CN1275559A - α,β-不饱和酮 - Google Patents
α,β-不饱和酮 Download PDFInfo
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Abstract
本发明涉及式Ⅰ所示的新型α、β-不饱和酮,式Ⅰ中符号如权利要求1所定义。这种新型化合物带有水果底味的一种浓烈的非常持久的新鲜波斯树脂香味。
Description
本发明涉及新型的具有新鲜波斯树脂味、清新(金属味、十一碳三烯味)及菠萝味和/或黑茶藨子味的α、β-不饱和酮,以及这些新型化合物在不同组合物中作为芳香物质的用途。
便宜的植物香型和有着浓烈菠萝味和波斯树脂底味的新鲜芳香物在香料工业中是非常需要的。但是,许多天然的和市场上提供的化合物,例如波斯树脂油非常昂贵,并缺乏稳定性。七十所代中期得到了中等弱的波斯树脂型化合物,包括烯丙基戊基甘油醇酸酯(国际香味和香料公司)和Cyclogalbanate(Doagocco S.A.)。该族内另一类物质,烯丙基环戊基甘醇酸酯如US4 735 932所述。但是,甘醇酸酯在碱性、酸性或氧化介质中通常是不稳定的。
Morris,A.F,Naf,F;Snowdon,R.L.在《香料和香味)》1991(16),33中描述了作为香料中的重要化合物的1-(5,5-二甲基-1-环己烯-1-基)-4-戊烯-1-酮。该化合物具有浓烈的菠萝和风信子型波斯树脂的金属气息,可给香水和香料制品加上清新、新鲜、植物和水果香型。
本发明的目的在于提供新型的具有浓烈和持久的新鲜波斯树脂味的化合物,同时伴随着各种的水果味,主要是菠萝味。
R1、R2、R3、R4和R5分别为氢、甲基或乙基,R1、R4和R5可在环的任意位置,n和m分别为0、1、2或3,式A中的虚线,如果需要的话,代表双键,式B中的虚线代表1或2位上的双键。这种化合物具有浓烈的、相当持久的带水果底味的新鲜波斯树脂型香味。这些特征使这种新型化合物非常适于不同官能型香料应用中,以及适于给精细香料制品赋于独特的新鲜波斯树脂味和水果味。
上述分子式包括所有可能的不同立体和双键异构体。
其它优选的化合物有:
2-环己基庚-1,6-二烯-3-酮
(E)-和(Z)-3-环己基辛-2,7-二烯-4-酮
2-环戊基庚-1,6-二烯-3-酮
1-(3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
除了上述优异性质之外,还发现本发明的化合物具有卓越的分散性和/或良好的亲和性,后者意味着香味的持久。用含有一种或多种此类新型α、β-不饱和酮的洗涤剂洗涤或软化剂处理的织物上,可感觉到很好的分散性和亲和性。典型的清新味已能在湿织物上以及后来在干织物上强烈地感受到。
由于其优异的香味和应用性,此类新型化合物作为卓越的芳香物可用于精细和官能性香料的任意领域中,比如香水、家用产品、洗衣用品、护肤品和化妆品。
流程1
流程1中式(a)所示的原料可通过相应醇的氧化来制备。通过甲醛的亚甲基化作用(Mannich反应),可得到式(b)所示的,其中R2、R3为氢的醛。
相应于式I所示的化合物,其中R为式A残基,R2和/或R3不是氢的α、β-不饱和醛,可通过例如用Mukaiyama条件下的交叉(cross)3-羟基丁醛缩合反应,然后脱水来制备(T.Mukaiyama,K.Banno,K.Narasaka:
J.Amer.Chem.Soc.1974(96),7503)。
格氏反应也可用合适的取代腈来进行。这一反应得到了α、β-不饱和酮的良好收率。2-取代-3-三甲基甲硅烷氧基丙腈特别适于该转化反应。后者可根据.A.Marshall,R.D.Carroll:J.Org.Chem
1965(30),2748的方法,分别通过例如环酮和乙基氰基乙酸酯制备,然后用三甲基氯硅烷保护羟基。
另一种可能制备R为残基A的式I所示的α、β-不饱和酮的方法是通过相应的乙烯醚的Claisen转移反应来制备。其类似于T.Masso,A.Portella,E.Rus(香料和香味1990(15),39),用适当的取代3-丁烯-2-酮(例如通过R.A.Cormier,W.L.Schreiber,W.C.Agosta:
J.Amer.Chem.Soc.1973(95),4873)为原料。
流程2
原料酮或是商购的,或从相应取代或未取代甲基乙烯酮甲酮的Robinson消除反应,然后用Pd/C的选择氢化反应(例如G.Stork,A.Brizzolara,H.Landesman,J.Szmuskovicz,R.Terrell:
J.Amer.Chem.Soc 1963(85),207)来合成。
R为式B残基的α、β-不饱和酮通常以顺/反异构体混合物的形式得到。双键在1或2位。不同异构体的香味均为相同的“新鲜”型,但是GC的临界值在较宽范围内变化。最强的异构体,n=m=1,R4=R5=H,即顺-1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮的GC临界值仅为10pg/l。
