DE1205532B - Process for the preparation of 1,4-dicaffeylquinic acid - Google Patents
Process for the preparation of 1,4-dicaffeylquinic acidInfo
- Publication number
- DE1205532B DE1205532B DEF19150A DEF0019150A DE1205532B DE 1205532 B DE1205532 B DE 1205532B DE F19150 A DEF19150 A DE F19150A DE F0019150 A DEF0019150 A DE F0019150A DE 1205532 B DE1205532 B DE 1205532B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- barium hydroxide
- preparation
- hydroxide solution
- moles
- 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.)
- Pending
Links
- IYXQRCXQQWUFQV-RDJMKVHDSA-N 1,4-Di-O-caffeoylquinic acid Chemical compound C1([C@H](O)CC(C[C@H]1O)(OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C(O)=O)OC(=O)\C=C\C1=CC=C(O)C(O)=C1 IYXQRCXQQWUFQV-RDJMKVHDSA-N 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 10
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- 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 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 quinic acid lactone Chemical class 0.000 description 2
- 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 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 210000000941 bile Anatomy 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SWUARLUWKZWEBQ-VQHVLOKHSA-N phenethyl caffeate Chemical compound C1=C(O)C(O)=CC=C1\C=C\C(=O)OCCC1=CC=CC=C1 SWUARLUWKZWEBQ-VQHVLOKHSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical class OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. α.:Int. α .:
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
C07cC07c
Deutsche Kl.: 12 ο - 25German class: 12 ο - 25
1205 532
F19150IVb/12o1205 532
F19150IVb / 12o
24. Dezember 1955December 24, 1955
25. November 1965November 25, 1965
Patent 1095 821 betrifft ein Verfahren zur Herstellung der Kaffeesäureester der Chinasäure bzw. des Chinasäurelactons, die eine energische Anregungswirkung auf die Galleabscheidung und den Cholesterinstoffwechsel besitzen.U.S. Patent 1,095,821 relates to a method of manufacture the caffeic acid ester of quinic acid or quinic acid lactone, which has an energetic stimulating effect on bile deposition and cholesterol metabolism own.
Das Verfahren ist dadurch gekennzeichnet, daß man 1 bis 3 Mol eines in bekannter Weise hergestellten Säurechlorids oder Säureanhydrids eines Kaffeesäurederivates, dessen phenolische Hydroxylgruppen entweder mit Essig-, Propion- oder Benzoesäure verestert ίο oder mit Phosgen in bekannter Weise zum cyclischen Kohlensäureester verestert worden sind, mit 1 bis 3 Mol Chinid oder seinem cyclischen 4,5-Alkylidenacetal, besonders seinem Isopropylidenketal oder dem l-Diacylkaffeesäurenchinidester bei Temperaturen von 110 bis 1800C in Gegenwart eines inerten Lösungsmittels, erforderlichenfalls auch eines säurebindenden Mittels, umsetzt und die gebildeten Verbindungen entweder mit 3 °/oiger Bariumhydroxydlösung bei Temperaturen von 0 bis 1300C unter Luftausschluß oder mit kalter verdünnter Mineralsäure bei Temperaturen von 0 bis 200C, oder mit wäßriger Essigsäure bei Temperaturen von 80 bis 1000C oder mit warmem Wasser, oder zuerst in der Kälte mit verdünnter Mineralsäure und dann mit 3 o/oigem Barium- «5 hydroxyd teilweise verseift.The process is characterized in that 1 to 3 moles of an acid chloride or acid anhydride of a caffeic acid derivative prepared in a known manner, the phenolic hydroxyl groups of which are either esterified with acetic, propionic or benzoic acid or have been esterified with phosgene in a known manner to give the cyclic carbonic acid ester, with 1 to 3 mol of quinide or its cyclic 4,5-alkylidene acetal, especially its isopropylidene ketal or the l-diacylkaffeesäurechinidester at temperatures of 110 to 180 0 C in the presence of an inert solvent, if necessary also an acid-binding agent, and the compounds formed either with 3 ° / o sodium Bariumhydroxydlösung at temperatures from 0 to 130 0 C with exclusion of air or with cold dilute mineral acid at temperatures of 0 to 20 0 C, or with aqueous acetic acid at temperatures of 80 to 100 0 C, or with hot water, or first in the cold with dilute mineral acid and then with 3 o / o barium hydroxide partially saponified.
