CN106748834B - A kind of method of 4,4- dimethoxys -2,2- bipyridyl silver catalytic hydrogenations aromatic nitro compound synthesis arylamine - Google Patents

A kind of method of 4,4- dimethoxys -2,2- bipyridyl silver catalytic hydrogenations aromatic nitro compound synthesis arylamine Download PDF

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CN106748834B
CN106748834B CN201710022970.5A CN201710022970A CN106748834B CN 106748834 B CN106748834 B CN 106748834B CN 201710022970 A CN201710022970 A CN 201710022970A CN 106748834 B CN106748834 B CN 106748834B
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aromatic nitro
arylamine
nitro compound
bipyridyl
silver
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CN106748834A (en
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李超群
周朋娟
肖建良
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Shaanxi Normal University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8

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Abstract

The invention discloses one kind 4,4 dimethoxys 2, the method that 2 bipyridyl silver catalytic hydrogenation aromatic nitro compounds synthesize arylamine, this method with it is cheap, be readily synthesized 4,4 dimethoxy, 2,2 bipyridyl silver is catalyst, using green, environmentally friendly, nontoxic hydrogen as hydrogen source, by aromatic nitro compound under relatively mild reaction conditions, single step reaction can synthesize arylamine.The present invention is easy to operate, and catalyst is cheap and easy to get and dosage is few, and reaction condition is gentle, preferable functional group's tolerance is shown to substrate, products collection efficiency is high, and industrial production cost is low, has good application prospect.

Description

A kind of 4,4- dimethoxys -2,2- bipyridyls silver catalytic hydrogenation aromatic nitro compound The method for synthesizing arylamine
Technical field
The invention belongs to the selective reduction technical field of nitro in aromatic nitro compound, and in particular to aromatic nitro Compound is under silver catalyst and hydrogen effect, the method that generates corresponding arylamine.
Background technology
Arylamine is important Organic Chemicals, is the intermediate for synthesizing many fine chemicals, in dyestuff, medicine, agriculture Had a wide range of applications in the industries such as medicine, surfactant, textile auxiliary, chelating agent, high molecular material.By aromatic nitro compound Thing is reduced to corresponding arylamine, and easy to operate, raw material is easy to get, therefore the common method of arylamine is prepared as fine chemistry industry production. The method of preparing arylamine by reducing aromatic nitro compound mainly include catalytic hydrogenation (hydrogen reduction method, hydrogen migration hydrogenization method), CO/H2O reduction methods, metal deoxidization, sodium sulfide reducing method, metal hydride reduction method and electrochemical reducing and photochemistry Reduction method etc..In catalytic hydrogenating reduction reaction process, harmful side product is not produced, exhaust gas, discharging of waste liquid are seldom.Due to catalysis The yield of hydrogenating reduction nitrobenzene aniline is big, and product quality is high, has significant superiority, mesh to solving problem of environmental pollution Preceding has been the main method of industrial production aniline.
The hydrogen reduction method of preparing arylamine by reducing aromatic nitro compound directly uses hydrogen as reducing agent, more with Pt, The metals such as Pd, Ni, Cu or its oxide are carried on SiO as catalyst2、Al2O3, on the carrier such as activated carbon, in high temperature height Pressure is reacted.Such as：2006, and Chen etc. (J Catal, 2006,242:227-230) nanometer Au is carried on first SiO2Original aromatic nitro compound is gone back in upper catalysis, with ethanol as solvent, H2Pressure 4.0MPa, reduces fragrance under conditions of 140 DEG C Nitro compound, such as adjacent// paranitrochlorobenzene, paranitrophenetole, para-nitrotoluene and p-nitrophenol, its corresponding virtue The yield of amine is 90% or so；Li et al. (J Molec Catal A in 2005:Chem,2005,226:101-105) Pt is loaded In the catalytic hydrogenation reaction that nitrobenzene is carried out in carbon nanotubes (CNTs), nitrobenzene is carried out under using ethanol as solvent normal temperature and pressure Reduction, react 40min, the yield of aniline is up to 90%；Nanometer Ag is carried on by Kiyotomi Kaneda seminars within 2012 CeO2On, with CO/H2O is hydrogen source, and original aromatic nitro compound is gone back in catalysis；(the J Molec Catal A such as Shen:Chem,2007, 273:265-276) with the hydrogenation reaction of Ni-Co-B amorphous alloy catalyst paranitrochlorobenzenes, and work as n (Ni):n(Co):n(B) =1:3:There is preferable catalytic effect, using absolute methanol as solvent, H when 32After pressure 1.2 MPa, 100 DEG C of reaction 170min, The conversion ratio of paranitrochlorobenzene reaches 100%, and the selectivity of parachloroanilinum is 96%.
