CN100358856C - 有机化合物 - Google Patents
有机化合物 Download PDFInfo
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- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
在第7位具有取代基的单取代的二环[2.2.1]庚烷或庚烯,其中所说的取代基选自直链或支链C2-10烷基或链烯基,和亚烷基;以及含有这种化合物的芳香组合物。
Description
本发明涉及某些7-取代的二环[2.2.1]庚烷和庚烯类芳香化合物,并且具体说涉及显示木香、花香、橙皮香和青香香调的这种化合物。
本发明第一个方面提供一种芳香组合物,该组合物含有在第7位具有取代基的单取代的二环[2.2.1]庚烷或庚烯,其中所说的取代基选自直链或支链C2-10烷基或链烯基,和亚烷基,例如直链或支链C1-10亚烷基。这些化合物在芳香剂应用中的用途迄今在文献中从未报导过。根据化合物的取代形式,化合物的气味可以在一个宽泛的嗅觉范围内变化,这个嗅觉范围包括木香、花香、橙皮香和青香味,并且它们在香料的选择中全部都是令人感兴趣的附加分子。
基本上所有的上述提及的二环[2.2.1]庚烷或庚烯在文献中都从未有过报导。因此,本发明另一个方面提供在第7位具有取代基的单取代的二环[2.2.1]庚烷或庚烯,其中所说的取代基选自烷基、链烯基和亚烷基,前提条件是不包括7-异亚丙基-二环[2.2.1]庚烷-2-羧酸甲基酯;7-异亚丙基-二环[2.2.1]庚烷-2-甲腈;7-异丁基二环[2.2.1]庚-2-烯-2-甲腈;7-异亚丙基[2.2.1]庚-5-烯-3-甲腈;和1-(7-异丁基-二环[2.2.1]庚-2-基)-乙酮(ethanone)。
以下通式(I)的化合物是特别优选的化合物:
其中
R1是氢或C1-6烷基;
R2是氢,C1-6烷基或C2-6链烯基;
R3是氢或C1-4烷基;或者
R1和R3与跟它们相连的碳原子一起形成5-或6-元碳环;
R4是腈基团,2-、3-或4-吡啶基,吡嗪基或羰基COR5,基团C(R7)2-OR8,或者肟或肟醚基团C=NOR13;
R5是氢、C1-5烷基,C2-5链烯基或OR6;
R6是C1-5烷基或C2-5链烯基;
R7独立地是氢或C1-4烷基;
R8是C1-5烷基,C2-5链烯基或羰基COR9;
R9是C1-4烷基,C2-5链烯基或OR6;
R10是氢或C1-4烷基;
R11是氢,或者直链或支链C1-4烷基;
R12是氢或C1-4烷基;
R13是氢或C1-4烷基;
C7和C8之间及C8和C9之间的键可以都是单键,或者C7和C8之间的键或C8和C9之间的键与虚线一起表示双键;并且C5和C6之间的键是单键,或者当R4是C(R7)2-OR8基团时,它与虚线一起表示双键。
本文中,针对本发明化合物或组合物所用的术语“烷基”、“链烯基”和“亚烷基”具有如下优选的含义:作为烷基,可以提及的是甲基,乙基,正丙基,异丙基,或者直链或支链丁基,戊基或己基;作为链烯基,可以提及的是乙烯基,烯丙基,或者直链或支链丁烯基或戊烯基;并且作为亚烷基,可以提及的是亚甲基,亚乙基或亚丙基或者不对称取代的亚烷基。
在一个优选的实施方案中,取代基R12与C5或C6上的环碳原子键合。
本发明的化合物可以含有一个或多个手性中心,并且就此它们可以是以对映异构体和非对映异构体的混合物的形式存在,或者可以将它们解析成对映异构体和非对映异构体纯的形式。然而,立体异构体的解析会增加制造的复杂性及将这些化合物纯化的过程,所以,出于经济原因,优选简单地以它们立体异构体混合物的形式使用化合物。然而,如果期望制备纯的立体异构体,则可以根据本领域已知的方法来实现。
