CN109503539A - 一种取代八氢香豆素及其制备方法 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring
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- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Abstract
本发明公开了一种取代八氢香豆素，其特征在于，所述取代八氢香豆素为八氢‑5,7,7‑三甲基‑2H‑1‑苯并吡喃‑2‑酮，如式(VI)所示。其中，所述的取代八氢香豆素为八氢‑5,7,7‑三甲基‑2H‑1‑苯并吡喃‑2‑酮。本发明还公开了其制备方法。本发明提供了一种新的取代八氢香豆素，为取代八氢香豆素领域增添了新的工业化选择。三甲基八氢香豆素(VI)具有新鲜香豆香，椰子似香甜气，以及甜美的药草气味，别具一格的暖香和辛香，留香时间长。
Description
技术领域
本发明涉及有机合成领域，具体涉及一种取代八氢香豆素及其制备方法。
背景技术
香豆素作为一种肉桂酸衍生的内酯，具有强烈、甜润的草香和辛香香气，可用于香水、化妆品等日用香精及烟用香精的配方中。天然存在于黑香豆、车前草以及薰衣草等植物中。它具有显著的生理活性，在农药、医药及工业方面有广泛应用。而它的许多衍生物也具有生理活性；分子量较小的衍生物，多具有特征的香气，因此它的衍生物的合成一直受到人们的关注。但由于香豆素、二氢香豆素被认为对皮肤有致敏作用，在日化香精的配方中的使用受到限制。而八氢香豆素则没有这种致敏作用，因此可以用于日化香精和烟用香精的配方之中；还被允许用于食用香精的调配，例如用于椰子、乳品调和剂、烘烤食品等香精中。因此八氢香豆素的衍生物就显示了一定的潜在生物活性及香料方面的使用可能性。它的合成也具有意义。
现有技术当中，八氢香豆素的合成一般采用香豆素催化氢化得到(Dana bilkova，《催化学报》，2015(7)：957-960)，60wt％香豆素的甲醇溶液，以0.5％香豆素质量的5％Ru/C为催化剂，在130℃，10MPa，香豆素转化完全，八氢香豆素的选择性为89.6％。
S.Sanghvi等人于J.Heterocyclic Chem.19.1377(1982)中以雷尼镍为催化剂，于180℃及10MPa条件下催化氢化4,7-二甲基香豆素得到异构体分布为40:25:35的三种异构体混合物，并利用红外光谱及核磁1H NMR研究了它们的结构，得到确认为是消旋顺/反式八氢-4,7-二甲基-2H-苯并吡喃-2-酮。并对它们的衍生物进行了研究。
因此对于八氢香豆素的衍生物进行进一步的工业应用的研究，具有一定的现实意义。
发明内容
为了克服现有技术当中所存在的上述缺陷，本发明的目的之一在于提供一种新合成的取代八氢香豆素。
本发明的目的之二在于提供一种取代八氢香豆素及其制备方法。
为了实现本发明的目的之一，所采用的技术方案是：
一种取代八氢香豆素，所述取代八氢香豆素为八氢-5,7,7-三甲基-2H-1-苯并吡喃-2-酮，如式(VI)所示：
其中，所述的取代八氢香豆素为八氢-5,7,7-三甲基-2H-1-苯并吡喃-2-酮。
为了实现本发明的目的之二，所采用的技术方案是：
一种取代八氢香豆素的制备方法，包括如下步骤：
以异佛尔酮(isophorone)为起始原料，首先催化氢化得到二氢异佛尔酮(II)；
二氢异佛尔酮(II)经与吗啡啉作用生产烯胺中间体(III)；
生产烯胺中间体(III)与丙烯酸甲酯发生加成反应得到3-(1-氧代-3,5,5-三甲基环己基)丙酸甲酯(IV)；
