生物质甘油在农药中间体合成中的应用研究
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摘要
近年来石化资源日益短缺,推动了生物柴油产业的迅速发展,2011年全球生物柴油产量预计达到2050万吨。在生物柴油生产过程中约有10%的副产物甘油产生,从而导致市场上甘油产量过剩,价格下跌。合理利用甘油可以有效降低生物柴油生产成本,提高资源利用率。因此,甘油作为一种可再生资源在化工领域的应用受到了广泛关注。本论文对甘油的应用现状进行了概述,在此基础上,设计了三条路线,分别是以甘油为原料合成农药及中间体3-甲氧基丙醛、异丙甲草胺和1,3-丙二醇,这对解决甘油的应用问题具有重要意义。
1. 3-甲氧基丙醛是合成高效低毒咪唑啉酮类除草剂甲氧咪草烟的重要原料之一。本论文以甘油为起始原料,经甲基化和脱水两步反应合成了3-甲氧基丙醛,发明了脱水反应所用的复合催化剂,在无水硫酸铜和PEG600共同催化作用下得到产物。与现有其它方法相比,本方法合成3-甲氧基丙醛具有原料易得、工艺简单、成本低等优势,具有应用潜力。
2.异丙甲草胺是一种广谱高活性氯代酰胺类除草剂,其销量大,效果得到人们的广泛认可,是目前我国使用的主要除草剂品种之一。本论文以甘油为起始原料,先脱水生成羟基丙酮,再与2-甲基-6-乙基苯胺缩合、加氢得到中间体N-(1-甲基-2-羟基乙基)-2-甲基-6-乙基苯胺,然后用氯乙酰氯酰化,最后用甲醇醚化得到除草剂异丙甲草胺。本方法合成N-(1-甲基-2-羟基乙基)-2-甲基-6-乙基苯胺的步骤未见文献报道,研究表明以氯化锌为催化剂、二甲苯为带水剂、酮胺摩尔比为2、氢气压力为3.2MPa和反应温度为150℃时,效果最好。该方法为甘油的深加工利用提供了一条可行性路线。
3.以甘油为起始原料,经缩醛保护、氯化、脱保护和脱氯加氢4步反应合成1,3-丙二醇。通过对醛的选择和处理方式的优化,可以得到高纯度的对甘油1,3-二羟基保护的缩醛——5-羟基-2-苯基-1,3-二氧六环,然后用双(三氯甲基)碳酸酯对未被保护的2-羟基进行氯化,最后脱保护和脱氯加氢,期望高选择性地得到1,3-丙二醇。然而,实验结果表明5-羟基-2-苯基-1,3-二氧六环在氯化时发生重排反应,最后得到的主要产物是1,2-丙二醇。本论文还考察了甘油缩合反应的催化剂和反应底物醛酮的类型对反应生成异构体比例的影响,为提高1,3-二羟基保护缩醛的选择性打下了基础。
此外,在本论文研究初期阶段,还进行了含氟农药中间体4-氯-2-三氟甲基苯胺的研究,结果表明:以邻三氟甲基苯胺为原料,使用双氧水/盐酸氯化体系,并加入二水氯化铜做催化剂,可以使主产物的选择性大大提高,达到80%以上,转化率为95%。该方法不仅合成路线短,而且反应条件温和,适宜工业化生产。
总之,本论文从甘油的利用角度出发,研究了其在精细化工中的应用,拓展了甘油的应用途径,为今后的工作打下了基础。
In recent years the shortage of fossil energy has promoted the the biodiesel industry developed rapidly, and global biodiesel production is expected to reach 20.5 million tons in 2011. Glycerol is the main by-product obtained and about 10wt% of glycerol is produced during the production of biodiesel. This is leading to excess output of glycerol on the market and price decline. The proper use of biomass glycerol can effectively reduce the cost of biodiesel and increase utilization rate of resourse. So it has attracted many researchers’interests. In this paper, the present applications of glycerol were reviewed and three new using strategies of glycerol were designed for the synthesis of pescitide and intermediates including 3-methoxypropanal, metolachlor and 1, 3-propanediol. This is important to solve application problems of glycerol.
1. 3-methoxypropanal is the intermediate of imidazolinone herbicide imazamox which is high-effective and low-toxic. Using glycerol as the starting material, 3-methoxypropanal was obtained via two reaction steps of methylation and dehydration. A new complex catalyst, consisting of anhydrous copper sulfate and PEG600, was invented for the dehydration reaction. Compared with other existing preparing methods of 3-methoxypropanal, this method had such advantages as raw materials available readily, operation process simple and low cost. The method has application potential in the synthesis of 3-methoxypropanal.
