CN107848924B - 作为香料成分的2,4,7-三甲基辛-6-烯-1-醇 - Google Patents
作为香料成分的2,4,7-三甲基辛-6-烯-1-醇 Download PDFInfo
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- CN107848924B CN107848924B CN201680043626.8A CN201680043626A CN107848924B CN 107848924 B CN107848924 B CN 107848924B CN 201680043626 A CN201680043626 A CN 201680043626A CN 107848924 B CN107848924 B CN 107848924B
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- Prior art keywords
- trimethyloct
- product
- dien
- perfume
- methyl
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- UHELJNANGXRBDI-UHFFFAOYSA-N 2,4,7-trimethyloct-6-en-1-ol Chemical compound CC(CO)CC(CC=C(C)C)C UHELJNANGXRBDI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003205 fragrance Substances 0.000 title claims abstract description 35
- 239000004615 ingredient Substances 0.000 title claims abstract description 23
- 239000002304 perfume Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 38
- 239000012437 perfumed product Substances 0.000 claims description 21
- PSIOIPWJOZPZPA-UHFFFAOYSA-N 2,4,7-trimethylocta-2,6-dien-1-ol Chemical compound CC(CC=C(C)C)C=C(C)CO PSIOIPWJOZPZPA-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 8
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 4
- KRLBLPBPZSSIGH-CSKARUKUSA-N (6e)-3,7-dimethylnona-1,6-dien-3-ol Chemical compound CC\C(C)=C\CCC(C)(O)C=C KRLBLPBPZSSIGH-CSKARUKUSA-N 0.000 claims description 4
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- 150000001299 aldehydes Chemical class 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 4
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- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 4
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- WNHPULBFSIXBBG-YFHOEESVSA-N (3Z)-2,4,7-trimethylocta-3,6-dien-1-ol Chemical compound CC(CO)\C=C(/CC=C(C)C)\C WNHPULBFSIXBBG-YFHOEESVSA-N 0.000 description 3
- VZIGDSZRIKPLQF-UHFFFAOYSA-N 2,4,7-trimethyloct-6-enal Chemical compound CC(C=O)CC(CC=C(C)C)C VZIGDSZRIKPLQF-UHFFFAOYSA-N 0.000 description 3
- ZTMMMLLHCCPSGH-UHFFFAOYSA-N 2,4,7-trimethyloct-7-en-1-ol Chemical compound CC(CO)CC(CCC(=C)C)C ZTMMMLLHCCPSGH-UHFFFAOYSA-N 0.000 description 3
