CN110372463A - A kind of method of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds - Google Patents

A kind of method of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds Download PDF

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CN110372463A
CN110372463A CN201910629817.8A CN201910629817A CN110372463A CN 110372463 A CN110372463 A CN 110372463A CN 201910629817 A CN201910629817 A CN 201910629817A CN 110372463 A CN110372463 A CN 110372463A
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aromatic
boronic acid
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acid compounds
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CN110372463B (en
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陈万芝
陈凯
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Zhejiang University ZJU
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    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
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    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring

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Abstract

The invention belongs to organic synthesis field, the methods for specifically disclosing a kind of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds, comprising: be SO with pyrosulfite in organic solvent2Source, heating carry out coupling reaction, obtain sulfonamide compounds using post-processing；The method of the present invention is easy to operate, is not necessarily to nitrogen protection, can carry out under air, nitro-aromatic and boronic acid compounds abundance, relative low price, reaction yield is high, and substrate applicability is wide, no metal residual.The method of the present invention can be used for synthesizing a series of sulfonamide compounds, and the compound of synthesis has a wide range of applications in pesticide, medicine and other fields.

Description

A kind of method of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds
Technical field
The present invention relates to organic synthesis fields, and in particular to a kind of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide The method of compound.
Background technique
Sulfamide compound is widely used (Scott, K.A. in pesticide, medicine and other fields；Njardarson, J.T.Top.Curr.Chem.(Z)2018,376,376).The method of conventional synthesis sulfonamide is made frequently with sulfonic acid chloride and amine in alkali Reacted under, although the method efficiently, due to sulfonic acid chloride exist it is more difficult preparation, functional group compatibility it is poor, to water sensitive, It is difficult to the disadvantages of saving, develops the new conjugation pattern being simple and efficient to substitute conventional synthesis sulfonamide method with important meaning Justice.
Nitro-aromatic is the Essential Chemistry raw material of industry, from a wealth of sources, cheap, and tradition prepares the original of sulfonamide Material amine is also from nitro reduction mostly.Sulfonamide is prepared by nitro-aromatic has document report ((a) Jiang, J.； Zeng,S.；Chen,D.；Cheng,C.；Deng,W.；Xiang,J.Org.Biomol.Chem.2018,16,5016；(b)Eid, N.；Karamé,I.；Andrioletti,B.Eur.J.Org.Chem.2018,2018,5016).But it is used in above-mentioned reaction Iron catalysis sulfonic acid chloride or sodium arylsulfinate and nitro-aromatic carry out reductive coupling and prepare sulfonamide, and one side metal residual exists Field of medicaments is the problem of cannot ignoring, and another aspect sulfonic acid chloride or sodium arylsulfinate type are few, and preparation is difficult, is lacked pervasive Property.
Therefore, develop it is a kind of with universality without metal catalytic nitro-aromatic prepare sulfonamide method have it is important Value.
Summary of the invention
The object of the present invention is to provide a kind of nitro-aromatics and boronic acid compounds coupling to synthesize sulfonamide compounds Method, this method is enriched without metal catalytic, raw material sources, good substrate applicability and yield are higher.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of method of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds, comprising: in organic solvent, It is SO with pyrosulfite using nitro-aromatic and boronic acid compounds as substrate2Source, heating carries out coupling reaction, using rear Processing obtains sulfonamide compounds；
Shown in the structure of the nitro-aromatic such as following formula (I):
Ar-NO2 (I)
Shown in the structure of the boronic acid compounds such as following formula (II):
R-B(OH)2 (II)
In formula (I), Ar is aryl or heteroaryl；In formula (II), R is aryl, heteroaryl or C1-C12Alkyl.
The reaction equation of the above method is as follows:
The reaction principle of the method for the invention are as follows: pyrosulfite forms RSO in conjunction with boronic acid compounds2 -, another party Face pyrosulfite restore nitro-aromatic after again with RSO2 -Coupling obtains sulfonamide.
Preferably, Ar is phenyl, substituted-phenyl, naphthalene aryl, hetero aryl group or oxygen heterocyclic aryl in formula (I)；Formula (II) in, R is phenyl, substituted-phenyl, naphthalene aryl, thienyl, benzothienyl, pyridyl group, indyl, benzofuranyl, different Oxazolyl or C1-C12Alkyl.
