CN116354847A - Cucumber aroma compound, preparation method thereof and cucumber aroma base - Google Patents
Cucumber aroma compound, preparation method thereof and cucumber aroma base Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及香料技术领域,具体涉及一种黄瓜香气化合物及其制备方法和黄瓜香型香基。The invention relates to the technical field of spices, in particular to a cucumber aroma compound, a preparation method thereof and a cucumber aroma base.
背景技术Background technique
黄瓜是人们日常食用的瓜果蔬菜之一,黄瓜特有的清香味香气赢得人们的青睐,2011年以来黄瓜风味逐渐在市场流行,五年间的市场增速就超过4倍。天然的黄瓜中,具有香气的化合物有70余种,其中特征香气主要来自于反,顺-2,6-壬二烯醛、反-4-壬烯醛、壬醛、反式石竹烯等少数化合物。所以,调香师在调配黄瓜香型香基时,用于体现其特征香气的香原料较为有限,因此开发具有黄瓜特征香气的化合物,有利于丰富香原料的使用范围。Cucumber is one of the fruits and vegetables that people eat daily. The unique fragrance of cucumber has won people's favor. Since 2011, the flavor of cucumber has gradually become popular in the market, and the market growth rate has exceeded 4 times in five years. In natural cucumber, there are more than 70 kinds of aroma compounds, among which the characteristic aroma mainly comes from a few such as trans,cis-2,6-nonadienal, trans-4-nonenal, nonanal, trans-caryophyllene, etc. compound. Therefore, when a perfumer blends a cucumber-flavored fragrance base, the aroma raw materials used to reflect its characteristic aroma are relatively limited. Therefore, the development of compounds with the characteristic aroma of cucumber is conducive to enriching the use range of aroma raw materials.
发明内容Contents of the invention
为了克服现有技术中存在的缺点和不足,本发明的目的在于提供一种黄瓜香气化合物,该化合物具有显著的黄瓜样香气和一定的果甜香气,其香气明显,留香时间长,在调香领域有重要的有利用途。In order to overcome the shortcomings and deficiencies in the prior art, the object of the present invention is to provide a cucumber aroma compound, which has a significant cucumber-like aroma and a certain fruity sweet aroma, and its aroma is obvious, and the fragrance lasts for a long time. The field of incense has important beneficial uses.
本发明的另一目的在于提供一种黄瓜香气化合物的制备方法,该制备方法简单高效,操作控制方便,生产的产品质量高,成本低,利于工业化生产,同时制得的黄瓜香气化合物具有类似于黄瓜样香气,可有效克服以往常规蔬菜香精作为香精添加剂存在的弊端。Another object of the present invention is to provide a preparation method of cucumber aroma compounds, the preparation method is simple and efficient, easy to operate and control, the product quality is high, the cost is low, and it is beneficial to industrial production. The cucumber-like aroma can effectively overcome the disadvantages of conventional vegetable flavors used as flavor additives in the past.
本发明的再一目的在于提供一种黄瓜香型香基,该香基通过添加黄瓜香气化合物使得最终制得的香基具有类似于黄瓜样香气和一定的果甜香气,有很好的的实用性。Another object of the present invention is to provide a cucumber-flavored fragrance base, which can make the finally prepared fragrance base have a cucumber-like aroma and a certain fruity-sweet aroma by adding cucumber aroma compounds, and has good practicality. sex.
本发明的目的通过下述技术方案实现:一种黄瓜香气化合物,具有如下结构式:The object of the present invention is achieved through the following technical solutions: a cucumber aroma compound has the following structural formula:
所述黄瓜香气化合物的名称为4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯。The name of the cucumber aroma compound is 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate.
本发明中的黄瓜香气化合物具有显著的黄瓜样香气和一定的果甜香气,其香气明显,留香时间长,在调香领域有重要的有利用途。The cucumber aroma compound in the present invention has significant cucumber-like aroma and certain fruity sweet aroma, has obvious aroma and long lasting aroma, and has important beneficial uses in the field of flavoring.
