TWI403497B - 6,8,10-十一碳三烯-3或4-醇及香料組成物 - Google Patents
6,8,10-十一碳三烯-3或4-醇及香料組成物 Download PDFInfo
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- TWI403497B TWI403497B TW097121835A TW97121835A TWI403497B TW I403497 B TWI403497 B TW I403497B TW 097121835 A TW097121835 A TW 097121835A TW 97121835 A TW97121835 A TW 97121835A TW I403497 B TWI403497 B TW I403497B
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- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- SLEGPTUZZMEOPB-UHFFFAOYSA-N [Na].C(CCCCCCCCC)N Chemical compound [Na].C(CCCCCCCCC)N SLEGPTUZZMEOPB-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical class CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008341 cosmetic lotion Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 239000004864 galbanum Substances 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 235000020333 oolong tea Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- SMPAPEKFGLKOIC-UHFFFAOYSA-N oxolane;hydrochloride Chemical compound Cl.C1CCOC1 SMPAPEKFGLKOIC-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- IQQBFWHNQBNSSQ-UHFFFAOYSA-N undeca-1,3,5,7-tetraene Chemical compound CCCC=CC=CC=CC=C IQQBFWHNQBNSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
-
- 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
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0007—Aliphatic compounds
- C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Description
本發明為有關作為香料化合物有用之6,8,10-十一碳三烯-3-醇或6,8,10-十一碳三烯-4-醇及以這些化合物為有效成分含有之香料組成物。
已知多不飽和化合物具有重要香氣特性,例如於特開昭50-32105號公報,揭示古蓬香(galbanum)精油中有(3E,5E)-1,3,5-十一碳三烯及(3E,5Z)-1,3,5-十一碳三烯之存在及合成這些化合物而鑑定,又於特開昭59-42326號公報揭示1,3,5,7-十一碳四烯作為香料之用途。更於J.Agric.Food Chem.,33(1985),232及J.Food Sci.,50(1985),1655報告於鳳梨、桃、芒果、奇異果中有(3E,5Z,8Z)-1,3,5,8-十一碳四烯之存在,於特表2005-515249號公報揭示2,4,7-癸三烯醛之縮醛作為香料之用途。
