CN116874459A - 一种安全、高效生产天然丁位十二内酯的方法 - Google Patents
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Abstract
本发明公开了一种安全、高效生产天然丁位十二内酯的方法,属于香料香精技术领域。本发明的目的其一寻求廉价高效的路线合成中间体天然庚基环戊酮;其二在于提供一种安全、高效、操作简便的合成天然丁十二内酯的方法。对于合成天然庚基环戊酮路线,本发明选用天然庚醛与天然环戊酮为原料,采用羟醛缩合的方法合成的路线成本低、收率较高且操作简便。对于合成天然丁位十二内酯的问题,本发明采用乙酸水溶液做溶剂,滴加双氧水,一锅法安全、高效合成天然丁十二内酯。本发明规避了丁位内酯香料生产过程中所产生的过氧化物的危险工艺,且同时废酸水可套用,提高资源综合利用率,一锅法合成丁位十二内酯合理高效、操作简便。
Description
技术领域
本发明属于香料香精技术领域,具体地,涉及一种安全、高效生产天然丁位十二内酯的方法。
背景技术
香料是由人工模仿水果和天然香料气味而合成的浓缩芳香油,多用于制造食品、饮料、化妆品和卷烟等。食用香精是参照天然食品的香味,采用天然和天然等同香料、合成香料经精心调配而成具有天然风味的各种香型的香精。包括水果类水质和油质、奶类、家禽类、肉类、蔬菜类、坚果类、蜜饯类、乳化类以及酒类等各种香精,适用于饮料、饼干、糕点、冷冻食品、糖果、调味料、乳制品、罐头、酒等食品中。
丁位十二内酯为无色至淡黄色澄清液体,有奶油香味和果香香气以及椰子果实的香气,在低浓度下呈奶油气味,闪点66℃,不溶于水,极易溶于乙醇、丙二醇和植物油。主要用于食用香精,用作高档食用香料、日用香精和其它功能添加剂。规定用量FEMA(mg/kg):糖果0.06;焙烤食品0.06;裱花层10;油脂35;人造奶油10mg/kg。天然丁位十二内酯,是目前具有广泛应用潜力的一款香料。
发明内容
本发明所要解决的技术问题有两个,其一寻求廉价高效的路线合成中间体天然庚基环戊酮;其二在于提供一种安全、高效、操作简便的合成天然丁十二内酯的方法。对于合成天然庚基环戊酮路线的问题,本发明选用天然庚醛与天然环戊酮为原料,采用羟醛缩合的方法合成天然庚基环戊酮的路线成本低、收率较高且操作简便。对于以天然庚基环戊酮为原料安全、高效的合成天然丁位十二内酯的问题,本发明采用乙酸水溶液做溶剂,滴加双氧水,一锅法安全、高效合成天然丁十二内酯。
本发明的目的可以通过以下技术方案实现:
一种安全、高效生产天然丁位十二内酯的方法,包括以下步骤:
(1)天然庚基环戊酮的合成:
分别称量天然环戊酮、稀氢氧化钠溶液依次加入干燥洁净的反应器中,开启加热与搅拌开关,边加热升温边滴加天然庚醛,达到保温要求时保温反应;反应结束后静置分液,收集有机相即反应所得粗产品2-亚庚基环戊酮,经5wt%的硫酸钠溶液洗涤后进行加氢、精馏,最终得到天然庚基环戊酮;
(2)天然丁十二内酯的合成:
分别称量天然庚基环戊酮、乙酸、浓硫酸并依次加入干燥洁净的三口烧瓶中,加热至反应温度,配制适宜浓度的双氧水溶液,缓慢滴入三口烧瓶中;滴完保温反应一段时间,结束反应降温并静置分层,收集得到上层有机相,即得到天然丁十二内酯粗品。
进一步地,步骤(1)中,所述环戊酮与庚醛的摩尔比为(0.9~1.1):1。
进一步地,步骤(1)中,所述稀氢氧化钠溶液的质量分数为1.0wt%~2.0wt%,采用稀氢氧化钠作为羟醛缩合反应的催化剂,其用量占环戊酮或庚醛的2.0mol%-8.0mol%。
进一步地,步骤(1)中,所述环戊酮与庚醛羟醛缩合反应低温时,得到β-羟基庚基环戊酮,加热至70℃-90℃会发生脱羟基反应生成2-亚庚基环戊酮,用稀碱液在85℃下将环戊酮与庚醛进行羟醛缩合,制得2-亚庚基环戊酮的收率65%-75%。
进一步地,步骤(1)中,所述2-亚庚基环戊酮粗品用5wt%的硫酸钠溶液水洗,主要除去粗品中残留的碱液,便于充分快速加氢,加氢后生成庚基环戊酮,抽滤,催化剂回收套用,得到粗产品庚基环戊酮,加氢反应收率约95%-100%。
进一步地,步骤(1)中,所述2-亚庚基环戊酮在加氢后进行精馏注意分割前馏、中馏、后馏,前馏中含有庚醛自身羟醛缩合副产物以及环戊酮自身羟醛缩合副产物,使所精分得庚基环戊酮产品纯度达到99%以上。
进一步地,步骤(2)中,所述庚基环戊酮、乙酸与双氧水的摩尔比为1:(4.5-6.0):(1.6-1.8);其中乙酸不仅参与反应而且充当溶剂。
进一步地,步骤(2)中,所述浓硫酸为催化剂,其用量占庚基环戊酮质量为2.5wt%~7.5wt%。
进一步地,步骤(2)中,所述反应温度为25℃-45℃,温度太低反应速度太慢效率太低,温度太高副产杂质增多产率下降。
进一步地,步骤(2)中,所述双氧水溶液浓度为25%-30%,保证一锅法反应平稳安全且效率高、操作简便,同时产生废酸液可实现部分套用,保证产出废水尽可能少;一锅法由庚基环戊酮合成丁十二内酯收率可达80%以上。
本发明的有益效果:
本发明规避了丁位内酯香料生产过程中所产生的过氧化物的危险工艺,且同时废酸水可套用,提高资源综合利用率,一锅法合成丁位十二内酯合理高效、操作简便。
