EP0018833B1 - Compounded perfumery composition - Google Patents
Compounded perfumery composition Download PDFInfo
- Publication number
- EP0018833B1 EP0018833B1 EP80301436A EP80301436A EP0018833B1 EP 0018833 B1 EP0018833 B1 EP 0018833B1 EP 80301436 A EP80301436 A EP 80301436A EP 80301436 A EP80301436 A EP 80301436A EP 0018833 B1 EP0018833 B1 EP 0018833B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- group
- formula
- compounds
- dihydropyran
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000004615 ingredient Substances 0.000 claims abstract description 15
- -1 triene alcohols Chemical class 0.000 claims abstract description 13
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 8
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 6
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 claims description 6
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 6
- 229930002839 ionone Natural products 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 claims description 3
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005770 Eugenol Substances 0.000 claims description 3
- 239000005792 Geraniol Substances 0.000 claims description 3
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 3
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 claims description 3
- 235000019501 Lemon oil Nutrition 0.000 claims description 3
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 3
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 claims description 3
- 235000000484 citronellol Nutrition 0.000 claims description 3
- 229960002217 eugenol Drugs 0.000 claims description 3
- 229940113087 geraniol Drugs 0.000 claims description 3
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002499 ionone derivatives Chemical class 0.000 claims description 3
- 239000010501 lemon oil Substances 0.000 claims description 3
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019502 Orange oil Nutrition 0.000 claims description 2
- 239000001926 citrus aurantium l. subsp. bergamia wright et arn. oil Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000010502 orange oil Substances 0.000 claims description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 28
- GQVMHMFBVWSSPF-SOYUKNQTSA-N (4E,6E)-2,6-dimethylocta-2,4,6-triene Chemical compound C\C=C(/C)\C=C\C=C(C)C GQVMHMFBVWSSPF-SOYUKNQTSA-N 0.000 abstract description 15
- GQVMHMFBVWSSPF-UHFFFAOYSA-N cis-alloocimene Natural products CC=C(C)C=CC=C(C)C GQVMHMFBVWSSPF-UHFFFAOYSA-N 0.000 abstract description 15
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 abstract description 15
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 abstract description 14
- 238000010478 Prins reaction Methods 0.000 abstract description 9
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 150000002012 dioxanes Chemical class 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000004880 oxines Chemical class 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- OFHHDSQXFXLTKC-UHFFFAOYSA-N 10-undecenal Chemical compound C=CCCCCCCCCC=O OFHHDSQXFXLTKC-UHFFFAOYSA-N 0.000 description 1
- FACFHHMQICTXFZ-UHFFFAOYSA-N 2-(2-phenylimidazo[1,2-a]pyridin-3-yl)ethanamine Chemical compound N1=C2C=CC=CN2C(CCN)=C1C1=CC=CC=C1 FACFHHMQICTXFZ-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- NFAVNWJJYQAGNB-UHFFFAOYSA-N 2-methylundecanal Chemical compound CCCCCCCCCC(C)C=O NFAVNWJJYQAGNB-UHFFFAOYSA-N 0.000 description 1
- PMRMCTRIVCIICU-UHFFFAOYSA-N 3,7-dimethylocta-1,3,5-triene Chemical compound CC(C)C=CC=C(C)C=C PMRMCTRIVCIICU-UHFFFAOYSA-N 0.000 description 1
- GMVPRGQOIOIIMI-DODZYUBVSA-N 7-[(1R,2R,3R)-3-hydroxy-2-[(3S)-3-hydroxyoct-1-enyl]-5-oxocyclopentyl]heptanoic acid Chemical compound CCCCC[C@H](O)C=C[C@H]1[C@H](O)CC(=O)[C@@H]1CCCCCCC(O)=O GMVPRGQOIOIIMI-DODZYUBVSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000717739 Boswellia sacra Species 0.000 description 1
- 235000005241 Cistus ladanifer Nutrition 0.000 description 1
- 240000008772 Cistus ladanifer Species 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- XRHCAGNSDHCHFJ-UHFFFAOYSA-N Ethylene brassylate Chemical compound O=C1CCCCCCCCCCCC(=O)OCCO1 XRHCAGNSDHCHFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004863 Frankincense Substances 0.000 description 1
- 235000018958 Gardenia augusta Nutrition 0.000 description 1