这种新型香料可与许多天然和/或合成的香料成分混合。天然香料的范围除了包括易挥发的成分,还包括中等及仅仅是少量挥发的成分。合成的香料包括所有实用的各类香料的代表物。下面列出已知的可与本发明化合物混合的香料的例子:
天然产物:树苔藓净油、罗勒油、热带水果油(如香柠檬油、橘子油等)、乳香油、桃金娘油、玫瑰草油、新鲜叶刺蕊草油、橙叶油、苦艾油、熏衣草油、玫瑰油、茉莉油、依兰油等;
醇:法呢醇、香叶醇、芫荽醇、橙花醇、苯乙醇、玫瑰醇、肉桂醇、(Z)-己-3-烯-1-醇、薄荷醇、α-松油醇等;
醛:柠檬醛、α-己基肉桂醛、铃兰醛、甲基紫罗兰酮、马鞭草烯酮、罗特卡酮、香叶丙酮等;
酯:苯氧基乙酸烯丙酯、水杨酸苄酯、丙酸肉桂酯、香茅醇乙酸酯、乙酸癸酯、乙酸二甲基苄基甲酯、丁酸二甲基苄基甲酯、乙酰乙酸乙酯、异丁基顺-3-己烯酯、水杨酸顺-3-己烯酯、醋酸里哪酯、二氢茉莉酮酸甲酯、丙酸styralyl酯、乙酸香根(vetiveryl)酯、乙酸苄酯、醋酸香叶酯等;
内酯:γ-十一烷酸内酯、δ-十烷酸内酯、十五烷酸内酯、12-氧杂十六烷内酯等;
乙缩醛:Viridine(苯乙醛二甲基乙缩醛)等;
其它常用于香料的组分:吲哚、对-薄荷-8-硫醇-3-酮、丁子香酚甲醚、丁子香酸、茴香脑等。
本发明的新型化合物与植物的气息(铃兰、玫瑰、鸢尾属植物、茉莉、依兰、水仙等的气味)尤其协调,也与木质、素心蓝、动物、烟草的气息如新鲜叶刺蕊草组合物等相协调。
在组合物中所用的本发明化合物的百分比可在很宽范围内变化,从每千克大规模市场产物(洗涤剂、除臭剂等)几份至在用于精细香料的酒精提取物中有百分之几。在所有情况下,式I化合物即使是少量,也提供了带新鲜波斯树脂味及浓烈的清新水果味的增香剂组合物,并显著地增加了体积(强度、扩散系数)及香味的持续时间(亲和性)。
关于制剂的类型及实际最终产物的目的并没有限制,从而科隆香水溶液,花露水,香水,香料,护肤品及化妆品,如面霜、香波、肥皂,家用品如洗涤剂,家用清洁剂,织物柔软剂等也在考虑之中。
通过下述实施例进一步阐明本发明,实施例并不是对本发明的限制。
所有的化合物通过其1H-NMR-(从TMS以ppm低磁场得到的化学位移(δ),偶合常数J,Hz)、IR-和MS-谱明确鉴别。
式I所示的化合物,R=A
实施例1
2-环己基庚-1,6-二烯-3-酮
a)2-环己基丙-2-烯-1-醛
于0℃,将62%的硫酸(79.4克,0.5摩尔)、35%甲醛水溶液(82克,1.0摩尔)和环己基乙醛(100.8克,0.8摩尔)慢慢地连续加入二乙胺(73克,1.0摩尔)中。在80℃搅拌过夜,用MTBE萃取反应混合物。合并的有机相用H2O洗涤,直至pH为中性,干燥(MgSO4)并在真空浓缩。用Widmer塔减压下(10乇,80℃)蒸馏粗产物,得到89.5克(81%)的无色油状纯产物。
1H-NMR(200MHz,CDCl3):9.5(s,1H,-CHO),6.22(s,1H,H-C(3)),5.95(s,1H,H′-C(3)),2.48(m,1H,-CH-),1.9-1.6(m,5H,-CH2-),1.5-1.0(m,5H,-CH2-),MS(EI):138(M+,40),123(22),109(73),95(90),91(28),79(61),67(100),55(39),41(53).IR(净):2927vs,2853s,1694vs,1449m cm-1.
b)2-环己基庚-1,6-二烯-3-醇
将在100毫升乙醚中的2-环己基丙-2-烯-1-醛(69克,0.5摩尔)慢慢加入至丁-1-烯基溴化镁中,该溴化镁通过在0℃,将在100毫升乙醚中的4-溴-丁-1-烯(81.0克,0.6摩尔)加入至在300毫升乙醚中的镁屑(13.2克,0.55摩尔)而制备。加入后,反应混合物温至室温,再搅拌另外3小时。用2NHCl淬灭后,分离有机相,用水洗涤,直至pH为中性,干燥(MgSO4)并在真空下蒸发溶剂。经Vigreux塔(0.15乇,91℃)蒸馏粗产物,得到85克(88%)无色油状纯产物。
1H-NMR(200MHz,CDCl3):5.85(ddt,J=17.2,10.4,6.6,1H,H-C(6)),5.05(ddt,J=17.2,2.0,1.6,1H,H-C(7)),5.02(dd,J=1.0,1.0,1H,H-C(1)),4.98(ddt,J=10.2,2.1,1.2,1H,H′-C(7)),4.88(d,J=1.0,1H,H′-C(1)),4.09(t,J=6.2,1H,H-C(3)),2.22-2.10(m,2H,H-C(5)),1.89(m,1H,-CH-),1.80-1.52(m,8H,-CH2-,-OH),1.38-1.24(m,5H,-CH2-),MS(EI): 194(M+,1),176(4),165(3),151(9),139(11),122(11),109(15),95(37),83(66),79(43),71(34),67(50),55(100),41(50),IR(净):3361s,2926vs,2852s,1641w,1448m cm-1.
