CH718647A2 - Process for the preparation of farnesylacetone. - Google Patents
Process for the preparation of farnesylacetone. Download PDFInfo
- Publication number
- CH718647A2 CH718647A2 CH00565/21A CH5652021A CH718647A2 CH 718647 A2 CH718647 A2 CH 718647A2 CH 00565/21 A CH00565/21 A CH 00565/21A CH 5652021 A CH5652021 A CH 5652021A CH 718647 A2 CH718647 A2 CH 718647A2
- Authority
- CH
- Switzerland
- Prior art keywords
- farnesylacetone
- farnesyl
- farnesylamine
- conversion
- double bond
- Prior art date
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- LTUMRKDLVGQMJU-IUBLYSDUSA-N farnesyl acetone Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)=O LTUMRKDLVGQMJU-IUBLYSDUSA-N 0.000 title claims abstract description 36
- LTUMRKDLVGQMJU-UHFFFAOYSA-N famesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O LTUMRKDLVGQMJU-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 3
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims description 34
- BDKQVCHNTAJNJR-UHFFFAOYSA-N 3,7,11-trimethyldodeca-2,6,10-trien-1-amine Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCN BDKQVCHNTAJNJR-UHFFFAOYSA-N 0.000 claims description 24
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims description 15
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- BJVUJIDTICYHLL-UHFFFAOYSA-N 1-chloro-3,7,11-trimethyldodeca-2,6,10-triene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCl BJVUJIDTICYHLL-UHFFFAOYSA-N 0.000 claims description 10
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 claims description 9
- 125000004030 farnesyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002585 base Substances 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- BJVUJIDTICYHLL-YFVJMOTDSA-N (2e,6e)-1-chloro-3,7,11-trimethyldodeca-2,6,10-triene Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCl BJVUJIDTICYHLL-YFVJMOTDSA-N 0.000 description 5
- -1 alkyl chloroformate Chemical compound 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BDKQVCHNTAJNJR-YFVJMOTDSA-N (2e,6e)-3,7,11-trimethyldodeca-2,6,10-trien-1-amine Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CN BDKQVCHNTAJNJR-YFVJMOTDSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 2
- JSNRRGGBADWTMC-NTCAYCPXSA-N trans-beta-farnesene Chemical compound CC(C)=CCC\C(C)=C\CCC(=C)C=C JSNRRGGBADWTMC-NTCAYCPXSA-N 0.000 description 2
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 description 1
- FOFMBFMTJFSEEY-YFVJMOTDSA-N (2e,6e)-1-bromo-3,7,11-trimethyldodeca-2,6,10-triene Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CBr FOFMBFMTJFSEEY-YFVJMOTDSA-N 0.000 description 1
- KOICZDDAVPYKKX-NCZFFCEISA-N (3e,7e)-4,8,12-trimethyltrideca-3,7,11-trien-1-ol Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCO KOICZDDAVPYKKX-NCZFFCEISA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- NRDQFWXVTPZZAZ-UHFFFAOYSA-N butyl carbonochloridate Chemical compound CCCCOC(Cl)=O NRDQFWXVTPZZAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium 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
- 239000000126 substance Substances 0.000 description 1
- 125000003299 trans-beta-farnesene group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- 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
- C07C45/63—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 introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Die vorliegende Erfindung ist ein Verfahren zur Herstellung von Farnesylaceton (1) welches die Kontrolle über die Konfiguration der Doppelbindung ermöglicht. Das Verfahren ist geeignet zur Herstellung von Farnesylaceton aus erneuerbaren Kohlenstoff-Quellen.The present invention is a process for the production of farnesylacetone (1) which enables control over the configuration of the double bond. The process is suitable for producing farnesylacetone from renewable carbon sources.
Description
[0001] Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Farnesylaceton. The present invention relates to a process for the production of farnesylacetone.
[0002] Farnesylaceton ist ein interessantes Ausgangs- oder Zwischenprodukt für die Herstellung neuer Moleküle in der Duftstoff-Forschung, insbesondere im Bereich der holzigen, Ambraartigen oder moschusartigen Duftstoffe. Farnesylacetone is an interesting starting material or intermediate for the production of new molecules in fragrance research, especially in the field of woody, ambergris-like or musky fragrances.
