CN112275322B - Preparation method and application of supported CNTs @ NHC-Cu catalytic material - Google Patents

Preparation method and application of supported CNTs @ NHC-Cu catalytic material Download PDF

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CN112275322B
CN112275322B CN202011207775.8A CN202011207775A CN112275322B CN 112275322 B CN112275322 B CN 112275322B CN 202011207775 A CN202011207775 A CN 202011207775A CN 112275322 B CN112275322 B CN 112275322B
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刘建华
张湘杰
汪兵洋
郧栋
许传芝
夏春谷
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B01J31/2265—Carbenes or carbynes, i.e.(image)
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    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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Abstract

The invention relates to a preparation method of a supported CNTs @ NHC-Cu catalytic material, which comprises the following steps: preparing 2- (2-bromoethoxy) pyrene; preparing 1- (2- (pyrene-2-oxyl) ethyl) -1H benzo [ d ] imidazole; preparing 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide: mixing 1- (2- (pyrene-2-oxyl) ethyl) -1H benzo [ d ] imidazole, acetonitrile and benzyl bromide, and stirring for reaction to obtain the compound; preparing a benzimidazolyl nitrogen heterocyclic carbene copper metal complex: under the protection of nitrogen, 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide, cuprous iodide, sodium tert-butoxide and tetrahydrofuran are mixed and stirred for reaction to obtain the compound; preparing a carbon nanotube solution; sixthly, preparing a supported CNTs @ NHC-Cu catalytic material: and dropwise adding the NHC-Cu mixed solution dissolved in dichloromethane into the carbon nano tube solution to obtain the nano carbon tube. The invention has simple process and mild condition, and the obtained catalyst can be applied to the Click cycloaddition reaction.

Description

Preparation method and application of supported CNTs @ NHC-Cu catalytic material
Technical Field
The invention relates to the technical field of catalysis, in particular to a preparation method and application of a supported CNTs @ NHC-Cu catalytic material.
Background
The copper-catalyzed 'Click' cycloaddition reaction (also called Huisgen cycloaddition reaction) of alkyne compounds and azide compounds to synthesize 1,2,3-triazole compounds is a typical atom economic catalytic reaction process and is widely applied to various pharmaceutical chemistry, materials, biology and the likeField (Adv. Drug Deliv. Rev., 2008, 60, 958-970；Macromol. Rapid Commun., 2008, 29, 952-981；Med. Res. Rev., 2008, 28, 78-308.). In most cases, the "Click" cycloaddition reaction proceeds requiring the presence of a co-catalyst, such as an ancillary ligand, a base (primarily an amine), and a reducing or oxidizing agent (depending on the copper source used) to enhance its catalytic activity.
In recent years, a single copper salt Cu (I) is researched and found to have the advantages of good regioselectivity, mild reaction conditions and the like in the 'Click' cycloaddition reaction as a catalyst, but the single Cu (I) salt has low catalytic activity, so that the dosage of the copper catalyst needs to be increased to ensure high activity of the catalyst. Thus, when Cu (I) is used to catalyze such reactions, various types of phosphine-and nitrogen-containing ligands are often used to accelerate the reaction process. Among a plurality of ligands, N-heterocyclic carbene (NHCs) has a special electronic structure, can be used as a sigma electron donor and a pi electron acceptor, has the characteristics of better thermal stability, air stability and the like compared with phosphine ligands, and has a small amount of application reports of N-heterocyclic carbene copper metal complexes in the 'Click' cycloaddition reaction (chem. -Eur. J., 2006, 12, 7558-Buck 7564; Angew. chem., int. Ed., 2008, 47, 8881-Buck 8884), but the adopted N-heterocyclic carbene copper metal complexes are homogeneous reaction systems, so that the aim of recycling the 'Click' cycloaddition reaction catalyst is always achieved.
Carbon Nanotubes (CNTs) are an excellent carrier material for supporting homogeneous catalysts due to their large specific surface area, good mechanical, thermal and modifiable properties. Carbon nanotube-supported homogeneous catalysts are generally prepared by two ways: 1) the covalent bond loading mode fully utilizes rich oxygen-containing functional groups on the post-treated carbon nano tube, and the homogeneous molecular catalyst is grafted on the carbon nano tube in the covalent bond bonding mode. However, this approach has the obvious disadvantage that modification of the covalent bond results in destruction of the CNT surface structure and its properties, and in addition, the process may also result in modification of the molecular catalyst structure and thus in modification of the catalyst activity. 2) Non-covalent bond loading mode, and utilization of large amount of sp existing in untreated carbon nano tube2The carbon atom hybridization and the large pi conjugated system enrichment are characterized in that the immobilization of the homogeneous molecular catalyst is realized by introducing fragments containing aromatic micromolecules or certain polymer conjugated structures on the side chain of the molecular catalyst and utilizing the function of pi-pi bond accumulation. The non-covalent bond interaction mode loading does not change the structures of the carrier and the molecular catalyst, and is favored by people. Olefin exchange reaction catalyzed by nitrogen heterocyclic carbene ruthenium complex loaded by a non-covalent bond manner, alkyne cyclization reaction catalyzed by nitrogen heterocyclic carbene gold complex and indole dehydrogenation reaction catalyzed by nitrogen heterocyclic carbene iridium complex are reported (Inorg. Chem, 2009, 48, 2383-. However, no report has been found on the nitrogen heterocyclic carbene copper metal complex loaded by the carbon nanotube through a non-covalent bond.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a supported CNTs @ NHC-Cu catalytic material with simple process and mild conditions.
