CN104402701B - 一种草莓酸合成新工艺 - Google Patents
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- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
本发明公开了一种草莓酸的合成新工艺。该工艺以水作溶剂,起始原料丙醛在碱催化作用下两分子缩合制得中间体2-甲基-2-戊烯醛;在相转移催化剂的作用下,中间体不经分离,直接在原水溶液中经亚氯酸钠氧化并制得食用香料草莓酸。本发明原料价廉易得,生产工艺简单,收率高,成本低,无污染,符合绿色化工发展要求。
Description
技术领域
本发明属于化学合成领域,具体涉及一种食用香料草莓酸的合成新工艺。
背景技术
上世纪末以来,随着人们对环境安全认识的深入,化工生产对环境造成的影响受到广泛关注,化工生产工艺绿色化呼声越来越高。因此,开发原料价廉易得,操作简单,成本低,污染小甚至没有污染的绿色化学生产工艺是必然的选择。
草莓酸是一种非常有用的食用香料,可用于调配多种食用香精。草莓酸的合成,已有多种工艺路线。其中,最经济的路线是以丙醛为原料经两分子自缩合得到2-甲基-2戊烯醛,再经氧化得到草莓酸。该工艺的难点在于2-甲基-2戊烯醛的氧化。2005年,张红等报道了以乙腈作溶剂,磷酸二氢钠作缓冲溶液的亚氯酸钠-过氧化氢氧化体系,草莓酸收率85%,两步总收率79%;2007年MinkyungLim等报道了以钯炭作催化剂,空气氧化2-甲基-2戊烯醛的工艺,草莓酸收率87%;最近,张小林等报道了以氯铬酸吡啶作氧化剂氧化2-甲基-2-戊醛,草莓酸总收率85.3%。上述工艺,由于丙醛的两分子缩合反应和2-甲基-2-戊醛的氧化反应分别在不同的溶剂中进行进行,步骤1得到的中间产物需要分离和纯化,步骤2用毒性较大的有机溶剂作溶剂,存在操作繁琐,溶剂有毒和生产成本较高的缺点。此外,氯铬酸吡啶氧化存在铬污染问题,钯炭可能存在重金属残留而且价格昂贵。
到目前为止,还没有以水为溶剂的一锅法草莓酸绿色合成工艺报道。
发明内容
本发明的目的在于克服现有技术之不足,提供一种草莓酸绿色合成新工艺。
本发明解决其技术问题所采用的技术方案是:一种草莓酸合成新工艺包括以下步骤:
步骤1:以水作溶剂,溶解碱性催化剂制得质量分数为1.0%-5.0%碱性水溶液,丙醛加入碱性水溶液中缩合生成2-甲基-2-戊烯醛,添加酸性化合物以中和所述碱性水溶液,形成含有2-甲基-2-戊烯醛的水溶液;
步骤2:在3-15℃条件下,向上述含有2-甲基-2-戊烯醛的中性水溶液中依次加入相转移催化剂、磷酸二氢钠及过氧化氢水溶液,滴加75-90%的亚氯酸钠,室温下反应1.5-5h,调节pH至3-5,加入乙酸乙酯萃取多次,采用无水硫酸钠干燥后加入阻聚剂,减压回收乙酸乙酯后制得草莓酸。
优选的,步骤1是在10-20℃的温度下滴加丙醛至碱性水溶液中,甲醛的滴加速度是50-60g/h,滴加完成后升温至35-45℃反应0.5-3h。
优选的,所述碱性催化剂包括氢氧化钠、氢氧化钾、氢氧化钙、氧化钠、氧化钾、氧化钙或氧化镁。
优选的,步骤1中,所述酸性化合物包括盐酸、硫酸、硝酸、磷酸、甲酸、乙酸、丙酸、磷酸二氢钠、磷酸二氢钾或硫酸氢钠。
优选的,所述相转移催化剂包括四丁基溴化铵、四丁基氯化铵、四丁基氢氧化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、苄基三甲基氯化铵、苄基三甲基溴化铵、聚乙二醇400、聚乙二醇600、聚乙二醇800、冠醚、吐温40、吐温60、吐温80、司班40、司班60或司班80。
优选的,所述相转移催化剂与2-甲基-2戊烯醛的摩尔比是1:10-200。
优选的,所述2-甲基-2-戊烯醛与亚氯酸钠及过氧化氢的摩尔比1:1.0-1.5:1.0-1.5。
