CN1248570A - 甲基环十四-5-烯-1-酮 - Google Patents
甲基环十四-5-烯-1-酮 Download PDFInfo
- Publication number
- CN1248570A CN1248570A CN99118478A CN99118478A CN1248570A CN 1248570 A CN1248570 A CN 1248570A CN 99118478 A CN99118478 A CN 99118478A CN 99118478 A CN99118478 A CN 99118478A CN 1248570 A CN1248570 A CN 1248570A
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- Prior art keywords
- methyl
- alkene
- ketone
- ring
- mixture
- Prior art date
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- Granted
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- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 57
- 239000002304 perfume Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000796 flavoring agent Substances 0.000 description 15
- 244000153234 Hibiscus abelmoschus Species 0.000 description 14
- 238000004611 spectroscopical analysis Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- 230000008020 evaporation Effects 0.000 description 11
- 235000019634 flavors Nutrition 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 241000402754 Erythranthe moschata Species 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- -1 rose oxide compound Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- 235000013599 spices Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000013375 chromatographic separation Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- OEYQBKYISMRWQB-UHFFFAOYSA-N Santal Chemical compound C=1C(OC)=CC(O)=C(C2=O)C=1OC=C2C1=CC=C(O)C(O)=C1 OEYQBKYISMRWQB-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000013355 food flavoring agent Nutrition 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VDNDILHUSVTMNI-UHFFFAOYSA-N 2-chlorocyclododecan-1-one Chemical compound ClC1CCCCCCCCCCC1=O VDNDILHUSVTMNI-UHFFFAOYSA-N 0.000 description 3
- VVHFPKUGTHYGAU-UHFFFAOYSA-N 4-ethenyl-2-methylcyclododecan-1-one Chemical compound CC1CC(C=C)CCCCCCCCC1=O VVHFPKUGTHYGAU-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 229910000105 potassium hydride Inorganic materials 0.000 description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000019605 sweet taste sensations Nutrition 0.000 description 3
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- PHMRPWPDDRGGGF-UHFFFAOYSA-N 2-bromoprop-1-ene Chemical group CC(Br)=C PHMRPWPDDRGGGF-UHFFFAOYSA-N 0.000 description 2
- HFCRIEXUIWLUKX-UHFFFAOYSA-N 4-ethenyl-3-methylcyclododecan-1-one Chemical compound CC1CC(=O)CCCCCCCCC1C=C HFCRIEXUIWLUKX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- IJXHLVMUNBOGRR-UHFFFAOYSA-N Methyl nonanoate Natural products CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- YPZUZOLGGMJZJO-UHFFFAOYSA-N ambrofix Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OCC2 YPZUZOLGGMJZJO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000000484 citronellol Nutrition 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- OSOIQJGOYGSIMF-UHFFFAOYSA-N cyclopentadecanone Chemical compound O=C1CCCCCCCCCCCCCC1 OSOIQJGOYGSIMF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008786 sensory perception of smell Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ORHSGDMSYGKJJY-SAIIYOCFSA-N (1'r,6's)-2,2,4',7',7'-pentamethylspiro[1,3-dioxane-5,5'-bicyclo[4.1.0]heptane] Chemical compound C12([C@H]3[C@H](C3(C)C)CCC2C)COC(C)(C)OC1 ORHSGDMSYGKJJY-SAIIYOCFSA-N 0.000 description 1