The invention also aims to provide application of the supported CNTs @ NHC-Cu catalytic material.
In order to solve the problems, the preparation method of the supported CNTs @ NHC-Cu catalytic material comprises the following steps:
preparation of 2- (2-bromoethoxy) pyrene (2- (2-bromoethoxy) pyrene)):
1-hydroxypyrene and Cs2CO3Mixing the 1, 2-dibromoethane and acetonitrile, and then refluxing and stirring at 60-80 ℃ for 24 h; cooling to room temperature after the reaction is finished to obtain a reaction solution A; adding water with the volume 2-5 times that of the reaction solution A into the reaction solution A, and sequentially extracting with dichloromethane, drying with anhydrous magnesium sulfate, filtering, performing rotary evaporation and purifying to obtain the catalyst; the 1-hydroxypyrene and the Cs2CO3The molar ratio of the 1, 2-dibromoethane is 1: 2: 4;
preparing 1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole (1- (2- (pyren-2-yloxy) ethyl) -1H-benzimidazole [ d ] imidazole):
mixing acetonitrile, benzimidazole and potassium hydroxide, refluxing for 30 minutes at 60-80 ℃, then adding the 2- (2-bromoethoxy) pyrene, and refluxing and stirring the obtained mixture for 24 hours at 60-80 ℃; cooling to room temperature after the reaction is finished to obtain a reaction solution B; adding n-hexane with the volume 2-5 times that of the reaction solution B into the reaction solution B, and sequentially filtering, washing and vacuum drying to obtain the catalyst; the molar ratio of the benzimidazole to the potassium hydroxide to the 2- (2-bromoethoxy) pyrene is 1: 1.2: 1;
preparing 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide (3-benzyl-1- (2- (pyren-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ium bromide):
mixing the 1- (2- (pyrene-2-oxy) ethyl) -1H benzo [ d ] imidazole, acetonitrile and benzyl bromide, and then refluxing and stirring at 60-80 ℃ for 24 hours; cooling to room temperature after the reaction is finished to obtain a reaction solution C; adding n-hexane with the volume 2-5 times that of the reaction solution C into the reaction solution C, and sequentially filtering, washing and vacuum drying to obtain the catalyst; the molar ratio of the 1- (2- (pyrene-2-oxy) ethyl) -1H benzo [ d ] imidazole to the benzyl bromide is 1: 1.1;
preparing a benzimidazolyl azacyclo-carbene copper metal complex (NHC-Cu):
under the protection of nitrogen, mixing the 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide, cuprous iodide, sodium tert-butoxide and tetrahydrofuran, and stirring to react for 4 hours at room temperature to obtain a suspension; filtering, washing and rotary steaming the suspension liquid in sequence to obtain a saturated filtrate; adding n-hexane with the volume of 3-8 times of the filtrate, and sequentially filtering, washing and vacuum drying to obtain the filtrate; the molar ratio of the 3-benzyl-1- (2- (pyrene-2-oxy) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide to the cuprous iodide to the sodium tert-butoxide is 1: 1: 1;
preparing a carbon nanotube solution:
mixing the carbon nano tube with a dichloromethane solution, and performing ultrasonic dispersion to obtain a solution with the concentration of 6 g/mL;
sixthly, preparing a supported CNTs @ NHC-Cu catalytic material:
dissolving the benzimidazolyl N-heterocyclic carbene copper metal complex (NHC-Cu) in dichloromethane to obtain a mixed solution with the concentration of 2.4 g/mL, dropwise adding the mixed solution into the carbon nanotube solution, stirring overnight, filtering and washing to obtain the benzimidazolyl N-heterocyclic carbene copper metal complex; the volume ratio of the mixed solution to the carbon nanotube solution is 1: 1 to 5.
The obtained supported CNTs @ NHC-Cu catalytic material exists in the form that:
Figure 505501DEST_PATH_IMAGE001
the synthesis process comprises the following steps:
Figure 259830DEST_PATH_IMAGE002
the application of the supported CNTs @ NHC-Cu catalytic material prepared by the method is characterized in that: the catalytic material is used for catalyzing a Click cycloaddition reaction of an azide compound and a terminal alkyne compound to synthesize a 1, 4-disubstituted-1, 2,3-triazole compound; the amount of the supported CNTs @ NHC-Cu catalytic material is 1% of the amount of the azide substance calculated as copper.
The reaction formula is as follows:
Figure 59159DEST_PATH_IMAGE003
the structural formula of the azide compound is as follows:
Figure 582544DEST_PATH_IMAGE004
(ii) a Wherein R is1Is one of phenyl, 2-iodophenyl, 3-bromophenyl, 4-acetonitrile phenyl, n-hexyl and n-octyl.
The structural formula of the terminal alkyne is as follows:
Figure 825438DEST_PATH_IMAGE005
(ii) a In the formula R2Is one of phenyl, 4-methoxyphenyl, 3-methylphenyl, 4-ethylphenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-fluorophenyl, 4-hexyloxyphenyl, n-pentyl and n-hexyl.
The "Click" cycloaddition reaction is solvent-free.
In the "Click" cycloaddition reaction, a reaction solvent is added, wherein the reaction solvent is one of toluene, tetrahydrofuran, acetonitrile, methanol and water, or is carried out under the condition of no solvent. Wherein the reaction is preferably carried out in the absence of a solvent.
The reaction temperature in the Click cycloaddition reaction is 20-60 ℃, and the reaction time is 2-10 h.