In view of the simplicity of raw material is easy to get, further preferably, in formula (I), the substituted-phenyl is alkyl, alkoxy, halogen The phenyl that element, morpholinyl, amino, ester group, acetyl group, carboxyl, cyano, methyl mercapto, amide groups, alkynyl or trifluoromethyl replace； The heteroaryl is pyridine, quinoline, isoquinolin, indoles, benzofurans heteroaryl.In formula (II), the substituted-phenyl is The phenyl that alkyl, alkoxy, trifluoromethyl, ester group or fluorine atom replace.
The pyrosulfite is potassium metabisulfite or sodium pyrosulfite.
The organic solvent is dioxane, toluene, tetrahydrofuran, acetonitrile, 1,2- dichloroethanes or dimethyl sulfoxide. With the molar amount of nitro-aromatic, the solvent usage is 1~10L/mol.
The considerations of for yield and solvent cost, preferably, the organic solvent be acetonitrile or dimethyl sulfoxide, with The molar amount of nitro-aromatic, the solvent usage are 3~6L/mol.
The temperature of the coupling reaction is 60~130 DEG C, and the reaction time is 12~48h.The considerations of for yield, reaction Temperature is preferably 100~130 DEG C, and the reaction time is preferably 12~36h.
The molar ratio of the nitro-aromatic and boronic acid compounds, pyrosulfite is 1:(1~4): (1~6), for receipts The considerations of rate and cost, preferably 1:(1.2~2): (2~4).
Preferably, be additionally added alkali in the coupling reaction, the alkali be tripotassium phosphate trihydrate, anhydrous phosphoric acid potassium, Potassium carbonate, cesium fluoride, cesium carbonate, potassium acetate, potassium fluoride, sodium carbonate or lithium carbonate；The molar ratio of the alkali and nitro-aromatic is (0.1~4): 1.This is because alkali is added in coupling reaction can be improved product yield.
Further preferably, the alkali is tripotassium phosphate trihydrate, anhydrous phosphoric acid potassium, potassium carbonate, cesium fluoride or fluorination The molar ratio of potassium, the alkali and nitro-aromatic is (1~2): 1, it can further improve the yield of product.
Preferably, being additionally added additive in the coupling reaction, the additive is tetrabutylammonium bromide, the tetrabutyl In ammonium chloride, tetrabutyl ammonium fluoride, tetrabutyl ammonium acetate, tetrabutyl ammonium hexafluorophosphate or 18- crown- 6, the additive and nitro The molar ratio of aromatic hydrocarbons is (0.2~2): 1.This is because additive is added in coupling reaction can be improved product yield.
The post-processing includes: to be filtered to remove insoluble matter first with diatomite and be spin-dried for solvent, then use silica gel column chromatography It is separated.
Compared with prior art, the invention has the following advantages that
(1) the method for the present invention is not necessarily to metal catalytic, three component one kettle way of nitro-aromatic, boronic acid compounds and pyrosulfite Coupling reaction prepares sulfonamide, and the operation is simple, and reaction condition is mild, is not necessarily to nitrogen protection, can carry out under air.
(2) the raw materials used nitro-aromatic of the method for the present invention and boronic acid compounds abundance, relative low price reduce Production cost, and the reaction yield is high, substrate applicability is wide, no metal residual, is suitble to large-scale production and application.
(3) the method for the present invention can be used for synthesizing a series of sulfonamide compounds, and the compound of synthesis is led in pesticide, medicine etc. Domain has a wide range of applications.
Specific embodiment
It will be helpful to understand the present invention by following embodiments, but the contents of the present invention are not limited to that.