优选的,所述黄瓜香气化合物通过如下步骤:Preferably, the cucumber aroma compound is carried out through the following steps:
S1、取邻氨基苯甲酸、甲苯和二氯亚砜,将邻氨基苯甲酸和甲苯加入反应装置中搅拌均匀,并冷却至-(0-2)℃,向反应装置加入二氯亚砜,之后将反应装置的温度恢复至室温,持续搅拌1-3h,得到邻氨基苯甲酰氯的甲苯溶液,备用;S1. Take anthranilic acid, toluene and thionyl chloride, add anthranilic acid and toluene into the reaction device and stir evenly, and cool to -(0-2)°C, add thionyl chloride to the reaction device, and then Return the temperature of the reaction device to room temperature, and continue to stir for 1-3h to obtain a toluene solution of anthranilic acid chloride, which is set aside;
S2、取大茴香醇和无水硫酸镁,将大茴香醇加入步骤S1中得到的邻氨基苯甲酰氯的甲苯溶液中,持续搅拌3-6h,随后取一定量质量浓度为8-12%的碳酸钠溶液,继续搅拌0.8-1.2h,静置分层,收集上层有机相,并将无水硫酸镁加入有机相,搅拌10-14h,过滤除去固体,回收滤液,得到4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液,备用;S2. Take anisyl alcohol and anhydrous magnesium sulfate, add anisyl alcohol to the toluene solution of anthranilic acid chloride obtained in step S1, keep stirring for 3-6 hours, and then take a certain amount of carbonic acid with a mass concentration of 8-12%. Sodium solution, continue to stir for 0.8-1.2h, let stand to separate layers, collect the upper organic phase, and add anhydrous magnesium sulfate to the organic phase, stir for 10-14h, filter to remove the solid, recover the filtrate to obtain 4-methoxybenzyl -Toluene solution of 2-aminobenzoate, for subsequent use;
S3、取顺-6-壬烯醛,将顺-6-壬烯醛加入步骤S2中得到的4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液中,再点加入一定量浓硫酸,搅拌混合均匀后,减压至450-550Pa,升温至76-80℃,继续反应2-5h,反应过程中使用分水器同步分离反应过程中产生的水分,接着继续升温至110-120℃,蒸馏除去溶剂,冷却至室温,得到4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯。S3, take cis-6-nonenal, add cis-6-nonenal to the toluene solution of 4-methoxybenzyl-2-aminobenzoate obtained in step S2, and then add a certain amount Concentrated sulfuric acid, stir and mix evenly, depressurize to 450-550Pa, heat up to 76-80°C, continue to react for 2-5h, use a water separator to separate the moisture generated during the reaction, and then continue to heat up to 110- The solvent was distilled off at 120°C, and cooled to room temperature to obtain 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate.
本发明中的黄瓜香气化合物通过采用上述方法制得,而利用上述方法制得的黄瓜香气化合物具有显著的黄瓜样香气和一定的果甜香气;而该制备方法简单高效,操作控制方便,生产的产品质量高,成本低,利于工业化生产,同时制得的黄瓜香气化合物具有类似于黄瓜样香气,可有效克服以往常规蔬菜香精作为香精添加剂存在的弊端。The cucumber aroma compound in the present invention is obtained by adopting the above-mentioned method, and the cucumber aroma compound prepared by the above-mentioned method has a remarkable cucumber-like aroma and a certain fruity sweet aroma; and the preparation method is simple and efficient, and the operation and control are convenient. The product has high quality and low cost, and is beneficial to industrialized production. At the same time, the prepared cucumber aroma compound has a cucumber-like aroma, which can effectively overcome the disadvantages of conventional vegetable essences used as flavor additives in the past.
优选的,步骤S1中,所述邻氨基苯甲酸、甲苯和二氯亚砜用量的重量比为0.6-0.7:0.7-0.8:0.5-0.6。Preferably, in step S1, the weight ratio of the anthranilic acid, toluene and thionyl chloride is 0.6-0.7:0.7-0.8:0.5-0.6.
优选的,步骤S2中所述大茴香醇、无水硫酸镁的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.4-0.7:0.2-0.5:0.6-0.8。Preferably, the weight ratio of the amount of anisyl alcohol and anhydrous magnesium sulfate in step S2 to the amount of anthranilic acid in step S1 is 0.4-0.7:0.2-0.5:0.6-0.8.
优选的,步骤S2中,加入碳酸钠溶液的体积与大茴香醇的体积比为0.9-1.2:0.4-0.6。Preferably, in step S2, the volume ratio of the added sodium carbonate solution to the anisyl alcohol is 0.9-1.2:0.4-0.6.
优选的,步骤S3中,所述顺-6-壬烯醛的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.3-0.5:0.5-0.6。Preferably, in step S3, the weight ratio of the amount of cis-6-nonenal to the amount of anthranilic acid in step S1 is 0.3-0.5:0.5-0.6.
优选的,步骤S3中,所述顺-6-壬烯醛与浓硫酸用量的重量比为0.3-0.5:0.001-0.004。Preferably, in step S3, the weight ratio of the amount of cis-6-nonenal to concentrated sulfuric acid is 0.3-0.5:0.001-0.004.
