CN101557857A - 环己烯基丁烯酮和包括它们的香料组合物 - Google Patents
环己烯基丁烯酮和包括它们的香料组合物 Download PDFInfo
- Publication number
- CN101557857A CN101557857A CNA2007800461665A CN200780046166A CN101557857A CN 101557857 A CN101557857 A CN 101557857A CN A2007800461665 A CNA2007800461665 A CN A2007800461665A CN 200780046166 A CN200780046166 A CN 200780046166A CN 101557857 A CN101557857 A CN 101557857A
- Authority
- CN
- China
- Prior art keywords
- ethyl
- methyl
- ketone
- thiazolinyl
- ene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000003205 fragrance Substances 0.000 title claims abstract description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 40
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000796 flavoring agent Substances 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 235000019634 flavors Nutrition 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000002537 cosmetic Substances 0.000 claims description 3
- 235000013355 food flavoring agent Nutrition 0.000 claims 3
- 230000002708 enhancing effect Effects 0.000 claims 1
- BYNGCOYMHJLARI-UHFFFAOYSA-N 1-(cyclohexen-1-yl)but-3-en-2-one Chemical class C=CC(=O)CC1=CCCCC1 BYNGCOYMHJLARI-UHFFFAOYSA-N 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000002304 perfume Substances 0.000 description 38
- 235000013599 spices Nutrition 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 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 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 230000035943 smell Effects 0.000 description 13
- 230000002159 abnormal effect Effects 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000220317 Rosa Species 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 6
- -1 Oleum Rosae Rugosae Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 235000013399 edible fruits Nutrition 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000001674 (E)-1-(2,6,6-trimethyl-1-cyclohexenyl)but-2-en-1-one Substances 0.000 description 5
- XEJGJTYRUWUFFD-FNORWQNLSA-N (e)-1-(2,6,6-trimethyl-1-cyclohex-3-enyl)but-2-en-1-one Chemical compound C\C=C\C(=O)C1C(C)C=CCC1(C)C XEJGJTYRUWUFFD-FNORWQNLSA-N 0.000 description 5
- BGTBFNDXYDYBEY-UHFFFAOYSA-N 1-(2,6,6-trimethylcyclohexen-1-yl)but-2-en-1-one Chemical compound CC=CC(=O)C1=C(C)CCCC1(C)C BGTBFNDXYDYBEY-UHFFFAOYSA-N 0.000 description 5
- POIARNZEYGURDG-UHFFFAOYSA-N beta-damascenone Natural products CC=CC(=O)C1=C(C)C=CCC1(C)C POIARNZEYGURDG-UHFFFAOYSA-N 0.000 description 5
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035807 sensation Effects 0.000 description 5
- 235000019615 sensations Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- NFAVNWJJYQAGNB-UHFFFAOYSA-N 2-methylundecanal Chemical compound CCCCCCCCCC(C)C=O NFAVNWJJYQAGNB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000628997 Flos Species 0.000 description 3
- 235000001466 Ribes nigrum Nutrition 0.000 description 3
- 241001312569 Ribes nigrum Species 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- PHXATPHONSXBIL-UHFFFAOYSA-N xi-gamma-Undecalactone Chemical compound CCCCCCCC1CCC(=O)O1 PHXATPHONSXBIL-UHFFFAOYSA-N 0.000 description 3
- WTOYNNBCKUYIKC-JMSVASOKSA-N (+)-nootkatone Chemical compound C1C[C@@H](C(C)=C)C[C@@]2(C)[C@H](C)CC(=O)C=C21 WTOYNNBCKUYIKC-JMSVASOKSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 2
- CRIGTVCBMUKRSL-FNORWQNLSA-N 1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-enone Chemical compound C\C=C\C(=O)C1C(C)=CCCC1(C)C CRIGTVCBMUKRSL-FNORWQNLSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 2
- 244000020998 Acacia farnesiana Species 0.000 description 2
- 235000003074 Acacia farnesiana Nutrition 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NUPSHWCALHZGOV-UHFFFAOYSA-N Decyl acetate Chemical compound CCCCCCCCCCOC(C)=O NUPSHWCALHZGOV-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
- UUQHKWMIDYRWHH-UHFFFAOYSA-N Methyl beta-orcinolcarboxylate Chemical group COC(=O)C1=C(C)C=C(O)C(C)=C1O UUQHKWMIDYRWHH-UHFFFAOYSA-N 0.000 description 2
- 240000005125 Myrtus communis Species 0.000 description 2
- 235000013418 Myrtus communis Nutrition 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- CRIGTVCBMUKRSL-UHFFFAOYSA-N alpha-Damascone Natural products CC=CC(=O)C1C(C)=CCCC1(C)C CRIGTVCBMUKRSL-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- HQKQRXZEXPXXIG-VJOHVRBBSA-N chembl2333940 Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@H]1[C@@](OC(C)=O)(C)CC2 HQKQRXZEXPXXIG-VJOHVRBBSA-N 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- JOZKFWLRHCDGJA-UHFFFAOYSA-N citronellol acetate Chemical compound CC(=O)OCCC(C)CCC=C(C)C JOZKFWLRHCDGJA-UHFFFAOYSA-N 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- IFYYFLINQYPWGJ-UHFFFAOYSA-N gamma-decalactone Chemical compound CCCCCCC1CCC(=O)O1 IFYYFLINQYPWGJ-UHFFFAOYSA-N 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 2
