CN112321628A - Preparation method of β-dimethylphenylsilicon substituted organic nitrile compounds - Google Patents
Preparation method of β-dimethylphenylsilicon substituted organic nitrile compounds Download PDFInfo
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Abstract
本发明公开了一种β‑二甲基苯基硅取代有机腈类化合物的制备方法，该方法首先向壳聚糖负载铜膜材料中加水，在室温条件下，搅拌均匀，得到混合液；向混合液中加入α,β‑不饱和羰基化合物I和(二甲基苯硅烷基)硼酸频那醇酯，在室温条件下搅拌至反应完全；反应结束后，进行过滤，过滤所得沉淀物分别用四氢呋喃，丙酮洗涤，得到滤液，并回收壳聚糖负载铜膜材料再利用；将滤液旋转蒸发浓缩，残留物经不同比例的乙酸乙酯/石油醚混合溶剂快速柱色谱，分离提纯得到有机腈类化合物II。本发明的方法中膜材料的催化活性很高，仅需要使用较低的催化剂用量，即可实现反应物较高的转化率。The invention discloses a preparation method of β-dimethylphenylsilicon-substituted organic nitrile compounds. The method firstly adds water to a chitosan-loaded copper film material, and stirs it uniformly at room temperature to obtain a mixed solution; Add α,β-unsaturated carbonyl compound I and (dimethylphenylsilyl) boronate pinacol ester to the mixed solution, and stir until the reaction is complete at room temperature; Tetrahydrofuran and acetone were washed to obtain the filtrate, and the chitosan-supported copper membrane material was recovered for reuse; the filtrate was concentrated by rotary evaporation, and the residue was separated and purified by flash column chromatography with different proportions of ethyl acetate/petroleum ether mixed solvent to obtain organic nitriles. Compound II. In the method of the present invention, the catalytic activity of the membrane material is very high, and a relatively high conversion rate of reactants can be achieved only by using a relatively low amount of catalyst.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of a beta-dimethyl phenyl silicon substituted organic nitrile compound.
Background
The organic nitrile compound is an important organic compound containing cyano (-CN), is a useful intermediate for organic synthesis, and is an important monomer for polymer synthesis. Due to the special properties, the material is widely applied to the fields of synthetic chemistry, materials and medicinal chemistry, in particular to the advanced fields of national defense science and technology, aerospace special materials and the like. Some nitriles may even be used directly as pesticides, fragrances, metal corrosion inhibitors or liquid crystal materials, etc. Organic nitriles can undergo a variety of chemical transformations, such as conversion to carboxylic acids, aldehydes, ketones, esters, amides, amines, tetrazoles and other nitrogen heterocycles, and the like. The synthesis method of the organic nitrile compound is various, wherein Rosenmund-von Braun reaction is the most traditional method, but a certain amount of highly toxic CuCN is required to be used, and the environmental pollution is caused; this disadvantage can be overcome by using transition metal catalysis and a safe source of cyanogen. However, many nitrile compounds are produced without the disadvantages of toxicity, use of precious metals, harsh reaction conditions, and generation of large amounts of pollutants, which have prevented their more general use in organic synthesis. In the synthesis research of beta-silicon substituted nitrile compounds, C (sp) is constructed in a cross-coupling mode3) the-Si bond is an important class of methods and pathways. In recent years, the use of (dimethylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin), an addition reaction of alpha, beta-unsaturated nitrile compounds to prepare organic nitrile compounds, gradually become a hotspot field of research.
At present, noble metals such as Pd, Rh and the like are generally required to be used as catalysts in the literature, and the method has high cost and large pollution and is not suitable for practical application. In the case of using cheap metal, copper salt is generally used as catalyst in the literature report, but ligand or strong base (sodium tert-butyl alkoxide, etc.) is required to be added, and the operation requirement is severe, such as low temperature and anhydrous oxygen-free operation, which greatly limits the application of the method in practical production.