Embodiment 1
The above-mentioned nitro-aromatic of 74mg, the phenyl boric acid of 88mg, the K of 267mg are added into dry tube sealing2S2O5, 160mg Tripotassium phosphate trihydrate, then the 18- crown- 6 of 32mg and the acetonitrile of 1.8mL are tightened tube sealing thread cap, are reacted at 100 DEG C 12h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 110mg, yield 79%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.83 (d, J=7.3Hz, 2H), 7.53-7.50 (m, 2H), 7.42 (t, J= 7.7Hz, 2H), 7.22 (t, J=7.8Hz, 2H), 7.13-7.07 (m, 3H)；13C NMR(100MHz,CDCl3)δ138.9, 136.5,133.1,129.3,129.1,127.3,125.4,121.6。
Embodiment 2
The above-mentioned nitro-aromatic of 82mg, the phenyl boric acid of 146mg, the Na of 456mg are added into dry tube sealing2S2O5, The tripotassium phosphate of 255mg, the tetrabutylammonium chloride of 334mg and the dimethyl sulfoxide of 3.6mL, then tighten tube sealing thread cap, and 130 36h is reacted at DEG C.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 89mg, yield 60%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.79 (d, J=7.2Hz, 2H), 7.52 (t, J=7.4Hz, 1H), 7.42 (t, J =7.6Hz, 2H), 7.18 (br, 1H), 7.03-6.96 (m, 4H), 2.26 (s, 3H)；13C NMR(100MHz,CDCl3)δ 139.0,135.5,133.7,132.9,129.9,129.0,127.3,122.4,20.9。
Embodiment 3
The above-mentioned nitro-aromatic of 92mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg Potassium carbonate, then the tetrabutylammonium bromide of 213mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 115mg, yield 73%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.72 (d, J=7.3Hz, 2H), 7.53 (t, J=7.4Hz, 1H), 7.42 (t, J =7.7Hz, 2H), 6.98 (d, J=8.9Hz, 2H), 6.82 (br, 1H), 6.75 (d, J=8.9Hz, 2H), 3.74 (s, 3H)；13C NMR(100MHz,CDCl3)δ158.1,138.9,132.9,129.0,128.6,127.3,125.7,114.5,55.4。
Embodiment 4
The above-mentioned nitro-aromatic of 124mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, The cesium fluoride of 182mg, the acetonitrile of tetrabutyl ammonium fluoride (the 1.0M in THF) and 3mL of 660 μ L, then tightens tube sealing thread cap, It is reacted for 24 hours at 130 DEG C.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 103mg, yield 54%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.73-7.71 (m, 2H), 7.50 (t, J=7.4Hz, 1H), 7.39 (t, J= 7.7Hz, 2H), 7.17 (s, 1H), 6.97 (d, J=9.0Hz, 2H), 6.74 (d, J=12.2Hz, 2H), 3.86-3.77 (m, 4H),3.11-3.02(m,4H)；13C NMR(100MHz,CDCl3)δ149.5,139.1,132.8,128.9,128.2,127.3, 125.0,116.1,66.8,49.2。
Embodiment 5
The above-mentioned nitro-aromatic of 85mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 70mg Potassium fluoride, then the tetrabutyl ammonium acetate of 199mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 96mg, yield 64%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.77-7.75 (m, 2H), 7.54 (t, J=7.5Hz, 1H), 7.44 (t, J= 7.7Hz, 2H), 7.33 (s, 1H), 7.10-7.02 (m, 2H), 6.91 (t, J=8.6Hz, 2H)；13C NMR(100MHz,CDCl3) δ 160.7 (d, J=244.0Hz), 138.6,133.2,132.2 (d, J=3.0Hz), 129.1,127.3,124.7 (d, J= 9.0Hz), 116.1 (d, J=23.0Hz)；19F NMR(376MHz,CDCl3)δ-116.1。
Embodiment 6
The above-mentioned nitro-aromatic of 115mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, The potassium carbonate of 166mg, the tetrabutyl hexafluorophosphoric acid amine of 256mg and the acetonitrile of 3mL, then tighten tube sealing thread cap, anti-at 130 DEG C It should for 24 hours.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 113mg, yield 63%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3)δ7.89-7.87(m,2H),7.79(s,1H),7.59-7.56(m,1H),7.52- 7.44 (m, 4H), 7.21 (d, J=8.4 Hz, 2H)；13C NMR(100MHz,CDCl3)δ139.8,138.6,133.6,129.4, 127.2,126.8 (q, J=32.0Hz), 126.7 (q, J=4.0Hz), 126.6 (q, J=270.0Hz), 119.8；19F NMR (376MHz,CDCl3)δ-62.3。