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 229930007744 linalool Natural products 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- FINOAUDUYKVGDS-UHFFFAOYSA-N (2-tert-butylcyclohexyl) acetate Chemical compound CC(=O)OC1CCCCC1C(C)(C)C FINOAUDUYKVGDS-UHFFFAOYSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 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
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-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
- DCSCXTJOXBUFGB-JGVFFNPUSA-N (R)-(+)-Verbenone Natural products CC1=CC(=O)[C@@H]2C(C)(C)[C@H]1C2 DCSCXTJOXBUFGB-JGVFFNPUSA-N 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- DCSCXTJOXBUFGB-SFYZADRCSA-N (R)-(+)-verbenone Chemical compound CC1=CC(=O)[C@H]2C(C)(C)[C@@H]1C2 DCSCXTJOXBUFGB-SFYZADRCSA-N 0.000 description 1
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 1
- IXLLBXDECOMIBP-FNORWQNLSA-N (e)-1-(2,2-dimethyl-6-methylidenecyclohexyl)but-2-en-1-one Chemical compound C\C=C\C(=O)C1C(=C)CCCC1(C)C IXLLBXDECOMIBP-FNORWQNLSA-N 0.000 description 1
- YJRODKCOICMRBO-BQYQJAHWSA-N (e)-4-(2,2,6-trimethylcyclohexyl)but-3-en-2-one Chemical compound CC1CCCC(C)(C)C1\C=C\C(C)=O YJRODKCOICMRBO-BQYQJAHWSA-N 0.000 description 1
- WSTQLNQRVZNEDV-CSKARUKUSA-N (e)-4-methyldec-3-en-5-ol Chemical compound CCCCCC(O)C(\C)=C\CC WSTQLNQRVZNEDV-CSKARUKUSA-N 0.000 description 1
- FXCYGAGBPZQRJE-ZHACJKMWSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-one Chemical compound CC1=CCCC(C)(C)C1\C=C\C(=O)CCC=C FXCYGAGBPZQRJE-ZHACJKMWSA-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
- YQYKESUTYHZAGG-BZNIZROVSA-N 1-[(1r,2s)-1,2,8,8-tetramethyl-1,3,4,5,6,7-hexahydronaphthalen-2-yl]ethanone Chemical compound C1([C@H]([C@@](CC2)(C)C(C)=O)C)=C2CCCC1(C)C YQYKESUTYHZAGG-BZNIZROVSA-N 0.000 description 1
- MZZRKEIUNOYYDF-UHFFFAOYSA-N 2,4-dimethylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1C=C(C)CCC1C=O MZZRKEIUNOYYDF-UHFFFAOYSA-N 0.000 description 1
- FAQVGPWFQGGIPP-UHFFFAOYSA-N 2-(2-methylpropyl)quinoline Chemical compound C1=CC=CC2=NC(CC(C)C)=CC=C21 FAQVGPWFQGGIPP-UHFFFAOYSA-N 0.000 description 1
- FLUWAIIVLCVEKF-UHFFFAOYSA-N 2-Methyl-1-phenyl-2-propanyl acetate Chemical compound CC(=O)OC(C)(C)CC1=CC=CC=C1 FLUWAIIVLCVEKF-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- ZHDQGHCZWWDMRS-UHFFFAOYSA-N 3,5-dimethylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1CC(C=O)CC(C)=C1 ZHDQGHCZWWDMRS-UHFFFAOYSA-N 0.000 description 1
- AUBLFWWZTFFBNU-UHFFFAOYSA-N 6-butan-2-ylquinoline Chemical compound N1=CC=CC2=CC(C(C)CC)=CC=C21 AUBLFWWZTFFBNU-UHFFFAOYSA-N 0.000 description 1
- NVIPUOMWGQAOIT-DUXPYHPUSA-N 7-hexadecen-1,16-olide Chemical compound O=C1CCCCC\C=C\CCCCCCCCO1 NVIPUOMWGQAOIT-DUXPYHPUSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000003097 Artemisia absinthium Nutrition 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- JOZKFWLRHCDGJA-LLVKDONJSA-N Citronellyl acetate Natural products CC(=O)OCC[C@H](C)CCC=C(C)C JOZKFWLRHCDGJA-LLVKDONJSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 241000147041 Guaiacum officinale Species 0.000 description 1
- DUKPKQFHJQGTGU-UHFFFAOYSA-N Hexyl salicylic acid Chemical compound CCCCCCOC(=O)C1=CC=CC=C1O DUKPKQFHJQGTGU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000032014 Java citronella Species 0.000 description 1
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- 240000000432 Pistacia chinensis Species 0.000 description 1
- 235000014123 Pistacia chinensis Nutrition 0.000 description 1
- 241000196435 Prunus domestica subsp. insititia Species 0.000 description 1
- 241000198945 Prunus domestica subsp. syriaca Species 0.000 description 1
- 240000005809 Prunus persica Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 244000181025 Rosa gallica Species 0.000 description 1
- 235000000533 Rosa gallica Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KGDJMNKPBUNHGY-RMKNXTFCSA-N [(e)-3-phenylprop-2-enyl] propanoate Chemical compound CCC(=O)OC\C=C\C1=CC=CC=C1 KGDJMNKPBUNHGY-RMKNXTFCSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002386 air freshener Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- HMKKIXGYKWDQSV-KAMYIIQDSA-N alpha-Amylcinnamaldehyde Chemical compound CCCCC\C(C=O)=C\C1=CC=CC=C1 HMKKIXGYKWDQSV-KAMYIIQDSA-N 0.000 description 1
- YPZUZOLGGMJZJO-UHFFFAOYSA-N ambrofix Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OCC2 YPZUZOLGGMJZJO-UHFFFAOYSA-N 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010619 basil oil Substances 0.000 description 1
- 229940018006 basil oil Drugs 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 239000001111 citrus aurantium l. leaf oil Substances 0.000 description 1
- 239000001071 citrus reticulata blanco var. mandarin Substances 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- BLBJUGKATXCWET-UHFFFAOYSA-N cyclaprop Chemical compound C12CC=CC2C2CC(OC(=O)CC)C1C2 BLBJUGKATXCWET-UHFFFAOYSA-N 0.000 description 1
- 239000001939 cymbopogon martini roxb. stapf. oil Substances 0.000 description 1
