US20010044407A1 - 1,2-substituted 2,3-dihydro-1H-5,9-dioxacyclohepta [ f ] inden -7- ones and 7-substituted benzo [ b ] [ 1,4 ] dioxepin -3-ones - Google Patents
1,2-substituted 2,3-dihydro-1H-5,9-dioxacyclohepta [ f ] inden -7- ones and 7-substituted benzo [ b ] [ 1,4 ] dioxepin -3-ones Download PDFInfo
- Publication number
- US20010044407A1 US20010044407A1 US09/816,631 US81663101A US2001044407A1 US 20010044407 A1 US20010044407 A1 US 20010044407A1 US 81663101 A US81663101 A US 81663101A US 2001044407 A1 US2001044407 A1 US 2001044407A1
- Authority
- US
- United States
- Prior art keywords
- dioxepin
- benzo
- dioxacyclohepta
- inden
- dihydro
- 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.)
- Abandoned
Links
- -1 7-substituted benzo [ b ] [ 1,4 ] dioxepin -3-ones Chemical class 0.000 title abstract description 8
- JTAHMTWJNXDJEG-UHFFFAOYSA-N 8,9-dihydro-7h-cyclopenta[h][1,5]benzodioxepin-3-one Chemical class C1=C2OCC(=O)COC2=CC2=C1CCC2 JTAHMTWJNXDJEG-UHFFFAOYSA-N 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000003205 fragrance Substances 0.000 claims abstract description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- WYCAMOVJBJBXCY-UHFFFAOYSA-N 7-prop-2-enyl-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CC=C)=CC=C21 WYCAMOVJBJBXCY-UHFFFAOYSA-N 0.000 claims description 14
- AWAHFLZWCBUHMX-UHFFFAOYSA-N 7-(3-methylbutyl)-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CCC(C)C)=CC=C21 AWAHFLZWCBUHMX-UHFFFAOYSA-N 0.000 claims description 13
- CPMKLLFIQWBDNP-UHFFFAOYSA-N 7-methyl-8,9-dihydro-7h-cyclopenta[h][1,5]benzodioxepin-3-one Chemical compound O1CC(=O)COC2=C1C=C1CCC(C)C1=C2 CPMKLLFIQWBDNP-UHFFFAOYSA-N 0.000 claims description 13
- ORSNFSKCWZUPRU-UHFFFAOYSA-N 7,7-dimethyl-8,9-dihydrocyclopenta[h][1,5]benzodioxepin-3-one Chemical compound O1CC(=O)COC2=C1C=C1CCC(C)(C)C1=C2 ORSNFSKCWZUPRU-UHFFFAOYSA-N 0.000 claims description 9
- IALLGZHDBYADNH-UHFFFAOYSA-N 7-(2-methylbutyl)-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CC(C)CC)=CC=C21 IALLGZHDBYADNH-UHFFFAOYSA-N 0.000 claims description 9
- VTIJTUYNPUHXBY-UHFFFAOYSA-N 7-hexyl-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CCCCCC)=CC=C21 VTIJTUYNPUHXBY-UHFFFAOYSA-N 0.000 claims description 9
- CTUMHGXIKKWYIG-UHFFFAOYSA-N 7-pentyl-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CCCCC)=CC=C21 CTUMHGXIKKWYIG-UHFFFAOYSA-N 0.000 claims description 9
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 7
- VFHUXRQVILWMJY-UHFFFAOYSA-N 7-(3-methylpentyl)-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CCC(C)CC)=CC=C21 VFHUXRQVILWMJY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- UUFFMMKIPIVKPB-UHFFFAOYSA-N 7-(2-ethylbutyl)-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CC(CC)CC)=CC=C21 UUFFMMKIPIVKPB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- DTFAFTRMUVAJMD-UHFFFAOYSA-N 7,8-dimethyl-8,9-dihydro-7h-cyclopenta[h][1,5]benzodioxepin-3-one Chemical compound O1CC(=O)COC2=C1C=C1CC(C)C(C)C1=C2 DTFAFTRMUVAJMD-UHFFFAOYSA-N 0.000 claims 3
- FYXIUUJQDCHVSF-UHFFFAOYSA-N 7-heptyl-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CCCCCCC)=CC=C21 FYXIUUJQDCHVSF-UHFFFAOYSA-N 0.000 claims 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
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- 0 CC1CC2=C(C=C3OCC(=O)COC3=C2)C~1(C)C Chemical compound CC1CC2=C(C=C3OCC(=O)COC3=C2)C~1(C)C 0.000 description 7
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 4
- UEGBWDUVDAKUGA-UHFFFAOYSA-N 2,6,10-trimethylundec-9-enal Chemical compound CC(C)=CCCC(C)CCCC(C)C=O UEGBWDUVDAKUGA-UHFFFAOYSA-N 0.000 description 3
- UBQVNQBOMHCYTR-UHFFFAOYSA-N 7-(2-methylpentyl)-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CC(C)CCC)=CC=C21 UBQVNQBOMHCYTR-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 239000000470 constituent Substances 0.000 description 3
- WTYGAUXICFETTC-UHFFFAOYSA-N cyclobarbital Chemical compound C=1CCCCC=1C1(CC)C(=O)NC(=O)NC1=O WTYGAUXICFETTC-UHFFFAOYSA-N 0.000 description 3
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- BGTBFNDXYDYBEY-FNORWQNLSA-N 4-(2,6,6-Trimethylcyclohex-1-enyl)but-2-en-4-one Chemical compound C\C=C\C(=O)C1=C(C)CCCC1(C)C BGTBFNDXYDYBEY-FNORWQNLSA-N 0.000 description 2
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- KQPGRKHBHURUAP-UHFFFAOYSA-N 7-propyl-1,5-benzodioxepin-3-one Chemical compound O1CC(=O)COC2=CC(CCC)=CC=C21 KQPGRKHBHURUAP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UHRHVWVPKJIJNH-UHFFFAOYSA-N C=CCC1=CC=C2OCC(=O)COC2=C1.CC(C)CCC1=CC=C2OCC(=O)COC2=C1.CC1(C)CCC2=C1C=C1OCC(=O)COC1=C2.CC1CC2=C(C=C3OCC(=O)COC3=C2)C1C.CC1CCC2=C1C=C1OCC(=O)COC1=C2.CCC(C)CC1=CC=C2OCC(=O)COC2=C1.CCC(C)CCC1=CC=C2OCC(=O)COC2=C1.CCCC(C)CC1=CC=C2OCC(=O)COC2=C1.CCCCCC1=CC=C2OCC(=O)COC2=C1.CCCCCCC1=CC=C2OCC(=O)COC2=C1 Chemical compound C=CCC1=CC=C2OCC(=O)COC2=C1.CC(C)CCC1=CC=C2OCC(=O)COC2=C1.CC1(C)CCC2=C1C=C1OCC(=O)COC1=C2.CC1CC2=C(C=C3OCC(=O)COC3=C2)C1C.CC1CCC2=C1C=C1OCC(=O)COC1=C2.CCC(C)CC1=CC=C2OCC(=O)COC2=C1.CCC(C)CCC1=CC=C2OCC(=O)COC2=C1.CCCC(C)CC1=CC=C2OCC(=O)COC2=C1.CCCCCC1=CC=C2OCC(=O)COC2=C1.CCCCCCC1=CC=C2OCC(=O)COC2=C1 UHRHVWVPKJIJNH-UHFFFAOYSA-N 0.000 description 1
- 240000007436 Cananga odorata Species 0.000 description 1
- 244000241235 Citrullus lanatus Species 0.000 description 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 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
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 229930186686 Jasmolactone Natural products 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- 235000019501 Lemon oil Nutrition 0.000 description 1
- 241000234269 Liliales Species 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 244000250129 Trigonella foenum graecum Species 0.000 description 1
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- YPZUZOLGGMJZJO-LQKXBSAESA-N ambroxan Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C)[C@@H]1[C@]2(C)OCC1 YPZUZOLGGMJZJO-LQKXBSAESA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- POIARNZEYGURDG-FNORWQNLSA-N beta-damascenone Chemical compound C\C=C\C(=O)C1=C(C)C=CCC1(C)C POIARNZEYGURDG-FNORWQNLSA-N 0.000 description 1
- FZJUFJKVIYFBSY-UHFFFAOYSA-N bourgeonal Chemical compound CC(C)(C)C1=CC=C(CCC=O)C=C1 FZJUFJKVIYFBSY-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- SWUIQEBPZIHZQS-UHFFFAOYSA-N calone Chemical compound O1CC(=O)COC2=CC(C)=CC=C21 SWUIQEBPZIHZQS-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- MIZGSAALSYARKU-UHFFFAOYSA-N cashmeran Chemical compound CC1(C)C(C)C(C)(C)C2=C1C(=O)CCC2 MIZGSAALSYARKU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000001071 citrus reticulata blanco var. mandarin Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- OBKCQZVABDJKQE-UHFFFAOYSA-N dioxepin-3-one Chemical compound O=C1OOC=CC=C1 OBKCQZVABDJKQE-UHFFFAOYSA-N 0.000 description 1
