Preparation method of benzylidene indene compound containing benzoyl
A cost-effective and environmentally friendly method for synthesizing benzylidene indene compounds using aldehyde compounds and benzoyl peroxide under microwave irradiation addresses the limitations of existing technologies by providing efficient and scalable production with minimal metal catalyst use.
Patent Information
- Application Number
- CN202311499431.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-13
- Publication Date
- 2024-12-24
AI Technical Summary
Existing methods for preparing benzylidene indene compounds containing benzoyl groups are costly, require strict reaction conditions, and involve the use of large amounts of metal catalysts, which do not align with the principles of green chemistry.
A method using cheap and readily available aldehyde compounds and benzoyl peroxide as an initiator under microwave irradiation to synthesize benzylidene indene compounds, employing simple reaction conditions and avoiding excessive metal catalysts, with purification by column chromatography.
The method achieves high efficiency, meets the requirements of green chemistry, and allows for the separation and purification of products with different configurations, while being suitable for industrial production.
Smart Images
Figure CN119176766A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic preparation, and in particular to a method for preparing a benzylidene indene compound containing a benzoyl group. Background Art
[0002] Benzylidene indene compounds containing benzoyl are an important class of ring structure sequences, which are widely present in bioactive molecules and medicinal compounds with anti-hypercholesterol, anti-allergic and antibacterial activities, and have broad application prospects in preparative chemistry, medicinal chemistry and materials science. The C-H bond tandem cyclization induced by free radicals shows unique advantages in the construction of C-C bond cyclic compounds, and is a simple, efficient and economical method for preparing complex carbon ring and heterocyclic skeleton compounds under mild conditions. In the existing methods for preparing a series of benzoyl benzylidene indene compounds, the raw materials are difficult to prepare, and the price is high. Strict reaction conditions and high costs are required, and a large amount of metal catalysts are also required, which does not meet the requirements of green chemistry.
[0003] However, there are currently no literature reports on the direct construction of benzylidene indene compounds containing benzoyl groups. Therefore, it is of great significance to explore new methods for preparing benzylidene indene compounds containing benzoyl groups under mild reaction conditions. Summary of the invention
[0004] The technical problem to be solved by the present invention is to provide a preparation method of a benzylidene indene compound containing a benzoyl group in view of the deficiencies of the above-mentioned prior art. The method adopts cheap and readily available aldehyde compounds as raw materials and benzoyl peroxide as an initiator to prepare the benzylidene indene compound containing a benzoyl group under microwave irradiation. The preparation method provided by the present invention has readily available raw materials, a wide range of substrates, simple reaction conditions, convenient operation and high atom economy, and is suitable for industrial production.
[0005] The present invention provides a method for preparing a benzylidene indene compound containing a benzoyl group, comprising the following steps:
[0006] S1, adding a dinitrile compound containing an aromatic acetylene group, benzaldehyde and an initiator benzoyl peroxide into anhydrous ethanol;
[0007] S2, stirring the mixed solution prepared in S1 under microwave to fully react, to obtain a reaction solution;
[0008] S3. The reaction solution prepared in S2 is concentrated in vacuo, and the obtained residue is separated and purified by column chromatography to obtain a benzylidene indene compound containing a benzoyl group.
[0009] According to the method for preparing benzylidene indene compounds containing benzoyl groups provided by the present invention, the molar volume ratio of the dinitrile compound containing aromatic acetylene groups, benzaldehyde, benzoyl peroxide and anhydrous ethanol in S1 is 0.1 mmol: 0.1 mmol: 0.015 mmol: 3 mL.
[0010] According to the method for preparing benzylidene indene compounds containing benzoyl provided by the present invention, the stirring speed in S2 is 300 rpm / min, the temperature condition for sufficient reaction is 100° C., and the time condition for sufficient reaction is 20 min.
[0011] According to the method for preparing benzylidene indene compounds containing benzoyl provided by the present invention, the eluent of the column chromatography in S3 is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to ethyl acetate is 20:1.
[0012] According to the preparation method of the benzylidene indene compound containing benzoyl provided by the present invention, the general reaction formula of the preparation method is:
[0013]
[0014] In the reaction formula, R 1 is hydrogen, methyl, halogen or trifluoromethyl, R 2 is hydrogen, tert-butyl, halogen, trifluoromethyl or methoxy.
