CN112979581A - Method for preparing benzothiazole compound from N- (2-bromophenyl) thioamide promoted by visible light - Google Patents
Method for preparing benzothiazole compound from N- (2-bromophenyl) thioamide promoted by visible light Download PDFInfo
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Abstract
The invention discloses a method for preparing benzothiazole compounds from N- (2-bromophenyl) thioamide promoted by visible light. Specifically, under the protection of inert gas, the reactants are added into a reaction container with a stirring device according to the molar ratio of N- (2-bromophenyl) thioamide to inorganic base =1:0.5, then dimethyl sulfoxide is added, and the reaction is stirred for 2-24 hours at room temperature under the irradiation of visible light, so that the benzothiazole compound is obtained. The method realizes a series of intramolecular cross-coupling reactions of N- (2-bromophenyl) thioamide under the irradiation of a 45W household compact fluorescent lamp by taking sodium phosphate as alkali without adding any photosensitizer or transition metal catalyst. In addition, the invention can obtain the benzothiazole compounds with high yield. The whole process is green, efficient and easy to operate, and is a good method for synthesizing benzothiazole compounds.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis methodology, and particularly relates to a method for preparing benzothiazole compounds from N- (2-bromophenyl) thioamide promoted by visible light.
Background
2-substituted benzothiazoles in pharmaceuticals, natural products, pesticides and functional materialsA widely existing structural unit. Their synthesis has therefore received extensive attention from organic chemists, and the early synthesis of such compounds has been dominated by: (1) oxidative condensation of 2-aminothiophenol with an aryl aldehyde; (2) intramolecular carbon-hydrogen bond activation or carbon-halogen bond cross coupling of the thiobenzamide; (3) reaction of benzothiazole with aryl halide, (4) oxidative coupling of thiophenol and aryl nitrile, and the like. These reactions are generally carried out at elevated temperatures, catalyzed by palladium or an equivalent transition metal or complex thereof. With the development of the photoredox organic synthesis methodology, the above reaction can also be carried out under visible or ultraviolet irradiation in [ Ru (bpy) ]3]2+，[Ir(ppy)3]And the like under the catalysis of a transition metal complex or an organic photosensitizer. However, these reactions often add additional equipment, reagents or separation costs and may introduce toxic heavy metals or organic contaminants.
Disclosure of Invention
In order to overcome the technical problems, the invention discloses a brand new visible light-promoted method for preparing benzothiazole compounds from N- (2-bromophenyl) thioamide. That is, a series of 2-substituted benzothiazole compounds were synthesized smoothly under visible light irradiation using N- (2-bromophenyl) thioamide such as N- (2-bromophenyl) thioamide derivatives as a raw material and sodium phosphate as a base. The reaction of the invention has wide substrate application range, and can obtain the required benzothiazole compound with higher yield. The whole reaction process is green, efficient and easy to operate, and the method is a good method for synthesizing the benzothiazole compounds.
Specifically, the invention adopts the following technical scheme:
the method for preparing the benzothiazole compound by using the N- (2-bromophenyl) thioamide promoted by visible light comprises the following steps of reacting N- (2-bromophenyl) thioamide as a raw material under the irradiation of visible light in the presence of alkali to prepare the benzothiazole compound.
The application of alkali in the preparation of benzothiazole compounds by taking N- (2-bromophenyl) thioamide as a raw material through reaction; preferably, the reaction is carried out under visible light.
In the invention, the reaction is carried out at room temperature for 2-24 hours; the reaction is carried out in a solvent under the protection of inert gas.
In the present invention, the molar ratio of the N- (2-bromophenyl) thioamide to the base is 1 (0.2 to 0.8), preferably 1:0.2 to 0.5, and most preferably 1: 0.5.
In the invention, the N- (2-bromophenyl) thioamide and the benzothiazole compounds respectively have the following structural general formulas:
wherein Ar is1Is phenyl or substituted phenyl, Ar2Is a substituent other than alkyl, such as phenyl, substituted phenyl, or a heterocyclic group.
Specifically, the N- (2-bromophenyl) thioamide has a general structural formula shown in any one of a formula (A) to a formula (L) and a formula (P):
wherein: r1Selected from hydrogen, fluoro or methyl; r2Selected from fluorine, chlorine, bromine or methyl; r3Selected from fluorine, bromine or methyl; r4Selected from fluoro, chloro, bromo, iodo, methyl, methoxy, tert-butyl or trifluoromethyl; r5Selected from fluorine, bromine, iodine or methyl; r6Selected from fluoro, methyl or methoxy; r7Selected from hydrogen or fluorine.
