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

Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof Download PDF

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CN115073259B
CN115073259B CN202210696616.1A CN202210696616A CN115073259B CN 115073259 B CN115073259 B CN 115073259B CN 202210696616 A CN202210696616 A CN 202210696616A CN 115073259 B CN115073259 B CN 115073259B
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CN115073259A (en
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唐天地
张原�
傅雯倩
朱超杰
黄瑛婕
刘长俊
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • Y02P20/584—Recycling of catalysts

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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

Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof
Technical Field
The application belongs to the technical field of organic synthetic chemistry, and relates to a preparation method of a Cu catalyst loaded by Beta zeolite as a carrier and a preparation method of a catalyst for catalyzing arene alkyne to self-couple to generate 1, 4-diphenyl-1, 3-diacetylene and derivatives thereof.
Background
The 1, 3-conjugated diacetylene compound generated by the self-coupling process of the arene alkyne has a rigid structural unit and unique electronic characteristics, is a main component of natural products and antibacterial drugs, is also a main functional group in the synthesis of functional molecular materials, and is widely applied to the field of synthetic chemistry. For example, synthesis of many types of acetylides, construction of macrocyclic acetylides, synthesis of natural products and applications in the supramolecular arts.
The reaction of aromatic alkyne self-coupling is widely believed to require Cu 2+ Salt catalysis, cu found by Bohlmann and his colleagues in 1964 2+ Salts can catalyze the coupling of alkynes (chem. Ber.,1964,97,794) and then Keigo Kamata et al uses TBA 4 [g-H 2 SiW 10 O 36 Cu 2 (m-1,1-N 3 ) 2 ]And (3) adding TBAB under the condition that benzyl cyanide is taken as a solvent, introducing oxygen, adding a Pd catalyst and CuI, and catalyzing the alkynyl coupling reaction (Angew.chem., 2008,47,2407). In the same year, kazuya Yamaguchi et al substituted [ gamma-H ] with a monomeric diketone 2 SiW 10 O 36 Cu 2 (μ-1,1-N 3 ) 2 ] 4- Cu 2+ The salt is used as a catalyst, but extra amine small organic molecules such as organic amine and the like are needed to realize the self-coupling of the arene alkyne. Thus, the self-coupling of arene alkynes currently has the following problems: (1) complicated metal Cu salts are required as catalysts, pd salts or organic amines are required to be added at the same time, (2) Cu is present 2+ The salt is easy to deposit, the system is difficult to separate, and (3) the reaction system is not environment-friendly and is not environment-friendly. Aiming at the problems existing in the existing arene alkyne self-coupling, the application adopts Cu/NH under the condition of not using extra metal Pd or organic additives 4 + Beta is used as a catalyst, the self-coupling of arene alkyne is directly realized, the method has high atom utilization rate, is green and environment-friendly, and the catalyst can be recycled.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide a preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene and derivatives thereof, which has high selectivity, high yield, easy separation and purification and environmental friendliness. By Cu/NH 4 + Beta zeolite material can realize the self-coupling of aromatic alkyne compounds under mild reaction conditions to synthesize the diacetylene compounds.
The specific synthesis method is as follows:
(1) The preparation method of the catalyst comprises the following steps: and (3) carrying out ammonium exchange on a certain amount of Beta zeolite and ammonium nitrate aqueous solution (0.6-1.0 mol/L) at a high temperature, wherein the liquid-solid mass ratio is 10-20:1, the temperature is 60-100 ℃, the exchange is carried out at 2-6 h, and after the ammonium exchange is finished, filtering and drying are carried out to obtain the ammonium Beta zeolite. Then weighing a certain amount of Cu (NO) 3 ) 2 Adding into distilled water to obtain clear and transparent solution, soaking in ammonium Beta zeolite, standing at room temperature, and drying to obtain Cu-supported ammonium Beta catalyst, namely Cu/NH 4 + -Beta。
Further, the zeolite Beta carrier is easily obtained by adopting the existing typical synthesis method of zeolite Beta, namely, silicon dioxide, sodium metaaluminate, tetrapropylammonium hydroxide and polydimethyldiallyl ammonium chloride are dissolved in water, and the mixture is subjected to high-temperature crystallization, filtration, washing, drying and calcination in a kettle.
