DE2302219A1 - NEW FRAGRANCES - Google Patents
NEW FRAGRANCESInfo
- Publication number
- DE2302219A1 DE2302219A1 DE19732302219 DE2302219A DE2302219A1 DE 2302219 A1 DE2302219 A1 DE 2302219A1 DE 19732302219 DE19732302219 DE 19732302219 DE 2302219 A DE2302219 A DE 2302219A DE 2302219 A1 DE2302219 A1 DE 2302219A1
- Authority
- DE
- Germany
- Prior art keywords
- acetonitrile
- cyclohexane
- isopropylidene
- isopropenyl
- mixture
- 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.)
- Pending
Links
- 239000003205 fragrance Substances 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 claims description 34
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- UJYNKPIXFNHCOE-UHFFFAOYSA-N 4-propan-2-ylidenecyclohexan-1-one Chemical compound CC(C)=C1CCC(=O)CC1 UJYNKPIXFNHCOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- YQMUZRNPCVSBEH-UHFFFAOYSA-N 4-prop-1-en-2-ylcyclohexan-1-one Chemical compound CC(=C)C1CCC(=O)CC1 YQMUZRNPCVSBEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- MXFPACNADGXIQY-UHFFFAOYSA-N 2-cyclohexylacetonitrile Chemical compound N#CCC1CCCCC1 MXFPACNADGXIQY-UHFFFAOYSA-N 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- XZFDKWMYCUEKSS-UHFFFAOYSA-N 6,6-Dimethylbicyclo[3.1.1]heptan-2-one Chemical compound C1C2C(C)(C)C1CCC2=O XZFDKWMYCUEKSS-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- -1 eth3 / 1 Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000035943 smell Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GUMOJENFFHZAFP-UHFFFAOYSA-N 2-Ethoxynaphthalene Chemical compound C1=CC=CC2=CC(OCC)=CC=C21 GUMOJENFFHZAFP-UHFFFAOYSA-N 0.000 description 1
- KWMBADTWRIGGGG-UHFFFAOYSA-N 2-diethoxyphosphorylacetonitrile Chemical compound CCOP(=O)(CC#N)OCC KWMBADTWRIGGGG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 240000005209 Canarium indicum Species 0.000 description 1
- 240000000467 Carum carvi Species 0.000 description 1
- 235000005747 Carum carvi Nutrition 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000007212 Verbena X moechina Moldenke Nutrition 0.000 description 1
- 240000001519 Verbena officinalis Species 0.000 description 1
- 235000001594 Verbena polystachya Kunth Nutrition 0.000 description 1
- 235000007200 Verbena x perriana Moldenke Nutrition 0.000 description 1
- 235000002270 Verbena x stuprosa Moldenke Nutrition 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000001111 citrus aurantium l. leaf oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000001941 cymbopogon citratus dc and cymbopogon flexuosus oil Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004862 elemi Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 239000001927 guaiacum sanctum l. gum oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic 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
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Description
J 7. Jaa 1973J 7. Jaa 1973
inn et* Tferrainn et * Tferra
rATENiANWAWTi 2302219RATENiANWAWTi 2302219
■ 6510/78 ■ 6510/78
L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Schweiz)L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Switzerland)
Neue RiechstoffeNew fragrances
Die Erfindung betrifft neue Riechstoffe. Es handelt sich hierbei um Verbindungen der allgemeinen FormelThe invention relates to new fragrances. These are compounds of the general formula
Ur/23.10.72Ur / 10/23/72
worin die gestrichelten Linien eine vom Cg-Atom ausgehende Doppelbindung bedeuten.where the dashed lines denote a double bond emanating from the Cg atom.
Die Formel I umfasst definitionsgemäss das 4-Isopropenyl-The formula I by definition includes the 4-isopropenyl
309834/1113309834/1113
Δ ^-cyclohexan-acetonitril und das 4-Isopropyliden-& >flc-cyclohexan-acetonitril. ,Δ ^ -cyclohexan-acetonitrile and the 4-isopropylidene- &> flc -cyclohexan -acetonitrile. ,
Die Erfindung betrifft auch ein Verfahren zur Herstellung der Verbindungen der Formel I, deren Verwendung als Riechstoffe und Riechstoffkompositionen, gekennzeichnet durch einen Gehalt an einer Verbindung der allgemeinen Formel I.The invention also relates to a process for the preparation of the compounds of the formula I, their use as fragrances and fragrance compositions, characterized by a content of a compound of the general Formula I.