Compared with the prior art, the invention has the following advantages:
1. based on the advantage that pyrene is used as a smaller aromatic structural unit and can be conveniently introduced into a side chain of the N-heterocyclic carbene metal complex, 1-hydroxypyrene and 1, 2-dibromoethane are used as raw materials, and 2- (2-bromoethoxy) pyrene is obtained by nucleophilic substitution reaction; then reacting with benzimidazole and benzyl bromide to obtain a product 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-bromate; then carrying out deprotonation on the copper complex under an alkaline condition and reacting the copper complex with CuI to obtain a benzimidazolyl N-heterocyclic carbene copper metal complex (NHC-Cu); and finally, loading the benzimidazolyl N-heterocyclic carbene copper metal complex (NHC-Cu) on Carbon Nanotubes (CNTs) in a pi-pi noncovalent bond interaction mode to obtain the loaded CNTs @ NHC-Cu catalytic material.
XRD patterns of the prepared non-covalent bond supported benzimidazolyl nitrogen heterocyclic carbene copper metal complex (CNTs @ NHC-Cu) catalytic material and carrier Carbon Nanotubes (CNTs) are shown in figure 3 through a pi-pi bond stacking mode. As can be seen from fig. 3: two samples are at 26oThere is a distinct diffraction peak on both the left and right, which is attributed to the (002) plane of the crystalline graphite-like material. The intensity of the diffraction peak is slightly reduced after the metal complex is loaded, which is probably because the complex loaded on the surface of the carbon nano tube increases crystalsThe disorder of lattices also proves that the benzimidazolyl nitrogen heterocyclic carbene copper metal complex is successfully loaded on the carbon nano tube carrier.
2. The method has the advantages of mild reaction conditions, simple and convenient process, convenient operation, easy realization of equipment requirements and reaction conditions, and suitability for large-scale production.
3. The catalyst of the invention has the advantages of easy preparation, simple catalyst system, small catalyst dosage and high catalytic efficiency.
4. In the application of the azide compound and the alkyne compound in the 'Click' cycloaddition reaction to generate the 1,2,3-triazole compound, the substrate application range is wider, and the 1, 4-disubstituted-1, 2,3-triazole compound with the purity of more than 95 percent can be obtained in high yield by simply filtering, washing and drying the reaction mixture.
5. The catalyst can be recycled by simple filtration, washing and drying modes, and the catalytic activity of the catalyst is not obviously reduced after the catalyst is recycled for many times.
[ catalyst circulation experiment ]
Primary reaction: into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for multiple times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole, the separation yield is 94%, and the purity of the product is over 95% through nuclear magnetic assay.
And (3) cyclic reaction: and drying the recovered catalyst, adding the dried catalyst into a Schlenk glass reaction bottle with a screw cap, adding 1.0mmol of benzyl azide and 1.2mmol of phenylacetylene, and reacting according to the conditions of the primary reaction to realize the recycling of the catalyst.
The catalyst recycle results are shown in table 1.
TABLE 1 Cyclic utilization of catalyst CNTs @ NHC-Cu in cycloaddition reaction of benzyl azide and phenylacetylene "Click
Figure DEST_PATH_IMAGE007
The result shows that the non-covalent bond supported benzimidazolyl N-heterocyclic carbene copper metal complex (CNTs @ NHC-Cu) catalytic material can still keep higher catalytic activity after 4 cycles, but the effect of the catalyst is greatly reduced in the 5 th cycle process, which is mainly caused by the loss of the catalyst in the filtration process of the catalyst.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a nuclear magnetic hydrogen spectrum of a pyrene-modified benzimidazolyl N-heterocyclic carbene copper metal complex.
FIG. 2 is a nuclear magnetic carbon spectrum of the pyrene-modified benzimidazolyl N-heterocyclic carbene copper metal complex.
FIG. 3 is an XRD (X-ray diffraction) spectrum of a non-covalent bond loaded benzimidazolyl N-heterocyclic carbene copper metal complex (CNTs @ NHC-Cu) catalytic material and a carrier Carbon Nanotube (CNTs) prepared by a pi-pi bond stacking mode.
Detailed Description
A preparation method of a supported CNTs @ NHC-Cu catalytic material comprises the following steps:
preparation of 2- (2-bromoethoxy) pyrene (2- (2-bromoethoxy) pyrene)):
to a 100 mL round-bottom flask was added 1-hydroxypyrene (2.18 g, 10 mmol), Cs2CO3(6.5 g, 20 mmol), 1, 2-dibromoethane (7.48 g, 40 mmol) and acetonitrile (35 mL) were stirred at 60-80 ℃ under reflux for 24 h. Cooling to room temperature after the reaction is finished to obtain a reaction solution A; water (50 mL) was added to the reaction solution A, and the resulting solution was extracted with dichloromethane (3X 30 mL), and the dichloromethane extract was dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to remove the solvent. The resulting product was purified by column chromatography (ethyl acetate: petroleum)Ether 1: 4) to obtain a yellow solid: 2- (2-bromoethoxy) pyrene in 70% yield.
Preparing 1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole (1- (2- (pyren-2-yloxy) ethyl) -1H-benzimidazole [ d ] imidazole):
acetonitrile (50 mL) was added to a 100 mL round-bottomed flask containing a mixture of benzimidazole (1.18 g, 10 mmol) and potassium hydroxide (1.13 g, 12 mmol), refluxed at 60-80 ℃ for 30 minutes, then added with 2- (2-bromoethoxy) pyrene (3.26 g, 10 mmol), and the resulting mixture was stirred at 60-80 ℃ under reflux for 24 hours. Cooling to room temperature after the reaction is finished to obtain a reaction solution B; to the reaction solution B was added 20 mL of n-hexane and filtered. The precipitate was washed 3 times with n-hexane and then dried under vacuum at 40 ℃ to give a pale yellow solid: 1- (2- (pyrene-2-oxy) ethyl) -1H benzo [ d ] imidazole, yield 75%.
