CN101113138B - 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 ferrocenyliminecomplex; 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 ofnitrogen, 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 synthesis technical field of organic intermediate, relate to synthetic method with various substituent fragrant nitriles and derivative thereof.
Background technology
Substituted aroma nitrile and derivative thereof are the important intermediate of medicine, agricultural chemicals, dyestuff, chemical industry etc., variation synthesizing aryl amine, acid amides, carboxylic acid and carboxylicesters that can be by itrile group, imidazoles etc., and Application Areas is very extensive.At present, the substituted aroma nitrile many under catalysis with KCN, NaCN, CuCN or Zn (CN)
2For the nitrile source synthetic, yet KCN and NaCN severe toxicity exist the potential environmental pollution; CuCN and Zn (CN)
2Can cause the transition metal waste of equivalent etc.; Now with K
4[Fe (CN)
6] be the synthetic method in nitrile source, except the needs catalyzer, also must use the auxiliary chelating of part, this synthetic method need be with special and expensive biphosphine ligand; And with Pd (OAc)
2Be the synthetic method of catalyzer, reaction substrate has great limitation, generally only selects the aromatic compound of bromo for use.
Summary of the invention
The purpose of this invention is to provide a kind of reaction conditions gentleness, raw material range extensively, the reaction specificity is strong, productive rate is high, environmentally safe utilize the method for ferrocenyl cycloimine palladium palladium complex for Preparation of Catalyst aromatic nitrile derivative.
The present invention realizes above-mentioned purpose by the following technical solutions: the synthetic method of aromatic nitrile derivative under the ferrocenyl cycloimine palladium palladium complex catalyst; its preparation process is as follows: with catalyzer, yellow prussiate of potash, alkali dissolution in organic solvent; add halogenated aromatic compound again, reacting by heating under protection of nitrogen gas, reaction finishes and drops to room temperature; water washing; extraction, drying concentrates; purifying promptly gets product, and the catalyzer of following general formula is used in reaction:
Described halogenated aromatic compound is the compound of following general formula: Aryl-X
Wherein X is Cl, Br or I; R is H, CH
3, CH
3CO, CH
3O, (CH
3)
2N or NO
2
The catalyzer of the preferred following general formula of above-mentioned reaction:
The halogenated aromatic compound of the preferred following general formula of above-mentioned reaction:
Aryl-Br
Wherein R is H, CH
3, CH
3CO, CH
3O, (CH
3)
2N or NO
2
The molecular fraction that described catalyst levels accounts for halogenated aromatic compound is 0.1%-5%.
The mol ratio of halogenated aromatic compound and alkali is 1: 0.5-5, the mol ratio of halogenated aromatic compound and yellow prussiate of potash is 1: 0.2-2, described alkali are yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium-acetate, Potassium ethanoate, sodium hydroxide or potassium hydroxide.
Described organic solvent is N, and dinethylformamide, N,N-dimethylacetamide or N-methylpyrroline ketone, the consumption of organic solvent are that the halogenated aromatic compound of every mmole uses the 0.5-5ml solvent.
Catalyzer ferrocene acetyl substituted benzene imide ring palladium derivative used in the present invention is synthetic by the following method: with 1 mole PdCl
2Be dissolved in the methyl alcohol with 2 moles LiCl, stir under the room temperature and became homogeneous solution in 24 hours, then its adding is contained in the methanol solution of 1 mole of NaOAc and 1 mole of ferrocene acetyl substituted benzene imine derivative, stirred 24 hours under the room temperature, filtration obtains red solid, methanol wash, oven dry promptly gets catalyzer ferrocene acetyl substituted benzene imide ring palladium derivative.
The present invention is a catalyzer with the ferrocenyl cycloimine palladium palladium complex, yellow prussiate of potash with asepsis environment-protecting is the nitrile source, by halogenated aryl hydrocarbon, halogenated heterocyclic compound be raw material can high productivity synthetic obtain corresponding nitrile compound have reaction conditions gentleness, raw material range extensively, the reaction specificity is strong, productive rate is high, to advantages such as the influence of environment are little.