2. Metolachlor is a wide-spectrum, highly-active and chlorinated amide herbicide. The effect is widely recognized by the people. It is one of the main herbicide used in China at present. The herbicide metolachlor was synthesized using glycerol as the starting material, comprising five reaction steps. Firstly, acetol was produced by dehydration of glycerol. Then the intermediate N-(1'-methyl-2'-hydroxyethyl)-2-ethyl-6-methylaniline was obtained by condensation and hydrogenation reactions of acetol and 2-methyl-6-ethylaniline. Finally, through acylation with chloroacetyl chloride and etherification with methanol, metolachlor was ontained. The noval synthetic process of N-(1'-methyl-2'-hydroxyethyl) - 2-ethyl-6-methylaniline from glycerol has not been reported before. The optimized operation conditions were that using zinc chloride as catalyst, xylene as solvent, the mole ratio of acetol and 2-methyl-6-ethylaniline being 2, reaction pressure at 3.2 MPa and reaction temperature at 150℃. This method provided a feasible route for deep processing of glycerol.
3. With glycerol as the starting material, 1, 3-propanediol was obtained via four reaction steps: protection as acetal, chlorination, hydrolysis and catalytic dechlorination-hydrogenation. Through the selection of aldehydes and the optimization of treatment, high purity 1, 3-protected product of 5-hydroxy-2-phenyl-1, 3-dioxane was obtained. Then the un-protected hydroxyl group was chlorinated with bis (trichloromethyl) carbonate, followed by deprotection and dechlorination-hydrogenation, 1, 3-propanediol was prospectively obtained with high selectivity. In our experimental results, however, a rearrangement reaction was conducted in the chlorination step, which causing the major product obtained was 1, 2-propanediol. This paper also examined the effect of catalysts and the types of substrate on the reaction of glycerol condensation, which laid a good foundation for improving the selectivity of 1, 3-protected product.
In addition, in the early stage, the synthesis of a fluorine-contained pesticide intermediate of 4-chloro-2-trifluoromethyl aniline was researched. The results showed that 4-chloro-2-trifluoromethyl aniline was obtained in 95% conversion and 80% selectivity using o-(trifluoromethyl) aniline as raw material, hydrogen peroxide/hydrochloric acid as chlorination reagents and chloride copper as catalyst. This synthetic route is shorter and reaction condition is mild, which is suitable for industrial production.
In summary, three new applications of glycerol in fine chemicals were developped, which expanded the application approaches of glycerol and laid a good foundation for the future work.
1. 3-甲氧基丙醛是合成高效低毒咪唑啉酮类除草剂甲氧咪草烟的重要原料之一。本论文以甘油为起始原料,经甲基化和脱水两步反应合成了3-甲氧基丙醛,发明了脱水反应所用的复合催化剂,在无水硫酸铜和PEG600共同催化作用下得到产物。与现有其它方法相比,本方法合成3-甲氧基丙醛具有原料易得、工艺简单、成本低等优势,具有应用潜力。
2.异丙甲草胺是一种广谱高活性氯代酰胺类除草剂,其销量大,效果得到人们的广泛认可,是目前我国使用的主要除草剂品种之一。本论文以甘油为起始原料,先脱水生成羟基丙酮,再与2-甲基-6-乙基苯胺缩合、加氢得到中间体N-(1-甲基-2-羟基乙基)-2-甲基-6-乙基苯胺,然后用氯乙酰氯酰化,最后用甲醇醚化得到除草剂异丙甲草胺。本方法合成N-(1-甲基-2-羟基乙基)-2-甲基-6-乙基苯胺的步骤未见文献报道,研究表明以氯化锌为催化剂、二甲苯为带水剂、酮胺摩尔比为2、氢气压力为3.2MPa和反应温度为150℃时,效果最好。该方法为甘油的深加工利用提供了一条可行性路线。
3.以甘油为起始原料,经缩醛保护、氯化、脱保护和脱氯加氢4步反应合成1,3-丙二醇。通过对醛的选择和处理方式的优化,可以得到高纯度的对甘油1,3-二羟基保护的缩醛——5-羟基-2-苯基-1,3-二氧六环,然后用双(三氯甲基)碳酸酯对未被保护的2-羟基进行氯化,最后脱保护和脱氯加氢,期望高选择性地得到1,3-丙二醇。然而,实验结果表明5-羟基-2-苯基-1,3-二氧六环在氯化时发生重排反应,最后得到的主要产物是1,2-丙二醇。本论文还考察了甘油缩合反应的催化剂和反应底物醛酮的类型对反应生成异构体比例的影响,为提高1,3-二羟基保护缩醛的选择性打下了基础。
此外,在本论文研究初期阶段,还进行了含氟农药中间体4-氯-2-三氟甲基苯胺的研究,结果表明:以邻三氟甲基苯胺为原料,使用双氧水/盐酸氯化体系,并加入二水氯化铜做催化剂,可以使主产物的选择性大大提高,达到80%以上,转化率为95%。该方法不仅合成路线短,而且反应条件温和,适宜工业化生产。
总之,本论文从甘油的利用角度出发,研究了其在精细化工中的应用,拓展了甘油的应用途径,为今后的工作打下了基础。
