CN110372463B - Method for synthesizing sulfonamide compound by coupling of nitroaromatic and boric acid compound - Google Patents
Method for synthesizing sulfonamide compound by coupling of nitroaromatic and boric acid compound Download PDFInfo
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Abstract
The invention belongs to the field of organic synthesis, and particularly discloses a method for synthesizing a sulfonamide compound by coupling nitroaromatic and a boric acid compound, which comprises the following steps: in organic solvent, pyrosulfite is used as SO2Heating to carry out coupling reaction, and carrying out post-treatment to obtain a sulfonamide compound; the method has simple operation, can be carried out under the air without the protection of nitrogen, has rich sources of the nitroaromatic and the boric acid compound, relatively low price and high reaction yield,the substrate has wide applicability and no metal residue. The method can be used for synthesizing a series of sulfonamide compounds, and the synthesized compounds have wide application value in the fields of pesticides, medicines and the like.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing sulfonamide compound by coupling nitroaromatic and boric acid compound.
Background
Sulfonamide compounds have been widely used in the fields of agricultural chemicals, medicines, and the like (Scott, k.a.; Njardarson, j.t.top. curr. chem. (Z)2018,376,376). The traditional method for synthesizing sulfamide usually adopts sulfonyl chloride and amine to react under the action of alkali, although the method is high in efficiency, because the sulfonyl chloride has the defects of difficult preparation, poor functional group compatibility, sensitivity to water, difficulty in storage and the like, the development of a new simple and high-efficiency coupling mode to replace the traditional method for synthesizing sulfamide is of great significance.
Nitroaromatic is a basic chemical industrial raw material, has wide source and low price, and most of raw material amines for preparing sulfonamide traditionally are reduced by nitryl. The preparation of sulfonamides starting from nitroaromatics has been reported ((a) Jiang, J.; Zeng, S.; Chen, D.; Cheng, C.; Deng, W.; Xiaong, J.org.Biomol.Chem.2018,16,5016; (b) Eid, N.; Karam, I.; Andriolet, B.Eur.J.org.Chem.2018,2018, 5016). However, in the above reaction, iron is used to catalyze sulfonyl chloride or sodium arylsulfinate to perform reductive coupling with nitroarene to prepare sulfonamide, on one hand, the problem that metal residues in the medical field cannot be ignored is solved, and on the other hand, the types of sulfonyl chloride or sodium arylsulfinate are few, the preparation is difficult and the universality is poor.
Therefore, the method for preparing the sulfamide by using the metal-free catalytic nitroaromatic with universality has important value.
Disclosure of Invention
The invention aims to provide a method for synthesizing sulfonamide compound by coupling nitroaromatic and boric acid compound, which has the advantages of no metal catalysis, abundant raw material sources, good substrate applicability and higher yield.
In order to achieve the above object, the technical solution of the present invention is as follows:
a method for synthesizing sulfonamide compound by coupling nitroarene and boric acid compound, comprising: in an organic solvent, nitro-arene and boric acid compounds are taken as substrates, and pyrosulfite is taken as SO2Heating to carry out coupling reaction, and carrying out post-treatment to obtain a sulfonamide compound;
the structure of the nitroarene is shown as the following formula (I):
Ar-NO2(I)
the structure of the boric acid compound is shown as the following formula (II):
R-B(OH)2(II)
in the formula (I), Ar is aryl or heteroaryl; in the formula (II), R is aryl, heteroaryl or C1-C12An alkyl group.
The reaction equation for the above process is as follows:
the reaction principle of the method is as follows: pyrosulfites combine with boric acid compounds to form RSO2 -On the other hand, the pyrosulfite is used for reducing the nitroarene and then is mixed with RSO2 -Coupling to obtain the sulfonamide.
Preferably, in formula (I), Ar is phenyl, substituted phenyl, naphthylaryl, azacycloaryl or oxacycloaryl; in the formula (II), R is phenyl, substituted phenyl, naphthylaryl, thienyl, benzothienyl, pyridyl, indolyl, benzofuranyl, isoxazolyl or C1-C12An alkyl group.
