DE1005952B - Process for the production of tertiary diaethylene alcohols - Google Patents

Process for the production of tertiary diaethylene alcohols

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Publication number
DE1005952B
DE1005952B DES47142A DES0047142A DE1005952B DE 1005952 B DE1005952 B DE 1005952B DE S47142 A DES47142 A DE S47142A DE S0047142 A DES0047142 A DE S0047142A DE 1005952 B DE1005952 B DE 1005952B
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DE
Germany
Prior art keywords
alcohols
tertiary
formula
production
diaethylene
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
Application number
DES47142A
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German (de)
Inventor
Henri Normant
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.)
Rhone Poulenc SA
Original Assignee
Rhone Poulenc SA
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 Rhone Poulenc SA filed Critical Rhone Poulenc SA
Publication of DE1005952B publication Critical patent/DE1005952B/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02Acyclic alcohols with carbon-to-carbon double bonds

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

Description

Verfahren zur Herstellung von tertiären Diäthylenalkoholen Die Erfindung betrifft die Herstellung von tertiären Diäthylenalkoholen der allgemeinen Formel In dieser Formel bedeuten R1 und R2 Wasserstoffatome oder niedrigermolekulare Alkylreste oder Arylreste, R3 ein Wasserstoffatom oder einen Methylrest, R4, R5 und Re Wasserstoffatome oder Alkylreste mit 1 bis 5 Kohlenstoffatomen.Process for the preparation of tertiary diethylene alcohols The invention relates to the preparation of tertiary diethylene alcohols of the general formula In this formula, R1 and R2 denote hydrogen atoms or lower molecular weight alkyl groups or aryl groups, R3 denotes a hydrogen atom or a methyl group, R4, R5 and Re denote hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.

Die Erfindung betrifft demnach die Herstellung neuer und analoger bereits bekannter tertiärer Diäthylenalkohole, z. B. vom Typ des Linalols. Das letztere entspricht der oben angegebenen allgemeinen Formel, wobei R4, R, und RB Wasserstoffatome sind. Die neuen Produkte der oben angegebenen allgemeinen Formel, wobei wenigstens eines der Symbole R4, R5 und R6 einen Alkylrest bedeutet, weisen angenehmen Bergamotte-Lavendelduft verschiedener Nuancen auf, wodurch sie in der Parfümerie verwendbar sind.The invention therefore relates to the manufacture of new and analogous ones already known tertiary diethylene alcohols, e.g. B. of the linalol type. The latter corresponds to the general formula given above, where R4, R, and RB are hydrogen atoms are. The new products of the general formula given above, where at least one of the symbols R4, R5 and R6 means an alkyl radical, have a pleasant bergamot-lavender scent different nuances, which makes them usable in perfumery.

Das erfindungsgemäße Verfahren besteht darin, daß ein y, 8-Äthylenketon der Formel worin R1, R2 und R3 die oben angegebenen Bedeutungen besitzen, mit einem Überschuß einer magnesiumorganischen Äthylenverbindung der Formel worin R4, R6 und R, Wasserstoffatome oder Alkylreste mit 1 bis 5 Kohlenstoffatomen und X ein Halogenatom, vorzugsweise Brom, bedeuten, kondensiert wird und daß man die erhaltene Komplexverbindung dann in üblicher Weise zersetzt, z. B. mittels einer gesättigten kalten Ammoniumchloridlösung. Die Reaktion kann folgendermaßen schematisch wiedergegeben werden. Die magnesiumorganischen Äthylenverbindungen können bekanntermaßen leicht in Tetrahydrofuran hergestellt werden.The process according to the invention consists in that a γ, 8-ethylene ketone of the formula in which R1, R2 and R3 have the meanings given above, with an excess of an organomagnesium ethylene compound of the formula wherein R4, R6 and R, hydrogen atoms or alkyl radicals having 1 to 5 carbon atoms and X is a halogen atom, preferably bromine, is condensed and that the complex compound obtained is then decomposed in a conventional manner, for. B. by means of a saturated cold ammonium chloride solution. The reaction can be shown schematically as follows. The organomagnesium ethylene compounds are known to be easily prepared in tetrahydrofuran.

