CN102603660B - Preparation method of 1H-1,2,3-triazole compound - Google Patents
Preparation method of 1H-1,2,3-triazole compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a 1H-1,2,3-triazole compound as shown in a formula (I), which comprises the following steps: mixing halide as shown in a formula (III) with alkyne-terminated compound as shown in a formula (II) and sodium azide, reacting for 5-85 hours at 25-80 DEG C in a reaction solvent under the catalytic action of porous copper; after finishing the reaction, performing after-treatment of the reaction solution to obtain the 1H-1,2,3-triazole compound as shown in the formula (I), wherein the solvent is de-ionized water, acetonitrile, anhydrous ethanol, toluene, acetone, N,N-dimethylformamide, tetrahydrofuran or dioxane. The preparation method provided by the invention adopts one-pot operation, the catalyst can be reused for multiple times, the reaction condition is mild, and the operation is easy and simple.
Description
(1) technical field
The present invention relates to a kind of 1H-1, the preparation method of 2,3-triazole compounds.
(2) background technology
1H-1,2,3-triazole class compounds, as important industrial chemicals intermediate, is widely used in the synthetic field such as agricultural chemicals, medicine.About 1H-1,2, up to the present the synthetic method of 3-triazole class compounds is reported less: 1. by polystyrene sulfonyl hydrazide and 1, the effect of 1-Dichloro acetone, obtains the chloroformyl sulphonyl hydrazone of α-bis-, then prepares (Makam S.Raghavendra and Yulin Lam with amine through cyclic action, Tetrahedron Letters, 2004,45,6129-6132).2. the click reaction of carrying out 1,3-dipole-ring addition (CuACC) by copper catalysis alkynes/trinitride is prepared (Christian W.
caspar Christensen, and Morten Melda.J.Org.Chem, 2002,67,3057-3064).3. take aniline as raw material, by the diazo transfer of copper (II) catalysis, then under the reductive action of sodium ascorbate, 1 of copper (I) catalysis alkynes/nitrine obtaining, 3-dipole-ring addition (Henning S.G.Beckmann and Valentin Wittmann.Org.Lett.2007,9 (1), 1-4).But still there are a lot of defects in above-mentioned preparation method: as catalyzer costliness, be difficult to obtain, easily generate by product, yield is not high, and the scope of application is wideless, and limitation is larger, and therefore condition harshness has limited its applicability.
(3) summary of the invention
The present invention seeks to improve the various defects of prior art, provide be easy to get the repeatedly recycling, mild condition, one kettle way easy and simple to handle of a kind of catalyzer to prepare 1H-1, the method for 2,3-triazole class compounds.
For achieving the above object, the technical solution used in the present invention is:
1H-1 shown in a kind of formula (I), 2, the preparation method of 3-triazole class compounds, described preparation method is: the halides shown in formula (III) is mixed with end-group alkyne compounds and sodiumazide shown in formula (II), in reaction solvent under the katalysis of Porous Cu in 25～80 ℃ reaction 5～85h, reaction finish after, reaction solution aftertreatment makes the 1H-1 shown in formula (I), 2,3-triazole class compounds; Described reaction solvent is deionized water, acetonitrile, dehydrated alcohol, toluene, acetone, DMF, tetrahydrofuran (THF) or dioxane;
In formula (I), formula (II) or formula (III), X is halogen, OAc, OMs (methylsulfonic acid base) or OTf (trifluoromethanesulfonic acid base); R
1for C1 to C13 alkyl, benzyl, substituted benzyl or ethyl acetate base, the substituting group on described substituted benzyl phenyl ring is monosubstituted halogen or monosubstituted C1 to C5 alkyl; R
2for C6 to C13 alkyl, 5 yuan to 9 yuan cycloalkenyl groups, phenyl, substituted-phenyl, phthalimide methyl or pyridyl, the substituting group of described substituted-phenyl is monosubstituted C1 to C5 alkoxyl group or monosubstituted halogen.
Further, X is preferably Br, Cl or I.
Further, R
1be preferably benzyl, C1 to C8 alkyl or ethyl acetate base.Further, the preferred ethyl of the alkyl of described C1 to C8 or butyl.
Further, R
2be preferably phenyl, p-methoxyphenyl, to ethoxyl phenenyl, rubigan, a fluorophenyl, 4-pyridyl, 1-cyclohexenyl, phthalimide methyl or C6 to C10 alkyl.Further, the preferred octyl group of described C6 to C10 alkyl.
Concrete, the end-group alkyne compounds shown in preferred formula of the present invention (II) is phenylacetylene, 4-anisole acetylene, 4-phenetole acetylene, 4-chlorobenzene acetylene, 3-fluorobenzene acetylene, 1-phthalic imidine propine, 4-pyrrole heavy stone used as an anchor acetylene, 1-cyclohexenyl acetylene or 1-octyne.
