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DE1041036B - Process for the production of unsaturated alcohols with special fragrance properties - Google Patents

Process for the production of unsaturated alcohols with special fragrance properties

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Publication number
DE1041036B
DE1041036B DEH24931A DEH0024931A DE1041036B DE 1041036 B DE1041036 B DE 1041036B DE H24931 A DEH24931 A DE H24931A DE H0024931 A DEH0024931 A DE H0024931A DE 1041036 B DE1041036 B DE 1041036B
Authority
DE
Germany
Prior art keywords
acetylene
production
unsaturated alcohols
special fragrance
fragrance properties
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
DEH24931A
Other languages
German (de)
Inventor
Joseph Donald Surmatis
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.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
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 F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Publication of DE1041036B publication Critical patent/DE1041036B/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
    • C07C33/042—Acyclic alcohols with carbon-to-carbon triple bonds with only one triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds

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

Description

Verfahren zur Herstellung von ungesättigten Alkoholen mit besonderen Riechstoffeigenschaften Die Erfindung betrifft ein Verfahren zur Herstellung von ungesättigten Alkoholen mit besonderen Riechsteffeigenschaften, welches dadurch gekennzeichnet ist, da,ß man in an sich bekannter Weise ein ungesättigtes Ketom der allgemeinen Formel in welcher R die Gruppe bedeutet, mittels einer metallorganischen Reaktion an Acetylen anlagert und das entstandene Acetylencarbinol an der Dreifachbindung partiell hydriert.The invention relates to a process for the production of unsaturated alcohols with special olfactory properties, which is characterized in that an unsaturated ketome of the general formula is obtained in a manner known per se in which R the group means, is added to acetylene by means of an organometallic reaction and the resulting acetylene carbinol is partially hydrogenated at the triple bond.

Zweckmäßig erfolgt die Anlagerung des Ketons an Acetylen in flüssigem Ammoniak mittels Natrium, z. B. durch Auflösen von metallischem Natrium in flüssigem Ammoniak und Einleiten von Acetylen in die Lösung, bis das Natrium in das Acetyli,d übergegangen ist, worauf das Keton in einem inerten Lösungsmittel langsam zugesetzt wird. Das erhaltene Acetylencarbino,l wird nun an der Dreifachbindung partiell hydriert. Dies geschieht mit Vorteil katalytisch in Gegenwart eines mit Blei desaktivierten Palladiumkatalysators, z. B. desjenigen nach L in dl ar (Helvetica Chimica Acta, 35, S.446 (1952j).The addition of the ketone to acetylene is expediently carried out in liquid Ammonia by means of sodium, e.g. B. by dissolving metallic sodium in liquid Ammonia and bubbling acetylene into the solution until the sodium enters the acetylene, i has passed, whereupon the ketone is slowly added in an inert solvent will. The acetylenecarbino, 1 obtained is now partially hydrogenated at the triple bond. This is advantageously done catalytically in the presence of one deactivated with lead Palladium catalyst, e.g. B. the one after L in dl ar (Helvetica Chimica Acta, 35, p.446 (1952j).

Die neuen erfindungsgemäß herstellbaren ungesättigten Alkohole besitzen die folgende allgemeine Formel: in welcher R die gleiche Bedeutung wie, oben hat. Sie weisen bisher unbekannte, neue Geruchsnuancen auf und können zur Herstellung von Riechstoffgemischen und Parfüms verwendet werden.The new unsaturated alcohols that can be prepared according to the invention have the following general formula: in which R has the same meaning as above. They have hitherto unknown, new odor nuances and can be used for the production of fragrance mixtures and perfumes.

Von dem bekannten Nerolidol unterscheiden sich die erfindungsgemäß herstellbaren Verbindungen überraschenderweise geruchlich durch eine zwar auch ma.iglöckchenartige, jedoch bedeutend holzigere Note. Außerdem weisen sie eine höhere Haftfestigkeit auf und eignen sich deshalb vorzüglich für die Herstellung von Parfümkompositionen.Those according to the invention differ from the known nerolidol compounds that can be produced, surprisingly odorless, thanks to a lily of the valley-like, but a significantly woodier note. They also have a higher adhesive strength and are therefore particularly suitable for the production of perfume compositions.