Preparing 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide (3-benzyl-1- (2- (pyren-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ium bromide):
1- (2- (pyrene-2-oxy) ethyl) -1H benzo [ d ] imidazole (2 mmol, 724 mg) was added to a 100 mL round bottom flask containing 20 mL acetonitrile followed by 2.2 mmol benzyl bromide, and stirred at 60-80 ℃ under reflux for 24H; cooling to room temperature after the reaction is finished to obtain a reaction solution C; adding n-hexane into the reaction solution C, filtering, washing the precipitate with n-hexane for 3 times, and vacuum-drying the obtained product at 40 ℃ to obtain a yellow solid substance: 3-benzyl-1- (2- (pyrene-2-oxy) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide in 56% yield.
Preparing a benzimidazolyl azacyclo-carbene copper metal complex (NHC-Cu):
to a Schlenk tube under nitrogen protection were added 3-benzyl-1- (2- (pyrene-2-oxy) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide (0.2 mmol, 98 mg), cuprous iodide (0.2 mmol, 20 mg) and sodium tert-butoxide (0.2 mmol, 20 mg), followed by 5ml of anhydrous THF. The mixture was stirred at room temperature for 4 h. After the reaction was complete, the suspension was filtered through celite and the precipitated material was washed three times with dichloromethane (3X 10 mL). The filtrate was concentrated to saturation by vacuum rotary evaporation and then added to n-hexane (30 mL) to precipitate a white precipitate, the resulting white solid was filtered and washed three times with n-hexane (3 × 10 mL) to give an off-white solid material: benzimidazolyl azacyclo-carbene copper metal complex 46mg, yield 42%.
The nuclear magnetic spectrum of the benzimidazolyl N-heterocyclic carbene copper metal complex is shown in figures 1-2, and detailed data are as follows:
1H NMR (400 MHz, DMSO) δ (ppm): 8.07 (dd, J = 14.0, 7.4 Hz, 4H), 8.00 – 7.86 (m, 3H), 7.80 (t, J = 8.5 Hz, 2H), 7.60 (d, J = 8.6 Hz, 1H), 7.43 (dd, J = 13.9, 7.3 Hz, 2H), 7.35 – 7.23 (m, 3H), 7.20 – 7.10 (m, 3H), 5.48 (s, 2H), 5.08 (t, J = 8.5 Hz, 2H), 4.78 (t, J = 4.5 Hz, 2H).
13C NMR (101 MHz, DMSO) δ (ppm): 194.6, 151.6, 136.4, 134.3, 133.2, 130.9, 130.7, 128.4, 127.5, 127.3, 127.1, 126.9, 126.2, 125.9, 125.5, 124.7,124.5, 124.2, 124.0, 123.7, 123.2, 120.7, 118.9, 111.8, 111.5, 109.2, 67.4, 50.8, 47.0.
preparing a carbon nanotube solution:
mixing the carbon nano tube with a dichloromethane solution, and performing ultrasonic dispersion to obtain a solution with the concentration of 6 g/mL.
Sixthly, preparing a supported CNTs @ NHC-Cu catalytic material:
dissolving benzimidazolyl N-heterocyclic carbene copper metal complex (NHC-Cu) in dichloromethane to obtain a mixed solution with the concentration of 2.4 g/mL, dropwise adding the mixed solution into a carbon nanotube solution, stirring overnight, filtering, and washing for multiple times to remove the complex which is not loaded on the carbon nanotube in a pi-pi bond conjugation mode. Finally, the CNTs @ NHC-Cu catalytic material is obtained, and the content of copper is measured to be 0.15mmol/g through ICP-AES.
The application of a supported CNTs @ NHC-Cu catalytic material comprises the following steps: the catalytic material is used for catalyzing a Click cycloaddition reaction of an azide compound and a terminal alkyne compound, the reaction temperature is 20-60 ℃, the reaction time is 2-10 hours, and a 1, 4-disubstituted-1, 2,3-triazole compound is synthesized.
The reaction formula is as follows:
Figure 67063DEST_PATH_IMAGE003
wherein: the structural formula of the azide compound is as follows:
Figure 404504DEST_PATH_IMAGE004
(ii) a Wherein R is1Is one of phenyl, 2-iodophenyl, 3-bromophenyl, 4-acetonitrile phenyl, n-hexyl and n-octyl.
The structural formula of the terminal alkyne is:
Figure 47975DEST_PATH_IMAGE005
(ii) a In the formula R2Is one of phenyl, 4-methoxyphenyl, 3-methylphenyl, 4-ethylphenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-fluorophenyl, 4-hexyloxyphenyl, n-pentyl and n-hexyl.
The "Click" cycloaddition reaction is solvent-free. Or adding a reaction solvent, wherein the reaction solvent is one of toluene, tetrahydrofuran, acetonitrile, methanol and water, or is carried out under the condition of no solvent. Wherein the reaction is preferably carried out in the absence of a solvent.
Example 1
In a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol% of NHC-Cu molecular catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the conditions of no solvent and reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole (1-benzyl-4-phenyl-1H-1,2, 3-triazole), the isolation yield was 93%, and the product purity was more than 95% as determined by nuclear magnetic resonance.
