CN102659646B - Method for preparing beta-amino-carbonyl compounds - Google Patents
Method for preparing beta-amino-carbonyl compounds Download PDFInfo
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- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 description 2
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Abstract
一种β－氨基羰基化合物的制备方法，该方法是将对甲苯磺酰亚胺类化合物、丙酮和氨基酸在室温下搅拌，硅胶GF254薄板检测反应完成，再加入蒸馏水搅拌，出现白色固体，将白色固体抽滤，水洗，得目标产物。本发明在常温常压下进行，反应条件温和；丙酮既做反应物，又做溶剂，无需采用另外的溶剂；目标产物后处理简单。易实现工业化。A preparation method of β-aminocarbonyl compound, the method is to stir p-toluenesulfonimide compound, acetone and amino acid at room temperature, and the silica gel GF254 thin plate detects that the reaction is completed, then add distilled water and stir, a white solid appears, and the white The solid was suction filtered and washed with water to obtain the target product. The invention is carried out at normal temperature and pressure, and the reaction conditions are mild; acetone is used as both a reactant and a solvent, without using another solvent; and the post-treatment of the target product is simple. Easy to realize industrialization.
Description
技术领域 technical field
本发明涉及一种有机高分子化合物的制备方法，具体说是一种β－氨基羰基化合物的制备方法。 The invention relates to a preparation method of an organic polymer compound, in particular to a preparation method of a β-aminocarbonyl compound.
背景技术 Background technique
Mannich反应被认为是最有用的制备β－氨基羰基化合物的方法之一。自从List等报道了L-脯氨酸催化酮、醛、芳胺的三组分Mannich反应，L-脯氨酸催化被广泛应用合成含硝基的化合物如氨基酸或氨基醇。尽管L-脯氨酸催化在科研和工业生产中被常用作Mannich反应催化剂，他的局限性在于必须以苯胺作为胺组分。虽然富电子的对甲氧基苯基（PMP）也可以当作保护基方便高效地除去，得到NH2-基。但是由于去除过程是在强氧化性条件下进行，很多底物在此条件下，会产生分解或发生副反应。因此找到能够在更温和条件下脱去的保护基，十分必要。最近，List等报道了L-脯氨酸催化的N-BOC(叔丁氧羰基)亚胺与脂肪醛的Mannich反应，叔丁氧羰基保护基可以在三氟乙酸中轻易的脱去，得到NH2-的三氟乙酸盐。这为L-脯氨酸催化的Mannich反应底物范围开拓了更广阔的天地。另一方面，Cordova等以非环状氨基酸高选择性地催化了酮、醛、对甲氧基苯胺的三组分Mannich反应，胺组分也仅限于对甲氧基苯胺。其底物胺也有待于进一步拓宽。 The Mannich reaction is considered to be one of the most useful methods for the preparation of β-aminocarbonyl compounds. Since List et al. reported that L-proline catalyzed the three-component Mannich reaction of ketones, aldehydes, and aromatic amines, L-proline catalysis has been widely used in the synthesis of nitro-containing compounds such as amino acids or aminoalcohols. Although L-proline catalysis is often used as a Mannich reaction catalyst in scientific research and industrial production, its limitation is that aniline must be used as the amine component. Although the electron-rich p-methoxyphenyl group (PMP) can also be used as a protecting group to remove it conveniently and efficiently to obtain NH 2 -group. However, since the removal process is carried out under strong oxidative conditions, many substrates will decompose or have side reactions under these conditions. Therefore, it is necessary to find protecting groups that can be removed under milder conditions. Recently, List et al. reported the Mannich reaction of L-proline catalyzed N-BOC (tert-butoxycarbonyl) imine with aliphatic aldehydes. The tert-butoxycarbonyl protecting group can be easily removed in trifluoroacetic acid to obtain NH 2 -Trifluoroacetate. This opens up a wider world for the substrate range of the Mannich reaction catalyzed by L-proline. On the other hand, Cordova et al. catalyzed the three-component Mannich reaction of ketones, aldehydes, and p-methoxyaniline with high selectivity using acyclic amino acids, and the amine component was also limited to p-methoxyaniline. Its substrate amines also need to be further broadened.
对甲苯磺酰基也是一种保护氨基的方法，经典的脱除对甲苯磺酰基是在酸性条件下进行的，最近有文献报道用镁屑在甲醇溶液中也能将其脱去。并且，对甲苯磺酰亚胺本身就是一种很活泼的亚胺，可以和许多底物发生加成反应。因此，我们研究用氨基酸来催化甲苯磺酰亚胺与酮的反应。希望能得到Mannich反应产物是一种以对甲苯磺酰基保护的胺，可以在反应后轻易脱去，以便进行下一步反应。同时也进一步拓宽氨基酸催化Mannich反应的底物范围，为氨基酸催化的运用进一步打下基础。 The p-toluenesulfonyl group is also a method for protecting the amino group. The classic removal of the p-toluenesulfonyl group is carried out under acidic conditions. Recently, it has been reported in the literature that it can also be removed with magnesium chips in methanol solution. Moreover, p-toluenesulfonylimide itself is a very active imine, which can undergo addition reactions with many substrates. Therefore, we investigated the use of amino acids to catalyze the reaction of tosyl imides with ketones. It is hoped that the obtained Mannich reaction product is an amine protected by a p-toluenesulfonyl group, which can be easily removed after the reaction for the next reaction. At the same time, it also further broadens the scope of amino acid-catalyzed Mannich reaction substrates, laying a foundation for the application of amino acid catalysis.