- 239000004869 Labdanum Substances 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- HMKKIXGYKWDQSV-KAMYIIQDSA-N alpha-Amylcinnamaldehyde Chemical compound CCCCC\C(C=O)=C\C1=CC=CC=C1 HMKKIXGYKWDQSV-KAMYIIQDSA-N 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 239000010627 cedar oil Substances 0.000 description 1
- SVURIXNDRWRAFU-OGMFBOKVSA-N cedrol Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1[C@@](O)(C)CC2 SVURIXNDRWRAFU-OGMFBOKVSA-N 0.000 description 1
- 229940026455 cedrol Drugs 0.000 description 1
- PCROEXHGMUJCDB-UHFFFAOYSA-N cedrol Natural products CC1CCC2C(C)(C)C3CC(C)(O)CC12C3 PCROEXHGMUJCDB-UHFFFAOYSA-N 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 239000001111 citrus aurantium l. leaf oil Substances 0.000 description 1
- 239000001524 citrus aurantium oil Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000001071 citrus reticulata blanco var. mandarin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093468 ethylene brassylate Drugs 0.000 description 1
- 239000001734 eugenia caryophyllata l. bud oleoresin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- SVURIXNDRWRAFU-UHFFFAOYSA-N juniperanol Natural products C1C23C(C)CCC3C(C)(C)C1C(O)(C)CC2 SVURIXNDRWRAFU-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000001469 lavandula hydrida abrial herb oil Substances 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 229940067137 musk ketone Drugs 0.000 description 1
- XMWRWTSZNLOZFN-UHFFFAOYSA-N musk xylene Chemical group CC1=C(N(=O)=O)C(C)=C(N(=O)=O)C(C(C)(C)C)=C1N(=O)=O XMWRWTSZNLOZFN-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 239000001738 pogostemon cablin oil Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
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 group of products may be obtained by means of a Prins reaction between allo-ocimene and formaldehyde.
- 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 alle 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, hydroxycitronellal, lauric aldehyde, undecylenic aldehyde, cinnamaldehyde,
- 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 percent of the dihydropyran.
- 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°.
Landscapes
- 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)
- Seasonings (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Pyrane Compounds (AREA)
- Cosmetics (AREA)
Abstract
Description
- The 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. Thus 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 hydrocarbbns. 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.
- We have now discovered that a group of products which may be prepared from the triene allo-ocimene (2,6 dimethyl-octa-3,5,7-triene) which are useful as ingredients of compounded perfumery compositions.
- This group of products may be obtained by means of a Prins reaction between allo-ocimene and formaldehyde.
- The Prins reaction between allo-ocimene and para-formaldehyde in dichloromethane under reflux in the presence of acetic acid has been reported in Nippon Kagaku Kaishi 1977 (8) p. 1253-5. The product of this reaction is reported to comprise a mixture of a dihydropyran having the formula:
- The synthesis of a number of pyrans and dioxanes has been reported in the literature together with, in some instances, an evaluation of the odiferous properties of these compounds. West German Patent 1467512, Swiss Patent 604560 (see especially column 3, line 1 thereof), Swiss Patent 414674 and French Patent 1310750 (see especially the left hand column on page 2, lines 33 to 40) all describe pyrans, and in some instances, the odiferous properties thereof. Belgian Patent 673628 and United States Patent 3423430 both describe the synthesis of dioxanes and the odiferous properties of some of these. We have now discovered that the products which may be obtained by the Prins reaction of allo-ocimene with formaldehyde possess attractive floral odours. Thus our invention provides a compounded perfumery composition which comprises a plurality of known odoriferous ingredients together with at least one compound having the formula 1:-
- The compound wherein X represents a methinyl group i.e. the dihydropyran and the compound wherein X represents an oxygen atom i.e. the dioxan both exist in two stereoisomeric forms i.e. cis and trans geometrical isomers. Mixtures of these isomers or the individual stereoisomers are useful according to our invention.