c)2-环己基庚-1,6-二烯-3-酮
于室温下,用在2升己烷中的MnO2(804克,9.2摩尔)氧化2-环己基庚-1,6-二烯-3-醇(85克,0.44摩尔)。搅拌96小时后,用Celite过滤反应混合物,并在真空中浓缩,得到71克黄色油。蒸馏(0.04乇/70℃)得到43.5克(51%)纯产物。
气味:新鲜波斯树脂味、菠萝味、金属味。1H-NMR(400MHz,CDCl3):5.95(s,1H,H-C(1)),5.85(ddt,J=17.0,10.2,6.4,1H,H-C(6)),5.65(d,J=1.2,1H,H′-C(1)),5.05(ddt,J=17.1,1.6,1.6,1H,H-C(7)),4.96(ddt,J=10.2,1.6,1.2,1H,H′-C(7)),2.78(t,J=7.4,2H,H-C(4)),2.59(m,1H,-CH-),2.35(m,2H,H-C(5)),1.80-1.65(m,5H,-CH2-),1.41-1.28(m,2H,-CH2-),1.22-1.00(m,3H,-CH2-).MS(EI):192(M+,11),177(4),163(50),149(29),137(78),121(9),109(65),95(22),81(34),77(12),67(100),55(61),41(29).IR(净):2926vs,2852s,1681vs,1449m cm-1.
按实施例1所述的步骤制备下述实施例。下面仅给出了波谱数据和溴觉性质。
实施例2
2-环戊基庚-1,6-二烯-3-酮
气味:新鲜波斯树脂味、洋茴香味、金属味。1H-NMR(400MHz,CDCl3):5.95(s,1H,H-C(1)),5.85(ddt,J=17.2,10.4,6.6,1H,H-C(6)),5.70(d,J=1.2,1H,H′-C(1)),5.04(ddt,J=17.1,1.8,1.6,1H,H-C(7)),4.98(ddt,J=10.2,1.6,1.2,1H,H′-C(7)),2.95(m,1H,-CH-),2.80(t,J=7.5,2H,H-C(4)),2.40(m,2H,H-C(5)),1.9 4-1.81(m,2H,-CH2-),1.75-1.55(m,4H,-CH2-),1.35-1.12(m,2H,-CH2-).MS(EI):178(M+,1),163(2),149(18),137(5),123(4 3),110(8),95(100),83(9),79(15),67(73),55(61),41(23).IR(净):2953vs,2869s,1681vs,1641m cm-1.
实施例3
2-(4-甲基环己基)庚-1,6-二烯-3-酮(顺/反异构体~1∶1)
气味:新鲜波斯树脂味、菠萝味。1H-NMR(400MHz,CDCl3):5.96+5.95(2s,1H,H-C(1)),5.83(ddt,J=17.2,10.4,6.6,1H,H-C(6)),5.69+5.65(2d,J=1.4,1H,H′-C(1)),5.00(m,2H,H-C(7)),2.77(t,J=7.6,2H,H-C(4)),2.55(m,1H,-CH-),2.35(m,2H,H-C(5)),1.94-1.22(m,7H,-CH-,-CH2-),1.19-1.00(m,2H,-CH2-),1.00+0.89(2d,J=7.2,6.4,3H,-CH3). MS(EI):206(M+,4),191(6),177(44),163(7),151(44),149(33),123(22),110(17),109(17),107(14),105(10),95(34),81(100),79(24),67(42),55(65),41(28).IR(neat):2922vs,2850s,1681vs,1641m cm-1.
实施例42-(3-甲基环己基)庚-1,6-二烯-3-酮(顺/反异构体~1∶1)
气味:新鲜水果味、带波斯树脂的菠萝味。1H-NMR(400MHz,CDCl3):5.96+5.95(2s,1H,H-C(1)),5.83(ddt,J=16.8,10.4,6.6,1H,H-C(6)),5.70(2d,J=1.2,1H,H′-C(1)),5.00(m,2H,H-C(7)),2.9(m,0.5H,-CH-), 2.77(m,2H,H-C(4)),2.61(m,0.5H,-CH-),2.46(m,2H,H-C(5)),2.01-1.09(m,9H, -CH-,-CH2-),1.03+0.88(2d,J=7.2,6.8,3H,-CH3).MS(EI):206(M+,4),191(6),177(30),163(18)151(49),149(11),123(20),110(22),109(15),107(13),105(8),95(33),81(100),79(22),67(42),55(60),41(28).IR(净):2923vs,2850s,1681vs,1641mcm-1.
