CN111732493B - Synthesis process of arylamine compound - Google Patents

Synthesis process of arylamine compound Download PDF

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CN111732493B
CN111732493B CN202010532379.6A CN202010532379A CN111732493B CN 111732493 B CN111732493 B CN 111732493B CN 202010532379 A CN202010532379 A CN 202010532379A CN 111732493 B CN111732493 B CN 111732493B
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ethyl acetate
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周海峰
周艳梅
皮单违
刘祈星
刘森生
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Yichang Shangnord Biomedical Technology Co ltd
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Abstract

The invention provides a synthesis process of an arylamine compound, which is characterized in that an arylamine compound (II) can be obtained by taking an aromatic nitro derivative (I) as a raw material, tetrahydroxy diboron as an additive, copper salt as a metal catalyst, acetonitrile as a solvent and reacting for 24 hours at the temperature of 80-100 ℃. Compared with the prior art, the method has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.

Description

Synthesis process of arylamine compound
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for reducing aromatic nitro into aromatic amine.
Background
Aromatic amines are also important organic synthesis intermediates and raw materials, and can be used for synthesizing various fine chemicals such as pesticides, medicines, rubber aids, dyes and pigments, synthetic resins, textile aids, surfactants, photosensitive materials and the like. In addition, aromatic amines are common building blocks in many biologically active drugs. Such as Adderall XR for treating hyperkinetic syndrome, mesalazine for resisting intestinal mucositis, and lereca for treating posttraumatic neuralgia.
With regard to the preparation of the arylamine compounds, the main methods reported so far can be obtained by the reduction of the corresponding aromatic nitro compounds, the industrial method for reducing aromatic nitro compound mainly includes metal (iron powder, zinc powder, etc.) reduction method,Catalytic hydrogenation reduction and alkali sulfide reduction, but other reduction methods are also numerous. From the viewpoint of the source of the reducing agent, hydrogen, sodium borohydride, formic acid, 9, 10-dihydroanthracene, 1, 4-dihydropyridine, thiol, (2-pyridyl) benzyl alcohol, hydrazine hydrate, trichlorosilane/triethylamine, alcohols, and the like are mainly used as the hydrogen source. However, these methods still have disadvantages: when using H 2 When the reducing agent is used, special high-pressure equipment and combustible gas are needed, and certain danger exists; when hydrazine hydrate is used as a reducing agent, the compound has poor selectivity if the compound contains carbon-carbon double bonds, carbon-carbon triple bonds and aldehyde groups.
Disclosure of Invention
1. The invention aims to provide a method for reducing aromatic nitro into aromatic amine, wherein the structural formula of the prepared aromatic amine compound is shown as follows:
Ar-NH 2
wherein Ar is selected from the following groups:
Figure BDA0002535088650000011
R 1 is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl radical, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups; x is any one of O and S;
the invention also aims to provide the method for reducing the aromatic nitro group into the arylamine, which has the advantages of mild reaction conditions, low cost, environmental friendliness and high yield and is suitable for industrial production. The arylamine compound (II) is obtained by taking the aromatic nitro derivative (I) as a raw material, water as a hydrogen source, tetrahydroxy diboron as an additive, a palladium compound as a catalyst, and any one of toluene, ethyl acetate, acetonitrile, 2-methyltetrahydrofuran, tetrahydrofuran, chloroform, protonic solvent water, methanol or isopropanol as a solvent, and reacting for 6-24 hours at 30-70 ℃, wherein the specific reaction equation is as follows:
Figure BDA0002535088650000021
the Pd metal catalyst is palladium acetate (Pd (OAc) 2 ) Palladium trifluoroacetate (Pd (CF) 3 COO) 2 ) Palladium on carbon (Pd/C), tris (dibenzylideneacetone) dipalladium-chloroform adduct (C) 52 H 43 Cl 3 O 3 Pd 2 ) Bis (acetylacetonato) palladium (Pd (acac) 2 ) Bis (triphenylphosphine) palladium dichloride (PdCl) 2 (PPh 3 ) 2 ) Tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And any one or mixture of any several of the corresponding hydrates;
the boron reagent is tetrahydroxy diboron (B) 2 (OH) 4 ) Boric acid (H) 3 BO 3 ) Phenylboronic acid (Ph (OH) 2 ) 4-Chlorobenzeneboronic acid (ClPh (OH) 2 ) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them;
in the aromatic nitro derivative (I), ar is selected from the following groups:
Figure BDA0002535088650000022
in the definitions of any of the compounds (I), (II) above, the terms used, whether used alone or in compound words, represent the following substituents: r is 1 Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl radical, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups; x is any one of O and S;
in the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine, iodine;
alkyl groups: refers to straight or branched chain alkyl;
halogenated alkyl groups: refers to straight-chain or branched alkyl groups in which the hydrogen atoms on these alkyl groups are partially or fully substituted by halogen atoms;
cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group;
substituted aryl ketones: phenyl ketone, pyridine ketone, furan ketone;
the invention provides a new method for synthesizing arylamine compounds. Compared with the prior art, the invention has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.
The invention aims to provide a method for reducing aromatic nitro into aromatic amine, wherein the structural formula of the prepared aromatic amine compound is shown as follows:
Ar-NH 2
wherein Ar is selected from the following groups:
Figure BDA0002535088650000031
R 1 is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl radical, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups; x is any one of O and S;
the invention also aims to provide the method for reducing the aromatic nitro group into the arylamine, which has the advantages of mild reaction conditions, low cost, environmental friendliness and high yield and is suitable for industrial production. The aromatic amine compound (II) can be obtained by taking the aromatic nitro derivative (I) as a raw material, tetrahydroxy diboron as an additive, copper salt as a metal catalyst and acetonitrile as a solvent and reacting for 24 hours at the temperature of 80-100 ℃, wherein the specific reaction equation is as follows:
Figure BDA0002535088650000032
the Cu metal catalyst is copper trifluoromethanesulfonate (Cu (CF) 3 SO 3 ) 2 ) Copper acetate (Cu (OAc) 2 ) Cuprous acetate (CuOAc), cupric bromide (CuBr) 2 ) Anhydrous copper chloride (CuCl) 2 ) Copper (I) iodide (CuI), copper (I) chloride (CuCl), copper fluoride
(CuF) and any one or a mixture of any more of the corresponding hydrates.
