A method for producing a 1,3,5-aryl-substituted benzene compound

Abstract

The application relates to the technical field of organic synthesis, in particular to a preparation method of a 1,3,5-aromatic group substituted benzene compound. The 1,3,5-aromatic group substituted benzene compound is obtained by taking substituted aromatic alkyne as raw material, combining with a solvent and a catalyst dimethyl titanium. In the process, the substituted aromatic alkyne, the dimethyl titanium and the organic solvent are mixed and then subjected to a cyclization reaction. The preparation method provided by the application has the characteristics of safe and inexpensive catalyst, simple operation and the like.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for preparing 1,3,5-aromatic substituted benzene compounds. Background Technology

[0002] 1,3,5-Aromatic substituted benzene compounds are important intermediates in organic synthesis and have wide applications in printing and dyeing, pharmaceuticals, and polymer materials. Furthermore, due to their unique conjugated structure, these compounds can also be used to prepare photosensitizers and photosensitive polymers for applications in photolithography, laser printing, and optical storage. 1,3,5-Aromatic substituted benzene compounds can also be used in the manufacture of displays, lighting, and electronic devices, particularly in the preparation of organic light-emitting diodes (OLEDs) and organic thin-film transistors (OTFTs).

[0003] Currently, the common synthetic strategies for 1,3,5-aromatic substituted benzene compounds are achieved through various coupling reactions such as Suzuki, Sonogashira, Negishi, and Heck. However, the palladium-based catalysts used in these reactions, such as bis(triphenylphosphine)palladium dichloride and tetra(triphenylphosphine)palladium, suffer from problems such as high cost and high heavy metal toxicity. Therefore, how to synthesize 1,3,5-aromatic substituted benzene compounds efficiently and selectively using pre-transition metal catalysts remains a major focus of the academic community. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing 1,3,5-aromatic substituted benzene compounds, which can efficiently and selectively produce 1,3,5-aromatic substituted benzene compounds.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] A method for preparing a 1,3,5-aromatic substituted benzene compound includes the following steps:

[0007] A cyclization reaction was carried out by mixing substituted aromatic yne, dimethyl diacetictene, and an organic solvent to obtain the 1,3,5-aromatic substituted benzene compound.

[0008] The structural formula of the substituted aromatic yne is:

[0009] R includes hydrogen, halogen, alkoxy, amino, or ferrocene.

[0010] Optionally, the substituted aromatic alkyne comprises at least one of phenylacetylene, 4-fluorophenylacetylene, and 4-aminophenylacetylene;

[0011] The organic solvent includes toluene.

[0012] Optionally, the molar ratio of the substituted aromatic yne, dimethyldicenoctanene and the organic solvent is 2:0.5-1.5:40-50.

[0013] Optionally, the molar ratio of the substituted aromatic yne, dimethyl diacetin, and organic solvent is 2:0.6-1.4:42-50.

[0014] Optionally, the cyclization reaction is carried out at a temperature of 85–105°C for a time of 6–24 hours.

[0015] Optionally, after the cyclization reaction is completed, the resulting product is further subjected to vacuum distillation and column chromatography separation in sequence.

[0016] Optionally, the vacuum distillation is carried out at a temperature of 60–75°C for a time of 10–20 min.

[0017] Optionally, the eluent used in the column chromatography separation is a mixture of dichloromethane and petroleum ether or a mixture of ethyl acetate and petroleum ether;

[0018] The volume ratio of dichloromethane to petroleum ether is 1:4 to 6;

[0019] The volume ratio of ethyl acetate to petroleum ether is 1:12 to 18.

[0020] Optionally, the silica gel used for column chromatography separation has a mesh size of 200 to 300 mesh.

[0021] This invention uses dimethyldicenocene as a catalyst, which is easy to prepare, safe, inexpensive, and non-toxic.

[0022] This invention provides a novel method for preparing 1,3,5-aromatic substituted benzene compounds. This method uses dimethyldicenocene as a catalyst to prepare 1,3,5-aromatic substituted benzene compounds in one step via a cyclization reaction. The preparation process is simple, uses readily available raw materials, is environmentally friendly, and yields 1,3,5-aromatic substituted benzene compounds with high purity. Detailed Implementation

[0023] This invention provides a method for preparing 1,3,5-aromatic substituted benzene compounds, comprising the following steps:

[0024] A cyclization reaction was carried out by mixing substituted aromatic yne, dimethyl diacetictene, and an organic solvent to obtain the 1,3,5-aromatic substituted benzene compound.

