JPH0259564A - Production of (r)-(-)-2-decen-5-olide - Google Patents
Production of (r)-(-)-2-decen-5-olideInfo
- Publication number
- JPH0259564A JPH0259564A JP63210791A JP21079188A JPH0259564A JP H0259564 A JPH0259564 A JP H0259564A JP 63210791 A JP63210791 A JP 63210791A JP 21079188 A JP21079188 A JP 21079188A JP H0259564 A JPH0259564 A JP H0259564A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- expressed
- acid
- hydroxy
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- NEDIAPMWNCQWNW-SECBINFHSA-N (2r)-2-pentyl-2,3-dihydropyran-6-one Chemical compound CCCCC[C@@H]1CC=CC(=O)O1 NEDIAPMWNCQWNW-SECBINFHSA-N 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004794 vinyl magnesium halides Chemical class 0.000 claims abstract description 7
- NDUPBTSXOSZHON-UHFFFAOYSA-N non-1-en-4-ol Chemical compound CCCCCC(O)CC=C NDUPBTSXOSZHON-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZCRWZHCZPMNQEJ-UHFFFAOYSA-N 1-(oxiran-2-yl)heptan-2-ol Chemical compound CCCCCC(O)CC1CO1 ZCRWZHCZPMNQEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 26
- 239000003205 fragrance Substances 0.000 claims description 22
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 7
- 239000000796 flavoring agent Substances 0.000 abstract description 17
- 235000019634 flavors Nutrition 0.000 abstract description 14
- 235000009508 confectionery Nutrition 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- -1 cyanogen compound Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 1
- 230000002085 persistent effect Effects 0.000 abstract 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 6
- 230000005923 long-lasting effect Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-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
- 239000003599 detergent Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 4
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000013355 food flavoring agent Nutrition 0.000 description 3
- NEDIAPMWNCQWNW-UHFFFAOYSA-N massoia lactone Chemical compound CCCCCC1CC=CC(=O)O1 NEDIAPMWNCQWNW-UHFFFAOYSA-N 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000014347 soups Nutrition 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 2
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-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
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- UBLAMKHIFZBBSS-UHFFFAOYSA-N 3-Methylbutyl pentanoate Chemical compound CCCCC(=O)OCCC(C)C UBLAMKHIFZBBSS-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
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 235000019568 aromas Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940007550 benzyl acetate Drugs 0.000 description 2
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000000484 citronellol Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 229930007744 linalool Natural products 0.000 description 2
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 2
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 description 1
- WJTCHBVEUFDSIK-NWDGAFQWSA-N (2r,5s)-1-benzyl-2,5-dimethylpiperazine Chemical compound C[C@@H]1CN[C@@H](C)CN1CC1=CC=CC=C1 WJTCHBVEUFDSIK-NWDGAFQWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-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
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- UAVFEMBKDRODDE-UHFFFAOYSA-N Vetiveryl acetate Chemical compound CC1CC(OC(C)=O)C=C(C)C2CC(=C(C)C)CC12 UAVFEMBKDRODDE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002386 air freshener Substances 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- JKRWZLOCPLZZEI-UHFFFAOYSA-N alpha-Trichloromethylbenzyl acetate Chemical compound CC(=O)OC(C(Cl)(Cl)Cl)C1=CC=CC=C1 JKRWZLOCPLZZEI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940062909 amyl salicylate Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 235000015155 buttermilk Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 239000001926 citrus aurantium l. subsp. bergamia wright et arn. oil Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 235000011850 desserts Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- NYNCZOLNVTXTTP-UHFFFAOYSA-N ethyl 2-(1,3-dioxoisoindol-2-yl)acetate Chemical compound C1=CC=C2C(=O)N(CC(=O)OCC)C(=O)C2=C1 NYNCZOLNVTXTTP-UHFFFAOYSA-N 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 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
- 235000019717 geranium oil Nutrition 0.000 description 1
- 239000010648 geranium oil Substances 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- 229940043353 maltol Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- XKBCNTPVQJGJPY-UHFFFAOYSA-N non-1-en-1-ol Chemical compound CCCCCCCC=CO XKBCNTPVQJGJPY-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- YYZUSRORWSJGET-UHFFFAOYSA-N octanoic acid ethyl ester Natural products CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000019719 rose oil Nutrition 0.000 description 1
- 239000010666 rose oil Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Landscapes
- Seasonings (AREA)
- Pyrane Compounds (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は下記式(1)
で示される(R)−(−)−2−デセン−5−オリドの
新規製法ならびに該式化合物を有効成分として含有する
持続性のある香料組成物に関する。Detailed Description of the Invention (Industrial Application Field) The present invention provides a novel method for producing (R)-(-)-2-decene-5-olide represented by the following formula (1), and a method for using the compound of the formula as an active ingredient. It relates to a long-lasting fragrance composition containing as.
更に詳しくは、本発明は(+)−1,2−エポキシヘプ
タンを出発原料として用い短い工程で上記式(1)の目
的化合物を合成する製法に関する。More specifically, the present invention relates to a method for synthesizing the target compound of formula (1) in a short process using (+)-1,2-epoxyheptane as a starting material.
更にまた、本発明は持続性のあるマイルドで天然調の甘
いラクトン様の香気香味を有し、さらに7アツテイー様
、バター様、ミルク様の香気香味を増強する特性を有す
る上記式(1)で示される(R)−(−)−2−デセン
−5−オリドを有効成分として含有する香料組成物に関
する。Furthermore, the present invention has a long-lasting, mild, natural sweet lactone-like aroma and flavor, and further has the property of enhancing the 7-acutey-like, butter-like, and milk-like aromas. The present invention relates to a fragrance composition containing the following (R)-(-)-2-decene-5-olide as an active ingredient.
