CN-121990891-A - Aldehyde group functionalized halogen-containing spiroalkene and preparation method thereof

Abstract

The invention relates to a preparation method of aldehyde group functionalized halogen-containing spiroalkene, which comprises the following steps of S1, dissolving terephthalaldehyde and parahalogen benzyl cyanide in ethanol, adding sodium ethoxide into the mixture to react, washing, filtering and drying a reaction product to obtain a solid A, S2, dissolving the solid A in toluene, adding iodine and propylene oxide to react, washing, filtering and drying the reaction product to obtain a solid B, S3, dissolving the solid B in methylene dichloride, adding n-butyllithium into the mixture, slowly adding methanol, water and hydrochloric acid into the mixture in sequence after the solution changes color, extracting organic filtrate after the reaction is completed, performing rotary evaporation on the organic filtrate, washing, filtering and drying to obtain the aldehyde group functionalized halogen-containing spiroalkene.

Inventors

• ZHI YONGFENG
• DONG RUNZE
• LIU LONGJIN

Assignees

• 海南大学

Dates

Publication Date

20260508

Application Date

20260114

Claims (9)

1. 1. The preparation method of the aldehyde group functionalized halogen-containing spiroalkene is characterized by comprising the following steps of: S1, dissolving terephthalaldehyde and p-halophenyl acetonitrile in ethanol, adding sodium ethoxide into the mixture to react, washing, filtering and drying a reaction product to obtain a solid A; S2, dissolving the solid A obtained in the step S1 in toluene, adding iodine and propylene oxide for reaction, washing, filtering and drying a reaction product to obtain a solid B; S3, dissolving the solid B obtained in the step S2 in dichloromethane, adding n-butyllithium into the solution, after the solution changes color, sequentially and slowly adding methanol, water and hydrochloric acid, extracting an organic filtrate after the reaction is completed, steaming the organic filtrate in a rotary way, and washing, filtering and drying the organic filtrate to obtain aldehyde group functionalized halogen-containing spiroalkene; Wherein, the chemical structural formula of the solid A is as follows: ; the chemical structural formula of the solid B is as follows: ; the chemical structural formula of the aldehyde group functionalized halogen-containing spiroalkene is as follows: ; x is F, cl, br or I.
2. 2. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S1, the molar ratio of terephthalaldehyde, p-halophenylacetonitrile and sodium ethoxide is 1 (2-4): 4-6.
3. 3. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S1, the feed liquid ratio of terephthalaldehyde to ethanol is 1 mmol (25-55) mL.
4. 4. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S2, the feed liquid ratio of the solid a, iodine and propylene oxide is 1 mmol (2-4) mmol (15-25) mL.
5. 5. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S2, the feed liquid ratio of the solid a to toluene is 1 mmol (1.5-2.5) L.
6. 6. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S3, the feed liquid ratio of the solid B to the n-butyllithium is 1 mmol (10-20) mL.
7. 7. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S3, the feed liquid ratio of the solid B to the dichloromethane is 1mmol (250-350) mL.
8. 8. The method for preparing aldehyde group functionalized halogen-containing spiroalkene according to claim 1, wherein in the step S3, the feed liquid ratio of the solid B, methanol, water and hydrochloric acid is 1 mmol (5-7) mL, (8-12) mL, and wherein the concentration of hydrochloric acid is (4-8) mmol/mL.
9. 9. An aldehyde-functionalized halogen-containing spiroalkene, characterized in that the aldehyde-functionalized halogen-containing spiroalkene is prepared by the preparation method according to any one of claims 1 to 8.

