DE1817950C3 - The use of trans-l, 7,7-trimethyl-bicyclo (4,4,0) -decanone as a fragrance - Google Patents
The use of trans-l, 7,7-trimethyl-bicyclo (4,4,0) -decanone as a fragranceInfo
- Publication number
- DE1817950C3 DE1817950C3 DE19681817950 DE1817950A DE1817950C3 DE 1817950 C3 DE1817950 C3 DE 1817950C3 DE 19681817950 DE19681817950 DE 19681817950 DE 1817950 A DE1817950 A DE 1817950A DE 1817950 C3 DE1817950 C3 DE 1817950C3
- Authority
- DE
- Germany
- Prior art keywords
- trans
- bicyclo
- trimethyl
- decanone
- fragrance
- 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
- 239000003205 fragrance Substances 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002304 perfume Substances 0.000 claims description 6
- NKXXEFVIPNMHCH-ZWNOBZJWSA-N (4aR,8aR)-5,5,8a-trimethyl-3,4,4a,6,7,8-hexahydro-2H-naphthalen-1-one Chemical compound C1CCC(=O)[C@@]2(C)[C@H]1C(C)(C)CCC2 NKXXEFVIPNMHCH-ZWNOBZJWSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012437 perfumed product Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000284 extract Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HQKQRXZEXPXXIG-VJOHVRBBSA-N Cedryl acetate Natural products C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@H]1[C@@](OC(C)=O)(C)CC2 HQKQRXZEXPXXIG-VJOHVRBBSA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N Cinnamyl alcohol Natural products OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N Coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- OEYQBKYISMRWQB-UHFFFAOYSA-N Santal Chemical compound C=1C(OC)=CC(O)=C(C2=O)C=1OC=C2C1=CC=C(O)C(O)=C1 OEYQBKYISMRWQB-UHFFFAOYSA-N 0.000 description 2
- KMPQYAYAQWNLME-UHFFFAOYSA-N Undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XHODMTAOVMFHQJ-UHFFFAOYSA-N aluminum;propan-2-ol Chemical compound [Al].CC(C)O XHODMTAOVMFHQJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000005712 crystallization Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 geranyl halide Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000010666 rose oil Substances 0.000 description 2
- 235000019719 rose oil Nutrition 0.000 description 2
- WLAUCMCTKPXDIY-JXMROGBWSA-N (2E)-1-chloro-3,7-dimethylocta-2,6-diene Chemical compound CC(C)=CCC\C(C)=C\CCl WLAUCMCTKPXDIY-JXMROGBWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000001725 2-hexylcyclopent-2-en-1-one Substances 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N 3-Pentanone Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- WXCMHFPAUCOJIG-UHFFFAOYSA-N 4'-tert-Butyl-2',6'-dimethyl-3',5'-dinitroacetophenone Chemical compound CC(=O)C1=C(C)C([N+]([O-])=O)=C(C(C)(C)C)C([N+]([O-])=O)=C1C WXCMHFPAUCOJIG-UHFFFAOYSA-N 0.000 description 1
- 229960000583 Acetic Acid Drugs 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 240000008772 Cistus ladanifer Species 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- FLKPEMZONWLCSK-UHFFFAOYSA-N Diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 1
- HFJRKMMYBMWEAD-UHFFFAOYSA-N Dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 1
- CBOQJANXLMLOSS-UHFFFAOYSA-N Ethylvanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 241000282375 Herpestidae Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- 240000009136 Monarda didyma Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- 240000002505 Pogostemon cablin Species 0.000 description 1
- 235000011751 Pogostemon cablin Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 240000008975 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].OC(O)=O LKZMBDSASOBTPN-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 229930007907 citral Natural products 0.000 description 1
- 239000001555 commiphora myrrha gum extract Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940073505 ethyl vanillin Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010656 jasmine oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N n-pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-YFHOEESVSA-N neral Chemical compound CC(C)=CCC\C(C)=C/C=O WTEVQBCEXWBHNA-YFHOEESVSA-N 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Description
und ist aus J. Chem. Soc. 1967, S. 1878, bekannt.and is from J. Chem. Soc. 1967, p. 1878.