In view of easy availability of the raw materials, it is further preferred that in formula (I), the substituted phenyl group is a phenyl group substituted with an alkyl group, an alkoxy group, a halogen group, a morpholinyl group, an amino group, an ester group, an acetyl group, a carboxyl group, a cyano group, a methylthio group, an amide group, an alkynyl group, or a trifluoromethyl group; the heteroaryl is pyridine, quinoline, isoquinoline, indole or benzofuran heteroaryl. In the formula (II), the substituted phenyl is alkyl, alkoxy, trifluoromethyl, ester group or phenyl substituted by fluorine atom.
The pyrosulfite is potassium pyrosulfite or sodium pyrosulfite.
The organic solvent is dioxane, toluene, tetrahydrofuran, acetonitrile, 1, 2-dichloroethane or dimethyl sulfoxide. And the dosage of the solvent is 1-10L/mol based on the molar weight of the nitroaromatic.
In view of yield and solvent cost, the organic solvent is preferably acetonitrile or dimethyl sulfoxide, and the amount of the solvent is 3-6L/mol based on the molar amount of the nitroarene.
The temperature of the coupling reaction is 60-130 ℃, and the reaction time is 12-48 h. In view of yield, the reaction temperature is preferably 100-130 ℃, and the reaction time is preferably 12-36 h.
The molar ratio of the nitroaromatic to the boric acid compound to the pyrosulfite is 1: (1-4): (1 to 6), from the viewpoint of yield and cost, it is preferably 1: (1.2-2): (2-4).
Preferably, a base is further added in the coupling reaction, and the base is tripotassium phosphate trihydrate, anhydrous potassium phosphate, potassium carbonate, cesium fluoride, cesium carbonate, potassium acetate, potassium fluoride, sodium carbonate or lithium carbonate; the molar ratio of the alkali to the nitroaromatic is (0.1-4): 1. this is because the addition of a base to the coupling reaction increases the yield of the product.
More preferably, the alkali is tripotassium phosphate trihydrate, anhydrous potassium phosphate, potassium carbonate, cesium fluoride or potassium fluoride, and the molar ratio of the alkali to the nitroarene is (1-2): 1, the yield of the product can be further improved.
Preferably, an additive is further added in the coupling reaction, the additive is tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium acetate, tetrabutylammonium hexafluorophosphate or 18-crown-6, and the molar ratio of the additive to the nitroaromatic is (0.2-2): 1. this is because the addition of additives to the coupling reaction increases the product yield.
The post-treatment comprises the following steps: the insoluble matter was removed by filtration with celite, and the solvent was dried by spin drying, followed by separation with silica gel column chromatography.
Compared with the prior art, the invention has the following advantages:
(1) according to the method, metal catalysis is not needed, the sulfonamide is prepared through a one-pot coupling reaction of three components, namely the nitroaromatic, the boric acid compound and the pyrosulfite, the reaction is simple to operate, the reaction condition is mild, nitrogen protection is not needed, and the method can be carried out in the air.
(2) The method has the advantages of rich sources of the raw materials of the nitroaromatic and the boric acid compound, relatively low price, high reaction yield, wide applicability of the substrate, no metal residue and suitability for large-scale production and application, and reduces the production cost.
(3) The method can be used for synthesizing a series of sulfonamide compounds, and the synthesized compounds have wide application value in the fields of pesticides, medicines and the like.
Detailed Description
The following examples will help to understand the present invention, but the contents of the present invention are not limited thereto.
