CN1600782B - 多烷基二环衍生物 - Google Patents
多烷基二环衍生物 Download PDFInfo
- Publication number
- CN1600782B CN1600782B CN200410045639.8A CN200410045639A CN1600782B CN 1600782 B CN1600782 B CN 1600782B CN 200410045639 A CN200410045639 A CN 200410045639A CN 1600782 B CN1600782 B CN 1600782B
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- China
- Prior art keywords
- methyl
- compound
- mixture
- hydrogen
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 23
- 150000002431 hydrogen Chemical group 0.000 claims description 21
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
- C07C35/32—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system being a (4.3.0) system, e.g. indenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C43/188—Unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
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Abstract
揭示了用于具有如下通式结构的香料成分的多烷基二环化学衍生物:
Description
发明领域
本发明涉及新颖的化学物质,和所述新颖化学物质作为芳香化学品的掺合及应用。
发明背景
分子化学结构的不同导致其气味、香韵以及分子特征存在显著的差异。在研制新颖的香料时,发现和使用所述新化学物质的这些变化和当前需求使得调香师能使用新的化合物来产生新的香气。
美国专利No.5,227,367揭示了羟基五甲基1,2-二氢化茚羧基醛(carboxaldehyde)及其制备方法、其感官应用以及包含它们的化妆和医药组合物。
美国专利No.5,733,866揭示了甲基取代的六氢茚满醇及其在增加或增强香料组合物、古龙香水和有香味制品的香料中的应用。
美国专利No.5,665,698揭示了甲基取代的四氢1,2-二氢化茚烷基烯醇醚及其在增加、增强或赋于香料组合物、古龙香水和有香味制品件的香料中的应用。也揭示了其制备方法和工艺中间体。
发明概述
本发明提供化学物质,以及所述化学物质在增强香水、花露水、古龙香水、个人用品等的香料的应用。此外,本发明涉及使用所述化学物质来增强香水、花露水、古龙香水、个人用品等的香气。
更具体的是,本发明涉及如下结构所示的化合物:
式中,m是0或1;
各虚线表示碳碳单键或者碳碳双键,其前提是不会有一条以上的虚线表示碳碳双键;
X表示氢或甲基;
R1、R2、R3和R4各自表示甲基或乙基,其前提是当X是甲基时,R1、R2、R3和R4各自为甲基,当X是氢时,R1、R2、R3和R4中的一个是乙基;
式中,当两虚线均不是双键时,D是=0或-OH;当两虚线之一为双键时,D为-0R5;当所述位于Δ4,5位上的虚线为双键时,D为-0R7;或者当所述位于Δ3A,4位上虚线表示双键时,D为
R6是氢或甲基;
R7表示C1-C3烷基;
R5表示C4-C7环烷基、C4-C7羟基链烯基或者三-C1-C3烷基甲硅烷基;
式中,当两虚线均不是双键时,E是氢或
其前提是当D是=0或-OH时,E是
式中,当两虚线均不是双键且D不是=0时,F是氢;
式中,当两虚线均不是双键时,D和E一起表示如下所述部分:
式中,R和R’各自表示氢或甲基,其前提是R和R’中至少一个是甲基。
本发明还提供制备这些化合物的方法。
本发明另一实施方式是通过加入嗅觉可接受量的一种或多种上述提供的化合物来增强香气的方法。
本发明其它实施方式是制备上述提供的化合物的方法。通过阅读以下说明书,本发明的这些和其它实施方式将显而易见。
发明详述
通过以下结构更加完全地说明本发明新颖的化合物:
式中,R1、R2、R3、R4、R5、R6、R7、X和m如上所述。
