A 1,3,5-triaryIbenzene compound and a method for preparing the same

Abstract

This invention provides a 1,3,5-triarylbenzene compound and its preparation method, which involves uniformly mixing α,β-unsaturated ketones, 2-phenylpropanal, and elemental iodine, followed by heating to react, thereby obtaining the compound. Compared with existing technologies, this invention has the following advantages: the reaction conditions are mild, the method is simple and rapid, and the substrate applicability is wide, which is beneficial for industrial production. Furthermore, the structure of the prepared 1,3,5-triarylbenzene compound is more complex and diverse.

Description

Technical Field

[0001] This invention relates to the field of organic compounds, specifically to a 1,3,5-triarylbenzene compound and its preparation method. Background Technology

[0002] 1,3,5-Triarylbenzenes are a class of aromatic compounds with unique C3 symmetry structures, serving as important functional modules for constructing dendritic macromolecules, organic conductive polymers, and polarization nonlinear optical materials. In recent years, due to their special properties, they have found significant applications in pharmaceuticals, photosensitive materials for photographic technology, and the synthesis of conjugated star-shaped aryl polymers. They are also a promising class of electroluminescent organic molecules and important intermediates in organic synthesis; triphenylbenzene, with the introduction of certain functional groups, can serve as a core functional module for further constructing dendritic macromolecules and various polyphenylene compounds. Therefore, the synthesis of 1,3,5-triarylbenzene compounds has become a meaningful research topic.

[0003] In 2022, Midya used palladium-catalyzed nitroolefins to obtain symmetrical 1,3,5-triarylbenzene compounds in high yields. The broad substrate range, functional group tolerance, and product diversity make this method very attractive [Organic Letters 2022, 24(24), 4438-4443], but it requires palladium catalysis, which is costly.

[0004]

[0005] The method for synthesizing a 1,3,5-triarylbenzene compound disclosed in CN105037072A published on November 11, 2015, involves dissolving a chalcone derivative and an inorganic base in dimethyl sulfoxide, reacting the mixture in air at 40–80°C for 3–8 hours, and then separating and purifying the mixture to obtain the 1,3,5-triarylbenzene compound.

[0006] It requires the use of dimethyl sulfoxide, which has a certain degree of toxicity. Summary of the Invention

[0007] The purpose of this invention is to provide a 1,3,5-triarylbenzene compound and its preparation method, which is prepared by heating α,β-unsaturated ketone, 2-phenylpropanal and iodine; the reaction conditions are mild, the method is simple and rapid, the substrate applicability is wide, and there is no need to use toxic solvents such as dimethyl sulfoxide, and the prepared structure is more complex and diverse.

[0008] The specific technical solution of this invention is as follows:

[0009] A method for preparing a 1,3,5-triarylbenzene compound, specifically comprising: mixing α,β-unsaturated ketone, 2-phenylpropanal and elemental iodine evenly, and heating to react, thereby obtaining the compound.

[0010] The molar ratio of α,β-unsaturated ketone, 2-phenylpropanal, and iodine is 0.2-0.6:10-30:0.1-0.3.

[0011] The structural formula of the α,β-unsaturated ketone is:

[0012] Wherein, R1 is hydrogen, halogen, nitro, cyano, methyl, methoxy, or phenyl;

[0013] R2 is hydrogen, halogen, nitro, cyano, methyl, methoxy, or phenyl;

[0014] Preferably, the α,β-unsaturated structural formula is as follows:

[0015]

[0016] The structure of 2-phenylpropanal is as follows:

[0017] The heating reaction temperature is 80-120℃; the reaction time is 8-12h.

[0018] After the heating reaction was completed, the compound was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0019] This invention provides a 1,3,5-triarylbenzene compound, prepared using the method described above. The structural formula of the 1,3,5-triarylbenzene compound is as follows:

[0020] Where R1 is hydrogen, halogen, nitro, cyano, methyl, methoxy, or phenyl;

[0021] R2 is hydrogen, halogen, nitro, cyano, methyl, methoxy, or phenyl;

[0022] Preferably, R1 is hydrogen, chlorine, methyl, methoxy, or bromine;

[0023] Preferably, R2 is hydrogen, chlorine, methyl, methoxy, or bromine;

[0024] Preferably, the 1,3,5-triarylbenzene compound has the following structural formula:

[0025]

[0026]

[0027] Compared with the prior art, the present invention has the following advantages: the reaction conditions of the present invention are mild, the method is simple and fast, the substrate applicability is wide, which is beneficial to industrial production, and the structure of the 1,3,5-triarylbenzene compound prepared is more complex and diverse. Attached Figure Description

[0028] Figure 1 The hydrogen spectrum of the 1,3,5-triarylbenzene compound prepared in Example 1;

[0029] Figure 2 The carbon spectrum of the 1,3,5-triarylbenzene compound prepared in Example 1;

[0030] Figure 3 The hydrogen spectrum of the 1,3,5-triarylbenzene compound prepared in Example 2;