实施例5
2-(2-甲基环己基)庚-1,6-二烯-3-酮(顺/反异构体~1∶1)
气味:新鲜波斯树脂味、蘑菇味、带茉莉味的菠萝味。1H-NMR(400MHz,CDCl3):6.06+6.02(2s,1H,H-C(1)),5.82(m,1H,H-C(6)),5.70+5.52(2d,J=1.2,1H,H′-C(1)),5.00(m,2H,H-C(7)),2.80(m,2.5H,H-C(4),-CH-),2.38(m,2H,H-C(5)),1.95(m,0.5H,-CH-),1.82-1.00(m,9H,-CH-,-CH2-),0.71+0.69(2d,J=6.4,7.2,3H,-CH3).MS(EI):206(M+,15),191(10),177(33),164(23)151(50),149(32),133(124),123(27),109(28),107(22),105(22),95(49),81(89),79(35),67(51),55(100),41(44).IR(净):2925vs,2853s,1681vs,1641m cm-1.
实施例6
2-(2-甲基环戊基)庚-1,6-二烯-3-酮(顺/反异构体-1∶1)
气味:新鲜波斯树脂味、菠萝味、带回香味的葡萄味。1H-NMR(400MHz,CDCl3):6.08+6.01(2s,1H,H-C(1)),5.82(m,1H,H-C(6)),5.70+5.66(2d,J=1.2,1H,H′-C(1)),5.02(m,2H,H-C(7)),3.10-1.20(5m,12H),0.90+0.54(2d,J=6.4,6.8,3H,-CH3).MS(EI):192(M+,4),177(14),163(68),150(23),137(63),133(124),123(11),119(25),109(63),107(23),105(9),95(37),81(56),79(33),67(95),55(100),41(47).IR(净):2954vs,2869s,1681vs,1641mcm-1.
实施例7
2-环庚基庚-1,6-二烯-3-酮
气味:新鲜波斯树脂味、水果味、花味(椴树花)。1H-NMR(400MHz,CDCl3):5.95(s,1H,H-C(1)),5.85(ddt,J=17.2,10.4,6.4,1H,H-C(6)),5.68(d,J=1.2,1H,H′-C(1)),5.05(ddt,J=17.2,1.6,1.6,1H,H-C(7)),4.96(ddt,J=10.4,1.6,1.2,1H,H′-C(7)),2.77(t,J=7.2,2H,H-C(4)),2.72(m,1H,-CH-),2.37(m,2H,H-C(5)),1.74-1.29(m,12H,-CH2-).MS(EI):206(M+,3),191(2),177(27),165(9),151(38),149(22),135(6),123(11),121(13),109(22),95(30),81(100),67(96),55(100),41(51).IR(净):2924vs,2855s,1680vs,1641m cm-1.
实施例8
2-环辛基庚-1,6-二烯-3-酮
气味:新鲜波斯树脂味、木质味、海生物的脂肪味。1H-NMR(400MHz,CDCl3):5.95(s,1H,H-C(1)),5.85(ddt,J=17.1,10.1,6.6,1H,H-C(6)),5.69(d,J=1.1,1H,H′-C(1)),5.05(ddt,J=17.1,1.7,1.7,1H,H-C(7)),4.96(ddt,J=10.2,1.6,1.2,1H,H′-C(7)),2.96(m,1H,-CH-),2.75(t,J=7.4,2H,H-C(4)),2.35(m,2H,H-C(5)),1.80-1.45(m,14H,-CH2-).MS(EI):220(M+,4),205(2),191(30),179(19),177(14),149(28),137(15),135(17),123(21),121(24),109(32),110(22),95(94),81(79),67(54),55(100),41(47).IR(净):2920vs,2851s,1680vs,1641mcm-1.
实施例9
3-环己基辛-2,7-二烯-4-酮
a)3-环己基丁-2-烯醛
于-70℃,将[(2-环己基乙烯基)氧基)]三甲基硅烷(19.8克,0.1摩尔)和乙醛(4.4克,0.1摩尔)的混合物慢慢加入至四氯化钛(11毫升,0.1摩尔)和异丙氧基钛(IV)(0.59毫升,0.02摩尔)的CH2Cl2(50毫升)的混合物中。搅拌1小时后,用饱和的NH4Cl溶液淬灭反应,并用乙醚(2×100毫升)萃取两次。合并的有机相洗至pH为中性,干燥(MgSO4)并在真空中浓缩。用5厘米Widmer塔(0.1乇,120℃)通过与I2一起蒸馏(200毫克)将粗产物脱水,得到7.7克(50%)E/Z为~7∶1的混合物的3-环己基丁-2-烯醛。1H-NMR((E)-异构体,200MHz,CDCl3):
9.31(d,J=1.0,1H,-CHO),6.48(q,J=7.5,1H,H-C(3)),2.55(m,1H,-CH-),2.05(d,J=7.5,3H,CH2),2.00-1.05(m,10H,-CH2-).MS(EI):152(M+,72),137(29),134(14),123(100),119(24),109(43),105(25),95(57),91(37),84(21),81(68),79(45),77(24),69(31),67(72),55(48),41(50).IR(净):2927vs,2853s,2704w,1689s,1634m,1449m cm-1.
