WO1992000267A1 - Oxyacetaldehydes - Google Patents
Oxyacetaldehydes Download PDFInfo
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- WO1992000267A1 WO1992000267A1 PCT/EP1991/001172 EP9101172W WO9200267A1 WO 1992000267 A1 WO1992000267 A1 WO 1992000267A1 EP 9101172 W EP9101172 W EP 9101172W WO 9200267 A1 WO9200267 A1 WO 9200267A1
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- Prior art keywords
- oxyacetaldehydes
- glycerol
- formula
- octadienyl
- ether
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, 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
- C11B9/00—Essential oils; Perfumes
- C11B9/0007—Aliphatic compounds
- C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
-
- 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
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/198—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
Definitions
- the invention relates to oxyacetaldehydes, obtainable by cleaving glycerol ethers with alkali periodates, a process for their preparation and their use as fragrances.
- Oxyacetaldehydes based on citronellol, geranol, phenylethanol or benzyl alcohol and their use as fragrances have long been known [Am.Perf.Cosm. f April 83, 219 (1968)].
- n-octyloxyacetaldehyde A process for the preparation of n-octyloxyacetaldehyde is also known from Koryo, 107, 33 (1974), in which n-octanol is first catalysed with bromoacetaldehyde acetal and then acid-catalyzed to hydrolyze the oxyacetaldehyde.
- the product has a pleasant natural, vegetal smell.
- processes of the type mentioned have the disadvantage that they start from acetals of halogenated acetaldehydes, their availability is limited and their handling is problematic for reasons of occupational safety.
- the object of the invention was therefore to provide oxyacetaldehydes, the production of which is free from the disadvantages described.
- the invention relates to oxyacetaldehydes of the formula (I)
- R1 represents an aliphatic, linear or branched hydrocarbon radical with 8 carbon atoms and 2 double bonds, obtainable by reacting glycerol ethers of the formula (II),
- Oxyacetaldehydes which are particularly easily accessible, are obtained if one starts from glycerol ethers produced by palladium-catalyzed telomerization of 1,3-butadiene with glycerol and cleaves them with sodium periodate.
- Glycerol ethers of the formula (II) in which R * is a branched hydrocarbon radical having 8 carbon atoms can be obtained by for example reacting glycerol with a branched C ⁇ -alkyl chloride in a manner known per se.
- Oxyacetaldehydes of the formula (I) in which R is a 2,7- and / or 3,8-octadienyl radical have a particularly intense fragrance.
- the invention further relates to a process for the preparation of oxyacetaldehydes of the formula (III),
- R 2 represents an aliphatic linear or branched hydrocarbon radical with 8 carbon atoms and 0 or 2 double bonds, characterized in that glycerol ethers of the formula (IV),
- R 2 has the meaning given above, cleaves with alkali metal iodates.
- glycerol ethers of the formula (IV) which have been prepared by transition metal-catalyzed telomerization of 1,3-butadiene with glycerol and in which R 2 for a 2,7- and / or 3,8-octa-dienyl radical.
- Glycerol ethers of the type mentioned are known compounds and are preferably prepared by telomerizing 2 moles of 1,3-butadiene with one mole of glycerol in the presence of palladium acetylacetonate and triphenylphosphine. The essence of the method is described in German patent application DE-A-18 07 491.
- Glycerol ethers of the type mentioned are complex mixtures and contain 2,7-, and to a lesser extent, 3,8-0ctadienyl-1-glycerol ether as the main component.
- the corresponding di- and triether, octatriene and unreacted glycerol are also found.
- glycol cleavage of both the octadienyl and the octyl ether can be carried out according to Criegee with lead tetraacetate or phenyl iodosodiacetate.
- the glycerol ethers are cleaved according to the Malaprade using alkali periodates such as, for example, lithium, potassium or preferably sodium periodate, the carbon-carbon bond of the glycol being separated oxidatively to give two aldehyde groups [L. Fieser (Ed.), Organic Che ⁇ ie, Verlag Che ⁇ ie, Weinheim-New York, 1979, pp. 213-214].
