CN109485611A - A kind of preparation method of triazole derivatives - Google Patents

A kind of preparation method of triazole derivatives Download PDF

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Publication number
CN109485611A
CN109485611A CN201811618082.0A CN201811618082A CN109485611A CN 109485611 A CN109485611 A CN 109485611A CN 201811618082 A CN201811618082 A CN 201811618082A CN 109485611 A CN109485611 A CN 109485611A
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preparation
triazole derivatives
reaction
added
aminophenol
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毕晶晶
张继昊
谭强
李青
李颖
黄心洁
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Henan Normal University
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Henan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of preparation methods of triazole derivatives, the described method includes: using arylsulfonyl azido derivant and acetylene-derivative as raw material, cuprous iodide and o-aminophenol are that triazole derivatives are prepared by cyclization under the conditions of aprotic polar solvent in catalyst.The preparation method reaction substrate universality of triazole derivatives of the present invention is wide, and reaction condition is mild, easy to operate, high income.

Description

A kind of preparation method of triazole derivatives
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of triazole derivatives.
Background technique
Triazole derivatives are shown as a kind of very valuable 5-member heterocyclic ring containing nitrogen skeleton due to its complex Excellent optics, antiseptic property, are applied to the neighborhoods such as organic catalysis, material science extensively.In addition, triazole derivatives table The good bioactivity revealed also has important purposes in pharmacy industry, pesticide.Therefore, the conjunction of triazole compound It is had received widespread attention at application.
Till now, researcher has discovered that the synthetic method of many triazole compounds, but most of The step of synthetic method, is cumbersome, and reaction condition is complicated, low yield.Therefore, it is necessary to which to research and develop a kind of reaction substrate universality wide, Reaction condition mild, easy to operate, high income method is effectively synthesized triazole derivative compound.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of triazole derivatives, reaction substrate universality is wide, instead Answer mild condition, easy to operate, high income.
In order to achieve the above purpose, technical scheme is as follows:
A kind of preparation method of triazole derivatives, comprising the following steps:
Using arylsulfonyl azido derivant and acetylene-derivative as raw material, cuprous iodide and o-aminophenol are catalyst, Under the conditions of aprotic polar solvent, triazole derivatives are prepared by cyclization；
Wherein, the general structure of the arylsulfonyl azido derivant is as follows:
Ar is selected from substituted aromatic base, and the aromatic radical includes but is not limited to phenyl, substituted-phenyl, naphthalene, substituted naphthyl, thiophene Pheno base, substituted thiophene base；
The general structure of the acetylene-derivative is as follows:
R1Selected from alkyl, aromatic radical, the aromatic radical include but is not limited to phenyl, substituted-phenyl, naphthalene, substituted naphthyl, Thienyl, substituted thiophene base；
The general structure of the triazole derivatives is as follows:
Preferably, the structure of the arylsulfonyl azido derivant is as follows in above-mentioned technical proposal:
Preferably, the structure of the acetylene-derivative is as follows in above-mentioned technical proposal:
Preferably, the reaction dissolvent is acetonitrile in above-mentioned technical proposal.
Preferably, the reaction temperature is room temperature in above-mentioned technical proposal.
Preferably, the additional amount of the catalyst o-aminophenol is 5%-20%, described to urge in above-mentioned technical proposal The additional amount of agent cuprous iodide is 5%-20%.
Preferably, the additional amount of the catalyst o-aminophenol is 5%, the catalyst in above-mentioned technical proposal It is 10% that the amount of cuprous iodide, which enters amount,.
According to the preparation method of above-mentioned triazole derivatives, the triazole that inventor has been synthetically prepared such as flowering structure is derivative Object:
Compared with the prior art, the invention has the following beneficial effects: the present invention by copper be catalyzed aryl azide chemical combination object and The method that alkynes carries out cycloaddition synthesizes 1,2,3- triazole compounds, and this method has reaction substrate universality wide, reacts item The advantages that part is mild, easy to operate, high income.
Specific embodiment
The present invention is clearly and completely described below by specific embodiment, it is clear that described embodiment is only It is a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, this neighborhood ordinary skill people Member's every other embodiment obtained, belongs to protection scope of the present invention.