[0015] According to the preparation method of the benzylidene indene compound containing benzoyl group provided by the present invention, the structural formula of the benzylidene indene compound containing benzoyl group is any one of the following:
[0016]
[0017] Compared with the prior art, the present invention has the following advantages:
[0018] The invention adopts benzaldehyde with low cost as a reaction raw material, synthesizes a benzylidene indene compound containing a benzoyl group with potential application value in one step, and the two products with different configurations have different polarities and can be separated and purified by column chromatography. The preparation method of the invention avoids using too much metal catalyst, the reaction time is only 20 minutes, the efficiency is high, and the requirements of green chemistry are met. At the same time, it also has the advantages of simple equipment requirements, simple operation, mild reaction conditions, and a wide range of substrates. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 is the benzylidene indene compound (3a) containing a benzoyl group in Example 1 1 HNMR spectrum.
[0020] Figure 2is the benzylidene indene compound (3a) containing a benzoyl group in Example 1 13 CNMR image.
[0021] Figure 3 is the benzylidene indene compound (3a') containing a benzoyl group in Example 1 1 H NMR spectra.
[0022] Figure 4 is the benzylidene indene compound (3a') containing a benzoyl group in Example 1 13 C NMR spectrum.
[0023] Figure 5 is the benzylidene indene compound (3b) containing a benzoyl group in Example 2 1 HNMR spectrum.
[0024] Figure 6 is the benzylidene indene compound (3b) containing a benzoyl group in Example 2 13 C NMR spectrum.
[0025] Figure 7 is the benzylidene indene compound (3b') containing benzoyl in Example 2 1 H NMR spectra.
[0026] Figure 8 is the benzylidene indene compound (3b') containing benzoyl in Example 2 13 C NMR spectrum.
[0027] Fig. 9 is the benzylidene indene compound (3c) containing a benzoyl group in Example 3 1 HNMR spectrum.
[0028] Fig.10 is the benzylidene indene compound (3c) containing a benzoyl group in Example 3 13 C NMR spectrum.
[0029] Fig.11 is the benzylidene indene compound (3c) containing a benzoyl group in Example 3 19 F NMR spectrum.
[0030] Fig.12 is the benzylidene indene compound (3c') containing a benzoyl group in Example 3 1 H NMR spectra.
[0031] Fig.13 is the benzylidene indene compound (3c') containing a benzoyl group in Example 3 13 C NMR spectrum.
[0032] Fig.14 is the benzylidene indene compound (3c') containing a benzoyl group in Example 3 19 F NMR spectra
[0033] Fig.15 is the benzylidene indene compound (3d) containing a benzoyl group in Example 4 1 H NMR spectra.
[0034] Fig.16 is the benzylidene indene compound (3d) containing a benzoyl group in Example 4 13 C NMR spectrum.
[0035] Fig.17 is the benzylidene indene compound (3d) containing a benzoyl group in Example 4 19 F NMR spectrum.
[0036] Fig.18 is the benzylidene indene compound (3d') containing benzoyl in Example 4 1 H NMR spectra.
[0037] Fig.19 is the benzylidene indene compound (3d') containing benzoyl in Example 4 13 C NMR spectrum.
[0038] Fig. 20 is the benzylidene indene compound (3d') containing benzoyl in Example 4 19 F NMR spectrum.
[0039] Fig.21 is the benzylidene indene compound (3e) containing a benzoyl group in Example 5 1 H NMR spectra.
[0040] Fig. 22 is the benzylidene indene compound (3e) containing a benzoyl group in Example 5 13 C NMR spectrum.
[0041] Fig.23 is the benzylidene indene compound (3f) containing a benzoyl group in Example 6 1 H NMR spectra.
[0042] Fig.24 is the benzylidene indene compound (3f) containing a benzoyl group in Example 6 13 C NMR spectrum.
[0043] Fig.25 is the benzylidene indene compound (3 g) containing benzoyl in Example 7 1H NMR spectra.