The technical scheme of the invention can be expressed as follows:
wherein A is N- (2-bromophenyl) thioamide, and B is the obtained benzothiazole compound.
The reaction of the invention is carried out under the condition of no photosensitizer or transition metal catalyst, thus effectively solving the problem that the prior art needs an auxiliary (transition) catalyst; the reaction can be carried out by simple 45W household compact fluorescent lamp irradiation, and unexpected technical effect is achieved.
In the invention, the inert gas is selected from any one of nitrogen, helium, neon and argon, preferably nitrogen; the alkali is any one of inorganic alkali, the inorganic alkali is any one of sodium phosphate, sodium carbonate, potassium hydroxide, sodium hydroxide and sodium acetate, and sodium phosphate is preferred; the solvent is dimethyl sulfoxide (DMSO), DMF, Tetrahydrofuran (THF), methanol, ethanol, acetonitrile (MeCN), etc.
Compared with the prior art, the invention adopting the technical scheme has the following advantages: the method realizes a series of intramolecular cross-coupling reactions of N- (2-bromophenyl) thioamide under the irradiation of a 45W household compact fluorescent lamp by taking sodium phosphate as alkali without adding any photosensitizer or transition metal catalyst. In addition, the invention can obtain the benzothiazole compounds with high yield. The whole process is green, efficient and easy to operate, and is a good method for synthesizing benzothiazole compounds.
Detailed Description
The invention discloses a method for preparing benzothiazole compounds by using N- (2-bromophenyl) thioamide promoted by visible light, which comprises the following steps: adding the reactants into a reaction container with a stirring device under the protection of inert gas according to the molar ratio of N- (2-bromophenyl) thioamide to inorganic base =1:0.5, adding dimethyl sulfoxide, and stirring and reacting for 2-24 hours at room temperature under the irradiation of a 45W household compact fluorescent lamp to obtain the benzothiazole compound. The method does not need other reagents and reaction steps, and can simply and efficiently obtain the benzothiazole compound. The stirring device is a magnetic stirring device; the reaction vessel is a sealed reaction tube.
In the invention, the bromine site in the N- (2-bromophenyl) thioamide reacts with the sulfur site to prepare the benzothiazole compound, and the reaction is clear. The invention will be further described with reference to specific embodiments. Unless otherwise indicated, reagents, materials, instruments and the like used in the following examples are commercially available. The reaction is carried out in the absence of a photosensitizer or a transition metal catalyst, and only N- (2-bromophenyl) thioamide, inorganic base and DMSO are used as raw materials; the reaction of the present example was carried out at room temperature using a 45W household compact fluorescent lamp as the visible light source. The specific experiment and test method of the invention is conventional technology.
Example 1: visible light promotes the reaction of the N- (2-bromophenyl) thiobenzamide.
N- (2-bromophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography is carried out to obtain the target product, wherein the separation yield is 98% and the HPLC yield is 99%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.09–8.07 (m, J = 7.7 Hz, 3H), 7.90 (d, J = 7.9 Hz, 1H), 7.49 (m, 4H), 7.38 (t, J = 7.5 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.1, 154.2, 135.1, 133.6, 131.0, 129.0, 127.6, 126.3, 125.2, 123.2, 121.6。
On the basis of the above experiment, the following experiment was obtained by varying the single conditions:
mixing Na3PO4Change to Na2CO3Or Et3N, the rest is unchanged, and the HPLC yields of the products are 86% and 87%, respectively.
Mixing Na3PO4The dosage is moreThe equivalent was changed to 0.2, the remainder was unchanged, and the product HPLC yield was 91%.
The DMSO was replaced with DMF and the rest was unchanged, the product HPLC yield was 77%. The DMSO was replaced with a mixture of 1 mL THF and 1 mL acetonitrile, and the remainder was unchanged, resulting in a product HPLC yield of 47%. The DMSO was replaced with a mixture of 1 mL THF and 1 mL methanol, and the remainder was unchanged, resulting in a 53% HPLC yield of the product.
No Na addition3PO4I.e. no base, the remainder was unchanged, the product HPLC yield was 76%.
