Polyaryl sulfone compound and synthesis method thereof

Abstract

The invention belongs to the technical field of organic chemistry, and discloses a polyaryl sulfone compound and a synthesis method thereof. The preparation method comprises the following steps: dissolving an allene amine compound 1 in a solvent, then adding bis (hexafluoroethyl acetone) copper, and carrying out heating reaction to prepare a polyaryl sulfone compound 2. The method for simply and efficiently preparing the polyaryl sulfone compound is simple and feasible, the raw materials are cheap and easy to obtain, the experimental operation is simple, and the application prospect is wide.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and particularly relates to a polyaryl sulfone compound and a synthesis method thereof. Background Art

[0002] Polyaryl sulfone structures are important intermediates for the preparation of natural products and drug molecules, so it is necessary to explore a simple synthetic method for this type of structure. Allenes are a class of 1,2-propene-type compounds containing cumulative double bonds. They are composed of two adjacent carbon-carbon double bonds and are an important class of synthons. Compared with alkenes, allenes have higher reactivity due to their higher tension. In recent years, allenes have attracted extensive attention from scientific researchers due to their unique reactivity, selectivity, availability and stability. Under the action of transition metals, allenes can undergo various types of addition reactions, thereby achieving the efficient construction of a series of carbon-hydrogen bonds, carbon-carbon bonds and carbon-hetero bonds. Subsequently, through subsequent cycloaddition reactions, very useful carbon heterocyclic compounds can be prepared in synthesis. Compared with traditional catalytic systems, transition metal catalysis has higher efficiency, better thermal and chemical stability, and longer catalytic cycle life. Among them, under transition metal catalysis, when metal-activated allenes are captured by nucleophiles, a very important class of reaction intermediates, metal carbenes, can be constructed. The previous synthesis method for preparing metal carbene is mainly produced by metal decomposition of explosive diazo compounds, which is highly dangerous and thus limits the further application of the method, especially in large-scale actual production. The strategy of using allene as a precursor to construct metal carbene replaces the method of producing such carbene intermediates by explosive diazo compounds in the previous synthetic route, which makes the generation of metal carbene intermediates safer and more efficient. Prior art CN105884670A discloses a class of copper-catalyzed allene synthesis of five-membered ring pyrrole structure, which can only synthesize five-membered ring pyrrole compounds, and the catalyst cuprous oxide used only plays the role of an oxidant, and the scope of action is very limited, and it is also impossible to apply other types of reactions. Therefore, the method is still mainly limited to precious metal catalysis to date. If it can be expanded to cheap metal catalysis, it will be of great significance for the development of allene chemistry. Summary of the invention

[0003] In view of the technical problem that the existing allene synthesis of polyaryl sulfone compounds requires the use of precious metal catalysts with high toxicity, poor stability and high price, the present invention provides a method for synthesizing polyaryl sulfone compounds from allenes using copper catalysis with low toxicity, good stability and low price. The synthesis method synthesizes polyaryl sulfone compounds through tandem reactions such as cyclization of allene amine compounds, bond breaking and formation, etc., and has the advantages of simple operation, mild conditions, wide substrate range, etc., and has excellent application prospects.

[0004] To achieve the above object, the technical solution of the present invention is implemented as follows:

[0005] A method for synthesizing a polyaryl sulfone compound comprises the following steps: dissolving an allenamine compound 1 in a solvent, then adding a catalyst bis(hexafluoroethylacetone)copper complex, and then heating the mixture to obtain a polyaryl sulfone compound 2. The reaction equation in the method is:

[0006]

[0007] Where R 1 It is phenyl or substituted phenyl, and the substituent on the benzene ring of the substituted phenyl is chlorine.

[0008] Where R 2 It is phenyl or substituted phenyl, the substituent on the benzene ring of the substituted phenyl is fluorine or methyl, and the substituent position can be at the para position or the meta position of the benzene ring.

[0009] Where R 3 It is phenyl or substituted phenyl, the substituent on the benzene ring of the substituted phenyl is chlorine or methyl, and the substituent position can be at the para position or the meta position of the benzene ring.

[0010] Where R 4 It is p-toluenesulfonyl or benzenesulfonyl.

[0011] Furthermore, the reaction solvent is used to dissolve the raw materials, and is preferably 1,2-dichloroethane, dichloromethane, toluene, chlorobenzene or trifluorotoluene.

[0012] Furthermore, the above reaction is carried out in air at a temperature of 60-140° C. and a reaction time of 15-20 h.

