GB802669A - Process for the preparation of 1, 4-dicaffeylquinic acid - Google Patents
Process for the preparation of 1, 4-dicaffeylquinic acidInfo
- Publication number
- GB802669A GB802669A GB15272/55A GB1527255A GB802669A GB 802669 A GB802669 A GB 802669A GB 15272/55 A GB15272/55 A GB 15272/55A GB 1527255 A GB1527255 A GB 1527255A GB 802669 A GB802669 A GB 802669A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- dicaffeylquinic
- lead
- treated
- barium
- 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
Links
- 238000000034 method Methods 0.000 title abstract 7
- 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 abstract 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 6
- 244000019459 Cynara cardunculus Species 0.000 abstract 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 5
- 239000002244 precipitate Substances 0.000 abstract 5
- 235000016520 artichoke thistle Nutrition 0.000 abstract 4
- 150000003839 salts Chemical class 0.000 abstract 4
- 235000019106 Cynara scolymus Nutrition 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 3
- 229910052788 barium Inorganic materials 0.000 abstract 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 3
- 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 abstract 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 abstract 2
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 abstract 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 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 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 abstract 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 2
- 239000012535 impurity Substances 0.000 abstract 2
- 229940046892 lead acetate Drugs 0.000 abstract 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract 2
- 239000003960 organic solvent Substances 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 2
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract 1
- MCGBIXXDQFWVDW-UHFFFAOYSA-N 4,5-dihydro-1h-pyrazole Chemical compound C1CC=NN1 MCGBIXXDQFWVDW-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 235000003200 Cynara cardunculus Nutrition 0.000 abstract 1
- 230000021736 acetylation Effects 0.000 abstract 1
- 238000006640 acetylation reaction Methods 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 abstract 1
- 229910001863 barium hydroxide Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 abstract 1
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000010828 elution Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000001640 fractional crystallisation Methods 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000011987 methylation Effects 0.000 abstract 1
- 238000007069 methylation reaction Methods 0.000 abstract 1
- 235000019260 propionic acid Nutrition 0.000 abstract 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 abstract 1
- GBNSPDJKJDIAFT-UHFFFAOYSA-N quinic acid methyl ester Natural products COC(=O)C1(O)CC(O)C(O)C(O)C1 GBNSPDJKJDIAFT-UHFFFAOYSA-N 0.000 abstract 1
- 238000007127 saponification reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
- A61K31/192—Carboxylic acids, e.g. valproic acid having aromatic groups, e.g. sulindac, 2-aryl-propionic acids, ethacrynic acid
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
- A61K31/216—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acids having aromatic rings, e.g. benactizyne, clofibrate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/28—Asteraceae or Compositae (Aster or Sunflower family), e.g. chamomile, feverfew, yarrow or echinacea
-
- 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
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Natural Medicines & Medicinal Plants (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Alternative & Traditional Medicine (AREA)
- Mycology (AREA)
- Microbiology (AREA)
- Medical Informatics (AREA)
- Botany (AREA)
- Biotechnology (AREA)
- Engineering & Computer Science (AREA)