- 229940095104 dimethyl benzyl carbinyl acetate Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HLOLVQSTCUVLJD-UHFFFAOYSA-N ethyl 3-oxobutanoate 3-oxohexanoic acid Chemical compound CCCC(=O)CC(O)=O.CCOC(=O)CC(C)=O HLOLVQSTCUVLJD-UHFFFAOYSA-N 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- IFYYFLINQYPWGJ-VIFPVBQESA-N gamma-Decalactone Natural products CCCCCC[C@H]1CCC(=O)O1 IFYYFLINQYPWGJ-VIFPVBQESA-N 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
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 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
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 1
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 1
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- UFLHIIWVXFIJGU-UHFFFAOYSA-N hex-3-en-1-ol Natural products CCC=CCCO UFLHIIWVXFIJGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001675 jasminum grandiflorum l. oil Substances 0.000 description 1
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229940043353 maltol Drugs 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- YAHNYLGSSPTTAG-UHFFFAOYSA-N methyl n-(3,4-dichlorophenyl)carbamodithioate Chemical compound CSC(=S)NC1=CC=C(Cl)C(Cl)=C1 YAHNYLGSSPTTAG-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000001738 pogostemon cablin oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-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
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- DCSCXTJOXBUFGB-UHFFFAOYSA-N verbenone Natural products CC1=CC(=O)C2C(C)(C)C1C2 DCSCXTJOXBUFGB-UHFFFAOYSA-N 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
- 239000010457 zeolite Substances 0.000 description 1
- USMNOWBWPHYOEA-MRTMQBJTSA-N α-thujone Chemical compound O=C([C@@H]1C)C[C@@]2(C(C)C)[C@@H]1C2 USMNOWBWPHYOEA-MRTMQBJTSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Abstract
本发明涉及下式的取代的环己烯基丁烯酮;其中R1、R2、R3、R4和R5独立地选自氢、甲基或乙基;且碳原子的总数为11-15;也涉及它们的生产方法以及包括它们的香料组合物和香料用品。
Description
本发明涉及一类具有类似突厥酮气味香型的新型取代环己烯基丁烯酮,和它们作为增香剂的用途。本发明另外涉及它们的生产方法和包括它们的香料组合物。
在香料业中持续需要增强、改变或改善气味香型的新型化合物。突厥酮,又名玫瑰酮,构成一类重要的香料成分。它们呈现特定的花香(玫瑰)-果香香型,使人想起干果香。因此,持续希望发现具有类似突厥酮气味香型的新型化合物。
α-、β-、δ-突厥酮(A)和β-突厥酮(C)被认为是花香果香香料成分范畴中的亚科,因为它们呈现非常典型且复合的玫瑰香和果香(如具有黑醋栗香调的苹果或李子)气味。因此,尽管α-突厥酮具有玫瑰香、苹果香、黑醋栗香的气味,而β-突厥酮具有更多的黑醋栗香、李子香以及还有玫瑰香。δ-突厥酮的嗅觉香型比α-突厥酮具有更多的红玫瑰香和更少的苹果香以及比β-突厥酮具有更少的李子香,而β-突厥酮嗅觉上描述为玫瑰香、李子香、悬钩子香、甜香(A.Williams;Perfumer&Flavorist 2002,27,18-31)。
在文献中已描述了大量的环己烯基丁烯酮,其作为突厥酮的类似物。然而,通常保留突厥酮的环己烯环的偕甲基。例如,异突厥酮(B),其具有天然的类似水果的香调和增加的类似酒的香调以及新鲜的类似花的香调(US3,822,315),或γ-突厥酮,其比具有显著花香、玫瑰香、青香香型的α-和β-突厥酮具有更多的果香。(A.Williams;Perfumer&Flavorist 2002,27,18-31)。实际上,在环己烯环上不具有偕双甲基的δ-突厥酮的结构类似物呈现与典型突厥酮香型非常不同的气味香型。例如,在US4,392,993中公开的、使香波具有“药物型”气味香型的1-(1,3/4-二甲基-环己-3-烯-1-基)丁-2-烯-1-酮(D)描述为果香,但使人想起甜瓜香,而它们的花香香型使人想起甘菊香和芳香香型为草本香、类似侧柏酮香。1-(1,2,4,6-四甲基环己-3-烯-1-基)丁-2-烯-1-酮(E)被描述为木香-松脂香和蔬菜香。(Andreev,V.M.;Andreeva,L.K.;Ratnikova,E.V.;Fomchenko,Z.V.;Grigor′eva,L.T.Gidroliznaya i LesokhimicheskayaPromyshlennost,1993,1,23-4)。或者在JP-A-59-146中公开的、其中R为氢或甲基的式F的丁烯酮,仅仅描述为具有类似花或类似果香的气味,对于具有典型的突厥酮气味香型的嗅觉类似,没有任何提及。
因此,在现有技术中的一切都显示出为了保持典型的突厥酮气味香型,偕甲基是化合物的重要结构特征。
令人惊讶地,我们发现了环己烯环上存在偕甲基在某些情形中对于获得强烈的干果气味香型不是必需的,与突厥酮的气味香型非常相似。
因此,本发明在一方面涉及一种式(I)的化合物
其中
在侧链中的双键为E构型;
R1、R2、R3、R4和R5独立地选自氢、甲基或乙基;和
碳原子的总数为11-15,优选11-14,例如12或13;
条件是
如果R2为氢则R5为甲基或乙基;
如果R5为氢则R2为甲基或乙基;和
如果R4为甲基或乙基则R5为甲基或乙基。
特别的实施方式为式(I)的化合物,其中
i)R1为氢、甲基或乙基,R2为甲基或乙基,且R3、R4和R5为氢;
ii)R1和R2独立地选自氢、甲基或乙基,R3和R4为氢且R5为甲基或乙基;
iii)R1选自氢、甲基或乙基,R2为甲基或乙基,R3为甲基或乙基,且R4和R5为氢;
iv)R1和R2独立地选自氢、甲基或乙基,R4和R5独立地选自甲基或乙基,且R3为氢;
v)R1和R2独立地选自氢、甲基或乙基,R4为氢且R3和R5独立地选自甲基或乙基;或
vi)R1和R2独立地选自氢、甲基或乙基,R3、R4和R5独立地选自甲基或乙基。
式(I)的化合物包括至多四个手性中心,因而可以作为立体异构体的混合物存在,或者可以将它们拆分为异构体纯形式。拆分立体异构体增加了制备和纯化这些化合物的复杂性,因此仅仅出于经济原因,优选使用其立体异构体混合物形式的化合物。然而,如果希望制备单一的立体异构体,则可以根据本领域已知的方法来实现,所述已知的方法例如制备型HPLC和GC、结晶或立体选择性合成。
特别感兴趣的是其中残基R2、R3、R4和R5中的至少一个为乙基的式(I)的化合物。
特别优选的式(I)的化合物为
(2E)-1-(6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2-乙基-6-甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(6-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2-二甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,5-二甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,6-二甲基-2-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,5-二甲基-6-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3-二甲基-6-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3,6-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,5,6-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,3-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,3,5-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,3,6-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3-二甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3,5-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,6-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,5-三甲基环己-3-烯基)丁-2-烯-1-酮,和
(2E)-1-(1,6-二甲基环己-3-烯基)丁-2-烯-1-酮。
这些化合物之中,发现当与δ-突厥酮相比,单独在吸墨纸上闻或者以配制剂即与其他香料成分结合的形式闻时,例如(2E)-1-(6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮具有更清香的气味并且具有更少的软木香调。
根据本发明的化合物可以单独使用或与已知的增香剂分子结合使用,所述增香剂分子选自宽范围的目前可获得的天然分子或合成分子,如精油和提取物、醇类、醛类和酮类、醚类和缩醛类、酯类和内酯类、大环化合物类和杂环化合物类、和/或与一种或多种通常与香料组合物中的增香剂结合使用的成分或赋形剂,例如载体材料,以及其他常用在本领域的助剂结合使用。
