CN114380693B - 一种甲基环戊烯醇酮香叶醇碳酸酯香料及其合成方法与应用 - Google Patents
一种甲基环戊烯醇酮香叶醇碳酸酯香料及其合成方法与应用 Download PDFInfo
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- -1 Methyl cyclopentenol ketogeraniol carbonate Chemical compound 0.000 title claims description 19
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000005792 Geraniol Substances 0.000 claims abstract description 31
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- 229940113087 geraniol Drugs 0.000 claims abstract description 31
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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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
- A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
-
- 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
- A24B15/42—Treatment of tobacco products or tobacco substitutes by chemical substances by organic and inorganic substances
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture Of Tobacco Products (AREA)
Abstract
本发明公开了一种甲基环戊烯醇酮香叶醇碳酸酯香料及其合成方法与应用,其化学结构式为:
Description
技术领域
本发明属于香精香料领域,具体涉及一种甲基环戊烯醇酮香叶醇碳酸酯香料,其化学结构稳定、香气保持较好,适用于烟用香精、洗涤用品、烘焙食品等产品中产生香气。
背景技术
随着精细化工和食品工业的迅速发展,不仅对传统香料的需求量逐年增长,对能提供新香气的新型香料需求也越来越旺盛。
碳酸酯类香料具有稳定性高、香气丰富的优点,可广泛应用于各种食品饮料类香精配方中。目前我国《食品添加剂使用标准》(GB 2760)批准使用的碳酸酯类香料只有三种:l-薄荷醇乙二醇碳酸酯(FEMA号为3805),无色液体,具有薄荷样的凉味;l-薄荷醇丙二醇碳酸酯(FEMA号为3806),无色液体,具有薄荷样的凉味;dl-薄荷脑(+/-)-1,2-丙二醇碳酸酯(FEMA号为3992),无色清凉液体,具有薄荷香气。
甲基环戊烯醇酮是白色结晶性粉末,具有焦甜香,稀释时有枫槭-甘草样香气,广泛应用于咖啡、巧克力、坚果等食用香精以及烟用香精的调配,起到增香增甜、改善口感的效果。但是,甲基环戊烯醇酮在加工或贮藏过程暴露在空气中容易氧化变质,使香气发生变化。
香叶醇具有玫瑰似的香气,主要用于调配桃、杏、苹果、草莓等型香精,但是由于沸点不高,易挥发,造成使用过程中香气逐渐变弱,破坏产品整体香韵。
因此制备基于甲基环戊烯醇酮的新型碳酸酯香料一方面可以增加香料稳定性,降低使用量,同时在加热时分解释放出甲基环戊烯醇酮和香叶醇,使之均匀稳定释放,保证香气一致性;另一方面可以赋予甲基环戊烯醇酮新的香味,满足人们对新香味日益增长的需求。
发明内容
本发明的目的在于提供一种化学结构稳定、香气保持较好且具有特殊香气的新型单体香料甲基环戊烯醇酮香叶醇碳酸酯香料,适用于烟用香精、洗涤用品、烘焙食品等产品中产生香气。
本发明为实现目的,采用如下技术方案:
本发明所提供的甲基环戊烯醇酮香叶醇碳酸酯香料,其化学结构式如式(1)所示:
本发明所述甲基环戊烯醇酮香叶醇碳酸酯香料的合成反应式如下:
合成方法包括如下步骤:
