CN111592509B - Method for synthesizing aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis - Google Patents
Method for synthesizing aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis, which comprises the steps of taking a 2- (1-hydroxy-3-arylpropyl-2-alkyne-1-yl) phenol compound shown in a formula (1) and p-toluenesulfonyl methyl isocyano shown in the formula (2) as raw materials and cuprous iodide as a catalyst in an organic solvent system, heating and stirring for reaction, tracking and detecting by TLC until the reaction is complete, and carrying out aftertreatment on a reaction solution to obtain the aryl (3-sulfuryl benzofuran-2-yl) ketone compound shown in the formula (3). The method has the advantages of simple operation, cheap and easily-obtained raw materials, mild reaction conditions, environment-friendly reaction system, easy separation and purification of products, suitability for synthesizing various functionalized aryl (3-sulfuryl benzofuran-2-yl) ketone compounds, particular suitability for large-scale industrial production, capability of preparing high-purity aryl (3-sulfuryl benzofuran-2-yl) ketone compounds with high efficiency and high yield and widening the synthesis method of benzofuran and sulfuryl compounds.
Description
Technical Field
The invention belongs to the field of organic synthesis, relates to a copper catalytic synthesis reaction, and particularly relates to a method for synthesizing an aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis.
Background
Benzofuran is an important organic small molecular skeleton, not only a key structural unit of a plurality of bioactive natural products, medicines, organic conductive materials and the like, but also a multipurpose organic synthon, so that the development of a synthesis method of benzofuran is one of important research subjects of organic synthetic chemistry. Among the various natural and synthetic benzofuran derivatives, they exhibit good physiological activities against tumors, viruses, fungi, oxidation, tuberculosis, immunosuppressants, etc., such as: benzbromoranone (uricosuric), amiodarone (antiarrhythmic), obovaten (antitumor activity), saprisartan (treatment of hypertension) and AngioprissinA (antimicrobial agent). In recent years, several strategies for the efficient construction of benzofuran compounds have been developed (nat. Chem.2019,11,797, org. Lett.2019,21,955, org. Lett.2019,21,8008, adv.synth.cat.2016, 358,2984, angelw.chem.int.ed.2013, 52,4607, j.am.chem.soc.2009,131, 17387etc.. However, most of the methods are development of developed strategies, cannot fundamentally solve the limitations in the synthesis of benzofuran, and are lack of practical value. One of the most common methods for the synthesis of benzofuran to date has been the use of base-mediated nucleophilic conjugates followed by transition metal-catalyzed activation of alkynes with cyclization of 2-halophenol Heck to the target compound. This disclosed catalytic strategy also suffers from several drawbacks such as: poor regioselectivity, the need to use strong oxidants and expensive ligands, as well as the limitations of various substituents, harsh reaction conditions, low product yields, and the like. Therefore, there is an urgent need for scientists to develop a new simple and efficient method for preparing benzofuran.
Sulphonyl (sulphone) s are another general class of fragments, widely present among many natural products and drug molecules with high biological activity, and very useful in organic synthesis and pharmaceutical chemistry. Because of the important position of the sulfonyl compounds in medicinal chemistry, the research and development of the synthesis based on the sulfonyl compounds under mild conditions have important significance, a new channel can be opened for the synthesis of the sulfonyl group-containing medicaments and derivatives thereof, and a new means is provided for organic synthesis. Meanwhile, sulfonyl compounds with similar structures obtained by using the developed methodology can be directly used for high-throughput screening of some specific biological targets. Once the small molecule compound library is screened by a valuable biological model, the result not only can provide possibility for obtaining a lead compound with high activity and good selectivity, but also the structure-activity relationship obtained in the process can establish a more solid and reliable database for more accurately revealing the life process. Therefore, it is of great significance to introduce the sulfone functional group into the benzofuran skeleton with special bioactivity and further culture the biological characteristics of the benzofuran skeleton widely. However, a great deal of literature research finds that only a few examples relate to the synthesis of the compounds, and the existing methods generally have the defects of pre-designed substrate molecules, low yield, harsh reaction conditions, complicated reaction steps, environmental friendliness and the like. In recent years, copper-catalyzed organic chemical reactions have become one of the hot spots of current organic chemical research, and various copper-catalyzed chemical reactions have been reported, such as carbon-carbon coupling reactions, carbon-heteroatom coupling reactions, intramolecular reactions, multicomponent reactions, and the like. With the rapid deterioration of global ecological environment, how to realize sustainable development becomes a major problem facing human beings, and green chemical research, which is centered on eliminating pollution from the source and saving resources, has become a powerful means for solving the increasingly serious ecological environment problem. The reaction of isocyanine with alkyne has the advantages of environmental friendliness, low price and the like, and the advantages make the isocyanine particularly suitable for chemical industrial production.
