CN101528655A - 用作增香剂的2,3,3-三甲基环戊-3-烯甲醛衍生物 - Google Patents
用作增香剂的2,3,3-三甲基环戊-3-烯甲醛衍生物 Download PDFInfo
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- CN101528655A CN101528655A CNA200780038827XA CN200780038827A CN101528655A CN 101528655 A CN101528655 A CN 101528655A CN A200780038827X A CNA200780038827X A CN A200780038827XA CN 200780038827 A CN200780038827 A CN 200780038827A CN 101528655 A CN101528655 A CN 101528655A
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- alcohol
- thiazolinyl
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Abstract
描述了式(I)的2,2,3-三甲基环戊-3-烯甲醛衍生物,其中R1-R7与说明书给出的含义相同。本发明进一步涉及该衍生物的生产方法和涉及包括该衍生物的香料组合物。
Description
本发明涉及一类用作增香剂的新型2,2,3-三甲基环戊-3-烯甲醛衍生物。本发明进一步涉及该衍生物的生产方法和涉及包括该衍生物的香料组合物。
在香料业中持续需要增强或改善气味香型(note)或赋予新气味香型的新化合物。令人吃惊地,发现了一类新型化合物,其具有木香、檀香、琥珀香、广藿香、花香、青香、内酯香(lactonic)香型。
因此,本发明在一方面涉及一种式(I)的化合物
其中:
R1、R2、R3和R4独立地选自氢、甲基或乙基;
R5是氢、甲基或乙基;和R6是羟基;或
R5和R6与它们相连的碳原子一起形成羰基;
R7是氢并且C-3和C-4之间的键为单键或者虚线与C-3和C-4之间的键一起表示双键;或者
R7是与C-3和C-4形成环丙烷环的亚甲基。
式(I)的化合物可以包括几个手性中心,因而可以作为立体异构混合物存在,或者可以将它们拆分为异构体纯形式。拆分立体异构体增加了制备和纯化这些化合物的复杂性,因此仅仅出于经济原因,优选使用其立体异构体混合物形式的化合物。然而,如果希望制备单一的立体异构体,则可以根据本领域已知的方法来实现,所述已知的方法例如制备型HPLC和GC、结晶或通过从手性起始材料分离(例如从对映异构体纯或富含的原料如萜类化合物开始)、和/或通过使用立体选择性合成。
因此,本发明在另一方面涉及富含式(A)或式(B)的化合物的式(I)的化合物,优选二者的比例为约1∶9-约9∶1,例如约3∶2,
其中R1-R7与上述式(I)给出的含义相同。
特别优选的式(I)的化合物为
2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇,
2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙醛,
3-甲基-3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇,
3-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丁-2-醇,
3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇,
1-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇,
2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-1-醇,
2-甲基-2-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-1-醇,
1-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-2-醇,
2-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-1-醇,
2-甲基-2-[(1,2,2-三甲基二环[3.1.0]己-3-基)甲氧基]丙-1-醇,和
2-甲基-2-[(2,2,3-三甲基环戊基)甲氧基]丙-1-醇。
根据本发明的化合物可以单独使用或与已知的增香剂分子结合使用,所述增香剂分子选自宽范围的目前可获得的天然分子或合成分子,如精油和提取物、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香剂结合使用的成分或赋形剂,例如载体材料,以及其他常用在本领域的助剂结合使用。
下列清单包括已知的增香剂分子的实例,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、(3-甲基-5-(2,2,3-三甲基-3-环戊烯-1-基)-4-戊烯-2-醇)、丁子香酚、法呢醇、香叶醇、Super MuguetTM(6-乙基-3-甲基-6-辛烯-1-醇)、里哪醇、薄荷醇、橙花醇、苯乙醇、玫瑰醇、(5-(2,2,3-三甲基-3-环戊烯基)-3-甲基戊-2-醇)、萜品醇或(1-(2,2,6-三甲基环己基)己-3-醇)。