[0013] Furthermore, the molar ratio of the allenamine compound 1 to bis(hexafluoroethylacetone)copper is 1:(0.05-0.15).

[0014] The polyaryl sulfone compounds are synthesized by the above-mentioned synthesis method.

[0015] Furthermore, the polyaryl sulfone compound is any one of the following compounds:

[0016]

[0017] The above-mentioned polyaryl sulfone compounds are used as intermediates in the chemical field.

[0018] The beneficial effects produced by the present invention are:

[0019] (1) The synthesis process is simple and efficient, and polyaryl sulfone compounds are directly obtained in a one-step reaction through the tandem reaction of allenamine compounds; (2) The raw materials are cheap and readily available; (3) The reaction conditions are mild and the operation is simple; (4) The substrate has good universality and a wide range of applications. Therefore, the present invention provides an economical, practical and green new method for the synthesis of polyaryl sulfone compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0021] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of compound 2a prepared in Example 1 of the present invention.

[0022] Figure 2 This is the carbon NMR spectrum of compound 2a prepared in Example 1 of the present invention.

[0023] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of compound 2b prepared in Example 2 of the present invention.

[0024] Figure 4 This is the carbon NMR spectrum of compound 2b prepared in Example 2 of the present invention.

[0025] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of compound 2c prepared in Example 3 of the present invention.

[0026] Figure 6 This is the carbon NMR spectrum of compound 2c prepared in Example 3 of the present invention.

[0027] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of compound 2d prepared in Example 4 of the present invention.

[0028] Figure 8 This is the carbon NMR spectrum of compound 2d prepared in Example 4 of the present invention.

[0029] Fig. 9 This is the hydrogen nuclear magnetic resonance spectrum of compound 2e prepared in Example 5 of the present invention.

[0030] Fig.10 This is the carbon NMR spectrum of compound 2e prepared in Example 5 of the present invention.

[0031] Fig.11This is the hydrogen nuclear magnetic resonance spectrum of compound 2f prepared in Example 6 of the present invention.

[0032] Fig.12 This is the carbon NMR spectrum of compound 2f prepared in Example 6 of the present invention.

[0033] Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of compound 2g prepared in Example 7 of the present invention.

[0034] Fig.14 This is the carbon NMR spectrum of compound 2g prepared in Example 7 of the present invention.

[0035] Fig.15 This is the hydrogen nuclear magnetic resonance spectrum of compound 2h prepared in Example 8 of the present invention.

[0036] Fig.16 This is the carbon NMR spectrum of compound 2h prepared in Example 8 of the present invention.

[0037] Fig.17 This is the hydrogen nuclear magnetic resonance spectrum of compound 2i prepared in Example 9 of the present invention.

[0038] Fig.18 This is the carbon NMR spectrum of compound 2i prepared in Example 9 of the present invention. DETAILED DESCRIPTION

[0039] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] Example 1

[0041] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0042]

[0043] To a 10mL Shrek tube, allenamine 1a (0.2mmol, 90.4mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg) were added in sequence, and the reaction system was then heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2a (49.4mg, 81%). The characterization data of the compound are as follows:1 H NMR (400 MHz, CDCl 3 )δ7.65(d,J=8.1Hz,2H),7.34-7.27(m,4H),7.27-7.18(m,9H),7.16-7.07(m,6H),6.95(d,J=7.7Hz,2H),6.44 (d,J=7.9Hz,2H),6.29(d,J=11.4Hz,1H),4.64(d,J=11.4Hz,1H),4.51-4.36(m,2H),2.45(s,3H),2.38(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.51,143.67,142.61,136.85,136.36,133.99,133.92,132.89,129.66,129.44 ,129.36,129.24,128.95,128.69,128.57,128.51,128.42,128.21,127.73,127.60,1 21.10,77.32,77.00,76.68,70.58,52.48,21.60,21.59;IR(neat):2928,1767,1672 ,1543,1476,1429,1371,1334,1258,1193,1142,1077,967,668; HRMS(ESI)m / z:[M+H] + Calculate for C 36 H 36 NO 4 S 2 610.2080, found 610.2084. H NMR spectrum and C NMR spectrum are as follows Figure 1 and Figure 2 shown.

