CN100465182C - Cyclo palladium diferrocenyl imine amino phosphine compound and its application - Google Patents
Cyclo palladium diferrocenyl imine amino phosphine compound and its application Download PDFInfo
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- CN100465182C CN100465182C CNB2006100485949A CN200610048594A CN100465182C CN 100465182 C CN100465182 C CN 100465182C CN B2006100485949 A CNB2006100485949 A CN B2006100485949A CN 200610048594 A CN200610048594 A CN 200610048594A CN 100465182 C CN100465182 C CN 100465182C
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Abstract
The present invention belongs to the field of organic compound synthesis and application technology, relates to a cyclopalladic ferrocene imine-aminophosphine coordination compound and its application. Said invention also provides its chemical structure formula. The preparation of arylamine derivative adopts the following steps: adding catalyst, alkali, halogenated aromatic compound and amine into solvent water, under the protection of chlorine gas making them be reacted, extracting, drying and purifying so as to obtain product.
Description
Technical field
The invention belongs to the synthetic and applied technical field of organic compound, relate to a kind of ring palladium ferrocenyl imine-amino phosphine composition and application thereof.
Background technology
Aromatic amine derivant is very important organic raw material, be widely used as the generation of medicine, dyestuff, agrochemicals, additive, tensio-active agent, textile auxiliary agent, sequestrant and polymkeric substance, fire retardant etc., Application Areas is very extensive, along with China's industry and expanding economy, each relevant industries will be increasing to the demand of aromatic amine derivant.
The synthetic method of classical aromatic amine derivant has the restore nitrification method, Ulmann synthesis method and SNAr synthesis method.But these method versatilities are poor, and synthesis step is many, and chemistry is selected uncertain, needs exacting terms.At present, researcher transition metal-catalyzed halogenated aromatic compound and the direct synthetic aroma sulfonamide derivativess of amine of adopting more, in employed catalyzer, the good catalytic activity of palladium salt and copper salt catalyst, but catalyst consumption is bigger, and need a large amount of parts that adds usually, and troublesome poeration, preparation cost is higher; The reactant halogenated aromatic compound mostly is active relative higher bromo aromatic compound with price and iodo aromatic compound; Aromatic amine derivant preparation many in organic solvent catalyzed reaction, use organic solvents such as toluene, N,N-dimethylacetamide, expense is higher.The also favourable synthetic method that uses water as the aryl amine derivatives of solvent in the bibliographical information, but need phase-transfer catalyst in the reaction, reactant has great limitation, and productive rate neither be very high.
The ring palladium compound prepares easily, stable in properties, but ferrocenyl cycloimine palladium palladium dimer is catalysis chlorinated aromatic compound and amine reaction generation aromatic amine derivant directly, amino phosphine part 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl is a good part of this class reaction of catalysis, but amino phosphine part is not very stable, if with ferrocenyl cycloimine palladium palladium dimer is the palladium source, with the reaction at aqueous phase of amino phosphine part catalysis chlorinated aromatic compound together and amine, its reaction yield neither be very high.
Summary of the invention
The purpose of this invention is to provide a kind of ring palladium ferrocenyl imine-amino phosphine composition.
Further aim of the present invention provides a kind of utilization ring palladium ferrocenyl imine-amino phosphine composition as catalyzer, is prepared the method for aromatic amine derivant by chlorinated aromatic compound at aqueous phase.
The present invention realizes above-mentioned purpose by the following technical solutions: ring palladium ferrocenyl imine-amino phosphine composition is the title complex of following general formula:
R wherein
1Be H or CH
3R
2Be Cy (cyclohexyl), i-Pr (sec.-propyl), p-CH
3-C
6H
4, p-OCH
3-C
6H
4, p-OEt-C
6H
4, p-Br-C
6H
4, p-Cl-C
6H
4Or o-Cl-C
6H
4Cy is a cyclohexyl.