Embodiment
The present invention is a raw material with halogenated aryl hydrocarbon, yellow prussiate of potash, is under the condition of catalyzer at ferrocenyl methyl ketone to toluene imines palladium complex, and one-step synthesis replaces fragrant nitrile.It comprises catalyst dissolution in the organic solvents such as dinethylformamide or N,N-dimethylacetamide, drops into alkali such as yellow soda ash, salt of wormwood at N simultaneously, adds halogenated aromatic compound again, under protection of nitrogen gas 100-150 ℃ of reaction 1-20 hour.Reaction is finished, and drops to room temperature, uses methylene dichloride, the dilution of ethyl acetate equal solvent, and water washing, extraction, drying concentrates, and purifying promptly gets product.The general formula of described reaction is:
Further describe the present invention below in conjunction with embodiment:
Embodiment 1, cyanobenzene synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml; with nitrogen replacement reaction tubes 4 times, under the pressure-fired nitrogen protection, add the bromobenzene of 1mmol (105 μ l) with syringe; under magnetic agitation, be heated to 120 ℃ then, reacted 3 hours with oil bath.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure cyanobenzene 96mg (purity＞98%, colourless liquid).Separation yield 93%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.48 (m, 2H, 2CH), 7.59 (m, 1H, 1CH), 7.54 (M, 2H, 2CH)
13C NMR δ=112.3,118.5,129.1,132.1,132.7
Embodiment 2, synthetic to methyl benzonitrile: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 0.5mmol (83mg) yellow soda ash and 1ml; with nitrogen replacement reaction tubes 4 times, under the pressure-fired nitrogen protection, add 1mmol to the methyl bromobenzene with syringe; under magnetic agitation, be heated to 120 ℃ then, reacted 3 hours with oil bath.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product to methyl benzonitrile 96mg (purity＞98%, colourless liquid).Isolated yield 82%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝2.43(s，3H，1CH
3)，7.27(d，2H，2CH，J＝7.9)，7.54(d，2H，2CH，J＝8.1)?
13C?NMR?δ＝21.9，109.3，119.2，129.8，132.1，143.7.
Embodiment 3,2-methyl benzonitrile synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 5mmol (530mg) yellow soda ash and 5ml; with nitrogen replacement reaction tubes 4 times, under the pressure-fired nitrogen protection, add 1mmol 2-methyl bromobenzene with syringe; under magnetic agitation, be heated to 120 ℃ then, reacted 3 hours with oil bath.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 2-methylbenzene nitrile 111mg (purity＞98%, colourless liquid).Isolated yield 95%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝2.55(s，3H，1CH
3)，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.
Embodiment 4,2,6-dimethyl benzene formonitrile HCN synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml is used nitrogen replacement reaction tubes 4 times, adds 2 of 1mmol again, and the 6-dimethyl bromobenzene is heated to 120 ℃ with oil bath then under magnetic agitation, reacted 3 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 2,6-dimethyl benzene nitrile 106mg (purity＞98%, colourless liquid).Isolated yield 81%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝2.53(s，6H，2CH
3)，7.12(d，2H，2CH，J＝7.7)，7.35(t，2H，2CH)?
13C?NMR?δ＝20.8，113.3，117.3，127.3，132.1，142.1.
Embodiment 5,4-anisole formonitrile HCN synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N of 1mmol (106mg) yellow soda ash and 0.5ml, the N-dimethylacetamide solvent, with nitrogen replacement reaction tubes 4 times, under the pressure-fired nitrogen protection, the 4-methoxyl group bromobenzene with syringe adding 1mmol is heated to 120 ℃ with oil bath then under magnetic agitation, reacted 3 hours. remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times merges organic phase and with anhydrous MgSO4 drying 30 minutes, filtration; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography. obtain straight product 4-anisole nitrile 126mg (purity＞98%, colorless solid). and the nucleus n-ness spectrum data of isolated yield 95%. these compounds are as follows.
1H NMR δ=3.87 (s, 3H, 1CH
3), 6.96 (d, 2H, 2CH), 7.60 (d, 2H, 2CH).
13C NMR δ=55.6,103.9,114.7,119.3,134.0,162.8.