Example 1
74mg of the above-mentioned nitroaromatic, 88mg of phenylboronic acid and 267mg of K are introduced into a dry sealed tube2S2O5160mg of tripotassium phosphate trihydrate, 32mg of 18-crown-6 and 1.8mL of acetonitrile, followed by screwing the sealed tube screw cap and reacting at 100 ℃ for 12 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 110mg of a product in 79% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.83(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。
example 2
To the dried sealed tube were added 82mg of the above nitroarene, 146mg of phenylboronic acid, 456mg of Na2S2O5255mg of tripotassium phosphate, 334mg of tetrabutylammonium chloride and 3.6mL of dimethyl sulfoxide, then screwing a pipe sealing threaded cap, and reacting at 130 ℃ for 36 hours. Filtering with diatomaceous earth, concentrating, and passing through silica gelColumn, product 89mg, yield 60%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.79(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)δ139.0,135.5,133.7,132.9,129.9,129.0,127.3,122.4,20.9。
example 3
92mg of the above nitroaromatic, 146mg of phenylboronic acid and 460mg of K are introduced into the dry sealed tube2S2O5166mg of potassium carbonate, 213mg of tetrabutylammonium bromide and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 115mg of a product in 73% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.72(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)；13CNMR(100MHz,CDCl3)δ158.1,138.9,132.9,129.0,128.6,127.3,125.7,114.5,55.4。
example 4
Into the dried tube, 124mg of the above nitroaromatic, 146mg of phenylboronic acid and 460mg of K were added2S2O5182mg of cesium fluoride, 660. mu.L of tetrabutylammonium fluoride (1.0M in THF) and 3mL of acetonitrile, followed by screwing the screw cap of the sealed tube, and reacting at 130 ℃ for 24 h. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 103mg of a product in 54% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.73-7.71(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。
example 5
To the dried lock tube was added 85mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O570mg of potassium fluoride, 199mg of tetrabutylammonium acetate and 3mL of acetonitrile, followed by screwing the screw cap of the sealed tube, and reacting at 130 ℃ for 24 hours. After the reaction, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 96mg of a product with a yield of 64%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.77-7.75(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)δ160.7(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。
example 6
115mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K were added to the dried sealed tube2S2O5166mg of potassium carbonate, 256mg of tetrabutylammonium hexafluorophosphate and 3mL of acetonitrile were added, followed by screwing the screw cap of the sealed tube and reacting at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 113mg of a product in yield63％。
The product prepared in this example was subjected to nmr analysis:
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。
example 7
89mg of the above-mentioned nitroaromatic, 146mg of phenylboronic acid and 460mg of K are introduced into the dried tube2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 121mg of a product in 78% yield.
The product prepared in this example was subjected to nmr analysis:
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。
example 8
117mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K were added to the dried sealed tube2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 146mg of a product with a yield of 80%.
The product prepared in this example was subjected to nmr analysis:
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。
example 9
99mg of the abovementioned nitroaromatic, 146mg of phenylboronic acid and 460mg of K are added to the dried vial2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 119mg of a product in a yield of 72%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.91-7.79(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。
example 10
To the dried lock tube was added 120mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 120mg of a product with a yield of 65%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.86-7.84(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。
example 11
To the dried lock tube, 83mg of the above nitroaromatic, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 101mg of a product with a yield of 68%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,DMSO-d6)δ9.47(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)；13CNMR(100MHz,DMSO-d6)δ146.5,139.7,132.4,128.9,126.7,125.2,124.7,113.9。
example 12
To the dried lock tube was added 100mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 106mg of a product with a yield of 64%.