Disclosure of Invention
The invention aims to provide a method for synthesizing an aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis, which has the advantages of cheap and easily obtained raw materials and environmental friendliness.
In order to realize the purpose, the technical scheme adopted by the invention is as follows: a method for synthesizing an aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis comprises the steps of taking 2- (1-hydroxy-3-arylprop-2-yne-1-yl) phenol shown in a formula (1) and p-toluenesulfonyl methyl isocyanide shown in a formula (2) as raw materials in an organic solvent system, taking cuprous iodide as a catalyst, heating and stirring for reaction, tracking and detecting by TLC until the reaction is complete, and carrying out aftertreatment on a reaction solution to obtain the aryl (3-sulfuryl benzofuran-2-yl) ketone compound shown in the formula (3); wherein the feeding molar ratio of the 2- (1-hydroxy-3-arylprop-2-yne-1-yl) phenol to the p-toluenesulfonylmethylisocyan is 1.5:1;
in the formula, R 1 Is hydrogen, methoxy, methyl, fluorine or chlorine, ar is phenyl, substituted phenyl, heteroaryl or condensed aryl, wherein the substituent is methyl, ethyl, methoxy, ethoxy, fluorine or chlorine.
Preferably, the organic solvent is selected from one of acetonitrile, 1,2-dichloroethane, 1,4-dioxane, N-dimethylformamide, dimethyl sulfoxide and toluene.
More preferably, the organic solvent is selected from acetonitrile.
Preferably, the amount of the cuprous iodide is 10mol% based on the amount of the substance of 2- (1-hydroxy-3-arylprop-2-yn-1-yl) phenol represented by formula (1).
Preferably, the reaction temperature is 60 to 100 ℃.
Preferably, the reaction solution post-treatment method comprises: after the reaction is finished, pouring the reaction solution into saturated saline solution, extracting by using dichloromethane, then backwashing an organic phase by using the saturated saline solution, drying by using anhydrous calcium chloride, carrying out suction filtration, carrying out reduced pressure distillation, then carrying out silica gel column chromatography separation, carrying out reduced pressure distillation on the obtained eluent, and drying to obtain the aryl (3-sulfonyl benzofuran-2-yl) ketone compound shown in the formula (3).
Preferably, the eluent of the silica gel column chromatography is petroleum ether: ethyl acetate =4:1,V/V.
Compared with the prior art, the method has the advantages of simple operation, easily obtained raw materials and reagents, mild conditions, environment-friendly reaction system, easy separation and purification of products, suitability for synthesizing various highly functionalized aryl (3-sulfuryl benzofuran-2-yl) ketone compounds, particular suitability for large-scale industrial production, and capability of preparing high-purity aryl (3-sulfuryl benzofuran-2-yl) ketone compounds with high efficiency and high yield (more than 75%).
