CN106946705B - 一种合成(1r,2s)-二氢茉莉酮酸甲酯的方法 - Google Patents

一种合成(1r,2s)-二氢茉莉酮酸甲酯的方法 Download PDF

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CN106946705B
CN106946705B CN201611259187.2A CN201611259187A CN106946705B CN 106946705 B CN106946705 B CN 106946705B CN 201611259187 A CN201611259187 A CN 201611259187A CN 106946705 B CN106946705 B CN 106946705B
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张国清
杨大志
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Beijing Asrl Technology Co ltd
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Abstract

本发明公开了一种利用不对称Michael加成反应合成(1R,2S)‑二氢茉莉酮酸甲酯的新方法。该方法以环戊酮为起始原料，在碱性条件下先与正戊醛发生羟醛缩合反应，生成2‑戊叉基环戊酮2，再在酸性条件下发生双键转位得到2‑正戊基‑2‑环戊烯酮3。然后在手性氨基酸锂盐催化下，与丙二酸二甲酯发生Michael加成反应，经过两次硅胶柱色谱分离，得到(1S,2S)‑2‑正戊基‑3‑丙二酸二甲酯基环戊酮4。最后经水解脱羧反应，得到(1R,2S)‑二氢茉莉酮酸甲酯。本发明合成路线简捷，反应条件温和，仅四步反应就能制得目标化合物。