Die erfindungsgemässen Verbindungen können dadurch erhalten werden, dass man eine Verbindung der allgemeinen FormelThe compounds according to the invention can be obtained by a compound of the general formula
IIII
worin die gestrichelten Linien obige Bedeutung haben,
der Cyanmethylenierung unterwirft.where the dashed lines have the above meaning,
subject to cyanomethylenation.
Die Cyanmethylenierung kann nach an sich bekannten Methoden durchgeführt werden, zweckmässigerweise dadurch, dass man die Verbindung der Formel II mit einem Di-niederalkylphosphono-acetonitril der FormelThe cyanomethylenation can be carried out by methods known per se, expediently in that the compound of formula II with a di-lower alkylphosphono-acetonitrile the formula
^- CH9-Cs=N IH^ - CH 9 -Cs = N IH
' RO'RO
worin R nieder-Alkyl, wie Methyl, Aeth3/1, Propyl etc., vorzugsweise Aethyl bedeutet, zur Umsetzung bringt.wherein R is lower-alkyl, such as methyl, eth3 / 1, propyl etc., preferably ethyl, brings to implementation.
30983A/1 1 1330983A / 1 1 13
Die Umsetzung der Verbindung II mit der Verbindung III wird zweckmässigerweise in einem organischen Lösungsmittel in Anwesenheit einer Base durchgeführt. Beispiele von Basen sind Alkalihydride, z.B. Natrium- oder Kaliumhydrid, Alkalimetallalkoholate, wie Eatriummethylat, Kalrumäthylat, oder Alkaliamide, wie Natriumamid. Mittels solcher Basen wird die Verbindung III in die Phosphonatform übergeführt, die.schliesslich mit der Verbindung II reagiert.The implementation of the compound II with the compound III is conveniently carried out in an organic solvent in the presence of a base. Examples of bases are alkali hydrides, e.g. sodium or potassium hydride, alkali metal alcoholates, such as sodium methylate, potassium ethylate, or alkali amides such as sodium amide. The compound III is converted into the phosphonate form by means of such bases, die.schllich reacts with compound II.
Als Lösungsmittel eignen sich beispielsweise aromatische Kohlenwasserstoffe, wie Benzol, Toluol, etc.; Aether, wie Tetrahydrofuran, Dioxan, 1,2-Dimethoxyäthan; oder Dimethylformamid .Examples of suitable solvents are aromatic hydrocarbons such as benzene, toluene, etc .; Ethers, such as tetrahydrofuran, Dioxane, 1,2-dimethoxyethane; or dimethylformamide .
Die Reaktionstemperatur kann zwischen etwa 0° und der Rückflusstemperatur des Reaktionsgemisches liegen. Sie liegt bevorzugt zwischen etwa 5 und 25°.The reaction temperature can be between about 0 ° and the reflux temperature of the reaction mixture. she lies preferably between about 5 and 25 °.
Das Verhältnis der Reaktionspartner beträgt zweckmässigerweise etwa 1:1, doch kann die Komponente III auch im lieber schuss vorhanden sein.The ratio of the reactants is expediently about 1: 1, but component III also be present in the dear shot.
Die Reaktionsdauer beträgt in der Regel 1 bis 16 Stunden, beispielsweise 2 Stunden.The reaction time is generally 1 to 16 hours, for example 2 hours.
Aus dem Reaktionsgemisch kann die entstandene Verbindung der Formel I auf an sich bekannte Art isoliert werden, zweckmässig durch Zugabe von Wasser und Extraktion mittels eines organischen Lösungsmittels. Die Reinigung geschieht am besten durch Destillation.The compound of the formula I formed can be isolated from the reaction mixture in a manner known per se, expediently by adding water and extracting with an organic solvent. The purification happens preferably by distillation.