本发明还提供一种黄瓜香型香基,包括如下重量份的原料:甜瓜醛7.6-8.0份、壬醛3.0-3.5份、顺-6-壬烯醛5.3-5.7份、顺-2,6-壬二烯醛4.4-4.8份、反-4-壬烯醛3.4-3.8份、反式石竹烯1.6-2.0份、榄青酮1.1-1.5份、叶醇7.0-7.3份、乙酸香芹酯11-12份、乙酸叶醇酯5.0-5.4份、己酸叶醇酯2.0-2.5份、4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯8.0-9.0份、1,2-丙二醇15-16份和乙醇20-24份。The present invention also provides a cucumber-flavored fragrance base, comprising the following raw materials in parts by weight: 7.6-8.0 parts of melon aldehyde, 3.0-3.5 parts of nonanal, 5.3-5.7 parts of cis-6-nonenal, 5.3-5.7 parts of cis-6-nonenal, cis-2,6 4.4-4.8 parts of -nonadienal, 3.4-3.8 parts of trans-4-nonenal, 1.6-2.0 parts of trans-caryophyllene, 1.1-1.5 parts of elemene, 7.0-7.3 parts of leaf alcohol, carvyl acetate 11-12 parts, 5.0-5.4 parts of phyllyl acetate, 2.0-2.5 parts of phyllyl hexanoate, 4-methoxybenzyl 2-((E)-((Z)-6-nonene-1- subunit) amino) benzoate 8.0-9.0 parts, 1,2-propanediol 15-16 parts and ethanol 20-24 parts.
优选的,所述黄瓜香型香基通过如下步骤制得:Preferably, the cucumber-flavored fragrance base is prepared through the following steps:
1)按照重量份称取原料,备用;1) take the raw material according to the weight part, and set aside;
2)将上述原料加入反应装置中混合,反复震荡摇匀,得到黄瓜香型香基。2) Add the above-mentioned raw materials into the reaction device and mix them, shake them repeatedly to obtain a cucumber-flavored fragrance base.
本发明中的香基通过添加黄瓜香气化合物使得最终制得的香基具有类似于黄瓜样香气和一定的果甜香气,有很好的的实用性。The fragrance base in the present invention is added with cucumber aroma compounds so that the finally prepared fragrance base has a cucumber-like aroma and a certain fruity sweet aroma, and has good practicability.
本发明的有益效果在于:本发明的化合物具有显著的黄瓜样香气和一定的果甜香气,其香气明显,留香时间长,在调香领域有重要的有利用途。The beneficial effect of the present invention is that: the compound of the present invention has remarkable cucumber-like aroma and certain fruity sweet aroma, and has obvious aroma and long fragrance retention time, and has an important beneficial application in the field of perfumery.
本发明一种黄瓜香气化合物的制备方法简单高效,操作控制方便,生产的产品质量高,成本低,利于工业化生产,同时制得的黄瓜香气化合物具有类似于黄瓜样香气,可有效克服以往常规蔬菜香精作为香精添加剂存在的弊端。The preparation method of a cucumber aroma compound of the present invention is simple and efficient, and the operation and control are convenient. The produced product has high quality and low cost, which is beneficial to industrialized production. The disadvantages of flavor as a flavor additive.
附图说明Description of drawings
图1是本发明的实施例4中制得4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯的气相色谱图。Fig. 1 is the gas chromatogram of 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene) amino) benzoate obtained in Example 4 of the present invention picture.
具体实施方式Detailed ways
为了便于本领域技术人员的理解,下面结合实施例及附图1对本发明作进一步的说明,实施方式提及的内容并非对本发明的限定。In order to facilitate the understanding of those skilled in the art, the present invention will be further described below in conjunction with the embodiments and the accompanying drawing 1, and the contents mentioned in the embodiments are not intended to limit the present invention.