- SFCVUROYEXWUIY-UHFFFAOYSA-N 2,4-dimethyl-6-propan-2-ylcyclohex-3-en-1-ol Chemical compound C(C)(C)C1CC(=CC(C1O)C)C SFCVUROYEXWUIY-UHFFFAOYSA-N 0.000 description 3
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
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- 238000007865 diluting Methods 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 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
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- 229940073505 ethyl vanillin Drugs 0.000 description 1
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- 239000002979 fabric softener Substances 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 239000010648 geranium oil Substances 0.000 description 1
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- UKPNWAXOLLMNHR-UHFFFAOYSA-N hexyl 2-hydroxybenzoate 2-hydroxybenzoic acid Chemical compound C(C=1C(O)=CC=CC1)(=O)O.C(C=1C(O)=CC=CC1)(=O)OCCCCCC UKPNWAXOLLMNHR-UHFFFAOYSA-N 0.000 description 1
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- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
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- 229940041616 menthol Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000001738 pogostemon cablin oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019719 rose oil Nutrition 0.000 description 1
- 239000010666 rose oil Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 239000001290 saussurea lappa clarke root oil Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- DCSCXTJOXBUFGB-UHFFFAOYSA-N verbenone Natural products CC1=CC(=O)C2C(C)(C)C1C2 DCSCXTJOXBUFGB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/342—Alcohols having more than seven atoms in an unbroken chain
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- A—HUMAN NECESSITIES
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0007—Aliphatic compounds
- C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
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Abstract
用作香料成分的2,4,7‑三甲基辛‑6‑烯‑1‑醇。
Description
本发明涉及2,4,7-三甲基辛-6-烯-1-醇。本发明还涉及它作为高盛放(blooming)香料成分的用途,以及包含它的香料组合物和加香产品。本发明还涉及它的生产方法。
具有“盛放”的香料在香料工业中具有高关注度,主要是因为盛放是一种通常令人愉快的、令人惊讶的感官效果,其指示强效的香料。这种感官效果为消费者提供了即时的感觉,例如嗅觉效果或新鲜感的印象。盛放可以被认为是加香产品的特征谐香,因此是强烈影响消费者对加香产品的接受度的重要特征。因此,香料工业对具有盛放效果的香料的需求日益增加。