发明内容 Contents of the invention
本发明的目的是提供一种工艺简单可行的β－氨基羰基化合物的制备方法，按该方法制备的化合物具有稳定的固体且易于储存。 The object of the present invention is to provide a method for preparing a β-aminocarbonyl compound with simple and feasible process, and the compound prepared by the method has a stable solid and is easy to store.
本发明提供的一种β－氨基羰基化合物的制备方法，该方法是将对甲苯磺酰亚胺类化合物、丙酮和氨基酸在室温下搅拌，硅胶GF254薄板检测反应完成，再加入蒸馏水搅拌，出现白色固体，将白色固体抽滤，水洗，得目标产物； The invention provides a preparation method of β-aminocarbonyl compound. The method is to stir p-toluenesulfonylimide compound, acetone and amino acid at room temperature, and the silica gel GF254 thin plate detects that the reaction is completed, and then adds distilled water to stir, and a white color appears. solid, the white solid was suction filtered and washed with water to obtain the target product;
其中，对甲苯磺酰亚胺类化合物、丙酮和氨基酸的投料比例为0.4～0.6mmol：3～5ml：0.12～0.18mmol；蒸馏水的加入量按体积计为丙酮1～2倍；所述的氨基酸为L-脯氨酸、L-色氨酸、L-苯丙氨酸、L-甲硫氨酸、L-亮氨酸、L-亮氨酸或L-丙氨酸。 Among them, the feeding ratio of p-toluenesulfonylimide compound, acetone and amino acid is 0.4～0.6mmol: 3～5ml: 0.12～0.18mmol; the amount of distilled water added is 1～2 times of acetone by volume; the amino acid is L-proline, L-tryptophan, L-phenylalanine, L-methionine, L-leucine, L-leucine, or L-alanine.
上述中，优选的是，对甲苯磺酰亚胺类化合物、丙酮和氨基酸的投料比例为0.5mmol：4ml：0.15mmol。 Among the above, preferably, the feeding ratio of p-toluenesulfonylimide compound, acetone and amino acid is 0.5mmol: 4ml: 0.15mmol.
在上述中，所述的氨基酸为L-脯氨酸或L-色氨酸，水洗的次数为3次以上。 In the above, the amino acid is L-proline or L-tryptophan, and the times of washing with water are more than 3 times.
在本发明中，一般地，对甲苯磺酰亚胺类化合物都是适宜的，所得到的最后产物都是稳定的固体且易于储存，但是从后续处理来说，比较理想的是具有下述化学结构式的对甲苯磺酰亚胺类化合物： In the present invention, generally, p-toluenesulfonylimide compounds are suitable, and the final products obtained are all stable solids and are easy to store, but from the follow-up treatment, it is more desirable to have the following chemical The p-toluenesulfonylimide compound of structural formula:
式中，R为H，CH3，Cl，Br或CH3O。 In the formula, R is H, CH 3 , Cl, Br or CH 3 O.
优选的是，R为H，CH3，或CH3O。 Preferably, R is H, CH3 , or CH3O .
该对甲苯磺酰亚胺类化合物可按常规的方法制备。 The p-toluenesulfonylimide compounds can be prepared by conventional methods.
相应地制备得到的β－氨基羰基化合物的化学结构式为： The chemical structural formula of the correspondingly prepared β-aminocarbonyl compound is:
式中，R与对甲苯磺酰亚胺类化合物中的相同，Ts为对甲苯璜酰基。 In the formula, R is the same as that in p-toluenesulfonylimide compounds, and Ts is p-toluenesulfonyl.
本发明具有如下优点：制备是在常温常压下进行，反应条件温和；丙酮既做反应物，又做溶剂，无需采用另外的溶剂；目标产物后处理简单，加入蒸馏水，搅拌，即可，因此易实现工业化。 The present invention has the following advantages: the preparation is carried out at normal temperature and pressure, and the reaction conditions are mild; acetone is used as both a reactant and a solvent, and no other solvent is needed; the post-treatment of the target product is simple, just add distilled water and stir. Easy to realize industrialization.