下列清单包括已知的增香剂分子的实例,其可以与本发明的化合物结合:
-醚香油和提取物,例如橡苔净油、罗勒油、热带果油如香柠檬油和橘子油、黄连木净油、香桃木油、玫瑰草油、广藿香油、橙叶油、苦艾油、熏衣草油、玫瑰油、茉莉油、依兰-依兰油和檀香油。
-醛类和酮类,例如柠檬醛、羟基香茅醛、甲基壬基乙醛、茴香醛、烯丙基紫罗兰酮、马鞭草烯酮、诺卡酮、香叶基丙酮、α-戊基肉桂醛、GeorgywoodTM、羟基香茅醛、Iso E (甲基紫罗兰酮)、麦芽酚、甲基柏木酮和香草醛。
-酯类和内酯类,例如乙酸苄酯、乙酸柏木酯、γ-癸内酯、γ-十一烷酸内酯、乙酸岩兰草酯、丙酸肉桂酯、乙酸香茅酯、乙酸癸酯、乙酸二甲基苄基原酯、乙酰乙酸乙酯(ethylacetoacetate)、乙酰乙酸乙酯(ethyl acetylacetate)、顺式-3-己烯基异丁酸酯、乙酸里哪醇酯和乙酸香叶酯。
-杂环化合物类,例如异丁基喹啉。
本发明的化合物可以用在宽范围的香料应用中,例如在精细和功能香料的任何领域中,如香水、家用产品、洗衣产品、身体护理产品和化妆品。取决于特定应用以及其他增香剂成分的性质和数量,该化合物可以以宽范围变化的用量使用。其比例通常为用品的0.0001-2wt%。在一个实施方式中,本发明的化合物可以0.0001-0.005wt%的量用在织物软化剂中。在另一个实施方式中,本发明的化合物可以0.01-3wt%,更优选0.5-2wt%的量用在醇溶液中。然而,这些值仅仅是以实例的形式给出,因为有经验的香料商还可以通过较低或较高浓度(例如至多为香料组合物的约20wt%)获得效果或者可以得到新的谐香。
简单地通过将香料组合物与香料用品直接混合就可以将本发明的化合物用在香料用品中,或者可以在之前的步骤中用捕集材料对其进行捕集,所述捕集材料例如为聚合物、胶囊、微胶囊和纳米胶囊、脂质体、成膜剂、吸收剂如碳或沸石、环状低聚糖及其混合物,或者其可以化学键合在基质上,键合后的物质在经历诸如光、酶等外部刺激时易于释放香料分子,随后与用品混合。
因此,本发明另外提供一种制造香料用品和由此得到的消费品的方法。该方法包括使用常规技术和方法,或者通过将化合物直接混入用品中,或者通过混合包括式(I)化合物的香料组合物,随后可以将其混入到香料用品中,从而将式(I)的化合物作为香料成分结合进来。通过加入嗅觉可接受量的本发明化合物,香料用品的气味香型将会得到改善、增强或改变。
因此,本发明另外提供一种通过向其中加入嗅觉可接受量的式(I)化合物或其混合物来改善、增强或改变香料用品的方法。
本发明还提供一种香料用品,包括:
a)作为增香剂的式(I)化合物或其混合物;和
b)消费品基体(base)。
在此使用的“香料用品”是指任何产品,如精细香料,例如香水和化妆水;家用产品,例如洗碗机用的洗涤剂、表面清洁剂、空气清新剂;洗衣产品,例如软化剂、漂白剂、洗涤剂;身体护理产品,例如须后水、香波、洗浴凝胶、淋浴和沐浴盐、卫生产品;和化妆品,例如除臭剂、雪花膏,包括增香剂。所列产品仅仅用于说明,不应将其视为以任何方式进行限制。
通过Diels-Alder环加成,继之以与乙醛进行醇醛缩合并在现有技术已知的条件下除去水,可以制备式(I)的化合物。
现在将参考以下非限制性实施例对本发明作进一步描述。这些实施里仅仅用于说明,并且应当理解本领域技术人员可以对其作出改变和改进。
实施例1:(2E)-1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)
丁-2-烯-1-酮
A)在-15℃下,使用3-己烯-2-酮(220.1g,纯度89%,2mol)在10分钟内处理BF3·OEt2(54g,0.38mol)的二氯甲烷(680ml)溶液。然后添加1,3-戊二烯(490g,7.2mol,在0℃下预先冷却)并将得到的溶液在0℃下搅拌30分钟,然后在0℃下冷却之前在20℃下搅拌1小时,并使用20%的K2CO3(250ml)水溶液处理。将得到的混合物搅拌40分钟并浓缩(43℃直到300mbar)。将水相用己烷(500ml)洗涤并将混合的有机相用20%的K2CO3水溶液(100ml)洗涤,用饱和NaCl水溶液洗涤三次,干燥(MgSO4)并浓缩。将粗产物(400g)进行Sulzer-蒸馏(0.4-0.1mbar),产生1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)乙烯-1-酮(326g,产量98%)。
沸点:45℃(0.1mbar)。
1H-NMR(400MHz,CDCl3):δ5.70-5.59(m,H-C(3′),H-C(4′)),2.72(dd,J=5.3,10.6,H-C(1′)),2.57-2.48(m,H-C(2′)),2.25-2.17(m,H-C(5′)),2.15(s,MeCO),1.96-1.85(m,H-C(6′)),1.73-1.62(m,H-C(5′)),1.62-1.51(m,C(6′)CHMe),1.16-1.03(m,C(6′)CHMe),0.86(t,J=7.3,MeCH2),0.85(d,J=7.1,MeC(2′))。
13C-NMR(100MHz,CDCl3):δ210.73(s,CO),131.21(d,C(3′)),125.19(d,C(4′)),55.61(d,C(1′)),30.76(q,C(2)),30.67(d,C(2′)),30.33(d, C(6′)),29.71(t,C(5′)),26.33(t,CH2Me)),16.95(q,MeC(2′)),10.68(q,CH2Me)。
MS(EI):166(14),151(7),137(30),123(64),108(11),95(23),94(14),93(39),91(17),81(100),79(32),77(25),67(33),55(26),43(98),41(26),39(20)。
B)在-78℃下,使用正丁基锂(21ml,以1.6M溶在己烷中,34mmol)处理二异丙胺(6.6g,34mmol)的四氢呋喃(23ml)溶液。将得到的溶液加热到0℃,冷却到-78℃,并用1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)乙烯-1-酮(4.5g,27mmol)的四氢呋喃(23ml)溶液处理。将得到的溶液在-20℃下搅拌20分钟,冷却到-78℃并用乙醛(1.8g,41mmol)的四氢呋喃(23ml)溶液处理。在搅拌1小时后,添加1N含水HCl(50ml)并将反应混合物加热到20℃。将水相用乙醚萃取并将混合的有机相干燥(MgSO4)和浓缩。使用对-甲苯磺酸一水合物(20mg)处理残留物(4.9g)的甲苯(4.9ml)溶液并整夜回流。将反应混合物冷却,用饱和NaHCO3水溶液处理并将水相用乙醚萃取。将混合的有机相干燥(MgSO4)并浓缩。将粗产物进行快速色谱分离(550g SiO2,己烷/乙醚9∶1),产生(2E)-1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮(2.9克,56%)。
沸点:96℃(0.7mbar)。
1H-NMR(400MHz,CDCl3):δ6.87(dq,J=6.8,15.7,H-C(3)),6.16(dq,J=1.7,15.7,H-C(2)),5.70-5.60(m,H-C(3′),H-C(4′)),2.89(dd,J=5.4,10.7,H-C(1′)),2.52-2.41(m,H-C(2′)),2.27-2.18(m,H-C(5′)),2.03-1.93(m,H-C(6′)),1.90(dd,J=1.8,6.8,MeC(3)),1.74-1.65(m,H-C(5′)),1.61-1.50(m,C(6′)CHMe),1.16-1.03(m,C(6′)CHMe),1.07(t,J=7.5,MeCH2),0.83(d,J=7.1,MeC(2′))。
13C-NMR(100MHz,CDCl3):δ201.58(s,CO),141.80(d,C(3)),132.07(d,C(2)),131.38(d,C(3′)),125.03(d,C(4′)),52.29(d,C(1′)),31.21(d,C(2′)),30.11(d,C(6′)),29.73(t,C(5′)),26.16(t,CH2Me)),18.05(q,C(4)),16.82(q,MeC(2′)),10.49(q,CH2Me)。
MS(EI):192(6),177(6),163(19),149(3),145(3),137(6),123(18),108(26),93(26),91(10),81(35),79(16),77(12),69(100),55(17),41(37),39(17)。
IR:vmax3020,2964,2914,2875,1694,1665,1629,1443,1375,1290,1217,1197,1172,1136,1117,1092,1048,970,902,714cm-1。
气味描述:类似突厥酮香,木香,乡土香(agrestic),辛香。
实施例2:(2E)-1-(rel-(1S,2S,6S)-6-乙基-2-甲基环己-3-烯基)
丁-2-烯-1-酮
A)在20℃下,向乙醇(80ml)中添加钠(0.11g,4.8mmol)并将得到的溶液用1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)乙烯-1-酮(8.6g,48mmol)处理。在回流26小时后,将得到的黄色溶液冷却,倒入冰冷的水(1升)中并将水相用甲基叔丁基醚萃取。将混合的有机相用水洗涤,然后用饱和NaCl水溶液洗涤,干燥(MgSO4)并浓缩。粗产物(8.15g)为1-(rel-(1S,2S,6S)-6-乙基-2-甲基环己-3-烯基)乙烯-1-酮/1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)乙烯-1-酮/未确定的立体异构体的70∶26∶4混合物。
1-(rel-(1S,2S,6S)-6-乙基-2-甲基环己-3-烯基)乙烯-1-酮的数据:
1H-NMR(400MHz,CDCl3):δ5.55(dquint,J=2.3,9.9,H-C(3′/4′)),5.49(dsext,J=1.1,10.1,H-C(4′/3′),2.59-2.48(m,H-C(2′)),2.46(dd,J=3.2,8.7,H-C(1′)),2.25-2.15(m,H-C(5′)),2.17(s,MeCO),2.13-2.04(m,H-C(5′)),1.98-1.89(m,H-C(6′)),1.33-1.13(m,CH2Me),0.94(d,J=6.8,MeC(2′)),0.87(t,J=7.5,MeCH2)。
13C-NMR(100MHz,CDCl3):δ210.70(s,CO),131.96(d,C(3′)),123.35(d,C(4′)),58.60(d,C(1′)),35.74(d,C(2′)),29.70(q,C(2)),28.54(t,C(5′)),27.85(d,C(6′)),21.15(t,CH2Me)),20.60(q,MeC(2′)),12.56(q,CH2Me)。
