CN105073698B - 具有环丙烷环的化合物及包含其的香料组合物和/或芳香组合物 - Google Patents
具有环丙烷环的化合物及包含其的香料组合物和/或芳香组合物 Download PDFInfo
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- CN105073698B CN105073698B CN201480013139.8A CN201480013139A CN105073698B CN 105073698 B CN105073698 B CN 105073698B CN 201480013139 A CN201480013139 A CN 201480013139A CN 105073698 B CN105073698 B CN 105073698B
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- methyl
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- cyclopropyl
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- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000000796 flavoring agent Substances 0.000 title claims abstract description 18
- 235000019634 flavors Nutrition 0.000 title claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- -1 1- hydroxyl -1- propyl group Chemical group 0.000 claims description 12
- 239000002537 cosmetic Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 230000003203 everyday effect Effects 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 6
- 210000000214 mouth Anatomy 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 230000037213 diet Effects 0.000 claims description 3
- 235000005911 diet Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000003205 fragrance Substances 0.000 abstract description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 98
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000003756 stirring Methods 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 15
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 14
- 238000004064 recycling Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000010898 silica gel chromatography Methods 0.000 description 12
- 239000002304 perfume Substances 0.000 description 11
- PJGJQVRXEUVAFT-UHFFFAOYSA-N chloroiodomethane Chemical compound ClCI PJGJQVRXEUVAFT-UHFFFAOYSA-N 0.000 description 10
- GUDMZGLFZNLYEY-UHFFFAOYSA-N cyclopropylmethanol Chemical compound OCC1CC1 GUDMZGLFZNLYEY-UHFFFAOYSA-N 0.000 description 10
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 235000013599 spices Nutrition 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C([C@](C)*)[C@](*)([C@]1C)N1*=I)C#CC=CC#CC Chemical compound CC(C([C@](C)*)[C@](*)([C@]1C)N1*=I)C#CC=CC#CC 0.000 description 3
- 150000004808 allyl alcohols Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002084 enol ethers Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KKNJSACQBILGKK-VNXPTHQBSA-N 2-[(1r,2s)-1-methyl-2-(1-phenylethyl)cyclopropyl]acetaldehyde Chemical compound C=1C=CC=CC=1C(C)[C@@H]1C[C@]1(C)CC=O KKNJSACQBILGKK-VNXPTHQBSA-N 0.000 description 1
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- MIXDGMXIZOJVNL-CSUXEGHOSA-N CCN(C)/S=C(\C)/[C@H](C1C)[C@H]1C=C Chemical compound CCN(C)/S=C(\C)/[C@H](C1C)[C@H]1C=C MIXDGMXIZOJVNL-CSUXEGHOSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001122315 Polites Species 0.000 description 1
- 241000221035 Santalaceae Species 0.000 description 1
- 235000008632 Santalum album Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003779 hair growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/34—Monohydroxylic alcohols containing six-membered aromatic rings and other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/28—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
- C07C47/293—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings with three- or four-membered ring
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/52—Adding ingredients
- A23L2/56—Flavouring or bittering agents
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/203—Alicyclic compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/13—Monohydroxylic alcohols containing saturated rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/105—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing rings