- the molar ratio of glycerol ether to periodate can be 1: 0.1 to 1: 2, in particular 1: 0.7 to 1: 1.2.
- the periodate cleavage is carried out at a temperature of 0 to 20 ° C and over a period of 2 to 24 h.
- the sensitive one Fragrance not contaminated by unwanted by-products or traces of heavy metals.
- the oxyacetaldehydes obtainable in the sense of the invention have a smell of cod liver oil in concentrated form, and a pleasant floral fragrance in diluted form, which is characterized by good olfactory sustainability.
- the oxyacetaldehydes according to the invention are suitable for the production of new, interesting fragrance compositions.
- the content of the fragrance mixtures according to the invention is between 1 and 50, preferably between 1 and 25% by weight.
- the rest of 100% by weight can be supplemented by other known fragrances.
- the compositions can be used for perfuming technical articles, such as cleaning and disinfecting agents, textile treatment agents, all kinds of cosmetics, such as fragrant waters, creams, lotions, aerosols, toilet soaps,
- fragrance compositions in the perfumed products is between 2 and 20% by weight.
- Octadienyl-1-glycerol ether (A). 0.0038 g (0.0125 mmol) of palladium (II) acetyl acetonate, 0.0066 g (0.025 mmol) of triphenylphosphine, 28.8 g (313 mmol) of glycerol and 35 ml of propanol-2 were placed in a 400 ml glass autoclave with magnetic stirring and evacuated three times and charged with argon. Subsequently, 37.8 g (700 mmol) of 1,3-butadiene were transferred into the autoclave with the aid of a lifter. The autoclave was closed and at 12 h
- Tri-octadienyl-1,2,3-glycerol ether 2.1% by weight
- the octadienyl ether was used in the periodate cleavage.
- Octadienyl-1-oxyacetaldehyde 45 g (210 mol) of sodium periodate in 100 ml of ether were placed in a 250 ml flask with magnetic stirring and at a temperature of 0 ° C. and covered with nitrogen with a solution of 62.4 g (310 mmol) of Glycerin ether A overlaid in 100 ml of diethyl ether.
- the two-phase solution was mixed with vigorous stirring for 10 min at 0 ° C and then for 3 h at 20 ° C. The mixture was left at 20 ° C. for 12 h. 100 ml of water were then added and the ethereal phase was separated off using a separating funnel.
- the aqueous phase was extracted several times with 25 ml portions of diethyl ether and the combined ethereal phases were washed with brine. After drying over sodium sulfate and concentrating the organic phases, the residue was subjected to fractional distillation. At a top temperature of 70 to 72 ° C / 0.08 mbar, 35 g of main run were obtained, which consisted essentially of 2,7-octa-dienyl-1-oxyacetaldehyde. The smell of the compound smelled strongly of fatty aldehyde, reminiscent of cod liver oil. When diluted, the smell was felt to be similar to that of cis-4-decenal (waxy, flowery).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Oxyacetaldehyde Oxyacetaldehydes
Die Erfindung betrifft Oxyacetaldehyde, erhältlich durch Spaltung von Glycerinethern mit Alkaliperiodaten, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Riechstoffe.The invention relates to oxyacetaldehydes, obtainable by cleaving glycerol ethers with alkali periodates, a process for their preparation and their use as fragrances.
Oxyacetaldehyde auf Basis von Citronellol, Geranol, Phenylethanol oder Benzylalkohol und ihre Verwendung als Riechstoffe sind seit langem bekannt [Am.Perf.Cosm.f 83. April, 219 (1968)].Oxyacetaldehydes based on citronellol, geranol, phenylethanol or benzyl alcohol and their use as fragrances have long been known [Am.Perf.Cosm. f April 83, 219 (1968)].
Die US-Patentschrift US 4,152,987 beschreibt zu ihrer Herstellung ein Verfahren, bei dem man zunächst gesättigte, ein- oder zweifach ungesättigte Alkohole einer nicht näher definierten Anzahl von Kohlenstoffatomen unter den Bedingungen der Phasentransferkatalyse mit C2-4-Acetalen halogenierter Acetaldehyde umsetzt und das Reak¬ tionsprodukt anschließend zu den entsprechenden Oxyacetaldehyden hydrolysiert.The US Pat. No. 4,152,987 describes a process for its preparation in which first saturated, mono- or di-unsaturated alcohols of an unspecified number of carbon atoms are reacted with C2-4-acetals of halogenated acetaldehydes under the conditions of phase transfer catalysis and the reaction tion product then hydrolyzed to the corresponding oxyacetaldehydes.
Aus Koryo, 107. 33 (1974) ist ferner ein Verfahren zur Herstellung von n-Octyloxyacetaldehyd bekannt, bei dem zunächst n-Octanol ba¬ senkatalysiert mit Bromacetaldehydacetal umgesetzt und dann säure¬ katalysiert zum Oxyacetaldehyd hydrolysiert wird. Das Produkt be¬ sitzt einen angenehmen natürlichen, pflanzlichen Geruch. Verfahren der genannten Art weisen jedoch den Nachteil auf, daß sie als Einsatzstoff von Acetalen halogenierter Acetaldehyde aus¬ gehen, deren Verfügbarkeit begrenzt und deren Handhabung aus Grün¬ den der Arbeitssicherheit mit Problemen belastet ist.A process for the preparation of n-octyloxyacetaldehyde is also known from Koryo, 107, 33 (1974), in which n-octanol is first catalysed with bromoacetaldehyde acetal and then acid-catalyzed to hydrolyze the oxyacetaldehyde. The product has a pleasant natural, vegetal smell. However, processes of the type mentioned have the disadvantage that they start from acetals of halogenated acetaldehydes, their availability is limited and their handling is problematic for reasons of occupational safety.
Die Aufgabe der Erfindung bestand somit darin, Oxyacetaldehyde zur Verfügung zu stellen, deren Herstellung frei von den geschilderten Nachteilen ist.The object of the invention was therefore to provide oxyacetaldehydes, the production of which is free from the disadvantages described.
Gegenstand der Erfindung sind Oxyacetaldehyde der Formel (I),The invention relates to oxyacetaldehydes of the formula (I)
Ri-O-CJ^-CHO (I)Ri-O-CJ ^ -CHO (I)
in der Rl für einen aliphatischen, linearen oder verzweigten Koh¬ lenwasserstoffrest mit 8 Kohlenstoffatomen und 2 Doppelbindungen steht, dadurch erhältlich, daß man Glycerinether der Formel (II),in which R1 represents an aliphatic, linear or branched hydrocarbon radical with 8 carbon atoms and 2 double bonds, obtainable by reacting glycerol ethers of the formula (II),
OHOH
Ri-O-CJ^-CH-Cf^-OH (II)Ri-O-CJ ^ -CH-Cf ^ -OH (II)
in der R* die oben angegebene Bedeutung besitzt, mit Alkyliperio- daten spaltet.in which R * has the meaning given above, cleaves with alkyliperiodates.
Oxyacetaldehyde, die besonders leicht zugänglich sind, werden er¬ halten, wenn man von Glycerinethern, hergestellt durch palladium¬ katalysierte Telomerisation von 1,3-Butadien mit Glycerin, ausgeht und diese mit Natriumperiodat spaltet. Glycerinether der Formel (II), in denen R* für einen verzweigten Kohlenwasserstoffrest mit 8 Kohlenstoffatomen steht, können werden erhalten, indem man beispielsweise Glycerin in an sich bekannter Weise mit einem ver¬ zweigten Cβ-Alkylchlorid umsetzt.Oxyacetaldehydes, which are particularly easily accessible, are obtained if one starts from glycerol ethers produced by palladium-catalyzed telomerization of 1,3-butadiene with glycerol and cleaves them with sodium periodate. Glycerol ethers of the formula (II) in which R * is a branched hydrocarbon radical having 8 carbon atoms can be obtained by for example reacting glycerol with a branched Cβ-alkyl chloride in a manner known per se.
Oxyacetaldehyde der Formel (I), in der R- für einen 2,7- und/oder 3,8-Octadienylrest steht, weisen eine besonders intensive Duft¬ note auf.Oxyacetaldehydes of the formula (I) in which R is a 2,7- and / or 3,8-octadienyl radical have a particularly intense fragrance.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Oxyacetaldehyden der Formel (III),The invention further relates to a process for the preparation of oxyacetaldehydes of the formula (III),
R2-0-CH2-CH0 (III)R2-0-CH 2 -CH0 (III)
in der R2 für einen aliphatischen linearen oder verzweigten Koh- lenwasserstoffrest mit 8 Kohlenstoffatomen und 0 oder 2 Doppel¬ bindungen steht, dadurch gekennzeichnet, daß man Glycerinethern der Formel (IV),in which R 2 represents an aliphatic linear or branched hydrocarbon radical with 8 carbon atoms and 0 or 2 double bonds, characterized in that glycerol ethers of the formula (IV),
OHOH
R2-0-CH2-CH-CH2-0H (IV)R 2 -0-CH 2 -CH-CH2-0H (IV)
in der R2 die oben angegebene Bedeutung besitzt, mit Alkaliper- iodaten spaltet.in which R 2 has the meaning given above, cleaves with alkali metal iodates.
Als besonders vorteilhaft hat es sich erwiesen, wenn man von Gly¬ cerinethern der Formel (IV) ausgeht, die durch übergangsmetallka- talysierte Telomerisation von 1,3-Butadien mit Glycerin herge¬ stellt wurden und bei denen R2 für einen 2,7- und/oder 3,8-Octa- dienylrest steht. Glycerinether der genannten Art stellen bekannte Verbindungen dar und werden vorzugsweise durch Telomerisation von 2 Mol 1,3-Buta- dien mit einem Mol Glycerin in Gegenwart von Palladiumacetylaceto- nat und Triphenylphosphin hergestellt. Das Verfahren ist seinem Wesen nach in der deutschen Patentanmeldung DE-A-18 07 491 be¬ schrieben. Glycerinether der genannten Art stellen komplexe Ge¬ mische dar und enthalten als Hauptkomponente 2,7-, untergeordnet auch 3,8-0ctadienyl-l-glycerinether. Daneben finden sich auch die entsprechenden Di- und Triether, Octatrien und nichtu gesetztes Glycerin. Um unerwünschte Nebenreaktionen im Verlauf der weiteren Verabeitung zu vermeiden, empfiehlt es sich, daß Octatrien destil- lativ aus dem Gemisch zu entfernen. Falls dies gewünscht wird, kann sich an die Destillation eine Hydrierung des Octadienylethers zum Octylether anschließen, die in an sich bekannter Weise in Ge¬ genwart üblicher Hydrierkatalysatoren (z. B. Raney-Nickel) durch¬ geführt wird.It has proven to be particularly advantageous to start from glycerol ethers of the formula (IV) which have been prepared by transition metal-catalyzed telomerization of 1,3-butadiene with glycerol and in which R 2 for a 2,7- and / or 3,8-octa-dienyl radical. Glycerol ethers of the type mentioned are known compounds and are preferably prepared by telomerizing 2 moles of 1,3-butadiene with one mole of glycerol in the presence of palladium acetylacetonate and triphenylphosphine. The essence of the method is described in German patent application DE-A-18 07 491. Glycerol ethers of the type mentioned are complex mixtures and contain 2,7-, and to a lesser extent, 3,8-0ctadienyl-1-glycerol ether as the main component. The corresponding di- and triether, octatriene and unreacted glycerol are also found. In order to avoid undesirable side reactions in the course of further processing, it is advisable to remove octatriene from the mixture by distillation. If this is desired, the distillation can be followed by hydrogenation of the octadienyl ether to octyl ether, which is carried out in a manner known per se in the presence of conventional hydrogenation catalysts (for example Raney nickel).
Die Glycolspaltung sowohl der Octadienyl- als auch der Octylether kann nach Criegee mit Bleitetraacetat oder Phenyliodosodiacetat durchgeführt werden. Im Sinne der Erfindung werden die Glycerin¬ ether jedoch mit Alkaliperiodaten wie beispielweise Lithium-, Ka¬ lium oder vorzugsweise Natriumperiodat nach Malaprade gespalten, wobei die Kohlenstoff-Kohlenstoffbindung des Glycols unter Erhalt zweier Aldehydgruppen oxidativ aufgetrennt wird [L.Fieser (Ed.), Organische Cheβie, Verlag Cheβie, Weinheim-New York, 1979, S. 213 -214]. Das molare Verhältnis von Glycerinether zu Periodat kann dabei 1 : 0,1 bis 1 : 2, insbesondere 1 : 0,7 bis 1 : 1,2 betragen. Die Periodat-Spaltung wird bei einer Temperatur von 0 bis 20°C und über einen Zeitraum von 2 bis 24 h durchgeführt. Im Gegensatz zu den anderen genannten Verfahren wird der empfindliche Riechstoff nicht durch unerwünschte Nebenprodukte oder Spuren von Schwermetallen verunreinigt.The glycol cleavage of both the octadienyl and the octyl ether can be carried out according to Criegee with lead tetraacetate or phenyl iodosodiacetate. For the purposes of the invention, however, the glycerol ethers are cleaved according to the Malaprade using alkali periodates such as, for example, lithium, potassium or preferably sodium periodate, the carbon-carbon bond of the glycol being separated oxidatively to give two aldehyde groups [L. Fieser (Ed.), Organic Cheβie, Verlag Cheβie, Weinheim-New York, 1979, pp. 213-214]. The molar ratio of glycerol ether to periodate can be 1: 0.1 to 1: 2, in particular 1: 0.7 to 1: 1.2. The periodate cleavage is carried out at a temperature of 0 to 20 ° C and over a period of 2 to 24 h. In contrast to the other methods mentioned, the sensitive one Fragrance not contaminated by unwanted by-products or traces of heavy metals.
Die im Sinne der Erfindung erhältlichen Oxyacetaldehyde weisen in konzentrierter Form einen Geruch nach Lebertran, in verdünnter Form eine angenehme blumige Duftnote auf, die sich durch gute geruchliche Nachhaltigkeit auszeichnet.The oxyacetaldehydes obtainable in the sense of the invention have a smell of cod liver oil in concentrated form, and a pleasant floral fragrance in diluted form, which is characterized by good olfactory sustainability.
Die erfindungsgemäßen Oxyacetaldehyde eignen sich zur Herstellung neuer interessanter Riechstoffkompositionen. Bezogen auf die ge¬ samte Komposition liegt der Gehalt der erfindungsgemäßen Riech¬ stoffgemische zwischen 1 und 50, vorzugsweise zwischen 1 und 25 Gew.-%. Der Rest zu 100 Gew.-% kann durch andere bekannte Duft¬ stoffe ergänzt werden. Die Kompositionen können zur Parfumierung von technischen Artikeln, wie Reinigungs- und Desinfektionsmit¬ teln, von Textilbehandlungsmitteln, von Kosmetika aller Art, wie Duftwässern, Cremes, Lotionen, Aerosolen, Toilettenseifen,The oxyacetaldehydes according to the invention are suitable for the production of new, interesting fragrance compositions. Based on the overall composition, the content of the fragrance mixtures according to the invention is between 1 and 50, preferably between 1 and 25% by weight. The rest of 100% by weight can be supplemented by other known fragrances. The compositions can be used for perfuming technical articles, such as cleaning and disinfecting agents, textile treatment agents, all kinds of cosmetics, such as fragrant waters, creams, lotions, aerosols, toilet soaps,
Schminken und Lippenstiften sowie in der Extraitparfuπierie einge¬ setzt werden. In den parfümierten Produkten liegt der Gehalt der Riechstoffkompositionen zwischen 2 und 20 Gew.-%.Make-up and lipsticks as well as in the exhaustion perfumery. The content of the fragrance compositions in the perfumed products is between 2 and 20% by weight.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
I. Herstellung des Glvcerinethers durch Butadien-Telomerisation:I. Preparation of the Glvcerinether by Butadiene Telomerization:
Octadienyl-1-glycerinether (A). In einem 400 ml Glasautoklaven mit Magnetrührung wurden 0.0038 g (0.0125 mmol) Palladium-(II)-acetyl- acetonat, 0,0066 g (0.025 mmol) Triphenylphosphin, 28,8 g (313 mmol) Glycerin und 35 ml Propanol-2 vorgelegt und insgesamt drei¬ mal evakuiert und mit Argon beaufschlagt. Im Anschluß daran wurden mit Hilfe eines Hebers 37,8 g (700 mmol) Butadien-1,3 in den Auto¬ klaven überführt. Der Autoklav wurde verschlossen und 12 h beiOctadienyl-1-glycerol ether (A). 0.0038 g (0.0125 mmol) of palladium (II) acetyl acetonate, 0.0066 g (0.025 mmol) of triphenylphosphine, 28.8 g (313 mmol) of glycerol and 35 ml of propanol-2 were placed in a 400 ml glass autoclave with magnetic stirring and evacuated three times and charged with argon. Subsequently, 37.8 g (700 mmol) of 1,3-butadiene were transferred into the autoclave with the aid of a lifter. The autoclave was closed and at 12 h
70°C gehalten. Nach Abkühlen und Entspannen wurde eine farblose Flüssigkeit der folgenden Zusammensetzung gewonnen:Kept at 70 ° C. After cooling and relaxing, a colorless liquid of the following composition was obtained:
Octadienyl-1-glycerinether : 34,0 Gew.-Octadienyl-1-glycerol ether: 34.0% by weight
Di-octadienyl-1,2-glycerinether +Di-octadienyl-1,2-glycerol ether +
Di-octadienyl-1,3-glycerinether 21,7 Gew.-%Di-octadienyl-1,3-glycerol ether 21.7% by weight
Tri-octadienyl-1,2,3-glycerinether 2,1 Gew.-%Tri-octadienyl-1,2,3-glycerol ether 2.1% by weight
Glycerin 11,3 Gew.-%Glycerin 11.3% by weight
Octatrien 2,8 Gew.-%Octatriene 2.8% by weight
Propanol-2 28,1 Gew.-%Propanol-2 28.1% by weight
Nach destillativer Abtrennung des Octatriens wurde der Octadienyl' ether in die Periodat-Spaltung eingesetzt. After the octatriene had been removed by distillation, the octadienyl ether was used in the periodate cleavage.