[0044] Fig.26 is the benzylidene indene compound (3 g) containing benzoyl in Example 7 13 C NMR spectrum.
[0045] Fig. 27 is the benzylidene indene compound (3 g) containing benzoyl in Example 7 19 F NMR spectrum.
[0046] Fig.28 is the benzylidene indene compound (3h) containing benzoyl in Example 8 1 H NMR spectra.
[0047] Fig.29 is the benzylidene indene compound (3h) containing benzoyl in Example 8 13 C NMR spectrum.
[0048] Fig.30 This is the X-ray crystallographic data of the benzylidene indene compound (3a) containing a benzoyl group in Example 1.
[0049] Fig.31 This is the X-ray crystallographic data of the benzylidene indene compound (3a′) containing a benzoyl group in Example 1. DETAILED DESCRIPTION
[0050] Example 1
[0051] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0052] S1. Add 0.1 mmol of dinitrile compound 1a containing an aromatic ethynyl group, 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0053] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0054] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound containing a benzoyl group, which are compounds 3a and 3a' of two different configurations, cis and trans, with a total yield of 89%.
[0055] The reaction formula of the preparation method provided in this embodiment is as follows:
[0056]
[0057] A green and pollution-free microwave radiation reaction is selected, which is environmentally friendly, has a high atomic utilization rate and a short reaction time; organic aromatic aldehydes are selected as nucleophilic reagents, and benzaldehyde compounds are easy to form benzoyl radicals under the action of initiators, and the free radical coordination is strong, which is conducive to the reaction.
[0058] The structural characterization data of the above compound 3a are as follows:
[0059] 1 H NMR (600MHz, CDCl3) δ: 8.13–8.11 (m, 2H), 7.75–7.72 (m, 1H), 7.63–7.60 (m, 2H), 7.49–7.47 (m, 2H), 7.4 –7.37(m, 3H), 7.33–7.32(m, 2H), 7.22–7.19(m, 1H), 7.17–7.15(m, 1H), 7.14–7.11(m, 1H), 5.68(s, 1H).
[0060] 13 C NMR (150MHz, CDCl3) δ: 192.2, 138.3, 135.0, 134.9, 134.9, 134.6, 134.5, 130.2, 129. 3, 129.3, 129.1, 128.8, 128.7, 128.7, 128.3, 125.8, 125.7, 115.6, 113.7, 58.1, 44.0.
[0061] HRMS(ESI)m / z calcd for C 25 H 17 N2O + (M+H) + 361.1335, found 361.1333.
[0062] The structural characterization data of compound 3a' are as follows:
[0063] 1 H NMR (600MHz, CDCl3) δ: 8.08–8.06 (m, 2H), 7.72–7.67 (m, 2H), 7.63–7.61 (m, 2H), 7.59–7.56 (m, 2H), 7.50–7.48 (m, 3H), 7.43–7.40 (m, 2H), 7.29 (td, J=7.6, 1.1Hz, 1H), 7.16–7.15 (m, 1H), 5.79 (s, 1H).
[0064] 13 C NMR (150MHz, CDCl3) δ: 192.4, 138.0, 136.4, 134.8, 134.7, 133.6, 133.5, 130.2, 1 29.9, 129.3, 129.3, 129.2, 128.6, 127.2, 125.6, 122.2, 115.2, 112.1, 60.3, 40.1.
[0065] HRMS(ESI)m / z calcd for C 25 H 17 N2O + (M+H) + 361.1335, found 361.1331.
[0066] Single crystals of compound 3a were grown from slow evaporation of dichloromethane solution at room temperature. The data of the crystal structure 3a have been deposited in the Cambridge Crystallographic Data Center and assigned the deposit number: (CCDC:2160671);
[0067] Single crystals of compound 3a' were grown from slow evaporation of dichloromethane solution at room temperature. The crystal structure data of 3a' have been deposited in the Cambridge Crystallographic Data Center and assigned the deposit number: (CCDC:2160672).
[0068] Example 2
[0069] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0070] S1, adding 0.1 mmol of dinitrile compound 1b containing an aromatic ethynyl group, 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0071] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0072] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound containing a benzoyl group, which are compounds 3b and 3b' of two different configurations, cis and trans, with a total yield of 76%.