- AVJMJMPVWWWELJ-DHZHZOJOSA-N (2e)-1-methoxy-3,7-dimethylocta-2,6-diene Chemical compound COC\C=C(/C)CCC=C(C)C AVJMJMPVWWWELJ-DHZHZOJOSA-N 0.000 description 1
- NVIPUOMWGQAOIT-UHFFFAOYSA-N (E)-7-Hexadecen-16-olide Natural products O=C1CCCCCC=CCCCCCCCCO1 NVIPUOMWGQAOIT-UHFFFAOYSA-N 0.000 description 1
- RNLHVODSMDJCBR-VURMDHGXSA-N (z)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol Chemical compound CC(O)C(C)\C=C/C1CC=C(C)C1(C)C RNLHVODSMDJCBR-VURMDHGXSA-N 0.000 description 1
- FVUGZKDGWGKCFE-UHFFFAOYSA-N 1-(2,3,8,8-tetramethyl-1,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanone Chemical compound CC1(C)CCCC2=C1CC(C(C)=O)(C)C(C)C2 FVUGZKDGWGKCFE-UHFFFAOYSA-N 0.000 description 1
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 1
- QUMXDOLUJCHOAY-UHFFFAOYSA-N 1-Phenylethyl acetate Chemical compound CC(=O)OC(C)C1=CC=CC=C1 QUMXDOLUJCHOAY-UHFFFAOYSA-N 0.000 description 1
- YGXQOFXPYXFZFY-UHFFFAOYSA-N 2-bromocyclododecan-1-one Chemical compound BrC1CCCCCCCCCCC1=O YGXQOFXPYXFZFY-UHFFFAOYSA-N 0.000 description 1
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- XQJMXPAEFMWDOZ-UHFFFAOYSA-N 3exo-benzoyloxy-tropane Natural products CN1C(C2)CCC1CC2OC(=O)C1=CC=CC=C1 XQJMXPAEFMWDOZ-UHFFFAOYSA-N 0.000 description 1
- INIOTLARNNSXAE-UHFFFAOYSA-N 4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1h-azulen-6-ol Chemical compound CC1CC(O)C=C(C)C2CC(=C(C)C)CC12 INIOTLARNNSXAE-UHFFFAOYSA-N 0.000 description 1
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- WTYGAUXICFETTC-UHFFFAOYSA-N cyclobarbital Chemical compound C=1CCCCC=1C1(CC)C(=O)NC(=O)NC1=O WTYGAUXICFETTC-UHFFFAOYSA-N 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- ODGMPRNNVXITJQ-UHFFFAOYSA-N ethyl 6-acetyloxyhexanoate Chemical compound CCOC(=O)CCCCCOC(C)=O ODGMPRNNVXITJQ-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography 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
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002596 lactones Chemical class 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
- 239000006210 lotion Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- BOPPSUHPZARXTH-UHFFFAOYSA-N ocean propanal Chemical compound O=CC(C)CC1=CC=C2OCOC2=C1 BOPPSUHPZARXTH-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001738 pogostemon cablin oil Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000019719 rose oil Nutrition 0.000 description 1
