A process for the preparation of 5-benzoyldihydrofuran-2(3H)-one and derivatives thereof

Abstract

The application belongs to the field of chemical synthesis, and particularly relates to a preparation method of 5-benzoyl dihydrofuran-2(3H)-one and derivatives thereof. The preparation method is as follows: five-membered ring, six-membered ring aromatic and heterocyclic compounds, and substituted glutaric anhydride are used as raw materials, aluminum chloride is used as a catalyst, a solvent is simply distilled out, and phenyl dihydrofuran-2(3H)-one and derivatives are prepared by one-pot method with iodobenzene acetate as an oxidant. The reaction condition is simple, the reaction temperature is 40-60 DEG C, no noble metal catalyst is used in the scheme disclosed in the application, no heavy metal residue is caused, the raw materials used are commercial products, the oxidant and the catalyst are relatively inexpensive and easy-to-obtain substances, the reaction operation is simple, and the reaction product is easy to purify and the post-treatment is convenient.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis, specifically relating to 5-benzoyldihydrofuran-2(3 H Preparation methods of )-ketones and their derivatives. Background Technology

[0002]

[0003] Having 5-benzoyl dihydrofuran-2(3 H Representative compounds with a )-ketone structure.

[0004] The family of γ-lactones, including phenyl-substituted γ-butyrolactones, possesses important biological activities, such as anticancer, antibacterial, and anti-inflammatory activities. Phenatic acid B can inhibit the growth of various bacteria, Nong-kang 101 F can inhibit fungal growth, EPDF has sedative and hypnotic effects, and Boiviniamin A is a natural product. These structures have significant application prospects and high drug development potential. Currently reported synthetic methods include a three-step synthesis of alkynyl alcohols via hexamethyldisilamide lithium dehydrogenation, as shown in Formula I; or synthesis using catalysts such as palladium acetate, silver, and ligands, as shown in Formula II. These methods require stringent reaction conditions or require the prior synthesis of compounds with specific functional groups, and also utilize noble metal catalysts. The known synthetic routes involve demanding reaction conditions and high costs.

[0005] Summary of the Invention

[0006] The technical problem to be solved by this invention is to address the shortcomings of existing solutions by providing a synthesis method with easily controllable reaction conditions and lower cost, which is more suitable for large-scale production.

[0007] To achieve the above objectives, the preparation method used in this invention is as follows: a 5-benzoyl dihydrofuran-2(3 H The method for preparing )-ketones and their derivatives, wherein the structure of the compound is shown in formula (I):

[0008] According to some embodiments of the present invention, the structure of Formula I includes a five-membered or six-membered aromatic ring and a heterocyclic aromatic ring, wherein X in the structure of Formula I can be an oxygen or sulfur atom, R1 in the structure of Formula I is hydrogen, an alkylalkoxy group, or a polysubstituted alkyl group, and R2 in the structure of Formula I is hydrogen or an alkyl group.

[0009]

[0010] According to some embodiments of the present invention, raw material 1 in the reaction raw materials is an aromatic compound and its derivatives, and raw material 2 is glutaric anhydride and its derivatives.

[0011] According to some embodiments of the present invention, the additive is AlCl3, iodobenzene acetate, or potassium bromide.

[0012] According to some embodiments of the present invention, the solvent is a polar solvent, an N,N-dialkyl-substituted amide solvent.

[0013] According to some embodiments of the present invention, the preparation temperature is 40~60°C.

[0014] According to some embodiments of the present invention, the preparation time of the compound is 1 to 12 hours.

[0015] According to some embodiments of the present invention, the molar ratio of the reactants in the preparation reaction is 1:2:3:4, which is 1.1:1:2 to 2.2:1.1 to 1.5.

[0016] According to some embodiments of the present invention, the purification method for the preparation of the reaction product involves, after the reaction is completed, pouring the product into a quantitative amount of ethyl acetate, washing it three times with water, washing it once with saturated sodium carbonate, concentrating the dried organic phase, and then purifying it by silica gel column chromatography, with petroleum ether:ethyl acetate (15:1~7:1) as the eluent. Attached Figure Description

[0017] Figure 1 This is a simplified diagram illustrating the preparation methods of 5-benzoyldihydrofuran-2(3H)-one and its derivatives.

