CN101263100B - 含氧的三-或四-环萜类化合物 - Google Patents
含氧的三-或四-环萜类化合物 Download PDFInfo
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- CN101263100B CN101263100B CN200680033964XA CN200680033964A CN101263100B CN 101263100 B CN101263100 B CN 101263100B CN 200680033964X A CN200680033964X A CN 200680033964XA CN 200680033964 A CN200680033964 A CN 200680033964A CN 101263100 B CN101263100 B CN 101263100B
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
- C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
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- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
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- C07C43/00—Ethers; Compounds having groups, groups or groups
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- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
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- C07C47/105—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing rings
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Abstract
式(I)化合物作为香料成分的用途以及包含所述化合物的香料用品:其中R1和Y与说明书中给出的含义相同。
Description
本发明涉及一类新的具有木香、琥珀香和麝香气味香型的含氧的三-和四环萜类化合物,及其作为增味剂的用途。本发明还涉及它们的制备方法和包含它们的香料组合物。
在现代香料中,木香、琥珀香和麝香香型起决定性作用。其形成许多香料的基础,难以想象出一种没有任何木香或琥珀香香型的香料。令人惊讶地,现在发现某些含氧的三-和四-环萜类化合物具有非常强烈的琥珀香、木香和麝香气味。
许多具有异长叶烷环系的含氧的萜类化合物都是已知的,其中的一些具有特有的气味香型并因此适宜用在香料中,例如Folenox(A)、Piconia(B)、YsamberK(C)和乙酰基异长叶烯(D),然而另一方面,大量的萜类化合物都已知是没有或基本上没有气味性质的。但是,人们从未将结构和气味完全关联起来,因此通常不可能预测哪个化合物具有有用或令人愉快的气味,或者任意给定的化合物会具有何种特殊的气味性质。
衍生自现有技术中已知的异长叶烯的化合物通常具有下述性质:发香中心,即氧原子,通过C1-间隔基团或者直接地与环系,即分子的亲油部分相连。令人惊讶地,已经发现当分子的发香中心与亲油中心之间的距离较大时,可能获得在施用于有生命或无生命的表面,例如纤维、毛发和皮肤上时拥有非常高的直接性(气味长期性)的非常有效的分子。
因此,本发明的一个方面涉及一种香料组合物,其包含式(I)的含氧的三-或四-环萜类化合物:
其中
R1为氢或C1-C3烷基,例如甲基、乙基或异丙基;
Y为选自-CR2O和-CHR2OR3的单价残基,
其中R2为氢或C1-C3烷基,例如甲基、乙基或异丙基;和
R3为氢或C1-C3烷基,例如甲基、乙基或异丙基;或
Y为式-CHR2OCHR2-的二价残基,该二价残基与C-2、C-5’和C-4’的碳原子一起形成6-元环系,
其中R2为氢或甲基;
且C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键,或者C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键中的一个与虚线一起表示双键;
条件是式(I)化合物的碳原子总数为20或更小,例如17、18或19个碳原子。
式(I)化合物包括若干个手性中心,这样就可以作为立体异构体混合物存在,或者其可以被拆分为异构纯的形式。立体异构体的拆分给这些化合物的制备和纯化增加了复杂性,因此仅仅出于经济原因优选使用作为立体异构体的混合物形式的化合物。但是,如果希望制备单独的立体异构体,则可以根据现有技术中已知的方法,例如制备性HPLC和GC、结晶或立体选择性合成来实现。
特殊的实施方案是具有下述结构的式(I)化合物:其中如果C-4’和C-5’的键与虚线一起表示双键,则环系的相对构型为(1’S,6’R,8’S)。
优选的是下述的式(I)化合物:其中C-2和C-5’之间的键与虚线一起代表单键的化合物;其中R1为氢、甲基或乙基,且R2和R3为氢的化合物;和其中R1为氢或甲基,Y为式-CH2OCH2-的二价残基,该二价残基与C-2,C-5’和C-4’的碳原子一起形成6-元环系,且C-4’和C-5’之间的键与虚线一起表示双键的化合物。