b)3-环己基辛-2,7-二烯-4-酮(E/Z为10∶1的混合物)
按实施例1a和1c所述的实验步骤制备。
气味:新鲜波斯树脂味、菠萝味、黑茶藨子味
1H-NMR((E)-异构体,400MHz,CDCl3):1H-NMR((E)-异构体,400MHz,CDCl3):6.50(q,J=7.0,1H,H-C(2)),5.80(ddt,J=16.8,10.4,6.4,1H,H-C(7)),5.01(ddt,J=17.1,1.6,1.6,1H,H-C(8)),4.96(ddt,J=10.2,1.8,1.2,1H,H′-C(8)),2.68(t,J=7.6,2H,H-C(5)),2.55(tt,J=12.2,3.4,1H,-CH-),2.35(m,2H,H-C(6)),1.88(d,J=6.8,-CH3),1.85-1.60(m,5H,-CH2-),1.50-1.10(m,5H,-CH2-).MS(EI):206(M+,10),191(15),177(16),164(9),151(100),123(19),109(8),95(12),81(80),79(18),67(43),55(49),41(20).IR(净):2926vs,2852s,1672s,1641m,1450mcm-1.
实施例10
4-环己基壬-3,8-二烯-5-酮(E/Z为20∶1的混合物)
按3-环己基辛-2,7-二烯-4-酮(实施例9)所述的一般步骤制备。
气味:新鲜水果味、苹果味、菠萝味、波斯树脂味、洋茴香味
1H-NMR((E)-异构体,400MHz,CDCl3):
1H-NMR((E)-异构体,400MHz,CDCl3):6.35(t,J=7.4,1H,H-
C(3)),5.82(ddt,J=17.0,10.4,6.4,1H,H-C(8)),5.01
(ddt,J=17.1,1.8,1.7,1H,H-C(9)),4.96(ddt,J=10.2,
1.8,1.2,1H,H′-C(9)),2.70(t,J=7.6,2H,H-C(6)),2.51
(tt,J=12.0,3.6,1H,-CH-),2.39-2.30(m,2H,H-C(7)),
2.29(q,J=7.6,H-C(2)),1.82-1.60(m,5H,-CH2-),1.45(m,
2H,-CH2-),1.32-1.18(m,3H,-CH2-),1.08(t,J=7.6,-CH3).
MS(EI,(E)-异构体):220(M+,10),191(43),177(9),165(100),
149(5),137(11),123(7),109(12),95(86),81(72),79(23),
67(34),55(63),41(26).IR(净):2927vs,2852s,1672s,
1641m,1450m cm-1.
式I化合物,R=B
实施例11
1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(1,2,3,4,5,6,7,8-八氢化萘-2-基)戊-4-烯-1-酮
a)2-乙炔基十氢化萘-2-醇
于0℃,将乙炔气经4小时鼓入叔丁醇钾(95.8克,0.85毫尔)的THF(1升)混合物。在室温下,将2-癸酮(100克,0.66摩尔)慢慢加入到该微黄色悬浮液中,得到的混合物再搅拌3.5小时,用饱和的NH4Cl(500毫升)溶液淬灭,并用MTBE(2×700毫升)萃取。合并的有机相用NH4Cl(500毫升)、H2O(2×500毫升)、饱和NaCl(500毫升)溶液洗至pH为中性,干燥(MgSO4)并在真空中浓缩。闪蒸(0.1乇,88-90℃)黄色油状粗产物,得到100.6克(86%)2-乙炔基十氢化萘-2-醇。
b)2-(戊-4-烯-1-炔基)十氢化萘-2-醇
于0℃,氮气气氛下,将2-乙炔基十氢化萘-2-醇(100.6克。0.56摩尔)的异丙醇(300毫升)溶液慢慢加至KOH(47.5克)、K2CO3(6.5克)和CuCl(4.4克)的MeOH(300毫升)的混合物中。于0℃再搅拌30分钟后,经25分钟慢慢加入烯丙基溴(102克,0.85摩尔)。反应混合物在室温下搅拌过夜,用NH4Cl淬灭并在真空下浓缩。残余物用饱和NH4Cl(500毫升)溶液吸收,并用MTBE(2×400毫升)萃取。合并的有机相用饱和NH4Cl溶液(500毫升)、H2O(2×500毫升)、饱和NaCl(500毫升)溶液洗至pH为中性,干燥(MgSO4)并在真空蒸发,得到120克粗产物,该粗产物在后一步中无需进一步纯化即可使用。
c)1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(1,2,3,4,5,6,7,8-八氢化萘-2-基)戊-4-烯-1-酮
将2-(戊-4-烯-1-炔基)十氢化萘-2-醇(120克,0.55摩尔)的HCOOH 80%(200毫升)溶液在90℃加热16小时。冷却至室温后,得到的棕褐色混合物用饱和Na2CO3中和,并用MTBE(2×400毫升)萃取。合并的有机相用NaHCO3(2×400毫升)、H2O(2×400毫升)洗涤,用MgSO4干燥。用Vigreux塔蒸馏后,以5种异构体形式得到54.2克(45%)的嗅觉的纯产物。
气味:(5种异构体的混合物):新鲜波斯树脂味,水果味1H-NMR(200MHz,CDCl3):6.90(m,~0.9H),6.85(m,1H),5.00(m,2H),2.82-1.20(m,18H).MS(EI):Peak 1(22%):218(M+,18),176(6),163(30),135(100),119(7),107(9),105(8),93(23),91(38),79(22),67(24),55(33),41(12);峰2(8%):218(M+,55), 177(54), 163(100),145(19),135(92),119(13),107(24),105(18),93(47),91(57), 79(49),67(68),55(54),41(25);峰3(15%):218(M+,46),177(50),163(87),145(19),135(100),119(12),107(24),105(16),93(47),91(50),79(47),67(67),55(47),41(27);峰4(13%):218(M+,11),177(1),163(100),145(2),135(11),107(7),93(25),91(15),79(20),67(20),55(18),41(11);峰5(42%):218(M+,8),177(2),163(100),145(4),135(11),107(12),93(24),91(16),79(21),67(21),55(20),41(11).IR(5个异构体的混合物,净):2923s,2853m,1669vs,1640m cm-1.