[0073] The reaction formula of the preparation method provided in this embodiment is as follows:
[0074]
[0075] The structural characterization data of compound 3b are as follows:
[0076] 1 H NMR (600MHz, CDCl3) δ: 8.12–8.10 (m, 2H), 7.73–7.71 (m, 1H), 7.61–7.59 (m, 2H), 7.49–7.48 (m, 2H), 7.43–7.37(m, 3H), 7.29(s, 1H), 7.14(s, 1H), 7.05–6.99(m, 2H), 5.62(s, 1H), 2.14(s, 3H).
[0077] 13 C NMR (150MHz, CDCl3) δ: 192.3, 139.2, 135.6, 135.0, 134.9, 134.7, 134.6, 134.5, 131. 3, 129.3, 128.7, 128.7, 128.3, 128.3, 126.1, 125.5, 115.7, 113.8, 57.9, 44.2, 21.3.
[0078] HRMS(ESI)m / z calcd for C 26 H 19 N2O + (M+H) + 375.1492, found 375.1490.
[0079] The structural characterization data of compound 3b' are as follows:
[0080] 1 H NMR (600MHz, CDCl3) δ: 8.07–8.05 (m, 2H), 7.71–7.68 (m, 1H), 7.62–7.61 (m, 2H), 7.58–7.56 (m, 2H), 7.50–7. 47 (m, 3H), 7.45 (s, 1H), 7.42–7.40 (m, 1H), 7.11–7.09 (m, 1H), 7.04–7.03 (m, 1H), 5.74 (s, 1H), 2.40 (s, 3H).
[0081] 13C NMR (150MHz, CDCl3) δ: 192.5140.1, 138.0, 134.8, 134.7, 133.7, 133.7, 133.6, 131.2, 1 29.3, 129.3, 129.2, 129.1, 128.6, 126.8, 125.3, 122.6, 115.4, 112.2, 60.1, 40.3, 21.4.
[0082] HRMS(ESI)m / z calcd for C 26 H 19 N2O + (M+H) + 375.1492, found 375.1495.
[0083] Example 3
[0084] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0085] S1. Add 0.1 mmol of dinitrile compound 1c containing an aromatic ethynyl group, 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0086] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0087] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound containing a benzoyl group, which are compounds 3c and 3c' of two different configurations, cis and trans, with a total yield of 87%.
[0088] The reaction formula of the preparation method provided in this embodiment is as follows:
[0089]
[0090] The structural characterization data of compound 3c are as follows:
[0091] 1H NMR (600MHz, CDCl3) δ: 8.12–8.10 (m, 2H), 7.75–7.72 (m, 1H), 7.63–7.60 (m, 2H), 7.47–7.45 (m, 3H), 7.44–7.40 (m, 2 H), 7.38 (s, 1H), 7.13 (dd, J=8.5, 4.9Hz, 1H), 6.97 (dd, J=9.2, 2.5Hz, 1H), 6.91 (td, J=8.4, 2.5Hz, 1H), 5.64 (s, 1H).
[0092] 13 C NMR (150MHz, CDCl3) δ: 192.09, 162.73 (d, J = 248.7Hz), 136.98 (d, J = 9.7Hz), 135.00, 134.41, 134.18 (d, J = 3.7Hz), 133.97 (d, J = 2.6Hz), 133.83, 1 30.22, 129.39, 129.25, 129.15, 128.99, 128.11, 127.18 (d, J=9.2Hz), 11 7.72 (d, J=23.8Hz), 115.31, 113.40, 112.55 (d, J=25.1Hz), 57.31, 44.27.
[0093] 19 F NMR (565MHz, CDCl3) δ: -110.43.
[0094] HRMS(ESI)m / z calcd for C 25 H 16 FN2O + (M+H) + 379.1241, found 379.1240.
[0095] The structural characterization data of compound 3c' are as follows:
[0096] 1 H NMR (600MHz, CDCl3) δ: 8.07–8.05 (m, 2H), 7.73–7.70 (m, 1H), 7.62–7.60 (m, 2H), 7.58 (t, J=7.8Hz, 2H), 7.50 (t, J=7.6Hz, 2H), 7.46–7.42 (m, 3H), 7.34 (dd, J=8.5, 2.4Hz, 1H), 7.14–7.12 (m, 1H), 5.75 (s, 1H).
