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DE1192771B - Fragrances and fragrance compositions - Google Patents

Fragrances and fragrance compositions

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Publication number
DE1192771B
DE1192771B DEV25022A DEV0025022A DE1192771B DE 1192771 B DE1192771 B DE 1192771B DE V25022 A DEV25022 A DE V25022A DE V0025022 A DEV0025022 A DE V0025022A DE 1192771 B DE1192771 B DE 1192771B
Authority
DE
Germany
Prior art keywords
fragrances
iii
weight
parts
aldehyde
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
DEV25022A
Other languages
German (de)
Inventor
Dipl-Chem Karl Ebert
Dr Dieter Merkel
Dr Manfred Muehlstaedt
Hans Koll
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.)
Filmfabrik Wolfen VEB
Original Assignee
Filmfabrik Wolfen VEB
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 Filmfabrik Wolfen VEB filed Critical Filmfabrik Wolfen VEB
Priority to DEV25022A priority Critical patent/DE1192771B/en
Publication of DE1192771B publication Critical patent/DE1192771B/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00Essential oils; Perfumes
    • C11B9/0042Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C11B9/0046Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13Monohydroxylic alcohols containing saturated rings
    • C07C31/137Monohydroxylic alcohols containing saturated rings polycyclic with condensed ring systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/20Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/225Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)

Description

Riechstoffe und Riechstoffkompositionen Die Erfindung betrifft Riechstoffe und Riechstoff kompositionen, welche 3-(Camphenyl-8)-2-methylpropen-3-al-1 (I) und seine Hydrierungsprodukte, 3 - (Camphenyl - 8) - 2 - methyl -1- hydroxypropan (II) und 3-(Isocamphanyl-8)-2-methyl-l-hydroxypropan (III) sowie deren Mischungen und Ester enthalten. Gegenüber geruchlich ähnlichen Riechstoffen auf Camphenbasis, wie z. B. den bekannten perhydrierten Additionsprodukten von Camphen und Phenoläthern, haben die hier beschriebenen Produkte - abgesehen von ihren neuartigen, die Riechstoffpalette bereichernden Geruchsnoten - den Vorteil der technisch einfacheren Herstellbarkeit und der absoluten Seifenechtheit der Alkohole (II) und (III). Es wurde gefunden, daß der bei der Kondensation des 8-Formylcamphens mit Propionaldehyd in Gegenwart von stark basischen Katalysatoren, beispielsweise Natriumalkoholaten, entstehende a-,(3-, y-,ä-ungesättigte Aldehyd (I) sowie seine Hydrierungsprodukte (II) und (III) und deren Ester mit niederen Fettsäuren ausgezeichnete Riechstoffe darstellen.Fragrances and fragrance compositions The invention relates to fragrances and fragrance compositions which 3- (camphenyl-8) -2-methylpropen-3-al-1 (I) and its hydrogenation products, 3 - (camphenyl-8) -2-methyl -1- hydroxypropane (II) and 3- (isocamphanyl-8) -2-methyl-1-hydroxypropane (III) and mixtures and esters thereof. Compared to odor-similar odorous substances based on camphene, such as. B. the well-known perhydrogenated addition products of camphene and phenol ethers, the products described here - apart from their novel odor notes enriching the range of fragrances - have the advantage that alcohols (II) and (III) are technically easier to manufacture and that they are absolutely soap-fast. It has been found that the α-, (3-, γ-, γ-unsaturated aldehyde (I) and its hydrogenation products (II) and formed during the condensation of 8-formylcamphene with propionaldehyde in the presence of strongly basic catalysts, for example sodium alcoholates (III) and their esters with lower fatty acids are excellent fragrances.

Der Aldehyd (1) hat einen starken holzig-grünen und haftenden Geruch und ist als solcher in Kompositionen gut verwendbar.The aldehyde (1) has a strong woody-green and sticky odor and as such is well usable in compositions.