Description

一种合成(1R,2S)-二氢茉莉酮酸甲酯的方法
技术领域
本发明涉及一种新的合成(1R,2S)-二氢茉莉酮酸甲酯的方法，属于香料香精化学领域。
背景技术
二氢茉莉酮酸甲酯(Methyl dihydrojasmonate)具有浓郁的茉莉花香与水果香，广泛应用于化妆品、香水工业，是目前使用量最大的一类香料(Frater,G.；Bajgrowicz,J.A.；Kraft,P.Tetrahedron 1998,54,7633.Kraft,P.；Bajgrowicz,J.A.；Denis,C.；Frater,G.Angew.Chem.,Int.Ed.,2000,39,2980.)。二氢茉莉酮酸甲酯于1962年，被首次合成(Firmenich,A.；Firmenich,R.；Firmenich,G.；Firmenich,R.E.Patent GB 907431A,1962,3,3.)。二氢茉莉酮酸甲酯结构中有两个手性碳原子，具有四个不同的立体异构体(式1)，手性结构对二氢茉莉酮酸甲酯的香气特征具有重要的影响。(1R,2S)-二氢茉莉酮酸甲酯具有最强的香气，具有强烈的茉莉花香与水果香。其对映体(1S,2R)-二氢茉莉酮酸甲酯具有很弱的草药香与花香。两个反式立体异构体，(1R,2R)-二氢茉莉酮酸甲酯与(1S,2S)-二氢茉莉酮酸甲酯具有最弱的香气，具有极其淡的茉莉花香与水果香(Werkhoff,P.；Krammer,G.；Brennecke,S.；Roloff,M.；Bertram,H.J.Food Rev.Int.,2002,18,103.)。目前广泛使用的二氢茉莉酮酸甲酯香料，商品名为Hedione，是四个立体异构体的混合物，顺式与反式的比例约为10:90(Nakano,T.；Irifune,S.；Umano,S.；Inada,A.；Ishii,Y.；Ogawa,M.J.Org.Chem.,1987,52,2239.)。在Hedione香料中，真正起作用的立体异构体是(1R,2S)-二氢茉莉酮酸甲酯。
Figure BDA0001199503170000011
使用二氢茉莉酮酸甲酯立体异构体的混合物作为香料不仅造成原料浪费，增加环境污染，而且影响化妆品与食品的香味。因而，研究合成(1R,2S)-二氢茉莉酮酸甲酯单一立体异构体，进而替代二氢茉莉酮酸甲酯立体异构体的混合物作为香料具有重要的应用价值。目前，合成(1R,2S)-二氢茉莉酮酸甲酯的方法主要有三种，即手性源法、酶催化法与不对称催化合成法。
(1)手性源法是以(3aS,4S,-6aR)-羟甲基内酯为原料，经硫醚化、还原、保护羟基、氧化、等八步反应得到手性羟基环戊烷乙酸，最后经酯化与DMP氧化得到目标产物(1R,2S)-二氢茉莉酮酸甲酯(Porta,A.；Vidari,G.；Zanoni,G.J.Org.Chem.,2005,70,4876.Vidari,G.；Zanoni,G.；Porta,A.Patent WO2004/108652 A2,2004,12,16.)。
(2)酶催化法是利用酯化酶Novozym 435催化外消旋环戊烯醇的酯化反应，得到(R)-环戊烯醇丙二酸酯，再经Claisen重排，得到(R)-环戊烯乙酸酯，最后经环氧化与1,2-氢迁移反应得到目标产物(1R,2S)-二氢茉莉酮酸甲酯(Fehr,C.；Galindo,J.,Angew.Chem.,Int.Ed.,2000,39,569.)。
(3)不对称催化合成法是利用手性膦配体与金属钌形成的手性配位化合物作为催化剂，催化2-正戊基-3-羰基环戊烯乙酸甲酯的不对称氢化反应，得到(1R,2S)-二氢茉莉酮酸甲酯(Dobbs,D.A.；Vanhessche,K.P.M.；Brazi,E.；Rautenstrauch,V.；Lenoir,J.-Y.；Genet,J.-P.；Wiles,J.；Bergens,S.H.Angew.Chem.,Int.Ed.,2000,39,1992.)。
虽然关于合成(1R,2S)-二氢茉莉酮酸甲酯的研究已有几例报道，但现有方法存在需要化学剂量的手性试剂、对温度敏感的酶、合成路线繁琐等问题。因此，研究新的、高效的、简捷的合成(1R,2S)-二氢茉莉酮酸甲酯的方法，具有重要的意义。
发明内容
本发明旨在提供一种利用不对称Michael加成反应合成(1R,2S)-二氢茉莉酮酸甲酯的新方法。本发明以环戊酮为起始原料，在碱性条件下先与正戊醛发生羟醛缩合反应，生成2-戊叉基环戊酮2，再在酸性条件下发生双键转位得到2-正戊基-2-环戊烯酮3。然后在手性氨基酸锂盐催化下，与丙二酸二甲酯发生不对称Michael加成反应，经过两次硅胶柱色谱分离，得到(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4。最后经水解脱羧反应，得到(1R,2S)-二氢茉莉酮酸甲酯。本发明合成路线简捷，反应条件温和，仅四步反应就能制得目标化合物。本发明合成(1R,2S)-二氢茉莉酮酸甲酯的具体路线参见式2。
Figure BDA0001199503170000031
本发明合成(1R,2S)-二氢茉莉酮酸甲酯的方法具体包括下列步骤。
(1)2-戊叉基环戊酮2的合成
氮气保护下，将正戊醛滴入环戊酮的NaOH水溶液中，在室温下搅拌反应1h。反应结束后，用乙酸将反应液调至中性。减压蒸馏制得2-戊叉基环戊酮2。
(2)2-正戊基-2-环戊烯酮3的合成
在2-戊叉基环戊酮2中，搅拌下加入含5％HBr的正丁醇溶液。将反应混合液加热至回流，继续搅拌反应2h。反应结束后，降至室温，用5％的Na2CO3水溶液将反应液调至中性。减压蒸馏制得2-正戊基-2-环戊烯酮3。
(3)(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4的合成