In 2008, the article (Angewandte Chemie International Edition 2008,47,3818) reported as [ 2 ], [ solution ]Rh(cod)2]OTf is used as catalyst, R- (+) -1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine is used as ligand, and 1,4-dioxane/H is used2O (10:1) as solvent, adding alkali Et3N, at 50 ℃ to first effect the (dimethylsilyl) boronic acid pinacol ester Me2Beta-silicon addition reaction of PhSi-Bpin to alpha, beta-unsaturated carbonyl compound to obtain beta-dimethyl phenyl silicon substituted organic nitrile compound. However, in this method, 5 mol% of noble metal catalyst and 10 mol% of toxic ligand are used, and the whole reaction system is a homogeneous catalytic system, so that the product is difficult to separate, and the residual metal, ligand and solvent cause product and environmental pollution. In 2010, the literature (Journal of the American Chemical society2010,132,2898) reported that pinacol ester of (dimethylsilyl) borate Me was achieved using 1 mol% of CuCl as catalyst, adding 2.2 mol% of NaOt-Bu base, at-78 ℃ in the absence of a proton source2Beta-silicon addition reaction of PhSi-Bpin to alpha, beta-unsaturated carbonyl compound to obtain beta-dimethyl phenyl silicon substituted organic nitrile compound with enantioselectivity. The method uses metal cuprous salt, does not need a proton source, but needs strong base and expensive NHC ligand, and has complex post-treatment and no environmental friendliness. In 2015, the use of Cu (acac) was reported in the literature (Journal of the American Chemical Society2015,137,15422)2With a tailored chiral bipyridine ligand with H2And O is a solvent, and the beta-silicon substituted organic nitrile compound is prepared by catalysis at room temperature. The method is the simplest way for preparing the beta-dimethyl phenyl silicon substituted organic nitrile compound at present, but the method has complex ligand preparation, is not commercialized, limits the reaction cost and is not beneficial to actual production.
Therefore, it is very urgent to develop a new method which is simple, convenient and easy to operate, mild in condition, low in cost, green and environment-friendly and suitable for large-scale production of beta-dimethylphenyl silicon-substituted organic nitrile compounds.
Disclosure of Invention
The invention aims to provide a preparation method of a beta-dimethylphenyl silicon substituted organic nitrile compound, aiming at overcoming the following defects in the prior art to at least a certain extent:
1) when noble metal is used as a catalyst for synthesizing the beta-dimethyl phenyl silicon substituted organic nitrile compound as a synthesis raw material, the cost is high, and industrialization cannot be realized;
2) when monovalent copper is used as a catalyst, the operation process is complex, severe conditions such as strong alkali (sodium tert-butoxide and the like), low temperature, strict anhydrous and the like are required, and the production cost is also high;
3) when divalent copper is used as a catalyst, a special chiral bipyridine ligand needs to be added, the preparation of the ligand is complex, the cost is high, and the commercialization cannot be realized.
Therefore, the invention aims to develop an environment-friendly new method for efficiently preparing the beta-dimethyl phenyl silicon substituted organic nitrile compound by using the low-cost chitosan loaded copper film material without adding any ligand.
In order to achieve the purpose, the invention adopts the following technical measures:
a method for preparing beta-dimethyl phenyl silicon substituted organic nitrile compounds by catalyzing chitosan loaded copper film materials is synthesized as follows:
wherein R is any one of phenyl, p-methoxyphenyl, p-fluorophenyl, thiophene and methyl;
the synthesis steps are as follows:
1) adding water into a chitosan loaded copper film material (CP @ Cu NPs), and stirring uniformly at room temperature to obtain a mixed solution;
2) adding an alpha, beta-unsaturated carbonyl compound I and (dimethylsilyl) boronic acid pinacol ester Ph to the mixture2MeSi-B (pin) is stirred under the condition of room temperature until the reaction is complete; wherein the alpha, beta-unsaturated carbonyl compound I is reacted with (dimethylsilyl) boronic acid pinacol ester Ph2The mass ratio of MeSi-B (pin) is 1: 1.2-2.0; and the dosage of the chitosan loaded copper film material per millimole (mmol) of the alpha, beta-unsaturated carbonyl compound I is 25-80 mg;
3) after the reaction is finished, filtering, washing precipitates obtained by filtering with tetrahydrofuran and acetone respectively to obtain filtrate, and recycling the chitosan loaded copper film material for reuse;
4) and (3) performing rotary evaporation and concentration on the filtrate, separating and purifying residues by using ethyl acetate/petroleum ether mixed solvent flash column chromatography with different proportions to obtain the organic nitrile compound II (the proportion of the ethyl acetate/petroleum ether mixed solvent is selected according to different polarities of products, and the flash column chromatography adopts silica gel as a stationary phase).