在优选实施方式中,所述分子包含所述环状结构,式中,R6是甲基,m=0;且这种优选的分子具有如下结构:
式中,R1、R2、R3、R4和X如上所述。
在更加优选的实施方式中,上述四种结构各自表示混合物,在所述各混合物中,所述主要分子(大于或等于约90%)是其中X表示甲基且R1、R2、R3和R4各自表示甲基的分子,所述量少的分子(小于或等于约10%)是其中X是氢、R1、R2、R3和R4中的一个是乙基且其它的R1、R2、R3和R4各自为甲基的分子。
本发明最优选的化合物是如下结构的化合物:
(3,3,10,10,11,12,12-七甲基-4-氧三环[7.3.0.0<1,5>]十二烷);也称为十氢-2,2,4,4,5,6,6-七甲基茚并[4,3A-B]呋喃异构体,例如具有如下结构:
这种异构体可以单独使用或者混合使用,按照本发明的实践用于配制香料组合物。更具体的是这种异构体如下表I所示:
(1R,5R,9R,11R)-Z | (1R,5S,9R,11S)-Z |
(1R,5R,9R,11S)-Z | (1R,5R,9S,11S)-Z |
(1R,5R,9S,11R)-Z | (1R,5S,9S,11R)-Z |
(1R,5S,9R,11R)-Z | (1R,5S,9S,11S)-Z |
(1S,5R,9R,11R)-Z | (1S,5R,9S,11S)-Z |
(1S,5R,9R,11S)-Z | (1S,5S,9R,11S)-Z |
(1S,5R,9S,11R)-Z | (1S,5S,9S,11R)-Z |
(1S,5S,9R,11R)-Z | (1S,5S,9S,11S)-Z |
其中,“Z”表示化合物的名称,3,3,10,10,11,12,12-七甲基-4-氧杂三环[7.3.0.0<1,5>]十二烷。
因此本领域的那些技术人员应意识到,本发明的化合物具有许多手性中心,由此提供所述化合物的许多异构体。此处规定,本文所述的化合物包括这种化合物的异构体混合物,以及使用本领域那些技术人员已知的技术分离得到的那些异构体。合适的技术包括色谱法如HPLC、尤其是凝胶色谱法和固相微萃取(“SPME”)。
所述化合物具有如下结构:
通过在约85-105℃下,在催化量的质子酸,较好是对甲苯磺酸或者甲磺酸存在下,使烯丙醇或甲基烯丙醇和相应的C1-C3烷基烯醇醚进行交换反应来制备,反应如下:
所得烯丙基或甲基烯丙基烯醇醚可以被回收,并使用其感官性质,或者通过在约190-210℃下,在酸催化剂,较好是弱酸催化剂如磷酸、磷酸二氢钾、磷酸二氢钠、硫酸氢钠、酸性离子交换催化剂、AMBERLYST15(Rohm and Haas Company ofPhiladelphia,Pa.,USA的商品名,)、柠檬酸二钠或者对苯二酚存在下进行Claisen重排反应,使它们各自重排,反应如下:
可以分离所得3A-烯丙基或3A-甲基烯丙基-4-酮衍生物,并利用其各自的感官性质,或者使用金属氢化物还原剂例如LiA1H4或者氢化二(2-甲氧基乙氧基)铝钠(VITRIDE)使它们进行羰基还原反应,形成相应的3A-烯丙基或3A-甲基烯丙基-4-羟基衍生物,反应如下:
可以回收所得3A-烯丙基或3A-甲基烯丙基-4-羟基衍生物,并使用其感官性质,或者在18-40℃下,在硝基丙烷中用质子酸环化试剂,较好是甲磺酸进行环化,反应如下:
具有如下结构的化合物通过以下任一反应制备:
所述反应如下:
其中,R5是三烷基甲硅烷基;或者
其中,R5是C4-C7环烷基或者C4-C7羟基链烯基,所述虚线表示了双键位置不同的异构体混合物,在这种混合物中,一根虚线表示碳碳双键,另一虚线表示碳碳单键。在两种情况下,所述Δ3A,4和Δ4,5双键位置的异构体以混合物的形式制得,若需要的话,可以在使用其各自感官性质之前按照本领域普通技术人员熟知的技术进行分离。
所述具有如下结构的化合物通过以下任一反应制备:
所述反应如下:
该反应在γ-氧化铝存在下进行;或者
其中,形成双键位置异构体的混合物,一根虚线是碳碳双键,另一虚线为碳碳单键,或者
该反应在约125-150℃下,在γ-氧化铝以及大气压下沸点大于160℃的惰性溶剂如甲苯或对二甲苯存在下进行。R7最好是甲基。
所述后两个反应各自形成Δ3A,4和Δ4,5双键位置异构体的混合物,若需要的话,可以使用本领域技术人员熟知的技术进行分离。
本发明的化合物以及混合物具有浓烈且真实的带芳香麝香、龙涎香、乳香的头香和浓烈的花香、雪松、香脂、芳香麝香、龙涎香及木香的底香的木香、烟香椿香、龙涎香香味。
本发明化合物可以广泛地用于目前的香料产品,包括制备香料和古龙香水,对个人护理产品如肥皂、沐浴凝胶和护发品以及空气清新剂和化妆制品加香。本发明也可以用于为清洁剂,例如(但不限于)洗涤剂、洗餐具材料、擦洗组合物、窗户清洁剂等加香。