The preparation of compound 1:
Embodiment 1
It will be to Methyl benzenesulfonyl nitrine (1.0mmol), phenylacetylene (1.1mmol), o-aminophenol (0.2mmol), iodate Cuprous (0.1mmol), it is dissolved in 1mL acetonitrile, reacts at room temperature 3h, 2mL saturated ammonium chloride quenching reaction is added, water is added Organic phase is collected in 30mL, methylene chloride 40mL × 3 extraction, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes solvent, through silicagel column Chromatography obtains white solid, yield 32%.
1H NMR (400MHz, CDCl3): δ 8.32 (s, 1H), 8.03 (d, J=8.4Hz, 2H), 7.82 (d, J=7.2Hz, 2H),7.45–7.38(m,5H),2.44(s,3H)。
Embodiment 2
It will be to Methyl benzenesulfonyl nitrine (1.0mmol), phenylacetylene (1.1mmol), o-aminophenol (0.1mmol), iodate Cuprous (0.1mmol), it is dissolved in 1mL acetonitrile, reacts at room temperature 3h, 2mL saturated ammonium chloride quenching reaction is added, water is added Organic phase is collected in 30mL, methylene chloride 40mL × 3 extraction, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes solvent, through silicagel column Chromatography obtains white solid, yield 38%.
Embodiment 3
It will be to Methyl benzenesulfonyl nitrine (1.0mmol), phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), iodate Cuprous (0.1mmol), it is dissolved in 1mL acetonitrile, reacts at room temperature 3h, 2mL saturated ammonium chloride quenching reaction is added, water is added Organic phase is collected in 30mL, methylene chloride 40mL × 3 extraction, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes solvent, through silicagel column Chromatography obtains white solid, yield 75%.
Embodiment 4
It will be to Methyl benzenesulfonyl nitrine (1.0mmol), phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), iodate Cuprous (0.2mmol), it is dissolved in 1mL acetonitrile, reacts at room temperature 3h, 2mL saturated ammonium chloride quenching reaction is added, water is added Organic phase is collected in 30mL, methylene chloride 40mL × 3 extraction, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes solvent, through silicagel column Chromatography obtains white solid, yield 60%.
Embodiment 5
It will be to Methyl benzenesulfonyl nitrine (1.0mmol), phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), iodate Cuprous (0.05mmol), it is dissolved in 1mL acetonitrile, reacts at room temperature 3h, 2mL saturated ammonium chloride quenching reaction is added, water is added Organic phase is collected in 30mL, methylene chloride 40mL × 3 extraction, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes solvent, through silicagel column Chromatography obtains white solid, yield 30%.
The preparation of 6 compound 2 of embodiment
By 4- Methoxy-phenylacetylene (1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to methyl Benzenesulfonyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in saturated ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, Vacuum rotary steam removes solvent, separates to obtain white solid, yield 90% through silica gel column chromatography.
1H NMR (600MHz, CDCl3): δ 8.21 (s, 1H), 8.02 (d, J=8.4Hz, 2H), 7.75 (d, J=8.8Hz, 2H), 7.38 (d, J=8.4Hz, 2H), 6.95 (d, J=8.8Hz, 2H), 3.84 (s, 3H), 2.45 (s, 3H).
The preparation of 7 compound 3 of embodiment
By positive octyne (1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), p-toluene sulfonyt azide (2mmol) is dissolved in 1mL acetonitrile, and for 24 hours, 2mL saturated ammonium chloride is added after completion of the reaction and quenches for contact plate monitoring reaction for room temperature reaction It goes out reaction, water 30mL is added, methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes Solvent, through the isolated colourless transparent liquid yield 20% of silica gel column chromatography.
1H NMR (400MHz, CDCl3): δ 7.97 (d, J=8.4Hz, 2H), 7.83 (s, 1H), 7.36 (d, J=8.4Hz, 2H), 2.69 (t, J=8.0Hz, 2H), 2.44 (s, 3H), 1.65-1.62 (m, 2H), 1.31-1.25 (m, 6H), 0.86 (t, J= 7.2Hz,3H)。
The preparation of 8 compound 4 of embodiment
By 3- Methoxy-phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to first Benzenesulfonyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in saturated ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, Vacuum rotary steam removes solvent, through the isolated white solid 286mg of silica gel column chromatography, yield 87%.