据我们所知,2,4,7-三甲基辛-6-烯-1-醇(I)从未在文献中被描述过。WO2012160189中报道的结构最接近的类似物是2,4,7-三甲基辛-2,6-二烯-1-醇(A),其具有显著不同的气味特征。
鉴于2,4,7-三甲基辛-2,6-二烯-1-醇(A)被描述为具有花香、玫瑰香香型,同时具有一些香叶柑橘样副香型(side notes),所以2,4,7-三甲基辛-6-烯-1-醇(I)具有清晰的主柑橘香质与清晰的青香圆柚/大黄内涵(connotation)。
除了其如上所述的气味特征之外,令人惊讶地发现,2,4,7-三甲基辛-6-烯-1-醇(I)增强了加入其的加香产品的新鲜度(freshness)和清洁度(cleanness)属性,而没有改变所述加香产品的整体气味特征。作为实例,可以提及的是向馥奇香型香料中加入2,4,7-三甲基辛-6-烯-1-醇(I),得到一种香料谐香,其更为新鲜,但仍然是馥奇香型特征,并不会改变柑橘、药草香、青香、花香和动物类私密香型,其通常表征了这类香料(馥奇香型)。
更令人惊讶的是,虽然2,4,7-三甲基辛-2,6-二烯-1-醇(A)不具有盛放,但2,4,7-三甲基辛-6-烯-1-醇(I)是一个高度盛放的香料成分。
香料“盛放”是指在离香料源一定距离处的成分的短期影响。短期是指外部作用施加到香料成分自身后的几秒到几分钟。这种作用(或事件)本质上可以是多重的。打开香料瓶,在空气中或在皮肤上喷洒香料溶液,使加香产品接触表面或水,且特别是用水稀释加香产品,这些都是典型的能够诱导盛放的作用。香精和单独香料成分都可以分成低盛放到高盛放香精/香料成分,而在当今市场上消费者高度期望高盛放。
尽管“盛放”典型地是香料的时间依赖性动态性能属性,但是可以在作用发生后一定时间之后,但不迟于30分钟,优选15-20分钟进行测量。典型地,评价是在封闭的空气中进行的,例如在非通风的隔离间内进行。典型地,小组成员通过在隔离间内经仅在评价期间打开的小窗口嗅吸一定体积的空气(例如一次或两次呼吸)来进行评价。典型地,窗口位于离来源0.5米至2米之间,优选在0.8米至1.5米之间,例如1.3米。实验装置的确切几何形状并不重要,但必须从一次评价到另一次评估可重现。
以上提到的所有特征一起使得2,4,7-三甲基辛-6-烯-1-醇对于香料工业来说是高度理想的。
因此,在第一个方面提供了2,4,7-三甲基辛-6-烯-1-醇及其作为香料的用途。2,4,7-三甲基辛-6-烯-1-醇可以其非对映异构纯形式(顺式-2,4,7-三甲基辛-6-烯-1-醇;反式-2,4,7-三甲基辛-6-烯-1-醇)或非对映异构体混合物形式使用,例如80:20-20:80之比的混合物,例如60:40-40:60之比的混合物,包括1:1、1:1.5、7:3和3:7的混合物。
在另一个方面,提供了包含2,4,7-三甲基辛-6-烯-1-醇(其包括2,4,7-三甲基辛-6-烯-1-醇的非对映异构纯和/或对映异构纯形式或非对映异构体和/或对映异构体混合物形式)的香料组合物或者加香产品。
在一个实施方案中,提供了富含rel.(2S,4S)-2,4,7-三甲基辛-6-烯-1-醇(即顺式-2,4,7-三甲基辛-6-烯-1-醇)的2,4,7-三甲基辛-6-烯-1-醇作为香料的用途。
在另一个实施方案中,提供了富含rel.(2S,4R)-2,4,7-三甲基辛-6-烯-1-醇(即反式-2,4,7-三甲基辛-6-烯-1-醇)的2,4,7-三甲基辛-6-烯-1-醇作为香料的用途。
另一方面,提供了赋予加香产品新鲜度和清洁度的方法,该方法包括将2,4,7-三甲基辛-6-烯-1-醇掺入所述加香产品的步骤。
可以将2,4,7-三甲基辛-6-烯-1-醇直接添加到产品中,或者可以将其与已知的其它香料成分混合,得到香料组合物,然后加入到产品中。
下列清单包括已知香料成分的实例,其可以与2,4,7-三甲基辛-6-烯-1-醇结合:
-精油和提取物,例如,海狸香、广木香根油、橡苔净油、香叶油、树苔净油、罗勒油、果油如香柠檬油和红桔油、香桃木油、玫瑰草油(palmarose oil)、广藿香油、橙叶油、茉莉油、玫瑰油、檀香木油、苦艾油、薰衣草油和/或依兰依兰油;
-醇类,例如肉桂醇((E)-3-苯基丙-2-烯-1-醇);顺式-3-己烯醇((Z)-己-3-烯-1-醇);香茅醇(3,7-二甲基辛-6-烯-1-醇);二氢月桂烯醇(2,6-二甲基辛-7-烯-2-醇);黑檀醇(EbanolTM)((E)-3-甲基-5-(2,2,3-三甲基环戊-3-烯-1-基)戊-4-烯-2-醇);丁香酚(4-烯丙基-2-甲氧基苯酚);乙基芳樟醇((E)-3,7-二甲基壬-1,6-二烯-3-醇);金合欢醇((2E,6Z)-3,7,11-三甲基十二碳-2,6,10-三烯-1-醇);香叶醇((E)-3,7-二甲基辛-2,6-二烯-1-醇);Super MuguetTM((E)-6-乙基-3-甲基辛-6-烯-1-醇);芳樟醇(3,7-二甲基辛-1,6-二烯-3-醇);薄荷醇(2-异丙基-5-甲基环己醇);橙花醇(3,7-二甲基-2,6-辛二烯-1-醇);苯基乙基醇(2-苯基乙醇);玫瑰醇(RhodinolTM)(3,7-二甲基辛-6-烯-1-醇);檀香(SandaloreTM)(3-甲基-5-(2,2,3-三甲基环戊-3-烯-1-基)戊-2-醇);松油醇(2-(4-甲基环己-3-烯-1-基)丙-2-醇);或木醇(TimberolTM)(1-(2,2,6-三甲基环己基)己-3-醇);2,4,7-三甲基辛-2,6-二烯-1-醇;和/或[1-甲基-2(5-甲基己-4-烯-2-基)环丙基]-甲醇;