Beispiel 1 In einer Wolffschen Flasche wird 11 Ammoniak kondensiert. Dem flüssigen Ammoniak werden 27,6 g (1,2 Mol) von in kleine Stücke geschnittenem Natriummetall zugesetzt. Die erhaltene Lösung nimmt eine intensiv blaue Farbe an. In das Reaktionsgemisch wird mit einer Geschwindigkeit von etwa 1 Mol pro Stunde Acetylen, das durch Schwefelsäure hindurchgeleitet wird, eingeleitet. Nach Verschwinden der vom Natriummetall herrührenden blauen Farbe (etwa nach 11/4 Stunde) wird noch während 1/z Stunde Acetylen eingeleitet.Example 1 Ammonia is condensed in a Wolff bottle. The liquid ammonia is added 27.6 g (1.2 moles) of cut into small pieces Sodium metal added. The resulting solution takes on an intense blue color. Into the reaction mixture is added at a rate of about 1 mole per hour Acetylene, which is passed through sulfuric acid, initiated. After disappearing the blue color from the sodium metal (after about 11/4 hours) will still be introduced acetylene for 1 / z hour.

Hierauf wird der ainmoniakaUschen Natriumacetylidlösung eine: Lösung von 208 g (1,0 Mol) 6,9,10-Trimetvl-undecadien-(5,9)-on-(2) in 250 cm3 trockenem Äther tropfenweise im Verlauf einer halben Stunde zugesetzt. Während der Zugabe dieser Lösung und anschließend noch 3 Stunden länger wird im Reaktionsgefäß ein leichter Acetylenüberdruck aufrechterhalten. Das Gemisch wird anschließend während 15 Stunden gerührt.The ammoniacal sodium acetylide solution then becomes a solution of 208 g (1.0 mol) 6,9,10-trimetvl-undecadiene- (5,9) -one- (2) in 250 cm3 dry Ether added dropwise over half an hour. During the encore this solution and then another 3 hours longer becomes a in the reaction vessel Maintain slight acetylene pressure. The mixture is then used during Stirred for 15 hours.

Dann wird das Ammoniak durch Hindurchleiten von trockenem Stickstoff durch das Reaktionsgenisch abgedampft. Das Gemisch wird durch Eintragen in 1500 cms verdünnter wäßri.ger Schwefelsäure (hergestellt durch Verdünnen von 50 cm3 konzentrierter Schwefelsäure mit 1500 cm3 Wasser) abgeschreckt. Die wäß.rige saure Schicht wird 2mal mit je 300 cm3 Äther extrahiert, worauf die mit den Ätherextrakten vereinigte organische Schicht 3mal mit je 300 cm3 Wasser gewaschen wird. Die ätherische Lösung wird über Calciumchlorid getrocknet und vom Lösungstnittelbefreit. Der Rückstand wird durch eine Vigreuxkolonne destilliert. Die bei 121 bis 123° C/0,5 bis 0,7 mm überdestillierende Fraktion, die einen Brechungsindex von ;i.-'D5= 1.4787 aufweist, besteht aus 3, 7,10,11-Tetramethy 1-dodecadien-(6,10)-in-(1)-ol-(3) . Diese Verbindung besitzt einen an Bergamottö1 erinnernden Geruch.Then the ammonia is removed by bubbling dry nitrogen through it evaporated by the reaction mixture. The mixture is made by entering in 1500 cms of dilute aqueous sulfuric acid (produced by diluting 50 cm3 of concentrated Sulfuric acid quenched with 1500 cm3 of water). The aqueous acidic layer becomes Extracted twice with 300 cm3 ether each time, whereupon it combined with the ether extracts organic layer is washed 3 times with 300 cm3 of water each time. The essential solution is dried over calcium chloride and freed from the solvent. The residue is by a Vigreux column distilled. The one at 121 to 123 ° C / 0.5 to 0.7 mm distilling fraction which has a refractive index of; i .- 'D5 = 1.4787 consists of 3, 7,10,11-tetramethy 1-dodecadiene- (6,10) -in- (1) -ol- (3) . This compound has a smell reminiscent of bergamot oil.