Embodiment 7
The above-mentioned nitro-aromatic of 89mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg Potassium carbonate, then the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 121mg, yield 78%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3)δ7.91-7.84(m,2H),7.62-7.58(m,2H),7.55-7.47(m,4H), 7.19 (d, J=8.8Hz, 2H)；13C NMR(100MHz,CDCl3)δ140.8,138.5,133.8,133.6,129.5,127.2, 119.5,118.4,107.9。
Embodiment 8
The above-mentioned nitro-aromatic of 117mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 146mg, yield 80%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6)δ10.87(s,1H),7.84-7.80(m,4H),7.64-7.52(m,3H), 7.23 (d, J=8.7Hz, 2H), 4.22 (q, J=7.1Hz, 2H), 1.24 (t, J=7.1Hz, 3H)；13C NMR(100MHz, DMSO-d6)δ165.1,142.2,139.2,133.2,130.5,129.4,126.6,124.7,118.2,60.4,14.1。
Embodiment 9
The above-mentioned nitro-aromatic of 99mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg Potassium carbonate, then the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 119mg, yield 72%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.91-7.79 (m, 5H), 7.56 (t, J=7.4Hz, 1H), 7.46 (t, J= 7.6Hz, 2H), 7.19 (d, J=8.8Hz, 2H), 2.53 (s, 3H)；13C NMR(100MHz,CDCl3)δ197.1,141.2, 138.8,133.5,133.3,130.0,129.3,127.2,119.0,26.4。
Embodiment 10
The above-mentioned nitro-aromatic of 120mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 120mg, yield 65%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.86-7.84 (m, 2H), 7.57-7.39 (m, 9H), 7.33 (t, J=7.3Hz, 1H), 7.22 (s, 1H), 7.17 (d, J=8.6Hz, 2H)；13C NMR(100MHz,CDCl3)δ140.0,139.1,138.3, 135.6,133.1,129.1,128.8,128.0,127.4,127.3,126.8,122.0。
Embodiment 11
The above-mentioned nitro-aromatic of 83mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg Potassium carbonate, then the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 101mg, yield 68%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6) δ 9.47 (s, 1H), 7.63 (d, J=7.2Hz, 2H), 7.58 (t, J=7.3Hz, 1H), 7.51 (t, J=7.4Hz, 2H), 6.66 (d, J=8.6Hz, 2H), 6.37 (d, J=8.6Hz, 2H), 4.97 (s, 2H)；13C NMR(100MHz,DMSO-d6)δ146.5,139.7,132.4,128.9,126.7,125.2,124.7,113.9。
Embodiment 12
The above-mentioned nitro-aromatic of 100mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 106mg, yield 64%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6)δ12.69(br,1H),10.78(br,1H),7.83-7.79(m,4H),7.63 (t, J=7.3Hz, 1H), 7.58-7.54 (m, 2H)；13C NMR(100MHz,DMSO-d6)δ166.7,141.9,139.2, 133.2,130.7,129.4,126.6,125.6,118.1。
Embodiment 13
The above-mentioned nitro-aromatic of 101mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 125mg, yield 75%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.78 (d, J=7.3Hz, 2H), 7.53 (t, J=7.4Hz, 1H), 7.43 (t, J =7.7Hz, 2H), 7.20 (s, 1H), 7.10 (d, J=8.7Hz, 2H), 7.01 (d, J=8.7Hz, 2H), 2.41 (s, 3H)；13C NMR(100MHz,CDCl3)δ138.8,135.7,133.6,133.1,129.1,127.6,127.3,122.8,16.1。
Embodiment 14
The above-mentioned nitro-aromatic of 100mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 124mg, yield 75%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6) δ 10.7 (s, 1H), 7.81-7.79 (m, 3H), 7.72 (d, J=8.7Hz, 2H), 7.62 (t, J=7.3Hz, 1H), 7.56 (t, J=7.3Hz, 2H), 7.25 (br, 1H), 7.13 (d, J=8.7Hz, 2H)；13C NMR(100MHz,DMSO-d6)δ167.1,140.4,139.3,133.1,129.4,129.4,128.7,126.6,118.2。
Embodiment 15
The above-mentioned nitro-aromatic of 152mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 86mg, yield 39%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.81-7.78 (m, 2H), 7.55 (t, J=7.4Hz, 1H), 7.47-7.41 (m, 4H), 7.37 (d, J=8.6Hz, 2H), 7.06 (d, J=8.6Hz, 2H), 7.01 (br, 1H), 6.86 (d, J=8.8Hz, 2H), 3.82(s,3H)；13C NMR(100MHz,CDCl3)δ159.7,138.8,136.0,133.2,133.0,132.5,129.2, 127.2,121.1,120.7,115.1,114.0,89.8,87.2,55.3。