在这些制剂中,本发明的化合物可以单独使用或者和其它加香组合物、溶剂、助剂等混合使用。也可以使用的其它成分的性质和种类为本领域技术人员所知。
本发明可以使用许多类型的香味,唯一的限制就是和所用的其它组分的相容性。合适的香味包括但不限于水果如杏仁、苹果、樱桃、葡萄、梨、菠萝、橙子、草莓、木莓,麝香及花香如熏衣草类、玫瑰类、鸢尾属植物和康乃馨。其它怡人的香味包括草药的香味和来自松树、云杉和其它树木的森林味道。香味也可以来自各种油,如香精油,或者来自植物材料如薄荷、留兰香等。
在美国专利No.4,534,891中提供了一系列合适的香味,其内容全文参考引用于此。在Perfumes,Cosmetics and Soaps(第二版,W.A.Poucher编著,1959)中发现了合适香味的另一来源。这一论述中提供的香味是阿拉伯树胶、金合欢、素心兰、仙客来红素、香蕨、栀子、山楂、天芥莱、金银花、风信子、茉莉、紫丁香、百合、木兰、含羞草、水仙、刚收割的牧草、橙花、兰花、木犀草、香豌豆、三叶草、晚香玉、香草、紫罗兰、罗兰花等。
嗅觉有效量应理解为是指香料组合物中化合物的量,各组分将提供其特有的嗅觉特征,但是所述香料组合物的嗅觉效果将是各香味或香味成分效果的总和。因此,本发明化合物可以用于改变所述香料组合物的香味特征,或者通过组合物中的另一成分来改变所述嗅觉反应。所述量将取决于许多因素,包括其它成分、相对量以及所需的效果。
在所述香味制品中使用的本发明化合物的含量约为0.005-10重量%,较好是约0.5-8重量%,最好是约1-7重量%。除了所述化合物外,可以混合使用所述香料和其它试剂。在不偏离本发明范围的条件下,也可以使用熟知的材料如表面活性剂、乳化剂和包封所述香料的聚合物。
记录所述香味组合物中本发明化合物量的另一方法是将化合物记录为赋于所需香味的加入材料的重量百分数。本发明化合物约为所述香味组合物的0.005-70重量%,较好是约0.1-50重量%,最好是约0.2-25重量%。本领域技术人员可以使用所需量的本发明化合物,来提供所需的香味和强度。
以下将提供本发明具体的实施方式。本发明其它修改对本领域技术人员来说显而易见。应理解,这种修改在本发明的范围内。
除非另有说明,如本文所用的所有百分数均是重量%,ppm是指百万分率;mm是指毫米,ml是指毫升,Bp是指沸点,THF是指四氢呋喃,Hg是指汞,g是指克,实施例中所用的IFF应理解为International Flavors&Fragrances Inc.,NewYork,N.Y.USA。
实施例I
制备1,1,2,3,3-五甲基-7-(2-甲基丙-2-烯基氧基)-2,3,4,5,6,3A-六氢茚
反应:
往装有热电偶、接有馏出闪蒸器(take-off rushorer still)的12″Goodloe填充柱、机械搅拌器、氮气管和进料漏斗的5升反应器中加入507g(2摩尔)按照美国专利No.5,665,698中实施例I的步骤制备的1,1,2,3,3-五甲基-7-(2-甲氧基)-2,3,4,5,6,3A-六氢茚、288g(4摩尔)甲基丙烯醇和1.1g对甲苯磺酸。
在搅拌下将所得反应混合物加热至85℃,并在此温度保持5小时,并蒸馏出所述甲醇反应产物。
然后,通过加入1.5g30%甲醇钠溶液来淬天所得反应混合物,然后通过真空蒸发来除去轻组分。然后,将所得产物转移到快速蒸馏装置中,在1.8-2.0mmHg下蒸馏。
在3.01-3.25mmHg的压力下,在129-131℃的蒸气温度范围内在18″Goodloe柱中蒸馏所述粗物料。
所述产品具有如下结构(一种混合物,在其主要化合物(90%)中,X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
0.68-1.1ppm(ms,15H),1.25-2.2ppm(m,7H),1.75ppm(s,3H),4.4ppm(d,2H),4.85-5.1ppm(2s,2H)
所述产物具有带雪松底香的浓烈和真实的木香、烟香椿味香。
实施例II
制备八氢-1,1,2,3,3-五甲基-3A-(2-甲基-2-丙烯基)-4H-二氢茚-4-酮
反应如下:
往装有热电偶、冷凝器、机械搅拌器、氮气管和进料流体计量泵的5升反应烧瓶中加入50g Primol(矿物油)和1g NaH2PO4。
在搅拌下,将所得混合物加热至190-195℃。使用所述计量泵,在将所述反应混合物温度保持在190-210℃的1.5小时内,往所述反应混合物中加入538g(1.72摩尔)实施例1的产物(包含90%1,1,2,3,3-五甲基-7-(2-甲基丙-2-烯基氧基)-2,3,4,5,6,3A-六氢茚)。
