CN1240660C - 聚烷基二环衍生物 - Google Patents
聚烷基二环衍生物 Download PDFInfo
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Abstract
公开了如下式的化合物见右式(I),其中A是见右式(II);B是见右式(III)或A和B合起来形成环结构见右式(IV);和X,R′和R分别是H和CH3和m=0或1。和该化合物用于制造香料和加香剂,如香水、古龙水和个人护理产品等物品中的用途。
Description
发明领域
本发明涉及新化学物质和该化学物质作为芳香化学物质的掺入和用途。
发明背景
美国专利号5,227,367;5,733,866;和5,665,698(在此引入以供参考)在其内容中公开了适合用于芳香化学制剂的多环化学制剂。本领域技术人员理解分子中化学结构的差异是如何能导致一个分子的气味、香调和特征显著不同的。这些变化和不断增长的对新香料开发中发现和使用新化学物质的需要使得香料制造者使用新的化合物创造新香料。
发明简述
本发明提供了新颖化学物质及该化学物质用于增强香水、花露水、古龙水、个人护理产品等香味的用途。另外,本发明还针对该新颖化学物质增强香水、花露水、古龙水、个人护理产品等香味的用途。
更特别的,本发明针对新颖化合物,由下式I代表:
本发明的其他实施例是一种增强香味的方法,通过掺入嗅觉可按受量的上述提供的化合物。
阅读下面的说明书将使本发明的这些和其他实施例变得更清楚。
发明详述
下面的结构更加完整的描述了本发明的新颖化合物
其中X、A和B如上所述。
本领域的技术人员将理解虚线代表单键或双键。在优选实施例中该分子不含双键。在更优选的实施例中该分子含有不含双键,且m=0的环结构。这些分子由下列结构代表:
其中A、B和X具有上述定义。在本发明的优选例中,化合物具有如下结构
最优选的,m=0且R和R’分别选自H和CH3。
本发明非常优选的实施例是以下化合物,其中当用于式I的化合物时,取代基具有下列值
化合物 | A,B,X,M值 | |||
4,10,10,11,12-12-六甲基-3-噁三环[7.3.0.0,<2,6>]十二烷 | A和B合起来形成5元环结构,R是H,R’是CH3 | (有意空白) | X是CH3 | M=0;环是饱和的 |
4,4,10,10,11,12,12-七 | A和B合起来形成 | (有意空白) | X是CH3 | M=0;环是饱和的 |
甲基-3-噁三环[7.3.0.0,<2,6>]十二烷 | 5元环结构,R是H,R’是CH3 | |||
1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮 | A是=0 | B是酮结构,R是H | X是CH3 | M=0;双键存在 |
1,1,2,3,3-五甲基-5-(2-甲基丙-2-烯基)-2,3,5,6,7-五氢茚-4-酮 | A是=0 | B是酮结构,R是CH3 | X是CH3 | M=0;双键存在 |
用下列数个反应顺序之一制备本发明的新颖化合物。按该顺序制备了下列实施例1,2,3,8,9,10,12,13和14的化合物:
X=H,CH3 X=H,CH3 M=0,1
M=0,1 R=H,CH3 Y=CH2,Br
X=H,CH3 M=0,1 X=H,CH3 M=0,1
R=H,CH3 Y=CH2,Br R=H,CH3 R′=H,CH3
下列反应总结了上述反应顺序。第一个反应是一个三(3)碳通过烯丙醇Claisen重排加成或用甲基烯丙基氯碳烷基化。该反应(Claisen重排)通常是在约150℃-250℃的温度下进行的。在优选实施例中,用酸催化剂,优选甲磺酸或对甲苯磺酸催化反应。碳加成反应后,进行氢化铝酮还原反应。还原酮形成相应的醇。上述的最后一个反应是酸催化的醚形成,在约70-130℃进行。该反应通常在溶剂如二甲苯或甲苯中进行,甲苯是优选溶剂。
用下列通用顺序制备了实施例5-7的化合物:
X=H,CH3 X=H,CH3 M=0,1 X=H,CH3 M=0,1
M=0,1 R=H,CH3 R=H,CH3
X=H,CH3 M=0,1 X=H,CH3 M=0,1
R=H,CH3 R=H,CH3
第一个反应是碳烷基化反应,视所需R基是H或CH3而定使用烯丙基氯或甲基烯丙基氯。该反应通常在约23-100℃下进行。反应通常用碱催化剂,如甲醇钠或氢氧化钠进行。下一个反应是热Claisen重排,在约170-250℃进行。第三个反应是酸催化的醚形成,使用如上所述的相似温度和催化剂,然后催化性氢化,使用铑或铂作为催化剂。
用下列顺序制备了实施例4和11的化合物:
X=H,CH3 X=H,CH3 M=0,1
M=0,1 R=H,CH3