Embodiment 6,4-(N, N-dimethyl amido) cyanobenzene synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml adds 4-(N, the N-dimethyl amido) bromobenzene of 1mmol again, with nitrogen replacement reaction tubes 4 times, is heated to 120 ℃ with oil bath then under magnetic agitation, reacts 1 hour.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 4-(N, N-dimethyl amido) cyanobenzene 141mg (purity＞98%, colorless solid).Isolated yield 97%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝3.04(s，6H，2CH
3)，6.64(d，2H，2CH，J＝8.9)，7.46(d，2H，2CH，J＝8.9)?
13C?NMR?δ＝40.0，97.3，111.4，120.8，133.4，152.4
Embodiment 7,2-nitrobenzonitrile synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml adds the 2-nitro bromobenzene of 1mmol again, with nitrogen replacement reaction tubes 4 times, is heated to 120 ℃ with oil bath then under magnetic agitation, reacts 8 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 2-p-nitrile 127mg (purity＞98%, colorless solid).Isolated yield 86%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝7.85(m，2H，2CH)，7.95(m，1H，2CH)，9.36(m，1H，2CH)
13C?NMR?δ＝108.0，115.0，125.6，133.8，134.4，135.6，148.5.
Embodiment 8,4-nitrobenzonitrile synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml is used nitrogen replacement reaction tubes 4 times, adds the 4-nitro bromobenzene of 1mmol again.Under magnetic agitation, be heated to 120 ℃ then, reacted 8 hours with oil bath.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 4-p-nitrile 96mg (purity＞98%, colorless solid).Isolated yield 65%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝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.
Embodiment 9,4-acetylbenzene formonitrile HCN synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.05mmol (46mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml; with nitrogen replacement reaction tubes 4 times, under the pressure-fired nitrogen protection, add 1mmol 4-ethanoyl bromobenzene with syringe; under magnetic agitation, be heated to 120 ℃ then, reacted 3 hours with oil bath.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography. obtain straight product 4-acetylbenzene nitrile 126mg (purity＞98%, colorless solid). and the nuclear magnetic data of isolated yield 87%. these compounds is as follows.
1H NMR δ=2.66 (s, 3H, 1CH
3), 7.78 (d, 2H, 2CH, J=8.8), 8.05 (d, 2H, 2CH, J=8.8).
13C NMR δ=26.8,116.4,118.0,128.7,132.5,139.9,196.6
Embodiment 10,1,4-dinitrile benzene synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 2mmol (845mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml adds 1mmol 1 again, and the 4-dibromobenzene is used nitrogen replacement reaction tubes 4 times, is heated to 120 ℃ with oil bath then under magnetic agitation, reacts 3 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 1,4-dinitrile benzene 124mg (purity＞98%, colorless solid).Isolated yield 97%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝7.804(s，4H，4CH)
13C?NMR?δ＝116.7，117.0，132.8.
Embodiment 11,1,4-dinitrile benzene synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.001mmol (0.9mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml adds 1mmol4-itrile group bromobenzene again, uses nitrogen replacement reaction tubes 4 times, is heated to 120 ℃ with oil bath then under magnetic agitation, reacts 3 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 1,4-dinitrile benzene 122mg (purity＞98%, colorless solid).Isolated yield 95%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝7.804(s，4H，4CH)?
13C?NMR?δ＝116.7，117.0，132.8.
Embodiment 12,4-chlorobenzonitrile synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml adds 1mmol 4-chloro-bromobenzene again, uses nitrogen replacement reaction tubes 4 times, is heated to 120 ℃ with oil bath then under magnetic agitation, reacts 1 hour.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 4-chlorobenzonitrile 96mg (purity＞98%, colorless solid).Isolated yield 70%.The nuclear magnetic data of this compound is as follows.
1HNMR?δ＝7.47(d，2H，2CH，J＝8.5)，δ＝7.60(d，2H，2CH，J＝8.5)?
13C?NMR?δ＝110.8，118.0，129.7，133.4，139.6.