Die genannte Verbindung besitzt besonders interessante und wertvolle Geruchseigenschaften und ist deshalb als Riechstoff in der Parfümindustrie verwendbar. Der Riechstoff kann insbesondere zur Herstellung von verdünnten oder konzentrierten Parfümen und zum Parfümieren von Produkten, wie Seifen, Wasch- und Reinigungsmitteln, kosmetischen Produkten, Wachsen und allgemeinen Produkten, die aus verkaufstechnischen Gründen normalerweise parfümiert werden, verwendet werden. Die Verbindung entwickelt einen intensiven edelholzartigen Geruch mit einer ambraartigen Duftnote.The compound mentioned has particularly interesting and valuable odor properties and is therefore usable as a fragrance in the perfume industry. The fragrance can in particular be used for production of diluted or concentrated perfumes and for perfuming products such as soaps, detergents and Detergents, cosmetic products, waxes and general products that result from sales-related Reasons normally perfumed should be used. The connection develops you intense noble wood-like smell with an amber-like scent note.
Die Mengenverhältnisse, in welchen die genannte Verbindung zur Erzielung der gewünschten Geruchseffekte verwendet werden kann, schwanken innerhalb ziemlich weiter Grenzen und richten sich nach der Beschaffenheit der Produkte, welchen der neue Riechstoff zugesetzt wird. Bei der Herstellung von Parfümen werden beispielsweise mit Mengen von 0,5 bis 10% der Riechstoffe, bezogen auf das Gesamtgewicht des Parfüms, interessante Resultate erzielt. Wenn die Verbindung zusammen mit anderen Riechstoffen zum Parfümieren von Produkten verwendet wird, kann sie beispielsweise in Mengen von 0,001 bis 0,5%, bezogen auf das Gewicht des zu parfümierenden Produktes, zugesetzt werden. In anderen Fällen, beispielsweise bei der Herstellung von Konzentraten, die vor Gebrauch mit Lösungsmitteln verdünnt oder mit anderen Riechstoffen vermischt werden, oder die als sogenannte Parfümbasen dienen, kann die Konzentration der genannten Verbindung höher als 10%, z.B. bis 15% oder noch höher sein.The proportions in which the compound mentioned to achieve the desired odor effects can be used vary within fairly wide limits and depend on the Nature of the products to which the new fragrance is added. In the manufacture of Perfumes are, for example, in amounts of 0.5 to 10% of the fragrances, based on the total weight of the perfume, achieved interesting results. If the compound is used together with other fragrances Perfuming of products is used, it can for example in amounts of 0.001 to 0.5%, based based on the weight of the product to be perfumed. In other cases, for example with the production of concentrates, which are diluted with solvents or with other fragrances before use be mixed, or serve as so-called perfume bases, the concentration of said compound can be higher than 10%, e.g. up to 15% or even higher.
Die oben angeführten Mengenbereiche stellen keine absoluten Werte dar, sondern sind lediglich alsThe quantity ranges listed above do not represent absolute values, but are only intended as
beispielhafte Angaben zu verstehen. Je nach den besonderen Geruchseffekten, die man erzielen will, können selbstverständlich andere Konzentrationen verwendet werden.understand exemplary information. Depending on the particular olfactory effects that you want to achieve, other concentrations can of course be used.
Das trans-1,7,7-Trimethyl-bicyclo(4,4,0)-decanon kann dadurch erhalten werden, daß man 1,7,7-Trimethyl-bicyclo(4,4,0)decanol-(3) oxydiert. Die Oxydation kann nach bekannten Methoden, beispielsweise mittels Silbercarbonat in Gegenwart von Diatomeenerde, oderThe trans-1,7,7-trimethyl-bicyclo (4,4,0) -decanone can be obtained by 1,7,7-trimethyl-bicyclo (4,4,0) decanol- (3) oxidized. The oxidation can by known methods, for example by means of silver carbonate in the presence of diatomaceous earth, or
mittels Oxydationsprodukten von Übergangsmetallen, z. B. Chrom und Kupfer (siehe beispielsweise »Organic Chemistry« von D. J. Cram und G. S. Hammond [1959], S. 432-436, McGraw-Hill, New York), durchgeführt werden. Die Oxydation kann auch mittels eines Ketons in Gegenwart eines Aluminiumalkoholates nach der Methode von Oppenauer durchgeführt werden. Als Ketone eignen sich beispielsweise Aceton, Cyclohexanon, Diäthylketon, Methyläthylketon und Methylhexylketon, während als Alkoholate beispielsweise Aluminiumbutylat, Aluminiumisobutylat oder Aluminiumisopropylat verwendet werden können. Vorzugsweise wird die Oxydation entweder mit CK>3 oder mit Methyläthylketon in Gegenwart von Aluminiumisopropylat durchgeführt. by means of oxidation products of transition metals, e.g. B. Chromium and copper (see for example »Organic Chemistry "by D. J. Cram and G. S. Hammond [1959], pp. 432-436, McGraw-Hill, New York). The oxidation can also be carried out by means of a Ketones can be carried out in the presence of an aluminum alcoholate according to the Oppenauer method. When Ketones are, for example, acetone, cyclohexanone, diethyl ketone, methyl ethyl ketone and methyl hexyl ketone, while as alcoholates, for example, aluminum butoxide, aluminum isobutoxide or aluminum isopropoxide can be used. The oxidation is preferably carried out either with CK> 3 or with methyl ethyl ketone carried out in the presence of aluminum isopropoxide.