Concrete, the halides shown in preferred formula of the present invention (III) is benzyl bromine, benzyl chlorine, iodoethane, bromination of n-butane or 1-ethyl bromoacetate.
In the present invention, described reaction solvent is preferably deionized water, has environmental protection, cost is low, reaction yield is high advantage.
In the present invention, described catalyzer is Porous Cu, and aperture is preferably 5～150 μ m, and more preferably 5～50 μ m, are further preferably 5～20 μ m, most preferably are 5 μ m.In the present invention, Porous Cu uses commercial goods.
In the present invention, described halides (III) is 1: 1.0～1.2: 1.2～2: 0.05～0.15 with the ratio of the amount of substance that feeds intake of end-group alkyne compounds (II), sodiumazide, copper catalyst, most preferably is 1: 1.1: 2: 0.05.
In the present invention, the volumetric usage of described reaction solvent is counted 4～10ml/mmol with the mole number of halides (III), most preferably is 4ml/mmol.
Reaction conditions gentleness of the present invention, preferable reaction temperature is at 55～60 ℃, and the preferred reaction time is 8～50h.
The present invention is after reaction finishes, and gained reaction solution can obtain target product through conventional aftertreatment.The present invention recommends described post-treating method to be: after reaction finishes, gained reaction solution is extracted with ethyl acetate, saturated sodium-chloride washing, organic phase is dry, concentrated, then using volume ratio as the sherwood oil of 5: 1 and ethyl acetate as developping agent, carry out column chromatography, collect R
fthe elutriant of value 0.3～0.35, underpressure distillation, dry, obtain 1H-1,2,3-triazole class compounds.
The described 1H-1 of the concrete recommendation of the present invention, 2, the preparation method of 3-triazole class compounds carries out according to following steps: the halides shown in formula (III) is mixed with end-group alkyne compounds and sodiumazide shown in formula (II), in deionized water, under the katalysis of Porous Cu, react 8～50h in 55 ℃～60 ℃, after reaction finishes, gained reaction solution is extracted with ethyl acetate, saturated sodium-chloride washing, organic phase is dry, concentrated, then using volume ratio as the sherwood oil of 5: 1 and ethyl acetate as developping agent, carry out column chromatography, collect R
fthe elutriant of value 0.3～0.35, underpressure distillation, dry, obtain the 1H-1 shown in (I), 2,3-triazole class compounds; Described halides (III) is 1: 1.1: 2 with the ratio of the amount of substance that feeds intake of end-group alkyne compounds (II), sodiumazide, Porous Cu: 0.05; The volumetric usage of described deionized water is counted 4ml/mmol with the mole number of halides (III).
Compared with prior art, 1H-1 provided by the invention, the preparation method's of 2,3-triazole class compounds advantage is:
(1) the present invention has adopted one kettle way method to prepare 1H-1,2,3-triazole class compounds, and reaction conditions gentleness, easy to operate.
(2) the present invention has selected the Porous Cu being cheaply easy to get as catalyzer, and this catalyzer do not need process just can reuse repeatedly, meet atom economy principle; The present invention has simultaneously selected deionized water as solvent, and environmentally friendly, cost is low, and reaction yield is high, good product quality.
In view of 1H-1,2,3-triazole class compounds has stronger biological activity, as has antianaphylaxis, antibacterial, HIV (human immunodeficiency virus)-resistant activity, therefore in medicinal design, is widely used, and therefore the present invention has prospects for commercial application widely.
(4) embodiment
Below will by embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
The Porous Cu that the embodiment of the present invention is used is produced by Changsha Liyuan New Material Co., Ltd..
Embodiment 1: the preparation of the 1-benzyl-4-phenyl-1,2,3-triazoles shown in formula (I-1)
By the benzyl bromine (171.0mg shown in formula (III-1), 1mmol), sodiumazide (130mg, 2mmol), the phenylacetylene (112.3mg shown in formula (II-1), 1.1mmol), Porous Cu (5 μ m apertures, 3.2mg, 0.05mmol) mixes in deionized water (4ml), stirring reaction 29h in 55 ℃ of oil baths, TLC follows the tracks of reaction.After reaction finishes, with ethyl acetate (10mL × 3) extraction, saturated common salt water washing, merges organic phase, and anhydrous sodium sulfate drying filters, concentrated, column chromatography (sherwood oil: ethyl acetate=5: 1), collect R
fthe elutriant of value 0.3～0.35, underpressure distillation, is dried and obtains target compound 224.6mg, and yield is 95.47%, white needle-like crystals.