[0044] Example 2

[0045] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0046]

[0047] To a 10mL Shrek tube, allenamine 1b (0.2mmol, 93.2mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg) were added in sequence, and the reaction system was then heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2b (52.5mg, 84%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 )δ7.65(d,J=7.2Hz,2H),7.31(d,J=7.2Hz,3H),7.28-7.26(m,5H),7.25-7.20(m,4H),7.17-7.14(m,2H),7.09(d,J=7.5Hz,2H),6.95(d,J =7.8Hz,2H),6.90(d,J=7.6Hz,2H),6.34-6.24(m,3H),4.67(d,J=11.3Hz,1H),4.50-4.36(m,2H),2.44(s,3H),2.38(s,3H),2.29(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.47,143.59,142.58,138.93,136.95,136.51,133.95,133.01,130.99,129.61,12 9.48,129.39,129.21,128.94,128.83,128.64,128.55,128.46,128.39,127.71,127.53, 120.78,77.32,77.00,76.68,70.64,52.36,21.60,21.57,21.20;IR(neat):2924,1773,1 652,1504,1473,1406,1386,1343,1242,1171,1106,1043,967,617; HRMS(ESI)m / z:[M+H] + Calculate for C 37 H 38 NO 4 S 2 624.2237, found 624.2235. The H NMR spectrum and C NMR spectrum are as follows Figure 3 and Figure 4 shown.

[0048] Example 3

[0049] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0050]

[0051] To a 10 mL Shrek tube, allenamine 1c (0.2 mmol, 94.0 mg), 1,2-dichloroethane (4.0 mL), bis(hexafluoroethylacetone)copper (0.02 mmol, 9.6 mg) were added in sequence, and the reaction system was then heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2c (46.6 mg, 74%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 )δ7.76(d,J=8.3Hz,1H),7.64(d,J=8.3Hz,2H),7.32-7.30(m,3H),7.29-7 .27(m,6H),7.21-7.18(m,2H),7.17-7.14(m,2H),7.11-7.07(m,3H),6.97 -6.93(m,3H),6.33(d,J=7.7Hz,1H),6.27(d,J=11.4Hz,1H),6.00-5.95(m ,1H),4.60(d,J=11.4Hz,1H),4.51-4.39(m,2H),2.46(s,3H),2.38(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.74,143.97,141.38,136.79,136.34,136.21,135.98,133.80,132.50,129.76,129.71,129.34 ,129.23,128.86,128.66,128.63,128.51,128.03,127.89,127.84,127.78,127.69,127.15,126.62,1 24.81,122.15,116.05,115.84,115.61,77.32,77.00,76.68,70.47,52.77,47.24,21.58; IR(neat): 2923,1772,1634,1572,1485,1402,1376,1315,1272,1194,1125,1073,996,608; HRMS(ESI)m / z:[M+H] +Calculate for C 36 H 35 FNO 4 S 2 628.1986, found 628.1985. The H NMR spectrum and C NMR spectrum are as follows Figure 5 and Figure 6 shown.

[0052] Example 4

[0053] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0054]

[0055] To a 10mL Shrek tube, allenamine 1d (0.2mmol, 93.2mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg) were added in sequence, and then the reaction system was heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2d (51.3mg, 82%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 )δ7.56(d,J=8.2Hz,2H),7.28-7.23(m,3H),7.22(s,1H),7.20-7.18(m,4H),7.17(s ,2H),7.15(d,J=8.0Hz,2H),7.08-7.05(m,2H),7.02(d,J=8.1Hz,2H),6.95(d,J=7.5 Hz,1H),6.92-6.87(m,3H),6.27(d,J=11.4Hz,1H),6.10(d,J=7.5Hz,1H),5.82(s,1H ),4.55(d,J=11.4Hz,1H),4.40-4.27(m,2H),2.36(s,3H),2.30(s,3H),1.97(s,3H); 13 C NMR (100 MHz, CDCl 3)δ144.44,143.61,142.39,137.76,136.99,136.53,133.88,133.58,132.94,129.61,129.45 ,129.36,129.22,128.64,128.47,128.43,128.34,127.96,127.80,127.67,127.49,127.11, 126.09,121.18,77.32,77.00,76.68,70.56,52.33,21.58,21.51,21.10; IR(neat):2924,17 67,1652,1573,1484,1409,1343,1302,1243,1164,1125,1073,982,637; HRMS(ESI)m / z:[M+H] + Calculate for C 37 H 38 NO 4 S 2 624.2237, found 624.2238. The H NMR spectrum and C NMR spectrum are as follows Figure 7 and Figure 8 shown.