今回、上記式(1)の化合物は優れた持続性のある香気
香味を有し、各種の香料組成物の持続性香気香味付与乃
至変調剤として、飲食品(嗜好品を含有する)、香粧品
類、保健・医薬品などの広い分野において有用であるこ
とが発見された。This time, the compound of the above formula (1) has an excellent long-lasting aroma and flavor, and can be used as a long-lasting aroma and flavor imparting or modulating agent for various fragrance compositions, food and beverages (including luxury goods), cosmetics, etc. It has been discovered that it is useful in a wide range of fields such as medicine, health care, and pharmaceuticals.
従って、本発明の目的は、上記式(1)の(R)−(−
)−2−デセン−5−オリドの新規製法を提供すること
、及び法式(1)の化合物を有効成分とする各種の分野
で利用出来る香料組成物を提供することである。Therefore, the object of the present invention is to provide (R)-(-
)-2-Decene-5-olide, and to provide a fragrance composition that can be used in various fields and contains a compound of formula (1) as an active ingredient.
(従来の技術)
本発明の上記式(1)で示される光学的に活性な(R)
−(−) −2−デセン−5−オリドは、砂糖きびの糖
みつに含まれる香気成分として単離、同定され、砂糖様
香気を有することが知られている[Agr、 Bio
1. Chem、 32 (10) 。(Prior art) Optically active (R) represented by the above formula (1) of the present invention
-(-)-2-Decene-5-olide was isolated and identified as an aroma component contained in sugarcane molasses, and is known to have a sugar-like aroma [Agr, Bio
1. Chem, 32 (10).
1306〜1309 (1968)]。1306-1309 (1968)].
一方、光学的に不活性な2−デセン−5−オリドはバタ
ー様の香気を有していることが知られている(特公昭4
6−41183号公報)。そして本出願人は、先にその
改善された製造方法を提案している(特開昭63−57
583号公報)。この提案によれば、光学的に不活性な
4−ヒドロキシ−1−ノネンをエポキシ化剤と反応させ
て、光学的に不活性な4−ヒドロキシ−1,2−エポキ
シノナンを合成し、次に、該エポキシ化物をシアン化ナ
トリウムと反応させて光学的に不活性な2゜4−ジヒド
ロキシノニルニトリルとなし、更に、該ニトリルを酸で
処理して光学的に不活性な2−デセン−5−オリドを合
成している。On the other hand, optically inactive 2-decene-5-olide is known to have a butter-like aroma (Japanese Patent Publication No. 4
6-41183). The present applicant has previously proposed an improved manufacturing method (Japanese Unexamined Patent Publication No. 63-57
Publication No. 583). According to this proposal, optically inactive 4-hydroxy-1-nonene is reacted with an epoxidizing agent to synthesize optically inactive 4-hydroxy-1,2-epoxynonane, and then , the epoxide is reacted with sodium cyanide to form optically inactive 2°4-dihydroxynonylnitrile, and the nitrile is further treated with acid to form optically inactive 2-decene-5- Synthesizing oride.
(発明が解決しようとする課題)
上述の従来提案においては、本発明の式(1)の化合物
を砂糖きびの糖みつの香気成分として単離、同定し、砂
糖様の香気を有していることを確認したのみで、該化合
物の有用性ならびに香気香味付与剤としての香料用途に
ついては全く記載も示唆もされていない。更に、本出願
人が先に提案した製造方法は光学的に不活性な2−デセ
ン−5−オリドの合成法であり、光学的に活性な本発明
の式(1)の化合物の製造法についてはいまだ提案され
ていない。(Problems to be Solved by the Invention) In the above-mentioned conventional proposal, the compound of formula (1) of the present invention was isolated and identified as an aroma component of sugarcane molasses, and it was found that it has a sugar-like aroma. However, there is no description or suggestion of the usefulness of the compound or its use as a flavoring agent. Furthermore, the manufacturing method previously proposed by the applicant is a method for synthesizing optically inactive 2-decene-5-olide, and the method for manufacturing the optically active compound of formula (1) of the present invention is Yes, it has not been proposed yet.
本発明者等は鋭意研究の結果、今回、市場で容易に入手
できる(十)−1,2−エポキシエタンを原料として選
ぶことにより、少ない工程数でかつ副生成物を伴うこと
なく高純度で式(1)の化合物が合成できることを発見
した。更に、香気香味付与剤として香料組成物に使用し
た場合、本発明の方法により製造した光学的に活性な式
(1)の化合物の香気特性は、従来の光学的に不活性な
2−デセン−5−オリドの香気特性と比較して、持続性
のあるマイルドな天然調の甘さに優れ、さらにファンテ
ィー様、バター様、ミルク様の香気香味を増強させるこ
とに優れていることを発見して本発明を完成した。As a result of intensive research, the present inventors have now selected (10)-1,2-epoxyethane, which is easily available on the market, as a raw material to achieve high purity with a small number of steps and without by-products. It has been discovered that the compound of formula (1) can be synthesized. Furthermore, when used as an aroma flavoring agent in a perfume composition, the aroma properties of the optically active compound of formula (1) produced by the method of the present invention are superior to those of the conventional optically inactive 2-decene- We discovered that compared to the aroma characteristics of 5-olide, it has a long-lasting, mild natural sweetness, and is also excellent in enhancing fanty-like, butter-like, and milk-like aromas. The present invention was completed.