Drawings
FIG. 1 shows the 1H-NMR spectrum of an aryl (3-sulfuryl benzofuran-2-yl) methanone derivative 3 a;
FIG. 2 is a nuclear magnetic resonance spectrum of 13C-NMR of an aryl (3-sulfurylbenzofuran-2-yl) methanone derivative 3 a;
FIG. 3 is a nuclear magnetic resonance spectrum of 1H-NMR of an aryl (3-sulfuryl benzofuran-2-yl) methanone derivative 3 b;
FIG. 4 is a nuclear magnetic resonance spectrum of 13C-NMR of an aryl (3-sulfurylbenzofuran-2-yl) methanone derivative 3 b;
FIG. 5 is a nuclear magnetic resonance spectrum of 1H-NMR of an aryl (3-sulfuryl benzofuran-2-yl) methanone derivative 3 c;
FIG. 6 is a nuclear magnetic resonance spectrum of 13C-NMR of an aryl (3-sulfurylbenzofuran-2-yl) methanone derivative 3C;
FIG. 7 is a nuclear magnetic resonance spectrum of 1H-NMR of an aryl (3-sulfurylbenzofuran-2-yl) methanone derivative 3 d;
FIG. 8 shows the 13C-NMR nuclear magnetic resonance spectrum of aryl (3-sulfuryl benzofuran-2-yl) methanone derivative 3 d;
FIG. 9 shows the 1H-NMR spectrum of aryl (3-sulfuryl benzofuran-2-yl) methanone derivative 3 e;
FIG. 10 shows a nuclear magnetic resonance spectrum of 13C-NMR of an aryl (3-sulfurylbenzofuran-2-yl) methanone derivative 3 e.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1: preparation of phenyl (3-sulfuryl benzofuran-2-yl) methanone derivative 3a
Adding CH into 25mL pressure-resistant pipe with magnetic stirring device 3 CN (4 mL), 2- (1-hydroxy-3-arylprop-2-yn-1-yl) phenol 1a (0.224g, 1.0 mmol) and p-toluenesulfonylmethylisoch 2 NC2a (0.293g, 1.5mmol), cuprous iodide (0.019g, 0.1mol) was added and stirred uniformly, and then the mixture was put into an oil bath at 80 ℃ and stirred continuously. TLC detects the disappearance of the substrate and the reaction is finished. Pouring the reaction solution into saturated sodium chloride aqueous solution (10 mL), extracting with dichloromethane (3X 10 mL), combining organic phases, then backwashing the organic phases with water (3X 10 mL), drying with anhydrous calcium chloride, filtering, distilling under reduced pressure to obtain viscous solid, and finally performing silica gel column chromatography (eluent is V) Petroleum ether :V Ethyl acetate = 4:1) to yield a yellow solid, which was confirmed by NMR, MS to be phenyl (3-sulfuryl benzofuran-2-yl) methanone derivative 3a with a yield of 91%.
Spectrogram analysis data 3a:
yellow solid, m.p.115-116 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.22-8.20(m,1H,ArH),8.14-8.12(m,2H,ArH),7.95-7.92(m,2H,ArH),7.69-7.65(m,1H,ArH),7.57-7.46(m,5H,ArH),7.34(d,J＝8.0Hz,2H,ArH),2.41(s,3H,CH 3 ) (FIG. 1); 13 C NMR(CDCl 3 ,100MHz):δ C 184.7,153.7,152.7,144.8,138.1,135.6,134.6,130.3,129.8,128.8,128.2,127.8,125.54,125.45,123.7,122.3,112.4,21.7 (fig. 2); HRMS (ESI-TOF, m/z): calcd for C 22 H 17 O 4 S[M+H] + :377.0842,found 377.0839.
Example 2: in contrast to example 1, the organic solvent was selected from 1,2-dichloroethane with a yield of 83%.
Example 3: in contrast to example 1, the organic solvent was selected from 1,4-dioxane with a yield of 75%.
Example 4: in contrast to example 1, the organic solvent was selected from N, N-dimethylformamide with a yield of 87%.
Example 5: in contrast to example 1, the organic solvent was selected from dimethyl sulfoxide, the yield of which was 84%.
Example 6: in contrast to example 1, the organic solvent was selected from toluene, with a yield of 82%.
Example 7: in contrast to example 1, the reaction temperature was 60 ℃ and the yield was 77%
Example 8: unlike example 1, the reaction temperature was 100 ℃ and the yield was 88%.