Further, R is any one of phenyl, p-fluorophenyl and thiophene;
still further, in the step 2), the α, β -unsaturated carbonyl compound I and (dimethylsilyl) boronic acid pinacol ester Ph2The mass ratio of MeSi-B (pin) is 1: 1.2-1.6; and the dosage of the chitosan loaded copper film material per millimole (mmol) of the alpha, beta-unsaturated carbonyl compound I is 30-70 mg.
Still further, in the step 2), the reaction time is stirred for 5-10 h.
And further, in the step 3), the recovered chitosan-loaded copper film material is washed by distilled water and then is dried in an oven at 120 ℃ for 5 hours, and the chitosan-loaded copper film material is used in the preparation step of the organic nitrile compound again.
The technical idea of the invention is as follows:
the method takes a Chitosan/Polyvinyl Alcohol loaded Nano Copper composite membrane (Chitosan/Polyvinyl Alcohol supported Nano Copper, CP @ Cu NPs) as a catalyst, and the preparation method of the Chitosan/Polyvinyl Alcohol loaded Copper membrane catalytic material is carried out according to a reported method. (Dimethylphenylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin) (Annaiji chemical) is used as a reaction reagent, water is used as a solvent, and a copper catalytic material and Ph are loaded under the catalysis of a chitosan loaded copper film material (CP @ Cu NPs)2MeSi-B (pin) is complexed, and is added with a substrate containing different substituent groups to generate silicon substitution reaction, so that the preparation of the target beta-dimethyl phenyl silicon substituted organic nitrile compound is realized. After the reaction is finished, the catalyst can be simply filtered to be recovered by utilizing the advantage that the membrane material catalyst is easy to separate and recoverThe chitosan loaded copper film material is collected, so that the catalyst is easy to recycle subsequently, the cost is reduced, and the method is more green, economic and environment-friendly.
The invention has the beneficial effects that:
1. the invention adopts the chitosan loaded copper film material for the first time, provides a new method for preparing the organic nitrile compound besides the previously reported method of catalyzing by the cuprous salt, and has completely different reaction mechanisms and processes.
2. The method does not need to add any toxic ligand, and also realizes the efficient preparation of the beta-dimethyl phenyl silicon substituted organic nitrile compound, thereby not only reducing the cost, but also reducing the difficulty of subsequent separation and purification;
3. in the method, the catalytic activity of the membrane material is very high, and the higher conversion rate of reactants can be realized only by using lower catalyst dosage;
4. the method has mild reaction conditions, takes pure water as a solvent, carries out the reaction at room temperature, and is simple and easy to operate;
5. the method has wide application range, can be used for various different types of alpha, beta-unsaturated carbonyl compounds, and successfully prepares the corresponding beta-dimethyl phenyl silicon substituted organic nitrile compounds.
6. In the method, the chitosan loaded copper film material is used as the catalyst, the whole reaction system is heterogeneous, and the catalyst can be conveniently removed by filtration after the reaction is finished.
7. According to the method, the chitosan loaded copper film material is recycled and subjected to simple post-treatment, can be reused, is subjected to catalytic reaction, and has no obvious activity loss. The recycling experimental data are shown below. Taking I-1 as a raw material to generate a product II-1 as an example, after the reaction is finished, recovering a chitosan loaded copper film material through filtration, carrying out post-treatment on the chitosan loaded copper film material for the next round of reaction, and repeating the steps for five times to obtain the target products with yields of 94%, 92%, 89%, 90% and 91%, respectively, so that the catalytic material is proved to be recyclable.
