DE218466C - - Google Patents
Info
- Publication number
- DE218466C DE218466C DE1907218466D DE218466DA DE218466C DE 218466 C DE218466 C DE 218466C DE 1907218466 D DE1907218466 D DE 1907218466D DE 218466D A DE218466D A DE 218466DA DE 218466 C DE218466 C DE 218466C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- glycol
- ethylene
- water
- acid ester
- 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.)
- Expired - Lifetime
Links
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 13
- -1 ethylene halides Chemical class 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 229960004889 salicylic acid Drugs 0.000 description 5
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 4
- 229960004025 sodium salicylate Drugs 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-Dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 229960000953 salsalate Drugs 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-Chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229940005667 ethyl salicylate Drugs 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 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
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
-JVl 218466-KLASSE 12 q. GRUPPE -JVl 218466- CLASS 12 q. GROUP
Es wurde gefunden, daß sich der therapeutisch wertvolle Glykolmonosalicylsäureester leicht erhalten läßt durch Umsetzung von salicylsauren Salzen mit Äthylenhalogeniden bei Gegenwart von Wasser. Zur Darstellung dieses Körpers sind bereits zwei Verfahren bekannt, nämlich dasjenige der Patentschrift 164128 — Esterificieren von Salicylsäure mit Glykol durch starke Säuren — und dasjenige der Patentschrift 173776 — Behandeln von salicylsauren Salzen mit Äthylenhalogenhydrinen —. Von diesen beiden Methoden unterscheidet sich aber die neue Darstellungsweise ganz wesentlich. Da nämlich unter den Be-It has been found that the therapeutically valuable glycol monosalicylic acid ester Can be easily obtained by reacting salicylic acid salts with ethylene halides in the presence of water. Two methods are already known to represent this body, namely that of patent specification 164128 - esterification of salicylic acid with Glycol by strong acids - and that of patent 173776 - treat salicylic acid salts with ethylene halohydrins -. It differs from these two methods but the new way of representation is very important. Because under the
dingungen des neuen Verfahrens aus Äthylenhalogenid und Wasser kein Glykol entsteht (vgl. auch die Angaben von Lietzenmeyer — Ann. 180 [1876], S. 282 ff.), so verläuft die nunmehr gefundene Reaktion nicht im Sinne des aus der erstgenannten Patentschrift bekannten Verfahrens, abgesehen davon, daß überhaupt aus Glykol und Salicylsäure bei Anwesenheit der nach der Vorschrift, des vorliegenden Verfahrens anzuwendenden Wassermengen sich Salicylglykolester nur in ganz geringer Menge bildet. Da ferner die Bildung von Äthylenchlorhydrin bzw. -bromhydrin bei der Einwirkung von Wasser auf Äthylenhalogenide niemals beobachtet wurde, so erweist sich auch das Verfahren der Patentschrift 173776 als völlig verschieden von dem vorliegenden. Vor beiden bekannten Verfahren hat die neue Darstellungsweise außerdem den technischen Vorteil, daß an Stelle von Glykol und Äthylenhalogenhydrin die technisch leichter zugänglichen Äthylenhalogenide zur Verwendung kommen.conditions of the new process from ethylene halide and water no glycol is formed (cf. also the information from Lietzenmeyer - Ann. 180 [1876], p. 282 ff.) The reaction that has now been found is not in the sense of that known from the first-mentioned patent specification Process, apart from that at all from glycol and salicylic acid Presence of the amount of water to be used according to the instructions of the present process Salicylglycol ester is only formed in very small quantities. There is also education of ethylene chlorohydrin or bromohydrin in the action of water on ethylene halides has never been observed, the patent specification proves to be the same 173776 as completely different from the present one. Before both known procedures The new representation also has the technical advantage that instead of glycol and ethylene halohydrin, the technically more readily available ethylene halides for use come.