Der bei vollständiger Hydrierung des I, z. B. mit Raney-Nickel als Katalysator und 50 at Wasserstoff bei Temperaturen von etwa 90 bis 100°C, in guter Ausbeute erhaltene Alkohol (III) besitzt einen feinen Duft nach Zedern und Sandelholz. Man kann die Hydrierung jedoch auch so leiten, daß im Endprodukt der Aldehyd (I) und die Alkohole (II) und (III) vorliegen, beispielsweise durch Unterbrechen der Hydrierung nach Aldehydbestimmung. Dabei hat sich gezeigt, daß auf diese Weise erhaltene Mischungen, die z. B. 3 bis 5% Aldehyd (1), 50 bis 60% Alkohol (II) und 30 bis 40% Alkohol (III) enthalten, außerordentlich gut verwendbar sind, da sie die holzig-grüne Note des Aldehyds (I) mit der milden holzigen Note der Alkohole (II) und (III) vereinen.When the I is fully hydrogenated, e.g. B. with Raney nickel as Catalyst and 50 atm of hydrogen at temperatures of about 90 to 100 ° C, in good Alcohol (III) obtained in the yield has a fine scent of cedar and sandalwood. However, the hydrogenation can also be conducted in such a way that the aldehyde (I) in the end product and the alcohols (II) and (III) are present, for example by interrupting the Hydrogenation according to aldehyde determination. It has been shown that obtained in this way Mixtures z. B. 3 to 5% aldehyde (1), 50 to 60% alcohol (II) and 30 to 40% Alcohol (III) contain, are extremely useful, since they are the woody-green Combine the note of the aldehyde (I) with the mild woody note of the alcohols (II) and (III).

Auch kann die Hydrierung so geleitet werden, daß das Produkt aldehydfrei anfällt und nur die Alkohole (II) und (III) enthält. Dieses Gemisch zeichnet sich besonders durch die Haltbarkeit der Verbindungen und des Geruchs in Seifen aus.The hydrogenation can also be conducted in such a way that the product is free from aldehyde is obtained and only contains the alcohols (II) and (III). This mixture stands out especially by the durability of the compounds and the smell in soaps.

Je nach gewünschtem Verwendungszweck ist es also möglich, durch einfache katalytische Hydrierung wertvolle seifenechte Riechstoffe aus dem Aldehyd (I) herzustellen. Die durch Umsetzung der Alkohole mit niederen Fettsäuren erhältlichen Ester, z. B. 3-(Isocamphanyl-8)-2-methyl-l-acetoxypropan, zeichnen sich ebenfalls durch einen angenehmen Holzgeruch aus und lassen sich gut als Komponenten von Riechstoffmischungen verwenden. Beispiel 1 Kondensation von 8-Formylcamphen mit Propionaldehyd In einem 6-1-Sulfierkolben mit Rührer, Tropftrichter und Thermometer werden 250 g 10%ige Natriummethylatlösung und 100 ml Methanol vorgelegt und auf + 10°C abgekühlt. Bei dieser Temperatur läßt man eine Mischung aus 640 g 8-Formylcamphen, 320 g Propionaldehyd und 500 m1Methanol unter Rühren schnell zulaufen. Die Temperatur wird dabei zwischen 10 und 20°C gehalten. Die Zulaufzeit soll etwa 10 bis 15 Minuten betragen. Dann wird unter Rühren 3 Stunden auf 20 bis 25°C gehalten, mit Essigsäure neutralisiert und über Nacht stehengelassen. Am nächsten Tag wird mit Wasser verdünnt, bis sich das 0l gut abscheidet. Das Öl wird im Scheidetrichter abgetrennt und die wäßrige Schicht einmal mit Benzol extrahiert. Die Ölschicht und die Benzollösung werden vereinigt, mit Wassergewaschen, mit Natriumsulfat getrocknet, vom Benzol befreit und der Rückstand im Vakuum destilliert. Man erhält 420 g (I) als gelbliche stark viskose Flüssigkeit vom Kp.o,o5 bis o,oa 92 bis 99°C (nö° = 1,5665 bis 1,5670) und gewinnt etwa 270 bis 290 g 8-Formylcamphen zurück, das nochmals zur Reaktion gebracht werden kann.Depending on the intended use, it is therefore possible to produce valuable, soap-resistant fragrances from the aldehyde (I) by simple catalytic hydrogenation. The esters obtainable by reacting the alcohols with lower fatty acids, e.g. B. 3- (Isocamphanyl-8) -2-methyl-l-acetoxypropane, are also characterized by a pleasant wood odor and can be used well as components of odoriferous mixtures. Example 1 Condensation of 8-formylcamphene with propionaldehyde 250 g of 10% sodium methylate solution and 100 ml of methanol are placed in a 6-1 sulphonation flask equipped with a stirrer, dropping funnel and thermometer and the mixture is cooled to + 10.degree. At this temperature, a mixture of 640 g of 8-formylcamphene, 320 g of propionaldehyde and 500 ml of methanol is allowed to run in rapidly with stirring. The temperature is kept between 10 and 20 ° C. The feed time should be about 10 to 15 minutes. The mixture is then kept at 20 to 25 ° C. for 3 hours with stirring, neutralized with acetic acid and left to stand overnight. The next day, it is diluted with water until the oil separates out well. The oil is separated off in a separatory funnel and the aqueous layer is extracted once with benzene. The oil layer and the benzene solution are combined, washed with water, dried with sodium sulfate, freed from benzene, and the residue is distilled in vacuo. 420 g of (I) are obtained as a yellowish, highly viscous liquid with a boiling point of 0.05 to 0.02 ° C. to 99 ° C. (nö ° = 1.5665 to 1.5670) and about 270 to 290 g of 8-formylcamphene are recovered that can be reacted again.

