CN101113138A - Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex - Google Patents
Method for synthesizing aryl radical nitrile derivant under catalysis of cyclopalladated ferrocenylimines complex Download PDFInfo
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Abstract
The invention pertains to the synthesizing technology field of organic intermediate, relating to a synthesizing method of derivative of aryl nitrie by the catalysis of cyclopalladated ferrocenylimine complex; the preparation steps are that: catalyst, potassium ferrocyanide and alkali are dissolved into an organic solvent, then halonitroaromatic compound is added to be reacted in the protection of nitrogen, and is cooled down to room temperature after the reaction is completed, the product can be acquired after the mixture being washed with water, extracted, dried, concentrated and purified. The reaction uses the universal catalyst, wherein Y is H or CH3; Z is H, CH3, OCH3 or OC2H5. The invention has the advantages of mild reaction conditions, universal material scope, good reaction specificity, high yielding and free of environmental pollution.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic intermediates, and relates to a synthesis method of aromatic nitriles and derivatives thereof with various substituents.
Background
The substituted aromatic nitrile and the derivative thereof are important intermediates of medicines, pesticides, dyes, chemical engineering and the like, can be used for synthesizing arylamine, amide, carboxylic acid, carboxylic ester, imidazole and the like through the change of nitrile groups, and have wide application fields. At present, the substituted aromatic nitrile is catalyzed by KCN, NaCN, CuCN or Zn (CN)2The method is synthesized from nitrile source, however, KCN and NaCN are extremely toxic, and potential environmental pollution exists; CuCN and Zn (CN)2Equivalent transition metal waste and the like can be caused; now with K4[Fe(CN)6]For the synthesis of nitrile sources, ligand-assisted chelation must be used in addition to the need for catalysts, which requires the use of special and expensive bisphosphine ligands; and Pd (OAc)2The reaction substrate is very limited for the synthesis method of the catalyst, and only brominated aromatic compounds are generally selected.
Disclosure of Invention
The invention aims to provide a method for preparing aryl nitrile derivatives by using ferrocenylimine cyclopalladated complex as a catalyst, which has the advantages of mild reaction conditions, wide raw material range, strong reaction specificity, high yield and no pollution to the environment.
The invention adopts the following technical scheme to realize the purpose: the synthesis method of aryl nitrile derivatives under catalysis of the ferrocenylimine cyclopalladated complex comprises the following preparation steps: dissolving a catalyst, potassium ferrocyanide and alkali in an organic solvent, adding a halogenated aromatic compound, heating for reaction under the protection of nitrogen, cooling to room temperature after the reaction is finished, washing with water, extracting, drying, concentrating and purifying to obtain the product, wherein the catalyst of the following general formula is used for the reaction:
The halogenated aromatic compound is a compound of the following general formula: Aryl-X
Wherein X is Cl, Br or I; r is H, CH3、CH3CO、CH3O、(CH3)2N or NO2。
The reaction is preferably a catalyst of the general formula:
The above reaction is preferably a halogenated aromatic compound of the following general formula:
wherein R is H, CH3、CH3CO、CH3O、(CH3)2N or NO2。
The amount of the catalyst accounts for 0.1 to 5 percent of the mole percentage of the halogenated aromatic compound.
The molar ratio of the halogenated aromatic compound to the alkali is 1: 0.5-5, the molar ratio of the halogenated aromatic compound to the potassium ferrocyanide is 1: 0.2-2, and the alkali is sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate, potassium acetate, sodium hydroxide or potassium hydroxide.
The organic solvent is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidinone, and the amount of the organic solvent is 0.5 to 5ml per millimole of the halogenated aromatic compound.
The catalyst ferrocene acetyl substituted phenylimine cyclopalladated derivative used in the invention is synthesized by the following method: 1 mol of PdCl2And dissolving 2 moles of LiCl in methanol, stirring for 24 hours at room temperature to obtain a uniform solution, then adding the uniform solution into a methanol solution containing 1 mole of NaOAc and 1 mole of ferrocene acetyl substituted benzimine derivative, stirring for 24 hours at room temperature, filtering to obtain a red solid, washing with methanol, and drying to obtain the catalyst ferrocene acetyl substituted benzimine cyclopalladated derivative.