Catalyst rings palladium ferrocenyl imine-amino phosphine composition is synthetic by the following method:
1, according to document (Shou Quan Huo, Yang Jie Wu, Chen Xia Du, Ying Zhu, HanZhen Yuan and Xi An Mao, Journal of Organometallic Chemistry, 1994,483,139-146) described method prepares ferrocenyl cycloimine palladium palladium dimer.Concrete grammar is: with PdCl
2Be dissolved in the methyl alcohol with LiCl, stir under the room temperature, then it is joined in the methanol solvate that contains NaOAc and ferrocenyl imine, filter and obtain red solid, methanol wash is drying to obtain ferrocenyl cycloimine palladium palladium dimer.
2, with 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl and ferrocenyl cycloimine palladium palladium dimer stirring at room reaction in organic solvent, evaporate to dryness then, recrystallization obtains red solid, filter, be drying to obtain catalyst rings palladium ferrocenyl imine-amino phosphine composition, wherein 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl and the dimeric mol ratio of ferrocenyl cycloimine palladium palladium are 2-4:1, and the reaction times is 20-40 minutes.
The preparation aryl amine derivatives adopts following steps: will encircle palladium ferrocenyl imine-amino phosphine composition catalyst, alkali, chlorinated aromatic compound, amine and join in the aqueous solvent; under nitrogen protection; in 90-100 ℃ of reactions 12-48 hours; reaction is finished; drop to room temperature, extraction, drying; concentrate, purifying promptly gets product.
Described chlorinated aromatic compound is the compound of following general formula: Aryl-Cl
R is H, CH
3, CH
3CO, CH
3O or NO
2
Described amine is the compound of following general formula: R
3-NH-R
4
R
3, R
4Be H, n-Bu (normal-butyl), C
6H
11, C
6H
5CH
2, C
4H
8O or Aryl, wherein
R is H, CH
3, CH
3CO, CH
3O or NO
2
The general formula of described ring palladium ferrocenyl imine-amino phosphine composition is:
R wherein
1Be H or CH
3R
2Be cyclohexyl, sec.-propyl, p-CH
3-C
6H
4, p-OCH
3-C
6H
4, p-OEt-C
6H
4, p-Br-C
6H
4, p-Cl-C
6H
4Or o-Cl-C
6H
4
The molecular fraction that the consumption of ring palladium ferrocenyl imine-amino phosphine composition accounts for chlorinated aromatic compound is 0.1%-2%.
Add alcohol in aqueous solvent, the mol ratio of described alcohol, alkali and chlorinated aromatic compound is 3-12:1-5:1, and the consumption of described water is that every mmole chlorinated aromatic compound uses 3-9mL water.
Described alkali is yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide or potassium hydroxide, and described alcohol is the trimethyl carbinol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, ethanol, propyl alcohol or Virahol.
The present invention amino phosphine part 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl this be not that very stable part is incorporated in the ferrocenyl cycloimine palladium palladium compound, prepare ring palladium ferrocenyl imine-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl] title complex, the preparation method is simple for this title complex, good stability, and this title complex of evidence has good catalytic performance, catalytic amount is less relatively, easy to operate, reaction yield is very high.Ferrocenyl imine-amino phosphine composition is a catalyzer with the ring palladium in the preparation of aryl amine derivatives, with water is solvent, need not to add a spot of alcohols with special phase-transfer catalyst, use cheap alkali, being that raw material is can high productivity synthetic by chlorinated aromatic compound and various amine obtains the corresponding aroma sulfonamide derivatives, and this method has the reaction conditions gentleness, and the reaction substrate scope is wide, the reaction specificity is strong, the productive rate height, economy is to advantages such as environmental influence are little.
