CN114920646A - 一种2-正丁基乙酰乙酸乙酯的新合成方法 - Google Patents
一种2-正丁基乙酰乙酸乙酯的新合成方法 Download PDFInfo
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims abstract description 20
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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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
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Abstract
本发明提出一种2‑正丁基乙酰乙酸乙酯的新合成方法,包括:将乙酰乙酸乙酯和正丁醛,在铑碳催化剂下依次进行缩合、加氢反应,得到2‑正丁基乙酰乙酸乙酯。本发明提出的一种2‑正丁基乙酰乙酸乙酯的新合成方法,其合成方法简单,收率高且纯度好,无需进行复杂的后处理,便于后续放大生产。
Description
技术领域
本发明涉及药物中间体合成技术领域,尤其涉及一种2-正丁基乙酰乙酸乙酯的新合成方法。
背景技术
二甲嘧酚是属于嘧啶类内吸性杀菌剂,兼有治疗作用,对各种作物白粉病有特效,主要用于瓜类、蔬菜、甜菜及麦类、橡胶树、柞树等。乙嘧酚对热以及在酸性和碱性溶液中均稳定,对草莓、西瓜、黄瓜、葡萄等许多作物白粉病的有特殊药效。
2-正丁基乙酰乙酸乙酯作为二甲嘧酚和乙嘧酚的重要中间体,现有报道中,其主要的合成方法是卤代烷烃法和催化加氢法。
卤代烷烃法是以乙酰乙酸乙酯和卤(氯,溴,碘)代正丁烷为原料,在碱(甲醇钠,乙醇钠)的作用下合成2-正丁基乙酰乙酸乙酯。该方法不可避免地生成双正丁基取代副产物,且难以分离,影响产品的含量和收率,另外还存在原材料成本高,产生大量含盐废水,工业化操作难度大等缺点。如《Journal of the American Chemical Society》[2015,137(1),508-517]中报道采用乙酰乙酸乙酯和1-溴丁烷为原料合成2-正丁基乙酰乙酸乙酯,不仅收率低,而且产品品质差,还生成了难以去除的双正丁基杂质。
催化加氢法是利用乙酰乙酸乙酯和正丁醛直接加氢制备2-正丁基乙酰乙酸乙酯。《精细化工中间体》[2014,44(4),23-25]报道了镍催化,含量和收率都不高,且避免不了部分正丁醛被加氢成正丁醇。1974年美国专利(US3839418)报道了钯催化加氢法,但是此方法仅当加入助催化剂哌啶类化合物才能获得好的收率,并且钯催化剂仅使用一次价格昂贵。
由上述已有的合成方法可知,其工艺路线复杂,且反应产率低,不利于放大工艺生产。
发明内容
基于背景技术存在的技术问题,本发明提出了一种2-正丁基乙酰乙酸乙酯的新合成方法,其合成方法简单,收率高且纯度好,无需进行复杂的后处理,便于后续放大生产。
本发明提出的一种2-正丁基乙酰乙酸乙酯的新合成方法,包括:将乙酰乙酸乙酯和正丁醛,在铑碳催化剂下进行缩合、加氢反应,得到2-正丁基乙酰乙酸乙酯;
优选地,所述乙酰乙酸乙酯和正丁醛的摩尔比为1:1.1-1.3,优选为1:1.2。
由于正丁醛用量的增加,产物的收率上升,但当正丁醛用量继续增加后,产物收率却没有提高趋势,因此本发明控制乙酰乙酸乙酯和正丁醛的摩尔比为1:1.1-1.3。
优选地,所述铑碳催化剂中铑活性组分的含量为1-10wt%。
优选地,所述铑碳催化剂的加入量是乙酰乙酸乙酯的0.5-3wt%。
铑碳催化剂的加入量会影响产物的纯度和收率,本发明控制铑碳催化剂的加入量是乙酰乙酸乙酯的0.5-3wt%为最适宜。
优选地,所述铑碳催化剂除了具有铑活性组分以外,还具有钴活性组分;
优选地,所述钴活性组分的含量为1-5wt%。