本发明的特别优选的化合物由下式表示:
式IA的化合物具有铃兰醛-甲基柏木酮型味;IB显示出橙叶-青香型味;IC显示胡椒-木香型味;ID具有类似苹果、桃金娘(myrtille)和黑莓的气味;IE类似芳樟醇-木香;并且IF具有木香-花香气味。
由于这些化合物所具有的广泛的气味范围(取决于取代的形式),这些化合物可以在几乎所有香料领域的许多可能的应用中得到使用,例如在精细香料或在所有类型的增香产品中,例如高级香水、美容制品、消费者保健产品或家用制品,例如洗剂、洗涤剂和香皂。
在这些应用中,化合物、特别是式(I)的化合物可以单独使用,也可以与其它芳香剂掺混使用。然而,优选将化合物与其它芳香分子掺混使用。当在芳香组合物中与其它芳香分子掺混使用时,本发明的化合物可以按照所需要的具体的芳香和谐性以不同的量使用,例如芳香组合物重量的0.1-99.9%。
本发明化合物在此方面的用途不限于任何具体的香料类型,也不限于任何具体的嗅觉方向、增味剂或物质类别。由此,本发明的化合物可以与诸如以下的物质混合:
-精油和醚萃取物,例如海狸香,广木香根油,橡苔净油,香叶油,茉莉净油,广藿香油,玫瑰油,檀香油或衣兰油;
-醇类,例如香茅醇,乌木醇(Ebanol),丁子香酚,香叶醇,SuperMuguet,芳樟醇,苯乙醇,檀香醇(Sandalore),萜品醇或Timberol;-醛类和酮类,例如α-戊基肉桂醛,Georgywood,羟基香茅醛,Iso ESuper,异甲基紫罗兰酮,二氢茉莉酮酸甲酯,麦芽酚,甲基柏木基酮,甲基紫罗兰酮或香草醛;
-醚类和缩醛类,例如降龙涎香醚,香叶甲醚,氧化玫瑰或香辣醚(Spirambrene);
-酯类和内酯类,例如乙酸苄酯,乙酸柏木酯,环麝香(Cyclomusk),γ-癸内酯,Helvetolide,γ-十一内酯或乙酸岩兰草酯;
-大环化合物类,例如黄葵内酯,巴西酸亚乙酯或环十五内酯;和
-杂环化合物,例如异丁基喹啉。
除与其它芳香化合物掺混外,本发明的化合物还可以与一种或多种在常规芳香组合物中与芳香剂联用的成分或赋形剂(例如载体物料)及本领域常用的其它辅剂掺混。
本发明的化合物可以是以净成分的形式添加至芳香组合物中,或者可以将它们掺入本领域公知的传输体系中。例如,可以根据已知技术,如喷雾干燥、凝聚、挤出或包衣,将化合物包封在包胶介质中。
本发明的芳香组合物在本发明消费者用产品组合物中使用的比例可以在大数值范围内变化,并且取决于人们所期望增香的组合物的性质,例如共同成分的性质和香料调配者所寻求的特定效果。然而,通常来说,可以在精细香料中使用最多约30%重量和在其它增香产品中使用最多约50%重量。
本发明的另一个方面是提供制备本发明上述化合物的方法。由此,可以按照如下方法制备上述的化合物:将适宜取代的富烯与适宜取代的亲双烯体如α,β-不饱和酮或酯类或者乙烯基吡啶类,在公知的Diels-Alder条件下反应,得到本发明的二环[2.2.1]庚烯,可以将其进一步氢化,例如在室温下使用碳载钯催化剂,或者根据常规的合成法还原和酯化,得到本发明的附加化合物。
适宜取代的富烯可以商购获得,或者可以按照文献中公知的技术,使用诸如吡咯烷(pyrollidine)的碱,由环戊二烯或烷基化的环戊二烯例如甲基环戊二烯和适宜取代的羰基化合物例如酮,在醇介质中方便地合成。
获得本发明化合物用的适宜取代的亲双烯体可以商购获得,或者可以用容易获得的起始物料方便地合成。
其它具体的反应条件在实施例中给出。
下面是一系列实施例,它们起举例说明本发明的作用。
实施例1
1[7-(1-乙基-亚丙基)-二环[2.2.1]庚-2-基]乙酮