這些多不飽和化合物具有優異香氣,例如於特開昭50-32105號公報記載1,3,5-十一碳三烯具有像花般,例如想起洋水仙、三色菫、水仙、薰衣草、梔子花之香氣、漂香於其底之葉之香氣發現或強化類似天然之性質,又於特開昭59-42326號公報記載1,3,5,7-十一碳四烯具有土壤及樹木般之香氣,而於特表2005-515249號公報記載2,4,7-癸三烯醛之縮醛具有舒適天然之青香韻。
但上述化合物之香氣特性乃強調新鮮水果感,與充滿天然感之香氣完全不同。
近年,因消費者之嗜好性之多樣化,故使用於飲食品、香妝品等之香料,也要求具有天然感、新鮮感之素材,僅組合從來之香料物質,則不能充分對應其要求為現狀。
故本發明之目的為提供能再現充滿天然感、新鮮感之香氣之新穎香料化合物及其製造方法。
本發明者等鑑於前述多不飽和化合物具有優異香氣特性,而合成種種多不飽和化合物之衍生物,檢討其香氣特性,結果這回偶然發現6,8,10-十一碳三烯-3-或4-醇具有優異香氣特性,其香氣意外不僅具有伴隨木頭風味青香韻(green note),且具有充滿天然感、新鮮感之水果般香氣,終於完成本發明。
如此本發明提供如下式(1)文獻未記載之新穎化合物6,8,10-十一碳三烯-3或4-醇
[式中R1及R2之一者為氫原子而另一者為羥基,波線之鍵結為順型或反型或順型與反型之任意比例之混合物]。
本發明又提供以上述式(1)之6,8,10-十一碳三烯-3或4-醇為有效成分含有為特徴之香料組成物。
本發明更提供將如下式(2)鏻鹽
[式中R3為芳基,X為鹵素]或如下式(3)膦酸酯
[式中R4為碳數1~8之烷基或芳基],與如下式(4)內醚醇(lactol)
予以維蒂希(Wittig)反應或霍納-埃蒙斯(Horner-Emmons)反應為特徴之如下式(5)6,8,10-十一碳三烯-3-醇之製造方法
[式中波線之鍵結為順型或反型或順型與反型之任意之比例之混合物]。
本發明更提供將如下式(6)6,8,10-十一碳三烯-4-酮
[式中波線之鍵結為順型或反型或順型與反型之任意之比例之混合物]還原為特徴之如下式(7)6,8,10-十一碳三烯-4-醇之製造方法
[式中波線之鍵結為順型或反型或順型與反型之任意之比例之混合物]。
本發明之式(1)之化合物,除木頭風味青香韻之外,尚具有充滿天然感、新鮮感之水果般香氣.香味及其優異持續性,有效作為飲食品類、香妝品類、保健.衛生.醫藥品等所用香料組成物之調合素材使用。
以下更詳細說明本發明之化合物、其製造方法及作為香料組成物之用途。
本發明之式(1)化合物所包含式(5)之6,8,10-十一碳三烯-3-醇(R1=OH,R2=H之式(1)之化合物)可依如下反應途徑1合成。
本說明書中,「芳基」為單環式或多環式之芳香族烴基,例如各可依場合而為可有取代之苯基、甲苯基、萘基等,宜苯基。
「烷基」為直鏈狀或分枝鏈狀之飽和烴基,例如甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、正己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三
甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、正庚基、正辛基等,尤宜碳原子數1~4之烷基。
X所示特宜鹵素為Cl、Br。
式(2)之鏻鹽與式(4)之內醚醇之維蒂希反應、或式(3)之膦酸酯與式(4)之內醚醇之霍納-埃蒙斯反應可依文獻(參照例如新實驗化學講座14有機化合物之合成與反應[I]p224-243)記載之這些反應典型條件下實施。