特别优选的化合物可以选自下述的式(I)化合物:其中R1为甲基,Y为-CHO,且C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键;R1为甲基,Y为-CHO,且C-5’和C-6’或者C-4’和C-5’之间的键与虚线一起表示双键;R1为甲基,Y为-CH2OH,且C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键;R1为甲基,Y为-CH2OH,且C-5’和C-6’或C-4’和C-5’之间的键与虚线一起表示双键;R1为乙基,Y为-CHO,且C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键;R1为乙基,Y为-CHO,且C-5’和C-6’或C-4’和C-5’之间的键与虚线一起表示双键;R1为乙基,Y为-CH2OH,且C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键;R1为乙基,Y为-CH2OH,且C-5’和C-6’或C-4’和C-5’之间的键与虚线一起表示双键;R1为氢,Y为式-CH2OCH2-的二价残基,该二价残基与C-2、C-5’和C-4’的碳原子一起形成6-元环系,且C-4’和C-5’之间的键与虚线一起表示双键;和其中R1为甲基,Y为式-CH2OCH2-的二价残基,该二价残基与C-2、C-5’和C-4’的碳原子一起形成6-元环系,且C-5’和C-6’之间的键与虚线一起表示双键的式(I)化合物。
式(I)化合物可以单独使用、作为其混合物使用,或者与基料结合使用。如本文中所用的,“基料”包括选自目前能够获得的大范围天然产品和合成分子的所有已知的增味剂分子,例如精油;醇类、醛类和酮类;醚类和缩醛类;酯类和内酯类;大环化合物类和杂环化合物类,和/或与一种或多种通常与香料组合物中的增味剂结合使用的成分或赋型剂,例如载体物质,以及其它常用在本领域中的助剂混合。
下列物质清单包括已知的增味剂分子的例子,其可以与本发明的化合物结合:
-精油和提取物,例如,树苔净油、罗勒油、果油如香柠檬油和橘子油、香桃木油、玫瑰草油、广藿香油、橙叶油、茉莉油、玫瑰油、檀香油、苦艾油、熏衣草油或依兰-依兰油;
-醇类,例如,肉桂醇、顺式3-己烯醇、香茅醇、EbanolTM、丁子香酚、法呢醇、香叶醇、Super MuguetTM、里哪醇、薄荷醇、橙花醇、苯乙醇、玫瑰醇、SandaloreTM、萜品醇或TimberolTM。
-醛类和酮类,例如,茴香醛、α-戊基苯乙烯醛、GeorgywoodTM、羟基香茅醛、Iso ESuper、Isoraldeine、Hedione、Lilial、麦芽酚、甲基柏木酮、甲基紫罗兰酮、马鞭草烯酮或香草醛。
-醚类和缩醛类,例如,AmbroxTM、香叶基甲基醚、氧化玫瑰或Spirambrene。
-杂环化合物类,例如异丁基喹啉。
根据式(I)的化合物可以用在大范围的香料应用中,例如用在精细和实用香料的任何领域,例如香水、家用产品、洗涤产品、身体护理产品和化妆品中。取决于特定应用以及其它添味成分的性质和量,该化合物可以以大大不同的量来使用。其比例通常为用品的0.001-20wt%。在一个实施方案中,本发明的化合物可以以0.001-0.05wt%用在纤维软化剂中。在另一个实施方案中,本发明的化合物可以以0.1-20wt%,更优选0.1-5wt%的量用在精细香料中。但是,这些值只是以例子的形式给出,因为有经验的香料商还可以由较低或较高的浓度获得效果或者可以得到新产品。
简单地通过将香料组合物与香料用品直接混合就可以将上述化合物用在香料用品中,或者可以在之前的步骤中用捕集物质对其进行捕集,所述捕集物质例如为聚合物、胶囊、微胶囊和纳米胶囊、脂质体、膜形成物、吸收剂,例如碳或沸石、环状低聚糖及其混合物,或者其可以化学键合在基质上,键合后的物质在经历诸如光、酶等的外部刺激时易于释放香料分子,随后释放物再与用品混合。
因此,本发明还提供一种制备香料用品的方法,包括使用常规技术和方法将化合物直接混入用品中,或者混合包括式(I)化合物的香料组合物,随后可以再将其混入到香料用品中,从而将式(I)化合物作为香料成分结合进来。
如本文中所用的,“香料用品”意指包含增味剂的任何产品,例如精细香料,例如香水和装饰香水;家用产品,例如洗碗机用的洗涤剂、表面清洁剂;洗涤产品,例如软化剂、漂白剂、洗涤剂;身体护理产品,例如洗发香波、洗浴胶;和化妆品,例如除臭剂、雪花膏。该列产品只是用于说明,不应将其视为以任何方式进行限制。
除了3-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-2-酮,即其中R1为氢,Y为-C(CH3)O和C-5’和C-6’之间的键为双键的式(I)化合物之外,式(I)化合物均未在文献中被描述,因此其是新的。上面提及的化合物在Francis J.McQuillin等人的,J.Chem.Research(S),1977,61中有所描述,其为将有机基团加成到异长叶烯中所得的中间体。但是该文献中并未提及其气味性质。因此,本发明的另一方面提供上述定义的式(I)化合物,条件是如果R1为氢且C-5’和C-6’之间的键为双键,则Y不为-C(CH3)O。
本发明的化合物可以以可商购获得的异长叶烷-8-酮1为原料,经由在本领域熟练技术人员已知的条件下通过Wittig-Horner烯化作用而得到的适当的5-亚烷基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷2而制得。后者再根据热或催化Prins反应的常用条件与相应的式R2CHO醛反应,如方案1所示生成式3和4的烯醇与式5的四环醚的混合物,其拥有非常强烈的气味香型。通过改变反应条件或通过常规的产品纯化/富集过程或者二者兼用可以富集混合物的任意成分。特别优选的是包含各自约4-90wt%的化合物3和4以及最多90wt%的化合物5的混合物。尤其优选的实施方案是包含约40-70wt%式3化合物,约30-50wt%的式4化合物,和最多20wt%,例如0.5-10wt%的式5化合物的混合物。
方案1:
因此,本发明的进一步方面涉及一种香料组合物,其包含下面的混合物:
其中
R1为氢或C1-C3烷基,例如甲基、乙基或异丙基;
R2为氢或C1-C3烷基,例如甲基、乙基或异丙基;和
在式5中,C-5’和C-6’之间的键为单键,C-4’和C-5’之间的键与虚线一起表示双键;或C-4’和C-5’之间的键为单键,和C-5’和C-6’之间的键与虚线一起表示双键,