- 239000010666 rose oil Substances 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N trans-Rosenoxid Natural products CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0038—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing more than six carbon atoms
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- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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Abstract
通式Ⅰ化合物具有强类麝香气味。在式中,R1和R2是氢或甲基,先决条件是,当R1是甲基,R2是氢,和当R1是氢时,R2是甲基,通式Ⅰ化合物可以是Z-型和/或E-型的。
Description
本发明涉及甲基环十四-5-烯-1-酮类化合物和含至少一种甲基环十四-5-烯-1-酮的香味组合物。
尽管G.Ohloff,Fortschritte der chemischen Forschung[化学研究的进展],Vol.12/2,201陈述了具有多于13,少于19个碳原子的大环羰基化合物与获得的麝香味有关,但所有的商品麝香香料具有15,16或17个碳原子的环大小。有关14节环酮的嗅觉性能则了解得很少,只有个别情况。
US-A4,183,965描述了为减少食品的苦味,而使用2-和3-环十四烯-1-酮的混合物。该化合物也可用于香料中并且该化合物具有甜味,类麝香、类环十五烷酮,蜡质,似根味。
JP-A55-66534描述了通过加热1-乙烯基-3-顺式-环十二烯-1-醇与碱金属或碱金属氢化物而合成具有类麝香特征的5-顺式-环十四烯-1-酮。E.Yoshi和S.Kimoto.Chem.Pharm.Bull 17,629,1969和后来的M.Karpf和A.S.Dreiding:Helvetica chimica Acta,Vol.58(8),2409,1975叙述了顺式-和反式-3-甲基环十四-2-烯-1-酮和3-甲基环十四-3-烯-1-酮混合物的合成。但未给出这些化合物的嗅觉性质。
R.W.Thies和K.P.Daruwala:J.Org.Chem.1978,52,3798叙述了通过用氢化钾在六甲基磷酰胺中处理反式-或顺式-1-(1-丙烯基)-反式-环十三-3-烯-1-醇而制备3-甲基-反式-环十五-5-烯酮。
US-A5,354,735描述了作为香味成分的具有类麝香性质的3-甲基环十五-5-烯-1-酮的顺式-和反式异构体。顺式异构体更强些,更优美且具有更强的麝香味而且比反式异构体的动物味更少些,它具有较强的硝基麝香特征和黄葵种子味。
意外的是,现已发现通式I化合物,式中R1和R2是氢或甲基,先决条件是,当R1是甲基,则R2是氢,和当R1是氢,则R2是甲基,就通式I化合物来说有可能是Z-型和/或E型,具有强麝香样,即类硝基麝香,粉末的,水果味,且同时具有低阈值和很好的延缓性。
通式I最佳化合物是E-3-甲基环十四-5-烯-1-酮,意外的是,它具有比相应的Z-化合物、Z-3-甲基环十四-5-烯-1-酮强十倍以上的气味。E-3-甲基环十四-5-烯-1-酮具有0.2ng的气相色谱阈值而Z-3-甲基环十四-5-烯-1-酮为2.2ng。
通式I化合物和已知的麝香味一样被广泛使用,即它们与经常在香味组合物中使用的大量天然和合成产品相一致。尤其是基本特征方面,它们与类琥珀和木质谐香剂,如绿味油和柏木及檀香木味一起使用时能获得有利的效应。花体(中间)的香韵赋于通式I化合物以优雅和光亮。协调特别好的物质类的一些实例是:
天然产品,如橡苔净油、香叶油、茉莉净油、绿叶油、玫瑰油、檀香木油、岩兰草醇和依兰油等。
醇,如香茅醇、Ebanol、香叶醇、沉香醇、苯基乙基醇和Sandalore等。
醛和酮,如Florozone、(3-(4-乙基苯基)-2,2-二甲基丙醛)、羟基香茅醛、Iso-E-Super、Isoraldein、麦芽酚、甲基柏木酮、甲基紫罗酮和香兰素等。
醚和乙缩醛,如降龙涎香醚(ambrox)、香叶基甲基醚、玫瑰氧化物(RoseOxide)和Spirambrene、(2′,2′,3,7,7-五甲基-螺[双环[4.1.0]庚-2-5′-[1,3]二噁烷])等。
酯和内酯,如Berryflor、r-癸内酯和r-十一烷酸内酯等。
化合物I可在组合物的制剂中使用并且如上述所示,可以使用于范围很宽的已知香味剂和香味剂混合物。
通式I化合物的有利性质是可以广泛并各种各样的使用,首先在甜味的东方型产品中使用,其次用于有“馥奇香(fougere)”型、“素心兰香(chypre)”型和“花香”型趋向的香料中。
由于式I化合物的阈值低且优良的耐久性,所以它能用在高档的香精中,化妆品组合物中,并且适于大量生产的产品,如洗涤剂中。
通式I化合物可在很宽的浓度范围内使用,例如在洗涤剂中约0.1%而在醇溶液中的约40%(重量)。优选浓度为3-20%(重量)。但上限外的浓度也是有可能的,因为经验丰富的香料制造者使用较低或较高浓度时也能获得新的效果。包含一种或多种式I化合物的组合物可用于所有类型的加香日用品,如科隆香水、化妆水、香精、洗液、霜、香波、皂、润肤膏、底粉、祛臭剂、洗涤剂以及其它家用产品等。
在组合物的制剂中,通式I化合物可按已知方式,例如,通过1974年,伦敦,查普曼和霍尔公司出版的W.A.Poucher著的香料、化妆品、肥皂,第七版,第2卷(Perfumes,Cosmetics,Soaps,Vol.2,7th edition Chapman and Hall,London 1974)所描述的与其它香味剂或香味剂混合物一起使用。
通式I化合物可通过各种方法制备。
R1为H和R2为CH3的通式I化合物可通过第一方法以与通式II化合物的混合物形式制备。即顺式和反式-4-甲基环十四-6-烯-1-酮。为此,先使(4-羧基-3-甲基丁基)三苯基膦鎓溴化物经Wittig反应处理,例如,通过在四氢呋喃中用叔丁醇钾处理,其后加入9-氧代壬酸甲酯。所得产品,3-甲基十四-5-烯二酸二甲酯再经过偶姻缩合,然后用乙酐/吡啶处理。得到主要是Z-4-甲基-2-氧代环十四-6-烯基乙酸酯和Z-3-甲基-14-氧代环十四-5-烯基乙酸酯的混合物,用钙在氨中于低温下(-30℃→-70℃)处理,用溴苯破坏过量的钙。
这种方法产生一种混合物,包括:
E-3-甲基-环十四-5-烯酮 11%
Z-3-甲基-环十四-5-烯酮 35%
Z-4-甲基-环十四-6-烯酮 49%。
气味:强麝香味(硝基麝香),粉末状。