将6,6-二乙基-富烯(按J.Org.Chem.,1990,55,3395中所述制备;86.0g,0.64mol)和甲基乙烯基酮(44.9g,0.64mol)的混合物在50℃下搅拌5h。将混合物冷却至室温并且用甲苯/己烷(1/9,600ml)稀释。将此溶液在常压下使用碳载钯(10%)催化剂氢化。5h后将混合物过滤,真空浓缩并且将残余物蒸馏(沸点70℃/0.01托),得到标题化合物(65.5g,50%),其是2种异构体以3∶1的比例的混合物。气味描述:木香,花香,甲基柏木酮,铃兰醛,龙涎香(ambery)。
1H-NMR(CDCl3,400MHz):(major isomer)2.98(t,J=4.4Hz,1H,1-H),2.87-2.81(m,1H,2-H),2.61(t,J=4.4Hz,1H,4-H),2.15(s,3H,COCH3),2.13-1.97(m,4H,=C(CH2CH3)2),1.87(dd,J=12.1Hz,5.0Hz,1H,3-Hn),1.55-1.20(m,5H,3-Hx,5-H,6-H),1.02-0.88(m,3H,=C(CH2CH3)2)ppm.GC/MS(EI):(major isomer):206(M+,22),177(12),163(32),148(43),135(45),107(83),93(62),79(69),43(100);(minorisomer):206(M+,13),177(8),163(66),148(22),135(37),107(93),93(50),79(60),43(100).IR(atr):2960s,2870s,1708vs,1463m,1357m,1172s,840w cm-1.
(注:major isomer:主要异构体,minor isomer:次要异构体,下同)
实施例2-9
按照实施例1的合成过程,由相应的取代起始物料制备以下化合物:
内-1-(7-异亚丙基-二环[2.2.1]庚-2-基)]-乙酮
气味描述:玫瑰,芍药,苹果,仙客来,新鲜,木香。1H-NMR(CDCl3,400MHz):2.98(t,J1.5x=J1,2=4.5Hz,1H,1-H),2.86-2.81(m,J2.1=4.5Hz,J2.3n=5.0Hz,J=2.0Hz,1H,2-H),2.61(t,J4.3x=J4.5x=4.5Hz,1H,4-H),2.15(s,3H,COCH3),1.86(dd,J3n.3x=12.1Hz,J3.2=5.0Hz,1H,3-Hn),1.70(s,3H,C(CH3)a(CH3)b),1.65(s,3H,C(CH3)a(CH3)b),1.55-1.20(m,5H,3-Hx,5-H,6-H)ppm.GC/MS(EI):178(M+,25),163(6),135(34),120(60),107(100),93(92),91(96),79(50),43(59).IR(atr):2955s,2871m,1706vs,1447m,1357s,1173s,959w cm-1.
1-(7-仲-亚丁基-二环[2.2.1]庚-2-基)-乙酮
4种异构体,比例为1∶1.5∶2.9∶2.8。气味描述:木香,花香,芳樟醇,甲基柏木酮,龙涎香。
1H-NMR(CDCl3,400MHz):3.01-2.44(m,3H),2.15/2.11/2.10(4s,3H),2.11-2.82(m,3H),1.69/1.65/1.63/1.62(4s,3H),1.65-1.20(m,5H),1.02-0.91(m,3H)ppm.GC/MS(EI):(major isomer):192(M+,16),163(9),149(48),134(41),121(57),107(54),93(92),79(52),43(100).IR(atr):2960s,2870m,1707vs,1453w,1356m,1172s,960w cm-1.