然后,将所述反应混合物转移到快速蒸馏装置上,在1.0-2.0mmHg的压力下蒸馏所述粗物料。然后将所述产物转移到18″Goodloe柱中,并在1.8mmHg下在165℃下进行分馏。
所得产物具有如下结构(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
0.76-1.13ppm(ms,15H),1.57ppm(s,3H),1.7ppm(m,2H),1.85ppm(m,2H),1.95-2.86ppm(m,7H),4.68-4.86ppm(2s,2H)
所述产物具有带浓烈龙涎香头香的木香香味。
实施例III
制备八氢-1,1,2,3,3-五甲基-3A-(2-甲基-2-丙烯基)-4H-茚-4-酚
反应如下:
往装有热电偶、机械搅拌器、氮气管和进料漏斗的5升反应烧瓶中加入718g(2.74摩尔)实施例II制备的八氢-1,1,2,3,3-五甲基-3A-(2-甲基-2-丙烯基)-4H-二氢茚-4-酮。
缓慢加入550g在250ml四氢呋喃中的LiAlH4,同时小心冷却所述反应物质,使所述反应温度升至最高70℃。
在搅拌下,将所述反应物质在70℃下保持0.5小时。
在0.5小时结束后,最初用乙酸乙酯淬灭所述反应物质(为了分解过量的LiAlH4),之后加入1000ml3M的NaOH水溶液。
所述反应物质形成两相:水相和有机相。分离所述水层,并再用2×1000ml浓NaCl水溶液洗涤所述有机层两次,并在无水Na2SO4上干燥,并经过硅藻土(WorldMinerals Inc.)过滤。
然后,将所述有机层转移到快速蒸馏装置中,在该装置中,开始除去470g溶剂,之后通过在107-151℃和5-9mmHg压力下蒸馏制得粗产物。然后该产物在175℃和6.5mmHg压力下在18″×1.5″Goodloe柱上进行蒸馏。
所得产物具有如下结构(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
1.25-1.78ppm(m,9H),0.7-1.1ppm(ms,15H),1.86ppm(s,3H),2.05-2.65ppm(m,4H),4.8-4.95ppm(2s,2H)
所述产物具有带浓烈龙涎香头香的木香香味。
实施例IV
制备十氢-2,2,4,4,5,6,6-七甲基-茚并[4,3A-B]呋喃
反应如下
往装有热电偶、机械搅拌器、氮气管、进料漏斗和快速蒸馏柱的5升反应烧瓶中加入300gl-硝基丙烷和452g(1.17摩尔)实施例III制备的八氢-1,1,2,3,3-五甲基-3A-(2-甲基-2-丙烯基)-4H-茚-4-酚。
在搅拌下,往所得混合物中缓慢加入10ml甲磺酸,使所述混合物的温度升至30℃。然后,将所述反应物质搅拌0.5小时。然后在搅拌下,往所述反应混合物中加入5ml甲磺酸,同时将温度保持在30℃。然后,搅拌所述反应物质0.5小时。然后在搅拌下,往所述反应混合物中再加入15ml甲磺酸,同时将温度保持在30℃。然后将所述反应物质搅拌0.5小时。然后,将所述反应物质再搅拌4小时,同时将温度保持在30℃。
四小时后,用250ml的Na2CO3淬灭所述反应物质,并搅拌15分钟。这时,所述反应物质的pH为9-9.5。然后在搅拌条件下往所述反应物质中加入250ml水,并再继续搅拌0.5小时。
所述反应物质形成两相:水相和有机相。将所述有机相转移到快速蒸馏装置中,在175℃和6.5mmHg下开始除去470g溶剂,之后除去未反应的八氢-1,1,2,3,3-五甲基-3A-(2-甲基-2-丙烯基)-4H-茚-4-酚。
然后,通过18″×1.5″Goodloe柱以3∶1的回流比分馏所述粗制快速蒸馏物料,得到17馏分。在91℃和6.5mmHg压力下蒸馏得到的馏分6-16显得很多。
所得产物具有如下结构(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
0.65-1.07ppm(ms,15H),1.3ppm(s,3H),1.4ppm(s,3H),1.55-2.46ppm(m,7H)所述产物具有带芳香麝香头香和香脂底香的浓烈且真实的木香龙涎香味。
实施例V
制备1,1,2,3,3-五甲基-7-(丙-2-烯基氧基)-2,3,4,5,6,3A-六氢茚
反应如下:
往装有热电偶、接有馏出闪蒸器的12″Goodloe填充柱、机械搅拌器、氮气管和进料漏斗的5升反应器中加入507g(2摩尔)按照美国专利No.5,665,698中实施例I的步骤制备的1,1,2,3,3-五甲基-7-(2-甲氧基)-2,3,4,5,6,3A-六氢茚、240g(4摩尔)烯丙醇和1.1g对甲苯磺酸。
在搅拌下将所得反应混合物加热至85℃,并在此温度下保持5小时,并蒸馏出所述甲醇反应产物。
