WO2007054429A1 - Process for the production of (10/11/12)-pentadecen-15-olide starting from 11- and/or 12-pentadecen-15-olide - Google Patents
Process for the production of (10/11/12)-pentadecen-15-olide starting from 11- and/or 12-pentadecen-15-olide Download PDFInfo
- Publication number
- WO2007054429A1 WO2007054429A1 PCT/EP2006/067748 EP2006067748W WO2007054429A1 WO 2007054429 A1 WO2007054429 A1 WO 2007054429A1 EP 2006067748 W EP2006067748 W EP 2006067748W WO 2007054429 A1 WO2007054429 A1 WO 2007054429A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pentadecen
- olide
- chloride
- rhodium
- palladium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- AGZBJJSLDGWKSU-UHFFFAOYSA-N 1-oxacyclohexadec-13-en-2-one Chemical compound O=C1CCCCCCCCCCC=CCCO1 AGZBJJSLDGWKSU-UHFFFAOYSA-N 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 64
- 229910052703 rhodium Inorganic materials 0.000 claims description 33
- 239000010948 rhodium Substances 0.000 claims description 33
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 31
- 229910052763 palladium Inorganic materials 0.000 claims description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 12
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 12
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 7
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 3
- 241000694408 Isomeris Species 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- -1 undecylenic acid hexenol ester Chemical class 0.000 description 6
- 241000402754 Erythranthe moschata Species 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- MTTKFVBUVGIIIF-UHFFFAOYSA-N 1-oxacyclohexadec-11-en-2-one Chemical compound O=C1CCCCCCCCC=CCCCCO1 MTTKFVBUVGIIIF-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- GVLGAFRNYJVHBC-UHFFFAOYSA-N hydrate;hydrobromide Chemical compound O.Br GVLGAFRNYJVHBC-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- JHEPBQHNVNUAFL-AATRIKPKSA-N (e)-hex-1-en-1-ol Chemical compound CCCC\C=C\O JHEPBQHNVNUAFL-AATRIKPKSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- QJOTXZRMMLQXTG-UHFFFAOYSA-N 14a-hydroperoxy-2,3,4,4a,5,6,7,8,9,10,11,12,13,14-tetradecahydrocyclododeca[b]pyran Chemical compound C1CCCCCCCCCC2CCCOC21OO QJOTXZRMMLQXTG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VJRVVBJENDJBLJ-UHFFFAOYSA-N 3,4,5,6,7,8,9,10,11,12,13,14-dodecahydro-2h-cyclododeca[b]pyran Chemical compound C1CCCCCCCCCC2=C1CCCO2 VJRVVBJENDJBLJ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000016477 Taralea oppositifolia Nutrition 0.000 description 1
- 241001358109 Taralea oppositifolia Species 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- DWRLRVWRQLAHEW-UHFFFAOYSA-N bicyclo[2.2.1]hepta-2,5-diene hydrochloride Chemical compound Cl.C1=CC2C=CC1C2 DWRLRVWRQLAHEW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- XWDKRVSSHIJNJP-UHFFFAOYSA-N carbon monoxide;iridium Chemical group [Ir].[Ir].[Ir].[Ir].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] XWDKRVSSHIJNJP-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AGCOMFFHXJMNLN-UHFFFAOYSA-N dichloromethane;dihydrochloride Chemical compound Cl.Cl.ClCCl AGCOMFFHXJMNLN-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- UTSOXZIZVGUTCF-UHFFFAOYSA-N hydrate;hydroiodide Chemical compound O.I UTSOXZIZVGUTCF-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000005872 self-metathesis reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- UBKOPMLYPZOPAX-UHFFFAOYSA-N tricyclohexylphosphanium;chloride Chemical compound Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1 UBKOPMLYPZOPAX-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- CUGZEDSDRBMZMY-UHFFFAOYSA-N trihydrate;hydrochloride Chemical compound O.O.O.Cl CUGZEDSDRBMZMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
Definitions
- the present invention relates to a process for the production of a mixture of (10/1 1/12)-pentadecen-15-olide starting from 11 - and/or 12-pentadecen-15-olide.
- the compounds 1 1-pentadecen-15-olide and 12-pentadecen-15-olide and mixtures thereof are known and important musk fragrances. Both the particular (E) and (Z) forms and the mixtures thereof are here also of interest from the point of view of odour. EP 0 424 787 describes the odorous properties of these substances. It is likewise known that 15- pentadecanolide (15-hydroxypentadecanoic acid lactone), which is likewise usable as a musk fragrance, may be obtained by means of hydrogenation from 1 1 (12)-pentadecen-15-olides.
- (1 1/12)-Pentadecen-15-olides may advantageously be produced starting from 13-oxabicyclo[10.4.0]hexadec-1 (12)-ene (DDP, see for example US 3,856,815).
- DDP 13-oxabicyclo[10.4.0]hexadec-1 (12)-ene
- 1 -Hydroperoxy-16-oxabicyclo[10.4.0]hexadecane DDP-hydroperoxide, DDP- OOH
- DDP- OOH is obtained by acid-catalysed addition of hydrogen peroxide onto DDP.
- DDP- OOH is cleaved to form the macrocyclic ring. This cleavage is usually performed in the presence of catalysts such as Cu(OAc) 2 (see for example EP 1 375 491 or WO 2005/035519) and optionally FeSO 4 .
- US 4,490,404 describes the production of 10-pentadecen-15-olide. Starting from undecylenic acid methyl ester and hexenol, the corresponding undecylenic acid hexenol ester is produced, which, after intramolecular metathesis, yields 10- pentadecen-15-olide. 10-Pentadecen-15-olide (with E or Z configuration) is distinguished by a sweet, coumarin-like, animal musk odour, which is in part combined with tonka features.
- each of the double bond isomers 10-, 11 - or 12-pentadecen-15-olide may here assume the form of the E and/or Z isomer.
- the mixtures of 10-, 11 - and 12-pentadecen-15-olide with any desired configuration at the particular double bond (E or Z) are hereinafter denoted (E,Z)-10,11 ,12-pentadecen-15-olide.
- a simple and efficient process is accordingly sought for the production of a mixture of (10/1 1/12)-pentadecen-15-olides (respectively having E and/or Z configuration), which comprises all the characteristic features of the musk odour of the individual isomers and is furthermore suitable for large scale industrial production.
- an isomer mixture of (10/11/12)-pentadecen- 15-olides may simply be obtained by isomerising 1 1- and/or 12-pentadecen-15- olide.
- the corresponding reaction is shown diagrammatically below for the 11- /12-pentadecen-15-olide isomer mixture as starting material (educt): in the starting material, each of the introduced 11- and/or 12-pentadecen-15-olides may assume the form of the E and/or Z isomer.
- the present invention accordingly relates to a process for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, comprising the following step:
- An (E 1 Z)-(1 1/12)-pentadecen-15-olide isomer mixture is preferably introduced into the isomerisation.
- the resultant (E 1 Z)- (10/1 1/12)-pentadecen-15-olide isomer mixture regularly comprises a proportion of at least 5 wt.% of (E 1 Z)-I O-pentadecen-15-olide, relative to the total quantity of (E 1 Z)-I O-, (E 1 Z)-H- and (E 1 Z)-12-pentadecen-15-olide.
- the educt to be introduced into the isomerisation already comprises (E 1 Z)-I O-pentadecen-15- olide, with this however preferably not being the case, the corresponding quantity of (E 1 Z)-I O-pentadecen-15-olide is not included in the calculation.
- Isomer mixtures in which the proportion of (E 1 Z)-I O-pentadecen-15-olide is in the range from 5-20 wt.%, relative to the total quantity of (E 1 Z)-I O-, (E 1 Z)-H- and (E 1 Z)-12- pentadecen-15-olide, are particularly valuable from the point of view of odour.
- the process according to the invention is preferably performed in such a manner that at least a yield of 3% of (E 1 Z)-10-pentadecen-15-olide is obtained, the product mixture still additionally comprising at least 40 wt.% of (E 1 Z)-I O-, (E 1 Z)- 1 1- and (E 1 Z)-12-pentadecen-15-olides, relative to the introduced quantity of (E 1 Z)-H- and (E 1 Z)-12-pentadecen-15-olide.
- the following thus preferably applies:
- n(educt10) means the quantity of (E 1 Z)-10-pentadecen-15-olide in the educt mixture
- n(educt1 1 ) means the quantity of (E 1 Z)-11-pentadecen-15-olide in the educt mixture
- n(educt12) means the quantity of (E,Z)-12-pentadecen-15-olide in the educt mixture
- n(producti ⁇ ) means the quantity of (E 1 Z)-I O-pentadecen-15-olide in the product mixture
- n(product1 1 ) means the quantity of (E 1 Z)-11-pentadecen-15-olide in the product mixture
- n(product12) means the quantity of (E 1 Z)-12-pentadecen-15-olide in the product mixture
- the process according to the invention is preferably performed in such a manner that the (E 1 Z)-H- and/or (E 1 Z)-12-pentadecen-15-olide is brought into contact with
- the resultant (E 1 Z)-10,11 ,12-pentadecen-15-olide isomer mixture conventionally contains 5-15 wt. % of (E 1 Z)-I O-pentadecen-15-olide (wherein any (E 1 Z)-I O-pentadecen-15- olide already present in the educt mixture is not included in the calculation), 4-40 wt. % of (E 1 Z)-11-pentadecen-15-olide and 30-50 wt.% of (E 1 Z)-12-pentadecen- 15-olide isomers, in each case relative to the total quantity of the stated isomers.
- a reaction according to the invention using a catalyst containing an element of subgroup VIII results in only small quantities of other double bond isomers, lsomerisation with a random distribution of the double bond isomers is not observed.
- catalysts comprising an element of subgroup VIII are used as catalysts for the isomerisation, said elements in particular comprise ruthenium, rhodium, palladium, osmium, iridium and platinum. It is particularly preferred to use ruthenium, rhodium, palladium and iridium as the element of subgroup VIII in a or as the catalyst for the isomerisation reaction.
- the stated elements of subgroup VIII may be used as catalyst in the elemental, metallic form, in which case they are generally applied onto a support.
- Support materials such as activated carbon, aluminium oxide or silicon oxide are preferred for this purpose.
- concentration of the elemental catalyst present in metallic form on the support material is here preferably between 5 and 10 wt.%, relative to the weight of the support material.
- the elements of subgroup VIII are preferably used in a form complexed with ligands.
- the (optionally complexed) elements of subgroup VIII are generally present formally in zero-valent form or bearing a single, double or triple positive charge.
- Counterions which may be used are, for example, chloride, bromide, iodide, sulfate, nitrate, sulfonate, or borate.
- Suitable ligands are, for example, acetonitrile, benzonitrile, diethyl ether, carbon monoxide, tetrahydrofuran, hydrogen, amines, ketones, phosphanes, ethyl acetate, dimethyl sulfoxide, dimethylformamide or hexamethylphosphoric acid triamide.
- Rhodium catalysts The following catalysts may be mentioned by way of example: Rhodium catalysts:
- ruthenium(lll) bromide hydrate ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(lll) iodide, ruthenium carbonyl, ruthenium(l) acetate polymer, ruthenium(lll) acetonylacetonate, ruthenium(ll)-(1 ,5-cyclooctadiene) chloride polymer, ruthenium(ll)-tris-(triphenylphosphine) chloride, ruthenium(ll) tricarbonyl chloride dimer, ruthenium(ll) carbonyldihydrido-tris-(triphenylphosphine), ruthenium(lll) 2,4-pentanedionate,
- catalysts are rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(l)-bis-(triphenylphosphine)carbonyl chloride, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(ll)-tris-(triphenylphosphine) chloride, iridium(l)-bis-(triphenylphosphine)carbonyl chloride, palladium(ll)-bis- (benzonitrile) chloride, and palladium, preferably in the form of palladium on activated carbon.
- the isomerisation catalysed by such a metal catalyst is preferably performed in the temperature range from 40 to 250°C, longer reaction times being required at lower temperatures and, in particular at higher temperatures, decomposition reactions possibly occurring to a certain extent.
- a particularly preferred temperature range is between 150 and 230°C.
- Isomerisation is performed preferably using quantities or concentrations of catalyst of at least 0.03 wt.%, preferred concentrations are in the range from
- the support material is here not regarded as a constituent of the catalyst. It goes without saying that the catalyst in turn preferably contains an element of subgroup VIII; the above explanations regarding preferred catalysts also apply in connection with the preferred concentrations.
- the isomerisation according to the invention which is preferably catalysed by one of the above-stated catalysts, may be performed not only using an inert solvent such as for example toluene, xylene, cyclohexane but also without solvent, the latter variant being particularly preferred.
- an inert solvent such as for example toluene, xylene, cyclohexane but also without solvent, the latter variant being particularly preferred.
- reaction conditions catalyst: ruthenium(ll)-tris-(triphenylphosphine) chloride (0.3 wt.%), no solvent; temperature: 170°C, reaction time: 16 hours
- catalyst palladium on activated carbon (type 87L Paste, source: Johnson Matthey Catalysts) (Pd content: 5 %, water content: 58.9 %, corresponding to a Pd concentration of 2.055 wt.%); no solvent; temperature: 220°C, reaction time: 8 hours
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process is described for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, which process comprises the following step: partial isomerisation of (E1Z)-H - and/or (E,Z)-12-pentadecen-15-olide, such that the (E1Z)-(10/1 1/12)-pentadecen-15-olide isomer mixture is obtained.
Description
Symrise GmbH & Co. KG Mϋhlenfeldstraβe 1 , 37603 Holzminden
Process for the production of (10/11/12)-pentadecen-15-olide starting from 11- and/or 12-pentadecen-15-olide
The present invention relates to a process for the production of a mixture of (10/1 1/12)-pentadecen-15-olide starting from 11 - and/or 12-pentadecen-15-olide.
The compounds 1 1-pentadecen-15-olide and 12-pentadecen-15-olide and mixtures thereof ((1 1/12)-pentadecen-15-olides) are known and important musk fragrances. Both the particular (E) and (Z) forms and the mixtures thereof are here also of interest from the point of view of odour. EP 0 424 787 describes the odorous properties of these substances. It is likewise known that 15- pentadecanolide (15-hydroxypentadecanoic acid lactone), which is likewise usable as a musk fragrance, may be obtained by means of hydrogenation from 1 1 (12)-pentadecen-15-olides.
(1 1/12)-Pentadecen-15-olides may advantageously be produced starting from 13-oxabicyclo[10.4.0]hexadec-1 (12)-ene (DDP, see for example US 3,856,815). 1 -Hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (DDP-hydroperoxide, DDP- OOH) is obtained by acid-catalysed addition of hydrogen peroxide onto DDP. In
a second step in the synthesis to yield the 1 1 (12)-pentadecen-15-olides, DDP- OOH is cleaved to form the macrocyclic ring. This cleavage is usually performed in the presence of catalysts such as Cu(OAc)2 (see for example EP 1 375 491 or WO 2005/035519) and optionally FeSO4.
US 4,490,404 describes the production of 10-pentadecen-15-olide. Starting from undecylenic acid methyl ester and hexenol, the corresponding undecylenic acid hexenol ester is produced, which, after intramolecular metathesis, yields 10- pentadecen-15-olide. 10-Pentadecen-15-olide (with E or Z configuration) is distinguished by a sweet, coumarin-like, animal musk odour, which is in part combined with tonka features.
Mixtures of 10-, 11 - and 12-pentadecen-15-olide are musk fragrance compositions which are of great interest from the point of view of odour. In such a mixture, each of the double bond isomers 10-, 11 - or 12-pentadecen-15-olide may here assume the form of the E and/or Z isomer. The mixtures of 10-, 11 - and 12-pentadecen-15-olide with any desired configuration at the particular double bond (E or Z) are hereinafter denoted (E,Z)-10,11 ,12-pentadecen-15-olide.
A simple and efficient process is accordingly sought for the production of a mixture of (10/1 1/12)-pentadecen-15-olides (respectively having E and/or Z configuration), which comprises all the characteristic features of the musk odour of the individual isomers and is furthermore suitable for large scale industrial production.
It has surprisingly been found that an isomer mixture of (10/11/12)-pentadecen- 15-olides may simply be obtained by isomerising 1 1- and/or 12-pentadecen-15- olide. The corresponding reaction is shown diagrammatically below for the 11- /12-pentadecen-15-olide isomer mixture as starting material (educt): in the starting material, each of the introduced 11- and/or 12-pentadecen-15-olides may assume the form of the E and/or Z isomer.
The present invention accordingly relates to a process for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, comprising the following step:
partial isomerisation of (E1Z)-H- and/or (E1Z)-12-pentadecen-15-olide, such that the (E1Z)-(10/1 1/12)-pentadecen-15-olide isomer mixture is obtained.
An (E1Z)-(1 1/12)-pentadecen-15-olide isomer mixture, as is obtainable for example according to EP 1 375 491 or WO 2005/035519, is preferably introduced into the isomerisation.
While isomerisation reactions of aliphatic olefins, such as for example allyl rearrangements, are comprehensively described in the literature, there are no references in the literature to shifting double bonds in macrocyclic ring systems by just one carbon atom.
The Journal of the Chemical Society, 1963, 4091-4096 describes a double bond isomerisation with triethylborane at 200°C for macrocyclic alkadienes with a ring size of 12 to 22 ring atoms. However, under these conditions, a double bond isomer mixture is obtained which has a random distribution of the theoretically possible double bond isomers. In the Journal of the Chemical Society, 1965, 3118-3126, the same authors also report a random product distribution on the isomerisation of macrocyclic alkadienes with potassium tert.-butylate.
The Journal of the American Chemical Society, 1976, 98, 7102-7104 has described for α-alkyl-substituted cycloalkenones with 6 to 8 ring atoms a migration of the double bond over the ring to form the more stable α,β- unsaturated isomers by 3 hours' heating with rhodium(lll) chloride trihydrate.
It is utterly surprising and unexpected that, starting from (E1Z)-1 1 ,12-pentadecen- 15-olides, a selective shift of the double bond by just one or two carbon atoms is obtained. In the process according to the invention, the resultant (E1Z)- (10/1 1/12)-pentadecen-15-olide isomer mixture regularly comprises a proportion of at least 5 wt.% of (E1Z)-I O-pentadecen-15-olide, relative to the total quantity of (E1Z)-I O-, (E1Z)-H- and (E1Z)-12-pentadecen-15-olide. If the educt to be introduced into the isomerisation already comprises (E1Z)-I O-pentadecen-15- olide, with this however preferably not being the case, the corresponding quantity of (E1Z)-I O-pentadecen-15-olide is not included in the calculation. Isomer mixtures in which the proportion of (E1Z)-I O-pentadecen-15-olide is in the range from 5-20 wt.%, relative to the total quantity of (E1Z)-I O-, (E1Z)-H- and (E1Z)-12- pentadecen-15-olide, are particularly valuable from the point of view of odour.
The process according to the invention is preferably performed in such a manner that at least a yield of 3% of (E1Z)-10-pentadecen-15-olide is obtained, the product mixture still additionally comprising at least 40 wt.% of (E1Z)-I O-, (E1Z)- 1 1- and (E1Z)-12-pentadecen-15-olides, relative to the introduced quantity of (E1Z)-H- and (E1Z)-12-pentadecen-15-olide. The following thus preferably applies:
A. [n(productiθ) - n(educt10) + n(productH ) + n(product12)] : [n(educt1 1 ) + n(educt12)] > 0.4
and simultaneously
B. [n(productiθ) - n(educt10)] : [n(educt1 1 ) + n(educt12)] > 0.03.
In the above inequalities:
n(educt10) means the quantity of (E1Z)-10-pentadecen-15-olide in the educt mixture n(educt1 1 ) means the quantity of (E1Z)-11-pentadecen-15-olide in the educt mixture n(educt12) means the quantity of (E,Z)-12-pentadecen-15-olide in the educt mixture
n(producti θ) means the quantity of (E1Z)-I O-pentadecen-15-olide in the product mixture n(product1 1 ) means the quantity of (E1Z)-11-pentadecen-15-olide in the product mixture n(product12) means the quantity of (E1Z)-12-pentadecen-15-olide in the product mixture
The process according to the invention is preferably performed in such a manner that the (E1Z)-H- and/or (E1Z)-12-pentadecen-15-olide is brought into contact with
(i) a catalyst containing an element of subgroup VIII in such a manner
that it partially isomerises to form the (E1Z)-(10/11/12)-pentadecen-15-olide isomer mixture. When the stated catalyst is used, the yields and product mixtures characterised by the above inequalities A and B may particularly straightforwardly be obtained; the person skilled in the art can determine by means of a few preliminary tests how the process conditions (in particular reaction temperature and reaction time) should be adjusted in order to satisfy the above inequalities.
When a catalyst containing an element of subgroup VIII is used, the resultant (E1Z)-10,11 ,12-pentadecen-15-olide isomer mixture conventionally contains 5-15 wt. % of (E1Z)-I O-pentadecen-15-olide (wherein any (E1Z)-I O-pentadecen-15- olide already present in the educt mixture is not included in the calculation), 4-40 wt. % of (E1Z)-11-pentadecen-15-olide and 30-50 wt.% of (E1Z)-12-pentadecen- 15-olide isomers, in each case relative to the total quantity of the stated isomers. A reaction according to the invention using a catalyst containing an element of subgroup VIII results in only small quantities of other double bond isomers, lsomerisation with a random distribution of the double bond isomers is not observed.
If catalysts comprising an element of subgroup VIII are used as catalysts for the isomerisation, said elements in particular comprise ruthenium, rhodium,
palladium, osmium, iridium and platinum. It is particularly preferred to use ruthenium, rhodium, palladium and iridium as the element of subgroup VIII in a or as the catalyst for the isomerisation reaction.
The stated elements of subgroup VIII may be used as catalyst in the elemental, metallic form, in which case they are generally applied onto a support. Support materials such as activated carbon, aluminium oxide or silicon oxide are preferred for this purpose. The concentration of the elemental catalyst present in metallic form on the support material is here preferably between 5 and 10 wt.%, relative to the weight of the support material.
In order to enhance activity and/or selectivity, the elements of subgroup VIII are preferably used in a form complexed with ligands. In the transition metal compounds, the (optionally complexed) elements of subgroup VIII are generally present formally in zero-valent form or bearing a single, double or triple positive charge. Counterions which may be used are, for example, chloride, bromide, iodide, sulfate, nitrate, sulfonate, or borate. Suitable ligands are, for example, acetonitrile, benzonitrile, diethyl ether, carbon monoxide, tetrahydrofuran, hydrogen, amines, ketones, phosphanes, ethyl acetate, dimethyl sulfoxide, dimethylformamide or hexamethylphosphoric acid triamide.
In summary, preferred processes according to the invention using a catalyst containing an element of subgroup VIII are those in which the element of subgroup VIII is present
(a) in elemental form,
(b) in complexed or uncomplexed form as a salt formally having an oxidation number of one to three,
or
(c) as a complex compound in which it is formally zero-valent.
The following catalysts may be mentioned by way of example:
Rhodium catalysts:
rhodium(lll) bromide hydrate, rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(lll) iodide hydrate, rhodium(lll) nitrate, rhodium(lll) phosphate, rhodium(lll) sulfate, rhodium(ll) acetate dimer, rhodium(lll) acetonylacetonate, rhodium(l)-bis-(1 ,5-cyclooctadiene) tetrafluoroborate hydrate, rhodium(l)-bis-(1 ,5- cyclooctadiene) acetylacetonate, rhodium(l)-bis-(1 ,5-cyclooctadiene) chloride dimer, rhodium(l)-bis-(1 ,5-cyclooctadiene) trifluoromethanesulfonate dimer, rhodium(l)-[1 ,4-bis-(diphenylphosphino)-butane]-(1 c,5c)-cyclooctadiene) tetrafluoroborate, rhodium(l)-[1 ,4-bis-(diphenylphosphino)-butane]-((2,5- norbornanediene) tetrafluoroborate, rhodium(l)-(2,5-norbornanediene) perchlorate, rhodium(l)-bis-(triphenylphosphine)-carbonyl chloride, rhodium(ll) trifluoroacetate dimer, rhodium(l)-tris-(triphenylphosphine) bromide, rhodium(l)- tris-(triphenylphosphine) chloride, rhodium(l) dicarbonyl acetylacetonate, rhodium(l) dicarbonyl chloride dimer,
Ruthenium catalysts:
ruthenium(lll) bromide hydrate, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(lll) iodide, ruthenium carbonyl, ruthenium(l) acetate polymer, ruthenium(lll) acetonylacetonate, ruthenium(ll)-(1 ,5-cyclooctadiene) chloride polymer, ruthenium(ll)-tris-(triphenylphosphine) chloride, ruthenium(ll) tricarbonyl chloride dimer, ruthenium(ll) carbonyldihydrido-tris-(triphenylphosphine), ruthenium(lll) 2,4-pentanedionate,
Palladium catalysts:
palladium(ll) acetate, palladium(ll) acetonylacetonate, palladium(ll)-bis- (acetonitrile) chloride, palladium(ll)-bis-(benzonitrile) chloride, palladium(ll)-[1 ,2- bis-(diphenylphosphino)-ethane] chloride, palladium(ll)-bis-
(tricyclohexylphosphine) chloride, palladium(ll)-bis-(triphenylphosphine) chloride, palladium(ll)-bis-(triphenylphosphine) bromide, palladium(ll) bromide, palladium(ll) chloride, palladium(ll) diammine chloride, palladium(ll) iodide, palladium(ll) nitrate, palladium(ll) 2,5-norbornadiene chloride, palladium(ll)
sulfate, palladium(ll) tetrammine chloride, palladium(ll)-[1 ,1 '- ferrocenylbis(diphenylphosphane)] dichloride dichloromethane, palladium on activated carbon, palladium on aluminium oxide,
Iridium catalysts:
iridium acetate, iridium(lll) acetylacetonate, iridium(l)-bis-(triphenylphosphine) carbonyl chloride, iridium(lll) bromide hydrate, iridium carbonyl, iridium(lll) chloride, iridium(lll) chloride hydrate, iridium(l) (1 ,5-cyclooctadiene) acetylacetonate.
Particularly preferred catalysts are rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(l)-bis-(triphenylphosphine)carbonyl chloride, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(ll)-tris-(triphenylphosphine) chloride, iridium(l)-bis-(triphenylphosphine)carbonyl chloride, palladium(ll)-bis- (benzonitrile) chloride, and palladium, preferably in the form of palladium on activated carbon.
The isomerisation catalysed by such a metal catalyst is preferably performed in the temperature range from 40 to 250°C, longer reaction times being required at lower temperatures and, in particular at higher temperatures, decomposition reactions possibly occurring to a certain extent. A particularly preferred temperature range is between 150 and 230°C.
Isomerisation is performed preferably using quantities or concentrations of catalyst of at least 0.03 wt.%, preferred concentrations are in the range from
0.05-5 wt.%, preferably 0.05-1 wt.%, in each case relative to the total mass of
(E1Z)-1 1- and/or (E1Z)-12-pentadecen-15-olide introduced into the isomerisation.
The support material is here not regarded as a constituent of the catalyst. It goes without saying that the catalyst in turn preferably contains an element of subgroup VIII; the above explanations regarding preferred catalysts also apply in connection with the preferred concentrations.
The isomerisation according to the invention, which is preferably catalysed by one of the above-stated catalysts, may be performed not only using an inert
solvent such as for example toluene, xylene, cyclohexane but also without solvent, the latter variant being particularly preferred.
Examples
The educt used in the isomerisation examples contained
48.6%- (E1Z)-1 1-pentadecen-15-olide (mixture of E and Z isomer) 44.7%- (E1Z)-12-pentadecen-15-olide (mixture of E and Z isomer)
and contained no (E1Z)-I O-pentadecen-15-olide.
Transisomerisation with catalysts based on metals of subgroup VIII
Example 1
Reaction conditions: catalyst: ruthenium(ll)-tris-(triphenylphosphine) chloride (0.3 wt.%), no solvent; temperature: 170°C, reaction time: 16 hours
100 g of (E1Z)-1 1 ,12-pentadecen-15-olide are heated for 16 hours at 170°C with 0.3 g of ruthenium(ll)-tris-(triphenylphosphine) chloride, then fractionally distilled and the majority distillate is subjected to steam distillation. 67 g of product (yield: 67% of theoretical) of the following composition are obtained (values in wt.% relative to the total mass of the product):
Reaction conditions: catalyst: palladium on activated carbon (type 87L Paste, source: Johnson Matthey Catalysts) (Pd content: 5 %, water content: 58.9 %, corresponding to a Pd concentration of 2.055 wt.%); no solvent; temperature: 220°C, reaction time: 8 hours
100 g of (E1Z)-1 1 ,12-pentadecen-15-olide are heated for 8 hours at 220°C with 3 g of type 87L Paste palladium on activated carbon, then fractionally distilled and the majority distillate is subjected to steam distillation. 70 g of product (yield: 70% of theoretical) of the following composition are obtained (values in wt.% relative to the total mass of the product):
Claims
1. A process for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, comprising the following step:
- partial isomerisation of (E1Z)-H- and/or (E1Z)-12-pentadecen-15-olide, such that the (E1Z)-(10/1 1/12)-pentadecen-15-olide isomer mixture is obtained.
2. A process according to claim 1 , wherein the isomer mixture comprises a proportion of at least 5 wt.% of (E1Z)-I O-pentadecen-15-olide, relative to the total quantity of (E1Z)-I O-, (E1Z)-H- and (E1Z)-12-pentadecen-15-olide, wherein the quantity of (E1Z)-I O-pentadecen-15-olide optionally already present in the educt mixture is not included in the calculation.
3. A process according to claim 1 , wherein an (E1Z)-(1 1/12)-pentadecen-15- olide isomer mixture is introduced into the isomerisation.
4. A process according to any one of the preceding claims, wherein the (E1Z)- 1 1- and/or (E1Z)-12-pentadecen-15-olide is brought into contact with
(I) a catalyst containing an element of subgroup VIII in such a manner,
that it partially isomerises to form the (E1Z)-(10/11/12)-pentadecen-15-olide isomer mixture.
5. A process according to claim 4, wherein the element of subgroup VIII is selected from the group consisting of ruthenium, rhodium, palladium and iridium.
6. A process according to claim 4 or claim 5, wherein the catalyst containing an element of subgroup VIII is present
(a) in elemental form, (b) in complexed or uncomplexed form as a salt formally having an oxidation number of one to three,
or
(c) as a complex compound in which it is formally zero-valent.
7. A process according to any one of claims 4 to 6, wherein the catalyst containing an element of subgroup VIII is selected from the group consisting of rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(l)-bis- (triphenylphosphine)-carbonyl chloride, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(ll)-tris-(triphenylphosphine) chloride, iridium(l)-bis- (triphenylphosphine)-carbonyl chloride, palladium(ll)-bis-(benzonitrile) chloride, and palladium, preferably in the form of palladium on activated carbon.
8. A process according to any one of claims 4 to 7, wherein the quantity of catalyst is in the range from 0.05-5 wt.%, relative to the total mass of (E1Z)-11- and/or 12-pentadecen-15-olide introduced into the isomerisation.
9. A process according to any one of the preceding claims, wherein the isomerisation is performed at a temperature in the range from 40 to 250°C, preferably 150 to 230°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE112006002818.9T DE112006002818B4 (en) | 2005-11-09 | 2006-10-25 | Process for the preparation of (10/11/12) pentadecene-15-olide starting from 11- and / or 12-pentadecene-15-olide |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US73478505P | 2005-11-09 | 2005-11-09 | |
| US60/734,785 | 2005-11-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007054429A1 true WO2007054429A1 (en) | 2007-05-18 |
Family
ID=37691813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2006/067748 WO2007054429A1 (en) | 2005-11-09 | 2006-10-25 | Process for the production of (10/11/12)-pentadecen-15-olide starting from 11- and/or 12-pentadecen-15-olide |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE112006002818B4 (en) |
| WO (1) | WO2007054429A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230031807A1 (en) * | 2019-12-20 | 2023-02-02 | Firmenich Sa | Powdery, Musky Odorant Macrocycles |
| US11690825B2 (en) | 2016-03-09 | 2023-07-04 | Board Of Regents, The University Of Texas System | 20-HETE receptor (GPR75) antagonists and methods of use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012315A1 (en) * | 2003-07-29 | 2005-02-10 | University Of Ottawa | Ruthenium compounds, their production and use |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE786518A (en) | 1971-07-21 | 1973-01-22 | Haarmann & Reimer Gmbh | OXA-BICYCLO-ALCENES PREPARATION PROCESS |
| US4490404A (en) | 1983-07-18 | 1984-12-25 | International Flavors & Fragrances Inc. | Flavoring with macrocyclic lactone |
| DE69028755T2 (en) | 1989-10-27 | 1997-06-05 | Firmenich & Cie | Use of unsaturated macrocyclic ketones and perfume ingredients |
| DE10227483A1 (en) | 2002-06-19 | 2004-01-08 | Symrise Gmbh & Co. Kg | Process for the preparation of 11 (12) -pentadecen-15-olides |
| DE10348168A1 (en) | 2003-10-16 | 2005-05-12 | Symrise Gmbh & Co Kg | Process for the preparation of 1-hydroperoxy-16-oxabicyclo [40.4.0] hexadecane |
-
2006
- 2006-10-25 DE DE112006002818.9T patent/DE112006002818B4/en active Active
- 2006-10-25 WO PCT/EP2006/067748 patent/WO2007054429A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012315A1 (en) * | 2003-07-29 | 2005-02-10 | University Of Ottawa | Ruthenium compounds, their production and use |
Non-Patent Citations (2)
| Title |
|---|
| FURSTNER, ALOIS ET AL: "Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands", CHEMISTRY--A EUROPEAN JOURNAL , 7(15), 3236-3253 CODEN: CEUJED; ISSN: 0947-6539, 2001, XP002418756 * |
| GRIECO P A ET AL: "Remote double bond migration via rhodium catalysis: a novel enone transposition", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 98, no. 22, 27 October 1976 (1976-10-27), pages 7102 - 7104, XP002354942, ISSN: 0002-7863 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11690825B2 (en) | 2016-03-09 | 2023-07-04 | Board Of Regents, The University Of Texas System | 20-HETE receptor (GPR75) antagonists and methods of use |
| US20230031807A1 (en) * | 2019-12-20 | 2023-02-02 | Firmenich Sa | Powdery, Musky Odorant Macrocycles |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112006002818T5 (en) | 2008-09-25 |
| DE112006002818B4 (en) | 2016-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Stolle et al. | Hydrogenation of citral: a wide-spread model reaction for selective reduction of α, β-unsaturated aldehydes | |
| Matsuda et al. | Ready access of. alpha.-(triorganosilyl) methylene. beta.-lactones by means of rhodium-catalyzed cyclocarbonylation of substituted propargyl alcohols | |
| DE69231750T2 (en) | Process for the extraction of precious metal catalyst on a metallic support | |
| Sharma et al. | Selective double bond isomerization of allyl phenyl ethers catalyzed by ruthenium metal complexes | |
| JP4731685B2 (en) | Cationic ruthenium complex, its production and use | |
| RU2007133670A (en) | METHOD FOR CLEANING NOROXYMORPHONE COMPOUNDS | |
| Martínez-Martínez et al. | Solid–state molecular organometallic catalysis in gas/solid flow (flow-SMOM) as demonstrated by efficient room temperature and pressure 1-butene isomerization | |
| Tallarico et al. | Selectivity in ring-opening metatheses | |
| JPH06206838A (en) | Method for catalytic isomerization of alpha-alkenol | |
| EP2953920B1 (en) | Process for the isomerisation of an exo double bond | |
| WO2007054429A1 (en) | Process for the production of (10/11/12)-pentadecen-15-olide starting from 11- and/or 12-pentadecen-15-olide | |
| JP2006509806A (en) | Method for producing 1,6-hexanediol | |
| Zhang et al. | Rh‐Catalyzed Kinetic Resolution‐Based Enantioselective [4+ 2]‐Cycloaddition‐Isomerization of Allene‐1, 3‐dienes. | |
| Li et al. | Syntheses and characterizations of iridium complexes containing bidentate phosphine ligands and their catalytic hydrogenation reactions to α, β-unsaturated aldehydes | |
| Speziali et al. | Selective hydrogenation of myrcene catalyzed by complexes of ruthenium, chromium, iridium and rhodium | |
| JP6054386B2 (en) | Method for preparing palladium(I) tri-t-butylphosphine bromide dimer and process for its use in isomerization reactions | |
| JP3961938B2 (en) | Production of tetrahydrogeraniol | |
| Cenini et al. | Diruthenium (II, II) tetrakis (acetate) as a catalyst of choice for intermolecular insertion of stabilized diazocompounds into O H bonds | |
| Tsukada et al. | Rhodium-catalyzed allylation of styrenes with allyltosylate | |
| JP2642138B2 (en) | Method for producing pentenoate from formyl valerate | |
| Moura et al. | Unique catalytic behaviour of Ir4 clusters for the selective hydrogenation of 1, 5-cyclooctadiene | |
| EP1771404B1 (en) | Improved method for the production of (e,z)-7,8-cyclohexadecene-1-on | |
| Ou et al. | A review on chemical synthesis of leaf alcohol | |
| JP7152715B2 (en) | Method for producing alicyclic oxygen-containing compound | |
| JP2000026361A (en) | Production of muscone, novel intermediate and perfume composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 1120060028189 Country of ref document: DE |
|
| RET | De translation (de og part 6b) |
Ref document number: 112006002818 Country of ref document: DE Date of ref document: 20080925 Kind code of ref document: P |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 06807528 Country of ref document: EP Kind code of ref document: A1 |