式(2)之鏻鹽與式(4)之內醚醇之維蒂希反應,可於惰性有機溶劑中有鹼之存在下施行,有機溶劑可為例如醚(例:乙醚、二異丙醚、甲基第三丁醚、1,4-二烷、四氫呋喃等)、鹵化烴(例:二氯甲烷、氯仿等)、芳香族烴(例:苯、甲苯、二甲苯等)、極性溶劑(例:二甲基甲醯胺、二甲亞碸、乙腈等),尤宜甲苯、四氫呋喃,二甲亞碸、二甲基甲醯胺或這些混合溶劑。
上述鹼只要為維蒂希反應通常使用之鹼皆有使用可能,例如鹼金屬氫氧化物(例:氫氧化鈉、氫氧化鉀、氫氧化鋰等)、鹼金屬氫化物(例:氫化鈉、氫化鉀等)、有機鋰化合物(例:正丁基鋰、第三丁基鋰、苯基鋰等)、鹼金屬醯胺(例:醯胺鋰、醯胺鉀、醯胺鈉、二異丙基醯胺鋰等)、鹼金屬六甲基二矽疊氮、鹼金屬烷氧化物(例:甲醇鈉、乙醇鈉等)、這些鹼之使用量可對式(2)之鏻鹽通常用0.8~5當量,宜1~3當量之範圍內。
又對式(2)之鏻鹽、式(4)之內醚醇之使用量為對式(2)之鏻
鹽、通常可用0.8~5當量,宜1~3當量之範圍內。
上述維蒂希反應、通常於-78~60℃,宜-10~25℃之範圍內之溫度、通常施行0.5~24小時,宜0.5~2小時之程度。
式(3)之膦酸酯與式(4)之內醚醇之霍納-埃蒙斯反應,可上述之式(2)之鏻鹽與式(4)之內醚醇之維蒂希反應同樣施行。
如此依所用反應條件、式(5)之波線之鍵結中順:反比一般為10:1~1:10,宜7:3~3:7之範圍內之式(5)之6,8,10-十一碳三烯-3-醇以幾何異構物混合物之形態而得。
作為出發物質使用之式(4)之內醚醇可用依任何製法而得者皆可使用,例如可依如下反應途徑2來合成。
式(2)之鏻鹽或式(3)之膦酸酯本身為既知之物質,可依特
開昭50-32105號公報記載之方法合成,可為例如反應途徑3。
式(9)之格任亞試藥與式(10)之甲酸乙酯之反應通常於-10~40℃,宜0~15℃之範圍內之溫度施行。反應終了後,可依常法,例如萃取、洗淨、乾燥、濃縮,必要時蒸餾來精製,而得式(11)之醇。
又上述之格任亞反應中,式(10)之甲酸乙酯代之以丙烯醛也可同樣得式(11)之醇。
次令式(11)之醇以鹵化氫(HX)施行親核取代反應,則得式(12)之鹵化物。本反應可於溶劑,例如乙醚、四氫呋喃等之存在下或不存在下,於式(11)之醇添加鹵化氫之20~40%水溶液來施行。使用可能之鹵化氫(HX)可為例如氯化氫、溴化氫、碘化氫等,其添加量可為對式(11)之醇每莫耳用1~2莫耳之範圍內。又添加時間通常為0.5~3小時,宜1~2小時,反應溫度通常為-10~40℃,宜0~15℃之範圍內。反應終了後,可依常法,例如萃取、洗淨、乾燥、濃縮,必要時蒸餾來精製,得式(12)之鹵化物。
次令式(12)之鹵化物與膦[P(R1)3]或亞磷酸酯[P(OR2)3]依常法反應,則可生成式(2)之鏻鹽或式(3)之膦酸酯。本反應可於溶劑之存在下或不存在下施行,可使用之溶劑為例如甲醇、乙醇、丙醇、異丙醇、丁醇、氯仿、二氯甲烷、1,2-二氯乙烷、四氫呋喃、二甲醚、二甲基甲醯胺、二甲亞碸、甲苯等,此等溶劑可各單獨或組合2種以上來使用。又其使用量無特限,例如對式(12)之鹵化物用1~50重量倍,宜2~10重量倍左右。又上述反應一般可於約-20~約100℃之範圍內之溫度施行1~72小時左右,則可得式(2)之鏻鹽或式(3)之膦酸酯。所得式(2)之鏻鹽或式(3)之膦酸酯可由結晶化等而容易分離。
包括於本發明之式(1)化合物之式(7)6,8,10-十一碳三烯-4-醇(R1=H,R2=OH之式(1)化合物)可依如下反應途徑4合成
。
式(6)之6,8,10-十一碳三烯-4-酮之還原可令酮還原成醇之反應上典型條件下實施,具體而言,可依例如文獻(參照例如新實驗化學講座15氧化與還原[II])記載之用氫化二異丁基鋁之還原、用氫化鋁鋰之還原、用氫化硼鈉之還原、Meerwein-Ponndorf-Verley還原等來施行。尤宜用氫化二異丁基鋁之還原、用氫化鋁鋰之還原、用氫化硼鈉之還原。
如此依所用出發物質及/或反應條件,使式(7)之波線之鍵結中順:反比一般為10:1~1:10,宜7:3~3:7之範圍內之式(7)之6,8,10-十一碳三烯-4-醇以幾何異構物混合物之形態而得。
