CH370771A - Process for the production of caffeic acid esters of quinic acid and quinides - Google Patents
Process for the production of caffeic acid esters of quinic acid and quinidesInfo
- Publication number
- CH370771A CH370771A CH1258560A CH1258560A CH370771A CH 370771 A CH370771 A CH 370771A CH 1258560 A CH1258560 A CH 1258560A CH 1258560 A CH1258560 A CH 1258560A CH 370771 A CH370771 A CH 370771A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- quinide
- quinic
- quinic acid
- caffeic
- Prior art date
Links
- AAWZDTNXLSGCEK-LNVDRNJUSA-N (3r,5r)-1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid Chemical compound O[C@@H]1CC(O)(C(O)=O)C[C@@H](O)C1O AAWZDTNXLSGCEK-LNVDRNJUSA-N 0.000 title claims description 10
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 title claims description 10
- AAWZDTNXLSGCEK-ZHQZDSKASA-N Quinic acid Natural products O[C@H]1CC(O)(C(O)=O)C[C@H](O)C1O AAWZDTNXLSGCEK-ZHQZDSKASA-N 0.000 title claims description 10
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical class OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims 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 claims description 11
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 8
- 239000007859 condensation product Substances 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 1
- 229910001863 barium hydroxide Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910052601 baryte Inorganic materials 0.000 description 3
- 239000010428 baryte Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940074360 caffeic acid Drugs 0.000 description 2
- 235000004883 caffeic acid Nutrition 0.000 description 2
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- QFKJCKFAYFUXRQ-UHFFFAOYSA-N barium;hydrate Chemical compound O.[Ba] QFKJCKFAYFUXRQ-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- -1 thionylcaffeic acid Chemical compound 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
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Tea And Coffee (AREA)
Description
Verfahren zur Herstellung von Kaffeesäureestern der Chinasäure und der Chinide Im Hauptpatent Nr. 338825 wird ein Verfahren beschrieben zur Herstellung der Kaffeesäureester der Chinasäure und des zugehörigen Chinides der For meln (I)
EMI0001.0008
worin T, V und W = Wasserstoff oder einen Kaffeeyl- rest mit freien oder veresterten Oxygruppen bedeu ten.
Dieses Verfahren ist dadurch gekennzeichnet, d'ass man das Säurechlorid oder Anhydrid eines Kaffee säurederivates der Formel (II)
EMI0001.0016
worin R' und R" Acetyl, Propionyl, Benzoyl oder gemeinsam -CO- bedeuten, mit Chinid oder einem 4,5-Alkyliden-chinid kondensiert und das sich bil dende Kondensationsprodukt einer Verseifung unter solchen Bedingungen unterwirft,
dass in 1- und'loder 4-Stellung der Chinid'komponenten eingeführte Kaffeeylreste nicht wieder abgespalten werden.
Die vorliegende Erfindung betrifft nun ein Ver fahren zur Herstellung von Kaffeesäureestern der Chinasäure, das dadurch gekennzeichnet ist, d'ass man das Säurechlorid oder -anhydrid der Thio- nylkaffeesäure der Formel
EMI0001.0039
mit Chinasäure, Chinid oder einem 4,5-Alkyliden- chimd kondensiert, und dass man das.
sich bildende Kondensationszwischenprodukt einer Verseifung unter solchen Bedingungen unterwirft, dass 1,4-Dikaffeeyl- chinasäure oder 1-Kaffeeyl-chinasäure als Endprodukt erhalten werden.
Die Kondensation erfolgt vorzugsweise durch Mi schung von 1 bis 4 Mol Thionylkaffeesäurechlorid mit 4 bis 1 Mol Chinasäure oder Chinid und Er wärmen des Gemisches auf eine Temperatur von 110 his 180 C während 15 bis 90 Minuten.
Zur selek tiven Verseifung wird das Kondensationsprodukt zweckmässig mit einer 3%igen Bariumhyd'ratlösung zwischen 0 und 30 C 1 bis 40 Stunden lang unter Luftausschluss behandelt.
Das Thionylkaffeesäurech'lorid gewinnt man durch Sieden von Kaffeesäure mit Thionylchlorid unter Rückfluh bis zu dessen Auflösung und anschliessen des Eindampfen, bis das Chlorid kristallisiert, wel ches aus einem inerten Lösungsmittel (Kohlenwas serstoff, chlorierter Kohlenwasserstoff) umkristalli- siert werden kann.
<I>Beispiel 1</I> 10,0 g Thionylkaffeesäurechlorid und 2,93 g Chinasäure werden innerhalb 1,5 Stunden bei 155 unter Vakuum erhitzt. Man erhält eine geschmolzene Masse, welche in Dioxan gelöst und in 1000 em33 3 %iges Barytwasser geschüttet wird,
wobei in einer Inertgasströmung gearbeitet wird. Nach 40 Stunden wird der gelbe Niederschlag filtriert und mit ver dünntem HCl, mit Natriumbicarbonat und schliess- lich mit frischer verdünnter HCl behandelt.
Die so erhaltene rohe 1,4-Dikaffeeyl-chinasäure wird wie üblich aus wässriger Essigsäure umkristallisiert. <I>Beispiel 2</I> 10,0 g Thionylkaffeesäurechlorid werden mit 3,56 g Chinid nach den im Beispiel 1 angegebenen Modalitäten kondensiert. Man gewinnt eine ge schmolzene Masse, die in Dioxan gelöst und in 1 Liter 3%iges Barytwasser geschüttet wird, wobei unter Stickstoffstrom gearbeitet wird.