1-[7-(1,2-二甲基-亚丙基)-二环[2.2.1]庚-2-基]-乙酮
4种异构体,比例为1∶1∶2.2∶1.9。气味描述:木香,柏木香,花香,铃兰醛。
1H-NMR(CDCl3,400MHz):3.29-2.42(m,4H),2.14/2.11/2.09(4s,3H),1.88-1.81(m,1H),1.60/1.55/1.53(4s,3H),1.65-1.19(m,5H),1.01-0.90(m,6H)ppm.GC/MS(EI):(majorisomer):206(M+,24),163(64),148(36),135(33),121(76),107(65),93(75),79(32),43(100).IR(atr):2958s,2869m,1708vs,1464w,1358m,1173m,1080w cm-1
1-[7-(15-二甲基-亚己-4-烯基)-二环[2.2.11庚-2-基]-乙酮
4种异构体,比例为1∶1.5∶3∶2.5。气味描述:木香,柏木香,橙皮香,水果香,花香。
1H-NMR(CDCl3,400MHz):5-15-5.04(m,1H),2.96-2.43(m,3H),2.26-1.83(m,8H),1.75-1.05(m,14H)ppm.GC/MS(EI):(major isomer):246(M+,5),203(7),177(31),159(9),135(38),119(25),107(41),91(40),69(26),43(100).IR(atr):2940s,2868s,1708vs,1451m,1376w,1356m,1172s,1059w,960w cm-1.
1-(7-环亚己基-二环[2.2.1]庚-2-基]-乙酮
2种异构体A和B,比例为1∶2。气味描述:皮革味,苔藓,辣椒香,pyralone。
1H-NMR(CDCl3,400MHz):3.02(t,J=4.4Hz,2/3H,1-HA),2.90(d,J=4Hz,1/3H,1-HB),2.85-2.80(m,J=12.1Hz,4.8Hz,1.6Hz,2/3H,2-Ha),2.68/s.64(2t,J=4.4Hz,1H,4-H),2.47(dd,J=9.2Hz,5.2Hz,1/3H,2-HA),2.14,2.10(2s,3H,COCH3),2.18-2.01(m,4H),1.86(dd,J=12.1Hz,4.8Hz,2/3H,3-HAn),1.65-1.20(m,11H)ppm.GC/MS(EI):(major isomer):218(M+,18),175(54),160(100),148(59),131(30),117(38),105(42),91(92),79(94),67(44),43(g6).IR(atr):2922s,2851m,1707vs,1447m,1356m,1172s,1002w,851w cm-1.
1-(7-异丁基-二环[2.2.1]庚-2-基]-乙酮
4种异构体,比例为1.5∶1∶8∶22。气味描述:木香,青香,葡萄柚,glycolierral。
1H-NMR(CDCl3,400MHz):2.98-2.83(m,1H),2.40-2.32(m,1H),2.16/2.14/2.11/2.10(4s,3H),2.05-1.93(m,1H),1.88-1.73(m,2H),1.67-1.40(m,4H),1.29-1.05(m,4H),0.95-0.82(m,6H)ppm.GC/MS(EI):(major isomer):194(M+,4),136(100),121(54),95(28),79(25),71(30),67(48),43(78).
7-异丙基-二环[2.2.1]庚烷-2-甲酸乙基酯
4种异构体,比例为1∶35∶11∶16。气味描述:大黄,水果香,梨,青香,苹果。
1H-NMR(CDCl3,400MHz):4.18-4.06(m,2H),2.87-2.73(m,1H),2.41-2.26(m,2H),2.19-2.06(m,1H),1.97-1.15(m,10H),0.95-0.86(m,6H)ppm.GC/MS(EI):(majorisomer):210(M+,3),164(10),137(13),122(15),110(92),101(100),95(25),81(42),73(48),41(34).IR(atr):2956s,2874m,1731vs,1467m,1367m,1179vs,1042m,866w cm-1.