实施例1Example 1
一种黄瓜香气化合物,名称为4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯,具有如下结构式:A cucumber aroma compound, named 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene) amino) benzoate, has the following structural formula:
所述黄瓜香气化合物通过如下步骤:Described cucumber aroma compound passes through the following steps:
S1、取邻氨基苯甲酸、甲苯和二氯亚砜,将邻氨基苯甲酸和甲苯加入反应装置中搅拌均匀,并冷却至0℃,向反应装置加入二氯亚砜,之后将反应装置的温度恢复至室温,持续搅拌3h,得到邻氨基苯甲酰氯的甲苯溶液,备用;S1. Take anthranilic acid, toluene and thionyl chloride, add anthranilic acid and toluene into the reaction device and stir evenly, and cool to 0°C, add thionyl chloride to the reaction device, and then reduce the temperature of the reaction device Return to room temperature and continue stirring for 3h to obtain a toluene solution of anthraniloyl chloride for subsequent use;
S2、取大茴香醇和无水硫酸镁,将大茴香醇加入步骤S1中得到的邻氨基苯甲酰氯的甲苯溶液中,持续搅拌6h,随后取一定量质量浓度为12%的碳酸钠溶液,继续搅拌1.2h,静置分层,收集上层有机相,并将无水硫酸镁加入有机相,搅拌14h,过滤除去固体,回收滤液,得到4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液,备用;S2, take anisyl alcohol and anhydrous magnesium sulfate, add anisyl alcohol to the toluene solution of anthraniloyl chloride obtained in step S1, continue stirring for 6 hours, then take a certain amount of sodium carbonate solution with a mass concentration of 12%, and continue Stir for 1.2h, let stand to separate layers, collect the upper organic phase, and add anhydrous magnesium sulfate to the organic phase, stir for 14h, filter to remove the solid, reclaim the filtrate to obtain 4-methoxybenzyl-2-aminobenzoate Toluene solution, spare;
S3、取顺-6-壬烯醛,将顺-6-壬烯醛加入步骤S2中得到的4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液中,再点加入一定量浓硫酸,搅拌混合均匀后,减压至550Pa,升温至80℃,继续反应5h,反应过程中使用分水器同步分离反应过程中产生的水分,接着继续升温至120℃,蒸馏除去溶剂,冷却至室温,得到4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯。S3, take cis-6-nonenal, add cis-6-nonenal to the toluene solution of 4-methoxybenzyl-2-aminobenzoate obtained in step S2, and then add a certain amount Concentrated sulfuric acid, stir and mix evenly, decompress to 550Pa, heat up to 80°C, continue to react for 5h, use a water separator to separate the water generated during the reaction, then continue to heat up to 120°C, distill off the solvent, cool At room temperature, 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate was obtained.
步骤S1中,所述邻氨基苯甲酸、甲苯和二氯亚砜用量的重量比为0.7:0.8:0.6。In step S1, the weight ratio of the anthranilic acid, toluene and thionyl chloride is 0.7:0.8:0.6.
步骤S2中所述大茴香醇、无水硫酸镁的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.7:0.5:0.8。The weight ratio of the amount of anisyl alcohol and anhydrous magnesium sulfate described in step S2 to the amount of anthranilic acid in step S1 is 0.7:0.5:0.8.
步骤S2中,加入碳酸钠溶液的体积与大茴香醇的体积比为1.2:0.6。In step S2, the volume ratio of the added sodium carbonate solution to the volume of anisyl alcohol is 1.2:0.6.
步骤S3中,所述顺-6-壬烯醛的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.5:0.6。In step S3, the weight ratio of the amount of cis-6-nonenal to the amount of anthranilic acid in step S1 is 0.5:0.6.
步骤S3中,所述顺-6-壬烯醛与浓硫酸用量的重量比为0.5:0.004。In step S3, the weight ratio of the amount of cis-6-nonenal to concentrated sulfuric acid is 0.5:0.004.
一种黄瓜香型香基包括如下重量份的原料:甜瓜醛8.0份、壬醛3.5份、顺-6-壬烯醛5.7份、顺-2,6-壬二烯醛4.8份、反-4-壬烯醛3.8份、反式石竹烯2.0份、榄青酮1.5份、叶醇7.3份、乙酸香芹酯12份、乙酸叶醇酯5.4份、己酸叶醇酯2.5份、4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯9.0份、1,2-丙二醇16份和乙醇24份。A cucumber-flavored fragrance base includes the following raw materials in parts by weight: 8.0 parts of melon aldehyde, 3.5 parts of nonanal, 5.7 parts of cis-6-nonenal, 4.8 parts of cis-2,6-nonadienal, trans-4 - 3.8 parts of nonenal, 2.0 parts of trans-caryophyllene, 1.5 parts of elemene, 7.3 parts of leaf alcohol, 12 parts of carvyl acetate, 5.4 parts of phyllyl acetate, 2.5 parts of phylloyl hexanoate, 4-methyl 9.0 parts of oxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate, 16 parts of 1,2-propanediol and 24 parts of ethanol.
所述黄瓜香型香基通过如下步骤制得:The cucumber-flavored fragrance base is prepared through the following steps:
1)按照重量份称取原料,备用;1) take the raw material according to the weight part, and set aside;
2)将上述原料加入反应装置中混合,反复震荡摇匀,得到黄瓜香型香基。2) Add the above-mentioned raw materials into the reaction device and mix them, shake them repeatedly to obtain a cucumber-flavored fragrance base.