Example 9:
the yield was 87% under the same conditions as in example 1 except that 1b was used instead of 1a in example 1.
Spectrogram analysis data 3b:
yellow solid, m.p.112-113 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H .8.12(d,J＝8.0Hz,2H,ArH),7.98-7.93(m,3H,ArH),7.70-7.66(m,1H,ArH),7.55-7.51(m,2H,ArH),7.43-7.38(m,1H,ArH),7.35(d,J＝8.0Hz,2H,ArH),7.26-7.21(m,1H,ArH),2.40(s,3H,CH 3 ) (FIG. 3); 13 C NMR(CDCl 3 ,100MHz):δ C 184.2,153.5,147.9(d,J F-C ＝251.9Hz),145.1,141.1(d,J F-C ＝12.5Hz),137.6,135.2,134.8,130.3,129.8,128.8,128.2,126.8(d,J F-C ＝2.2Hz),126.3(d,J F-C ＝5.7Hz),125.1(d,J F-C ＝2.2Hz),117.7(d,J F-C ＝4.6Hz),113.8(d,J F-C =15.5 Hz), 21.6 (fig. 4); HRMS (ESI-TOF, m/z): calcd for C 22 H 16 FO 4 S[M+H] + :395.0748,found 395.0752.
Example 10:
the yield was 79% under the same conditions as in example 1 except that 1c was used instead of 1a in example 1.
Spectrogram analysis data 3c:
yellow solid, m.p.102-103 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.11(d,J＝8.0Hz,2H,ArH),8.00(d,J＝8.0Hz,1H,ArH),7.96-7.04(m,2H,ArH),7.69-7.64(m,1H,ArH),7.54-7.50(m,2H,ArH),7.38-7.28(m,4H,ArH),2.47(s,3H,CH 3 ),2.39(s,3H,CH 3 ) (FIG. 5); 13 C NMR(CDCl 3 ,100MHz):δ C 184.9,152.9,152.4,144.7,138.1,135.6,134.5,130.3,129.7,128.7,128.5,128.1,125.6,125.3,123.1,122.7,119.4,21.6,14.8 (fig. 6); HRMS (ESI-TOF, m/z): calcd for C 23 H 19 O 4 S[M+H] + :391.0999,found 391.0986.
Example 11:
the yield thereof was 81% under the same conditions as in example 1 except that 1d was used instead of 1a in example 1.
Spectrogram analysis data 3d:
white solid, m.p.121-122 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.11(d,J＝8.4Hz,2H,ArH),7.96-7.04(m,2H,ArH),7.74(dd,J＝8.0Hz and 0.8Hz,1H,ArH),7.68-7.63(m,1H,ArH),7.53-7.49(m,2H,ArH),7.40-7.32(m,3H,ArH),6.97(dd,J＝8.0Hz and 0.8Hz,1H,ArH),3.96(s,3H,OCH 3 ),2.40(s,3H,CH 3 ) (FIG. 7); 13 C NMR(CDCl 3 ,100MHz):δ C 184.6,152.9,145.8,144.8,143.4,138.0,135.5,134.5,130.3,129.7,128.7,128.1,126.3,125.4,125.2,113.6,109.2,56.2,21.6 (fig. 8); hRMS(ESI-TOF,m/z):Calcd for C 23 H 19 O 5 S[M+H] + :407.0948,found 407.0952.
Example 12:
the yield thereof was 74% under the same conditions as in example 1 except that 1e was used instead of 1a in example 1.
Spectrogram analysis data 3e:
white solid, m.p.132-133 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.15(d,J＝8.8Hz,1H,ArH),8.12-8.09(m,2H,ArH),7.93-7.91(m,2H,ArH),7.70-7.66(m,1H,ArH),7.58(d,J＝2.0Hz,1H,ArH),7.55-7.51(m,2H,ArH),7.47(dd,J＝8.4Hz and2.0Hz,1H,ArH),7.35(d,J＝8.4Hz,2H,ArH),2.41(s,3H,CH 3 ) (FIG. 9); 13 C NMR(CDCl 3 ,100MHz):δ C 184.1,153.5,153.0,145.1,137.8,135.3,134.7,134.0,130.2,129.8,128.8,128.2,126.5,125.6,122.9,122.4,112.8,21.7 (fig. 10); HRMS (ESI-TOF, m/z): calcd for C 22 H 16 ClO 4 S[M+H] + :411.0452,found 411.0461.