2-(7-异亚丙基-二环[2.2.1 ]庚-2-基)-吡啶
按照实施例1由二甲基富烯和2-乙烯基吡啶制备。2种异构体,比例为6∶4。气味描述:青香,橙叶,腌菜味,龙蒿。endo-Isomer:1H-NMR(CDCl3,400MHz):8.58-8.56(m,1H,Ar-H),7.60(dt,J=7.6Hz,2.0Hz,1H,Ar-H),7.22(d,J=7.6Hz,1H,Ar-H),7.10-7.07(m,1H,Ar-H),3.30-3.33(m,1H,2-H),2.97(t,J=4.4Hz,1H,1-H),2.72(t,J=4.4Hz,1H,4-H),2.06-1.97(m,1H),1.87(dd,J=12.0Hz,5.6Hz,1H,3-Hn),1.73(s,3H,C=C(CH3)(CH3)),1.79(s,3H,),1.61-1.53(m,1H),1.42-1.24(m,4H)ppm.GC/MS(EI):213(M+,3),159(8),158(5),117(5),106(100),93(28),77(7),51(3),41(4).IR(atr):3064w,2944vs,2869s,1589s,1568m,1472s,1432s,1372m,1171m,1146m,790m,747s cm-1. exo-Isomer:1H-NMR(CDCl3,400MHz):8.46-8.44(m,1H,Ar-H),7.55(dt,J=7.6 Hz,2.0Hz,1H,Ar-H),7.11(d,J=7.6Hz,1H,Ar-H)7.06-7.03(m,1H,Ar-H),3.04(dd,J=9.2Hz,5.4Hz,1H,2-H),2.75(t,J=4.0Hz,1H,4-H),2.71(d,J=3.2Hz,1H,1-H),1.92(dd,J=12.4Hz,9.2Hz,1H,3-H),1.72(s,3H,C=C(CH3)(CH3)),1.55(s,3H,C=C(CH3)(CH3)),1.89-1.38(m,5H)ppm.GC/MS(EI):213(M+,8),172(5),158(60),117(5),106(100),93(40),77(9),41(5).IR(atr):3063w,2948vs,2867s,2726w,1590s,1569m,1472,s,1433s,1371m,1148m,768m,747s cm-1.
(注:endo-isomer:内异构体;exo-isomer:外异构体,下同)
实施例10
乙酸7-异亚丙基-2,5-二甲基-二环[2.2.1]庚-5-烯-2-基甲基酯
步骤A:(7-异亚丙基-2,5-二甲基-二环[2.2.1]庚-5-烯-2-基)-甲醇
将5-异亚丙基-2-甲基-环戊-1,3-二烯(26.4g,0.22mol)和2-甲基丙烯醛(methacroleine)(29.4g,0.42mol)的混合物在室温下搅拌2天。将混合物用二乙醚(50ml)稀释并且在0℃下滴加至LiAlH4(6.25g,0.16mol)在醚(100ml)中的悬浮液中。室温下搅拌1h后,将混合物顺序用水(6ml)、NaOH(15%,6ml)和水(6ml)逐滴猝灭。将混合物过滤,真空浓缩并且将残余物通过在硅胶上的色谱法纯化(己烷∶MTBE=9∶1),得到21.6g无色油。
步骤B:乙酸7-异亚丙基-2,5-二甲基-二环[2.2.1]庚-5-烯-2-基甲基酯向(7-异亚丙基-2,5-二甲基-二环[2.2.1]庚-5-烯-2-基)-甲醇(4.32g,22.5mmol)、吡啶(3.55g,45mmol)和DMAP(50mg)在二氯甲烷(50mol)中的溶液添加乙酰氯(2.47g,31.5mmol),同时冷却。将混合物在室温下搅拌1h,然后用水稀释并且用戊烷萃取(3×80ml)。将有机相用1N HCl、水和盐水洗涤,干燥(MgSO4)并且真空浓缩。残余物通过在硅胶上的色谱法纯化(己烷∶MTBE=9∶1),得到4.25g异构体混合物形式的无色油。气味描述:雪松油,胡萝卜,verdyl,麝香。1H-NMR(CDCl3,400MHz):5.93-5.72(m,1H),3.94-3.73(m,2H),3.10-2.78(m,2H),2.09-2.03(m,3H),1.85-1.53(m,9H1.50-1.15(m,2H),1.09/0.97/0.92/0.89(4s,3H)ppm.GC/MS(EI):main isomer:234(M+, trace),159(3),120(100),105(46),91(11),77(7),43(15).IR(atr):2927m,2726w,1741s,1446m,1369m,1233vs,1031s,986m,802m cm-1.