其中,该混合物包含:
a)约4-90wt%的式3化合物;
b)约4-90wt%的式4化合物;和
c)最多约90wt%的式5化合物。
通过在现有技术中已知的条件下进行简单的化合物转化,例如氢化、酯化、异构化或氧化可以对所得的烯醇3和4进行进一步衍生,以生成进一步的式(I)化合物,即相应的醛或酸。所述醛和酸可以与有机金属化合物进一步反应得到式(I)的仲醇或酮。
现在参考下列非限制性实施例对本发明作进一步描述。
实施例中描述的所有产物都是以可商购获得的异长叶烷-8-酮(2,2,7,7-四甲基三环[6.2.1.01,6]十一烷-5-酮),非对映异构的两对对映异构体的混合物为原料制得的。快速色谱:Merck硅胶60(230-400目)。
如果没有特别说明,则报告的NMR谱图是在CDCl3中测定的;以由TMS向低场的ppm来报告化学位移(δ);偶合常数J以Hz表示。
实施例1:2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b),2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丙-1-醇(4b),和2,2,8,11,11-五甲基-6-氧杂四环[10.2.1.01,10.04,9]十五碳-9-烯(5b)
a)5-亚乙基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷(2b)
将叔丁氧基钾(13.0g,0.116mol)和溴化乙基三苯基(41.6g,0.112mol)加入到2,2,7,7-四甲基三环[6.2.1.01,6]十一烷-5-酮(1,20.0g,0.091mol)的环己烷(200ml)溶液中,在室温下搅拌反应混合物78小时并用Celite过滤。浓缩滤液并减压蒸馏,得到(95℃/0.1mbar)5-亚乙基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷(2b,13.1g,产率62%,无色液体)。
1H NMR(C6D6):δ5.65(qt,J=6.6,2.2,1H),2.50(ddd,J=15.0,4.6,2.71H),2.18(m,1H),1.81-1.72(m,2H),1.62(ddd,J=6.6,2.2,1.6,3H),1.57(m,1H),1.39(m,1H),1.37-1.28(m,3H),1.27-1.19(m,1H),1.23(s,3H),1.16(ddd,J=13.1,5.0,2.7,1H),1.09(dd,J=9.5,1.4,1H),1.06(s,3H),1.00(s,3H),0.90(s,3H)。
13C NMR(C6D6):δ138.2(s),116.0(d),57.4(s),54.6(d),50.1(d),39.3(s),37.6(t),36.2(t),33.7(q),33.6(s),27.4(t),26.8(q),25.9(t),25.5(q),23.4(q),21.6(t),13.3(q).MS:232(M+,19),217(23),203(10),189(36),175(12),161(10),150(21),149(100),147(14),135(27),119(19),107(28),105(25),93(24),91(34),79(21),55(26),41(29)。
b)2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b)和2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丙-1-醇(4b)
在高压釜中于180℃下搅拌粗5-亚乙基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷(2b,纯度~93%,16.0g,0.064mol)和低聚甲醛(纯度95%,2.58g,0.082mol)6小时。过滤反应混合物并在5cm的Vigreux柱上蒸馏得到6b,其为分别含有53%和34.5%的2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b)和2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丙-1-醇(4b);非对映异构的两对对映异构体:30+4.5%)的混合物(10.3g,产率61%,白色浆液);分离出混合物的另一个纯度较差的馏分(4.8g),但未进行进一步的纯化。使用30m×0.25mm的Rtx-Wax柱分离分析6b,通过常用GC/嗅觉技术评价各成分的气味。
气味性状(6b=3b和4b(非对映异构体混合物)的混合物):琥珀香、木香。
气味性状(4b,主要的非对映异构体):琥珀香、木香、甜香。
气味性状(4b,较少的非对映异构体):琥珀香、木香。
气味性状(3b):参见下文。
c)2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b)
将混合物6b(6.5g,0.025mol)的试样溶解在环己烷(180ml)中,加入碘(2.5g,9.8×10-3mol),在回流下加热所得悬浮液24小时。用NaHSO3水溶液和盐水依次洗涤之后,干燥有机相(MgSO4),真空浓缩并用快速色谱(MTBE/己烷1∶6)纯化,得到2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b),其具有可接受的气味性质(1.89g,29%,缓慢固化无色液体)。
1H NMR(C6D6):δ3.42(dd,J=10.0,8.9,1H),3.33(dd,J=10.0,6.6,1H),2.89(m,1H),1.80-1.71(m,3H),1.65-1.58(m,2H),1.44-1.30(m,3H),1.21-1.16(m,1H),1.18(s,3H),1.17(s,3H),1.12(dd,J=9.5,1.4,1H),1.12-1.05(m,1H),0.92(s,3H),0.87(d,J=6.9,3H),0.86(s,3H)。