The reaction was carried out in air, the remainder was unchanged, and the product HPLC yield was 61%.
Under the condition of keeping out of the light, the rest is not changed, and the product cannot be obtained; the reaction was protected from light at 80 ℃ and still no product was obtained.
The irradiation of a 45W household compact fluorescent lamp is changed into the irradiation of a green LED, the rest is unchanged, and the HPLC yield of the product is 4 percent.
The substituent bromine was replaced with chlorine, the remainder was unchanged, and the product was obtained in 24% yield by HPLC.
The following examples relate to isolated yields of the products.
Example 2: the reaction of N- (2-bromo-5-methylphenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-5-methylphenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 97%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.06 (d, J = 3.7 Hz, 2H), 7.87 (s, 1H), 7.74 (d, J = 8.1 Hz, 1H), 7.52–7.40 (m, 3H), 7.19 (d, J = 8.1 Hz, 1H), 2.49 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 167.1, 153.5, 135.3, 132.7, 131.0, 129.8, 127.9, 126.4, 125.8, 122.2, 120.0, 20.4。
Example 3: the reaction of N- (2-bromo-5 fluorophenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-5-fluorophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 96%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.15–8.00 (m, 2H), 7.82 (dd, J = 8.6, 5.2 Hz, 1H), 7.75 (dd, J = 9.5, 1.7 Hz, 1H), 7.56–7.44 (m, 3H), 7.16 (td, J = 8.7, 1.9 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 170.7, 162.1 (d, 1 J C-F = 243.3 Hz), 155.2 (d, 3 J C-F = 12.1 Hz), 133.6, 131.4, 130.6 (d, 4 J C-F = 1.7 Hz), 129.2, 127.7, 122.4 (d, 3 J C-F = 9.7 Hz), 114.0 (d, 2 J C-F = 25.1 Hz), 109.5 (d, 2 J C-F = 23.5 Hz)。19F NMR (377 MHz, CDCl3, ppm) δ -115.7。
Example 4: the reaction of N- (2-bromo-4-methylphenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-4-methylphenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 98%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.13–8.02 (m, 2H), 7.95 (d, J = 8.3 Hz, 1H), 7.70 (s, 1H), 7.52–7.45 (m, 3H), 7.30 (d, J = 8.2 Hz, 1H), 2.50 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 167.0, 152.3, 135.4, 135.2, 133.8, 130.8, 129.0, 128.0, 127.4, 122.7, 121.4, 21.6。
Example 5: the reaction of N- (2-bromo-4-fluorophenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-4-fluorophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 98%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.03 (d, J = 3.1 Hz, 2H), 7.99 (dd, J = 9.0, 4.9 Hz, 1H), 7.59–7.51 (dd, 1H), 7.48 (d, J = 2.4 Hz, 3H), 7.21 (td, J = 8.9, 2.0 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ167.8, 160.5 (d, 1 J C-F = 245.7 Hz), 150.8 (d, 4 J C-F = 1.4 Hz, 1H)., 136.0 (d, 3 J C-F = 11.2 Hz), 133.4, 131.0, 129.0, 127.4, 124.1 (d, 3 J C-F = 9.4 Hz), 114.9 (d, 2 J C-F = 24.7 Hz), 107.8 (d, 2 J C-F = 26.8 Hz)。19F NMR (377 MHz, CDCl3, ppm) δ -115.8。
Example 6: the reaction of N- (2-bromo-4-chlorophenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-4-chlorophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 96%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.04 (s, 2H), 7.95 (d, J = 8.6 Hz, 1H), 7.84 (s, 1H), 7.49 (s, 3H), 7.43 (d, J = 8.7 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.5, 152.7, 136.2, 133.2, 131.2, 131.1, 129.1, 127.5, 127.1, 123.9, 121.2。
Example 7: the visible light promotes the reaction of the N- (2, 4-dibromophenyl) thiobenzamide.