I. 110 Teile Natriumsalicylat werden mit 60 Teilen Äthylenbromid und 80 Teilen Wasser zusammengegeben. Es ist vorteilhaft, diesem Gemisch noch 60 Teile Salicylsäure hinzuzufügen, weil durch diesen Zusatz das Entstehen einer klaren Lösung befördert und auch die schädliche Bildung von Natriumphenolat aus dem Salicylat hintangehalten wird. Das Ganze wird unter Rückfluß während 48 Stunden auf 120° erhitzt und gibt zunächst eine klare Lösung, die sich gegen Ende der Operation in zwei Schichten trennt. Man gießt in Wasser, macht mit Soda alkalisch und extrahiert die gebildeten Ester. Durch Destillation im Vakuum erhält man 45 Teile Glykolmonosalicylsäureester und daneben 4 Teile GIykoldisalicylsäureester. I. 110 parts of sodium salicylate are mixed with 60 parts of ethylene bromide and 80 parts of water put together. It is advantageous to add 60 parts of salicylic acid to this mixture, because this addition promotes the creation of a clear solution and also the harmful formation of sodium phenolate from which salicylate is held back. The whole is refluxed for 48 hours heated to 120 ° and first gives a clear solution, which is towards the end of the operation separates into two layers. It is poured into water, made alkaline with soda and extracted the esters formed. By distillation 45 parts of glycol monosalicylic acid ester and 4 parts of glycol disalicylic acid ester are obtained in vacuo.
II. 60 Teile Äthylenbromid, 100 Teile Natriumsalicylat, 30 Teile Salicylsäure, 240 Teile Phenol und 40 Teile Wasser werden unter Rückfluß während 100 Stunden auf iio° erhitzt. Man destilliert im Vakuum den größten Teil des Phenols ab und behandelt dann wie bei Beispiel I. Man erhält 40 Teile Monoester und 6 Teile Diester. II. 60 parts of ethylene bromide, 100 parts of sodium salicylate, 30 parts of salicylic acid, 240 parts of phenol and 40 parts of water are refluxed to 100 hours. Most of the phenol is distilled off in vacuo and then treated as in Example I. 40 parts of monoester and 6 parts of diester are obtained.
III. 50 Teile Äthylenchlorid, 160 Teile Natriumsalicylat, 70 Teile Salicylsäure, 150 Teile III. 50 parts of ethylene chloride, 160 parts of sodium salicylate, 70 parts of salicylic acid, 150 parts
Phenol und 50 Teile Wasser werden während 50 Stunden auf 1200 erwärmt und wie oben beschrieben weiterverarbeitet. Man erhält 41 Teile Glykolrtionosalicylsäureester neben 14 Teilen Glykoldisalicylsäureester.Phenol and 50 parts of water are heated for 50 hours at 120 0 and further processed as described above. 41 parts of glycolrtionosalicylic acid ester and 14 parts of glycol disalicylic acid ester are obtained.
IV. 75 Teile Äthylenchlorid, 240 Teile Natriumsalicylat und 90 Teile 80 prozentiger Alkohol werden während 60 Stunden im geschlossenen Gefäß auf 120 ° erwärmt und wie oben aufgearbeitet. Es werden erhalten Teile Glykolmonosalicylsäureester neben wenig Glykoldisalicylat und Äthylsalicylat.IV. 75 parts of ethylene chloride, 240 parts of sodium salicylate and 90 parts of 80 percent alcohol are heated to 120 ° for 60 hours in a closed vessel and how worked up above. Parts of glycol monosalicylic acid ester are obtained in addition to a little glycol disalicylate and ethyl salicylate.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT44963D AT44963B (en) | 1907-12-02 | 1909-03-27 | Process for the preparation of glycol monosalicylic acid ester. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE218466C true DE218466C (en) |
Family
ID=479685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1907218466D Expired - Lifetime DE218466C (en) | 1907-12-02 | 1907-12-02 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE218466C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428450A (en) * | 1941-03-01 | 1947-10-07 | Allied Chem & Dye Corp | Preparing purified mixtures of esters |
-
1907
- 1907-12-02 DE DE1907218466D patent/DE218466C/de not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428450A (en) * | 1941-03-01 | 1947-10-07 | Allied Chem & Dye Corp | Preparing purified mixtures of esters |
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