在室温下，将手性氨基酸锂盐Cat.1与2-正戊基-2-环戊烯酮3依次加入二甲基亚砜与二氯甲烷的混合溶液。然后加入丙二酸二甲酯，在室温下继续搅拌反应48h。反应结束后，用饱和NaCl水溶液萃灭反应，分出有机相，水相用乙醚萃取。合并有机相，经干燥、减压浓缩得到粗产物。最后经过两次硅胶柱色谱纯化，制得(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4。
(4)(1R,2S)-二氢茉莉酮酸甲酯的合成
在(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4的二甲基亚砜溶液中，加入微量去离子水。将反应混合液加热至190℃搅拌反应10h。反应结束后，降至室温，用乙醚稀释反应液。有机相经水与食盐水洗涤，干燥、减压浓缩得到粗产物。最后用硅胶柱色谱纯化，制得(1R,2S)-二氢茉莉酮酸甲酯。
具体实施方式
实施例1
2-戊叉基环戊酮2的合成
氮气保护下，在100mL四口瓶中加入NaOH(0.20g,0.5mmol)与水15mL，搅拌溶解。室温下缓慢加入环戊酮1(8.40g,100mmol)，搅拌均匀后，通过滴液漏斗滴加正戊醛(5.18g,60mmol)。滴加完毕后，在室温下继续搅拌反应1h。反应结束后，用乙酸将反应液调至中性。减压蒸馏得到无色油状物2-戊叉基环戊酮2(7.30g，产率80％)。1H NMR(400MHz,CDCl3)δ6.20(t,J＝6.1Hz,1H),2.80-2.71(m,2H),2.50-2.40(m,2H),2.23-2.14(m,2H),1.51-1.44(m,2H),1.43-1.30(m,4H),0.89(t,J＝6.7Hz,3H).HRMS(APCI-TOF)calcd for C10H17O[M+H]+153.1279,found 153.1272.
实施例2
2-正戊基-2-环戊烯酮3的合成
在100mL反应瓶中加入2-戊叉基环戊酮2(4.57g,30mmol)，搅拌下加入含5％HBr的正丁醇溶液30mL。将反应混合液加热至回流，继续搅拌反应2h。反应结束后，将反应液温度降至室温，用5％的Na2CO3水溶液将反应液调至中性。减压蒸馏得到无色油状物2-正戊基-2-环戊烯酮3(3.88g，产率85％)。1H NMR(400MHz,CDCl3)δ6.22(t,J＝6.0Hz,1H),2.78-2.69(m,2H),2.50-2.42(m,2H),2.21-2.12(m,2H),1.51-1.43(m,2H),1.42-1.28(m,4H),0.88(t,J＝6.7Hz,3H).HRMS(APCI-TOF)calcd for C10H17O[M+H]+153.1279,found 153.1274.
实施例3
(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4的合成
在室温下，将5mL二甲基亚砜与10mL二氯甲烷加入50mL Schlenk反应瓶中，搅拌下依次加入手性氨基酸锂盐Cat.1(0.72g,2mmol)与2-正戊基-2-环戊烯酮3(1.52g,10mmol)，搅拌均匀。然后加入丙二酸二甲酯(2.64g,20mmol)，将反应混合液在室温下继续搅拌反应48h。反应结束后，加入15mL饱和NaCl水溶液萃灭反应。分出有机相，水相用乙醚(3×20mL)萃取。合并有机相，用无水Na2SO4干燥，减压浓缩得到粗产物。用硅胶柱色谱纯化(石油醚/乙酸乙酯10:1)，得到浅黄色油状物(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮与(1S,2R)-2-正戊基-3-丙二酸二甲酯基环戊酮4的混合物(1.79g，产率63％)。最后将(1S,2S)-4与(1S,2R)-4的混合物用硅胶柱色谱分离(正己烷/乙醚8:1)，得到(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4(0.70g)。1H NMR(400MHz,CDCl3)δ3.72(s,6H),3.46(d,J＝7.2Hz,1H),2.67-2.54(m,1H),2.37-1.92(m,4H),1.77-1.12(m,8H),0.81(t,J＝6.7Hz,3H).HRMS(APCI-TOF)calcd for C15H25O5[M+H]+285.1702,found 285.1690.
实施例4
(1R,2S)-二氢茉莉酮酸甲酯的合成
在50mL反应瓶中加入(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮4(0.57g,2mmol)和15mL二甲基亚砜，再加入50μL去离子水。将反应混合液加热至190℃，在此温度下继续搅拌反应10h。反应结束后，将反应混合液温度降至室温，然后小心倒入150mL乙醚。有机相依次用水(3×20mL)与饱和食盐水20mL洗涤，经无水Na2SO4干燥，减压浓缩得到粗产物。最后用硅胶柱色谱(正己烷/乙醚4:1)纯化，得到无色油状物(1R,2S)-二氢茉莉酮酸甲酯(0.27g,产率60％)。[α]D 20＝+75(c 1.2,CH2Cl2).1H NMR(400MHz,CDCl3)δ3.66(s,3H),2.85-2.74(m,1H),2.42(dd,J＝15.7,5.4Hz,1H),2.30(dd,J＝15.7,5.4Hz,1H),2.26-2.05(m,5H),1.88-1.78(m,1H),1.60-1.51(m,1H),1.50-1.13(m,6H),0.89(t,J＝6.9Hz,3H).HRMS(APCI-TOF)calcd for C13H23O3[M+H]+227.1647,found 227.1640。