N- (2, 4-dibromophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 90%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.04 (s, 2H), 7.99 (s, 1H), 7.89 (d, J= 8.5 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.49 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.5, 153.0, 136.7, 133.2, 131.2, 129.8, 129.1, 127.5, 124.3, 124.1, 118.7。
Example 8: the reaction of N- (2-bromo-3-methylphenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-3-methylphenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 95%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.09 (d, J = 2.3 Hz, 2H), 7.91 (d, J = 8.0 Hz, 1H), 7.47 (s, 3H), 7.39 (t, J = 7.5 Hz, 1H), 7.16 (d, J = 7.0 Hz, 1H), 2.57 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 167.5, 154.0, 135.6, 133.7, 131.7, 130.8, 129.0, 127.5, 126.4, 125.4, 120.7, 21.4。
Example 9: the reaction of N- (2-bromo-6-methylphenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-6-methylphenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 95%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.11 (d, J = 3.9 Hz, 2H), 7.78–7.67 (m, 1H), 7.48 (d, J = 4.6 Hz, 3H), 7.27 (d, J = 5.2 Hz, 2H), 2.81 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.6, 153.6, 135.0, 134.0, 133.4, 130.7, 129.0, 127.5, 126.8, 125.1, 119.0, 18.4。
Example 10: the reaction of N- (2-bromo-6-fluorophenyl) thiobenzamide is promoted by visible light.
N- (2-bromo-6-fluorophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed byN for the reaction tube2The reaction was stirred for 3 hours under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 85%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.01-8.21 (m, 2H), 7.64 (d, J = 7.9 Hz, 1H), 7.49 (s, 3H), 7.32 (dd, J = 12.1, 7.5 Hz, 1H), 7.18 (t, J = 9.2 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.6, 156.0 (d, 1 J C-F = 256.4 Hz), 143.0 (d, 2 J C-F = 13.5 Hz), 137.7 (d, 4 J C-F = 3.6 Hz), 133.2, 131.3, 129.0, 127.8, 125.9 (d, 3 J C-F = 7.2 Hz, 1H), 117.3 (d, 3 J C-F = 4.3 Hz, 1H), 112.0 (d, 2 J C-F = 18.0 Hz, 1H)。19F NMR (377 MHz, CDCl3, ppm) δ -121.9。
Example 11: visible light promotes the reaction of the N- (2, 6-dibromophenyl) thiobenzamide.
N- (2, 6-dibromophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 3 hours under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 90%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.11 (d, J = 4.3 Hz, 2H), 7.80 (d, J = 7.9 Hz, 1H), 7.66 (d, J = 7.6 Hz, 1H), 7.56-7.39 (m, 3H), 7.20 (t, J = 7.8 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.5, 152.3, 135.9, 133.2, 131.3, 129.7, 129.0, 127.7, 125.9, 120.8, 116.9。
Example 12: visible light promotes the reaction of N- (2-bromophenyl) -4-methylthiobenzamide.
N- (2-bromophenyl) -4-methylthiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 3 hours under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 98%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.05 (d, J = 8.1 Hz, 1H), 7.97 (d, J = 7.9 Hz, 2H), 7.87 (d, J = 7.9 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.35 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.8 Hz, 2H), 2.40 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.2, 154.2, 141.4, 135.0, 131.0, 129.7, 127.5, 126.2, 125.0, 123.1, 121.6, 21.5。
Example 13: the reaction of N- (2-bromophenyl) -4-tert-butyl thiobenzamide is promoted by visible light.
Reacting N- (2-bromophenyl) -4-tert-butyl-thiobenzamide（0.2 mmol），Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 3 hours under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 98%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.07 (d, J = 8.2 Hz, 1H), 8.03 (d, J = 8.3 Hz, 2H), 7.90 (d, J = 7.9 Hz, 1H), 7.54–7.46 (m, 3H), 7.37 (t, J = 7.5 Hz, 1H), 1.37 (s, 9H)。13C NMR (101 MHz, CDCl3 ppm) δ 168.2, 154.6, 154.2, 135.0, 130.9, 127.4, 126.2, 126.0, 125.0, 123.1, 121.6, 35.0, 31.2。
Example 14: the visible light promotes the reaction of the N- (2-bromophenyl) -4-methoxythiobenzamide.
N- (2-bromophenyl) -4-methoxythiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 2 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 98%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.06–7.97 (m, J = 8.6 Hz, 3H), 7.85 (d, J = 7.9 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 6.97 (d, J = 8.6 Hz, 2H), 3.85 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 167.8, 161.9, 154.2, 134.8, 129.1, 126.4, 126.2, 124.8, 122.8, 121.5, 114.3, 55.4。
Example 15: the visible light promotes the reaction of the N- (2-bromophenyl) -4-fluorosulphonamide.