(本発明を解決するための手段)
かくして、本発明によれば、下記式(5)で示される(
−)−4−ヒドロキシ−1,2−エポキシノナンを形成
させ、次いで、法式(3)の化合物をシアン化ナトリウ
ム、シアン化カリウムもしくはシアン化水素と反応させ
て、下記式(2)で示される(+)−1,2−エポキシ
ヘプタンをビニルマグネシウムハライドと反応させてる
ことを特徴とする、下記式(4)
で示される(−)−2,4−ジヒドロキシノニルニトリ
ルを形成させ、更に、法式(2)の化合物を酸の存在下
に加熱反応させることを特徴とする下記式(1)
で示される(+)−4−ヒドロキシ−1−ノネンの製造
方法が提供される。(Means for solving the present invention) Thus, according to the present invention, (
-)-4-hydroxy-1,2-epoxynonane is formed, and then the compound of formula (3) is reacted with sodium cyanide, potassium cyanide or hydrogen cyanide to form (+)- (-)-2,4-dihydroxynonylnitrile represented by the following formula (4) is formed by reacting 1,2-epoxyheptane with vinylmagnesium halide, and further, by reacting 1,2-epoxyheptane with vinylmagnesium halide, There is provided a method for producing (+)-4-hydroxy-1-nonene represented by the following formula (1), which comprises subjecting a compound to a heating reaction in the presence of an acid.
本発明によればさらに、上記式(4)の化合物をエポキ
シ化剤と反応させて、下記式(3)で示される(R)−
(−)−2−デセン−5−オリドの製造方法が提供され
る。According to the present invention, the compound of the above formula (4) is further reacted with an epoxidizing agent to form a (R)-
A method for producing (-)-2-decene-5-olide is provided.
かかる本発明の方法によれば、上記式(1)の化合物が
容易な操作で工業的に高純度且つ安価に製造できる。According to the method of the present invention, the compound of formula (1) above can be produced industrially with high purity and at low cost through easy operations.
本発明の上記式(1)の化合物の製造方法を工程図で示
すと以下のとおりである。The method for producing the compound of formula (1) of the present invention is shown in the following process diagram.
m−CPBA:m−クロル過安息香酸
本発明の(R)−(−)−2−デセン−5−オリドの製
造方法を上記工程図に従って以下にさらに詳細に説明す
る。m-CPBA: m-chloroperbenzoic acid The method for producing (R)-(-)-2-decene-5-olide of the present invention will be explained in more detail below according to the above process diagram.
上記式(5)の(+)−1,2−エポキシヘプタンから
上記式(4)の(+)−4−ヒドロキシ−1−ノネンを
合成するには、式(5)の化合物を有機溶媒中、金属ハ
ロゲン化物の存在下にビニルマグネシウムハライドと反
応させることにより容易に合成することができる。To synthesize (+)-4-hydroxy-1-nonene of formula (4) above from (+)-1,2-epoxyheptane of formula (5) above, the compound of formula (5) is mixed in an organic solvent. , can be easily synthesized by reacting with vinyl magnesium halide in the presence of a metal halide.
反応は、通常、約−80℃〜約60℃、より好ましくは
約−40℃〜約20℃程度の範囲内の温度で、例えば、
約0.5時間〜約4時間、より好ましくは約1時間〜約
2時間程度で行うことができる。The reaction is usually carried out at a temperature in the range of about -80°C to about 60°C, more preferably about -40°C to about 20°C, for example,
It can be carried out for about 0.5 hours to about 4 hours, more preferably about 1 hour to about 2 hours.
この反応に使用するビニルマグネシウムハライドの具体
例としては、例えば、ビニルマグネシウムクロライド、
ビニルマグネシウムブロマイドなどを好ましく例示する
ことができる。ビニルマネシウムハライドの使用量は、
厳密に制限されるものではないが、一般には、式(5)
の化合物1モルに対して約1.0モル−約10モル程度
の範囲、より好ましくは約1モル〜約2モル程度の範囲
を挙げることができる。また、金属ハロゲン化物の具体
例としては、例えば、ヨウ化銅、臭化銅、塩化銅などを
挙げることができる。これら金属ハロゲン化物の使用量
は触媒量で十分であるが、例えば、式(5)の化合物1
モルに対して約0.O1モル〜約0.5モル程度の範囲
を挙げることができる。また、上記反応に使用する有機
溶媒としては、テトラヒドロフラン、エーテル、ジオキ
サンなどを例示することができる。これらの有機溶媒の
使用量は、特に制限されるものではないが、式(5)の
化合物に対して約2〜約10重量倍程度の範囲を好まし
く例示することができる。Specific examples of vinylmagnesium halides used in this reaction include vinylmagnesium chloride,
Preferred examples include vinylmagnesium bromide. The amount of vinyl manesium halide used is
Although not strictly limited, in general, formula (5)
A range of about 1.0 mol to about 10 mol, more preferably about 1 mol to about 2 mol, can be mentioned per 1 mol of the compound. Further, specific examples of metal halides include copper iodide, copper bromide, copper chloride, and the like. A catalytic amount of these metal halides is sufficient, but for example, compound 1 of formula (5)
Approximately 0.0% per mole. A range of about 1 mol to about 0.5 mol of O can be mentioned. Furthermore, examples of the organic solvent used in the above reaction include tetrahydrofuran, ether, and dioxane. The amount of these organic solvents to be used is not particularly limited, but a preferred range is about 2 to about 10 times the weight of the compound of formula (5).
反応終了後、常法に従って中和、水洗浄、濃縮、乾燥後
、必要により、例えば、蒸留などの手段で精製して式(
4)の化合物を高純度で得ることができる。After the reaction is completed, it is neutralized, washed with water, concentrated, and dried according to conventional methods, and if necessary, purified by means such as distillation to obtain the formula (
The compound 4) can be obtained with high purity.
上述のようにして得ることのできる式(4)の(+)−
4−ヒドロキシ−1−ノネンから上記式(3)の(−)
−4−ヒドロキシ−1,2−エポキシノナンを合成する
には、式(4)の化合物を有機溶媒中、エポキシ化剤と
反応させることにより容易に合成することができる。(+)− of equation (4) that can be obtained as described above
(-) of the above formula (3) from 4-hydroxy-1-nonene
-4-hydroxy-1,2-epoxynonane can be easily synthesized by reacting the compound of formula (4) with an epoxidizing agent in an organic solvent.