Used catalyst usually requires to prepare at high temperature in the above method, and preparation condition is harsh, and through handling or being modified Hydrogenation catalyst activity and stability declined, cause catalyst amount to increase, and to the catalysis of some substrates Hydrogenating reduction remains selective problems.Therefore a kind of catalyst simple and easy to get is sought to realize aromatic nitro compound Selective reduction be necessary.
The content of the invention
The technical problems to be solved by the invention are that providing a kind of silver catalyst catalytic hydrogenation aromatic nitro compound closes Into the method for arylamine.
Technical solution is used by solving above-mentioned technical problem：Using 1,4- dioxane as solvent, 4,4- dimethoxys- 2,2- bipyridyls silver for catalyst, potassium tert-butoxide as alkali under the conditions of, by aromatic nitro compound Hydrogen Vapor Pressure be 3.0~ Under 5.0MPa, when 80~100 DEG C of reactions 8~48 are small, isolate and purify, obtain arylamine.
Above-mentioned 4,4- dimethoxy -2,2- bipyridyl silver is by AgBF4Pressed with 4,4'- dimethoxy -2,2'- bipyridyls Molar ratio is 1:1 be stirred at room temperature in tetrahydrofuran 1 it is small when after remove the obtained white solid product of tetrahydrofuran.
The dosage of above-mentioned 4,4- dimethoxys -2,2- bipyridyls silver be preferably aromatic nitro compound mole 2%~ 5%.
The dosage of above-mentioned potassium tert-butoxide is preferably the 8%~12% of aromatic nitro compound mole.
Above-mentioned aromatic nitro compound is amino, acetyl group, propiono, halogen, C1~C4In alkoxy, amide groups extremely A kind of few substituted nitrobenzene, or any one in nitroindoline, nitroquinoline, nitro tetrahydroquinoline.
The present invention with 4,4- dimethoxys -2,2- bipyridyl silver for catalyst, using cleaning, environmentally friendly hydrogen as hydrogen source, Catalytic hydrogenation aromatic nitro compound synthesizes arylamine.Compared with the conventional method, used catalyst of the present invention is with AgBF4For silver Source, with 4,4- dimethoxys -2,2- bipyridyl for ligand, is prepared, preparation method is simple, and catalyst by being stirred at room temperature Dosage is few, and preferable functional group's tolerance is shown to substrate, and reaction condition is more gentle, easy to operate, environmentally protective, reaction Yield is high, and industrial production cost is low.
Embodiment
With reference to example, the present invention is described in more detail, but protection scope of the present invention is not limited only to these implementations Example.
Embodiment 1
By taking the following 3- antifebrins of composite structure formula as an example, raw materials used and synthetic method is：
By 16.44mg (0.04mmol) 4,4- dimethoxy -2,2- bipyridyls silver and 11.22mg (0.1mmol) tert-butyl alcohol Potassium, 1mL Isosorbide-5-Nitraes-dioxane are added in autoclave, are stirring evenly and then adding into 165.15mg (1mmol) m-nitroacetophenone, When Hydrogen Vapor Pressure is that the lower 80 DEG C of reactions 8 of 4.0MPa are small, after question response, reaction solution water and dichloromethane is extracted, collected Organic phase, organic phase is through anhydrous Na2SO4Drying, suction filtration, rotary evaporation, column chromatography for separation, obtain yellow solid 3- antifebrins, Its yield is 96%, and spectral data is：1H NMR(400MHz,CDCl3):δ 7.34 (d, J=7.6Hz, 1H), 7.33-7.23 (m, 2H), 6.88 (dd, J=7.6,1.6Hz, 1H), 3.84 (br s, 2H), 2.57 (s, 3H)；13C NMR (100MHz, CDCl3):δ 198.6,146.9,138.3,129.5,119.8,118.9,114.1,26.8；HRMS (ESI) theoretical values C8H9NNaO[M+Na]+ =158.0582, measured value=158.0589.
Embodiment 2
By taking the following paraphenetidine of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar paranitroanisole, is in Hydrogen Vapor Pressure When the lower 100 DEG C of reactions 24 of 4.0MPa are small, other steps are same as Example 1, obtain paraphenetidine, its yield is 75%, Spectral data is：1H NMR(400MHz,CDCl3):δ 6.75 (d, J=8.8Hz, 2H), 6.65 (d, J=8.8Hz, 2H), 3.75 (s,3H),3.42(br s,2H)；13C NMR(100MHz,CDCl3):δ152.8,140.1,116.4,114.9,55.8；HRMS m/z(ESI):Theoretical value C7H10NO[M+H]+=124.0762, measured value=124.0760.
