CN109438375B - Preparation method of 4, 5-diphenyl substituted triazole compound - Google Patents
Preparation method of 4, 5-diphenyl substituted triazole compound Download PDFInfo
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- CN109438375B CN109438375B CN201811508253.4A CN201811508253A CN109438375B CN 109438375 B CN109438375 B CN 109438375B CN 201811508253 A CN201811508253 A CN 201811508253A CN 109438375 B CN109438375 B CN 109438375B
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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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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Abstract
The invention relates to a preparation method of a 4, 5-diphenyl substituted triazole compound, which comprises the following steps:
reacting the compound of the formula I with anhydrous hydrazine at the reflux temperature in anhydrous ethanol for 5-6 hours, adding benzonitrile and the biochar-loaded base, and continuing the reflux reaction for 4-5 hours to obtain a 4, 5-diphenyl-substituted triazole compound with a structure II; wherein R is1Selected from C1-C3 alkyl, C1-C3 alkoxy, halogen and the like, and n is an integer of 0-5; the mol ratio of the compound of the formula I, the anhydrous hydrazine and the benzonitrile is 1:1.2-1.5: 0.8-1.0; the amount of biochar-supported base is 10-15mg biochar-supported base per millimole of compound of formula I.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a 4, 5-diphenyl substituted triazole compound.
Background
Triazole structure is an important group in bioactive compounds, and is an important structure of numerous chemical and medical intermediates. Triazole compounds show various biological activities in the aspects of medicines, pesticides and the like, particularly in the aspect of agricultural fungicides, and more than 20 triazole fungicides which are commercialized at present are available. The synthesis method of the triazole compound mainly comprises the following steps: (1) alkyne reacts with sodium azide for preparation; (2) benzaldehyde, nitromethane and sodium azide. The methods all need explosive sodium azide and have harsh reaction conditions. Therefore, it is difficult to develop a method for preparing triazole compounds without using sodium azide.
Disclosure of Invention
The invention provides a preparation method of a 4, 5-diphenyl substituted triazole compound with a structure shown in formula II, which is characterized by comprising the following steps:
reacting the compound of the formula I with anhydrous hydrazine at the reflux temperature in anhydrous ethanol for 5-6 hours, adding benzonitrile and biochar loaded alkali, and continuing the reflux reaction for 4-5 hours to obtain a 4, 5-diphenyl substituted triazole compound with a structure II; wherein R is1Selected from C1-C3 alkyl, C1-C3 alkoxy, halogen and the like, and n is an integer of 0-5;
the mol ratio of the compound of the formula I, the anhydrous hydrazine and the benzonitrile is 1:1.2-1.5: 0.8-1.0; the amount of biochar-supported base is 10-15mg biochar-supported base per millimole of compound of formula I.
The preparation method of the biochar supported alkali comprises the following steps:
(1) cleaning folium Ginkgo, drying to constant weight, and adding into N2In the presence of the carbon, the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for carbonization for 3 hours, and then the temperature is reduced to room temperature to obtain the biochar;
(2) and (2) soaking the biochar obtained in the step (1) in alkali liquor for 12 hours, washing with water, and drying to obtain the biochar loaded alkali.
In the step (2), the alkali liquor is selected from an aqueous solution of alkali metal hydroxide, and the concentration of the alkali liquor is 4-6 mol/L; the alkali metal hydroxide is preferably one or more of sodium hydroxide, potassium hydroxide and cesium hydroxide. The dosage of the alkali liquor is proper to be capable of fully soaking, and 10-15mL of alkali liquor is preferably used per gram of biochar.
In another embodiment the present invention provides a process for the preparation of a compound of formula II as described above, characterized in that n is 0.
Another embodiment of the present invention provides a process for the preparation of a compound of formula II as described above, characterized in that n is 1 or 2, R1Is methyl, methoxy or halogen.