- Emergency Medicine (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention comprises 1,4-dicaffeylquinic acid of the formula <FORM:0802669/IV (b)/1> and a process for its isolation from a decoction liquor containing it (preferably obtained from leaves of cardoon, Cynara cardunculus, or artichoke, Cynara scolymus) by treating the liquor with an excess of a water-soluble salt of barium or lead, respectively in the cold or with heating, and freeing the resulting separated precipitate, which contains the barium or lead salt of 1,4-dicaffeylquinic acid, from impurities by selective separation under acid conditions. Three methods for the selective separation are described: (a) fractional elution of precipitated lead salts with 30-50 per cent acetic acid at 60-80 DEG C., the active substance being recovered from the acid solution thus obtained by removal of lead with sulphuric acid and H2S, and concentration of the remaining liquid; (b) total dissolution of the barium or lead salt in a very slight excess of 10 per cent nitric acid, followed by fractional crystallization; (c) dissolution of the accompanying impurities in a slight excess of dilute sulphuric acid and then extraction of 1,4-dicaffeylquinic acid from the insoluble residue with an organic solvent, e.g. methanol, ethanol or dioxane. The crude caffeylquinic acid obtained by the above methods is further purified by crystallization from dilute acetic acid or water. In examples: (1) carbon leaves are boiled with water, the hot liquor treated with excess lead acetate solution, the precipitate separated by filtration or centrifugation and 1,4-dicaffeylquinic acid isolated by method (a) above; (2) artichloke leaves are boiled with water, filtered, the decoction concentrated under reduced pressure and treated with barium nitrate and barium hydroxide, yielding a yellow precipitate which is treated by method (c), extracting dicaffeylquinic acid with alcohol; (3) the yellow precipitate obtained as in (2) is treated with dilute nitric acid and allowed to stand, when the quinic acid crystallizes; (4) the precipitate obtained by treating a decoction of cardoon or artichoke leaves with lead acetate solution is treated by method (c), using ethanol as the organic solvent. The structure of 1,4-dicaffeylquinic acid is confirmed (a) by acetylation to a hexa-acetate, which on hydrogenation gives a tetrahydro derivative; (b) by alkaline fusion to 3,4-dihydroxybenzoic acid; (c) saponification of the substance and of its tetrahydro derivative giving quinic acid together with 3,4-dihydroxy cinnamic acid or b -(3,4-dihydroxyphenyl) propionic acid respectively; and (d) by methylation to 1,4 - di - (31,41 - dimethoxycinnamoyl) quinic acid methyl ester. Specification 802,668 is referred to.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT336819X | 1954-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB802669A true GB802669A (en) | 1958-10-08 |
Family
ID=11238053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB15272/55A Expired GB802669A (en) | 1954-05-28 | 1955-05-26 | Process for the preparation of 1, 4-dicaffeylquinic acid |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE538205A (en) |
| CH (1) | CH336819A (en) |
| FR (1) | FR1212005A (en) |
| GB (1) | GB802669A (en) |
| NL (1) | NL98113C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003013562A1 (en) * | 2001-08-08 | 2003-02-20 | Lichtwer Pharma Ag | Artichoke leaf extracts |
| WO2003057655A1 (en) * | 2002-01-07 | 2003-07-17 | Biogaia Fermentation Ab | Process for the isolation of polyhydroxy cyclic carboxylic acids |
| CN1301721C (en) * | 2003-07-23 | 2007-02-28 | 昆明英之源农业科技开发有限公司 | Artichoke natural antioxidant and its extraction method |
-
1955
- 1955-05-16 BE BE538205A patent/BE538205A/xx unknown
- 1955-05-24 FR FR1212005D patent/FR1212005A/en not_active Expired
- 1955-05-26 GB GB15272/55A patent/GB802669A/en not_active Expired
- 1955-05-27 CH CH336819D patent/CH336819A/en unknown
- 1955-05-28 NL NL251702A patent/NL98113C/xx active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003013562A1 (en) * | 2001-08-08 | 2003-02-20 | Lichtwer Pharma Ag | Artichoke leaf extracts |
| WO2003057655A1 (en) * | 2002-01-07 | 2003-07-17 | Biogaia Fermentation Ab | Process for the isolation of polyhydroxy cyclic carboxylic acids |
| CN1301721C (en) * | 2003-07-23 | 2007-02-28 | 昆明英之源农业科技开发有限公司 | Artichoke natural antioxidant and its extraction method |
Also Published As
| Publication number | Publication date |
|---|---|
| NL98113C (en) | 1961-05-15 |
| CH336819A (en) | 1959-03-15 |
| FR1212005A (en) | 1960-03-21 |
| BE538205A (en) | 1955-06-15 |
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