The boron reagent is tetrahydroxy diboron (B) 2 (OH) 4 ) Boric acid (H) 3 BO 3 ) Phenylboronic acid (Ph (OH) 2 ) 4-Chlorobenzeneboronic acid (ClPh (OH) 2 ) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them.
In the aromatic nitro derivative (I), ar is selected from the following groups:
Figure BDA0002535088650000033
in the definitions of any of the compounds (I), (II) above, the terms used, whether used alone or in compound words, represent the following substituents: r is 1 Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl radical, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups; x is any one of O and S.
In the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: refers to fluorine, chlorine, bromine, iodine.
Alkyl groups: refers to straight or branched chain alkyl groups.
Halogenated alkyl groups: refers to straight or branched chain alkyl groups in which the hydrogen atoms are partially or fully substituted with halogen atoms.
Cycloalkyl: refers to a saturated or unsaturated cycloalkyl group.
Substituted aryl ketones: phenyl ketone, pyridine ketone and furan ketone.
The invention provides a new method for synthesizing arylamine compounds. Compared with the prior art, the invention has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.
The invention aims to provide a method for reducing aromatic nitro into aromatic amine, wherein the structural formula of the prepared aromatic amine compound is shown as follows:
Ar-NH 2
wherein Ar is selected from the following groups:
Figure BDA0002535088650000041
R 1 is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl radical, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups; x is any one of O and S;
the invention also aims to provide the method for reducing the aromatic nitro group into the arylamine, which has the advantages of mild reaction conditions, low cost, environmental friendliness and high yield and is suitable for industrial production. The aromatic amine compound (II) can be obtained by taking the aromatic nitro derivative (I) as a raw material, water as a hydrogen source and a solvent, a diboron reagent as an additive and no metal catalyst, wherein the reaction temperature is 30-100 ℃, and the reaction time is 4-24 hours, and the specific reaction equation is as follows:
Figure BDA0002535088650000042
the boron reagent is tetrahydroxy diboron (B) 2 (OH) 4 ) Boric acid (H) 3 BO 3 ) Phenylboronic acid (Ph (OH) 2 ) 4-Chlorobenzeneboronic acid (ClPh (OH) 2 ) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them;
in the aromatic nitro derivative (I), ar is selected from the following groups:
Figure BDA0002535088650000043
in the definitions of any of the compounds (I), (II) above, the terms used, whether used alone or in compound words, represent the following substituents: r 1 Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl radical, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups; x is any one of O and S;
in the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine and iodine;
alkyl groups: refers to straight or branched chain alkyl;
halogenated alkyl groups: refers to straight or branched alkyl groups in which the hydrogen atoms are partially or fully substituted by halogen atoms;
cycloalkyl: refers to a saturated or unsaturated cycloalkyl group;
substituted aryl ketones: phenyl ketone, pyridine ketone, furan ketone;
the invention provides a new method for synthesizing arylamine compounds. The boron atoms in the boron reagent have strong affinity to oxygen atoms and nitrogen atoms, water can be activated, boric acid is the only byproduct, and the boron reagent is an ideal water activator. Compared with the prior art, the method has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.
Example 1
Synthesis of anilines
Figure BDA0002535088650000051
Nitrobenzene (0.6mmol, 74.0mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg), tetrahydroxydiboron (1.5mmol, 134.5mg), toluene (1 mL), under the protection of nitrogen, reacted at 50 ℃ for 24h, monitored by tlc, added with 10mL of water, extracted with ethyl acetate (10 mL × 3), combined organic phases, dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and subjected to column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400 MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H),3.66 (s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 2
Synthesis of anilines
Figure BDA0002535088650000052
Nitrobenzene (0.6mmol, 74.0)mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.5mmol, 134.5mg), tetrahydrofuran (1 mL), under nitrogen protection, 50 ℃ reaction 24h, tlc monitoring the reaction, adding 10mL of water, ethyl acetate (10 mL × 3) extraction, combining organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3), obtaining 32.4mg of colorless liquid, i.e. the target compound, yield 58%. 1 H NMR (400MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H), 3.66(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 3
Synthesis of anilines
Figure BDA0002535088650000061
Nitrobenzene (0.6mmol, 74.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.5mmol, 134.5mg), methanol (1 mL), under nitrogen protection, 50 ℃ reaction 24h, tlc monitoring the reaction, adding 10mL of water, ethyl acetate (10 mL × 3) extraction, combining organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3), obtaining 33.0mg of colorless liquid, i.e. the target compound, yield 59%. 1 H NMR(400MHz,CDCl 3 )δ: 7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H),3.66(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 4
Synthesis of anilines
Figure BDA0002535088650000062
Nitrobenzene (0.6mmol, 74.0mg), methanol (6 mmol, 192.2mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.5mmol, 134.5mg), acetonitrile (1 mL), reacted at 50 ℃ for 24h under nitrogen protection, the reaction was monitored by TLC, and10mL of water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, and column chromatography (V petroleum ether: V ethyl acetate =3: 1) to obtain 55.4mg of a colorless liquid, which is the target compound, in 99% yield. 1 H NMR(400 MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H),3.66 (s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 5
Synthesis of anilines
Figure BDA0002535088650000063
Nitrobenzene (0.6mmol, 74.0mg), water (6 mmol, 108.0mg), pd (OAc) 2 (0.03mmol, 0.7mg) and tetrahydroxydiboron (1.5mmol, 134.5mg), acetonitrile (1 mL), under nitrogen protection, reaction at 50 ℃ for 24h, tlc monitoring, addition of 10mL of water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 55.4mg of a colorless liquid, i.e., the desired compound in 99% yield. 1 H NMR (400MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H), 3.66(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 6
Synthesis of anilines
Figure BDA0002535088650000071