Another embodiment of the present invention provides a method for preparing 4, 5-diphenyl-2H-1, 2, 3-triazole, characterized by comprising the steps of:
dissolving benzaldehyde in absolute ethyl alcohol, adding anhydrous hydrazine, heating to reflux temperature for reaction for 5-6 hours, adding benzonitrile and the biochar-loaded alkali, and continuing reflux reaction for 4-5 hours to obtain 4, 5-diphenyl-2H-1, 2, 3-triazole.
The molar ratio of benzaldehyde, anhydrous hydrazine and benzonitrile is 1:1.2-1.5: 0.8-1.0; the amount of biochar-supported base is 10-15mg biochar-supported base per millimole of benzaldehyde.
Compared with the prior art, the invention has the advantages that: the biochar supported base obtained by the invention can be used as a catalyst for catalyzing optionally substituted benzaldehyde, anhydrous hydrazine and benzonitrile to synthesize the 4, 5-diphenyl substituted triazole compound, provides a new thought for the synthesis of the triazole compound, and avoids using explosive azide.
Drawings
FIG. 1 is an SEM image of product A;
fig. 2 is a diagram of HRMS of example 3.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1 preparation of biochar-supported base
(1) Cleaning folium Ginkgo (200g), drying to constant weight, and adding into N2In the presence of the carbon, the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for carbonization for 3 hours, and then the temperature is reduced to room temperature to obtain the biochar;
(2) and (2) soaking 10g of the biochar obtained in the step (1) in a sodium hydroxide solution (6mol/L, 100mL) for 12 hours, washing with water, and drying to obtain the biochar-loaded alkali (hereinafter referred to as a product A, shown in figure 1).
Example 2
The biochar (10g) obtained in the step (1) in the example 1 is soaked in potassium hydroxide solution (4mol/L, 150mL) for 12 hours, washed with water and dried to obtain biochar-supported alkali (hereinafter referred to as product B, which is consistent with the figure 1).
EXAMPLE 34 preparation of 5-Diphenyl-2H-1, 2, 3-triazole
Benzaldehyde (2mmol) is dissolved in absolute ethyl alcohol (20mL), anhydrous hydrazine (2.4mmol) is added, after the mixture is heated to the reflux temperature for reaction for 6 hours, benzonitrile (1.6mmol) and a product A (20mg) are added, after the reflux reaction is continued for 5 hours, the product A is recovered by filtration, after the filtrate is concentrated, the filtrate is diluted by chloroform and washed by water and saturated sodium chloride in turn, dried by anhydrous sodium sulfate, filtered and concentrated, and then is subjected to silica gel column chromatography (200-300 mesh silica gel) and petroleum ether/ethyl acetate (15:1-10:1) is used as an eluent, so that 329mg of a white solid, namely the 4, 5-diphenyl-2H-1, 2, 3-triazole compound is obtained, and the yield is about 92.9 percent.1H NMR(CDCl3,400MHz),:12.82(br s,1H),7.54(d,J＝3.3Hz,4H),7.38-7.36(m,6H).13C NMR(CDCl3100MHz), 142.8,130.4,128.7,128.6,128.3 HRMS (as shown in figure 2).
Example preparation of 44- (3-bromophenyl) -5-phenyl-2H-1, 2, 3-triazole
Dissolving m-bromobenzaldehyde (1.0mmol) in absolute ethyl alcohol (15mL), adding anhydrous hydrazine (1.5mmol), heating to reflux temperature for reaction for 5 hours, adding benzonitrile (1.0mmol) and product B (15mg), continuing to reflux for reaction for 4 hours, filtering and recovering product B, concentrating the filtrate, diluting with chloroform, washing with water and saturated sodium chloride in sequence, drying with anhydrous sodium sulfate, filtering, concentrating, performing silica gel column chromatography (200-mesh silica gel with 300 meshes), and using petroleum ether/ethyl acetate (15:1-10:1) as an eluent to obtain solid 268mg, namely 4- (3-bromophenyl) -5-phenyl-2H-1, 2, 3-triazole with the yield of about 89.3%.1H NMR(CDCl3,400MHz),:7.76(s,1H),7.55-7.39(m,4H),7.36-7.34(m,3H),7.20-7.17(m,1H).13C NMR(CDCl3,100MHz),:132.3,131.6,131.1 130.2,129.2.HRMS Calcd(ESI)m/z forC14H10BrN3:[M+H]+300.0131,found:300.0125,[M+2+H]+302.0111,found:302.0106.
