CN106496030A - 烟用潜香单体对甲氧基苯甲酸酯类的制备方法及其应用 - Google Patents
烟用潜香单体对甲氧基苯甲酸酯类的制备方法及其应用 Download PDFInfo
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims abstract description 7
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/301—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by aromatic compounds
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
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Abstract
一种烟用潜香单体对甲氧基苯甲酸酯类的制备方法,包括如下步骤:取对甲氧基苯甲酸和单羟基醇溶于干燥的二氯甲烷中,搅拌10min‑30min,加入4‑二甲氨基吡啶(DMAP)和1‑乙基‑(3‑二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCHCl),室温搅拌4‑12h,TLC监测反应,跟踪反应终点,向有机相中加水洗涤,分液,再用饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩得粗产物,然后进行柱层析分离即得所述烟用单体香料对甲氧基苯甲酸酯。本发明制备的产物可以显著的提高在卷烟中的添加量,而不影响卷烟的外香品种,将其作为烟草增香剂应用于卷烟中,可降低卷烟的刺激性和杂气,提高卷烟烟气圆润感和舒适性。
Description
技术领域
本发明涉及香精香料和烟草加工领域,具体是一种烟用潜香单体对甲氧基苯甲酸酯类的制备方法及其应用。
背景技术
许多优异的香料由于其高温热稳定性差、挥发性较强、留香时间短等问题限制了其广泛的应用。潜香物质是一类相对分子质量大、沸点较高的物质,香气较少或本身没有香气,但经过化学水解、酶解或微生物作用、热解、光裂解等途径可以释放出具有香气香味的化合物。因其安全性较好,国际上将其列入天然香料范畴,用其调配某些风味食用香精效果很好。与挥发性和半挥发性香味物质不同,潜香类化合物在减少人为的香吃味补偿痕迹的同时不会导致卷烟主流烟气中烟碱、焦油等物质递送量的显著变化,能更持久稳定提供烟气特征香味。在现有技术上,潜香物质广泛的应用在卷烟烟丝的添加工艺中,本发明提供一种烟用潜香单体对甲氧基苯甲酸酯类的制备方法,并探讨其在卷烟加香中的应用。
发明内容
本发明为了开发新型的烟用潜香物质,提供一种新的烟用潜香单体对甲氧基苯甲酸酯类的制备方法及其在卷烟中的应用。
为实现上述目的,本发明采用如下技术方案:
一种烟用单体香料对甲氧基苯甲酸酯的制备方法,其包括如下步骤:
取对甲氧基苯甲酸和单羟基醇溶于干燥的二氯甲烷中,搅拌10min-30min,加入4-二甲氨基吡啶(DMAP)和1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCHCl),室温搅拌4-12h,TLC监测反应(石油醚:乙酸乙酯=10:1,Rf=0.5,紫外254nm显色),跟踪反应终点,向有机相中加水洗涤,分液,再用饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩得粗产物,然后进行柱层析分离即得所述烟用单体香料对甲氧基苯甲酸酯。
进一步的,所述的柱层析分离洗脱液为乙酸乙酯和石油醚,两者的体积比100:1-20:1。
进一步的,所述的对甲氧基苯甲酸与单羟基醇的摩尔比例在0.9:1-1:0.9之间。
进一步的,所述的单羟基醇为香叶醇或紫罗兰醇,当单羟基醇为香叶醇时,得到的产物为甲氧基苯甲酸香叶醇酯,当单羟基醇为紫罗兰醇时,得到的产物为甲氧基苯甲酸-β-紫罗兰醇酯,两者结构式如下:
进一步的,如上所述方法制备的烟用单体香料对甲氧基苯甲酸酯作为烟草增香剂在卷烟中的应用,将其作为烟草增香剂应用于卷烟中,添加量为烟丝重量的0.01-0.05%。
本发明化合物对甲氧基苯甲酸香叶醇酯和对甲氧基苯甲酸-β-紫罗兰醇酯为一种潜香化合物,常温下其性质稳定,为无色液体,但其通过加热可裂解产生具有明显增加烟草香气物质。如3-氧代-β-紫罗兰酮、香叶醇、单萜烯类化合物。
和现有技术相比,本发明的有益效果:
1.本发明制备对甲氧基苯甲酸香叶醇酯和对甲氧基苯甲酸-β-紫罗兰醇酯较香叶醇和β-紫罗兰醇母体物,可以显著的提高在卷烟中的添加量,而不影响卷烟的外香品种。