Die Cyanmethylenierung kann auf an sich bekannte Art auch durch Erwärmen der Verbindung II mit Acetonitril in Anwesenheit eines Alkalialkoholates als Katalysator bewerkstelligt werden.The cyanomethylenation can also be carried out in a manner known per se by heating the compound II with acetonitrile in the presence accomplished an alkali alcoholate as a catalyst will.
309834/1113309834/1113
Als Katalysatoren finden zweckmässigerweise Alkalialkoholate höher siedender Alkohole, wie z.B. Natrium-noctylat "Verwendung.Alkali metal alcoholates are expediently found as catalysts higher boiling alcohols such as sodium noctylate "Use.
Die Umsetzung wird vorzugsweise in einem organischen Lösungsmittel unter Rückfluss ausgeführt. Das bei der Reaktion sich bildende Wasser wird vorteilhaft nach Massgabe seiner Bildung aus dem Reaktionsgemisch entfernt, vorzugsweise durch azeotrope Destillation. Im allgemeinen kann eine Vielzahl von organischen Lösungsmitteln, insbesondere aromatischen Kohlenwasserstoffen, wie Xylol, Aethylbenzol und ähnliche, verwendet werden. Man verwendet jedoch vorzugsweise solche Lösungsmittel, die relativ billig sind und azeotrope Gemische mit Wasser im Temperaturbereich bilden, bei welchem die Reaktion ausgeführt wird, beispielsweise Benzol und Toluol.The reaction is preferably carried out under reflux in an organic solvent. That at the Water which forms in the reaction is advantageously removed from the reaction mixture according to its formation, preferably by azeotropic distillation. In general, a variety of organic solvents, in particular aromatic hydrocarbons such as xylene and ethylbenzene and the like can be used. However, it is preferred to use solvents which are relatively cheap and form azeotropic mixtures with water in the temperature range at which the reaction is carried out, for example Benzene and toluene.
Die Reaktionszeit ist im allgemeinen nicht kritisch. Sie hängt hauptsächlich von der Menge der Reaktionsteilnehmer und der Reaktionstemperatur ab. Die Reaktion lässt sich bequem anhand des sich bildenden Wassers verfolgen. Wenn man kein Wasser mehr auffangen kann, so kann man daraus schliessen, dass die Reaktion praktisch beendet ist.The reaction time is generally not critical. It mainly depends on the number of respondents and the reaction temperature. The reaction can be easily followed using the water that forms. If one can no longer collect water, one can conclude from this that the reaction has practically ended.
Obschon man äquimolare Mengen der Reaktionsteilnehmer anwenden kann, zieht man die Verwendung eines Ueberschusses an Acetonitril, z.B. bis zu 100$, vor, da dieses das billigere Reagens ist.Although equimolar amounts of the reactants can be used, an excess is preferred of acetonitrile, e.g. up to $ 100, as this which is the cheaper reagent.
309834/1113309834/1113
Als Ausgangsmaterial für das erfindungsgemässe Verfahren setzt man gemäss einer bevorzugten Ausführungsart Gemische von 4-Isopropenyleyclohexanon (V) und 4-Isoprppylidencyclohexanon (VI) im Verhältnis von etwa 6:4 bis 9:1 ein, insbesondere solche Gemische, wie sie erhalten werden, wenn Nopinon (IV) in Gegenwart eines sauren Katalysators, wie Schwefelsäure mit Orthoameisensäuremethylester behandelt und das dabei gebildete ümsetzungsprodukt hydrolysiert wird:According to a preferred embodiment, mixtures are used as the starting material for the process according to the invention of 4-isopropenyl cyclohexanone (V) and 4-isopropylidenecyclohexanone (VI) in the ratio of about 6: 4 to 9: 1, in particular such mixtures as are obtained when Nopinone (IV) in the presence of an acidic catalyst such as Sulfuric acid treated with methyl orthoformate and the resulting reaction product is hydrolyzed:
VIVI
Die erfindungsgemässen Verbindungen der Formel I zeichnen sich durch interessante Riechstoffeigenschaften aus. Ihr Geruch kann als grün, kümmel- und citralartig, sowie frisch würzig bezeichnet werden. Geruchsintensität und Haftfestigkeit sind stark ausgeprägt.The compounds of the formula I according to the invention are distinguished by interesting fragrance properties. Their smell can be described as green, caraway and citral-like, as well as freshly spicy. Odor intensity and adhesive strength are very pronounced.