-醛类和酮类,例如,大茴香醛(4-甲氧基苯甲醛);α戊基肉桂醛(2-亚苄基庚醛);GeorgywoodTM(1-(1,2,8,8-四甲基-1,2,3,4,5,6,7,8-八氢萘-2-基)乙酮);羟基香茅醛(7-羟基-3,7-二甲基辛醛);龙涎酮(Iso E)(1-(2,3,8,8-四甲基-1,2,3,4,5,6,7,8-八氢萘-2-基)乙酮);异甲基紫罗兰酮(异甲基)((E)-3-甲基-4-(2,6,6-三甲基环己-2-烯-1-基)丁-3-烯-2-酮);二氢茉莉酮酸甲酯(3-氧代-2-戊基环戊烷乙酸甲酯);3-(4-异丁基-2-甲基苯基)丙醛;麦芽酚;甲基柏木酮;甲基紫罗兰酮;马鞭草烯酮;和/或香草醛;
-醚类和缩醛类,例如,龙涎醚(3a,6,6,9a-四甲基-2,4,5,5a,7,8,9,9b-八氢-1H-苯并[e][1]苯并呋喃);香叶基甲基醚((2E)-1-甲氧基-3,7-二甲基辛-2,6-二烯);玫瑰醚(4-甲基-2-(2-甲基丙-1-烯-1-基)四氢-2H-吡喃);和/或香辣醚(2',2',3,7,7-五甲基螺[二环[4.1.0]庚烷-2,5'-[1,3]二噁烷]);
-酯类和内酯类,例如,乙酸苄酯、乙酸柏木酯(乙酸(1S,6R,8aR)-1,4,4,6-四甲基八氢-1H-5,8a-亚甲基甘菊环-6-基酯)、丙位癸内酯(6-戊基四氢-2H-吡喃-2-酮)、海佛麝香(丙酸2-(1-(3,3-二甲基环己基)乙氧基)-2-甲基丙酯);丙位十一内酯(5-庚基氧戊环-2-酮);和/或乙酸香根酯(乙酸(4,8-二甲基-2-丙-2-亚基-3,3a,4,5,6,8a-六氢-1H-甘菊环-6-基)酯);
-杂环化合物类,例如,异丁基喹啉(2-异丁基喹啉)。
可以与2,4,7-三甲基辛-6-烯-1-醇合并的已知香料成分的另外的实例包括6-甲氧基-2,6-二甲基庚-1-醛(甲氧基甜瓜醛);5,9-二甲基-4,8-癸二烯醛(香叶醛);八氢-8,8-二甲基萘-2-甲醛(环月桂醛);5-甲基-2-(1-甲基丁基)-5-丙基-1,3-二噁烷(Troenan);3,7,11-三甲基十二碳-1,6,10-三烯-3-醇(任选地作为异构体混合物)(橙花叔醇);2-甲基-4-苯基丁-2-醇(二甲基苯基乙基甲醇);1-(1-羟基乙基)-4-(1-甲基乙基)环己烷(任选地作为非对映异构体混合物)(新铃兰醇(Mugetanol));(4-甲基-3-戊烯基)环己烯甲醛(柑青醛);3-(对-(2-甲基丙基)苯基)-2-甲基丙醛(银醛);3-对-枯烯基-2-甲基丙醛(仙客来醛);以及顺式-四氢-2-异丁基-4-甲基吡喃-4-醇和反式-四氢-2-异丁基-4-甲基吡喃-4-醇的混合物。
已知香料成分的另外的实例可以包括水杨酸戊酯(2-羟基苯甲酸戊酯);橙花素((E)-2-((7-羟基-3,7-二甲基亚辛基)氨基)苯甲酸甲酯);水杨酸苄酯(2-羟基苯甲酸苄酯);水杨酸顺式-3-己烯酯(2-羟基苯甲酸(Z)-己-3-烯-1-基酯);香茅基氧基乙醛(2-((3,7-二甲基辛-6-烯-1-基)氧基)乙醛);环铃兰醛(3-(4-丙-2-基苯基)丙醛);水杨酸环己酯(2-羟基苯甲酸环己酯);环月桂醛(8,8-二甲基-1,2,3,4,5,6,7,8-八氢萘-2-甲醛);Cyclopentol(2-戊基环戊-1-醇);Cymal(4-(4-羟基-4-甲基戊基)环己-3-烯甲醛);道比卡尔((E)-4-((3aS,7aS)-六氢-1H-4,7-亚甲基茚-5(6H)-亚基)丁醛);超级铃兰醛((4E)-4,8-二甲基癸-4,9-二烯醛);花青醛(3-(3-异丙基苯基)丁醛);白花醇(2-异丁基-4-甲基四氢-2H-吡喃-4-醇);吉兰吡喃(2-丁基-4,6-二甲基-3,6-二氢-2H-吡喃);水杨酸己酯(2-羟基苯甲酸己酯);新洋茉莉醛(3-(1,3-苯并间二氧杂环戊烯-5-基)-2-甲基丙醛);新铃兰醛(4-(4-羟基-4-甲基戊基)环己-3-烯甲醛);美研醇(2,2-二甲基-3-(间甲苯基)丙-1-醇);五月铃兰醇((4-异丙基环己基)-甲醇);美乐馥(8,8-二甲基-2,3,4,5,6,7-六氢-1H-萘-2-甲醛);甜瓜醛(2,6-二甲基庚-5-烯醛);Muguesia(3-甲基-4-苯基丁-2-醇);铃兰醇(3-环己基-2,2-二甲基丙-1-醇);菩提花酯((E)-2-((3-(4-(叔丁基)苯基)-2-甲基丙-1-烯-1-基)氨基)苯甲酸甲酯);牡丹腈(2-亚环己基-2-苯基乙腈);苯乐戊醇(3-甲基-5-苯基戊-1-醇);(3-异丁基-1-甲基环己醇);高砂(Suzaral)(2-甲基-3-[4-(2-甲基丙基