[0003] Das derzeit kommerziell erhältliche Farnesylaceton wird vor allem petrochemisch gewonnen. Um jedoch neue, kostengünstige und aus erneuerbaren Quellen erhältliche Duftstoffe entwickeln zu können, sind Ausgangsmaterialien aus erneuerbaren Kohlenstoff-Quellen, sowie geeignete Verfahren zu ihrer Umsetzung notwendig. Bei der Kohlenstoff-Quelle kann es sich z.B. um einen Zucker, oder um andere Kohlenstoffquelle wie ein Acetat oder Glycerol handeln. The currently commercially available farnesylacetone is mainly obtained petrochemically. However, in order to be able to develop new, inexpensive fragrances that are available from renewable sources, starting materials from renewable carbon sources and suitable processes for their conversion are necessary. The carbon source can be, for example, a sugar, or it can be another carbon source such as an acetate or glycerol.
[0004] Es ist daher eine Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung von Farnesylaceton bereitzustellen. Insbesondere ermöglicht dieses Verfahren eine Kontrolle über die Konfiguration der Doppelbindungen, vor allem über die Konfiguration der CC Doppelbindung nahe der funktionellen Gruppe. It is therefore an object of the present invention to provide a process for the production of farnesylacetone. In particular, this method allows control over the configuration of the double bonds, especially over the configuration of the CC double bond close to the functional group.
[0005] Die vorliegende Erfindung ist ein Verfahren zur Herstellung von Farnesylaceton (1) umfassend die folgenden Schritte: a) Bereitstellen von β-Farnesen (2) The present invention is a process for producing farnesylacetone (1) comprising the following steps: a) providing β-farnesene (2)
b) Umsetzung von β-Farnesen (2) zu Farnesylamin (3) b) Conversion of β-farnese (2) to farnesylamine (3)
c) Umsetzung von Farnesylamin (3) zu Farnesylchlorid (4) c) Conversion of farnesylamine (3) to farnesyl chloride (4)
d) Umsetzung von Farnesylchlorid (4) zu Farnesylalkylacetoacetat (5) und e) Umsetzung von Farnesylalkylacetoacetat (5) zu Farnesylaceton (1), wobei es sich bei den Resten R1und R2des Farnesylamins (3) um C1 bis C6 Alkylreste handelt, und wobei es sich bei dem Rest R3im Farnesylalkylacetoacetat (5) um einen C1 bis C3 Alkylrest handelt. d) Conversion of farnesyl chloride (4) to farnesyl alkyl acetoacetate (5) and e) Conversion of farnesyl alkyl acetoacetate (5) to farnesyl acetone (1), where the radicals R1 and R2 of the farnesylamine (3) are C1 to C6 alkyl radicals and the radical R3 in the farnesyl alkyl acetoacetate (5) is a C1 to C3 alkyl group is.
[0006] Das erfindungsgemässe Verfahren ist in Abbildung 1 schematisch dargestellt. The inventive method is shown in Figure 1 schematically.
[0007] Mit diesem Verfahren kann Farnesylaceton (1) in guten Ausbeuten ohne nennenswerte Isomerisierung der Doppelbindungen erhalten werden, insbesondere ohne Isomerisierung der CC-Doppelbindung an Position C5 in Farnesylaceton (1), die sich näher an der funktionellen Gruppe befindet, welche während des Verfahrens transformiert wird als die CC-Doppelbindung an Position C9. With this process, farnesylacetone (1) can be obtained in good yields without appreciable isomerization of the double bonds, in particular without isomerization of the CC double bond at position C5 in farnesylacetone (1), which is closer to the functional group which is present during the Process is transformed as the CC double bond at position C9.
[0008] Wenn in dieser Beschreibung für eine bestimmte Verbindung keine Doppelbindungskonfiguration angegeben ist, dann ist die Konfiguration entweder nicht spezifiziert oder bezieht sich auf ein Gemisch von Isomeren. Für eine bestimmte Konfiguration einer Verbindung werden die Präfixe E- und Z- verwendet, zum Beispiel (E)-2oder (5E,9E)-1. [0008] Where no double bond configuration is given for a particular compound in this specification, then the configuration is either unspecified or refers to a mixture of isomers. For a specific configuration of a connection, the prefixes E- and Z- are used, for example (E)-2 or (5E,9E)-1.