附图说明
下面结合附图对本发明作进一步的说明。
图1为庚基环戊酮的核磁氢谱图。
图2为丁十二内酯的核磁氢谱图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
向2000mL四口烧瓶中加入6.1g氢氧化钠固体和393.9g水,机械搅拌下加热至80℃,用恒压滴液漏斗滴加342.6g(3.0mol)庚醛与277.2g环戊酮混合液,滴加两小时,保温反应一小时,取样GC检测原料残留和产物含量,待反应完毕则降温,静置分层取上层有机相即反应生成2-亚庚基环戊酮559.8g。GC检测纯度81.9%,内标法计算该步收率约80.8%。
所得2-亚庚基环戊酮粗品经5%硫酸钠溶液洗涤后,用钯炭在40-80℃下进行加氢,加氢完成后得到2-庚基环戊酮粗品,再用填料塔进行精馏,收集1mmHg取98℃-105℃馏分451.2g,GC含量98.8%。
向干燥洁净的1000ml三口烧瓶加入上述精馏所得庚基环戊酮190g(1mol),加入乙酸260g,浓硫酸5.0g,缓慢加热至温度35℃,滴加现配浓度为27.5%的双氧水240g,滴加时长3小时,保温反应5小时,取样GC检测结果:庚基环戊酮残留4.2%,产物含量88.1%;整个反应过程未发现放热现象。反应结束后降温,静置分层,分出上层有机相210.8g。
实施例2
合成庚基环戊酮方法步骤均与实例1相同,在此不在赘述。
向干燥洁净的1000ml三口烧瓶加入上述精馏所得庚基环戊酮196g(1mol),加入乙酸287g,浓硫酸15.0g,缓慢加热至温度45℃,滴加现配浓度为27.5%的双氧水240g,滴加时长3小时,保温反应5小时,取样GC检测结果:庚基环戊酮残留2.0%,产物含量79.9%;整个反应过程未发现放热现象。反应结束后降温,静置分层,分出上层有机相229.1g。
以上具体实施方式部分对本发明所涉及的分析方法进行了具体的介绍。应当注意的是,上述介绍仅是为了帮助本领域技术人员更好地理解本发明的方法及思路,而不是对相关内容的限制。在不脱离本发明原理的情况下,本领域技术人员还可以对本发明进行适当的调整或修改,上述调整和修改也应当属于本发明的保护范围。
Claims (9)
1.一种安全、高效生产天然丁位十二内酯的方法,其特征在于,包括以下步骤:
(1)天然庚基环戊酮的合成:
分别称量天然环戊酮、稀氢氧化钠溶液依次加入干燥洁净的反应器中,开启加热与搅拌开关,边加热升温边滴加天然庚醛,达到保温要求时保温反应;反应结束后静置分液,收集有机相即反应所得粗产品2-亚庚基环戊酮,经5wt%的硫酸钠溶液洗涤后进行加氢、精馏,最终得到天然庚基环戊酮;
(2)天然丁十二内酯的合成:
分别称量天然庚基环戊酮、乙酸、浓硫酸并依次加入干燥洁净的三口烧瓶中,加热至反应温度,配制适宜浓度的双氧水溶液,缓慢滴入三口烧瓶中;滴完保温反应一段时间,结束反应降温并静置分层,收集得到上层有机相,即得到天然丁十二内酯粗品。
2.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(1)中,所述环戊酮与庚醛的摩尔比为(0.9~1.1):1。
3.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(1)中,所述稀氢氧化钠溶液的质量分数为1.0wt%~2.0wt%,采用稀氢氧化钠作为羟醛缩合反应的催化剂,其用量占环戊酮或庚醛的2.0mol%-8.0mol%。
4.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(1)中,所述环戊酮与庚醛羟醛缩合反应低温时,得到β-羟基庚基环戊酮,加热至70℃-90℃会发生脱羟基反应生成2-亚庚基环戊酮,用稀碱液在85℃下将环戊酮与庚醛进行羟醛缩合,制得2-亚庚基环戊酮的收率65%-75%。
5.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(1)中,所述2-亚庚基环戊酮在加氢后进行精馏注意分割前馏、中馏、后馏,前馏中含有庚醛自身羟醛缩合副产物以及环戊酮自身羟醛缩合副产物,使所精分得庚基环戊酮产品纯度达到99%以上。
6.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(2)中,所述庚基环戊酮、乙酸与双氧水的摩尔比为1:(4.5-6.0):(1.6-1.8);其中乙酸不仅参与反应而且充当溶剂。
7.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(2)中,所述浓硫酸为催化剂,其用量占庚基环戊酮质量为2.5wt%~7.5wt%。
8.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(2)中,所述反应温度为25℃-45℃。
9.根据权利要求1所述的一种安全、高效生产天然丁位十二内酯的方法,其特征在于,步骤(2)中,所述双氧水溶液浓度为25%-30%。
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