用预备的GLC分离主要的及最重要的异构体,即GC-香味临界值为10pg的顺-1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮,用以1H-NMR分析。
1H-NMR(400MHz,CDCl3):6.85(m,1H,CH=C),5.85(ddt,1H,J=17.0,10.2,6.6,H-C(4)),5.05(ddt,J=17.1,1.6,1.6,1H,H-C(5)),4.98(ddt,J=10.1,1.8,1.2,H′-C(5)),2.74(t,J=7.6,H-C(2)),2.35(m,2H,-CH2-),2.30-2.13(m,4H,-CH2-),1.85(m,2H,-CH-),1.57(m,2H,-CH2-),1.47-1.32(m,6H,-CH2-).
下述实施例的化合物均按实施例11所述的一般步骤进行制备。下列各个实施例仅给出了波谱数据和香味性质。
实施例12
1-(2,3,3a,4,7,7a-六氢-1H-茚-5-基)戊-4-烯-1-酮
1-(2,3,3a,6,7,7a-六氢-1H-茚-5-基)戊-4-烯-1-酮
1-(2,3,4,5,6,7-六氢-1H-茚-5-基)戊-4-烯-1-酮
气味(3种异构体的混合物):新鲜波斯树脂味、黑茶藨子味、博伊增莓味、金属味。 1H-NMR(200MHz,CDCl3):6.90(m,~0.8H),6.85(m,1H),5.00(m,2H),2.82-1.20(m,16H).MS(EI):峰1(16%):204(M+,18),162(7),149(34),121(100),107(5),105(7),93(25),91(37),79(39),67(14),55(35),41(11);峰2(61%):204(M+,14),163(16),149(100),131(17),121(22),107(13),105(11),93(25),91(23),79(34),67(12),55(18),41(10);Peak3(23%):204(M+,7),163(2),149(100),131(6),121(7),107(5),105(7),93(26),91(16),79(32),67(13),55(19),41(9).IR(3个异构体的混合物,净):2943s,2867m,1710w,1668vs,1639m cm-1.
实施例13
1-(4a-甲基-3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(4a-甲基-1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
气味(4种异构体的混合物):紫罗兰味、木质味、新鲜波斯树脂味、菠萝味1H-NMR(200MHz,CDCl3):6.85+6.75(2m,1H,CH=C),5.85(m,1H,CH=CH2),5.00(m,2H,CH=CH2),2.75(m,2H),2.60-1.00(m,15H),0.95+0.89+0.78(3s,3H).MS(EI):峰1(32%):232(M+,56),217(32),204(3),191(44),177(100),159(20),149(26),135(18),121(16),109(84),96(23),93(24),91(55),81(52),79(39),67(65),55(68),41(30);峰2(52%):232(M+,15),217(5),204(3),191(2),177(100),159(3),149(16),137(7),121(3),109(9),107(9),96(10),93(13),91(16),81(73),67(14),55(23),41(10);峰3(2%):232(M+,46),217(25),191(35),177(43),161(12),159(11),149(100),135(13),121(12),109(70),107(27),93(42),91(48),81(52),67(55),55(67),41(30);峰4(14%):232(M+,8),217(3),204(2),191(2),177(100),159(3),149(8),121(5),109(7),107(16),93(16),91(12),81(34),67(14),55(20),41(10);IR(4个异构体的混合物,净):2925vs,2860s,1668vs,1640m cm1.
实施例14
1-(4-甲基-1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(4-甲基-3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮
1-(4-甲基-1,2,3,4,5,6,7,8,-八氢化萘-2-基)戊-4-烯-1-酮
气味(3种异构体的混合物):木质味、新鲜波斯树脂味、水果味、脂肪味1H-NMR(200MHz,CDCl3):6.62+6.59(2m,~0.8H,CH=C),5.82(m,1H,CH=CH2),5.00(m,2H,CH=CH2),2.75(m,2H),2.68-0.70(m ,18H).MS(EI):峰:1(11%):232(M+,4),217(1),203(3),190(8),177(22),159(3),149(100),133(14),121(6),119(8),105(37),91(39),81(24),79(22),67(15),55(53),41(20);峰2(56%):232(M+,42),217(5),203(3),191(33),177(100),159(11),149(75),135(9),133(14),121(16),109(31),107(26),93(40),91(44),81(48),67(57),55(74),41(44);峰3(33%):232(M+,78),217(7),203(3),191(73),177(100),159(15),149(32),135(13),121(21),109(57),107(35),93(47),91(43),81(56),67(68),55(80),41(50).IR(3个异构体的混合物,净):2922vs,2852s,1711m,169vs,1640m cm1.