- 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.
- The 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 esential 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, hydroxycitronellal, lauric aldehyde, undecylenic aldehyde, cinnamaldehyde, amyl cinnamic aldehyde, vanillin or heliotropin; acetals derived from such aldehydes; ketones such as methyl hexyl ketone, the ionones and the methylionones; phenolic compounds such as eugenol and isoeugenol; synthetic musks such as musk xylene, musk ketone and ethylene brassylate; and other materials commonly employed in the art of perfumery. Typically at least five, and usually at least ten of such materials will be present as compounds of the active ingredient.
- 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 compounds of the formula I blend readily with other conventional ingredients of a compounded perfumery composition. They may be present as a major or a minor ingredient of such compositions but in general they will comprise from 0.5 to 10.0 preferably from 1.0 to 5.0% by weight of the compounded composition.
- 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.
- The use of the dioxan in isolation as an ingredient of a compounded perfumery composition is less preferred. However, 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 percent of the dihydropyran.
- Mixtures of the cis and trans dihydropyran which comprise at least 10% by weight of the trans isomer are believed to be novel.
- Preferably at least 25% and more preferably at least 40% by weight 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. For reasons of convenience we prefer to react 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. The use of 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 formaldehyde 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. 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. Preferably where. it is used 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 of dihydropyrans and dioxans. These triene alcohols are:
- 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(cisl-5(trans)-7-triene-1-ol.
- The components of the volatile fraction can be separated by fractional 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.
- The composition of this mixture is influenced by the conditions under which the reaction is carried out. In particular 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.
- We have also discovered that it is possible to convert the dioxans and triene alcohols to the dihydropyrans by heating them in a polar protic solvent.
- The dioxans and triene alcohols are preferably produced by the Prins reaction of formaldehyde and allo-ocimene as hereinabove 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.
- We have also discovered 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°.
- This invention is illustrated by the following examples.
-
-
-
-
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80301436T ATE5083T1 (en) | 1979-05-04 | 1980-05-01 | FRAGRANCE COMPOSITION. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7915620 | 1979-05-04 | ||
GB7915620 | 1979-05-04 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0018833A2 EP0018833A2 (en) | 1980-11-12 |
EP0018833A3 EP0018833A3 (en) | 1981-01-28 |
EP0018833B1 true EP0018833B1 (en) | 1983-10-19 |
Family
ID=10504966
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80301436A Expired EP0018833B1 (en) | 1979-05-04 | 1980-05-01 | Compounded perfumery composition |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0018833B1 (en) |
JP (1) | JPS55149207A (en) |
AT (1) | ATE5083T1 (en) |
AU (1) | AU5803380A (en) |
DE (1) | DE3065352D1 (en) |
GB (1) | GB2049422A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU9756098A (en) * | 1997-11-12 | 1999-05-31 | Quest International B.V. | Prins reaction products of 5,7-dimethyl-oct-6-en-2-one and their use as fragrance materials |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH414674A (en) * | 1961-03-15 | 1966-06-15 | Givaudan & Cie Sa | Process for the preparation of substituted tetrahydro-pyranes |
FR1310750A (en) * | 1961-11-04 | 1962-11-30 | Firmenich & Cie | cyclic ether and its preparation |
US3326746A (en) * | 1962-09-04 | 1967-06-20 | Lever Brothers Ltd | 1, 3-dioxane cleaning compositions |
US3455957A (en) * | 1963-10-21 | 1969-07-15 | Lever Brothers Ltd | Dihydropyran perfume |
GB1079421A (en) * | 1964-06-18 | 1967-08-16 | Boake Roberts & Co Ltd | Chlorinated citronellol and its conversion to rose oxide |