反応は、通常、約2〜約10℃程度の範囲内の温度で、
例えば、約2時間〜約48時間程度の反応時間で行うこ
とができる。The reaction is usually carried out at a temperature within the range of about 2 to about 10°C,
For example, the reaction time can be about 2 hours to about 48 hours.
この反応に使用するエポキシ化剤の具体例としては、例
えば、m−クロル過安息香酸、過安息香酸、過酢酸、過
ギ酸などを挙げることができる。Specific examples of the epoxidizing agent used in this reaction include m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, performic acid, and the like.
これらのエポキシ化剤の使用量は特に制限されないが、
一般には、式(4)の化合物1モルに対して約1モル〜
約1.5モル程度の範囲を例示することができる。また
、この反応に使用する有機溶媒としては、例えば、塩化
メチレン、クロロホルム、四塩化炭素、トルエン、ヘキ
サンなどを挙げることができる。これらの有機溶媒の使
用量も制限されるものではないが、例えば、式(4)の
化合物に対して約l〜約20重量倍程度の範囲を好まし
く例示することができる。The amount of these epoxidizing agents used is not particularly limited, but
Generally, about 1 mol to 1 mol of the compound of formula (4)
A range of about 1.5 moles can be exemplified. Furthermore, examples of the organic solvent used in this reaction include methylene chloride, chloroform, carbon tetrachloride, toluene, and hexane. The amount of these organic solvents to be used is also not limited, but preferably ranges from about 1 to about 20 times the weight of the compound of formula (4).
反応終了後、常法に従って水洗浄、濃縮後、必要により
、例えば、蒸留のごとき手段で精製して式(3)の化合
物を高純度で得ることができる。After the reaction is completed, the compound of formula (3) can be obtained in high purity by washing with water and concentrating according to a conventional method, and then purifying, for example, by means such as distillation, if necessary.
次に、上述のようにして得ることのできる式(3)の化
合物から、上記式(2)の(−) −2,4−ジヒドロ
キシノニルニトリルを合成するには、例えば、式(3)
の化合物をシアン化カリウム、シアン化ナトリウムもし
くはシアン化水素などのシアン化物と反応させることに
より容易に行なうことができる。この反応は、適宜、通
常、水、メタノール、エタノール、テトラヒドロ7ラン
の如き溶媒中で、酢酸、プロピオン酸、硫酸マグネシウ
ム、塩化アンモニウムの如き酸の存在下に行われる。Next, in order to synthesize the (-)-2,4-dihydroxynonylnitrile of the above formula (2) from the compound of the formula (3) that can be obtained as described above, for example, the compound of the formula (3)
This can be easily carried out by reacting the compound with a cyanide such as potassium cyanide, sodium cyanide or hydrogen cyanide. This reaction is suitably carried out, usually in a solvent such as water, methanol, ethanol, or tetrahydro7rane, in the presence of an acid such as acetic acid, propionic acid, magnesium sulfate, or ammonium chloride.
上記反応の反応温度及び反応時間は適宜に選択して行う
ことができ、例えば、約り0℃〜約100℃程度の範囲
の反応温度で、及び、約1時間〜約lO時間程度の反応
時間を好ましく例示することができる。この反応に使用
するシアン化物の使用量としては、通常、式(3)の化
合物1モルに対して約1モル〜約2モル程度の量を好ま
しく例示することができる。また、上記のごとき溶媒の
使用量には特別な制限はなく、適宜に選択することがで
きるが、例えば、式(3)の化合物に対して約2〜約2
0重量倍程度の範囲で使用しうる。The reaction temperature and reaction time of the above reaction can be appropriately selected and carried out, for example, at a reaction temperature in the range of about 0°C to about 100°C, and a reaction time of about 1 hour to about 10 hours. can be exemplified preferably. The amount of cyanide used in this reaction is usually preferably about 1 mol to about 2 mol per 1 mol of the compound of formula (3). Further, the amount of the solvent used as described above is not particularly limited and can be selected as appropriate, but for example, about 2 to about 2
It can be used within a range of about 0 times the weight.
また、上述の酸の使用量も特に制限されるものではない
が、一般には、式(3)の化合物1モルに対して約1〜
約2モル程度の範囲を好ましく例示することができる。Further, the amount of the above-mentioned acid used is not particularly limited, but is generally about 1 to 1 to 1 mole of the compound of formula (3).
A preferable example is a range of about 2 moles.
反応終了後、抽出、水洗浄、乾燥、濃縮などの処理を行
うことにより、式(2)の化合物を容易に得ることがで
きる。After the reaction is completed, the compound of formula (2) can be easily obtained by performing treatments such as extraction, water washing, drying, and concentration.
上述のようにして得られる式(2)の化合物から目的と
する式(1)の(R) −(−)、−2−デセン−5−
オリドの合成は、例えば、前記式(2)の化合物を酸の
存在下に加熱反応させることにより容易に行なうことが
できる。From the compound of formula (2) obtained as described above, the desired compound of formula (1) (R) -(-), -2-decene-5-
Olide can be easily synthesized, for example, by subjecting the compound of formula (2) to a heating reaction in the presence of an acid.
上記反応は、例えば、約り0℃〜約100°C程度の反
応温度、及び、約0.5時間〜約10時間程度の反応時
間で行うことができる。The above reaction can be carried out, for example, at a reaction temperature of about 0° C. to about 100° C. and a reaction time of about 0.5 hour to about 10 hours.
