CN112321628B - Preparation method of beta-dimethylphenyl silicon substituted organic nitrile compound - Google Patents
Preparation method of beta-dimethylphenyl silicon substituted organic nitrile compound Download PDFInfo
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of beta-dimethylphenyl silicon substituted organic nitrile compound, which comprises the steps of firstly adding water into a chitosan loaded copper film material, and uniformly stirring at room temperature to obtain a mixed solution; adding alpha, beta-unsaturated carbonyl compound I and (dimethylbenzene silane group) boric acid pinacol ester into the mixed solution, and stirring at room temperature until the reaction is complete; after the reaction is finished, filtering, respectively washing precipitates obtained by filtering with tetrahydrofuran and acetone to obtain filtrate, and recycling the chitosan loaded copper film material; the filtrate is concentrated by rotary evaporation, and the residue is subjected to flash column chromatography by using ethyl acetate/petroleum ether mixed solvents with different proportions, and the organic nitrile compound II is obtained by separation and purification. The catalytic activity of the membrane material in the method is very high, and the higher conversion rate of the reactant can be realized only by using lower catalyst dosage.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of beta-dimethylphenyl silicon substituted organic nitrile compounds.
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 high molecular synthesis. Because of its special properties, it is widely used in the fields of synthetic chemistry, materials and pharmaceutical chemistry, especially in the advanced fields of national defense advanced science and technology, aerospace special materials and the like. Some nitriles can even be used directly as pesticides, fragrances, metal corrosion inhibitors or liquid crystal materials, etc. The organic nitrile compounds can undergo a variety of chemical transformations, such as conversion to carboxylic acids, aldehydes, ketones, esters, amides, amines, tetrazoles, and other nitrogen heterocyclic compounds. There are many synthetic methods of organic nitriles, of which the Rosenmund-von Braun reaction is the most traditional method, but requires the use of a certain amount of highly toxic CuCN, which can cause environmental pollution; this disadvantage can be overcome by methods employing transition metal catalysis and a safe source of cyanide. However, many nitrile compound production processes cannot avoid the use of toxic, precious metals, and are harshThe reaction conditions, the production of large amounts of contaminants, have prevented its more widespread use in organic synthesis. In the synthesis research of beta-silicon substituted nitrile compound, a cross coupling mode is adopted to construct C (sp 3 ) Si bonds are an important class of methods and pathways. In recent years, pinacol esters Ph have been used as (dimethylbenzene silyl) borates 2 The preparation of organic nitriles by addition reaction of MeSi-B (pin) to α, β -unsaturated nitriles is becoming a growing field of research.
At present, noble metals are usually required to be used as catalysts in the literature, such as Pd, rh and the like, and the method has high cost and large pollution and is not suitable for practical application. In the case of inexpensive metals, copper salts are generally used as catalysts in the literature report, but the addition of ligands or strong bases (sodium tert-butoxide, etc.) is required, and the operation requirements are severe, such as low temperature and anhydrous and anaerobic operation, which greatly limit the large number of applications of such methods in practical production.
In 2008, document (Angewandte Chemie International Edition 2008,47,3818) reported in [ Rh (cod) 2 ]OTf is used as a catalyst, R- (+) -1,1 '-binaphthyl-2, 2' -diphenylphosphine is used as a ligand, and 1,4-dioxane/H is used as a catalyst 2 O (10:1) as solvent, adding alkali Et 3 N, reacting at 50 ℃ to realize the pinacol ester Me of (dimethylbenzenyl) boric acid for the first time 2 And performing beta-silicon addition reaction on the cyano-substituted alkenyl compound by PhSi-Bpin to obtain the beta-dimethylphenyl silicon-substituted organic nitrile compound. However, the method uses 5mol% of noble metal catalyst and 10mol% of toxic ligand, and the whole reaction system is a homogeneous catalysis system, so that the product is difficult to separate, and the residual metal, ligand and solvent can cause pollution to the product and the environment. In 2010, document (Journal of the American Chemical Society 2010,132,2898) reported that pinacol (dimethylbenzyl) borate Me was achieved using 1mol% CuCl as catalyst, adding 2.2mol% NaOt-Bu base at-78℃without the presence of a proton source 2 The beta-silicon addition reaction of PhSi-Bpin on cyano-substituted alkenyl compound can obtain beta-dimethylphenyl silicon-substituted organic nitrile compound, and has enantioselectivity. The method comprisesThe method uses metal monovalent copper salt, does not need proton source, but needs strong alkali and NHC ligand with high price, and has complex post-treatment and is not friendly to environment. In 2015, document (Journal of the American Chemical Society 2015,137,15422) reported the use of Cu (acac) 2 With a specially prepared chiral bipyridine ligand, by H 2 O is solvent, and under the condition of room temperature, the beta-silicon substituted organic nitrile compound is prepared by catalysis. The method is the simplest way for preparing the beta-dimethylphenyl silicon substituted organic nitrile compound at present, but the ligand is complex to prepare, does not realize commercialization, limits the reaction cost and is not beneficial to actual production.
Therefore, the development of a new method for substituting the organic nitrile compound with beta-dimethylphenyl silicon, which is simple and easy to operate, mild in condition, low in cost, environment-friendly and suitable for mass production, is very urgent.
Disclosure of Invention
The invention aims to provide a preparation method of beta-dimethylphenyl silicon substituted organic nitrile compound, which aims to overcome the following defects in the prior art to at least a certain extent:
1) When noble metal is used as a catalyst for synthesizing beta-dimethylphenyl silicon to replace organic nitrile compounds 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, and severe conditions such as strong alkali (sodium tert-butoxide and the like), low temperature, strict anhydrous and the like are required, so that the production cost is high;
3) When bivalent copper is used as a catalyst, special chiral bipyridine ligand needs to be added, and the ligand is complex to prepare, high in cost and cannot be commercialized.
Therefore, the invention aims to develop an environment-friendly novel method for efficiently preparing the beta-dimethylphenyl silicon substituted organic nitrile compound by using a low-cost chitosan loaded copper film material without adding any ligand.
In order to achieve the above object, the present invention adopts the following technical measures:
a method for preparing beta-dimethylphenyl silicon substituted organic nitrile compounds by catalysis of a chitosan-supported copper film material comprises the following steps:
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 uniformly stirring at room temperature to obtain a mixed solution;
2) Adding cyano-substituted alkenyl compound I and pinacol (dimethylbenzenyl) borate Ph to the mixture 2 MeSi-B (pin) is stirred at room temperature until the reaction is complete; wherein cyano-substituted alkenyl compound I is reacted with pinacol ester of (dimethylbenzylboronic acid Ph 2 The ratio of the amounts of the substances of MeSi-B (pin) is 1:1.2-2.0; and the dosage of the chitosan loaded copper film material is 25-80mg per millimole (mmol) of cyano-substituted alkenyl compound I;
3) After the reaction is finished, filtering, respectively washing precipitates obtained by filtering with tetrahydrofuran and acetone to obtain filtrate, and recycling the chitosan loaded copper film material;
4) The filtrate is concentrated by rotary evaporation, and the residue is subjected to flash column chromatography by ethyl acetate/petroleum ether mixed solvent with different proportions, and organic nitrile compound II is obtained by separation and purification (the proportion of the ethyl acetate/petroleum ether mixed solvent is selected according to different polarities of products, and silica gel is adopted as a stationary phase for flash column chromatography).
Further, R is any one of phenyl, p-fluorophenyl and thiophene;
still further, in said step 2), cyano-substituted alkenyl compound I is reacted with pinacol (dimethylbenzylborate) Ph 2 The ratio of the amounts of the substances of MeSi-B (pin) is 1:1.2-1.6; and the dosage of the chitosan loaded copper film material is 30-70 mg per millimole (mmol) of cyano-substituted alkenyl compound I.
Still further, in the step 2), the reaction time is stirred for 5 to 10 hours.
And 3) washing the recovered chitosan loaded copper film material by distilled water, and drying the material in an oven at 120 ℃ for 5 hours, namely, reusing the material in the preparation step of the organic nitrile compound.
The technical conception of the invention is as follows:
the method of the invention takes Chitosan/polyvinyl alcohol loaded nano copper composite membrane (Chitosan/Polyvinyl Alcohol Support Nano Copper, CP@Cu NPs) as a catalyst, and the preparation method of the Chitosan/polyvinyl alcohol loaded nano copper composite membrane catalytic material is carried out according to the reported method. (Dimethyldisilyl) boronic acid pinacol ester Ph 2 MeSi-B (pin) (An Naiji chemistry) is used as a reactant, water is used as a solvent, and under the catalysis of a chitosan supported copper film material (CP@Cu NPs), a copper catalytic material and Ph are supported 2 The MeSi-B (pin) is complexed and added with substrates containing different substituents to generate silicon substitution reaction, thus realizing the preparation of the target beta-dimethylphenyl silicon substituted organic nitrile compound. After the reaction is finished, the chitosan-supported copper film material can be simply recovered by filtering by utilizing the advantage that the film material catalyst is easy to separate and recover, the recycling of the catalyst is easy to realize in the follow-up process, the cost is reduced, and the catalyst is more green and economical and is 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 method of the monovalent copper salt catalysis reported in the past, and has completely different reaction mechanisms and processes.
2. The invention does not need to add any toxic ligand, and also realizes the efficient preparation of the beta-dimethylphenyl silicon substituted organic nitrile compound, thereby not only reducing the cost, but also reducing the difficulty of subsequent separation and purification;
3. the catalytic activity of the membrane material in the method is very high, and the higher conversion rate of the reactant can be realized only by using lower catalyst dosage;
4. the method has mild reaction conditions, takes pure water as a solvent, and is simple and easy to operate, and the reaction is carried out at room temperature;
5. the method disclosed by the invention has a wide application range, and can be used for various cyano-substituted alkenyl compounds to successfully prepare the corresponding beta-dimethylphenyl silicon-substituted organic nitrile compounds.
6. In the method, the chitosan loaded copper film material is used as a catalyst, the whole reaction system is heterogeneous, and the catalyst can be conveniently removed by filtration after the reaction is finished.
7. In the method, the chitosan loaded copper film material is recycled and subjected to simple post-treatment, can be reused, and can be subjected to catalytic reaction without 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, filtering and recovering the chitosan loaded copper film material, and carrying out post-treatment for the next round of reaction, wherein the step is repeated five times to obtain the target product with the yield of 94%,92%,89%,90% and 91%, which proves that the catalytic material can be recycled.
Detailed Description
The present invention is described in further detail below in conjunction with specific embodiments for understanding by those skilled in the art.
Example 1
The preparation method of the organic nitrile compound II-1 comprises the following steps:
1) 5mg of chitosan-supported copper film material (CP@Cu NPs) is added into a 2.5mL reaction tube, 2.0mL of water is added, and the mixture is stirred for 10 minutes at room temperature to obtain a mixed solution;
2) To the mixture was added cyano-substituted alkenyl compound I-1 (25.8 mg,0.2 mmol) and pinacol (dimethylbenzylborate Ph) 2 MeSi-B (pin) (62.9 mg,0.24 mmol); stirring and reacting for 5h 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) The filtrate was concentrated by rotary evaporation, and the residue was subjected to column chromatography using a 6:1 ethyl acetate/petroleum ether mixture, and separated and purified to give 47.8mg of organic nitrile compound II-1 in 90% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (the organic nitrile compound II-1) are shown as follows:
1 H 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).
13 C 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) 8mg of chitosan-supported copper film material (CP@Cu NPs) is added into a 2.5mL reaction tube, 2.0mL of water is added, and the mixture is stirred for 10 minutes at room temperature to obtain a mixed solution;
2) To the mixture was added cyano-substituted alkenyl compound I-2 (31.8 mg,0.2 mmol) and pinacol (dimethylbenzylborate) Ph 2 MeSi-B (pin) (62.9 mg,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) The filtrate was concentrated by rotary evaporation, and the residue was subjected to column chromatography using a 9:1 ethyl acetate/petroleum ether mixture, and separated and purified to give organic nitrile compound II-2 in an yield of 50.2mg and 85%.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (the organic nitrile compound II-2) are shown as follows:
1 H 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)；
13 C 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) 12mg of chitosan-supported copper film material (CP@Cu NPs) is added into a 2.5mL reaction tube, 2.0mL of water is added, and the mixture is stirred for 10 minutes at room temperature to obtain a mixed solution;
2) To the mixture was added cyano-substituted alkenyl compound I-3 (29.4 mg,0.2 mmol) and pinacol (dimethylbenzylborate Ph) 2 MeSi-B (pin) (104.9 mg,0.4 mmol); stirring and reacting for 10h 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) The filtrate is concentrated by rotary evaporation, and the residue is subjected to column chromatography by a 9:1 ethyl acetate/petroleum ether mixed solvent, and the organic nitrile compound II-3 is obtained by separation and purification, so as to obtain 51.0mg with the yield of 90%. The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (the organic nitrile compound II-3) are shown as follows:
1 H 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)；
13 C 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) 16mg of chitosan-supported copper film material (CP@Cu NPs) is added into a 2.5mL reaction tube, 2.0mL of water is added, and the mixture is stirred for 10 minutes at room temperature to obtain a mixed solution;
2) To the mixture was added cyano-substituted alkenyl compound I-4 (23.8 mg,0.2 mmol) and pinacol (dimethylbenzylborate Ph) 2 MeSi-B (pin) (62.9 mg,0.24 mmol); stirring and reacting for 10h 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) The filtrate was concentrated by rotary evaporation, and the residue was subjected to column chromatography using a 6:1 ethyl acetate/petroleum ether mixture, and separated and purified to give 48.5mg of organic nitrile compound II-4 in 95% yield. The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (the organic nitrile compound II-4) are shown as follows:
1 H 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)；
13 C 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) 5mg of chitosan-supported copper film material (CP@Cu NPs) is added into a 2.5mL reaction tube, 2.0mL of water is added, and the mixture is stirred for 10 minutes at room temperature to obtain a mixed solution;
2) To the mixture was added cyano-substituted alkenyl compound I-5 (13.4 mg,0.2 mmol) and pinacol (dimethylbenzylborate) Ph 2 MeSi-B (pin) (62.9 mg,0.24 mmol); stirring and reacting for 7h 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) The filtrate was concentrated by rotary evaporation, and the residue was subjected to column chromatography using a 9:1 ethyl acetate/petroleum ether mixture, and separated and purified to give organic nitrile compound II-5 in a yield of 89% and 36.2 mg.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (the organic nitrile compound II-5) are shown as follows:
1 H 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)；
13 C 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 foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (5)
1. A method for preparing beta-dimethylphenyl silicon substituted organic nitrile compounds by catalyzing chitosan loaded copper film material is characterized by comprising the following steps: the synthesis is 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 the chitosan loaded copper film material, and uniformly stirring at room temperature to obtain a mixed solution; the chitosan loaded copper film material is prepared by the following steps:
200mg of chitosan powder is added into 10mL of acetic acid solution and stirred for 5 hours at room temperature, 100mg of polyvinyl alcohol is added into 10mL of distilled water and stirred at 80 ℃ until the polyvinyl alcohol is completely dissolved; mixing and stirring chitosan solution and polyvinyl alcohol solution for half an hour at room temperature until uniformity,then 80 mu L of glutaraldehyde solution with the mass fraction of 25w/w% is added dropwise while stirring, and then the mixed solution is poured into a culture dish and dried in an oven at 40 ℃ for 24 hours until the water is completely evaporated; peeling the chitosan/polyvinyl alcohol film from the culture dish, soaking in 100mL of 0.1mol/L sodium hydroxide solution for 5 minutes, washing with distilled water for several times until the pH test paper is neutral, and drying the CP film in a 40 ℃ oven for 24 hours; immersing CP film in 25mL of 0.2mol/L CuCl 2 ·2H 2 O solution for 2.5h, then collecting and adsorbing Cu 2+ Cp@cu of ion 2+ Drying the film in a baking oven at 40 ℃ for 24 hours; CP@Cu 2+ Soaking the membrane in a freshly prepared 100mL 50mmol/L sodium borohydride solution for 15 minutes, taking out the membrane, washing the membrane with distilled water for several times, and continuously putting the membrane into a 40 ℃ oven for drying for 24 hours to obtain a CP membrane loaded with copper nano particles, namely a chitosan loaded copper membrane material CP@Cu NPs;
2) Adding cyano-substituted alkenyl compound I and pinacol (dimethylbenzenyl) borate Ph to the mixture 2 MeSi-B (pin) is stirred at room temperature until the reaction is complete; wherein cyano-substituted alkenyl compound I is reacted with pinacol ester of (dimethylbenzylboronic acid Ph 2 The ratio of the amounts of the substances of MeSi-B (pin) is 1:1.2-2.0; and the dosage of the chitosan loaded copper film material is 25-80mg per millimole of cyano substituted alkenyl compound I;
3) After the reaction is finished, filtering, respectively washing precipitates obtained by filtering with tetrahydrofuran and acetone to obtain filtrate, and recycling the chitosan loaded copper film material;
4) The filtrate is concentrated by rotary evaporation, and the residue is subjected to flash column chromatography by using ethyl acetate/petroleum ether mixed solvents with different proportions, and the organic nitrile compound II is obtained by separation and purification.
2. The method for preparing the beta-dimethylphenyl silicon substituted organic nitrile compound by catalyzing the chitosan-supported copper film material according to claim 1, which is characterized in that: and R is any one of phenyl, p-fluorophenyl and thiophene.
3. The chitosan according to claim 1The method for preparing the beta-dimethylphenyl silicon substituted organic nitrile compound by catalyzing the copper-loaded film material is characterized by comprising the following steps of: in said step 2), cyano-substituted alkenyl compound I is reacted with pinacol (dimethylbenzylsilyl) borate Ph 2 The ratio of the amounts of the substances of MeSi-B (pin) is 1:1.2-1.6; and the dosage of the chitosan loaded copper film material is 30-70 mg per millimole of cyano substituted alkenyl compound I.
4. The method for preparing the beta-dimethylphenyl silicon substituted organic nitrile compound by catalyzing the chitosan-supported copper film material according to claim 1, which is characterized in that: in the step 2), the reaction time is 5-10h.
5. The method for preparing the beta-dimethylphenyl silicon substituted organic nitrile compound by catalyzing the chitosan-supported copper film material according to claim 1, which is characterized in that: and 3) washing the recovered chitosan loaded copper film material by distilled water, and drying the material in an oven at 120 ℃ for 5 hours, namely, reusing the material in the preparation step of the organic nitrile compound.
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| CN106892935A (en) * | 2016-04-27 | 2017-06-27 | 湖北工程学院 | A kind of immobilized copper catalysis of shitosan prepare method and the application of organoboron compound |
| CN107163073A (en) * | 2017-06-08 | 2017-09-15 | 湖北工程学院 | A kind of method that divalence copper catalysis prepares organo-silicon compound and β hydroxy compounds |
| CN109096318A (en) * | 2018-08-14 | 2018-12-28 | 湖北工程学院 | The method that load copper ion Y type molecular sieve catalysis prepares organoboron compound and beta-hydroxy compound |
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