Besonderes geruchliches Interesse beanspruchen Gemische von 4-Isopropenyl-A ' -cyclohexan-acetonitril und 4-Isopropyliden-Δ'"-cyclohexan-acetonitril, insbesondere Gemische im Verhältnis von 6:4 bis 9:1, wie beispielsweise 7:3.Mixtures of 4-isopropenyl-A '-cyclohexane-acetonitrile and 4-isopropylidene-Δ' "- cyclohexane-acetonitrile are of particular interest in terms of smell, in particular mixtures in a ratio of 6: 4 to 9: 1, such as 7: 3, for example.
Die Verbindungen der Pormel I bzw. deren Gemische können auf Grund ihrer interessanten olfaktorischen Eigenschaften ab Kiech-The compounds of formula I or their mixtures can be used due to their interesting olfactory properties from Kiech-
309834/1113309834/1113
stoffe Verwendung finden, z.B. in der Parfumerie zur Herstellung von Riechstoffkompositionen, wie Parfüms, bzw. zur Parfümierung von Produkten aller Art, wie z.B. Seifen (für die sie sich wegen ihrer chemischen Stabilität besonders eignen), Waschmitteln, Detergentien, Aerosolen oder andern kosmetischen Produkten, wie Salben, Gesichtsmilch, Schminke, Badesalzen etc.materials are used, e.g. in perfumery for production of fragrance compositions, such as perfumes, or for perfuming of products of all kinds, such as soaps (for which they are particularly suitable due to their chemical stability), Detergents, detergents, aerosols or other cosmetic products such as ointments, facial milk, make-up, Bath salts etc.
Die Konzentration der erfindungsgemässen Verbindungen I kann je nach dem Verwendungszweck innerhalb weiter Grenzen variieren, beispielsweise zwischen etwa 1 und etwa 10 Gew.$ (in Parfumbasen). Für Riechstoffkompositionen liegen die bevorzugten Konzentrationen im Bereich von etwa 0,1 bis etwa 0,5 Gew.$. Die Konzentration der Parfumbase kann in Seifen z.B. etwa 0,8-2 Gew.$, in Waschmitteln,0,1-0,3 Gew.$ betragen.The concentration of the compounds I according to the invention can be within wide limits depending on the intended use vary, for example between about 1 and about 10 wt. $ (in perfume bases). The preferred ones are for fragrance compositions Concentrations ranging from about 0.1 to about 0.5 wt. The concentration of the perfume base can be found in soaps e.g., about 0.8-2 wt. $, in detergents, 0.1-0.3 wt. $.
Im nachfolgenden Beispiel sind die Temperaturen in Celsiusgraden angegeben.In the following example, the temperatures are given in degrees Celsius.
a) In einem 4-Hals-Sulfierkolben, der mit Tropf trichter, Rührer, Thermometer, Rückflusskühler, Stickstoffeinleitungsrohr und Calciumchloridrohr versehen ist, werden 96 g (2MoI) einer 50$igen Natriumhydrid-Dispersion in Paraffinöl mit 3,35 labs. Benzol überschichtet. Man kühlt das Gemisch mittels Eisbad auf +5° und lässt 354 g (2MoI) Diäthylphosphonoacetonitril zutropfen. Man rührt nierauf 15 Minuten bei +5° und hierauf eine Stunde bei Zimmertemperatur. 176 g (2 Mol) eines Gemisches von 4-Isopropenylcyclohexanon (79$) und 4-Isopropylidencyclohexanon (21$) werden unter Wasserkühlung so zugetropft, dass die Reaktionstemperatur 25° nicht übersteigt. Man rührt das Gemisch 2 Stunden bei Zimmertemperatur und bringta) In a 4-neck sulphonation flask fitted with a dropping funnel, Stirrer, thermometer, reflux condenser, nitrogen inlet tube and calcium chloride tube are 96 g (2MoI) of a 50% sodium hydride dispersion in paraffin oil with 3.35 labs. Benzene layered. The mixture is cooled by means of Ice bath at + 5 ° and leaves 354 g (2MoI) diethylphosphonoacetonitrile drip. The mixture is stirred for 15 minutes at + 5 ° and then for one hour at room temperature. 176 g (2 moles) a mixture of 4-isopropenylcyclohexanone ($ 79) and 4-isopropylidenecyclohexanone ($ 21) are added dropwise with water cooling so that the reaction temperature does not exceed 25 °. The mixture is stirred for 2 hours at room temperature and brought
309834/1113309834/1113
dann die zähe Reaktionsmasse mit Wasser in Lösung. Die organische Phase wird im Scheidetrichter abgetrennt, mit Wasser neutralgewaschen und mit Magnesiumsulfat getrocknet. Nach dem Abdampfen des Lösungsmittels destilliert man den Rückstand über eine Vigreux-Kolonne. Man erhält 286 g eines Rohproduktes vom Sdp. 90-100°/0,3 Torr. Die Reindestillation über eine Raschigring-Kolonne (50 cm) ergibt 210 g einesthen the viscous reaction mass with water in solution. The organic phase is separated off in a separating funnel, with Washed water until neutral and dried with magnesium sulfate. After the solvent has been evaporated off, the residue is distilled over a Vigreux column. 286 g of one are obtained Crude product from bp 90-100 ° / 0.3 Torr. Purification by distillation through a Raschigring column (50 cm) gives 210 g of one
1 a.