Embodiment
Further describe the present invention below in conjunction with example:
Example 1; ring palladium formyl radical ferrocene cyclohexyl imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] preparation of title complex: in being housed, the 50mL there-necked flask of stirring and refluxing device adds formyl ferrocene (0.64g; 3mmol), hexahydroaniline (0.36g; 3.6mmol) and the 20mL dehydrated alcohol; stirring and refluxing under nitrogen atmosphere adds active A l
2O
3, the 2h after-filtration is used CH after steaming ethanol
2Cl
2With the sherwood oil recrystallization, obtain 0.76g sorrel crystal, i.e. formyl radical ferrocene cyclohexyl imines, productive rate 85.8%.IR:3100,2923,2852,1642,1453,1103,1004,813,487cm
-1. get this imines 106mg (0.4mmol) and add 4mL 0.1M Li
2PdCl
4Solution, 33mg (0.4mmol) NaOAc, stirring at room 20 hours leaches the red solid of generation, i.e. formyl radical ferrocene cyclohexyl imide ring palladium dimer 130mg, productive rate 83.1%.IR (KBr pellet): 3447,1623,1578,1459,1106,1001,816cm
-1. get above-mentioned product 58mg (0.067mmol) and 64mg (0.15mmol) 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl is at 10mL CH
2Cl
2Stirred 0.5 hour, and filtered, use CH after filtrate is spin-dried for
2Cl
2Obtain the 78mg red crystals with the sherwood oil recrystallization, promptly get and encircle palladium ferrocenyl imine-amino phosphine composition, productive rate 70.7% accordingly.IR(KBr，cm
-1):2926，2851，1600，1448，1314，1265，1106，1051，1002.
1HNMR:δ＝8.09(bs，1H，CH)，8.01(s，1H，Ph-H)，7.07-7.33(m，7H，Ph-H)，4.43(s，1H，C
5H
3)，4.26(s，2H，C
5H
3)，4.04(s，5H，C5H5)，2.95(s，1H，CHC
5H
10)，2.53(d，6H，CH
3)，2.42(d，2H，CHC
5H
10)，1.15-2.04(m，30H，C
6H
11).
Example 2; ring palladium ferrocenyl methyl ketone to phenetole imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] preparation of title complex: ferrocenyl methyl ketone is pressed document (Shou Quan Huo, Yang Jie Wu, Chen Xia Du to phenetole imide ring palladium dimer; Ying Zhu; Han Zhen Yuan and Xi An Mao, Journal of Organometallic Chemistry, 1994; 483,139-146) preparation.Get above-mentioned product 65mg (0.067mmol) and 64mg (0.15mmol) 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl stirred 0.5 hour in the 10mL chloroform, filtration is used CH after filtrate is spin-dried for
2Cl
2Obtain the 78mg red crystals with the sherwood oil recrystallization, promptly get and encircle palladium ferrocenyl imine-amino phosphine composition, productive rate 83.5%.IR(KBr，cm
-1):2930，2852，1568，1504，1469，1235，1108，1048.
1H?NMR:δ＝8.05(bs，1H，CH)，7.49(s，1H，Ph-H)，7.07-7.40(m，5H，Ph-H)，6.90(d，4H，Ph-H)，4.56(s，1H，C
5H
3)，4.40(m，2H，C
5H
3)，4.24(s，5H，C
5H
5)，4.03(m，2H，OCH
2)，2.53(d，6H，2CH
3)，2.00(s，3H，CH
3)，1.64-0.86(m，25H，C
6H
11+CH
3).
Example 3; ring palladium ferrocenyl methyl ketone to bromobenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] preparation of title complex: ferrocenyl methyl ketone is pressed document (Shou Quan Huo, Yang Jie Wu, Chen Xia Du to bromobenzene imide ring palladium dimer; Ying Zhu; Han ZhenYuan and Xi An Mao, Journal of Organometallic Chemistry, 1994; 483,139-146) preparation.Get above-mentioned product 67mg (0.067mmol) and 64mg (0.15mmol) 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl is at 10mL CH
2Cl
2Stirred 0.5 hour, and filtered, use CH after filtrate is spin-dried for
2Cl
2Obtain the 78mg red crystals with the sherwood oil recrystallization, promptly get and encircle palladium ferrocenyl imine-amino phosphine composition, productive rate 88.6%.IR(KBr，cm
-1):2928，2852，1567，1466，1317，1230，1106，1006.
1H?NMR:δ＝8.01(bs，1H，CH)，7.50(m，3H，Ph-H)，7.07-7.40(m，6H，Ph-H)，6.88(d，2H，Ph-H)，4.38(s，1H，C
5H
3)，4.14(s，2H，C
5H
3)，4.11(s，5H，C
5H
5)，2.54(d，6H，CH
3)，2.08(s，3H，CH
3)，1.68-0.83(m，22H，C
6H
11).