この反応に使用しうる酸としては、例えば、塩酸、硫酸
、リン酸の如き酸を例示することができる。これらの酸
の使用量には、特別な制約はなく適宜選択すればよく、
例えば、式(2)の化合物1モルに対して約1モル〜約
lOモル程度の量を好ましく挙げることができる。Examples of acids that can be used in this reaction include hydrochloric acid, sulfuric acid, and phosphoric acid. There are no special restrictions on the amount of these acids used, and they can be selected as appropriate.
For example, an amount of about 1 mol to about 10 mol can be preferably mentioned per 1 mol of the compound of formula (2).
反応終了後、抽出、洗浄、濃縮などの処理をして、目的
化合物である式(1)の(R) −(−)−2−デセン
−5−オリドを得ることができる。After completion of the reaction, the target compound (R)-(-)-2-decene-5-olide of formula (1) can be obtained by performing treatments such as extraction, washing, and concentration.
得られる式(1)の化合物は、必要により、蒸留のごと
き手段でさらに精製することができる。The obtained compound of formula (1) can be further purified by means such as distillation, if necessary.
上述のようにして合成することのできる式(1)の化合
物は、持続性のあるマイルドで天然調の甘いラクトン様
の香気香味を有し、さらに7アツテイー様、バター様、
ミルク様の香気香味を増強する特性を有し、各種の合成
香料、天然精油などとよく調和するという特性を有して
おり、従って、法式(1)化合物を利用すれば新規な各
種の香料組成物を調製することができる。香料組成物に
おける上記式(1)の化合物の配合量は、配合される香
料組成物の種類や用途等によって異なるが、例えば、一
般的には全体の約0.001〜約30重量%程度の範囲
を挙げることができる。The compound of formula (1), which can be synthesized as described above, has a long-lasting, mild and natural sweet lactone-like aroma and flavor, and also has a 7-starchy, butter-like,
It has the property of enhancing the milk-like aroma and flavor, and has the property of harmonizing well with various synthetic fragrances, natural essential oils, etc. Therefore, if the compound of formula (1) is used, various new fragrance compositions can be created. can prepare things. The amount of the compound represented by formula (1) in the fragrance composition varies depending on the type and use of the fragrance composition, but generally it is about 0.001 to about 30% by weight of the total. I can list a range.
かくして、本発明は、式(1)の化合物を有効成分とし
て含有する香料組成物を提供するものであり、該組成物
を利用して、式(1)の化合物を香気香味成分として含
有することを特徴とする飲食品類;式(1)の化合物を
香喫味成分として含有することを特徴とするタバコ製品
;式(1)化合物を香気成分として含有することを特徴
とする化粧品類;式(1)化合物を香気香味成分として
含有することを特徴とする保健・衛生・医薬品などを提
供することができる。より具体的に例えば、バター ミ
ルクのごとき乳製品類;果汁飲料類、果実酒類、乳飲料
類、炭酸飲料の如き飲料類;アイスクリーム類、シャー
ベット類、アイスキャンデー類のごとき冷菓類;和・洋
菓子類、ジャム類、チューインガム類、パン類、コーヒ
ー、ココア、紅茶、緑茶、タバコのごとき嗜好品類;和
風スープ類、洋風スープ類のごときスープ類−風味調味
料、各種インスタント飲料類ないし食品類、各種スナッ
ク食品類などに適当量を配合して香気香味を付与した飲
食品類を提供することができる。また、例えば、シャン
プー類、ヘアークリーム類、ポマード、その他の毛髪用
化粧料基剤;オシロイ、口紅、その他の化粧用基剤や化
粧用洗剤基剤などに適当量を配合して香気を付与した化
粧品類を提供することができる。更にまた、洗潅用洗剤
類、消毒用洗剤類、防臭洗剤類、室内芳香消臭剤その他
各種の保健・衛生用洗剤類;歯磨き、ティッシュ−トイ
レットペーパーなどの各種の保健・衛生材料類;医薬品
の服用を容易にするための矯味、賦香剤などの保健・衛
生・医薬品類に適当量を配合して香気香味を付与した保
健・衛生・医薬品類を提供することもできる。Thus, the present invention provides a fragrance composition containing the compound of formula (1) as an active ingredient, and the composition can be used to contain the compound of formula (1) as an aromatic flavor ingredient. Food and drink products characterized by; Tobacco products characterized by containing the compound of formula (1) as a flavor component; Cosmetics characterized by containing the compound of formula (1) as a flavor component; Formula (1) ) Compounds can be provided as health, hygiene, pharmaceuticals, etc., which are characterized by containing the compound as an aromatic flavor component. More specifically, for example, dairy products such as butter milk; beverages such as fruit juice drinks, fruit alcoholic beverages, milk drinks, and carbonated drinks; frozen desserts such as ice creams, sherbet, and popsicles; Japanese and Western sweets. luxury goods such as jams, chewing gums, breads, coffee, cocoa, black tea, green tea, and tobacco; soups such as Japanese soups and Western soups - flavor seasonings, various instant beverages or foods, various It is possible to provide food and drink products with aroma and flavor by adding an appropriate amount to snack foods and the like. For example, fragrance can be added to shampoos, hair creams, pomades, and other hair cosmetic bases; by adding an appropriate amount to shampoos, hair creams, pomades, and other hair cosmetic bases; Cosmetics can be provided. Furthermore, cleaning detergents, disinfectant detergents, deodorizing detergents, indoor air fresheners and other various health and hygiene detergents; various health and hygiene materials such as toothpaste, tissues and toilet paper; and pharmaceuticals. It is also possible to provide health, hygiene, and pharmaceutical products that have been blended with appropriate amounts of flavoring and flavoring agents to make them easier to take.
以下、本発明について実施例をあげてさらに詳細に説明
する。Hereinafter, the present invention will be explained in more detail by giving examples.