Es wurde nun gefunden, daß man viel bessere Ausbeuten an 1,4-Dikaffeylchinasäure erhält, 61 bis 62°/o der Theorie im Vergleich zum älteren Patent 1 095 821, wonach man Ausbeuten von 46 bis 47 % erhält, wenn man die nach der Kondensation erhaltene geschmolzene Masse zuerst mit verdünnter Mineralsäure und anschließend mit 3%iger Bariumhydroxydlösung behandelt, wenn man die bei der Veresterung und anschließenden partiellen Verseifung mit wäßriger Essigsäure (30 bis 70°/0) bei 80 bis 100°C erhaltene 1,4,5-Trikaffeylchinasäure mit 3%iger Bariumhydroxydlösung bei 0 bis 300C weiter partiell verseift.It has now been found that much better yields of 1,4-dicaffeylquinic acid are obtained, 61 to 62% of theory in comparison with the earlier patent 1,095,821, according to which yields of 46 to 47% are obtained if the according to the The molten mass obtained by condensation is treated first with dilute mineral acid and then with 3% strength barium hydroxide solution if the 1,4,5 obtained in the esterification and subsequent partial saponification with aqueous acetic acid (30 to 70 ° / 0 ) at 80 to 100 ° C -Tricaffeylquinic acid with 3% barium hydroxide solution at 0 to 30 0 C further partially saponified.
Das folgende Beispiel erläutert die Erfindung:The following example explains the invention:
a) 11,6 g Carbonylkaffeesäurechlorid werden mit 3,06 g Chinid gemischt und allmählich 1,5 Stunden auf 18O0C erwärmt. Man erhält eine geschmolzene Masse, aus der, wenn sie mit Aceton wieder aufgenommen wird, das Tricarbonat des 1,4,5-Trikaffeylchinides, Schmelzpunkt 280 bis 285°C (Zersetzung); [α] » = + 189 ± 1° (c = 1,0; Dioxan) kristallisiert. Ausbeute 9,85 g.a) 11.6 g Carbonylkaffeesäurechlorid are mixed with 3.06 g Chinid and gradually heated 1.5 hours to 18O 0 C. A molten mass is obtained from which, when it is taken up again with acetone, the tricarbonate of 1,4,5-tricaffeylquinide, melting point 280 to 285 ° C. (decomposition); [α] »= + 189 ± 1 ° (c = 1.0; dioxane) crystallizes. Yield 9.85g.
b) 5,0 g Tricarbonat des 1,4,5-Trikaffeylchinides
werden unter Rückfluß 6 Stunden mit 200 ecm 50%iger Essigsäure gekocht. Man erhält eine Lösung,
Verfahren zur Herstellung der
1,4-Dikaffeylchinasäureb) 5.0 g of tricarbonate of 1,4,5-tricaffeylquinides are refluxed for 6 hours with 200 ecm of 50% acetic acid. A solution is obtained, a process for the preparation of the
1,4-dicaffeylquinic acid
Zusatz zum Patent: 1 095 821Addendum to the patent: 1 095 821
Anmelder:Applicant:
Farmaceutici Italia S. Α., Mailand (Italien)Farmaceutici Italia S. Α., Milan (Italy)
Vertreter:Representative:
Dipl.-Ing. Dipl.-Chem. Dr. phil. Dr. techn.Dipl.-Ing. Dipl.-Chem. Dr. phil. Dr. techn.