Embodiment 16
The above-mentioned nitro-aromatic of 109mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 111mg, yield 65%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.81 (t, J=7.4Hz, 2H), 7.77-7.71 (m, 3H), 7.49-7.33 (m, 7H),7.18(br,1H)；13C NMR(100MHz,CDCl3)δ139.2,134.2,133.0,131.3,129.0,129.0, 128.4,127.4,127.3,126.7,126.3,125.4,123.2,121.5。
Embodiment 17
The above-mentioned nitro-aromatic of 75mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg Potassium carbonate, then the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 101mg, yield 72%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6) δ 10.58 (br, 1H), 8.27 (d, J=2.4Hz, 1H), 8.24 (dd, J= 4.7,1.2Hz, 1H), 7.77-7.75 (m, 2H), 7.63 (t, J=7.3Hz, 1H), 7.56 (t, J=7.4Hz, 2H), 7.51- 7.48 (m, 1H), 7.28 (dd, J=8.3,4.7Hz, 1H)；13C NMR(100MHz,DMSO-d6)δ145.3,141.7,139.0, 134.3,133.2,129.4,127.4,126.6,124.0。
Embodiment 18
The above-mentioned nitro-aromatic of 105mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 129mg, yield 76%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 8.90 (d, J=2.9Hz, 1H), 8.36 (d, J=8.5Hz, 1H), 8.02 (d, J =8.5Hz, 1H), 7.71 (d, J=7.6Hz, 2H), 7.59-7.52 (m, 2H), 7.43-7.36 (m, 3H), 7.27-7.21 (m, 2H)；13C NMR(100MHz,CDCl3)δ150.8,148.7,138.7,133.2,131.3,131.2,129.3,129.1, 128.8,127.4,125.5,124.5,121.5。
Embodiment 19
The above-mentioned nitro-aromatic of 105mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 92mg, yield 54%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6) δ 10.45 (s, 1H), 9.26 (s, 1H), 8.39 (d, J=6.0Hz, 1H), 7.98 (d, J=8.2Hz, 1H), 7.79 (d, J=6.0Hz, 1H), 7.67-7.65 (m, 2H), 7.61-7.56 (m, 2H), 7.50-7.43 (m,3H)；13C NMR(100MHz,DMSO-d6)δ152.4,142.9,139.5,132.9,131.6,131.5,129.2, 128.8,127.2,126.9,126.6,126.2,115.6。
Embodiment 20
The above-mentioned nitro-aromatic of 97mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg Potassium carbonate, then the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Instead It is filtered, is concentrated with diatomite after answering, crossed silicagel column, obtain product 111mg, yield 68%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6) δ 11.04 (s, 1H), 9.81 (s, 1H), 7.67 (d, J=7.4Hz, 2H), 7.57-7.46 (m, 3H), 7.29 (s, 1H), 7.23-7.21 (m, 2H), 6.81 (d, J=8.5Hz, 1H), 6.32 (br, 1H)；13C NMR(100MHz,DMSO-d6)δ139.6,133.6,132.4,128.9,128.8,127.6,126.7,126.2,117.1, 113.8,111.5,101.0。
Embodiment 21
The above-mentioned nitro-aromatic of 142mg, the phenyl boric acid of 146mg, the K of 460mg are added into dry tube sealing2S2O5, Then the potassium carbonate of 166mg, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted at 130 DEG C 24h.It is filtered, is concentrated with diatomite after reaction, crossed silicagel column, obtain product 193mg, yield 93%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.73 (d, J=7.3Hz, 2H), 7.53 (t, J=7.5Hz, 1H), 7.46 (d, J =2.1Hz, 1H), 7.43-7.39 (m, 4H), 7.10 (dd, J=9.0,2.2Hz, 1H), 7.04 (br, 1H), 4.43 (q, J= 7.1Hz, 2H), 1.41 (t, J=7.1Hz, 3H)；13C NMR(100MHz,CDCl3)δ159.3,153.7,146.9,138.6, 133.2,132.3,129.1,127.6,127.3,123.7,117.2,113.6,113.0,61.7,14.3。
Embodiment 22
The nitrobenzene of 74mg, the above-mentioned phenyl boric acid of 163mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg's Then potassium carbonate, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction After filtered with diatomite, be concentrated, cross silicagel column, obtain product 101mg, yield 68%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.68 (d, J=8.3Hz, 2H), 7.25-7.21 (m, 4H), 7.11-7.07 (m, 3H),7.04(br,1H),2.37(s,3H)；13C NMR(100MHz,CDCl3)δ143.9,136.6,136.0,129.7, 129.3,127.3,125.3,121.5,21.6。