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- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/235—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings and other rings
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- 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
- C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11B9/00—Essential oils; Perfumes
- C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/005—Compositions containing perfumes; Compositions containing deodorants
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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- Food Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Seasonings (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明的目的在于,提供一种可以赋予花香、柠檬样香味的具有环丙烷环的化合物。本发明提供一种含有至少1种式(1)所示的化合物的香料组合物。(式中,R1、R2、R3及R5表示氢原子或碳数1~3的烷基,R1、R2、R3及R5中,2个以上的基团为烷基。R4表示选自甲酰基、羟基甲基、1‑羟基‑1‑乙基、1‑羟基‑1‑丙基、1‑羟基‑1‑丁基及2‑羟基‑1‑丙基中的基团。m为0~2,n为0或1。波状线表示相对于环丙烷环的2位为顺式构型、反式构型或顺式构型和反式构型的混杂)。
Description
技术领域
本发明涉及一种含有具有环丙烷环的化合物的香料组合物。
背景技术
在具有环丙烷环的化合物中,已知有存在作为调制香料原料的有用的化合物。例如,[1-甲基-2-(5-甲基-4-己烯-2-基)环丙基]甲醇为玫瑰样的花香调,具有类似于柠檬和3-甲基-5-苯基-1-戊醇的香味(WO 2012/160189 Al)。另外,1-甲基-2-[(2,2,3-三甲基环戊基)甲基]环丙基]甲醇具有存在自然感的檀香木样香味(US 2010/0069508 Al)。另外,作为具有环丙烷环和苯环的化合物,已知有2-(1-苯基乙基)环丙基甲醇等,但与香味有关的记载则没有(Synthesis(1999),No.6,1063-1075)。
发明内容
近年来,伴随各种香妆品、保健卫生材料、药品等制品的多样化,与以往相比,在香妆品及保健卫生材料用香料、进而药品用香料中,更需要开发扩散性强、香质独特、嗜好性高、保留性强、稳定性良好、且安全性高的香料物质。尤其是关于具有花香和柠檬样香味的香料原料,满足这种要求的香料原料不足,除现有公知的香料物质之外,期待进一步开发满足上述特性的新的香料原料。
因此,本发明的目的在于,提供一种满足上述要求的可以赋予花香和柠檬样香味的化合物。
在这样的实情下,本发明人等进行了潜心研究,结果发现:将烯丙醇衍生物进行环丙烷化而得到的化合物具有强的花香和柠檬样香味,可成为有用的赋香剂,完成了本发明。即,本发明包含以下的[1]~[7]的内容。
[1]一种化合物,其用式(1)表示。
(式(1)中,R1、R2、R3及R5表示氢原子或碳数1~3的烷基,R1、R2、R3及R5中,2个以上的基团为烷基。R4表示选自甲酰基、羟基甲基、1-羟基-1-乙基、1-羟基-1-丙基、1-羟基-1-丁基及2-羟基-1-丙基中的基团。m为0~2,n为0或1。波状线表示相对于环丙烷环的2位为顺式构型、反式构型或顺式构型和反式构型的混杂)。
[2]根据上述[1]所述的化合物,其中,R4为选自羟基甲基、1-羟基-1-乙基、1-羟基-1-丙基、1-羟基-1-丁基及2-羟基-1-丙基中的基团。
[3]根据上述[2]所述的化合物,其中,R1及R3均为甲基。
[4]根据上述[2]所述的化合物,其中,R1及R2及R3均为甲基。
[5]根据上述[2]~[4]所述的化合物,其中,R5为甲基。
[6]一种香料组合物,其特征在于,含有至少1种上述[1]~[5]所述的化合物。
[7]一种饮食品、香妆品、芳香剂、日用品、口腔用组合物、护发制品、护肤制品、身体清洗剂、衣料用洗剂、衣料用柔软整理剂、化妆品制品、纤维及纤维制品、服装或药品,其中,含有上述[6]所述的香料组合物。
本发明的化合物为嗜好性高、香味赋予性也优异、扩散性及残香性优异的非常有用的香料原料。通过配合这些本发明的化合物,可以提供嗜好性高的香味赋予剂。
具体实施方式
本发明的化合物用式(1)表示。
[化1]
(式中,R1、R2、R3及R5表示氢原子或碳数1~3的烷基,R1、R2、R3及R5中,2个以上的基团为烷基。作为碳数1~3的烷基,例如为甲基。R4表示选自甲酰基、羟基甲基、1-羟基-1-乙基、1-羟基-1-丙基、1-羟基-1-丁基及2-羟基-1-丙基中的基团。R4选自例如甲酰基、羟基甲基及1-羟基-1-乙基。m为0~2,例如为0或1。n为0或1。波状线表示相对于环丙烷环的2位为顺式构型、反式构型或顺式构型和反式构型的混杂)。
式(1)中,n为0、R4为羟基甲基的化合物通过例如以下所示的方法来合成。
[化2]
首先,通过使由二乙基锌和氯碘甲烷制备的卡宾体与烯丙醇衍生物(3)反应来合成具有环丙烷环的化合物(4)。具有环丙烷环的化合物(4)作为具有下述所示的相对构型的非对映异构体的混合物得到,(4b)的香味阈值与(4a)相比相对地低。
[化3]
式(1)中,n为0、m为0、R1及R3为甲基、R4为1-羟基-1-乙基的化合物通过例如以下所示的方法来合成。
[化4]
首先,通过将具有环丙烷环的化合物(5)进行氧化而得到醛化合物(6),接着,通过进行格利雅反应,可以合成化合物(7)。作为氧化的方法,可以使用TEMPO(四甲基哌啶氧化物)氧化、植村氧化、奥尔布莱特·高曼氧化、向山氧化、Leigh GRIFFITHS氧化、斯文氧化等反应。具有环丙烷环的化合物(7)作为具有下述所示的相对构型的异构体的混合物得到,(R*)-1-[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]乙醇(7a)的香味阈值与(S*)-1-[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]乙醇(7b)相比相对地低100倍以上。
[化5]
式(1)中,n为1、m为0、R1及R3为甲基、R4为甲酰基的具有环丙烷环的化合物通过例如以下所示的方法来合成。
[化6]
首先,在化合物(6)中进行Wittig反应,合成烯醇醚体(8)。通过将得到的烯醇醚体在酸催化剂的存在下进行水解,可以容易地合成具有环丙烷环的化合物(9)。作为在此所使用的酸,可列举醋酸、柠檬酸、盐酸、硫酸等。
这样得到的本发明的化合物可以根据需要进行离析及精制。作为离析及精制的方法,可列举例如柱色谱法、减压蒸留、结晶等,可以将这些方法单独或并用而进行。
对式(1)所示的化合物的香料组合物的配合量没有特别限定,优选相对于香料组合物为0.01~60重量%,特别优选为0.1~40重量%。
另外,在本发明的香料组合物中,可以配合通常使用的调制香料。这样得到的香料组合物可以提供新鲜且嗜好性高的香味赋予。另外,可以将本发明的香料组合物作为香味成分,配合于饮食品、香妆品、芳香剂、日用品、口腔用组合物、护发制品、护肤制品、身体清洗剂、衣料用洗剂、衣料用柔软整理剂、化妆品制品、纤维及纤维制品、服装或药品等中。即,在洗发液、洗涤类、香水、科隆类、生发香水、发膏类、润发油等毛发用化妆料基材、肥皂、洗盘子洗剂、洗涤用洗剂、柔软剂类、消毒用洗剂类、防臭洗剂类、室内芳香剂、消毒剂、杀虫剂、漂白剂、其它各种保健卫生用洗剂类、牙膏、口腔清洁剂、手纸、用于使药品的服用容易的赋香剂等中配合该业界中通常所配合的量,可以赋予其独特的香味,可以提高商品价值。