[0097] 13C NMR (150MHz, CDCl3) δ: 192.32, 163.83 (d, J = 249.6Hz), 140.28 (d, J = 9.2Hz), 134.92, 134.53, 133.07, 132.55 (d, J = 3.6Hz), 132.02 (d, J = 2.6Hz), 1 29.48, 129.36, 129.32, 129.23, 128.69, 128.57, 127.20 (d, J=9.2Hz), 11 7.60 (d, J=23.5Hz), 114.90, 111.77, 108.97 (d, J=24.0Hz), 59.50, 40.51.
[0098] 19 F NMR (565MHz, CDCl3) δ: -110.62.
[0099] HRMS(ESI)m / z calcd for C 25 H 16 FN2O + (M+H) + 379.1241, found 379.1243.
[0100] Example 4
[0101] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0102] S1. Add 0.1 mmol of dinitrile compound 1d containing an aromatic ethynyl group, 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0103] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0104] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound containing a benzoyl group, which are compounds 3d and 3d' of two different configurations, cis and trans, with a total yield of 87%.
[0105] The reaction formula of the preparation method provided in this embodiment is as follows:
[0106]
[0107] The structural characterization data of compound 3d are as follows:
[0108] 1 H NMR (600MHz, CDCl3) δ: 8.08–8.06 (m, 2H), 7.76–7.72 (m, 4H), 7.72–7.69 (m, 2H), 7.60– 7.58 (m, 2H), 7.47–7.43 (m, 2H), 7.35–7.32 (m, 1H), 7.19 (d, J=7.8Hz, 1H), 5.82 (s, 1H).
[0109] 13 C NMR (150MHz, CDCl3) δ: 192.24, 137.42, 137.00, 136.82, 135.56, 134.96, 134.54, 130.98, 130.75, 130.01, 129. 65, 129.32 (d, J=8.9Hz), 125.77, 125.67 (q, J=3.8Hz), 125.32, 124.77, 122.43, 115.02, 111.88, 60.25, 39.94.
[0110] 19 F NMR (565MHz, CDCl3) δ: -62.70.
[0111] HRMS(ESI)m / z calcd for C 26 H 16 F3N2O + (M+H) + 429.1209, found 429.1210.
[0112] The structural characterization data of compound 3d' are as follows:
[0113] 1 H NMR (600MHz, CDCl3) δ: 8.08–8.07 (m, 2H), 7.78 (d, J=8.2Hz, 1H), 7.73 (t, J=7.6Hz, 1H), 7.68 (d, J= 8.2Hz, 1H), 7.63–7.57 (m, 4H), 7.57 (s, 1H), 7.49 (t, J=7.7Hz, 2H), 7.45–7.41 (m, 2H), 5.83 (s, 1H).
[0114] 13C NMR (150MHz, CDCl3): δ: 192.14, 141.56, 137.11, 135.23, 134.51, 132.89, 132.09, 132.03 (q, J=33.1Hz), 130.08, 129.77, 129.46, 129.43, 129.27, 128.78, 127.04 (q, J=3.8Hz), 123.38 (d, J=272.7Hz), 122.91 (q, J=4.0Hz), 122.40, 114.57, 111.54, 59.76, 40.31.
[0115] 19 F NMR (565MHz, CDCl3) δ: -62.51.
[0116] HRMS(ESI)m / z calcd for C 26 H 16 F3N2O + (M+H) + 429.1209, found 429.1206.
[0117] Example 5
[0118] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0119] S1. Add 0.1 mmol of dinitrile compound 1e containing an aromatic ethynyl group, 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0120] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0121] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound 3e containing a benzoyl group, with a total yield of 87%.
[0122] The reaction formula of the preparation method provided in this embodiment is as follows:
[0123]
[0124] The structural characterization data of compound 3e are as follows:
[0125] 1H NMR (600MHz, CDCl3) δ: 8.13–8.11(m, 2H), 7.74–7.72(m, 1H), 7.62–7.60(m, 2H), 7.49–7.48(m, 1H), 7.43(s, 4H), 7.27(s, 1H), 7.22–7.19(m, 1H), 7.17–7.15(m, 2H), 5.66(s, 1H), 1.36(s, 9H).