(実施例)
実施例1
+ −4−ヒドロキシ−1−ノネン 4±遣j■」
11床
フラスコにマグネシウム1.17g (48,8ミリモ
ル)、テトラヒドロ7ラン5 m l仕込み、これにビ
ニルブロマイド5.63gのテトラヒドロフラン溶液2
0m1を1時間で滴下する。滴下終了後、更に1.5時
間撹拌し、この溶液に触媒量のヨウ化銅を加え、1時間
撹拌した後、(+)−1,2−エポキシへブタン4.O
Og (35゜1ミリモル)のテトラヒドロフラン溶液
30m1を滴下する。滴下終了後、0°Cの温度で1.
5時間撹拌して反応させる。反応終了後、反応液を塩化
アンモニウム水溶液に注ぎ、エーテルで抽出し、抽出液
を洗浄、乾燥、濃縮した後減圧下で蒸留して式(4)の
化合物4.12g(収率:82.7%)を得た。(Example) Example 1 + -4-Hydroxy-1-nonene 4±
A 11-bed flask was charged with 1.17 g (48.8 mmol) of magnesium and 5 ml of tetrahydrofuran, and to this was added a solution of 5.63 g of vinyl bromide in tetrahydrofuran 2.
Drop 0ml in 1 hour. After the dropwise addition was completed, the solution was further stirred for 1.5 hours, and a catalytic amount of copper iodide was added to this solution, and after stirring for 1 hour, (+)-1,2-epoxyheptane 4. O
30 ml of a solution of Og (35° 1 mmol) in tetrahydrofuran are added dropwise. After dropping, 1. at a temperature of 0°C.
Stir and react for 5 hours. After the reaction was completed, the reaction solution was poured into an aqueous ammonium chloride solution, extracted with ether, and the extract was washed, dried, concentrated, and then distilled under reduced pressure to obtain 4.12 g of the compound of formula (4) (yield: 82.7 %) was obtained.
瀦点:47℃〜48℃/2.0mmHg旋光度:[、]
]’鳳−7.95’ (c−1,56:エタノール)
実施例2
−4−ヒドロキシ−1,2−エポキシノナン 式(3化
合物 の合成
フラスコにジクロルメタン30m1%m−クロル過安息
香酸2.68g (15,5ミリモル)、(+)−4−
ヒドロキシ−1−ノネン2.00g(14,1ミリモル
)を仕込み、8時間撹拌する。Point: 47℃~48℃/2.0mmHg Optical rotation: [,]
]'Otori-7.95' (c-1,56: ethanol) Example 2 -4-Hydroxy-1,2-epoxynonane Formula (3 compounds) In a synthesis flask, add 30ml of dichloromethane and 1% m-chloroperbenzoic acid 2. 68 g (15,5 mmol), (+)-4-
2.00 g (14.1 mmol) of hydroxy-1-nonene was charged and stirred for 8 hours.
撹拌後、更にm−クロル過安息香酸1.34g加え、8
時間撹拌して反応させる。反応終了後、反応液を濾過、
水洗、乾燥、濃縮し、更にシリカゲルカラムクロマトグ
ラフィー(n−ヘキサン:酢g1工fル= 3 : 1
)で精製して純粋な式(3)の化合物1.76g (
収率ニア9%)を得る。After stirring, 1.34 g of m-chloroperbenzoic acid was added, and 8
Stir for some time to react. After the reaction is complete, filter the reaction solution.
Washing with water, drying, concentrating, and further silica gel column chromatography (n-hexane: vinegar g1 ml = 3:1
1.76 g of pure compound of formula (3) purified by (
A yield of near 9% is obtained.
旋光度゛ [“]b′″″−9・60° (°″″l・
25・エタノール)
実施例3
フラスコにシアン化ナトリウム0.37g (7゜12
ミリモル)、水1.5ml、 エタ/−ルl。Optical rotation ゛ [“]b′″″−9・60° (°″″l・
25・Ethanol) Example 3 0.37 g of sodium cyanide (7°12
mmol), 1.5 ml of water, ethanol/l.
5ml、(−)−4−ヒドロキシ−1,2−エポキシノ
ナンO−9g (5,7ミリモル)、酢酸0゜43gを
仕込む。温度を55°Cにし、撹拌しながら4時間反応
させる。反応終了後、ジクロルメタンで抽出し、抽出層
を水洗、乾燥、濃縮して式(2)の化合物0.97g(
収率:92%)を得る。5 ml, (-)-4-hydroxy-1,2-epoxynonane O-9 g (5.7 mmol), and acetic acid 0.43 g were charged. The temperature is brought to 55°C and the reaction is allowed to proceed for 4 hours with stirring. After the reaction was completed, extraction was performed with dichloromethane, and the extracted layer was washed with water, dried, and concentrated to obtain 0.97 g of the compound of formula (2) (
Yield: 92%).
実施例4
フラスコに(−)−2,4−ジヒドロキシノニルニトリ
ル0.97g (5,2ミリモル)、濃塩酸0.62g
を仕込み、100℃に加熱して3時間反応させる。反応
終了後、エーテルで抽出し抽出液を水洗、乾燥、濃縮す
る。更に、シリカゲルカラムクロマトグラフィー(ヘキ
サン:酢酸エチル)で精製して純粋な式(1)の化合物
を0.42g(収率:43.8%)得る。Example 4 0.97 g (-)-2,4-dihydroxynonylnitrile (5.2 mmol) and 0.62 g of concentrated hydrochloric acid were placed in a flask.
was charged, heated to 100°C, and reacted for 3 hours. After the reaction is complete, extract with ether, wash the extract with water, dry and concentrate. Further, the product was purified by silica gel column chromatography (hexane:ethyl acetate) to obtain 0.42 g (yield: 43.8%) of the pure compound of formula (1).