实施例
下面列举实施例,详细地说明本发明,但本发明并不受这些实施例任何限定。需要说明的是,实施例中的各物性值的测定使用以下的设备装置类而进行。
NMR使用Bruker社制DRX500进行测定。在溶剂中使用CDCl3,化学软件以TMS为基准,用ppm进行记载。耦合常数J用Hz进行记载。
GC/MS使用Agirent Technologies HP6890GC***和HP5973MS检测器进行测定。柱使用InertCap 1(GL科学社制,长度30m×内径0.25mm、液相膜厚0.25μm),注入口温度为250℃,检测器温度为250℃,升温条件为100℃(15℃/分钟)300℃。
GC纯度使用Agirent Technologies7890A GC***进行测定。柱使用InertCap 1(GL科学社制,长度20m×内径0.18mm、液相膜厚0.18μm),注入口温度为250℃,检测器温度为250℃,升温条件为100℃(15℃/分钟)230℃。
(实施例1)
1-甲基-2-(1-苯基乙基)环丙基甲醇的合成
[化7]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的200ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、37.9g、46.0mmol),冷却至-20℃。向滴液漏斗中加入氯碘甲烷(16.22g、92.0mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-10~-15℃下搅拌30分钟之后,冷却至-25℃,在-20~-25℃的范围内滴加(E)-2-甲基-4-苯基五-2-烯-1-醇(4.11g、23.3mmol)60分钟。滴加结束后,在-15~-25℃下继续搅拌60分钟。接着,加入20%硫酸水溶液(17.0ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(20ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=8:2)进行精制,得到作为主要异构体的[(1R*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]甲醇(1.85g、9.74mmol、收率42%)、作为次要异构体的[(1R*,2S*)-1-甲基-2-((S*)-1-苯基乙基)环丙基]甲醇(0.55g、2.9mmol、收率12%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
190(M+,<1),172(1),159(7),146(9),131(17),118(80),117(100),106(60),105(80),91(45),77(20)
1H(500MHz、CDCl3):
7.31(ddm,J=8.3,7.1,2H),7.27(dm,J=8.3,2H),7.20(tm,J=7.1,1H),3.41(d,J=11.0,1H),3.35(d,J=11.0,1H),2.31(dq,J=10.6,7.0,1H),1.34(d,J=7.0,3H),1.28(s,3H),0.87(ddd,J=10.6,8.8,5.7,1H),0.52(dd,J=8.8,4.9,1H),0.12(dd,J=5.7,4.9,1H)
13C(125MHz,CDCl3)
147.2(s),128.3(d),126.0(d),126.0(d),72.4(t),39.8(d),29.7(d),23.6(s),22.6(q),16.6(t),15.3(q)
次要异构体
GC/MS(m/e):
190(M+,<1),172(1),159(7),146(5),131(17),118(80),117(100),106(60),105(80),91(45),77(20)
1H(500MHz、CDCl3):
7.29(ddm,J=8.3,7.1,2H),7.26(dm,J=8.3,2H),7.18(tm,J=7.1,1H),3.33(d,J=10.4,1H),3.27(d,J=10.4,1H),2.34(dq,J=10.5,7.0,1H),1.35(d,J=7.0,3H),1.06(s,3H),0.97(ddd,J=10.5,8.9,5.5,1H),0.70(dd,J=8.9,4.7,1H),0.18(dd,J=5.5,4.7,1H)
13C(125MHz,CDCl3)
147.7(s),128.4(d),126.6(d),125.9(d),72.2(t),40.0(d),29.2(d),23.4(s),23.3(q),16.5(t),15.7(q)
(实施例2)
1-甲基-2-(1-苯基乙基)环丙基甲醇的合成
[化8]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、69.8g、84.8mmol),冷却至-20℃。向滴液漏斗中加入氯碘甲烷(29.9g、169.6mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-10~-15℃下搅拌30分钟之后冷却至-25℃,在-20~-25℃的范围内滴加(Z)-2-甲基-4-苯基五-2-烯-1-醇(7.59g、42.4mmol)60分钟。滴加结束后,在-15~-25℃下继续搅拌60分钟。接着,加入20%硫酸水溶液(31.3ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(30ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=8:2)进行精制,得到作为主要异构体的[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]甲醇(4.93g、25.9mmol、收率61%)、作为次要异构体的[(1S*,2S*)-1-甲基-2-((S*)-1-苯基乙基)环丙基]甲醇(0.61g、3.2mmol、收率7.5%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
172(M+-H2O,1),157(5),146(20),131(27),118(72),117(100),106(65),105(75),91(53),77(25)
1H(500MHz、CDCl3):
7.30(ddm,J=7.9,7.2,2H),7.25(dm,J=7.9,2H),7.19(tm,J=7.2,1H),3.70(m,2H),2.35(dq,J=10.6,7.0,1H),1.38(d,J=7.0,3H),1.30(m,OH),1.21(s,3H),0.94(ddd,J=10.6,8.4,5.9,1H),0.45(dd,J=8.4,4.8,1H),0.21(dd,J=5.9,4.8,1H)
13C(125MHz,CDCl3)
147.3(s),128.3(d),126.9(d),125.9(d),67.1(t),40.0(d),33.3(d),23.5(s),23.0(q),22.9(q),17.3(t)
次要异构体
GC/MS(m/e):
190(M+,<1),172(4),157(10),143(7),131(17),118(72),117(100),106(65),105(67),91(44),77(20)
1H(500MHz、CDCl3):
7.32(ddm,J=8.3,7.1,2H),7.28(dm,J=8.3,2H),7.21(tm,J=7.1,1H),3.52(dd,J=11.6,9.1,1H),3.33(d,J=11.6,1H),2.34(dq,J=10.6,6.9,1H),1.34(d,J=6.9,3H),1.13(s,3H),1.06(ddd,J=10.6,8.3,5.5,1H),0.66(dd,J=8.3,4.6,1H),0.40(m,OH),0.27(dd,J=5.5,4.6,1H)
13C(125MHz,CDCl3)
147.7(s),128.8(d),126.4(d),126.4(d),67.3(t),40.9(d),31.9(d),24.1(q),23.1(s),22.6(q),17.8(t)
(实施例3)
(1S*,2S*)-1-甲基-2-[(R*)-1-苯基乙基]环丙烷甲醛的合成