[0056] Example 5

[0057] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0058]

[0059] To a 10mL Shrek tube, allenamine 1e (0.2mmol, 97.2mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg) were added in sequence, and the reaction system was then heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2e (48.9mg, 76%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3)δ7.67(d,J=7.0Hz,2H),7.37-7.30(m,3H),7.28-7.25(m,6H),7.23-7.19(m,3H),7.15-7.09(m,6H),6.89(d,J=6.9Hz, 2H),6.39(d,J=7.6Hz,2H),6.24(d,J=11.3Hz,1H),4.60(d,J=11.3Hz,1H),4.50-4.34(m,2H),2.46(s,3H),2.40(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.79,143.80,142.74,136.93,136.27,134.78,133.65,133.60,131.47,130.67 ,129.69,129.37,129.05,128.86,128.69,128.45,128.43,128.29,127.66,127.62,1 20.53,77.32,77.00,76.68,69.80,52.25,21.62,21.57;IR(neat):2922,1786,1625 ,1594,1487,1416,1394,1353,1237,1146,1102,1073,985,648; HRMS(ESI)m / z:[M+H] + Calculate for C 36 H 35 ClNO 4 S 2 644.1691, found 644.1693. The H NMR spectrum and C NMR spectrum are as follows Fig. 9 and Fig.10 shown.

[0060] Example 6

[0061] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0062]

[0063] To a 10mL Shrek tube, allenamine 1f (0.2mmol, 93.2mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg) were added in sequence, and the reaction system was then heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2f (53.8mg, 86%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 )δ7.65(d,J=8.2Hz,2H),7.30(d,J=8.3Hz,3H),7.25-7.21(m,5H),7.21-7.17(m ,1H),7.13-7.09(m,3H),7.08-7.06(m,3H),7.05-6.99(m,3H),6.95(d,J=7.3Hz, 2H),6.47(d,J=7.3Hz,2H),6.26(d,J=11.4Hz,1H),4.65(d,J=11.4Hz,1H),4.45( d,J=15.1Hz,1H),4.34(d,J=15.0Hz,1H),2.45(s,3H),2.38(s,3H),2.34(s,3H); 13 CNMR (100MHz, CDCl 3 )δ144.56,143.67,142.66,137.27,136.88,134.16,133.97,133.32,132.94,1 29.69,129.52,129.41,129.28,129.14,129.00,128.61,128.53,128.25,127.7 7,121.10,70.60,52.32,21.67,21.65,21.22;IR(neat):2924,1727,1676,1554 ,1476,1405,1373,1343,1252,1194,1162,1072,982,664; HRMS(ESI)m / z:[M+H] + Calculate for C 37 H 38 NO 4 S 2 624.2237, found 624.2236. The H NMR spectrum and C NMR spectrum are as follows Fig.11 and Fig.12 shown.

[0064] Example 7

[0065] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0066]

[0067] Add 1g (0.2mmol, 97.2mg) of allenamine, 1,2-dichloroethane (4.0mL), and bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg) to a 10mL Shrek tube, then heat the reaction system to 120°C, stir for 16 hours, and track the reaction by TLC. After the reaction is completed, cool the reaction system to room temperature. Then filter and concentrate in turn. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave 2g (50.4mg, 78%) of an oily product. The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 )δ7.66(d,J=8.2Hz,2H),7.34-7.29(m,4H),7.28-7.26(m,4H),7.25-7. 21(m,4H),7.14-7.10(m,4H),7.09-7.06(m,2H),6.94(d,J=7.4Hz,2H), 6.40(d,J=7.5Hz,2H),6.32(d,J=11.4Hz,1H),4.64(d,J=11.4Hz,1H),4 .44(d,J=15.3Hz,1H),4.34(d,J=15.2Hz,1H),2.45(s,3H),2.39(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.67,143.87,142.29,136.59,134.91,133.84,133.77,133.47,132.85,129 .95,129.73,129.38,129.31,129.26,129.06,128.84,128.57,128.32,127.70,1 21.24,77.32,77.00,76.68,70.57,51.73,21.60;IR(neat):2928,1753,1676,15 46,1485,1462,1373,1304,1252,1184,1153,1018,905,637; HRMS(ESI)m / z:[M+H] + Calculate for C 36 H 35 ClNO 4 S 2644.1691, found 644.1692. The H NMR spectrum and C NMR spectrum are as follows Fig.13 and Fig.14 shown.