)苯基]丙醛);别罗勒烯醇(3,7-二甲基辛-4,6-二烯-3-醇);四氢芳樟醇(3,7-二甲基辛-3-醇);Acalea((2E)-2-[(4-甲基苯基)亚甲基]-庚醛);二氢异茉莉酮酸酯(2-己基-3-氧代环戊烷-1-甲酸甲酯);己基肉桂醛((E)-2-亚苄基辛醛);3-羟基-2-丁酮(3-羟基丁-2-酮);阿道克醛(2,6,10-三甲基十一碳-9-烯醛);(7-丙基-2H-1,5-苯并二氧杂环庚三烯-3(4H)-酮);((4aR,5R,7aS,9R)-八氢-2,2,5,8,8,9a-六甲基-4H-4a,9-亚甲基甘菊环并[5,6-d]-1,3-间二氧杂环戊烯);龙涎呋喃(Ambroxan)(3a,6,6,9a-四甲基-2,4,5,5a,7,8,9,9b-八氢-1H-苯并[e][1]苯并呋喃);白檀醇((E)-2-乙基-4-(2,2,3-三甲基环戊-3-烯-1-基)丁-2-烯-1-醇);海酮(Calone)(7-甲基-2H-苯并[b][1,4]二氧杂环庚三烯-3(4H)-酮);超级龙涎醚(3a,6,6,9a-四甲基-2,4,5,5a,7,8,9,9b-八氢-1H-苯并[e][1]苯并呋喃);肉桂醇((E)-3-苯基丙-2-烯-1-醇);柠檬醛((E)-3,7-二甲基辛-2,6-二烯醛);异丁酸三环癸烯酯(异丁酸(3aR,6S,7aS)-3a,4,5,6,7,7a-六氢-1H-4,7-亚甲基茚-6-基酯);乙酸三环癸烯酯(CyclacetTM)(乙酸(3aR,6S,7aS)-3a,4,5,6,7,7a-六氢-1H-4,7-亚甲基茚-6-基酯);丙酸三环癸烯酯(丙酸(3aR,6S,7aS)-3a,4,5,6,7,7a-六氢-1H-4,7-亚甲基茚-6-基酯);环十六内酯;环十六烯酮;环十五烷酮;丁位突厥酮((E)-1-(2,6,6-三甲基环己-3-烯-1-基)丁-2-烯-1-酮);超级爱林太尔(3-(1-乙氧基乙氧基)-3,7-二甲基辛-1,6-二烯);乙基香草醛(3-乙氧基-4-羟基苯甲醛);环十五烯酮((4Z)-环十五碳-4-烯-1-酮);清风醛(3-(4-乙基苯基)-2,2-二甲基丙醛);浆果乙酯(环己烷-1,4-二甲酸二乙酯);环十五烯内酯((E)-氧杂环十六碳-12-烯-2-酮);佳乐麝香(4,6,6,7,8,8-六甲基-1,3,4,6,7,8-六氢-环戊并[g]异色烯);(2-环十二烷基丙-1-醇);Myraldene(4-(4-甲基戊-3-烯-1-基)环己-3-烯甲醛);乙酸茉莉酯(乙酸3-戊基四氢-2H-吡喃-4-基酯);爪哇檀香((1-甲基-2-((1,2,2-三甲基二环[3.1.0]己-3-基)甲基)环丙基)甲醇);月桂醛(十二醛);梅弗兰醛(3-甲基-5-苯基戊醛);麝香烯酮((Z)-3-甲基环十五碳-5-烯酮);吐纳麝香(1-(3,5,5,6,8,8-六甲基-5,6,7,8-四氢萘-2-基)乙酮);仙酒酮(2-(2-(4-甲基环己-3-烯-1-基)丙基)环戊酮);赛木香醇(1-(2,2,6-三甲基环己基)己-3-醇);覆盆子酮(4-(4-羟基苯基)丁-2-酮);松乙醛(3-(6,6-二甲基二环[3.1.1]庚-2-烯-2-基)丙醛);罗曼麝香(乙酸(1-氧代丙氧基)-,1-(3,3-二甲基环己基)乙酯);圣檀醇((E)-2-乙基-4-(2,2,3-三甲基环戊-3-烯-1-基)丁-2-烯-1-醇);和/或环十六烯酮((Z)-环十六碳-5-烯酮)。
香料组合物不必限于上面列出的香料成分。可以使用香料中通常使用的其它香料成分,例如描述于“Perfume and Flavour Chemicals”,S.Arctander,Allured PublishingCorporation,1994,IL,USA中的任意那些成分,其通过引用并入本文,包括精油、植物提取物、净油、香树脂、得自天然产物的香味剂等。
在一个具体的实施方案中,2,4,7-三甲基辛-6-烯-1-醇可以与其它醇类组合,例如二氢月桂烯醇、芳樟醇、乙基芳樟醇和6-异丙基-2,4-二甲基-环己-3-烯-1-醇(气味描述:强烈的,青香,根似的,壤香,吡嗪-样)及其混合物。
在另一个实施方案中,2,4,7-三甲基辛-6-烯-1-醇可以与水杨酸酯类例如水杨酸戊酯、水杨酸苄酯、水杨酸顺式-3-己烯酯、水杨酸环己酯和水杨酸己酯和/或二氢茉莉酮酸甲酯(3-氧代-2-戊基环戊烷乙酸甲酯)及其混合物组合。
在另一个实施方案中,2,4,7-三甲基辛-6-烯-1-醇可以与2,4,7-三甲基辛-2,6-二烯-1-醇((E)-2,4,7-三甲基辛-2,6-二烯-1-醇和/或(Z)-2,4,7-三甲基辛-2,6-二烯-1-醇)、[1-甲基-2(5-甲基己-4-烯-2-基)环丙基]-甲醇、2-(2-甲基-2-(3-甲基丁-2-烯-1-基)环丙基)丙-1-醇、(2-(1-(2,2-二甲基环丙基)丙-2-基)-1-甲基环丙基)甲醇(气味描述:花香玫瑰香,檀香样)、2,4,7-三甲基辛-3,6-二烯-1-醇((E)-2,4,7-三甲基辛-3,6-二烯-1-醇和/或(Z)-2,4,7-三甲基辛-3,6-二烯-1-醇)和/或2,4,7-三甲基辛-7-烯-1-醇及其混合物组合。