[0031] Figure 4 The carbon spectrum of the 1,3,5-triarylbenzene compound prepared in Example 2;

[0032] Figure 5 The hydrogen spectrum of the 1,3,5-triarylbenzene compound prepared in Example 3;

[0033] Figure 6 The carbon spectrum of the 1,3,5-triarylbenzene compound prepared in Example 3;

[0034] Figure 7 The hydrogen spectrum of the 1,3,5-triarylbenzene compound prepared in Example 4;

[0035] Figure 8 The carbon spectrum of the 1,3,5-triarylbenzene compound prepared in Example 4;

[0036] Figure 9 The hydrogen spectrum of the 1,3,5-triarylbenzene compound prepared in Example 5;

[0037] Figure 10 The carbon spectrum of the 1,3,5-triarylbenzene compound prepared in Example 5;

[0038] Figure 11 The hydrogen spectrum of the 1,3,5-triarylbenzene compound prepared in Example 6;

[0039] Figure 12 The carbon spectrum of the 1,3,5-triarylbenzene compound prepared in Example 6;

[0040] Figure 13 This is a mechanism diagram of the reaction in Example 1. Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments 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 some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.

[0043] Unless otherwise specified in the embodiments, the techniques or conditions described in the literature in this field or in accordance with the product manual may be followed.

[0044] Example 1

[0045] A method for preparing a 1,3,5-triarylbenzene compound includes the following steps:

[0046] Add 1 mmol of α,β-unsaturated ketone, with the structural formula [structure not provided], sequentially into the sealing tube. 3 mL of 2-phenylpropanal and 0.5 mmol of elemental iodine were added. The reaction system was heated to 100 °C and reacted for 8 h. After the reaction was complete, the mixture was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0047] The reaction formula is as follows:

[0048]

[0049] The compound prepared in Example 1 was characterized by NMR, and the proton NMR spectrum is shown below. Figure 1 As shown, the C spectrum is as follows Figure 2 As shown, its NMR data is as follows: 1 H NMR (400MHz, CDCl3) δ7.79 (s, 3H), 7.70 (d, J = 5.6Hz, 6H), 7.49 (m, 6H), 7.39 (t, J = 7.3Hz, 3H).

[0050] 13 C NMR (101MHz, CDCl3) δ142.4,141.2,128.9,127.6,127.4,125.2.

[0051] Preparation mechanism of Example 1 is as follows Figure 13As shown, intermediate I is formed by the Prince reaction of chalcone and 2-phenylpropanal under iodine catalysis. Intermediate I then undergoes dehydration and deprotonation to generate intermediate II, which in turn undergoes isomerization to generate intermediate III. Further, intermediate III undergoes an intramolecular Prince reaction to generate intermediate IV, which is then dehydrated and deprotonated to yield the final product.

[0052] Example 2

[0053] A method for preparing a 1,3,5-triarylbenzene compound includes the following steps:

[0054] Add 1 mmol of α,β-unsaturated ketone, with the structural formula [structure not provided], sequentially into the sealing tube. 3 mL of 2-phenylpropanal and 0.5 mmol of elemental iodine were added. The reaction system was heated to 90 °C and reacted for 10 h. After the reaction was complete, the mixture was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0055] The reaction formula is as follows:

[0056]

[0057] The compound prepared in Example 2 was characterized by NMR, and the proton NMR spectrum is shown below. Figure 3 As shown, the C spectrum is as follows Figure 4 As shown, its NMR data is as follows:

[0058] 1 H NMR (400MHz, CDCl3) δ7.75(s,2H),7.69–7.67(m,3H),7.61–7.59(m,4H),7.55–7.54(m 2H),7.52–7.41(m,5H).

[0059] 13 C NMR (100MHz, CDCl3) δ142.7,141.3,140.8,139.9,139.4,133.8,132.0,129.1,129.0,129.0,128.6,127.8,127.4,125.4,125.2,124.7,122.0.

[0060] Example 3

[0061] A method for preparing a 1,3,5-triarylbenzene compound includes the following steps:

[0062] Add 1 mmol of α,β-unsaturated ketone, with the structural formula [structure not provided], sequentially into the sealing tube. 3 mL of 2-phenylpropanal and 0.5 mmol of elemental iodine were added. The reaction system was heated to 100 °C and reacted for 10 h. After the reaction was complete, the mixture was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0063] The reaction formula is as follows:

[0064]

[0065] The compound prepared in Example 3 was characterized by NMR, and the proton NMR spectrum is shown below. Figure 5 As shown, the C spectrum is as follows Figure 6 As shown, its NMR data is as follows:

[0066] 1 H NMR (400MHz, CDCl3) δ7.75 (s, 3H), 7.69 (d, J = 6Hz, 2H), 7.60 (d, J = 6.4Hz, 4H), 7.48 (t, J=6Hz, 2H), 7.39 (d, J=5.6Hz, 1H), 7.29 (d, J=6.4Hz, 4H), 2.42 (s, 6H).