181 g (0.7711o1) 3,7,10,11-Tetramethyl-dodecadien-(6.10)-in-(1)-ol-(3), gelöst in Petroläther, werden bei einem Wasserstoffdruck von 1 Atm. unter Verwendung von 1S g von 5 o/oigem Blei-Palladium-Katalysator auf Calciumcarhonat (L i n d l ar, a. a. O.) hydriert. Nachdem 16,11 Wasserstoff absorbiert worden sind, hört die @@'asserstoffaufnahme auf, wobei die Acetylenprobe negativ ausfällt. Der Katalysator wird abfiltriert, worauf das Lösungsmittel im Vakuum abgedampft und der Rückstand fraktioniert wird. Die hei 111 his 112'C/0,35 mm überdestillierende und einen Brechungsindex ttä = 1.4788 aufweisende Fraktion besteht zur Hauptsache aus 3,7,10,11-Tetrametlivl-dodecatrieii-(1.6.101-ol-(3). Diese Verbindung besitzt einen an Änfel und Rosen erinnernden blumigen und fruchtigen Duft. Beispiel 2 23 g Natriummetall werden in 1 1 flüssigem Ammoniak gelöst. In die gerührte Lösung wird so lange Acetylen eingeleitet, bis die Farbe der Lösung von Blau nach Weiß umgeschlagen hat. In das gerührte Reaktionsgemisch wird im Verlauf einer Stunde eine Lösung von 163 g 6.10-Dimethyl-undecen-(5)-on-(2) in 200 cm3 Diäthyläther eingetragen. Anschließend wird das Reaktionsgemisch noch während 3 Stunden gerührt. während ein schwacher Acetylenstrom eingeleitet wird. Dann wird die Acetylenzufuhr unterbrochen, hingegen das Rühren während 15 Stunden fortgesetzt. Das Ammoniak wird abdestilliert, worauf der Rückstand im Reaktionsgefäß mit 21 5 o/oiger wäßriger Schwefelsäure gewaschen wird. Das gewaschene Produkt wird dann noch mit Wasser gewaschen. über wasserfreiem Ca!lciumsulfat getrocknet und fraktioniert, um das bei 93 bis 94° C/0,8 min überdestillierende und einen Brechungsindex na ö5 von 1.4609 aufweisende 3, 7,11-Trimethyl - dodecen- (6) -in-(1)-ol-(3) zu erhalten. Diese Verbindung besitzt einen rosen- und lavendelartigen angenehmen Geruch und eignet sich als Riechstoff zur Herstellung von Parfüms und parfümerierten Gemischen. 108,2 g (etwa 0,49 Mol) 3,7,11-Trimethy 1- dodecen-(6)-in-(1)-ol-(3) werden zusammen mit 12g 5 o/oigem Blei-Palladium-Katailysatar auf Calciumcarbonat (Lind 1 a r , a. a. O.) und 150 cm3 Petroläther in einen mit einem Rührwerk ausgerüsteten Reaktionskolben. eingetragen und bei 25 bis 30° C und einem Wasserstoffdruck von 1 Atm. hydriert, bis 0,49 Mol Wasserstoff verbraucht worden sind. Durch Fraktionieren des Hydrierungsproduktes wird das bei 98 bis 100° C/1,0 mm überdestillierende und einen Brechungsindex iiö5von 1,4608 aufweisende 3,7.11-Trimethyl-dodecadien-(1,6)-ol-(3) erhalten. Diese Verbindung besitzt einen an Rosen erinnernden Duft und eignet sich für die Herstellung von Parfümstoffen.181 g (0.7711o1) 3,7,10,11-tetramethyl-dodecadiene- (6.10) -in- (1) -ol- (3), dissolved in petroleum ether, are at a hydrogen pressure of 1 atm. hydrogenated using 15 g of 5% lead-palladium catalyst on calcium carbonate (L indl ar, loc. cit.). After 16.11 hydrogen has been absorbed, the uptake of hydrogen ceases, with the acetylene sample being negative. The catalyst is filtered off, whereupon the solvent is evaporated off in vacuo and the residue is fractionated. The fraction which distills over hot from 111 to 112 ° C / 0.35 mm and has a refractive index tt = 1.4788 consists mainly of 3,7,10,11-tetrametal-dodecatrieii- (1.6.101-ol- (3). This compound has a floral and fruity scent reminiscent of apples and roses. Example 2 23 g of sodium metal are dissolved in 1 liter of liquid ammonia. Acetylene is introduced into the stirred solution until the color of the solution has changed from blue to white In the course of one hour, a solution of 163 g of 6.10-dimethyl-undecen- (5) -one- (2) in 200 cm3 of diethyl ether is introduced into the reaction mixture, and the reaction mixture is stirred for a further 3 hours while a gentle stream of acetylene is passed in the supply of acetylene is interrupted, but stirring is continued for 15 hours, the ammonia is distilled off, and the residue in the reaction vessel is washed with 21 5% aqueous sulfuric acid d then washed with water. dried over anhydrous calcium sulfate and fractionated to remove the 3, 7,11-trimethyl-dodecen- (6) -in- (1) which distills over at 93 to 94 ° C / 0.8 min and has a refractive index na ö5 of 1.4609 -ol- (3). This compound has a rose-like and lavender-like pleasant odor and is suitable as a fragrance for the production of perfumes and perfumed mixtures. 108.2 g (about 0.49 mol) of 3,7,11-trimethyl-1-dodecen- (6) -in- (1) -ol- (3) are added together with 12 g of 5% lead-palladium catalyst on calcium carbonate (Lind 1 ar, loc. cit.) and 150 cm3 petroleum ether in a reaction flask equipped with a stirrer. entered and at 25 to 30 ° C and a hydrogen pressure of 1 atm. hydrogenated until 0.49 moles of hydrogen have been consumed. By fractionating the hydrogenation product, 3,7.11-trimethyl-dodecadiene- (1,6) -ol- (3) which distills over at 98 to 100 ° C / 1.0 mm and has a refractive index of 1.4608 is obtained. This compound has a scent reminiscent of roses and is suitable for the manufacture of perfumes.