N- (2-bromophenyl) -4-fluorosulfanylbenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 97%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.17–8.02 (m, 3H), 7.91 (d, J = 7.9 Hz, 1H), 7.50 (t, J = 7.6 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 7.19 (t, J = 8.3 Hz, 2H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.8, 164.5 (d, 1 J C-F = 251.8 Hz), 154.1, 135.1, 130.0 (d, 4 J C-F = 3.2 Hz), 129.5 (d, 3 J C-F = 8.7 Hz), 126.4, 125.3, 123.2, 121.6, 116.2 (d, 2 J C-F = 22.3 Hz)。19F NMR (377 MHz, CDCl3, ppm) δ -108.9。
Example 16: the visible light promotes the reaction of the N- (2-bromophenyl) -4-chlorothiobenzamide.
Reacting N- (2-bromophenyl) -4-Chlorothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 93%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.05 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 7.8 Hz, 2H), 7.87 (d, J = 7.8 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.43 (d, J = 7.9 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.6, 154.1, 137.0, 135.1, 132.1, 129.3, 128.7, 126.5, 125.4, 123.3, 121.7。
Example 17: the visible light promotes the reaction of the N- (2-bromophenyl) -4-bromothiobenzamide.
N- (2-bromophenyl) -4-bromothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 91%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.05 (d, J = 8.0 Hz, 1H), 7.93 (d, J = 8.1 Hz, 2H), 7.88 (d, J = 7.8 Hz, 1H), 7.60 (d, J = 8.1 Hz, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.38 (t, J = 7.2 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.8, 154.2, 135.2, 132.7, 132.4, 129.1, 126.7, 125.6, 125.6, 123.5, 121.8。
Example 18: the visible light promotes the reaction of the N- (2-bromophenyl) -4-iodothiobenzamide.
N- (2-bromophenyl) -4-iodothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 86%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.06 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.86–7.78 (m, 4H), 7.50 (t, J = 7.5 Hz, 1H), 7.40 (t, J = 7.4 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.8, 154.1, 138.2, 135.0, 133.1, 128.9, 126.5, 125.5, 123.3, 121.7, 97.5。
Example 19: the visible light promotes the reaction of the N- (2-bromophenyl) -4-trifluoromethyl-thiobenzamide.
N- (2-bromophenyl) -4-trifluoromethylthiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 24 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. Reaction junctionAfter the end, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, the organic phases are combined, the organic phase is dried by anhydrous sodium sulfate, filtered, and the filtrate is concentrated by rotary evaporation and then separated by thin layer chromatography on silica gel to obtain the target product with the yield of 94%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.19 (d, J = 7.9 Hz, 2H), 8.10 (d, J = 8.1 Hz, 1H), 7.92 (d, J = 7.9 Hz, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.52 (t, J = 7.6 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.0, 154.1, 136.8, 135.2, 132.5 (q, 2 J C-F = 32.8 Hz, 1H), 127.8, 126.7, 126.0 (q, 3 J C-F = 3.8 Hz, 5H), 125.8, 123.8 (q, 1 J C-F = 272.3 Hz, 1H) 123.6, 121.8。19F NMR (377 MHz, CDCl3, ppm) δ -62.8。
Example 20: visible light promotes the reaction of the N- (2-bromophenyl) -3-methylthiobenzamide.
N- (2-bromophenyl) -3-methylthiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 6 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 96%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.07 (d, J = 8.1 Hz, 1H), 7.94 (s, 1H), 7.88 (dd, J = 13.2, 7.9 Hz, 2H), 7.49 (t, J = 7.6 Hz, 1H), 7.38 (t, J = 7.6 Hz, 2H), 7.30 (d, J = 7.4 Hz, 1H), 2.45 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.3, 154.1, 138.9, 135.0, 133.5, 131.8, 128.9, 128.0, 126.3, 125.1, 124.9, 123.2, 121.6, 21.4。
Example 21: the visible light promotes the reaction of the N- (2-bromophenyl) -3-methoxythiobenzamide.