Nitrobenzene (0.6mmol, 74.0mg), water (6 mmol, 108.0mg), pd (CF) 3 COO) 2 (0.03mmol, 1.0mg) and tetrahydroxydiboron (1.5mmol, 134.5mg), acetonitrile (1 mL), reacting at 50 ℃ for 24h under the protection of nitrogen, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, and concentrating under reduced pressureAnd column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6 Hz,2H),3.66(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 7
Synthesis of aniline
Figure BDA0002535088650000072
Nitrobenzene (0.6mmol, 74.0mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg), pinacol diboron (1.5mmol, 380.9mg), acetonitrile (1 mL) and under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H), 3.66(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 8
Synthesis of anilines
Figure BDA0002535088650000073
Nitrobenzene (0.6mmol, 74.0mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg), tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), under the protection of nitrogen, reacted at 50 ℃ for 24h, monitored by tlc, added with 10mL of water, extracted with ethyl acetate (10 mL × 3), combined organic phases, dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and subjected to column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400 MHz,CDCl 3 )δ:7.27-7.23(m,2H),6.86-6.83(m,1H),6.76(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,2H),3.66 (s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.50,129.38,118.60,115.18
Example 9
Synthesis of 2-aminotoluene
Figure BDA0002535088650000081
2-nitrotoluene (0.6mmol, 82.3mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), reacting at 50 ℃ for 24h under the protection of nitrogen, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl 3 )δ:7.08(d,J＝7.6Hz,2H),6.75-6.69(m,2H),3.61(s,br,2H),2.20(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:144.63,130.50,127.02,122.38,118.67,114.97
Example 10
Synthesis of 4-aminotoluene
Figure BDA0002535088650000082
4-nitrotoluene (0.6mmol, 82.3mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg), tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl3)δ:7.03(d,J＝8.0Hz,2H),6.67(d,J＝8.4Hz,2H),3.59(s,br,2H),2.30(s,3H)； 13 C NMR(100MHz,CDCl3)δ:143.85,129.81,127.83,115.31,20.53
Example 11
Synthesis of o-phenylenediamine
Figure BDA0002535088650000083
2-nitroaniline (0.6mmol, 82.9mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL) were reacted at 50 ℃ for 24h under the protection of nitrogen, the reaction was monitored by TLC, 10mL of water was added, ethyl acetate (10 mL. Times.3) was extracted, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and subjected to column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 48.0mg of a white solid, i.e., the objective compound in 74% yield. 1 H NMR (400MHz,CDCl 3 )δ:6.78-6.73(m,4H),3.34(s,br,4H)； 13 C NMR(100MHz,CDCl 3 )δ:134.76, 120.31,116.77
Example 12
Synthesis of 3-bromo-aniline
Figure BDA0002535088650000091
3-bromonitrobenzene (0.6mmol, 121.3mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL) were reacted at 50 ℃ for 24h under the protection of nitrogen, the reaction was monitored by TLC, 10mL of water was added, ethyl acetate (10 mL. Times.3) was extracted, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and subjected to column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 64.0mg of a white solid, i.e., the objective compound in 62% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.04(t,J＝8.0Hz,1H),6.92-6.87(m,2H),6.64-6.61(m,1H),3.75 (s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:147.81,130.64,123.07,121.39,117.84,113.65.
Example 13
Synthesis of 2, 5-dibromo-aniline
Figure BDA0002535088650000092
2, 5-dibromo-nitrobenzene (0.6 mmol, 168.5mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reaction at 50 ℃ for 24h under nitrogen protection, reaction monitoring by tlc, addition of 10mL of water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 109.9mg of a white solid, i.e., the objective compound in 73% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.28(d,J＝8.4Hz,1H),6.94(d,J＝2.0Hz,1H),6.77(dd, J 1 ＝2.0Hz,J 2 ＝8.4Hz,1H),4.18(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:145.30,133.64, 122.17,121.76,118.13,107.77
Example 14
Synthesis of 3-methyl-4-aminoanisole
Figure BDA0002535088650000093
3-methyl-4-nitrobenzyl ether (0.6mmol, 100.3mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reacting at 50 ℃ for 24h under the protection of nitrogen, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:6.73(s,1H),6.72-6.67(m,2H),3.79(s,3H), 3.40(s,br,2H),2.22(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:152.71,138.27,124.07,116.40, 116.05,112.12,55.75,17.79.
Example 15
Synthesis of 4' -aminoacetophenone
Figure BDA0002535088650000101
4' -nitroacetophenone (0.6mmol, 99.1mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400MHz,CDCl 3 )δ:7.85(dd,J 1 ＝1.6Hz,J 2 ＝8.4Hz,2H),6.69(dd,J 1 ＝1.6Hz,J 2 ＝ 8.8Hz,2H),4.18(s,br,2H),2.54(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.55,151.14,130.84, 127.87,113.74,26.14.
Example 16
Synthesis of 4-aminobenzophenone
Figure BDA0002535088650000102
4-nitrobenzophenone (0.6mmol, 99.1mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400MHz,CDCl 3 )δ:7.77-7.75(m,4H),7.60-7.56(m,1H),7.51-7.47(m,2H), 6.73-6.70(m,2H),4.19(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:195.35,150.93,138.88,132.98, 131.45,129.56,128.11,127.46,113.66.
Example 17
Synthesis of 2-cyanoaniline
Figure BDA0002535088650000103
2-nitrobenzyl cyanide (0.6mmol, 88.9 mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL) and under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl 3 )δ:7.42-7.34(m,2H),6.79-6.75(m,2H),4.46(s,br,2H)； 13 C NMR(100MHz, CDCl 3 )δ:149.67,134.06,132.39,118.02,117.70,115.20,96.00.
Example 18
Synthesis of 3-cyanoaniline
Figure BDA0002535088650000111
3-nitrobenzyl cyanide (0.6mmol, 88.9 mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), reacting at 50 ℃ for 24h under the protection of nitrogen, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl3)δ:7.26(t,J＝8.0Hz,1H),7.07-7.04(m,1H),6.94-6.89(m,2H),3.92(s,br, 2H)； 13 C NMR(100MHz,CDCl3)δ:146.92,130.10,122.05,119.20,117.47,112.99.
Example 19
Synthesis of 4-cyanoaniline
Figure BDA0002535088650000112
4-nitrobenzyl cyanide (0.6 mmol,88.9 mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg) and tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL) were reacted at 50 ℃ under nitrogen for 2 h4h, tlc monitored the reaction, added 10mL of water, extracted with ethyl acetate (10 mL × 3), combined organic phases, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and column chromatographed (V petroleum ether: V ethyl acetate = 3). 1 H NMR (400MHz,CDCl3)δ:7.45(dd,J 1 ＝3.6Hz,J 2 ＝8.4Hz,2H),6.68(d,J＝8.8Hz,2H),4.20(s,br, 2H)； 13 C NMR(100MHz,CDCl3)δ:150.47,133.85,120.23,114.46,100.11.