Claims (1)

PATLNTA'N SPRUCII Verfahren zur Herstellung von besondere Riechstoffeigenschaften besitzenden ungesättigten Alkoholen der allgemeinen Formel in welcher R die Gruppe bedeutet, dadurch gekennzeichnet, daß man in an sich bekannter Weise ein ungesättigtes Keton der allgemeinen Formel in der R die vorstehende Bedeutung hat, mittels einer metallorganischen Reaktion an Acetylen anlagert und das entstandene Acetylencarbinol an der D,reifachbindung partiell hydriert. In. Betracht gezogene Druckschriften: Deutsche Patentschrift Nr. 859 616; britische Patentschriften Nr. 665 147, 674 059.PATLNTA'N SPRUCII Process for the production of unsaturated alcohols of the general formula which have special odorous properties in which R the group means, characterized in that an unsaturated ketone of the general formula is used in a manner known per se in which R has the above meaning, is added to acetylene by means of an organometallic reaction and the acetylene carbinol formed is partially hydrogenated at the D, triple bond. In. Documents considered: German Patent No. 859 616; British Patent Nos. 665 147, 674 059.
DEH24931A 1954-09-15 1955-09-10 Process for the production of unsaturated alcohols with special fragrance properties Pending DE1041036B (en)

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US1041036XA 1954-09-15 1954-09-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296080A (en) * 1963-08-08 1967-01-03 Rhodia Linalool homologues

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB665147A (en) * 1949-03-22 1952-01-16 Glaxo Lab Ltd Improvements in or relating to the preparation of a new unsaturated carbinol
GB674059A (en) * 1949-03-22 1952-06-18 Glaxo Lab Ltd Improvements in or relating to the preparation of new unsaturated carbinols
DE859616C (en) * 1951-05-22 1952-12-15 Hoffmann La Roche Ag Deutsche Process for the preparation of doubly unsaturated aliphatic-cyclic 2-methylbutanal compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB665147A (en) * 1949-03-22 1952-01-16 Glaxo Lab Ltd Improvements in or relating to the preparation of a new unsaturated carbinol
GB674059A (en) * 1949-03-22 1952-06-18 Glaxo Lab Ltd Improvements in or relating to the preparation of new unsaturated carbinols
DE859616C (en) * 1951-05-22 1952-12-15 Hoffmann La Roche Ag Deutsche Process for the preparation of doubly unsaturated aliphatic-cyclic 2-methylbutanal compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296080A (en) * 1963-08-08 1967-01-03 Rhodia Linalool homologues

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