CN115073259B - Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof - Google Patents

Abstract

The application belongs to the technical field of organic synthetic chemistry, and relates to a preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof. The application firstly carries out NH on Beta zeolite ₄ ⁺ Exchange and then Cu ²⁺ Loaded on NH ₄ ⁺ Exchanging acid sites on Beta to obtain Cu/NH ₄ ⁺ Beta catalyst for catalyzing the self-coupling reaction of aromatic alkyne compound, i.e. adding aromatic alkyne, catalyst and solvent into glass reaction tube successively, reacting at 80-140 deg.c for some period, centrifuging to separate catalyst, and low pressure rotary evaporating to obtain fraction. Final Cu/NH ₄ ⁺ The Beta catalyst is favorable for the self-coupling of arene alkyne, greatly improves the reaction activity, has mild specific reaction conditions, is easy to recycle, and has the advantages of simple post-treatment, high selectivity, high yield and the like.

Description

A preparation method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives

Technical field

The invention belongs to the technical field of organic synthetic chemistry and relates to a catalyst preparation method using Beta zeolite as a carrier to support Cu and its catalytic self-coupling of aromatic hydrocarbons and alkynes to generate 1,4-diphenyl-1,3-butadiyne and its Methods for Preparing Derivatives.

Background technique

The 1,3-conjugated diynes generated by the self-coupling process of aromatic alkynes have rigid structural units and unique electronic properties. They are the main components of natural products and antibacterial drugs, and are also the main functional groups in the synthesis of functional molecular materials. In addition, aromatic hydrocarbon-alkyne coupling reactions have also been widely used in the field of synthetic chemistry. For example, synthesis of various types of alkynes, construction of macrocyclic alkynes, natural product synthesis and applications in supramolecular fields.

It is generally believed that the self-coupling reaction of aromatic hydrocarbons and alkynes requires Cu ²⁺ salts for catalysis. In 1964, Bohlmann and his colleagues discovered that Cu ²⁺ salts can catalyze the coupling of alkynes (Chem. Ber., 1964, 97, 794), and then Keigo Kamata et al. used the TBA ₄ [gH ₂ SiW ₁₀ O ₃₆ Cu ₂ (m-1,1-N ₃ ) ₂ ] catalytic system. With phenylacetonitrile as the solvent, TBAB was added, oxygen was introduced, and Pd catalyst and CuI were added. , catalyze the alkynyl coupling reaction (Angew. Chem., 2008, 47, 2407). In the same year, Kazuya Yamaguchi et al. used a monomer diketone substitute [γ-H ₂ SiW ₁₀ O ₃₆ Cu ₂ (μ-1,1-N ₃ ) ₂ ] ^4- Cu ²⁺ salt as a catalyst, but additional Only with organic amines and other amine organic small molecules can the self-coupling of aromatic hydrocarbons and alkynes be realized. Therefore, the self-coupling of aromatic hydrocarbons and alkynes currently has the following problems: ① It requires complex metal Cu salts as catalysts, and Pd salts or organic amines need to be added at the same time. ② The presence of Cu ²⁺ salts is easy to precipitate and the system is difficult to separate. ③ The reaction system is not Environmentally friendly, not environmentally friendly. In view of the current problems in the self-coupling of aromatic hydrocarbons and alkynes, this patent application uses Cu/NH ₄ ⁺ -Beta as a catalyst to directly realize the self-coupling of aromatic hydrocarbons and alkynes without using additional metal Pd or organic additives. This method has high atom utilization rate, is green and environmentally friendly, and the catalyst can be reused.

Contents of the invention

The object of the present invention is to overcome the deficiencies of the prior art and provide a synthetic 1,4-diphenyl-1,3-butadiyne with high selectivity, high yield, easy separation and purification, and environmental friendliness and its Methods for Preparing Derivatives. Cu/NH ₄ ⁺ -Beta zeolite material can realize the self-coupling of aromatic acetylenic compounds under mild reaction conditions, and synthesize bi-alkyne compounds.