-醛类和酮类,例如茴香醛、α-戊基肉桂醛、GeorgywoodTM(1-(1,2,8,8-四甲基-1,2,3,4,5,6,7,8-八氢化萘-2-基)乙酮)、羟基香茅醛、Iso E(1-(2,3,8,8-四甲基-1,2,3,4,5,6,7,8-八氢化萘-2-基)乙酮)、(4-(2,6,6-三甲基-2-环己烯基)-3-甲基-3-丁烯-2-酮)、(甲基(3-氧代-2-戊基环戊基)乙酸酯)、(3-(4-叔丁基苯基)-2-甲基丙醛)、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(3a,6,6,9a-四甲基十二氢化萘并[2,1-b]呋喃)、香叶草基甲醚、氧化玫瑰或Spirambrene(2,2,3’,7’,7’-五甲基螺(1,3-二噁烷-5,2’-降蒈烯))。
-酯类和内酯类,例如乙酸苄酯、乙酸柏木酯、γ-癸内酯、(2-[1-(3,3-二甲基环己基)乙氧基]-2-甲基丙-1-醇丙酸酯)、γ-十一烷酸内酯或乙酸岩兰草酯。
-杂环化合物类,例如异丁基喹啉。
本发明的化合物可以用在宽范围的香料应用中,例如在精细和功能香料的任何领域中,如香水、家用产品、洗衣产品、身体护理产品和化妆品。取决于特定应用以及其他增香剂成分的性质和质量,该化合物可以以宽范围变化的用量使用。其比例通常为用品的0.001至20wt%。在一个实施方式中,本发明的化合物可以0.001-0.05wt%的量用在织物软化剂中。在另一个实施方式中,本发明的化合物可以0.1-30wt%,更优选5-20wt%的量用在醇溶液中。然而,这些值仅仅是以实例的形式给出,因为有经验的香料商还可以通过较低或较高浓度(例如最多为香料组合物的约50wt%)获得效果或者可以得到新的香调(accord)。
简单地通过将香料组合物与香料用品直接混合就可以将本发明的化合物用在香料用品中,或者可以在之前的步骤中用捕集材料对其进行捕集,所述捕集材料例如为聚合物、胶囊、微胶囊和纳米胶囊、脂质体、成膜剂、吸收剂如碳或沸石、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,本发明进一步提供一种制备香料用品和由此得到的消费品的方法。该方法包括使用常规技术和方法,或者通过将化合物直接混入用品中,或者通过混合包括式(I)化合物的香料组合物,随后可以将其混入到香料用品中,从而将式(I)的化合物作为香料成分结合进来。通过加入嗅觉可接受量的本发明化合物,香料用品的气味香型将会得到改善、增强或改变。
因此,本发明进一步提供一种通过向其中加入嗅觉可接受量的式(I)化合物或其混合物来改善、增强或改变香料用品的方法。
本发明还提供一种香料用品,包括:
a)作为增香剂的式(I)化合物或其混合物;和
b)消费品基体(base)。
在此使用的“香料用品”是指任何产品,如精细香料,例如香水和化妆水;家用产品,例如洗碗机用的洗涤剂、表面清洁剂;洗衣产品,例如软化剂、漂白剂、洗涤剂;身体护理产品,例如洗发香波、洗浴凝胶;和化妆品,例如除臭剂、雪花膏,包括增香剂。所列产品仅仅用于说明,不应将其视为以任何方式进行限制。
在此使用的“香料组合物”是指任何组合物,包括至少一种增香剂分子和一种通常与增香剂一起用在香料组合物中的稀释剂,如一缩二丙二醇(DPG)、肉豆蔻酸异丙酯(IMP)、柠檬酸三乙酯(TEC)和醇(例如乙醇)。
本发明的化合物可以根据方案1制备,从市场上可买到的任意对映异构体比例的α-龙脑烯醛(纯(R)或(S)或两种对映异构体的任意混合物,例如约9∶1-约1∶9(R/S))开始,经由相应品质的其低级同系物α-龙脑醛(1),这描述于文献Y.Bessière-Chrétien et al.,Comptes Rendusdes Séances de l′Académie des Sciences,Série C:Sciences Chimiques(1971),273(3),272-275中。后者可以还原成已知的α-龙脑醇(2;R1=H),或与格氏试剂起反应从而生成1-取代α-龙脑醇2。上述醇2与取代环氧乙烷在碱例如氢化钠或酸例如四氯化锡的存在下起反应,生成相应的2-[(2,3,3-三甲基环戊-3-烯基)甲氧基]乙醇3。环氧乙烷开环很少具有高区域选择性;通常获得区域异构体的混合物(3+3’,其中成对的取代基对R2+R3和R4+R5改变位置)。在其中1-取代基(R4和/或R5)之一为氢的情况下,3可以氧化成相应的醛或酮4并再次与有机金属试剂例如格氏试剂起反应,从而产生不同取代的3。醇3可以通过本领域知的方法分别环丙烷化或氢化成5和6。可以通过首先将α-龙脑醇2环丙烷化或氢化,然后进行环氧乙烷的开环步骤,任选继之以氧化和添加有机金属试剂的步骤,以此来制备醇5和6。3、5和6的制备也可以包括使α-龙脑醛或其环丙烷化或氢化类似物与取代的乙二醇反应并将得到的二氧戊环还原。制备醇3、5和6的另外别的方法由以下组成,将龙脑醇2或其环丙烷化或氢化类似物转化成相应的卤化物,并使它们进行Williamson反应。
方案1:
a)NaBH4或R1MgX;其中X=卤素,例如Cl、Br、I;b)适当取代的环氧乙烷,SnCl4或NaH;c)Dess-Martin氧化剂;d)R5MgX;e)CH2I2、Et3Al;或CH2Br2、Zn、CuBr;f)H2、Pd/C;R1-R5与式(I)所给出的含义相同。
现在将参考以下非限制性实施例对本发明作进一步描述。这些实施里仅仅用于说明,并且应当理解本领域技术人员可以对其作出改变和改进。