N- (2-bromophenyl) -3-methoxythiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 95%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.07 (d, J = 8.1 Hz, 1H), 7.87 (d, J = 7.9 Hz, 1H), 7.67 (s, 1H), 7.62 (d, J = 7.5 Hz, 1H), 7.47 (t, J = 7.5 Hz, 1H), 7.36 (t, J = 7.3 Hz, 2H), 7.02 (d, J = 8.0 Hz, 1H), 3.89 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 167.9, 160.0, 154.0, 135.1, 134.9, 130.0, 126.3, 125.2, 123.2, 121.6, 120.2, 117.3, 112.0, 55.5。
Example 22: the visible light promotes the reaction of the N- (2-bromophenyl) -3-fluorosulphonamide.
N- (2-bromophenyl) -3-fluorosulfanylbenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrerFollowed by the reaction tube N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 95%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.07 (d, J = 8.1 Hz, 1H), 7.88 (d, J = 7.9 Hz, 1H), 7.82 (d, J = 7.9 Hz, 2H), 7.49 (t, J = 7.6 Hz, 1H), 7.44–7.37 (m, 2H), 7.17 (t, J = 8.0 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.4 (d, 4 J C-F = 3.3 Hz), 163.0 (d, 1 J C-F = 247.3 Hz), 154.0, 135.7 (d, 3 J C-F = 8.0 Hz), 135.1, 130.6 (d, 3 J C-F = 8.1 Hz), 126.5, 125.5, 123.4, 123.3 (d, 4 J C-F = 2.9 Hz), 121.7, 117.8 (d, 2 J C-F = 21.3 Hz), 114.3 (d, 2 J C-F = 23.6 Hz)。19F NMR (377 MHz, CDCl3, ppm) δ -112.0。
Example 23: the visible light promotes the reaction of the N- (2-bromophenyl) -3-bromothiobenzamide.
N- (2-bromophenyl) -3-bromothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction, 4 mL of water was added, followed by extraction with 3X 4 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was filteredAfter the evaporation and the concentration, the target product is obtained by silica gel chromatography thin layer chromatography separation, and the yield is 85 percent.
1H NMR (400 MHz, CDCl3, ppm) δ 8.27 (s, 1H), 8.08 (d, J = 8.1 Hz, 1H), 7.98 (d, J = 7.7 Hz, 1H), 7.90 (d, J = 7.9 Hz, 1H), 7.60 (d, J = 7.8 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 7.35 (t, J = 7.9 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.1, 154.0, 135.5, 135.1, 133.8, 130.5, 130.3, 126.6, 126.2, 125.6, 123.5, 123.2, 121.7。
Example 24: the visible light promotes the reaction of the N- (2-bromophenyl) -3-iodothiobenzamide.
N- (2-bromophenyl) -3-iodothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 85%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.45 (s, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.98 (d, J = 7.7 Hz, 1H), 7.88 (d, J = 7.9 Hz, 1H), 7.78 (d, J = 7.7 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.18 (t, J = 7.7 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 165.9, 153.9, 139.7, 136.0, 135.4, 135.0, 130.5, 126.7, 126.5, 125.5, 123.4, 121.6, 94.7。
Example 25: visible light promotes the reaction of N- (2-bromophenyl) -2-methylthiobenzamide.
N- (2-bromophenyl) -2-methylthiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 88%.
1H NMR (400 MHz, CDCl3 ppm) δ 8.10 (d, J = 8.1 Hz, 1H), 7.92 (d, J = 7.9 Hz, 1H), 7.75 (d, J = 7.5 Hz, 1H), 7.51 (t, J = 7.5 Hz, 1H), 7.44–7.27 (m, 4H), 2.66 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.0, 153.8, 137.2, 135.6, 133.1, 131.5, 130.5, 130.0, 126.1, 126.1, 125.1, 123.4, 121.4, 21.3。
Example 26: the visible light promotes the reaction of the N- (2-bromophenyl) -2-methoxythiobenzamide.
N- (2-bromophenyl) -2-methoxythiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The replacement was carried out 3 times, and the reaction was stirred for 8 hours under irradiation of a 45W household compact fluorescent lamp. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 91%.
1H NMR (400 MHz, CDCl3 ppm) δ 8.53 (d, J = 7.7 Hz, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.91 (d, J = 7.8 Hz, 1H), 7.53–7.41 (m, 2H), 7.35 (t, J = 7.4 Hz, 1H), 7.12 (t, J = 7.4 Hz, 1H), 7.04 (d, J = 8.2 Hz, 1H), 4.02 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 163.1, 157.2, 152.2, 136.1, 131.8, 129.5, 125.9, 124.6, 122.8, 122.3, 121.2, 121.2, 111.7, 55.7。
Example 27: the visible light promotes the reaction of the N- (2-bromophenyl) -2-fluorosulphonamide.