Example 20
Synthesis of 2' -aminoacetanilide
Figure BDA0002535088650000113
2' -nitroacetanilide (0.6mmol, 108.1mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400MHz,CDCl3)δ:7.52(s,br,1H),7.17(d,J＝7.6Hz,1H),7.11-7.07(m,1H), 6.83-6.80(m,2H),3.92(s,br,2H),2.18(s,3H)； 13 C NMR(100MHz,CDCl3)δ:169.06,140.96, 127.36,125.51,124.24,119.54,118.16,23.68.
Example 21
Synthesis of 2-aminobenzoic acid
Figure BDA0002535088650000121
2-nitrobenzoic acid (0.6mmol, 100.3mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reacting for 24h at 50 ℃ under the protection of nitrogen, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, and passing throughFiltration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:7.98(d,J＝8.0Hz,1H),7.38-7.34(m,1H),6.72(d,J＝6.8Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ:173.63,151.14,135.15,132.17,116.83,116.50,109.59.
Example 22
Synthesis of 2-aminobenzamides
Figure BDA0002535088650000122
2-nitrobenzamide (0.6mmol, 99.7mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL) are reacted at 50 ℃ under the protection of nitrogen, reaction is monitored by TLC, 10mL of water is added, ethyl acetate (10 mL. Times.3) is extracted, organic phases are combined, anhydrous sodium sulfate is dried, filtering is carried out, concentration is carried out under reduced pressure, column chromatography is carried out (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400MHz,CDCl 3 )δ:7.40(dd,J 1 ＝1.6Hz,J 2 ＝8.0Hz,1H),7.29-7.25(m,1H),6.73-6.66 (m,2H),5.93(s,br,2H),5.72(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:171.67,149.48,133.06, 128.03,117.48,116.43,113.96.
Example 23
Synthesis of methyl 2-aminobenzoate
Figure BDA0002535088650000123
Methyl 2-nitrobenzoate (0.6mmol, 108.7mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reaction at 50 ℃ under nitrogen protection 24h, reaction monitoring by TLC, addition of 10mL of water, extraction with ethyl acetate (10 mL. Times.3), combination of the organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 1),60.9mg of oily liquid was obtained, giving the desired compound in 65% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.90(dd,J 1 ＝1.6Hz,J 2 ＝8.0Hz,1H),7.33-7.28(m,1H), 6.71-6.66(m,2H),5.76(s,br,2H),3.91(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:168.63,150.46, 134.14,131.25,116.71,116.31,110.76,51.57.
Examples 24
Synthesis of 2-amino-N- (o-toluamide)
Figure BDA0002535088650000131
2-nitro-N- (o-toluamide) (0.6 mmol, 153.8mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg), tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), 50 ℃ reaction for 24h under nitrogen protection, tlc monitoring, addition of 10mL of water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 134.4mg of a white solid, i.e., the target compound in 99% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.87(d,J＝8.0Hz,1H),7.65(s,br,1H),7.54(dd,J 1 ＝1.2Hz, J 2 ＝8.4Hz,1H),7.33-7.27(m,3H),7.19-7.15(m,1H),6.79-6.75(m,2H),5.60(s,br,2H),2.37(s, 3H)； 13 C NMR(100MHz,CDCl 3 )δ:167.59,149.15,135.72,132.81,130.66,129.89,127.18, 126.84,125.45,123.55,117.64,116.88,116.12,17.98.
Example 25
Synthesis of 2-amino-N- (p-toluamide)
Figure BDA0002535088650000132
2-Nitro-N- (p-toluamide) (0.6mmol, 153.8mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reaction at 50 ℃ under nitrogen protection 24h, monitoring the reaction by TLC, adding 10mL of water, ethyl acetate (10 mL. Times.3)Extraction, combined organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:7.73(s,br,1H),7.51-7.47(m,3H),7.31-7.27(m,1H),7.21(d,J ＝8.0Hz,2H),6.77-6.74(m,2H),5.54(s,br,2H),2.38(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ: 167.51,148.96,135.26,134.22,132.66,129.58,127.13,120.67,117.53,116.83,116.39,20.92.
Example 26
Synthesis of 2-amino-N- (4-methoxyphenyl) benzamide
Figure BDA0002535088650000141
2-nitro-N- (4-methoxyphenyl) benzamide (0.6mmol, 163.4mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reacted at 50 ℃ for 24h under nitrogen protection, the reaction was monitored by TLC, 10mL of water was added, ethyl acetate (10 mL. Times.3) was extracted, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and subjected to column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400MHz,CDCl 3 )δ:7.71(s,br,1H),7.51-7.48(m,3H), 7.31-7.27(m,1H),6.97-6.93(m,2H),6.77-6.73(m,2H),5.55(s,br,2H),3.85(s,3H)； 13 C NMR (100MHz,CDCl 3 )δ:167.55,156.69,148.91,132.65,130.80,127.13,122.61,117.54,116.85, 116.30,114.27,55.55.
Example 27
Synthesis of 2-amino-N- (4-chlorophenyl) benzamide
Figure BDA0002535088650000142
2-Nitro-N- (4-chlorophenyl) benzamide (0.6 mmol,166.0 mg), water (6 mmol,108.0 mg), pd/C (0.03 mmol,6.4 mg) and tetrahydroxydiboron (1.98mmol, 17 mmol, 17. Sup. Th.)7.5 mg), acetonitrile (1 mL), nitrogen atmosphere, reaction at 50 ℃ 24h, reaction monitoring by tlc, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to afford 137.7mg of a grey solid, which gave the desired compound in 93% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.83(s,br,1H),7.56(d,J＝8.8Hz,2H),7.49(d, J＝7.6Hz,1H),7.36(d,J＝8.8Hz,2H),7.32-7.28(m,1H),6.77-6.73(m,2H),5.52(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:167.52,149.05,136.47,133.01,129.47,129.10,127.14,121.75, 117.67,116.92,115.80.
Example 28
Synthesis of 2-amino-N- (3-chlorophenyl) benzamide
Figure BDA0002535088650000151
2-nitro-N- (3-chlorophenyl) benzamide (0.6 mmol,166.0 mg), water (6 mmol,108.0 mg), pd/C (0.03 mmol,6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), reacted at 50 ℃ for 24h under nitrogen protection, monitored by tlc, 10mL of water was added, ethyl acetate (10 mL × 3) was extracted, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and separated by column chromatography (V petroleum ether: V ethyl acetate = 3) to give 146.8mg of a white solid, which was the target compound in 87% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.81(s,br,1H),7.77(t,J＝2.0Hz,1H),7.49(dd, J＝1.2Hz,J＝8.4Hz,1H),7.45-7.42(m,1H),7.34-7.29(m,2H),7.17-7.15(m,1H),6.78-6.74(m, 2H),5.55(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:167.49,149.12,139.07,134.75,133.09, 130.04,127.10,124.48,120.49,118.33,117.71,116.93,115.66.