其中反应是通过烯丙醇Claisan重排的三(3)碳原子加成,或甲基烯丙基氯的碳烷基化,使用上述条件和催化剂。
当M=0,上述反应的起始材料可在美国专利号5,227,367、5,733,866和5,665,698中找到。类似的,当M=1时,上述物质的起始材料可在美国专利号3,927,083(在此引入以供参考)、德国专利2330648和日本专利09249584中找到。
本领域技术人员将意识到本发明的化合物具有几个手性中心,从而提供了所要求保护的化合物的许多异构体。如本文所用的,本文所述的化合物包括化合物的异构混合物,以及可用本领域技术人员已知的技术分开的异构体。合适的技术包括层析、特别是凝胶层析。
下表提供了化合物4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷的光学异构体。本领域技术人员将能用一种或多种下列异构体和异构体的混合物配制香料组合物:
(1R,2R,4R,6R,9R,11R)-Z | (1S,2S,4R,6R,9S,11S)-Z | (1S,2R,4R,6R,9S,11S)-Z |
(1R,2R,4R,6R,9R,11S)-Z | (1R,2S,4R,6S,9R,11S)-Z | (1R,2R,4R,6S,9S,11S)-Z |
(1R,2R,4R,6R,9S,11R)-Z | (1S,2S,4S,6R,9S,11R)-Z | (1S,2R,4R,6R,9R,11S)-Z |
(1R,2R,4R,6S,9R,11R)-Z | (1S,2S,4R,6S,9R,11S)-Z | (1S,2S,4S,6S,9S,11S)-Z |
(1R,2R,4S,6R,9R,11R)-Z | (1S,2R,4S,6R,9S,11S)-Z | (1S,2R,4S,6S,9R,11S)-Z |
(1R,2S,4R,6R,9R,11R)-Z | (1R,2S,4R,6S,9S,11S)-Z | (1S,2S,4R,6R,9R,11S)-Z |
(1S,2R,4R,6R,9R,11R)-Z | (1S,2S,4R,6R,9S,11R)-Z | (1S,2S,4S,6R,9R,11R)-Z |
(1R,2R,4R,6R,9S,11S)-Z | (1S,2R,4R,6S,9S,11R)-Z | (1S,2S,4R,6S,9S,11R)-Z |
(1R,2R,4R,6S,9S,11R)-Z | (1S,2R,4R,6S,9R,11S)-Z | (1R,2R,4S,6S,9S,11S)-Z |
(1R,2R,4S,6S,9R,11R)-Z | (1R,2R,4S,6R,9S,11S)-Z | (1S,2R,4S,6R,9S,11S)-Z |
(1R,2S,4S,6R,9R,11R)-Z | (1R,2R,4S,6S,9R,11S)-Z | (1S,2R,4S,6S,9R,11S)-Z |
(1S,2S,4R,6R,9R,11R)-Z | (1R,2S,4R,6R,9S,11R)-Z | (1S,2S,4R,6R,9S,11R)-Z |
(1R,2R,4R,6S,9S,11S)-Z | (1R,2S,4R,6S,9R,11R)-Z | (1S,2R,4R,6S,9S,11S)-Z |
(1R,2R,4S,6S,9S,11R)-Z | (1R,2R,4S,6R,9R,11S)-Z | (1S,2S,4R,6R,9S,11S)-Z |
(1R,2S,4S,6S,9R,11R)-Z | (1R,2S,4R,6R,9S,11R)-Z | (1S,2S,4S,6R,9R,11S)-Z |
(1S,2S,4S,6R,9R,11R)-Z | (1R,2R,4S,6S,9R,11R)-Z | (1S,2S,4S,6S,9R,11R)-Z |
(1R,2S,4S,6S,9S,11R)-Z | (1S,2R,4S,6R,9S,11R)-Z | (1R,2S,4S,6S,9S,11S)-Z |
(1R,2R,4R,6S,9R,11S)-Z | (1S,2S,4S,6S,9S,11R)-Z | (1S,2S,4R,6S,9R,11R)-Z |
(1R,2R,4S,6R,9S,11R)-Z | (1S,2S,4S,6S,9R,11S)-Z | (1R,2S,4S,6R,9S,11R)-Z |
(1R,2S,4R,6S,9R,11R)-Z | (1S,2S,4S,6R,9S,11S)-Z | (1R,2S,4S,6R,9R,11S)-Z |
(1S,2R,4S,6R,9R,11R)-Z | (1S,2S,4R,6S,9S,11S)-Z | (1S,2R,4S,6S,9S,11S)-Z |
(1R,2R,4S,6S,9R,11S)-Z |