Example 4; the adjacent chlorobenzene imines of ring palladium ferrocenyl methyl ketone-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] preparation of title complex: the adjacent chlorobenzene imide ring of ferrocenyl methyl ketone palladium dimer is pressed document (Shou Quan Huo, Yang Jie Wu, Chen Xia Du; Ying Zhu; Han ZhenYuan and Xi An Mao, Journal of Organometallic Chemistry, 1994; 483,139-146) preparation.Get above-mentioned product 64mg (0.067mmol) and 64mg (0.15mmol) 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl is at 10mL CH
2Cl
2Stirred 0.5 hour, and filtered, use CH after filtrate is spin-dried for
2Cl
2Obtain the 78mg red crystals with the sherwood oil recrystallization, promptly get and encircle palladium ferrocenyl imine-amino phosphine composition, productive rate 78.2%.IR(KBr，cm
-1):2926，2851，1573，1460，1316，1121，1054，1002.
1H?NMR:δ＝8.02(bs，1H，CH)，6.93-7.51(m，11H，Ph-H)，4.40-4.58(m，3H，C
5H
3)，4.21(s，5H，C
5H
5)，2.59(d，6H，CH
3)，2.04(s，3H，CH
3)，1.64-1.06(m，22H，C
6H
11).
Example 5; synthesizing of pentanoic: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.005mmol (4.3mg) ring palladium formyl radical ferrocene cyclohexyl imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; the aniline of (0.6mmol 54 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure pentanoic 78mg (purity〉99%, faint yellow solid).Separation yield 92%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.26 (t, 4H, 4CH), 7.06 (d, 4H, 4CH), 6.92 (t, 2H, 2CH), 5.63 (bs, 1H, NH).
Example 6; synthesizing of 4-methyldiphenylamine: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.005mmol (4.2mg) ring palladium formyl radical ferrocene sec.-propyl imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products 4-methyldiphenylamine 90mg (purity〉99%, faint yellow solid).Isolated yield 98%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.23 (t, 2H, 2CH), 7.08 (d, 2H, 2CH), 7.01 (m, 4H, 4CH), 6.88 (t, 1H, 1CH), 5.53 (bs, 1H, NH), 2.30 (s, 3H, CH
3).
Example 7; synthesizing of 4-methyldiphenylamine: under rare gas element (as high pure nitrogen) protection; the ring palladium formyl radical ferrocene that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to methylbenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (60mg) water of sodium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products 4-methyldiphenylamine 58mg (purity〉99%, faint yellow solid).Isolated yield 63%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.23 (t, 2H, 2CH), 7.08 (d, 2H, 2CH), 7.01 (m, 4H, 4CH), 6.88 (t, 1H, 1CH), 5.53 (bs, 1H, NH), 2.30 (s, 3H, CH
3).
Example 8; synthesizing of 3-methoxy diphenylamine: under rare gas element (as high pure nitrogen) protection; the ring palladium ferrocenyl methyl ketone that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to chlorobenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; 3-the anisidine of (0.6mmol 68 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products 3-methoxy diphenylamine 88mg (purity〉99%, faint yellow solid).Isolated yield 88%.The nmr analysis data of this compound are as follows:
1HNMR δ=7.26 (m, 2H, 2CH), 7.15 (t, 1H, 1CH), 7.08 (d, 2H, 2CH), 6.93 (t, 1H, 1CH), 6.64 (m, 2H, 2CH), 6.47 (dd, 1H, CH), 5.70 (bs, 1H, NH), 3.76 (s, 3H, CH
3).
Example 9; synthesizing of 2-methoxy diphenylamine: under rare gas element (as high pure nitrogen) protection; the ring palladium formyl radical ferrocene that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to anisole imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; 2-the anisidine of (0.6mmol 68 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products 2-methoxy diphenylamine 78mg (purity〉99%, colourless liquid).Isolated yield 72%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.28 (m, 3H, 3CH), 7.14 (d, 2H, 2CH), 6.90 (m, 4H, 4CH), 6.14 (bs, 1H, NH), 3.89 (s, 3H, CH
3).