13C NMR(C6D6):δ149.2(s),125.3(s),65.6(t),57.4(s),49.8(d),42.9(s),38.0(d),36.4(t),34.1(t),31.3(s),29.4(t),27.8(q),26.5(q),26.3(q),25.3(t),24.4(q),20.8(t),15.7(q).MS:262(M+,31),233(45),231(100),219(76),203(45),175(81),161(28),147(28),133(32),119(45),105(42),91(41),69(28),55(31),41(43)。
气味性状:琥珀香、木香。
d)2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丙-1-醇(4b)
主要的非对映异构体,(1’S*,6’R*,8’S*):
1H NMR:δ5.42(m,1H),3.51-3.44(m,1H),3.40(dd,J=10.1,6.1,1H),2.49(sx,J=6.2,1H),2.07(m,1H),1.94(m,1H),1.76(m,1H),1.73-1.64(m,1H),1.61(ddd,J=17.4,5.6,1.8,1H),1.49-1.39(m,1H),1.38(m,1H),1.30-1.20(m,2H),1.12(d,J=9.4,1H),1.10(s,3H),1.08(d,J=7.1,3H),1.04(s,3H),0.91(s,3H),0.81(s,3H)。
13C NMR:δ140.0(s),122.1(d),68.3(t),55.2(d),55.0(s),51.0(d),39.4(t),38.4(d),37.7(s),36.1(t),33.7(q),32.6(s),26.6(t),24.7(q),24.1(q),23.8(q),22.5(t),15.7(q).MS:262(M+,38),233(36),231(100),219(91),203(62),175(47),161(40),147(34),133(40),121(36),119(56),105(43),91(40),55(33),41(40)。
较少的非对映异构体,(1’S*,6’S*,8’S*):
1H NMR(C6D6):δ5.34(db,J=6.9,1H),3.41(ddd,J=11.0,7.7,3.6,1H),3.23(ddd,J=11.0,5.7,3.6,1H),2.14(m,1H),2.01(db,J=17.0,1H),1.73(m,1H),1.66(sb,1H),1.57-1.45(m,4H),1.33(m,1H),1.11(s,3H),1.08(d,J=6.9,3H),0.99(db,J=9.6,1H),0.95-0.85(m,2H),0.90(s,3H),0.86(s,3H),0.77(s,3H)。
13C NMR(C6D6;从HSQC试验中提取的位移):δ119.4(d),66.8(t),56.7(d),49.6(d),40.7(d),39.1(t),37.0(t),30.1(t),29.0(q),25.7(q),25.6(q),25.1(t),23.6(q),14.6(q).MS:262(M+,57),247(13),231(66),219(52),203(85),201(53),179(31),175(30),163(43),161(74),149(60),133(74),121(72),119(100),105(68),91(63),55(46),41(45)。
气味性状:参见上述实施例1b。
e)2,2,8,11,11-五甲基-6-氧杂四环[10.2.1.01,10.04,9]十五碳-9-烯(5b)
将5-亚乙基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷(2b,4.0g,0.017mol)、低聚甲醛(2.5g,0.079mol)和蒙脱土K-10(2.5g)的悬浮液回流2小时,过滤、真空浓缩并用快速色谱纯化(MTBE/己烷1∶15;粗产物含有37%的3b和22.5%的5b),得到2,2,8,11,11-五甲基-6-氧杂四环[10.2.1.01,10.04,9]十五碳-9-烯(5b,1.3g,产率27%,蜡状白色固体)。
13C NMR(C6D6+Cr(acac)3):δ143.9(s),127.5(s),74.1(t),73.9(t),57.3(s),49.5(d),43.4(s),36.9(2t),33.9(d),32.6(d),31.3(s),29.3(t),28.2(q),27.2(q),27.0(q),25.7(q),25.1(t),17.7(q).MS:274(M+,40),259(15),246(19),245(100),231(78),187(12),173(17),159(21),145(30),133(16),119(25),105(30),91(39),55(26),41(36)。
气味性状:木香、琥珀香、干香(dry)、类似Iso E的气味。
实施例2:2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一烷-5-基)丙-1-醇(7b)
在110℃和60巴的高压釜内,在钯存在下,在活性碳(10%,0.55g)上氢化混合物6b(5.0g,0.019mol)的乙醇(25ml)溶液3小时。过滤掉催化剂,真空蒸发溶剂,将剩余物(4.5g)溶解在环己烷(500ml)中,并且在室温下与MCPBA(70%,4.9g,0.020mol)和NaHCO3(3.0g,0.036mol)一起搅拌18小时。用NaHSO3水溶液和盐水依次洗涤之后,干燥有机相(MgSO4)、真空浓度并用快速色谱(MTBE/己烷1∶4)纯化,得到纯的2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一烷-5-基)丙-1-醇试样(7b,0.3g,产率6%,蜡状白色固体)和富集了饱和醇7b的7b+3b馏分(2.2g)。