在实施例中描述的所有产品从市场上可买到品质的9∶1或2∶3(R/S)对映异构体比例的α-龙脑烯醛。它们被转换成相应的已知α-龙脑醛(1)的对映异构体混合物。快速色谱:Merck硅胶60(230-400目)。记录的NMR谱在CDCl3中测量;化学位移(δ)以ppm表示,以TMS为内标;耦合常数J以Hz为单位。
实施例1:2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇(3a);(1”R/S)=3∶2
在15℃下将四氯化锡(0.65g,2.5mmol)添加到冰冷的2,2-二甲基环氧乙烷(4.5g,63mmol)的龙脑醇(2a,(R/S)=3∶2,35.5g,0.25mol)溶液中。使反应混合物的温度升高到25℃。在15℃下另外搅拌1.5小时后,将反应混合物注入水中,使用饱和碳酸氢钠水溶液碱化并使用MTBE(2x)萃取水层。将混合的有机相用水洗涤至pH等于7,干燥(MgSO4)并浓缩。将残留物(38.8g)减压蒸馏,从而得到未反应的起始醇(24.0g)和粗产品(8.9g),将所述粗产品通过快速色谱(MTBE/己烷1∶3)进一步纯化,从而获得2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇(3a,7.2g,产量54%,无色液体)。
1H NMR:δ5.20(sb,1H),3.49(dd,J=8.6,6.8,1H),3.43(d,JAB=10.9,1H),3.39(d,JAB=10.9,1H),3.34(dd,J=8.6,7.6,1H),2.30(m,1H),2.21(sb,1H),2.06(m,1H),1.90(m,1H),1.59(s,3H),1.17(s,3H),1.16(s,3H),1.06(s,3H),0.85(s,3H)。13C NMR:δ148.2(s),121.3(d),74.6(s),69.9(t),62.6(t),49.7(d),46.4(s),33.7(t),26.9(q),21.9(q),21.6(q),19.8(q),12.2(q)。MS:197(1),181(4),139(5),123(73),122(46),107(100),95(23),91(18),81(47),73(18),55(26),43(19),41(19)。
气味描述:檀香、花香、油脂香、小山羊皮味(suede)、奶油香。
实施例2:2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙醛(4a);(1”R/S)=3∶2
在氩气下将Dess-Martin氧化剂(18.5g,44mmol)逐滴添加到来自实施例1的2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇(3a)(5.7g,27mmol)的二氯甲烷(75ml)溶液中。在室温下另外搅拌30分钟后,将反应混合物注入冰水中,使用饱和水性碳酸氢钠溶液碱化,使用己烷稀释并过滤。将分离的有机层用水(2x)洗涤、干燥(MgSO4)、在真空中浓缩并通过快速色谱(MTBE/己烷1∶9)纯化,从而获得2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙醛(4a,2.0g,产量35%,无色油)。
1H NMR:δ9.59(s,1H),5.20(m,1H),3.53(dd,J=8.6,6.8,1H),3.32(dd,J=8.6,7.71H),2.33(m,1H),2.14(dtd,J=9.1,7.8,7.1,1H),1.92(m,1H),1.59(dt,J=2.5,1.6,3H),1.27(s,3H),1.26(s,3H),1.08(s,3H),0.83(s,3H)。13C NMR:δ204.8(d),148.1(s),121.2(d),79.6(s),65.3(t),49.7(d),46.4(s),33.6(t),26.7(q),20.9(q),20.4(q),19.7(q),12.2(q)。MS:210(M+,1),181(8),123(100),122(25),107(49),95(15),91(16),81(65),79(16),67(15),57(18),4(21),41(21)。
气味描述:木香、醛香、青香、金属香、檀香、奶油香、油脂香、内酯香、水香(watery)。
实施例3:3-甲基-3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇;(3b)(1”R/S)=3∶2
在0℃下将溶于THF(2ml)的来自实施例2的2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙醛(4a)(1.0g,4.8mmol)在30分钟内逐滴添加到2.9M的甲基氯化镁的THF溶液(2.0g,5.8mmol)中。将反应混合物注入饱和柠檬酸的冰水溶液中并使用MTBE(3x)萃取水层。将混合的有机相用水洗涤到pH等于7,干燥(MgSO4),在真空中浓缩并通过快速色谱(MTBE/己烷1∶9)纯化,从而获得3-甲基-3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇(3b,0.7g,产量65%,无色油),其为非对映异构的对映异构体对的~1∶1混合物。