制备化合物I(R1=H,R2=CH3)的第二种方法,优选反式,从2-氯代环十二烷酮或2-溴代环十二烷酮开始,这些化合物以一步法从环十二烷酮制得的(JP 491 093 39,EP-A-051 233)。用碳酸锂在N-甲基吡咯烷酮中于回流温度下处理2-氯代环十二烷酮而产生下列的混合物,
5% Z-环十二-2-烯-1-酮
6% E-环十二-2-烯-1-酮
13% 环十二烷酮
57% E-环十二-3-烯-1-酮
16% Z-环十二-3-烯-1-酮。
上述混合物用1-溴-1-丙烯基镁溴化物在四氢呋喃中处理。处理后产生主要是顺式/反式-1-(1-丙烯基)环十二碳-3-烯-1-醇的混合物。在N-甲基吡咯烷酮中用氢化钠处理后,该化合物产生E-3-甲基环十四-5-烯-1-酮,Z-3-甲基环十四-5-烯-1-酮(E∶Z=3∶1)和两种非对映体的3-甲基-4-乙烯基环十二烷酮的混合物。
该混合物具有非常强的类麝香(硝基麝香)的气味,粉末状,直链,象新洗的衣服(在日光下干燥)。两种非对映体的3-甲基-4-乙烯基环十二烷酮的弱的、木质味完全为本发明两种麝香化合物E-3-甲基环十四-5-烯-1-酮和Z-3-甲基-环十四-5-烯-1-酮所掩蔽。
类似的E-和Z-3-甲基环十四-5-烯-1-酮的混合物可通过热解顺式/反式丙烯基环十二碳-3-烯-1-醇的甲硅烷基醚而制得。
式I化合物(R1=CH3,R2=H)可按下制备:
主要为E-环十二碳-3-烯-1-酮(74%)和Z-环十二碳-3-烯-1-酮(19%)的混合物在四氢呋喃中用异丙烯基镁溴化物处理,主要产生E-1-异丙烯基环十二碳-3-烯-1-醇。纯化的E-1-异丙烯基环十二碳-3-烯-1-醇是在有18-冠醚-6存在下,在N,N-二甲基乙酰胺中用氢化钾处理,得到非对映体的2-甲基-4-乙烯基环十二烷酮和E-2-甲基环十四-5-烯-1-酮的混合物。
E-2-甲基环十四-5-烯-1-酮的气味:麝香(硝基麝香),粉末状,甜味。
通过参照下面的实施例进一步说明本发明,但不对其进行限制。实施例1
把143g(0.313mol)的(4-羧基-3-甲基丁基)-三苯基膦鎓溴化物粉碎后引入630ml的四氢呋喃中。将生成的悬浮液搅拌10分钟,再冷却至-20℃并与70g(0.625mol)叔-丁醇钾的315ml四氢呋喃一起迅速制浆。把温度升至0℃,反应混合物转变成橙色。然后在-5℃-0℃下搅拌混合物45分钟。混合物冷却至-20℃,并加入76g(纯度70%)(0.285mol)的9-氧代壬酸甲酯。温度升至-1℃。放置使混合物热至室温(1小时30分钟)并于40℃下再搅拌1小时。把反应混合物倒入1.5升的冰水中,使用25ml 30%NaOH调节pH至14,用2×700ml的***萃取。水相的pH用100ml的正磷酸调至2-3;并用2×500ml***萃取水相。用300ml水和300ml饱和氯化钠溶液洗涤有机相。在Na2SO4上干燥并蒸发浓缩。粗制品102.9g用360ml甲醇稀释,再往其中加入3.4g对-甲苯磺酸,混合物回流3小时30分钟。加入过量的NaHCO3(固体)再通过蒸发浓缩混合物。粗制品(108.9g)在1kg硅胶60(Merck)(0.040mm-0.063mm)柱上用6升己烷/***4∶1和2升己烷/***3∶1洗脱进行色谱分离,可以获得57.3克Z-3-甲基十四-5-烯二酸二甲酯。
制品的光谱数据:IR(液相):3004;2928;2855;1740;1458;1436;1364;1251;1198;1168;
1011。NMR: (CDCl3,200MHz)5.4(2H)m;3.66(6H)s。MS: 298(0.8);266(20);248(7);235(34);224(60);206(10);
192(28);175(8);164(19);150(25);136(19);123(18);
109(38);95(66);87(30);81(94);75(69);68(69);59(75);
55(100);41(88);29(27)。实施例2
带油浴的干燥装置中装有2升的二甲苯,并通入氩气30分钟。油浴被加热至148℃。从100℃的内部温度起,将17.2g(0.750mol)的钠分成多份加入。在4小时期间内滴加56g(0.188mol)Z-3-甲基十四-5-烯二酸二甲酯的150ml二甲苯溶液。
内部温度升至134℃。在该温度下搅拌混合物30分钟然后冷却至室温,滴加120ml乙醇和50ml水。用400ml水和200ml饱和氯化钠溶液洗涤有机相,在Na2SO4上干燥并蒸发浓缩。以这种方法,可以获得36.6g粗制品。把该粗制品溶解于75ml的吡啶中,加入15.4g乙酐,混合物于80℃下搅拌4小时。制品倒入400ml冰水中,用浓盐酸调节pH至2再用2×200ml***萃取。用水和饱和氯化钠溶液洗涤有机相,于硫酸钠上干燥再通过蒸发浓缩。
该方法可得到41.5g的粗制品,将它在1kg硅胶60(Merek)(0.040mm-0.063mm)柱上进行色谱提纯。可以获得30.9g主要是Z-4-甲基-2-氧代-环十四-6-烯基乙酸酯和Z-3-甲基-14-氧代-环十四-5-烯基乙酸酯的混合物。
混合物的光谱数据:IR(液相):3006;2928;2857;1746;1727;1461;1373;1236;1087;1026。NMR: (CDCl3,200MHz)5.45(2H)m;5.1(2H)m;2.15(3H)s。MS: 280(1);238(9);220(9);202(3);191(1);177(4);163(4);
149(5);135(7);121(12);111(16);95(20);81(28);67(18);
55(28);43(100);29(8)。实施例3
往35.8g(0.893mol)的钙中,于-50℃下和20分钟过程中加完1.4升氨,混合物在-60℃下搅拌20分钟。在-50℃下和2小时过程中滴加30g主要为Z-4-甲基-2-氧代-环十四-6-烯基乙酸酯和Z-3-甲基-14-氧代-环十四-5-烯基乙酸酯在330ml四氢呋喃中的混合物,该混合物在-70℃下搅拌15分钟。再于30分钟期间滴加160ml的溴苯。放置混合物使其热至室温,通过蒸发除去氨。把产品倒在冰上,用正磷酸酸化至pH3,再用***萃取。用水和饱和氯化钠溶液洗涤有机相,于Na2SO4上干燥,并蒸发浓缩。粗制品(39.8g)在800g的硅胶60(Merck)(0.040-0.063mm)柱上进行色谱提纯。该法可得到13.7g以下的混合物:
E-3-甲基-环十四-5-烯酮 11%
Z-3-甲基-环十四-5-烯酮 35%
Z-4-甲基-环十四-6-烯酮 49%
混合物的气味:麝香(硝基麝香),粉末状。
E-3-甲基环十四-5-烯酮的气味:麝香,粉末状,动物的,类龙涎香状。
使用10%硝酸银通过硅胶柱(0.040-0.063mm)上进行另外的色谱分离可获得纯的单个化合物。