In recent years the shortage of fossil energy has promoted the the biodiesel industry developed rapidly, and global biodiesel production is expected to reach 20.5 million tons in 2011. Glycerol is the main by-product obtained and about 10wt% of glycerol is produced during the production of biodiesel. This is leading to excess output of glycerol on the market and price decline. The proper use of biomass glycerol can effectively reduce the cost of biodiesel and increase utilization rate of resourse. So it has attracted many researchers’interests. In this paper, the present applications of glycerol were reviewed and three new using strategies of glycerol were designed for the synthesis of pescitide and intermediates including 3-methoxypropanal, metolachlor and 1, 3-propanediol. This is important to solve application problems of glycerol.
1. 3-methoxypropanal is the intermediate of imidazolinone herbicide imazamox which is high-effective and low-toxic. Using glycerol as the starting material, 3-methoxypropanal was obtained via two reaction steps of methylation and dehydration. A new complex catalyst, consisting of anhydrous copper sulfate and PEG600, was invented for the dehydration reaction. Compared with other existing preparing methods of 3-methoxypropanal, this method had such advantages as raw materials available readily, operation process simple and low cost. The method has application potential in the synthesis of 3-methoxypropanal.
2. Metolachlor is a wide-spectrum, highly-active and chlorinated amide herbicide. The effect is widely recognized by the people. It is one of the main herbicide used in China at present. The herbicide metolachlor was synthesized using glycerol as the starting material, comprising five reaction steps. Firstly, acetol was produced by dehydration of glycerol. Then the intermediate N-(1'-methyl-2'-hydroxyethyl)-2-ethyl-6-methylaniline was obtained by condensation and hydrogenation reactions of acetol and 2-methyl-6-ethylaniline. Finally, through acylation with chloroacetyl chloride and etherification with methanol, metolachlor was ontained. The noval synthetic process of N-(1'-methyl-2'-hydroxyethyl) - 2-ethyl-6-methylaniline from glycerol has not been reported before. The optimized operation conditions were that using zinc chloride as catalyst, xylene as solvent, the mole ratio of acetol and 2-methyl-6-ethylaniline being 2, reaction pressure at 3.2 MPa and reaction temperature at 150℃. This method provided a feasible route for deep processing of glycerol.
3. With glycerol as the starting material, 1, 3-propanediol was obtained via four reaction steps: protection as acetal, chlorination, hydrolysis and catalytic dechlorination-hydrogenation. Through the selection of aldehydes and the optimization of treatment, high purity 1, 3-protected product of 5-hydroxy-2-phenyl-1, 3-dioxane was obtained. Then the un-protected hydroxyl group was chlorinated with bis (trichloromethyl) carbonate, followed by deprotection and dechlorination-hydrogenation, 1, 3-propanediol was prospectively obtained with high selectivity. In our experimental results, however, a rearrangement reaction was conducted in the chlorination step, which causing the major product obtained was 1, 2-propanediol. This paper also examined the effect of catalysts and the types of substrate on the reaction of glycerol condensation, which laid a good foundation for improving the selectivity of 1, 3-protected product.
In addition, in the early stage, the synthesis of a fluorine-contained pesticide intermediate of 4-chloro-2-trifluoromethyl aniline was researched. The results showed that 4-chloro-2-trifluoromethyl aniline was obtained in 95% conversion and 80% selectivity using o-(trifluoromethyl) aniline as raw material, hydrogen peroxide/hydrochloric acid as chlorination reagents and chloride copper as catalyst. This synthetic route is shorter and reaction condition is mild, which is suitable for industrial production.
In summary, three new applications of glycerol in fine chemicals were developped, which expanded the application approaches of glycerol and laid a good foundation for the future work.
引文
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