旋光度: EaE も’=−112,2@(C−2,
52CHCl3)
実施例5
下記の各成分(重量部)を混合してバター様の調合香料
組成物を得た。Optical rotation: EaE'=-112,2@(C-2,
52CHCl3) Example 5 The following components (parts by weight) were mixed to obtain a butter-like blended fragrance composition.
エチルアセテート 3エチルブチレ
ート 2アセトイン
13ジアセチル
82−へブタノン 32−ノナノ
ン 92−ウンデカノン
4酪酸
432−トリデカノン 6カプロ
ン酸 18δ−オクタラクトン
3カプリル酸
31δ−デカラクトン 10δ−
ウンデカラクトン 5カプリン酸
6δ−ドデカラクトン
36植物油 800合計
1000
上記組成物98gに(R)−(−)−2−デセン−5−
オリド2gを混合してバター様の新規調合香料組成物を
調製した。この新規調合香料組成物と該化合物を加えて
いない上記の調合香料組成物について、専門パネラ−1
0人により比較した。ethyl acetate 3 ethyl butyrate 2 acetoin
13 diacetyl
82-hebutanone 32-nonanone 92-undecanone
4 butyric acid
432-tridecanone 6-caproic acid 18δ-octalactone 3-caprylic acid
31δ-decalactone 10δ-
undecalactone 5-capric acid
6δ-dodecalactone
36 vegetable oil 800 total 1000 (R)-(-)-2-decene-5- to 98g of the above composition
A new butter-like blended fragrance composition was prepared by mixing 2 g of Oride. Regarding this new blended fragrance composition and the above blended fragrance composition to which the compound is not added, expert panel 1
Comparison was made by 0 people.
その結果、専門パネラ−1O人の全員が該化合物を加え
た新規調合香料組成物は、バターらしさが強調され、か
つ天然的な感じ及び持続性の点で格段に優れているとし
た。As a result, all 10 expert panelists agreed that the newly formulated fragrance composition to which the compound was added had an emphasized butteriness, and was significantly superior in terms of natural feel and sustainability.
実施例6
パイナツプル様香気香味成分として下記の各成分(重量
)を混合した。Example 6 The following components (by weight) were mixed as a pineapple-like flavor component.
エチルアセテート 300エチルブ
チレート 250イソアミルアセテ
ート 100イソアミルバレレート
55イソ酪酸
70イソ吉草酸 3
0アリルカプロエート 35エチル
カプロエート20
エチルカプリレート15
エチルカプレート 20合計
1000
上記組成物100gに式(1)化合物を8g加えること
により、マイルド感が強調された天然のパイナツプルの
香気と同等の優れた持続性を有する新規なパイナツプル
香料組成物が得られた。Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate 100 Isoamyl valerate
55 isobutyric acid
70 Isovaleric acid 3
0 Allyl caproate 35 Ethyl caproate 20 Ethyl caprylate 15 Ethyl caproate 20 total
1000 By adding 8 g of the compound of formula (1) to 100 g of the above composition, a novel pineapple fragrance composition having an excellent persistence equivalent to that of natural pineapple fragrance with an emphasis on mildness was obtained.
実施例7 ブーケタイプの調合香料として下記の成分を混合した。Example 7 The following ingredients were mixed as a bouquet type perfume.
フェニルエチルアルコール 180リナリルア
セテート 30ベルガモツト油
40ロジノール
50ベンジルアセテート 40
へすオトロビン 80ゲラニオー
ル 110インアミルアルコール
ジエチルマロネート
シトラール1
リナロール
マルトール
ローズアブソリュ−1−10
β−イオノン 100ラベンダ
ー 20ジヤスミンアブソリ
ユートlO
アミルサリシレート 45リナリル
アセテート 135ベチバーアセテート
100シトロネロール
50合計 1000
上記組成物98gに(R)−(−)−2−デセン−5−
オリド2gを加えることにより、天然的の甘さを有した
フローラルな持続性を有する新規なブーケ調の調合香料
組成物が得られた。Phenylethyl alcohol 180 Linalyl acetate 30 Bergamot oil
40 rhodinol
50 Benzyl acetate 40
Hes Othrobin 80 Geraniol 110 Inamyl Alcohol Diethyl Malonate Citral 1 Linalool Maltol Rose Absolute-1-10 β-Ionone 100 Lavender 20 Diasmine Absolute 1O Amyl Salicylate 45 Linalyl Acetate 135 Vetiver Acetate 100 Citronellol
50 total 1000 (R)-(-)-2-decene-5- to 98g of the above composition
By adding 2 g of Oride, a novel bouquet-like perfume composition with natural sweetness and floral persistence was obtained.
実施例8
0−ズタイブの調合香料として下記の各成分(重量部)
を調合した。Example 8 Each of the following components (parts by weight) as a blended fragrance for 0-ztive
was prepared.
フェニルエチルアルコール 200ゲラニオー
ル 50ヘリ、オトロビン
20シトロネロール
10ネロール
100ヒドロキシシトロネラール 30メ
チルフエニルカルビニルアセテート5ゼラニウム油
30リナロール
30ベンジルアセテート
35ベンジルアルコール
20ローズフエノン 10ロジ
ノール 280ローズ油
lOβ−ヨノン
50ベンジルサリシレート
40シクロベンタデカツライド
30グアイヤウツド油 50
合計 1000
上記組成物97gに式(1)の(R)−(−)−2−デ
セン−5−オリド3gを加えることにより天然らしさが
強調された新規なローズ調の調合香料組成物が得られた
。専門パネラ−10人により本発明品を加えた調合香料
組成物と加えていない調合香料組成物を比較検討した。Phenylethyl alcohol 200 Geraniol 50 Heli, Otrobin
20 citronellol
10 nerol
100 Hydroxycitronellal 30 Methyl phenyl carbinyl acetate 5 Geranium oil
30 linalool
30 benzyl acetate
35 benzyl alcohol
20 rose phenone 10 rhodinol 280 rose oil
lOβ-ionone
50 benzyl salicylate
40 cyclobentadecaturide
30 Guaiyaud oil 50
Total 1000 By adding 3 g of (R)-(-)-2-decene-5-olide of formula (1) to 97 g of the above composition, a novel rose-like blended fragrance composition with emphasized naturalness was obtained. Ta. Ten expert panelists conducted a comparative study of a blended fragrance composition to which the product of the present invention was added and a blended fragrance composition to which it was not added.