步骤1、向圆底烧瓶中加入固体三光气、碱和溶剂,搅拌过程中缓慢加入香叶醇,于室温下反应3-5h;用水洗涤反应液两次,合并水相并用二氯甲烷萃取,有机相经无水硫酸钠干燥,过滤后减压旋蒸,得到氯甲酸香叶酯粗产品(其结构参见反应式中的A1);
步骤2、向步骤1所得粗产品中直接加入甲基环戊烯醇酮、碱和二氯甲烷,20-50℃下搅拌3-6h;反应结束后水洗,静置分出水相和有机相,水相再用二氯甲烷萃取;合并有机相,无水硫酸钠干燥后过滤,硅胶柱色谱分离,即获得甲基环戊烯醇酮香叶醇碳酸酯香料。
进一步地,步骤1中,所述的溶剂为四氢呋喃、二氧六环、二氯甲烷、甲苯、乙酸乙酯、二甲亚砜和石油醚中的至少一种,更优选为甲苯。
进一步地,步骤1中,所述的碱优选为氢氧化钾、氢氧化钠、碳酸钾、DBU、吡啶和三乙胺中的至少一种,更优选为吡啶。
进一步地,步骤1中,所述的三光气、碱和香叶醇的摩尔比优选为1:2-3:1.5-2.5,更优选为1:2.4:2。
进一步地,步骤2中,所述的碱优选为氢氧化钾、氢氧化钠、碳酸钾、DBU、吡啶和三乙胺中的至少一种,更优选为碳酸钾。
进一步地,步骤2中,氯甲酸香叶酯粗产品与甲基环戊烯醇酮的摩尔比优选为1:0.7-1.1,更优选为1:0.83。
进一步地,步骤2中,氯甲酸香叶酯粗产品与碱的摩尔比为1:0.6-1,更优选为1:0.67。
进一步地,步骤2中,硅胶柱色谱分离所用洗脱剂由石油醚与乙酸乙酯按体积比1-10:1构成,优选为3:1。
本发明的新型单体香料甲基环戊烯醇酮香叶醇碳酸酯在使用时,可以溶解在醇或醇水混合溶剂中,然后添加到烟草中,所述单体香料的添加量为烟草重量的0.0001%-0.01%,更优选为0.0005%。所述烟草为烤烟型卷烟或者是新型烟草制品。
与现有技术相比,本发明的有益效果体现在:
1、本发明首次合成了新型香料甲基环戊烯醇酮香叶醇碳酸酯,其兼具焦甜香、花香、蜜甜香香韵,作为烟草增香剂添加至卷烟中可以提升卷烟香气的丰富性和稳定性,赋予卷烟焦甜香、花香、蜜甜香香韵,增加烟气浓度,使烟气细腻柔和。
2、本发明的反应步骤简单,易于操作,采用固体三光气代替剧毒的气体光气作为原料,大大提高了反应的安全性,便于工业化生产。
3、与甲基环戊烯醇酮相比,甲基环戊烯醇酮香叶醇碳酸酯热稳定性大大提高,热分解温度由原来的114℃提高到173℃,且最大热失重温度由151℃提升至293℃。由此可知,甲基环戊烯醇酮香叶醇碳酸酯结构更加稳定,不易氧化变质,在卷烟中可添加较少的量达到相同的感官效果。
附图说明
图1为甲基环戊烯醇酮香叶醇碳酸酯的1H NMR谱图。
图2为甲基环戊烯醇酮香叶醇碳酸酯的13C NMR谱图。
图3为甲基环戊烯醇酮、甲基环戊烯醇酮香叶醇碳酸酯的热重分析(TG-DTG)图。
具体实施方式
以下内容仅仅是对本发明的构思所做的举例和说明,所属本技术领域的技术人员对所描述的具体实施案例做各种各样的修改或补充或采用类似的方式代替,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
实施例1
本实施例按如下步骤合成甲基环戊烯醇酮香叶醇碳酸酯:
步骤1:向50mL圆底烧瓶中加入固体三光气(30mmol,8.9g)和60mL甲苯,在冰水浴中加入吡啶(72mmol,5.7g),然后缓慢加入香叶醇(60mmol,9.3g)。25℃下反应4h。用水洗涤反应液两次,合并水相并用二氯甲烷萃取,有机相经无水硫酸钠干燥,过滤后减压旋蒸,得到氯甲酸香叶酯粗产品。
步骤2:向第一步粗产品中直接加入甲基环戊烯醇酮(50mmol,5.6g)、碳酸钾(40mmol,5.5g)和二氯甲烷(60mL),25℃下搅拌6h。反应结束后,将反应液倒入装有40mL水的分液漏斗中,剧烈摇晃后静置分层,然后分出水相和有机相,水相再用20mL二氯甲烷萃取。合并有机相,适量无水硫酸钠干燥后过滤,硅胶柱色谱分离出甲基环戊烯酮香叶醇碳酸酯,无色油状物,总收率为78%。
产物经核磁谱图表征,数据如下:
1H NMR(500MHz,CDCl3)δ5.41(t,J=6.4Hz,1H),5.09(t,J=6.3Hz,1H),4.75(d,J=7.1Hz,2H),2.62-2.55(m,2H),2.51-2.45(m,2H),2.15-2.05(m,7H),1.74(s,3H),1.69(s,3H),1.61(s,3H);13C NMR(125MHz,CDCl3)δ199.6,160.3,151.9,146.2,144.0,131.9,123.6,117.0,66.0,39.5,32.4,27.7,26.2,25.7,17.7,16.6,15.1.