优选的,步骤2中,萃取之前还包括加入亚硫酸氢钠饱和水溶液至淀粉氧化钾试纸不变色以除去过量过氧化氢的步骤。
优选的,还包括将制得的草莓酸重结晶的步骤。
本发明草莓酸合成的新工艺在反应过程均采用水作溶剂,步骤1反应加入的水直接作为步骤2反应的溶剂,无需分离中间体2-甲基-2戊烯醛,操作更为简单且中间体无损失,同时减少了水的消耗量,没有使用有机溶剂,安全又环保。此外,加入相转移催化剂促进了相间离子的转移,使反应物之间充分接触,促使反应发生,提高反应速度,草莓酸的收率最高可达90%。
以下实施例对本发明作进一步详细说明;但本发明的一种草莓酸合成新工艺不局限于实施例。
具体实施方式
实施例1
步骤1,在2000ml三口烧瓶中,加入质量分数2.0%的氢氧化钠水溶液200ml,于10℃-20℃下滴加丙醛58g,1h内滴完,然后升温至40℃继续反应1h,自然冷却至室温后加入85%磷酸15g。
步骤2,5℃-10℃条件下,向上述溶液中加入四丁基溴化铵8g,磷酸二氢钠8g,30%过氧化氢水溶液80ml,加完后再缓慢滴加82%的亚氯酸钠89g溶于700ml水的溶液,3h内滴完,滴完后室温下继续反应3h;反应完成后,加入适量亚硫酸氢钠饱和水溶液直到淀粉碘化钾试纸不变色;用稀盐酸调pH=4;加入乙酸乙酯搅拌萃取3次,每次用乙酸乙酯100ml,有机层合并后用无水硫酸钠干燥,加入少量阻聚剂,减压回收乙酸乙酯后得草莓酸粗品58.1g,含量86.0%,收率87.3%(以丙醛为基准计算);粗品重结晶后得产品46.2g,熔点24℃-26℃,折光率1.4576-1.4578。
实施例2
步骤1,在2000ml三口烧瓶中,加入质量分数1.5%的氢氧化钠水溶液200ml,于10℃-20℃下滴加丙醛58g,1h内滴完,然后升温至45℃继续反应0.5h,自然冷却至室温后加入85%磷酸15g。
步骤2,5℃-10℃条件下,向上述溶液中加入四丁基溴化铵12g,磷酸二氢钠8g,30%过氧化氢水溶液80ml,加完后再缓慢滴加82%的亚氯酸钠89g溶于700ml水的溶液,3h内滴完,滴完后室温下继续反应1.5h;反应完成后,加入适量亚硫酸氢钠饱和水溶液直到淀粉碘化钾试纸不变色;用稀盐酸调pH=4;加入乙酸乙酯搅拌萃取3次,每次用乙酸乙酯100ml,有机层合并后用无水硫酸钠干燥,加入少量阻聚剂,减压回收乙酸乙酯后得草莓酸粗品59.0g,含量87.1%,总收率90.0%;粗品重结晶后得产品48.2g,熔点24℃-26℃,折光率1.4576-1.4578。
实施例3
步骤1,在2000ml三口烧瓶中,加入质量分数1.5%的氢氧化钾水溶液200ml,于10℃-20℃下滴加丙醛58g,1h内滴完,然后升温至30℃继续反应3h,自然冷却至室温后加入85%盐酸5g。
步骤2,5℃-10℃条件下,向上述溶液中加入四丁基溴化铵5g,磷酸二氢钠8g,30%过氧化氢水溶液80ml,加完后再缓慢滴加82%的亚氯酸钠89g溶于700ml水的溶液,3h内滴完,滴完后室温下继续反应2h;反应完成后,加入适量亚硫酸氢钠饱和水溶液直到淀粉碘化钾试纸不变色;用稀盐酸调pH=4;加入乙酸乙酯搅拌萃取3次,每次用乙酸乙酯100ml,有机层合并后用无水硫酸钠干燥,加入少量阻聚剂,减压回收乙酸乙酯后得草莓酸粗品54.1g,含量86.5%,总收率82.0%;粗品重结晶后得产品42.7g,熔点24℃-26℃,折光率1.4576-1.4578。
实施例4
步骤1,在2000ml三口烧瓶中,加入质量分数3.0%的氧化钾水溶液200ml,于10℃-20℃下滴加丙醛58g,1h内滴完,然后升温至40℃继续反应1h,自然冷却至室温后加入85%磷酸15g。