Further, the loading amount of Cu is 1 to 5wt.%.
In the preparation method of the catalyst, the high-temperature drying temperature is 80-120 ℃.
(2)Cu/NH 4 + The Beta-catalyzed aromatic alkyne self-coupling reaction proceeds as follows: aromatic alkyne, metal zeolite catalyst Cu/NH 4 + Beta and solvent are added into a glass reaction tube in sequence to react for a period of time at 80-140 ℃, after the reaction is finished, the catalyst is centrifugally separated, and the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, thus obtaining the product.
Further, the general structural formula of the aromatic alkyne isWherein R can be positioned in the ortho-para position, and R can be H, methyl, ethyl, methoxy, butyl, chlorine, fluorine, bromine or benzene ring.
Further, the aromatic alkyne can be replaced by a cyclic compound with alkyne and thiophene alkyne.
In the self-coupling reaction of arene alkyne, the solvent is cyclohexane, benzene and dichloroethane, and is preferably cyclohexane.
In the self-coupling reaction of arene alkyne, the reaction temperature is 80-140 ℃, preferably 100-120 ℃, and the reaction time is 3-24 hours, preferably 4-14 hours.
Compared with the prior art, the application has the following technical advantages:
(1)Cu 2+ directly supported on NH 4 + Exchange of acidic sites on Beta, providing Cu for the reaction 2+ And NH 4 + A site. The aromatic alkyne is firstly converted into the carbocation of the aromatic alkyne on the catalyst and attacks Cu 2+ And the combined aromatic alkynes, thereby forming the desired product. Cu/NH 4 + Beta-catalyst is favorable for self-coupling of arene alkyne, and greatly improves the reactivity.
(2) The reaction system has the advantages of mild reaction conditions, easy recovery of the catalyst, simple post-treatment, high selectivity, high yield and the like.
Drawings
FIG. 1 is a graph of the hydrogen 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).
FIG. 2 is a graph of the hydrogen spectrum of the p-tolane coupling product of example 3.
1 H NMR(500MHz,CDCl 3 ),δ:7.45(d,J＝8.1Hz,4H),7.17(d,J＝7.9Hz,4H), 2.39(s,6H).
Detailed Description
The zeolite carrier synthesized was labeled Beta (see ACS catalyst, 2018,8,9043, 2.1 Materials synthesis, which is typically synthesized by the mesoporous Beta zeolite method), and the catalyst was prepared by an ammonium exchange followed by impregnation, as follows: 2g zeolite Beta and 20mL of 0.8mol/L ammonium nitrate aqueous solution are exchanged for 4 hours at 80 ℃, filtered and dried; 0.2265g of copper nitrate trihydrate is weighed and dissolved in 2.0g g of water, then the solution is poured into 1.0g of zeolite carrier, and the mixture is stood at room temperature and dried to obtain the target catalyst Cu/NH 4 + Beta, wherein the loading of Cu is 3wt.%. The catalyst was used in the examples.
Example 1:
the Beta catalyst loaded with Cu after ammonium exchange is applied to the alkyne coupling reaction:
0.2mmol phenylacetylene, 30mg Cu/NH 4 + Beta and 1mL of solvent Cyclohexane (CYH) are sequentially added into a glass reaction tube, the reaction is carried out for 4 hours at the temperature of 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent, so that the product can be obtained. In addition, the reaction liquid phase was analyzed by Gas Chromatography (GC), and the conversion and selectivity of the reaction were calculated.
The reaction structural formula is as follows:
example 2:
0.2mmol of p-fluorophenylacetylene and 30mg of Cu/NH 4 + Beta and 1mL of solvent benzene are sequentially added into a glass reaction tube to react for 4 hours at the temperature of 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and pure petroleum ether is used as an eluent to perform column chromatography separation and purification, so that the product is obtained. GC analysis was performed on the reaction liquid phase to calculate the conversion and selectivity of the reaction.