Z-3-甲基-环十四-5-烯-1-酮的光谱数据:IR:(液相):3008;2929;2859;1710;1460;1408;1369;1047;718。1H-NMR: (CDCl3 200MHz)5.46(2H)m;1.0(3H)d;J=7.5Hz。13C-NMR:(CDCl3)211.2(s);131.6(d);126.7(d);49.6(t);40.2;(t)32.8(t);30.6(d);
27.3(t);26.1(t);25.6(t);25.0(t);24.7(t);21.1(t);20.1(q)。MS: 222(25);207(5);193(4);179(11);164(17);147(8);135(17);121(19);
109(33);95(58);81(100);68(94);55(89);41(94);29(25)。
Z-4-甲基-环十四-6-烯-1-酮的光谱数据:IR(液相):3007;2928;2858;1711;1461;1408;1375;1287;1124;1046;712。1H-NMR: (CDCl3,200MHz)5.35(1H)m;5.48(1H)m;0.96(2H)d;J=
7.5Hz。13C-NMR:(CDCl3)212.1(s);130.8(d);127.7(d);40.2(t);39.7(t);33.4(d);
33.4(t);30.8(t);27.0(t);26.7(t);26.1(t);25.5(t);25.2(t);23.2(t);
19.6(q)。MS: 222(33);204(4);193(3);179(15);165(14);147(10);135(12);125(21);
111(47);98(56);81(60);67(55);55(100);41(70);29(23)。
E-3-甲基-环十四-5-烯-1-酮的光谱数据:IR(液相):2928;2856;1708;1458;1441;1365;970H-NMR: (CDCl3 400MHz)5.32(2H)m;2.86(1H)dd,J=17Hz,J=2Hz;
2.33(1H)m;0.95(3H)d;J=6.6Hz。13C-NMR:(CDCl3)212.4(s);132.8(d);129.9(d);46.2(t);42.9(t);31.1(t);29.0(d);
27.2(t);26.5(t);25.2(t);24.8(t);24.5(t);23.3(t);21.1(q)。MS: 222(69);207(14);193(6);179(15);164(34);154(1);147(12);135(30);
123(26);109(41);95(69);81(100);67(76);55(63);41(57);
28(16)。实施例4
往1.2升的N-甲基吡咯烷酮中添加100g的碳酸锂(1.35mol,粉状)和260g(1.2mol)的2-氯代环十二烷酮。搅拌下把混合物加热到180°-185℃,且消除CO2(时间:3小时)。冷却粗制混合物,倒入2.5升的水中并用己烷振荡萃取三次,有机相用水洗三遍,干燥和蒸发浓缩。在高真空(0.1mm)下蒸馏粗制品(238g)。初馏份(4.9g)后,可获得沸点为89-95℃/0.1mm的105g制品。气相色谱分析表明:
5% Z-环十二碳-2-烯-1-酮
6% E-环十二碳-2烯-1-酮
13% 环十二烷酮
57% E-环十二碳-3-烯-1-酮
16% Z-环十二碳-3-烯-1-酮。
Z-环十二碳-3-烯-1-酮的光谱数据:13C-NMR:(CDCl3)211.0(s);132.0(d);122.9(d);43.4(t);37.7(t);26.6(t);26.3(t);
24.3(t);24.1(t);23.5(t);23.0(t);22.6(t)。MS: 180(62);162(6);151(19);137(25);123(25);111(52);98(100);81(68);
67(82);54(84);41(60);27(12)。
E-环十二碳-3-烯-1-酮的光谱数据:H-NMR:(CDCl3 400MHz)5.7-5.61 d,t,t(1H);J=15.3Hz;J=1.2Hz;J
=7.4Hz;5.34-5.43 d,t,t(1H);J=15.2Hz;J=1.2Hz;J=
7.6Hz;3.04(2H)d;J=7.6Hz;2.48(2H)t;J=6.8Hz;
2.03(2H)m。13C-NMR:(CDCl3)209.7(s);136.3(d);122.8(d);48.3(t);39.6(t);32.2(t);26.3(t);
25.4(t);24.9(t);24.1(t);23.9(t);22.1(t)。MS: 180(68);162(62);151(17);137(23);123(23);111(51);98(100);81(63);
67(80);54(86);41(61);27(12)。实施例5
8.26g的镁(0.34mol)用少量碘晶体活化,加入25ml的四氢呋喃,并在70℃下缓慢滴加(滴加时间1小时30分钟)溶解于120ml四氢呋喃中的41g(0.34mol)1-溴-1-丙烯(顺/反混合物)。混合物在该温度下搅拌3小时。然后冷却至0℃,再于30分钟期间滴加完溶解于100ml四氢呋喃中主要为按实施例4制备的E-环十二碳-3-烯-1-酮(62%),Z-环己-3-烯-1-酮(18%)和E-环十二碳-2-烯-1-酮(7%)的51.2g混合物。混合物于室温下搅拌1小时30分钟,加入冰中冷却的饱和氯化铵溶液和水,再加入100ml***和37g磷酸。相分离后用***萃取两次。有机相用饱和氯化钠溶液洗涤,干燥并蒸发浓缩。获得60.7g(96%)粗制产品,这种产品是一种主要为1-顺式/1-反式-丙烯基环十二烷-3-烯-1-醇的混合物。为了表征形成的化合物,将3.6g粗制产物在110g硅胶60(Merck)柱(0.04-0.063mm)上进行色谱纯化(洗脱液:己烷/***,首先9∶1,之后2∶1)。
(1E,3E)-1-(1-丙烯基)环十二烷-3-烯-1-醇的光谱数据:H-NMR:(CDCl3 400MHz)5.71-5.51(3H)m;5.51-5.4(1H)m;ABX体系:
2.33(1H)dd,J=7.6;J=14Hz,2.25(1H)dd J=6Hz,J=14Hz;
2.1(2H)dd;J=5.6;J=5.6;1.7(3H)d,J=5Hz。13C-NMR:(CDCl3)138.1(d);134.7(d);125.3(d);122.8(d);74.7(s);43.0(t);
37.1(t);33.3(t);28.6(t);27.0(t);26.0(t);25.5(t);24.3(t);19.0(t);