The product prepared in this example was subjected to nmr analysis:
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。
example 13
Into the dried sealed tube were added 101mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 125mg of a product with a yield of 75%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.78(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)；13CNMR(100MHz,CDCl3)δ138.8,135.7,133.6,133.1,129.1,127.6,127.3,122.8,16.1。
example 14
To the dried lock tube was added 100mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 124mg of a product with a yield of 75%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,DMSO-d6)δ10.7(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)；13CNMR(100MHz,DMSO-d6)δ167.1,140.4,139.3,133.1,129.4,129.4,128.7,126.6,118.2。
example 15
Into the dried sealed tube were added 152mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 86mg of a product in 39% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.81-7.78(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。
example 16
To the dried tube, 109mg of the above nitroaromatic, 146mg of phenylboronic acid and 460mg of K were added2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 111mg of a product with a yield of 65%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.81(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。
example 17
To the dried lock tube was added 75mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 101mg of a product with a yield of 72%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,DMSO-d6)δ10.58(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。
example 18
105mg of the above nitroaromatic, 146mg of phenylboronic acid and 460mg of K are introduced into the dry sealed tube2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 129mg of a product with a yield of 76%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ8.90(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。
example 19
105mg of the above nitroaromatic, 146mg of phenylboronic acid and 460mg of K are introduced into the dry sealed tube2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 92mg of a product with a yield of 54%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,DMSO-d6)δ10.45(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。
example 20
To the dried lock tube was added 97mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 111mg of a product in 68% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,DMSO-d6)δ11.04(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)；13CNMR(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。
example 21
To the dried lock tube was added 142mg of the above nitroarene, 146mg of phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 193mg of a product in 93% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.73(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。
example 22
To the dried lock tube was added 74mg of nitrobenzene, 163mg of the above phenylboronic acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 101mg of a product with a yield of 68%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.68(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。
example 23
To the dried lock tube was added 74mg of nitrobenzene, 182mg of the above phenylboronic acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 118mg of a product with a yield of 75%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.73(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)δ163.1,136.7,130.5,129.5,129.3,125.2,121.5,114.2,55.6。
example 24
To the dried lock tube was added 74mg of nitrobenzene, 228mg of the above phenylboronic acid and 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 110mg of a product in a yield of 61%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.93(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。
example 25
To the dried lock tube was added 74mg of nitrobenzene, 168mg of the above phenylboronic acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 103mg of a product in 68% yield.
The product prepared in this example was subjected to nmr analysis:
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)δ166.5(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。
example 26
To the dried lock tube was added 74mg of nitrobenzene, 233mg of the above phenylboronic acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 129mg of a product with a yield of 70%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ8.07(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。
example 27
To the dried lock tube was added 74mg of nitrobenzene, 72mg of the above boric acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 72mg of a product with a yield of 70%.
The product prepared in this example was subjected to nmr analysis:
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。
example 28
To the dried lock tube was added 74mg of nitrobenzene, 207mg of the above boric acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 126mg of a product in 74% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ8.41(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。
example 29
To the dried lock tube was added 74mg of nitrobenzene, 154mg of the above boric acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 113mg of a product in 79% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.89(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。
example 30
To the dried lock tube was added 74mg of nitrobenzene, 214mg of the above boric acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 125mg of a product with a yield of 72%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.79-7.77(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。
example 31
74mg of nitrobenzene, 195mg of the abovementioned boric acid and 460mg of K are added to the dry lock tube2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After the reaction was completed, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 65mg of a product with a yield of 40%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,DMSO-d6)δ10.94(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)δ154.9,149.4,136.6,129.2,128.0,125.6,124.6,124.4,123.3,120.2,113.1,112.0。
example 32
74mg of nitrobenzene, 194mg of the abovementioned boric acid and 460mg of K are added to the dry lock2S2O5166mg of potassium carbonate and 3mL of acetonitrile were added, and then the screw cap was screwed down and reacted at 130 ℃ for 24 hours. After the reaction, the reaction mixture was filtered through celite, concentrated, and passed through a silica gel column to obtain 81mg of a product with a yield of 50%.
The product prepared in this example was subjected to nmr analysis:
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。
example 33
To the dried lock tube was added 74mg of nitrobenzene, 148mg of the above boric acid, 460mg of K2S2O5184mg of tetrabutylammonium chloride and 3mL of acetonitrile were then screwed down and reacted at 130 ℃ for 24 h. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 69mg of a product in 49% yield.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ8.98(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。
example 34
To the dried lock tube was added 74mg of nitrobenzene, 169mg of the above boric acid, 460mg of K2S2O5166mg of potassium carbonate, 184mg of tetrabutylammonium chloride and 3mL of acetonitrile, followed by screwing of the screw cap of the sealed tube, and reaction at 130 ℃ for 24 hours. After completion of the reaction, the reaction mixture was filtered through Celite, concentrated and passed through a silica gel column to obtain 86mg of a product in a yield of 57%.