1H NMR (600MHz, CDCl3): δ 8.30 (s, 1H), 8.02 (d, J=8.4Hz, 2H), 7.41-7.33 (m, 5H), 6.91(m,1H),3.85(s,3H),2.44(s,3H)。
The preparation of 9 compound 5 of embodiment
By 2- chlorobenzene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 2h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 70%.
1H NMR (600MHz, CDCl3): δ 8.74 (s, 1H), 8.20 (dd, J=7.8Hz, 1.2Hz, 1H), 8.04 (d, J =7.8Hz, 2H), 7.46 (d, J=7.8Hz, 1H), 7.40 (d, J=8.4Hz, 2H), 7.36 (t, J=7.8Hz, 1H), 7.30 (t, J=7.8Hz, 1H), 2.45 (s, 3H).
The preparation of 10 compound 6 of embodiment
By 3- chlorobenzene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 75%.
1H NMR (400MHz, CDCl3): δ 8.33 (s, 1H), 8.03 (d, J=8.4Hz, 2H), 7.82 (s, 1H), 7.70 (dt, J=7.2,1.6Hz, 1H), 7.40 (m, 2H), 7.34 (m, 2H), 2.45 (s, 3H).
The preparation of 11 compound 7 of embodiment
By 4- fluorobenzene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 75%.
1H NMR (600MHz, CDCl3): δ 8.27 (s, 1H), 8.03 (d, J=8.4Hz, 2H), 7.80 (dd, J=8.4, 5.4Hz, 2H), 7.39 (d, J=8.4Hz, 2H), 7.12 (t, J=9.0Hz, 2H), 2.45 (s, 3H).
The preparation of 12 compound 8 of embodiment
By 4- chlorobenzene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 87%.
1H NMR (600MHz, CDCl3): δ 8.30 (s, 1H), 8.03 (d, J=8.4Hz, 2H), 7.76 (d, J=9.0Hz, 2H), 7.41 (dd, J=8.4 5.4Hz, 4H), 2.45 (s, 3H).
The preparation of 13 compound 9 of embodiment
By 3- fluorobenzene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 70%.
1H NMR (400MHz, CDCl3): δ 8.32 (s, 1H), 8.03 (d, J=8.0Hz, 2H), 7.59-7.54 (m, 2H), 7.39 (d, J=8.0Hz, 3H), 7.06 (t, J=8.0Hz, 1H), 2.45 (s, 3H).
The preparation of 14 compound 10 of embodiment
By 4- bromobenzene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 85%.
1H NMR (600MHz, CDCl3): δ 8.31 (s, 1H), 8.02 (d, J=8.4Hz, 2H), 7.70 (d, J=8.4Hz, 2H), 7.56 (d, J=8.4Hz, 2H), 7.39 (d, J=8.4Hz, 2H), 2.45 (s, 3H).
The preparation of 15 compound 11 of embodiment
By 4- trifluoromethyl phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), right Tosyl nitrine (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 12h, and contact plate monitoring reaction is added after completion of the reaction Water 30mL is added in 2mL saturated ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry Dry, vacuum rotary steam removes solvent, through the isolated white solid of silica gel column chromatography, yield 40%.
1H NMR (400MHz, CDCl3): δ 8.40 (s, 1H), 8.04 (d, J=8.4Hz, 2H), 7.95 (d, J=8.1Hz, 2H), 7.69 (d, J=8.4Hz, 2H), 7.41 (d, J=8.2Hz, 2H), 2.46 (s, 3H).
The preparation of 16 compound 12 of embodiment
By 4- methyl phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene Sulfonyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and it is full that 2mL is added in contact plate monitoring reaction after completion of the reaction With ammonium chloride quenching reaction, water 30mL is added, methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, subtracts Pressure revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 90%.
1H NMR (400MHz, CDCl3): δ 8.26 (s, 1H), 8.02 (d, J=8.0Hz, 2H), 7.71 (d, J=7.6Hz, 2H), 7.39 (d, J=8.4Hz, 2H), 7.23 (d, J=8.0Hz, 2H), 2.45 (s, 3H), 2.38 (s, 3H).