出發物質即式(6)之6,8,10-十一碳三烯-4-酮可用依任何製法所得者,可依例如以下之反應途徑5來合成。
式(2)之鏻鹽與式(13)之醛之維蒂希反應或式(3)之膦酸酯與式(13)之醛之霍納-埃蒙斯反應,可與上述式(2)之鏻鹽與式(4)之內醚醇之維蒂希反應同樣施行,由此式(14)之三烯縮醛可以順/反幾何異構物混合物之形態而得。
由式(14)之三烯縮醛之脫縮醛化來生成式(6)之6,8,10-十一碳三烯-4-酮之反應,可依文獻(參照例如PROTECTIVE GROUPS IN ORGANIC SYNTHESIS,GREENE WUTS,p317-322)記載之通常使用之脫縮醛化反應條件下實施,例如用酸觸媒(例如對甲苯磺酸吡錠(PPTS)-丙酮-水、對甲苯磺酸(TsOH)-丙酮等)之縮醛交換反應、用酸觸媒(例如鹽酸-四氫呋喃、乙酸、過氯酸等)之加水分解、或氧化(DDQ-乙腈-水等)等來施行。
出發物質式(13)之醛也可用依任何製法所得者,例如可依以下之反應途徑6合成。
次將式(16)之化合物於惰性大氣下,用例如氫化二異丁基鋁(DIBAL)等還原劑,於甲苯、己烷等惰性有機溶劑中施行還原反應,得式(13)之醛。
由本發明提供之式(1)之化合物可於香料組成物以特定之比例配合,則於香料組成物賦與新鮮而充滿天然感之香氣。
如此依本發明,可提供以式(1)之化合物為有效成分含有為特徴之香料組成物。
配合於香料組成物之式(1)之化合物只要為前述式(1)中波線所示部分之鍵結為順型或反型或順型與反型之任意比例之混合物,皆具有如上述香氣.香味特性,故本發明之化合物無論為波線所示部分之幾何學配置皆可於香料組成物中使用。
將式(1)之化合物配合於香料組成物時,其配合量依配合之目的或香料組成物之種類等而異,以香料組成物全量為基準,通常可例示0.00001~10重量%,宜0.001~0.1重量%之範圍內。
如此於例如水果(例:草莓、藍莓、樹莓、蘋果、櫻桃、李、杏、桃、鳳梨、香蕉、香瓜、芒果、木瓜、奇異果、梨、葡萄、慕斯卡(Muscat)、巨峰等)、柑橘類(例:檸檬、橘子、葡萄柚、來檬、溫州蜜柑等)、和柑橘類(例:蜜柑、香酸柑橘(Cabos)、醋橘(Citrus sudachi)、八朔、伊予柑、柚子(Citrus junos)、香檬(Citrus depressa)、金柑等)、茶類(例:紅茶、烏龍茶、綠茶等)等香料組成物,按上述比例添加式(1)化合物,則可強調成新鮮天然而有水果感。又於香檸檬(bergamot)般、天竺葵(geranium)般、玫瑰般、花束(bouquet)般、洋水仙般、蘭般、花香般等調合香料、按上述比例添加式(1)化合物,則可更強調其香氣之特徴,可再現天然精油本來具有之充満新鮮天然感之香氣。
更依本發明,以式(1)化合物為有效成分含有之香料組成物配合於飲食品類、香妝品類、保健.衛生.醫藥品類等製品,則可提供以式(1)化合物為香氣.香味成分含有之飲食品類、香妝品類、保健.衛生.醫藥品類等。
例如於碳酸飲料、果汁飲料、水果酒飲料類、乳飲料等飲料類;冰淇淋類、冰沙(sherbet)類、冰棒類等冷餅類;東.西洋餅、口香糖類、麵包類、咖啡、紅茶、茶、香菸等嗜好品類;日式湯類、洋式湯類等湯類;火腿、香腸等
畜肉加工品;風味調味料、各種速食飲料或食品類、各種點心類等,添加適當量以式(1)化合物為有效成分含有之香料組成物,則可提供賦與其獨特香氣.香味之飲食品類。又於例如洗髮精類、髮霜類、其他毛髮化妝料基劑;白粉、口紅、其他化妝用基劑或化妝用洗劑類基劑等,適當量添加以式(1)化合物為有效成分含有之香料組成物,則可提供賦與其獨特香氣之化妝品類。更又令以式(1)化合物為有效成分含有之香料組成物,於例如洗衣用洗劑類、消毒用洗劑類、防臭洗劑類、其他各種保健.衛生用洗劑類;牙膏、面紙、衛生紙等適當量配合,則可提供賦與其獨特香氣之各種保健.衛生材料類;醫藥品類等。
以下以實施例更具體說明本發明。
依下述一連反應式來合成式(5)之6,8,10-十一碳三烯-3-醇。工程編號下之括弧內之百分率乃示各工程之產率。
