CN1520801B - 固相苯并吡喃组合物,其制备方法和其感官用途 - Google Patents
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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
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
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- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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Abstract
公开固相苯并吡喃组合物,其主要包含1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃和至少一种其他苯并吡喃化合物。此新的组合物用向如香料组合物,加香制品包括肥皂,洗涤剂,织物软化剂组合物,织物软化剂制品,芳香蜡烛,化妆品,美发用品,加香聚合物和古龙香水的消费性材料中增加,增强和/或赋于香味。还描述制备固相苯并吡喃组合物的方法。
Description
技术领域
本发明涉及一种新的固相芳香产品,其主要由1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(cyclopenta)(G)-2-苯并吡喃组成并还含有另外的苯并吡喃物质。此芳香产品可以用于香料组合物和消费品。
背景技术
液相苯并吡喃组合物含有70-81%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃,其具有如下结构(已知为“GALAXOLIDE100”,纽约的International Flavors & Fragrances Inc.的注册商标):
其溶液,例如,50%邻苯二甲酸二乙酯(已知为“GALAXOLIDE 50”,纽约的International Flavors & Fragrances Inc.的注册商标)溶液是现在用于商业上的最大宗的芳香化合物之一。已知此物质赋于包括香精和香水的可消耗材料持久而大量的麝香气味,该消耗材料用于功能性产物如肥皂和洗涤剂。生产的液相苯并吡喃组合物称为“GALAXOLIDE”,含有70-75%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃,其具有如下结构:
其结构含有四种非对映异构体,其包括4R-顺式和反式异构体以及4S-顺式和反式异构体。Frater等的美国专利5,635,471(其说明书在此一并作为参考材料)揭示7R和7S非对映异构体的混合物具有更强的麝香香味。Frater等在Helvetica Chimica Acta.82卷,1999,pp.1656-1665揭示最强的异构体为(-)-(4S,7R)异构体。GALAXOLIDE已工业化生产并且可以按例如美国专利3,360,530的技术所揭示的方法,(该专利说明书一并作为参考资料)生产,其由可在冷温,如0℃下固化的粘稠液体组成。本领域的熟练技术人员完全知道,
这种材料不管是高度浓缩的粘性液体还是稀释于溶剂如邻苯二甲酸二乙酯,苯甲酸苄酯,肉豆蔻酸异丙酯和/或二丙二醇都难以操作。典型的,其被稀释所以主要的异构体组成50%重量的溶液,该异构体结构如下所示:
据报道,目前生产的,和现有技术公开的GALAXOLIDE对环境有一些不利影响。因此,存在提供一种形式的GALAXOLIDE的需求,其可以以比本领域至今所知的显著低的剂量用于香水,古龙香水和加香制品,从而保护环境。
已有技术公开的固体形式的GALAXOLIDE,包括
(a)Sprecker,美国专利4,650,603,其揭示材料包括在参考材料中;
(b)Frater等美国专利5,635,471。
但是,在现有技术公开的GALAXOLIDE的固态形式不包含必需的和希望的高百分比,85-95%重量的具有如下的结构的异构体:
高百分比使得本发明的固相苯并吡喃组合物具有不明显的,意想不到的和优异的关于香味品质,香强度和直接性的感官性能。
发明内容
我们已经发现苯并吡喃异构体混合物的一种新形式,其为颗粒,白色粉末物质形式,具有令人惊奇的容易操作性。因此,本发明的新组合物很容易配制成芳香制剂。相比于现在使用的GALAXOLIDE形式,本发明的新的固相苯并吡喃组合物需要显著少的量就能提供用更多量的现在使用的现有技术的苯并吡喃组合物才能提供的相同感官的麝香。相应的,作为本发明的组合物的商业应用的结果,用本发明的固相苯并吡喃组合物取代现有技术的苯并吡喃组合物,将显著降低苯并吡喃散发环境中。
更具体的是,我们的发明涉及固相苯并吡喃组合物,其主要由约85-95%重量的具有如下结构的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃组成,并还含有至少一种选自下列的的苯并吡喃:
(a)1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃,其具有如下结构:
(b)1,3,4,6,7,8-六氢-8-乙基-4,6,6,8-四甲基环戊二烯并(G)-2-苯并吡喃,其具有如下结构:
(c)1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃,其具有如下结构:
(d)1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃,其具有如下结构:
(e)1,2,4,7,8,9-六氢-1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃,其具有如下结构:
(f)1,3,4,7,8,9-六氢-4,7,7,8,9,9-六甲基环戊二烯并(H)-2-苯并吡喃,其具有如下结构:
其中所述的固相苯并吡喃组合物的纯度大于98%重量。
较佳的,我们的发明涉及固相苯并吡喃组合物,其由下列化合物组成:
约85%到95%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃;
约2.5%到5.5%重量的1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃;
约2.5%到5.5%重量的1,3,4,6,7,8-六氢-8-乙基-4,6,6,8-四甲基环戊二烯并(G)-2-苯并吡喃;
约0.2%到0.5%重量的1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃;
约0.2%到0.5%重量的1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃;
约2.2%到4.0%重量的1,2,4,7,8,9-六氢1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃;和
约0.7%到1.3%重量的1,3,4,7,8,9-六氢-4,7,7,8,9,9-六甲基环戊二烯并(H)-2-苯并吡喃。
本发明的固相苯并吡喃组合物用于在或向消费性材料增加、增强和/或赋于香味,该消费性材料包括,但不是限定,香料组合物,加香制品包括肥皂,洗涤剂,织物软化剂组合物,织物软化剂制品。
本发明的固相苯并吡喃组合物根据两种可选择的方法生产。
第一种方法包括步骤:
i.混合液相苯并吡喃组合物和合适的溶剂,从而形成液相苯并吡喃-溶剂混合物,该苯并吡喃组合物主要由下列组合物组成:约70%-81%重量的具有如下结构的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃:
约4%-10%重量的化合物(a)和(b)的混合物,所述化合物有(a)为具有如下结构的1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃,
和所述化合物(b)为具有如下结构的1,3,4,6,7,8-六氢-8-乙基-4,6,6,8-四甲基环戊二烯并(G)-2-苯并吡喃:
约1%-4%重量的化合物(a)和(b)的混合物,所述化合物(a)为其具有如下结构的1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃:
和所述化合物(b)为具有如下结构的1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃:
约2%-5%重量的具有如下结构的1,2,4,7,8,9-六氢-1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃:
约2%-5%重量的具有如下结构的1,3,4,7,8,9-六氢-4,7,7,8,9,9-六甲基环戊二烯基[H]-2-苯并吡喃;
该合适的溶剂为一种或多种C4-C10烃类,例如,甲苯,正辛烷和正己烷,低级链烷醇,例如,乙醇,正丙醇和异丙醇,低级二烷基酮,例如,丙酮和甲乙酮,低级链烷酸低级烷基酯,例如,乙酸乙酯,二低级烷基醚,例如,二乙醚,和低级环脂醚,例如四氢呋喃,所述的溶剂的重量百分比以所述的液相苯并吡喃组合物重量计约为20%-80%重量;
ii.调节所述的液相苯并吡喃-溶剂混合物的温度至约-40-0℃的温度范围保持一段固相产物沉淀的时间,例如3小时,从而形成固相苯并吡喃组合物和液相苯并吡喃-溶剂混合物的混合物;然后
iii.例如用过滤或离心方法从所述液相苯并吡喃-溶剂混合物中分离所述固相苯并吡喃组合物。
第二种方法包括如下步骤:
i.混合液相苯并吡喃组合物和水性溶剂,从而形成液相苯并吡喃-水性溶剂混合物,该苯并吡喃组合物主要由下列化合物组成:约70%-81%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃;约4%-10%重量化合物(a)1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃,和(b)1,3,4,6,7,8-六氢-8-乙基-4,6,6,8-四甲基环戊二烯并(G)-2-苯并吡喃的混合物;约1%-4%重量化合物(a)1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃:和(b)1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃的混合物;约2%-5%重量的1,2,4,7,8,9-六氢1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃;约2%-5%重量的1,3,4,7,8,9-六氢-4,7,7,8,9,9-六甲基环戊二烯并(H)-2-苯并吡喃;该水性溶剂含有约2%-20%重量的水和约80%-98%重量的有机溶剂组分,该有机溶剂组分为至少一种低级链烷醇,例如,乙醇,异丙醇和/或正丙醇,低级二烷基酮,例如,丙酮,低级链烷酸低级烷基酯,例如,乙酸乙酯,二乙醚和/或四氢呋喃,所述的水性溶剂的重量百分比以所述液相苯并吡喃组合物的重量计约为20%-80%重量;
ii.调节所述的液相苯并吡喃-水性溶剂混合物的温度至约-10-25℃的温度范围保持一段固相产物沉淀的时间,例如3小时,从而形成固相苯并吡喃组合物和液相苯并吡喃-水性溶剂混合物的混合物;
iii.例如用过滤或离心法从所述液相苯并吡喃-水性溶剂混合物中分离所述固相苯并吡喃组合物。
辅助香水组分包括,例如,醛,腈,酯,环酯,酮,除了本发明的固相苯并吡喃化合物之外的醚,天然香精油,合成香精油,萜烯硫醇和烃,可以将本发明的固相苯并吡喃组合物和一种或多种辅助香水组分混合,这样各组分的混合气味产生令人愉快和希望的芳香,特别在麝香和“动物般”芳香区。本发明的固相苯并吡喃,即使在相对的低浓度,例如,0.005%也会把芳香的,麝香“动物般”香味赋于高级香水,肥皂,阴离子,阳离子,无离子和两性离子洗涤剂,织物软化剂组合物,织物软化剂制品,如Procter & Gamble Co.ofCincinnati,Ohio,的注册商标BOUNCE,室内增味剂和除味剂,防晒剂,粉末如滑石,美发用品和织物调理剂。因此,本发明固相苯并吡喃组合物可单独使用或和一种或多种其他辅助香水成分混合使用,所述组合物可以用于高级香水或加香制品或加香聚合物,该组合物的浓度可以变化,以高级香水或加香制品的重量计,约为0.005%到50%重量,较佳约为0.01-20%重量,更佳约为0.1-10%重量。在本发明的其他实例中,本发明的新化合物加入量以加香制品重量计约为0.005%到5%重量,或者约为0.005%到50%重量,该加香制品例如是美国专利6,090,774具体说明的高密度聚乙烯,该专利的揭示内容一起作为参考资料。
另外,本发明的香料组合物或芳香组合物可以含有本发明的固相苯并吡喃组合物的媒介物或载体,其可单独使用或者还可以和一种或多种辅助香水组分一起使用。媒介物可以为液体如无毒醇类,例如,乙醇,无毒二醇,例如二丙二醇,或类似物。载体可以为吸收性固体如树脂,包括阿拉伯树胶,瓜耳树胶或鹿角菜胶或使用例如,微胶囊聚合物基质如聚氨酯基质或脲-甲醛基质或改性淀粉基质使组成物微胶囊化的组分或使固相苯并吡喃组合物颗粒微胶囊化的组分如用凝聚法的凝胶。
附图说明
图1:按下面所述的实例1制备的固相苯并吡喃组合物的GLC图(条件:50m×0.32mm×0.5μ甲基硅氧烷柱,程序升温:以每分钟2℃的升温速度从75℃升到225℃)
图1A:图1中所示“FIG.1A”的部分的放大图,图形的详细描述。
参照图1,由参考数字10所示的峰是1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃非对映异构体混合物的峰,参考数字11表示的峰是正己烷反应溶剂。
参照图1A,由参考数字10所示的峰是1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃非对映异构体混合物的峰。
由参考数字12A和12b所示的峰是以下非对映异构体的混合物的峰:1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃和1,3,4,6,7,8-六氢-8-乙基-4,6,6,8-四甲基环戊二烯并(G)-2-苯并吡喃。
由参考数字13A和13b所示的峰是以下非对映异构体的混合物的峰:1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃和1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃。
由参考数字14A和14b所示的峰是以下非对映异构体的混合物的峰:1,2,4,7,8,9-六氢-1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃。
由参考数字15A和15b所示的峰是以下非对映异构体的混合物的峰:1,3,4,7,8,9-六氢-4,7,7,8,9,9-六甲基环戊二烯并(H)-2-苯并吡喃。
下列的实施例是说明性的,本发明仅受所附的权利要求书的限制。除非另有说明,本文中所有的份数和百分比都以重量计。
具体实施方式
实施例I
固相苯并吡喃组合物的制备
750克的液相苯并吡喃混合物按美国专利3,360,530(所述专利的说明书一并作为参考资料)的实施例15制备,所述混合物含有78%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃和500克己烷,将混合物所含的两种组分混合然后搅拌冷却至-30℃。连续搅拌1小时,此时固相颗粒正好开始沉淀。此混合物再搅拌3小时同时缓慢升高苯并吡喃-溶剂混合物温度至0℃,在0℃过滤白色固体,最后得到240克含有如下重量百分比物质的混合物:
(a)88.6%重量1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃;
(b)2.75%重量1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃;
(c)2.75%重量1,3,4,6,7,8-六氢-8-乙基-4,6,8,8-四甲基环戊二烯并
(G)-2苯并吡喃;
(d)0.5%重量的1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃和1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃;
(e)4.0%重量1,2,4,7,8,9-六氢-1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃,
(f)1.3%重量1,3,4,7,8,9-六氢4,7,7,8,9,9-六甲基环戊二烯并(H)-2-苯并吡喃。
实施例II
固相苯并吡喃组合物的制备
200克液相苯并吡喃混合物按按美国专利3,360,530,的实施例15制备,所述混合物含有78%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃和100克10%水性乙醇,将混合物的两种组分混合然后搅拌冷却至+5℃。连续搅拌2小时,此时固相颗粒开始沉积。此混合物再在5℃下搅
拌3小时,在5℃下过滤得42克白色晶体物质。所得到的组合物是固相
苯并吡喃混合物,所述混合物含有91%重量的熔点为31℃的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃。
实施例III
麝香香料组合物
制备下列麝香香料组合物:
组分 | 实施例III (A)- 重量份 | 实施例III(B)- 重量份 |
葵子麝香 | 200 | 200 |
麝香酮 | 200 | 200 |
β-紫罗兰酮 | 50 | 50 |
乙酸岩兰草酯 | 50 | 50 |
檀香木油,E.I. | 100 | 100 |
β-二氢大马酮 | 80 | 80 |
实施例I中的固相苯并吡喃组合物 | 10 | 0 |
实施例II中的固相苯并吡喃组合物 | 0 | 10 |
实施例I和II的固相苯并吡喃组合物分别赋于此麝香配制物天然,芳香的,麝香,玫瑰香味和此香味具有动物型头香并且很强烈和直接,每个组合物和配制物能很好混合,不需要使用任何溶剂。
实施例IV
制备肥皂组合物
100克肥皂片和各种表I中的香料组合物1克混合直到获得基本上均匀的组合物。此香皂具有优良的下列表I中的香味。
香料组分 | 香味 |
实施例I中的固相苯并吡喃组合物 | 麝香,动物型香味 |
实施例II中的固相苯并吡喃组合物 | 麝香,动物型香味 |
实施例III(A)的香料组合物 | 带有芳香的麝香味,玫瑰底香和动物型头香的麝香香味 |
实施例III(B)的香料组合物 | 带有芳香的麝香味,玫瑰底香和动物型头香性的麝香香味 |
实施例V
古龙和手帕香水的制备
上面实施例IV的表I中的各种香料物质按在80%,85%,90%和95%水性
乙醇中浓度2.5%,3.0%,3.5%和4.0%加入古龙香水中。按在85%,90%和95%水性乙醇中浓度15%,20%,25%和30%加入手帕香水中。将实施例IV的表I中特殊芳香在所列的各含量下赋于各种古龙香水配制物和各种手帕香水配制物。
Claims (3)
1.一种固相苯并吡喃组合物,所述组合物由下列化合物组成:
85%到95%重量的1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊二烯并(G)-2-苯并吡喃;
2.5%到5.5%重量的1,3,4,6,7,8-六氢-6-乙基-4,6,8,8-四甲基环戊二烯并(G)-2-苯并吡喃;
2.5%到5.5%重量的1,3,4,6,7,8-六氢-8-乙基-4,6,6,8-四甲基环戊二烯并(G)-2-苯并吡喃;
0.2%到0.5%重量的1,3,4,7,8,9-六氢-7-乙基-4,7,9,9-四甲基环戊二烯并(H)-2-苯并吡喃;
0.2%到0.5%重量的1,3,4,7,8,9-六氢-9-乙基-4,7,7,9-四甲基环戊二烯并(H)-2-苯并吡喃;
2.2%到4.0%重量的1,2,4,7,8,9-六氢-1,7,7,8,9,9-六甲基环戊二烯并(F)-2-苯并吡喃;和
0.7%到1.3%重量的1,3,4,7,8,9-六氢-4,7,7,8,9,9-六甲基环戊二烯并(H)-2-苯并吡喃,其中,所述组合物的总量以100重量%为基准。
2.一种在或向消费性材料增加、增强和/或赋于芳味的方法,所述消费性材料选自加香制品,香料组成物,古龙香水和加香聚合物,所述方法包括混合所述消费性材料和权利要求1所述的赋于增加或增强香味的量和浓度的组合物的步骤。
3.权利要求1的组合物,其特征在于在1绝对大气压下所述组合物的熔点为34℃。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3360530A (en) * | 1962-07-23 | 1967-12-26 | Int Flavors & Fragrances Inc | Tricyclic isochromans and processes for making same |
US4301076A (en) * | 1979-08-03 | 1981-11-17 | International Flavors & Fragrances Inc. | Isochroman musk compounds and organoleptic uses thereof |
US4308412A (en) * | 1979-08-03 | 1981-12-29 | International Flavors & Fragrances Inc. | Indane alkanols and tricyclic isochromans and organoleptic uses thereof |
US4650603A (en) * | 1985-07-26 | 1987-03-17 | International Flavors & Fragrances Inc. | Single phase liquid mixture of tricyclic isochroman derivative mixture and acetyl tetrahydronaphthalene derivative mixture |
US5376630A (en) * | 1994-03-17 | 1994-12-27 | International Flavors & Fragrances Inc. | Methyl, substituted propyl-substituted pentamethyl indane derivatives, processes for producing same and perfumery uses thereof |
EP1061125A2 (en) * | 1999-06-18 | 2000-12-20 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Composition containing di(2-ethylhexyl) adipate and tricyclic isochroman compounds and use thereof in enzyme-active detergents and fabric softeners |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4265818A (en) | 1979-08-03 | 1981-05-05 | International Flavors & Fragrances Inc. | Indane alkanols and tricyclic isochromans and organoleptic uses thereof |
SG69962A1 (en) | 1994-03-10 | 2000-01-25 | Givaudan Roure Int | Indan |
US5502031A (en) * | 1994-03-17 | 1996-03-26 | International Flavors & Fragrances Inc. | Methyl substituted propyl-substituted pentamethyl indane derivatives processes for producing same and perfumery uses thereof |
US5494892A (en) * | 1994-03-17 | 1996-02-27 | International Flavors & Fragrances Inc. | Methyl substituted propyl-substituted pentamethyl indane derivatives processes for producing same and perfumery uses thereof |
US6090774A (en) | 1998-10-13 | 2000-07-18 | International Flavors & Fragrances Inc. | Single phase liquid mixture of benzophenone and mixture of at least two other normally solid perfumery substances and perfumery uses thereof |
-
2003
- 2003-02-10 US US10/361,748 patent/US7407928B2/en active Active
-
2004
- 2004-02-09 EP EP04100466A patent/EP1447077B1/en not_active Expired - Lifetime
- 2004-02-09 ES ES04100466T patent/ES2325258T3/es not_active Expired - Lifetime
- 2004-02-09 DE DE602004020697T patent/DE602004020697D1/de not_active Expired - Lifetime
- 2004-02-10 CN CN200410005305.8A patent/CN1520801B/zh not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3360530A (en) * | 1962-07-23 | 1967-12-26 | Int Flavors & Fragrances Inc | Tricyclic isochromans and processes for making same |
US4301076A (en) * | 1979-08-03 | 1981-11-17 | International Flavors & Fragrances Inc. | Isochroman musk compounds and organoleptic uses thereof |
US4308412A (en) * | 1979-08-03 | 1981-12-29 | International Flavors & Fragrances Inc. | Indane alkanols and tricyclic isochromans and organoleptic uses thereof |
US4650603A (en) * | 1985-07-26 | 1987-03-17 | International Flavors & Fragrances Inc. | Single phase liquid mixture of tricyclic isochroman derivative mixture and acetyl tetrahydronaphthalene derivative mixture |
US5376630A (en) * | 1994-03-17 | 1994-12-27 | International Flavors & Fragrances Inc. | Methyl, substituted propyl-substituted pentamethyl indane derivatives, processes for producing same and perfumery uses thereof |
EP1061125A2 (en) * | 1999-06-18 | 2000-12-20 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Composition containing di(2-ethylhexyl) adipate and tricyclic isochroman compounds and use thereof in enzyme-active detergents and fabric softeners |
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ES2325258T3 (es) | 2009-08-31 |
CN1520801A (zh) | 2004-08-18 |
US20040157764A1 (en) | 2004-08-12 |
EP1447077A1 (en) | 2004-08-18 |
EP1447077B1 (en) | 2009-04-22 |
DE602004020697D1 (de) | 2009-06-04 |
US7407928B2 (en) | 2008-08-05 |
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