本发明的化合物具有强烈的琥珀香味,具有柔和的树木香调。
本发明化合物的用途广泛用于现在的香料产品,包括香水和古龙水的制备、个人护理产品(如肥皂、沐浴乳)和美发护理产品、空气清新剂和化妆品的加香。本发明还可用于清洁剂(例如但不限于去污剂、餐具洗涤材料、洗涤组合物、窗户清洁剂等)的加香。
在这些制备物中,本发明的化合物可单独或与其他加香组合物、溶剂、辅助剂等联合使用。还可使用的其他成分的性质和种类是本领域技术人员已知的。
在本发明中可使用许多种类香味,唯一的限制是和所用的其他成分的相容性。合适的香味包括但不限于水果(如杏、苹果、樱桃、葡萄、梨、菠萝、桔子、草莓、悬钩子);麝香;花香(如熏衣草类、玫瑰类、鸢尾类、康乃馨类)。其他怡人的香味包括草本和森林香,来自松树、云衫和其他森林香味。香味还可来自各种油,如精油,或来自植物材料,如薄荷、留兰香等。
美国专利号4,534,891提供了合适的香味表,其内容在此完整引入以供参考。其他合适香味的来源可在
Perfumes,Cosmetics and Soaps,第二版,W.A.Poucher编,1959中找到。该文章中提供的香味中有洋槐、肉桂、檀香、樱草、蕨类、栀子、山楂、向日葵、忍冬、风信子、茉莉、紫丁香、百合、木兰花、含羞草、水仙、新鲜收割的稻草、桔子花、兰花、木犀、香豌豆、三叶草、晚香玉、香子兰、紫罗兰、桂足香等。
嗅觉有效量理解为指香料组合物中化合物量,其单一组分对于它的具体嗅觉特征起作用,但香料组合物的总的嗅觉效果将是各香料或香味成分的效果的总和。因此,可用本发明的化合物,或通过改变组合物中其他成分引起的嗅觉反应改变香料组合物的芳香特征。量将随着许多因素(包括其他成分,它们的相对量和所需的效果)改变。
在加香物品中使用的本发明化合物的水平是约0.005-10重量%,优选约0.5-8,最优选约1-7重量%。除了化合物,可用其他试剂与香料联用。在不违背本发明的范围的情况下,还可使用熟知的物质,如表面活性剂、乳化剂、聚合物来包装香料。
另一种报道本发明的化合物在加香组合物中的水平的方法,即化合物作为加入以赋予所需香味的物质的重量百分数。本发明的化合物的范围可占约0.005-70重量百分数的加香组合物,优选约0.1-50,最优选约0.2-25重量百分数。本领域技术人员可使用所需水平的本发明的化合物,来提供所需香味和强度。
下面是本发明的具体实施例。本领域技术人员可容易的理解本发明的其他改变。这些改变被理解成在本发明的范围内。本发明所用的所有百分数,除非另外说明,是重量百分数,ppm理解成指百万分之一;mm理解成毫米,ml理解成毫升,Bp理解成沸点,THF理解成四氢呋喃,Hg理解成汞,g理解成克。在实施例中使用的IFF理解成指International Flavors & Fragrances Inc.,Hazlet,NJ,USA。
实施例1
7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-酮的制备
美国专利号5,227,367,美国专利号5,733,866,美国5,665,698中列出了本实施例起始材料的合成。
在装有vigreux柱和蒸馏头的3升烧瓶中装入624克(3摩尔)7,7,8,9,9-五甲基二环[4.3.0]壬-2-酮、435克(7.5摩尔)烯丙醇、97克(1.6摩尔)乙酸和15克(0.16摩尔)甲磺酸。加热混合物至80-85℃。用24小时加入原甲酸三甲酯350克(3.3摩尔),空气除去轻馏份(甲醇)。将反应物加热到180℃,除去轻馏份,并在180℃陈化2小时。冷却粗反应物,加入800毫升水和400毫升甲苯。丢弃水层,用盐水洗涤有机层。
蒸馏粗有机层,回收甲苯和285克作为异构体混合物的7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-酮(1毫米汞柱下Bp 106℃)。
7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-酮的核磁共振谱如下:0.68-1.13ppm(ms,15H),1.34-1.63ppm(m,5H),1.77-2.50ppm(m,4H),4.93ppm(m,2H),5.74ppm(m,1H)。
实施例2
7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-醇的制备
将VITRIDE(Zeeland Chemicals)70%的甲苯溶液,338克(1.17摩尔)和甲苯(732毫升)加热到100℃。用2小时加入7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-酮,290克(1.17摩尔)。用2-丙醇(105克)中和过量的VITRIDE,用氢氧化钠水溶液(280克50%NaOH)淬灭反应物。丢弃下面的水层,用盐水洗涤有机层。