实施例15
1-(3a,4,5,6,7,7a-六氢-1H-茚-2-基)戊-4-烯-1-酮
1-(2,3,4,5,6,7-六氢-1H-茚-2-基)戊-4-烯-1-酮
气味(3种异构体的混合物)水果味、菠萝味、新鲜波斯树脂味。1H-NMR(400MHz,CDCl3):6.69(m,0.8H,CH=C),5.83(m,1H,CH=CH2),5.05(m,1H,CH=CH2),4.98(m,1H,CH=CH2),2.75(m,2H),2.60-2.20(m,5H),1.90(m,1H),1.78-0.25(m,8H).MS(EI):峰1(3%):204(M+,5),149(3),121(100),105(3),93(20),91(13),79(30),77(12),67(12),55(13),41(6);峰2(16%):204(M+,16),189(9),162(4),149(34),131(2),121(100),107(9),105(5),93(18),91(28),79(27),77(14),67(11),55(20),41(9);峰3(79%):204(M+,12),189(1),163(14),149(100),131(11),121(47),107(7),105(8),93(29),91(21),79(37),77(17),67(14),55(18),41(9);IR(3个异构体的混合物,净):2925vs,2851s,1667vs,1641m cm-1.
实施例16女性化妆用品的组合物
重量份Adoxal(10% DPG) 10Ambrofix 3β-紫罗兰酮 10香柠檬油abergapt 50Calone 1951(10% DPG) 10Cepionate 200香茅醇 30Dasmascenone(10% DPG) 10二氢月桂烯醇 30乙基里哪醇 40Florhydral 5佳乐麝香50% PHT 200α-己基肉桂醛 80苯乙醇 50吲哚(10%DPG) 5
Iso E super 40
Isoraldeine 95 50
顺茉莉酮(10% DPG) 10
铃兰醛 50
2,6-二甲基-5-庚烯-1-醛(10% DPG) 5
邻氨基苯甲酸甲酯(10% DPG) 10
甲基pamplemousse(1,1-二甲氧基-2,2,5- 20
三甲基-4-己烯)
Nectaryl 2
Radjanol 20
Tropional 15
三环萜醛(10% DPG) 10
香草醛(10% DPG) 5
锰红柱石(10% DPG) 10
夷兰油 10
2-环己基-庚-1,6-二烯-3-酮(10% DPG) 10
1000
在该女性配方中,2-环己基-庚-1,6-二烯-3-酮增加了柑果味,赋予香味活跃的性质。其持久的效应益于保持香味清新。
实施例17
用于化妆用品的新鲜海洋组合物
重量份
Acetal CD(苯乙醛甘油基乙缩醛) 40
Acetal R(乙醛苯乙基丙基乙缩醛) 2
Adoxal 10% DPG(2,6,10-三甲基-9-十一碳烯醛) 1.5
苯氧基乙醇 70
苯甲酸里哪酯 100
酸橙油 10
Clonal(10% DPG) 5
β-二氢大马酮 5
双甲醇(2,6-二甲基-2-庚醇) 25
Disopropylene glycol 375
Florhydral 20
Glycolierral 60
(z)-己-3-烯-1-醇 5
(z)-己-3-烯-1-基乙酸酯 2.5
(z)-己-3-烯-1-基甲酸酯 5
(z)-己-3-烯-1-基水杨酸酯 5
丙酸己酯 10
β-紫罗兰酮 10
里哪醇 100
里哪醇Oxyde(10% DPG) 2.5
2,6-二甲基-5-庚烯-1-醛(1% DPG) 2.5
Menthe Crepue Ess USA(10% DPG) 10
橙花醇 80
橙花叔醇 40
Radjanol 5
锰红柱石(10% PE) 5
2-环己基庚-1,6-二烯-3-酮(10% DPG) 4
1000
该新化合物,即2-环己基庚-1,6-二烯-3-酮,赋予香料组合物清新、天然波斯树脂味,增加了其扩散性并加入了清新的菠萝味。
实施例18
用于织物软化剂的花香组合物
重量份
乙酸酯PA(乙酸2-丙烯基苯氧基酯) 15
烯丙基戊基羟乙酸盐 15
Ambrofix 1
乙酸苄酯 60
香茅醇extra 50
醋酸香茅酯 30
Cyclal C 10
二氢月桂烯醇 50
Ebanol 10
Freskomenthe 5
佳乐麝香50% PHT 60
Geranitrile 12
Givescone 7
α-己基肉桂醛 200
Iso E Super 30
里哪醇 60
铃兰醛 60
Nectaryl 5
Neroline crist 5
Rosacetol 20
Roseoxyde 8
萜品醇 60
10-十一碳烯醛 2
Verdyl乙酸酯 200
夷兰油 15
2-环己基-庚-1,6-二烯-3-酮(10%DPG) 10
1000
在该花香配方中,2-环己基庚-1,6-二烯-3-酮以其新鲜波斯树脂味赋予香味以清新的效果,无论是在湿的和干的洗好的衣服上。
实施例19
用于软化剂的清新的花香组合物
重量份
Adoxal(10% DPG) 1
Agrumex 40
Amberketal(10% IPM) 15
黄葵酮 10
酸橙油 20
香茅醇 35
β-二氢大马酮 2.5
乙酸二甲基苄基甲酯 75
Ebanol 20
Fixambrene 10
Florhydral 10
Gardenol 7.5
α-己基肉桂醛 70
水杨酸己酯 100
β-紫罗兰酮 40
Isoraldeine 30
Jasmin reconst. 15
Jasmonyl 25
铃兰醛 70
2-甲基十一碳烯醛 5
柑橘晶体 4
苯乙醇 85
Rosacetol 30
四氢里哪醇 100
Thibetolide 20
Undecavertol 25
9-十一碳烯醛 5
Verdyl丙酸酯 55
Vertofix coeur 55
1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)
戊-4-烯-1-酮 20
1-(3,4,4a,5,6,7,8,8a-八氢化萘-2-基)
戊-4-烯-1-酮
1000
该新化合物赋予香味组合物清新的波斯树脂味,增加了其体积,扩散性及持久性。
对于上述提及的常用名的精确定义,参见《香味和香料物质》1998,Allured印刷公司,Carol Stream,Illinois,美国,或参见Arctander,《香料和香味化学》-1969,由作者Montclair出版,新泽西,美国。
Claims (10)
3.权利要求1所述的2-环己基庚-1,6-二烯-3-酮。
4.权利要求1所述的(E)-和(Z)-3-环己基辛-2,7-二烯-4-酮。
5.权利要求1所述的2-环戊基庚-1,6-二烯-3-酮。