The preparation of 17 compound 13 of embodiment
By 3- thiophene acetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 70%.
1H NMR (400MHz, CDCl3): δ 8.20 (s, 1H), 8.01 (d, J=8.0Hz, 2H), 7.75 (s, 1H), 7.40- 7.37(m,4H),2.44(s,3H)。
The preparation of 18 compound 14 of embodiment
By 3- methyl phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to toluene Sulfonyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and it is full that 2mL is added in contact plate monitoring reaction after completion of the reaction With ammonium chloride quenching reaction, water 30mL is added, methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, subtracts Pressure revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 89%.
1H NMR (600MHz, CDCl3): δ 8.29 (s, 1H), 8.02 (d, J=8.4Hz, 2H), 7.66 (s, 1H), 7.60 (d, J=7.8Hz, 1H), 7.39 (d, J=8.4Hz, 2H), 7.31 (t, J=7.8Hz, 1H), 7.18 (d, J=7.8Hz, 1H), 2.45(s,3H),2.39(s,3H)。
The preparation of 19 compound 15 of embodiment
By phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to methoxybenzene sulphur Acyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturation is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in ammonium chloride quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression Revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 85%.
1H NMR (400MHz, CDCl3): δ 8.31 (s, 1H), 8.08 (d, J=9.2Hz, 2H), 7.82 (d, J=6.8Hz, 2H), 7.43 (t, J=7.2Hz, 2H), 7.37 (d, J=7.2Hz, 1H), 7.03 (d, J=9.2Hz, 2H), 3.88 (s, 3H).
The preparation of 20 compound 16 of embodiment
By phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), o-methyl-benzene sulphonyl Nitrine (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL is added after completion of the reaction and is saturated chlorine for contact plate monitoring reaction Change ammonium quenching reaction, water 30mL is added, methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, decompression rotation Solvent is evaporated off, through the isolated white solid of silica gel column chromatography, yield 75%.
1H NMR (600MHz, CDCl3): δ 8.36 (s, 1H), 8.25 (d, J=7.8Hz, 1H), 7.84 (d, J=7.2Hz, 2H), 7.61 (t, J=7.2Hz, 1H), 7.46-7.43 (m, 3H), 7.38 (q, J=13.8 7.2Hz, 2H), 2.70 (s, 3H).
The preparation of 21 compound 17 of embodiment
Phenylacetylene (1.1mmol), adjacent aminobenzene (0.05mmol), cuprous iodide (0.1mmol), Methyl benzenesulfonyl is folded Nitrogen (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL is added after completion of the reaction and is saturated chlorination for contact plate monitoring reaction Water 30mL is added in ammonium quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, anhydrous sodium sulfate is dry, vacuum rotary steam Solvent is removed, through the isolated white solid of silica gel column chromatography, yield 80%.
1H NMR (600MHz, CDCl3): δ 8.33 (s, 1H), 7.95-7.93 (d, J=12.0Hz 2H), 7.83 (d, J= 7.8Hz, 2H), 7.51 (d, J=7.8Hz, 1H), 7.47 (t, J=7.8Hz, 1H), 7.43 (t, J=7.8Hz, 2H), 7.37 (t, J=7.2Hz, 1H), 2.44 (s, 3H).
The preparation of 22 compound 18 of embodiment
Phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), 2- thiophenesulfonyl is folded Nitrogen (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 3h, and 2mL is added after completion of the reaction and is saturated chlorination for contact plate monitoring reaction Water 30mL is added in ammonium quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, anhydrous sodium sulfate is dry, vacuum rotary steam Solvent is removed, through the isolated white solid of silica gel column chromatography, yield 70%.
1H NMR (600MHz, CDCl3): δ 8.33 (s, 1H), 8.03 (m, 1H), 7.86-7.84 (m, 3H), 7.45 (t, J =7.2Hz, 2H), 7.39 (t, J=7.8Hz, 1H), 7.20 (t, J=4.2Hz, 1H).
The preparation of 23 compound 19 of embodiment
By phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), 1- naphthalene sulfonyl nitrine (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 3h, and 2mL saturated ammonium chloride is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes Solvent is removed, through the isolated white solid of silica gel column chromatography, yield 60%.