实施例2Example 2
一种黄瓜香气化合物,名称为4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯,具有如下结构式:A cucumber aroma compound, named 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene) amino) benzoate, has the following structural formula:
所述黄瓜香气化合物通过如下步骤:Described cucumber aroma compound passes through the following steps:
S1、取邻氨基苯甲酸、甲苯和二氯亚砜,将邻氨基苯甲酸和甲苯加入反应装置中搅拌均匀,并冷却至-2℃,向反应装置加入二氯亚砜,之后将反应装置的温度恢复至室温,持续搅拌1h,得到邻氨基苯甲酰氯的甲苯溶液,备用;S1. Take anthranilic acid, toluene and thionyl chloride, add anthranilic acid and toluene into the reaction device and stir evenly, and cool to -2°C, add thionyl chloride to the reaction device, and then put the reaction device The temperature was returned to room temperature, and the stirring was continued for 1 h to obtain a toluene solution of anthranilic acid chloride, which was set aside;
S2、取大茴香醇和无水硫酸镁,将大茴香醇加入步骤S1中得到的邻氨基苯甲酰氯的甲苯溶液中,持续搅拌3h,随后取一定量质量浓度为8%的碳酸钠溶液,继续搅拌0.8h,静置分层,收集上层有机相,并将无水硫酸镁加入有机相,搅拌10h,过滤除去固体,回收滤液,得到4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液,备用;S2, take anisyl alcohol and anhydrous magnesium sulfate, add anisyl alcohol to the toluene solution of anthraniloyl chloride obtained in step S1, continue stirring for 3 hours, then take a certain amount of sodium carbonate solution with a mass concentration of 8%, and continue Stir for 0.8h, let stand to separate layers, collect the upper organic phase, and add anhydrous magnesium sulfate to the organic phase, stir for 10h, filter to remove the solid, reclaim the filtrate to obtain 4-methoxybenzyl-2-aminobenzoate Toluene solution, spare;
S3、取顺-6-壬烯醛,将顺-6-壬烯醛加入步骤S2中得到的4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液中,再点加入一定量浓硫酸,搅拌混合均匀后,减压至450Pa,升温至76℃,继续反应2h,反应过程中使用分水器同步分离反应过程中产生的水分,接着继续升温至110℃,蒸馏除去溶剂,冷却至室温,得到4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯。S3, take cis-6-nonenal, add cis-6-nonenal to the toluene solution of 4-methoxybenzyl-2-aminobenzoate obtained in step S2, and then add a certain amount Concentrated sulfuric acid, stir and mix evenly, decompress to 450Pa, heat up to 76°C, continue to react for 2h, use a water separator to separate the moisture generated during the reaction, then continue to heat up to 110°C, distill off the solvent, cool At room temperature, 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate was obtained.
步骤S1中,所述邻氨基苯甲酸、甲苯和二氯亚砜用量的重量比为0.6:0.7:0.5。In step S1, the weight ratio of the anthranilic acid, toluene and thionyl chloride is 0.6:0.7:0.5.
步骤S2中所述大茴香醇、无水硫酸镁的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.4:0.2:0.6。The weight ratio of the amount of anisyl alcohol and anhydrous magnesium sulfate described in step S2 to the amount of anthranilic acid in step S1 is 0.4:0.2:0.6.
步骤S2中,加入碳酸钠溶液的体积与大茴香醇的体积比为0.9:0.4。In step S2, the volume ratio of the added sodium carbonate solution to the volume of anisyl alcohol is 0.9:0.4.
步骤S3中,所述顺-6-壬烯醛的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.3:0.5。In step S3, the weight ratio of the amount of cis-6-nonenal to the amount of anthranilic acid in step S1 is 0.3:0.5.
步骤S3中,所述顺-6-壬烯醛与浓硫酸用量的重量比为0.3:0.001。In step S3, the weight ratio of the amount of cis-6-nonenal to concentrated sulfuric acid is 0.3:0.001.
一种黄瓜香型香基包括如下重量份的原料:甜瓜醛7.6份、壬醛3.0份、顺-6-壬烯醛5.3份、顺-2,6-壬二烯醛4.4份、反-4-壬烯醛3.4份、反式石竹烯1.6份、榄青酮1.1份、叶醇7.0份、乙酸香芹酯11份、乙酸叶醇酯5.0份、己酸叶醇酯2.0份、4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯8.0份、1,2-丙二醇15份和乙醇20份。A cucumber-flavored fragrance base includes the following raw materials in parts by weight: 7.6 parts of melon aldehyde, 3.0 parts of nonanal, 5.3 parts of cis-6-nonenal, 4.4 parts of cis-2,6-nonadienal, trans-4 - 3.4 parts of nonenal, 1.6 parts of trans-caryophyllene, 1.1 parts of elemene, 7.0 parts of leaf alcohol, 11 parts of carvyl acetate, 5.0 parts of phyllyl acetate, 2.0 parts of phylloyl hexanoate, 4-methyl 8.0 parts of oxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate, 15 parts of 1,2-propanediol and 20 parts of ethanol.