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PHXATPHONSXBIL-JTQLQIEISA-N gamma-Undecalactone Natural products CCCCCCC[C@H]1CCC(=O)O1 PHXATPHONSXBIL-JTQLQIEISA-N 0.000 description 1
- 229940020436 gamma-undecalactone Drugs 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 1
- 239000010651 grapefruit oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- NBCMACYORPIYNY-UHFFFAOYSA-N jasmolactone Chemical compound CC=CCCC1CCCC(=O)O1 NBCMACYORPIYNY-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229940089454 lauryl aldehyde Drugs 0.000 description 1
- 239000010501 lemon oil Substances 0.000 description 1
- SDQFDHOLCGWZPU-UHFFFAOYSA-N lilial Chemical compound O=CC(C)CC1=CC=C(C(C)(C)C)C=C1 SDQFDHOLCGWZPU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000001738 pogostemon cablin oil Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- KWVISVAMQJWJSZ-VKROHFNGSA-N solasodine Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CN1 KWVISVAMQJWJSZ-VKROHFNGSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000001019 trigonella foenum-graecum Nutrition 0.000 description 1
- WXETUDXXEZHSCS-MAVITOTKSA-N vertofix coeur Chemical compound C[C@@H]1CC[C@@]2(C(/CC3)=C\C(C)=O)[C@@H]3C(C)(C)[C@@H]1C2 WXETUDXXEZHSCS-MAVITOTKSA-N 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 229930007850 β-damascenone Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/0084—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing more than six atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
Definitions
- the invention relates to 1,2-substituted 2,3-dihydro-1H-5,9-dioxacyclohepta[f]inden-7-ones and 7-substituted benzo[b][1,4]dioxepin-3-ones and to the use of these compounds in fragrance compositions.
- One embodiment of the present invention is a compound of the general formula I:
- R 1 ⁇ H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 ) 2 ,
- R 3 ⁇ H, CH 3 , or CH 2 CH 3 ,
- the dashed line may be a double bond or a ring closure to form an indane ring system where, in the case of a double bond R 1 ⁇ R 2 ⁇ H, and in all other cases, the total number of carbon atoms of all residues is given by C 8 >R 1 +R 2 +R 3 >C 1 .
- a further embodiment of the present invention is a fragrance composition containing at least one compound according to formula I:
- R 1 is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 ) 2 ,
- R 2 is H, or CH 3 ;
- R 3 is H, CH 3 , or CH 2 CH 3 ,
- the dashed line is a double bond or a ring closure forming an indane ring system where, in the case of a double bond R 1 ⁇ R 2 ⁇ H, and in all other cases, the total number of carbon atoms of all residues in formula I is given by C 8 >R 1 +R 2 +R 3 >C 1 .
- Another embodiment of the present invention is a method for providing a fragrance by applying to a substrate a fragrance composition containing at least one compound according to formula I:
- R 1 is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 )2,
- R 2 is H, or CH 3 ;
- R 3 is H, CH 3 , or CH 2 CH 3 ,
- the dashed line is a double bond or a ring closure forming an indane ring system where, in the case of a double bond R 1 ⁇ R 2 ⁇ H, and in all other cases, the total number of carbon atoms of all residues in formula I is given by C 8 >R 1 +R 2 +R 3 >C 1 .
- R 1 ⁇ H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 ) 2 , or CH 2 CH 2 CH 2 CH 3 ,
- R 2 ⁇ H, or CH 3 .
- R 3 ⁇ H, CH 3 , or CH 2 CH 3 .
- the dashed line is an optional double bond or an optional ring closure to form the indane ring system, where in the case of a double bond R 1 ⁇ R 2 ⁇ H, and in all other cases the total number of carbon atoms of all residues is given by C 8 >R 1 +R 2 +R 3 >C 1 .
- R 1 or R 2 is preferably CH 3 .
- the compounds of the general formula I generally have a fresh, marine fragrance, generally with predominantly aldehydic, floral characters and are therefore particularly suitable for building up fresh, marine and aquatic effects, in particular, for instance, for modern marine Fougere perfumes and floral-aquatic women's fragrances.
- Those which are of particular interest for perfumes are harmonious blends of compound 1 with Tropional®, Melonal®, or Floralozon®. However, the use is neither restricted to these harmonious blends nor to specific fragrances, classes of substances or fragrance odors. Examples of further classes of substances which harmonize well include:
- Essential oils and extracts e.g. bergamot oil, grapefruit oil, jasmine absolue, mandarin oil, patchouli oil, vetiver oil, ylang-ylang oil, lemon oil.
- Alcohols, ethers, acetals e.g. Acetal E®, citronellol, dihydromyrcenol, Ebanol®, eugenol, Florol®, geraniol, Helional®, cis-hex-3-enol, Mayol®, 2-phenylethyl alcohol, Sandalor®, Spirambren®.
- Aldehydes and ketones e.g. Adoxal®, Bourgeonal®, Cyclohexal®, damascone, damascenone, Florhydral®, Hedion®, Iralia®, Iso E Super®, lauryl aldehyde, Lilial®, methyl ionone, 2-methylundecanal, Myralden®, undecanal, Vertofix®.
- Esters and lactones e.g. allyl amyl glycolate, benzyl salicylate, Cyclogalbanat®, gamma-decalactone, Gardenol®, geranyl acetate, cis-hex-3-enyl acetate, linalyl acetate, gamma-undecalactone, Verdox®.
- Macrocycles, polycycles, heterocycles e.g. Ambroxan®, Cashmeran®, Galaxolid®, Habanolid®, Thibetolid®.
- the compounds of the present invention may be incorporated into fragrance compositions, which may be applied to various substrates, such as skin, hair, and articles of clothing, etc.
- Odor linear, very intensive marine-floral odor with nuances of ozone, watermelons and fatty aldehydes.
- - IR (film): ⁇ 1502/1581/1436/1639 cm ⁇ 1 ( ⁇ C ⁇ C, Ar), 1742 cm ⁇ 1 ( ⁇ C ⁇ O), 1267/1305 cm ⁇ 1 ( ⁇ ring), 1051 cm ⁇ 1 ( ⁇ C—O—C).
- the mixture was stirred for 48 h at room temperature, in the course of which, after 6 h, a further 6.50 g (30.5 mmol) of sodium periodate and 0.3 g (1.5 mmol, 5 mol %) of ruthenium (III) chloride hydrate were added.
- the reaction mixture was then poured into 500 ml of water and the product was extracted three times, each time with 200 ml of dichloromethane.
- the combined organic extracts were washed with 200 ml of 20% sodium hydrogen sulfite solution and 200 ml of water and dried over sodium sulfate.
- Odor Linear, very intensive marine odor with strongly floral aspects.