1H NMR (600MHz, CDCl3) δ 8.88 (d, J=8.4Hz, 1H), 8.65 (d, J=7.8Hz, 1H), 8.41 (s, 1H), 8.23 (d, J=7.8Hz, 1H), 7.96 (d, J=7.8Hz, 1H), 7.80 (d, J=7.2Hz, 2H), 7.75 (t, J= 7.8Hz, 1H), 7.67 (t, J=7.8Hz, 1H), 7.63 (t, J=7.8Hz, 1H), 7.42 (t, J=7.8Hz, 2H), 7.36 (t, J=7.8Hz, 1H).
The preparation of 24 compound 20 of embodiment
By phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), benzenesulfonyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and 2mL saturated ammonium chloride is added in contact plate monitoring reaction after completion of the reaction Water 30mL is added in quenching reaction, and methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, and vacuum rotary steam removes Solvent is removed, separates to obtain white solid, yield 85% through silica gel column chromatography.
1H NMR (400MHz, CDCl3): δ 8.33 (s, 1H), 8.16 (d, J=8.4Hz, 2H), 7.83 (d, J=6.8Hz, 2H), 7.73 (t, J=7.6Hz, 1H), 7.61 (t, J=8.0Hz, 2H), 7.51-7.32 (m, 3H).
The preparation of 25 compound 21 of embodiment
By phenylacetylene (1.1mmol), o-aminophenol (0.05mmol), cuprous iodide (0.1mmol), to Ethyl formate benzene Sulfonyl azide (1.0mmol) is dissolved in 1mL acetonitrile, reacts at room temperature 1h, and it is full that 2mL is added in contact plate monitoring reaction after completion of the reaction With ammonium chloride quenching reaction, water 30mL is added, methylene chloride 40mL × 3 is extracted, and collects organic phase, and anhydrous sodium sulfate is dry, subtracts Pressure revolving removes solvent, through the isolated white solid of silica gel column chromatography, yield 41%.
1H NMR (400MHz, CDCl3): δ 8.34 (s, 1H), 8.26-8.21 (m, 4H), 7.82 (d, J=6.8Hz, 2H), 7.46-7.38 (m, 3H), 4.41 (q, J=7.2Hz, 2H), 1.40 (t, J=7.2Hz, 3H).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, all any modification, equivalent substitution, improvement and etc. be should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of triazole derivatives, which comprises the following steps:
Using arylsulfonyl azido derivant and acetylene-derivative as raw material, cuprous iodide and o-aminophenol are catalyst, non- Under the conditions of proton polar solvent, triazole derivatives are prepared by cyclization；
Wherein, the general structure of the arylsulfonyl azido derivant is as follows:
Ar is selected from substituted aromatic base, and the aromatic radical includes but is not limited to phenyl, substituted-phenyl, naphthalene, substituted naphthyl, thiophene Base, substituted thiophene base；
The general structure of the acetylene-derivative is as follows:
R1Selected from alkyl, aromatic radical, the aromatic radical includes but is not limited to phenyl, substituted-phenyl, naphthalene, substituted naphthyl, thiophene Base, substituted thiophene base；
The general structure of the triazole derivatives is as follows:
2. the preparation method of triazole derivatives as described in claim 1, which is characterized in that the arylsulfonyl nitrine is derivative The structure of object is as follows:
3. the preparation method of triazole derivatives as described in claim 1, which is characterized in that the structure of the acetylene-derivative It is as follows:
4. the preparation method of triazole derivatives as described in claim 1, which is characterized in that the reaction dissolvent is acetonitrile.
5. the preparation method of triazole derivatives as described in claim 1, which is characterized in that the reaction temperature is room temperature.
6. the preparation method of triazole derivatives as described in claim 1, which is characterized in that the catalyst o-aminophenol Additional amount be 5%-20%, the additional amount of the catalyst cuprous iodide is 5%-20%.
7. the preparation method of triazole derivatives as described in claim 1, which is characterized in that the catalyst o-aminophenol Additional amount be 5%, the amount of the catalyst cuprous iodide enter amount be 10%.
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