Example 5
Benzaldehyde (2mmol) is dissolved in absolute ethyl alcohol (20mL), anhydrous hydrazine (2.4mmol) is added, after the mixture is heated to the reflux temperature for reaction for 6 hours, benzonitrile (1.6mmol) is added, after the reflux reaction is continued for 5 hours, TLC detection shows that no 4, 5-diphenyl-2H-1, 2, 3-triazole compound is generated.
Claims (3)
1. A preparation method of a 4, 5-diphenyl substituted triazole compound with a structure shown in a formula II is characterized by comprising the following steps:
reacting the compound of the formula I with anhydrous hydrazine at the reflux temperature in anhydrous ethanol for 5-6 hours, adding benzonitrile and biochar loaded alkali, and continuing the reflux reaction for 4-5 hours to obtain a 4, 5-diphenyl substituted triazole compound with a structure II; wherein R is1Selected from C1-C3 alkyl, C1-C3 alkoxy and halogen, n is an integer of 0-5;
the mol ratio of the compound of the formula I, the anhydrous hydrazine and the benzonitrile is 1:1.2-1.5: 0.8-1.0;
the amount of biochar-supported base is 10-15mg biochar-supported base per millimole of compound of formula I;
the preparation method of the biochar loaded alkali comprises the following steps:
(1) cleaning folium Ginkgo, drying to constant weight, and adding into N2In the presence of the carbon, the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for carbonization for 3 hours, and then the temperature is reduced to room temperature to obtain the biochar;
(2) soaking the biochar obtained in the step (1) in alkali liquor for 12 hours, washing with water, and drying to obtain biochar loaded alkali; the alkali liquor is selected from an aqueous solution of alkali metal hydroxide, and the concentration of the alkali liquor is 4-6 mol/L; the alkali metal hydroxide is selected from one or more of sodium hydroxide, potassium hydroxide and cesium hydroxide.
2. The method of claim 1, wherein n is 0.
3. The process according to claim 1, wherein n is 1 or 2, R1Is methyl, methoxy or halogen.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009086303A2 (en) * | 2007-12-21 | 2009-07-09 | University Of Rochester | Method for altering the lifespan of eukaryotic organisms |
| CN103030680A (en) * | 2011-09-28 | 2013-04-10 | 李守明 | Novel anti-hepatitis C virus inhibitor and preparation method thereof |
| CN108794412A (en) * | 2018-09-10 | 2018-11-13 | 海南师范大学 | A kind of preparation method of 4,5- diaryl -2H-1,2,3- triazole compounds |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009086303A2 (en) * | 2007-12-21 | 2009-07-09 | University Of Rochester | Method for altering the lifespan of eukaryotic organisms |
| CN103030680A (en) * | 2011-09-28 | 2013-04-10 | 李守明 | Novel anti-hepatitis C virus inhibitor and preparation method thereof |
| CN108794412A (en) * | 2018-09-10 | 2018-11-13 | 海南师范大学 | A kind of preparation method of 4,5- diaryl -2H-1,2,3- triazole compounds |
Non-Patent Citations (1)
| Title |
|---|
| "Transition Metal, Azide, and Oxidant-Free Homo- and Heterocoupling of Ambiphilic Tosylhydrazones to the Regioselective Triazoles and Pyrazoles";Subhankar Panda et al.,;《Org. Lett.》;20170324;第19卷;1534-1537 * |
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