The reaction structural formula is as follows:
example 3:
0.2mmol of p-tolane, 30mg of Cu/NH 4 + Beta and 1mL of solvent cyclohexane are sequentially added into a glass reaction tube to react for 4 hours at the temperature of 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent to obtain the product. In addition, GC analysis was performed on the reaction liquid phase, and the conversion and selectivity of the reaction were calculated.
The reaction structural formula is as follows:
example 4:
0.2mmol of p-tolane, 30mg of Cu/NH 4 + Beta and 1mL of solvent toluene are sequentially added into a glass reaction tube, the reaction is carried out for 4 hours at 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent. Further, GC analysis was performed on the reaction solution, and the conversion and selectivity of the reaction were calculated.
Example 5:
0.2mmol phenylacetylene, 30mg Cu/NH 4 + Beta and 1mL of solvent dichloroethane are sequentially added into a glass reaction tube, the reaction is carried out for 4 hours at 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent. Further, GC analysis was performed on the reaction solution, and the conversion and selectivity of the reaction were calculated.
Example 6:
0.2mmol phenylacetylene, 30mg Cu/NH 4 + Beta and 1mL of solvent cyclohexane are sequentially added into a glass reaction tube, the reaction is carried out for 4 hours at 120 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent. Further, GC analysis was performed on the reaction solution, and the conversion and selectivity of the reaction were calculated.
Example 7:
0.2mmol phenylacetylene, 30mg Cu/NH 4 + Beta and 1mL of solvent cyclohexane are sequentially added into a glass reaction tube to react for 10 hours at 80 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent. Further, GC analysis was performed on the reaction solution, and the conversion and selectivity of the reaction were calculated.
Example 8:
0.2mmol phenylacetylene, 30mg Cu/NH 4 + Beta and 1mL of solvent cyclohexane are sequentially added into a glass reaction tube to react for 4 hours at 80 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain fractions, and the fractions are subjected to column chromatography separation and purification by using pure petroleum ether as an eluent. Further, GC analysis was performed on the reaction solution, and the conversion and selectivity of the reaction were calculated.
Comparative example 1
Directly apply Beta catalyst to alkyne coupling reaction:
0.2mmol phenylacetylene, 30mg Beta and 1mL cyclohexane solvent are sequentially added into a glass reaction tube, the reaction is carried out for 4 hours at 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, the obtained liquid phase product is subjected to low-pressure rotary evaporation to obtain a fraction, and the fraction is subjected to column chromatography separation and purification by using pure petroleum ether as an eluent. In addition, the reaction solution was subjected to GC analysis to calculate the conversion and selectivity of the reaction.
Comparative example 2
Loading 3wt% Cu and then carrying out ammonium exchange to obtain NH 4 + The preparation method of the Cu/Beta catalyst is as follows: 0.2265g of copper nitrate trihydrate is weighed and dissolved in 2.0g of water, then the solution is poured into 2.0g of Beta zeolite carrier, and the mixture is kept stand at room temperature and dried, and the obtained catalyst is marked as Cu/Beta.2.0g of Cu/Beta zeolite and 20mL of 0.8mol/L ammonium nitrate aqueous solution are exchanged for 4 hours at 80 ℃, filtered and dried to obtain the catalyst NH 4 + /Cu/Beta。
0.2mmol phenylacetylene and 30mgNH 4 + Cu Beta and 1mL of solvent cyclohexane are sequentially added into a glass reaction tube to react for 4 hours at the temperature of 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, and the obtained reaction liquid is subjected to GC analysis to calculate the conversion rate and the selectivity of the reaction.
Comparative example 3
The direct Cu-supported Beta catalyst is applied to the coupling reaction of alkyne, and the catalyst is prepared as follows: 0.2265g of copper nitrate trihydrate is weighed and dissolved in 2.0g of water, then the solution is poured into 2.0g of zeolite carrier, and the mixture is kept stand at room temperature and dried, and the obtained catalyst is marked as Cu/Beta.
