DE239650C - - Google Patents
Info
- Publication number
- DE239650C DE239650C DENDAT239650D DE239650DA DE239650C DE 239650 C DE239650 C DE 239650C DE NDAT239650 D DENDAT239650 D DE NDAT239650D DE 239650D A DE239650D A DE 239650DA DE 239650 C DE239650 C DE 239650C
- Authority
- DE
- Germany
- Prior art keywords
- cinnamic acid
- parts
- acid esters
- alcohols
- 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.)
- Active
Links
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 229930016911 cinnamic acid Natural products 0.000 claims description 5
- 235000013985 cinnamic acid Nutrition 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000001851 cinnamic acid derivatives Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000006011 modification reaction Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N Cinnamic acid Chemical compound OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 cinnamic acid-γ-chloroxypropyl ester Chemical compound 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LECCRMLPHATJIB-UHFFFAOYSA-N 2,3-dihydroxypropyl 3-phenylprop-2-enoate Chemical compound OCC(O)COC(=O)C=CC1=CC=CC=C1 LECCRMLPHATJIB-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-Chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-MCPD Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 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
- 230000000875 corresponding Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
- M 239650 KLASSE 12 o. GRUPPE- M 239650 CLASS 12 or GROUP
Patentiert im Deutschen Reiche vom 25. Oktober 1910 ab. Längste Dauer: 18.Mai 1925. Patented in the German Empire on October 25, 1910. Longest duration: May 18, 1925.
Durch das Hauptpatent ist ein Verfahren zur Darstellung von Monozimtsäureestern mehrwertiger Alkohole geschützt, das darin besteht, daß man Zimtsäure, ihre Salze oder Derivate mit mehrwertigen Alkoholen verestert, oder zimtsaure Salze mit den mehrwertigen Alkoholen entsprechenden Dihalogeniden und Wasser erhitzt.The main patent describes a process for the preparation of monocinnamic acid esters which are polyvalent Protected alcohols, which consists in the fact that one cinnamic acid, its salts or derivatives Esterified with polyhydric alcohols, or cinnamic acid salts with the polyhydric alcohols corresponding dihalides and water heated.
Es wurde nun gefunden, daß man Mono- ^* 10 zimtsäureester mehrwertiger Alkohole auch dadurch erhalten kann, wenn man Zimtsäureester
von halogensubstituierten Alkoholen mit wässerigen Lösungen von Salzen schwacher Säuren,
zweckmäßig unter Druck, erhitzt.
Von dem Verfahren der Patentschrift 225984 unterscheidet sich das vorliegende durch die
Verwendung ungesättigter Säureester halogensubstituierter Alkohole.It has now been found that mono- cinnamic acid esters of polyhydric alcohols can also be obtained by heating cinnamic acid esters of halogen-substituted alcohols with aqueous solutions of salts of weak acids, advantageously under pressure.
The present invention differs from the process of patent specification 225984 by the use of unsaturated acid esters of halogen-substituted alcohols.
100 Teile Zimtsäure-ß-chloräthylester100 parts of cinnamic acid-ß-chloroethyl ester
C6H5-C H :C H. COOC H2: C H2-ClC 6 H 5 -CH: C H. COOC H 2 : CH 2 -Cl
werden mit 70 Teilen kristallisiertem Natriumacetat und 80 Teilen verdünnter Essigsäure im Autoklaven auf 1400 erhitzt. Nach dem Erkalten wird die Reaktionsmasse mit Äther , ausgezogen, mit Sodalösung ausgeschüttelt und * dann destilliert. Der Monozimtsäureglykolester destilliert bei 15 mm Druck bei 170 bis 1750 C. Der als Ausgangsmaterial benutzte Zimtsäure - β - chloräthylester wird erhalten durch 40 are heated to 140 0 with 70 parts of crystallized sodium acetate and 80 parts of dilute acetic acid in an autoclave. After cooling, the reaction mass is extracted with ether, extracted with soda solution and then distilled. The Monozimtsäureglykolester distilled at 15 mm pressure at 170 to 175 0 C. The used as a starting material cinnamic - β - chloräthylester obtained by 40
Verestern von Zimtsäure und Chloräthylalkohol bei Gegenwart von konzentrierter Schwefelsäure. Dieser Ester destilliert als farblose Flüssigkeit bei 20 mm Druck bei 188 bis 191° über. Er erstarrt alsbald zu einem weißen Körper, der bei -f- 31° schmilzt.Esterification of cinnamic acid and chloroethyl alcohol in the presence of concentrated sulfuric acid. This ester distills as a colorless liquid at a pressure of 20 mm at 188 ° to 191 ° above. It soon solidifies to a white body that melts at -f- 31 °.