[0018] Beneficial effects Due to the use of the above technical solution, the present invention has the following advantages compared with the prior art: the present invention can avoid multi-step reaction, avoid the use of precious metals, and directly complete multi-step reaction in one operation. The raw materials are commercial reagents that are simple and easy to obtain, with low time cost, simple reaction operation, and low economic cost. Detailed Implementation

[0019] Example 1 The structure of the compound prepared in this embodiment is as follows:

[0020] Glutaric anhydride (1 mmol), aluminum trichloride (2.2 mmol), and dichloromethane (5 mL) were added to a round-bottom cake and stirred until homogeneous at 0 °C. Diphenyl ether (1.1 mmol) was then added. The reaction was continued at 0 °C for 1 hour. After removing excess solvent by distillation, iodobenzene acetate (1.5 equivalents) was added, followed by DMF (2 mL). The reaction was continued at 50 °C for 5 hours. Thin-layer chromatography was used to monitor the reaction progress. Ethyl acetate (15 mL) was added. After the reaction was complete, the mixture was washed three times with water (15 mL) and three times with saturated sodium bicarbonate (15 mL). The mixture was dried and purified by silica gel column chromatography. The product was a yellow solid with a yield of 81%. NMR and high-resolution data for the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.93(d, J = 8.9 Hz, 2H), 7.39 (dd, J = 8.5, 7.4 Hz, 2H), 7.22–7.16 (m, 1H), 7.05(dd, J = 8.6, 1.2 Hz, 2H), 7.00 (d, J = 8.9 Hz, 2H), 5.80–5.71 (m, 1H), 2.62–2.51 (m, 3H), 2.46–2.37 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ 193.0, 176.6,163.1, 154.9, 131.2, 130.2, 128.0, 125.1, 120.4, 117.4, 78.2, 26.9, 25.1.HRMS (ESI) m / z [M+Na] + calcd for C 17 H 14 O4Na: 305.0790; found: 305.0787.

[0021] Example 2 The structure of the compound prepared in this embodiment is as follows:

[0022] In this example, the specific preparation method is basically the same as in Example 1, except that anisole is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography, and the product is a white solid with a yield of 90%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 9.0 Hz, 2H), 6.97 (d, J= 9.0 Hz, 2H), 5.80–5.71 (m, 1H), 3.88 (s, 3H), 2.64–2.50 (m, 3H), 2.50–2.42 (m, 1H).

[0023] Example 3

[0024] The structure of the compound prepared in this embodiment is as follows:

[0025] In this example, the specific preparation method is basically the same as in Example 1, except that biphenyl is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography, and the product is a white solid with a yield of 70%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.5 Hz, 2H), 7.73 (d, J = 8.5 Hz, 2H), 7.66–7.59 (m, 2H), 7.52–7.39 (m, 3H), 5.88–5.79 (m, 1H), 2.67–2.55 (m, 3H), 2.54–2.46 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ 194.0, 176.4, 147.0, 139.5, 132.3, 129.4, 129.1, 128.6, 127.6, 127.3, 78.4, 26.9, 25.0.

[0026] Example 4 The structure of the compound prepared in this embodiment is as follows:

[0027] In this example, the specific preparation method is basically the same as in Example 1, except that toluene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a white solid with a yield of 78%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 5.82–5.74 (m, 1H), 2.60–2.54 (m, 3H), 2.48–2.45 (m, 1H), 2.43 (s, 3H). 13C NMR (101MHz, CDCl3) δ 193.9, 176.4, 145.5, 131.1, 129.7, 128.9, 78.2, 26.9, 25.1,21.8.

[0028] Example 5 The structure of the compound prepared in this embodiment is as follows:

[0029] In this example, the specific preparation method is basically the same as in Example 1, except that isopropylbenzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a transparent oil with a yield of 82%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 5.83–5.75 (m, 1H), 2.63–2.54 (m, 3H), 2.51–2.41 (m, 1H), 1.34 (s, 9H). 13 C NMR (101MHz, CDCl3) δ 194.0, 176.4, 158.3, 131.0, 128.8, 126.0, 78.3, 35.3, 31.0, 26.9, 25.1.

[0030] Example 6 The structure of the compound prepared in this embodiment is as follows:

[0031]

[0032] In this example, the specific preparation method is basically the same as in Example 1, except that benzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product was purified by silica gel column chromatography, and the product was a white solid with a yield of 65%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.98 (dd, J = 8.4, 1.4 Hz, 2H), 7.65 (t, J = 7.4 Hz, 1H), 7.52 (t, J = 7.7 Hz, 2H), 5.86–5.76 (m, 1H), 2.64–2.54 (m, 3H), 2.53–2.45 (m,1H). 13C NMR (101 MHz, CDCl3) δ 194.3, 176.3, 134.3, 133.6, 129.1, 128.8,78.3, 26.8, 25.0.