GB1099061A (en) * | 1964-12-18 | 1968-01-10 | Int Flavors & Fragrances Inc | m-dioxane derivatives, methyl isogeraniol and its esters |
DE1467512A1 (en) * | 1965-11-18 | 1969-01-23 | Schering Ag | Fragrance compositions |
NL6802619A (en) * | 1968-02-23 | 1969-08-26 | ||
CH604560A5 (en) * | 1975-04-11 | 1978-09-15 | Firmenich & Cie | Use of di:hydro pyran cpds. in perfumes and flavours |
-
1980
- 1980-05-01 EP EP80301436A patent/EP0018833B1/en not_active Expired
- 1980-05-01 DE DE8080301436T patent/DE3065352D1/en not_active Expired
- 1980-05-01 AT AT80301436T patent/ATE5083T1/en active
- 1980-05-02 AU AU58033/80A patent/AU5803380A/en not_active Abandoned
- 1980-05-06 JP JP5877180A patent/JPS55149207A/en active Pending
- 1980-05-06 GB GB8014970A patent/GB2049422A/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
EP0018833A3 (en) | 1981-01-28 |
DE3065352D1 (en) | 1983-11-24 |
EP0018833A2 (en) | 1980-11-12 |
ATE5083T1 (en) | 1983-11-15 |
GB2049422A (en) | 1980-12-31 |
JPS55149207A (en) | 1980-11-20 |
AU5803380A (en) | 1980-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4311617A (en) | Perfumery compositions | |
US4252986A (en) | Fixative for perfume compositions | |
EP0017396B1 (en) | Hepteno-nitriles, process for their preparation and perfumery compositions containing them | |
US4313855A (en) | Fixative for perfume compositions | |
US4100110A (en) | Isolongifolene Prins reaction compounds in perfumery | |
US3948814A (en) | Acetaldehyde ethyl linalyl acetal perfume compositions | |
US3962148A (en) | Odorant compositions containing 4,4,6-trimethyl-2-cyclohexenone | |
EP0018833B1 (en) | Compounded perfumery composition | |
GB1590909A (en) | Perfume compositions containing substituted 1,3-dioxans | |
US3910853A (en) | 1,1,4,4-Tetra methyl-alkyl-nitriles-tetrahydronaphthalene perfume compositions | |
US4671798A (en) | 1,2,3,4,4a,5,8,8a-octahydro-2,2,6,8-tetramethyl-1-naphthalenol, its use as perfuming ingredient and process for making same | |
US4880775A (en) | Poly-alkylated benzodioxin musk compositions | |
US4011177A (en) | Chemicals and their use in perfumery | |
US4774225A (en) | Odorants | |
US3875241A (en) | Bis-enolethers of substituted acetyl cyclohexanones | |
US3579550A (en) | Oxygenated derivatives of acyclic olefins | |
US3963648A (en) | Perfume chemicals | |
EP0162465A2 (en) | Novel compounds useful in perfumes | |
US4113664A (en) | 2,4-Dioxa-spiro(5,5)undec-8-ene perfume compositions | |
CA1115284A (en) | Derivatives of 3,3,7,8-tetramethyl-2-oxabicyclo-¬4, 4,0|-decane and their use in perfumery | |
US4177170A (en) | 3,3,7,8-Tetramethyl-2-oxabicyclo-[4,4,0]-decane derivatives and their use in perfume compositions | |
US3953516A (en) | Mono-enol ethers of 4-acetyl-3,3,5,5-tetramethylcyclohexanone | |
GB2048253A (en) | 4,8-Dimethyl-4,9-decanedianel and its Use in Perfumery | |
JPH05262757A (en) | Cyclic isolongifolanone-ketals, their production and their use | |
US4438023A (en) | Oxygenated tricyclic derivatives of norbornane and use of same as perfuming ingredients |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19810703 |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 5083 Country of ref document: AT Date of ref document: 19831115 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3065352 Country of ref document: DE Date of ref document: 19831124 |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19840319 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19840412 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19840419 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19840630 Year of fee payment: 5 Ref country code: BE Payment date: 19840630 Year of fee payment: 5 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19860512 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19860531 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19870501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19870502 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19870531 Ref country code: CH Effective date: 19870531 |
|
BERE | Be: lapsed |
Owner name: BUSH BOAKE ALLEN LTD Effective date: 19870531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19871201 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19880129 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19880202 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19880501 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19890531 |
|
EUG | Se: european patent has lapsed |
Ref document number: 80301436.4 Effective date: 19880330 |