Aldehyde group functionalized halogen-containing helicene and preparation method thereof

Abstract

The invention relates to a preparation method of aldehyde group functionalized halogen-containing helicene, which comprises the following steps: S1, dissolving terephthalaldehyde and p-halobenzyl cyanide in ethanol, adding sodium ethoxide into the solution for reaction, and washing, filtering and drying a reaction product to obtain a solid A; s2, dissolving the solid A in methylbenzene, then adding iodine and epoxypropane for reaction, and washing, filtering and drying a reaction product to obtain a solid B; s3, dissolving the solid B in dichloromethane, adding n-butyllithium into the dichloromethane, sequentially and slowly adding methanol, water and hydrochloric acid after the color of the solution is changed, extracting an organic filtrate after the reaction is completed, carrying out rotary evaporation on the organic filtrate, washing, filtering and drying to obtain aldehyde group functionalized halogen-containing helicene; the invention provides the aldehyde group functionalized halogen-containing helicene and the preparation method thereof, the method is simple to operate, the reaction is simple and convenient, the expansion is flexible, the aldehyde group is successfully introduced into the compound, the reaction steps are reduced, and the experiment complexity is reduced.

Description

Technical Field

[0001] This invention relates to halogen-containing compounds, and in particular to an aldehyde-functionalized halogen-containing helicene and its preparation method. Background Technology

[0002] Fused-ring aromatic hydrocarbons (FROs) are a class of π-conjugated molecules consisting of two or more benzene rings fused together by sharing two adjacent carbon atoms. They are an important component of organic conjugated functional materials and have broad application prospects in optoelectronic devices, information storage, biological probes, and semiconductors. With the development and continuous improvement of organic synthesis methods, more novel FROs with superior optoelectronic properties can be designed and synthesized. Helene, as a typical FRO, has attracted increasing attention due to its unique spatial configuration and large π-conjugated structure.

[0003] Currently, due to their large molecular weight, existing helicene compounds have not been thoroughly explored in terms of their reaction pathways, resulting in difficulties in their preparation. They also suffer from numerous drawbacks such as lengthy reaction steps, low yields, high production costs, and time consumption. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an aldehyde-functionalized halogenated helicene and its preparation method. The method is simple to operate, easy to react, and flexible to expand, successfully introducing an aldehyde group into the compound, reducing reaction steps and experimental complexity.

[0005] The first aspect of this invention provides a method for preparing aldehyde-functionalized halogenated helicenes, comprising the following steps:

[0006] S1. Dissolve terephthalaldehyde and p-halophenylacetonitrile in ethanol, add sodium ethoxide to react, and wash, filter and dry the reaction product to obtain solid A.

[0007] S2. Dissolve solid A obtained in step S1 in toluene, then add iodine and propylene oxide to react. After washing, filtering and drying the reaction product, solid B is obtained.

[0008] S3. Take the solid B obtained in step S2 and dissolve it in dichloromethane. Add n-butyllithium to it. After the solution changes color, slowly add methanol, water and hydrochloric acid in sequence. After the reaction is complete, extract the organic filtrate. Rotary evaporate the organic filtrate, and after washing, filtering and drying, obtain aldehyde-functionalized halogenated helicene.

[0009] The chemical structural formula of solid A is as follows:

[0010] ;

[0011] The chemical structural formula of solid B is:

[0012] ;

[0013] The chemical structural formula of aldehyde-functionalized halogenated helicene is:

[0014] ;

[0015] X is F, Cl, Br, or I.

[0016] Preferably, in step S1, the molar ratio of terephthalaldehyde, p-halophenylacetonitrile and sodium ethoxide is 1 : (2-4) : (4-6).

[0017] Preferably, in step S1, the ratio of terephthalaldehyde to ethanol is 1 mmol : (25-55) mL.

[0018] Preferably, in step S2, the ratio of solid A, iodine and propylene oxide is 1 mmol : (2-4) mmol : (15-25) mL.

[0019] Preferably, in step S2, the ratio of solid A to toluene is 1 mmol : (1.5-2.5) L.

[0020] Preferably, in step S3, the ratio of solid B to n-butyllithium is 1 mmol : (10-20) mL.

[0021] Preferably, in step S3, the ratio of solid B to dichloromethane is 1 mmol : (250-350) mL.

[0022] Preferably, in step S3, the ratio of solid B, methanol, water and hydrochloric acid is 1 mmol : (5-7) mL : (5-7) mL : (8-12) mL; wherein the concentration of hydrochloric acid is (4-8) mmol / mL.

[0023] A second aspect of the present invention also provides an aldehyde-functionalized halogenated helicene, which is prepared by the above method.

[0024] Advantages of the present invention: The present invention provides an aldehyde-functionalized halogenated helicene and its preparation method. The method is simple to operate, easy to react, and flexible to expand. It successfully introduces an aldehyde group into the compound, reduces reaction steps, and lowers experimental complexity. Attached Figure Description

[0025] Figure 1 The 1H NMR spectrum of the aldehyde-functionalized halogenated helicene prepared in the example is shown below.

[0026] Figure 2The infrared spectrum of the aldehyde-functionalized halogenated helicene prepared as an example. Detailed Implementation

[0027] To enhance understanding of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. These embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0028] Example

[0029] Weigh out terephthalaldehyde (1.0 g, 7.455 mmol) and p-bromophenylacetonitrile (5.12 g, 24.1 mmol), dissolve them in 250 mL of ethanol, and then add sodium ethoxide (2.54 g, 37.3 mmol). After the reaction is complete, wash, filter and dry the reaction product to obtain solid A.