[0033] Example 7 The structure of the compound prepared in this embodiment is as follows:

[0034]

[0035] In this example, the specific preparation method is basically the same as in Example 1, except that fluorobenzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography, and the product is a yellow solid with a yield of 55%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 8.06–7.98 (m, 2H), 7.18 (t, J = 8.6 Hz, 2H), 5.78–5.70 (m,1H), 2.64–2.46 (m, 4H). 13 C NMR (101 MHz, CDCl3) δ 192.8, 176.1, 167.6, 165.1,131.8, 131.7, 130.1, 130.1, 116.4, 116.2, 78.3, 26.9, 24.7. 19 F NMR (376 MHz, CDCl3) δ -102.4.

[0036] Example 8 The structure of the compound prepared in this embodiment is as follows:

[0037] In this example, the specific preparation method is basically the same as in Example 1, except that fluorobenzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography, and the product is a yellow solid with a yield of 63%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.6 Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 5.74 (dd, J = 8.3, 4.6 Hz, 1H), 2.63–2.53 (m, 3H), 2.52–2.40 (m, 1H). 13C NMR (101MHz, CDCl3) δ 193.3, 176.1, 140.9, 132.0, 130.3, 129.4, 78.3, 26.8, 24.7.

[0038] Example 9 The structure of the compound prepared in this embodiment is as follows:

[0039]

[0040] In this example, the specific preparation method is basically the same as in Example 1, except that bromobenzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography, and the product is a yellow solid with a yield of 64%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.6 Hz, 2H), 7.59 (d, J = 8.6 Hz, 2H), 5.74 (dd, J = 8.5, 4.7 Hz, 1H), 2.62–2.49 (m, 3H), 2.42–2.32 (m, 1H). 13 C NMR (101MHz, CDCl3) δ 193.7, 176.3, 132.3, 130.3, 129.6, 78.3, 26.8, 24.9.

[0041] Example 10 The structure of the compound prepared in this embodiment is as follows:

[0042]

[0043] In this example, the specific preparation method is basically the same as in Example 1, except that iodobenzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a yellow solid with a yield of 62% and a melting point of 102–103 °C. The product NMR data are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.6 Hz, 2H), 7.61 (d, J = 8.6Hz, 2H), 5.74 (dd, J = 8.5, 4.4 Hz, 1H), 2.65–2.47 (m, 3H), 2.47–2.33 (m,1H). 13C10 NMR (101 MHz, CDCl3) δ 193.7, 176.3, 132.4, 132.3, 130.3, 129.7, 78.3, 26.8, 24.8. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 11 H9O3NaI:338.9494; found: 338.9488.

[0044] Example 11 The structure of the compound prepared in this embodiment is as follows:

[0045] In this example, the specific preparation method is basically the same as in Example 1, except that 2,5-methoxybenzene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a colorless oil with a yield of 94%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 3.2 Hz, 1H), 7.12 (dd, J = 9.1, 3.3 Hz, 1H), 6.95 (d, J = 9.0 Hz, 1H), 5.83 (dd, J = 8.8, 3.5 Hz, 1H), 3.90 (s, 3H), 3.79 (s, 3H), 2.63–2.45 (m, 3H), 2.35–2.24 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ 196.0, 177.2, 153.9, 153.7, 124.1, 122.4, 114.2, 113.2, 81.5, 56.2, 55.9, 26.3, 25.3. Product high-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 13 H 14 O5Na:273.0739; found: 273.0749.

[0046] Example 12 The structure of the compound prepared in this embodiment is as follows:

[0047] In this example, the specific preparation method is basically the same as in Example 1, except that 1,4-benzodioxane is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a brown solid with a yield of 97% and a melting point of 110–111 °C. (Product NMR data are also provided.) 1 H NMR (400 MHz, CDCl3) δ 7.44 (dq, J = 4.5, 2.2 Hz, 2H), 6.89 (d, J = 9.0 Hz, 1H), 5.72 (dd, J = 8.5, 4.2 Hz, 1H), 4.31–4.27 (m, 2H), 4.26–4.22(m, 2H), 2.58–2.48 (m, 3H), 2.38–2.30 (m, 1H). 13 C10 NMR (101 MHz, CDCl3) δ 192.9, 176.7, 149.1, 143.7, 127.1, 122.9, 118.1, 117.7, 78.1, 64.8, 64.1, 26.8, 25.4. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 13 H 12 O5Na:271.0582; found: 271.0583.