- Odor Very intensive and diffuse, linear, marine odor with nuances of Adoxal® (2,6,10-trimethylundec-9-en-1-al).
- Odor Marine-aldehyde-like, floral-rosy odor with nuances of citronelloxyacetaldehyde [(3,7-dimethyl-6-octenyl)oxyacetaldehyde].
- Odor Intensive, marine-floral odor.
- IR (film): ⁇ 1501/1434/1460/1580 cm ⁇ 1 ( ⁇ C ⁇ C, Ar), 1265/1302/1201 cm ⁇ 1 ( ⁇ ring), 1050 cm ⁇ 1 ( ⁇ C—O—C), 1740 cm ⁇ 1 ( ⁇ C ⁇ O).
- Odor Marine, animalic, civet-like, floral-aldehyde odor, also somewhat pronounced of citronelloxyacetaldehyde ([3,7-dimethyl-6-octenyl]oxy-acetaldehyde).
- Odor Marine, floral-aldehyde odor.
- - IR (film): ⁇ 1502/1418/1466/1580 cm ⁇ 1 ( ⁇ C ⁇ C, Ar) , 1265/1304/1201 cm ⁇ 1 ( ⁇ ring), 1050 cm ⁇ 1 ( ⁇ C—O—C), 1741 cm ⁇ 1 ( ⁇ C ⁇ O).
- the compounds 7-(2-ethylbutyl)benzo[b][1,4]dioxepin-3-one and 7-heptylbenzo[b][1,4]dioxapin-3-one also have the faceted marine odor typical of this class of compound and are therefore suitable, as are the abovementioned compounds, for preparing harmonious fragrance blends having marine notes.
- the abovementioned compounds 1 and 3 are particularly outstanding, as shown by the examples below.
- Floral-marine-fruity women's fragrance containing compound 1 Contents by weight in parts per No. Compound/constituent thousand 1. Citronellol extra 30 2. Cyclohexal 150 3. Damascone 10% in DPG 2 4. gamma-Decalactone 2 5. beta-Dihydroionone 55 6. DPG (dipropylene glycol) 76 7. Eugenol, pure 35 8. Galaxolid 50 BB 275 9. Hedion 110 10, Iso E Super 145 11. Jasmolactone (Firmenich) 1 25 percent strength in DPG 12. Linalool, synthetic 30 13 Compound 1, 10% in DPG 65 1000
- composition produces a feminine-sensual, transparent, modern perfume with a rosy-floral, fresh jasmine-like head and floral-fruity heart note with spicy aspects on a musky-wooden base.
- Compound 1 gives the composition its marine aspects, and gives it its radiance and richness in character. It transforms the traditional floral fragrance into a modern-transparent, trend perfume.
- compound 1 is much more intense and, at the same dosage, is accompanied by a much stronger marine impression without transition into fishy or salty, as is the case with Calon 1951® at the high dosage here.
- the compound 1 is much more floral than Calon 1951® and therefore harmonizes much better with the floral elements of the composition. It develops the floral-aquatic accord, while remaining transparent.
- Feminine floral-marine perfume containing compound 3 Contents by weight in parts per No. Compound/constituent thousand 1. Algenon PB 100 2. Benzyl salicylate 110 3. Bergamot oil, Italian 50 4. Boisambren forte 10 5. Cyclohexal 12 6. Dihydromyrcenol 35 7. DPG (dipropylene glycol) 358 8. Eugenol, pure 10 9. Fixolid 10 10. Galaxolid 50 PHT 65 11. Georgywood 25 12. Hedion 20 13. Linalool, synthetic 10 14. Linalyl acetate, synthetic 30 15. Sandela 25 16. Tropional 75 17. Vertofix Coeur 35 18. Compound 3, 10% in DPG 20 1000
- Compound 3 enhances the fresh, marine impression of the composition. It combines harmoniously with the hesperidic topnote, emphasizes the floral heart note and finally blends in the base with woody and musk-like notes to give a character harmonious composition.
- Compound 3 provides volume, radiance and body to the composition. It gives the impression of a fresh sea breeze. Compared with Calon 1951® (see Example 12), compound 3 is much more intense, but nevertheless does not have a heavy or suppressive effect on the other constituents of the composition. In contrast, compound 3 brings the perfume more radiance, diffusivity and volume than Calon 1951®.
Abstract
Description
- The invention relates to 1,2-substituted 2,3-dihydro-1H-5,9-dioxacyclohepta[f]inden-7-ones and 7-substituted benzo[b][1,4]dioxepin-3-ones and to the use of these compounds in fragrance compositions.
- With the launch of an unusual marine women's fragrance, a new trend began to be established in perfumery at the beginning of the 1990s, which was continued in numerous similar marine fragrance creations and peaked in very successful feminine perfumes in 1996 and 1997. However, as soon as 1991 a successful marine men's fragrance also appeared on the market and in 1997 a bodycare series having an extremely marine effect. Virtually all of these marine fragrances are based on 7-methylbenzo[b][1,4]dioxepin-3-one (Calon 1951®). This key compound is described in Beereboom, et al. U.S. Pat. No. 3,647,479 (“Beereboom”) together with derivatives which bear methyl, ethyl, propyl and butyl groups in the 7 position. Published patent EP 0 902 024 A1 describes the compound 7-propylbenzo[b][1,4]dioxepin-3-one and its use in perfumery. This compound comes under the general formula of Beereboom and has a similar odor to the abovementioned methyl derivative. To date, no further compounds of similar marine odor are known in perfumery.
- Accordingly, it would be advantageous to provide novel compounds with a marine odor for use in perfumery.
-
- wherein
- R1═H, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2,
- CH2CH2CH2CH3,
- R2═H, or CH3, and
- R3═H, CH3, or CH2CH3,
- and the dashed line may be a double bond or a ring closure to form an indane ring system where, in the case of a double bond R1═R2═H, and in all other cases, the total number of carbon atoms of all residues is given by C8>R1+R2+R3>C1.
-
- wherein
- R1 is H, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2,
- CH2CH2CH2CH3;
- R2 is H, or CH3; and
- R3 is H, CH3, or CH2CH3,
- and the dashed line is a double bond or a ring closure forming an indane ring system where, in the case of a double bond R1═R2═H, and in all other cases, the total number of carbon atoms of all residues in formula I is given by C8>R1+R2+R3>C1.
-
- wherein
- R1 is H, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2,
- CH2CH2CH2CH3;
- R2 is H, or CH3; and
- R3 is H, CH3, or CH2CH3,
- and the dashed line is a double bond or a ring closure forming an indane ring system where, in the case of a double bond R1═R2═H, and in all other cases, the total number of carbon atoms of all residues in formula I is given by C8>R1+R2+R3 >C1.
-
- where
- R1═H, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, or CH2CH2CH2CH3,
- R2═H, or CH3, and
- R3═H, CH3, or CH2CH3, and
- the dashed line is an optional double bond or an optional ring closure to form the indane ring system, where in the case of a double bond R1═R2═H, and in all other cases the total number of carbon atoms of all residues is given by C8>R1+R2+R3>C1.
- In the case of the indane ring system, R1 or R2 is preferably CH3.
-
- The compounds of the general formula I generally have a fresh, marine fragrance, generally with predominantly aldehydic, floral characters and are therefore particularly suitable for building up fresh, marine and aquatic effects, in particular, for instance, for modern marine Fougere perfumes and floral-aquatic women's fragrances. Those which are of particular interest for perfumes are harmonious blends of compound 1 with Tropional®, Melonal®, or Floralozon®. However, the use is neither restricted to these harmonious blends nor to specific fragrances, classes of substances or fragrance odors. Examples of further classes of substances which harmonize well include:
- Essential oils and extracts, e.g. bergamot oil, grapefruit oil, jasmine absolue, mandarin oil, patchouli oil, vetiver oil, ylang-ylang oil, lemon oil.