蒸馏有机层得到甲苯和163克7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-醇,它是异构体的混合物(3毫米汞柱下Bp128-130℃)。
7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-醇的核磁共振谱如下:0.59-1.02ppm(ms,15H),1.14-1.58ppm(m,5H),1.66-2.53ppm(m,4H),3.25-3.87ppm(dd,1H),3.93-4.05ppm(bs,1H),4.98-5.11ppm(m,2H),5.70-5.94ppm(m,1H)。
实施例3
4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷
加热7,7,8,9,9-五甲基-3-丙-2-烯基二环[4.3.0]壬-2-醇,163克(0.65摩尔)、甲苯163克和甲磺酸11.5克(0.11摩尔)的混合物至80-90℃。反应物陈化24小时,然后冷却到室温。用10%碳酸钠水溶液(50毫升)淬灭反应。用10%碳酸钠水溶液(50毫升)洗涤有机层2次,然后用盐水洗涤。
蒸馏有机层,回收甲苯和112克4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷的异构体混合物(2mmHg时Bp 95℃)。
4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷的核磁共振谱如下:0.63-0.96(ms,18H),1.0-2.15ppm(m,9H),3.94-4.28ppm(m,2H)。
实施例4
1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮的制备
将CASHMERAN(IFF)1000克(4.85摩尔)、烯丙醇1245克(21.46摩尔)和甲磺酸(MSA)50克(0.52摩尔)加热到80-90℃。收集挥发性有机物24小时。用25%甲醇钠的甲醇溶液(142克)中和MSA,将反应物加热到180℃5小时。冷却混合物,加入甲苯1000毫升。用盐水洗涤粗产物2次。
蒸馏有机层回收甲苯、CASHMERAN(IFF)(490克)、和205克1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮(7mmHg下Bp139-141℃)。
1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮的核磁共振谱如下:0.87-1.22ppm(ms,15H),1.56-1.78ppm(m,2H),1.99-2.38ppm(m,3H),2.55-2.68ppm(m,1H),5.02-5.11ppm(m,2H),5.72-5.88ppm(m,1H)。
实施例5
4-(烯丙氧基)-1,1,2,3,3-五甲基二氢化茚的制备
美国专利号5,227,367、美国专利号5,733,866、美国专利号5,665,698中列出了该实施例起始材料的合成。
搅拌1,1,2,3,3-五甲基-4-二氢化茚醇,195克(0.95摩尔)、甲醇(880毫升)、碘化钠0.32克(0.002摩尔)和25%甲醇钠的甲醇溶液395克(1.82摩尔)的混合物,加热到40℃。经3小时滴加烯丙基氯151克(1.96摩尔)。40℃陈化反应混合物24小时。将反应物冷却到室温,用2升水稀释。用100毫升浓盐酸(37%盐酸)调节pH。加入甲苯(390毫升)丢弃下方的水层。用300毫升10%碳酸钠水溶液洗涤有机层,然后用盐水洗涤2次。
蒸馏有机层,回收甲苯和122克4-(烯丙氧基)-1,1,2,3,3-五甲基二氢化茚(8.7mmHg下Bp134-137℃)。
4-(烯丙氧基)-1,1,2,3,3-五甲基二氢化茚的核磁共振谱如下:0.96-1.41ppm(ms,15H),1.83ppm(q,1H),4.49ppm(dd,2H),5.18-5.42ppm(m,2H),5.95-6.08ppm(m,1H),6.52ppm(d,1H),6.67ppm(d,1H),7.00ppm(t,1H)。
实施例6
1,1,2,3,3-五甲基-5-丙-2-烯基二氢化茚-4-醇的制备
将5-(烯丙氧基)-1,1,2,3,3-五甲基茚122克(0.5摩尔)和PRIMOL(Exxon)36克加热到180-200℃12小时。