Example 10; synthesizing of 4-oxethyl diphenylamine: under rare gas element (as high pure nitrogen) protection; the ring palladium formyl radical ferrocene that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to phenetole imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; 4-the phenetidine of (0.6mmol 78 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.This synthetic raw material that sets out is chlorobenzene and 4-phenetidine.Obtain pure products 4-oxethyl diphenylamine 100mg (purity〉99%, yellow solid).Isolated yield 94%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.21 (t, 2H, 2CH), 7.07 (d, 2H, 2CH), 6.92 (d, 2H, 2CH), 6.85 (m, 3H, 3CH), 4.01 (m, 2H, CH
2), 1.41 (t, 3H, CH
3).
Example 11; synthesizing of N-methyldiphenylamine: under rare gas element (as high pure nitrogen) protection; the ring palladium ferrocenyl methyl ketone that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to phenetole imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; N-the monomethylaniline of (0.6mmol 66 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-methyldiphenylamine 74mg (purity〉99%, colourless liquid).Isolated yield 81%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.26 (m, 4H, 4CH), 7.01 (d, 4H, 4CH), 6.94 (t, 2H, 2CH), 3.30 (s, 3H, NCH
3).
Example 12; synthesizing of N-phenylbenzylamine: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.005mmol (4.3mg) the adjacent chlorobenzene imines of ring palladium formyl radical ferrocene-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; the benzylamine of (0.6mmol 66 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-phenylbenzylamine 88mg (purity〉99%, yellow solid).Isolated yield 96%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.32 (m, 5H, 5CH), 7.18 (t, 2H, 2CH), 6.77 (t, 1H, 1CH), 6.70 (d, 2H, 2CH), 4.34 (s, 2H, CH
2).
Example 13; synthesizing of N-cyclohexyl aniline: under rare gas element (as high pure nitrogen) protection; the ring palladium ferrocenyl methyl ketone that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to methylbenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 1.5mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; the ethylenimine of (0.6mmol 70 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-cyclohexyl aniline 58mg (purity〉99%, colourless liquid).Isolated yield 67%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.15 (t, 2H, 2CH), 6.67 (t, 1H, 1CH), 6.61 (d, 2H, 2CH), 3.24 (m, 1H, NCHC
5H
10), 1.14-2.07 (m, 10H, C
6H
11).
Example 14; N-(2; the 5-dimethyl) phenylaniline is synthetic: under rare gas element (as high pure nitrogen) protection; the ring palladium formyl radical ferrocene that adds 0.005mmol (4.4mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to chlorobenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; (0.6mmol 74 μ l) 2; 5-xylidine and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(2, the 5-dimethyl) phenylaniline 96mg (purity〉99%, colourless liquid).Isolated yield 90%.The nmr analysis data of this compound are as follows: 1H NMR δ=7.25 (t, 2H, 2CH), δ=7.08 (m, 2H, 2CH), 6.95 (d, 2H, 2CH), 6.90 (t, 1H, 1CH), 6.76 (d, 1H, 1CH), 5.76 (bs, 1H, NH), 2.27 (s, 3H, CH
3), 2.21 (s, 3H, CH
3).
Example 15; synthesizing of N-(4-methyl) phenyl-1-naphthylamines: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.005mmol (4.4mg) the adjacent chlorobenzene imines of ring palladium ferrocenyl methyl ketone-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; 1-the chloronaphthalene that adds 0.5mmol (68 μ l) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(4-methyl) phenyl-1-naphthylamines 112mg (purity〉99%, yellow solid).Isolated yield 97%.The nmr analysis data of this compound are as follows:
1H NMR δ=8.02 (d, 1H, 1CH), 7.84 (d, 1H, 1CH), 7.47 (m, 3H, 3CH), 7.34 (t, 1H, 1CH), 7.27 (d, 1H, 1CH), 7.07 (d, 2H, 2CH), 6.93 (d, 2H, 2CH), 5.86 (bs, 1H, 1NH), 2.30 (s, 3H, CH
3).
