DE702490C - Process for the resolution of the racemic condensation product of phytyl halides and trimethylhydroquinone - Google Patents

Process for the resolution of the racemic condensation product of phytyl halides and trimethylhydroquinone

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Publication number
DE702490C
DE702490C DE1939H0159452 DEH0159452D DE702490C DE 702490 C DE702490 C DE 702490C DE 1939H0159452 DE1939H0159452 DE 1939H0159452 DE H0159452 D DEH0159452 D DE H0159452D DE 702490 C DE702490 C DE 702490C
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DE
Germany
Prior art keywords
condensation product
trimethylhydroquinone
phytyl
halides
racemic
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
Application number
DE1939H0159452
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German (de)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HOFFMANNI LA ROCHE and CO AKT GE
Original Assignee
HOFFMANNI LA ROCHE and CO AKT GE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by HOFFMANNI LA ROCHE and CO AKT GE filed Critical HOFFMANNI LA ROCHE and CO AKT GE
Application granted granted Critical
Publication of DE702490C publication Critical patent/DE702490C/en
Expired legal-status Critical Current

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Classifications

    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Zerlegung des racemischen Kondensationsproduktes aus Phytylhalogeniden und Trimethylhydrochinon Es wurde gefunden, daß es gelingt, das durch Einwirkung von Trimethylhydrochinon auf Phytylhalogenide erhältliche racemische Kondensationsprodukt mit 3-Bromcamphersulfonsäurehalogenid in die optisch aktiven Formen zu zerlegen.Process for the resolution of the racemic condensation product from Phytyl halides and trimethylhydroquinone It has been found that it succeeds racemic ones obtainable by the action of trimethylhydroquinone on phytyl halides Condensation product with 3-bromocamphorsulfonic acid halide into the optically active Disassemble shapes.

Die schwer lösliche Fraktion des Bromcamphersulfonats kristallisiert in Nädelchen und schmilzt bei 48 bis 5o°. Dieser Schmelzpunkt liegt gleich hoch wie derjenige des 3-Bromcamphersulfonats des a-Tocopherols. In Mischung zeigen die beiden Verbindungen keine Schmelzpunktsdepression. Die spezifische Drehung des Bromcamphersulfonats des Kondensationsproduktes beträgt [a] - -h- 3o° (± 2°) und stimmt mit derjenigen des Bromcamphersulfonats des natürlichen a-Tocopherols überein. Beispiel i Teil des Kondensationsproduktes aus Phytylbromid und Trimethylhydrochinonwird in 8 Teilen absolutem Pyridin gelöst und mit 3 Teilen fein gepulvertem 3-Bromca.mphersulfonsäurechlorid versetzt. Hierauf erhitzt man die Lösung q. Stunden auf 6o bis 8o°. Dann wird sie in Eiswasser gegossen und aus;-geäthert. Der Ätherauszug wird nacheinander mit Wasser, verdünnter Schwefelsäure, Bicarbonatlösung und schließlich nochmals mit Wasser gewaschen. Nach dem Verdampfen des Äthers hinterbleibt ein Öl, das in 2o Teilen absolutem Alkohol aufgenommen wird. Beim Stehen dieser Lösung in der Kälte scheidet sich zunächst eine kleine Menge eines öligen Produktes ab, von dem abgegossen wird. Nach einigen Tagen beginnt in der Lösung die Kristallisation des Bromcamphersulfonats, die sich im Laufe mehrerer Tage vermehrt. Die Verbindung wird- durch nochmaliges Umkristallisieren aus absolutem Alkohol gereinigt.The sparingly soluble fraction of the bromocamphor sulfonate crystallizes in needles and melts at 48 to 50 °. This melting point is the same like that of the 3-bromocamphor sulfonate of α-tocopherol. In the mix they show both compounds show no depression of the melting point. The specific rotation of the bromocamphor sulfonate of the condensation product is [a] - -h- 30 ° (± 2 °) and agrees with that of the bromocamphor sulfonate of the natural α-tocopherol. Example i part of the condensation product of phytyl bromide and trimethylhydroquinone is divided into 8 parts dissolved in absolute pyridine and mixed with 3 parts of finely powdered 3-Bromca.mphersulfonsäurechlorid offset. The solution q is then heated. Hours at 6o to 8o °. Then she will poured into ice water and from; -ethered. The ether extract is successively mixed with water, diluted sulfuric acid, bicarbonate solution and finally washed again with water. After evaporation of the ether, an oil remains, which in 20 parts of absolute alcohol is recorded. When this solution is left in the cold, it initially separates a small amount of an oily product to be poured off. After some Days, the bromocamphor sulfonate begins to crystallize in the solution increased over the course of several days. The compound is - by repeated recrystallization Purified from absolute alcohol.

Durch alkalische Verseifung wird die Bromcamphersulfonsäure abgetrennt, das Verseifungsprodukt zeigt mit dem a-Tocopherol übereinstimmende Eigenschaften.The bromocamphor sulfonic acid is separated off by alkaline saponification, the saponification product shows properties identical to those of α-tocopherol.

Claims (1)

PATENTANSPRUCH Verfahren zur Zerlegung des racemischen Kondensationsproduktes aus Phytylhalogeniden und Trimethylhydrochinon, dadurch gekennzeichnet, daß man das Kondensationsprodukt in das 3-Bromcamphersulfonat überführt und dieses fraktioniert kristallisiert. PATENT CLAIM Process for the decomposition of the racemic condensation product from phytyl halides and trimethylhydroquinone, characterized in that the condensation product is converted into 3-bromocamphor sulfonate and this is crystallized in a fractional manner.
DE1939H0159452 1938-05-24 1939-04-29 Process for the resolution of the racemic condensation product of phytyl halides and trimethylhydroquinone Expired DE702490C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH702490X 1938-05-24

Publications (1)

Publication Number Publication Date
DE702490C true DE702490C (en) 1941-02-08

Family

ID=4530146

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1939H0159452 Expired DE702490C (en) 1938-05-24 1939-04-29 Process for the resolution of the racemic condensation product of phytyl halides and trimethylhydroquinone

Country Status (1)

Country Link
DE (1) DE702490C (en)

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