100 Teile Zimtsäure-y-chloroxypropylester
C6 H5-CH:CH-COOCH2- CH2 -OH-CH2Cl 100 parts of cinnamic acid-γ-chloroxypropyl ester
C 6 H 5 -CH: CH-COOCH 2 -CH 2 -OH-CH 2 Cl
werden mit 75 Teilen Natriumacetat und 80 Teilen verdünnter Essigsäure im Autoklaven auf 1500 erhitzt. Nach dem Erkalten wird die Reaktionsmasse mit Äther ausgezogen, mit Sodalösung geschüttelt, getrocknet und der Äther verdampft. Es hinterbleibt der Monozimtsäureglycerinester.are heated to 150 0 in an autoclave with 75 parts of sodium acetate and 80 parts of dilute acetic acid. After cooling, the reaction mass is extracted with ether, shaken with soda solution, dried and the ether evaporated. The glycerol monocinnamate remains.
Der als Ausgangsmaterial benutzte Zimtsäure-y-chloroxypropylester wird erhalten durch Verestern von Zimtsäure und Monochlorhydrin bei Gegenwart von konzentrierter Schwefelsäure. Dieser Ester destilliert als gelblich gefärbte Flüssigkeit von glycerinartiger Konsistenz bei 20 mm Druck von 210 bis 218 ° über.The γ-chlorooxypropyl cinnamic acid used as starting material is obtained by esterifying cinnamic acid and monochlorohydrin in the presence of concentrated sulfuric acid. This ester distills as a yellowish liquid with a glycerine-like consistency at 20 mm pressure from 210 to 218 ° above.
4545
5°5 °
5555
200 Teile Zimtsäure-ß-chloräthylester200 parts of cinnamic acid-ß-chloroethyl ester
C6H5-CHiCH-COOCH2-CH2ClC 6 H 5 -CHiCH-COOCH 2 -CH 2 Cl
werden mit 200 Teilen festem Natriumacetat und 160 Teilen verdünnter Essigsäure 2 Tagewith 200 parts of solid sodium acetate and 160 parts of dilute acetic acid for 2 days
gekocht. Nach dem Erkalten wird die Reaktionsmasse mit Äther ausgezogen, mit Sodalösung gewaschen und im Vakuum destilliert. Es ging der Monozimtsäureglykolester bei 15 mm Druck von 170 bis 1750 über.cooked. After cooling, the reaction mass is extracted with ether, washed with soda solution and distilled in vacuo. The monocinnamic acid glycol ester went over from 170 to 175 0 at a pressure of 15 mm.
Das Verfahren ist auch für Zimtsäureester anderer halogensubstituierter Alkohole, wie Zimtsäüre-ß-bromäthylester, anwendbar. Ebenso kann das ftatriumacetat durch andere Salze schwacher Säuren, wie Dinatriumphosphat, Natriumsalicylat usw., ersetzt werden.The procedure is also applicable to cinnamic acid esters of other halogen-substituted alcohols, such as Cinnamic acid-ß-bromoethyl ester, applicable. Likewise, the sodium acetate can be replaced by other salts weak acids such as disodium phosphate, sodium salicylate, etc. can be replaced.
Claims (1)
Abänderung des durch Patent 235357 geschützten Verfahrens zur Darstellung von Monozimtsäureestern mehrwertiger Aikohole, dadurch gekennzeichnet, daß man, anstatt die freie Zimtsäure und ihre Derivate usw. zu verestern, hier Zimtsäureester von halogensubstituierten Alkoholen mit wässerigen Lösungen von Salzen schwacher Säuren, zweckmäßig unter Druck, erhitzt.Patent claim:
Modification of the process protected by patent 235357 for the preparation of monocinnamic acid esters of polyvalent alcohols, characterized in that instead of esterifying the free cinnamic acid and its derivatives etc., cinnamic acid esters of halogen-substituted alcohols are heated with aqueous solutions of salts of weak acids, advantageously under pressure .
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE239650C true DE239650C (en) |
Family
ID=499074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT239650D Active DE239650C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE239650C (en) |
Cited By (2)
| 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 |
| US2454275A (en) * | 1945-06-25 | 1948-11-23 | Celanese Corp | Manufacture of mixed esters of poly-hydroxy compounds |
-
0
- DE DENDAT239650D patent/DE239650C/de active Active
Cited By (2)
| 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 |
| US2454275A (en) * | 1945-06-25 | 1948-11-23 | Celanese Corp | Manufacture of mixed esters of poly-hydroxy compounds |
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