[0048] Example 13 The structure of the compound prepared in this embodiment is as follows:

[0049] In this example, the specific preparation method is basically the same as in Example 1, except that m-toluene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a colorless oil with a yield of 76%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 7.8 Hz, 1H), 7.09 (d, J = 7.9 Hz, 2H), 5.24(dd, J = 8.9, 4.8 Hz, 1H), 2.72–2.60 (m, 2H), 2.49 (s, 3H), 2.46–2.35 (m,4H), 2.36 (s, 3H), 2.30–2.16 (m, 1H). 13C NMR (101 MHz, CDCl3) δ 195.7, 178.9, 143.2, 140.2, 133.2, 132.0, 129.0, 126.5, 58.7, 30.2, 28.4, 21.5, 21.5.

[0050] Example 14 The structure of the compound prepared in this embodiment is as follows:

[0051] In this example, the specific preparation method is basically the same as in Example 1, except that p-toluene (1.1 mmol) is used instead of diphenyl ether. After the reaction, the product is purified by silica gel column chromatography. The product is a colorless oil with a yield of 76%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 1.8 Hz, 1H), 7.26 (d, J = 3.3 Hz, 1H), 7.19(d, J = 7.9 Hz, 1H), 5.74–5.66 (m, 1H), 2.68–2.50 (m, 3H), 2.47 (s, 3H), 2.37(d, J = 3.8 Hz, 4H). 13 C NMR (101 MHz, CDCl3) δ 198.0, 176.5, 136.8, 135.6, 133.7, 133.4, 132.4, 129.5, 79.3, 26.9, 25.2, 21.0, 20.9.

[0052] Example 15 The structure of the compound prepared in this embodiment is as follows:

[0053] In this example, the specific preparation method is basically the same as in Example 1, except that thiophene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a white solid with a yield of 70%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.90 (dd, J = 3.9, 1.1 Hz, 1H), 7.77 (dd, J = 4.9, 1.1 Hz, 1H), 7.19 (dd, J= 5.0, 3.9 Hz, 1H), 5.55 (t, J = 6.5 Hz, 1H), 2.66–2.47 (m,4H). 13 C NMR (101 MHz, CDCl3) δ 188.0, 176.1, 140.2, 135.7, 134.1, 128.7,79.3, 26.9, 25.4.

[0054] Example 16 The structure of the compound prepared in this embodiment is as follows:

[0055] In this example, the specific preparation method is basically the same as in Example 1, except that benzothiophene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a brown oil with a yield of 65%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 8.74–8.48 (m, 1H), 8.16–7.81 (m, 2H), 7.52–7.36 (m, 2H), 5.74–5.63 (m, 1H), 2.71–2.44 (m, 4H). 13 C10 NMR (101 MHz, CDCl3) δ 189.6, 189.5, 176.5, 176.3, 142.8, 139.7, 139.5, 139.4, 139.0, 136.7, 131.6, 131.5, 128.3, 126.6, 126.3, 126.0, 125.4, 125.4, 122.9, 122.4, 79.3, 79.3, 27.0, 26.9, 25.4, 25.2; High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 13 H 10 O3NaS:269.2043; found: 269.2046.

[0056] Example 17 The structure of the compound prepared in this embodiment is as follows:

[0057] In this example, the preparation method is basically the same as in Example 1, except that 2-chlorobenzothiophene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a brown solid with a yield of 70% and a melting point of 142–143 °C. The product NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.0 Hz, 1H), 7.86 (d, J =8.1 Hz, 1H), 7.63–7.50 (m, 2H), 6.11 (dd, J = 9.1, 3.2 Hz, 1H), 2.83–2.71 (m,1H), 2.64–2.56 (m, 2H), 2.51–2.42 (m, 1H). 13 C10 NMR (101 MHz, CDCl3) δ 188.9, 176.3, 139.8, 137.1, 133.6, 129.3, 126.0, 125.7, 124.4, 123.1, 79.5, 26.3, 25.4. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 13 H9O3NaSCl: 302.9859; found: 302.9862.