1H NMR(C6D6):δ3.74(dd,J=9.8,4.4,1H),3.26(dd,J=9.8,8.7,1H),2.01(m,1H),1.75(m,1H),1.72-1.67(m,2H),1.57(m,1H),1.52(m,1H),1.47-1.40(m,2H),1.38-1.10(m,6H),1.17(s,3H),1.09(d,J=7.1,3H),1.05(s,3H),1.02(s,3H),1.01(s,3H)。
13C NMR(C6D6):δ64.7(t),56.0(s),50.4(d),49.9(d),38.0(d),37.7(t),36.9(t),36.8(d),33.7(s),33.5(q),27.1(t),27.1(q),23.2(q),22.1(t),21.4(q),20.6(t),17.1(q).MS:264(M+,6),249(4),221(11),206(18),205(100),177(6),163(14),149(26),135(15),123(25),109(67),107(35),95(33),93(31),81(30),69(42),55(36),41(40)。
气味性状(7b):琥珀香、木香、轻微粉香/土香。
实施例3:5-(1-甲氧基丙-2-基)-2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯(8b)
将3b(1.0g,3.8×10-3mol)的DMF(5ml)溶液加入到氢化钠(0.27g,以50%分散在矿物油中,用己烷洗涤两次,5.6×10-3mol)的THF(8ml)悬浮液中。室温下搅拌3小时后,在冷却下加入碘甲烷(1.6g,0.011mol),室温下再搅拌反应混合物4小时,倾入冰冷的2M HCl(100ml)并用MTBE(2×100ml)萃取。用盐水(2×50ml)洗涤有机相、干燥(MgSO4)、真空浓缩和快速色谱纯化(MTBE/己烷1∶20),得到5-(1-甲氧基丙-2-基)-2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯(8b,0.73g,产率69%,无色油)。
1H NMR:δ3.32(s,3H),3.31-3.22(m,2H),2.98(m,1H),1.88(ddd,J=17.1,6.2,1.4,1H),1.78-1.59(m,4H),1.45-1.33(m,3H),1.22-1.16(m,1H),1.21(s,3H),1.17(dd,J=9.5,1.4,1H),1.13(s,3H),1.08(m,1H),0.98(d,J=6.8,3H),0.90(s,3H),0.82(s,3H)。
13C NMR:δ146.9(s),125.6(s),76.8(t),58.8(d),56.8(s),49.4(q),42.7(s),36.1(t),35.3(d),33.9(t),31.1(s),29.1(t),27.3(q),26.3(q),26.1(q),25.0(t),24.1(q),21.2(t),16.1(q).MS:276(M+,16),247(6),232(18),231(100),203(10),175(70),161(19),145(13),133(16),119(21),105(21),91(19),69(14),55(13),45(24),41(18)。
气味性状:土香/苔香、木香(石竹烯)、花香、辛香、甜香。
实施例4:2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙醛(9b)
室温下将乙酸钠(0.1g)和PCC(6.6g,0.031mol,逐份)依次加入到剧烈搅拌的3b(6.0g,0.023mol)的二氯甲烷(200ml)溶液中。再搅拌3小时之后,用Celite过滤黑色的反应混合物,真空浓缩滤液并用快速色谱纯化(MTBE/己烷1∶10),得到2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙醛(9b,3.8g,产率64%,白色固体)。
1H NMR:δ9.59(d,J=0.5,1H),3.62(q,J=6.8,1H),1.89(ddd,J=17.4,6.3,1.4,1H),1.81-1.65(m,3H),1.58(m,1H),1.53-1.37(m,3H),1.27-1.21(m,2H),1.23(s,3H),1.20(s,3H),1.14(d,J=6.8,3H),1.14-1.08(m,1H),0.93(s,3H),0.85(s,3H)。
13C NMR:δ203.5(d),152.5(s),120.3(s),57.5(s),49.7(d),49.3(d),43.1(s),36.2(t),33.8(t),31.0(s),29.0(t),28.1(q),26.1(q),25.8(q),24.9(t),24.1(q),22.8(t),11.5(q).MS:260(M+,15),245(2),232(19),231(100),217(21),203(9),189(7),175(79),161(23),147(15),133(21),119(24),105(25),91(28),69(18),55(18),41(25)。
气味性状:木香、琥珀香、花香。
实施例5:3-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丁-2-醇(10b)
10℃下将二乙醚(50ml)中的9b(1.7g,6.5×10-3mol)滴加到同一溶剂(50ml)中的甲基溴化镁(3ml的3M二乙醚溶液,9.0×10-3mol)溶液中。室温下再搅拌反应混合物2小时,将其倾入到冰冷的0.1M HCl(100ml)中并用MTBE(100ml)萃取。用盐水(2×50ml)洗涤有机相、干燥(MgSO4)、真空浓缩并从己烷中重结晶而纯化,得到3-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丁-2-醇(10b,1.1g,产率61%,白色多面固体,m.p.119-121℃)。