Der Vorteil des erfindungsgemäßen Verfahrens gegenüber der bisher bekannten Arbeitsweise ist aus dem folgenden Beispiel an Hand der Herstellung des dl-Linalols ersichtlich. Die Synthese des dl-Linalols wurde von Ruzicka und Fornasir [vgl. Helv. Chim. Acta 2, 184 (1919)] durch Fixierung von 1 Mol Acetylen an 1 Mol 2-Methylhepten-(2)-on-(6) und Umwandlung der acetylenischen Dreifachbindung des Reaktionsproduktes in eine Äthylendoppelbindung durch vorsichtige Hydrierung beschrieben.The advantage of the method according to the invention over the previous one known working method is from the following example on the basis of the production of the dl-Linalols can be seen. The synthesis of dl-linalol was carried out by Ruzicka and Fornasir [see. Helv. Chim. Acta 2, 184 (1919)] by fixing 1 mol of acetylene to 1 mol 2-Methylhepten- (2) -one- (6) and conversion of the acetylenic Triple bond of the reaction product into an ethylene double bond by careful hydrogenation described.

Durch das erfindungsgemäße Verfahren wird die Synthese des dl-Linalols in einem einzigen Arbeitsgang in vorzüglicher Ausbeute ermöglicht.The process according to the invention enables the synthesis of dl-linalol made possible in a single operation in excellent yield.

Das folgende Beispiel soll die Erfindung näher erläutern, ohne sie zu beschränken. Beispiel Man gibt in 200 cem trockenes Tetrahydrofuran, das eine Spur Jod enthält, 24 g Magnesium und läßt dann nach und nach unter Rühren eine Lösung von 107 g Vinylbromid in der gleichen Gewichtsmenge Tetrahydrofuran eintropfen. Die so erhaltene magnesiumorganische Lösung wird in Eis gekühlt. Man führt dann unter gutem Rühren eine Lösung von 101 g 2-Methyl-hepten-(2)-on-(6) in einem gleichen Volumen wasserfreiem Äther ein. Nach beendeter Zugabe wird noch 1 Stunde gerührt und das Ganze dann 12 Stunden stehen gelassen. Dann gibt man eine gesättigte Ammoniumchloridlösung zu, damit die Magnesiumkomplexverbindung zersetzt wird. Es findet Trennung in zwei Schichten statt; die organische Schicht wird abdekantiert, über wasserfreiem Kaliumcarbonat getrocknet, durch Erhitzen auf dem Wasserbad von Lösungsmitteln befreit und dann durch Destillation unter vermindertem Druck rektifiziert. Unter einem Druck von 12,5 mm Hg werden bei 83 bis 85° 103 g dl-Linalol von guter Reinheit abgetrennt, was einer Ausbeute von 83 °/o entspricht.The following example is intended to explain the invention in more detail without it to restrict. Example It is 200 cem of dry tetrahydrofuran, the one Trace iodine contains 24 g of magnesium and then gradually leaves a solution with stirring drop in 107 g of vinyl bromide in the same amount by weight of tetrahydrofuran. The organomagnesium solution obtained in this way is cooled in ice. One then leads with good stirring a solution of 101 g of 2-methyl-hepten- (2) -one- (6) in a same Volume of anhydrous ether. After the addition has ended, stirring is continued for 1 hour and then left it to stand for 12 hours. A saturated ammonium chloride solution is then added so that the magnesium complex compound is decomposed. It finds separation in two Shifts instead; the organic layer is decanted over anhydrous potassium carbonate dried, freed from solvents by heating on a water bath and then rectified by distillation under reduced pressure. Under a pressure of 12.5 mm Hg are separated at 83 to 85 ° 103 g dl-linalol of good purity, which corresponds to a yield of 83%.