[0025] The structural formula of the substituted aromatic yne is:

[0026] R includes hydrogen, halogen, alkoxy, amino, or ferrocene.

[0027] The reaction formula for the preparation method of 1,3,5-aromatic substituted benzene compounds provided by this invention is as follows:

[0028]

[0029] In this invention, the substituted aromatic yne preferably comprises at least one of phenylacetylene, 4-fluorophenylacetylene, and 4-aminophenylacetylene;

[0030] The organic solvent preferably includes toluene.

[0031] In this invention, the molar ratio of the substituted aromatic yne, dimethyldicenoctane and the organic solvent is preferably 2:0.5-1.5:40-50, more preferably 2:0.6-1.4:42-50, further preferably 2:0.8-1.3:44-48, and even more preferably 2:1-1.1:47-47.3.

[0032] In this invention, the temperature of the cyclization reaction is preferably 85-105°C, more preferably 90-102°C, and even more preferably 95-100°C.

[0033] The preferred time is 6 to 24 hours, more preferably 9 to 18 hours, and even more preferably 12 to 15 hours.

[0034] In this invention, after the cyclization reaction is completed, it is preferable to further perform vacuum distillation and column chromatography separation on the obtained product in sequence.

[0035] In this invention, the temperature of the vacuum distillation is preferably 60-75°C, and more preferably 65-70°C;

[0036] The preferred time is 10-20 min, further preferred is 12-18 min, and even more preferred is 15-16 min.

[0037] In this invention, the eluent used for column chromatography separation is preferably a mixture of dichloromethane and petroleum ether or a mixture of ethyl acetate and petroleum ether;

[0038] The preferred volume ratio of dichloromethane to petroleum ether is 1:4 to 6, and more preferably 1:5;

[0039] The volume ratio of ethyl acetate to petroleum ether is preferably 1:12-18, more preferably 1:12-17, further preferably 1:13-16, and even more preferably 1:14-15.

[0040] In this invention, the silica gel used for column chromatography separation is preferably 200-300 mesh, more preferably 210-300 mesh, and even more preferably 220-300 mesh.

[0041] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0042] Example 1

[0043] 612.3 mg (6.0 mmol) of phenylacetylene, 2 mL (2.0 mmol) of dimethyl diacetene, and 10 mL (94.6 mmol) of toluene were added to a 25 mL sealed reactor and stirred at 100 °C for 12 hours. After cooling to room temperature, the solvent toluene was removed by rotary evaporation at 70 °C under reduced pressure for 15 min to obtain the crude product.

[0044] Using dichloromethane and petroleum ether at a volume ratio of 1:5 as eluent, column chromatography (300 mesh silica gel) was performed to obtain 191.7 mg of colorless solid 1,3,5-triphenylbenzene with a purity of 99%, a separation yield of 31.0%, and a melting point of 175 °C.

[0045] The structural formula of the obtained 1,3,5-triphenylbenzene is as follows:

[0046]

[0047] The obtained 1,3,5-phenylbenzene was subjected to infrared spectroscopy, and the results were as follows:

[0048] Infrared spectrum IR(KBr)ν: 691, 750, 872, 1027, 1075, 1410, 1496, 1593, 3058 cm⁻¹ -1 .

[0049] The obtained 1,3,5-phenylbenzene was subjected to nuclear magnetic resonance detection, and the results were as follows:

[0050] Nuclear magnetic resonance data: 1 HNMR (500MHz, C2D6SO): δ7.38-7.41(t,3H),7.47-7.50(t,6H),7.83-7.86(m,9H)ppm.

[0051] 13 CNMR (500MHz, C2D6SO): δ124.8,127.6,128.2,129.4,140.6,142.1ppm.

[0052] Example 2

[0053] 712.2 mg (6.0 mmol) of 4-fluorophenylacetylene, 2 mL (2.0 mmol) of dimethyldicenocene, and 10 mL (94.6 mmol) of toluene were added to a 25 mL sealed reactor and stirred at 100 °C for 12 hours. After cooling to room temperature, the solvent toluene was removed by rotary evaporation at 70 °C under reduced pressure for 15 min to obtain the crude product.

[0054] Using dichloromethane and petroleum ether at a volume ratio of 1:5 as eluent, column chromatography (300 mesh silica gel) was performed to obtain 108.3 mg of colorless solid 1,3,5-tris(4-fluorophenyl)benzene with a purity of 99%, the separation yield was 15.0%, and the melting point was 238 °C.