[0009] Wird zum Beispiel β-Farnesen (2) bzw. Farnesylamin (3) mit einer bestimmten Doppelbindungskonfiguration bereitgestellt oder hergestellt, so wird diese Konfiguration in den Zwischenprodukten sowie im resultierenden Farnesylaceton (1) beibehalten. Liegt β-Farnesen (2) bzw. Farnesylamin (3) als ein Gemisch von Doppelbindungsisomeren vor, so wird das resultierende Farnesylaceton (1) als ein Gemisch von Doppelbindungsisomeren mit einem entsprechenden Verhältnis erhalten. Das erfindungsgemässe Verfahren ist geeignet, um Farnesylaceton (1) mit einer gewünschten Doppelbindungskonfiguration zu erhalten, da die Konfiguration der Doppelbindungen während der gesamten Reaktionsfolge vom Ausgangsmaterial bzw. vom Zwischenprodukt Farnesylamin (3) bis zum Endprodukt erhalten bleibt. Das erfindungsgemässe Verfahren ist geeignet, um Farnesylaceton (1) mit einer beliebigen Doppelbindungskonfiguration bereitzustellen. Insbesondere ist es geeignet, um (5E,9E)-1bereitzustellen. So weisen zum Beispiel die Zwischenprodukte bei der Herstellung von (5E,9E)-1ebenfalls die E,E-Konfiguration der jeweiligen beiden Doppelbindungen auf, also (2E,6E)-Farnesylamin ((2E,6E)-3oder (E,E)-3), (2E,6E)-Farnesylchlorid ((2E,6E)-4oder (E,E)-4), und Farnesylalkylacetoacetat ((4E,8E)-5oder (E,E)-5). If, for example, β-farnesene (2) or farnesylamine (3) is provided or prepared with a specific double bond configuration, this configuration is retained in the intermediates and in the resulting farnesylacetone (1). When β-farnesene (2) or farnesylamine (3) is present as a mixture of double bond isomers, the resulting farnesylacetone (1) is obtained as a mixture of double bond isomers with a corresponding ratio. The process according to the invention is suitable for obtaining farnesylacetone (1) with a desired double bond configuration since the configuration of the double bonds is retained throughout the reaction sequence from the starting material or from the intermediate farnesylamine (3) to the end product. The process according to the invention is suitable for providing farnesylacetone (1) with any double bond configuration. In particular, it is suitable to provide (5E,9E)-1. For example, the intermediates in the preparation of (5E,9E)-1 also have the E,E configuration of the respective two double bonds, i.e. (2E,6E)-farnesylamine ((2E,6E)-3or (E,E) -3), (2E,6E)-farnesyl chloride ((2E,6E)-4 or (E,E)-4), and farnesyl alkyl acetoacetate ((4E,8E)-5 or (E,E)-5).
[0010] Das erfindungsgemässe Verfahren bietet Zugang zu Farnesylaceton (1) und insbesondere auch zu (5E,9E)-1aus erneuerbaren Kohlenstoff-Quellen zur Verwendung für die Herstellung von Duftstoffen. The inventive method provides access to farnesylacetone (1) and in particular to (5E,9E)-1 from renewable carbon sources for use in the manufacture of fragrances.
[0011] Das erfindungsgemässe Verfahren bietet ebenfalls die Möglichkeit, β-Farnesen (2) in Farnesylaceton (1) umzuwandeln, ohne das Zwischenprodukt Farnesol herstellen zu müssen. The inventive method also offers the possibility of converting β-farnesene (2) to farnesylacetone (1) without having to produce the intermediate farnesol.
[0012] In Schritt a) wird das Ausgangsmaterial β-Farnesen (2) bereitgestellt. In step a), the starting material β-farnesene (2) is provided.
[0013] β-Farnesen (2) kann entweder aus petrochemischen Ausgangssubstanzen hergestellt werden, oder aus erneuerbaren Rohstoffen durch ein biochemisches Verfahren mit Mikroorganismen. In einer Ausführungsform stammt das bereitgestellte Ausgangsmaterial aus erneuerbaren Rohstoffen und wurde mittels Biotransformation hergestellt. [0013] β-farnesene (2) can be produced either from petrochemical feedstocks or from renewable raw materials by a biochemical process using microorganisms. In one embodiment, the starting material provided originates from renewable raw materials and has been produced by means of biotransformation.
