein hellbräunliches öl zurück, das sich nach Reinigung durch das Chlorhydrat als mit dem nach Beispiel I dargestellten Salicylsäurediäthylaminoäthanolester identisch erweist.40 parts of the salicylic acid glycol chlorohydrin ester obtained by prolonged heating of salicylic acid with glycol chlorohydrin and a little sulfuric acid are gently boiled with 50 parts of diethylamine for ιJ hours, then diluted with water, calcined with 15 parts. Soda was added and shaken out with ether. After the ether has been distilled off, a light brownish oil remains which, after purification by the chlorohydrate, proves to be identical to the salicylic acid diethylaminoethanol ester shown in Example I.
Beispiel III.Example III.
5555
Gleiche Teile Salicylid (dargestellt nach Anschütz, Annalen 273, S. 78) und Diäthylaminoäthanol werden 7 Stunden auf i6o° erhitzt. Die erkaltete braune Masse wird unter Kühlung mit verdünnter Salzsäure angesäuert und zerrieben und die salzsaure Lösung von etwas braunem Öl abfiltriert. Dieselbe erstarrt beim Eindampfen im Vakuum nach einigen Tagen zum Kristallbrei, der auf Ton von anhängendem Syrup befreit wird. Durch Umkristallisieren aus Aceton erhält man daraus das reine Chlorhydrat des Salicyl-Equal parts of salicylide (shown according to Anschütz, Annalen 273, p. 78) and diethylaminoethanol are heated to 160 ° for 7 hours. The cooled brown mass becomes acidified while cooling with dilute hydrochloric acid and triturated and the hydrochloric acid solution filtered off from some brown oil. On evaporation in a vacuum, the same solidifies after a few days to form a crystal pulp, which opens up Clay is freed from adhering syrup. Obtained by recrystallization from acetone from it the pure chlorohydrate of salicylic
säurediäthvlaminoäthanolesters in Form weißer Kristalle vom Schmelzpunkt 146 ° (vergl. Beispiel I).acid dietvlaminoethanol ester in the form of white crystals with a melting point of 146 ° (see example I).
. Beispiel IV.. Example IV.
Ein Gemisch von 80 g Salicylsäure und 51,0g Oxäthylpiperidin wird mit trockenem Salzsäuregas gesättigt und dann bei 115 bis I2O° während 50 Stunden trockenes SaIzsäuregas eingeleitet. Nach Erkalten wird inWasser gelöst, mit Soda alkalisch gemacht und mit Äther ausgeschüttelt. Leitet man in die ätherische Lösung trockenes Salzsäuregas ein, so fällt das Chlorhydrat des Salicylsäureoxäthylpiperidylesters als weißer Kristallbrei aus. Durch Umkristallisieren aus Aceton erhält man das Chlorhydrat in reiner Form vom Schmelzpunkt 174°. A mixture of 80 g of salicylic acid and 51.0 g of oxethylpiperidine is saturated with dry hydrochloric acid gas and then dry hydrochloric acid gas is passed in at 115 to 10 ° for 50 hours. After cooling, it is dissolved in water, made alkaline with soda and shaken out with ether. If dry hydrochloric acid gas is introduced into the ethereal solution, the hydrochloride of the oxethylpiperidyl salicylate precipitates as a white crystal pulp. Recrystallization from acetone gives the hydrochloride in pure form with a melting point of 174 °.
Claims (3)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE188571C true DE188571C (en) |
Family
ID=452181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT188571D Active DE188571C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE188571C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4830334A (en) * | 1988-10-03 | 1989-05-16 | Welker Robert H | Resilient plug construction for a flow regulator incorporating stress limiting means |
-
0
- DE DENDAT188571D patent/DE188571C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4830334A (en) * | 1988-10-03 | 1989-05-16 | Welker Robert H | Resilient plug construction for a flow regulator incorporating stress limiting means |
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