Semicarbazon, F. 207 bis 209°C (aus Äthanol). 2,4-Dinitrophenylhydrazon, F. 228 bis 229°C (aus Athylacetat). Beispiel 2 Hydrierung des 3-(Camphenyl-8)-2-methylpropen-3-als-1 (I) 800g (1) werden in 420m1 960%igem Äthanol gelöst und mit 80g Raney-Nickel bei 80 bis 90°C und 50 at Wasserstoff hydriert, bis keine Wasserstoffaufnahme mehr erfolgt. Insgesamt werden etwa 120l Wasserstoff aufgenommen. Das Reaktionsprodukt wird vom Katalysator und Äthanol befreit und fraktioniert destilliert. Man erhält etwa 60 g Vorlauf und etwa 650 g reines 3-(Isocamphanyl-8)-2-methyl-l-hydroxypropan (III) als farblose, viskose Flüssigkeit mit angenehm mildem Holzgeruch; Kp.o,2 bis o,a 107 bis 112°C (nö = 1,4925 bis 1,4928).Semicarbazone, m.p. 207-209 ° C (from ethanol). 2,4-dinitrophenylhydrazone, Mp 228-229 ° C (from ethyl acetate). Example 2 Hydrogenation of 3- (camphenyl-8) -2-methylpropene-3-than-1 (I) 800g (1) are dissolved in 420m1 960% ethanol and mixed with 80g Raney nickel 80 to 90 ° C and 50 atm hydrogen hydrogenated until there is no more hydrogen uptake. A total of around 120 liters of hydrogen are absorbed. The reaction product is from Catalyst and ethanol freed and fractionally distilled. You get about 60 g first run and about 650 g pure 3- (isocamphanyl-8) -2-methyl-l-hydroxypropane (III) as a colorless, viscous liquid with a pleasantly mild wood odor; Kp.o, 2 to o, a 107 to 112 ° C (nö = 1.4925 to 1.4928).