Nach der gleichen Arbeitsweise kann man mit ähnlichen Ausbeuten die folgenden Verbindungen herstellen: aus 1-Brom-propen-(1) das 2, 6-Dimethyl-nonadien-(2, 7)-o1-(6); Kp.13 = 99 bis 100°; d22 = 0,864; nDP = 1,4652; aus 1-Brom-hepten-(1) das 2, 6-Dimethyl-tridekadien-(2, 7)-o1-(6); Kp." = 154 bis 156°; d22 = 0,842; n@ö = 1,4661; aus 1-Brom-isobuten-(1) das 2, 6, 8-Trimethyl-nonadien-(2, 7)-o1-(6); Kp." = 106 bis 107°; d" = 0,866; 2D = 1,4692; aus 2-Brom-propen-(2) das 2, 6, 7-Trimethyl-octadien-(2, 7)-o1-(6) ; Kp.13 = 98 bis 99°; d22 = 0,866; no =1,4658.The same procedure can be used with similar yields produce the following compounds: from 1-bromo-propen- (1) the 2,6-dimethyl-nonadiene- (2, 7) -o1- (6); Bp 13 = 99 to 100 °; d22 = 0.864; nDP = 1.4652; from 1-bromo-hepten- (1) the 2,6-dimethyl-tridecadiene- (2,7) -o1- (6); Kp. "= 154 to 156 °; d22 = 0.842; n @ ö = 1.4661; from 1-bromo-isobutene- (1) the 2, 6, 8-trimethyl-nonadiene- (2, 7) -o1- (6); Bp "= 106 to 107 °; d" = 0.866; 2D = 1.4692; from 2-bromo-propen- (2) the 2, 6, 7-trimethyl-octadiene- (2, 7) -o1- (6); Bp 13 = 98 to 99 °; d22 = 0.866; no = 1.4658.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von tertiären Diäthylenalkoholen der Formel worin R1 und R2 Wasserstoffatome oder niedrigermolekulare Alkylreste oder Arylreste, R3 ein Wasserstoffatom oder einen Methylrest und R4, R5 und Re Wasserstoffatome oder Alkylreste mit 1 bis 5 Kohlenstoffatomen bedeuten, dadurch gekennzeichnet, daß man ein y, 8-Äthylenketon der Formel mit einer magnesiumorganischen Äthylenverbindung der Formel worin R4, R, und R6 die obige Bedeutung haben und worin X ein Halogenatom bedeutet, umsetzt und die gebildete Komplexverbindung in üblicher Weise zersetzt. PATENT CLAIM: Process for the production of tertiary diethylene alcohols of the formula in which R1 and R2 are hydrogen atoms or lower molecular weight alkyl radicals or aryl radicals, R3 is a hydrogen atom or a methyl radical and R4, R5 and Re are hydrogen atoms or alkyl radicals having 1 to 5 carbon atoms, characterized in that a γ, 8-ethylene ketone of the formula with an organomagnesium ethylene compound of the formula in which R4, R and R6 have the above meaning and in which X is a halogen atom, reacted and the complex compound formed decomposed in the usual manner.
DES47142A 1955-02-03 1956-01-19 Process for the production of tertiary diaethylene alcohols Pending DE1005952B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1005952X 1955-02-03

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DE1005952B true DE1005952B (en) 1957-04-11

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DES47142A Pending DE1005952B (en) 1955-02-03 1956-01-19 Process for the production of tertiary diaethylene alcohols

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1073477B (en) * 1960-01-21 Lovens kemiske Fabrik ved A. Kongsted, Kopenhagen Process for the production of 2-phenyl- and 2-p-chlorophenyl- 3-methyl-2,3-dihydroxy-hexene- (5) effective as sedatives
DE1170397B (en) * 1960-04-22 1964-05-21 Geigy Ag J R Process for the production of bis-tertiary glycols
WO2014095321A1 (en) 2012-12-20 2014-06-26 Firmenich Sa Sage odorant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1073477B (en) * 1960-01-21 Lovens kemiske Fabrik ved A. Kongsted, Kopenhagen Process for the production of 2-phenyl- and 2-p-chlorophenyl- 3-methyl-2,3-dihydroxy-hexene- (5) effective as sedatives
DE1170397B (en) * 1960-04-22 1964-05-21 Geigy Ag J R Process for the production of bis-tertiary glycols
WO2014095321A1 (en) 2012-12-20 2014-06-26 Firmenich Sa Sage odorant
US9284513B2 (en) 2012-12-20 2016-03-15 Firmenich Sa Sage odorant

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