於氬大氣下2L燒瓶,投入鎂48.6g(2.00mol)、四氫呋喃300mL及碘(觸媒量),於室溫邊攪拌邊滴下溴乙烯214.0g(2.00mol)之四氫呋喃(780mL)溶液約20ml。反應溶液加熱至30~40℃而開始反應,以1小時滴下殘餘溴乙烯之四氫呋喃溶液使反應溫度為30~40℃。滴下終了後,於室溫攪拌1.5小時,其後以冰水冷却。於5~15℃以1小時滴下式(10)之甲酸乙酯74.0g(1.00mol),其後於室溫攪拌1小時。反應溶液注入1L飽和氯化銨水溶液,分離有機層,水層以乙醚萃取。合併有機層,以飽和氯化銨水溶液、飽和氯化鈉水溶液之順序洗淨後,有機層用硫酸鎂乾燥,減壓蒸除溶劑。令所得殘渣(96.7g)減壓下蒸餾(~54℃/7.8kPa),得式(11)之醇68.2g(0.811mol,產率81%,純度96%)。
於300mL燒瓶投入式(11)醇52.5g(0.625mol),以甲醇-冰邊冷却邊以1.5小時滴下48%溴化氫水溶液126.2g(0.749mol)。分離有機層,以水洗淨,用硫酸鎂乾燥,得式(16)之溴化物57.1g(0.388mol,產率62%,純度97%)。
於500mL燒瓶投入三苯膦106.8g(0.407mol)及甲苯250mL,於室溫以15分滴下式(18)之溴化物57.1g(0.388mol)。更於室溫攪拌22小時後,濾集析出之結晶,得式(19)之鏻鹽
132.4g(0.323mol,產率83%)。
於氬大氣下500mL燒瓶投入γ-己內酯(8)11.4g(0.100mol)及甲苯200mL,於-63~-61℃以30分滴下氫化二異丁基鋁(DIBAL)之1.01M甲苯溶液109mL(0.110mol)。滴下終了後就此溫度攪拌1小時,加甲醇20mL、矽藻土及乙醚,於室溫攪拌一夜。令反應溶液過濾,減壓蒸除溶劑。令所得殘渣13.5g減壓蒸餾(~55℃/0.5kPa),得式(4)之內醚醇6.00g(0.0517mol,產率52%,純度93%)。
於氬大氣下,100mL燒瓶投入二甲亞碸(DMSO)20mL,於室溫加氫化鈉(60%油分散)1.38g(34.4mmol),就此攪拌1小時。加溶解於DMSO10mL之式(19)之鏻鹽14.1g(34.4mmol)之溶液,於室溫攪拌10分,次於室溫加溶解於DMSO10mL之式(4)之內醚醇2.00g(17.2mmol)溶液。攪拌一夜後,反應溶液注入水,以乙醚萃取,有機層以水、飽和氯化鈉水溶液順序洗淨,用硫酸鎂乾燥,過濾而減壓濃縮。於殘渣加乙醚,濾除析出之結晶,將濾液減壓濃縮。再於殘渣加乙醚,濾除析出之結晶,將濾液減壓濃縮。所得殘渣以矽膠柱層析精製(己烷:乙酸乙酯=30:1),得式(5)之6,8,10-十一碳三烯-3-醇2.04g(12.3mmol,產率71%)。
6位之幾何異構物比:E:Z=10:7
1H-NMR(6位之幾何異構物混合物,CDCl3,400MHz):δ 0.92(3H,t,J=7.2),1.40-1.57(4H,m),2.02-2.32(2H,m),3.52(1H,br qui,J=3.6),5.03,5.07(共1H,各d,J=10.0,J=10.4),5.15,5.20(共1H,各d,J=16.4,J=16.8),547,5.72(共1H,各dt,J=7.6,10.8,J=6.8,15.6),5.99-6.54(4H,m).
13C-NMR(6位之幾何異構物混合物,CDCl3,100MHz):δ 9.86,9.88,24.2,29.1,30.2,30.3,36.3,36.6,72.7,116.5,117.1,128.3,128.8,130.5,131.3,132.6,133.2,133.3,135.2,137.0,137.1.MS(m/z):31(13),41(34),57(27),67(21),79(63),91(100),105(52),119(25),166(M+,11)
依下述一連之反應式合成式(7)之6,8,10-十一碳三烯-4-醇。工程編號之下之括弧內之百分率表示各工程之產率。