再经碱性条件下水解，硼氢化钾还原羰基，最后经酸催化羟基酸(V)发生分子内酯化环合生成八氢-5,7,7-三甲基-2H-苯并吡喃-2-酮(5,7，7-三甲基八氢香豆素，VI)，制备总反应式如下：
本发明的有益效果在于：
提供了一种新的取代八氢香豆素，为取代八氢香豆素领域增添了新的工业化选择。
三甲基八氢香豆素(VI)具有新鲜香豆香，椰子似香甜气，以及甜美的药草气味，别具一格的暖香和辛香，留香时间长。
附图说明
图1为本发明的13C NMR图。
图2为本发明的1H NMR图。
图3为本发明的红外光谱图。
具体实施方式
实施例1
3-(1-氧代-3,5,5-三甲基环己基)丙酸甲酯(IV)的合成
1000ml三口瓶，置于电磁搅拌的油浴中，安装温度计、油水分离器及回流冷凝管。加入150g二甲苯，73.8g(0.527mol)二氢异佛尔酮和68g吗啡啉(0.78mol)及0.9g对甲苯磺酸，加热回流至无水分出。反应液冷却到室温，加入0.5g 30％甲醇钠的甲醇溶液中和，换成蒸馏装置。先用水环真空泵减压蒸出二甲苯及少量未转化的二氢异佛尔酮。再换成油泵减压蒸馏，收集92～93℃/0.6kpa的馏分，得到二氢异佛尔酮吗啉烯胺(III)82.3g，收率74.8％。
500ml三口瓶，置于电磁搅拌的油浴中，安装温度计、恒压分液漏斗及球形冷凝管。加入66g二氢异佛尔酮吗啉烯胺(0.31mol)，105g无水甲醇；搅拌下加热到回流，滴加60g丙烯酸甲酯(0.69mol)的26g甲醇溶液，约1小时滴加完毕。继续回流反应8小时。反应液冷却到室温。水环真空泵减压蒸馏回收甲醇及剩余的丙烯酸甲酯。
水浴冷却下，于上述浓缩余液中加入200ml甲基叔丁基醚，搅拌下滴加6％稀盐酸200ml，加完继续搅拌4小时。物料转移至分液漏斗中，静置，分出上层油相，水相用2x 100ml甲基叔丁基醚萃取两次；合并后的油相用100ml饱和盐水洗涤至中性。放出水相，油相用无水硫酸钠干燥。过滤，常压回收甲基叔丁基醚，浓缩液减压蒸馏，收集114～124℃/0.8kpa馏分47.8g.收率68.2％.[MS:m/z,226(M+，13),179(100),139(71),125(35),83(75),69(31),55(48),41(46)].
实施例2
3-(6-羟基-2,4,4-三甲基环己基)丙酸(V)的合成
250ml三口瓶，置于电磁搅拌的水浴中，安装温度计、球形冷凝管。加入35％的氢氧化钠40g(0.35mol)和160g甲醇，搅拌下加入45.4g(0.2mol)酮酯(IV)，25-30℃搅拌反应3小时；在2小时内分批加入5.5g硼氢化钾，加完，继续搅拌2小时。气相色谱检测反应至反应物转化完全。用1N稀盐酸中和反应液至pH3,用3x 70ml甲基叔丁基醚萃取，合并油相，油相用3x 50ml饱和盐水洗涤；分出油相，常压蒸出溶剂，余液用水环真空泵减压蒸出低沸点组分。剩余液体为粉红色液体40.4g。
实施例3
八氢-5,7,7-三甲基-2H-苯并吡喃-2-酮的合成
500ml三口瓶，500ml三口瓶，置于电磁搅拌的油浴中，安装温度计、油水分离器及回流冷凝管。上述40.4g液体加入瓶中，加入150g甲苯，1.3g对甲苯磺酸。搅拌下将混合物加热，回流分水至油水分水器中不再有水分出为止。物料冷却至室温后，转移至分液漏斗中，加入50ml水，用5％碳酸氢钠水溶液中和，分出下层水相；油相用2x 50ml饱和食盐水洗涤至中性；油相经水环真空泵减压回收甲苯，剩余物料用油泵减压蒸馏，收集99～101℃/0.6kpa馏分，得到30.7g无色液体，室温放置，逐渐凝固得到白色固体。气相色谱检测，为多个异构体混合物，主要异构体含量分别为83.1％、12.8％、4.1％。固体用二氯甲烷重结晶两次，得到白色针状晶体。熔点：67.5～68℃；主要异构体含量97％；旋光度为零。说明目标物为消旋体。