The specific synthesis method is as follows:

(1) Preparation method of catalyst: A certain amount of Beta zeolite and ammonium nitrate aqueous solution (0.6~1.0mol/L) are used for ammonium exchange at high temperature, where the liquid-to-solid mass ratio is 10~20:1, and the temperature is 60~100℃ , exchange for 2 to 6 hours. After the ammonium exchange is completed, filter and dry to obtain ammonium-type Beta zeolite. Then weigh a certain amount of Cu(NO ₃ ) ₂ and add it to distilled water to obtain a clear and transparent solution, which is then immersed in ammonium-type Beta zeolite, left to stand at room temperature, and dried to obtain a Cu-supported ammonium-type Beta catalyst, which is Cu/NH. ₄ ⁺ -Beta.

Furthermore, the Beta zeolite carrier is easily obtained by using the existing typical synthesis method of Beta zeolite, that is, dissolving silica, sodium metaaluminate, tetrapropylammonium hydroxide and polydimethyldiallylammonium chloride in water, and loading The kettle is used for high-temperature crystallization, filtration, washing, drying and calcining.

Furthermore, the loading amount of Cu is 1 to 5 wt.%.

In the preparation method of the catalyst, the temperature for high-temperature drying is 80 to 120°C.

(2) The Cu/NH ₄ ⁺ -Beta-catalyzed self-coupling reaction process of aromatic acetylenic compounds is as follows: add aromatic acetylene, metal zeolite catalyst Cu/NH ₄ ⁺ -Beta and solvent into a glass reaction tube in sequence, 80~140℃ The reaction lasts for a period of time. After the reaction is completed, the catalyst is separated by centrifugation, and the product can be obtained from the fraction obtained by low-pressure rotary evaporation of the liquid phase product.

Furthermore, the general structural formula of aromatic alkynes is Wherein R can be located in the ortho-para position, and R can be H, methyl, ethyl, methoxy, butyl, chlorine, fluorine, bromine or benzene ring.

Furthermore, aromatic alkynes can also be replaced by cyclic compounds with alkynes and thiophene alkynes.

In the aromatic-alkyne self-coupling reaction, the solvent is cyclohexane, benzene, and dichloroethane, preferably cyclohexane.

In the aromatic alkyne self-coupling reaction, the reaction temperature is 80-140°C, preferably 100-120°C, and the reaction time is 3-24h, preferably 4-14h.

Compared with the existing technology, the present invention has achieved the following technical advantages:

(1) Cu ²⁺ is directly loaded on the acidic site on NH ₄ ⁺ exchange Beta, providing Cu ²⁺ and NH ₄ ⁺ sites for the reaction. The aromatic alkyne is first converted into the carbocation of the aromatic alkyne on the catalyst, and attacks the aromatic alkyne combined with Cu ²⁺ to form the target product. The catalyst Cu/NH ₄ ⁺ -Beta is beneficial to the self-coupling of aromatic hydrocarbons and alkynes, which greatly improves the reaction activity.

(2) The reaction system in the present invention has the advantages of mild reaction conditions, easy recovery of the catalyst, simple post-treatment, high selectivity and high yield.

Description of the drawings

Figure 1 is a hydrogen spectrum spectrum of the p-fluorophenylacetylene coupling product of Example 2;

¹ H NMR (500MHz, CDCl ₃ ), δ: 7.53 (dd, J=8.7, 5.4Hz, 4H), 7.06 (t, J=8.6Hz, 4H).

Figure 2 is a hydrogen spectrum spectrum of the p-toluene acetylene coupling product in Example 3.

¹ H NMR (500MHz, CDCl ₃ ), δ: 7.45 (d, J = 8.1 Hz, 4H), 7.17 (d, J = 7.9 Hz, 4H), 2.39 (s, 6H).

Detailed ways

The synthesized zeolite carrier is labeled Beta (synthesized by referring to the typical mesoporous Beta zeolite method in 2.1 Materials synthesis in ACS Catal., 2018, 8, 9043), and then the catalyst is prepared by ammonium exchange first and then impregnation, as follows: 2g Beta zeolite and 20mL 0.8mol/L ammonium nitrate aqueous solution were exchanged at 80°C for 4 hours, filtered, and dried; weigh 0.2265g copper nitrate trihydrate and dissolve it in 2.0g water, and then pour the solution into 1.0g of the above zeolite carrier. Leave to stand and dry at room temperature to obtain the target catalyst Cu/NH ₄ ⁺ -Beta, in which the Cu loading amount is 3wt.%. Catalysts were used in the examples.