17.8(q)。MS: 222(2);207(17);204(64);189(7);179(9);175(10);161(12);147(16);
133(26);119(33);105(51);97(60);91(58);84(69);79(55);69(100);
55(29);41(35);29(6)。
(1-Z,3E)-1-(1-丙烯基)环十二烷-3-烯-1-醇的光谱数据:H-NMR:(CDCl3,400MHz)5.69-5.3(4H)m,2.4(2H)d,J=6.5Hz,2.11(2H)dd
J=6Hz,J=6Hz,1.9(3H)d J=5.5Hz。13C-NMR:(CDCl3)136.2(d);134.9(d);126.5(d);125.3(d);75.8(s);44.6(t);
37.8(t);33.3(t);28.5(t);27.1(t);26.0(t);25.1(t);24.3(t);19.1(t);
14.5(q)。MS: 222(1);208(14);204(27);189(3);179(7);175(6);166(5);161(6);
151(9);147(8);133(12);124(12);119(16);105(25);97(44);91(28);
84(51);79(29);69(100);55(20);41(25);29(4)。实施例6
干燥设备装有11.1g按实施例5制备的丙烯基环十二烷-3-烯-1-醇(粗制品)的150ml N-甲基吡啶烷酮溶液,再加入4.8g氯化钠(55%)。氢以中等速度开始放出,温度升至30℃。然后于85℃下搅拌混合物5小时,冷却,滴加20ml的水。制品倒入200ml冰冷却的水中,用10ml的磷酸调节至pH5并用***萃取。有机相用水和饱和氯化钠溶液洗涤,干燥并蒸发浓缩。产品(13.6g)经色谱分离(380g硅胶,0.04-0.063mm;洗脱:己烷/***19∶1和8∶1)。除2.7g原料外,可获得3.6g制品。该制品由主要是E-3-甲基-环十四-5-烯-1-酮、Z-3-甲基环十四-5-烯-1-酮(E∶Z=3∶1)和赤型与苏型3-甲基-4-乙烯基环十二烷酮的混合物组成。该混合物具有非常强的类麝香(硝基麝香)气味,粉末状,直链,类似新洗的衣服(日光下干燥的)。各个化合物都能通过10%AgNO3硅胶的另外色谱纯化。
3-甲基-4-乙烯基环十二烷酮(1·非对映异构体)的光谱数据:IR(液相):3074;2932;2866;1707;1637;1467;1445;1368;1323;1173;1037;
994;911。H-NMR:(CDCl3,200MHz 5.7(1H)m;5.08(1H)m;5.0(1H)m;2.96(1H)dd;J=
18Hz;J=11Hz;0.84(3H)d;J=7.5Hz。13C-NMR:(CDCl3)211.6(s);141.3(d);114.8(t);44.4(t);43.4(t);41.1(d);31.8(d);
26.0(t);24.4(t);23.5(t);23.0(t);22.7(t);22.5(t);14.9(q)。MS: 222(1);207(2);193(5);165(4);151(8);37(14);123(17);109(29);
95(42);81(60);67(90);55(98);41(100);29(27)。
3-甲基-4-乙烯基环十二烷酮(2·非对映异构体)的光谱数据:H-NMR:(CDCl3,400MHz;5.55(1H)m;5.08(1H)m;5.05(1H)m;
0.9(3H)d;J=7Hz。13C-NMR:(CDCl3)211.7(s);138.6(d);116.4(t);49.6(t);43.10(d);38.2(t);
32.1(d);30.7(t);26.0(t);23.87(t);23.85(t);23.5(t);22.8(t);21.7(t);
16.0(q)。MS: 222(15);207(22);193(28);180(6);179(24);175(27);165(25);151(31);
137(54);123(58);109(70);95(76);81(84);67(95);55(100);41(81);
29(15)。实施例7
7g(0.3mol)镁涂上一层少量的四氢呋喃(50ml),再加入3g 2-溴丙烯的28ml四氢呋喃溶液。混合物简单地加热,反应开始。在90分钟期间滴加溶解在160ml四氢呋喃中的27g 2-溴丙烯。把冰浴用于冷却,以便使温度保持在55℃和60℃之间。混合物回流20分钟后冷却(20℃),再于1小时期间滴加溶解在50ml四氢呋喃中的40g(0.222mol)主要为E-环十二碳-3-烯-1-酮(74%)和Z-环十二碳-3-烯-1-酮(19%)的混合物。温度不得超过35℃。混合物再于室温下搅拌20分钟。反应产物倒入冰/水和氯化铵的混合物中,用甲基叔-丁基醚萃取,用水和饱和氯化钠溶液洗涤,在硫酸镁上干燥并蒸发浓缩。粗制品(48g)用色谱分离(己烷,甲基叔-丁基醚9∶1)。该法可产生37g的E-1-异丙烯基环十二烷-3-烯-1-醇。重结晶可得到纯度为95%的制品(33g)。
E-1-异丙烯基环十二烷-3-烯-1-醇的光谱数据:IR(KBr):3285;2988;2932;2861;1641;1448;1396;1368;1212;1024;1003;
981;898;700。H-NMR: (CDCl3,400MHz);5.43-5.73(2H)m;4.8-5(2H)m;1.8(3H)m。13C-NMR:(CDCl3)150.22(s);134.67(d);125.71(d);110.30(t);76.66(s);41.27(t);
34.64(t);33.24(t);28.42(t);26.98(t);26.00(t);24.93(t);24.42(t);
19.22(t);18.81(q)。实施例8
往25g(0.125mol)的氢化钾(20%油溶液)中加入200ml N,N-二甲基乙酰胺,34g 18-冠醚-6(Fluka)。再加入18g(0.085mol)的E-1-异丙烯基环十二烷-3-烯-1-醇(纯度95%)并迅速地加热至120℃,形成橙色溶液,该溶液在120℃下保持1分钟然后使其冷却至室温。反应混合物倒入水、冰和柠檬酸中并用己烷萃取。用水和饱和氯化钠溶液洗涤有机相直到中性,在硫酸镁上干燥并蒸发浓缩。粗制品(20g)用己烷和甲基叔-丁基醚进行色谱分离。产生4.2g非对映体环十二烷酮混合物,6.2g非对映体2-甲基-4-乙烯基环十二烷酮、E-2-甲基环十四-5-烯-1-酮的混合物和3g纯的E-2-甲基环十四-5-烯-1-酮。
非对映体的2-甲基-4-乙烯基环十二烷酮混合物的光谱数据:IR(液相):3075;2931;2864;1705;1639;1465;1444;1360;912。H-NMR:(CDCl3,200MHz)5.25-5.65(1H)m;5.1-4.9(2H)m;1.11(3H)d;J