在另一个实施方案中,2,4,7-三甲基辛-6-烯-1-醇可以与2,4,7-三甲基辛-2,6-二烯-1-醇((E)-2,4,7-三甲基辛-2,6-二烯-1-醇和/或(Z)-2,4,7-三甲基辛-2,6-二烯-1-醇)、2,4,7-三甲基辛-3,6-二烯-1-醇((E)-2,4,7-三甲基辛-3,6-二烯-1-醇和/或(Z)-2,4,7-三甲基辛-3,6-二烯-1-醇)、2,4,7-三甲基辛-7-烯-1-醇和/或6-异丙基-2,4-二甲基环己-3-烯-1-醇(例如rel.(1R,2S,6S)-6-异丙基-2,4-二甲基环己-3-烯-1-醇)及其混合物组合。
在另一个实施方案中,2,4,7-三甲基辛-6-烯-1-醇可以与2,4,7-三甲基辛-2,6-二烯-1-醇((E)-2,4,7-三甲基辛-2,6-二烯-1-醇和/或(Z)-2,4,7-三甲基辛-2,6-二烯-1-醇)、2,4,7-三甲基辛-3,6-二烯-1-醇((E)-2,4,7-三甲基辛-3,6-二烯-1-醇和/或(Z)-2,4,7-三甲基辛-3,6-二烯-1-醇)、2,4,7-三甲基辛-7-烯-1-醇和6-异丙基-2,4-二甲基环己-3-烯-1-醇(例如rel.(1R,2S,6S)-6-异丙基-2,4-二甲基环己-3-烯-1-醇)组合,例如其比例为约70:14:14:1:1至约95:2:2:0.5:0.5。
2,4,7-三甲基辛-6-烯-1-醇在香料组合物中可以以任意量存在,视香料制造者希望达到的特定效果而定。在本发明的一个具体的实施方案中,香料组合物可以包含用量占该组合物至多为30%重量例如0.2-20%(例如约0.5%、1%、1.5%、2%、3%、4%、5%、6%、7%、8%、9%、10%、11%、12%、13%、14%、15%、16%、17%、18%、19%重量)的2,4,7-三甲基辛-6-烯-1-醇。
如本文所用,“香料组合物”是指包含2,4,7三甲基辛-6-烯-1-醇和基质材料的任意组合物,所述基质材料例如为常用于与香料成分联用的稀释剂,例如邻苯二甲酸二乙酯(DEP)、一缩二丙二醇(DPG)、肉豆蔻酸异丙酯(IPM)、柠檬酸三乙酯(TEC)和醇(例如乙醇)。任选地,所述组合物可以包含抗氧化剂助剂。所述抗氧化剂可以选自TT(BASF)、Q(BASF)、生育酚(包括其异构体CAS 59-02-9;364-49-8;18920-62-2;121854-78-2)、2,6-双(1,1-二甲基乙基)-4-甲基苯酚(BHT,CAS 128-37-0)和相关酚类、氢醌类(CAS 121-31-9)。
2,4,7-三甲基辛-6-烯-1-醇可用于多种加香产品中,例如精细和功能性香料的任何领域,例如香精、浓香水(Eau de Parfum)、科隆香水(Eau de Cologne)、淡香水(Eau deToilette)、空气护理产品、家用用品、洗衣和织物护理产品、身体护理产品和化妆品。根据具体应用和其它香料成分的性质和数量的不同,这些化合物的用量可以变化很大。该比例典型地占所述用品的0.001-30(包括,例如5、10、15、20、25)重量百分比。在一个实施方案中,本发明的化合物可以以0.001-0.3重量百分比的量用于香料产品例如织物柔软剂中。在另一个实施方案中,本发明的化合物可以0.1-30重量百分比(例如高达约20重量百分比)、更优选0.5-15重量百分比的量用于精细香料中。然而,这些数值仅作为例子给出,因为经验丰富的调香师也可以实现效果,或者可以产生具有较低(例如占加香产品0.0001重量%或以下)或更高浓度(例如占加香产品35、40、45重量%乃至更高)的新的谐香。
2,4,7-三甲基辛-6-烯-1-醇可以简单地通过直接混合2,4,7-三甲基辛-6-烯-1-醇或包含2,4,7-三甲基辛-6-烯-1-醇的香料组合物与消费品基质而用于消费品基质中,或者其可以在早期步骤中用俘获材料例如聚合物、胶囊、微胶囊和纳米胶囊、脂质体、成膜剂、吸收剂例如碳或沸石、环状寡糖类及其混合物俘获,或者其可以化学键合到适于在施加外部刺激例如光、酶等的情况下释放香味分子的底物上,且然后与消费品基质混合。
因此,在另一个方面提供了一种制造加香产品的方法,该方法包括掺入作为香料成分的2,4,7-三甲基辛-6-烯-1-醇,通过直接混合该化合物与消费品基质,或通过混合包含2,4,7-三甲基辛-6-烯-1-醇的香料组合物、然后使用常规技术和方法将其与消费品基质混合来进行。
本发明还提供了一种加香产品,其包含:
a)作为香料成分的至少2,4,7-三甲基辛-6-烯-1-醇;和
b)消费品基质。
在另一个实施方案中,提供了加香产品,其包含:
a)作为香料成分的至少2,4,7-三甲基辛-6-烯-1-醇;
b)至少另一种香料成分;和
c)消费品基质。
如本文所用,“消费品基质”是指用作消费品以实现特定作用(例如清洁、软化和护理等)的组合物。这类产品的实例包括:精细香料,例如香料、浓香水、科隆香水和淡香水;织物护理产品、家用产品和个人护理产品,例如洗衣护理洗涤剂、漂洗调理剂、个人清洁组合物、洗碗机用洗涤剂、表面清洁剂;洗衣产品,例柔软剂、漂白剂、洗涤剂;身体护理产品,例如香波、沐浴露;空气护理产品和化妆品,例如除臭剂、雪花膏。这个产品清单是作为示例给出,但不视为任何方式进行限制。
现在参考以下非限制性实施例进一步描述本发明。这些实施例仅用于示例目的,并且应当理解,本领域技术人员可以进行变化和修改。
实施例1:2,4,7-三甲基辛-6-烯-1-醇的合成
方法A
将2,4,7-三甲基辛-2,6-二烯-1-醇(10.1g,60.0mmol)和锂颗粒(0.46g,66.0mmol)的混合物在80℃加热16小时。然后将反应混合物冷却至室温,用THF(20.0ml)稀释,用冷水(50.0ml)淬灭。将有机层分离,并将水层用乙酸乙酯(2×30mL)萃取。将合并的有机层用盐水洗涤一次,然后用MgSO4干燥。将溶剂在旋转蒸发器除去。将粗产物通过柱色谱法(异己烷/乙酸乙酯,50:1)和随后的库格尔若蒸馏纯化,得到4.00g(40%)的2,4,7-三甲基辛-6-烯-1-醇,为无色有香气的液体。B.p.94℃/0.10mbar。两种异构体的比例是45:55。
GC/MS(EI),170(M+,3),151(1),137(2),123(2),112(20),96(42),83(75),69(62),55(100),41(59)。1H-NMR(300MHz,CDCl3):δ=5.12(t,J=7.5Hz,1H,Me2C=CHCH2),3.54-3.35(m,2H,CH2OH),1.99-1.74(m,2H,=CHCH2),1.74-1.66(m,1H,=CHCH2CH),1.70(s,3H,MeCH3C=CH),1.59(s,3H,MeCH3C=CH),1.56-1.49(m,1H,CHCH2OH),1.38-1.09(m,2H,CHCH2CH),0.94-0.83(m,6H,2CHCH3)ppm。
13C-NMR(75MHz,CDCl3):δ=132.1,132.0(2s,Me2C=CH),123.2,123.0(2d,Me2C=CH),69.0,68.3(2t,CH2OH),40.6,40.3(2t,CHCH2CH),36.3,35.0(2t,Me2C=CHCH2),33.3,33.2(2d,CHCH2OH),31.0,30.8(2d,Me2C=CHCH2CH),26.0(q,MeCH3C=CH),20.3,19.2(q,4-Me),17.8(q,MeCH3C=CH),17.3,16.3(q,2-Me)ppm。
气味描述:清晰的主柑橘香质与清晰的青香圆柚/大黄内涵。
方法B
1)在氩气氛中,向安装有磁力搅拌器和气体入口的100mL三颈烧瓶中加入林德拉(Lindlar)Pd(Pd/CaCO3,铅中毒的,0.40g)、(E)-2,4,7-三甲基辛-2,6-二烯醛(9.00g,54.1mmol)和乙酸乙酯(40.0ml)。在氢气气氛中将反应混合物在室温搅拌过夜。将反应混合物通过硅胶小垫过滤,并用MTBE(2×30mL)洗涤硅胶。将合并的滤液通过旋转蒸发器浓缩。对粗产物进行库格尔若蒸馏,得到2,4,7-三甲基辛-6-烯醛(8.0g,47.5mmol,88%收率;沸点:80℃/0.15mbar),为无色液体。
1H NMR(300MHz,CDCl3):δ=9.59,9.57(2d,1H,J=2.1Hz,CHO),5.11(t,J=7.8Hz,1H,Me2C=CHCH2),2.51-2.35(m,1H,CHCHO),2.03-1.77(m,2H,=CHCH2),1.70(s,3H,MeCH3C=CH),1.59(s,3H,MeCH3C=CH),1.56-1.14(m,3H,=CHCH2CHCH2),1.09,1.07(2d,J=6.5Hz,3H,2-Me),0.89,0.87(2d,J=6.0Hz,3H,4-Me)。
13C NMR(CDCl3):δ=205.2(d,CHO),132.5(s,Me2C=CH),122.5,122.6(2d,Me2C=CH),44.3,44.2(2d,CHCHO),37.8,37.2(2t,CHCH2CH),35.6,35.1(2t,=CHCH2),31.2,31.1(2d,Me2C=CHCH2CH),25.8(q,MeCH3C=CH),19.8,19.2(2q,4-Me),17.8(q,MeCH3C=CH),14.1,13.3(2q,2-Me)。
气味描述(2,4,7-三甲基辛-6-烯醛):柠檬醛柠檬草马鞭草,甜瓜香。
2)向安装有磁力搅拌器、温度计和气体入口的100mL三颈烧瓶中加入2,4,7-三甲基辛-6-烯醛(8.00g,47.5mmol)和甲醇(50.0ml)。将该混合物冷却至0℃。在0℃下将NaBH4分小部分加入,历时20分钟,然后将反应混合物温热至室温并搅拌30分钟。将甲醇用旋转蒸发器除去。将残余物用水(60.0ml)稀释并用乙酸乙酯(3×30ml)萃取。将合并的有机层用盐水(10.0mL)洗涤。将有机层用MgSO4干燥,过滤,并用旋转蒸发器浓缩。将粗产物通过柱色谱法(异己烷:乙酸乙酯=10:1)和随后的库格尔若蒸馏(94℃/0.10mbar)纯化,得到2,4,7-三甲基辛-6-烯-1-醇(6.00g,35.2mmol,74.1%收率),为无色液体。分析数据与从方法A获得的那些产品相同。