Example 16; synthesizing of N-(4-methyl) phenyl-3-pyridine amine: under rare gas element (as high pure nitrogen) protection; the ring palladium formyl radical ferrocene that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to bromobenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; 3-the chloropyridine that adds 0.5mmol (48 μ l) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(4-methyl) phenyl-3-pyridine amine 72mg (purity〉99%, yellow solid).Isolated yield 78%.The nmr analysis data of this compound are as follows:
1H NMR δ=8.33 (s, 1H, 1CH), 8.11 (s, 1H, 1CH), 7.33 (d, 1H, 1CH), 7.13 (m, 3H, 3CH), 7.00 (d, 2H, 2CH), 5.81 (bs, 1H, NH), 2.32 (s, 3H, CH
3).
Example 17; synthesizing of N-(4-methyl) phenyl-4-monomethylaniline: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.005mmol (4.2mg) ring palladium ferrocenyl methyl ketone Hexamethyleneimine-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; 4-methyl the chlorobenzene that adds 0.5mmol (60 μ l) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(4-methyl) phenyl-4-monomethylaniline 96mg (purity〉99%, yellow solid).Isolated yield 97%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.05 (d, 4H, 4CH), 6.94 (d, 4H, 4CH), 2.28 (s, 6H, 2CH
3).
Example 18; synthesizing of n-phenylmorpholine coffee quinoline: under rare gas element (as high pure nitrogen) protection; the ring palladium formyl radical ferrocene that adds 0.005mmol (4.3mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to methoxyl group imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; the chlorobenzene that adds 0.5mmol (52 μ l) with syringe; the morphine quinoline of (0.6mmol 54 μ l) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:l sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure n-phenylmorpholine coffee quinoline 30mg (purity〉99%, faint yellow solid).Separation yield 73%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.29 (m, 2H, 2CH), 6.92 (m, 3H, 2CH), 3.88 (s, 4H, 2CH
2), 3.17 (s, 4H, 2CH
2).
Example 19; synthesizing of N-(4-methyl) phenyl-4-ethanoyl aniline: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.0025mmol (2.13mg) ring palladium ferrocenyl methyl ketone sec.-propyl imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 2.5mmol (140mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; 4-ethanoyl the chlorobenzene that adds 0.5mmol (66 μ l) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 12 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(4-methyl) phenyl-4-ethanoyl aniline 110mg (purity〉99%, yellow solid).Isolated yield 98%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.80 (d, 1H, 1CH), 7.27 (m, 1H, 1CH), 7.15 (m, 5H, 5CH), 6.69 (m, 1H, 1CH), 2.64 (s, 3H, CH
3), 2.34 (s, 3H, CH
3).
Example 20; synthesizing of N-(4-methyl) phenyl-3-N-methyl-p-nitroaniline: under rare gas element (as high pure nitrogen) protection; to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) add 0.0005mmol (0.42mg) ring palladium formyl radical ferrocene Hexamethyleneimine-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 0.5mmol (28mg) water of potassium hydroxide and 4.5mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; 3-the nitro-chlorobenzene that adds 0.5mmol (80mg) with syringe; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 90 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 48 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(4-methyl) phenyl-3-N-methyl-p-nitroaniline 84mg (purity〉99%, yellow solid).Isolated yield 70%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.76 (t, 1H, 1CH), 7.63 (dd, 1H, 1CH), 7.33 (t, 1H, 1CH), 7.19 (m, 3H, 3CH), 7.05 (d, 2H, 2CH), 2.34 (s, 3H, CH
3).
Example 21; N-(4-methyl) phenyl-(2; 6-dimethyl) aniline is synthetic: under rare gas element (as high pure nitrogen) protection; the ring palladium ferrocenyl methyl ketone that adds 0.01mmol (8.6mg) to the Schlenk of 10mL reaction tubes (anhydrous and oxygen-free when operation a kind of glassware commonly used) to bromobenzene imines-amino phosphine [2-two cyclohexyl phosphino-s-2 '-(N; N-dimethylamino) biphenyl] title complex makes catalyzer; 1.5mmol (84mg) water of potassium hydroxide and 3mL; with nitrogen replacement reaction tubes 4 times; and continue with under the pressure-fired nitrogen protection; add 2 of 0.5mmol (68 μ l) with syringe; 4-dimethylated chlorobenzene; 0.6mmol 4-monomethylaniline (64mg) and 2.0mmol (the 180 μ l) trimethyl carbinol; be heated to 100 ℃ (reactor temperatures) with oil bath then under magnetic agitation, reaction refluxed 24 hours.Remove oil bath, water-bath drops to room temperature; With the dichloromethane extraction of 5mL three times, merge organic phase and use anhydrous MgSO
4Dry 30 minutes, filter; Rotatory evaporator concentrates, and raffinate is a developping agent with 1:1 sherwood oil/methylene dichloride, separates with silica gel thin-layer chromatography.Obtain pure products N-(4-methyl) phenyl-(2,6-dimethyl) aniline 64mg (purity〉99%, colourless liquid).Isolated yield 61%.The nmr analysis data of this compound are as follows:
1H NMR δ=7.10 (m, 3H, 3CH), 6.96 (d, 2H, 2CH), 6.43 (d, 2H, 2CH), 2.24 (s, 3H, CH
3), 2.20 (s, 6H, 2CH
3).