N- (2-bromophenyl) -2-fluorothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 24 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 84%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.42 (t, J = 7.4 Hz, 1H), 8.13 (d, J = 8.1 Hz, 1H), 7.95 (d, J = 7.9 Hz, 1H), 7.47 (ddd, J = 26.6, 15.2, 7.4 Hz, 3H), 7.32 (t, J = 7.5 Hz, 1H), 7.25 (dd, J = 10.3, 8.8 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ161.1 (d, 3 J C-F = 5.7 Hz), 160.6 (d, 1 J C-F = 253.3 Hz), 152.6, 135.8 (d, 3 J C-F = 7.9 Hz), 132.2 (d, 2 J C-F = 8.7 Hz), 129.8 (d, 4 J C-F = 2.3 Hz), 126.3, 125.3, 124.7 (d, 3 J C-F = 3.3 Hz), 123.3, 121.5, 121.4, 116.4 (d, 2 J C-F = 21.9 Hz)。19F NMR (377 MHz, CDCl3, ppm) δ -111.9。
Example 28: the visible light promotes the reaction of the N- (2-bromophenyl) -3, 4-dimethoxythiobenzamide.
N- (2-bromophenyl) -3, 4-dimethoxythiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 2 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography separation is carried out, so that the target product is obtained, and the yield is 98%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.03 (d, J = 8.1 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.70 (s, 1H), 7.58 (d, J = 8.2 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.35 (t, J = 7.5 Hz, 1H), 6.92 (d, J = 8.3 Hz, 1H), 4.01 (s, 3H), 3.94 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 167.9, 154.1, 151.6, 149.3, 134.9, 126.6, 126.2, 124.9, 122.8, 121.5, 121.1, 111.0, 109.7, 56.1, 56.0。
Example 29: the visible light promotes the reaction of the N- (2-bromophenyl) thionaphthalene-2-formamide.
N- (2-bromophenyl) thionaphthalene-2-carboxamide (0.2 mmol), Na3PO4(0.1 mmol) ofAnd DMSO (2 mL) was added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 86%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.54 (s, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.10 (d, J = 8.1 Hz, 1H), 7.97–7.81 (m, 4H), 7.56–7.46 (m, 3H), 7.37 (t, J = 7.5 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.1, 154.2, 135.1, 134.6, 133.2, 131.0, 128.8, 127.8, 127.6, 127.4, 126.8, 126.4, 125.2, 124.4, 123.2, 121.6。
Example 30: visible light promotes the reaction of N- (2-bromophenyl) thiopyridine-4-formamide.
N- (2-bromophenyl) thiopyridine-4-carboxamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 20 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 84%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.78 (d, J = 5.3 Hz, 2H), 8.13 (d, J = 8.1 Hz, 1H), 7.95 (d, J = 4.1 Hz, 3H), 7.55 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 165.1, 154.0, 150.8, 140.5, 135.2, 126.8, 126.2, 123.9, 121.9, 121.2。
Example 31: visible light promotes the reaction of N- (2-bromophenyl) thiofuran-2-formamide.
N- (2-bromophenyl) thiofuran-2-carboxamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 67%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.05 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 7.9 Hz, 1H), 7.61 (s, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.19 (d, J = 2.8 Hz, 1H), 6.60 (s, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 157.6, 153.8, 148.8, 144.7, 134.3, 126.5, 125.2, 123.1, 121.6, 112.5, 111.4。
Example 32: the visible light promotes the reaction of the N- (2-bromophenyl) thiothiophene-2-formamide.
N- (2-bromophenyl) thiothiophene-2-carboxamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction, 4 mL of water was added, followed by extraction with 3X 4 mL of ethyl acetate, the organic phases were combined and the organic phase was again driedDrying with sodium sulfate, filtering, concentrating the filtrate by rotary evaporation, and separating by silica gel chromatography thin layer chromatography to obtain the target product with yield of 92%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.02 (d, J = 8.1 Hz, 1H), 7.83 (d, J = 7.9 Hz, 1H), 7.64 (d, J = 3.2 Hz, 1H), 7.51–7.42 (m, 2H), 7.35 (t, J = 7.5 Hz, 1H), 7.12 (t, J = 4.1 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 161.4, 153.7, 137.4, 134.7, 129.3, 128.6, 128.0, 126.4, 125.2, 123.0, 121.4。
Example 33: the reaction of the N- (2-bromo-5-fluorophenyl) -3, 4-dimethoxythiobenzamide is promoted by visible light.