1H NMR:δ3.70(dq,J=9.6,6.2,1H),2.57(dq,J=9.5,6.8,OH),1.89(ddd,J=17.2,6.2,1.1,1H),1.79-1.60(m,4H),1.44-1.33(m,4H),1.23-1.18(m,1H),1.20(s,3H),1.16(s,3H),1.20(d,J=6.3,3H),1.09(d,J=6.7,3H),0.91(s,3H),0.81(s,3H)。
13C NMR:δ147.3(s),126.0(s),70.9(d),57.0(s),49.6(d),43.3(d),42.7(s),36.0(t),33.8(t),31.2(s),29.1(t),27.8(q),26.4(q),26.1(q),25.0(t),24.3(q),22.5(q),21.3(t),16.6(q).MS:276(M+,8),232(20),231(100),203(6),189(7),176(12),175(83),161(22),133(14),119(18),105(18),91(17),69(14),55(12),45(15),41(14)。
气味性状:琥珀香、木香、花香、果香。
实施例6:
下列在表1中列出的化合物已经根据实施例1-5中的一般步骤,分别以5-亚甲基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷(2a)和5-亚丙基-2,2,7,7-四甲基三环[6.2.1.01,6]十一烷(2c)为原料制得。在吸墨纸上评价其气味。
表1
化合物 | R1 | Y | -C=C- | 气味性状 |
2c | Et | ---- | 2,5’ | 木香,乡土味(agrestic),土香/苔香 |
3a | H | -CH2OH | 5’,6’ | 琥珀香,木香,花香,麝香 |
3c | Et | -CH2OH | 5’,6’ | 琥珀香,木香,果香,粉香 |
4a | H | -CH2OH | 4’,5’ | 与3a混合的4a(68∶30.5):琥珀香,木香(紫罗兰酮),麝香,粉香,乡土味 |
4c | Et | -CH2OH | 4’,5’ | 与3c混合的4c(44.5∶55.5):琥珀香,木香,粉香,青香 |
5a | H | -CH2OCH2- | 4’,5’ | 麝香,果香,木香,轻微的Cashmeran型 |
8a | H | -CH2OMe | 5’,6’ | 琥珀香,木香,乡土味,麝香 |
8c | Et | -CH2OMe | 5’,6’ | 木香(石竹烯),土香/苔香,甜香,花香(玫瑰) |
化合物2c:
1H NMR:δ2.45(ddd,J=14.7,4.6,3.0,1H),2.11(m,1H),2.10-1.92(m,2H),1.82-1.68(m,2H),1.58(m,1H),1.39(ddt,J=9.6,3.0,1.8,1H),1.34-1.15(m,4H),1.20(s,3H),1.11(dd,J=9.4,1.5,1H),1.02(2s,6H),0.95(t,J=7.3,3H),0.89(s,3H)。
13C NMR:136.9(s),123.9(d),57.2(s),54.0(d),49.7(d),39.2(s),37.7(t),36.0(t),33.6(q),33.5(s),27.0(t),26.7(q),26.0(t),25.4(q),23.4(q),21.2(t),20.9(t),14.9(q).MS:246(M+,36),231(41),217(17),203(72),190(13),175(26),164(28),163(100),149(36),147(26),133(23),121(32),119(30),107(68),105(45),93(45),91(59),79(41),55(58),41(75)。
化合物3a:
1H NMR:δ3.75-3.64(m,2H),2.44-2.32(m,2H),1.95(ddd,J=17.3,12.1,6.3,1H),1.84(ddd,J=17.3,6.2,1.0,1H),1.75(m,1H),1.70-1.62(m,2H),1.48-1.36(m,4H),1.23(s,3H),1.22-1.16(m,2H),1.12(s,3H),1.11-1.04(m,1H),0.92(s,3H),0.82(s,3H)。
13C NMR:δ150.1(s),119.4(s),61.4(t),57.1(s),49.1(d),42.7(s),36.2(t),36.1(t),33.9(t),31.1(s),29.2(t),27.4(q),26.8(t),26.3(2q),24.9(t),24.3(q).MS:248(M+,33),233(11),219(71),217(16),205(100),203(28),173(22),161(30),159(29),147(23),131(22),119(29),105(33),91(35),41(26)。
化合物3c:
1H NMR:δ3.62-3.43(m,2H),2.80(tt,J=8.7,6.4,1H),1.89-1.73(m,3H),1.73-1.65(m,2H),1.48-1.37(m,4H),1.37-1.28(m,1H),1.28-1.18(m,2H),1.25(s,3H),1.18-1.07(m,1H),1.16(s,3H),0.93(s,3H),0.87(t,J=7.5,3H),0.83(s,3H)。
13C NMR:δ151.7(s),122.7(s),64.6(t),57.5(s),49.5(d),44.5(d),42.8(s),36.1(t),33.6(t),31.1(s),29.2(t),28.3(q),26.9(q),26.3(q),25.1(t),24.4(q),22.9(t),20.4(t),11.9(q).MS:276(M+,24),247(31),246(20),245(100),233(52),203(36),189(61),161(18),147(24),133(27),119(33),105(32),91(33),69(24),55(26),41(32)。