[0067] 13 C NMR (100MHz, CDCl3) δ142.3,142.2,141.3,138.3,137.4,129.6,128.9,127.5,127.4,127.2,124.9,124.8,21.2.

[0068] Example 4

[0069] A method for preparing a 1,3,5-triarylbenzene compound includes the following steps:

[0070] Add 1 mmol of α,β-unsaturated ketone, with the structural formula [structure not provided], sequentially into the sealing tube. 3 mL of 2-phenylpropanal and 0.5 mmol of elemental iodine were added. The reaction system was heated to 120 °C and reacted for 11 h. After the reaction was complete, the mixture was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0071]

[0072] The compound prepared in Example 4 was characterized by NMR, and the proton NMR spectrum is shown below. Figure 7 As shown, the C spectrum is as follows Figure 8 As shown, its NMR data is as follows:

[0073] 1H NMR (400MHz, CDCl3) δ7.77(s,3H),7.70(d,J=5.6Hz,4H),7.60(d,J=6.4Hz,2H), 7.48(t,J=5.6Hz,4H), 7.40(t,J=6.4Hz,2H), 7.29(d,J=6.4Hz,2H), 2.42(s,3H).

[0074] 13 C NMR (100MHz, CDCl3) δ142.3,142.3,141.2,138.2,137.4,129.6,128.9,127.6,127.4,127.2,125.0,125.0,21.2.

[0075] Example 5

[0076] A method for preparing a 1,3,5-triarylbenzene compound includes the following steps:

[0077] Add 1 mmol of α,β-unsaturated ketone, with the structural formula [structure not provided], sequentially into the sealing tube. 3 mL of 2-phenylpropanal and 0.5 mmol of elemental iodine were added. The reaction system was heated to 110 °C and reacted for 8 h. After the reaction was complete, the mixture was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0078] The reaction formula is as follows:

[0079]

[0080] The compound prepared in Example 5 was characterized by NMR, and the proton NMR spectrum is shown below. Figure 9 As shown, the C spectrum is as follows Figure 10 As shown, its NMR data is as follows:

[0081] 1 H NMR (400MHz, CDCl3) δ7.74(s,3H),7.70(d,J=6Hz,4H),7.64(d,J=6.8Hz,2H),7 .48(t,J=6Hz,4H),7.35(t,J=75.6Hz,2H),7.02(d,J=6.8Hz,2H),3.87(s,3H).

[0082] 13 C NMR (100MHz, CDCl3) δ159.4,142.3,141.9,141.3,133.6,128.9,128.4,127.6,127.4,124.8,124.7,114.3,55.4.

[0083] Example 6

[0084] A method for preparing a 1,3,5-triarylbenzene compound includes the following steps:

[0085] Add 1 mmol of α,β-unsaturated ketone, with the structural formula [structure not provided], sequentially into the sealing tube. 3 mL of 2-phenylpropanal and 0.5 mmol of elemental iodine were added. The reaction system was heated to 120 °C and reacted for 11 h. After the reaction was complete, the mixture was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

[0086] The reaction formula is as follows:

[0087]

[0088] The compound prepared in Example 6 was characterized by NMR, and the proton NMR spectrum is shown below. Figure 11 As shown, the C spectrum is as follows Figure 12 As shown, its NMR data is as follows:

[0089] 1 H NMR (400MHz, CDCl3) δ7.79 (s, 1H), 7.76 (s, 2H), 7.72 (m, 4H), 7.65 (d, J = 6.4Hz, 2H), 7.50–7.39 (m, 8H).

[0090] 13 C NMR (101MHz, CDCl3) δ142.6,141.1,141.0,139.6,133.8,129.1,129.0,128.6,127.7,127.4,125.6,125.0.

[0091] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a 1,3,5-triarylbenzene compound, characterized in that, The preparation method is as follows: α,β-unsaturated ketone, 2-phenylpropanal and iodine are mixed evenly and heated to react, and the product is obtained. The structural formula of the α,β-unsaturated ketone is: ; Wherein, R1 is hydrogen, halogen, nitro, cyano, methyl, methoxy, or phenyl; R2 is hydrogen, halogen, nitro, cyano, methyl, methoxy, or phenyl; The heating reaction temperature is 80-120℃.

2. The preparation method according to claim 1, characterized in that, The molar ratio of α,β-unsaturated ketone, 2-phenylpropanal, and iodine is 0.2-0.6:10-30:0.1-0.

3.

3. The preparation method according to claim 1 or 2, characterized in that, R1 is hydrogen, chlorine, methyl, methoxy, or bromine; R2 is hydrogen, chlorine, methyl, methoxy, or bromine.

4. The preparation method according to claim 1 or 2, characterized in that, The heating reaction takes 8-12 hours.

5. The preparation method according to claim 1 or 2, characterized in that, After the heating reaction was completed, the compound was separated by column chromatography using petroleum ether as the eluent to obtain 1,3,5-triarylbenzene.

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