Claims (7)
1, ring palladium ferrocenyl imine-amino phosphine composition is characterized in that, is the title complex of following general formula:
R wherein
1Be H or CH
3R
2Be cyclohexyl, sec.-propyl, p-CH
3-C
6H
4, p-OCH
3-C
6H
4, p-OEt-C
6H
4, p-Br-C
6H
4, p-Cl-C
6H
4Or o-Cl-C
6H
4Cy is a cyclohexyl.
2, the method for preparation ring palladium ferrocenyl imine as claimed in claim 1-amino phosphine composition, it is characterized in that, with 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl and ferrocenyl cycloimine palladium palladium dimer room temperature reaction in organic solvent, solvent evaporated, recrystallization, filtration drying promptly get product.
3, the method for preparing ring palladium ferrocenyl imine-amino phosphine composition as claimed in claim 2, it is characterized in that, 2-two cyclohexyl phosphino-s-2 '-(N, N-dimethylamino) biphenyl and the dimeric mol ratio of ferrocenyl cycloimine palladium palladium are 2-4:1, the reaction times is 20-40 minutes.
4, the synthetic method of aryl amine derivatives; it is characterized in that; use ring palladium ferrocenyl imine-amino phosphine composition as catalyzer; the preparation aryl amine derivatives adopts following steps: will encircle palladium ferrocenyl imine-amino phosphine composition, alkali, chlorinated aromatic compound, amine and join in the aqueous solvent; under nitrogen protection, reacted 12-48 hours in 90-100 ℃; reaction is finished; drop to room temperature; extraction; dry; concentrate, purifying promptly gets product, and described chlorinated aromatic compound is the compound of following general formula: Aryl-Cl
R is H, CH
3, CH
3CO, CH
3O or NO
2
Described amine is the compound of following general formula: R
3-NH-R
4
R wherein
3, R
4Be H, n-Bu, C
6H
11, C
6H
5CH
2, C
4H
8O or Aryl, wherein
R is H, CH
3, CH
3CO, CH
3O or NO
2,
The general formula of described ring palladium ferrocenyl imine-amino phosphine composition is:
5, the synthetic method of aryl amine derivatives as claimed in claim 4 is characterized in that, the molecular fraction that the consumption of ring palladium ferrocenyl imine-amino phosphine composition accounts for chlorinated aromatic compound is 0.1%-2%.
6, the synthetic method of aryl amine derivatives as claimed in claim 5, it is characterized in that, add alcohol in aqueous solvent, the mol ratio of described alcohol, alkali and chlorinated aromatic compound is 3-12:1-5:1, and the consumption of described water is that every mmole chlorinated aromatic compound uses 3-9mL water.
7, the synthetic method of aryl amine derivatives as claimed in claim 6, it is characterized in that, described alkali is yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide or potassium hydroxide, and described alcohol is the trimethyl carbinol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, ethanol, propyl alcohol or Virahol.
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| CN103242379B (en) * | 2013-05-20 | 2015-09-02 | 洛阳师范学院 | 2-ferrocenyl-aryl quinoline and preparation method thereof |
| CN103254250B (en) * | 2013-05-20 | 2015-06-10 | 洛阳师范学院 | Ferrocenyl pyridine cyclic Pd-N heterocyclic carbene compound as well as preparation method and application thereof |
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