具体实施方式 Detailed ways
实施例一： Embodiment one:
在25ml圆底烧瓶中分别加入4ml丙酮、0.5mmol对甲苯磺酰亚胺类化合物、0.15mmolL-脯氨酸, 室温搅拌，硅胶GF254薄板检测反应完成。加入10ml蒸馏水搅拌，出现白色固体，抽滤，水洗4次，得目标产物。 Add 4ml of acetone, 0.5mmol of p-toluenesulfonimide compound, and 0.15mmol of L-proline to a 25ml round bottom flask, stir at room temperature, and detect the completion of the reaction on a silica gel GF254 thin plate. Add 10ml of distilled water and stir, a white solid appears, filter with suction, and wash with water 4 times to obtain the target product.
其中该对甲苯磺酰亚胺类化合物的化学结构式为： Wherein the chemical structural formula of this p-toluenesulfonylimide compound is:
式中，R为H。 In the formula, R is H.
目标产物的化学结构式为： The chemical structural formula of target product is:
式中，R为H。 In the formula, R is H.
实施例二：同实施例一，只是采用下述化学结构式的对甲苯磺酰亚胺类化合物： Embodiment two: with embodiment one, just adopt the p-toluenesulfonylimide compound of following chemical structural formula:
式中，R为CH3。 In the formula, R is CH 3 .
目标产物的化学结构式为： The chemical structural formula of target product is:
式中，R为CH3。 In the formula, R is CH 3 .
实施例三：同实施例一，只是采用下述化学结构式的对甲苯磺酰亚胺类化合物： Embodiment three: with embodiment one, just adopt the p-toluenesulfonylimide compound of following chemical structural formula:
式中，R为CH3O。 In the formula, R is CH 3 O.
目标产物的化学结构式为： The chemical structural formula of target product is:
式中，R为CH3O。 In the formula, R is CH 3 O.
比较实例： Comparison example:
1、按实施例一方法和反应条件，采用不同天然氨基酸对反应催化效果的影响，其结果见表1。 1. According to the method and reaction conditions of Example 1, the effects of using different natural amino acids on the catalytic effect of the reaction, the results are shown in Table 1.
表1： Table 1:
a分离产率。 a Isolated yield.
由表中结果可以看出环状氨基酸和非环状氨基酸对模型反应都有催化活性。其中L-脯氨酸和L-色氨酸的催化效果较为理想，产率分别为81％和83％(序号 1,2)。其他的一些线性氨基酸如L-苯丙氨酸、L-甲硫氨酸、L-亮氨酸、L-异亮氨酸、L-丙氨酸都可以得到适中的目标产物(序号 3-7)。一般线性氨基酸催化模型反应所需要的时间要比L-脯氨酸所耗费的时间长。因此， L-脯氨酸和L-色氨酸是该模型反应较为理想的催化剂。 It can be seen from the results in the table that both cyclic amino acids and acyclic amino acids have catalytic activity for the model reaction. Among them, the catalytic effects of L-proline and L-tryptophan are ideal, and the yields are 81% and 83% respectively (No. 1, 2). Some other linear amino acids such as L-phenylalanine, L-methionine, L-leucine, L-isoleucine, and L-alanine can obtain moderate target products (No. 3-7 ). Generally, the time required for the linear amino acid catalyzed model reaction is longer than that of L-proline. Therefore, L-proline and L-tryptophan are ideal catalysts for this model reaction.
2、按实施例一方法和反应条件，采用不同的对甲苯磺酰亚胺类化合物对结果的影响，见表2。 2. According to the method and reaction conditions of Example 1, the influence of different p-toluenesulfonimide compounds on the results is shown in Table 2.
表 2： Table 2:
a分离产率。 a Isolated yield.
由表中数据可以看出，在催化体系的底物中，带有给电子基取代基和吸电子基取代基的对甲苯磺酰亚胺化合物都能与丙酮顺利的反应。但是具有给电子取代基的底物（序号 1-6）反应产率反而高于带有吸电子取代基的反应底物（序号 7-16）, L-色氨酸与L-脯氨酸有着相似的催化效果，但是L-色氨酸的反应时间明显比L-脯氨酸要长。本催化体系得到最后产物都是稳定的固体，易于储存。并且后处理简单，无需通过柱色谱分离，加入蒸馏水，搅拌，即可得到目标产物。因此易实现工业化。 It can be seen from the data in the table that in the substrate of the catalytic system, p-toluenesulfonylimide compounds with electron-donating substituents and electron-withdrawing substituents can react smoothly with acetone. However, the reaction yield of substrates with electron-donating substituents (No. 1-6) is higher than that of substrates with electron-withdrawing substituents (No. 7-16). L-tryptophan and L-proline have Similar catalytic effect, but the reaction time of L-tryptophan is significantly longer than that of L-proline. The final products obtained by the catalytic system are all stable solids, which are easy to store. Moreover, the post-treatment is simple, and the target product can be obtained by adding distilled water and stirring without column chromatographic separation. Therefore, it is easy to realize industrialization.
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