[0126] 13 C NMR (150MHz, CDCl3) δ: 192.2, 152.1, 138.3, 135.1, 134.8, 134.7, 134.1, 131.4, 130.1, 129 .3, 129.3, 129.0, 128.9, 128.1, 125.8, 125.6, 125.6, 115.6, 113.8, 58.1, 44.1, 34.8, 31.3.
[0127] HRMS(ESI)m / z calcd for C 29 H 25 N2O + (M+Na) + 417.1961, found 417.1960.
[0128] Example 6
[0129] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0130] S1, add 0.1mmol of dinitrile compound 1f containing aromatic ethynyl group, 0.1mmol of benzaldehyde 2a and 0.015mmol of initiator benzoyl peroxide into 3mL of anhydrous ethanol;
[0131] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0132] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound 3f containing a benzoyl group, with a total yield of 80%.
[0133] The reaction formula of the preparation method provided in this embodiment is as follows:
[0134]
[0135] The structural characterization data of compound 3f are as follows:
[0136] 1 H NMR (600MHz, CDCl3) δ: 8.12–8.11 (m, 2H), 7.75–7.73 (m, 1H), 7.63–7.60 (m, 2H), 7.56–7.54 (m, 2 H), 7.37–7.35 (m, 2H), 7.31 (d, J=7.9Hz, 1H), 7.24–7.22 (m, 2H), 7.19–7.16 (m, 2H), 5.68 (s, 1H).
[0137] 13 C NMR (150MHz, CDCl3) δ: 192.1, 138.5, 135.7, 134.9, 134.6, 134.5, 133.4, 132.1, 130. 5, 130.0, 129.3, 129.3, 129.2, 127.2, 126.0, 125.6, 122.8, 115.4, 113.6, 58.1, 44.0.
[0138] HRMS(ESI)m / z calcd for C 25 H 16 BrN2O + (M+Na) + 439.0441, found 439.0440.
[0139] Example 7
[0140] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0141] S1. Add 1 g of a dinitrile compound containing an aromatic ethynyl group (0.1 mmol), 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0142] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0143] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., 3 g of a benzylidene indene compound containing a benzoyl group, with a total yield of 80%.
[0144] The reaction formula of the preparation method provided in this embodiment is as follows:
[0145]
[0146] The structural characterization data of compound 3g are as follows:
[0147] 1 H NMR (600MHz, CDCl3) δ: 8.13–8.12 (m, 2H), 7.75–7.73 (m, 1H), 7.69 (d, J=8.1Hz, 2H), 7.63–7.6 0(m, 4H), 7.30(s, 1H), 7.26–7.23(m, 2H), 7.21–7.19(m, 1H), 7.17–7.14(m, 1H), 5.71(s, 1H).
[0148] 13 C NMR (150MHz, CDCl3) δ: 192.14, 138.69, 138.21, 136.82, 134.97, 134.31 (d, J=19.2Hz), 130.77, 130.74, 130.20 (d, J=31.4Hz), 129 .34, 129.28, 129.27, 128.71, 126.65, 126.06, 125.81 (q, J=3.8Hz), 125.61, 123.89 (q, J=272.4Hz), 115.27, 113.52, 58.10, 44.07.
[0149] 19 F NMR (565MHz, CDCl3) δ: -62.63.
[0150] HRMS(ESI)m / z calcd for C 26 H 16 F3N2O + (M+H) + 429.1209, found 429.1206.
[0151] Example 8
[0152] This embodiment provides a method for preparing a benzylidene indene compound containing a benzoyl group, and the specific steps are as follows:
[0153] S1, add 0.1 mmol of dinitrile compound 1h containing aromatic ethynyl group, 0.1 mmol of benzaldehyde 2a and 0.015 mmol of initiator benzoyl peroxide into 3 mL of anhydrous ethanol;
[0154] S2, placing the mixed solution prepared in S1 into a quartz microwave reaction tube, stirring at a speed of 300 rpm / min under microwave radiation, and reacting at a temperature of 100° C. for 20 min to obtain a reaction solution;
[0155] S3. The reaction solution prepared in S2 was concentrated in vacuo, and the residue was separated and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 as eluent to obtain a colorless solid, i.e., a benzylidene indene compound 3h containing a benzoyl group, with a total yield of 80%.