目标物的质谱、红外光谱及核磁数据如下：
[MS:m/z,196(M+，5),153(100),109(74),95(51),67(34),55(80),41(75)]。
[IR(neat):1734.8(-O-C＝O)cm-1]。
[1HNMR(CDCl3:δ0.97(6H,S,2CH3)；δ1.02(3H,d,CH3)；δ4.51(1H,H-C-O),CH]；δ2.47(2H,m,O＝C-CH2)；δ1.98(1H,m，CH,C-10)；δ1.85(2H,m,CH2,C-4)；δ1.45-1.68(2H,m，CH2,C-6)；δ1.42(2H,d，CH2,C-8)；13C NMR(CDCl3)：δ172.54(C＝O)；δ79.39(H-C-O)；δ77.06(C-10)；δ48.03(C-8)；δ42.24(C-6)；δ39.21(C-7)；δ33.66(C-5)；δ30.13(C-3)；δ26.82(C-4)；δ22.29(CH3-7)；δ19.39(CH3-5)]。
目标物的分子结构式见式VI：
实施例4
三甲基八氢香豆素(VI)具有新鲜香豆香，椰子似香甜气，以及甜美的药草气味，别具一格的暖香和辛香，留香时间长。与香豆素比较，香气更细腻、饱满；在日化香精的调配中具有一定使用价值。该三甲基八氢香豆素(VI)可以用以制备香草香精。
表1为香草香精一个配比实施例的重量百分比；当然作为香草香精配方人员而言，也可以根据需要采用另外的配方。
表1
| 品名 | 重量百分比 |
| 香兰素 | 12 |
| 乙基香兰素 | 6 |
| 洋茉莉醛 | 2 |
| 三甲基八氢香豆素 | 2.5 |
| 丙位壬内酯 | 1.5 |
| 大茴香油 | 0.2 |
| 乙酸异戊酯 | 0.1 |
| 二丙二醇 | 74.7 |
| 丙位十一内酯 | 0.5 |
| 甜橙油 | 0.2 |
| 2，3-戊二酮 | 0.05 |
| 丁酰乳酸丁酯 | 0.25 |
| 100％ |
本发明的原理在于：以常见易得的基本有机化工原料异佛尔酮为原料，经催化氢化得到二氢异佛尔酮；二氢异佛尔酮的烯胺与丙烯酸酯的Michael加成产物再经还原及分子内酯化环合得到目标物5,7，7-三甲基八氢香豆素。
Claims (2)
1.一种取代八氢香豆素，其特征在于，所述取代八氢香豆素为八氢-5,7,7-三甲基-2H-1-苯并吡喃-2-酮，如式(VI)所示：
其中，所述的取代八氢香豆素为八氢-5,7,7-三甲基-2H-1-苯并吡喃-2-酮。
2.一种取代八氢香豆素的制备方法，其特征在于，包括如下步骤：
以异佛尔酮(isophorone)为起始原料，首先催化氢化得到二氢异佛尔酮(II)；
二氢异佛尔酮(II)经与吗啡啉作用生产烯胺中间体(III)；
生产烯胺中间体(III)与丙烯酸甲酯发生加成反应得到3-(1-氧代-3,5,5-三甲基环己基)丙酸甲酯(IV)；
再经碱性条件下水解，硼氢化钾还原羰基，最后经酸催化羟基酸(V)发生分子内酯化环合生成八氢-5,7,7-三甲基-2H-苯并吡喃-2-酮(5,7，7-三甲基八氢香豆素，VI)，制备总反应式如下：
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