=6.5Hz。MS: 222(14);207(7);193(24);180(8);179(17);175(19);175(22);150(75);
137(27);123(53);109(77);95(83);81(100);67(90);55(99);41(80);
29(15)。
E-2-甲基环十四-5-烯-1-酮的光谱数据:IR(液相):2929;2854;1704;1458;1374;972。H-NMR:(CDCl3,200MHz);5.35(2H)m;1.05(3H)d;J=6.5Hz。13C-NMR:(CDCl3)215.75(s);132.05(d);130.34(d);41.08(t);40.58(d);31.41(t);
30.81(t);29.38(t);26.88(t);26.33(t);25.93(t);24.63(t);24.61(t);
22.92(t);15.14(q)。MS: 222(100);207(4);193(41);175(17);165(31);150(46);140(34);135(24);
121(40);109(61);95(77);81(85);67(94);55(89);41(77);99(15)。织物柔软剂谐香剂
重量份E-3-甲基环十四-5-烯-1-酮(实施例3) 30乙酸苯基乙酯 30苄醇额外附加物 100己基肉桂醛 150香茅醇额外附加物 50香豆素 20Dynascone 10 1Floralozon 4Isoraldein 70 100百合醛[商] 250沉香醇,合成 100甲基苯乙酮 5甲基雪松酮 50Radjanol 10水杨酸戊酯 50萜品醇 50
1000
按实施例3制备的化合物使适于织物柔软剂的这种花香、木质谐香剂具有容积和洁。净度。作为良好的实质性的结果,使新鲜和洁净度保留在干洗的衣物上。优质香料谐香剂
比例(重量)E-3-甲基环十四-5-烯-1-酮(实施例3) 50乙酸苄酯 15乙酰乙酸乙酯 25乙基苯基醇 60己基肉桂醛 70黄葵内酯 10Ambrofix 2十三烷二酸亚乙酯 100香茅醇额外附加物 50Cyclogalbonate 4环己醛(cyclohexal) 20乙基沉香醇 80氧化八氢化萘甲酸酯 15栀子醇(Gardenol) 2Givescon 15Hedion 300吲哚10%PE 2Isoraldein 95 35顺式-茉莉酮 3百合醛 80Methyl pamplemousse 20黑胡椒香精 10三环萜醛 2托品醛(Tropional) 30
1000
按实施例3制备的化合物使这种适合醇香料的这种花香、透明的谐香剂具有浓厚、类麝香粉末效应,该效应与谐香剂的花香,水果香部分和谐地结合在一起。
Claims (10)
1.一种通式I的化合物,式中R1和R2是氢或甲基,先决条件是,当R1是甲基,R2是氢,和当R1是氢,则R2是甲基,就通式I的化合物来说有可以是呈Z-型和/或E-型。
2.E-3-甲基环十四-5-烯-1-酮。
3.Z-3-甲基环十四-5-烯-1-酮。
4.R-E-3-甲基环十四-5-烯-1-酮。
5.S-E-3-甲基环十四-5-烯-1-酮。
6.R-Z-3-甲基环十四-5-烯-1-酮。
7.S-Z-3-甲基环十四-5-烯-1-酮。
8.E-2-甲基环十四-5-烯-1-酮。
9.Z-2-甲基环十四-5-烯-1-酮。
10.一种香味组合物,它含有至少一种权利要求1-9中任一项所述的化合物。
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN99118478A Expired - Lifetime CN1113842C (zh) | 1998-09-03 | 1999-09-02 | 甲基环十四-5-烯-1-酮 |
Country Status (11)
Country | Link |
---|---|
US (1) | US6326349B1 (zh) |
EP (1) | EP0983989B1 (zh) |
JP (1) | JP3297408B2 (zh) |
CN (1) | CN1113842C (zh) |
AU (1) | AU720133B2 (zh) |
BR (1) | BR9903981B1 (zh) |
CA (1) | CA2281336A1 (zh) |
DE (1) | DE59901046D1 (zh) |
ES (1) | ES2172967T3 (zh) |
SG (1) | SG80643A1 (zh) |
ZA (1) | ZA995325B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106999619A (zh) * | 2014-12-18 | 2017-08-01 | 弗门尼舍有限公司 | 作为恶臭抵消成分的大环酮 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6720303B2 (en) * | 2001-11-01 | 2004-04-13 | International Flavors & Fragrances Inc. | Macrocyclic musk composition, organoleptic uses thereof and process for preparing same |
CA2520732C (en) | 2003-03-28 | 2012-12-04 | Sloan-Kettering Institute For Cancer Research | Migrastatin analogs and uses thereof |
WO2006001967A2 (en) * | 2004-05-25 | 2006-01-05 | Sloan-Kettering Institute For Cancer Research | Migrastatin analogs in the treatment of cancer |
WO2006034478A2 (en) * | 2004-09-23 | 2006-03-30 | Sloan-Kettering Institute For Cancer Research | Isomigrastatin analogs in the treatment of cancer |
EP1972632A1 (de) | 2007-03-21 | 2008-09-24 | Symrise GmbH & Co. KG | Oxabicycloalkanone als Riechstoffe |