B)在-78℃下,用二异丙胺(5.8g,57mmol)的四氢呋喃(35ml)溶液处理正丁基锂溶液(37.3ml,以1.6M溶在己烷中,59mmol)。将得到的溶液加热到-20℃,冷却到-78℃,并用粗1-(6-乙基-2-甲基环己-3-烯基)乙烯-1-酮混合物(8.1g)的四氢呋喃(40ml)溶液处理。将得到的溶液在-70℃下搅拌1小时,加热到0℃,在-70℃下冷却并用乙醛(10.5g,239mmol)的四氢呋喃(40ml)溶液处理。搅拌1小时后,添加2N含水HCl(50ml)和饱和NaCl水溶液(50ml)的混合物并将该反应混合物加热到0℃。将水相用乙醚(2×100ml)萃取并将混合的有机相用饱和NaHCO3水溶液和水洗涤,干燥(MgSO4)并浓缩。将溶于甲苯(50ml)的残留物(13.4g)用对-甲苯磺酸一水合物(0.5g,2.6mmol)处理,并在1小时内回流。将反应混合物冷却,用饱和Na2CO3水溶液处理并将水相用环己烷(90ml)萃取。将混合的有机相用饱和NaCl水溶液洗涤,干燥(MgSO4)并浓缩。将粗产物进行快速色谱分离(SiO2,己烷/甲基叔丁基醚20∶1),产生(2E)-1-(rel-(1S,2S,6S)-6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮(0.7g,3步:7%)和(2E)-1-(rel-(1S,2S,6S)-6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮/(2E)-1-(rel-(1R,2S,6S)-6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮/未确定的立体异构体的67∶27∶6混合物(5.7g,3步:58%)。
沸点:72℃(0.1mbar)。
1H-NMR(400MHz,C6D6):δ6.79(dq,J=6.9,15.6,H-C(3)),6.07(dq,J=1.7,15.5,H-C(2)),5.63-5.55(m,H-C(3′),H-C(4′)),2.96-2.86(m,H-C(2′)),2.54(dd,J=3.0,9.1,H-C(1′)),2.16-2.03(m,2H-C(5′)),1.89-1.81(m,H-C(6′)),1.55-1.35(m,CH2Me),1.46(dd,J=1.6,7.0,MeC(3)),1.07(d,J=6.8,MeC(2′)),0.83(t,J=7.5,MeGH2)。
13C-NMR(100MHz,C6D6):δ199.31(s,CO),140.69(d,C(3)),132.36(d,C(3′)),131.10(d,C(2)),123.22(d, C(4′)),55.82(d,C(1′)),35.95(d,C(6′)),28.53(t,C(5′)),27.82(d, C(2′)),20.71(t,CH2Me)),20.33(q,MeC(2′)),17.36(q,C(4)),12.35(q,CH2Me)。
MS(EI):192(6),177(4),163(7),145(2),135(4),123(12),109(6),93(21),91(11),81(32),79(18),77(16),69(100),55(11),41(29),39(15)。
气味描述:果香,类似突厥酮香,干无花果香,乡土香,青香,甜香。
实施例3:(2E)-1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)
丁-2-烯-1-酮
A)按照实施例1的描述,从1,3-己二烯(10g,0.122mol,异构体混合物)和3-戊烯-2-酮(5.7g,纯度60%,0.04mol)起始,制备(2E)-1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮(6.28g,92%)。
1H-NMR(400MHz,CDCl3):δ5.80(m,J=1.8,2.3,4.5,10.1,1H),5.65(m,J=1.5,2.8,4.3,10.1,1H),2.62(dd,J=5.3,10.1,H-C(1′)),2.36-2.28(m,1H),2.21-2.12(m,1H),2.15(s,MeC(3)),2.11-2.01(m,1H),1.65(ddq,J=2.5,9.1,17.9,1H),1.35-1.20(m,2H),0.93(d,J=6.3,MeC(6′)),0.90(t,J=7.3,MeCH2)。
13C-NMR(100MHz,CDCl3):δ210.67(s,CO),128.94(d),125.98(d),57.63(d),37.28(d),33.19(t),30.64(q),25.12(d),24.96(t),20.30(q),11.98(q)。
MS(EI):166(17),151(11),137(20),123(55),109(11),95(16),94(7),93(34),91(9),85(58),82(23),81(70),79(26),77(21),67(30),55(19),43(100),41(18),39(12)。
B)按照实施例1描述,从(2E)-1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮(3.1g,18.6mmol),通过缩醛反应(LDA,AcH,THF)和除水(PTSA·H2O,环己烷,回流,1小时)制备(2E)-1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)丁-2-烯-1-酮(1.75g,49%)。
沸点:90℃(0.12mbar)。
1H-NMR(400MHz,CDCl3):δ6.87(dq,J=6.8,15.7,H-C(3)),6.17(dq,J=1.7,15.6,H-C(2)),5.83-5.77(m,1H),5.69-5.64(m,1H),2.78(dd,J=5.3,10.1,H-C(1′)),2.30-2.23(m,1H),2.23-2.06(m,2H),1.90(dd,J=1.8,6.8,MeC(3)),1.72-1.62(m,1H),1.32-1.18(m,2H),0.92(d,J=6.1,MeC(6′)),0.86(t,J=7.5,MeCH2)。
13C-NMR(100MHz,CDCl3):δ201.62(s,CO),141.87(d),132.15(d),129.22(d),125.95(d),54.57(d),37.73(d),33.31(t),25.14(d),24.88(t),20.30(q),18.18(q),11.96(q)。
MS(EI):192(3),177(3),163(9),149(2),145(1),137(3),123(12),111(100),93(14),91(9),81(32),79(17),77(13),69(95),55(16),41(44),39(19)。
IR:vmax3024,2960,2930,2912,2871,2830,1693,1664,1629,1442,1377,1299,1246,1214,1172,1138,1052,968,920,889,794,707cm-1。
气味描述:果香,红果香,花香,玫瑰香,类似突厥酮香,乡土香,香桃木香,艾蒿净油香(armoise absolute)。
实施例4:(2E)-1-(rel-(1S,2S,6S)-2-乙基-6-甲基环己-3-烯基)
丁-2-烯-1-酮
按照实施例2描述,通过在回流下(25h),在乙醇(30ml)中的1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮(3.15g,18.9mmol,实施例3)的EtONa催化差向异构化作用,制备1-(rel-(1S,2S,6S)-/1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮的80∶20混合物(2.6g)。经过缩醛反应(LDA,AcH,THF)和除去水(PTSA·H2O,环己烷,回流,45分钟),产生1-(rel-(1S,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮/1-(rel-(1R,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮的83∶17混合物(1.27g,2步:42%)。
沸点(非对映异构混合物):72℃(0.11mbar)。
气味描述(非对映异构混合物):果香,类似突厥酮香,薄荷香,乡土香。
A)1-(rel-(1S,2S,6S)-2-乙基-6-甲基环己-3-烯基)乙烯-1-酮:
1H-NMR(400MHz,CDCl3):δ5.65-5.56(m,2H),2.56(dd,J=3.1,9.0,H-C(1′)),2.47-2.39(m,1H),2.36-2.28(m,1H),2.28-2.19(m,1H),2.16(s,MeCO),1.94-1.86(m,1H),1.46-1.34(m,1H),1.27-1.14(m,1H),0.90(t,J=7.3,MeCH2),0.84(d,J=7.3,MeC(6′))。
13C-NMR(100MHz,CDCl3):δ210.75(s,CO),129.08(d),123.86(d),55.77(d),33.46(d),32.75(t),29.73(q,MeCO),28.26(d),27.00(t),14.99(q),10.88(q)。
MS(EI):166(21),151(2),137(17),123(82),109(7),107(8),95(29),94(9),93(35),91(21),81(56),79(30),77(13),67(17),55(19),43(100),41(21),39(19)。
B)(2E)-1-(rel-(1S,2S,6S)-2-乙基-6-甲基环己-3-烯基)丁-2-
烯-1-酮:
1H-NMR(400MHz,CDCl3):δ6.87(dq,J=6.9,15.6,H-C(3)),6.20(dq,J=1.7,15.6,H-C(2)),5.66-5.58(m,2H),2.72(dd,J=3.2,9.2,H-C(1′)),2.55-2.46(m,1H),2.37-2.28(m,1H),2.23-2.14(m,1H),1.94-1.85(m,1H),1.90(dd,J=1.8,6.8,MeC(3)),1.45-1.34(m,1H),1.26-1.13(m,1H),0.89(t,J=7.5,MeCH2),0.83(d,J=7.1,MeC(6′))。
13C-NMR(100MHz,CDCl3):δ201.62(s,CO),141.87(d),131.44(d),129.40(d),123.93(d),52.88(d),33.40(d),32.79(t),28.58(d),26.93(t),18.15(q),14.82(q),10.93(q)。
MS(EI):192(8),177(5),163(11),149(3),145(2),137(2),123(14),111(3),108(3),93(13),91(8),81(25),79(14),77(10),69(100),55(12),41(31),39(14)。
IR:vmax3021,2961,2909,2875,2837,1693,1664,1629,1442,1379,1341,1286,1212,1179,1142,1122,1088,1050,968,901,810,688cm-1。
实施例5:(2E)-1-(rel-(1S,6S)-6-乙基-环己-3-烯基)丁-2-烯
-1-酮