化合物4a(非对映异构的两对对映异构体(1∶1.4);主要的非对映异构体的谱图):
13C NMR:δ136.5(s),122.3(d),60.7(t),55.6(d),55.1(s),49.2(d),42.3(s),39.7(t),39.0(t),36.7(t),32.5(s),30.2(t),28.5(q),25.4(q),25.3(q),24.7(t),23.6(q).MS:248(M+,67),233(19),215(24),205(75),187(59),165(40),150(49),149(75),147(81),133(81),117(37),119(84),105(100),91(97),79(50),55(65),41(81)。
化合物4c(非对映异构的两对对映异构体(1∶2.1);主要的非对映异构体的谱图):
1H NMR:δ5.42(m,1H),3.54-3.43(m,2H),2.37(tt,J=7.3,4.4,1H),2.06(m,1H),1.97(ddb,J=17.7,4.8,1H),1.76(m,1H),1.73-1.60(m,2H),1.58(qi,J=7.3,2H),1.48-1.41(m,1H),1.37(m,1H),1.36-1.30(m,1H),1.27-1.20(m,1H),1.15-1.11(m,1H),1.08(s,3H),1.06(s,3H),0.94(t,J=7.3,3H),0.91(s,3H),0.81(s,3H)。
13C NMR:δ138.6(s),122.3(d),65.1(t),55.1(s),54.4(d),51.0(d),45.6(d),39.4(t),37.8(s),36.0(t),33.8(q),32.5(s),26.7(t),24.7(q),24.1(2q),22.6(t),22.4(t),12.4(q).MS:276(M+,20),247(27),246(21),245(100),233(56),203(50),189(41),161(26),147(28),133(52),119(67),105(57),91(58),69(34),55(65),41(71)。
化合物5a:
1H NMR(C6D6):δ4.04(db,J=15.5,1H),3.85(ddd,J=10.7,5.2,3.61H),3.80(db,J=15.5,1H),3.46(ddd,J=10.7,8.9,3.8,1H),2.16(m,1H),1.80-1.69(m,2H),1.57-1.52(m,2H),1.52-1.41(m,2H),1.40-1.30(m,2H),1.05(s,3H),0.99(d,J=15.1,1H),0.97-0.93(m,1H),0.94(s,3H),0.92(m,1H),0.84(s,3H),0.75(s,3H)。
13C NMR(C6D6):δ127.9(s),126.4(s),69.2(t),64.8(t),58.4(d),55.3(s),49.5(d),42.7(s),39.0(t),37.0(t),32.7(s),30.6(t),30.4(t),28.4(q),25.5(2q),25.0(t),23.4(q).MS:260(M+,40),245(5),231(5),217(24),177(100),161(19),133(30),119(15),105(25),91(32),79(17),55(25),41(30)。
化合物8a:
1H NMR:δ3.47-3.35(m,2H),3.34(s,3H),2.43-2.29(m,2H),1.95(ddd,J=17.3,12.1,6.3,1H),1.83(ddd,J=17.3,6.3,1.1,1H),1.74(m,1H),1.69-1.59(m,2H),1.46-1.35(m,3H),1.22(s,3H),1.21-1.15(m,2H),1.11-1.03(m,1H),1.10(s,3H),0.91(s,3H),0.81(s,3H)。
13C NMR:δ148.4(s),120.1(s),72.4(t),58.5(q),56.9(s),49.1(d),42.7(s),36.1(t),34.1(t),33.3(t),31.1(s),29.1(t),27.5(t),27.1(q),26.3(q),26.0(q),24.9(t),24.2(q).MS:263(11),262(M+,55),247(9),233(83),219(100),217(51),215(25),203(31),201(26),187(31),173(52),161(88),159(66),145(49),131(56),119(61),105(72),91(66),69(34),45(73),41(43)。
化合物8c:
1H NMR:δ3.34-3.27(m,2H),3.31(s,3H),2.80(tt,J=9.2,5.6,1H),1.85(ddd,J=17.2,6.2,1.4,1H),1.81-1.59(m,5H),1.46-1.29(m,4H),1.24(s,3H),1.23-1.06(m,3H),1.11(s,3H),0.91(s,3H),0.83(t,J=7.5,3H),0.81(s,3H)。
13C NMR:δ148.4(s),121.7(s),76.8(t),58.9(q),57.2(s),49.4(d),42.8(s),42.1(d),36.0(t),33.9(t),31.1(s),29.2(t),27.6(q),26.8(q),26.4(q),25.1(t),24.2(q),23.2(t),21.3(t),11.9(q).MS:290(M+,13),261(5),246(19),245(100),203(11),189(60),175(8),161(12),145(14),133(16),119(18),105(18),91(18),69(15),55(14),45(23),41(14)。
实施例7:用于古龙香水(eau de Cologne)的木香-橘皮味香料组合物