Example 29
Synthesis of 2-amino-N- (3, 4-dichlorochlorophenyl) benzamide
Figure BDA0002535088650000152
2-nitro-N- (3, 4-dichlorochlorophenyl) benzamide (0.6 mmol,186.7 mg), water (6 mmol,108.0 mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), reacted at 50 ℃ for 24h under nitrogen protection, monitored by tlc, 10mL of water was added, ethyl acetate (10 mL × 3) was extracted, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and column chromatographed (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:7.89(d,J＝2.0Hz,1H),7.81(s,br, 1H),7.48-7.46(m,1H),7.44-7.40(m,2H),7.34-7.29(m,1H),6.78-6.74(m,2H),5.55(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:167.42,149.18,137.43,133.25,132.87,130.55,127.58,127.06, 122.03,119.55,117.78,116.96,115.31
Example 30
Synthesis of 2-amino-N- (phenylmethyl) benzamide
Figure BDA0002535088650000153
2-nitro-N- (benzyl) benzamide (0.6 mmol, 153.8mg), water (6 mmol, 108.0mg), pd/C (0.03 mmol,6.4 mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:7.40-7.34(m,6H),7.27-7.23(m,1H),6.73(d,J＝ 8.4Hz,1H),6.67(t,J＝7.6Hz,1H),6.38(s,br,2H),5.60(s,br,2H),4.65(d,J＝5.6Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ:169.17,148.87,138.28,132.45,128.83,127.85,127.61,127.11,117.40, 116.64,115.80,43.76
Example 31
Synthesis of 2-chloro-3-aminopyridine
Figure BDA0002535088650000161
2-chloro-3-nitropyridine (0.6 mmol, 95.1mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), under nitrogen protection, reaction at 50 ℃ for 24h, reaction monitoring by TLC, addition of 10mL of water, extraction with ethyl acetate (10 mL. Times.3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 62.5mg of a white solid, i.e., the objective compound in a yield of 81%. 1 H NMR(400MHz,CDCl 3 )δ:7.83(t,J＝3.2Hz,1H),7.07(d,J＝2.8Hz,2H),4.13(s,br,1H)； 13 C NMR(100MHz,CDCl 3 )δ:139.67,138.67,136.98,123.39,122.44
Example 32
Synthesis of 5-bromo-3-aminopyridine
Figure BDA0002535088650000162
5-bromo-3-nitropyridine (0.6mmol, 121.8mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), under nitrogen protection, reaction at 50 ℃ for 24h, reaction monitoring by TLC, addition of 10mL of water, extraction with ethyl acetate (10 mL. Times.3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:8.13(d,J＝2.4Hz,1H),7.52(dd,J 1 ＝2.4Hz,J 2 ＝8.8Hz,1H), 6.45(d,J＝8.8Hz,1H),4.56(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:157.06,148.73,140.15, 110.09,108.32
Example 33
Synthesis of 5-aminoquinolines
Figure BDA0002535088650000171
5-nitroquinoline (0.6mmol, 114.1mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl 3 )δ:8.92(dd,J 1 ＝1.6Hz,J 2 ＝4.0Hz,1H),8.22(d,J＝8.4Hz,1H),7.62-7.53(m, 2H),7.39(dd,J 1 ＝4.4Hz,J 2 ＝8.8Hz,1H),6.86(dd,J 1 ＝0.8Hz,J 2 ＝7.2Hz,1H),4.26(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:150.27,149.11,142.28,130.06,129.57,120.17,119.63,118.74, 110.07
Examples 34
Synthesis of 6-aminoquinoline
Figure BDA0002535088650000172
6-nitroquinoline (0.6mmol, 114.1mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl 3 )δ:8.69(dd,J 1 ＝1.6Hz,J 2 ＝4.4Hz,1H),7.96-7.92(m,2H),7.31(dd,J 1 ＝4.4 Hz,J 2 ＝8.4Hz,1H),7.20(dd,J 1 ＝2.4Hz,J 2 ＝8.8Hz,1H),6.94(d,J＝2.4Hz,1H),4.01(s,br, 2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.89,144.61,143.48,133.82,130.60,129.80,121.59, 121.44,107.46
Example 35
Synthesis of 8-aminoquinoline
Figure BDA0002535088650000173
8-nitroquinoline (0.6mmol, 114.1mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR (400MHz,CDCl 3 )δ:8.81(dd,J 1 ＝2.0Hz,J 2 ＝4.4Hz,1H),8.11(dd,J 1 ＝1.6Hz,J 2 ＝8.4Hz,1H), 7.42-7.36(m,2H),7.20(dd,J 1 ＝1.2Hz,J 2 ＝8.4Hz,1H),6.98(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,1H),5.03 (s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:147.48,143.95,138.45,136.04,128.88,127.40,121.39, 116.09,110.09
Example 36
Synthesis of 2-methyl-8-aminoquinoline
Figure BDA0002535088650000181
2-methyl-8-nitroquinoline (0.6mmol, 113.0mg), water (6 mmol, 108.0mg), pd/C (0.03mmol, 6.4mg) and tetrahydroxydiboron (1.98mmol, 177.5mg), acetonitrile (1 mL), reacting at 50 ℃ for 24h under the protection of nitrogen, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3). 1 H NMR(400MHz,CDCl 3 )δ:7.99(d,J＝8.4Hz,1H),7.32-7.27(m,2H),7.15(dd,J 1 ＝1.2 Hz,J 2 ＝8.4Hz,1H),6.95(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,1H),5.00(s,br,2H),2.75(s,3H)； 13 C NMR (100MHz,CDCl 3 )δ:156.20,143.38,136.11,126.89,126.33,122.18,115.93,110.16,102.89
Example 37
Synthesis of 5-aminoisoquinoline
Figure BDA0002535088650000182
5-nitroisoquinoline (0.6mmol, 104.5mg), water (6mmol, 108.0mg), pd/C (0.03mmol, 6.4 mg), tetrahydroxydiboron (1.98mmol, 177.5 mg), acetonitrile (1 mL), under the protection of nitrogen, reacting at 50 ℃ for 24h, monitoring the reaction by TLC, adding 10mL of water, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3. 1 H NMR(400MHz,CDCl 3 )δ:9.22(s,1H),8.53(d,J＝5.6Hz,1H),7.62(d,J＝6.0Hz,1H),7.45 (d,J＝4.0Hz,2H),7.99(t,J＝4.4Hz,1H),4.28(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ: 153.01,142.07,141.37,129.43,127.80,126.00,118.02,114.09,113.10
Example 38
Synthesis of 3-bromo-aniline
Figure BDA0002535088650000191