[0014] Vorteilhafterweise handelt es sich bei der Ausgangssubstanz um (E)-β-Farnesen ((E)-2, CAS-Nr. 18794-84-8), welches auch ein Bestandteil verschiedener ätherischer Öle ist. Advantageously, the starting substance is (E)-β-farnesene ((E)-2, CAS No. 18794-84-8), which is also a component of various essential oils.
[0015] In Schritt b) wird β-Farnesen (2) zu Farnesylamin (3) umgesetzt. Dazu wird z.B. β-Farnesen (2) mit einem Amin NHR1R2in Anwesenheit einer starken Base umgesetzt. In step b), β-farnesene (2) is converted to farnesylamine (3). For example, β-farnesene (2) is reacted with an amine NHR1R2 in the presence of a strong base.
[0016] Bei den Resten R1und R2des Amins bzw. des Farnesylamins (3) handelt es sich vorteilhafterweise um C1 bis C6 Alkylreste, z.B. um Ethyl, n-Propyl, iso-Propyl, n-Butyl, isoButyl oder tert-Butyl Reste, wobei die beiden Reste gleich oder unterschiedlich gewählt werden können. In einigen Ausführungsformen ist R1Methyl, Ethyl oder Propyl. In einigen Ausführungsformen ist R2Methyl, Ethyl oder Propyl. In einigen Ausführungsformen sind R1und R2jeweils Ethyl oder jeweils n-Propyl. The radicals R1 and R2 of the amine or farnesylamine (3) are advantageously C1 to C6 alkyl radicals, e.g. ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl radicals, where the two radicals can be chosen to be the same or different. In some embodiments, R1 is methyl, ethyl, or propyl. In some embodiments, R2 is methyl, ethyl, or propyl. In some embodiments, R 1 and R 2 are each ethyl or each n-propyl.
[0017] Bei der starken Base kann es sich um ein Reagenz handeln, welches ein Alkalimetall enthält, zB. Natrium, Lithium oder Kalium. In einigen Ausführungsformen ist die starke Base Natriummetall oder Lithiummetall. In anderen Ausführungsformen umfasst die starke Base Kaliumhydroxid oder Natriumhydroxid. Es kann sich bei der Base auch um eine Organolithiumverbindung handeln, z.B. Alkyllithium- (n-Butyllithium, sec-Butyllithium oder tert-Butyllithium) oder Aryllithium-Verbindungen. The strong base can be a reagent containing an alkali metal, eg. sodium, lithium or potassium. In some embodiments, the strong base is sodium metal or lithium metal. In other embodiments, the strong base includes potassium hydroxide or sodium hydroxide. The base can also be an organolithium compound such as alkyllithium (n-butyllithium, sec-butyllithium or tert-butyllithium) or aryllithium compounds.
[0018] In einigen Ausführungsformen wird Schritt b) ohne zusätzliches Lösungsmittel durchgeführt. In einigen Ausführungsformen wird Schritt b) in einem organischen Lösungsmittel oder in einem Gemisch organischer Lösungsmittel durchgeführt. Bei dem organischen Lösungsmittel kann es sich z.B. um Isopropylalkohol handeln. In some embodiments, step b) is carried out without additional solvent. In some embodiments, step b) is carried out in an organic solvent or in a mixture of organic solvents. For example, the organic solvent may be isopropyl alcohol.
[0019] Bei dieser Umsetzung wird die Konfiguration der Doppelbindung nahe der funktionellen Gruppe definiert. So wird z. B. unter den angegebenen Reaktionsbedingungen aus (E)-β-Farnesen ((E)-2) hauptsächlich (2E,6E)-Farnesylamin ((2E,6E)-3) erhalten. In this reaction, the configuration of the double bond is defined near the functional group. So e.g. B. obtained from (E)-β-farnesene ((E)-2) mainly (2E,6E)-farnesylamine ((2E,6E)-3) under the stated reaction conditions.
[0020] In Schritt c) wird Farnesylamin (3) in Farnesylchlorid (4) umgewandelt. Dazu wird z. B. das Farnesylamin (3) aus dem vorangehenden Schritt mit einem Alkylchloroformat (z.B. Methylchloroformat, Butylchloroformat) umgesetzt. In step c) farnesylamine (3) is converted to farnesyl chloride (4). For this z. B. the farnesylamine (3) from the previous step is reacted with an alkyl chloroformate (e.g. methyl chloroformate, butyl chloroformate).