Embodiment 23
The nitrobenzene of 74mg, the above-mentioned phenyl boric acid of 182mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg's Then potassium carbonate, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction After filtered with diatomite, be concentrated, cross silicagel column, obtain product 118mg, yield 75%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.73 (d, J=9.0Hz, 2H), 7.22 (t, J=8.0Hz, 2H), 7.15 (br, 1H), 7.10-7.07 (m, 3H), 6.88 (d, J=9.0Hz, 2H), 3.81 (s, 3H)；13C NMR(100MHz,CDCl3)δ 163.1,136.7,130.5,129.5,129.3,125.2,121.5,114.2,55.6。
Embodiment 24
The nitrobenzene of 74mg, the above-mentioned phenyl boric acid of 228mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg's Then potassium carbonate, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction After filtered with diatomite, be concentrated, cross silicagel column, obtain product 110mg, yield 61%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.93 (d, J=8.2Hz, 2H), 7.69 (d, J=8.3Hz, 2H), 7.45 (s, 1H), 7.25 (t, J=8.0Hz, 2H), 7.19-7.08 (m, 3H)；13C NMR(100MHz,CDCl3)δ142.4,135.8, 134.7 (q, J=33.0Hz), 129.6,127.8,126.3 (q, J=4.0Hz), 126.0,123.1 (q, J=272.0Hz), 122.0；19F NMR(376MHz,CDCl3)δ-63.2。
Embodiment 25
The nitrobenzene of 74mg, the above-mentioned phenyl boric acid of 168mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg's Then potassium carbonate, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction After filtered with diatomite, be concentrated, cross silicagel column, obtain product 103mg, yield 68%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3)δ7.83-7.78(m,2H),7.26-7.22(m,3H),7.14-7.07(m,5H) ；13C NMR(100MHz,CDCl3) δ 166.5 (d, J=254.0Hz), 136.2,134.9 (d, J=3.0Hz), 130.1, (130.0,129.4,125.7,121.8,116.5 d, J=23.0Hz)；19F NMR(376MHz,CDCl3)δ-104.4。
Embodiment 26
The nitrobenzene of 74mg, the above-mentioned phenyl boric acid of 233mg, the K of 460mg are added into dry tube sealing2S2O5, 166mg's Then potassium carbonate, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction After filtered with diatomite, be concentrated, cross silicagel column, obtain product 129mg, yield 70%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 8.07 (d, J=8.6Hz, 2H), 7.85 (d, J=8.6Hz, 2H), 7.48 (s, 1H), 7.23 (m, 2H), 7.11 (m, 3H), 4.38 (q, J=7.1Hz, 2H), 1.38 (t, J=7.1Hz, 3H)；13C NMR (100MHz,CDCl3)δ165.2,142.7,136.0,134.4,130.2,129.5,127.3,125.8,121.9,61.8, 14.2。
Embodiment 27
The nitrobenzene of 74mg, the above-mentioned boric acid of 72mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then sour potassium, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction knot The filtering of Shu Houyong diatomite, concentration cross silicagel column, obtain product 72mg, yield 70%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3)δ7.38-7.32(m,2H),7.24-7.17(m,3H),6.95(s,1H,),3.01 (s,3H)；13C NMR(100MHz,CDCl3)δ39.3,120.9,125.2,129.8,136.8。
Embodiment 28
The nitrobenzene of 74mg, the above-mentioned boric acid of 207mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then sour potassium, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction knot The filtering of Shu Houyong diatomite, concentration cross silicagel column, obtain product 126mg, yield 74%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 8.41 (s, 1H), 7.86 (t, J=9.3Hz, 3H), 7.81 (dd, J=8.7, 1.7Hz, 1H), 7.61 (t, J=7.4Hz, 1H), 7.56 (t, J=8.0Hz, 1H), 7.41 (s, 1H), 7.20 (d, J=8.0Hz, 2H), 7.14 (d, J=8.7Hz, 2H), 7.07 (t, J=7.2Hz, 1H)；13C NMR(100MHz,CDCl3)δ136.5,135.9, 134.9,132.0,129.5,129.4,129.3,128.9,127.9,127.5,125.4,122.3,121.6。