所述黄瓜香型香基通过如下步骤制得:The cucumber-flavored fragrance base is prepared through the following steps:
1)按照重量份称取原料,备用;1) take the raw material according to the weight part, and set aside;
2)将上述原料加入反应装置中混合,反复震荡摇匀,得到黄瓜香型香基。2) Add the above-mentioned raw materials into the reaction device and mix them, shake them repeatedly to obtain a cucumber-flavored fragrance base.
实施例3Example 3
一种黄瓜香气化合物,名称为4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯,具有如下结构式:A cucumber aroma compound, named 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene) amino) benzoate, has the following structural formula:
所述黄瓜香气化合物通过如下步骤:Described cucumber aroma compound passes through the following steps:
S1、取邻氨基苯甲酸、甲苯和二氯亚砜,将邻氨基苯甲酸和甲苯加入反应装置中搅拌均匀,并冷却至1℃,向反应装置加入二氯亚砜,之后将反应装置的温度恢复至室温,持续搅拌2h,得到邻氨基苯甲酰氯的甲苯溶液,备用;S1. Take anthranilic acid, toluene and thionyl chloride, add anthranilic acid and toluene into the reaction device and stir evenly, and cool to 1°C, add thionyl chloride to the reaction device, and then reduce the temperature of the reaction device Return to room temperature and continue to stir for 2h to obtain a toluene solution of anthraniloyl chloride for subsequent use;
S2、取大茴香醇和无水硫酸镁,将大茴香醇加入步骤S1中得到的邻氨基苯甲酰氯的甲苯溶液中,持续搅拌4h,随后取一定量质量浓度为10%的碳酸钠溶液,继续搅拌10h,静置分层,收集上层有机相,并将无水硫酸镁加入有机相,搅拌12h,过滤除去固体,回收滤液,得到4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液,备用;S2. Take anisyl alcohol and anhydrous magnesium sulfate, add anisyl alcohol to the toluene solution of anthraniloyl chloride obtained in step S1, continue stirring for 4 hours, then take a certain amount of sodium carbonate solution with a mass concentration of 10%, and continue Stir for 10h, let stand to separate layers, collect the upper organic phase, and add anhydrous magnesium sulfate to the organic phase, stir for 12h, filter to remove the solid, reclaim the filtrate to obtain 4-methoxybenzyl-2-aminobenzoate Toluene solution, spare;
S3、取顺-6-壬烯醛,将顺-6-壬烯醛加入步骤S2中得到的4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液中,再点加入一定量浓硫酸,搅拌混合均匀后,减压至500Pa,升温至78℃,继续反应3h,反应过程中使用分水器同步分离反应过程中产生的水分,接着继续升温至115℃,蒸馏除去溶剂,冷却至室温,得到4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯。S3, take cis-6-nonenal, add cis-6-nonenal to the toluene solution of 4-methoxybenzyl-2-aminobenzoate obtained in step S2, and then add a certain amount Concentrated sulfuric acid, stir and mix evenly, decompress to 500Pa, heat up to 78°C, continue to react for 3h, use a water separator to separate the moisture generated during the reaction, then continue to heat up to 115°C, distill off the solvent, cool At room temperature, 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate was obtained.
步骤S1中,所述邻氨基苯甲酸、甲苯和二氯亚砜用量的重量比为0.65:0.75:0.55。In step S1, the weight ratio of the anthranilic acid, toluene and thionyl chloride is 0.65:0.75:0.55.
步骤S2中所述大茴香醇、无水硫酸镁的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.5:0.4:0.7。The weight ratio of the amount of anisyl alcohol and anhydrous magnesium sulfate described in step S2 to the amount of anthranilic acid in step S1 is 0.5:0.4:0.7.
步骤S2中,加入碳酸钠溶液的体积与大茴香醇的体积比为1.0:0.5。In step S2, the volume ratio of the added sodium carbonate solution to the volume of anisyl alcohol is 1.0:0.5.
步骤S3中,所述顺-6-壬烯醛的用量与步骤S1中邻氨基苯甲酸用量的重量比为0.4:0.55。In step S3, the weight ratio of the amount of cis-6-nonenal to the amount of anthranilic acid in step S1 is 0.4:0.55.
步骤S3中,所述顺-6-壬烯醛与浓硫酸用量的重量比为0.4:0.003。In step S3, the weight ratio of the amount of cis-6-nonenal to concentrated sulfuric acid is 0.4:0.003.