The nuclear magnetic data of the product are as follows:
1H NMR (CDCl3, 400 MHz) δ (ppm): 5.53 (s,2H), 7.26–7.41 (m, 6H), 7.69 (s, 1H), 7.79–7.82 (m, 4H)
13C NMR (CDCl3, 101 MHz) δ (ppm): 54.1, 119.7, 125.7, 128.0, 128.2, 128.7, 128.8, 129.1, 130.6, 134.7, 148.1
example 2
Adding 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol percent of NHC-Cu molecular catalyst (relative to the benzyl azide) into a Schlenk glass reaction bottle with a screw cap, stirring and reacting for 3 hours at the reaction temperature of 30 ℃ by taking 3 mL of methanol as a solvent, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for multiple times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole, the separation yield is 66%, and the purity of the product is over 95% through nuclear magnetic assay.
Example 3
Adding 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol percent of NHC-Cu molecular catalyst (relative to the benzyl azide) into a Schlenk glass reaction bottle with a screw cap, stirring and reacting for 3 hours at the reaction temperature of 30 ℃ by taking 3 mL of toluene as a solvent, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for multiple times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole, the separation yield is 35%, and the purity of the product is over 95% through nuclear magnetic assay.
Example 4
Adding 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol percent of NHC-Cu molecular catalyst (relative to the benzyl azide) into a Schlenk glass reaction bottle with a screw cap, stirring and reacting for 3 hours at the reaction temperature of 30 ℃ by taking 3 mL of tetrahydrofuran as a solvent, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for multiple times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole, the separation yield is 50%, and the purity of the product is over 95% through nuclear magnetic assay.
Example 5
Adding 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol percent of NHC-Cu molecular catalyst (relative to the benzyl azide) into a Schlenk glass reaction bottle with a screw cap, stirring and reacting for 3 hours at the reaction temperature of 30 ℃ by taking 3 mL of water as a solvent, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for multiple times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole, the separation yield is 39%, and the purity of the product is over 95% through nuclear magnetic assay.
Example 6
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for multiple times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-phenyl-1, 2,3-triazole, the separation yield is 95%, and the purity of the product is over 95% through nuclear magnetic assay.
Example 7
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of n-heptyne and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-n-pentyl-1, 2,3-triazole (1-benzyl-4-benzyl-1H-1,2, 3-triazole), the isolation yield is 82%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.32 – 7.23 (m, 3H), 7.19 – 7.14 (m, 2H), 7.12 (s, 1H), 5.41 (s, 2H), 2.68 – 2.49 (m, 2H), 1.63 – 1.50 (m, 2H), 1.31 – 1.19 (m, 4H), 0.84 – 0.76 (m, 3H)
13C NMR (101 MHz, CDCl3) δ (ppm): 151.3, 148.2, 134.8, 129.1, 128.7, 128.0, 127.7, 125.7, 125.4, 119.3, 54.2, 34.7, 31.3.
example 8
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 4-hexyloxyphenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-p-hexyloxyphenyl-1, 2,3-triazole (1-benzyl-4- (4- (hexyloxy) phenyl) -1H-1,2, 3-triazole), the isolation yield is 91%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.76 – 7.65 (m, 2H), 7.57 (s, 1H), 7.42 – 7.33 (m, 3H), 7.32 – 7.25 (m, 2H), 6.95 – 6.88 (m, 2H), 5.54 (s, 2H), 3.96 (t, J = 6.6 Hz, 2H), 1.83 – 1.73 (m, 2H), 1.50 – 1.31 (m, 4H), 0.92 (dd, J = 13.5, 6.4 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ (ppm): 149.0, 135.0, 129.0, 128.6, 127.9, 120.5, 54.0, 30.4, 32.9, 29.1, 26.0, 22.5, 14.0.
example 9
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 4-tert-butyl phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The crude product obtained is washed several times with n-hexane and water to remove unreacted substrate, and thenDrying at 60 ℃ to obtain the target product 1-benzyl-4-p-tert-butylphenyl-1, 2,3-triazole (1-benzyl-4- (4- (tert-butyl) phenyl) -1H-1,2, 3-triazole), the isolation yield was 86%, and the product purity was more than 95% as determined by nuclear magnetic resonance. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.73 (d, J = 8.4 Hz, 2H), 7.64 (s, 1H), 7.42 (d, J = 8.4 Hz, 2H), 7.39 – 7.34 (m, 3H), 7.28 (dd, J = 10.6, 5.2 Hz, 2H), 5.56 (s, 2H), 1.33 (s, 9H).
13C NMR (101 MHz, CDCl3) δ (ppm): 151.3, 148.2, 134.8, 129.1, 128.7, 128.0, 127.7, 125.7, 125.4, 119.3, 54.2, 34.7, 31.3.
example 10
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 3-methylphenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-m-methylphenyl-1, 2,3-triazole (1-benzyl-4- (o-tolyl) -1H-1,2, 3-triazole), the isolation yield is 87%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.65 (s, 2H), 7.56 (d, J = 7.7 Hz, 1H), 7.43 – 7.33 (m, 3H), 7.32 – 7.23 (m, 3H), 7.12 (d, J = 7.6 Hz, 1H), 5.55 (s, 2H), 2.36 (s, 3H).