- Alcohols, ethers, acetals, e.g. Acetal E®, citronellol, dihydromyrcenol, Ebanol®, eugenol, Florol®, geraniol, Helional®, cis-hex-3-enol, Mayol®, 2-phenylethyl alcohol, Sandalor®, Spirambren®.
- Aldehydes and ketones, e.g. Adoxal®, Bourgeonal®, Cyclohexal®, damascone, damascenone, Florhydral®, Hedion®, Iralia®, Iso E Super®, lauryl aldehyde, Lilial®, methyl ionone, 2-methylundecanal, Myralden®, undecanal, Vertofix®.
- Esters and lactones, e.g. allyl amyl glycolate, benzyl salicylate, Cyclogalbanat®, gamma-decalactone, Gardenol®, geranyl acetate, cis-hex-3-enyl acetate, linalyl acetate, gamma-undecalactone, Verdox®.
- Macrocycles, polycycles, heterocycles, e.g. Ambroxan®, Cashmeran®, Galaxolid®, Habanolid®, Thibetolid®.
- The compounds of the present invention may be incorporated into fragrance compositions, which may be applied to various substrates, such as skin, hair, and articles of clothing, etc.
- The following examples are provided to further illustrate the compounds of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.
- A solution of 354 ml (2.30 mmol) of eugenol and 292 g (6.89 mol) of lithium chloride in 3.7 l of N,N-dimethylformamide was refluxed for a total of 44 hours (h), and, after 4 h, 22 h and 29 h, a further 292 g (6.89 mol) of lithium chloride were added each time. After cooling, 2 l of toluene were added and the resultant precipitate was filtered off with suction and extracted with toluene. The organic extracts were combined and concentrated on a rotary evaporator. After flash chromatography (ether/pentane, 1:1, Rf=0.37) on silica gel, 173 g (50%) of 4-allylcatechol were obtained.
- 12.8 g (225 mmol) of 95% pure sodium methoxide were introduced into a solution of 16.8 g (112 mmol) of 4-allylcatechol in 250 ml of methanol, with stirring, followed by 21 ml (225 mmol) of methyl bromoacetate. After refluxing for 8 h, a further 21 ml (225 mmol) of methyl bromoacetate were added, and, after a further 4 h of heating, a further 12.8 g (225 mmol) of sodium methoxide and a further 21 ml (225 mmol) of methyl bromoacetate. After a further 4 h under reflux, the mixture was worked up by adding 500 ml of ether and filtering off the precipitate formed. The filtrate was concentrated on a rotary evaporator and taken up in ether/water/saturated ammonium chloride solution (1:1:1). The organic phase was separated off, and the aqueous phase was extracted three times, each time with 200 ml of ether. The combined organic phases were dried over sodium sulfate and concentrated to dryness on a rotary evaporator. After flash chromatography (ether/pentane, 1:1, Rf=0.35) on silica gel, 21.4 g (65%) of methyl 4-allyl-2-(ethoxycarbonylmethoxy)phenoxyacetate were obtained.
- A solution of 69.0 g (234 mmol) of methyl 4-allyl-2-(ethoxycarbonylmethoxy)phenoxyacetate was added dropwise in the course of 2.5 h to a suspension of 12.0 g (500 mmol) of sodium hydride in 500 ml of tetrahydrofuran. The reaction mixture was then refluxed for 20 h and, after cooling, poured into 1.5 l of ice water. The resultant mixture was acidified to pH 2 with 2N hydrochloric acid and extracted three times, each time with 2 l of ether. The combined ether extracts were dried over sodium sulfate, freed from solvent on a rotary evaporator and taken up into 400 ml of ethanol. 400 ml of 2N hydrochloric acid were added and the mixture was refluxed for 20 h. The mixture was then poured into 1.5 l of ice water, the product was extracted four times, each time with 1.5 l of ether, and the combined ether extracts were washed with 1 l of water and 100 ml of saturated sodium chloride solution. After drying over sodium sulfate, concentration on a rotary evaporator and flash chromatography (pentane/ether, 4:1, Rf=0.37) on silica gel, 20.0 g (42%) of 7-allylbenzo[b][1,4]dioxepin-3-one (1) were obtained as a colorless liquid. Odor: linear, very intensive marine-floral odor with nuances of ozone, watermelons and fatty aldehydes. - IR (film): ν=1502/1581/1436/1639 cm−1 (ν C═C, Ar), 1742 cm−1 (ν C═O), 1267/1305 cm−1 (ν ring), 1051 cm−1 (ν C—O—C). - 1H-NMR (CDCl3): δ=3.30 (d, J=6.8 Hz, 2H, 1′-H2), 4.68 (d, J=7.2 Hz, 2-, 4-H2) 5.05-5.10 (m, 2H, 3′-H2), 5.92 (mc, 1H, 2′-H), 6.77-6.93 (m, 3H, 6-, 8-, 9-H). - 13C-NMR (CDCl3): δ=39.15 (t, C-1′), 75.41/75.63 (2t, C-2,-4), 116.00 (t, C-3′), 120.67/120.73 (2d, C-6,-9), 123.73 (d, C-8), 135.94 (s, C-7), 136.88 (d, C-2′), 146.46 (s, C-9a), 148.00 (s, C-5a), 204.61 (s, C-3). - MS (EI): m/z (%)=91 (97) [C7H7 +], 120 (25) [C7H4O2 +], 161 (13) [M+-C2H3O], 175 (6) [M+-CHO], 204 (100) [M+].
- A mixture of 19.1 ml (150 mmol) of veratrol and 19.2 ml (225 mmol) of vinylacetic acid in 230 g of 83% polyphosphoric acid was stirred for 15 h at 60° C. and then poured into 500 ml of ice water. After 30 minutes (min) of stirring, the product was extracted three times, each time with 200 ml of ether. The combined organic phases were washed twice, each time with 100 ml of 2N NaOH, once with 100 ml of water and once with 50 ml of saturated sodium chloride solution, dried over sodium sulfate and freed from solvent on a rotary evaporator. After recrystallizing the residue (in AcOEt/pentane), 22.8 g (74%) of 5,6-dimethoxy-3-methylindan-1-one were obtained.
- To a suspension of 53.3 g (815 mmol) of zinc dust in 74 ml of water were added 4 ml of concentrated hydrochloric acid. The supernatant was decanted off after stirring for 30 min, and to the residue were added, with ice cooling, 42 ml of water and then, dropwise, 55 ml of concentrated hydrochloric acid. 28.0 g (136 mmol) of 5,6-dimethoxy-3-methylindan-1-one dissolved in 53 ml of toluene were added and the mixture was refluxed for 3 days (d), in the course of which, after 48 h, a further 55 ml of concentrated hydrochloric acid were added. After cooling, the reaction mixture was poured into 200 ml of water and the product was extracted twice in 300 ml of ether. The combined extracts were washed with 100 ml of water and 25 ml of saturated sodium chloride solution, dried over sodium sulfate and concentrated on a rotary evaporator. After flash chromatography (pentane/ether, 9:1, Rf=0.23) on silica gel, 19.6 g (75%) of 5,6-dimethoxy-1-methylindane were obtained.
- Over 90 min at room temperature, 27.5 ml (202 mmol) of iodotrimethylsilane were added dropwise with stirring to a solution of 19.4 g (101 mmol) of 5,6-dimethoxy-1-methylindane in 150 ml of acetonitrile. The mixture was stirred for a further 2.5 d at room temperature, in the course of which, after 48 h, again 10 ml (73.5 mmol) of iodotrimethylsilane were added. The reaction mixture was then poured into 500 ml of water and the product was extracted twice, each time with 200 ml of ether. The combined extracts were washed with 100 ml of 40% sodium hydrogen sulfite solution, 100 ml of water and 50 ml of saturated sodium chloride solution, dried over sodium sulfate and concentrated on a rotary evaporator. After flash chromatography (pentane/ether, 2:1, Rf=0.28) on silica gel, 15.5 g (93%) of 1-methylindane-5,6-diol were obtained.