按照实施例1描述,从1,3-丁二烯(8.2g,151mmol)和3-己烯-2-酮(9.9g,101mmol)的甲苯(56ml)溶液起始,在BF3·OEt2(3.6g,25mmol)的存在下制备1-(rel-(1R,6S)-6-乙基-环己-3-烯基)乙烯-1-酮(5g,32%),并通过缩醛反应(LDA,AcH,THF)和除水(cat.PTSA·H2O,甲苯,20℃,15小时)将其转化成(2E)-1-(rel-(1S,6S)-6-乙基-环己-3-烯基)丁-2-烯-1-酮(1.34g,23%,12∶88的非对映异构混合物)。在进行快速色谱分离后回收得1-(rel-(1S,6S)-6-乙基-环己-3-烯基)乙烯-1-酮(1.6g,32%)。
A)1-(rel-(1S,6S)-6-乙基-环己-3-烯基)乙烯-1-酮:
1H-NMR(400MHz,CDCl3):δ5.71-5.63(m,H-C(3′),H-C(4′)),2.72(ddd,J=6.6,8.3,9.2,H-C(1′)),2.28-2.17(m,1H),2.17-2.12(m,1H),2.12(s,MeCO),1.90-1.79(m,1H),1.76-1.66(m,1H),1.51-1.40(m,1H),1.24-1.12(m,1H),0.90(t,J=7.5,MeCH2)。
13C-NMR(100MHz,CDCl3):δ212.69(s,CO),125.98,124.48(2d,C(3′),C(4′)),52.41(d,C(1′)),36.12(d,C(6′)),29.10(t),28.99(q,C(2)),27.37(t),26.49(t),10.84(q,CH2Me)。
B)(2E)-1-(rel-(1S,6S)-6-乙基-环己-3-烯基)丁-2-烯-1-酮:
沸点:90℃(0.5mbar)。
1H-NMR(400MHz,CDCl3):主要非对映异构体(1S,6S)。:δ6.91(dq,J=6.8,15.7,H-C(3)),6.23(dq,J=1.7,15.6,H-C(2)),5.72-5.64(m,H-C(3′),H-C(4′)),2.72(dt,J=5.6,9.6,H-C(1′)),2.24(dm,J=18.2,H-C(2′)),2.19-2.13(m,H-C(5′)),2.13-2.05(dm,J=18.2,H-C(2′)),1.91(dd,J=1.5,6.8,MeC(3)),1.92-1.82(m,H-C(6′)),1.77-1.67(m,H-C(5′)),1.51-1.40(m,C(6′)CHMe),1.19-1.06(m,C(6′)CHMe),0.87(t,J=7.3,MeCH2);较少非对映异构体(1R,6S):δ6.89(dq,J=6.8,15.6,H-C(3)),6.26(dq,J=1.7,15.5,H-C(2)),5.70-5.58(m,H-C(3′),H-C(4′)),2.91(ddd,J=3.0,5.6,8.9,H-C(1′)),2.42-2.31(m,1H),1.91(dd,J=1.8,6.8,MeC(3)),0.86(t,J=7.5,MeCH2)。
13C-NMR(100MHz,CDCl3):主要非对映异构体:δ203.88(s,CO),142.57(d,C(3)),131.21(d,C(2)),126.05(d,C(3′)),124.93(d,C(4′)),49.06(d,C(1′)),36.37(d,C(6′)),29.48(t,C(5′)),28.36(t,C(2′)),26.60(t,CH2Me)),18.15(q,C(4)),10.84(q,CH2Me);较少非对映异构体:δ201.71(s,CO),141.77(d,C(3)),130.07(d,C(2)),125.32(d,C(3′)),124.97(d,C(4′)),47.87(d,C(1′)),36.07(d,C(6′)),31.47(t,C(5′)),28.73(t,C(2′)),26.79(t,CH2Me),18.15(q,C(4)),12.29(q,CH2Me)。
MS(EI):178(6),163(5),149(12),145(1),137(2),135(2),131(4),121(4),109(12),108(7),95(6),94(8),93(5),91(7),81(5),79(25),77(11),69(100),67(24),55(10),41(33),39(18)。
IR:vmax3026,2963,2913,1691,1666,1627,1438,1377,1294,1218,1177,1130,1080,1060,970,937,892,660,631cm-1。
气味描述:苹果香,玫瑰香,类似突厥酮香,果香,辛香,木香。
实施例6:(2E)-1-(1,2,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮
按照实施例1描述,从2,4-己二烯(3.5g,42.5mmol)和3-甲基-3-戊烯-2-酮(3.4g,35mmol)的甲苯(17ml)溶液起始,在BF3·OEt2(1.2g,8.8mmol)的存在下制备1-(1,2,5,6-四甲基环己-3-烯基)乙烯-1-酮(0.9g,14%,58∶42非对映异构体混合物),并通过缩醛反应(LDA,AcH,THF;FC)和除水(cat.PTSA·H2O,甲苯,20℃,15小时)将部分(0.66g,3.7mmol)转化成(2E)-1-(1,2,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮(0.150g,20%,57∶43的非对映异构混合物)。
A)1-(1,2,5,6-四甲基环己-3-烯基)乙烯-1-酮:
1H-NMR(400MHz,CDCl3):主要非对映异构体δ5.56(ddd,J=2.3,5.3,9.9,H-C(3′/4′),5.41(ddd,J=1.0,2.0,9.9,H-C(4′/3′)),2.34-2.21(m,1H),2.14(s,MeCO),2.14-2.04(m,1H),1.75-1.65(m,1H),1.18(s,MeC(1)),1.04(d,J=6.8,Me),0.88(d,J=6.3,Me),0.80(d,J=7.6,Me)。
较少非对映异构体:δ5.61(dt,J=3.1,10.0,H-C(3′/4′),5.36(dt,J=2.1,10.0,H-C(4′/3′)),2.77-2.67(m,1H),2.14-2.04(m,1H),2.11(s,MeCO),1.82(dq,J=6.3,9.6,1H),0.95(d,J=7.3,Me),0.92(s,MeC(1)),0.84(d,J=6.8,Me),0.77(d,J=7.1,Me)。
B)(2E)-1-(1,2,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮:
沸点:50℃(0.15mbar)。
1H-NMR(400MHz,CDCl3):主要非对映异构体δ6.93(dq,J=6.9,15.2,H-C(3)),6.50(dq,J=1.6,15.1,H-C(2)),5.57(ddd,J=2.3,5.3,9.9,H-C(3′/4′),5.42(br.d,J=9.9,H-C(4′/3′)),2.35-2.24(m,1H),2.14-2.04(m,1H),1.89(dd,J=1.8,6.8,MeC(3)),1.79-1.68(m,1H),1.16(s,MeC(1)),1.06(d,J=7.1,Me),0.91(d,J=6.3,Me),0.78(d,J=7.1,Me);较少非对映异构体:δ6.97(dq,J=6.8,15.2,H-C(3)),6.59(dq,J=1.5,14.9,H-C(2)),5.61(dt,J=3.3,10.1,H-C(3′/4′),5.38(dt,J=2.0,10.1,H-C(4′/3′)),2.78-2.68(m,1H),2.14-2.04(m,1H),1.89(MeC(3)),1.90-1.83(m,1H),0.95(d,J=7.3,Me),0.93(s,MeC(1)),0.81(d,J=6.8,Me),0.77(d,J=7.6,Me)。
MS(EI):主要非对映异构体:206(3),191(3),177(4),150(3),149(4),138(11),137(100),136(27),135(70),134(12),121(38),109(22),107(19),95(79),93(14),91(23),81(29),79(16),77(16),69(55),57(27),55(22),41(59),39(26)。
IR:vmax3026,2967,2876,1687,1625,1445,1375,1288,1184,1137,1065,1042,967,928,860,790,750,721,643cm-1。
气味描述:果香,类似突厥酮香,布拉斯李香(mirabelle),干果香,金合欢香,薄荷香。
实施例7:(2E)-1-(1,2-二甲基环己-3-烯基)丁-2-烯-1-酮
按照实施例1描述,从1,3-戊二烯(10.6g,156mmol)和3-甲基-3-丁烯-2-酮(10.9g,130mmol)的甲苯(65ml)溶液起始,在BF3-OEt2(4.6g,32mmol)的存在下制备1-(1,2-二甲基环己-3-烯基)乙烯-1-酮(13g,66%),并通过缩醛反应(LDA,AcH,THF;FC,2.4g回收的起始材料)和除水(cat.PTSA·H2O,甲苯,回流,2小时)将部分(7g,46mmol)转化成(2E)-1-(1,2-二甲基环己-3-烯基)丁-2-烯-1-酮(1.54g,2步:19%)。
A)1-(1,2-二甲基环己-3-烯基)乙烯-1-酮:
沸点:100℃(15mbar)。
1H-NMR(400MHz,CDCl3):δ1H-NMR(400MHz,CDCl3):δ5.64-5.55(m,H-C(3′),H-C(4′),2.26-2.18(m,1H),2.14(s,MeCO),2.13-1.93(m,2H),1.81(ddd,J=6.6,11.1,13.6,1H),1.48(ddm,J=6.2,13.7,1H),1.16(s,MeC(1)),0.85(d,J=7.1,Me)。
MS(EI):152(6),137(3),110(9),109(100),95(2),91(11),85(5),81(23),79(13),77(13),69(5),67(63),55(15),53(11),43(48),41(19),39(15)。
IR:vmax3020,2967,1702,1454,1433,1375,1355,1248,1223,1202,1103,1085,1042,972,951,865,804,756,707,657cm-1。
B)(2E)-1-(1,2-二甲基环己-3-烯基)丁-2-烯-1-酮:
沸点:70℃(15mbar)。
1H-NMR(400MHz,CDCl3):δ1H-NMR(400MHz,CDCl3):δ6.98(dq,J=6.9,15.2,H-C(3)),6.50(dq,J =1.7,15.2,H-C(2)),5.64-5.56(m,H-C(3′),H-C(4′),2.31-2.21(m,1H),2.15-1.94(m,2H),1.90(dd,J=1.6,6.9,MeC(3)),1.79(ddd,J=6.7,10.8,13.9,1H),1.55(ddm,J=6.1,13.9,1H),1.15(s,MeC(1)),0.84(d,J=7.1,Me)。