Das durch Oxydation des Carbinols erhaltene Oxydationsprodukt besteht aus einem Gemisch der cis- und trans-Isomeren von 1,7,7-Trimethyi-bicyclo(4,4,0)decanon-(3). Durch Kristallisation dieses Gemisches erhält man das feste cis-Isomere in reiner Form.The oxidation product obtained by oxidation of the carbinol consists of a mixture of the cis- and trans isomers of 1,7,7-trimethyl bicyclo (4,4,0) decanone- (3). Crystallization of this mixture gives the solid cis isomer in pure form.
Das flüssige trans-Isomere kann aus den bei der fraktionierten Kristallisation anfallenden Mutterlaugen isoliert werden, z. B. durch Destillation oder durch präparative Gaschromatographie.The liquid trans isomer can be obtained from the mother liquors obtained in the fractional crystallization be isolated, e.g. B. by distillation or by preparative gas chromatography.
Das zur Herstellung der trans-Verbindung verwendete Carbinol der Formel I (siehe das folgende Reaktionsschema) kann beispielsweise durch Verseifung der Ester der Formel II erhalten werden. Die Verseifung kann nach bekannten Methoden, beispielsweise mittels Alkalien, z. B. KOH, NaOH und LiOH, in Gegenwart von wäßrigen Alkoholen, z. B. Methanol oder Amylalkohol, durchgeführt werden.The carbinol of formula I used to prepare the trans compound (see the following Reaction scheme) can be obtained, for example, by saponification of the esters of the formula II. the Saponification can be carried out by known methods, for example by means of alkalis, e.g. B. KOH, NaOH and LiOH, in Presence of aqueous alcohols, e.g. B. methanol or amyl alcohol can be carried out.
Das zur Herstellung der Ester II verwendete 6,10-Dimethyl-undeeatrien-(l,5,9) der Formel III kann durch Umsetzung eines Geranylhalogenids IV, z. B. des Chlorids oder Bromids, mit einem Allylhalogenid V, z. B. dem Chlorid oder Bromid, unter üblichen Grignard-Reaktionsbedingungen erhalten werden. Im folgenden Reaktionsschema steht X für Halogen und R für einen geraden oder verzweigten, gesättigten, aliphatischen Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen oder einen geraden oder verzweigten, ungesättigten aliphatischen Kohlenwasserstoffrest mit 2 bis 6 Kohlenstoffatomen.The 6,10-dimethyl-undeeatriene- (1,5,9) of the formula III used to prepare the ester II can by reacting a geranyl halide IV, e.g. B. the chloride or bromide, with an allyl halide V, z. B. the chloride or bromide, under the usual Grignard reaction conditions can be obtained. In the following reaction scheme, X stands for halogen and R for one straight or branched, saturated, aliphatic hydrocarbon radical with 1 to 6 carbon atoms or a straight or branched, unsaturated aliphatic hydrocarbon radical with 2 to 6 Carbon atoms.
CH2XCH 2 X
MineralsäureMineral acid
— >->
+ R-COOH+ R-COOH
(V) CH2-X(V) CH 2 -X
VerseifungSaponification
— -
VeresterungEsterification
(II) O—CO—R(II) O-CO-R
erfindungsgemäßaccording to the invention
verwendeteused
Verbindungconnection
Oxydationoxidation
cis-Isomerescis isomer
Durch Mischen der nachstehend angeführten Sub- 30 stanzen wurde eine Riechstoffkomposition von der »Chypre«-Art hergestellt:By mixing the substances listed below, a fragrance composition was obtained from the "Chypre" type made:
3535
4040
4545
5555
6060
Dieser Mischung wurden 50 g trans-l,7,7-Trimethyl- 65 bicyclo(4,4,0)decanon-(3) zugesetzt. Man erhielt auf diese Weise eine Riechstoffkomposition, die eine gefällige, ambraartige und holzige Duftnote aufwies.To this mixture 50 g of trans-1,7,7-trimethyl-65 bicyclo (4,4,0) decanone (3) were added. One received on in this way a fragrance composition that had a pleasing, amber-like and woody scent note.