3-Bromobenzophenone (0.6mmol, 121.3mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 66.1mg of a white solid, which is the target compound, in 64% yield. 1 H NMR(400MHz, CDCl 3 )δ:7.04(t,J＝8.0Hz,1H),6.92-6.87(m,2H),6.64-6.61(m,1H),3.75(s,br,2H)； 13 C NMR (100MHz,CDCl 3 )δ:147.81,130.64,123.07,121.39,117.84,113.65
Example 39
Synthesis of 2, 5-dibromo-aniline
Figure BDA0002535088650000192
2, 5-dibromo-nitrobenzene (0.6mmol, 168.5mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and column chromatography (V petroleum ether: V ethyl acetate = 3) to give 134.0mg of a white solid, which is the target compound, in 89% yield. 1 H NMR(400 MHz,CDCl 3 )δ:7.28(d,J＝8.4Hz,1H),6.94(d,J＝2.0Hz,1H),6.77(dd,J 1 ＝2.0Hz,J 2 ＝8.4 Hz,1H),4.18(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:145.30,133.64,122.17,121.76, 118.13,107.77
Example 40
Synthesis of 4' -aminoacetophenone
Figure BDA0002535088650000193
4' -nitroacetophenone (0.6mmol, 99.1mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen, reaction at 100 ℃ for 24h, tlc monitoring, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 47.8mg of a yellow solid, which is the target compound in 59% yield. 1 H NMR(400MHz, CDCl 3 )δ:7.85(dd,J 1 ＝1.6Hz,J 2 ＝8.4Hz,2H),6.69(dd,J 1 ＝1.6Hz,J 2 ＝8.8Hz,2H),4.18(s,br, 2H),2.54(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.55,151.14,130.84,127.87,113.74,26.14
Example 41
Synthesis of 4-aminobenzophenone
Figure BDA0002535088650000201
4-Nitrobenzophenone (0.6 mmol, 99.1mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ for 24h, tlc monitoring, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 82.8mg of a yellow solid, which is the desired compound in 70% yield. 1 H NMR(400MHz, CDCl 3 )δ:7.77-7.75(m,4H),7.60-7.56(m,1H),7.51-7.47(m,2H),6.73-6.70(m,2H),4.19(s,br, 2H)； 13 C NMR(100MHz,CDCl 3 )δ:195.35,150.93,138.88,132.98,131.45,129.56,128.11, 127.46,113.66
Example 42
Synthesis of 2-cyanoaniline
Figure BDA0002535088650000202
2-Nitrobenzylcyanide (0.6 mmol,88.9 mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ for 24h, tlc monitoring, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 36.9mg of oily liquid, which is the target compound in 52% yield. 1 H NMR(400MHz, CDCl 3 )δ:7.42-7.34(m,2H),6.79-6.75(m,2H),4.46(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ: 149.67,134.06,132.39,118.02,117.70,115.20,96.00
Example 43
Synthesis of 3-cyanoaniline
Figure BDA0002535088650000203
3-Nitrobenzylcyanide (0.6 mmol,88.9 mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and column chromatography (V petroleum ether: V ethyl acetate = 3) to give 44.7mg of a yellow solid, which is the target compound, in 63% yield. 1 H NMR(400MHz, CDCl3)δ:7.26(t,J＝8.0Hz,1H),7.07-7.04(m,1H),6.94-6.89(m,2H),3.92(s,br,2H)； 13 C NMR(100MHz,CDCl3)δ:146.92,130.10,122.05,119.20,117.47,112.99
Example 44
Synthesis of 4-cyanoaniline
Figure BDA0002535088650000211
4-Nitrobenzylcyanide (0.6 mmol,88.9 mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen, reaction at 100 ℃ for 24h, tlc monitoring, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 56.7mg of a yellow solid, which gives the desired compound in 80% yield. 1 H NMR(400MHz, CDCl3)δ:7.45(dd,J 1 ＝3.6Hz,J 2 ＝8.4Hz,2H),6.68(d,J＝8.8Hz,2H),4.20(s,br,2H)； 13 C NMR(100MHz,CDCl3)δ:150.47,133.85,120.23,114.46,100.11
Example 45
Synthesis of 2-aminobenzoic acid
Figure BDA0002535088650000212
2-nitrobenzophenonesAcid (0.6mmol, 100.3mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and column chromatography (V petroleum ether: V ethyl acetate = 3) to give 44.4mg of a white solid, i.e., the target compound, in 54% yield. 1 H NMR(400MHz, CDCl 3 )δ:7.98(d,J＝8.0Hz,1H),7.38-7.34(m,1H),6.72(d,J＝6.8Hz,2H)； 13 C NMR(100 MHz,CDCl 3 )δ:173.63,151.14,135.15,132.17,116.83,116.50,109.59
Example 46
Synthesis of 5-aminoquinolines
Figure BDA0002535088650000213
5-Nitro-quinoline (0.6 mmol, 114.1mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ for 24h, tlc monitoring, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 68.3mg of a white solid, i.e. the target compound, in 79% yield. 1 H NMR(400MHz, CDCl 3 )δ:8.92(dd,J 1 ＝1.6Hz,J 2 ＝4.0Hz,1H),8.22(d,J＝8.4Hz,1H),7.62-7.53(m,2H),7.39 (dd,J 1 ＝4.4Hz,J 2 ＝8.8Hz,1H),6.86(dd,J 1 ＝0.8Hz,J 2 ＝7.2Hz,1H),4.26(s,br,2H)； 13 C NMR (100MHz,CDCl 3 )δ:150.27,149.11,142.28,130.06,129.57,120.17,119.63,118.74,110.07
Example 47
Synthesis of 6-aminoquinoline
Figure BDA0002535088650000221
6-nitro radicalQuinoline (0.6 mmol, 114.1mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen, reaction at 100 ℃ for 24h, tlc monitoring, addition of 10mL water, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 77.9mg of a white solid, which is the target compound, in 90% yield. 1 H NMR(400MHz, CDCl 3 )δ:8.69(dd,J 1 ＝1.6Hz,J 2 ＝4.4Hz,1H),7.96-7.92(m,2H),7.31(dd,J 1 ＝4.4Hz,J 2 ＝8.4 Hz,1H),7.20(dd,J 1 ＝2.4Hz,J 2 ＝8.8Hz,1H),6.94(d,J＝2.4Hz,1H),4.01(s,br,2H)； 13 C NMR (100MHz,CDCl 3 )δ:146.89,144.61,143.48,133.82,130.60,129.80,121.59,121.44,107.46
Example 48
Synthesis of 8-aminoquinoline
Figure BDA0002535088650000222