- A suspension of 25.7 g (186 mmol) of potassium carbonate were heated to reflux with stirring. At this temperature, over the course of 5 h, a mixture of 15.3 g (93.2 mmol) of 1-methylindane-5,6-diol and 11.6 g (92.8 mmol) of 3-chloro-2-chloromethylprop-1-ene dissolved in 50 ml of dioxane was added dropwise. When addition was complete, the mixture was stirred for a further 1 h under reflux and the inorganic solids precipitated out were filtered off with suction after cooling the reaction mixture. The solids were washed with acetone and the combined organic phases freed from solvent on a rotary evaporator. After flash chromatography (pentane/ether, 19:1, Rf=0.66) on silica gel, 7.3 g (36%) of 1-methyl-7-methylene-2,3,7,8-tetrahydro-1H,6H-5,9-dioxacyclohepta[f]indene were obtained.
- 6.6 g (30.5 mmol) of 1-methyl-7-methylene-2,3,7,8-tetrahydro-1H,6H-5,9-dioxacyclohepta[f]indene were dissolved in a mixture of 140 ml of acetonitrile, 140 ml of water and 90 ml of carbon tetrachloride. 6.50 g (30.5 mmol) of sodium periodate were added at room temperature with stirring, with the temperature falling to 15° C. After stirring for 30 min, 0.3 g (1.5 mmol, 5 mol %) of ruthenium (III) chloride hydrate were then added, with the temperature increasing back to 30° C. The mixture was stirred for 48 h at room temperature, in the course of which, after 6 h, a further 6.50 g (30.5 mmol) of sodium periodate and 0.3 g (1.5 mmol, 5 mol %) of ruthenium (III) chloride hydrate were added. The reaction mixture was then poured into 500 ml of water and the product was extracted three times, each time with 200 ml of dichloromethane. The combined organic extracts were washed with 200 ml of 20% sodium hydrogen sulfite solution and 200 ml of water and dried over sodium sulfate. After removing the solvent on a rotary evaporator and flash chromatography (pentane/ether, 4:1, Rf=0.32) on silica gel, 3.3 g (50%) of 1-methyl-2,3-dihydro-1H-5,9-dioxacyclohepta[f]inden-7-one (2) were obtained as colorless crystals of m.p. 79-80° C.
- Odor: Linear, very intensive marine odor with strongly floral aspects. -IR (film): ν=1323/1280/1256/1351 cm−1 (n ring), 1735 cm−1 (ν C═O), 1041 cm−1 (ν C—O—C sym), 1482/1439/1577 cm−1 (ν C═C, Ar), 1155 cm−1 (ν C—O—C asym). -1H-NMR (CDCl3): δ=1.24 (d, J=7.0 Hz, 3H, 1-Me), 1.60 (qd, J=12.4, 8.7 Hz, 1H, 2-Hb), 2.30 (tdd, J=12.4, 7.7, 3.9 Hz, 1H, 2-Ha), 2.74 (ddd, J=15.7, 8.7, 7.7 Hz, 1H, 3-Hb), 2.82 (ddd, J=15.7, 8.7, 3.9 Hz, 1H, 3-Ha) 3.10 (br. sext, J=7.0 Hz, 1H, 1-H), 4.66 (d, J=1.6 Hz, 4H, 6-,8-H2), 6.80 (s, 1H, 4-H), 6.83 (s, 1H, 10-H). -13C-NMR (CDCl3): δ=19.78 (q, 1-Me), 30.70 (t, C-2), 35.13 (t, C-3), 38.88 (d, C-1), 75.49/75.53 (2t, C-6,-8), 115.15/116.17 (2d, C-4,-10), 139.19 (s, C-10a), 144.39 (s, C-3a), 146.82/146.97 (2s, C-4a, 9a), 205.03 (s, C-7). -MS (EI): m/z (%)=91 (97) [C7H7 +], 103 (20) [C8H7 +], 115 (13) [C8H19 +], 175 (14), [M+-CH3-CO], 203 (100) M+-CH3], 218 (57) [M+].
- The compounds of the general formula I listed in the examples below were synthesized according to the process of Example 2 by reaction of veratrol with the corresponding unsaturated and saturated carboxylic acids. Therefore, of these, only the odor descriptions and the spectroscopic data are listed.
- Odor: Very intensive and diffuse, linear, marine odor with nuances of Adoxal® (2,6,10-trimethylundec-9-en-1-al). - IR (film): ν=1502/1435/1581/1467 cm−1 (ν C═C, Ar), 1265/1304/1201 cm−1 (ν ring), 1050 cm−1 (ν C—O—C sym), 1740 cm−1 (ν C═O), - 1H-NMR (CDCl3): δ=0.92 (d, J=6.4 Hz, 6H, 3′-Me2), 1.46/1.47 (2dd, J=8.0, 6.8 Hz, 2H, 2′-H2), 1.57 (nonett, J=6.8 Hz, 1H, 3′-H), 2.52 (t, J=8.0 Hz, 2H, 1′-H2), 4.68 (d, J=9.2 Hz, 4H, 2-, 4-H2), 6.77 (dd, J=8.2, 2.4 Hz, 1H, 8-H), 6.82 (d, J=2.4 Hz, 1H, 6-H), 6.90 (d, J=8.4 Hz, 1H, 9-H). - 13C-NMR (CDCl3) δ=22.36 (2q, 3′-Me2), 27.43 (d, C-3′), 32.69 (t, C-1′), 40.53 (t, C-2′), 75.35/75.63 (2t, C-2,-4), 120.27/120.50 (d, C-6,-9), 123.45 (d, C-8), 138.99 (s, C-7), 146.00/147.86 (2s, C-5a,-9a), 204.71 (s, C-3). - MS (EI): m/z (%)=77 (26) [C6H6 +], 135 (12) [M+-C4H9—C2H2O], 149 (21) [M+-C4H9—CO], 177 (100) [M+-C4H9], 191 (7) [M+-C3H7], 234 (52) [M+].
- Odor: Marine-aldehyde-like, floral-rosy odor with nuances of citronelloxyacetaldehyde [(3,7-dimethyl-6-octenyl)oxyacetaldehyde]. - IR (film): ν=1322/1253/1281/1350 cm−1 (ν ring), 1040/1067 cm−1 (ν C—O—C), 1484/1438 cm−1 (ν C═C, Ar), 1736 cm−1 (ν C═O). 1H-NMR (CDCl3) δ=1.22 (s, 6H, 1-Me2), 1.92 (t, J=7.2 Hz, 2H, 2-H2), 2.79 (t, J=7.2 Hz, 2H, 3-H2), 4.67 (d, J=2.8 Hz, 4H, 6-, 8-H2), 6.75 (s, 1H, 4-H), 6.81 (s, 1H, 10-H). - 13C-NMR (CDCl3): δ=28.43 (2q, 1-Me2), 29.29 (t, C-3), 41.68 (t, C-2), 43.61 (s, C-1), 75.47/75.51 (2t, C-6,-8), 113.99 (d, C-10), 116.31 (d, C-4), 138.98 (s, C-3a), 146.83/147.22 (2s, C-4a, -9a), 148.30 (s, C-10a), 205.06 (s, C-7). - MS (EI): m/z (%)=133 (33) [C9H9O+], 145 (6) [C11H13 +], 161 (7) [M+-CH3-2CO], 189 (2) [M+-CH3CO], 217 (100) [M+-CH3], 232 (30) [M+].