[0058] Example 18 The structure of the compound prepared in this embodiment is as follows:

[0059] In this example, the preparation method is basically the same as in Example 1, except that naphthalene is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a mixture, yellow and oily, and the two products are difficult to separate. The yield is 78%. The NMR data for the mixture product are as follows. 1 H NMR (400 MHz, CDCl3) δ 8.61–8.39 (m, 1H), 8.01–7.76 (m, 4H), 7.62–7.41 (m, 2H), 6.00–5.79 (m, 1H), 2.69–2.47 (m, 3H), 2.44–2.25(m, 1H). 13C NMR (101 MHz, CDCl3) δ 198.1, 194.6, 176.8, 135.9, 134.3, 133.9,132.3, 131.3, 130.9, 130.8, 130.6, 129.8, 129.3, 129.1, 129.0, 128.7, 128.7,127.9, 127.2, 126.9, 125.3, 124.4, 123.7, 79.6, 78.4, 27.0, 26.9, 25.4, 25.3.

[0060] Example 19 The structure of the compound prepared in this embodiment is as follows:

[0061] In this example, the specific preparation method is basically the same as in Example 1, except that 2,3-dihydrobenzofuran is used instead of diphenyl ether (1.1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a mixture, colorless oil, and the two products are difficult to separate. The yield is 85%. The NMR data of the mixed product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.85–7.68 (m, 2H), 6.79(d, J = 8.4 Hz, 1H), 5.76–5.66 (m, 1H), 4.70 (dt, J = 41.0, 8.8 Hz, 2H), 3.36–3.17 (m, 2H), 2.62–2.30 (m, 4H). 13 C NMR (101 MHz, CDCl3) δ 192.7, 192.0,176.8, 176.5, 165.4, 161.1, 130.8, 130.5, 129.9, 128.5, 127.9, 126.7, 126.1,124.4, 115.6, 109.5, 78.1, 73.3, 72.5, 29.6, 28.8, 26.9, 26.9, 25.4, 25.0.HRMS (ESI) m / z [M+Na] + calcd for C 13 H 12 O4Na: 255.0633; found: 255.0635.

[0062] Example 20 The structure of the compound prepared in this embodiment is as follows:

[0063] In this example, the specific preparation method is basically the same as in Example 1, except that 3-methylglutaric anhydride is used instead of glutaric anhydride (1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a pale yellow oil with a yield of 85%. The NMR data for the product are as follows. 1 HNMR (400 MHz, CDCl3) δ 7.98–7.89 (m, 2H), 7.40 (dd, J = 8.6, 7.4 Hz, 2H), 7.21 (t, J = 7.4 Hz, 1H), 7.10–6.97 (m, 4H), 5.31 (d, J = 3.5 Hz, 1H), 2.85–2.68 (m, 2H), 2.27–2.12 (m, 1H), 1.30 (d, J = 6.8 Hz, 3H). 13 C10 NMR (101 MHz, CDCl3) δ 192.7, 175.9, 163.1, 155.0, 131.3, 131.2, 130.2, 130.2, 128.4, 125.1, 121.7, 120.5, 117.5, 117.4, 84.5, 35.0, 33.2, 19.3. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 18 H 16 O43Na: 319.0946; found: 319.0947.

[0064] Example 21 The structure of the compound prepared in this embodiment is as follows:

[0065] In this example, the specific preparation method is basically the same as in Example 1, except that 1,1-cyclohexyldiacetic anhydride is used instead of glutaric anhydride (1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a colorless oil with a yield of 84%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.92 (dd, J = 8.9, 5.1 Hz, 2H), 7.44–7.34 (m, 2H), 7.23 (dd, J = 14.7, 7.2 Hz, 1H), 7.08 (d,J = 7.5 Hz, 1H), 7.02 (dd, J = 8.8, 3.2 Hz, 3H), 5.46 (d, J = 1.6 Hz, 1H), 2.53 (d, J = 4.3 Hz, 2H), 1.87–1.78(m, 1H), 1.73–1.56 (m, 3H), 1.51–1.28 (m, 3H), 1.23–1.06 (m, 3H). 13 C10 NMR (101MHz, CDCl3) δ 194.5, 194.5, 176.1, 176.1, 163.2, 162.7, 154.8, 153.5, 131.0, 131.0, 130.8, 130.4, 130.3, 130.2, 130.2, 125.2, 121.8, 120.6, 117.4, 117.3, 85.4, 45.0, 45.0, 37.3, 36.2, 32.9, 32.9, 25.3, 23.2, 22.2. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 22 H 22 O4Na: 373.1416; found: 373.1418.