8-Nitro-quinoline (0.6 mmol, 114.1mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen, reaction at 100 ℃ for 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 75.3mg of a white solid, which is the target compound, in 87% yield. 1 H NMR(400MHz, CDCl 3 )δ:8.81(dd,J 1 ＝2.0Hz,J 2 ＝4.4Hz,1H),8.11(dd,J 1 ＝1.6Hz,J 2 ＝8.4Hz,1H),7.42-7.36 (m,2H),7.20(dd,J 1 ＝1.2Hz,J 2 ＝8.4Hz,1H),6.98(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,1H),5.03(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:147.48,143.95,138.45,136.04,128.88,127.40,121.39,116.09, 110.09
Example 49
Synthesis of 2-methyl-8-aminoquinoline
Figure BDA0002535088650000231
2-methyl-8-nitroquinoline (0.6mmol, 113.0mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and column chromatography (V petroleum ether: V ethyl acetate = 3) to give 84.5mg of a white solid, which is the target compound, in 89% yield. 1 H NMR(400MHz, CDCl 3 )δ:7.99(d,J＝8.4Hz,1H),7.32-7.27(m,2H),7.15(dd,J 1 ＝1.2Hz,J 2 ＝8.4Hz,1H),6.95 (dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,1H),5.00(s,br,2H),2.75(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ: 156.20,143.38,136.11,126.89,126.33,122.18,115.93,110.16,102.89
Example 50
Synthesis of 5-aminoisoquinoline
Figure BDA0002535088650000232
5-Nitroisoquinoline (0.6 mmol, 104.5mg), cu (OAc) 2 (0.03mmol, 6.0 mg) and tetrahydroxydiboron (0.9 mmol, 80.7 mg), acetonitrile (1 mL), under nitrogen protection, reaction at 100 ℃ 24h, monitoring the reaction by tlc, adding 10mL of water, extracting with ethyl acetate (10 mL × 3), combining the organic phases, drying over anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and column chromatography (V petroleum ether: V ethyl acetate = 3) to give 65.7mg of a white solid, i.e., the target compound, in 76% yield. 1 H NMR(400MHz, CDCl 3 )δ:9.22(s,1H),8.53(d,J＝5.6Hz,1H),7.62(d,J＝6.0Hz,1H),7.45(d,J＝4.0Hz,2H), 7.99(t,J＝4.4Hz,1H),4.28(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:153.01,142.07,141.37, 129.43,127.80,126.00,118.02,114.09,113.10
Example 51
Synthesis of 4' -aminoacetophenone
Figure BDA0002535088650000233
4' -nitroacetophenone (0.6mmol, 99.1mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), reaction at 100 ℃ for 8h under the protection of nitrogen, reaction monitoring by tlc, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying with anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3), and 36.5mg of a yellow solid was obtained, i.e. the target compound, in a yield of 45%. 1 H NMR(400MHz,CDCl 3 )δ:7.85(dd,J 1 ＝1.6Hz,J 2 ＝8.4Hz,2H),6.69 (dd,J 1 ＝1.6Hz,J 2 ＝8.8Hz,2H),4.18(s,br,2H),2.54(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ: 196.55,151.14,130.84,127.87,113.74,26.14
Example 52
Synthesis of 4-aminobenzophenone
Figure BDA0002535088650000241
4-nitrobenzophenone (0.6mmol, 99.1mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), reaction at 100 ℃ for 8h under nitrogen protection, tlc monitoring, extraction with ethyl acetate (10 mL × 3), combination of organic phases, drying over anhydrous sodium sulfate, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to give 69.8mg of a yellow solid, which gives the desired compound in 59% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.77-7.75(m,4H),7.60-7.56(m,1H), 7.51-7.47(m,2H),6.73-6.70(m,2H),4.19(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:195.35, 150.93,138.88,132.98,131.45,129.56,128.11,127.46,113.66
Example 53
Synthesis of 2-cyanoaniline
Figure BDA0002535088650000242
2-nitrobenzyl cyanide (0.6mmol, 88.9mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), reaction at 100 ℃ for 8h under the protection of nitrogen, tlc monitoring reaction, ethyl acetate (10 mL × 3) extraction, organic phases combination, anhydrous sodium sulfate drying, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 58.8mg of oily liquid, namely the target compound with the yield of 83%. 1 H NMR(400MHz,CDCl 3 )δ:7.42-7.34(m,2H),6.79-6.75(m,2H),4.46(s, br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:149.67,134.06,132.39,118.02,117.70,115.20,96.00
Example 54
Synthesis of 3-cyanoaniline
Figure BDA0002535088650000243
3-nitrobenzyl cyanide (0.6mmol, 88.9mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), under the protection of nitrogen, reacting at 100 ℃ for 8h, monitoring the reaction by TLC, extracting with ethyl acetate (10 mL. Times.3), combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating by column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 61.0mg of a yellow solid, namely the target compound with the yield of 86%. 1 H NMR(400MHz,CDCl3)δ:7.26(t,J＝8.0Hz,1H),7.07-7.04(m,1H), 6.94-6.89(m,2H),3.92(s,br,2H)； 13 C NMR(100MHz,CDCl3)δ:146.92,130.10,122.05,119.20, 117.47,112.99
Example 55
Synthesis of 4-cyanoaniline
Figure BDA0002535088650000251