- Odor: Intensive, marine-floral odor. IR (film): ν=1501/1434/1460/1580 cm−1 (ν C═C, Ar), 1265/1302/1201 cm−1 (ν ring), 1050 cm−1 (ν C—O—C), 1740 cm−1 (ν C═O). - 1H-NMR (CDCl3): δ=0.84 (d, J=6.4 Hz, 3H, 2′-Me), 0.90 (t, J=7.5 Hz, 3H, 4′-H2), 1.16 (mc, 1H, 3′-Hb), 1.39 (m1c, 1H, 3′-Ha), 160 (mc, 1H, 2′-H), 2.28 (dd, J=11.6, 8.0 Hz, 1H, 1′-Hb), 2.53 (dd, J=11.6, 6.0 Hz, 1H, 1′-Ha), 4.69 (d, J=8.4 Hz, 4H, 2-, 4-H2), 6.74 (dd, J=8.0, 2.0 Hz, 1H, 8-H), 6.78 (d, J=2.0 Hz, 1H, 6-H), 6.90 (d, J=8.0 Hz, 1H, 9-H). - 13C-NMR (CDCl3): δ=11.32 (q, C-4′), 18.75 (q, 2′-Me), 28.95 (t, C-3′), 36.42 (d, C-2′), 42.22 (t, C-1′), 75.36/75.64 (2t, C-2,-4), 120.30/121.03 (2d, C-6,-9), 124.27 (d, C-8), 137.62 (s, C-7), 146.06/147.70 (2s, C-5a,-9a) , 204.74 (s, C-3), - MS (EI): m/z (%)=77 (11) [C8H5 +], 91 (7) [C7H7 +], 135 (5) [M+-C4H9—C2O], 149 (4) [M+-C4H9—CO], 177 (100) [M+-C4H9], 191 (2) [M+-C3H7], 205 (1) [M+-C2H5], 219 (1) [M+-CH3], 234 (26) [M+].
- Odor: Marine, floral odor with aldehydic nuances. -IR (film): ν=1502/1435/1580 cm−1 (ν C═C, Ar), 1265/1304/1201 cm−1 (ν ring), 1050 cm−1 (ν C—O—C), 1740 cm−1 (ν C═O). - 1H-NMR (CDCl3): δ=0.89 (t, J=7.0 Hz, 3H, 5′-H2), 1.28-1.35 (m, 4H, 3′-, 4′-H2), 1.59 (br. quint, J=7.6 Hz, 2H, 2′-H2), 2.51 (t, J=7.8 Hz, 2H, 1′-H2), 4.69 (d, J=9.6 Hz, 4H, 2-, 4-H2), 6.77 (dd, J=8.0, 2.0 Hz, 1H, 8-H), 6.81 (d, J=2.0 Hz, 1H, 6-H), 6.90 (d, J=8.0 Hz, 1H, 9-H). - 13C-NMR (CDCl3): δ=13.88 (q, C-5′), 22.38 (t, C-4′), 30.90/31.26 (2t, C-2′, -3′), 34.84 (t, C-1′), 75.35/75.64 (2t, C-2,-4), 120.31/120.47 (2d, C-6,-9), 123.51 (d, C-8), 138.85 (s, C-7), 146.03/147.83 (2s, C-5a,-9a), 204.72 (s, C-3-). - MS (EI): m/z (%) =77 (18) [C6H5 +], 91 (10) [C7H7 +], 135 (9) [M+-C4H9—C2H2O], 149 (22) [M+-C4H9—CO], 177 (100) [M+-C4H9], 191 (8) [M+-C3H7], 205 (1) [M+-C2H5], 234 (42) [M+].
- Odor: Mixed odor of walnuts, Trigonella foenum-graecum, seawater and moss. - IR (film): ν=1736 cm−1 (ν C═O), 1324/1263/1289/1352 cm−1 (ν ring), 1484/1439 cm−1 (ν C═C, Ar), 1042 cm−1 (ν C—O—C sym), 1159 cm−1 (ν C—O—C asym). - 1H-NMR (CDCl3): δ=0.95/1.08/1.17/1.24 (4d, J=7.0 Hz, 6H, 1-, 2-Me), 1.91-2.02 (m, 1H, 2-H), 2.41 (dd, J=15.0, 9.6 Hz)/ 2.49 (dd, J=15.0, 6.4 Hz)/ 2.55 (dd, J=14.0, 6.8 Hz)/ 2.59 (dd, J=14.0, 7.2 Hz) [2H, 3-H2], 2.89 (td, J=15.7, 7.2 Hz)/3.06 (quint, J=7.2 Hz) [1H, 1-H], 4.66 (d, J=1.6 Hz, 4H 4-, 8-H2), 6.76-6.80 (m, 2H, 4-, 10-H). - 13C-NMR (CDCl3): δ=14.50/15.00/17.54/18.31 (4q, 1,-2-Me), 38.64/39.38 (2t, C-3), 38.24/41.83/44.41/46.18 (4d, C-1,-2), 75.49/75.50/75.53/75.54 (4d, C-6,-8), 115.11/115.56/116.06/116.39 (4d, C-4,-10), 138.26/138.43 (2s, C-3a), 144.22/144.37 (2s, C-10a), 146.73/146.79/146.91/146.95 (4s, C-4a, -9a), 205.03/205.10 (2s,C-7). - MS (EI): m/z (%)=77 (13)/91(19)/105(20)/133(20)/161(7)/175(4) [CnH2n7 +], 189 (18) [M+-CH3—CO], 203 (1) [M+-C2H5], 217 (100) [M+-CH3], 232 (70) [M+].
- Odor: Marine, aquatic. - IR (film): ν=1502/1435/1580 cm−1 (ν C═C, Ar), 1265/1304/1201 cm−1 (ν ring), 1051 cm−1 (ν C—O—C), 1741 cm−1 (ν C═O). - 1H-NMR (CDCl3): δ=0.88 (t, J=6.8 Hz, 3H, 6′-H2), 1.27-1.35 (m, 6H, 3′-H2-5′-H2), 1.57 (br. quint, J=8.0 Hz, 2H, 2′-H2), 2.51 (t, J=7.8 Hz, 2H, 1′-H2), 4.68 (d, J=8.0 Hz, 4H, 2-, 4-H2), 6.77 (dd, J=8.0, 4.0 Hz, 1H, 8-H), 6.81 (d, J=4.0 Hz, 1H, 6-H), 6.90 (d, J=8.0 Hz, 1H, 9-H). - 13C-NMR (CDCl3): δ=13.96 (q, C-6′), 22.46 (t, C-5′), 28.77 (t, C-3′), 31.19/31.56 (2t,C-2′,-4′), 34.89 (t, C-1′), 75.35/75.63 (2t, C-2,-4), 120.31/120.47 (2d, C-6,-9), 123.50 (d, C-8), 138.85 (s, C-7), 146.03/147.83 (2s, C-5a,-9a), 204.73 (s, C-3). - MS (EI): m/z (%)=77 (16) [C8H6 +], 91 (9) [C7H7 +], 135 (9) [M+-C5H11—C2H2O], 149 (21) [M+-C5H11—CO], 177 (100) [M+-C5H11], 191 (2) [M+-C4H9], 205 (3) [M+-C3H7], 248 (43) [M+].