EP2665715B1 (en) | 2011-01-18 | 2014-11-26 | Firmenich SA | Spiroepoxy macrocycles as perfuming ingredients |
US8450265B2 (en) | 2011-08-22 | 2013-05-28 | International Flavors & Fragrances Inc. | 3-methyl-6-cyclohexadecen-1-one and its use in perfume compositions |
BR112017007586B1 (pt) | 2014-11-07 | 2020-12-01 | Givaudan Sa | composição para perfume encapsulado, seu método de formação e produto para higiene pessoal sem enxague |
JP2017534639A (ja) * | 2014-11-07 | 2017-11-24 | ジボダン エス エー | 有機化合物におけるまたは関連する改良 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU627118A1 (ru) * | 1977-04-25 | 1978-10-05 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Способ получени 2-метилциклотетрадеканона |
JPS5566534A (en) * | 1978-11-13 | 1980-05-20 | Takasago Corp | Novel cyclic ketone compound and its preparation |
US4183965A (en) | 1978-12-26 | 1980-01-15 | International Flavors & Fragrances Inc. | 2- and 3-Cyclotetradecen-1-ones as bitterness depressants |
DE2934683A1 (de) * | 1979-08-28 | 1981-03-12 | Haarmann & Reimer Gmbh, 3450 Holzminden | 3-methyl-cyclohexadecen-5-on-1, verfahren zu seiner herstellung und seine verwendung als riechstoff. |
DE69314121T2 (de) * | 1992-07-30 | 1998-02-26 | Firmenich & Cie | Verwendung einer Cyclopentadecenone als Parfümszutat |
JPH10175882A (ja) * | 1996-12-13 | 1998-06-30 | Studienges Kohle Mbh | 閉環メタセシスによる機能化された大環状化合物の合成 |
-
1999
- 1999-08-18 SG SG9904121A patent/SG80643A1/en unknown
- 1999-08-19 ES ES99116318T patent/ES2172967T3/es not_active Expired - Lifetime
- 1999-08-19 DE DE59901046T patent/DE59901046D1/de not_active Expired - Lifetime
- 1999-08-19 EP EP99116318A patent/EP0983989B1/de not_active Expired - Lifetime
- 1999-08-20 ZA ZA9905325A patent/ZA995325B/xx unknown
- 1999-09-01 AU AU45867/99A patent/AU720133B2/en not_active Expired
- 1999-09-01 US US09/388,020 patent/US6326349B1/en not_active Expired - Lifetime
- 1999-09-01 BR BRPI9903981-8A patent/BR9903981B1/pt not_active IP Right Cessation
- 1999-09-02 CA CA002281336A patent/CA2281336A1/en not_active Abandoned
- 1999-09-02 JP JP24888499A patent/JP3297408B2/ja not_active Expired - Lifetime
- 1999-09-02 CN CN99118478A patent/CN1113842C/zh not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106999619A (zh) * | 2014-12-18 | 2017-08-01 | 弗门尼舍有限公司 | 作为恶臭抵消成分的大环酮 |
Also Published As
Publication number | Publication date |
---|---|
JP3297408B2 (ja) | 2002-07-02 |
EP0983989A1 (de) | 2000-03-08 |
ES2172967T3 (es) | 2002-10-01 |
AU720133B2 (en) | 2000-05-25 |
CN1113842C (zh) | 2003-07-09 |
DE59901046D1 (de) | 2002-05-02 |
JP2000178223A (ja) | 2000-06-27 |
BR9903981A (pt) | 2000-09-12 |
CA2281336A1 (en) | 2000-03-03 |
ZA995325B (en) | 2000-02-22 |
US6326349B1 (en) | 2001-12-04 |
AU4586799A (en) | 2000-03-30 |
EP0983989B1 (de) | 2002-03-27 |
BR9903981B1 (pt) | 2010-08-24 |
SG80643A1 (en) | 2001-05-22 |
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