钴活性组分的存在使得铑碳催化剂中铑活性组分在碳载体上的分布效率得以提高,因此促进了铑碳催化剂的加氢反应效率。
优选地,所述铑碳催化剂是以活性碳为载体,加入铑盐和钴盐在活性碳载体上沉积,再经还原后得到。
优选地,所述缩合、加氢反应的溶剂为醇,优选为甲醇。
优选地,所述缩合、加氢反应的温度为70-120℃。
当反应温度太低时,反应速度太慢,但当反应温度太高时,生成的副产物较多,因此本发明控制反应温度为60-120℃,使得反应效率最高。
优选地,所述缩合、加氢反应的氢气压力为0.5-2MPa。
优选地,所述新合成方法具体包括:将乙酰乙酸乙酯和正丁醛加入高压反应釜中,再加入铑碳催化剂,氮气置换后,通入氢气,保温保压反应至完全,即得到所述2-正丁基乙酰乙酸乙酯;
优选地,在保温保压反应完全之后,还包括将反应液进行蒸馏提纯。
本发明提供的一种2-正丁基乙酰乙酸乙酯的新合成方法,相对于之前的文献和专利报道,明显降低了杂质的含量,提高了收率和产品纯度,整个反应操作简单,无需进行复杂的后处理,加氢所用催化剂可以反复多次利用,大大降低了生产成本,有利于工业化生产。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明,但是应该明确提出这些实施例用于举例说明,但是不解释为限制本发明的范围。
实施例1
2-正丁基乙酰乙酸乙酯的新合成方法:
将100g乙酰乙酸乙酯和66.49g正丁醛加入至高压反应釜中,再加入100mL甲醇,接着加入1.2g铑碳催化剂(Rh/C,Rh含量为5%),盖上釜盖,氮气置换三次后用氢气置换三次,通入氢气加压至0.8MPa,升温至80℃,保温保压反应12h后排空氢气,降温,过滤,铑碳催化剂回收套用,滤液蒸馏去除甲醇和多余的正丁醛,即得到132.7g 2-正丁基乙酰乙酸乙酯,收率为92.7%,GC纯度为98.6%;
该实施例中,所述铑碳催化剂采用下述方法制成:
将氯化铑(III)水合物加入水中,配置成10mL的盐活性组分溶液(Rh含量为0.05g/mL),再将10g活性炭加入500mL水中,配置成载体悬浊液;在40℃条件下将所述盐活性组分溶液加入到载体悬浊液中,再加入氨水(25-28%)维持pH为9-10,保温搅拌4h后使盐活性组分吸附沉积在活性炭上,过滤,水洗,干燥后,将所得固体在马弗炉中焙烧,从室温以10℃/min的速率升温至400℃后,保温焙烧4h,再在300℃下于氢气中还原反应6h,缓慢降温至室温,即得到所述铑碳催化剂。
实施例2
2-正丁基乙酰乙酸乙酯的新合成方法:
将100g乙酰乙酸乙酯和66.49g正丁醛加入至高压反应釜中,再加入100mL甲醇,接着加入1.2g铑碳催化剂(Rh/C,Rh含量为5%),盖上釜盖,氮气置换三次后用氢气置换三次,通入氢气加压至2MPa,升温至60℃,保温保压反应12h后排空氢气,降温,过滤,铑碳催化剂回收套用,滤液蒸馏去除甲醇和多余的正丁醛,即得到129.1g 2-正丁基乙酰乙酸乙酯,收率为90.2%,GC纯度为99.0%。
实施例3
2-正丁基乙酰乙酸乙酯的新合成方法:
将100g乙酰乙酸乙酯和66.49g正丁醛加入至高压反应釜中,再加入100mL甲醇,接着加入1.2g铑碳催化剂(Rh/C,Rh含量为5%),盖上釜盖,氮气置换三次后用氢气置换三次,通入氢气加压至0.5MPa,升温至120℃,保温保压反应12h后排空氢气,降温,过滤,铑碳催化剂回收套用,滤液蒸馏去除甲醇和多余的正丁醛,得130.6g 2-正丁基乙酰乙酸乙酯产率,收率为91.2%,GC纯度为98.0%。
实施例4
2-正丁基乙酰乙酸乙酯的新合成方法:
将100g乙酰乙酸乙酯和66.49g正丁醛加入至高压反应釜中,再加入100mL甲醇,接着加入1.2g铑碳催化剂(Rh-Co/C,Rh含量为5%,Co含量为3%,),盖上釜盖,氮气置换三次后用氢气置换三次,通入氢气加压至0.8MPa,升温至80℃,保温保压反应12h后排空氢气,降温,过滤,铑碳催化剂回收套用,滤液蒸馏去除甲醇和多余的正丁醛,得136.9g 2-正丁基乙酰乙酸乙酯,收率为95.6%,GC纯度为99.4%;