Herstellung des trans-1,7,7-Trimethylbicyclo(4,4,0)decanon Preparation of the trans-1,7,7-trimethylbicyclo (4,4,0) decanone
a) 6,10- Dimethyl-undeca trien-( 1,5,9)a) 6,10-dimethyl-undeca triene- (1,5,9)
84 g (3,5 Mol) entfettete Magnesiumspäne wurden in 100 ml absolutem Äther suspendiert. Das Magnesium wurde mit einem Jodkristall aktiviert. Innert 3 Stunden wurden zuerst 300 g (1,75 Mol) Geranylchlorid und dann eine Lösung von 268 g (3,5 Mol) Allylchlorid in 800 ml Äther tropfenweise zugesetzt. Das Reaktionsgemisch wurde während 4 Stunden zum Sieden erhitzt, dann abgekühlt und in eine Lösung von 200 g NH4Cl in 1 Liter Eiswasser gegossen. Die Lösung wurde mit Äther extrahiert. Die Extrakte lieferten nach Einengung 384 g rohes 6,10-Dimethyl-undecatrien-(l,5,9), das ohne vorherige Reinigung weiterverarbeitet wurde.84 g (3.5 mol) of defatted magnesium turnings were suspended in 100 ml of absolute ether. The magnesium was activated with an iodine crystal. Within 3 hours, first 300 g (1.75 mol) of geranyl chloride and then a solution of 268 g (3.5 mol) of allyl chloride in 800 ml of ether were added dropwise. The reaction mixture was heated to boiling for 4 hours, then cooled and poured into a solution of 200 g of NH 4 Cl in 1 liter of ice water. The solution was extracted with ether. After concentration, the extracts yielded 384 g of crude 6,10-dimethyl-undecatriene- (1.5,9), which was further processed without prior purification.
b) 1,7,7-Trimethyl-bicyclo(4,4,0)decanol-(3)b) 1,7,7-trimethyl-bicyclo (4,4,0) decanol- (3)
Die gemäß Absatz a) erhaltenen 384 g Trien wurden innert etwa I1/2 Stunden bei 50° tropfenweise einem Gemisch von 2,7 kg 98%iger Ameisensäure, 270 g konzentrierter Schwefelsäure und 1000 ml Dioxan zugesetzt. Das Reaktionsgemisch wurde während 3 Stunden bei 60° gerührt, dann abgekühlt und dann auf Eis gegossen. Nach Extraktion mit Äther wurden die Extrakte mit 10%igem wäßrigem Natriumbicarbonat neutralisiert und mit Wasser neutral gewaschen. Der Extrakt wurde in üblicher Weise getrocknet unJ eingeengt. Der Rückstand (430 g) wurde mit 140 {. Kaliumhydroxyd, 140 ml Wasser und 1500 ml Methanol gemischt und während 4 Stunden bei Rückflußtemperatur gerührt. Nach Entfernung des Methanols unter vermindertem Druck wurde der Rückstand mit Äther extrahiert. Der Extrakt wurde in üblicher Weise neutralisiert, gewaschen und getrocknet. Durch Einengen des Extraktes und Einengung des Rückstandes (350 g) im Vakuum wurde 1,7,7-Trimethyl-bicyclo(4,4,0)decanol-(3) (Sdp. 114- 125°/0,001 Torr, Smp. 53-54°) erhalten.The 384 g of triene obtained in accordance with paragraph a) were added dropwise to a mixture of 2.7 kg of 98% strength formic acid, 270 g of concentrated sulfuric acid and 1000 ml of dioxane over a period of about 1 1/2 hours at 50 °. The reaction mixture was stirred at 60 ° for 3 hours, then cooled and then poured onto ice. After extraction with ether, the extracts were neutralized with 10% aqueous sodium bicarbonate and washed neutral with water. The extract was dried and concentrated in the usual way. The residue (430 g) was treated with 140 {. Potassium hydroxide, 140 ml of water and 1500 ml of methanol are mixed and the mixture is stirred at reflux temperature for 4 hours. After removing the methanol under reduced pressure, the residue was extracted with ether. The extract was neutralized, washed and dried in the usual manner. Concentration of the extract and concentration of the residue (350 g) in vacuo gave 1,7,7-trimethyl-bicyclo (4,4,0) decanol- (3) (bp. 114-125 ° / 0.001 torr, m.p. 53 -54 °).