13C NMR (101 MHz, CDCl3) δ (ppm): 148.3, 138.5, 134.8, 130.4, 129.2, 129.0, 128.8, 128.1, 126.4, 122.8, 119.6, 54.2, 21.4.
example 11
In a Schlenk glass reaction flask with a screw cap, 1.0mmol of benzyl azide, 1.2mmol of 4-ethyl phenylacetylene and 1mol percent of supported CNTs @ NHC-Cu catalyst are added(relative to the benzyl azide). Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-p-ethylphenyl-1, 2,3-triazole (1-benzyl-4- (4-ethylphenyl) -1H-1,2, 3-triazole) with an isolation yield of 90% and a purity of more than 95% as determined by nuclear magnetic resonance. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ(ppm): 7.76 – 7.67 (m, 2H), 7.63 (s, 1H), 7.40 – 7.33 (m, 3H), 7.31 – 7.27 (m, 2H), 7.22 (d, J = 8.3 Hz, 2H), 5.55 (s, 2H), 2.65 (q, J = 7.6 Hz, 2H), 1.23 (t, J = 7.6 Hz, 4H).
13C NMR (101 MHz, CDCl3) δ(ppm): 148.3, 144.4, 134.8, 129.1, 128.7, 128.3, 128.1, 128.0, 125.7, 54.2, 28.7, 15.6.
example 12
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 4-butylbenzene acetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-p-ethylphenyl-1, 2,3-triazole (1-benzyl-4- (4-butylphenyl) -1H-1,2, 3-triazole), the isolation yield is 84%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ(ppm): 7.70 (d, J = 8.2 Hz, 2H), 7.63 (s, 1H), 7.39 – 7.31 (m, 3H), 7.30 – 7.24 (m, 2H), 7.20 (d, J = 8.2 Hz, 2H), 5.53 (s, 2H), 2.68 – 2.51 (m, 2H), 1.59 (dq, J = 12.8, 7.5 Hz, 2H), 1.34 (dq, J = 14.6, 7.3 Hz, 2H), 0.90 (dt, J = 8.9, 4.6 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ(ppm): 148.3, 143.1, 134.8, 129.1, 128.9, 128.7, 128.0, 128.0, 125.6, 119.3, 54.2, 35.4, 33.6, 22.3, 14.0.
example 13
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 4-aminophenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-p-aminophenyl-1, 2,3-triazole (1-benzyl-4- (4-amino phenyl) -1H-1,2, 3-triazole) with an isolation yield of 95% and a purity of more than 95% as determined by nuclear magnetic resonance. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm):7.54 (s, 1H), 7.35 – 7.26 (m, 3H), 7.24 – 7.17 (m, 2H), 7.15 (s, 1H), 7.09 (t, J = 7.7 Hz, 1H), 7.02 (d, J = 7.7 Hz, 1H), 6.56 (d, J = 6.8 Hz, 1H), 5.48 (s, 2H), 3.67 (s, 2H).
13C NMR (101 MHz, CDCl3) δ (ppm):148.3, 146.9, 134.7, 131.5, 129.7, 129.2, 128.8, 128.1, 119.6 (, 116.0, 114.9, 112.2, 54.2.
example 14
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 4-methoxyphenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4-p-methoxyphenyl-1, 2,3-triazole (1-benzyl-4- (4-methoxyphenyl) -1H-1,2, 3-triazole), the isolation yield is 94%, and the purity of the product is more than 95% by nuclear magnetic assay. Nucleus of productThe magnetic data are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.76 – 7.68 (m, 2H), 7.58 (s, 1H), 7.41 – 7.33 (m, 3H), 7.30 (dd, J = 5.0, 2.6 Hz, 2H), 6.99 – 6.85 (m, 2H), 5.54 (s, 2H), 3.81 (s, 3H).
13C NMR (101 MHz, CDCl3) δ (ppm): 159.6, 148.1, 134.8, 129.1, 128.7, 128.1, 127.0, 123.3, 118.8, 114.2, 55.3, 54.2.
example 15
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of 3-fluoroacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-benzyl-4- (3-fluorophenyl) -1,2,3-triazole (1-benzyl-4- (3-fluorophenyl) -1H-1,2, 3-triazole), the isolation yield is 77%, the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm):7.70 (s, 1H), 7.57 – 7.49 (m, 2H), 7.40 – 7.33 (m, 3H), 7.33 – 7.27 (m, 2H), 7.03 – 6.93 (m, 1H), 5.55 (s, 2H).
13C NMR (101 MHz, CDCl3) δ (ppm): 164.4, 161.9, 147.1, 134.5, 132.74, 130.4, 129.2, 128.9, 128.1, 121.3, 120.0, 115.1, 114.8, 112.7, 112.5, 54.3.
example 16
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of benzyl azide, 1.2mmol of n-octyne and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. Washing the obtained crude product with n-hexane and water for several times to remove unreacted substrate, and drying at 60 deg.C to obtain targetThe product 1-benzyl-4-n-hexyl-1, 2,3-triazole (1-benzyl-4-hexyl-1H-1,2, 3-triazole), the isolation yield is 89%, the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.34 – 7.24 (m, 2H), 7.19 (ddd, J = 7.1, 5.1, 1.5 Hz, 2H), 7.12 (d, J = 7.4 Hz, 1H), 5.42 (s, 2H), 2.72 – 2.50 (m, 2H), 1.64 – 1.49 (m, 2H), 1.29 – 1.16 (m, 7H), 0.84 – 0.74 (m, 3H).
13C NMR (101 MHz, CDCl3) δ (ppm): 149.0, 135.0, 129.0, 128.6, 127.9, 120.5, 54.0, 33.5, 30.5, 29.1, 26.0, 22.5, 14.0.
example 17
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of 2-iodobenzyl azide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1- (2-iodobenzyl) -4-phenyl-1, 2,3-triazole (1- (2-iodophenyl) -4-phenyl-1H-1,2, 3-triazole), the isolation yield is 97%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.95 – 7.87 (m, 1H), 7.85 – 7.79 (m, 2H), 7.77 (s, 1H), 7.45 – 7.37 (m, 2H), 7.37 – 7.28 (m, 2H), 7.12 (dd, J = 7.7, 1.5 Hz, 1H), 7.06 (td, J = 7.7, 1.6 Hz, 1H), 5.66 (s, 2H).