实施例11:应用
用于粉状洗涤剂或织物柔软剂的香料
乙酸PTBCH 8
Agrumex 8
己基肉桂醛 16
C10醛 0.3
C12醛MNA 0.3
邻氨基苯甲酸甲酯 0.3
香茅醇 5
香草醛 0.3
女贞醛(Cyclal C) 0.2
Gardenol 0.5
二氢茉莉酮酸甲酯 3
γ-甲基紫罗兰酮 5
芳樟醇 15
异己烯基四氢苯甲醛 1
橙油 5
甲基萘基酮 0.3
γ-十一内酯 2
Radjanol 1.8
水杨酸己酯 5
Thibetolide 3
1[7-(1-乙基-亚丙基)-二环[2.2.1]庚-2-基-]-乙酮 20
100
在此配方中,1[7-(1-乙基-亚丙基)-二环[2.2.1]庚-2-基-]-乙酮使得花香-铃兰香与木香多种香味得到调和,与其中二环[2.2.1]化合物被等量铃兰醛或甲基柏木酮或者被铃兰醛和甲基柏木酮的混合物所替换的配方相比,香味和谐性显得更平衡和更新鲜。
Claims (9)
1、以下通式的化合物:
其中
R1是氢或C1-6烷基;
R2是C1-6烷基或C2-6链烯基;
R3是氢或C1-4烷基;或者
R1和R3与它们所相连的碳原子一起形成5-或6-元碳环;
R4是腈基团,2-、3-或4-吡啶基,吡嗪基或羰基COR5,或基团C(R7)2-OR8;
R5是氢、C1-5烷基,C2-5链烯基或OR6;
R6是C1-5烷基或C2-5链烯基;
R7独立地是氢或C1-4烷基;
R8是C1-5烷基,C2-5链烯基或羰基COR9;
R9是C1-4烷基或C1-4链烯基;
R10是氢或C1-4烷基;
R11是氢或C1-4烷基;
R12是氢或C1-4烷基;
R13是氢或C1-4烷基;
C5和C6之间的键是单键,或者当R4是C(R7)2-OR8基团时,它与虚线一起表示双键。
3、一种芳香组合物,包含至少一种权利要求1定义的化合物。
4、含有权利要求1定义的化合物或者权利要求3定义的组合物的消费者用产品组合物。
5、权利要求4的消费者用产品组合物,选自精细香料组合物或增香产品,所述增香产品选自高级香水、美容制品、消费者保健产品或家用产品。
6、权利要求5的消费者用产品组合物,含有0.001wt%-10wt%的权利要求1定义的化合物。
7、权利要求5的消费者用产品组合物,其中所述家用产品包括洗剂、洗涤剂和香皂。
8、权利要求6的消费者用产品组合物,含有0.01wt%-1wt%的权利要求1定义的化合物。
9、增香权利要求5的消费者用产品组合物的方法,包括将权利要求1定义的化合物或权利要求3定义的组合物与所述消费者用产品组合物混合的步骤。
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US7517840B2 (en) | 2005-04-07 | 2009-04-14 | Givaudan Fragrances Corporation | Optimized perfumery for rinse-off products |
WO2008090397A1 (en) * | 2007-01-23 | 2008-07-31 | Quest International Services B.V. | Optimized perfumery for rinse-off products |
KR101378321B1 (ko) | 2007-05-25 | 2014-03-28 | (주)아모레퍼시픽 | 해당화의 향취를 재현한 향료 조성물 |
KR100927969B1 (ko) * | 2007-10-31 | 2009-11-24 | 주식회사 코리아나화장품 | 천연 백합향을 이용하여 백합의 향취를 재현한 향료 조성물 |
WO2011154859A1 (en) * | 2010-06-08 | 2011-12-15 | Firmenich Sa | Bicyclo-ketones as perfuming ingredients |
US8829228B2 (en) * | 2010-11-12 | 2014-09-09 | Mitsubishi Gas Chemical Company, Inc. | Carboxylate compound and method of producing the same and perfume composition thereof |
US9156774B2 (en) | 2011-03-25 | 2015-10-13 | Mitsubishi Gas Chemical Company, Inc. | Carboxylic acid ester compound and method for producing same, and fragrance composition |
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US4229600A (en) * | 1977-07-28 | 1980-10-21 | Takasago Perfumery Co., Ltd. | Norbornane and norbornene derivatives |
US4354043A (en) * | 1981-09-17 | 1982-10-12 | International Flavors & Fragrances Inc. | Norbornyl oxyacetaldehyde |