Embodiment 13, and 1-itrile group naphthalene is synthetic: under rare gas element (as high pure nitrogen) protection, add 0.22mmol (93mg) K to the Schlenk of 20mL reaction tubes (a kind of glassware of using always during the anhydrous and oxygen-free operation)
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml is used nitrogen replacement reaction tubes 4 times, and under the pressure-fired nitrogen protection, the 1-bromonaphthalene with syringe adding 1mmol is heated to 120 ℃ with oil bath then under magnetic agitation, reacted 3 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography. obtain straight product 1-itrile group naphthalene 150mg (purity＞98%, colorless solid). and the nuclear magnetic data of isolated yield 98%. these compounds is as follows.
1H NMR δ=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).
13CNMR δ=110.1,117.9,124.9,125.1,127.6,128.6,128.7,132.3,132.6,132.9,133.3
Embodiment 14, and 1-itrile group naphthalene is synthetic: under rare gas element (as high pure nitrogen) protection, add 0.22mmol (93mg) K to the Schlenk of 20mL reaction tubes (a kind of glassware of using always during the anhydrous and oxygen-free operation)
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=OCH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml is used nitrogen replacement reaction tubes 4 times, and under the pressure-fired nitrogen protection, the 1-bromonaphthalene with syringe adding 1mmol is heated to 120 ℃ with oil bath then under magnetic agitation, reacted 3 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 1-itrile group naphthalene 144mg (purity＞98%, colorless solid).Isolated yield 92%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝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).
13CNMR?δ＝110.1，117.9，124.9，125.1，127.6，128.6，128.7，132.3，132.6，132.9，133.3
Embodiment 15, and 1-itrile group naphthalene is synthetic: under rare gas element (as high pure nitrogen) protection, add 0.22mmol (93mg) K to the Schlenk of 20mL reaction tubes (a kind of glassware of using always during the anhydrous and oxygen-free operation)
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=OCH
2CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml is used nitrogen replacement reaction tubes 4 times, and under the pressure-fired nitrogen protection, the 1-bromonaphthalene with syringe adding 1mmol is heated to 120 ℃ with oil bath then under magnetic agitation, reacted 3 hours.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 1-itrile group naphthalene 121mg (purity＞98%, colorless solid).Isolated yield 78%.The nuclear magnetic data of this compound is as follows.
1H?NMR?δ＝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).
13CNMR?δ＝110.1，117.9，124.9，125.1，127.6，128.6，128.7，132.3，132.6，132.9，133.3
Embodiment 16,3-itrile group pyridine synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N,N-dimethylacetamide solvent of 1mmol (106mg) yellow soda ash and 1ml; with nitrogen replacement reaction tubes 4 times, under the pressure-fired nitrogen protection, add the 3-bromopyridine of 1mmol with syringe; under magnetic agitation, be heated to 150 ℃ then, reacted 18 hours with oil bath.Remove oil bath, water-bath drops to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain straight product 3-itrile group pyridine 74mg (purity＞98%, colorless solid).Isolated yield 71%.The nuclear magnetic data of this compound is as follows:
1H NMR δ=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 NMR δ=110.3,116.5,123.7,139.3,152.5,153.0.
Embodiment 17, cyanobenzene synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3), the N of 1mmo1 anhydrous phosphoric acid potassium and 1ml, dinethylformamide (DMF) solvent, with nitrogen replacement reaction tubes 4 times, and continue to use the pressure-fired nitrogen protection, and add the iodobenzene of 1mmol (114 μ l) with syringe, under magnetic agitation, be heated to 100 ℃ then with oil bath, reacted 5 hours. remove oil bath, water-bath cools to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure cyanobenzene 84mg (purity＞98%, little yellow liquid).Separation yield 81%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.47 (m, 2H, 2CH), 7.61 (m, 1H, 1CH), 7.67 (m, 2H, 2CH).