然后,通过加入1.5g30%甲醇钠溶液来淬灭所得反应混合物,然后通过真空蒸发来除去轻组分。
然后,将所得产物转移到快速蒸馏装置中进行蒸馏,制得具有如下结构的化合物(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
所述产物具有带芳香麝香底香的桃花心木香味。
实施例VI
制备八氢-1,1,2,3,3-五甲基-3A-(2-丙烯基)-4H-二氢茚-4-酮
反应如下:
往装有热电偶、冷凝器、机械搅拌器、氮气管和进料流体计量泵的5升反应烧瓶中加入50g Primol(矿物油)和5g KH2PO4。
在搅拌下,将所得混合物加热至190-195℃。使用所述计量泵,在将所述反应混合物温度保持在190-210℃的1.5小时内,往所述反应混合物中加入312g实施例V的产物(包含90%1,1,2,3,3-五甲基-7-(丙-2-烯基氧基)-2,3,4,5,6,3A-六氢茚)。
然后,将所述反应混合物转移到快速蒸馏装置上,蒸馏所述粗物料。
所述产物具有带龙涎底香的强烈木香香味。
所得产物具有如下结构(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
0.73-1.06ppm(ms,15H),1.2-2.4ppm(m,8H),5.1ppm(m,2H),5.5ppm(m,1H)。
实施例VII
制备八氢-1,1,2,3,3-五甲基-3A-(2-丙烯基)-4H-茚-4-酚
反应如下:
往装有热电偶、机械搅拌器、氮气管和进料漏斗的5升反应烧瓶中加入656g(1.77摩尔)实施例VI制备的八氢-1,1,2,3,3-五甲基-3A-(2-丙烯基)-4H-二氢茚-4-酮。
缓慢加入21.7g在260ml四氢呋喃中的LiAlH4,同时小心冷却所述反应物质,使所述反应温度升至最高70℃。
在搅拌下,将所述反应物质在70℃下保持0.5小时。
在0.5小时结束后,最初用20%乙酸水溶液淬灭所述反应物质(为了分解过量的LiAlH4),之后加入1000ml20%的NaHCO3水溶液。
所述反应物质形成两相:水相和有机相。分离所述水层,并再用2×1000ml浓NaCl水溶液洗涤所述有机层两次,并在无水Na2SO4上干燥,并经过硅藻土过滤。
然后,将所述有机层转移到快速蒸馏装置中,在该装置中开始除去470g溶剂,之后蒸馏得到粗产物。然后在18″×1.5″Goodloe柱上进行蒸馏。
所述产物具有浓烈真实木香的龙涎香味。
所得产物具有如下结构(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
0.7-1.1ppm(ms,15H),1.35-1.8ppm(m,7H),2.25-2.6ppm(m,2H),3.95ppm(m,1H),5.15ppm(m,2H),6ppm(m,1H)。
红外光谱如下:
3431cm-1(-OH),3074,2958cm-1(-CH),909cm-1(>=CH2)。
实施例VIII
制备十氢-2,4,4,5,6,6-六甲基-茚并[4,3A-B]呋喃
反应如下
往装有热电偶、机械搅拌器、氮气管、进料漏斗和快速蒸馏柱的5升反应烧瓶中加入300gl-硝基丙烷和452g实施例VII制备的八氢-1,1,2,3,3-五甲基-3A-(2-丙烯基)-4H-茚-4-酚。
在搅拌下,往所得混合物中缓慢加入10ml甲磺酸,使所述混合物的温度升至30℃。然后,将所述反应物质搅拌0.5小时。然后在搅拌下,往所述反应混合物中加入5ml甲磺酸,同时将温度保持在30℃。然后,搅拌所述反应物质0.5小时。然后在搅拌下,往所述反应混合物中再加入15ml甲磺酸,同时将温度保持在30℃。然后搅拌所述反应物质0.5小时。然后,将所述反应物质再搅拌4小时,同时将温度保持在30℃。
四小时后,用250ml的Na2CO3淬灭所述反应物质,并搅拌15分钟。这时,所述反应物质的pH为9-9.5。然后在搅拌下往所述反应物质中加入250ml的水,并再继续搅拌0.5小时。
所述反应物质形成两相:水相和有机相。将所述有机相转移到快速蒸馏装置中,在该装置中开始除去溶剂。然后,将所述产物转移到18″×1.5″Goodloe柱中,分馏制得带芳香麝香头香和香脂底香的浓烈且真实的木香龙涎香香味的产物以及具有如下结构的化合物(一种混合物,在所述主要化合物中(90%),X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
实施例IX
制备4-[(2,3,5,6,7,7A-六氢-1,1,2,3,3-五甲基-1H-茚-4-基)氧基]2Z-丁烯
-1-醇
反应如下:
(其中,所述虚线表示了双键位置不同的异构体混合物,在这种混合物的各化合物中,一根虚线表示碳碳双键,另一虚线表示碳碳单键)
往装有热电偶、接有馏出闪蒸器的12″Goodloe填充柱、机械搅拌器、氮气管和进料漏斗的5升反应容器中加入507g(2摩尔)按照美国专利No.5,665,698中实施例I的步骤制备的1,1,2,3,3-五甲基-7-(2-甲氧基)-2,3,4,5,6,3A-六氢茚、240gl,4-二羟基-2Z丁烯和1.1g对甲苯磺酸。
在搅拌下将所得反应混合物加热至85℃,并在此温度下保持5小时,并蒸馏出所述甲醇反应产物。
然后,通过加入1.5g30%甲醇钠溶液来淬灭所得反应混合物,然后通过真空蒸发来除去较轻组分。然后,将所得产物转移到快速蒸馏装置中,进行蒸馏。制得具有如下结构的化合物(一种混合物,在其主要化合物(90%)中,X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR光谱如下:
0.64-1.09ppm(ms,15H),1.61-2.12ppm(m,7H),2.88ppm(s,1H),4ppm(m,2H),4.37ppm(m,2H),5.66ppm(m,1H),5.80ppm(m,1H)
所述产物具有带花香底香的木香芳香麝香香味。
实施例X
制备7-(环己氧基)-2,3,3A,4,5,6-六氢-1,1,2,3,3-五甲基-1H-茚
反应如下:
(其中,所述虚线表示了双键位置不同的异构体混合物,在这种混合物的各化合物中,一根虚线表示碳碳双键,另一虚线表示碳碳单键)。
往装有热电偶、接有馏出闪蒸器的12″Goodloe填充柱、机械搅拌器、氮气管和进料漏斗的5升反应器中加入109g按照美国专利No.5,665,698中实施例I的步骤制备的1,1,2,3,3-五甲基-7-(2-甲氧基)-2,3,4,5,6,3A-六氢茚、100g环己醇和0.34g对甲苯磺酸。
在搅拌条件下将所得反应混合物加热至90℃,并在此温度下保持2.5小时,并蒸馏出所述甲醇反应产物。
然后,通过加入1.5g30%甲醇钠溶液来淬灭所得反应混合物,然后通过真空蒸发来除去轻组分。然后,将所得产物转移到快速蒸馏装置中,进行蒸馏。制得具有如下结构(Δ7,7A和Δ6,7A双键位置异构体化合物的2∶1混合物)的化合物(一种混合物,在其主要化合物(90%)中,X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
它具有带龙涎香头香的木香芳香麝香香味,其NMR谱如下:
0.68-0.95ppm(ms,15H),1.1-2.3ppm(m,17H),3.8ppm(s,1H),5.25ppm(m,1H)。
实施例XI
制备[(2,3,5,6,7,7A-六氢-1,1,2,3,3五甲基-1H-茚-4-基)氧基]三甲基硅烷
反应如下:
(其中,所述虚线表示了双键位置不同的异构体混合物,在这种混合物的各化合物中,一根虚线表示碳碳双键,另一虚线表示碳碳单键)。
往装有搅拌器、温度计、加热套、氮气管、进料漏斗和回流冷凝器的5升反应器中加入二甲基甲酰胺、三乙胺和三甲基甲硅烷基氯。在搅拌下,在氮气气氛中将所得混合物加热至70℃。在0.25小时内,在搅拌下往所述反应物质中加入具有以下结构的二氢开司米酮(6,7-二氢-1,1,2,3,3-五甲基-(4(5H)-茚满酮):
将所述反应物质加热至80℃,并在80℃下保持10小时。将所述反应物质冷却至室温,然后在搅拌下加入200g甲苯。然后,用400ml水淬灭所述反应物质,然后用200ml的水洗涤所得有机相。在120℃和3mmHg压力下蒸馏所得产物,制得具有如下结构的化合物(一种混合物,在其主要化合物(90%)中,X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基):
其NMR谱如下:
0.18ppm(s,9H),0.58-1.1ppm(ms,15H),1.38-2.2ppm(m,7H)。
所述产物具有带软木香乳香的头香的木香花香香味。
实施例XII
制备2,3,3A,4,5,7A-六氢-7-甲氧基-1,1,2,3,4-五甲基-1H-茚
反应如下:
(其中,R7是甲基)。
往所述装有温度计、回流冷凝器、迪安和斯塔克分水器、搅拌器和加热套的5升反应器中加入10gγ-氧化铝(在200℃下活化0.25小时的氧化铝)、100g甲苯和200g按照美国专利No.5,665,698所述步骤制备的1,1,2,3,3-五甲基-4,4-二甲氧基1,2-二氢化茚。在搅拌条件下,将所得混合物加热回流9小时,同时在迪安和斯塔克分水器中收集反应产物。所得产物在蒸馏前是Δ4,5和Δ3A,4双键异构体的6∶1混合物。
所述主要产物的结构如下:
其中,R7是甲基,所得产物是一种混合物,在其主要化合物(90%)中,X、R1、R2、R3和R4各自为甲基;在次要化合物中,X是氢,R1、R2、R3和R4之一是乙基,R1、R2、R3和R4中其它的为甲基;所述产物的NMR谱如下:
0.68-1.1ppm(ms,15H),1.27-2.15ppm(m,7H),3.45ppm(s,3H),4.45ppm(m,1H)
所述产物具有带香脂底香的浓烈且真实木香芳香麝香香味。
实施例XIII
香料配方
按照如下配方制备香料:
实施例IV和VIII的茚并呋喃各自将浓烈且真实的木香、龙涎香和香脂底香味和芳香麝香头香赋于该柑桔香料。因此,实施例XIII(a)和XIII(c)的香料可以被形容为具有浓烈且真实木香、龙涎香以及香脂底香以及芳香麝香头香的柑桔香味。
实施例XI的茚基硅烷将木香和花香的底香以及软木香和乳香的头香赋于该柑桔香料。因此,实施例XIII(B)的香味可以被形容为带木香和花香的底香以及软木香和乳香的头香的柑桔香味。
实施例XIV
制备化妆品粉末组合物
通过在球磨机中混合100g滑石粉和0.25g下表II中所列的各物质来制备化装品粉末组合物。各化装品粉末组合物具有优良的香味,如下表II所述。
表 II
物质 | 香味描述 |
实施例I制备的1,1,2,3,3-五甲基-7-(2-甲基丙-2-烯基氧基)-2,3,4,5,6,3A-六氢茚 | 带雪松底香的浓烈且真实的木香、烟香椿香味 |
实施例IV制备的十氢-2,2,4,4,5,6,6-七甲基-茚并[4,3A-B]呋喃 | 带芳香麝香头香和香脂底香的浓烈且真实的木香龙涎香香味 |
实施例XI制备的[(2,3,5,6,7,7A-六氢-1,1,2,3,4五甲基-1H-茚-4-基)氧基]三甲基硅烷 | 具有带软木香乳香的头香的木香、花香 |
实施例VIII制备的十氢-2,4,4,5,6,-7-六甲基-茚并[4,3A-B]呋喃 | 带芳香麝香头香和香脂底香的浓烈且真实的木香龙涎香香味 |
实施例XII制备的2,3,3A,4,5,7A-六氢-7-甲氧基-1,1,2,3,4-五甲基-1H-茚 | 带香脂底香的浓烈且真实木香芳香麝香香味 |
实施例XIII(a)制备的香味组合物 | 带浓烈且真实的木香、龙涎香和香脂的底香和芳香麝香头香的柑桔香味 |
实施例XIII(b)制备的香味组合物 | 带木香和花香的底香以及软木香和乳香的头香的柑桔香味 |
实施例XIII(c)制备的香味组合物 | 带浓烈且真实的木香、龙涎香和香脂的底香和芳香麝香头香的柑桔香味 |
实施例XV
制备肥皂组合物
Claims (17)
5.一种具有如下结构的化合物的混合物:
在含量占90%的主要化合物中,X、R1、R2、R3和R4各自为甲基,在次要化合物中,X为氢,R1、R2、R3和R4之一为乙基,R1、R2、R3和R4中的其它为甲基。
8.权利要求7所述的混合物,其中所述的化合物包含选自以下的旋光异构体:
其中,Z表示化合物3,3,10,10,11,12,12-七甲基-4-氧杂三环[7.3.0.0<1,5>]十二烷。
10.一种用于提高、增强或改变香料香味性质的方法,所述方法是加入嗅觉可接受量的权利要求9所述的混合物。
11.一种用于提高、增强或改变香料香味性质的方法,所述方法是加入嗅觉可接受量的权利要求3所述的混合物。
12.一种用于提高、增强或改变香料香味性质的方法,所述方法是加入嗅觉可接受量的权利要求4所述的混合物。
13.一种用于提高、增强或改变香料香味性质的方法,所述方法是加入嗅觉可接受量的权利要求7所述的混合物。
14.一种用于提高、增强或改变香料香味性质的方法,所述方法是加入嗅觉可接受量的权利要求8所述的混合物。
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US10/672,339 US7312187B2 (en) | 2001-05-17 | 2003-09-26 | Polyalkylbicyclic derivatives |
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MX2018004471A (es) | 2015-10-12 | 2018-08-15 | Int Flavors & Fragrances Inc | Compuestos novedosos de propanal octahidroindenilo. |