1H NMR:δ5.20(m,2H),3.65(dq,J=6.5,3.0,1H),3.63(dq,J=6.5,3.0,1H),3.50(dd,J=8.6,6.9,1H),3.48(dd,J=8.6,7.1,1H),3.38(t,J=7.2,1H),3.35(t,J=7.1,1H),2.66(d,J=3.0,1H),2.64(d,J=3.0,1H),2.33-2.24(m,2H),2.11-2.02(m,2H),1.95-1.85(m,2H),1.59(dt,J=2.5,1.6,6H),1.13(s,6H),1.12(d,J=6.5,6H),1.11(s,3H),1.09(s,3H),1.07(s,3H),1.06(s,3H),0.85(2s,6H)。13C NMR:δ148.2(2s),121.3(d),121.2(d),77.2(2s),73.5(d),72.9(d),62.3(t),62.2(t),49.8(d),49.7(d),46.4(2s),33.6(2t),27.0(q),26.9(q),21.3(q),21.2(q),19.8(2q),18.6(q),18.1(q),16.8(q),16.7(q),12.2(2q)。MS:208(1),181(7),139(3),123(100),122(28),107(48),95(14),87(13),81(45),69(12),57(13),45(10),43(14),41(16)。
气味描述:琥珀香、青香、干香、檀香、粉香。
实施例4:3-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丁-2-醇(3c);(1”R/S)=3∶2
a)1-(2,2,3-三甲基环戊-3-烯基)乙醇(2b);(1”R/S)=3∶2
从相应对映异构体比例的龙脑醛1起始,根据实施例3获得2b。将粗产品通过减压蒸馏纯化;产量19%,无色油,非对映异构的对映异构体对的1∶1.4混合物。通过快速色谱(MTBE/己烷1∶4)分离而获得两对分析样品。
主要非对映异构体:1H NMR:δ5.17(m,1H),3.90(dqb,J=8.3,6.2,1H),2.18-2.06(m,1H),1.85-1.75(m,2H),1.58(dt,J=2.5,1.5,3H),1.45(sb,1H),1.19(d,J=6.2,3H),1.17(s,3H),0.97(s,3H)。13C NMR:δ149.0(s),120.6(d),69.8(d),57.5(d),47.0(s),33.2(t),27.6(q),23.8(q),19.6(q),12.3(q)。MS:154(M+,4),139(1),136(15),121(40),109(5),105(4),96(8),95(100),93(8),91(6),79(9),67(17),55(8),45(11),43(9),41(8)。
次要的非对映异构体:1H NMR:δ5.26(m,1H),3.93(qi,J=6.3,1H),2.38-2.29(m,1H),2.25-2.16(m,1H),1.80(dt,J=8.3,6.3,1H),1.64(sb,1H),1.59(dt,J=2.5,1.6,3H),1.25(d,J=6.3,3H),1.04(s,3H),0.92(s,3H)。13C NMR:δ148.1(s),121.6(d),68.6(d),56.7(d),46.5(s),31.5(t),26.9(q),23.4(q),20.0(q),12.3(q)。MS:154(M+,4),139(1),136(21),122(10),121(100),107(6),109(5),105(11),95(73),93(14),91(10),79(13),67(19),55(10),45(12),43(11),41(11)。
b)3-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丁-2-醇(3c);(1”R/S)=3∶2
通过使1-(2,2,3-三甲基环戊-3-烯基)乙醇(2b)与根据实施例1的实验步骤的顺/反式2,3-环氧丁烷反应获得3c;产量19%,无色油;非对映异构的对映异构体对的混合物(大约1∶1∶1∶1比例的4对,占~90%的混合物)。进行快速色谱(MTBE/己烷1∶4)分离,获得每2对的2种混合物。
1H NMR:2种首先洗脱(FC)出的对映异构体对:δ5.28(m,1H),5.17(m,1H),3.74(dq,J=9.3,5.9,1H),3.58(dq,J=7.9,6.0,1H),3.56-3.44(m,2H),3.38(dq,J=7.0,6.2,1H),3.26(dq,J=7.2,6.0,1H),2.88(d,J=1.9,1H),2.81(d,J=2.2,1H),2.34(m,1H),2.19-2.03(m,2H),1.95-1.78(m,3H),1.58(m,6H),1.21(d,J=6.0,3H),1.15(d,J=6.0,3H),1.14(d,J=6.0,3H),1.12(s,3H),1.11(d,J=6.2,3H),1.10(d,J=5.9,3H),1.07(d,J=5.9,3H),1.06(s,3H),0.90(s,3H),0.86(s,3H)。
13C NMR:2种首先洗脱(FC)出的对映异构体对:δ149.3(s),147.8(s),121.6(d),120.5(d),75.9(d),74.6(d),72.6(d),72.1(d),71.2(d),71.0(d),56.2(d),56.0(d),46.8(s),46.0(s),33.4(t),33.3(t),27.3(q),26.8(q),19.7(q),19.4(q),19.2(q),18.5(q),18.4(q),18.1(q),15.4(q),15.0(q),12.3(2q);2种第二洗脱(FC)出的对映异构体对:δ148.4(s),147.0(s),121.5(d),121.0(d),79.6(d),77.7(d),77.4(d),75.5(d),71.3(d),70.8(d),56.7(d),55.1(d),46.4(s),46.1(s),33.9(t),31.9(t),27.2(q),26.9(q),21.9(q),20.0(q),19.5(q),18.5(q),18.4(q),18.2(q),17.6(q),16.9(q),12.3(2q)。MS:2种首先洗脱(GC)出的对映异构体对:181(2),137(65),136(46),121(100),107(15),95(34),81(14),73(54),57(16),55(25),45(10),43(16),41(13);第三洗脱(GC)出的对映异构体对:181(1),137(100),136(52),121(61),107(16),95(53),91(14),81(21),73(93),57(22),55(34),45(22),43(20),41(17);第四洗脱(GC)出的对映异构体对:181(1),137(40),136(36),121(100),107(11),95(24),81(10),73(27),57(12),55(17),45(12),43(12),41(10)。
气味描述:木香、檀香、广藿香。
从α-龙脑醇(2a,(R/S)=3∶2或1∶9)或1-(2,2,3-三甲基环戊-3-烯基)乙醇(2b)和适当的环氧乙烷起始,根据实施例1中给出的通用步骤制备下列化合物(实施例5-9)
实施例5:3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇(3d);(1”R/S)=3∶2;4对非对映异构的对映异构体对的混合物(大约~3∶3∶1∶1)
2对主要的对映异构体:1H NMR:δ5.23-5.19(m,2H),3.77(dd,J=8.9,6.6,1H),3.59(dd,J=9.1,7.7,1H),3.58-3.50(m,2H),3.43(dd,J=9.1,6.6,1H),3.27(dd,J=8.9,7.7,1H),3.13(dq,J=15.3,6.2,1H),3.13(qb,J=6.2,1,1,1H),2.86(d,J=2.3,1H),2.81(d,J=2.5,1H),2.38-2.27(m,2H),2.18-2.09(m,2H),1.99-1.88(m,2H),1.59(dt,J=2.5,1.6,6H),1.15(d,J=6.3,3H),1.14(d,J=6.3,3H),1.12(d,J=6.2,3H),1.115(d,J=6.2,3H),1.07(s,3H),1.0.6(s,3H),0.85(s,3H),0.84(s,3H)。13C NMR:δ148.0(s),147.9(s),121.3(2d),80.9(d),80.3(d),71.1(d),71.0(d),70.5(t),70.1(t),49.6(d),49.4(d),46.4(s),46.3(s),33.7(2t),26.9(q),26.8(q),19.9(q),19.7(q),18.5(q),18.4(q),15.2(q),15.1(q),12.2(2q)。MS:167(4),123(46),122(38),107(100),95(12),91(13),81(32),79(10),73(11),67(9),57(10),55(16),45(9),43(10),41(11)。
2对次要的对映异构体:13C NMR:δ148.1(s),148.0(s),121.2(2d),79.0(d),78.8(d),70.3(d),70.1(d),69.3(t),69.1(t),49.5(d),49.4(d),46.4(s),46.3(s),33.5(2t),26.9(q),26.8(q),19.9(q),19.7(q),17.7(q),17.6(q),13.7(q),13.4(q),12.2(2q)。MS:167(4),123(51),122(41),107(100),95(13),91(14),81(36),79(11),73(12),67(10),57(12),55(17),45(10),43(12),41(13)。
气味描述:木香、檀香、内酯香、香豆素香、花香,比实施例6的3d’更具有木香/檀香。
实施例6:3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇(3d’);(1”R/S)=1∶9;对应于实施例5的主要对映异构体对(相同谱)的2对非对映异构的对映异构体对的混合物(大约~1∶1),含有7%的另一对。
气味描述:木香、檀香、内酯香、香豆素香、花香,比实施例5的3d更具有花香。
实施例7:1-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇和2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-1-醇的2∶1混合物(3e’);(1”R/S)=1∶9;非对映异构体比~1∶1
主要的区域异构体(2对对映异构体):13C NMR:δ148.1(s),148.0(s),121.3(d),121.2(d),75.0(t),74.9(t),72.8(2t),71.7(d),71.6(d),49.1(2d),46.4(2s),33.5(t),33.4(t),26.8(2q),26.1(2t),19.8(2q),12.2(2q),9.9(q),9.8(q)。MS:123(8),122(25),108(9),107(100),93(6),91(9),81(9),79(6),73(3),67(5),55(12),41(7)。
次要的区域异构体(2对对映异构体):13C NMR:δ148.1(s),148.0(s),121.3(d),121.2(d),81.5(d),81.3(d),70.9(t),70.8(t),63.8(t),63.6(t),49.6(d),49.5(d),46.4(s),46.3(s),33.9(t),33.6(t),26.8(q),26.7(q),23.5(t),23.3(t),19.9(q),19.7(q),12.2(2q),9.7(q),9.6(q)。MS:181(3),123(28),122(32),107(100),95(10),91(11),81(22),57(8),55(18),43(9),41(10)。
气味描述:木香、檀香、奶油香、青香、蜜香。
实施例8:2-甲基-2-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-1-醇(3f);(1”R/S)=3∶2;非对映异构体比~1∶1.1
主要的非对映异构体(首先洗脱):13C NMR:δ148.7(s),120.9(d),75.1(s),71.5(t),69.8(d),56.3(d),46.6(s),32.5(t),27.3(q),23.6(q),23.3(q),21.7(q),19.8(q),12.4(q)。MS:195(1),138(10),137(100),136(46),121(66),109(28),107(12),95(80),93(15),91(16),81(21),73(97),67(17),59(6),57(21),55(34),43(24),41(26)。
次要的非对映异构体(第二洗脱):13C NMR:δ147.9(s),121.6(d),75.3(s),71.3(t),69.8(d),57.0(d),45.9(s),34.7(t),26.9(q),23.8(q),23.5(q),22.7(q),19.3(q),12.4(q)。MS:195(1),153(2),137(49),136(36),121(100),109(34),107(10),95(42),93(13),91(12),81(13),73(35),67(13),59(4),57(14),55(22),43(19),41(15)。
气味描述:木香、檀香、柏木香、轻微乡土香(agrestic)和广藿香。
实施例9:1-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-2-醇和2-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-1-醇的4∶1混合物(3g);(1”R/S)=3∶2)
主要的区域异构体(4对对映异构体):13C NMR:δ149.0(s),148.9(s),147.6(2s),121.6(d),121.5(d),120.5(2d),77.7(d),77.5(d),77.4(d),76.7(d),76.1(d),73.9(d),73.52(d),73.4(d),66.9(t),66.8(t),66.7(t),66.6(t),56.1(d),56.0(d),55.6(d),55.5(d),47.0(s),46.9(s),46.3(2s),33.2(t),31.1(t),32.1(2t),27.6(q),27.5(q),26.9(2q),20.1(q),20.0(q),19.8(q),19.7(q),19.2(2q),19.0(q),18.8(q),18.7(q),18.5(q),18.2(q),18.1(q),12.3(4q)。MS:137(11),136(37),122(10),121(100),107(11),103(12),95(13),93(9),91(9),79(8),67(6),59(68),55(7),45(12),43(9),41(12)。
次要的区域异构体(4对对映异构体):13C NMR(选择的峰):67.1(t),66.8(t),66.3(2t)。MS:181(1),137(30),136(40),122(10),121(100),107(11),103(12),95(24),93(12),91(12),81(9),79(10),77(8),67(9),59(64),57(10),55(10),45(15),43(12),41(16)。
气味描述:木香、广藿香、檀香、乡土香、奶油香。
实施例10:2-甲基-2-[(1,2,2-三甲基二环[3.1.0]己-3-基)甲氧基]丙-1-醇(5a);(3”R/S)=3∶2
在10℃下于1小时内将15%三乙基铝的己烷溶液(11.5ml,10.3mmol)添加到来自实施例1的2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇(3a)(1.0g,4.7mmol)和二碘甲烷(2.9g,11mmol)的己烷(40ml)溶液中。在室温下另外搅拌90小时后,将反应混合物注入冰水中,使用1N硫酸将其酸化到pH等于5并使用MTBE(3x)萃取水层。将混合的有机相用水洗涤,干燥(MgSO4)并在真空浓缩。结果证实通过色谱法分离未反应的3a有困难。将乙酸钠(0.2g,2.4mmol)和MCPBA(0.6g,70%纯度,2.4mmol)添加到溶于二氯甲烷(2ml)的粗产品(0.9g)中,并在室温下另外搅拌1小时后,将反应混合物注入冰水中,使用饱和的碳酸氢钠水溶液碱化并使用己烷(3x)萃取水层。将混合的有机相用水洗涤、干燥(MgSO4)、在真空中浓缩并通过快速色谱(MTBE/己烷1∶5)纯化,从而获得2-甲基-2-[(1,2,2-三甲基二环[3.1.0]己-3-基)甲氧基]丙-1-醇;(5a,0.3g,产量28%,无色油)其为一对对映异构体(GC纯度96.5%)。
1H NMR:δ3.40(d,JAB=10.8,1H),3.36(d,JAB=10.8,1H),3.32(dd,J=8.7,5.7,1H),3.17(dd,J=8.7,7.0,1H),2.07(sb,1H),1.75(m,1H),1.49-1.38(m,2H),1.14(s,3H),1.13(s,3H),1.02(s,3H),0.99(m,1H),0.98(s,3H),0.81(s,3H),0.45(m,1H),0.04(dd,J=7.8,4.8,1H)。13C NMR:δ74.5(s),69.8(t),62.8(t),44.4(d),40.9(s),31.7(s),30.8(t),23.8(q),22.6(d),21.9(q),21.5(q),19.6(q),16.9(q),14.0(t)。MS:211(1),195(11),154(9),139(60),137(76),136(37),123(23),121(90),109(25),107(29),95(95),93(50),81(100),73(76),69(52),67(40),57(52),55(82),43(40),41(56)。
气味描述:檀香、木香、粉香、青香、内酯香。
实施例11:2-甲基-2-[(2,2,3-三甲基环戊基)甲氧基]丙-1-醇(6a);(1”R/S)=3∶2
在常压下和在常温下,在位于活性炭上的钯(5%,0.55g)的存在下,将来自实施例1的2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇(3a)(1.0g,4.7mmol)的乙醇(10ml)溶液于3小时内氢化。滤出催化剂,使溶剂在真空中蒸发并将残留物蒸馏(球对球(bulb-to-bulb)),从而获得2-甲基-2-[(2,2,3-三甲基环戊基)甲氧基]丙-1-醇(3b,0.65g,产量64%,无色液体),其为非对映异构的对映异构体对的9∶1混合物。
主要的对映异构体对:1H NMR:δ3.42(dd,J=8.5,5.9,1H),3.42-3.37(m,2H),3.19(dd,J=8.5,7.8,1H),2.22(tb,J=5.7,1H),1.87-1.66(m,3H),1.61-1.49(m,1H),1.28-1.17(m,2H),1.16(s,3H),1.15(s,3H),0.96(s,3H),0.82(d,J=6.8,3H),0.56(s,3H)。13C NMR:δ74.5(s),69.7(t),63.2(t),50.4(d),45.6(d),41.7(s),30.1(t),26.6(q),26.5(t),21.9(q),21.5(q),14.6(q),13.3(q)。MS:183(7),126(7),125(77),109(6),83(34),73(12),70(8),69(100),67(9),59(11),57(22),55(35),43(15),41(25)。
次要的对映异构体对:13C NMR:δ74.5(s),69.8(t),63.4(t),48.6(d),44.3(d),41.5(s),31.6(t),27.4(t),24.4(q),23.6(q),21.8(q),21.6(q),15.4(q)。MS:183(7),126(8),125(75),109(12),83(36),73(14),70(9),69(100),67(8),59(10),57(20),55(32),43(13),41(26)。
气味描述:木香、乡土香、花香、果香、比不饱和的类似物3a弱。
实施例12:用于古龙香水(eau de Cologne)的花香-木香香料组合物
成分 重量份
Adoxal(2,6,10-三甲基-9-十一碳烯醛) 2
黄葵内酯(氧杂环十七碳-10-烯-2-酮) 14
Bourgeonal(4-(1,1-二甲基乙基)苯丙醛) 3
CosmoneTM(3-甲基-5-环十四碳烯-1-酮) 10
Damascenone 10%在DEP(邻苯二甲酸二乙酯)中 3
(1-(2,6,6-三甲基-1,3-环己二烯-1-基)-2-丁烯-1-酮)
δ-癸内酯 8
十三烷二酸亚乙基酯 45
丁子香酚 7
(4,6,6,7,8,8-六甲基-1,3,4,6,7,8-六氢环戊(g)-2-苯并吡喃)
乙酸苏合香酯(α-甲苯苄基乙酸酯) 5
Georgywood 35
(1-(1,2,3,4,5,6,7,8-八氢-1,2,8,8-四甲基-2-萘基)乙酮)
乙酸顺式-3-己烯基酯 1
水杨酸顺式-3-己烯基酯 45
Indolene 10
里哪醇 55
甲基异丁子香酚 15
(2,4-二甲基-2-(1,1,4,4-四甲基四氢萘-6-基)-1,3-二氧戊环)
来自实施例6的化合物3d’ 55
700
来自实施例6的3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇(3d’)使香调具有奶油香香型并且增强了感官上的晚香玉型香型。它增加了组合物的浓郁(volume)、圆和(roundness)与光泽(radiance)。
Claims (10)
4.根据权利要求1的化合物,其选自
2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙-1-醇,
2-甲基-2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丙醛,
3-甲基-3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇,
3-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丁-2-醇,
3-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇,
1-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-2-醇,
2-[(2,2,3-三甲基环戊-3-烯基)甲氧基]丁-1-醇,
2-甲基-2-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-1-醇,
1-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-2-醇,
2-[1-(2,2,3-三甲基环戊-3-烯基)乙氧基]丙-1-醇,
2-甲基-2-[(1,2,2-三甲基二环[3.1.0]己-3-基)甲氧基]丙-1-醇,和
2-甲基-2-[(2,2,3-三甲基环戊基)甲氧基]丙-1-醇。
5.一种香料组合物,其包括如上述权利要求任一项所定义的化合物。
6.一种香料用品,其包括
a)如权利要求1-4任一项所定义的式(I)的化合物;和
b)消费品基体。
7.根据权利要求6的香料用品,其中消费品基体选自精细香料、家用产品、洗衣产品、身体护理产品和化妆品。
8.如权利要求1-4任一项所定义的化合物作为香料成分的用途。
9.一种制造香料组合物的用途,包括向基体材料中引入有效量的如权利要求1-4任一项所定义的式(I)的化合物,或其混合物。
10.一种改善、增强或改变香料组合物或香料用品香味的方法,包括如下步骤:向基体材料中引入有效量的如权利要求1-4任一项所定义的式(I)的化合物,或其混合物。
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CN104433927A (zh) * | 2014-10-23 | 2015-03-25 | 广东比伦生活用纸有限公司 | 一种手帕纸的加香工艺及制得的香味手帕纸 |
CN113015716A (zh) * | 2018-11-14 | 2021-06-22 | 奇华顿股份有限公司 | 用作增香剂的乙酸酯化合物 |
US12012570B2 (en) | 2018-11-14 | 2024-06-18 | Givaudan Sa | Acetate compounds useful as odorants |
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GB0802526D0 (en) | 2008-02-12 | 2008-03-19 | Givaudan Sa | Organic compounds |
WO2019230974A1 (en) * | 2018-06-01 | 2019-12-05 | Takasago International Corporation | Fragrance material |
US11999691B2 (en) | 2020-12-19 | 2024-06-04 | Actera Ingredients, Inc. | Odorless active agents |
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DE3562901D1 (en) * | 1984-03-23 | 1988-06-30 | Firmenich & Cie | Hydroxylated derivatives of campholenic aldehyde, their use as flavouring agents and flavouring compositions containing them |
EP0801049B1 (en) * | 1996-04-09 | 2001-11-21 | Givaudan SA | Cyclopentanebutanol derivatives as odorants |
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CN104433927A (zh) * | 2014-10-23 | 2015-03-25 | 广东比伦生活用纸有限公司 | 一种手帕纸的加香工艺及制得的香味手帕纸 |
CN113015716A (zh) * | 2018-11-14 | 2021-06-22 | 奇华顿股份有限公司 | 用作增香剂的乙酸酯化合物 |
US12012570B2 (en) | 2018-11-14 | 2024-06-18 | Givaudan Sa | Acetate compounds useful as odorants |
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