[0156] The reaction formula of the preparation method provided in this embodiment is as follows:
[0157]
[0158] The structural characterization data of compound 3h are as follows:
[0159] 1 H NMR (600MHz, CDCl3) δ: 8.13–8.12 (m, 2H), 7.74–7.71 (m, 1H), 7.61 (t, J=7.8Hz, 2H), 7.50–7.48 (m, 1H), 7.40 (d, J=7.8Hz, 1H), 7.39–7.3 6 (m, 1H), 7.34 (s, 1H), 7.20–7.18 (m, 1H), 7.16–7.12 (m, 2H), 6.97 (dd, J=8.4, 1.0Hz, 1H), 6.94–6.91 (m, 1H), 5.67 (s, 1H), 3.87 (s, 3H).
[0160] 13 C NMR (150MHz, CDCl3) δ: 192.3, 157.3, 138.2, 135.3, 134.8, 134.0, 130.5, 129.9, 129.3, 1 29.3, 129.0, 125.7, 125.6, 125.5, 123.2, 120.3, 115.6, 113.9, 111.0, 58.2, 55.5, 44.0.
[0161] HRMS(ESI)m / z calcd for C 26 H 19 N2O2 + (M+H) + 391.1441, found 391.1440.
[0162] Comparative Example 1
[0163] When the solvent was changed, the raw materials in Example 1 were used for preparation, and the proportions of products 3a and 3a' were as shown in Table 1 below:
[0164] Table 1
[0165]
[0166]
[0167] Comparative Example 2
[0168] When the reaction temperature and reaction time are changed, the raw materials in Example 1 are used for preparation, and the proportions of products 3a and 3a' are as shown in Table 2 below:
[0169] Table 2
[0170] Serial number Solvents 3a(％) 3a’(％) 1 140 20 40 2 120 20 30 3 120 15 21 4 100 20 18 5 80 20 37
[0171] The above is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent change made to the above embodiment according to the technical essence of the invention still falls within the protection scope of the technical solution of the present invention.
Claims
1. A method for preparing a benzylidene indene compound containing a benzoyl group, characterized in that: The following steps are involved: S1, adding a dinitrile compound containing an aromatic acetylene group, benzaldehyde and an initiator benzoyl peroxide into anhydrous ethanol; S2, stirring the mixed solution prepared in S1 under microwave to fully react, to obtain a reaction solution; S3. The reaction solution prepared in S2 is concentrated in vacuo, and the obtained residue is separated and purified by column chromatography to obtain a benzylidene indene compound containing a benzoyl group.
2. The method for preparing a benzylidene indene compound containing a benzoyl group according to claim 1, characterized in that: The molar volume ratio of the dinitrile compound containing an aromatic acetylene group, benzaldehyde, benzoyl peroxide and anhydrous ethanol in S1 is 0.1 mmol: 0.1 mmol: 0.015 mmol: 3 mL.
3. The method for preparing a benzylidene indene compound containing a benzoyl group according to claim 1, characterized in that: The stirring speed in S2 is 300 rpm / min, the temperature condition for the full reaction is 100° C., and the time condition for the full reaction is 20 min.
4. The method for preparing a benzylidene indene compound containing a benzoyl group according to claim 1, characterized in that: The eluent of the column chromatography in S3 is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to ethyl acetate is 20:
1.
5. The method for preparing a benzylidene indene compound containing a benzoyl group according to claim 1, characterized in that: The general reaction formula of the preparation method is: In the reaction formula, R 1 is hydrogen, methyl, halogen or trifluoromethyl, R 2 is hydrogen, tert-butyl, halogen, trifluoromethyl or methoxy.
6. The method for preparing a benzylidene indene compound containing a benzoyl group according to claim 1, characterized in that: The structural formula of the benzylidene indene compound containing benzoyl group is any one of the following: