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WO1992000267A1 - Oxyacetaldehydes - Google Patents

Oxyacetaldehydes Download PDF

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Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
oxyacetaldehydes
glycerol
formula
octadienyl
ether
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.)
Ceased
Application number
PCT/EP1991/001172
Other languages
German (de)
English (en)
Inventor
Thomas Markert
Bert Gruber
Klaus Bruns
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1992000267A1 publication Critical patent/WO1992000267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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).

Landscapes

  • 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

On produit, par clivage des éthers d'octyle et d'octadiényle de la glycérine avec des périodates alcalins, des oxyacétaldéhydes substitués utilisables comme parfums.
PCT/EP1991/001172 1990-07-02 1991-06-24 Oxyacetaldehydes Ceased WO1992000267A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904021015 DE4021015A1 (de) 1990-07-02 1990-07-02 Oxyacetaldehyde
DEP4021015.4 1990-07-02

Publications (1)

Publication Number Publication Date
WO1992000267A1 true WO1992000267A1 (fr) 1992-01-09

Family

ID=6409494

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001172 Ceased WO1992000267A1 (fr) 1990-07-02 1991-06-24 Oxyacetaldehydes

Country Status (2)

Country Link
DE (1) DE4021015A1 (fr)
WO (1) WO1992000267A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2594626A1 (fr) * 2011-11-18 2013-05-22 Symrise AG Utilisation d'oxyacétaldéhydes comme parfums sentant le muguet

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, unexamined apolications, C field, Band 12, Nr. 40, 5. Februar 1988, The Patent Office Japanese Governme *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2594626A1 (fr) * 2011-11-18 2013-05-22 Symrise AG Utilisation d'oxyacétaldéhydes comme parfums sentant le muguet

Also Published As

Publication number Publication date
DE4021015A1 (de) 1992-01-09

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