13C NMR (101 MHz, CDCl3) δ (ppm): 148.2, 139.9, 137.4, 130.5, 129.6, 129.1, 128.9, 128.3, 125.8, 119.9, 98.7, 58.5.
example 18
In a Schlenk glass reaction flask with screw cap, 1.0mmol of 3-bromobenzylazide, 1.2mmol of phenylacetylene and 1mol% of minusSupported CNTs @ NHC-Cu catalyst (vs. benzyl azide). Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1- (3-bromobenzyl) -4-phenyl-1, 2,3-triazole (1- (3-bromophenyl) -4-phenyl-1H-1,2, 3-triazole), the isolation yield was 93%, and the product purity was more than 95% as determined by nuclear magnetic resonance. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.73 (dt, J = 8.2, 1.8 Hz, 2H), 7.67 (s, 1H), 7.63 – 7.55 (m, 2H), 7.40 – 7.22 (m, 5H), 5.57 (s, 2H).
13C NMR (101 MHz, CDCl3) δ (ppm): 148.7, 139.9, 132.9, 130.1, 128.9, 128.5, 128.4, 125.7, 119.7, 118.2, 112.8, 53.5.
example 19
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of 4-bromobenzylazide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to the benzylazide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1- (4-bromobenzyl) -4-phenyl-1, 2,3-triazole (1- (4-bromophenyl) -4-phenyl-1H-1,2, 3-triazole) with an isolation yield of 90% and a purity of more than 95% as determined by nuclear magnetic resonance. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.76 – 7.66 (m, 2H), 7.60 (d, J = 6.3 Hz, 1H), 7.48 – 7.36 (m, 2H), 7.36 – 7.27 (m, 2H), 7.26 – 7.15 (m, 1H), 7.09 (t, J = 5.4 Hz, 2H), 5.42 (s, 2H).
13C NMR (101 MHz, CDCl3) δ (ppm): 148.4, 133.7, 132.3, 130.4, 129.7, 128.9, 128.3, 125.7, 122.9, 119.6, 53.5.
example 20
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of 4-nitrile benzyl azide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 3h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by n-hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1- (4-nitrile benzyl) -4-phenyl-1, 2,3-triazole (1- (4-cyano phenyl) -4-phenyl-1H-1,2, 3-triazole), the isolation yield is 92%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ（ppm）: 7.74 (dd, J = 8.7, 7.4 Hz, 2H), 7.63 (s, 1H), 7.40 (dt, J = 13.9, 3.9 Hz, 2H), 7.34 (dd, J = 10.3, 4.7 Hz, 2H), 7.25 (t, J = 7.4 Hz, 1H), 7.21 – 7.10 (m, 2H), 5.48 (d, J = 13.7 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ (ppm):147.4 , 135.9, 130.9, 129.9, 129.7, 129.3, 127.8, 127.3, 125.5, 124.7, 122.1, 118.5, 52.4.
example 21
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of hexyl azide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 10 h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-hexyl-4-phenyl-1, 2,3-triazole (1-hexyl-4-phenyl-1H-1,2, 3-triazole), the isolation yield is 92%, and the purity of the product is more than 95% by nuclear magnetic assay. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.81 – 7.71 (m, 2H), 7.67 (s, 1H), 7.34 (dd, J = 10.4, 4.7 Hz, 2H), 7.28 – 7.21 (m, 1H), 4.29 (t, J = 7.3 Hz, 2H), 1.93 – 1.76 (m, 2H), 1.35 – 1.11 (m, 6H), 0.80 (t, J = 6.9 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ (ppm): 147.6 (s), 130.7(s), 128.8(s), 128.1 (s), 125.7(s), 119.5(s), 50.4 (s), 31.2 (s), 30.3 (s), 26.2(s), 22.4 (s), 14.0 (s).
example 22
Into a Schlenk glass reaction flask with screw cap, 1.0mmol of octyl azide, 1.2mmol of phenylacetylene and 1mol% of supported CNTs @ NHC-Cu catalyst (relative to benzyl azide) were added. Stirring and reacting for 10 h under the condition of not adding a solvent and the reaction temperature of 30 ℃, dissolving the product, filtering, and removing the solvent by rotary evaporation. The obtained crude product is washed by normal hexane and water for a plurality of times to remove unreacted substrates, and then is dried at 60 ℃ to obtain the target product 1-octyl-4-phenyl-1, 2,3-triazole (1-octyl-4-phenyl-1H-1,2, 3-triazole), the isolation yield was 93%, and the product purity was more than 95% as determined by nuclear magnetic resonance. The nuclear magnetic data of the product are as follows:
1H NMR (400 MHz, CDCl3) δ (ppm): 7.78 – 7.70 (m, 2H), 7.67 (s, 1H), 7.30 (dd, J = 10.4, 4.7 Hz, 2H), 7.24 – 7.17 (m, 1H), 4.24 (t, J = 7.3 Hz, 2H), 1.80 (p, J = 7.2 Hz, 2H), 1.37 – 1.03 (m, 10H), 0.77 (t, J = 6.8 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ (ppm): 147.6 (s), 130.8 (s), 128.8 (s), 128.0 (s), 125.9 (s), 125.6 (s), 119.6 (s), 50.4(s), 31.7 (s), 30.3 (s), 29.0 (d, J = 8.4 Hz), 26.5 (s), 22.6 (s), 14.1 (s), 1.0 (s).