Example 1:

The Beta catalyst loaded with Cu is applied to the coupling reaction of alkynes after first ammonium exchange:

Add 0.2 mmol phenylacetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent cyclohexane (CYH) into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged, and the liquid phase product obtained is passed through low pressure The fraction obtained after rotary evaporation is separated and purified by column chromatography using pure petroleum ether as the eluent to obtain the product. In addition, the reaction liquid phase was analyzed by gas chromatography (GC) to calculate the conversion rate and selectivity of the reaction.

The reaction structural formula is:

Example 2:

Add 0.2 mmol p-fluorophenylacetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent benzene into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the liquid product obtained is evaporated by low pressure rotary evaporation. The obtained fraction is separated and purified by column chromatography using pure petroleum ether as the eluent to obtain the product. Perform GC analysis on the reaction liquid phase to calculate the conversion rate and selectivity of the reaction.

The reaction structural formula is:

Example 3:

Add 0.2 mmol p-toluene acetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent cyclohexane into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the liquid phase product obtained is passed through low pressure The fraction obtained after rotary evaporation is separated and purified by column chromatography using pure petroleum ether as the eluent to obtain the product. In addition, GC analysis was performed on the reaction liquid phase to calculate the conversion rate and selectivity of the reaction.

The reaction structural formula is:

Example 4:

Add 0.2 mmol p-toluene acetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent toluene into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the liquid product obtained is rotary evaporated under low pressure. The fraction obtained was separated and purified by column chromatography using pure petroleum ether as the eluent. In addition, GC analysis was performed on the reaction solution to calculate the conversion rate and selectivity of the reaction.

Example 5:

Add 0.2 mmol phenylacetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent dichloroethane into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the liquid product obtained is rotary evaporated under low pressure. The fraction obtained was separated and purified by column chromatography using pure petroleum ether as the eluent. In addition, GC analysis was performed on the reaction solution to calculate the conversion rate and selectivity of the reaction.

Example 6:

Add 0.2 mmol phenylacetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent cyclohexane into the glass reaction tube in sequence, and react at 120°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the liquid product obtained is evaporated by low pressure rotary evaporation. The obtained fractions were separated and purified by column chromatography using pure petroleum ether as the eluent. In addition, GC analysis was performed on the reaction solution to calculate the conversion rate and selectivity of the reaction.

Example 7:

Add 0.2 mmol phenylacetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent cyclohexane into the glass reaction tube in sequence, and react at 80°C for 10 hours. After the reaction is completed, the catalyst is centrifuged and the liquid product obtained is evaporated by low pressure rotary evaporation. The obtained fractions were separated and purified by column chromatography using pure petroleum ether as the eluent. In addition, GC analysis was performed on the reaction solution to calculate the conversion rate and selectivity of the reaction.

Example 8:

Add 0.2 mmol phenylacetylene, 30 mg Cu/NH ₄ ⁺ -Beta and 1 mL solvent cyclohexane into the glass reaction tube in sequence, and react at 80°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the liquid product obtained is evaporated by low pressure rotary evaporation. The obtained fractions were separated and purified by column chromatography using pure petroleum ether as the eluent. In addition, GC analysis was performed on the reaction solution to calculate the conversion rate and selectivity of the reaction.

Comparative Example 1

Direct application of Beta catalysts to alkynes coupling reactions:

Add 0.2 mmol phenylacetylene, 30 mg Beta and 1 mL solvent cyclohexane to the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is separated by centrifugation, and the liquid phase product obtained is subjected to low-pressure rotary evaporation. The fraction obtained is treated with pure petroleum. Ether was used as the eluent for column chromatography separation and purification. In addition, GC analysis was performed on the reaction solution to calculate the conversion rate and selectivity of the reaction.

Comparative Example 2

First load 3wt% Cu and then ammonium exchange to obtain the NH ₄ ⁺ /Cu/Beta catalyst. The catalyst preparation method is as follows: weigh 0.2265g copper nitrate trihydrate and dissolve it in 2.0g water, then pour the solution into 2.0g of the above-mentioned Beta zeolite carrier, Leave to stand and dry at room temperature, and the obtained catalyst is labeled Cu/Beta. 2.0g Cu/Beta zeolite and 20mL 0.8mol/L ammonium nitrate aqueous solution were exchanged at 80°C for 4 hours, filtered and dried, and the obtained catalyst was NH ₄ ⁺ /Cu/Beta.