その結果、専門パネラ−1O人全員がいずれも本発明品
を加えた調合香料組成物は天然ローズの特徴及びその持
続性のいずれについても格段に優れているとした。As a result, all 10 expert panelists agreed that the perfume composition containing the product of the present invention was significantly superior in both the characteristics of natural rose and its sustainability.
ほか−名Other names
Claims (1)
マグネシウムハライドと反応させることを特徴とする下
記式(4) ▲数式、化学式、表等があります▼(4) で示される(+)−4−ヒドロキシ−1−ノネンの製法
。 2、下記式(4) ▲数式、化学式、表等があります▼(4) で示される(+)−4−ヒドロキシ−1−ノネンをエポ
キシ化剤と反応させて、下記式(3)▲数式、化学式、
表等があります▼(3) で示される(−)−4−ヒドロキシ−1,2−エポキシ
ノナンを形成させ、次いで、該式(3)の化合物をシア
ン化ナトリウム、シアン化カリウムもしくはシアン化水
素と反応させて、下記式(2) ▲数式、化学式、表等があります▼(2) で示される(−)−2,4−ジヒドロキシノニルニトリ
ルを形成させ、更に、該式(2)の化合物を酸の存在下
に加熱反応せしめることを特徴とする下記式(1) ▲数式、化学式、表等があります▼(1) で示される(R)−(−)−2−デセン−5−オリドの
製法。 3、下記式(1) ▲数式、化学式、表等があります▼(1) で示される(R)−(−)−2−デセン−5−オリドを
有効成分として含有することを特徴とする香料組成物。[Claims] 1. The invention is characterized by reacting (+)-1,2-epoxyheptane represented by the following formula (5) ▲Mathematical formula, chemical formula, table, etc.▼(5) with vinylmagnesium halide The method for producing (+)-4-hydroxy-1-nonene shown by the following formula (4) ▲Mathematical formulas, chemical formulas, tables, etc.▼(4). 2. The following formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) By reacting (+)-4-hydroxy-1-nonene shown with an epoxidizing agent, the following formula (3) ▲ Mathematical formula ,Chemical formula,
There are tables etc. ▼(3) Forming (-)-4-hydroxy-1,2-epoxynonane shown by formula (3), then reacting the compound of formula (3) with sodium cyanide, potassium cyanide or hydrogen cyanide. , the following formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) Forming (-)-2,4-dihydroxynonylnitrile, and further adding the compound of formula (2) in the presence of an acid. A method for producing (R)-(-)-2-decene-5-olide represented by the following formula (1) ▲Mathematical formulas, chemical formulas, tables, etc.▼(1) characterized by a heating reaction. 3. A fragrance characterized by containing (R)-(-)-2-decene-5-olide as an active ingredient represented by the following formula (1) ▲ Numerical formula, chemical formula, table, etc. ▼ (1) Composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63210791A JPH0635456B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing (R)-(-)-2-decene-5-olide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63210791A JPH0635456B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing (R)-(-)-2-decene-5-olide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0259564A true JPH0259564A (en) | 1990-02-28 |
JPH0635456B2 JPH0635456B2 (en) | 1994-05-11 |
Family
ID=16595193
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63210791A Expired - Fee Related JPH0635456B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing (R)-(-)-2-decene-5-olide |
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JP (1) | JPH0635456B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011083264A (en) * | 2009-10-19 | 2011-04-28 | Soda Aromatic Co Ltd | Oil and fat feel enhancer |
WO2015128552A1 (en) | 2014-02-27 | 2015-09-03 | Charabot | Method for producing lactones from a strain of aureobasidium pullulans |
WO2016084749A1 (en) * | 2014-11-26 | 2016-06-02 | 不二製油グループ本社株式会社 | Milk-flavor-enhanced lipid, and method for enhancing milk flavor in food and beverage products |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6357583A (en) * | 1986-08-28 | 1988-03-12 | T Hasegawa Co Ltd | Production of 2-alkene-5-olides |
-
1988
- 1988-08-26 JP JP63210791A patent/JPH0635456B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6357583A (en) * | 1986-08-28 | 1988-03-12 | T Hasegawa Co Ltd | Production of 2-alkene-5-olides |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011083264A (en) * | 2009-10-19 | 2011-04-28 | Soda Aromatic Co Ltd | Oil and fat feel enhancer |
WO2015128552A1 (en) | 2014-02-27 | 2015-09-03 | Charabot | Method for producing lactones from a strain of aureobasidium pullulans |
US10196659B2 (en) | 2014-02-27 | 2019-02-05 | Charabot | Method for producing lactones from a strain of Aureobasidium pullulans |
WO2016084749A1 (en) * | 2014-11-26 | 2016-06-02 | 不二製油グループ本社株式会社 | Milk-flavor-enhanced lipid, and method for enhancing milk flavor in food and beverage products |
JPWO2016084749A1 (en) * | 2014-11-26 | 2017-09-14 | 不二製油株式会社 | Milk flavor enhancing oil and fat, and method for enhancing milk flavor of food and drink |
Also Published As
Publication number | Publication date |
---|---|
JPH0635456B2 (en) | 1994-05-11 |
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