Detailed Description
The present invention is described in further detail below with reference to specific examples so as to be understood by those skilled in the art.
Example 1
The preparation method of the organic nitrile compound II-1 comprises the following steps:
1) adding 5mg of chitosan loaded copper film material (CP @ Cu NPs) into a 2.5mL reaction tube, adding 2.0mL of water, and stirring at room temperature for 10 minutes to obtain a mixed solution;
2) to the mixture was added the α, β -unsaturated carbonyl compound I-1(25.8mg,0.2mmol) and (dimethylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin) (62.9mg,0.24 mmol); stirring and reacting for 5 hours at room temperature;
3) after the reaction is finished, filtering the whole reaction system, washing with 5mL of tetrahydrofuran and 5mL of acetone in sequence, and recovering the chitosan loaded copper film material;
4) concentrating the filtrate by rotary evaporation, carrying out column chromatography on the residue by using a 6:1 ethyl acetate/petroleum ether mixed solvent, and separating and purifying to obtain 47.8mg of the organic nitrile compound II-1 with the yield of 90%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (organic nitrile compound II-1) are shown as follows:
1H NMR(600MHz)；δ＝0.26(s,6H),2.58-2.64(m,3H),6.93(d,J＝7.0Hz,2H),7.15-7.17(m,1H),7.23-7.26(m,2H),7.35-7.40(m,5H).
13C NMR(150MHz)；δ＝-5.6,-4.1,18.8,33.0,119.6,126.0,127.4,128.0,128.5,129.8,134.0,135.1,139.6。
example 2
The preparation method of the organic nitrile compound II-2 comprises the following steps:
1) adding 8mg of chitosan loaded copper film material (CP @ Cu NPs) into a 2.5mL reaction tube, adding 2.0mL of water, and stirring at room temperature for 10 minutes to obtain a mixed solution;
2) to the mixture was added the α, β -unsaturated carbonyl compound I-2(31.8mg,0.2mmol) and (dimethylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin) (62.9mg,0.24 mmol); stirring and reacting for 8 hours at room temperature;
3) after the reaction is finished, filtering the whole reaction system, washing with 5mL of tetrahydrofuran and 5mL of acetone in sequence, and recovering the chitosan loaded copper film material;
4) concentrating the filtrate by rotary evaporation, carrying out column chromatography on the residue by using a 9:1 ethyl acetate/petroleum ether mixed solvent, and separating and purifying to obtain 50.2mg of the organic nitrile compound II-2 with the yield of 85%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (organic nitrile compound II-2) are shown as follows:
1H NMR(600MHz)；δ＝0.25(d,J＝2.7Hz,6H),2.50-2.60(m,3H),3.77(s,3H),6.78-6.86(m,4H),7.34-7.39(m,5H)；
13C NMR(150MHz)；δ＝-5.5,-4.0,19.2,32.0,55.2,114.0,119.7,128.0,128.4,129.8,131.6,134.0,135.4,157.8。
example 3
The preparation method of the organic nitrile compound II-3 comprises the following steps:
1) adding 12mg of chitosan loaded copper film material (CP @ Cu NPs) into a 2.5mL reaction tube, adding 2.0mL of water, and stirring at room temperature for 10 minutes to obtain a mixed solution;
2) to the mixture was added the α, β -unsaturated carbonyl compound I-3(29.4mg,0.2mmol) and (dimethylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin) (104.9mg,0.4 mmol); stirring and reacting for 10 hours at room temperature;
3) after the reaction is finished, filtering the whole reaction system, washing with 5mL of tetrahydrofuran and 5mL of acetone in sequence, and recovering the chitosan loaded copper film material;
4) concentrating the filtrate by rotary evaporation, carrying out column chromatography on the residue by using a 9:1 ethyl acetate/petroleum ether mixed solvent, and separating and purifying to obtain 51.0mg of the organic nitrile compound II-3 with the yield of 90%. The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (organic nitrile compound II-3) are shown as follows:
1H NMR(600MHz)；δ＝0.27(d,J＝3.4Hz,6H),2.56-2.63(m,3H),6.87-6.96(m,4H),7.35-7.40(m,5H)；
13C NMR(150MHz)；δ＝-5.5,-4.2,19.1,32.3,115.4(d),119.4,128.1,128.7(d),130.0,134.0,134.8,135.3,162.1。
example 4
The preparation method of the organic nitrile compound II-4 comprises the following steps:
1) adding 16mg of chitosan loaded copper film material (CP @ Cu NPs) into a 2.5mL reaction tube, adding 2.0mL of water, and stirring at room temperature for 10 minutes to obtain a mixed solution;
2) to the mixture was added α, β -unsaturated carbonyl compound I-4(23.8mg,0.2mmol) and (dimethylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin) (62.9mg,0.24 mmol); stirring and reacting for 10 hours at room temperature;
3) after the reaction is finished, filtering the whole reaction system, washing with 5mL of tetrahydrofuran and 5mL of acetone in sequence, and recovering the chitosan loaded copper film material;
4) concentrating the filtrate by rotary evaporation, carrying out column chromatography on the residue by using a 6:1 ethyl acetate/petroleum ether mixed solvent, separating and purifying to obtain 48.5mg of the organic nitrile compound II-4, wherein the yield is 95%. The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (organic nitrile compound II-4) are shown as follows:
1H NMR(600MHz)；δ＝0.27(s,3H),0.28(s,3H),3.23(dd,J＝3.7,13.3Hz,1H),4.47(dd,J＝3.9,13.7Hz,1H),4.80(t,J＝13.5Hz,1H),6.95(d,J＝7.2Hz,2H),7.12-7.15(m,1H),7.20-7.24(m,2H),7.35-7.43(m,5H)；
13C NMR(150MHz)；δ＝-5.5,-4.0,36.1,76.8,126.1,127.3,128.2,128.6,130.0,133.9,134.8,137.5。
example 5
The preparation method of the organic nitrile compound II-5 comprises the following steps:
1) adding 5mg of chitosan loaded copper film material (CP @ Cu NPs) into a 2.5mL reaction tube, adding 2.0mL of water, and stirring at room temperature for 10 minutes to obtain a mixed solution;
2) to the mixture was added the α, β -unsaturated carbonyl compound I-5(13.4mg,0.2mmol) and (dimethylsilyl) boronic acid pinacol ester Ph2MeSi-B (pin) (62.9mg,0.24 mmol); stirring and reacting for 7 hours at room temperature;
3) after the reaction is finished, filtering the whole reaction system, washing with 5mL of tetrahydrofuran and 5mL of acetone in sequence, and recovering the chitosan loaded copper film material;
4) concentrating the filtrate by rotary evaporation, carrying out column chromatography on the residue by using a 9:1 ethyl acetate/petroleum ether mixed solvent, and separating and purifying to obtain the organic nitrile compound II-5 with 36.2mg and 89% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (organic nitrile compound II-5) are shown as follows:
1H NMR(600MHz)；δ＝0.26(s,3H),0.27(s,3H),2.27(s,3H),3.18(dd,J＝3.8,13.4Hz,1H),4.44-4.47(m,1H),4.76(t,J＝13.4Hz,1H),6.84(d,J＝8.0Hz,2H),7.02(d,J＝7.7Hz,2H),7.36-7.41(m,5H)；
13C NMR(150MHz)；δ＝-5.5,-3.9,20.9,35.6,77.1,127.2,128.2,129.3,130.0,133.9,134.3,135.1,135.6。
other parts not described in detail are prior art. Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
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| CN115634718B (en) * | 2022-08-17 | 2024-02-06 | 湖北工程学院 | Preparation method and application of graphene oxide/chitosan/polyvinyl alcohol composite microspheres immobilized copper catalyst |
| CN116804026A (en) * | 2023-06-20 | 2023-09-26 | 湖北工程学院 | A method for catalytically preparing β-silyl azaarene compounds using chitosan Schiff base copper-based functional materials |
| CN116804026B (en) * | 2023-06-20 | 2025-02-11 | 湖北工程学院 | Method for preparing β-silyl azoaromatic compounds by catalysis of chitosan Schiff base copper-based functional materials |
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