於200ml燒瓶投入式(20)之3-氧己酸乙酯12.0g(78.9
mmol)、乙二醇9.40g(15lmmol)、對甲苯磺酸吡錠(PPTS)0.1g及環己烷50ml,加熱回流下,邊去除餾出之水邊反應9小時,次添加觸媒量對甲苯磺酸(TsOH),更加熱回流下,邊去除餾出之水邊反應6小時。冷却後,於反應溶液加飽和碳酸氫鈉水溶液,分離有機層,有機層以水、飽和氯化鈉水溶液順序洗淨後,用硫酸鎂乾燥,減壓蒸除溶劑。令所得殘渣(14.9g)減壓蒸餾(~77℃/0.2kPa),得式(21)之酯10.6g(52.4mmol,產率66%)。
於氬大氣下,200mL燒瓶投入式(21)之酯5.00g(24.7mmol)及甲苯50mL,於-65~-60℃邊攪拌邊以30分滴下氫化二異丁基鋁(DIBAL)之0.99M甲苯溶液27.5mL(27.2mmol),其後就此溫度攪拌30分。反應溶液注入5%草酸二水合物水溶液140ml,分離有機層,水層以乙酸乙酯萃取。合併全部有機層,以飽和氯化鈉水溶液洗淨後,用硫酸鎂乾燥,減壓蒸除溶劑。所得殘渣之醛4.20g(式(22))就此供下一工程。
於氮大氣下,200mL燒瓶投入式(22)之醛4.20g,與實施例1同樣反應所得式(19)之鏻鹽10.1g(27.2mmol)及二甲基甲醯胺(DMF)16g,邊以冰水冷却邊滴下甲醇鈉(28%甲醇溶液)5.00g(25.9mmol),其後,就此溫度攪拌1小時。反應溶液注入飽和氯化銨水溶液,加己烷,濾除析出之結晶。濾液以己烷萃取,用水、飽和氯化鈉水溶液順序洗淨後,用
硫酸鎂乾燥,減壓蒸除溶劑。令所得殘渣(5.92g)減壓蒸餾(~100℃/0.2kPa),得式(23)之三烯縮醛2.94g(14.1mmol,產率57%)。
於200mL燒瓶投入35%過氯酸水溶液40ml和乙醚10ml,邊以冰水冷却邊以10分滴下式(23)之三烯縮醛2.94g(14.1mmol)之乙醚溶液(30ml)。就此溫度攪拌20分後,用飽和碳酸氫鈉水溶液中和至pH7~8。反應溶液以乙醚萃取,有機層以水、飽和氯化鈉水溶液順序洗淨後,用硫酸鎂乾燥,減壓蒸除溶劑。所得殘渣(2.61g)以矽膠柱層析精製(己烷:乙酸乙酯=80:1),得式(6)之6,8,10-十一碳三烯-4-酮1.90g(11.6mmol,產率82%)。
於50mL燒瓶投入(6)之6,8,10-十一碳三烯-4-酮1.50g(9.13mmol)和95%乙醇10ml,邊以冰水冷却邊加氫化硼鈉(NaBH4)174mg(4.57mmol)。1小時後,徐徐加1N鹽酸10ml,於室溫下攪拌30分。反應溶液用乙酸乙酯萃取,有機層以飽和碳酸氫鈉水溶液、飽和食鹽水順序洗淨後,用硫酸鎂乾燥,減壓蒸除溶劑。所得殘渣(1.60g)以矽膠層析精製(己烷:乙酸乙酯=50:1),得精製物1.1g。令層析精製物482mg更減壓蒸餾(~140℃/0.3kPa),得式(7)之6,8,10-十一碳三烯-4-醇380mg(2.29mmol,產率59%)。
6位之幾何異構物比:E:Z=65:35
1H-NMR(6位之幾何異構物混合物,CDCl3,400MHz):δ 0.916,0.922(共3H,各t,J=6.8),1.32-1.50(5H,m),2.15-2.38(2H,m),3.52(1H,br d,J=5.6),5.06,5.09(共1H,各d,J=10.0,J=11.6),5.18,5.22(共1H,各d,J=12.4,J=12.4),5.51,5.71(共1H,各dt,J=8.0,10.4,J=7.2,15.2),6.10-6.52(4H,m)
13C-NMR(6位之幾何異構物混合物,CDCl3,100MHz):δ 14.1,18.88,18.94,35.9,39.0,39.1,41.0,70.9,71.2,117.0,117.6,128.1,128.3,131.0,131.2,132.1,132.9,133.3,134.1,136.9,137.0.