US4357949A (en) * | 1980-07-17 | 1982-11-09 | International Flavors & Fragrances Inc. | Carboamidoalkyl norbornanes, organoleptic uses thereof and process for preparing same |
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DE3410489A1 (de) * | 1984-03-22 | 1985-09-26 | Heraeus Elektroden GmbH, 6450 Hanau | Verfahren und vorrichtung, insbesondere zur desinfektion von wasser |
-
2001
- 2001-12-07 EP EP01129093A patent/EP1318190A1/en not_active Withdrawn
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2002
- 2002-12-04 AU AU2002342498A patent/AU2002342498A1/en not_active Abandoned
- 2002-12-04 EP EP02779096A patent/EP1451278B1/en not_active Expired - Lifetime
- 2002-12-04 BR BRPI0206922A patent/BRPI0206922B8/pt not_active IP Right Cessation
- 2002-12-04 DE DE60231143T patent/DE60231143D1/de not_active Expired - Lifetime
- 2002-12-04 MX MXPA04005308A patent/MXPA04005308A/es active IP Right Grant
- 2002-12-04 AT AT02779096T patent/ATE422531T1/de not_active IP Right Cessation
- 2002-12-04 US US10/497,323 patent/US7060664B2/en not_active Expired - Fee Related
- 2002-12-04 JP JP2003549465A patent/JP4316380B2/ja not_active Expired - Fee Related
- 2002-12-04 CN CNB028243951A patent/CN100358856C/zh not_active Expired - Fee Related
- 2002-12-04 ES ES02779096T patent/ES2320207T3/es not_active Expired - Lifetime
- 2002-12-04 WO PCT/CH2002/000657 patent/WO2003048285A1/en active Application Filing
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US4229600A (en) * | 1977-07-28 | 1980-10-21 | Takasago Perfumery Co., Ltd. | Norbornane and norbornene derivatives |
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US4357949A (en) * | 1980-07-17 | 1982-11-09 | International Flavors & Fragrances Inc. | Carboamidoalkyl norbornanes, organoleptic uses thereof and process for preparing same |
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JP4316380B2 (ja) | 2009-08-19 |
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JP2005511819A (ja) | 2005-04-28 |
AU2002342498A1 (en) | 2003-06-17 |
MXPA04005308A (es) | 2004-09-13 |
BR0206922A (pt) | 2004-02-03 |
EP1451278A1 (en) | 2004-09-01 |
US20050119157A1 (en) | 2005-06-02 |
ES2320207T3 (es) | 2009-05-20 |
BR0206922B1 (pt) | 2014-01-28 |
BRPI0206922B8 (pt) | 2016-05-10 |
DE60231143D1 (de) | 2009-03-26 |
CN1599788A (zh) | 2005-03-23 |
US7060664B2 (en) | 2006-06-13 |
EP1451278B1 (en) | 2009-02-11 |
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