Claims (5)

1.一种合成(1R,2S)-二氢茉莉酮酸甲酯的方法，其特征在于，包括如下步骤：先将环戊酮与正戊醛发生羟醛缩合反应，生成2-戊叉基环戊酮，再在酸性条件下发生双键转位得到2-正戊基-2-环戊烯酮；然后在手性氨基酸锂盐催化下，与丙二酸二甲酯发生Michael加成反应，经过两次硅胶柱色谱分离，得到(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮；最后经水解脱羧反应，得到(1R,2S)-二氢茉莉酮酸甲酯；
其中，合成(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮的方法为：在室温下，将手性氨基酸锂盐与2-正戊基-2-环戊烯酮加入二甲基亚砜与二氯甲烷的混合溶液，加入丙二酸二甲酯进行反应；
其中，合成(1R,2S)-二氢茉莉酮酸甲酯的方法为：在(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮的二甲基亚砜溶液中，加入微量去离子水，在190℃下搅拌反应；
其中，所述手性氨基酸锂盐的结构式为：
Figure FDA0003412647530000011
2.根据权利要求1所述的一种合成(1R,2S)-二氢茉莉酮酸甲酯的方法，其中，合成2-戊叉基环戊酮的方法为：氮气保护下，将正戊醛与环戊酮的NaOH水溶液，进行搅拌，反应结束后，用乙酸将反应液调至中性，减压蒸馏制得2-戊叉基环戊酮。
3.根据权利要求1所述的一种合成(1R,2S)-二氢茉莉酮酸甲酯的方法，其中，合成2-正戊基-2-环戊烯酮的方法为：将2-戊叉基环戊酮的含HBr的正丁醇溶液，加热回流，反应结束后，用Na2CO3水溶液将反应液调至中性，减压蒸馏制得2-正戊基-2-环戊烯酮。
4.根据权利要求1所述的一种合成(1R,2S)-二氢茉莉酮酸甲酯的方法，其中，合成(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮的方法为：在室温下，将手性氨基酸锂盐与2-正戊基-2-环戊烯酮加入二甲基亚砜与二氯甲烷的混合溶液，加入丙二酸二甲酯，继续搅拌反应，反应结束后，萃灭反应，经分液、萃取、干燥、减压浓缩得到粗产物，最后经过两次硅胶柱色谱分离，制得(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮。
5.根据权利要求1所述的一种合成(1R,2S)-二氢茉莉酮酸甲酯的方法，其特征在于合成(1R,2S)-二氢茉莉酮酸甲酯的方法为：在(1S,2S)-2-正戊基-3-丙二酸二甲酯基环戊酮的二甲基亚砜溶液中，加入微量去离子水，在190℃下搅拌反应，反应结束后，用有机溶剂稀释反应液；然后经洗涤、干燥、减压浓缩得到粗产物，最后用硅胶柱色谱纯化，制得(1R,2S)-二氢茉莉酮酸甲酯。
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