Claims (6)

1. the application of the supported CNTs @ NHC-Cu catalytic material is characterized in that: the supported CNTs @ NHC-Cu catalytic material is used for catalyzing a Click cycloaddition reaction of an azide compound and a terminal alkyne compound to synthesize a 1, 4-disubstituted-1, 2,3-triazole compound; the dosage of the supported CNTs @ NHC-Cu catalytic material is 1% of that of the azide compound substance calculated by copper; the preparation method of the supported CNTs @ NHC-Cu comprises the following steps:
preparing 1- (2-bromoethoxy) pyrene:
1-hydroxypyrene and Cs2CO3Mixing the 1, 2-dibromoethane and acetonitrile, and then refluxing and stirring at 60-80 ℃ for 24 h; cooling to room temperature after the reaction is finished to obtain a reaction solution A; adding water with the volume 2-5 times that of the reaction solution A into the reaction solution A, and sequentially extracting with dichloromethane, drying with anhydrous magnesium sulfate, filtering, performing rotary evaporation and purifying to obtain the catalyst; the 1-hydroxypyrene and the Cs2CO3The molar ratio of the 1, 2-dibromoethane is 1: 2: 4;
preparing 1- (2- (pyrene-2-oxyl) ethyl) -1H benzo [ d ] imidazole:
mixing acetonitrile, benzimidazole and potassium hydroxide, refluxing for 30 minutes at 60-80 ℃, then adding the 1- (2-bromoethoxy) pyrene, and refluxing and stirring the obtained mixture for 24 hours at 60-80 ℃; cooling to room temperature after the reaction is finished to obtain a reaction solution B; adding n-hexane with the volume 2-5 times that of the reaction solution B into the reaction solution B, and sequentially filtering, washing and vacuum drying to obtain the catalyst; the molar ratio of the benzimidazole to the potassium hydroxide to the 2- (2-bromoethoxy) pyrene is 1: 1.2: 1;
preparing 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide:
mixing the 1- (2- (pyrene-2-oxy) ethyl) -1H benzo [ d ] imidazole, acetonitrile and benzyl bromide, and then refluxing and stirring at 60-80 ℃ for 24 hours; cooling to room temperature after the reaction is finished to obtain a reaction solution C; adding n-hexane with the volume 2-5 times that of the reaction solution C into the reaction solution C, and sequentially filtering, washing and vacuum drying to obtain the catalyst; the molar ratio of the 1- (2- (pyrene-2-oxy) ethyl) -1H benzo [ d ] imidazole to the benzyl bromide is 1: 1.1;
preparing a benzimidazolyl nitrogen heterocyclic carbene copper metal complex:
under the protection of nitrogen, mixing the 3-benzyl-1- (2- (pyrene-2-oxyl) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide, cuprous iodide, sodium tert-butoxide and tetrahydrofuran, and stirring to react for 4 hours at room temperature to obtain a suspension; filtering, washing and rotary steaming the suspension liquid in sequence to obtain a saturated filtrate; adding n-hexane with the volume of 3-8 times of the filtrate, and sequentially filtering, washing and vacuum drying to obtain the filtrate; the molar ratio of the 3-benzyl-1- (2- (pyrene-2-oxy) ethyl) -1H-benzo [ d ] imidazole-3-ammonium bromide to the cuprous iodide to the sodium tert-butoxide is 1: 1: 1;
preparing a carbon nanotube solution:
mixing the carbon nano tube with a dichloromethane solution, and performing ultrasonic dispersion to obtain a solution with the concentration of 6 g/mL;
sixthly, preparing a supported CNTs @ NHC-Cu catalytic material:
dissolving the benzimidazolyl N-heterocyclic carbene copper metal complex in dichloromethane to obtain a mixed solution with the concentration of 2.4 g/mL, dropwise adding the mixed solution into the carbon nanotube solution, stirring overnight, filtering and washing to obtain the benzimidazolyl N-heterocyclic carbene copper metal complex; the volume ratio of the mixed solution to the carbon nanotube solution is 1: 1 to 5.
2. The application of the supported CNTs @ NHC-Cu catalytic material as claimed in claim 1, wherein: the structural formula of the azide compound is as follows:
Figure DEST_PATH_IMAGE001
(ii) a Wherein R is1Is one of phenyl, 2-iodophenyl, 3-bromophenyl, 4-acetonitrile phenyl, n-hexyl and n-octyl.
3. The application of the supported CNTs @ NHC-Cu catalytic material as claimed in claim 1, wherein: the structural formula of the terminal alkyne is as follows:
Figure 305264DEST_PATH_IMAGE002
(ii) a In the formula R2Is one of phenyl, 4-methoxyphenyl, 3-methylphenyl, 4-ethylphenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-fluorophenyl, 4-hexyloxyphenyl, n-pentyl and n-hexyl.
4. The application of the supported CNTs @ NHC-Cu catalytic material as claimed in claim 1, wherein: the "Click" cycloaddition reaction is solvent-free.
5. The application of the supported CNTs @ NHC-Cu catalytic material as claimed in claim 1, wherein: in the "Click" cycloaddition reaction, a reaction solvent is added, wherein the reaction solvent is one of toluene, tetrahydrofuran, acetonitrile, methanol and water.
6. The application of the supported CNTs @ NHC-Cu catalytic material as claimed in claim 1, wherein: the reaction temperature in the Click cycloaddition reaction is 20-60 ℃, and the reaction time is 2-10 h.
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