Example 13:
the yield was 75% under the same conditions as in example 1 except that 1f was used instead of 1a in example 1.
Spectrogram analysis data 3f:
white solid, m.p.113-114 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.22-8.20(m,1H,ArH),8.12(d,J＝8.4Hz,2H,ArH),8.01-7.96(m,2H,ArH),7.58-7.46(m,3HV),7.34(d,J＝8.0Hz,2H,ArH),7.22-7.17(m,2H,ArH),2.40(s,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 183.0,166.6(d,J F-C ＝256.6Hz),153.7,152.3,144.9,138.0,133.0(d,J F-C ＝9.6Hz),132.0(d,J F-C ＝2.7Hz),129.7,128.1,127.9,125.6,123.6,122.3(d,J F-C ＝22.3Hz),116.1,112.3,21.6；HRMS(ESI-TOF,m/z):Calcd for C 22 H 16 FO 4 S[M+H] + :395.0748,found 395.0738.
example 14:
the yield was 79% as in example 1 except that 1g was used instead of 1a in example 1.
3g of spectrogram analysis data:
white solid, m.p.137-138 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.22(dd,J＝6.8Hz and 1.6Hz,1H,ArH),8.13-8.11(m,2H,ArH),7.91-7.87(m,2H,ArH),7.58-7.46(m,5H,ArH),7.34(d,J＝8.0Hz,2H,ArH),2.40(s,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 183.3,153.7,152.0,144.9,141.1,137.9,133.9,131.5,129.7,129.1,128.1,128.0,125.8,125.6,123.6,122.3,112.3,21.6；HRMS(ESI-TOF,m/z):Calcd for C 22 H 16 ClO 4 S[M+H] + :411.0452,found 411.0451.
example 15:
the yield was 82% under the same conditions as in example 1 except that 1h was used instead of 1a in example 1.
Spectrogram analysis data 3h:
white solid, m.p.141-142 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.19(dd,J＝6.4Hz and 2.0Hz,1H,ArH),8.12(d,J＝8.4Hz,2H,ArH),7.84(d,J＝8.4Hz,2H,ArH),7.56-7.44(m,3H,ArH),7.34-7.31(m,4H,ArH),2.46(m,3H,CH 3 ),2.40(s,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 184.3,153.6,153.1,145.9,144.7,138.1,133.1,130.4,129.7,129.5,128.1,127.6,125.4,125.0,123.6,122.1,112.3,21.9,21.6；HRMS(ESI-TOF,m/z):Calcd for C 23 H 19 O 4 S[M+H] + :391.0999,found 391.0982.
example 16:
the yield thereof was 81% under the same conditions as in example 1 except that 1i was used instead of 1a in example 1.
Spectrogram analysis data 3i:
white solid, m.p.151-152 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.17(dd,J＝6.8Hz and 2.8Hz,1H,ArH),8.12(d,J＝8.0Hz,2H,ArH),7.93(d,J＝8.8Hz,2H,ArH),7.55-7.43(m,3H,ArH),7.33(d,J＝8.0Hz,2H,ArH),6.98(d,J＝8.8Hz,2H,ArH),3.90(m,3H,OCH 3 ),2.39(s,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 183.1,164.8,153.6,153.4,144.7,138.1,132.8,129.7,128.6,128.1,127.5,125.4,124.5,123.6,122.0,114.1,112.2,55.6,21.6；HRMS(ESI-TOF,m/z):Calcd for C 23 H 19 O 5 S[M+H] + :407.0948,found 407.0953.
example 17:
the yield was 87% under the same conditions as in example 1 except that 1j was used instead of 1a in example 1.