一种黄瓜香型香基包括如下重量份的原料:甜瓜醛7.8份、壬醛3.3份、顺-6-壬烯醛5.5份、顺-2,6-壬二烯醛4.6份、反-4-壬烯醛3.6份、反式石竹烯1.8份、榄青酮1.3份、叶醇7.2份、乙酸香芹酯11.5份、乙酸叶醇酯5.2份、己酸叶醇酯2.3份、4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯8.5份、1,2-丙二醇15.5份和乙醇22份。A cucumber-flavored fragrance base includes the following raw materials in parts by weight: 7.8 parts of melon aldehyde, 3.3 parts of nonanal, 5.5 parts of cis-6-nonenal, 4.6 parts of cis-2,6-nonadienal, trans-4 - 3.6 parts of nonenal, 1.8 parts of trans-caryophyllene, 1.3 parts of elemene, 7.2 parts of leaf alcohol, 11.5 parts of carvyl acetate, 5.2 parts of phyllyl acetate, 2.3 parts of phylloyl caproate, 4-methyl 8.5 parts of oxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate, 15.5 parts of 1,2-propanediol and 22 parts of ethanol.
所述黄瓜香型香基通过如下步骤制得:The cucumber-flavored fragrance base is prepared through the following steps:
1)按照重量份称取原料,备用;1) take the raw material according to the weight part, and set aside;
2)将上述原料加入反应装置中混合,反复震荡摇匀,得到黄瓜香型香基。2) Add the above-mentioned raw materials into the reaction device and mix them, shake them repeatedly to obtain a cucumber-flavored fragrance base.
实施例4Example 4
一种黄瓜香气化合物,名称为4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯,具有如下结构式:A cucumber aroma compound, named 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene) amino) benzoate, has the following structural formula:
所述黄瓜香气化合物通过如下步骤:Described cucumber aroma compound passes through the following steps:
S1、取658g邻氨基苯甲酸、850mL甲苯和0.36L二氯亚砜,将邻氨基苯甲酸和甲苯加入反应装置中搅拌均匀,并冷却至0℃,向反应装置加入二氯亚砜,之后将反应装置的温度恢复至室温,持续搅拌2h,得到邻氨基苯甲酰氯的甲苯溶液,备用;S1. Take 658g of anthranilic acid, 850mL of toluene and 0.36L of thionyl chloride, add anthranilic acid and toluene into the reaction device and stir evenly, and cool to 0°C, add thionyl chloride to the reaction device, and then The temperature of the reaction device was returned to room temperature, and the stirring was continued for 2 h to obtain a toluene solution of anthranilic acid chloride, which was set aside;
S2、取0.58L大茴香醇和380g无水硫酸镁,将大茴香醇加入步骤S1中得到的邻氨基苯甲酰氯的甲苯溶液中,持续搅拌4h,随后取1.1L质量浓度为10%的碳酸钠溶液,继续搅拌1h,静置分层,收集上层有机相,并将无水硫酸镁加入有机相,搅拌12h,过滤除去固体,回收滤液,得到4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液,备用;S2. Take 0.58L of anisyl alcohol and 380g of anhydrous magnesium sulfate, add the anisyl alcohol into the toluene solution of anthranilic acid chloride obtained in step S1, keep stirring for 4h, and then take 1.1L of sodium carbonate with a mass concentration of 10%. Solution, continue to stir for 1h, let stand to separate layers, collect the upper organic phase, and add anhydrous magnesium sulfate to the organic phase, stir for 12h, filter to remove the solid, reclaim the filtrate to obtain 4-methoxybenzyl-2-aminobenzyl Toluene solution of acid ester, for subsequent use;
S3、取483m L顺-6-壬烯醛,将顺-6-壬烯醛加入步骤S2中得到的4-甲氧基苄基-2-氨基苯甲酸酯的甲苯溶液中,再点加入一定量浓硫酸,搅拌混合均匀后,减压至500Pa,升温至78℃,继续反应4h,反应过程中使用分水器同步分离反应过程中产生的水分,接着继续升温至115℃,蒸馏除去溶剂,冷却至室温,得到4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯。S3, take 483mL cis-6-nonenal, add cis-6-nonenal to the toluene solution of 4-methoxybenzyl-2-aminobenzoate obtained in step S2, and then add A certain amount of concentrated sulfuric acid, stir and mix evenly, depressurize to 500Pa, heat up to 78°C, continue to react for 4h, use a water separator to separate the water generated during the reaction synchronously during the reaction, then continue to heat up to 115°C, and distill off the solvent , cooled to room temperature to give 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate.