步骤2,5℃-10℃条件下,向上述溶液中加入PEG-40010g,磷酸二氢钠8g,30%过氧化氢水溶液80ml,加完后再缓慢滴加82%的亚氯酸钠89g溶于700ml水的溶液,3h内滴完,滴完后室温下继续反应3h;反应完成后,加入适量亚硫酸氢钠饱和水溶液直到淀粉碘化钾试纸不变色;用稀盐酸调pH=4;加入乙酸乙酯搅拌萃取3次,每次用乙酸乙酯100ml,有机层合并后用无水硫酸钠干燥,加入少量阻聚剂,减压回收乙酸乙酯后得草莓酸粗品57.3g,含量85.8%,总收率86.2%;粗品重结晶后得产品45.7g,熔点24℃-26℃,折光率1.4576-1.4578。
实施例5
步骤1,在2000ml三口烧瓶中,加入质量分数2.0%的氢氧化钠水溶液200ml,于10℃-20℃下滴加丙醛58g,1h内滴完,然后升温至40℃继续反应1h,自然冷却至室温后加入85%磷酸15g。
步骤2,5℃-10℃条件下,向上述溶液中加入PEG-60015g,磷酸二氢钠8g,30%过氧化氢水溶液80ml,加完后再缓慢滴加82%的亚氯酸钠89g溶于700ml水的溶液,3h内滴完,滴完后室温下继续反应3h;反应完成后,加入适量亚硫酸氢钠饱和水溶液直到淀粉碘化钾试纸不变色;用稀盐酸调pH=4;加入乙酸乙酯搅拌萃取3次,每次用乙酸乙酯100ml,有机层合并后用无水硫酸钠干燥,加入少量阻聚剂,减压回收乙酸乙酯后得草莓酸粗品56.8g,含量86.1%,总收率86.7%;粗品重结晶后得产品45.2g,熔点24℃-26℃,折光率1.4576-1.4578。
上述实施例仅用来做进一步说明,但本发明一种草莓酸合成新工艺并不局限于实施例,凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均落入本发明技术方案的保护范围内。
Claims (9)
1.一种草莓酸合成新工艺,其特征在于包括以下步骤:
步骤1:以水作溶剂,溶解碱性催化剂制得质量分数为1.0%-5.0%的碱性水溶液,丙醛加入碱性水溶液中缩合生成2-甲基-2-戊烯醛,添加酸性化合物以中和所述碱性水溶液,形成含有2-甲基-2-戊烯醛的酸性水溶液;
步骤2:在3-15℃条件下,向上述含有2-甲基-2-戊烯醛的酸性水溶液中依次加入相转移催化剂、磷酸二氢钠及过氧化氢水溶液,滴加75%-90%的亚氯酸钠,室温下反应1.5-5h,调节pH至3-5,加入乙酸乙酯萃取多次,采用无水硫酸钠干燥后加入阻聚剂,减压回收乙酸乙酯后制得草莓酸。
2.根据权利要求1所述的草莓酸合成新工艺,其特征在于:步骤1是在10-20℃的温度下滴加丙醛至碱性水溶液中,升温至35-45℃反应0.5-3.0h。
3.根据权利要求1所述的草莓酸合成新工艺,其特征在于:所述碱性催化剂包括氢氧化钠、氢氧化钾、氢氧化钙、氧化钠、氧化钾、氧化钙或氧化镁。
4.根据权利要求1所述的草莓酸合成新工艺,其特征在于:步骤1中,所述酸性化合物包括盐酸、硫酸、硝酸、磷酸、甲酸、乙酸、丙酸、磷酸二氢钠、磷酸二氢钾或硫酸氢钠。
5.根据权利要求1所述的草莓酸合成新工艺,其特征在于:所述相转移催化剂包括四丁基溴化铵、四丁基氯化铵、四丁基氢氧化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、苄基三甲基氯化铵、苄基三甲基溴化铵、聚乙二醇400、聚乙二醇600、聚乙二醇800、冠醚、吐温40、吐温60、吐温80、司班40、司班60或司班80。
6.根据权利要求1所述的草莓酸合成新工艺,其特征在于:所述相转移催化剂与2-甲基-2戊烯醛的摩尔比是1:10-200。
7.根据权利要求1所述的草莓酸合成新工艺,其特征在于:所述2-甲基-2-戊烯醛与亚氯酸钠及过氧化氢的摩尔比1:1.0-1.5:1.0-1.5。
8.根据权利要求1所述的草莓酸合成新工艺,其特征在于:步骤2中,萃取之前还包括加入亚硫酸氢钠饱和水溶液至淀粉氧化钾试纸不变色以除去过量过氧化氢的步骤。
9.根据权利要求1所述的草莓酸合成新工艺,其特征在于:还包括将制得的草莓酸重结晶的步骤。
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