Spectrogram analysis data 3j:
white solid, m.p.144-145 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.19(dd,J＝6.4Hz and 2.0Hz,1H,ArH),8.13(d,J＝8.4Hz,2H,ArH),7.87-7.85(m,2H,ArH),7.55-7.44(m,3H,ArH),7.35-7.32(m,4H,ArH),2.75(q,J＝7.6Hz,2H,CH 2 ),2.40(s,3H,CH 3 ),1.28(t,J＝7.6Hz,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 184.4,153.7,153.2,152.0,144.8,138.2,133.4,130.6,129.8,128.4,128.2,127.7,125.5,125.0,123.7,122.2,112.3,29.2,21.7,15.1；HRMS(ESI-TOF,m/z):Calcd for C 24 H 21 O 4 S[M+H] + :405.1155,found 405.1161.
example 18:
the yield thereof was 81% under the same conditions as in example 1 except that 1k was used instead of 1a in example 1.
Spectrogram analysis data 3k:
white solid, m.p.145-147 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.16(dd,J＝6.0Hz and 1.6Hz,1H,ArH),8.12(d,J＝8.4Hz,2H,ArH),7.93-7.89(m,2H,ArH),7.55-7.52(m,1H,ArH),7.50-7.43(m,2H,ArH),7.32(d,J＝8.4Hz,2H,ArH),6.98-6.94(m,2H,ArH),4.13(q,J＝6.8Hz,2H,CH 2 ),2.39(s,3H,CH 3 ),1.45(t,J＝7.2Hz,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 183.2,164.4,153.7,153.6,144.8,138.3,132.9,129.8,128.5,128.2,127.6,125.5,124.5,123.7,122.1,114.6,112.4,64.1,21.7,14.7；HRMS(ESI-TOF,m/z):Calcd for C 24 H 21 O 5 S[M+H] + :421.1104,found 421.1121.
example 19:
the yield was 75% under the same conditions as in example 1 except that 1l was used instead of 1a in example 1.
Spectrogram analysis data 3l:
white solid, m.p.123-124 ℃; 1 H NMR(CDCl 3 ,400MHz):δ H 8.25-8.22(m,1H,ArH),8.14-8.12(m,2H,ArH),7.73-7.71(m,1H,ArH),7.68-7.65(m,1H,ArH),7.58-7.47(m,4H,ArH),7.39-7.34(m,3H,ArH),2.41(s,3H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz):δ C 183.2(d,J F-C ＝2.6Hz),162.6(d,J F-C ＝247.2Hz),153.7,151.8,144.9,137.9,137.4(d,J F-C ＝6.8Hz),130.5(d,J F-C ＝7.6Hz),129.8,128.2,128.1,126.2(d,J F-C ＝3.1Hz),126.1,125.7,123.6,122.3,121.6(d,J F-C ＝21.4Hz),116.6(d,J F-C ＝22.8Hz),112.4,21.7；HRMS(ESI-TOF,m/z):Calcd for C 22 H 16 FO 4 S[M+H] + :395.0748,found 395.0752.
example 20:
the yield was 85% under the same conditions as in example 1 except that 1m was used instead of 1a in example 1.
Spectrogram analysis data 3m:
white solid, m.p.152-153 ℃; 1 H-NMR(400MHz,CDCl 3 )δ8.32(s,1H),8.24-8.22(m,1H),8.10(d,J＝8.0Hz 2H),8.06(dd,J＝8.4Hz and 2.0Hz,1H),7.95(d,J＝8.8Hz,1H),7.91-7.87(m,2H),7.66-7.62(m,1H),7.59-7.47(m,4H),7.30(d,J＝8.4Hz,2H),2.38(s,3H)； 13 C-NMR(CDCl 3 ,100MHz)δ184.7,153.8,153.0,144.8,138.1,136.2,133.5,133.0,132.2,129.9,129.7,129.4,128.8,128.1,127.9,127.7,127.0,125.5,125.2,124.4,123.7,122.1,112.4,21.6.；HRMS(ESI-TOF)m/z calculated for C 26 H 19 O 4 S[M+H] + :427.0999 found:427.0992.
example 21:
the yield was 74% under the same conditions as in example 1 except that 1n was used instead of 1a in example 1.