蒸馏反应物,得到38克1,1,2,3,3-五甲基-5-丙-2-烯基二氢化茚-4-醇(5mmHg下Bp152-154℃)
1,1,2,3,3-五甲基-5-丙-2-烯基二氢化茚-4-醇的核磁共振谱如下:0.96-1.42ppm(ms,15H),1.87ppm(q,1H),3.39ppm(bd,2H),5.02ppm(bs,1H),5.16-5.27ppm(m,2H),5.98-6.10ppm(d,1H),6.95ppm(d,1H)。
实施例7
2,6,6,7,8,8-六甲基-2,3-二氢化茚并[4,5-b]呋喃的制备
将1,1,2,3,3-五甲基-5-丙-2-烯基二氢化茚-4-醇38克(0.15摩尔)、甲苯100毫升和对甲苯磺酸(ptsa)2.3克(0.01摩尔)加热到80-90℃15小时。将反应物冷却到室温,用10%碳酸钠水溶液(100毫升)淬灭。丢弃水层,用盐水再洗涤有机层一次。
蒸馏有机层,回收甲苯和2,6,6,7,8,8-六甲基-2,3-二氢化茚并[4,5-b]呋喃(4mmHg下Bp124℃)。
2,6,6,7,8,8-六甲基-2,3-二氢化茚并[4,5-b]呋喃的核磁共振谱如下:1.12-1.68ppm(ms,18H),2.07ppm(q,1H),2.92ppm(ddd,1H),3.41ppm(ddd,1H),5.01-5.16ppm(m,1H),6.75ppm(d,1H),7.07ppm(d,1H)。
实施例8
7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-酮的制备
将二异丙基氨基化锂1升(2.0M的THF溶液)冷却到-10℃。用2小时滴加7,7,8,9,9-五甲基二环[4.3.0]壬-2-酮320克(1.50摩尔)。室温陈化反应物2小时,然后用2小时加入购自Aldrich Chemicals的六甲基磷酰胺(HMPA)5.37克(2摩尔%)、碘化钠4.50克(2摩尔%)和甲代烯丙基氯150克(1.60摩尔)。加热反应物至回流8小时。冷却混合物至室温,用水450克淬灭。分离水层并丢弃。用盐水洗涤有机层。
蒸馏有机层得到THF和384克7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-酮(2mmHg下Bp110℃)。
7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-酮的核磁共振谱如下:0.68-1.25ppm(ms,15H),1.30-1.87ppm(m,6H),2.03-2.18ppm(m,2H),2.61ppm(bd,1H),4.58-4.73ppm(m,2H)。
实施例9
7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-醇的制备
将7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-酮140克(0.53摩尔)的甲苯(60克)溶液用3小时在室温下加到RED-AL(购自AldrichChemicals)(65%的甲苯溶液)231克(0.74摩尔)中。用苛性苏打(147克20%NaOH)淬灭反应物。加热反应物至65℃,然后加入水(500毫升)。分离水层,用甲苯抽提1次(86克)。用硫酸钠干燥合并的有机层。
蒸馏有机层,回收甲苯和7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-醇,作为异构体的混合物(3mmHg下Bp132-133℃)。
实施例10
4,4,10,10,11,12,12-七甲基-3-噁三环[7.3.0.0<2,6>]十二烷的制备
在室温下搅拌7,7,8,9,9-五甲基-3-(2-甲基丙-2-烯基)二环[4.3.0]壬-2-醇2.31克(8.8毫摩尔)、甲磺酸0.04克(0.4毫摩尔)和1-硝基丙烷2.31克的溶液24小时。用碳酸钠水溶液(10%溶液)中和反应物。分离水层并丢弃。在旋转蒸发器上浓缩有机层。
蒸馏得到作为异构体混合物的4,4,10,10,11,12,12-七甲基-3-噁三环[7.3.0.0<2,6>]十二烷(2mmHg下Bp98℃)。
4,4,10,10,11,12,12-七甲基-3-噁三环[7.3.0.0<2,6>]十二烷的核磁共振谱如下:0.61-1.27ppm(ms,21H),1.32-1.85ppm(m,6H),2.45-2.61ppm(m,1H),3.92-3.98ppm(m,1H)。
实施例11
1,1,2,3,3-五甲基-5-(2-甲基丙-2-烯基)-2,3,5,6,7-五氢茚-4-酮的制备