Embodiment 3
By taking the following p-phenylenediamine of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar paranitroanilinum, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 12 of 4.0MPa are small, other steps are same as Example 1, obtain p-phenylenediamine, its yield is 96%, wave spectrum number According to for：1H NMR(400MHz,CDCl3):δ6.58(s,4H),3.33(br s,4H)；13C NMR(100MHz,CDCl3):δ 138.7,116.8；HRMS m/z(ESI):Theoretical value C6H9N2[M+H]+=109.0766, measured value=109.0764
Embodiment 4
By taking the following N- of composite structure formula (4- aminophenyls) -2,2- dimethylpropionamides as an example, raw materials used and synthesis Method is：
In embodiment 1, m-nitroacetophenone used equimolar N- (4- nitrobenzophenones) -2,2- dimethylpropionamides Replace, when 80 DEG C of reactions 33 are small under Hydrogen Vapor Pressure is 4.0MPa, other steps are same as Example 1, obtain N- (4- aminobenzenes Base) -2,2- dimethylpropionamides, its yield is 70%, and spectral data is：1H NMR(400MHz,CDCl3):δ 7.25 (d, J= 9.2Hz, 2H), 7.14 (br s, 1H), 6.62 (d, J=8.8Hz, 2H), 3.57 (br s, 2H), 1.27 (s, 9H)；13C NMR (100MHz,CDCl3):δ176.5,143.3,129.5,122.2,115.5,39.4,27.8；HRMS m/z(ESI):Theoretical value C11H16N2NaO[M+Na]+=215.1160, measured value=215.1161.
Embodiment 5
By taking the following 5- amino indoles of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 5- nitroindolines, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 24 of 4.0MPa are small, other steps are same as Example 1, obtain 5- amino indoles, its yield is 98%, wave spectrum Data are：1H NMR(400MHz,CDCl3):δ 7.96 (brs, 1H), 7.20 (d, J=8.4Hz, 1H), 7.14 (s, 1H), 6.95 (s, 1H), 6.67 (d, J=8.4Hz, 1H), 6.38 (s, 1H), 3.51 (br s, 2H)；13C NMR(100MHz,DMSO-d6):δ 141.0,129.8,128.5,124.7,111.8,111.4,103.2,99.6；HRMS m/z(ESI):Theoretical value C8H9N2[M+H ]+=133.0760, measured value=133.0755.
Embodiment 6
By taking the following 6- amino indoles of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 6- nitroindolines, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 48 of 4.0MPa are small, other steps are same as Example 1, obtain 6- amino indoles, its yield is 94%, wave spectrum Data are：1H NMR(400MHz,CD3OD):δ 7.31 (d, J=8.4Hz, 1H), 7.00 (d, J=2.0Hz, 1H), 6.79 (s, 1H), 6.57 (d, J=8.4, Hz, 1H), 6.28 (d, J=2.0Hz, 1H)；13C NMR(100MHz,CDCl3):δ141.7, 137.1,122.5,121.2,121.1,110.8,101.9,97.1；HRMSm/z(ESI):Theoretical value C8H9N2[M+H]+= 133.0760 measured value=133.0754.
Embodiment 7
By taking the following 7- amino indoles of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 7- nitroindolines, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 48 of 4.0MPa are small, other steps are same as Example 1, obtain 7- amino indoles, its yield is 65%, wave spectrum Data are：1H NMR(400MHz,CDCl3):δ 8.02 (br s, 1H), 7.19 (d, J=9.2Hz, 2H), 6.97 (t, J= 7.6Hz, 1H), 6.60 (d, J=7.3Hz, 1H), 6.54 (s, 1H) 3.61 (br s, 2H)；13C NMR(100MHz,CDCl3):δ 131.0,129.0,127.0,124.3,120.7,112.9,108.7,103.3；HRMS m/z(ESI):Theoretical value C8H9N2[M+ H]+=133.0760, measured value=133.0758.