一种黄瓜香型香基包括如下重量份的原料:甜瓜醛7.8份、壬醛3.2份、顺-6-壬烯醛5.5份、顺-2,6-壬二烯醛4.5份、反-4-壬烯醛3.6份、反式石竹烯1.8份、榄青酮1.3份、叶醇7.1份、乙酸香芹酯11.5份、乙酸叶醇酯5.1份、己酸叶醇酯2.3份、4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯8.8份、1,2-丙二醇15.5份和乙醇22份。A cucumber-flavored fragrance base includes the following raw materials in parts by weight: 7.8 parts of melon aldehyde, 3.2 parts of nonanal, 5.5 parts of cis-6-nonenal, 4.5 parts of cis-2,6-nonadienal, trans-4 - 3.6 parts of nonenal, 1.8 parts of trans-caryophyllene, 1.3 parts of elemene, 7.1 parts of leaf alcohol, 11.5 parts of carvyl acetate, 5.1 parts of phylloyl acetate, 2.3 parts of phylloyl caproate, 4-methyl 8.8 parts of oxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate, 15.5 parts of 1,2-propanediol and 22 parts of ethanol.
所述黄瓜香型香基通过如下步骤制得:The cucumber-flavored fragrance base is prepared through the following steps:
1)按照重量份称取原料,备用;1) take the raw material according to the weight part, and set aside;
2)将上述原料加入反应装置中混合,反复震荡摇匀,得到黄瓜香型香基。制得4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯的质谱图如图一所示,质谱分析数据如下:2) Add the above-mentioned raw materials into the reaction device and mix them, shake them repeatedly to obtain a cucumber-flavored fragrance base. The mass spectrum of 4-methoxybenzyl 2-((E)-((Z)-6-nonen-1-ylidene)amino)benzoate is shown in Figure 1, and the mass spectrometry data are as follows :
MS(ESI,m/z)402.2(M+Na+);高分辨电喷雾电离质谱理论计算数据为[C24H29NNaO3]+(M+Na+)402.4812,实际测得数值为402.4810。MS (ESI, m/z) 402.2 (M+Na + ); the theoretical calculation data of high-resolution electrospray ionization mass spectrometry is [C 24 H 29 NNaO 3 ] + (M+Na + ) 402.4812, and the actual measured value is 402.4810.
香气评价:Aroma Evaluation:
5位5年以上工作经验的调香师实施例4中制得对4-甲氧基苄基2-((E)-((Z)-6-壬烯-1-亚基)氨基)苯甲酸酯的香气做出如下评价:其中,5位调香师认为该化合物呈现出明显的黄瓜特征香气。The 4-methoxybenzyl 2-((E)-((Z)-6-nonene-1-ylidene)amino)benzene was prepared in Example 4 of 5 perfumers with more than 5 years of work experience The aroma of formate was evaluated as follows: Among them, 5 perfumers believed that the compound presented an obvious characteristic aroma of cucumber.
上述实施例为本发明较佳的实现方案,除此之外,本发明还可以其它方式实现,在不脱离本发明构思的前提下任何显而易见的替换均在本发明的保护范围之内。The above-mentioned embodiments are preferred implementation solutions of the present invention. In addition, the present invention can also be realized in other ways, and any obvious replacements are within the protection scope of the present invention without departing from the concept of the present invention.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CN202310403724.XA CN116354847B (en) | 2023-04-13 | 2023-04-13 | A cucumber aroma compound and preparation method thereof and cucumber aroma base |
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US4853369A (en) * | 1987-12-18 | 1989-08-01 | International Flavors & Fragrances Inc. | Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof |
CN102257119A (en) * | 2008-12-16 | 2011-11-23 | 宝洁公司 | Perfume systems |
CN107033027A (en) * | 2016-11-17 | 2017-08-11 | 东莞波顿香料有限公司 | A kind of aromatic aldehyde schiff bases and its preparation method and application |
CN113613494A (en) * | 2019-05-23 | 2021-11-05 | 科迪华农业科技有限责任公司 | Fungicidal arylamidines |
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US4853369A (en) * | 1987-12-18 | 1989-08-01 | International Flavors & Fragrances Inc. | Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof |
CN102257119A (en) * | 2008-12-16 | 2011-11-23 | 宝洁公司 | Perfume systems |
CN107033027A (en) * | 2016-11-17 | 2017-08-11 | 东莞波顿香料有限公司 | A kind of aromatic aldehyde schiff bases and its preparation method and application |
CN113613494A (en) * | 2019-05-23 | 2021-11-05 | 科迪华农业科技有限责任公司 | Fungicidal arylamidines |
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