Fährt man dann wie im Beispiel 1 fort, so erhält man die 1,4- Dikaffeeylehinasäure, Schmelzpunkt 224 bis 227 C (Zers.). Das Thionylkaffeesäurechiorid wird dadurch hergestellt, dass man 30 g Kaffeesäure mit 90 cm?, Thionylchlorid zum Sieden bringt; nach 7 bis 8 Stunden hat man eine braune Lösung, die unter Va kuum verdampft wird. Durch Umkristallisieren des Rückstandes aus Trichloräthylen gewinnt man das Thionylkaffeesäurechlorid, Schmelzpunkt 88 bis 94 .
<I>Beispiel 3</I> 10 g Thionylkaffeesäurechlorid und 4,02 g Aze- tonchinid werden nach den im Beispiel 1 angege benen Modalitäten kondensiert. Man gewinnt eine geschmolzene Masse, die in Dioxan gelöst und in 1 Liter 3 %iges Barytwasser geschüttet wird, wobei unter Stickstoffstrom gearbeitet wird.
Fährt man dann wie im Beispiel 1 fort, so erhält man die 1-Kaffeeyl- chinasäure in Form von nicht kristallisierbarem Schaum; [a]2 = -8,3 (c = 3 in Wasser).
Process for the preparation of caffeic acid esters of quinic acid and the quinides In the main patent no. 338825 a process is described for the preparation of the caffeic acid esters of quinic acid and the associated quinide of the formulas (I)
EMI0001.0008
where T, V and W = hydrogen or a caffeyl radical with free or esterified oxy groups.
This process is characterized in that the acid chloride or anhydride of a coffee acid derivative of the formula (II)
EMI0001.0016
where R 'and R "are acetyl, propionyl, benzoyl or together -CO-, condensed with quinide or a 4,5-alkylidene-quinide and subjecting the condensation product to saponification under such conditions,
that caffeyl residues introduced in the 1- and / or 4-position of the quinide components are not split off again.
The present invention now relates to a process for the preparation of caffeic acid esters of quinic acid, which is characterized in that the acid chloride or anhydride of thionylcaffeic acid of the formula is used
EMI0001.0039
condensed with quinic acid, quinide or a 4,5-alkylidenechimd, and that one that.
The intermediate condensation product which forms is subjected to saponification under such conditions that 1,4-dikaffeeyl-quinic acid or 1-caffeyl-quinic acid are obtained as the end product.
The condensation is preferably carried out by mixing 1 to 4 moles of thionyl coffee acid chloride with 4 to 1 mole of quinic acid or quinide and heating the mixture to a temperature of 110 to 180 ° C. for 15 to 90 minutes.
For selective saponification, the condensation product is expediently treated with a 3% strength barium hydrate solution between 0 and 30 ° C. for 1 to 40 hours with the exclusion of air.
The thionyl coffee acid chloride is obtained by boiling caffeic acid with thionyl chloride under reflux until it dissolves and then evaporating it until the chloride crystallizes, which can be recrystallized from an inert solvent (hydrocarbon, chlorinated hydrocarbon).
<I> Example 1 </I> 10.0 g of thionyl coffee acid chloride and 2.93 g of quinic acid are heated under vacuum at 155 for 1.5 hours. A molten mass is obtained, which is dissolved in dioxane and poured into 1000 em33 3% barite water,
working in an inert gas flow. After 40 hours the yellow precipitate is filtered and treated with diluted HCl, with sodium bicarbonate and finally with freshly diluted HCl.
The crude 1,4-dikaffeeyl-quinic acid thus obtained is recrystallized as usual from aqueous acetic acid. <I> Example 2 </I> 10.0 g of thionyl coffee acid chloride are condensed with 3.56 g of quinide according to the modalities given in Example 1. A melted mass is obtained, which is dissolved in dioxane and poured into 1 liter of 3% barite water, working under a stream of nitrogen.
If one then continues as in Example 1, the 1,4-dicaffee eylinic acid is obtained, melting point 224 to 227 ° C. (decomp.). The thionyl coffee acid chloride is prepared by bringing 30 g caffeic acid with 90 cm ?, thionyl chloride to the boil; after 7 to 8 hours you have a brown solution which is evaporated under vacuum. The thionyl coffee acid chloride, melting point 88 to 94, is obtained by recrystallizing the residue from trichlorethylene.
<I> Example 3 </I> 10 g of thionyl coffee acid chloride and 4.02 g of acetonequinide are condensed according to the modalities given in Example 1. A molten mass is obtained, which is dissolved in dioxane and poured into 1 liter of 3% barite water, working under a stream of nitrogen.
If one then continues as in Example 1, 1-caffeylquinic acid is obtained in the form of non-crystallizable foam; [a] 2 = -8.3 (c = 3 in water).
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT338825X | 1954-05-28 | ||
| IT1711454 | 1954-12-28 | ||
| CH338825T | 1955-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH370771A true CH370771A (en) | 1963-07-31 |
Family
ID=27178391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1258560A CH370771A (en) | 1954-05-28 | 1955-11-21 | Process for the production of caffeic acid esters of quinic acid and quinides |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH370771A (en) |
-
1955
- 1955-11-21 CH CH1258560A patent/CH370771A/en unknown
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