[0030] The chemical structural formula of solid A is:

[0031] .

[0032] Solid A (0.51 g, 1 mmol) was weighed and dissolved in 2 L of toluene. Then, iodine (0.53 g, 2.1 mmol) and 17 mL of propylene oxide were added to the solution, and the reaction was allowed to proceed for 24 h. After the reaction was completed, the reaction product was washed, filtered, and dried to obtain solid B.

[0033] The chemical structural formula of solid B is:

[0034] .

[0035] Weigh solid B (0.50 g, 1 mmol) and add it to 300 mL of anhydrous dichloromethane under a nitrogen atmosphere. Stir until the solid is completely dissolved, then add 16 mL of n-butyllithium. After the solution changes from yellow-green to yellow, slowly add 6 mL of methanol, 6 mL of water and 10 mL of hydrochloric acid (6 M). Let stand overnight at room temperature, extract the reaction solution to obtain an organic filtrate, rotary evaporate the organic filtrate, wash, filter and dry to obtain aldehyde-functionalized bromospirene (0.18 g, 0.36 mmol).

[0036] The chemical structural formula of aldehyde-functionalized bromospirolene is:

[0037] .

[0038] In the above synthesis process, filtration can employ commonly used filtration methods in the chemical field, such as vacuum filtration. The specific implementation of the filtration method is not limited in this embodiment of the invention. Evaporation can employ commonly used evaporation methods in the chemical field, such as rotary evaporation. The temperature, vacuum level, and rotation speed of the rotary evaporator can be selected by those skilled in the art based on the actual situation.

[0039] Unless otherwise specified, all the raw materials used above are of commonly used specifications in the field of chemical synthesis. For example, deionized water is preferred for water, and anhydrous ethanol is preferred for ethanol. Those skilled in the art can select the appropriate specifications of the raw materials according to the technical solution of this invention; the specifications referred to here are the purity, concentration, etc. of the raw materials. It should be further noted that there are no special restrictions on the source of all the raw materials used in the embodiments of this invention; they can be purchased on the market or made in-house.

[0040] The experimental equipment used in the above synthesis process is all common equipment in the field, with no special requirements, and all are commercially available. Those skilled in the art can select appropriate experimental equipment based on the description of the technical solution of this invention; therefore, this invention does not impose specific limitations or descriptions on the experimental equipment.

[0041] The aldehyde-functionalized bromospirolene prepared in the examples was subjected to 1H NMR spectroscopy, and the specific results are as follows: Figure 1 As shown, the 1H NMR peak at 10.48 ppm is the peak of the aldehyde group, the peak at 7.26 ppm is the peak of the deuterated chloroform group, and the rest are the peaks of other groups of the helicene.

[0042] The aldehyde-functionalized bromospirolene prepared in the examples was subjected to infrared spectroscopy using a JASCO Fourier transform infrared spectrometer FT / IR-6800 (scanned at room temperature, test range 4000–400 cm⁻¹). -1 ), the specific results are as follows Figure 2 As shown, the highest peak is located at 1725 cm. -1 The peak at position 1 represents the aldehyde group, signifying the final synthesis of the aldehyde bond. Each of the other infrared absorption peaks corresponds one-to-one with the characteristic absorption peaks of the functional groups contained in the helicene material.

[0043] The above embodiments should not limit the present invention in any way. All technical solutions obtained by equivalent substitution or equivalent conversion fall within the protection scope of the present invention.

Claims

1. A method for preparing aldehyde-functionalized halogenated helicene, characterized in that, Includes the following steps: S1. Dissolve terephthalaldehyde and p-halophenylacetonitrile in ethanol, add sodium ethoxide to react, and wash, filter and dry the reaction product to obtain solid A. S2. Dissolve solid A obtained in step S1 in toluene, then add iodine and propylene oxide to react. After washing, filtering and drying the reaction product, solid B is obtained. S3. Take the solid B obtained in step S2 and dissolve it in dichloromethane. Add n-butyllithium to it. After the solution changes color, slowly add methanol, water and hydrochloric acid in sequence. After the reaction is complete, extract the organic filtrate. Rotary evaporate the organic filtrate, and after washing, filtering and drying, obtain aldehyde-functionalized halogenated helicene. The chemical structural formula of solid A is as follows: ； The chemical structural formula of solid B is: ； The chemical structural formula of aldehyde-functionalized halogenated helicene is: ； X is F, Cl, Br, or I.

2. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S1, the molar ratio of terephthalaldehyde, p-halophenylacetonitrile and sodium ethoxide is 1 : (2-4) : (4-6).

3. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S1, the ratio of terephthalaldehyde to ethanol is 1 mmol : (25-55) mL.

4. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S2, the ratio of solid A, iodine and propylene oxide is 1 mmol : (2-4) mmol : (15-25) mL.

5. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S2, the ratio of solid A to toluene is 1 mmol : (1.5-2.5) L.

6. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S3, the ratio of solid B to n-butyllithium is 1 mmol : (10-20) mL.

7. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S3, the ratio of solid B to dichloromethane is 1 mmol : (250-350) mL.

8. The method for preparing an aldehyde-functionalized halogenated helicene according to claim 1, characterized in that, In step S3, the ratio of solid B, methanol, water and hydrochloric acid is 1 mmol : (5-7) mL : (5-7) mL : (8-12) mL; wherein the concentration of hydrochloric acid is (4-8) mmol / mL.

9. An aldehyde-functionalized halogenated helicene, characterized in that, Aldehyde-functionalized halogenated helicenes prepared by the preparation method according to any one of claims 1-8.

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