[0066] Example 22 The structure of the compound prepared in this embodiment is as follows:

[0067] In this example, the specific preparation method is basically the same as in Example 1, except that 3,3-dimethylglutaric anhydride is used instead of glutaric anhydride (1 mmol). After the reaction, the product is purified by silica gel column chromatography. The product is a colorless oil with a yield of 86%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.92 (dd, J = 8.9, 5.3 Hz, 2H), 7.44–7.34 (m, 2H), 7.27–7.20 (m, 1H), 7.10–6.99 (m, 4H), 5.45 (d, J = 2.6 Hz, 1H), 2.57 (d, J =17.1 Hz, 1H), 2.32 (dd, J= 17.0, 2.9 Hz, 1H), 1.36 (s, 3H), 0.98 (s, 3H). 13 CNMR (101 MHz, CDCl3) δ 194.1, 194.0, 175.8, 175.7, 163.2, 162.6, 154.9, 153.5, 131.1, 131.0, 130.6, 130.3, 130.3, 130.2, 130.2, 125.1, 121.8, 120.5, 117.4, 117.3, 85.4, 41.9, 40.7, 40.6, 28.3, 28.3, 23.5, 23.5. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 19 H 18 O4Na: 333.1103; found: 333.1105.

[0068] Example 23 The structure of the compound prepared in this embodiment is as follows:

[0069] In this example, the specific preparation method is basically the same as in Example 1, except that p-toluene (1.1 mmol) is used instead of diphenyl ether, and 3,3-dimethylglutaric anhydride (1 mmol) is used instead of glutaric anhydride. After the reaction, the product was purified by silica gel column chromatography. The product was a gray oil, followed by a white solid, with a yield of 82%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 7.38 (s,1H), 7.19 (d, J = 9.6 Hz, 1H), 7.11 (d, J = 7.8 Hz, 1H), 5.41 (s, 1H), 2.49(d, J = 17.0 Hz, 1H), 2.40 (s, 3H), 2.32 (s, 3H), 2.27 (s, 1H), 1.23 (s, 3H), 0.93 (s, 3H). 13HRMS (ESI) m / z[M+Na] + calcd for C 15 H 18 O3Na: 269.1154; found: 269.1158.

[0070] Example 24 The structure of the compound prepared in this embodiment is as follows:

[0071] In this example, the specific preparation method is basically the same as in Example 1, except that p-biphenyl is used instead of diphenyl ether (1.1 mmol), and 3,3-dimethylglutaric anhydride is used instead of glutaric anhydride (1 mmol). After the reaction, the product is purified by silica gel column chromatography, and the product is a white solid with a yield of 82%. The NMR data for the product are as follows. 1 H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.3 Hz, 2H), 7.72 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 7.4 Hz, 2H), 7.52–7.36 (m, 3H), 5.58 (s, 1H), 2.58 (d, J = 17.0 Hz, 1H), 2.35 (d, J = 17.1 Hz,1H), 1.39 (s, 3H), 1.00 (s, 3H). 13 C10 NMR (101 MHz, CDCl3) δ 195.3, 175.9, 146.9, 139.3, 134.4, 129.2, 129.1, 128.7, 127.6, 127.3, 85.5, 41.9, 40.7, 28.3, 23.6. High-resolution mass spectrometry data: HRMS (ESI) m / z [M+Na] + calcd for C 19 H 18 O3Na:317.1154; found: 317.1155.

[0072] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. After reading the above content, those skilled in the art can make simple modifications or substitutions to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing phenyldihydrofuran-2(3H)-one and its derivatives, characterized in that... The method involves adding 1 mmol of raw material 1, 2.2 mmol of aluminum trichloride, and 5 mL of dichloromethane to a round-bottom flask, stirring thoroughly at 0°C, then adding 1.1 mmol of raw material 2, reacting at 0°C for 1 hour, removing excess solvent by distillation, adding 1.5 equivalents of iodobenzene acetate, followed by 2 mL of DMF, and reacting at 50°C for 5 hours. The reaction progress is monitored by thin-layer chromatography. After the reaction is complete, 15 mL of ethyl acetate is added, followed by washing three times with 15 mL of water and three times with 15 mL of saturated sodium bicarbonate. The mixture is dried and purified by silica gel column chromatography to obtain phenyl dihydrofuran-2(3H)-one and its derivatives. 。

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