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US4902672A (en) * | 1989-06-26 | 1990-02-20 | International Flavors & Fragrances Inc. | Polyalkyl indanyl n-propyl and allyl ethers and perfumery uses thereof |
EP0827945A1 (en) * | 1996-09-06 | 1998-03-11 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Methyl substituted tetrahydroindane methyl enol ethers, perfumery uses thereof, processes for preparing same, and process intermediates therefor |
EP1262481A1 (en) * | 2001-05-17 | 2002-12-04 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Indanone derivatives for use as fragrances |
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US3767713A (en) * | 1969-08-18 | 1973-10-23 | Int Flavors & Fragrances Inc | Saturated indane derivatives and processes for producing same |
US3847993A (en) * | 1971-06-21 | 1974-11-12 | Int Flavors & Fragrances Inc | Allylic oxidation of bicyclic hydrocarbons to alcohols and ketones |
US3927083A (en) * | 1972-06-15 | 1975-12-16 | Int Flavors & Fragrances Inc | Bicyclic compounds and processes for making and using same |
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 |
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 |
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 |
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 |
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2003
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2004
- 2004-02-26 EP EP04251077.6A patent/EP1524255B1/en not_active Expired - Lifetime
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US4902672A (en) * | 1989-06-26 | 1990-02-20 | International Flavors & Fragrances Inc. | Polyalkyl indanyl n-propyl and allyl ethers and perfumery uses thereof |
EP0827945A1 (en) * | 1996-09-06 | 1998-03-11 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Methyl substituted tetrahydroindane methyl enol ethers, perfumery uses thereof, processes for preparing same, and process intermediates therefor |
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US7312187B2 (en) | 2007-12-25 |
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