2.本发明以4-二甲氨基吡啶/1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐为对甲氧基苯甲酸和香叶醇、β-紫罗兰醇酯化反应缩合试剂,可以显著提高反应产率,简化后处理工艺。
3.本发明开发出的两种烟用单体香料,首次将其作为烟草增香剂应用于卷烟中,可降低卷烟的刺激性和杂气,提高卷烟烟气圆润感和舒适性。
附图说明
图1对甲氧基苯甲酸香叶醇酯1H NMR核磁谱图;
图2是对甲氧基苯甲酸香叶醇酯13C NMR核磁谱图;
图3是对甲氧基苯甲酸香叶醇酯HRMS高分辨谱图;
图4是对甲氧基苯甲酸-β-紫罗兰醇酯1H NMR核磁谱图;
图5是对甲氧基苯甲酸-β-紫罗兰醇酯13C NMR核磁谱图;
图6是对甲氧基苯甲酸-β-紫罗兰醇酯HRMS高分辨谱图。
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明,便于清楚地了解本发明的内容,但它们不对本发明构成限定。
实施例一
烟用香料单体对甲氧基苯甲酸香叶醇酯的制备方法:
取10mmol香叶醇和10mmol对甲氧基苯甲酸溶于100ml干燥的二氯甲烷中,搅拌10min后,加入4-二甲氨基吡啶(DMAP)(5mmol)和1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCHCl)(11mmol),室温搅拌,TLC监测反应,跟踪反应终点。向有机相中加水50mL洗涤,分液,再用50mL饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩得粗产物。粗产物用50mL二氯甲烷溶解,加入100-200目的硅胶4g,减压旋干拌样,用80g 100-200目的硅胶层析株中用石油醚:乙酸乙酯=60:1慢慢洗脱,浓缩、干燥后得到目标产物。
实施例二
烟用对甲氧基苯甲酸香叶醇酯的制备方法:
取10mmol香叶醇和1.05mmol对甲氧基苯甲酸溶于100ml干燥的二氯甲烷中,搅拌10min后,加入4-二甲氨基吡啶(DMAP)(4mmol)和1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCHCl)(11mmol),室温搅拌,TLC监测反应,跟踪反应终点。向有机相中加水50mL洗涤,分液,再用50mL饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩得粗产物。粗产物用50mL二氯甲烷溶解,加入100-200目的硅胶4g,减压旋干拌样,用80g 100-200目的硅胶层析株中用石油醚:乙酸乙酯=60:1慢慢洗脱,浓缩、干燥后得到目标产物。
实施例三
烟用香料单体对甲氧基苯甲酸-β-紫罗兰醇酯的制备方法:
在三口烧瓶中,加入称取的20mmolβ-紫罗兰醇和20mmol对甲氧基苯甲酸溶于200ml干燥的二氯甲烷中,搅拌10min后,加入4-二甲氨基吡啶(DMAP)(9mmol)和1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDC·HCl)(22mmol),室温下搅拌,TLC监测反应,跟踪反应至终点。向有机相中加纯净水100mL洗涤,分液,再用100mL饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩的粗产物。粗产物用10mL二氯甲烷溶解,加入100-200目的硅胶7g,减压旋干拌样,用100g 100-200目的硅胶层析柱分离,洗脱剂用石油醚:乙酸乙酯=80:1慢慢洗脱,浓缩、干燥后得到目标产物
实施例四
烟用香料单体对甲氧基苯甲酸-β-紫罗兰醇酯的制备方法:
在三口烧瓶中,加入称取的20mmolβ-紫罗兰醇和21mmol对甲氧基苯甲酸溶于200ml干燥的二氯甲烷中,搅拌10min后,加入4-二甲氨基吡啶(DMAP)(8mmol)和1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDC·HCl)(22mmol),室温下搅拌,TLC监测反应,跟踪反应至终点。向有机相中加纯净水100mL洗涤,分液,再用100mL饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩的粗产物。粗产物用10mL二氯甲烷溶解,加入100-200目的硅胶7g,减压旋干拌样,用100g 100-200目的硅胶层析柱分离,洗脱剂用石油醚:乙酸乙酯=80:1慢慢洗脱,浓缩、干燥后得到目标产物
(一)目标产物的结构表征
通过红高分辨质谱(HR-MS)、核磁共振碳谱(1H-NMR 13C-NMR)分别对实施例所得目标产物对甲氧基苯甲酸香叶醇酯和对甲氧基苯甲酸-β-紫罗兰醇酯进行结构表征,具体数据如下:
如图1-3所示,对甲氧基苯甲酸香叶酯:无色油状液体。1H NMR(400MHz,CDCl3)δppm8.00(d,J=8.46Hz,2H),6.91(d,J=8.76Hz,2H),5.55-5.40(m,1H),5.12(dd,J=11.16,3.77Hz,1H),4.80(dd,J=12.46,7.20Hz,2H),3.85(s,3H),2.13(ddd,J=18.10,13.31,6.88Hz,4H),1.77(d,J=12.47Hz,3H),1.67(s,3H),1.62(d,J=11.73Hz,3H);13C NMR(400MHz,CDCl3)δppm 166.43,163.24,142.46,131.61,123.80,122.95,119.50,118.63,113.53,61.63,55.41,39.58,26.33,25.72,17.73,16.58;HRMS:m/z(ESI)[M+Na]+理论值311.1623,实测值311.1621。
如图4-6所示,对甲氧基苯甲酸-β-紫罗兰醇酯:。1H NMR(400MHz,CDCl3)δppm8.03-8.01(m,1H),8.01-7.99(m,1H),6.93-6.92(m,1H),6.90(d,J=2.00Hz,1H),6.19(d,J=15.83Hz,1H),5.62(p,J=6.40,6.40,6.33,6.33Hz,1H),5.53(dd,J=15.83,6.82Hz,1H),3.85(s,3H),1.96(t,J=6.12,6.12Hz,2H),1.66(s,3H),1.63-1.55(m,2H),,1.47(d,J=6.39Hz,3H),1.45-1.41(m,2H),0.99(t,J=5.85,5.85Hz,6H);13C NMR(400MHz,CDCl3)δppm 165.65,163.19,136.62,133.07,131.53,129.87,129.04,123.38,113.52,71.83,55.41,39.36,33.90,32.66,28.66,21.32,20.76,19.24.[M+Na]+found351.1935(calcd.351.1936).
从谱图解析分析,结合红外光谱(IR)、高分辨率质谱(1HR-MS)和核磁共振碳谱(13C-NMR)可确定所得化合物即为对甲氧基苯甲酸香叶醇酯和对甲氧基苯甲酸-β-紫罗兰醇酯。
(二)目标产物在烟草中的加香研究
以95%乙醇作溶剂,将目标产物对甲氧基苯甲酸香叶醇酯和对甲氧基苯甲酸-β-紫罗兰醇酯分别配成质量分数1%的溶液。分别取0.5g、1.0g、5.0g、10.0g和15.0g上述含目标产物的溶液,然后均匀喷加到七份未加香加料的100g空白卷烟烟丝中,卷制,各挑选出100支同一重量卷烟,置于温度22℃±1℃,湿度60%±2%的恒温恒湿箱中平衡48h,评吸。对照样为空白卷烟,对照样同样在相同温、湿度条件下平衡48h。
表1对甲氧基苯甲酸香叶醇酯的加香评吸结果
表2对甲氧基苯甲酸-β-紫罗兰醇酯的加香评吸结果
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求的保护范围为准。
Claims (5)
1.一种烟用潜香单体对甲氧基苯甲酸酯类的制备方法,其特征在于包括如下步骤:
取对甲氧基苯甲酸和单羟基醇溶于干燥的二氯甲烷中,搅拌10min-30min,加入4-二甲氨基吡啶(DMAP)和1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCHCl),室温搅拌4-12h,TLC监测反应,跟踪反应终点,向有机相中加水洗涤,分液,再用饱和氯化钠溶液洗涤,分液,有机相用无水Na2SO4干燥,浓缩得粗产物,然后进行柱层析分离即得所述烟用单体香料对甲氧基苯甲酸酯。
2.如权利要求1所述的烟用潜香单体对甲氧基苯甲酸酯类的制备方法,其特征在于:所述的柱层析分离洗脱液为乙酸乙酯和石油醚,两者的体积比100:1-20:1。
3.如权利要求1所述的烟用潜香单体对甲氧基苯甲酸酯类的制备方法,其特征在于:所述的对甲氧基苯甲酸与单羟基醇的摩尔比例在0.9:1-1:0.9之间。
4.如权利要求1所述的烟用潜香单体对甲氧基苯甲酸酯类的制备方法,其特征在于:所述的单羟基醇为香叶醇或紫罗兰醇,当单羟基醇为香叶醇时,得到的产物为甲氧基苯甲酸香叶醇酯,当单羟基醇为紫罗兰醇时,得到的产物为甲氧基苯甲酸-β-紫罗兰醇酯,两者结构式如下:
5.如权利要求1-4中任一项所述方法制备的烟用潜香单体对甲氧基苯甲酸酯类作为烟草增香剂在卷烟中的应用,将其作为烟草增香剂应用于卷烟中,添加量为烟丝重量的0.01-0.05%。
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