[0068] Example 8

[0069] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0070]

[0071] To a 10mL Shrek tube, add allenamine 1h (0.2mmol, 93.2mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.02mmol, 9.6mg), then heat the reaction system to 120°C, stir for 16 hours, and track the reaction by TLC. After the reaction is completed, cool the reaction system to room temperature. Then filter and concentrate in turn. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) to obtain an oily product 2h (51.9mg, 83%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 )δ7.59(d,J=8.1Hz,2H),7.26-7.21(m,4H),7.18-7.14(m,4H),7.13-7.09 (m,1H),7.07-6.99(m,6H),6.98-6.93(m,1H),6.89-6.83(m,4H),6.39(d, J=7.6Hz,2H),6.20(d,J=11.4Hz,1H),4.59(d,J=11.4Hz,1H),4.39(d,J=1 5.1Hz,1H),4.27(d,J=15.1Hz,1H),2.38(s,3H),2.30(s,3H),2.18(s,3H); 13 C NMR (100 MHz, CDCl 3)δ144.48,143.63,142.61,138.01,136.83,136.15,134.01,133.88,132.88,129.63,12 9.39,129.33,129.29,129.21,128.94,128.68,128.50,128.27,128.15,127.73,125.58, 121.03,77.32,77.00,76.68,70.53,52.40,21.59,21.57,21.27;IR(neat):2924,1737,1 665,1572,1495,1446,1385,1335,1262,1185,1142,1061,902,637; HRMS(ESI)m / z:[M+H] + Calculate for C 37 H 38 NO 4 S 2 624.2237, found 624.2239. The H NMR spectrum and C NMR spectrum are as follows Fig.15 and Fig.16 shown.

[0072] Example 9

[0073] The synthesis method of the polyaryl sulfone compound of this embodiment, its synthesis equation and synthesis steps are as follows:

[0074]

[0075] To a 10 mL Shrek tube, allenamine 1i (0.2 mmol, 87.6 mg), 1,2-dichloroethane (4.0 mL), bis(hexafluoroethylacetone)copper (0.02 mmol, 9.6 mg) were added in sequence, and the reaction system was then heated to 120°C and stirred for 16 hours. The reaction was followed by TLC. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2a (44.3 mg, 76%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3 ) 1 H NMR (400 MHz, CDCl 3)δ7.78(d,J=7.4Hz,2H),7.60(t,J=7.5Hz,1H),7.55-7.51(m,1H),7.47-7.43(m,4H),7.35-7.28(m,4H),7.28-7.25(m,4H),7.25-7.21(m ,3H),7.15-7.07(m,4H),6.94(d,J=7.5Hz,2H),6.40-6.32(m,3H),4.65(d,J=11.4Hz,1H),4.51(d,J=15.2Hz,1H),4.39(d,J=15.2Hz,1H); 13 C NMR (100 MHz, CDCl 3 )δ142.54,139.77,136.81,136.20,133.71,133.55,132.88,132.65,129.37,129 .30,129.10,129.02,128.85,128.79,128.63,128.59,128.49,128.46,128.29,12 7.64,121.07,77.32,77.00,76.68,70.57,52.44; IR(neat):2922,1727,1664,15 52,1476,1431,1396,1352,1248,1176,1134,1058,962,643; HRMS(ESI)m / z:[M+H] + Calculate for C 34 H 32 NO 4 S 2 582.1767, found 582.1765. The H NMR spectrum and C NMR spectrum are as follows Fig.17 and Fig.18 shown.

[0076] Example 10

[0077] The synthesis method of the polyaryl sulfone compound of this embodiment comprises the following steps:

[0078] To a 10mL Shrek tube, allenamine 1a (0.2mmol, 90.4mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.03mmol, 14.4mg) were added in sequence, and then the reaction system was heated to 140°C and stirred for 15 hours. The reaction was monitored by TLC tracking. After the reaction was completed, the reaction system was cooled to room temperature. Then, it was filtered and concentrated in sequence. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) gave an oily product 2a (44.6mg, 73%). The characterization data of the compound are as follows:1 H NMR (400 MHz, CDCl 3 )δ7.65(d,J=8.1Hz,2H),7.34-7.27(m,4H),7.27-7.18(m,9H),7.16-7.07(m,6H),6.95(d,J=7.7Hz,2H),6.44 (d,J=7.9Hz,2H),6.29(d,J=11.4Hz,1H),4.64(d,J=11.4Hz,1H),4.51-4.36(m,2H),2.45(s,3H),2.38(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.51,143.67,142.61,136.85,136.36,133.99,133.92,132.89,129.66,129.44 ,129.36,129.24,128.95,128.69,128.57,128.51,128.42,128.21,127.73,127.60,1 21.10,77.32,77.00,76.68,70.58,52.48,21.60,21.59;IR(neat):2928,1767,1672 ,1543,1476,1429,1371,1334,1258,1193,1142,1077,967,668; HRMS(ESI)m / z:[M+H] + Calculate for C 36 H 36 NO 4 S 2 610.2080, found 610.2084.