重量份
Boisambrene Forte(1-(乙氧基甲氧基)-环十二烷) 15
得克萨斯杉木油 80
香豆素结晶 2
二丙二醇(DPG) 37
乙基里哪醇 25
六甲基-环戊-γ-2-苯并吡喃) 240
Georgywood(顺式-1-(1,2,3,4,5,6,7,8-八氢-1,2,8,8-
四甲基-2-萘基)-乙酮) 75
甲酸顺式-3-己烯酯(cis-3-Hexenyl formiate) 5
顺式-3-己烯醇 15
Iso E Super(7-乙酰基-1,2,3,4,5,6,7,8-八氢-
1,1,6,7-四甲基萘) 200
意大利柠檬油 75
在DPG中的10%的LiffaromeTM(顺式-3-己烯基甲基碳酸酯) 25
上等橙花油(3,7-二甲基辛-2,6-二烯-1-醇) 10
Nonadyl(6,8-二甲基壬-2-醇) 3
在DPG中的10%的Peach pure(5-庚基二氢-2(3H)-呋喃酮) 15
Tropional 8
Velvione(环十六碳-5-烯-1-酮) 20
925
将根据实施例1b得到的2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b)和2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丙-1-醇(4b)(53∶34.5)混合在DPG中形成10%的溶液。将75份该溶液加入到上述组合物中则带来强烈(volume)、圆满(roundness)和扩散性,同时保持了最上等橘皮气味的清新香型。其增强了麝香琥珀香香型,改善了木香-琥珀香的干燥脱水性能,并且有助于开发出非常有吸引力且感觉很好的香型。
Claims (8)
2.包含如权利要求1所定义的式(I)化合物的香料组合物。
5.一种制备香料用品的方法,包括将式(I)化合物结合至基料中的步骤:
其中,
R1为氢或C1-C3烷基;
Y为选自-CR2O和-CHR2OR3的单价残基,其中R2为氢或C1-C3烷基,且R3为氢或C1-C3烷基;
或者
Y为式-CHR2OCHR2-的二价残基,该二价残基与C-2,C-5’和C-4’的碳原子一起形成6-元环系,其中R2为氢或甲基;
并且
C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键;或C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键中的一个与虚线一起表示双键;
条件是式(I)化合物的碳原子总数为20或更少。
6.式(I)化合物:
其中
R1为氢或C1-C3烷基;
Y为选自-CR2O和-CHR2OR3的单价残基,其中R2为氢或C1-C3烷基,且R3为氢或C1-C3烷基;
或者
Y为式-CHR2OCHR2-的二价残基,该二价残基与C-2、C-5’和C-4’的碳原子一起形成6-元环系,其中R2为氢或甲基;
并且
C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间的键为单键;或者C-5’和C-6’、C-4’和C-5’以及C-2和C-5’之间键中的一个与虚线一起表示双键;
条件是:
I)式(I)化合物的碳原子总数为20或更少;
II)如果R1为氢且C-5’和C-6’之间的键为双键,则Y不为-C(CH3)O。
7.根据权利要求6的式(I)化合物,其中C-4’和C-5’之间的键与虚线一起表示双键;且环系的相对构型为(1’S,6’R,8’S)。
8.根据权利要求6的化合物,选自:
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙-1-醇(3b),
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丙-1-醇(4b),
2,2,8,11,11-五甲基-6-氧杂四环[10.2.1.01,1004,9]十五碳-9-烯(5b),
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳烷-5-基)丙-1-醇(7b),
5-(1-甲氧基丙-2-基)-2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯(8b),
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丙醛(9b),
3-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丁-2-醇(10b),
2-(2,2,7,7-四甲基三环-[6.2.1.01,6]十一碳-5-烯-5-基)乙醇(3a),
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯-5-基)丁-1-醇(3c),
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)乙醇(4a),
2-(2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-4-烯-5-基)丁-1-醇(4c),
5-(1-甲氧基乙-2-基)-2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯(8a),
5-(1-甲氧基丁-2-基)-2,2,7,7-四甲基三环[6.2.1.01,6]十一碳-5-烯(8c),和
2,2,11,11-四甲基-6-氧杂四环[10.2.1.01,10.04,9]十五碳-4(9)-烯(5a)。
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丁德生;龚隽芳.倍半萜类香料的合成.《实用合成香料》.1991,39-40. * |
龚隽芳.倍半萜类香料的合成.《实用合成香料》.1991,39-40. |
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