[0055] The structural formula of the obtained 1,3,5-tris(4-fluorophenyl)benzene is as follows:

[0056]

[0057] The prepared 1,3,5-tris(4-fluorophenyl)benzene was subjected to infrared spectroscopy, and the results were as follows:

[0058] Infrared spectrum IR (KBr)ν: 513, 709, 812, 1010, 1092, 1154, 1220, 1507, 1601, 3041 cm⁻¹ -1 .

[0059] The obtained 1,3,5-tris(4-fluorophenyl)benzene was subjected to nuclear magnetic resonance detection, and the results were as follows:

[0060] Nuclear magnetic resonance data: 1 HNMR (500MHz, CDCl3): δ7.15-7.18(m,6H),7.62-7.65(m,6H),7.66(s,3H)ppm;

[0061] 13 CNMR (500MHz, CDCl3): δ115.8,124.8,128.9,136.9,141.5,161.8ppm.

[0062] Example 3

[0063] 702.4 mg (6.0 mmol) of 4-aminophenylacetylene, 2 mL (2.0 mmol) of dimethyl diacetene, and 10 mL (94.6 mmol) of toluene were added to a 25 mL sealed reactor and stirred at 100 °C for 12 hours. After cooling to room temperature, the solvent toluene was removed by rotary evaporation at 70 °C under reduced pressure for 15 min to obtain the crude product.

[0064] Using ethyl acetate and petroleum ether at a volume ratio of 1:15 as eluent, column chromatography (300 mesh silica gel) was performed to obtain 85.1 mg of a pale yellow solid, 1,3,5-tris(4-aminophenyl)benzene, with a purity of 99%, a separation yield of 12.0%, and a melting point of 264 °C.

[0065] The structural formula of 1,3,5-tris(4-aminophenyl)benzene is as follows:

[0066]

[0067] The obtained 1,3,5-tris(4-aminophenyl)benzene was subjected to infrared spectroscopy, and the results were as follows:

[0068] Infrared spectrum IR(KBr)ν: 559, 826, 1010, 1184, 1277, 1516, 1618, 3029, 3345 cm⁻¹ -1 .

[0069] The obtained 1,3,5-tris(4-aminophenyl)benzene was subjected to nuclear magnetic resonance detection, and the results were as follows:

[0070] Nuclear magnetic resonance data: 1 HNMR (500MHz, C2D6SO): δ5.17(s,6H),6.63-6.65(d,6H),7.44(s,3H),7.46(d,6H)ppm;

[0071] 13 CNMR (500MHz, C2D6SO): δ114.6,120.8,127.9,128.5,142.0,148.8ppm.

[0072] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a 1,3,5-aromatic substituted benzene compound, characterized in that, Includes the following steps: A cyclization reaction was carried out by mixing substituted aromatic yne, dimethyl diacetictene, and an organic solvent to obtain the 1,3,5-aromatic substituted benzene compound. The substituted aromatic alkyne comprises at least one of phenylacetylene, 4-fluorophenylacetylene, and 4-aminophenylacetylene; The cyclization reaction occurs at a temperature of 85–105 °C.

2. The preparation method according to claim 1, characterized in that, The organic solvent is toluene.

3. The preparation method according to claim 1 or 2, characterized in that, The molar ratio of the substituted aromatic yne, dimethyldicenocene, and organic solvent is 2:0.5-1.5:40-50.

4. The preparation method according to claim 3, characterized in that, The molar ratio of the substituted aromatic yne, dimethyl diacetene, and organic solvent is 2:0.6-1.4:42-50.

5. The preparation method according to claim 1, characterized in that, The cyclization reaction takes 6 to 24 hours.

6. The preparation method according to claim 1, characterized in that, After the cyclization reaction is completed, the resulting product is then subjected to vacuum distillation and column chromatography separation in sequence.

7. The preparation method according to claim 6, characterized in that, The vacuum distillation is carried out at a temperature of 60–75°C for 10–20 minutes.

8. The preparation method according to claim 6, characterized in that, The eluent used in the column chromatography separation is a mixture of dichloromethane and petroleum ether or a mixture of ethyl acetate and petroleum ether; The volume ratio of dichloromethane to petroleum ether is 1:4 to 6; The volume ratio of ethyl acetate to petroleum ether is 1:12 to 18.

9. The preparation method according to claim 6, characterized in that, The silica gel used for column chromatography separation has a mesh size of 200-300.

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