Gemisches von 4-Isopropenyl-Ä ' -cyclohexan-acetonitril (71$)
und 4-Isopropyliden-A '"-cyclohexan-acetonitril (29$) mit
dem Sdp. 134-135°/12 Torr.1 a.
Mixture of 4-isopropenyl-A '-cyclohexane-acetonitrile ($ 71) and 4-isopropylidene-A'"-cyclohexane-acetonitrile ($ 29) with a boiling point of 134-135 ° / 12 Torr.
n£w : 1,5068; IR-Spektrum (CCl4): Banden bei 2240, 1638 und 895 cm"1; NMR-Spektrum (CDCl,): ^= 5,1 ppm (s, N=C-CH=C); 4,7 ppm (b, CH2=C); 1,73 ppm (b, CH,-C- undn £ w : 1.5068; IR spectrum (CCl 4 ): bands at 2240, 1638 and 895 cm "1; NMR spectrum (CDCl,): ^ = 5.1 ppm (s, N = C-CH = C); 4.7 ppm ( b, CH 2 = C); 1.73 ppm (b, CH, -C- and
~ CH2 ~ CH 2
Das Produkt riecht grün, kümmelartig.The product smells green, caraway-like.
Bin Teil des Gemisches wurde präparativ gaschromatographisch getrennt.Part of the mixture was prepared by gas chromatography separated.
4-Isopropenyl-A. '^-cyclohexan-acetonitril IR-Spektrum (CCl.): Banden bei 2240, 1638 und 895 cm ; NMR-Spektrum (CDCl,): S= 5,1 ppm (s, N=C-CH=C); 4,7 ppm (b, CH2=C); 1,73 ppm (b CH5-C ) 4-isopropenyl-A. ^ -cyclohexane-acetonitrile IR spectrum (CCl.): bands at 2240, 1638 and 895 cm; Nuclear Magnetic Resonance Spectrum (CDCI,): S = 5.1 ppm (s, N = C-CH = C); 4.7 ppm (b, CH 2 = C); 1.73 ppm (b CH 5 -C)
"1 „"1 "
4-IsoT?rop?^liden-A * -cyclohexan-acetonitril IR-Spektrum (CCl-): Banden bei 2250, I64O cm" ; MMR-Spektrum (CDCl,): «5= 5,1 ppm (s, N=C-CH=C), 1,72 ppm (s, «%>=). 4-IsoT? Rop? ^ Liden-A * -cyclohexane-acetonitrile IR spectrum (CCl-): bands at 2250, 1640 cm "; MMR spectrum (CDCl,): <5 = 5.1 ppm (s, N = C-CH = C), 1.72 ppm (s, «%> =).
309834/1113309834/1113
b) 13,8 g (0,1 Mol) eines Gemisches von 4-Isopropenylcyclohexanon (80^) und 4-Isopropylidencyclohexanon (20fo) werden zusammen mit 8,2 g (0,2 Mol) Acetonitril in 20 ml Benzol gelöst. Man versetzt das Gemisch mit 305 mg (0,002 Mol) Natrium-n-octylat und erhitzt 20 Stunden am Wasserabscheider zum Sieden. Zwecks Aufarbeitung wird das Reaktionsgemisch mit verdünnter Schwefelsäure und mit Wasser gewaschen. Nach Trocknen über Magnesiumsulfat und Abdampfen des Lösungsmittels erhält man 15,7 g Rohprodukt. Reindestillation über eine Vigreux-Kolonne ergibt 2,5 g eines Gemisches von 4-Isopropenyl Λ ^-cyelohexan-acetonitril (68%) und 4-Iso- propyliden-λ r -cyclohexan-acetonitril (32$) vom Siedepunkt 72-78°/0,02 Torr.b) 13.8 g (0.1 mol) of a mixture of 4-isopropenylcyclohexanone (80 ^) and 4-isopropylidenecyclohexanone (20fo) are dissolved together with 8.2 g (0.2 mol) of acetonitrile in 20 ml of benzene. 305 mg (0.002 mol) of sodium n-octylate are added to the mixture and the mixture is heated to boiling on a water separator for 20 hours. For work-up, the reaction mixture is washed with dilute sulfuric acid and with water. After drying over magnesium sulfate and evaporation of the solvent, 15.7 g of crude product are obtained. Purification by distillation through a Vigreux column gives 2.5 g of a mixture of 4-isopropenyl Λ ^ -cyelohexane-acetonitrile (68%) and 4-isopropylidene- λ r -cyclohexane-acetonitrile ($ 32) with a boiling point of 72-78 ° / 0.02 torr.
Die physikalischen und spektralen Daten des Produktes entsprechen den oben aufgeführten.The physical and spectral data of the product correspond to those listed above.
Das als Ausgangsmaterial verwendete Gemisch von 4-IsQpropenylcyclohexanon und 4-Isopropylidencyclohexanon kann wie folgt erhalten werden:The mixture of 4-isopropylidenylcyclohexanone and 4-isopropylidenecyclohexanone used as the starting material can be obtained as follows:
138 g (1,0 Mol) Nopinon werden unter Rühren bei 20° mit 117 g (1,1 Mol) Orthoameisensäuremethylester und 1 ml (1,85 g) Schwefelsäure konz. versetzt. Das Reaktionsgemisch wird 2 Stunden 30 Minuten bei 20° gerührt. Nach Zugabe von 1000 ml Aceton, 360 ml Wasser und 3,5 ml 2n Schwefelsäure wird das Gemisch weitere 2 Stunden gerührt und dann mit einer lösung von 2,3 g wasserfreiem Natriumcarbonat in 5 ml Wasser neutralisiert. Zur Aufarbeitung wird das Gemisch am Rotationsverdampfer bis zur Bildung von zwei Phasen eingedampft. Die organische Phase wird abgetrennt und die wässrige Phase 3 mal mit Aether ausgeschüttelt. Die gesammelten organischen Phasen werden dann mit einer gesättigten Natriumchloridlösung138 g (1.0 mol) of nopinone are mixed with 117 g (1.1 mol) of methyl orthoformate and 1 ml at 20 ° while stirring (1.85 g) sulfuric acid conc. offset. The reaction mixture is stirred at 20 ° for 2 hours 30 minutes. After adding 1000 ml of acetone, 360 ml of water and 3.5 ml of 2N sulfuric acid, the mixture is stirred for a further 2 hours and then with a solution of 2.3 g of anhydrous sodium carbonate in 5 ml of water neutralized. The mixture is worked up on a rotary evaporator evaporated until two phases are formed. The organic phase is separated off and the aqueous phase Shaken out 3 times with ether. The collected organic phases are then washed with a saturated sodium chloride solution
30 9 8 34/111330 9 8 34/1113
_. 9 —_. 9 -
gewaschen, mit Magnesiumsulfat'getrocknet und eingedampft. Man erhält 135 g eines Rohproduktes, welches an einer Yigreuxkolonne destilliert wird.washed, dried with magnesium sulfate and evaporated. Man receives 135 g of a crude product which is distilled in a Yigreux column.