将CASHMERAN(IFF)400克(1.94摩尔)和THF(200毫升)在-10℃加到二异丙基氨基化锂1升(2.0M的THF溶液)中。陈化反应物2小时,温至0℃。经2小时加入甲代烯丙基氯248克(2.7摩尔)。将反应物温至室温,然后加热到60℃20小时。冷却混合物,用10%盐酸(1升)淬灭。用盐水洗涤粗产物。
蒸馏有机层回收THF和310克1,1,2,3,3-五甲基-5-(2-甲基丙-2-烯基)-2,3,5,6,7-五氢茚-4-酮(2mmHg下Bp 142-143℃)。
1,1,2,3,3-五甲基-5-(2-甲基丙-2-烯基)-2,3,5,6,7-五氢茚-4-酮的核磁共振谱如下:0.86-1.23ppm(ms,15H),1.36-1.66ppm(m,2H),1.72ppm(bs,3H),1.75-2.39ppm(m,4H),2.59-2.71ppm(m,1H),4.70ppm(d,2H)。
实施例12
3-(2-溴乙基)-7,7,8,9,9-五甲基二环[4.3.0]壬-2-酮的制备
将7,7,8,9,9-五甲基二环[4.3.0]壬-2-酮200克(0.97摩尔)和THF(100毫升)在-30℃加到二异丙基氨基化锂1升(1.0M的THF溶液)和HMPA(10克,5摩尔%)中。陈化反应物2小时,温至0℃。经2小时加入1,2-二溴乙烷200克(1.06摩尔)。将反应物温至室温,陈化24小时。用10%盐酸(200毫升)淬灭混合物。用盐水洗涤粗产物。
蒸馏得到作为异构体的混合物的3-(2-溴乙基)-7,7,8,9,9-五甲基二环[4.3.0]壬-2-酮。
实施例13
3-(2-溴乙基)-7,7,8,9,9-五甲基二环[4.3.0]壬-2-醇的制备
将3-(2-溴乙基)-7,7,8,9,9-五甲基二环[4.3.0]壬-2-酮200克(0.63摩尔)的甲苯(60克)溶液在60℃用1小时加到RED-AL(65%的甲苯溶液)中。用苛性苏打水溶液(200克50%NaOH)在60℃淬灭反应物。用水(500毫升)稀释反应物,冷却至室温。分离水层并丢弃。
蒸馏得到作为异构体的混合物的3-(2-溴乙基)-7,7,8,9,9-五甲基二环[4.3.0]壬-2-醇。
实施例14
10,10,11,12,12-五甲基-3-噁三环[7.3.0.0<2,6>]十二烷的制备
将3-(2-溴乙基)-7,7,8,9,9-五甲基二环[4.3.0]壬-2-醇50克(0.16摩尔)和THF(100毫升)的溶液在室温下加到氢化钠6.4克(60%的矿物油分散体)和THF(300毫升)中。加热反应物至回流8小时,冷却至室温。用盐水(100毫升)淬灭反应物。分离水层并丢弃。
蒸馏得到作为异构体的混合物的10,10,11,12,12-五甲基-3-噁三环[7.3.0.0<2,6>]十二烷。
实施例15
根据下列配方制备了香料。
材料 | 份数 |
4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷 | 1 |
BORNAFIX(IFF) | 3 |
CEDRAFIX(IFF) | 2.5 |
CELESTOLIDE(IFF) | 4 |
CITRALVA(IFF) | 1 |
蒸馏过的柠檬油 | 12 |
CYCLACET(IFF) | 3 |
CYCLOGALBANIFF(IFF) | 1 |
二氢月桂烯醇 | 40 |
FLEURANIL(IFF) | 1 |
Geranium Bourbon Oliffac | 0.5 |
己基肉桂醛 | 4.5 |
ISO E SUPER(IFF) | 2.5 |
KHARISMAL(IFF) | 2 |
KOAVONE(IFF) | 1.5 |
乙酸里哪酯 | 5 |
PHENOXANOL(IFF) | 3 |
PRECYCLEMONE B(IFF) | 1.5 |
假乙酸里哪酯 | 5 |
乙酸α-甲基苄酯 | 1 |
VIGOFLOR | 1 |
ZENOLIDE(IFF) | 4 |
该香料被形容为具有桔子味。
实施例16
在上述实施例中制备的下列材料被描述成具有下列香味特征:
材料 | 气味 |
4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷 | 琥珀,树木 |
4,4,10,10,11,12,12-七甲基-3-噁三环[7.3.0.0<2,6>]十二烷 | 琥珀,树木 |
1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮 | 香,麝香,果香 |
1,1,2,3,3-五甲基-5-(2-甲基丙-2-烯基)-2,3,5,6,7-五氢茚-4-酮 | 香,悬钩子,麝香 |
Claims (10)
2.如权利要求1所述的化合物,其特征在于,该化合物被掺入香料组合物中。