The invention takes ferrocenylimine cyclopalladated complex as a catalyst, takes nontoxic and environment-friendly potassium ferrocyanide as a nitrile source, and takes halogenated aromatic hydrocarbon and halogenated heterocyclic compounds as raw materials to synthesize the corresponding nitrile compound with high yield. Has the advantages of mild reaction conditions, wide raw material range, strong reaction specificity, high yield, small influence on the environment and the like.
Detailed Description
The invention takes halogenated aromatic hydrocarbon and potassium ferrocyanide as raw materials, and synthesizes substituted aromatic nitrile in one step under the condition that acetyl ferrocene-p-toluidine palladium complex is used as a catalyst. It includes dissolving catalyst in N, N-dimethyl formamide or N, N-dimethyl acetamide and other organic solvent, adding sodium carbonate, potassium carbonate and other alkali, adding halogenated aromatic compound, and reaction at 100-150 deg.c under the protection of nitrogen for 1-20 hr. After the reaction is finished, cooling to room temperature, diluting with solvents such as dichloromethane, ethyl acetate and the like, washing with water, extracting, drying, concentrating and purifying to obtain the product. The general formula of the reaction is:
the invention is further described below with reference to the following examples:
example 1, synthesis of benzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, the reaction tube was replaced with nitrogen 4 times, 1mmol (105. mu.l) of bromobenzene was added by a syringe under a slight positive pressure nitrogen blanket, and then heated to 120 ℃ with magnetic stirring in an oil bath for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. 96mg of pure benzonitrile (>98% purity, colorless liquid) are obtained. The isolation yield was 93%. The nmr data for this compound are as follows:1H NMRδ＝7.48(m，2H，2CH)，7.59(m，1H，1CH)，7.54(M，2H，2CH)13C NMRδ＝112.3，118.5，129.1，132.1，132.7
example 2, synthesis of p-methylbenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 0.5mmol (83mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, placed under nitrogenThe reaction tube is changed for 4 times, 1mmol of p-methyl bromobenzene is addedby a syringe under the protection of micro-positive pressure nitrogen, and then the mixture is heated to 120 ℃ by an oil bath under the magnetic stirring for reaction for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product p-methyl benzonitrile 96mg (purity) is obtained>98%, colorless liquid). The isolated yield was 82%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝2.43(s，3H，1CH3)，7.27(d，2H，2CH，J＝7.9)，7.54(d，2H，2CH，J＝8.1)13C NMRδ＝21.9，109.3，119.2，129.8，132.1，143.7.
Example 3 synthesis of 2-methylbenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 5mmol (530mg) of sodium carbonate and 5ml of N, N-dimethylacetamide solvent, the reaction tube was replaced with nitrogen 4 times, 1mmol of 2-methylbromobenzene was added by a syringe under the protection of nitrogen at slight positive pressure, and then heated to 120 ℃ with magnetic stirring in an oil bath for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. 111mg of pure 2-methylbenzonitrile (purity>98%, colorless liquid) are obtained. The isolated yield was 95%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝2.55(s，3H，1CH3)，7.27(t，1H，1CH)，7.32(d，1H，1CH，J＝7.8)，7.48(t，1H，1CH)，7.59(d，1H，1CH，J＝7.7).13CNMRδ＝20.4，112.6，118.1，126.1，130.1，132.4，132.6，141.8.
Example 4 synthesis of 2, 6-dimethylbenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent were used to displace the reaction tube with nitrogen 4 times, 1mmol of 2, 6-dimethylbromobenzene was added thereto, and then the mixture was heated to 120 ℃ with magnetic stirring in an oil bath and reacted for 3 hours. Removing oil bath and water bathCooling to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography.The pure product 2, 6-dimethyl benzonitrile 106mg (purity>98%, colorless liquid) is obtained. The isolated yield was 81%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝2.53(s，6H，2CH3)，7.12(d，2H，2CH，J＝7.7)，7.35(t，2H，2CH)13C NMRδ＝20.8，113.3，117.3，127.3，132.1，142.1.