MS(EI):178(9),163(6),149(3),137(3),123(12),110(14),109(100),93(15),91(14),81(24),79(17),77(16),69(68),67(66),55(17),53(13),43(17),41(48),39(29)。
IR:vmax3019,2966,2874,1691,1628,1454,1444,1375,1320,1289,1188,1054,1027,968,932,868,842,766,749,706cm-1。
气味描述:果香,越桔香,金合欢香,乡土香,薄荷香,类似突厥酮香。
实施例8:(2E)-1-(2,5-二甲基环己-3-烯基)丁-2-烯-1-酮
按照实施例1描述,从2,4-己二烯(15g,183mmol)和甲基乙烯基酮(10.6g,152mmol)的甲苯(75ml)溶液起始,在BF3·OEt2(5.4g,38mmol)的存在下制备1-(2,5-二甲基环己-3-烯基)乙烯-1-酮(6.4g,28%),并通过缩醛反应(LDA,AcH,THF;FC)和除水将其转化成(2E)-1-(2,5-二甲基环己-3-烯基)丁-2-烯-1-酮(2.3g,2步:49%,75∶25的非对映异构混合物)。
A)1-(2,5-二甲基环己-3-烯基)乙烯-1-酮:
1H-NMR(400MHz,CDCl3):δ5.64(ddd,J=2.5,4.8,9.9,H-C(3′/4′),5.48(ddd,J=1.6,3.2,9.9,H-C(4′/3′)),2.76(ddd,J=2.4,5.4,12.6,H-C(6′)),2.73-2.64(m,1H),2.22-2.11(m,1H),2.15(s,MeCO),1.78(ddm,J=5.6,13.4,1H),1.27(ddd,J=11.1,12.5,13.5,1H),1.01(d,J=7.1,Me),0.82(d,J=6.8,Me)。
B)(2E)-1-(2,5-二甲基环己-3-烯基)丁-2-烯-1-酮:
1H-NMR(400MHz,CDCl3):主要非对映异构体:δ6.91(dq,J=6.8,15.7,H-C(3)),6.21(dq,J=1.7,15.6,H-C(2)),5.58(dddd,J=1.0,2.0,4.0,9.9,H-C(3′/4′),5.48(dt,J=1.8,10.0,H-C(4′/3′)),2.59-2.50(m,2H),2.33-2.23(m,1H),1.92(dd,J=1.8,6.8,MeC(3)),1.76(ddd,J=5.8,11.1,13.1,1H),1.56(dddd,J=1.0,2.8,3.0,13.4,1H),1.04(d,J=7.1,Me),0.92(d,J=6.8,Me);较少非对映异构体:δ6.90(dq,J=6.9,15.5,H-C(3)),6.22(dq,J=1.7,15.7,H-C(2)),5.63(ddd,J=2.5,4.8,9.9,H-C(3′/4′),5.49(dt,J=1.7,9.9,H-C(4′/3′)),2.96(ddd,J=2.5,5.6,12.6,H-C(6′)),2.67-2.56(m,1H),2.33-2.23(m,1H),1.90(dd,J=1.6,6.9,MeC(3)),1.79-1.70(m,1H),1.35(ddd,J=11.1,12.6,13.6,1H),1.02(d,J=7.1,Me),0.78(d,J=7.1,Me)
13C-NMR(100MHz,CDCl3):主要非对映异构体:δ202.98(s,CO),142.35(d),131.52(d),130.96(d),130.89(d),47.84(d,C(1′)),32.43(d),31.39(d),28.53(t,C(6′)),21.01(q),20.14(q),18.17(q,C(4));较少非对映异构体:δ201.98(s,CO),141.94(d),132.73(d),130.92(d),130.21(d),48.44(d,C(1′)),31.20(d),30.92(d),27.06(t,C(6′)),21.53(q),18.12(q,C(4)),16.12(q)。
MS(EI):178(3),163(4),149(1),145(2),135(2),123(6),109(25),108(11),93(10),91(11),81(6),79(11),77(10),69(100),67(17),65(4),55(10),41(32),39(19)。
IR:vmax3013,2957,2929,2871,1694,1667,1630,1443,1374,1289,1225,1198,1181,1150,1128,1087,1050,970,919,729cm-1。
沸点(非对映异构混合物):60℃(0.1mbar)。
气味描述:果香,类似突厥酮香,干果香,李子香,苹果香,乡土香。
实施例9:
根据实施例1的一般步骤制备下列化合物。
实施例9:用于肥皂的具有茶香味的香料组合物
化合物/成分 重量份1/1270
Evernyl(2,4-二羟基-3,6-二甲基苯甲酸甲酯) 1
Undecavertol(4-甲基-3-癸烯-5-醇) 1
爪哇香茅精油 2
Cyclal C(2,4-二甲基-3-环己烯-1-甲醛) 2
中国桉树精油 2
以10%溶于DPG(一缩二丙二醇)中的2-异丁基喹啉 2
Aldehyde C 12MNA(2-甲基十一醛) 3
以10%溶于DPG(一缩二丙二醇)中的Ambrofix(CAS 6790-58-5) 3
Aldehyde C 110Undecyl ic(十一醛) 10
Gaiacwood油 10
Peach Pure(γ-十一碳烷酸内酯) 10
香叶醇 20
Hedione(二氢茉莉酮酸甲酯) 32
β二氢紫罗兰酮 35
萜品醇 40
(1,3,4,6,7,8-六氢化-4,6,6,7,8,8-六甲基-环戊-γ-2-苯并吡喃) 70
β紫罗兰酮 70
水杨酸己酯 80
Bergamote Givco 104* 100
乙酸萜品酯 100
Agrumex(乙酸2-叔丁基环己酯) 100
再生的柠檬精油1385** 100
丙酸三环癸烯酯 100
α己基肉桂醛 150
里哪醇 200
以10%溶于DPG中的实施例1的丁烯酮 20
*可从Givaudan SA获得的基料(参见香料成分索引2004)
**产自:Givaudan SA,瑞士
实施例1的丁烯酮加重了茶香型的果香香调及其蜜香方面(facet)。
谐香更清新,比使用δ-突厥酮的情形具有更少的软木香调。
Claims (15)
2.根据权利要求1的化合物,其中
R1为氢、甲基或乙基,
R2为甲基或乙基,和
R3、R4和R5为氢。
3.根据权利要求1的化合物,其中
R1和R2独立地选自氢、甲基或乙基,
R3和R4为氢,和
R5为甲基或乙基。
4.根据权利要求1的化合物,其中
R1选自氢、甲基或乙基,
R2为甲基或乙基,
R3为甲基或乙基,和
R4和R5为氢。
5.根据权利要求1的化合物,其中
R1和R2独立地选自氢、甲基或乙基,
R4和R5独立地选自甲基或乙基,和
R3为氢。
6.根据权利要求1的化合物,其中
R1和R2独立地选自氢、甲基或乙基,
R4为氢,和
R3和R5独立地选自甲基或乙基。
7.根据权利要求1的化合物,其中
R1和R2独立地选自氢、甲基或乙基,和
R3、R4和R5独立地选自甲基或乙基。
8.根据权利要求1的化合物,其选自由下列化合物组成的项
(2E)-1-(6-乙基-2-甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2-乙基-6-甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(6-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2-二甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,5-二甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,6-二甲基-2-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,5-二甲基-6-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3-二甲基-6-乙基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3,6-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3,5,6-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,5,6-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,3-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,3,5-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,3,6-四甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3-二甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(2,3,5-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,6-三甲基环己-3-烯基)丁-2-烯-1-酮,
(2E)-1-(1,2,5-三甲基环己-3-烯基)丁-2-烯-1-酮,和
(2E)-1-(1,6-二甲基环己-3-烯基)丁烯-1-酮。
9.根据权利要求1的化合物,其中残基R2、R3、R4和R5中的至少一个是乙基。
10.一种调料或香料组合物,包括如前述权利要求中任意一项所定义的式(I)的化合物。
11.一种香料用品,包括
a)如权利要求1-9中任意一项所定义的式(I)的化合物;和
b)消费品基体。
12.根据权利要求11的香料用品,其中消费品基体选自精细香料、家用产品、洗衣产品、身体护理产品和化妆品。
13.一种制造调料或香料组合物的方法,所述方法包括以下步骤:向基体材料中引入有效量的如权利要求1-9中任意一项所定义的式(I)的化合物或其混合物。
14.一种改善、增强或改变香料组合物或香料用品香味的方法,所述方法包括向基体材料中引入有效量的如权利要求1-9中任意一项所定义的式(I)的化合物或其混合物。
15.如权利要求1-9中任意一项所定义的式(I)的化合物作为调料或香料成分的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0624814.0A GB0624814D0 (en) | 2006-12-13 | 2006-12-13 | Organic compounds |
GB0624814.0 | 2006-12-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101557857A true CN101557857A (zh) | 2009-10-14 |
Family