Embodiment 29
The nitrobenzene of 74mg, the above-mentioned boric acid of 154mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then sour potassium, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction knot The filtering of Shu Houyong diatomite, concentration cross silicagel column, obtain product 113mg, yield 79%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.89 (dd, J=3.0,1.3Hz, 1H), 7.38 (br, 1H), 7.33-7.31 (m, 1H),7.29-7.23(m,3H),7.14-7.10(m,3H)；13C NMR(100MHz,CDCl3)δ138.7,136.4,131.3, 129.4,128.0,125.6,125.4,121.7。
Embodiment 30
The nitrobenzene of 74mg, the above-mentioned boric acid of 214mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then sour potassium, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction knot The filtering of Shu Houyong diatomite, concentration cross silicagel column, obtain product 125mg, yield 72%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.79-7.77 (m, 3H), 7.44 (td, J=6.8,1.2Hz, 1H), 7.40 (td, J=7.6,1.2Hz, 1H), 7.28-7.24 (m, 2H), 7.20-7.18 (m, 3H), 7.14-7.15 (m, 1H)；13C NMR (100MHz,CDCl3)δ141.9,139.5,137.4,136.0,130.2,129.5,127.4,126.0,125.8,125.5, 122.7,121.9。
Embodiment 31
The nitrobenzene of 74mg, the above-mentioned boric acid of 195mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then sour potassium, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction knot The filtering of Shu Houyong diatomite, concentration cross silicagel column, obtain product 65mg, yield 40%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6) δ 10.94 (s, 1H), 7.75 (d, J=7.6Hz, 1H), 7.69 (d, J= 8.4Hz, 1H), 7.65 (d, J=0.7Hz, 1H), 7.53-7.49 (m, 1H), 7.36 (t, J=7.5Hz, 1H), 7.26 (t, J= 7.9Hz, 2H), 7.17 (d, J=7.5Hz, 2H), 7.06 (t, J=7.3Hz, 1H)；13C NMR(100MHz,DMSO-d6)δ 154.9,149.4,136.6,129.2,128.0,125.6,124.6,124.4,123.3,120.2,113.1,112.0。
Embodiment 32
The nitrobenzene of 74mg, the above-mentioned boric acid of 194mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then the acetonitrile of sour potassium and 3mL is tightened tube sealing thread cap, is reacted for 24 hours at 130 DEG C.It is filtered after reaction with diatomite, it is dense Contracting crosses silicagel column, obtains product 81mg, yield 50%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,DMSO-d6)δ11.58(s,1H),10.11(s,1H),8.04(s,1H),7.51-7.47(m, 3H), 7.16 (t, J=8.8Hz, 2H), 7.09 (d, J=7.6Hz, 2H), 6.93 (t, J=7.9Hz, 1H), 6.60-6.58 (m, 1H)；13C NMR(100MHz,DMSO-d6)δ138.3,137.4,129.8,129.0,127.9,126.6,123.4,120.3, 119.4,119.1,111.9,102.6。
Embodiment 33
The nitrobenzene of 74mg, the above-mentioned boric acid of 148mg, the K of 460mg are added into dry tube sealing2S2O5, the four of 184mg Then the acetonitrile of butyl ammonium chloride and 3mL is tightened tube sealing thread cap, is reacted for 24 hours at 130 DEG C.After reaction with diatomite mistake Filter, concentration cross silicagel column, obtain product 69mg, yield 49%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 8.98 (d, J=1.9Hz, 1H), 8.76 (dd, J=4.9,1.5Hz, 1H), 8.03-8.00 (m, 1H), 7.57 (s, 1H), 7.39 (dd, J=7.8,4.7Hz, 1H), 7.29-7.25 (m, 2H), 7.16 (t, J =7.4Hz, 1H), 7.12-7.10 (m, 2H)；13C NMR(100MHz,CDCl3)δ153.4,148.0,135.8,135.7, 135.0,129.6,126.2,123.7,122.2。
Embodiment 34
The nitrobenzene of 74mg, the above-mentioned boric acid of 169mg, the K of 460mg are added into dry tube sealing2S2O5, the carbon of 166mg Then sour potassium, the tetrabutylammonium chloride of 184mg and the acetonitrile of 3mL are tightened tube sealing thread cap, are reacted for 24 hours at 130 DEG C.Reaction knot The filtering of Shu Houyong diatomite, concentration cross silicagel column, obtain product 86mg, yield 57%.