Description

Aldehyde group functionalized halogen-containing spiroalkene and preparation method thereof Technical Field The invention relates to a halogen-containing compound, in particular to an aldehyde group functionalized halogen-containing spiroalkene and a preparation method thereof. Background The polycyclic aromatic hydrocarbon refers to pi conjugated molecules which are condensed with each other by two or more benzene rings in a mode of sharing two adjacent carbon atoms, is an important component of an organic conjugated functional material, and has wide application prospect in the fields of photoelectric devices, information storage, biological probes, semiconductors and the like. With the development and continuous perfection of organic synthesis methods, more novel polycyclic aromatic hydrocarbons with novel structure and more excellent photoelectric properties can be designed and synthesized, and the use of spiroalkene as a typical polycyclic aromatic hydrocarbon has been attracting more and more attention due to its special spatial configuration and large pi conjugated structure. At present, the existing spiroalkene compound has the defects of long reaction steps, low yield, high production cost, time consumption and the like because the reaction path of the related spiroalkene compound is not deeply explored due to the large molecular weight of the existing spiroalkene compound, so that the existing spiroalkene compound is difficult to prepare. Disclosure of Invention In order to solve the technical problems, the invention provides the aldehyde group functionalized halogen-containing spiroalkene and the preparation method thereof, the method is simple to operate, the reaction is simple and convenient, the flexible expansion is realized, the aldehyde group is successfully introduced into the compound, the reaction steps are reduced, and the experimental complexity is reduced. The first aspect of the invention provides a preparation method of aldehyde group functionalized halogen-containing spiroalkene, which comprises the following steps: S1, dissolving terephthalaldehyde and p-halophenyl acetonitrile in ethanol, adding sodium ethoxide into the mixture to react, washing, filtering and drying a reaction product to obtain a solid A; S2, dissolving the solid A obtained in the step S1 in toluene, adding iodine and propylene oxide for reaction, washing, filtering and drying a reaction product to obtain a solid B; S3, dissolving the solid B obtained in the step S2 in dichloromethane, adding n-butyllithium into the solution, after the solution changes color, sequentially and slowly adding methanol, water and hydrochloric acid, extracting an organic filtrate after the reaction is completed, steaming the organic filtrate in a rotary way, and washing, filtering and drying the organic filtrate to obtain aldehyde group functionalized halogen-containing spiroalkene; Wherein, the chemical structural formula of the solid A is as follows: ; the chemical structural formula of the solid B is as follows: ; the chemical structural formula of the aldehyde group functionalized halogen-containing spiroalkene is as follows: ; x is F, cl, br or I. Preferably, in the step S1, the molar ratio of terephthalaldehyde, parahalophenylacetonitrile and sodium ethoxide is 1 (2-4): 4-6. Preferably, in the step S1, the feed liquid ratio of terephthalaldehyde to ethanol is 1 mmol (25-55) mL. Preferably, in step S2, the feed liquid ratio of solid A, iodine and propylene oxide is 1 mmol (2-4) mmol (15-25) mL. Preferably, in step S2, the ratio of solid A to toluene is 1 mmol (1.5-2.5) L. Preferably, in step S3, the feed liquid ratio of the solid B and the n-butyllithium is 1 mmol (10-20) mL. Preferably, in step S3, the feed liquid ratio of the solid B and the methylene dichloride is 1 mmol (250-350) mL. Preferably, in the step S3, the feed liquid ratio of the solid B, the methanol, the water and the hydrochloric acid is 1 mmol (5-7) mL (8-12) mL, wherein the concentration of the hydrochloric acid is (4-8) mmol/mL. The invention also provides an aldehyde group functionalized halogen-containing spiroalkene, which is prepared by the method. The invention has the advantages that the aldehyde group functionalized halogen-containing spiroalkene and the preparation method thereof have simple operation, simple and convenient reaction and flexible expansion, successfully introduce aldehyde groups into the compound, reduce reaction steps and reduce experimental complexity. Drawings FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of an aldehyde group functionalized halogen-containing spiroalkene prepared in the example; FIG. 2 is an infrared spectrum of the aldehyde group functionalized halogen-containing spiroalkene prepared in the example. Detailed Description The present invention will be further described in detail with reference to the drawings and examples, which are only for the purpose of illustrating the invention and are not to be constr