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
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
  • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
  • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
• • 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
  • C07C45/61—Preparation 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
  • C07C45/67—Preparation 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
  • C07C45/68—Preparation 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
  • C07C45/72—Preparation 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
• • 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
  • C07C47/26—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups
  • C07C47/263—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups acyclic

Definitions

• i fl CH2 CH-- -CH2CH.
• hydroxysinensal being very similar to that of aand B-sinensal, it was reasonable to expect that hydroxysinensal would also have a similar odour, i.e., would develop a mandarinor tangerine-like odour or at least an odour reminiscent of mandarin or tangerine, as it is suggested in the above-mentioned West German patent application. However, I could not confirm this. To my surprise I found that the odour of hydroxysinensal is quite different from that of the sinensals. Its odour is not fruity but floral and reminiscent of the fragrance developed by the lily of the valley and is very tenacious.
• aldehyde I is free from the citrus note which characterizes the sinensals. Hydroxysinensal as such already constitutes a complete perfume. It can be used as a base in the preparation of perfumes or as a modifier to be added to perfume compositions and permits to obtain very interesting floral olfactive effects.
• Another object of the invention is to provide odoriferous compositions, such as perfumes, perfumed products and essential oils, having added thereto an odourmodifying amount of 2,6, lO-trimethyl-lO-hydroxydodeca-2,6,I l-trien- 1 -al.
• perfumed products includes e.g. soaps, cosmetic products, detergents and the like.
• Hydroxysinensal can be used alone, i.e., without being admixed to other odoriferous substances, as a fragrance. Preferably, it is used in diluted form.
• Hydroxysinensal as such can be used for perfuming soaps, cosmetic products, detergents and the like.
• hydroxysinensal When hydroxysinensal is used as perfume ingredient together with other odoriferous substances in perfume compositions, its concentration can vary within wide limits, e.g. between 2 and 20 based on the total weight of a perfume composition. However, the concentration of hydroxysinensal can exceed 20 and reach for example or more when special olfactive effects are to be obtained. As a rule, hydroxysinensal imparts strong floral odour notes to perfume compositions and enhances as well as harmonizes the floral odour component of the perfumes to which it is added.
• 2,6,IO-trimethyl-10- hydroxy-dodeca-2,6,I l-trien-I-al is prepared by reacting nerolidol (II) with N-bromosuccinimide in order to obtain 2-methyl-2-vinyl-5-( 1,5-dimethyl- 1 -bromo-hex- 4-en-1-yl)-tetrahydrofuran (III), converting the latter to its mono-ozonide and reducing the ozonide in order to obtain 2-methy1-2-vinyl-5-( 1-methyl-I-bromo-3-formyl-prop-1-y1)-tetrahydrofuran (IV), acetalizing the latter, reacting the resulting acetal (V) with a reducing metal in a substantially anhydrous medium and subsequently with water, hydrolysing the resulting acetal of 4,8-dimethyl-8-hydroxy-deca-4,9-dien- 1 -al (VI) in order to obtain 4,8-dimethyl-8
• the reaction between nerolidol and N-bromosuccinimide is conveniently carried out at temperatures neighbouring C, preferably at 1820C.
• the reaction time can vary between about 27 and 170 hours.
• the method described in Helv. Chim. Acta 54, 461 (1971) can be applied.
• the ozonolysis of compound III can be carried out by known methods, e.g. at 70C in methanol.
• a reducing agent for the reduction of the ozonide e.g. methyl sulphide, triphenylphosphine or trimethylphosphite can be used.
• the acetalisation of aldehyde VI can be carried out by usual methods.
• the acetal can be either cyclic of non-cyclic.
• the dehydrobromination of acetal V can be carried out by means of metallic sodium in a substantially anhydrous medium, e.g. in tetrahydrofuran, or by means of zinc powder in acetic acid.
• the Wittig reagent with which aldehyde VII is reacted can be obtained by the method described in I-Ielv. Chim. Acta 50, 2445 (1967).
• 2,6, 10-Trimethyl-10-hydroxy dodeca-2,6,l l-trienl-al can theoretically exist in the form of four configuration isomers, viz. the 2cis,6cis, 2cis,6trans, 2trans,6- trans and 2trans,6cis isomers.
• the isomers having cisconfiguration in position 2 are, however, not stable.
• mixtures of the 2trans,6- trans and 2trans,6cis isomers are formed as a rule.
• the ratio in which the two isomers are formed varies within VII certain limits and can, e.g., be about 30 of the 2trans,6cis isomer to of the 2trans,6trans isomer. Since the two isomers have similar olfactive properties, it is not necessary to separate them before they are used as perfuming agents.
• the mixture of isomers as obtained by the process of the invention can be used directly for perfuming purposes.
• a perfume base was prepared by mixing the following ingredients:
• Hydroxysinensal which has a discrete but very tenacious floral note enhances and harrnonizes the floral notes in perfumes and is, therefore, a very valuable perfume ingredient.
• Acetal V1 trans (1 0.9975; 11,, 1.4833;
• An odoriferous composition selected from the class consisting of perfumes, perfumed products and natural or artificial essential oils having added thereto an odour-modifying amount of 2,6,l0-trimethyl-l0- hydroxy-dodeca-2.6. 1 l trien- 1 al.
• a perfume composition which comprises as one of its odoriferous ingredients 2,6,10-trimethyl-l0- hydroxy-dodeca-2,6, 1 1 -trien-l-a1.
• a perfume composition which comprises 2,6,10- trimethyll 0-hydroxy-dodeca-2,6,l l-trien- 1 al and a diluent or a carrier.

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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)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

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ID=4352599

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (3)

Citations (1)

• 1973
  • 1973-06-29 CH CH949573A patent/CH576410A5/xx not_active IP Right Cessation
• 1974
  • 1974-06-27 DE DE2431039A patent/DE2431039A1/de active Pending
  • 1974-06-27 US US483553A patent/US3915901A/en not_active Expired - Lifetime
  • 1974-06-28 FR FR7422732A patent/FR2234889A1/fr not_active Withdrawn
  • 1974-06-28 NL NL7408761A patent/NL7408761A/xx unknown
  • 1974-06-29 JP JP49074906A patent/JPS5036651A/ja active Pending

Patent Citations (1)

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