实施例2热稳定性比较
由图3可知,甲基环戊烯醇酮在114℃时开始分解,在114-180℃温度区间出现明显的失重现象,且在151℃时失重速率最大,总失重率达97.8%。甲基环戊烯醇酮香叶醇碳酸酯在173℃时开始分解,在173-306℃温度区间出现明显的失重现象,且在293℃时失重速率最大,总失重率达97.9%。从数据上可知,与甲基环戊烯醇酮相比,甲基环戊烯醇酮香叶醇碳酸酯热分解温度由114℃提高至173℃,热稳定性大大提高,且最大热失重温度由151℃提升至293℃,与加热非燃烧卷烟的作用温度较接近,说明其在此类烟草制品配方设计中具有潜在应用价值。
实施例3香气评价
取0.01g单体香料甲基环戊烯醇酮香叶醇碳酸酯溶于丙二醇中,配制成质量浓度为10%的溶液。用闻香纸蘸取少量溶液,在无外界气味干扰下进行香气评价。
经专业调香人员评价甲基环戊烯醇酮香叶醇碳酸酯样品具有焦甜香、花香、蜜甜香。
实施例4感官评价
将甲基环戊烯醇酮、香叶醇、甲基环戊烯醇酮香叶醇碳酸酯溶于95%乙醇中,分别配置成质量浓度为0.1%的溶液。取1.0g 0.1%甲基环戊烯醇酮、香叶醇溶液混合后均匀喷洒至100g空白烟丝中,制备样品1;取0.1g、0.5g、1.0g 0.1%甲基环戊烯醇酮香叶醇碳酸酯溶液均匀喷洒至100g空白烟丝中,分别编号样品2、3、4。将上述样品放置2小时后卷制成样品卷烟。将样品卷烟放置在温度22℃±1℃,60%±2%的恒温恒湿箱中平衡48小时后,与在相同条件下放置的未加香样品对照评吸。感官评价结果如下表:
由上表可知,与混合添加甲基环戊烯醇酮和香叶醇相比,甲基环戊烯醇酮香叶醇碳酸酯香气更加丰富协调,余味更舒适,且添加量所需添加量更低,为5ppm。
以上仅为本发明的示例性实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所做的任何修改,等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种甲基环戊烯醇酮香叶醇碳酸酯香料,其特征在于,化学结构式如式(1)所示:
2.一种权利要求1所述甲基环戊烯醇酮香叶醇碳酸酯香料的合成方法,其特征在于,包括如下步骤:
步骤1、向圆底烧瓶中加入固体三光气、碱和溶剂,搅拌过程中缓慢加入香叶醇,于室温下反应3-5h;用水洗涤反应液两次,合并水相并用二氯甲烷萃取,有机相经无水硫酸钠干燥,过滤后减压旋蒸,得到氯甲酸香叶酯粗产品;
步骤2、向步骤1所得粗产品中直接加入甲基环戊烯醇酮、碱和二氯甲烷,20-50℃下搅拌3-6h;反应结束后水洗,静置分出水相和有机相,水相再用二氯甲烷萃取;合并有机相,无水硫酸钠干燥后过滤,硅胶柱色谱分离,即获得甲基环戊烯醇酮香叶醇碳酸酯香料。
3.根据权利要求2所述的合成方法,其特征在于:步骤1中,所述的溶剂为四氢呋喃、二氧六环、二氯甲烷、甲苯、乙酸乙酯、二甲亚砜和石油醚中的至少一种,所述的碱为氢氧化钾、氢氧化钠、碳酸钾、DBU、吡啶和三乙胺中的至少一种。
4.根据权利要求2所述的合成方法,其特征在于:步骤1中,三光气、碱和香叶醇的摩尔比为1:2-3:1.5-2.5。
5.根据权利要求2所述的合成方法,其特征在于:步骤2中,所述的碱为氢氧化钾、氢氧化钠、碳酸钾、DBU、吡啶和三乙胺中的至少一种。
6.根据权利要求2所述的合成方法,其特征在于:步骤2中,氯甲酸香叶酯粗产品与甲基环戊烯醇酮的摩尔比为1:0.7-1.1,氯甲酸香叶酯粗产品与碱的摩尔比为1:0.6-1。
7.根据权利要求2所述的合成方法,其特征在于:步骤2中,硅胶柱色谱分离所用洗脱剂由石油醚与乙酸乙酯按体积比1-10:1构成。
8.一种权利要求1所述甲基环戊烯醇酮香叶醇碳酸酯香料在烟草中的应用。
9.根据权利要求8所述的应用,其特征在于:将所述甲基环戊烯醇酮香叶醇碳酸酯香料溶解在醇或醇水混合溶剂中,然后添加到烟草中,所述香料的添加量为烟草重量的0.0001%-0.01%。
10.根据权利要求9所述的应用,其特征在于:所述烟草为烤烟型卷烟或者新型烟草制品。
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