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
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms

Definitions

• This invention relates to compounded perfumery compositions to ingredients of such compositions certain of which are believed to be novel and to processes for the preparation of these ingredients and novel intermediates for use in these processes.
• perfumery compositions to which this invention relates are those of the type where a number of odiferous materials of synthetic or natural origin are admixed or compounded to form a perfumery concentrate.
• Such concentrates may find use as such or after dilution but more usually they are added in small proportions to other materials such as to space sprays or to soap, detergent, cosmetic or deodorant compositions or to substrates such as fabric, fibre, or paper products in order to provide them with agreeable olfactory properties.
• Such concentrates are products of commerce and may comprise a simple or complex mixture of perfumery compounds.
• the perfumery industry devotes a great deal of effort to the evaluation of the odiferous properties of a variety of chemical compounds which may be obtained from synthetic or natural sources.
• One group of chemicals which are the subject of particular interest is composed of the synthetic derivatives of terpenic hydrocarbons. Of the many such derivatives which have been synthesised only a small proportion have proved to have sufficiently attractive odiferous properties to become widely used as ingredients of compounded perfumery compositions.
• This group of products may be obtained by means of a Prins reaction between allo-ocimene and formaldehyde,
• our invention provides a compounded perfumery composition which comprises a plurality of odoriferous ingredients together with at least one compound having the formula I:- wherein X may represent an oxygen atom in which case R 1 represents a 4-methyl penta-1,3-dien-1-yl group and R 2 represents a hydrogen atom or X may represent a methinyl group which is doubly bonded to C 1 and singly bonded to C 2 in which case R 1 disappears and R 2 represents a 2-methyl-prop-1-en-l-yl group.
• the dihydropyran has been discovered to possess an attractive floral odour.
• the dioxan has been discovered to possess a floral odour having a degree of citrus character.
• novel perfumery compositions may be compounded according to recognised techniques or perfumery employing known odiferous perfumery ingredients, e.g. techniques and ingredients mentioned in the standard textbooks "Soap, Perfumery and Cosmetics” by W.A. Poucher, 7th edition published by Chapman & Hall (London) 1959; "Perfume and Flavour Chemicals” by S. Arctander, published by the author (Montclair) 1959 and “Perfume and Flavour Materials of Natural Origin” also by S.Arctander, self-published, Elizabeth NJ, 1960.
• Typical perfumery materials which may form part of compounded composition include: natural essential oils such as lemon oil, mandarin oil, clove leaf oil, petitgrain oil, cedar wood oil, patchouli oil, lavandin oil, neroli oil, ylang oil, rose absolute or jasmin absolute; natural resins such as labdanum resin or olibanum resin; single perfumery chemicals which may be isolated from natural sources or manufactured synthetically, as for example alcohols such as geraniol, nerol, citronellol, linalol, tetrahydro- geraniol, betaphenylethyl alcohol, methyl phenyl carbinol, dimethyl benzyl carbinol, menthol or cedrol; acetates and other esters derived from such alcohols; aldehydes such as citral, citronellal, hydroxy-citronellal, lauric aldehyde, undecylenic aldehyde, cinnamaldehyde
• Particularly preferred odiferous ingredients of blending into the novel compositions of our invention include geraniol, phenyl ethyl alcohol, citronellol hydroxycitronellal, ionones and methyl ionones, eugenol, isoeugenol, amyl and hexyl cinnamic aldehydes, methyl nonyl acetaldehyde, lemon oil, orange oil and bergamot oil.
• the preferred compound for present use is the dihydropyran.
• a mixture of its cis and trans isomers e.g. mixtures comprising from 10 to 90% say from 25 to 75% especially 40 to 60% of the trans isomer exhibit especially attractive odours and are therefore preferred for present use.
• dioxan in isolation as an ingredient of a compounded perfumery composition is less preferred.
• the odours of the dihydropyran and the dioxan compliment one another and the use of a mixture of these two compounds as an ingredient of a compounded perfumery composition represents a preferred aspect of our invention.
• Such mixtures may for example comprise 10 to 90 mole percent e.g. from 25 to 75 mole percent most preferably from 40 to 60 mole per cent of the dihydropyran.
• At least 25% and more preferably at least 40% of this compound is present in the form of the trans isomer.
• the compounds which are useful according to our invention may conveniently be prepared by means of a Prins reaction between allo- ocimene and formaldehyde.
• a Prins reaction between allo- ocimene and formaldehyde.
• allo-ocimene with paraformaldehyde rather than formaldehyde itself.
• the reaction may conveniently be carried out in a suitable solvent in which the paraformaldehyde is soluble.
• a suitable solvent in which the paraformaldehyde is soluble.
• solvents which tend to cause polymerisation of the allo-ocimene e.g. protonic solvents is less preferred and should be avoided if possible.
• Preferred solvents for present use are methylene chloride, glacial acetic acid and chloroform.
• the reaction is preferably carried out by mixing an excess e.g. from 1.0 to 4.0 moles of allo-ocimene per mole of formaldehye with the formaldehyde and the solvent.
• the reactants are preferably maintained at a temperature of from 20° to 120°C, more preferably 40 to 65°C for a period of from 2 to 40 say 4 to 30 hours.