[0021] Es wird keine nennenswerte Isomerisierung der Doppelbindungen beobachtet. No significant isomerization of the double bonds is observed.
[0022] Alternativ könnte das erfindungsgemässe Verfahren auch via Farnesylbromid oder -iodid geführt werden, anstelle des Farnesylchlorids(4). Alternatively, the inventive method could also be performed via farnesyl bromide or iodide, instead of farnesyl chloride (4).
[0023] Die Herstellung von (2E,6E)-Farnesylchlorid ((2E,6E)-4) aus (E)-β-Farnesen ((E)-2, (6E)-7,11-Dimethyl-3-methylidendodeca-1,6,10-trien, CAS-Nr. 18794-84-8) wird in WO 2019237005 beschrieben. The preparation of (2E,6E)-farnesyl chloride ((2E,6E)-4) from (E)-β-farnesene ((E)-2,(6E)-7,11-dimethyl-3-methylidenedodeca -1,6,10-triene, CAS No. 18794-84-8) is described in WO 2019237005.
[0024] In Schritt d) wird Farnesylchlorid (4) zu Farnesylalkylacetoacetat (5) umgesetzt. Hierzu wird es z.B. mit einem Alkylacetoacetat (z.B. Methylacetoacetat, Ethylacetoacetat) in Anwesenheit einer starken Base, wie z.B. K2CO3, NaH, NaOMe umgesetzt. In step d), farnesyl chloride (4) is converted to farnesyl alkyl acetoacetate (5). To do this, it is reacted, for example, with an alkyl acetoacetate (e.g. methyl acetoacetate, ethyl acetoacetate) in the presence of a strong base, such as K2CO3, NaH, NaOMe.
[0025] Es wird keine nennenswerte Isomerisierung der Doppelbindungen beobachtet. No significant isomerization of the double bonds is observed.
[0026] In Schritt e) wird Farnesylalkylacetoacetat (5) zu Farnesylaceton (1) umgewandelt. Dazu wird das zuvor erhaltene Farnesylalkylacetoacetat (5) im Wesentlichen in Anwesenheit einer Base in einer wässrigen oder einer alkoholischen Lösung unter Rückfluss erhitzt. In step e) farnesyl alkyl acetoacetate (5) is converted to farnesyl acetone (1). To do this, the previously obtained farnesyl alkyl acetoacetate (5) is refluxed in an aqueous or an alcoholic solution essentially in the presence of a base.
[0027] Es wird keine nennenswerte Isomerisierung der Doppelbindungen beobachtet. No significant isomerization of the double bonds is observed.
[0028] In einer Ausführungsform werden die Schritte d) und e) direkt hintereinander ohne Reinigung des Zwischenprodukts durchgeführt. In one embodiment, steps d) and e) are carried out in direct succession without purification of the intermediate.
[0029] In einer Ausführungsform ist das E/Z-Verhältnis der Doppelbindung an C5 von Farnesylaceton (1), welches durch das erfindungsgemässe Verfahren erhalten wurde, größer als 80:20, insbesondere größer als 85:15, oder größer als 90:10. In one embodiment, the E/Z ratio of the double bond at C5 of farnesylacetone (1) obtained by the process according to the invention is greater than 80:20, in particular greater than 85:15, or greater than 90:10 .
[0030] In einer Ausführungsform ist (5E,9E)-1, welches durch das erfindungsgemässe Verfahren erhalten wurde, zu 50 oder mehr Prozent im Isomerengemisch vorhanden, insbesondere zu 75 Prozent, insbesondere zu 85 Prozent oder zu 90 Prozent oder mehr. In one embodiment, (5E,9E)-1, which was obtained by the process according to the invention, is present in the isomer mixture to an extent of 50 percent or more, in particular 75 percent, in particular 85 percent or 90 percent or more.
[0031] Reines, oder hoch angereichertes (5E,9E)-1ist z.B. als Ausgangsstoff für die Synthese von Homofarnesol von besonderem Interesse. Pure or highly enriched (5E,9E)-1 is of particular interest, for example, as a starting material for the synthesis of homofarnesol.