Spectrogram analysis data 3n:
white solid, m.p.125-126 ℃; 1 H-NMR(400MHz,CDCl 3 )δ8.34(d,J＝7.6Hz,1H),8.18(d,J＝8.0Hz,2H),7.97(d,J＝4.0Hz,1H),7.83(d,J＝4.4Hz,1H),7.61-7.48(m,3H),7.34(d,J＝8.0Hz,2H),7.23-7.20(m,1H),2.40(s,3H)； 13 C-NMR(CDCl 3 ,100MHz)δ174.9,153.4,151.2,144.8,142.1,138.2,136.4,136.2,129.6,128.6,128.3,128.3,126.2,125.6,124.1,122.9,112.3,21.7；HRMS(ESI-TOF)m/z calculated for C 20 H 15 O 4 S 2 [M+H] + :383.0406 found:383.0411.
Claims (7)
1. a method for synthesizing an aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis is characterized in that 2- (1-hydroxy-3-arylprop-2-yne-1-yl) phenol shown in a formula (1) and p-toluenesulfonyl methyl isocyanide shown in a formula (2) are used as raw materials in an organic solvent system, cuprous iodide is used as a catalyst, heating and stirring are carried out for reaction, tracking detection is carried out by TLC (thin layer chromatography) until the reaction is complete, and the aryl (3-sulfuryl benzofuran-2-yl) ketone compound shown in the formula (3) is obtained after the reaction liquid is subjected to aftertreatment; wherein the feeding molar ratio of the 2- (1-hydroxy-3-arylprop-2-yne-1-yl) phenol to the p-toluenesulfonylmethylisocyan is 1.5:1;
in the formula, R 1 Is hydrogen, methoxy, methyl, fluorine or chlorine, ar is phenyl, substituted phenyl, heteroaryl or condensed aryl, wherein the substituent is methyl, ethyl, methoxy, ethoxy, fluorine or chlorine.
2. The method for copper-catalyzed synthesis of aryl (3-sulfuryl benzofuran-2-yl) ketone compound according to claim 1, wherein the organic solvent is selected from one of acetonitrile, 1,2-dichloroethane, 1,4-dioxane, N-dimethylformamide, dimethyl sulfoxide and toluene.
3. The method for copper-catalyzed synthesis of aryl (3-sulfuryl benzofuran-2-yl) ketone compound according to claim 2, wherein the organic solvent is selected from acetonitrile.
4. The method for copper-catalyzed synthesis of aryl (3-sulfuryl benzofuran-2-yl) ketone compound according to claim 1, wherein the amount of cuprous iodide is 10mol% of the substance of 2- (1-hydroxy-3-arylprop-2-yn-1-yl) phenol represented by formula (1).
5. The method for copper-catalyzed synthesis of aryl (3-sulfuryl benzofuran-2-yl) ketone compound according to claim 1, wherein the reaction temperature is 60-100 ℃.
6. The method for synthesizing aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis according to claim 1, wherein the method for post-treating the reaction liquid comprises the following steps: after the reaction is finished, pouring the reaction solution into saturated saline solution, extracting by using dichloromethane, then backwashing an organic phase by using the saturated saline solution, drying by using anhydrous calcium chloride, carrying out suction filtration, carrying out reduced pressure distillation, then carrying out silica gel column chromatography separation, carrying out reduced pressure distillation on the obtained eluent, and drying to obtain the aryl (3-sulfonyl benzofuran-2-yl) ketone compound shown in the formula (3).
7. The method for copper-catalyzed synthesis of aryl (3-sulfuryl benzofuran-2-yl) ketone compound according to claim 6, wherein the eluent of the silica gel column chromatography is petroleum ether: ethyl acetate =4:1,V/V.
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