13C?NMR?δ＝112.5，118.9，129.1，132.2，132.8
Embodiment 18,4-methyl benzonitrile synthetic: in rare gas element (as high pure nitrogen) protection down, and to the Schlenk of 20mL reaction tubes (during the anhydrous and oxygen-free operation commonly used a kind of glassware) adding 0.22mmol (93mg) K
4[Fe (CN)
6] 3H
2O, the catalyzer (Y=CH of 0.0025mmol (2.3mg)
3Z=CH
3); the 10mg triphenyl phosphorus; the N of 1mmol (106mg) yellow soda ash and 1ml; the N-dimethylacetamide solvent; with nitrogen replacement reaction tubes 4 times, and continue to add the 4-methyl chlorobenzene of 1mmol (118 μ l) with syringe with under the pressure-fired nitrogen protection; under magnetic agitation, be heated to 140 ℃ then, reacted 20 hours with oil bath.Remove oil bath, water-bath cools to room temperature; The water that adds 3ml, and with the dichloromethane extraction of 3ml three times, merge organic phase and also use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 10: 1 petrol ether/ethyl acetate, separates with silica gel thin-layer chromatography.Obtain pure 4-methyl benzonitrile 71mg (purity＞98%, little yellow liquid).Separation yield 61%.The nmr analysis data of this compound are as follows:
1H NMR δ=2.41 (s, 3H, 1CH
3), 7.26 (d, 2H, 2CH, J=7.9), 7.52 (d, 2H, 2CH, J=8.1)
13C NMR δ=21.8,109.3,119.2,129.9,132.0,143.7.
Claims (9)
1. the synthetic method of aromatic nitrile derivative under the ferrocenyl cycloimine palladium palladium complex catalyst; its preparation process is as follows: catalyzer, yellow prussiate of potash, alkali dissolution in organic solvent, are added halogenated aromatic compound again, reacting by heating under protection of nitrogen gas; reaction finishes and drops to room temperature; water washing, extraction, drying; concentrate; purifying is characterized in that, the catalyzer of following general formula is used in reaction:
Wherein X is Cl, Br or I; R is H, CH
3, CH
3CO, CH
3O, (CH
3)
2N or NO
2
2. the synthetic method of aromatic nitrile derivative is characterized in that under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 1, and the catalyzer of following general formula is used in reaction:
3. the synthetic method of aromatic nitrile derivative is characterized in that under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 1, and described halogenated aromatic compound is the compound of following general formula: Aryl-Br
Wherein R is H, CH
3, CH
3CO, CH
3O, (CH
3)
2N or NO
2
4. the synthetic method of aromatic nitrile derivative is characterized in that under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 2, and described halogenated aromatic compound is the compound of following general formula: Aryl-Br
Wherein R is H, CH
3, CH
3CO, CH
3O, (CH
3)
2N or NO
2
5. the synthetic method of aromatic nitrile derivative is characterized in that under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 3, and the molecular fraction that described catalyst levels accounts for halogenated aromatic compound is 0.1%-5%.
6. the synthetic method of aromatic nitrile derivative is characterized in that under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 4, and the molecular fraction that described catalyst levels accounts for halogenated aromatic compound is 0.1%-5%.
7. the synthetic method of aromatic nitrile derivative under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 6, it is characterized in that, the mol ratio of described halogenated aromatic compound and alkali is 1: 0.5-5, the mol ratio of halogenated aromatic compound and yellow prussiate of potash is 1: 0.2-2, described alkali are yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium-acetate, Potassium ethanoate, sodium hydroxide or potassium hydroxide.
8. the synthetic method of aromatic nitrile derivative under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 7, it is characterized in that, described organic solvent is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or N-methylpyrroline ketone, the consumption of organic solvent are that the halogenated aromatic compound of every mmole uses the 0.5-5ml solvent.
9. the synthetic method of aromatic nitrile derivative is characterized in that under the ferrocenyl cycloimine palladium palladium complex catalyst as claimed in claim 8, and described temperature of reaction is 100-150 ℃, and the reaction times is 1-20 hour.
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| Title |
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| Schareina，T. |
| Schareina,T.;ZaPf,A.:Beller,M..Potassium hexacyanoferrate(ii)-a new eyanating agentfor the Palladium-catalyzed eyanation of aryl halides..Chem.Commun..2004,第1388-1389页. * |
| ZaPf，A.:Beller，M.. Potassium hexacyanoferrate(ii)-a new eyanating agentfor the Palladium-catalyzed eyanation of aryl halides..Chem.Commun..2004,第1388-1389页. |
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