MS(m/z):27(7),31(7),43(23),55(55),79(100),94(40),105(2),166(M+,7)
就實施例1所得6,8,10-十一碳三烯-3-醇、實施例2所得6,8,10-十一碳三烯-4-醇及特開昭50-32105號公報及特開昭59-42326號公報記載之1,3,5-十一碳三烯及1,3,5,7-十一碳四烯之各0.1%乙醇溶液,由訓練有素之評審員施行香氣評價。香氣評價為於30ml樣品瓶準備前述0.1%乙醇溶液,令瓶口之香氣及其溶液沾於聞嗅紙來施行。5名之平均香氣評價如表1。
作為鳳梨般之調合香料組成物,調製由下述表2所示成分而成之基本調合香料組成物。
於上述組成物99.9g混合實施例1製造之6,8,10-十一碳三烯-3-醇0.1g或實施例2製造之6,8,10-十一碳三烯-4-醇0.1g,而調製新穎鳳梨般之調合香料組成物。就此新穎調合香料組成物和未加該化合物之上述鳳梨般調合香料組成物之香氣,由10名專門評審員來比較。官能評價之結果如表3。
如上所述,10名專門評審員全員就調合任何香料化合物之鳳梨香料組成物也評價為掌握天然鳳梨之特徴而於持續性也特優。
作為洋水仙般之調合香料組成物,調製由如下表4所示成分而成之基本調合香料組成物。
如上所述,10名專門評審員全員就調合任何香料化合物之洋水仙調合香料組成物也評價為掌握天然洋水仙之特徴而於持續性也特優。
關於實施例1所得6位幾何異性為E:Z=10:7之6,8,10-十一碳三烯-3-醇,依氣層析聞嗅法評價(6E,8E)-6,8,10-十一碳三烯-3-醇和(6Z,8E)-6,8,10-十一碳三烯-3-醇之各別香氣。
(6E,8E)-6,8,10-十一碳三烯-3-醇:伴隨有新鮮感水果般香氣之木頭風味之青香韻。
(6Z,8E)-6,8,10-十一碳三烯-3-醇:伴隨有天然感、新鮮感
水果般香氣之鮮明而木頭風味之青香韻。
有關實施例1所得6位幾何異性為E:Z=65:35之6,8,10-十一碳三烯-4-醇,依氣層析聞嗅法評價(6E,8E)-6,8,10-十一碳三烯-4-醇和(6Z,8E)-6,8,10-十一碳三烯-4-醇之各別香氣。
(6E,8E)-6,8,10-十一碳三烯-4-醇:充滿柔軟青香韻及甘甜天然感、新鮮感之水果般香氣。
(6Z,8E)-6,8,10-十一碳三烯-4-醇:充滿木頭風味之青香韻及鮮明甘甜天然感、新鮮感之水果般香氣。
Claims (5)
- 一種如下式(1)6,8,10-十一碳三烯-3或4-醇,
- 一種香料組成物,其特徴為含有以如申請專利範圍第1項之式(1)之6,8,10-十一碳三烯-3或4-醇為有效成分。
- 一種製品,其特徴為含有如申請專利範圍第2項之香料組成物。
- 一種如下式(5)6,8,10-十一碳三烯-3-醇之製造方法,
- 一種如下式(7)6,8,10-十一碳三烯-4-醇之製造方法,
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JPS61111666A (ja) * | 1985-08-08 | 1986-05-29 | T Hasegawa Co Ltd | 持続性香味剤 |
JPS61172839A (ja) * | 1985-01-28 | 1986-08-04 | T Hasegawa Co Ltd | 持続性香気香味賦与乃至改良補強剤 |
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US4014951A (en) * | 1973-06-07 | 1977-03-29 | Firmenich S.A. | Process for the preparation of poly-unsaturated hydrocarbons |
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EP0100015B1 (fr) | 1982-07-22 | 1985-05-02 | Firmenich Sa | Hydrocarbure aliphatique polyinsaturé, procédé pour sa préparation et son utilisation en tant qu'ingrédient parfumant et aromatisant |
FR2587330B1 (fr) * | 1985-05-31 | 1987-10-30 | Oril Sa | Nouveau procede de preparation des undecatrienes |
EP0478977B1 (fr) * | 1990-10-03 | 1996-12-18 | Firmenich Sa | Procédé pour la préparation d'oléfines polyinsaturées |
DE60311066T2 (de) * | 2002-01-22 | 2007-11-08 | Firmenich S.A. | Acetale von 2,4,7-decatrienal als parfüm- oder geschmackstoffbestandteile |
US7268267B2 (en) * | 2003-03-21 | 2007-09-11 | Uop Llc | Alkylation process using UZM-8 zeolite |
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JP4057638B1 (ja) * | 2007-09-28 | 2008-03-05 | 長谷川香料株式会社 | 6,8,10−ウンデカトリエン−2−オンおよび香料組成物 |
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