- Odor: Marine, animalic, civet-like, floral-aldehyde odor, also somewhat reminiscent of citronelloxyacetaldehyde ([3,7-dimethyl-6-octenyl]oxy-acetaldehyde). - IR (film): ν=1502/1435/1460/1580 cm−1 (ν C═C, Ar), 1265/1304/1202 cm−1 (ν ring), 1051 cm−1 (ν C—C—C), 1741 cm−1 (ν C═O). - 1H-NMR (CDCl3): δ=0.87 (t, J=7.2 Hz, 3H, 5′-H3), 0.91 (d, J=6.4 Hz, 3H, 3′-Me), 1.18 (mc1 1H, 2′-Hb), 1.34-1.43 (m, 3H, 2′-Ha, 4′-H2), 1.56-1.62 (m, 1H, 3′-H), 2.48 (ddd, J=14.0, 10.0, 6.4 Hz, 1H, 1′-Ha), 2.56 (ddd, J=14.0, 10.4, 5.2 Hz, 1H, 1′-Hb), 4.67 (d, J=2.4 Hz, 4H, 2-,4-H2), 6.78 (dd, J=8.2, 2.4 Hz, 1H, 8-H), 6.82 (d, J=2.0 Hz, 1H, 6-H), 6.90 (d, J=8. 4 Hz, 1H, 9-H). - 13C-NMR (CDCl3): δ11.14 (q, C-5′), 18.93 (q, 3′-Me), 29.18 (t, C-4′), 32.42 (t, C-1′) 33.84 (d, C-3′) 38.23 (t, C-2′) 22.38 (t, C-4′), 30.90/31.26 (2t, C-2′,-3′), 75.35/75.64 (2t, C-2,-4), 120.27/120.51 (2d, C-6,-9), 123.45 (d, C-8), 139.11 (s, C-7), 146.00/147.86 (2s, C-5a,-9a) , 204.72 (s, C-3). -MS (EI): m/z (%)=77 (21) [C8H5 +], 92 (14) [C7H8 +], 135 (11) [M+-C5H11—C2H2O], 149 (16) [M+-C5H11—CO], 177 (100) [M+-C5H11], 191 (4) [M+-C4H9], 205 (7) [M+-C3H7], 248 (45) [M+].
- Odor: Marine, floral-aldehyde odor. - IR (film): ν=1501/1434/1460/1580 cm−1 (ν C═C, Ar), 1265/1303/1201 cm−1 (ν ring), 1049 cm−1 (ν C—O—C), 1740 cm−1 (ν C═O), - 1H-NMR (CDCl3): 5=0.83 (d, 3H, 2′-Me), 0.88 (t, J=7.0 Hz, 3H, 5′-H3), 1.11-1.40 (m, 4H, 3′-, 4′-H2), 1.68 (mc1 1H, 2′-H), 2.26 (dd, J=13.6, 8.4 Hz, 1H, 1′-Hb), 2.54 (dd, J=13.6, 6.0 Hz, 1H, 1′-Ha), 4.69 (d, J=8.4 Hz, 4H, 2-,4-H2), 6.73 (dd, J=8.0, 2.0 Hz, 1H, 8-H), 6.78 (d, J=2.0 Hz, 1H, 6-H), 6.89 (d, J=8.0 Hz, 1H, 9-H). - 13C-NMR (CDCl3): δ=14.15 (q, C-5′), 19.17 (q, 2′-Me), 20.02 (t, C-4′), 34.50 (d, C-2′), 38.77 (t, C-3′), 42.61 (t, C-1′), 75.36/75.63 (2t, C-2,-4), 120.30/121.04 (2d, C-6,-9), 124.28 (d, C-8), 137.61 (s, C-7), 146.05/147.70 (2s, C-5a,-9a), 204.77 (s, C-3). -MS (EI): m/z (%)=77 (9) [C6H5 +], 91 (6) [C7H7 +], 135 (5) [M+-C5H11-C2H2O], 149 (3) [M+-C5H11—CO], 177 (100) [M+-C5H11], 205 (2) [M+-C3H7], 248 (21) [M+].
- Odor: Marine, floral-aldehyde odor. - IR (film): ν=1502/1418/1466/1580 cm−1 (ν C═C, Ar) , 1265/1304/1201 cm−1 (ν ring), 1050 cm−1 (ν C—O—C), 1741 cm−1 (ν C═O). - 1H-NMR (CDCl3): δ=0.88 (2d, J=6.4 Hz, 6H, 4′-Me2), 1.18-1.24 (m, 2H, 3′-H2), 1.53-1.61 (m, 4H, 2′-H2, 4′-H), 2.50 (t, J=7.8 Hz, 2H, 1′-H2), 4.69 (d, J=8.0 Hz, 4H, 2-, 4-H2), 6.78 (dd, J=8.0, 4.0 Hz, 1H, 8-H), 6.82 (d, J=4.0 Hz, 1H, 6-H), 6.90 (d,J=8.0 Hz, 1H, 9-H). -13C-NMR (CDCl3): δ=22.44 (2q, 4′-Me2), 27.74 (d, C-4′), 29.07 (t, C-2′), 35.14 (t, C-1′), 38.39 (t, C-3′), 75.35/75.63 (2t, C-2,-4), 120.30/120.48 (2d, C-6,-9), 123.50 (d, C-8), 138.86 (s, C-7), 146.03/147.83 (2s, C-5a,-9a), 204.76 (s, C-3). -MS (EI): m/z (%)=77 (13) [C6H5 +], 91 (8) [C7H7 +], 135 (7) [M+-C5H11—C2H2O], 149 (16) [M+-C5H11—CO], 177 (100) [M+-C5H11], 191 (1) [M+-C4H9], 205 (3) [M+-C3H7], 248 (38) [M+].
- The compounds 7-(2-ethylbutyl)benzo[b][1,4]dioxepin-3-one and 7-heptylbenzo[b][1,4]dioxapin-3-one also have the faceted marine odor typical of this class of compound and are therefore suitable, as are the abovementioned compounds, for preparing harmonious fragrance blends having marine notes. In this regard, the abovementioned compounds 1 and 3 are particularly outstanding, as shown by the examples below.
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Floral-marine-fruity women's fragrance containing compound 1 Contents by weight in parts per No. Compound/constituent thousand 1. Citronellol extra 30 2. Cyclohexal 150 3. Damascone 10% in DPG 2 4. gamma-Decalactone 2 5. beta-Dihydroionone 55 6. DPG (dipropylene glycol) 76 7. Eugenol, pure 35 8. Galaxolid 50 BB 275 9. Hedion 110 10, Iso E Super 145 11. Jasmolactone (Firmenich) 1 25 percent strength in DPG 12. Linalool, synthetic 30 13 Compound 1, 10% in DPG 65 1000 - The composition produces a feminine-sensual, transparent, modern perfume with a rosy-floral, fresh jasmine-like head and floral-fruity heart note with spicy aspects on a musky-wooden base.
- Compound 1 gives the composition its marine aspects, and gives it its radiance and richness in character. It transforms the traditional floral fragrance into a modern-transparent, trend perfume. In comparison with the compound 7-methylbenzo[b][1.4]dioxepin-3-one, that is to say Calon 1951® mentioned at the outset, compound 1 is much more intense and, at the same dosage, is accompanied by a much stronger marine impression without transition into fishy or salty, as is the case with Calon 1951® at the high dosage here. The compound 1 is much more floral than Calon 1951® and therefore harmonizes much better with the floral elements of the composition. It develops the floral-aquatic accord, while remaining transparent.
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Feminine floral-marine perfume containing compound 3 Contents by weight in parts per No. Compound/constituent thousand 1. Algenon PB 100 2. Benzyl salicylate 110 3. Bergamot oil, Italian 50 4. Boisambren forte 10 5. Cyclohexal 12 6. Dihydromyrcenol 35 7. DPG (dipropylene glycol) 358 8. Eugenol, pure 10 9. Fixolid 10 10. Galaxolid 50 PHT 65 11. Georgywood 25 12. Hedion 20 13. Linalool, synthetic 10 14. Linalyl acetate, synthetic 30 15. Sandela 25 16. Tropional 75 17. Vertofix Coeur 35 18. Compound 3, 10% in DPG 20 1000 - Compound 3 enhances the fresh, marine impression of the composition. It combines harmoniously with the hesperidic topnote, emphasizes the floral heart note and finally blends in the base with woody and musk-like notes to give a character harmonious composition. Compound 3 provides volume, radiance and body to the composition. It gives the impression of a fresh sea breeze. Compared with Calon 1951® (see Example 12), compound 3 is much more intense, but nevertheless does not have a heavy or suppressive effect on the other constituents of the composition. In contrast, compound 3 brings the perfume more radiance, diffusivity and volume than Calon 1951®.
- The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are intended to be included within the scope of the following claims.