Der Vorlauf entfärbt KMn04-Lösung und zeigt damit den ungesättigten Charakter seiner Inhaltsstoffe (I) und (II) an. Beispiel 3 3-(Isocamphanyl-8)-2-methyl-l-acetoxypropan 125 g 3-(Isocamphanyl-8)-2-methyl-1-hydroxypropan (III), nö = 1,4928, werden mit 125 g frisch destilliertem Essigsäureanhydrid und 125 g getrocknetem Pyridin 3 Stunden am Rückfluß gekocht. Dann wird abgekühlt und bei 20°C mit 200 ml Wasser verdünnt. Die Mischung wird in einem Scheidetrichter viermal mit verdünnter Salzsäure zur Entfernung des Pyridins gewaschen, dann wird mit Wasser neutral gewaschen. Das Öl wird zur geruchlichen Reinigung nochmals mit Wasserdampf ausgeblasen. Nach dem Trocknen mit Natriumsulfat wird im Vakuum fraktioniert destilliert.The first run decolorizes KMn04 solution and shows the unsaturated one Character of its ingredients (I) and (II). Example 3 3- (Isocamphanyl-8) -2-methyl-1-acetoxypropane 125 g of 3- (isocamphanyl-8) -2-methyl-1-hydroxypropane (III), not = 1.4928, are mixed with 125 g of freshly distilled acetic anhydride and 125 g of dried pyridine for 3 hours refluxed. It is then cooled and diluted at 20 ° C. with 200 ml of water. The mixture is added four times with dilute hydrochloric acid in a separatory funnel Washed removal of the pyridine, then washed neutral with water. The oil is blown out again with steam to clean the odor. After drying fractional distillation is carried out in vacuo with sodium sulfate.

Kp.o,2 92 bis 98°C (n1 = 1,4792). Beispiel 4 Riechstoffmischung 7,0 Gewichtsteile Styrolylacetat, 5,0 Gewichtsteile Undecylenaldehyd (10°/oig), 3,0 Gewichtsteile Bergamotteöl, 10,0 Gewichtsteile 3-(Isocamphanyl-8)-2-methyl- 1-hydroxypropan (III), 2,0 Gewichtsteile Patchouli-Öl chin., 10,0 Gewichtsteile Cumarin, 5,0 Gewichtsteile Hydroxycitronellal, 2,0 Gewichtsteile Tibetolid (10°/oig), 3,0 Gewichtsteile ß-Jonon, 3,0 Gewichtsteile Cedrylacetat. 50,0 Gewichtsteile. Bp.292 to 98 ° C (n1 = 1.4792). Example 4 Fragrance mixture 7.0 parts by weight of styrene acetate, 5.0 parts by weight of undecylenic aldehyde (10%), 3.0 parts by weight of bergamot oil, 10.0 parts by weight 3- (isocamphanyl-8) -2-methyl- 1-hydroxypropane (III), 2.0 parts by weight of patchouli oil chin., 10.0 parts by weight of coumarin, 5.0 parts by weight hydroxycitronellal, 2.0 parts by weight of tibetolide (10%), 3.0 parts by weight of ß-ionone, 3.0 parts by weight of C edryl acetate. 50.0 parts by weight.

Claims (1)

Patentanspruch: Riechstoffe und Riechstoffkompositionen, g e -kennzeichnet durch den Gehalt an dem Aldehyd von der Formel und bzw. oder dessen Hydrierungsprodukten und bzw. oder und bzw. oder deren Ester mit niederen Fettsäuren.Claim: Fragrances and fragrance compositions, characterized by the content of the aldehyde of the formula and / or its hydrogenation products and or or and / or their esters with lower fatty acids.
DEV25022A 1963-08-14 1963-12-12 Fragrances and fragrance compositions Pending DE1192771B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEV25022A DE1192771B (en) 1963-08-14 1963-12-12 Fragrances and fragrance compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DD10016563 1963-08-14
DEV25022A DE1192771B (en) 1963-08-14 1963-12-12 Fragrances and fragrance compositions

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993002998A1 (en) * 1991-07-26 1993-02-18 Henkel Kommanditgesellschaft Auf Aktien Bicyclic compounds, their preparation and their use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993002998A1 (en) * 1991-07-26 1993-02-18 Henkel Kommanditgesellschaft Auf Aktien Bicyclic compounds, their preparation and their use

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