实施例2:柚子荔枝(pomelo lychee)谐香
1)4,7,7-三甲基-6-硫杂二环[3.2.1]辛烷
2)(1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊并[g]-2-苯并吡喃
3)1-甲基-2-[(1,2,2-三甲基二环[3.1.0]己-3-基)甲基]环丙基]甲醇
在上述谐香中,150份的DPG被等量的a)2,4,7-三甲基辛-6-烯-1-醇;或b)2,4,7-三甲基辛-2,6-二烯-1-醇替代。
添加15%重量的2,4,7-三甲基辛-6-烯-1-醇增强了柚子荔枝香型透发的柑橘香韵,并强化了所述香型的一般特征。相反,添加15%重量的2,4,7-三甲基辛-2,6-二烯-1-醇给柑橘香型带来更多的花香、玫瑰香韵。
实施例3:现代馥奇香型
4)2-(2,2,7,7-四甲基三环[6.2.1.0](1,6)十一碳-4/5-烯-5-基)丙-1-醇
5)1-甲基-4-(4-甲基戊-3-烯-1-基)环己-3-烯甲醛
气味描述(上述香型):新鲜和清晰的现代透明的馥奇香型
在上述香型中
a)100份DPG被100份2,4,7-三甲基辛-6-烯-1-醇替代;
b)200份DPG被200份2,4,7-三甲基辛-6-烯-1-醇替代;
c)100份DPG被100份2,4,7-三甲基辛-2,6-二烯-1-醇替代;或
d)200份DPG被200份2,4,7-三甲基辛-2,6-二烯-1-醇替代。
在总体馥奇香型特征方面,添加10%重量的2,4,7-三甲基辛-6-烯-1-醇带来良好可感知的新鲜度,而添加10%重量的2,4,7-三甲基辛-2,6-二烯-1-醇将气味特征转化为花香玫瑰香,这扭曲了初始气味特征。
在总体馥奇香型特征方面,添加20%重量的2,4,7-三甲基辛-6-烯-1-醇带来良好可感知的新鲜度,而添加20%重量的2,4,7-三甲基辛-2,6-二烯-1-醇使香味变单调,并使特征转化为花香玫瑰香,失去了新鲜和清洁的初始馥奇香型男性特征。
实施例4:香波中的“盛放”性能
来自实施例2的香料谐香和其中150份DPG被等量的a)2,4,7-三甲基辛-6-烯-1-醇或b)2,4,7-三甲基辛-2,6-二烯-1-醇替代的香料谐香被添加到@0.5%重量的香波基质中。
向密封在一个不通风的标准测试隔离间中的包含10升温水(约30℃-32℃)的容器中,在不混合的情况下加入4ml香波。使该容器位于距离隔离间门1.3米处。20分钟后,位于测试隔离间门上的一扇小窗口被打开,由一组经过训练的调香师评价“盛放”性能。而对于香波(a),注意到强烈的新鲜的圆柚“盛放”,而对于香波(b),仅注意到弱的、几乎没有的新鲜度。对于包含实施例2香料谐香的香波,仅注意到弱的、几乎没有的新鲜度(即原始香料谐香,其中DPG未被替代)。
实施例5:香波中单独的2,4,7-三甲基辛-6-烯-1-醇的“盛放”性能
向密封在一个不通风的标准测试隔离间中包含10升温水(约30℃-32℃)的容器中,在不混合的情况下加入4ml包含0.2%2,4,7-三甲基辛-6-烯-1-醇/2,4,7-三甲基辛-2,6-二烯-1-醇的香波。使该容器位于距离隔离间门1.3米处。20分钟后,位于测试隔离间门上一扇小窗口被打开,由一组经过训练的调香师评价“盛放”性能。要求小组成员从0至5的强度等级评价“盛放”强度(0:未感觉到1:极弱2:弱3:中等4:强5:极强)。结果如下所示。
正如从上述结果中可以观察到的,本发明的化合物(2,4,7-三甲基辛-6-烯-1-醇)具有明显更高的盛放。
Claims (12)
1.2,4,7-三甲基辛-6-烯-1-醇。
2.香料组合物或加香产品,包含2,4,7-三甲基辛-6-烯-1-醇。
3.权利要求2的香料组合物或加香产品,还包含另一种香料成分。
4.权利要求3的组合物或产品,其中所述另一种香料成分是香味醇。
5.权利要求4的组合物或产品,其中所述香味醇选自二氢月桂烯醇、芳樟醇、乙基芳樟醇及其混合物。
6.权利要求4的组合物或产品,其中所述香味醇选自2,4,7-三甲基辛-2,6-二烯-1-醇、[1-甲基-2(5-甲基己-4-烯-2-基)环丙基]-甲醇、2-(2-甲基-2-(3-甲基丁-2-烯-1-基)环丙基)丙-1-醇、和(2-(1-(2,2-二甲基环丙基)丙-2-基)-1-甲基环丙基)甲醇及其混合物。
7.权利要求3、4、5或6之一的产品,其中该产品选自精细香料、织物护理产品、家用产品、美容和个人护理产品和空气护理产品。
8.权利要求3、4、5或6之一的香料组合物,包含占该香料组合物至多30%重量的2,4,7-三甲基辛-6-烯-1-醇。
9.2,4,7-三甲基辛-6-烯-1-醇作为香料的用途。
10.将新鲜度和清洁度赋予加香产品的方法,该方法包括将2,4,7-三甲基辛-6-烯-1-醇掺入所述加香产品的步骤。
11.权利要求10的方法,其中掺入占所述加香产品至多30%重量的2,4,7-三甲基辛-6-烯-1-醇。
12.权利要求10的方法,其中掺入占所述加香产品至少0.001%重量的2,4,7-三甲基辛-6-烯-1-醇。
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