[0032] Die vorliegende Erfindung wird durch die folgenden, nicht einschränkenden Beispiele weiter veranschaulicht: The present invention is further illustrated by the following non-limiting examples:
Beispiel 1: Synthese von (5E,9E)-1Example 1: Synthesis of (5E,9E)-1
[0033] (E,E)-N,N-Dipropylfarnesylamin ((E,E)-3a) wurde aus (E)-β-Farnesen ((E)-2) gemäss WO 2019237005 erhalten. (E,E)-N,N-dipropylfarnesylamine ((E,E)-3a) was obtained from (E)-β-farnesene ((E)-2) according to WO 2019237005.
a) (E,E)-Farnesylchlorid ((E,E)-4)a) (E,E)-farnesyl chloride ((E,E)-4)
[0034] (E,E)-N,N-Dipropylfarnesylamin (100 g, 327 mmol) wurde in 150 mL Methyl-tert-butylether (MTBE) vorgelegt. Eine Lösung von Methylchloroformat (34 g, 360 mmol) in 100 mL MTBE wurde zugetropft, wobei die Temperatur der Reaktionsmischung unter 25 °C gehalten wurde. (E,E)-N,N-dipropylfarnesylamine (100 g, 327 mmol) was placed in 150 mL of methyl tert-butyl ether (MTBE). A solution of methyl chloroformate (34 g, 360 mmol) in 100 mL of MTBE was added dropwise, keeping the temperature of the reaction mixture below 25 °C.
[0035] Es wurde während 16 h gerührt, das Lösungsmittel wurde am Rotationsverdampfer entfernt. Das Nebenprodukt Methyldipropylcarbamat wurde mittels Vakuum-Destillation entfernt, und (E,E)-Farnesylchlorid wurde in Form einer hellbraunen Flüssigkeit erhalten (73.5 g, 95% Ausbeute). It was stirred for 16 h, the solvent was removed on a rotary evaporator. The by-product methyl dipropyl carbamate was removed via vacuum distillation and (E,E)-farnesyl chloride was obtained as a light brown liquid (73.5 g, 95% yield).
[0036] 1H NMR (400 MHz, CDCl3): δ ppm 5.40-5.50 (m, 1H), 5.06-5.13 (m, 2H), 4.11 (d, J= 7.5Hz, 2H), 2.02-2.19 (m, 6H), 1.97-2.03 (m, 2H), 1.74 (bs, 3H), 1.69 (bs, 3H), 1.61 (bs, 6H). 13C NMR (100 MHz, CDCI3): δ ppm 142.7, 135.6, 131.3, 124.3, 123.4, 120.3, 41.1, 39.7, 39.4, 26.7, 26.1, 25.7, 17.7, 16.1, 16.0. 1H NMR (400MHz, CDCl3 ): δ ppm 5.40-5.50 (m, 1H), 5.06-5.13 (m, 2H), 4.11 (d, J=7.5Hz, 2H), 2.02-2.19 (m, 6H), 1.97-2.03 (m, 2H), 1.74 (bs, 3H), 1.69 (bs, 3H), 1.61 (bs, 6H). 13C NMR (100MHz, CDCl3 ): δppm 142.7, 135.6, 131.3, 124.3, 123.4, 120.3, 41.1, 39.7, 39.4, 26.7, 26.1, 25.7, 17.7, 16.1, 16.0.
b) (E,E)-Farnesylaceton ((E,E)-1)b) (E,E)-farnesylacetone ((E,E)-1)
[0037] (E,E)-Farnesylchlorid (73.5 g, 238 mmol) wurde in 650 mL Aceton vorgelegt. Kaliumcarbonat (49.4g, 357 mmol) wurde hinzugegeben, und die Reaktionsmischung wurde auf 50 °C erwärmt. Bei 50 °C wurde Ethylacetoacetat (46.5 g, 357 mmol) hinzugegeben. Die Reaktionsmischung wurde während 4.5 h bei 50 °C gerührt und anschliessend auf Raumtemperatur abgekühlt. Feststoffe wurde abfiltriert, das Lösungsmittel wurde am Rotationsverdampfer entfernt und das Rohprodukt wurde als braune Flüssigkeit erhalten. (E,E)-farnesyl chloride (73.5 g, 238 mmol) was placed in 650 mL acetone. Potassium carbonate (49.4g, 357mmol) was added and the reaction mixture was heated to 50°C. At 50°C, ethyl acetoacetate (46.5 g, 357 mmol) was added. The reaction mixture was stirred at 50° C. for 4.5 h and then cooled to room temperature. Solids were filtered off, the solvent was removed on the rotary evaporator and the crude product was obtained as a brown liquid.