• the reaction may be carried out in the presence of a catalyst such as a Lewis acid.
• a catalyst such as a Lewis acid.
• the preferred catalysts for present use are stannic chloride and boron trifluoride.
• the preferred solvents for the catalysed reactions are those in which the catalysts is soluble e.g. chlorinated hydrocarbons such as chloroform.
• the catalysed reaction may conveniently be carried out at lower temperatures of from 0 to 60° preferably 20 to 40°C the reactants being maintained at temperatures for a period of from 1 to 24 hours the short timers referring to the higher temperatures.
• the use of such catalysts for the reaction is generally less preferable because of the increased tendency of the allo-ocimene to polymerise.
• the catalysts will be added in just sufficient a quantity as to be effective in catalysing the Prins reaction in order to minimise this tendency.
• the product of the reaction is worked up using the conventional techniques of synthetic organic chemistry.
• the volatile fraction which can be separated by distillation comprises unchanged allo- ocimene, the dihydropyran and the dioxan together with a mixture of three triene alcohols. These triene alcohols are novel and find use as intermediates in the preparation od dihydropyrans and dioxans.
• our invention provides the triene alcohols 2,7-dimethyl - 3 - methylene - octa - 4 (trans) - 6 - diene - ol; 2,3,7-trimethyl-octa - 3 (trans) - 5 (trans) - 7 - triene-1-ol and 2,3,7 trimethyl - octa - 3 (cis) - 5 (trans) - 7 - triene-l-ol.
• the components of the volatile fraction can be separated by frational distillation.
• the unreacted allo-ocimene is normally separated from the other components. It may be convenient or preferably to utilise the remaining product mixture directly as an ingredient of a compounded perfumery composition.
• composition of this mxiture is influenced by the conditions under which the reaction is carried out.
• the greater the mole ratio of allo-ocimene to formaldehyde the greater the proportion of dihydropyran which is produced.
• the formation of the dihydropyrans is also favoured by the utilisation of an allo-ocimene feedstock which contains an increased proportion of the 4E6E isomer.
• our invention provides a process for the preparation of a compound of the formula:- which comprises heating a dioxan or a triene alcohol as hereinbefore defined in a polar protic solvent.
• the dioxans and triene alcohols are preferably produced by the Prins reaction of formaldehyde and allo-ocimene as hereinabefore described. They may be separated from the other products of the Prins reaction prior to their conversion to dihydropyrans.
• the reaction is preferably carried out by heating the dioxans and/or triene alcohols to a temperature of from 50 to 100°C.
• the cis dihydropyran may be converted into its trans isomer. This conversion may be carried out by heating a dihydropyran comprising less than 50% of the trans isomer in a polar protic solvent or by treatment at room temperature with a Lewis acid. These conversions processes lead to the formation of an equilibrium mixture comprising 50% of the trans isomer. The preferred conversions may be carried out at a temperature of from 50 to 100 0.
• This product was then fractionally distilled under reduced pressure using a 30 cm Fenske column in order to remove unreacted allo-ocimene. 411 grams of material were removed the bulk of which was allo-ocimene. The residue was then distilled after removal of the column to give 195 gram of a product (obtained under pressure of 0.9 mm Hg; Pot temperature 72-92°C, still head temperature 56-75 0 C) which was shown to comprise the dihydropyran of Formula I by GLC analysis. This product had an attractive rose odour with a distinct metallic note.
• Non volatile residue constituted 25% of the charge for distillation.
• the cis and trans isomer of the dihydropyran were separated by spinning band fractionation.
• the cis isomer had fresh-rose odour with a hint of greenness.
• the trans isomer had a floral metalic rose character. The two isomers were combined to give a product with a fresh floral metallic rose character.
• Alloocimene (96% 4E6E), 160g 1.18 moles, was added to a stirred suspension of paraformaldehyde (24g, 0.8 mole) in glacial acetic acid (120 ml). The reaction mixture was stirred for 5 hours within the temperature range 55 to 50°C. After cooling, the reaction mixture was water washed to extract acetic acid. The oil layer was then distilled under vacuum to remove high boiling resinous product. The volatile product, 150g, had the following composition by GLC. (9'10% SP2100 on 80 to 100 supelcoport with Flame Ionisation Detector): Ratio of Pyrans: Dixons was 2.5.
• a compounded perfumery composition suitable for a query use (all parts by weight).
• a compounded perfumery composition suitable for use as a base in cosmetic preparations is provided.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Fats And Perfumes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Pyrane Compounds (AREA)
• Cosmetics (AREA)
• Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
• Seasonings (AREA)

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Publications (3)

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Family Applications (1)

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Cited By (1)

Citations (9)

• 1980
  • 1980-05-01 EP EP80301436A patent/EP0018833B1/de not_active Expired
  • 1980-05-01 DE DE8080301436T patent/DE3065352D1/de not_active Expired
  • 1980-05-01 AT AT80301436T patent/ATE5083T1/de active
  • 1980-05-02 AU AU58033/80A patent/AU5803380A/en not_active Abandoned
  • 1980-05-06 GB GB8014970A patent/GB2049422A/en not_active Withdrawn
  • 1980-05-06 JP JP5877180A patent/JPS55149207A/ja active Pending

Patent Citations (9)

Non-Patent Citations (2)

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