Add 0.2 mmol phenylacetylene, 30 mg NH ₄ ⁺ /Cu Beta and 1 mL solvent cyclohexane into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the obtained reaction liquid is analyzed by GC to calculate the conversion of the reaction. rate and selectivity.

Comparative Example 3

The direct Cu-supported Beta catalyst is applied to the coupling reaction of alkynes. The catalyst is prepared as follows: weigh 0.2265g copper nitrate trihydrate and dissolve it in 2.0g water, then pour the solution into 2.0g of the above zeolite carrier, let it stand at room temperature, and dry. The resulting catalyst is labeled Cu/Beta.

Add 0.2 mmol phenylacetylene, 30 mg Cu/Beta and 1 mL solvent cyclohexane into the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the obtained reaction liquid is analyzed by GC to calculate the conversion rate and Selectivity.

Comparative Example 4

The ammonium-exchanged Beta catalyst is applied to the coupling reaction of alkynes. The catalyst is prepared as follows: weigh 2g Beta zeolite and 20mL of 0.8mol/L ammonium nitrate aqueous solution, exchange them at 80°C for 4 hours, filter and dry, and the obtained catalyst is NH ₄ ⁺ -Beta.

Add 0.2 mmol phenylacetylene, 30 mg NH ₄ ⁺ -Beta and 1 mL solvent cyclohexane to the glass reaction tube in sequence, and react at 100°C for 4 hours. After the reaction is completed, the catalyst is centrifuged and the obtained reaction liquid is analyzed by GC to calculate the conversion rate of the reaction. and selectivity.

The conversion rate and selectivity after the reaction of the above embodiment are shown in Table 1.

Table 1:

Alternative embodiments of the invention have been described above to teach those skilled in the art how to practice and reproduce the invention. In order to teach the present invention, some conventional technical aspects have been simplified and omitted. Those skilled in the art should understand that modifications derived from this aspect are within the scope of the present invention.

Claims (6)

1. A preparation method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives, which is characterized by: Mix aromatic alkynes, Cu ²⁺ /NH ₄ ⁺ -Beta catalyst and solvent, and react for a period of time at 80~140 °C. After the reaction is completed, the catalyst is separated by centrifugation, and the obtained liquid phase product is rotary evaporated to obtain the product, namely 1, 4-Diphenyl-1,3-butadiyne or its derivatives; ; R is H, methyl, ethyl, methoxy, butyl, chlorine, fluorine, bromine or benzene ring; The Cu ²⁺ /NH ₄ ⁺ -Beta catalyst is prepared by first exchanging ammonium with Beta zeolite, and then impregnating and loading divalent copper salt. 2. The preparation method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives according to claim 1, characterized in that: the load of Cu in the Cu ²⁺ /NH ₄ ⁺ -Beta catalyst The amount is 1~5 wt.%. 3. The preparation method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives according to claim 1, characterized in that: the solvent is cyclohexane, benzene and dichloroethane one or more of them. 4. The method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives according to claim 3, characterized in that: the solvent is cyclohexane. 5. The preparation method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives according to claim 1, characterized in that: the reaction temperature is 100~120°C, and the reaction time is 3~24 hours. 6. The preparation method for synthesizing 1,4-diphenyl-1,3-butadiyne or its derivatives according to claim 1, characterized in that: the preparation of the Cu ²⁺ /NH ₄ ⁺ -Beta catalyst The method is: perform ammonium exchange between Beta zeolite and ammonium nitrate aqueous solution at high temperature, where the liquid-solid mass ratio is 10 ~ 20:1, the temperature is 60 ~ 100 ° C, exchange for 2 ~ 6 hours, after the ammonium exchange is completed, filter, Dry to obtain ammonium-type Beta zeolite; then weigh a certain amount of copper salt into distilled water to obtain a clear and transparent solution, then immerse it into ammonium-type Beta zeolite, let it stand at room temperature, and dry to obtain Cu ²⁺ -loaded ammonium-type Beta Catalyst, Cu ²⁺ /NH ₄ ⁺ -Beta.