3.一种改善、增强或改变香料的气味特征的方法,该方法在于,掺入嗅觉可接受量的权利要求1所述的化合物。
4.如权利要求3所述的方法,其特征在于,香料被掺入选自香水、古龙水、花露水、个人护理用品、清洁产品和空气清新剂的产品。
5.如权利要求4所述的方法,其特征在于,所述清洁产品选自去污剂、餐具清洁材料、洗涤组合物和窗户清洁剂。
6.如权利要求4所述的方法,其特征在于,所述产品是个人护理产品。
9.一种改善、增强或改变香料的气味特征的方法,其特征在于,该方法掺入嗅觉可接受量的权利要求8所述的化合物。
10.如权利要求9所述的方法,其特征在于,所述化合物选自4,10,10,11,12,12-六甲基-3-噁三环[7.3.0.0<2,6>]十二烷、4,4,10,10,11,12,12-七甲基-3-噁三环[7.3.0.0<2,6>]十二烷、1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮、和1,1,2,3,3-五甲基-5-丙-2-烯基-2,3,5,6,7-五氢茚-4-酮。
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US6906013B1 (en) | 2004-06-22 | 2005-06-14 | International Flavors & Fragrances Inc. | Cyclohexanbutanol derivative and fragrance use thereof |
US7026279B2 (en) * | 2004-06-24 | 2006-04-11 | International Flavors & Fragrances Inc. | Use of 3-(methoxymethyl)-2-pentylcyclopenta derivatives in perfume compositions |
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AU467695B2 (en) | 1972-06-15 | 1975-12-11 | International Flavors & Fragrances Inc | Bicyclic compounds and processes for making and using same |
US3927083A (en) | 1972-06-15 | 1975-12-16 | Int Flavors & Fragrances Inc | Bicyclic compounds and processes for making and using same |
DE2330646A1 (de) | 1973-06-15 | 1975-01-09 | Beckman Riic Ltd | Vorrichtung und verfahren zur aenderung der polarisation einer elektromagnetischen welle |
US4534891A (en) | 1982-11-12 | 1985-08-13 | International Flavors & Fragrances Inc. | Branched C13 -alk-1-en-5-ones and use thereof in perfumery |
US4902840A (en) | 1989-04-28 | 1990-02-20 | International Flavors And Fragrances Inc. | Substituted tetrahydroindane derivatives and organoleptic uses of substituted tetrahydroindanes |
JPH0669907B2 (ja) | 1989-04-28 | 1994-09-07 | 日本碍子株式会社 | 電子伝導性多孔質セラミックス管の製造方法 |
US4902672A (en) | 1989-06-26 | 1990-02-20 | International Flavors & Fragrances Inc. | Polyalkyl indanyl n-propyl and allyl ethers and perfumery uses thereof |