6.权利要求1所述的1-(3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮。
7.权利要求1所述的1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮。
8.权利要求1所述的1-(3,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮和1-(1,4,4a,5,6,7,8,8a-八氢化萘-2-基)戊-4-烯-1-酮的混合物。
9.含至少一种前述权利要求之一的式I化合物的香味组合物。
10.权利要求9的组合物,该组合物具有新鲜波斯树脂的清新味(金属型)和菠萝味和/或黑茶藨子味。
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JP (1) | JP3430205B2 (zh) |
CN (1) | CN1182097C (zh) |
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DE19830599A1 (de) * | 1998-07-09 | 2000-01-13 | Basf Ag | Verfahren zur stereoselektiven Herstellung von Grignardverbindungen und deren Verwendung |
TW554254B (en) * | 1999-08-06 | 2003-09-21 | Hyundai Electronics Ind | Novel photoresist monomers, polymers thereof and photoresist compositions using the same |
US7763238B2 (en) * | 2002-01-16 | 2010-07-27 | Monell Chemical Senses Center | Olfactory adaptation and cross-adapting agents to reduce the perception of body odors |
GB0506263D0 (en) * | 2005-03-29 | 2005-05-04 | Givaudan Sa | Skin lightening methods, composition and products |
GB201006042D0 (en) * | 2010-04-12 | 2010-05-26 | Givaudan Sa | Improvements in or relating to organic compounds |
MX2012013504A (es) | 2010-06-08 | 2013-01-24 | Firmenich & Cie | Biciclo-cetonas como ingredientes perfumantes. |
GB201409348D0 (en) * | 2014-05-27 | 2014-07-09 | Givaudan Sa | Perfume compositions |
EP3507352A1 (en) | 2016-09-01 | 2019-07-10 | Symrise AG | Product comprising a plastic container and a substance composition |
GB201615581D0 (en) | 2016-09-14 | 2016-10-26 | Givauden Sa | Improvements in or relating to organic compounds |
JP7050595B2 (ja) * | 2018-06-22 | 2022-04-08 | ライオン株式会社 | 香料組成物及び繊維製品用洗浄剤 |
US20240051905A1 (en) * | 2020-12-17 | 2024-02-15 | Basf Se | Bicyclic aroma chemicals |
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US4615830A (en) * | 1984-04-20 | 1986-10-07 | International Flavors & Fragrances Inc. | Isomer-directed process for producing asymmetric ketones using catalytic Claisen rearrangement of allylic ethers, intermediates, and uses of products and intermediates of process in perfumery |
US5118865A (en) * | 1990-03-26 | 1992-06-02 | Firmenich Sa | Cyclic ketones and their use as perfuming ingredients |
US5039659A (en) * | 1990-08-07 | 1991-08-13 | International Flavors & Fragrances Inc. | 2,2,3-trimethylcyclopentenyl acetone derivatives, organoleptic uses thereof and process for preparing same |
DE4121364A1 (de) * | 1991-06-28 | 1993-01-07 | Haarmann & Reimer Gmbh | Ether von 1-hydroxy-hex-5-en-2-on, verfahren zu ihrer herstellung und ihre verwendung als riechstoffe |
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SG85165A1 (en) | 2001-12-19 |
ZA200001596B (en) | 2000-10-16 |
US6184419B1 (en) | 2001-02-06 |
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JP2001002618A (ja) | 2001-01-09 |
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