II. Herstellung des Oxyacetaldehvds durch Periodat-Spaltunq:II. Preparation of the oxyacetaldehyde by periodate cleavage:
Octadienyl-1-oxyacetaldehyd. In einem 250 ml Kolben mit Magnetrüh¬ rung wurden 45 g (210 mol) Natriumperiodat in 100 ml Ether vor¬ gelegt und bei einer Temperatur von 0°C sowie unter Abdeckung mit Stickstoff mit einer Lösung von 62,4 g (310 mmol) des Glyce- rinethers A in 100 ml Diethylether überschichtet. Die zweiphasige Lösung wurde unter kräftigem Rühren 10 min bei 0°C und anschlies- send 3 h bei 20°C gemischt. Die Mischung wurde 12 h bei 20°C be¬ lassen. Anschließend wurden 100 ml Wasser zugegeben und die ethe- rische Phase über einen Scheidetrichter abgetrennt. Die wässrige Phase wurde mehrmals mit 25 ml Portionen Diethylether extrahiert und die vereinigten etherischen Phasen mit Kochsalzlösung gewa¬ schen. Nach Trocknung über Natriumsulfat und Einengen der organi¬ schen Phasen wurde der Rückstand einer fraktionierten Destillation unterworfen. Bei einer Kopftemperatur von 70 bis 72°C/0,08 mbar wurden 35 g Hauptlauf gewonnen, der im wesentlichen aus 2,7-Octa- dienyl-1-oxyacetaldehyd bestand. Im Angeruch roch die Verbindung intensiv nach Fettaldehyd, an Lebertran erinnernd. In Verdünnung wurde der Geruch ähnlich dem des cis-4-Decenals (wachsartig, blu¬ mig) empfunden. Octadienyl-1-oxyacetaldehyde. 45 g (210 mol) of sodium periodate in 100 ml of ether were placed in a 250 ml flask with magnetic stirring and at a temperature of 0 ° C. and covered with nitrogen with a solution of 62.4 g (310 mmol) of Glycerin ether A overlaid in 100 ml of diethyl ether. The two-phase solution was mixed with vigorous stirring for 10 min at 0 ° C and then for 3 h at 20 ° C. The mixture was left at 20 ° C. for 12 h. 100 ml of water were then added and the ethereal phase was separated off using a separating funnel. The aqueous phase was extracted several times with 25 ml portions of diethyl ether and the combined ethereal phases were washed with brine. After drying over sodium sulfate and concentrating the organic phases, the residue was subjected to fractional distillation. At a top temperature of 70 to 72 ° C / 0.08 mbar, 35 g of main run were obtained, which consisted essentially of 2,7-octa-dienyl-1-oxyacetaldehyde. The smell of the compound smelled strongly of fatty aldehyde, reminiscent of cod liver oil. When diluted, the smell was felt to be similar to that of cis-4-decenal (waxy, flowery).
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904021015 DE4021015A1 (en) | 1990-07-02 | 1990-07-02 | OXYACETALDEHYDE |
| DEP4021015.4 | 1990-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992000267A1 true WO1992000267A1 (en) | 1992-01-09 |
Family
ID=6409494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1991/001172 Ceased WO1992000267A1 (en) | 1990-07-02 | 1991-06-24 | Oxyacetaldehydes |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4021015A1 (en) |
| WO (1) | WO1992000267A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2594626A1 (en) * | 2011-11-18 | 2013-05-22 | Symrise AG | Use of oxyacetaldehyde as lily of the valley fragrance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2000604A (en) * | 1933-09-18 | 1935-05-07 | Eastman Kodak Co | Manufacture of alkoxyacetaldehydes and alkoxyacetic acids |
| US2170854A (en) * | 1936-02-24 | 1939-08-29 | Carbide & Carbon Chem Corp | Methoxy acetaldehyde and process of making alkoxy acetaldehydes |
-
1990
- 1990-07-02 DE DE19904021015 patent/DE4021015A1/en not_active Withdrawn
-
1991
- 1991-06-24 WO PCT/EP1991/001172 patent/WO1992000267A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2000604A (en) * | 1933-09-18 | 1935-05-07 | Eastman Kodak Co | Manufacture of alkoxyacetaldehydes and alkoxyacetic acids |
| US2170854A (en) * | 1936-02-24 | 1939-08-29 | Carbide & Carbon Chem Corp | Methoxy acetaldehyde and process of making alkoxy acetaldehydes |
Non-Patent Citations (1)
| Title |
|---|
| Patent Abstracts of Japan, unexamined apolications, C field, Band 12, Nr. 40, 5. Februar 1988, The Patent Office Japanese Governme * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2594626A1 (en) * | 2011-11-18 | 2013-05-22 | Symrise AG | Use of oxyacetaldehyde as lily of the valley fragrance |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4021015A1 (en) | 1992-01-09 |
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