Embodiment 8
By taking the following 6- aminoquinolines of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 6- nitroquinolines, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 48 of 4.0MPa are small, other steps are same as Example 1, obtain 6- aminoquinolines, its yield is 70%, wave spectrum Data are：1H NMR(400MHz,CDCl3):δ 8.66 (s, 1H), 7.92-7.88 (m, 2H), 7.26 (s, 1H), 7.15 (d, J= 8.9Hz,1H),6.90(s,1H),3.97(br s,2H)；13C NMR(150MHz, CDCl3):δ147.0,144.7,143.6, 133.9,130.7,129.9,121.7,121.5,107.6；HRMS m/z(ESI):Theoretical value C9H9N2[M+H]+= 145.0766 measured value=145.0757.
Embodiment 9
By taking the following 8- aminoquinolines of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 8- nitroquinolines, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 48 of 4.0MPa are small, other steps are same as Example 1, obtain 8- aminoquinolines, its yield is 81%, wave spectrum Data are：1H NMR(400MHz,CDCl3):δ 8.77 (dd, J=4.2,1.7Hz, 1H), 8.07 (dd, J=8.3,1.7Hz, 1H), 7.38-7.32 (m, 2H), 7.16 (dd, J=8.2,1.1H z, 1H), 6.93 (dd, J=7.5,1.2Hz, 1H), 4.99 (br s,2H)；13C NMR(100MHz,CDCl3):δ147.4,144.0,138.3,136.0,128.8,127.4,121.3, 116.0,110.0；HRMS m/z(ESI):Theoretical value C9H8N2Na[M+Na]+=167.0585, measured value=167.0577.
Embodiment 10
With the following 7- amino -1,2 of composite structure formula, exemplified by 3,4- tetrahydroquinolines, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used equimolar 7- nitro bases -1,2,3,4- tetrahydroquinolines are replaced, When 80 DEG C of reactions 48 are small under Hydrogen Vapor Pressure is 4.0MPa, other steps are same as Example 1, obtain 7- amino -1,2, and 3,4- Tetrahydroquinoline, its yield are 83%, and spectral data is：1H NMR(600MHz,CDCl3):δ 6.74 (d, J=11.9Hz, 1H), 6.01 (dd, J=11.9,3.3Hz, 1H), 5.85 (d, J=3.2Hz, 1H), 3.42 (br s, 2H), 3.25 (t, J=8.1Hz, 2H), 2.66 (t, J=9.5Hz, 2H), 1.90 (t, J=8.6Hz, 2H)；13C NMR(150MHz,CDCl3):δ145.5, 145.4,130.3,112.5,105.1,100.8,42.2,26.4,22.8；HRMS m/z(ESI):Theoretical value C9H13N2[M+H]+ =149.1079, measured value=149.1072.
Embodiment 11
By taking the following 4- fluoroanilines of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 4- fluoronitrobenzenes, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 48 of 4.0MPa are small, other steps are same as Example 1, obtain 4- fluoroanilines, its yield is 67%, wave spectrum number According to for：1H NMR(400MHz,CDCl3):δ6.88-6.83(m,2H),6.63-6.61(m,2H),3.54(br s,2H).13C NMR(100MHz,CDCl3):δ 156.5 (d, J=234.1Hz), 142.5,116.2 (d, J=7.5Hz), 115.8 (d, J= 22.2Hz)；HRMS m/z(ESI):Theoretical value C6H7FN[M+H]+=112.0563, measured value=112.0559.
Embodiment 12
By taking the following 4- aminoacenaphthenes of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with equimolar 4- nitros acetophenone, is in Hydrogen Vapor Pressure When the lower 80 DEG C of reactions 24 of 4.0MPa are small, other steps are same as Example 1, obtain 4- aminoacenaphthenes, its yield is 84%, ripple Modal data is：1H NMR(400MHz,CDCl3):δ 7.80 (d, J=8.4Hz, 2H), 6.63 (d, J=8.8Hz, 2H), 4.17 (br s,2H),2.50(s,3H).13C NMR(100MHz,CDCl3):δ196.6,151.3,130.9,128.0,113.8,26.2； HRMS m/z(ESI):Theoretical value C8H9NNaO[M+Na]+=158.0582, measured value=158.0582.
Embodiment 13
By taking the chloro- 4- amino anilines of the following 2- of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with the chloro- 4- nitroanilines of equimolar 2-, in Hydrogen Vapor Pressure For 4.0MPa it is lower 80 DEG C reaction 24 it is small when, other steps are same as Example 1, obtain 4- aminoacenaphthenes, its yield be 96%, Spectral data is：1H NMR(400MHz,CDCl3):δ 6.68 (d, J=2.4Hz, 1H), 6.63 (d, J=8.4Hz, 1H), 6.49 (dd, J=8.4,2.4Hz, 1H), 3.65 (br s, 2H) 3.35 (br s, 2H)；13C NMR(100MHz,CDCl3):δ139.2, 135.3,120.5,117.5,116.6,115.7；HRMS m/z(ESI):Theoretical value C6H8ClN2[M+H]+=143.0376, it is real Measured value=143.0362.