c) Oxydation von 1,7,7-Trimcthylbicyclo(4,4,0)decanol-(3) c) Oxidation of 1,7,7-trimethylbicyclo (4,4,0) decanol- (3)
Eine Lösung von 0,53 Mol CrOj in 200 ml Wasser wurde innen etwa 2 Stunden bei 40-45" in eine Lösung von 105 g (0,53 Mol) des gemäß Absatz b) hergestellten Carbinols in 800 ml Eisessig eingetropft. Das Gemisch wurde während 4 Stunden bei 70° erhitzt, dann abgekühlt und mit Äther extrahiert. Der Extrakt wurde in üblicher Weise behandelt und eingeengt. Man erhielt 95 g eines rohen Gemisches von eis- und trans-l,7,7-Tri· methyl-bicyc!o(4,4,0)decanon-(3) im Gewichtsverhiiltnis von etwa ι : 1. Durch zweimaliges Umkristallisieren des Rohproduktes in Hexan erhielt man 46,5 g reines cis-Isomer vom Smp. 46-47°. IR-Spektrum (flüssige Phase): 965, 1215, 1450, 1705, 2940 cm '; NMR-Spektrum (CCI4): 0,86 (6H1 s), 0,96 (3H1 s), 1,43 (8H, m), 1,95 (2H),2,23(2H,m)ppm(o).A solution of 0.53 mol of CrOj in 200 ml of water was dripped into a solution of 105 g (0.53 mol) of the carbinol prepared in accordance with paragraph b) in 800 ml of glacial acetic acid over a period of about 2 hours at 40-45 ". The mixture was heated for 4 hours at 70 °, then cooled and extracted with ether, the extract was treated and concentrated in the usual manner, giving 95 g of a crude mixture of cis- and trans-1,7,7-tri · methyl-bicyc! o (4,4,0) decanone- (3) in a weight ratio of about ι: 1. Recrystallizing the crude product twice in hexane gave 46.5 g of pure cis isomer with a melting point of 46-47 °. IR spectrum ( liquid phase): 965, 1215, 1450, 1705, 2940 cm '; NMR spectrum (CCI 4 ): 0.86 (6H 1 s), 0.96 (3H 1 s), 1.43 (8H, m) , 1.95 (2H), 2.23 (2H, m) ppm (o).
Die bei der Kristallisation angefallenen Mutterlaugen wurden eingeengt. Der gröütenteils aus dem trans-lsomeren bestehende Rückstand wurde durch präparative Gaschromatographie in einer üblichen Polyäthylenglykol-Kolonne von 2,5 m bei 150° mit einem Heliumstrom von 40 ml pro Minute gereinigt.. Das erhaltene Produkt wies das folgende NMR-Spektrum (CCI4) auf: 0,87 (6H, s),l,13(3H1s)1l,5(8H,m)12,2(4H1m)ppm(o).The mother liquors obtained during the crystallization were concentrated. The residue, consisting largely of the trans isomer, was purified by preparative gas chromatography in a conventional polyethylene glycol column of 2.5 m at 150 ° with a helium flow of 40 ml per minute. The product obtained had the following NMR spectrum (CCI 4 ) to: 0.87 (6H, s), 1.13 (3H 1 s) 1 1.5 (8H, m) 1 2.2 (4H 1 m) ppm (o).
Claims (1)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1674567A CH504526A (en) | 1967-11-25 | 1967-11-25 | Use of alicyclic ketones as odoriferous agents |
CH1674567 | 1967-11-29 | ||
CH1740568A CH511935A (en) | 1967-11-25 | 1968-11-22 | Use of oxygenated derivatives of decalin as odoriferous agents |
CH1740568 | 1968-11-22 |
Publications (3)
Publication Number | Publication Date |
---|---|
DE1817950A1 DE1817950A1 (en) | 1975-05-15 |
DE1817950B2 DE1817950B2 (en) | 1976-11-11 |
DE1817950C3 true DE1817950C3 (en) | 1977-07-07 |
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