Komposition vom 5?yp "Verbena", geeignet zur Parfümierung von Seifen.Composition from the 5? Yp "Verbena", suitable for perfuming of soaps.
4-Isopropenyl-Ä« ' -cyclohexan-acetonitril/ 4-Isopropyliden-A. * -cyclohexan-acetonitril (7:3) 100 ß-Naphtholäthyläther 154-isopropenyl-Ä «'-cyclohexane-acetonitrile / 4-isopropylidene-A. * -cyclohexane-acetonitrile (7: 3) 100 ß-naphthol ethyl ether 15
Petitgrainöl Paraguay - 100Petitgrain oil Paraguay - 100
Itesinoide Elemi 50Itesinoid Elemi 50
p-tert. Butyl-«-methylhydrozimtaldehyd 20p-tert. Butyl - «- methylhydrocinnamaldehyde 20
Orangenöl kalifornisch 100Orange Oil Californian 100
Geraniol 200Geraniol 200
Lemongrasöl 100Lemongrass Oil 100
Baccartol Givaudan 200Baccartol Givaudan 200
Guajakholzöl 50?δ in Phthalsäurediäthylester 100 Guaiac wood oil 50? Δ in phthalic acid diethyl ester 100
10001000
3098-34/1 1 133098-34 / 11 13
Claims (20)
CIICN
CII
CHON ·.
CH
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH209772A CH566969A5 (en) | 1972-02-12 | 1972-02-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2302219A1 true DE2302219A1 (en) | 1973-08-23 |
Family
ID=4225809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19732302219 Pending DE2302219A1 (en) | 1972-02-12 | 1973-01-17 | NEW FRAGRANCES |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS4886849A (en) |
| CH (1) | CH566969A5 (en) |
| DE (1) | DE2302219A1 (en) |
| FR (1) | FR2171427B1 (en) |
| GB (1) | GB1367060A (en) |
| NL (1) | NL7300692A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960923A (en) * | 1973-12-03 | 1976-06-01 | Rhodia, Inc. | Process for the preparation of α,β-unsaturated nitriles |
| EP0002743A1 (en) * | 1977-12-15 | 1979-07-11 | L. Givaudan & Cie Société Anonyme | Bicyclo (2.2.1)-hept-5-enes (anes) (I), process for their preparation, their use as perfumes and perfume compositions containing the bicyclic compounds (I) |
| US4728747A (en) * | 1985-01-03 | 1988-03-01 | Basf Aktiengesellschaft | Novel 2,3-disubstituted bicyclo(2.2.1)heptanes and heptenes, their preparation, and their use as scents |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008117254A1 (en) * | 2007-03-28 | 2008-10-02 | Firmenich Sa | Perfuming nitriles |
-
1972
- 1972-02-12 CH CH209772A patent/CH566969A5/xx not_active IP Right Cessation
-
1973
- 1973-01-17 NL NL7300692A patent/NL7300692A/xx unknown
- 1973-01-17 DE DE19732302219 patent/DE2302219A1/en active Pending
- 1973-02-08 JP JP1608873A patent/JPS4886849A/ja active Pending
- 1973-02-12 FR FR7304853A patent/FR2171427B1/fr not_active Expired
- 1973-02-12 GB GB680073A patent/GB1367060A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960923A (en) * | 1973-12-03 | 1976-06-01 | Rhodia, Inc. | Process for the preparation of α,β-unsaturated nitriles |
| EP0002743A1 (en) * | 1977-12-15 | 1979-07-11 | L. Givaudan & Cie Société Anonyme | Bicyclo (2.2.1)-hept-5-enes (anes) (I), process for their preparation, their use as perfumes and perfume compositions containing the bicyclic compounds (I) |
| US4728747A (en) * | 1985-01-03 | 1988-03-01 | Basf Aktiengesellschaft | Novel 2,3-disubstituted bicyclo(2.2.1)heptanes and heptenes, their preparation, and their use as scents |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS4886849A (en) | 1973-11-15 |
| FR2171427A1 (en) | 1973-09-21 |
| GB1367060A (en) | 1974-09-18 |
| NL7300692A (en) | 1973-08-14 |
| CH566969A5 (en) | 1975-09-30 |
| FR2171427B1 (en) | 1976-05-14 |
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