0.2mmol phenylacetylene, 30mg Cu/Beta and 1mL cyclohexane solvent are sequentially added into a glass reaction tube to react for 4 hours at 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, and the obtained reaction liquid is subjected to GC analysis to calculate the conversion rate and the selectivity of the reaction.
Comparative example 4
The Beta catalyst after ammonium exchange is applied to alkyne coupling reaction, and the catalyst is prepared as follows: 2g zeolite Beta and 20mL of 0.8mol/L ammonium nitrate aqueous solution are weighed, exchanged for 4 hours at 80 ℃, filtered and dried to obtain a catalyst NH 4 + -Beta。
0.2mmol phenylacetylene, 30mg NH 4 + Beta and 1mL of solvent cyclohexane are sequentially added into a glass reaction tube to react for 4 hours at 100 ℃, after the reaction is finished, the catalyst is centrifugally separated, and the obtained reaction liquid is subjected to GC analysis to calculate the conversion rate and the selectivity of the reaction.
The conversion and selectivity after the reaction of the above examples are shown in Table 1.
Table 1:
the foregoing describes alternative embodiments of the present application to teach those skilled in the art how to implement and reproduce the application. Some conventional technical aspects have been simplified and omitted in order to teach the inventive solution. Those skilled in the art will appreciate variations from this aspect that fall within the scope of the application.

Claims (6)

1. A preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof is characterized by comprising the following steps:
aromatic alkyne, cu 2+ /NH 4 + Mixing Beta catalyst and solvent, reacting for a period of time at 80-140 ℃, and centrifuging after the reaction is finishedSeparating the catalyst, and performing rotary evaporation on the obtained liquid phase product to obtain a product, namely 1, 4-diphenyl-1, 3-diacetylene or a derivative thereof;
；
r is H, methyl, ethyl, methoxy, butyl, chlorine, fluorine, bromine or benzene ring;
the Cu is 2+ /NH 4 + The Beta catalyst is prepared by the steps of firstly carrying out ammonium exchange on Beta zeolite and then impregnating and supporting bivalent copper salt.
2. The method for preparing the 1, 4-diphenyl-1, 3-diacetylene or the derivative thereof according to claim 1, wherein the method comprises the following steps: cu (Cu) 2+ /NH 4 + The loading of Cu in the Beta catalyst is 1-5 wt.%.
3. The method for preparing the 1, 4-diphenyl-1, 3-diacetylene or the derivative thereof according to claim 1, wherein the method comprises the following steps: the solvent is one or more of cyclohexane, benzene and dichloroethane.
4. A process for the synthesis of 1, 4-diphenyl-1, 3-diacetylene or a derivative thereof according to claim 3, wherein: the solvent is cyclohexane.
5. The method for preparing the 1, 4-diphenyl-1, 3-diacetylene or the derivative thereof according to claim 1, wherein the method comprises the following steps: the reaction temperature is 100-120 ℃, and the reaction time is 3-24 hours.
6. The method for preparing the 1, 4-diphenyl-1, 3-diacetylene or the derivative thereof according to claim 1, wherein the method comprises the following steps: the Cu is 2+ /NH 4 + The preparation method of the Beta catalyst comprises the following steps: performing ammonium exchange on Beta zeolite and ammonium nitrate aqueous solution at a high temperature, wherein the mass ratio of liquid to solid is 10-20:1, the temperature is 60-100 ℃, the exchange time is 2-6 hours, and after the ammonium exchange is finished, filtering and dryingDrying to obtain ammonium Beta zeolite; then weighing a certain amount of copper salt, putting into distilled water to obtain clear and transparent solution, soaking into ammonium type Beta zeolite, standing at room temperature, and drying to obtain Cu 2+ Supported ammonium Beta catalyst, cu 2+ /NH 4 + -Beta。
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