Embodiment 14
By taking the fluoro- Isosorbide-5-Nitrae-phenylenediamines of the following 2- of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with the fluoro- 4- nitroanilines of equimolar 2-, in Hydrogen Vapor Pressure For 4.0MPa it is lower 80 DEG C reaction 24 it is small when, other steps are same as Example 1, obtain the fluoro- Isosorbide-5-Nitrae-phenylenediamines of 2-, its yield is 93%, spectral data is：1H NMR(600MHz,CDCl3):δ 6.63 (t, J=8.4Hz, 1H), 6.42 (dd, J=12.6, 2.4Hz, 1H), 6.33 (dd, J=8.4,1.2Hz, 1H), 3.35 (br s, 4H)；13C NMR(100MHz,CDCl3):δ152.6 (d, J=236.6Hz), 139.3 (d, J=9.2Hz), 126.1 (d, J=13.4Hz), 118.6 (d, J=4.8Hz), 111.6 (d, J=3.1Hz), 103.6 (d, J=22.0Hz)；HRMS m/z(ESI):Theoretical value C6H8FN2[M+H]+=127.0672, it is real Measured value=127.0682.
Embodiment 15
By taking fluoro- 1, the 3- diaminobenzenes of the following 4- of composite structure formula as an example, raw materials used and synthetic method is：
In embodiment 1, m-nitroacetophenone used is replaced with the fluoro- 3- nitroanilines of equimolar 4-, in Hydrogen Vapor Pressure For 4.0MPa it is lower 80 DEG C reaction 48 it is small when, other steps are same as Example 1, obtain fluoro- 1, the 3- diaminobenzenes of 4-, its yield is 94%, spectral data is：1H NMR(400MHz,CDCl3):δ 6.76 (t, J=8.8Hz, 1H), 6.07 (dd, J=7.6, 2.4Hz,1H),5.99-5.96(m,1H),3.54(br s,4H)；13C NMR(100MHz,CDCl3):δ 144.8 (d, J= 227.5Hz), 142.0 (d, J=1.7Hz), 133.9 (d, J=13.9Hz), 114.5 (d, J=19.5Hz), 104.0 (d, J= 6.6Hz), 102.8 (d, J=2.6Hz)；HRMS m/z(ESI):Theoretical value C6H8FN2[M+H]+=127.0672, measured value= 127.0672。

Claims (4)

1. one kind 4, the method that 4'- dimethoxy -2,2'- bipyridyl silver catalytic hydrogenations aromatic nitro compound synthesizes arylamine, its It is characterized in that：Using 1,4- dioxane as solvent, 4,4'- dimethoxy -2,2'- bipyridyls silver be catalyst, potassium tert-butoxide makees Under the conditions of alkali, by aromatic nitro compound in the case where Hydrogen Vapor Pressure is 3.0~5.0 MPa, when 80~100 DEG C of reactions 8~48 are small, Isolate and purify, obtain arylamine；
Above-mentioned 4,4'- dimethoxy -2,2'- bipyridyl silver is by AgBF4Massaged with 4,4'- dimethoxy -2,2'- bipyridyls You are than being 1:1 be stirred at room temperature in tetrahydrofuran 1 it is small when after remove the obtained white solid product of tetrahydrofuran.
2. 4,4'- dimethoxys -2,2'- bipyridyl silver catalytic hydrogenations aromatic nitro compound according to claim 1 closes Into the method for arylamine, it is characterised in that：The dosage of the 4,4'- dimethoxys -2,2'- bipyridyls silver is aromatic nitro compound The 2%~5% of mole.
3. 4,4'- dimethoxys -2,2'- bipyridyl silver catalytic hydrogenations aromatic nitro compound according to claim 1 closes Into the method for arylamine, it is characterised in that：The dosage of the potassium tert-butoxide is the 8%~12% of aromatic nitro compound mole.
4. the 4,4'- dimethoxy -2,2'- bipyridyl silver catalytic hydrogenation fragrance nitre according to claims 1 to 3 any one The method that based compound synthesizes arylamine, it is characterised in that：The aromatic nitro compound is amino, acetyl group, propiono, halogen Element, C1~C4The nitrobenzene of at least one of alkoxy, amide groups substitution, or nitroindoline, nitroquinoline, nitro tetrahydrochysene Any one in quinoline.
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