N- (2-bromo-5-fluorophenyl) -3, 4-dimethoxythiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 24 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 93%.
1H NMR (400 MHz, CDCl3, ppm) δ 7.75 (dd, J = 8.6, 5.2 Hz, 1H), 7.72–7.63 (m, 2H), 7.58–7.50 (dd, J = 8.3 Hz, 1.1 Hz, 1H), 7.10 (td, J = 8.7, 1.9 Hz, 1H), 6.90 (d, J = 8.4 Hz, 1H), 4.01 (s, 3H), 3.94 (s, 3H)。13C NMR (101 MHz, CDCl3, ppm) δ 170.5, 162.0 (d, 1 J C-F = 242.8 Hz), 155.2 (d, 3 J C-F = 12.0 Hz), 151.9, 149.5, 130.4 (d, 4 J C-F = 2.0 Hz), 126.6, 122.2 (d, 3 J C-F = 9.9 Hz), 121.3, 113.5 (d, 2 J C-F = 24.9 Hz), 111.1, 109.1 (d, 2 J C-F = 23.6 Hz), 109.0, 56.2, 56.1。
19F NMR (377 MHz, CDCl3, ppm) δ -116.0。
Example 34: visible light promotes the reaction of the N- (2-bromophenyl) thiobenzamide.
N- (2-bromophenyl) thiobenzamide (1.17 g, 4 mmol), Na3PO4(0.5 equiv.) and DMSO (40 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The replacement is carried out for 3 times, and the reaction is carried out for 8 hours under the irradiation of sunlight by stirring. After the reaction, 80 mL of water is added, then the mixture is extracted by 3X 40 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, the mixture is filtered, filtrate is concentrated by rotary evaporation, and the target product is obtained by thin layer chromatography separation of silica gel chromatography, wherein the yield is 73 percent, and the weight is 0.85 g.
Example 35: visible light promotes the reaction of N, N' -bis (2-bromophenyl) -thioterephthalamide.
N, N' -bis (2-bromophenyl) -thioterephthalamide (0.2 mmol), Na3PO4(0.2 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 10 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, the precipitate is collected by filtration, recrystallized by DMF, filtered again, washed by ethanol and tetrahydrofuran and dried to obtain the target product with the yield of 82%. The product is slightly soluble in common known solvents,13the C NMR signal is weak, so only use is made1And H NMR characterization.
1H NMR (400 MHz, DMSO, ppm) δ 8.14 (s, 4H), 7.75 (d, J = 7.8 Hz, 2H), 7.58 (d, J = 7.8 Hz, 2H), 7.46 (t, J = 7.4 Hz, 2H), 7.26 (t, J = 7.4 Hz, 2H)。
Claims (10)
1. The method for preparing the benzothiazole compound by visible light promoted N- (2-bromophenyl) thioamide is characterized by comprising the following steps of reacting N- (2-bromophenyl) thioamide as a raw material under the irradiation of visible light and in the presence of alkali to prepare the benzothiazole compound; the N- (2-bromophenyl) thioamide has the following structural general formula:
2. The method according to claim 1, wherein the reaction is carried out in a solvent in the presence of a base under the protection of an inert gas.
3. The method according to claim 1, wherein the molar ratio of the N- (2-bromophenyl) thioamide to the base is 1 (0.2 to 0.8).
4. The method of claim 1, wherein the base is an inorganic base.
5. The method of claim 1, wherein Ar is Ar2Is phenyl, substituted phenyl or a heterocyclic group.
6. The method according to claim 1, wherein the reaction is carried out at room temperature for 2 to 24 hours.
7. The application of alkali in the preparation of benzothiazole compounds by taking N- (2-bromophenyl) thioamide as a raw material through reaction; the base is an inorganic base.
8. The use according to claim 7, wherein the base is selected from any one of sodium phosphate, sodium carbonate, potassium hydroxide, sodium hydroxide, and sodium acetate.
9. Use according to claim 7, characterized in that: the benzothiazole compound has the following structural general formula:
10. Benzothiazole compounds prepared according to the process of claim 1.
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