4-nitrobenzyl cyanide (0.6mmol, 88.9mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), reacting at 100 ℃ for 8h under the protection of nitrogen, monitoring the reaction by TLC, extracting by ethyl acetate (10 mL multiplied by 3), combining organic phases, drying by anhydrous sodium sulfate, filtering, decompressing, concentrating and concentratingCondensation, column chromatography (V petroleum ether: V ethyl acetate = 3) gave 70.2mg of a yellow solid, which gave the target compound in 99% yield. 1 H NMR(400MHz,CDCl3)δ:7.45(dd,J 1 ＝3.6Hz,J 2 ＝8.4Hz,2H),6.68 (d,J＝8.8Hz,2H),4.20(s,br,2H)； 13 C NMR(100MHz,CDCl3)δ:150.47,133.85,120.23,114.46, 100.11
Example 56
Synthesis of 5-aminoquinoline
Figure BDA0002535088650000252
5-nitroquinoline (0.6mmol, 114.1mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), reaction at 100 ℃ for 8h under the protection of nitrogen, tlc monitoring, ethyl acetate (10 mL × 3) extraction, organic phases combination, anhydrous sodium sulfate drying, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3), and 34.6mg of a white solid was obtained, i.e. the target compound, with a yield of 40%. 1 H NMR(400MHz,CDCl 3 )δ:8.92(dd,J 1 ＝1.6Hz,J 2 ＝4.0Hz,1H),8.22(d, J＝8.4Hz,1H),7.62-7.53(m,2H),7.39(dd,J 1 ＝4.4Hz,J 2 ＝8.8Hz,1H),6.86(dd,J 1 ＝0.8Hz,J 2 ＝7.2Hz,1H),4.26(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:150.27,149.11,142.28,130.06, 129.57,120.17,119.63,118.74,110.07
Example 57
Synthesis of 6-aminoquinoline
Figure BDA0002535088650000253
6-nitroquinoline (0.6mmol, 114.1mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), a reaction at 100 ℃ for 8h under the protection of nitrogen, TLC monitoring of the reaction, ethyl acetate (10 mL. Times.3) extraction, organic phase combination, anhydrous sodium sulfate drying, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3), and white solid 47.6mg is obtained, namely the target compound, wherein the yield is 47.6mg55％。 1 H NMR(400MHz,CDCl 3 )δ:8.69(dd,J 1 ＝1.6Hz,J 2 ＝4.4Hz,1H), 7.96-7.92(m,2H),7.31(dd,J 1 ＝4.4Hz,J 2 ＝8.4Hz,1H),7.20(dd,J 1 ＝2.4Hz,J 2 ＝8.8Hz,1H), 6.94(d,J＝2.4Hz,1H),4.01(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:146.89,144.61,143.48, 133.82,130.60,129.80,121.59,121.44,107.46
Example 58
Synthesis of 8-aminoquinoline
Figure BDA0002535088650000261
8-nitroquinoline (0.6mmol, 114.1mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), a reaction at 100 ℃ for 8h under the protection of nitrogen, tlc monitoring, ethyl acetate (10 mL × 3) extraction, organic phases combination, anhydrous sodium sulfate drying, filtration, concentration under reduced pressure, column chromatography (V petroleum ether: V ethyl acetate = 3), and 63.1mg of a white solid was obtained, i.e., the target compound, in 73% yield. 1 H NMR(400MHz,CDCl 3 )δ:8.81(dd,J 1 ＝2.0Hz,J 2 ＝4.4Hz,1H),8.11(dd,J 1 ＝ 1.6Hz,J 2 ＝8.4Hz,1H),7.42-7.36(m,2H),7.20(dd,J 1 ＝1.2Hz,J 2 ＝8.4Hz,1H),6.98(dd,J 1 ＝1.2 Hz,J 2 ＝7.6Hz,1H),5.03(s,br,2H)； 13 C NMR(100MHz,CDCl 3 )δ:147.48,143.95,138.45, 136.04,128.88,127.40,121.39,116.09,110.09
Example 59
Synthesis of 2-methyl-8-aminoquinoline
Figure BDA0002535088650000262
2-methyl-8-nitroquinoline (0.6mmol, 113.0mg), tetrahydroxydiboron (3.6mmol, 323mg), water (1 mL), nitrogen protection, 100 ℃ reaction for 8h, TLC monitoring reaction, ethyl acetate (10 mL. Times.3) extraction, organic phase combination, anhydrous sodium sulfate drying, filtration, reduced pressure concentrationAnd column chromatography (V petroleum ether: V ethyl acetate = 3) to obtain 28.5mg of a white solid, i.e., the objective compound in a yield of 30%. 1 H NMR(400MHz,CDCl 3 )δ:7.99(d,J＝8.4Hz,1H),7.32-7.27(m, 2H),7.15(dd,J 1 ＝1.2Hz,J 2 ＝8.4Hz,1H),6.95(dd,J 1 ＝1.2Hz,J 2 ＝7.6Hz,1H),5.00(s,br,2H), 2.75(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:156.20,143.38,136.11,126.89,126.33,122.18, 115.93,110.16,102.89。

Claims (1)

1. A synthesis method of an arylamine compound is characterized in that an arylamine compound (II) can be obtained by taking an aromatic nitro derivative (I) as a raw material, tetrahydroxy diboron as an additive, copper salt as a metal catalyst, acetonitrile as a solvent and reacting for 24 hours at the reaction temperature of 80-100 ℃, and the specific reaction equation is as follows:
Figure FDA0003953165530000011
said [ Cu ]]The metal catalyst is any one or mixture of any more of copper trifluoromethanesulfonate, copper acetate, cuprous acetate, copper bromide, anhydrous copper chloride, cuprous iodide, cuprous chloride, cuprous fluoride and corresponding hydrates;
ar is selected from the following groups:
Figure FDA0003953165530000012
any one of the above;
R 1 is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, C 1 —C 6 Alkyl radical, C 1 —C 6 Haloalkyl, C 3 —C 8 Cycloalkyl, C 1 —C 6 Alkyloxy, C 1 —C 6 Alkylamino radical, formic acid C 1 —C 6 Any one of alkyl ester groups;
in the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine, iodine;
alkyl groups: refers to straight or branched chain alkyl;
a haloalkyl group: refers to straight-chain or branched alkyl groups in which the hydrogen atoms on these alkyl groups are partially or fully substituted by halogen atoms;
cycloalkyl: refers to a saturated or unsaturated cycloalkyl group;
the aryl ketone is phenyl ketone, pyridine ketone, or furan ketone.
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