DE137585C - - Google Patents
Info
- Publication number
- DE137585C DE137585C DE1902137585D DE137585DA DE137585C DE 137585 C DE137585 C DE 137585C DE 1902137585 D DE1902137585 D DE 1902137585D DE 137585D A DE137585D A DE 137585DA DE 137585 C DE137585 C DE 137585C
- Authority
- DE
- Germany
- Prior art keywords
- salicylic acid
- benzene
- ester
- pressure
- mixture
- 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 compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- -1 halomethyl alkyl ethers Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 241000735588 Gaultheria Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 206010072736 Rheumatic disease Diseases 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011541 reaction 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
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 238000003756 stirring Methods 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
KLASSEGREAT
Bekanntlich wird der Methylester der Salicylsäure (das Gaultheriaöl) der folgenden Formel:As is well known, the methyl ester of salicylic acid (Gaultheria oil) has the following formula:
OH C6 H1^C O. OH C 6 H 1 ^ CO .
OCHOCH
vielfach als Mittel gegen rheumatische Erkrankungen verwendet. Seiner allgemeineren Anwendung steht jedoch der für viele Patienten unerträgliche Geruch im Wege.widely used as a remedy for rheumatic diseases. Its more general However, the odor, which is unbearable for many patients, stands in the way of application.
Es wurde nun gefunden, dafs die Alkyloxymethylester der Salicylsäure der folgenden Formel:It has now been found that the alkyloxymethyl esters of salicylic acid have the following Formula:
OHOH
C O -C O -
. OR,. OR,
in denen also ein Wasserstoffatom der im Gaultheriaöl enthaltenen Methylgruppe durch den Alkyloxylrest ersetzt ist, nahezu geruchlos sind, dabei aber die werthvollen Eigenschaften des Gaultheriaöls unverändert aufweisen und sich aufserdem vor diesem vorteilhaft noch durch eine erhöhte Reactionsfähigkeit auszeichnen. Diese Producte stellen daher hervorragende Rheumatica dar.So in which a hydrogen atom of the methyl group contained in Gaultheria oil through the alkyloxyl radical is replaced, are almost odorless, but the valuable properties of the Gaultheria oil have unchanged and are also advantageous before this characterized by an increased reactivity. These products are therefore excellent Rheumatica.
Zur Darstellung der neuen Körper verfährt man in der Weise, dafs man auf die Salze der Salicylsäure die Halogenmethylalkyläther der folgenden allgemeinen Formel·:To represent the new bodies one proceeds in such a way that one touches the salts of the Salicylic acid the halomethyl alkyl ethers of the following general formula:
X-CH2-ORX-CH 2 -OR
(worin X ein Halogenatom, R einen Alkylrest bedeutet) einwirken läfst,(in which X is a halogen atom, R is an alkyl radical)
1600 Th. trocknes salicylsaures Natron werden in 5000 Th. Benzol suspendirt und zu der Mischung nach und nach eine Mischung von 805 Th. Monochlordimethyläther mit 800 Th. Benzol zugefügt, wobei man dafür Sorge trägt, dafs die Temperatur 400 C. nicht wesentlich übersteigt. Es wird dann weiter bis zur Beendigung der Reaction gerührt und das Reactionsgemisch darauf mit sehr verdünnter Sodalösung zur Entfernung des gebildeten Chlornatriums und etwa vorhandener kleiner Mengen Salicylsäure gewaschen. Die Benzollösung wird darauf über Chlorcalcium getrocknet, das Benzol abdestillirt und der Rückstand im Vacuum destillirt. Das so erhaltene ω-Methyloxymethylsalicylat bildet eine fast färb- und geruchlose ölige Flüssigkeit, die bei 32 mm Druck bei 153° siedet. Erhitzt man den Ester bei gewöhnlichem Druck, so spaltet sich Formaldehyd ab. Bei Behandlung mit verdünnten Säuren tritt hydrolytische Spaltung in Salicylsäure, Formaldehyd und Methylalkohol ein.1600 Th. Of dry sodium salicylate are benzene suspended in 5000 Th. And added to the mixture gradually, a mixture of 805 Th. Monochlordimethyläther 800 Th. Benzene to give shall ensure the temperature does not DAF 40 0 C. substantially exceeding . Stirring is then continued until the reaction has ended and the reaction mixture is then washed with very dilute sodium carbonate solution to remove the sodium chloride formed and any small amounts of salicylic acid that may be present. The benzene solution is then dried over calcium chloride, the benzene is distilled off and the residue is distilled in vacuo. The ω-methyloxymethyl salicylate thus obtained forms an almost colorless and odorless oily liquid which boils at 153 ° under a pressure of 32 mm. If the ester is heated under normal pressure, formaldehyde is split off. When treated with dilute acids, hydrolytic cleavage occurs in salicylic acid, formaldehyde and methyl alcohol.
In analoger Weise verfährt man zur Darstellung der anderen Alkyloxymethylester, von denen beispielsweise der Aethylester bei 43 mm Druck bei 168 bis 1690 siedet und sich im Uebrigen dem Methylester analog verhält.The procedure for the preparation of the other alkyloxymethyl esters is analogous, of which, for example, the ethyl ester boils at 168 to 169 0 under a pressure of 43 mm and otherwise behaves analogously to the methyl ester.
Claims (1)
Verfahren zur Darstellung der Alkyloxymethylester der Salicylsäure, darin bestehend, dafs man auf die Salze der Salicylsäure die Halogenmethylalkyläther einwirken läfst.Patent claim:
Process for the preparation of the alkyloxymethyl esters of salicylic acid, consisting in allowing the halomethyl alkyl ethers to act on the salts of salicylic acid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT13098D AT13098B (en) | 1902-02-25 | 1902-10-24 | |
| AT17712D AT17712B (en) | 1902-02-25 | 1903-10-19 | Process for the preparation of alkyloxyalkylidene esters of salicylic acid. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE137585C true DE137585C (en) |
Family
ID=405456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1902137585D Expired - Lifetime DE137585C (en) | 1902-02-25 | 1902-02-25 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE137585C (en) |
-
1902
- 1902-02-25 DE DE1902137585D patent/DE137585C/de not_active Expired - Lifetime
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