Claims (13)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/424,612 US7022664B2 (en) | 2000-03-23 | 2003-04-28 | 1,2 Substituted 2,3-dihydro-1H-5,9 dioxacyclohepta[F]indden-7-ones and 7-substituted benzo[B][1,4]dioxepin-3-ones |
US11/218,108 US7235519B2 (en) | 2000-03-23 | 2005-09-01 | 1,2-substituted 2,3-dehydro-1H-5,9-dioxyacyclohepta[f]inden-7-ones and 7-substituted benzo[b]dioxepin-3-ones |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH20000557/00 | 2000-03-23 | ||
CH5572000 | 2000-03-23 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/424,612 Continuation US7022664B2 (en) | 2000-03-23 | 2003-04-28 | 1,2 Substituted 2,3-dihydro-1H-5,9 dioxacyclohepta[F]indden-7-ones and 7-substituted benzo[B][1,4]dioxepin-3-ones |
Publications (1)
Publication Number | Publication Date |
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US20010044407A1 true US20010044407A1 (en) | 2001-11-22 |
Family
ID=4520070
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/816,631 Abandoned US20010044407A1 (en) | 2000-03-23 | 2001-03-23 | 1,2-substituted 2,3-dihydro-1H-5,9-dioxacyclohepta [ f ] inden -7- ones and 7-substituted benzo [ b ] [ 1,4 ] dioxepin -3-ones |
US10/424,612 Expired - Fee Related US7022664B2 (en) | 2000-03-23 | 2003-04-28 | 1,2 Substituted 2,3-dihydro-1H-5,9 dioxacyclohepta[F]indden-7-ones and 7-substituted benzo[B][1,4]dioxepin-3-ones |
US11/218,108 Expired - Lifetime US7235519B2 (en) | 2000-03-23 | 2005-09-01 | 1,2-substituted 2,3-dehydro-1H-5,9-dioxyacyclohepta[f]inden-7-ones and 7-substituted benzo[b]dioxepin-3-ones |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/424,612 Expired - Fee Related US7022664B2 (en) | 2000-03-23 | 2003-04-28 | 1,2 Substituted 2,3-dihydro-1H-5,9 dioxacyclohepta[F]indden-7-ones and 7-substituted benzo[B][1,4]dioxepin-3-ones |
US11/218,108 Expired - Lifetime US7235519B2 (en) | 2000-03-23 | 2005-09-01 | 1,2-substituted 2,3-dehydro-1H-5,9-dioxyacyclohepta[f]inden-7-ones and 7-substituted benzo[b]dioxepin-3-ones |
Country Status (13)
Country | Link |
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US (3) | US20010044407A1 (en) |
EP (1) | EP1136481B1 (en) |
JP (1) | JP4860048B2 (en) |
CN (1) | CN1189464C (en) |
AT (1) | ATE227713T1 (en) |
AU (1) | AU2651001A (en) |
BR (1) | BR0101128B1 (en) |
CA (1) | CA2341133A1 (en) |
DE (1) | DE60100045T2 (en) |
ES (1) | ES2185605T3 (en) |
MX (1) | MXPA01002811A (en) |
SG (1) | SG165144A1 (en) |
ZA (1) | ZA200102392B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102007055124A1 (en) | 2007-11-19 | 2009-05-20 | Symrise Gmbh & Co. Kg | New 7-(3-methylbut-2-en-1-yl)-2H-1,5-benzodioxepin-3(4H)-one, useful as fragrance and/or flavor material, and in e.g. shampoo, softener, detergent, pre-shave product, floor cleaner, air freshener and sunscreen cream |
GB0906821D0 (en) * | 2009-04-21 | 2009-06-03 | Givaudan Sa | Compound |
GB201002216D0 (en) * | 2010-02-10 | 2010-03-31 | Givaudan Sa | Compounds |
BR112013007495A2 (en) | 2010-10-04 | 2024-03-12 | Firmenich & Cie | BENZODIOXOL DERIVATIVES AS AQUEOUS ODORANTS |
FR2975283B1 (en) | 2011-05-17 | 2019-04-05 | V. Mane Fils | SENSORY USE OF 6-CYCLOPENTYLIDENEHEXANE DERIVATIVES |
FR2981070B1 (en) | 2011-10-11 | 2014-01-10 | V Mane Fils | NOVEL CYCLOALCANIC ALDEHYDES, PROCESS FOR THEIR PREPARATION AND USE IN PERFUMERY |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3517031A (en) * | 1966-08-15 | 1970-06-23 | Pfizer & Co C | 1,5-benzoxepin- and -benzodioxepin-3-ones as flavor and odorant agents |
US3584002A (en) * | 1968-08-26 | 1971-06-08 | Frosst & Co Charles E | Process for the preparation of 3-oxo-benzodioxepin |
US3799892A (en) * | 1971-10-19 | 1974-03-26 | Pfizer | Benzoxepin-3-ones and benzodioxepin-3-ones as perfume odorants |
US3944560A (en) * | 1972-05-01 | 1976-03-16 | Merck & Co., Inc. | 3-Hydroxy-3-(1,2,5-thiadiazolyloxyalkanol)-3,4-dihydro-2H-1,5-benzodioxepin products |
DE69812256T2 (en) * | 1997-09-09 | 2004-01-29 | Firmenich & Cie | 7-Propylbenzodioxepin-3-one and its use in perfumery |
-
2001
- 2001-03-10 AT AT01105987T patent/ATE227713T1/en not_active IP Right Cessation
- 2001-03-10 ES ES01105987T patent/ES2185605T3/en not_active Expired - Lifetime
- 2001-03-10 DE DE60100045T patent/DE60100045T2/en not_active Expired - Lifetime
- 2001-03-10 EP EP01105987A patent/EP1136481B1/en not_active Expired - Lifetime
- 2001-03-13 SG SG200101513-0A patent/SG165144A1/en unknown
- 2001-03-13 AU AU26510/01A patent/AU2651001A/en not_active Abandoned
- 2001-03-16 MX MXPA01002811A patent/MXPA01002811A/en unknown
- 2001-03-21 CA CA002341133A patent/CA2341133A1/en not_active Abandoned
- 2001-03-22 JP JP2001081900A patent/JP4860048B2/en not_active Expired - Lifetime
- 2001-03-22 BR BRPI0101128-6A patent/BR0101128B1/en not_active IP Right Cessation
- 2001-03-22 ZA ZA200102392A patent/ZA200102392B/en unknown
- 2001-03-23 US US09/816,631 patent/US20010044407A1/en not_active Abandoned
- 2001-03-23 CN CNB011118822A patent/CN1189464C/en not_active Expired - Lifetime
-
2003
- 2003-04-28 US US10/424,612 patent/US7022664B2/en not_active Expired - Fee Related
-
2005
- 2005-09-01 US US11/218,108 patent/US7235519B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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BR0101128B1 (en) | 2012-09-04 |
CA2341133A1 (en) | 2001-09-23 |
DE60100045T2 (en) | 2003-05-28 |
JP4860048B2 (en) | 2012-01-25 |
DE60100045D1 (en) | 2002-12-19 |
MXPA01002811A (en) | 2002-06-04 |
ZA200102392B (en) | 2001-09-25 |
CN1319598A (en) | 2001-10-31 |
EP1136481B1 (en) | 2002-11-13 |
SG165144A1 (en) | 2010-10-28 |
EP1136481A1 (en) | 2001-09-26 |
US20050288518A1 (en) | 2005-12-29 |
US20030207788A1 (en) | 2003-11-06 |
US7235519B2 (en) | 2007-06-26 |
BR0101128A (en) | 2001-11-06 |
CN1189464C (en) | 2005-02-16 |
JP2001270882A (en) | 2001-10-02 |
US7022664B2 (en) | 2006-04-04 |
AU2651001A (en) | 2001-09-27 |
ES2185605T3 (en) | 2003-05-01 |
ATE227713T1 (en) | 2002-11-15 |
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