Example 5 synthesis of 4, 4-methoxybenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 0.5ml of N, N-dimethylacetamide solvent, the reaction tube was replaced with nitrogen 4 times, 1mmol of 4-methoxybromobenzene was added by a syringe under the protection of nitrogen at slight positive pressure, and then heated to 120 ℃ with magnetic stirring in an oil bath for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 4-methoxybenzonitrile 126mg (purity>98%, colourless solid) is obtained. The isolated yield was 95%. The nuclear magnetic mass spectrometry data of this compound are as follows.1H NMRδ＝3.87(s，3H，1CH3)，6.96(d，2H，2CH)，7.60(d，2H，2CH).13C NMRδ＝55.6，103.9，114.7，119.3，134.0，162.8.
Example 6, synthesis of 4- (N, N-dimethylamino) benzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ C)H3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, 1mmol of 4- (N, N-dimethylamino) bromobenzene was added, the reaction tube was replaced with nitrogen gas 4 times, and then heated to 120 ℃ with magnetic stirring in an oil bath for 1 hour. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 4- (N, N-dimethylamino) benzonitrile 141mg (purity>98%, colorless solid) is obtained. Isolated yield 97%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝3.04(s，6H，2CH3)，6.64(d，2H，2CH，J＝8.9)，7.46(d，2H，2CH，J＝8.9)13C NMRδ＝40.0，97.3，111.4，120.8，133.4，152.4
Example 7, synthesis of 2-nitrobenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, 1mmol of 2-nitrobromobenzene was added, the reaction tube was replaced with nitrogen gas 4 times, and then heated to 120 ℃ with magnetic stirring in an oil bath for 8 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1as developing agent by silica gel thin layer chromatography. The pure product 2-nitrobenzonitrile 127mg (purity>98%, colorless solid) was obtained. The isolated yield was 86%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.85(m，2H，2CH)，7.95(m，1H，2CH)，9.36(m，1H，2CH)13C NMRδ＝108.0，115.0，125.6，133.8，134.4，135.6，148.5.
Example 8, synthesis of 4-nitrobenzonitrile: under inert gasTo a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of a high purity nitrogen gas4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent were introduced into a reaction tube and the reaction tube was replaced with nitrogen 4 times, and 1mmol of 4-nitrobromobenzene was added thereto. Then heated to 120 ℃ with magnetic stirring with an oil bath and reacted for 8 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 4-nitrobenzonitrile 96mg (purity>98%, colorless solid) is obtained. The isolated yield was 65%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.90(d，2H，2CH，J＝8.7)，8.37(d，2H，2CH，J＝8.7)13C NMRδ＝116.8，118.3，124.3，133.5，150.0.
Example 9 synthesis of 4, 4-acetylbenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.05mmol (46mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, the reaction tube is replaced by nitrogen for 4 times, 1mmol of 4-acetylbromobenzene is added by a syringe under the protection of nitrogen at slight positive pressure, and then the mixture is heated to 120 ℃ by an oil bath under magnetic stirring for reaction for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; adding 3mlAnd extracted three times with 3ml of dichloromethane, the organic phases are combined and over anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 4-acetylbenzonitrile 126mg (purity>98%, colorless solid) is obtained. The isolated yield was 87%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝2.66(s，3H，1CH3)，7.78(d，2H，2CH，J＝8.8)，8.05(d，2H，2CH，J＝8.8).13C NMRδ＝26.8，116.4，118.0，128.7，132.5，139.9，196.6
Example 10 synthesis of 1, 4-dicyanobenzene: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 2mmol (845mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, 1mmol of 1, 4-dibromobenzene was added, the reaction tube was replaced with nitrogen gas 4 times, and then heated to 120 ℃ with an oil bath under magnetic stirring to react for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 1, 4-dinitrile benzene 124mg (purity>98%, colorless solid) is obtained. Isolated yield 97%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.804(s，4H，4CH)13C NMRδ＝116.7，117.0，132.8.
Example 11, synthesis of 1, 4-dicyanobenzene: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.001mmol (0.9mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, 1mmol of 4-cyanoborobenzene was added, the reaction tube was replaced with nitrogen gas 4 times, and then heated to 120 ℃ with magnetic stirring in an oil bath to react for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 1, 4-dinitrile benzene 122mg (purity>98%, colorless solid) is obtained. The isolated yield was 95%.The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.804(s，4H，4CH)13C NMRδ＝116.7，117.0，132.8.
Example 12 synthesis of 4, 4-chlorobenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol under protection of an inert gas (e.g., high purity nitrogen)(93mg)K4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, 1mmol of 4-chlorobromobenzene was added, the reaction tube was replaced with nitrogen gas 4 times, and then heated to 120 ℃ with magnetic stirring in an oil bath for 1 hour. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. The pure product 4-chlorobenzonitrile is obtained in an amount of 96mg (purity>98%, colorless solid). The isolated yield was 70%. The nuclear magnetic data of this compound are as follows.1HNMR δ＝7.47(d，2H，2CH，J＝8.5)，δ＝7.60(d，2H，2CH，J＝8.5)13C NMRδ＝110.8，118.0，129.7，133.4，139.6.
Example 13, 1-nitrilaphthalene synthesis: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, the reaction tube was replaced with nitrogen 4 times,1mmol of 1-bromonaphthalene was added by a syringe under the protection of nitrogen at slight positive pressure, and then heated to 120 ℃ with magnetic stirring in an oil bath to react for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, developing with 10: 1 petroleum ether/ethyl acetate as developer, and silica gel thin layerAnd (4) performing chromatographic separation. The pure product 1-nitrile naphthalene 150mg (purity>98%, colorless solid) is obtained. The isolated yield was 98%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.49(t，1H，1CH)，7.59(t，1H，1CH)，7.88(t，2H，1CH)，8.04(d，1H，1CH，J＝8.0)，8.20(d，1H，1CH，J＝8.4).13CNMRδ＝110.1，117.9，124.9，125.1，127.6，128.6，128.7，132.3，132.6，132.9，133.3
Example 14, 1-Nitrilonaphthalene Synthesis: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝OCH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, the reaction tube was replaced with nitrogen 4 times, 1mmol of 1-bromonaphthalene was added by a syringe under the protection of nitrogen at slight positive pressure, and then heated to 120 ℃ with magnetic stirring in an oil bath to react for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water was added to the reaction mixture,and extracted three times with 3ml of dichloromethane, the organic phases are combined and over anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. 144mg of pure product 1-nitrile naphthalene (purity>98 percent, colorless solid) is obtained. The isolated yield was 92%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.49(t，1H，1CH)，7.59(t，1H，1CH)，7.88(t，2H，1CH)，8.04(d，1H，1CH，J＝8.0)，8.20(d，1H，1CH，J＝8.4).13CNMRδ＝110.1，117.9，124.9，125.1，127.6，128.6，128.7，132.3，132.6，132.9，133.3
Example 15, 1-cyanonaphthalene synthesis: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝OCH2CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, and the reaction was replaced with nitrogenThe tube was placed 4 times, 1mmol of 1-bromonaphthalene was added with a syringe under a slight positive pressure nitrogen blanket, and then heated to 120 ℃ with magnetic stirring in an oil bath for 3 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. 121mg of pure product 1-nitrile naphthalene (purity>98 percent, colorless solid) is obtained. The isolated yield was 78%. The nuclear magnetic data of this compound are as follows.1H NMRδ＝7.49(t，1H，1CH)，7.59(t，1H，1CH)，7.88(t，2H，1CH)，8.04(d，1H，1CH，J＝8.0)，8.20(d，1H，1CH，J＝8.4).13CNMRδ＝110.1，117.9，124.9，125.1，127.6，128.6，128.7，132.3，132.6，132.9，133.3
Example 16, synthesis of 3-cyanopyridine: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide solvent, the reaction tube was replaced with nitrogen 4 times, 1mmol of 3-bromopyridine was added by a syringe under the protection of nitrogen at slight positive pressure, and then heated to 150 ℃ with magnetic stirring in an oil bath for 18 hours. Removing the oil bath, and cooling the water bath to room temperature; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, developing with 10: 1 petroleum ether/ethyl acetate as developer, and silica gel thin layerAnd (4) performing chromatographic separation. 74mg of pure product 3-cyanopyridine (purity>98 percent, colorless solid) is obtained. The isolated yield was 71%. The nuclear magnetic data for this compound are as follows:1H NMRδ＝7.45(m，1H，1CH)，7.98(d，1H，1CH，J＝8.0)，8.83(d，1H，1CH，J＝4.7)，8.91(s，1H，1CH).13C NMRδ＝110.3，116.5，123.7，139.3，152.5，153.0.
example 17, synthesis of benzonitrile: at inertiaTo a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K underprotection of a sex gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 1mmol of potassium phosphate anhydrous and 1ml of N, N-Dimethylformamide (DMF) solvent, the reaction tube was replaced with nitrogen gas 4 times and continuously protected with nitrogen gas under slight positive pressure, 1mmol (114. mu.l) of iodobenzene was added by a syringe, and then heated to 100 ℃ with magnetic stirring in an oil bath for 5 hours. Removing the oil bath, and cooling to room temperature in a water bath; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. 84mg of pure benzonitrile (>98% purity, yellowish liquid) are obtained. The isolation yield was 81%. The nmr data for this compound are as follows:1H NMRδ＝7.47(m，2H，2CH)，7.61(m，1H，1CH)，7.67(m，2H，2CH)。13C NMRδ＝112.5，118.9，129.1，132.2，132.8
example 18 synthesis of 4, 4-methylbenzonitrile: to a 20mL Schlenk reaction tube (a glass instrument commonly used for anhydrous and anaerobic operation) was added 0.22mmol (93mg) of K under protection of an inert gas (e.g., high purity nitrogen)4[Fe(CN)6]3H2O, 0.0025mmol (2.3mg) of catalyst (Y ═ CH)3Z＝CH3) 10mg of triphenylphosphine, 1mmol (106mg) of sodium carbonate and 1ml of N, N-dimethylacetamide as solvent, the reaction tube is replaced with nitrogen 4 times and 1mmol (118. mu.l) of 4-methylchlorobenzene is added by syringe under continuous nitrogen pressure, and the mixture is heated to 140 ℃ with magnetic stirring in an oil bath for 20 hours. Removing the oilbath, and cooling to room temperature in a water bath; 3ml of water are added and the mixture is extracted three times with 3ml of dichloromethane, the organic phases are combined and freed from anhydrous MgSO4Drying for 30 minutes and filtering; concentrating with rotary evaporator, separating the residual liquid with petroleum ether/ethyl acetate 10: 1 as developing agent by silica gel thin layer chromatography. Pure 4-methylbenzonitrile 71mg (purity>98%, yellowish liquid) was obtained. The isolation yield was 61%. Nuclear magnetic analysis data of the compoundThe following were used:1H NMRδ＝2.41(s，3H，1CH3)，7.26(d，2H，2CH，J＝7.9)，7.52(d，2H，2CH，J＝8.1)13C NMRδ＝21.8，109.3，119.2，129.9，132.0，143.7.
Claims (10)
1. the synthesis method of aryl nitrile derivatives under catalysis of the ferrocenylimine cyclopalladated complex comprises the following preparation steps: dissolving a catalyst, potassium ferrocyanide and alkali in an organic solvent, adding a halogenated aromatic compound, heating for reaction under the protection of nitrogen, cooling to room temperature after the reaction is finished, washing with water, extracting, drying, concentrating and purifying, wherein the catalyst of the following general formula is used in the reaction:
2. The method for synthesizing arylnitrile derivatives under catalysis of ferrocenylimine cyclopalladated complex according to claim 1, wherein the halogenated aromatic compound is a compound of the following general formula: Aryl-X
Wherein X is Cl, Br or I; r is H, CH3、CH3CO、CH3O、(CH3)2N or NO2。
3. A process for the synthesis of arylnitrile derivatives catalyzed by cyclopalladated ferrocenylimines according to claim 1 or 2, characterized in that the reaction uses a catalyst of the general formula:
wherein Y is CH3(ii) a Z is CH3、OCH3Or OC2H5。
4. The method for synthesizing arylnitrile derivatives under catalysis of the ferrocenylimine cyclopalladated complex as claimed in claim 1 or 2, wherein the halogenated aromatic compound is a compound of the following general formula: Aryl-Br
Wherein R is H, CH3、CH3CO、CH3O、(CH3)2N or NO2。
5. The method for synthesizing arylnitrile derivatives under catalysis of the ferrocenylimine cyclopalladated complex according to claim 3, wherein the halogenated aromatic compound is a compound of the following general formula: Aryl-Br
Wherein R is H, CH3、CH3CO、CH3O、(CH3)2N or NO2。
6. The method for synthesizing aryl nitrile derivatives under the catalysis of the cyclopalladated ferrocenylimine complex as claimed in claim 4, wherein the amount of the catalyst is 0.1-5% by mole of the halogenated aromatic compound.
7. The method for synthesizing aryl nitrile derivatives under the catalysis of the ferrocenylimine cyclopalladated complex as claimed in claim 5, wherein the amount of the catalyst is 0.1-5% by mole of the halogenated aromatic compound.
8. The method for synthesizing aryl nitrile derivatives under the catalysis of ferrocenylimine cyclopalladated complex as claimed in claim 7, wherein the molar ratio of the halogenated aromatic compound to the base is 1: 0.5-5, the molar ratio of the halogenated aromatic compound to the potassium ferrocyanide is 1: 0.2-2, and the base is sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate, potassium acetate, sodium hydroxide or potassium hydroxide.
9. The method for synthesizing arylnitrile derivatives under catalysis of the cyclopalladated ferrocenylimine complex according to claim 8, wherein the organic solvent is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidinone, and the amount of the organic solvent is 0.5-5ml per millimole of the halogenated aromatic compound.
10. The method for synthesizing arylnitrile derivatives under catalysis of the ferrocenylimine cyclopalladated complex as claimed in claim 9, wherein the reaction temperature is 100 ℃ and 150 ℃, and the reaction time is 1-20 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125875A (en) * | 2011-01-20 | 2011-07-20 | 郑州大学 | Application of cyclopalladated ferrocenylimine-phosphine adduct in synthesis of asymmetric biaryl compound |
| CN105130847A (en) * | 2015-09-10 | 2015-12-09 | 成都大学 | Method for preparing high-purity methylbenzenecarbonitrile and derivatives thereof |
| CN107262151A (en) * | 2017-06-29 | 2017-10-20 | 郑州大学 | Heteroaromatic alcohol ring palladium metal catalyst and its application |
| CN116410109A (en) * | 2022-11-07 | 2023-07-11 | 山东理工大学 | Solvent-free halogenated aromatic hydrocarbon cyanidation reaction method promoted by novel electromagnetic grinding equipment |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125875A (en) * | 2011-01-20 | 2011-07-20 | 郑州大学 | Application of cyclopalladated ferrocenylimine-phosphine adduct in synthesis of asymmetric biaryl compound |
| CN102125875B (en) * | 2011-01-20 | 2012-09-05 | 郑州大学 | Application of cyclopalladated ferrocenylimine-phosphine adduct in synthesis of asymmetric biaryl compound |
| CN105130847A (en) * | 2015-09-10 | 2015-12-09 | 成都大学 | Method for preparing high-purity methylbenzenecarbonitrile and derivatives thereof |
| CN107262151A (en) * | 2017-06-29 | 2017-10-20 | 郑州大学 | Heteroaromatic alcohol ring palladium metal catalyst and its application |
| CN107262151B (en) * | 2017-06-29 | 2020-02-14 | 郑州大学 | Aromatic heterocyclic alcohol ring palladium metal catalyst and application thereof |
| CN116410109A (en) * | 2022-11-07 | 2023-07-11 | 山东理工大学 | Solvent-free halogenated aromatic hydrocarbon cyanidation reaction method promoted by novel electromagnetic grinding equipment |
| CN116410109B (en) * | 2022-11-07 | 2024-06-07 | 山东理工大学 | Solvent-free halogenated aromatic hydrocarbon cyanidation reaction method promoted by novel electromagnetic grinding equipment |
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