US5227367A (en) | 1992-12-17 | 1993-07-13 | International Flavors & Fragrances Inc. | Oxypentamethylindane carboxaldehydes, methods for preparing same, organoleptic uses thereof and cosmetic and pharmaceutical compositions containing them |
JPH09249584A (ja) | 1996-03-19 | 1997-09-22 | Sumikin Chem Co Ltd | 1,1−ジ置換−1,2,3,4−テトラヒドロナフタレン化合物の製造方法 |
US5733866A (en) | 1996-08-22 | 1998-03-31 | International Flavors & Fragrances Inc. | Methyl substituted hexahydroindanols and alkyl ethers thereof, organoleptic uses thereof, processes for preparing same and process intermediates therefor |
US5665698A (en) | 1996-09-06 | 1997-09-09 | International Flavors & Fragrances Inc. | Methyl substituted tetrahydroindane alkyl enol ethers, perfumery uses thereof, processes for preparing same, and process intermediates |
US6271193B1 (en) * | 2000-10-11 | 2001-08-07 | International Flavors & Fragrances Inc. | Carbon containing functional group substituted 4,5,6,7-tetrahydro-polyalkylated-4-indanes, isomers thereof, processes for preparing same and uses thereof |
US6632788B2 (en) * | 2001-05-17 | 2003-10-14 | International Flavors & Fragrances Inc. | Polyalkylbicylic derivatives |
-
2001
- 2001-05-17 US US09/859,953 patent/US6632788B2/en not_active Expired - Lifetime
-
2002
- 2002-01-30 BR BRPI0200264A patent/BRPI0200264B1/pt active IP Right Grant
- 2002-05-16 DE DE60201463T patent/DE60201463T2/de not_active Expired - Lifetime
- 2002-05-16 EP EP02253426A patent/EP1262481B1/en not_active Expired - Lifetime
- 2002-05-17 CN CNB021200041A patent/CN1240660C/zh not_active Expired - Lifetime
-
2003
- 2003-08-07 US US10/635,954 patent/US7160852B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US7160852B2 (en) | 2007-01-09 |
EP1262481B1 (en) | 2004-10-06 |
US20040029769A1 (en) | 2004-02-12 |
BR0200264A (pt) | 2003-04-29 |
DE60201463D1 (de) | 2004-11-11 |
DE60201463T2 (de) | 2006-02-02 |
US6632788B2 (en) | 2003-10-14 |
EP1262481A1 (en) | 2002-12-04 |
BRPI0200264B1 (pt) | 2015-12-08 |
US20030004090A1 (en) | 2003-01-02 |
CN1390822A (zh) | 2003-01-15 |
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