CH208086A - Process for the preparation of dl-acetyl-a-tocopherol. - Google Patents
Process for the preparation of dl-acetyl-a-tocopherol.Info
- Publication number
- CH208086A CH208086A CH208086DA CH208086A CH 208086 A CH208086 A CH 208086A CH 208086D A CH208086D A CH 208086DA CH 208086 A CH208086 A CH 208086A
- Authority
- CH
- Switzerland
- Prior art keywords
- tocopherol
- acetyl
- preparation
- parts
- acetate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 claims description 7
- 239000011627 DL-alpha-tocopherol Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012345 acetylating agent Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229930003799 tocopherol Natural products 0.000 claims description 3
- 239000011732 tocopherol Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229960001295 tocopherol Drugs 0.000 claims description 2
- 235000010384 tocopherol Nutrition 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
- A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline
- A61K31/353—3,4-Dihydrobenzopyrans, e.g. chroman, catechin
- A61K31/355—Tocopherols, e.g. vitamin E
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Verfahren zur Darstellung von dl-Acetyl-a-tocopherol. Die kürzlich aufgefundene Synthese des Vitamin-E führt zu racemischen Toco- pherolen. So erhält man zum Beispiel durch Kondensation von Trimethylhydrochinon und Phytol das dl-a-Tocopherol. Dieses Produkt ist gegenüber Oxydationsmitteln (z. B. Luft) und Feuchtigkeit empfindlich.
Es wurde nun gefunden, dass das dl-Ace- tyl-a-tocopherol stärker wirksam und auch beständiger ist als das unveresterte Toco- pherol.
Gegenstand vorliegenden Patentes ist ein Verfahren zur Darstellung von dl-Acetyl-a- tocopherol, welches dadurch gekennzeichnet ist, dass man auf dl-a-Tocopherol Acetylie- rungsmittel einwirken lässt.
Das durch Einwirkung von Acetylie- rungsmitteln auf dl-a-Tocopherol hergestellte dl-Acetyl-a-tocopherol ist ein hellgelbes, sehr viscoses Öl; sein Brechungsexponent (ii2D) beträgt 1,4965. Es siedet bei einem Druck von 0,3 mm bei 224'. In methyl- alkoholischer Lösung reduziert es neutrales Silbernitrat nicht und Tollens Reagens nur allmählich.
Es löst sich in 25 Teilen Me- thyl- und in 5 Teilen Äthylalkohol. Spielend löslich ist es in Benzol, Äther, Petroläther, Aceton, Essigester und Chloroform. Alko holische Laugen verseifen das Acetat zu dl- a-Tocopherol.
Das dl - Acetyl - a - tocopherol soll. als Arzneimittel verwendet werden. <I>Beispiel:</I> 10 Teile dl-a-Tocopherol werden in 40 Teilen Essigsäureanhydrid gelöst. Man rührt die Mischung kräftig, leitet Wasserstoff ein und fügt eine kleine Menge konzentrierter Schwefelsäure zu. Die Lösung wird sofort rot und erwärmt sich. Dann wird die Farbe der Lösung bald graugrün.
Man hält die Temperatur für 2 Stunden auf 40 , neutrali siert darauf die Schwefelsäure durch Zu fügen von wenig Natriumacetat und dampft im Vakuum das Essigsäureanhydrid voll ständig ab. Der Rückstand wird im Hoch- vakuum destilliert oder in einer Molekular- Destillationsapparatur verdampft. Die Aus beute ist beinahe quantitativ.
Process for the preparation of dl-acetyl-a-tocopherol. The recently discovered synthesis of vitamin E leads to racemic tocopherols. For example, by condensing trimethylhydroquinone and phytol, dl-a-tocopherol is obtained. This product is sensitive to oxidizing agents (e.g. air) and moisture.
It has now been found that the dl-acetyl-a-tocopherol is more effective and also more stable than the unesterified tocopherol.
The subject of the present patent is a process for the preparation of dl-acetyl-a-tocopherol, which is characterized in that dl-a-tocopherol acetylating agent is allowed to act.
The dl-acetyl-a-tocopherol produced by the action of acetylating agents on dl-a-tocopherol is a light yellow, very viscous oil; its refraction exponent (ii2D) is 1.4965. It boils at a pressure of 0.3mm at 224 '. In methyl alcoholic solution it does not reduce neutral silver nitrate and Tollen's reagent only gradually.
It dissolves in 25 parts of methyl and 5 parts of ethyl alcohol. It is easily soluble in benzene, ether, petroleum ether, acetone, ethyl acetate and chloroform. Alcoholic alkalis saponify the acetate to dl-a-tocopherol.
The dl-acetyl-a-tocopherol is said to. be used as medicines. <I> Example: </I> 10 parts of dl-a-tocopherol are dissolved in 40 parts of acetic anhydride. The mixture is stirred vigorously, hydrogen is passed in and a small amount of concentrated sulfuric acid is added. The solution immediately turns red and warms up. Then the color of the solution will soon turn gray-green.
The temperature is kept at 40 for 2 hours, the sulfuric acid is then neutralized by adding a little sodium acetate and the acetic anhydride is completely evaporated in vacuo. The residue is distilled in a high vacuum or evaporated in a molecular distillation apparatus. The yield is almost quantitative.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH208086T | 1938-09-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH208086A true CH208086A (en) | 1939-12-31 |
Family
ID=4445888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH208086D CH208086A (en) | 1938-09-29 | 1938-09-29 | Process for the preparation of dl-acetyl-a-tocopherol. |
Country Status (6)
| Country | Link |
|---|---|
| CH (1) | CH208086A (en) |
| DE (1) | DE712744C (en) |
| DK (1) | DK59294C (en) |
| FR (1) | FR859834A (en) |
| GB (1) | GB532364A (en) |
| SE (1) | SE99384C1 (en) |
-
1938
- 1938-09-29 CH CH208086D patent/CH208086A/en unknown
-
1939
- 1939-08-19 DK DK59294D patent/DK59294C/en active
- 1939-08-19 DE DEH160431D patent/DE712744C/en not_active Expired
- 1939-08-25 SE SE460439A patent/SE99384C1/xx unknown
- 1939-08-28 GB GB2467639A patent/GB532364A/en not_active Expired
- 1939-09-01 FR FR859834D patent/FR859834A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR859834A (en) | 1940-12-30 |
| DK59294C (en) | 1941-12-15 |
| SE99384C1 (en) | 1940-07-16 |
| DE712744C (en) | 1941-10-24 |
| GB532364A (en) | 1941-01-22 |
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