[化9]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]甲醇(1.02g、5.37mmol)和溴化钾(0.36g)、2,2,6,6-四甲基哌啶1-氧基自由基(0.085g)及甲苯(10ml),冷却至0℃。向滴液漏斗中加入次氯酸钠水溶液(浓度约13.5%、5.0g、9.1mmol),以保持0℃的方式滴加。滴加结束后,用60分钟升温至18℃。其后将水层进行分液,将有机层用10%硫代硫酸钠水溶液和水清洗,在减压下回收溶剂,得到浓缩残渣(1S*,2S*)-1-甲基-2-[(R*)-1-苯基乙基]环丙烷甲醛(0.91g、4.8mmol、收率89%)。
GC/MS(m/e):
188(M+,5),159(7),141(5),128(20),118(82),117(100),115(45),105(43),91(60),83(60),77(44)
1H(500MHz、CDCl3):
9.37(s,1H)、7.34(ddm,J=8.3,7.2,2H),7.28(dm,J=8.3,2H),7.24(tm,J=7.2,1H),2.71(dq,J=10.4,7.0,1H),1.51-1.42(m,2H),1.32(s,3H),1.30(d,J=7.0,3H),1.09(dd,J=7.5,4.6,1H)
13C(125MHz,CDCl3)
202.7(d),145.6(s),128.5(d),126.7(d),126.5(d),40.1(d),38.8(d),32.9(s),22.5(t),21.9(q),18.4(q)
(实施例4)
1-[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]乙醇的合成
[化10]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入甲基溴化镁(0.97mol/L、四氢呋喃溶液、8.5ml、8.25mmol),冷却至-10℃。向滴液漏斗中加入(1S*,2S*)-1-甲基-2-[(R*)-1-苯基乙基]环丙烷甲醛(1.03g、5.5mmol),用5分钟滴加,使其保持-10℃。搅拌60分钟后,加入20%硫酸水溶液(4.5g)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=10:1)进行精制,得到作为主要异构体的(R*)-1-[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]乙醇(0.75g、3.68mmol、收率67%)、作为次要异构体的(S*)-1-[(1S*,2S*)-1-甲基-2-((R*)-1-苯基乙基)环丙基]乙醇(0.205g、1.0mmol、收率18%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
186(M+-H2O,1),171(6),160(15),145(7),131(29),118(87),117(100),106(68),105(86),91(53),77(26)、72(30),70(30)
1H(500MHz、CDCl3):
7.29(ddm,J=8.3,7.2,2H),7.24(dm,J=8.3,2H),7.19(tm,J=7.2,1H),3.60(q,J=6.4,1H),2.46(dq,J=10.4,6.9,1H),1.46(d,J=6.9,3H),1.31(d,6.4,3H),1.09(s,3H),0.92(ddd,J=10.4,8.5,5.9,1H),0.41(dd,J=8.5,4.9,1H),0.01(dd,J=5.9,4.9,1H)
13C(125MHz,CDCl3)
147.7(s),128.3(d),127.0(d),125.9(d),70.5(d),39.0(d),34.5(d),26.5(s),23.6(q),20.5(q),18.4(q)、17.5(t)
次要异构体
GC/MS(m/e):
186(M+-H2O,1),171(7),160(13),145(7),131(32),118(85),117(100),106(65),105(84),91(55),77(27)、72(21),70(29)
1H(500MHz、CDCl3):
7.30(ddm,J=8.3,7.2,2H),7.21(dm,J=8.3,2H),7.19(tm,J=7.2,1H),3.58(q,J=6.4,1H),2.39(dq,J=10.5,6.9,1H),1.37(d,J=6.4,3H),1.36(d,6.9,3H),1.09(s,3H),0.95(ddd,J=10.5,8.6,5.7,1H),0.46(dd,J=8.6,4.6,1H),0.19(dd,J=5.7,4.6,1H)
13C(125MHz,CDCl3)
147.5(s),128.3(d),126.9(d),126.0(d),70.8(d),39.1(d),34.1(d),27.5(s),23.6(q),20.4(q),18.9(t)、18.7(q)
(实施例5)
1,2-二甲基-2-(1-苯基乙基)环丙基甲醇的合成
[化11]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、10.9g、13.2mmol),冷却至-15℃。向滴液漏斗中加入氯碘甲烷(4.68g、26.5mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-15℃下搅拌30分钟之后冷却至-15℃,在-10~-15℃下滴加(Z)-2,3-二甲基-4-苯基五-2-烯-1-醇(1.26g、6.63mmol)20分钟。滴加结束后,在12℃下继续搅拌60分钟。接着,加入20%硫酸水溶液(4.8ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1S*,2S*)-1,2-二甲基-2-((S*)-1-苯基乙基)环丙基]甲醇(0.47g、2.3mmol、收率35%)、作为次要异构体的[(1S*,2S*)-1,2-二甲基-2-((R*)-1-苯基乙基)环丙基]甲醇(0.45g、2.2mmol、收率33%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
204(M+,<1),186(3),171(25),149(45),132(39),131(79),117(86),115(36),106(44),105(100),99(37),91(60),77(31)
1H(500MHz、CDCl3):
7.32-7.27(m,4H),7.20(m,1H),3.78(m,2H),2.68(q,7.2,1H),1.36(d,J=7.2,3H),1.35(OH),1.25(s,3H),0.92(s,3H),0.73(d,J=4.8,1H),0.22(d,J=4.8,1H)
13C(125MHz,CDCl3)
145.1(s),128.0(d),127.9(d),125.9(d),68.2(t),42.3(d),30.2(s),26.7(s),25.5(t),18.3(q),16.8(q),14.7(q)
次要异构体
GC/MS(m/e):
204(M+,<1),186(3),171(24),149(44),132(46),131(89),117(94),115(38),106(48),105(100),99(38),91(65),77(35)
1H(500MHz、CDCl3):
7.32(ddm,J=7.8,7.0,2H),7.28(dm,J=7.8,2H),7.19(tm,J=7.0,1H),3.64(m,2H),2.64(q,7.1,1H),1.40(d,J=7.1,3H),1.24(s,3H),1.08(s,3H),0.90(t,J=6.7,OH),0.45(d,J=4.6,1H),0.29(d,J=4.6,1H)
13C(125MHz,CDCl3)
145.3(s),128.4(d),127.5(d),126.0(d),68.3(t),42.5(d),29.3(s),28.5(s),25.1(t),18.9(q),18.2(q),15.6(q)
(实施例6)
1-甲基-2-(1-(4-甲基苯基)乙基)环丙基甲醇的合成
[化12]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、5.3g、6.4mmol),冷却至-20℃。向滴液漏斗中加入氯碘甲烷(2.26g、12.8mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-10~-15℃下搅拌10分钟之后冷却至-20℃,在同温度下滴加(E)-2-甲基-4-(4-甲基苯基)五-2-烯-1-醇(0.60g、3.2mmol)10分钟。滴加结束后,在-15~-25℃下继续搅拌60分钟。接着,加入20%硫酸水溶液(2.5ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1R*,2S*)-1-甲基-2-((R*)-1-(4-甲基苯基)乙基)环丙基]甲醇(0.24g、1.18mmol、收率36%)、作为次要异构体的[(1R*,2S*)-1-甲基-2-((S*)-1-(4-甲基苯基)乙基)环丙基]甲醇(0.013g、0.064mmol、收率2%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
186(M+-H2O,2),173(13),160(13),149(19),145(23),132(80),131(64),120(62),119(88),117(100),115(48),105(40),91(62),77(21)
1H(500MHz、CDCl3):
7.16(dm,J=8.2,2H),7.12(dm,J=8.2,2H),3.41(d,J=11.0,1H),3.35(d,J=11.0,1H),2.33(s,3H),2.27(dq,J=10.6,7.0,1H),1.32(d,J=7.0,3H),1.28(s,3H),0.84(ddd,J=10.6,8.8,5.7,1H),0.52(dd,J=8.8,4.8,1H),0.11(dd,J=5.7,4.8,1H)
13C(125MHz,CDCl3)
144.2(s),135.4(s),129.0(d),126.8(d),72.5(t),39.4(d),29.9(d),23.6(s),22.7(q),21.0(q),16.6(t),15.3(q)
次要异构体
GC/MS(m/e):
204(M+,<1),186(7),173(16),157(8),149(23),145(20),132(98),131(84),120(66),119(100),117(96),115(53),105(42),91(64),77(24)
1H(500MHz、CDCl3):
7.14(dm,J=8.2,2H),7.10(dm,J=8.2,2H),3.34(d,J=10.8,1H),3.27(d,J=10.8,1H),2.32(s,3H),2.31(dq,J=10.6,7.0,1H),1.33(d,J=7.0,3H),1.06(s,3H),0.95(ddd,J=10.6,8.9,5.6,1H),0.68(dd,J=8.9,4.7,1H),0.18(dd,J=5.6,4.7,1H)
13C(125MHz,CDCl3)
144.6(s),135.2(s),129.1(d),126.4(d),72.3(t),39.6(d),29.3(d),23.36(q),23.35(s),20.9(q),16.5(t),15.7(q)
(实施例7)
1-甲基-2-(1-(4-甲基苯基)乙基)环丙基甲醇的合成
[化13]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、9.4g、11.4mmol),冷却至-15℃。向滴液漏斗中加入氯碘甲烷(4.02g、22.8mmol),以保持-15℃的方式滴加。滴加结束后,在-10~-15℃下搅拌20分钟之后冷却至-25℃,在-20~-25℃下滴加(Z)-2-甲基-4-(4-甲基苯基)五-2-烯-1-醇(1.08g、5.7mmol)20分钟。滴加结束后,在-15~-25℃下继续搅拌60分钟。接着,加入20%硫酸水溶液(4.2ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1S*,2S*)-1-甲基-2-((R*)-1-(4-甲基苯基)乙基)环丙基]甲醇(0.79g、3.8mmol、收率68%)、作为次要异构体的[(1S*,2S*)-1-甲基-2-((S*)-1-(4-甲基苯基)乙基)环丙基]甲醇(0.21g、1.0mmol、收率18%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
186(M+-H2O,1),173(9),171(7),160(18),149(16),145(25),132(76),131(66),120(65),119(82),117(100),115(47),105(46),91(56),77(19)
1H(500MHz、CDCl3):
7.14(dm,J=8.3,2H),7.12(dm,J=8.3,2H),3.71(d,J=11.3,1H),3.69(d,J=11.3,1H),2.32(s,3H),2.32(dq,J=10.6,6.9,1H),1.36(d,J=6.9,3H),1.29(br.s,OH),1.20(s,3H),0.92(ddd,J=10.6,8.4,5.8,1H),0.44(dd,J=8.4,4.8,1H),0.20(dd,J=5.8,4.8,1H)
13C(125MHz,CDCl3)
144.3(s),135.4(s),129.0(d),126.7(d),67.1(t),39.6(d),33.4(d),23.5(s),23.1(q),22.9(q),21.0(q),17.3(t)
次要异构体
GC/MS(m/e):
186(M+-H2O,9),173(11),171(15),157(10),149(19),145(20),132(91),131(90),120(70),119(95),117(100),115(54),105(43),91(66),77(23)
1H(500MHz、CDCl3):
7.17(dm,J=8.2,2H),7.13(dm,J=8.2,2H),3.54(dd,J=12.6,9.7,1H),3.33(dd,J=12.6,1.2,1H),2.31(s,3H),2.30(dq,J=10.6,6.9,1H),1.32(d,J=6.9,3H),1.13(s,3H),1.03(ddd,J=10.6,8.3,5.4,1H),0.64(dd,J=8.3,4.6,1H),0.39(br.d,J=9、7,OH),0.25(dd,J=5.4,4.6,1H)
13C(125MHz,CDCl3)
144.7(s),135.9(s),129.5(d),126.3(d),67.4(t),40.5(d),32.0(d),24.2(q),23.1(s),22.6(q),21.0(q),17.9(t)
(实施例8)
1-甲基-2-(1-(3-甲基苯基)乙基)环丙基甲醇的合成
[化14]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、6.92g、8.4mmol),冷却至-25℃。向滴液漏斗中加入氯碘甲烷(2.96g、16.8mmol),以保持-20~-25℃的方式滴加。滴加结束后,在-10~-20℃下搅拌15分钟之后冷却至-25℃,在同温度下滴加(E)-2-甲基-4-(3-甲基苯基)五-2-烯-1-醇(0.80g、4.2mmol)20分钟。滴加结束后,在-10~-25℃下继续搅拌20分钟。接着,加入20%硫酸水溶液(3.1ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1R*,2S*)-1-甲基-2-((R*)-1-(3-甲基苯基)乙基)环丙基]甲醇(0.38g、1.9mmol、收率45%)、作为次要异构体的[(1R*,2S*)-1-甲基-2-((S*)-1-(3-甲基苯基)乙基)环丙基]甲醇(0.014g、0.069mmol、收率1.6%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
186(M+-H2O,1),173(16),160(15),145(30),132(81),131(66),120(73),119(81),117(100),115(46),105(36),91(49),77(16)
1H(500MHz、CDCl3):
7.19(dd,J=8.0,7.4,1H),7.07(br.s,1H),7.06(dm,8.0,1H),7.02(dm,7.4,1H),3.42(d,J=11.0,1H),3.36(d,J=11.0,1H),2.35(s,3H),2.26(dq,J=10.6,7.0,1H),1.33(d,J=7.0,3H),1.28(s,3H),0.86(ddd,J=10.6,8.8,5.7,1H),0.52(dd,J=8.8,4.8,1H),0.12(dd,J=5.7,4.8,1H)
13C(125MHz,CDCl3)
147.2(s),137.8(s),128.2(d),127.7(d),126.7(d),124.0(d),72.4(t),39.7(d),29.7(d),23.6(s),22.7(q),21.5(q),16.6(t),15.3(q)
次要异构体
GC/MS(m/e):
204(M+,<1),186(4),173(17),157(10),149(11),145(21),132(93),131(80),120(79),119(88),117(100),115(54),105(42),91(71),77(26)
1H(500MHz、CDCl3):
7.18(ddm,J=8.4,7.4,1H),7.06(br.s,1H),7.05(dm,8.4,1H),6.99(dm,7.4,1H),3.33(d,J=10.9,1H),3.27(d,J=10.9,1H),2.33(s,3H),2.30(dq,J=10.5,7.0,1H),1.34(d,J=7.0,3H),1.09(br.s,OH),1.06(s,3H),0.96(ddd,J=10.5,8.9,5.5,1H),0.68(dd,J=8.9,4.7,1H),0.17(dd,J=5.5,4.7,1H)
13C(125MHz,CDCl3)
147.6(s),137.8(s),128.3(d),127.4(d),126.6(d),123.6(d),72.2(t),39.9(d),29.2(d),23.34(s),23.28(q),21.5(q),16.5(t),15.7(q)
(实施例9)
1-甲基-2-(1-(3-甲基苯基)乙基)环丙基甲醇的合成
[化15]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、9.4g、0.0114mol),冷却至-15℃。向滴液漏斗中加入氯碘甲烷(4.02g、22.8mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-10~-15℃下搅拌20分钟之后冷却至-25℃,在-20~-25℃下滴加(Z)-2-甲基-4-(3-甲基苯基)五-2-烯-1-醇(1.09g、5.7mmol)20分钟。滴加结束后,在-15~-25℃下继续搅拌40分钟。接着,加入20%硫酸水溶液(4.2ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1S*,2S*)-1-甲基-2-((R*)-1-(3-甲基苯基)乙基)环丙基]甲醇(0.83g、4.1mmol、收率70%)、作为次要异构体的[(1S*,2S*)-1-甲基-2-((S*)-1-(3-甲基苯基)乙基)环丙基]甲醇(0.20g、0.99mmol、收率17%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
186(M+-H2O,1),171(7),160(20),145(30),132(66),131(65),120(69),119(71),117(100),115(50),105(46),91(62),77(21)
1H(500MHz、CDCl3):
7.19(dt,J=0.9,7.4,1H),7.05(s,1H),7.04(dm,J=7.4,1H),7.01(dm,J=7.4,1H),3.71(d,J=11.3,1H),3.68(d,J=11.3,1H),2.34(s,3H),2.32(dq,J=10.6,7.0,1H),1.36(d,J=7.0,3H),1.31(br.s,OH),1.20(s,3H),0.93(ddd,J=10.6,8.4,5.8,1H),0.44(dd,J=8.4,4.8,1H),0.21(dd,J=5.8,4.8,1H)
13C(125MHz,CDCl3)
147.3(s),137.8(s),128.2(d),127.7(d),126.7(d),123.9(d),67.1(t),40.0(d),33.3(d),23.5(s),23.1(q),22.9(q),21.5(q),17.3(t)
次要异构体
GC/MS(m/e):
186(M+-H2O,7),171(18),157(11),145(22),132(81),131(95),120(77),119(83),117(100),115(63),105(45),91(76),77(25)
1H(500MHz、CDCl3):
7.21(dd,J=8,7,1H),7.08(dm,J=7,1H),7.07(m,1H),7.02(dm,J=8,1H),3.53(dd,J=11.7,10.0,1H),3.34(dd,J=11.7,2.8,1H),2.34(s,3H),2.30(dq,J=10.6,6.9,1H),1.33(d,J=6.9,3H),1.13(s,3H),1.04(ddd,J=10.6,8.3,5.4,1H),0.64(dd,J=8.3,4.6,1H),0.42(dd,J=10.0,2.8,OH),0.26(dd,J=5.4,4.6,1H)
13C(125MHz,CDCl3)
147.7(s),138.4(s),128.7(d),127.3(d),127.2(d),123.4(d),67.4(t),40.8(d),31.9(d),24.1(q),23.1(s),22.6(q),21.5(q),17.9(t)
(实施例10)
1-甲基-2-(1-(2-甲基苯基)乙基)环丙基甲醇的合成
[化16]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、6.92g、8.4mmol),冷却至-20℃。向滴液漏斗中加入氯碘甲烷(2.96g、16.8mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-5~-15℃下搅拌10分钟后冷却至-25℃,在-20~-25℃下滴加(E)-2-甲基-4-(2-甲基苯基)五-2-烯-1-醇(0.80g、4.2mmol)20分钟。滴加结束后,在-15~-25℃下继续搅拌60分钟。接着,加入20%硫酸水溶液(3.1ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1R*,2S*)-1-甲基-2-((R*)-1-(2-甲基苯基)乙基)环丙基]甲醇(0.32g、1.6mmol、收率37%)、作为次要异构体的[(1R*,2S*)-1-甲基-2-((S*)-1-(2-甲基苯基)乙基)环丙基]甲醇(0.025g、0.12mmol、收率3%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
204(M+,<1),186(5),171(13),157(10),149(10),145(15),143(20),132(64),131(63),120(74),119(87),117(100),115(53),105(35),91(56),77(18)
1H(500MHz、CDCl3):
7.36(dd,J=7.7,1.0,1H),7.19(tm,J=7.7,1H),7.13(dm,J=7.7,1H),7.09(dt,J=1.4,7.7,1H),3.45(d,J=11.0,1H),3.38(d,J=11.0,1H),2.62(dq,J=10.5,6.9,1H),2.31(s,3H),1.30(s,3H),1.27(d,J=6.9,3H),0.99(ddd,J=10.5,8.9,5.8,1H),0.51(dd,J=8.9,4.9,1H),0.02(dd,J=5.8,4.9,1H)
13C(125MHz,CDCl3)
145.6(s),134.7(s),130.2(d),126.2(d),126.1(d),125.6(d),72.5(t),34.6(d),29.1(d),23.6(s),22.9(q),19.6(q),16.5(t),15.5(q)
次要异构体
GC/MS(m/e):
186(M+-H2O,6),173(17),171(15),157(14),149(17),143(25),132(62),131(70),129(30),128(40),120(52),119(72),117(100),115(66),105(32),91(60),77(23)
1H(500MHz、CDCl3):
7.33(dd,J=7.5,0.8,1H),7.19(dt,J=2.0,7.5,1H),7.11(dm,J=7.5,1H),7.08(dt,J=1.4,7.5,1H),3.35(d,J=10.8,1H),3.31(d,J=10.8,1H),2.48(dq,J=10.4,6.9,1H),2.29(s,3H),1.27(d,J=6.9,3H),1.15(ddd,J=10.4,8.8,5.4,1H),1.09(br.s),0.90(s,3H),0.74(dd,J=8.8,4.6,1H),0.22(dd,J=5.4,4.6,1H)
13C(125MHz,CDCl3)
146.2(s),134.4(s),130.2(d),126.3(d),125.6(d),125.2(d),72.2(t),36.3(d),28.5(d),23.0(s),22.9(q),19.2(q),17.3(t),15.5(q)
(实施例11)
1-甲基-2-(1-(2-甲基苯基)乙基)环丙基甲醇的合成
[化17]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的100ml烧瓶中加入二乙基锌的甲苯溶液(浓度15重量%、5.4g、0.0066mol),冷却至-20℃。向滴液漏斗中加入氯碘甲烷(2.33g、13.2mmol),以保持-15~-20℃的方式滴加。滴加结束后,在-5~-15℃下搅拌20分钟之后冷却至-25℃,在-20~-25℃下滴加(Z)-2-甲基-4-(2-甲基苯基)五-2-烯-1-醇(0.62g、3.3mmol)15分钟。滴加结束后,在-15~-25℃下继续搅拌20分钟。接着,加入20%硫酸水溶液(2.5ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=9:1)进行精制,得到作为主要异构体的[(1S*,2S*)-1-甲基-2-((R*)-1-(2-甲基苯基)乙基)环丙基]甲醇(0.47g、2.3mmol、收率70%)、作为次要异构体的[(1S*,2S*)-1-甲基-2-((S*)-1-(2-甲基苯基)乙基)环丙基]甲醇(0.12g、0.59mmol、收率17%)。主要异构体和次要异构体的相对构型通过测定NOESY来确定。
主要异构体
GC/MS(m/e):
186(M+-H2O,<1),173(4),171(6),160(8),149(9),145(18),143(15),132(55),131(62),120(76),119(77),117(100),115(56),105(38),91(59),77(19)
1H(500MHz、CDCl3):
7.35(dd,J=7,1.1,1H),7.19(dt,J=1.8,7,1H),7.12(dd,J=7,1.8,1H),7.08(dt,J=1.3,7,1H),3.725(d,J=11.5,1H),3.715(d,J=11.5,1H),2.67(dq,J=10.5,6.9,1H),2.29(s,3H),1.32(d,J=6.9,3H),1.23(s,3H),1.06(ddd,J=10.5,8.4,5.9,1H),0.43(dd,J=8.4,4.8,1H),0.11(dd,J=5.9,4.8,1H)
13C(125MHz,CDCl3)
145.8(s),134.7(s),130.2(d),126.2(d),126.1(d),125.6(d),67.3(t),34.8(d),32.6(d),23.5(s),23.2(q),23.0(q),19.6(q),17.1(t)
次要异构体
GC/MS(m/e):
186(M+-H2O,2),173(12),171(8),157(8),149(14),145(14),143(17),132(69),131(73),120(64),119(67),117(100),115(64),105(36),91(73),77(22)
1H(500MHz、CDCl3):
7.41(dd,J=7,0.9,1H),7.22(dt,J=2.2,7,1H),7.13(dm,J=7,1H),7.11(dt,J=1.3,7,1H),3.47(dd,J=11.7,9,1H),3.17(d,J=11.7,1H),2.52(dq,J=10.4,6.8,1H),2.30(s,3H),1.28(d,J=6.8,3H),1.18(ddd,J=10.4,8.2,5.4,1H),1.15(s,3H),0.70(dd,J=8.2,4.2,1H),0.29(dd,J=5.4,4.2,1H),0.17(br.d,J=9,OH)
13C(125MHz,CDCl3)
145.8(s),134.6(s),130.6(d),126.7(d),126.2(d),125.4(d),67.6(t),37.0(d),31.5(d),22.91(s),22.88(q),22.5(q),19.1(q),18.6(t)
(实施例12)
2-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]乙醛的合成
[化18]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的200ml烧瓶中加入氯化(甲氧基甲基)三苯基鏻(5.0g、14.6mmol)、四氢呋喃(20ml),冷却至-40℃。向滴液漏斗中加入叔丁醇钾(1.63g、14.5mmol)的四氢呋喃(10ml)溶液,以保持-35~-40℃的方式滴加。滴加结束后,仍旧在同温度下搅拌5分钟之后,滴加(1S*,2S*)-1-甲基-2-(1-苯基乙基)环丙烷甲醛(1.5g、8.0mmol、为非对映异构体混合物,成分比为1:2)5分钟。滴加结束后,将温度提高至-20℃,继续搅拌2小时。接着,加入饱和氯化铵水溶液(20ml)和己烷(30ml)并搅拌10分钟之后,将水层进行分液。将有机层用水(10ml)清洗2次,在减压下回收溶剂。过滤析出的白色固体,得到残渣。接着,在氮气氛围下,向带有搅拌装置、回流管、温度计的100ml烧瓶中加入上述中得到的残渣(1.33g)、乙腈(6ml)和5%硫酸水溶液(2ml),在55℃下搅拌1小时。之后,加入甲苯(10ml),将水层进行分液,将有机层水洗,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=8:2)进行精制,得到2-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]乙醛(非对映异构体混合物、0.56g、2.8mmol、收率35%)。
主要异构体
GC/MS(m/e):
202(M+,<1),187(<1),169(1),158(9),143(14),128(11),118(100),117(85),105(90),97(56),91(36),77(22)
次要异构体
GC/MS(m/e):
202(M+,<1),187(<1),169(1),158(9),143(16),128(11),118(99),117(76),105(100),97(51),91(39),77(23)
13C(125MHz,CDCl3):混合物的数据
203.5(d),203.1(d),146.9(s),146.8(s),128.5(d),128.4(d),126.9(d),126.6(d),126.1(d),48.0(t),47.9(t),41.4(d),40.6(d),31.7(d),30.6(d),25.5(q),25.2(q),23.8(q),22.5(q),18.6(t),18.3(t),17.1(s),16.7(s)
(实施例13)
2-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]乙醇的合成
[化19]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的30ml烧瓶中加入2-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]乙醛(为非对映异构体混合物,成分比为1:2、0.20g、0.99mmol)、环戊基甲基醚(4ml)和氢化硼钠(0.05g、1.3mmol),在20℃下搅拌下加入甲醇(0.05g),仍旧在同温度下搅拌60分钟。接着,加入5%硫酸水溶液(1.3g)并搅拌10分钟之后,将水层进行分液。将有机层用水(2ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。将其用硅胶柱色谱法(己烷:醋酸乙酯=8:2)进行精制,得到2-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]乙醇(为非对映异构体混合物,成分比为1:2、0.19g、0.93mmol、收率94%)。
主要异构体
GC/MS(m/e):
204(M+,<1),189(<1),171(1),159(7),143(6),131(23),118(100),117(51),105(87),91(28),77(15)
次要异构体
GC/MS(m/e):
204(M+,<1),189(<1),171(2),159(10),143(8),131(27),118(92),117(47),105(100),91(30),77(16)
13C(125MHz,CDCl3):混合物的数据
147.7(s),147.5(s),128.29(d),128.26(d),126.9(d),126.7(d),125.9(d),125.8(d),61.7(t),61.5(t),40.5(d),40.1(d),36.6(t),36.4(t),32.6(d),31.3(d),25.1(q),24.7(q),23.8(q),22.6(q),18.5(t),18.33(t),18.30(s),18.0(s)
(实施例14)
1-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]丙烷-2-醇的合成
[化20]
在氮气氛围下,向带有搅拌装置、滴液漏斗、温度计的30ml烧瓶中加入甲基溴化镁(0.97mol/L四氢呋喃溶液、3.0ml、2.9mmol),向滴液漏斗中加入2-[(1R*,2S*)-1-甲基-2-(1-苯基乙基)环丙基]乙醛(为非对映异构体混合物,成分比为1:2,0.20g、0.99mmol)和四氢呋喃(1ml),滴加该溶液5分钟,使其保持20℃,在同温度下搅拌30分钟。接着,加入5%硫酸水溶液(2.9g)并搅拌10分钟之后,将水层进行分液。将有机层用水(2ml)清洗2次,在减压下回收溶剂,得到浓缩残渣。关于浓缩残渣,GC分析的结果确认为4异构体混合物。将其用硅胶柱色谱法(己烷:醋酸乙酯=8:2)进行精制,用GC分析得到保持时间最长的成分(0.016g、0.07mmol、收率7%)。利用嗅闻气相色谱(GC-O)的评价的结果,该成分为在4异构体中香味阈值最低的成分。
GC/MS(m/e):
218(M+,<1),200(1),185(3),171(4),157(8),143(16),131(13),118(100),117(50),105(90),91(35),77(14)、69(18)
1H(500MHz、CDCl3):
7.29(ddm,J=7.5,7.2,2H),7.25(dm,J=7.5,2H),7.19(tm,J=7.2,1H),4.09(m,1H),2.29(dq,J=10.5,6.9,1H),2.03(ddd,J=13.6,5.9,1.3,1H),1.42(br.s,OH),1.33(d,J=6.9,3H),1.28(d,6.2,3H),1.27(dd,J=13.6,7.7,1H),1.11(s,3H),0.71(ddd,J=10.5,8.6,5.8,1H),0.44(ddd,J=8.6,4.7,1.3,1H),0.01(dd,J=5.8,4.7,1H)
13C(125MHz,CDCl3)
147.6(s),128.3(d),127.0(d),125.8(d),67.6(d),42.7(t),40.0(d),32.9(d),25.7(q),23.5(q),22.5(q),18.95(s)、18.90(t)
(实施例15)
2-[(1S*,2S*)-1-甲基-2-((R*)1-苯基乙基)环丙基]乙醇的合成
[化21]
在上述实施例3的方法中,将原料变更为2-[(1R*,2S*)-1-甲基-2-((R*)1-苯基乙基)环丙基]甲醇(2.04g、10.7mmol),通过进行与实施例3同样的方法,得到(1R*,2S*)-1-甲基-2-[(R*)-1-苯基乙基]环丙烷甲醛,接着,用与上述实施例12同样的方法得到2-[(1S*,2S*)-1-甲基-2-((R*)1-苯基乙基)环丙基]乙醛(1.26g、6.2mmol)。进而,用与上述实施例13同样的方法得到2-[(1S*,2S*)-1-甲基-2-((R*)1-苯基乙基)环丙基]乙醇(1.21g、5.9mmol)。总计收率为55%。
GC/MS(m/e):
204(M+,<1),189(<1),171(1),159(8),143(7),131(22),118(100),117(52),105(87),91(28),77(15)、
1H(500MHz、CDCl3):
7.30(ddm,J=8.3,7.1,2H),7.26(dm,J=8.3,2H),7.19(tm,J=7.1,1H),3.80(m,2H),2.28(dq,J=10.7.0,1H),1.68(ddd,J=13.8,7.6,6.5,1H),1.42(ddd,J=,13.8,7.7,6.7,1H),1.34(d,J=7.0,3H),1.27(m,OH),1.20(s,3H),0.78(ddd,J=10.6,8.7,5.7,1H),0.45(dd,J=8.7,4.7,1H),0.06(dd,J=5.7,4.7,1H)
13C(125MHz,CDCl3)
147.4(s),128.3(d),126.9(d),125.9(d),61.4(t),44.2(t),40.1(d),31.4(d),22.6(q),19.0(t),18.1(s)、17.5(q)
(香味质的评价)
关于上述的实施例1~15中合成的化合物,进行香质的评价。结果,香质分别示于下述表1~表3。
[表1]
[表2]
[表3]
(实施例16:铃兰调香料组合物)
按照下述表4的配方,使用上述实施例1、实施例2、实施例4、实施例8、实施例9或实施例10中合成的化合物制备香水用香料组合物。
[表4]
利用有5年以上经验的4人的专业小组成员的官能评价的结果,小组全体成员判断为:含有实施例1、实施例2、实施例4、实施例8、实施例9或实施例10的化合物的铃兰调香料组合物具有强的花香香味,另外,在扩散性方面也优异。
(实施例17:海洋调香料组合物)
按照下述表5的配方,使用实施例1、实施例2、实施例4、实施例8、实施例9或实施例10的化合物制备香水用香料组合物。
[表5]
利用有5年以上经验的4人的专业小组成员的官能评价的结果,小组全体成员判断为:含有实施例1、实施例2、实施例4、实施例8、实施例9或实施例10的化合物的海洋调香料组合物,清楚地看到海洋、臭氧感,另外,在扩散性方面也优异。
(实施例18:洗发液)
按照下述表6的配方,制备将实施例16及实施例17的香料组合物进行了1.0%赋香的洗发液(100g)。
Claims (10)
1.一种化合物,所述化合物用式(1)表示,
式中,R1、R2、R3及R5表示氢原子或碳数1~3的烷基,R1、R2、R3及R5中,2个以上的基团为烷基;R4表示选自甲酰基、羟基甲基、1-羟基-1-乙基、1-羟基-1-丙基、1-羟基-1-丁基及2-羟基-1-丙基中的基团;m为0~2,n为0或1;波状线表示相对于环丙烷环的2位为顺式构型、反式构型或顺式构型和反式构型的混杂。
2.根据权利要求1所述的化合物,其中,R4为选自羟基甲基、1-羟基-1-乙基、1-羟基-1-丙基、1-羟基-1-丁基及2-羟基-1-丙基中的基团。
3.根据权利要求2所述的化合物,其中,R1及R3均为甲基。
4.根据权利要求2所述的化合物,其中,R1及R2及R3均为甲基。
5.根据权利要求2~4中任一项所述的化合物,其中,R5为甲基。
6.一种香料组合物,其特征在于,所述香料组合物含有权利要求1~5中任一项所述的化合物。
7.一种日用品,其中,所述日用品含有权利要求6所述的香料组合物。
8.根据权利要求7所述的日用品,其中所述日用品是饮食品、香妆品、芳香剂、衣料用洗剂、衣料用柔软整理剂、化妆品制品、纤维及纤维制品或药品。
9.根据权利要求8所述的日用品,其中所述化妆品制品是口腔用组合物、护发制品、护肤制品、或身体清洗剂。
10.根据权利要求8所述的日用品,其中所述纤维及纤维制品是服装。
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US20150353461A1 (en) | 2015-12-10 |
EP2985273A1 (en) | 2016-02-17 |
EP2985273A4 (en) | 2016-07-13 |
JPWO2014142025A1 (ja) | 2017-02-16 |
US9296675B2 (en) | 2016-03-29 |
CN105073698A (zh) | 2015-11-18 |
EP2985273B1 (en) | 2018-07-04 |
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