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(400MHz,CDCl3) δ 7.30 (t, J=7.7Hz, 2H), 7.21 (t, J=7.4Hz, 1H), 7.17 (s, 1H), 7.10 (d, J=7.6Hz, 2H), 2.42 (s, 3H), 2.28 (s, 3H)；13C NMR(100MHz,CDCl3)δ174.1, 157.6,135.3,129.6,126.6,122.9,115.3,12.5,10.8。

Claims (10)

1. a kind of method of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds characterized by comprising having It is SO with pyrosulfite using nitro-aromatic and boronic acid compounds as substrate in solvent2Source, heating carry out coupling reaction, Sulfonamide compounds is obtained using post-processing；
Shown in the structure of the nitro-aromatic such as following formula (I):
Ar-NO2 (I)
Shown in the structure of the boronic acid compounds such as following formula (II):
R-B(OH)2 (II)
In formula (I), Ar is aryl or heteroaryl；In formula (II), R is aryl, heteroaryl or C1-C12Alkyl.
2. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is, in formula (I), Ar is phenyl, substituted-phenyl, naphthalene aryl, hetero aryl group or oxygen heterocyclic aryl；In formula (II), R is benzene Base, substituted-phenyl, naphthalene aryl, thienyl, benzothienyl, pyridyl group, indyl, benzofuranyl, isoxazolyl or C1-C12 Alkyl.
3. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is that the pyrosulfite is potassium metabisulfite or sodium pyrosulfite.
4. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is that the organic solvent is dioxane, toluene, tetrahydrofuran, acetonitrile, 1,2- dichloroethanes or dimethyl sulfoxide； With the molar amount of nitro-aromatic, the solvent usage is 1~10L/mol.
5. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is that the temperature of the coupling reaction is 60~130 DEG C, and the reaction time is 12~48h.
6. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is that the molar ratio of the nitro-aromatic and boronic acid compounds, pyrosulfite is 1:(1~4): (1~6).
7. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is, alkali is additionally added in the coupling reaction, and the alkali is tripotassium phosphate trihydrate, anhydrous phosphoric acid potassium, potassium carbonate, fluorination Caesium, cesium carbonate, potassium acetate, potassium fluoride, sodium carbonate or lithium carbonate.
8. the method for nitro-aromatic according to claim 7 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is that the molar ratio of the alkali and nitro-aromatic is (0.1~4): 1.
9. the method for nitro-aromatic according to claim 1 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is, additive is additionally added in the coupling reaction, and the additive is tetrabutylammonium bromide, tetrabutylammonium chloride, four Butyl ammonium fluoride, tetrabutyl ammonium acetate, tetrabutyl ammonium hexafluorophosphate or 18- crown- 6.
10. the method for nitro-aromatic according to claim 9 and boronic acid compounds coupling synthesis sulfonamide compounds, special Sign is that the molar ratio of the additive and nitro-aromatic is (0.2~2): 1.
CN201910629817.8A 2019-07-12 2019-07-12 Method for synthesizing sulfonamide compound by coupling of nitroaromatic and boric acid compound Active CN110372463B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170905A (en) * 2019-12-28 2020-05-19 台州学院 Synthetic method of sulfonamide compound
CN111393336A (en) * 2020-03-09 2020-07-10 华东师范大学 Sulfonamide compound, and metal-free catalysis construction method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553860A (en) * 2013-11-03 2014-02-05 杨雪飞 Method for synthesizing sulfamide compounds
CN103819369A (en) * 2014-03-11 2014-05-28 杨雪飞 Method for synthesizing benzene sulfonamide compounds
CN109438296A (en) * 2018-11-11 2019-03-08 华东师范大学 Sulfamide compound and its synthetic method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553860A (en) * 2013-11-03 2014-02-05 杨雪飞 Method for synthesizing sulfamide compounds
CN103819369A (en) * 2014-03-11 2014-05-28 杨雪飞 Method for synthesizing benzene sulfonamide compounds
CN109438296A (en) * 2018-11-11 2019-03-08 华东师范大学 Sulfamide compound and its synthetic method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ALEX S. DEEMING等: "Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO:A Redox-Neutral,Phosphine-Free Transformation", 《ANGEW. CHEM. INT. ED》 *
MILES W. JOHNSON等: "Application of Fundamental Organometallic Chemistry to the Development of a Gold-Catalyzed Synthesis of Sulfinate Derivatives", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 *
SHENGQING YE等: "A palladium-catalyzed three-component coupling of arylboronic acids,sulfur dioxide and hydrazines", 《CHEM. COMMUN》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170905A (en) * 2019-12-28 2020-05-19 台州学院 Synthetic method of sulfonamide compound
CN111170905B (en) * 2019-12-28 2022-04-29 台州学院 Synthetic method of sulfonamide compound
CN111393336A (en) * 2020-03-09 2020-07-10 华东师范大学 Sulfonamide compound, and metal-free catalysis construction method and application thereof

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