J. Reitstötter, Patentanwalt,J. Reitstötter, patent attorney,
München 15, Haydnstr. 5Munich 15, Haydnstr. 5
Als Erfinder benannt:Named as inventor:
Carlo G. Alberti,Carlo G. Alberti,
Alberto Vercellone,Alberto Vercellone,
Domenico Cattapan, Mailand (Italien)Domenico Cattapan, Milan (Italy)
Beanspruchte Priorität:Claimed priority:
Italien vom 28. Dezember 1954 (17 115)Italy of December 28, 1954 (17 115)
aus welcher durch Konzentrierung und Verdünnen mit Wasser die 1,4,5-Trikaffeylchinasäure auskristallisiert. Nach dem Umkristallisieren aus 30%iger Essigsäure erhält man ein Produkt mit dem Schmelzpunkt von 218 bis 22O0C (Zersetzung); [α] ψ = — 268 ± 1° (c = 2,0; Äthanol). Die Verbindung kristallisiert mit 3 Molekül Kristallwasser. Ausbeute 4,06 g.from which the 1,4,5-tricaffeylquinic acid crystallizes out by concentration and dilution with water. After recrystallization from 30% acetic acid gives a product with a melting point of 218 to 22O 0 C (decomposition); [α] ψ = - 268 ± 1 ° (c = 2.0; ethanol). The compound crystallizes with 3 molecules of water of crystallization. Yield 4.06g.
c) 6,0 g der in vorstehender Weise hergestellten rohen 1,4,5-Trikaffeylchinasäure werden in Aceton suspensiert und mit 450 ecm 3%iger Bariumhydroxydlösung unter Rühren im Stickstoffstrom versetzt. Nach 40 Stunden wird filtriert, mit 2 n-Hcl behandelt und dann wieder filtriert. Hierauf wird mit einer 10%igen Natriumbicarbonatlösung behandelt und nochmals nitriert.c) 6.0 g of the crude 1,4,5-tricaffeylquinic acid prepared in the above manner are dissolved in acetone suspended and with 450 ecm 3% barium hydroxide solution added with stirring in a stream of nitrogen. After 40 hours, it is filtered and treated with 2 n Hcl and then filtered again. It is then treated with a 10% sodium bicarbonate solution and nitrided again.
Der mit 2 n-HCl und Wasser gewaschene Kuchen wird in der Wärme in 55%iger Essigsäure gelöst. Die 1,4-Dikaffeylchinasäure kristallisiert mit einem Schmelzpunkt von 225 bis 227°C; [«] T = -65 ± 1° (c = 2,0; Äthanol). Ausbeute 2,95 g.The cake, washed with 2N HCl and water, is dissolved in 55% acetic acid while hot. 1,4-Dicaffeylquinic acid crystallizes with a melting point of 225 to 227 ° C; [«] T = -65 ± 1 ° (c = 2.0; ethanol). Yield 2.95g.
509 739/435509 739/435
Für die Herstellung der 1,4,5-Trikaffeylchinasäure wird Schutz im Rahmen der vorliegenden Erfindung nicht beansprucht.For the production of 1,4,5-tricaffeylquinic acid, protection is provided within the scope of the present invention unclaimed.
Claims (1)
C. Weygand, Organisch-chemische Experimentierkunst, 2. Auflage, 1948, S. 403.Considered publications:
C. Weygand, Organic-chemical Experimentierkunst, 2nd edition, 1948, p. 403.
Deutsches Patent Nr. 1 095 821.Legacy Patents Considered:
German Patent No. 1 095 821.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1205532X | 1954-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1205532B true DE1205532B (en) | 1965-11-25 |
Family
ID=11433322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF19150A Pending DE1205532B (en) | 1954-12-28 | 1955-12-24 | Process for the preparation of 1,4-dicaffeylquinic acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1205532B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057655A1 (en) * | 2002-01-07 | 2003-07-17 | Biogaia Fermentation Ab | Process for the isolation of polyhydroxy cyclic carboxylic acids |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1095821B (en) | 1954-05-28 | 1960-12-29 | Farmaceutici Italia | Process for the preparation of the coffee acid esters of the Chinese acid or the Chinese acid lactone |
-
1955
- 1955-12-24 DE DEF19150A patent/DE1205532B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1095821B (en) | 1954-05-28 | 1960-12-29 | Farmaceutici Italia | Process for the preparation of the coffee acid esters of the Chinese acid or the Chinese acid lactone |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057655A1 (en) * | 2002-01-07 | 2003-07-17 | Biogaia Fermentation Ab | Process for the isolation of polyhydroxy cyclic carboxylic acids |
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