[0079] Embodiment 11

[0080] The synthesis method of the polyaryl sulfone compound of this embodiment comprises the following steps:

[0081] To a 10mL Shrek tube, add allenamine 1h (0.2mmol, 93.2mg), 1,2-dichloroethane (4.0mL), bis(hexafluoroethylacetone)copper (0.01mmol, 4.8mg), then heat the reaction system to 60°C, stir for 20 hours, and track the reaction by TLC. After the reaction is completed, cool the reaction system to room temperature. Then filter and concentrate in turn. Column chromatography (petroleum ether / ethyl acetate = 15 / 1) to obtain an oily product 2h (24.5mg, 39%). The characterization data of the compound are as follows: 1 H NMR (400 MHz, CDCl 3)δ7.59(d,J=8.1Hz,2H),7.26-7.21(m,4H),7.18-7.14(m,4H),7.13-7.09 (m,1H),7.07-6.99(m,6H),6.98-6.93(m,1H),6.89-6.83(m,4H),6.39(d, J=7.6Hz,2H),6.20(d,J=11.4Hz,1H),4.59(d,J=11.4Hz,1H),4.39(d,J=1 5.1Hz,1H),4.27(d,J=15.1Hz,1H),2.38(s,3H),2.30(s,3H),2.18(s,3H); 13 C NMR (100 MHz, CDCl 3 )δ144.48,143.63,142.61,138.01,136.83,136.15,134.01,133.88,132.88,129.63,12 9.39,129.33,129.29,129.21,128.94,128.68,128.50,128.27,128.15,127.73,125.58, 121.03,77.32,77.00,76.68,70.53,52.40,21.59,21.57,21.27;IR(neat):2924,1737,1 665,1572,1495,1446,1385,1335,1262,1185,1142,1061,902,637; HRMS(ESI)m / z:[M+H] + Calculate for C 37 H 38 NO 4 S 2 624.2237, found 624.2239.

[0082] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a polyaryl sulfone compound, characterized in that: The allenamine compound 1 is dissolved in a solvent, and then bis(hexafluoroethylacetone)copper is added, and the temperature is raised to react to obtain a polyaryl sulfone compound 2; wherein the structural formula of the allenamine compound 1 is The structural formula of polyaryl sulfone compound 2 is Among them, R 1 is phenyl or substituted phenyl 1, R 2 is phenyl or substituted phenyl 2, R 3 is phenyl or substituted phenyl 3, R 4 It is p-toluenesulfonyl or benzenesulfonyl.

2. The method for synthesizing polyaryl sulfone compounds according to claim 1, characterized in that: The substituent on the benzene ring in the substituted phenyl 1 is chlorine; the substituent on the benzene ring in the substituted phenyl 2 is fluorine or methyl; and the substituent on the benzene ring in the substituted phenyl 3 is chlorine or methyl.

3. The method for synthesizing polyaryl sulfone compounds according to claim 2, characterized in that: The position of the substituent on the benzene ring in the substituted phenyl group 2 or the substituted phenyl group 3 is the para position or the meta position of the benzene ring.

4. The method for synthesizing polyaryl sulfone compounds according to claim 3, characterized in that: The molar ratio of the allenamine compound 1 to bis(hexafluoroethylacetone)copper is 1:(0.05-0.15).

5. The method for synthesizing polyaryl sulfone compounds according to claim 4, characterized in that: The solvent is 1,2-dichloroethane, dichloromethane, toluene, chlorobenzene or trifluorotoluene.

6. The method for synthesizing polyaryl sulfone compounds according to claim 5, characterized in that: The temperature of the heating reaction is 60-140°C.

7. The method for synthesizing polyaryl sulfone compounds according to claim 5, characterized in that: The time for the heating reaction is 15-20 hours.

8. A polyaryl sulfone compound synthesized by the synthesis method according to any one of claims 1 to 7.

9. The polyaryl sulfone compound according to claim 8, characterized in that: The polyaryl sulfone compound is any one of the following compounds:

10. Use of the polyaryl sulfone compound according to claim 8 as an intermediate in the chemical field.

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