[0038] Das Rohprodukt wurde in 300 mL Ethanol gelöst. Eine Lösung von KOH (40.1 g, 714 mmol) in 100 mL Ethanol wurde hinzugegeben, und die Reaktionsmischung wurde unter Rückfluss während 3 h gerührt. Anschliessend wurde die Reaktionsmischung zunächst auf Raumtemperatur und dann weiter mit einem Eisbad abgekühlt. Eine Lösung von 10 M HCl (71 mL) in 100 mL Wasser wurde hinzugegeben (pH 1 wurde eingestellt). Nach Zugabe von 100 mL EtOAc und 100 mL Wasser wurden die Phasen getrennt. Die organische Phase wurde mit 100 mL wässriger NaHCO3, 100 mL Wasser und 100 mL gesättigter NaOH-Lösung gewaschen, über MgSO4getrocknet, filtiert, und das Lösungsmittel wurde am Rotationsverdampfer entfernt. (E,E)-Farnesylaceton wurde als braune Flüssigkeit (75 g, 96% Ausbeute) isoliert und nicht weiter gereinigt. The crude product was dissolved in 300 mL ethanol. A solution of KOH (40.1 g, 714 mmol) in 100 mL of ethanol was added and the reaction mixture was stirred under reflux for 3 h. The reaction mixture was then cooled first to room temperature and then further with an ice bath. A solution of 10 M HCl (71 mL) in 100 mL water was added (pH 1 was adjusted). After adding 100 mL EtOAc and 100 mL water, the phases were separated. The organic phase was washed with 100 mL aqueous NaHCO3, 100 mL water and 100 mL saturated NaOH solution, dried over MgSO4, filtered, and the solvent was removed on a rotary evaporator. (E,E)-Farnesylacetone was isolated as a brown liquid (75 g, 96% yield) and not further purified.
[0039] 1H NMR (400 MHz, CDCI3): δ ppm 5.06-5.12 (m, 3H), 2.43-2.47 (m, 2H), 2.23-2.31 (m, 2H), 2.13 (s, 3H), 2.05-2.11 (m, 4H), 1.97-2.00 (m, 3H), 1.68 (s, 4H), 1.61 (s, 3H), 1.59-1.60 (m, 6H). 13C NMR (100 MHz, CDCl3): δ ppm 208.6, 136.2, 134.9, 131.1, 124.3, 123.9, 122.4, 43.6, 39.6, 39.5, 29.8, 26.7, 26.4, 25.6, 22.4, 17.6, 15.9, 15.9. 1H NMR (400MHz, CDCl 3 ): δ ppm 5.06-5.12 (m, 3H), 2.43-2.47 (m, 2H), 2.23-2.31 (m, 2H), 2.13 (s, 3H), 2.05- 2.11 (m, 4H), 1.97-2.00 (m, 3H), 1.68 (s, 4H), 1.61 (s, 3H), 1.59-1.60 (m, 6H). 13C NMR (100MHz, CDCl3): δppm 208.6, 136.2, 134.9, 131.1, 124.3, 123.9, 122.4, 43.6, 39.6, 39.5, 29.8, 26.7, 26.4, 25.6, 22.4, 17.9.6, 15.9.6, 15.9.6
[0040] MS (EI, 70 eV): 262 (1, [M]+·), 136 (48), 135 (32), 125 (24), 107 (38), 95 (23), 93 (27), 81 (43), 69 (100), 43 (78), 41 (39). MS (EI, 70 eV): 262 (1, [M]+ ), 136 (48), 135 (32), 125 (24), 107 (38), 95 (23), 93 (27 ), 81 (43), 69 (100), 43 (78), 41 (39).
[0041] Ausgehend von (E,E)-N,N-Dipropylfarnesylamin wurde (E,E)-Farnesylaceton erhalten. Andere Doppelbindungsisomere wurden nicht in nennenswerten Mengen gebildet. Starting from (E,E)-N,N-dipropylfarnesylamine, (E,E)-farnesylacetone was obtained. Other double bond isomers were not formed in significant amounts.
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