The product prepared in this example was subjected to nmr analysis:
1H NMR(400MHz,CDCl3)δ7.30(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 (8)
1. a method for synthesizing a sulfonamide compound by coupling nitroarene and a boric acid compound is characterized by comprising the following steps: in an organic solvent of acetonitrile or dimethyl sulfoxide, nitro-arene and boric acid compounds are taken as substrates, pyrosulfite is taken as SO2The source is tripotassium phosphate trihydrate, anhydrous potassium phosphate, potassium carbonate, cesium fluoride or potassium fluoride as base, and the base is raised under the condition of no metal catalysisCarrying out coupling reaction at a high temperature, and carrying out post-treatment to obtain a sulfonamide compound;
an additive is also added in the coupling reaction, and the additive is tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium acetate, tetrabutylammonium hexafluorophosphate or 18-crown-6;
the structure of the nitroarene is shown as the following formula (I):
Ar-NO2(I)
the structure of the boronic acid compound is shown as the following formula (II):
R-B(OH)2(II)
in the formula (I), Ar is aryl or heteroaryl; in the formula (II), R is aryl, heteroaryl or C1-C12An alkyl group.
2. The method for coupling and synthesizing sulfonamide compound of nitroarene and boric acid compound according to claim 1, wherein in formula (I), Ar is phenyl, substituted phenyl, naphthylaryl, azacycloaryl or oxocycloaryl, and the substituted phenyl is alkyl, alkoxy, halogen, morpholinyl, amino, ester, acetyl, carboxyl, cyano, methylthio, amide, alkynyl or trifluoromethyl substituted phenyl;
in the formula (II), R is phenyl, substituted phenyl, naphthylaryl, thienyl, benzothienyl, pyridyl, indolyl, benzofuranyl, isoxazolyl or C1-C12And the substituted phenyl is alkyl, alkoxy, trifluoromethyl, ester group or phenyl substituted by fluorine atom.
3. The method for coupling and synthesizing a sulfonamide compound of a nitroarene and a boric acid compound according to claim 1, wherein the pyrosulfite is potassium pyrosulfite or sodium pyrosulfite.
4. The method for synthesizing the sulfonamide compound through coupling the nitroarene and the boric acid compound according to claim 1, wherein the amount of the organic solvent is 1-10L/mol based on the molar amount of the nitroarene.
5. The method for synthesizing the sulfonamide compound by coupling the nitroarene and the boric acid compound according to claim 1, wherein the coupling reaction is carried out at a temperature of 60-130 ℃ for 12-48 hours.
6. The method for synthesizing sulfonamide compounds by coupling nitroarene and boric acid compounds according to claim 1, wherein the molar ratio of nitroarene to boric acid compound to pyrosulfite is 1: (1-4): (1-6).
7. The method for synthesizing the sulfonamide compound by coupling the nitroarene and the boric acid compound according to claim 1, wherein the molar ratio of the base to the nitroarene is (0.1-4): 1.
8. the method for synthesizing the sulfonamide compound by coupling the nitroarene and the boric acid compound according to claim 1, wherein the molar ratio of the additive to the nitroarene is (0.2-2): 1.
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| A palladium-catalyzed three-component coupling of arylboronic acids,sulfur dioxide and hydrazines;Shengqing Ye等;《Chem. Commun》;20120613;第48卷;全文 * |
| Application of Fundamental Organometallic Chemistry to the Development of a Gold-Catalyzed Synthesis of Sulfinate Derivatives;Miles W. Johnson等;《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》;20140422;第53卷(第17期);全文 * |
| Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO:A Redox-Neutral,Phosphine-Free Transformation;Alex S. Deeming等;《Angew. Chem. Int. Ed》;20151124;第55卷;全文 * |
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