ID=37712014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2007800461665A Pending CN101557857A (zh) | 2006-12-13 | 2007-12-11 | 环己烯基丁烯酮和包括它们的香料组合物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7812195B2 (zh) |
EP (1) | EP2094359A1 (zh) |
JP (1) | JP2010512347A (zh) |
CN (1) | CN101557857A (zh) |
BR (1) | BRPI0720294A2 (zh) |
GB (1) | GB0624814D0 (zh) |
MX (1) | MX2009005880A (zh) |
WO (1) | WO2008071026A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101768608B (zh) * | 2009-12-31 | 2012-02-08 | 杭州师范大学 | 一种一锅法合成维兰德-米歇尔酮类化合物的方法 |
CN103781890A (zh) * | 2011-09-12 | 2014-05-07 | 弗门尼舍有限公司 | 加香缩醛 |
CN109476570A (zh) * | 2016-07-27 | 2019-03-15 | 奇华顿股份有限公司 | 作为香料成分的6-异丙基-2,4-二甲基环己烯-1-醇化合物 |
CN108430963B (zh) * | 2015-12-09 | 2021-08-20 | 奇华顿股份有限公司 | 化合物 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH549951A (fr) * | 1971-08-17 | 1974-06-14 | Firmenich & Cie | Utilisation de composes alicycliques oxygenes comme agents aromatisants. |
US4311754A (en) * | 1978-12-15 | 1982-01-19 | International Flavors & Fragrances Inc. | Process for hydrogenation of 2,6,6-trimethyl cyclohexene derivatives and organoleptic uses of said products |
US4512928A (en) * | 1979-08-29 | 1985-04-23 | Kenrich Petrochemicals, Inc. | Pyrophosphato titanate adducts |
CH645337A5 (fr) * | 1980-08-22 | 1984-09-28 | Firmenich & Cie | Composes cycloaliphatiques insatures, procede pour leur preparation et composition parfumante les contenant. |
US4460792A (en) * | 1981-09-07 | 1984-07-17 | Firmenich S.A. | Process for the preparation of delta- and epsilon-damascones |
DE3360193D1 (en) | 1982-04-20 | 1985-06-27 | Firmenich & Cie | Process for the preparation of ketonic compounds |
JPS591462A (ja) | 1982-06-28 | 1984-01-06 | T Hasegawa Co Ltd | シクロヘキセン誘導体 |
DE3514665A1 (de) * | 1985-04-23 | 1986-10-30 | Consortium für elektrochemische Industrie GmbH, 8000 München | Trimethylcyclohexen-derivate, ihre herstellung und deren verwendung als duftstoffe |
EP0231556A1 (en) | 1986-01-23 | 1987-08-12 | Naarden International N.V. | Isopropyl-methyl-butenoyl-cyclohexenes and -cyclohexenes and -cyclohexadienes, and also perfume compositions and perfumed articles and materials which contain said compounds as a perfume ingredient |
CN100404487C (zh) * | 2003-12-16 | 2008-07-23 | 弗门尼舍有限公司 | 环己烯基烷基或烯基酮的异构化方法 |
-
2006
- 2006-12-13 GB GBGB0624814.0A patent/GB0624814D0/en not_active Ceased
-
2007
- 2007-12-11 CN CNA2007800461665A patent/CN101557857A/zh active Pending
- 2007-12-11 BR BRPI0720294-6A patent/BRPI0720294A2/pt not_active Application Discontinuation
- 2007-12-11 WO PCT/CH2007/000626 patent/WO2008071026A1/en active Application Filing
- 2007-12-11 US US12/518,591 patent/US7812195B2/en not_active Expired - Fee Related
- 2007-12-11 MX MX2009005880A patent/MX2009005880A/es not_active Application Discontinuation
- 2007-12-11 EP EP07845623A patent/EP2094359A1/en not_active Withdrawn
- 2007-12-11 JP JP2009540570A patent/JP2010512347A/ja active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101768608B (zh) * | 2009-12-31 | 2012-02-08 | 杭州师范大学 | 一种一锅法合成维兰德-米歇尔酮类化合物的方法 |
CN103781890A (zh) * | 2011-09-12 | 2014-05-07 | 弗门尼舍有限公司 | 加香缩醛 |
CN108430963B (zh) * | 2015-12-09 | 2021-08-20 | 奇华顿股份有限公司 | 化合物 |
CN109476570A (zh) * | 2016-07-27 | 2019-03-15 | 奇华顿股份有限公司 | 作为香料成分的6-异丙基-2,4-二甲基环己烯-1-醇化合物 |
CN109476570B (zh) * | 2016-07-27 | 2022-06-07 | 奇华顿股份有限公司 | 作为香料成分的6-异丙基-2,4-二甲基环己烯-1-醇化合物 |
Also Published As
Publication number | Publication date |
---|---|
US7812195B2 (en) | 2010-10-12 |
GB0624814D0 (en) | 2007-01-24 |
US20100016197A1 (en) | 2010-01-21 |
BRPI0720294A2 (pt) | 2014-02-04 |
JP2010512347A (ja) | 2010-04-22 |
EP2094359A1 (en) | 2009-09-02 |
WO2008071026A1 (en) | 2008-06-19 |
MX2009005880A (es) | 2009-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4038282B2 (ja) | 付臭性組成物 | |
EP2234948B1 (en) | Perfuming ingredients imparting sap and/or earthy type notes | |
CN1950490A (zh) | 脂环族羧酸氧基羰基甲基酯及其作为增香剂的用途 | |
CN101557857A (zh) | 环己烯基丁烯酮和包括它们的香料组合物 | |
JP5637856B2 (ja) | フレグランスとして有用なホモアリルアルコール類 | |
CN100360494C (zh) | 酯及其在香料中的应用 | |
CN101198585A (zh) | 亚环烷基-(邻取代苯基)-乙腈及其作为增味剂的用途 | |
JP3297408B2 (ja) | メチルシクロテトラデカ−5−エン−1−オン類 | |
GB2529901A (en) | Organic compounds | |
CA2884353C (en) | Method for synthesising cyclohexenones and the use of same in the perfume industry | |
JP5501524B1 (ja) | ニトリル化合物 | |
JP4859826B2 (ja) | フレグランス組成物の製造に好適な三置換フラン | |
CN101500656A (zh) | 环戊烷/环戊烯醛或酮衍生物和它们作为增香剂的用途 | |
JP6072797B2 (ja) | フレグランス化合物および組成物 | |
CN103201250A (zh) | 新型羧酸酯化合物及其制造方法以及其香料组合物 | |
EP2279235B1 (en) | Fragrance | |
JP2011511813A (ja) | 有機化合物 | |
CN100371307C (zh) | 4-甲基癸-4-烯-3-醇和芳香组合物 | |
JPH05140071A (ja) | シクロペンチル−シアノメチル−シクロペンテン類、それらの製造方法及び芳香物質としての利用 | |
JP2008507479A (ja) | サリチル酸4−ヘプテン−2−イルおよびフレグランス成分としてのその使用 | |
JP2007507434A (ja) | 3−イソプロピル−1−メチルシクロペンチル誘導体およびフレグランス製品におけるその使用 | |
CN101072857A (zh) | 有机化合物 | |
JP2004115514A (ja) | 大環状ケトン類およびラクトン類の製造方法 | |
JP2002187886A (ja) | 4−メチル−3−(z−2−ペンテニル)−2(5h)−フラノンおよび該化合物を含む香料組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091014 |