该实施例中,所述铑碳催化剂采用下述方法制成:
将氯化铑(III)水合物和六水合硝酸钴依次加入水中,配置成10mL的盐活性组分溶液(Rh含量为0.05g/mL、钴含量为0.03g/mL),再将10g活性炭加入500mL水中,配置成载体悬浊液;在40℃条件下将所述盐活性组分溶液加入到载体悬浊液中,再加入氨水(25-28%)维持pH为9-10,保温搅拌4h后使盐活性组分吸附沉积在活性炭上,过滤,水洗,干燥后,将所得固体在马弗炉中焙烧,从室温以10℃/min的速率升温至400℃后,保温焙烧4h,再在300℃下于氢气中还原反应6h,缓慢降温至室温,即得到所述铑碳催化剂。
实施例5
2-正丁基乙酰乙酸乙酯的新合成方法:
将100g乙酰乙酸乙酯和66.49g正丁醛加入至高压反应釜中,再加入100mL甲醇,接着加入1.2g铑碳催化剂(Rh/C,Rh含量为5%),盖上釜盖,氮气置换三次后用氢气置换三次,通入氢气加压至0.8MPa,升温至80℃,保温保压反应12h后排空氢气,降温,过滤,铑碳催化剂回收套用6次,滤液蒸馏去除甲醇和多余的正丁醛,即得到2-正丁基乙酰乙酸乙酯。
铑碳催化剂回收套用8次后的产品收率和纯度如下所示:
综上可知,本发明所述2-正丁基乙酰乙酸乙酯的合成方法中,可在较低温度和较低反应压力下催化加氢合成2-正丁基乙酰乙酸乙酯,收率在90%以上,纯度在98%以上,反应条件温和,安全系数大,并且催化剂可循环使用。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述乙酰乙酸乙酯和正丁醛的摩尔比为1:1.1-1.3,优选为1:1.2。
3.根据权利要求1或2所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述铑碳催化剂中铑活性组分的含量为1-10wt%。
4.根据权利要求3所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述铑碳催化剂的加入量是乙酰乙酸乙酯的0.5-3wt%。
5.根据权利要求1-4任一项所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述铑碳催化剂除了具有铑活性组分以外,还具有钴活性组分;
优选地,所述钴活性组分的含量为1-5wt%。
6.根据权利要求5所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述铑碳催化剂是以活性碳为载体,加入铑盐和钴盐在活性碳载体上沉积,再经还原后得到。
7.根据权利要求1-6任一项所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述缩合、加氢反应的溶剂为醇,优选为甲醇。
8.根据权利要求1-7任一项所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述缩合、加氢反应的温度为60-120℃。
9.根据权利要求1-8任一项所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述缩合、加氢反应的氢气压力为0.5-2MPa。
10.根据权利要求1-9任一项所述的2-正丁基乙酰乙酸乙酯的新合成方法,其特征在于,所述新合成方法具体包括:将乙酰乙酸乙酯和正丁醛加入高压反应釜中,再加入铑碳催化剂,氮气置换后,通入氢气,保温保压反应完全,即得到所述2-正丁基乙酰乙酸乙酯;
优选地,在保温保压反应完全之后,还包括将反应液进行蒸馏提纯。
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