1HNMR(CDCl
3)：δ＝7.81-7.83(m，2H)，7.68(s，1H)，7.39-7.43(m，5H)，7.32-7.34(m，3H)，5.59(s，2H)
Embodiment 2:
The amount of Porous Cu is increased to 6.4mg (0.10mmol), and the reaction times is 10 hours, and other operate with embodiment 1, and yield is 94.9%.
Embodiment 3:
The amount of Porous Cu is increased to 9.6mg (0.15mmol), and the reaction times is 29 hours, and other operate with embodiment 1, and yield is 94.81%.
Embodiment 4:
The amount of Porous Cu is increased to 12.8mg (0.20mmol), and the reaction times is 27.5 hours, and other operate with embodiment 1, and yield is 94.25%.
Embodiment 5:
By Porous Cu, (5 μ m) change Porous Cu into, and (m), the reaction times is 28 hours to 20 μ, and other operate with embodiment 1, and yield is 87.20%.
Embodiment 6:
By Porous Cu, (5 μ m) change Porous Cu into, and (m), the reaction times is 43.5 hours to 50 μ, and other operate with embodiment 1, and yield is 65.76%.
Embodiment 7:
By Porous Cu, (5 μ m) change Porous Cu into, and (m), the reaction times is 85 hours to 150 μ, and other operate with embodiment 1, and yield is 27.30%.
Embodiment 8:
Temperature of reaction is brought up to 80 ℃, and the reaction times is 11 hours, and other operate with embodiment 1, and yield is 94.99%.
Embodiment 9:
Change solvent deionized water into acetonitrile, the reaction times is 22.5 hours, and other operate with embodiment 1, and yield is 10.20%.
Embodiment 10:
Change solvent deionized water into dehydrated alcohol, the reaction times is 34 hours, and other operate with embodiment 1, and yield is 44.17%.
Embodiment 11:
Change solvent deionized water into toluene, the reaction times is 28.5 hours, and other operate with embodiment 1, and yield is trace.
Embodiment 12:
Change solvent deionized water into acetone, the reaction times is 24.5 hours, and other operate with embodiment 1, and yield is 58.78%.
Embodiment 13:
Change solvent deionized water into DMF, the reaction times is 52.5 hours, and other operate with embodiment 1, and yield is 28.10%.
Embodiment 14:
Change solvent deionized water into tetrahydrofuran (THF), the reaction times is 54.5 hours, and other operate with embodiment 1, and yield is 4.50%.
Embodiment 15:
Change solvent deionized water into dioxane, the reaction times is 69 hours, and other operate with embodiment 1, and yield is 5.30%.
Embodiment 16: the preparation of the 1-benzyl-4-p-methoxyphenyl-1,2,3-triazoles shown in formula (I-2)
With the alternative phenylacetylene of 145.4mg (1.1mmol) 4-anisole acetylene (II-2), other operate with embodiment 1, obtain target product (I-2) 257.9mg, and yield is 97.2%, white solid.
1HNMR(CDCl
3)：δ＝7.74(d，J＝8.5Hz，2H)，7.59(s，1H)，7.39-7.41(m，3H)，7.32-7.34(m，2H)，6.95(d，J＝8.5Hz，2H)，5.58(s，2H)，3.85(m，3H)
The preparation of embodiment 17:1-benzyl-4-(1-cyclohexenyl)-1,2,3-triazoles
With the alternative phenylacetylene of 116.8mg (1.1mmol) 1-cyclohexenyl phenylacetylene (II-3), other operate with embodiment 1, obtain target product (I-3) 135.5mg, and yield is 56.60%, white solid.
1HNMR(CDCl
3)：δ＝7.36-7.40(m，3H)，7.30(s，1H)，7.30-7.25(m，2H)，6.49-6.51(m，1H)，5.52(s，2H)，2.35-2.38(m，2H)，2.17-2.22(m，2H)，1.73-1.78(m，2H)，1.64-1.69(m，2H).
The preparation of embodiment 18:1-benzyl-4-hexyl-1,2,3-triazoles
With the alternative phenylacetylene of 121.2mg (1.1mmol) 1-octyne (II-4), other operate with embodiment 1, obtain target product (I-4) 222.7mg, and yield is 91.50%.
1HNMR(CDCl
3)：δ＝7.36-7.38(m，3H)，7.25-7.28(m，2H)，7.19(s，1H)，5.50(s，2H)，2.69(t，J＝7.8Hz，2H)，1.63-1.68(m，2H)，1.28-1.35(m，6H)，0.88(t，J＝6.9Hz，3H)
The preparation of embodiment 19:1-benzyl-4-to ethoxyl phenenyl-1,2,3-triazoles
With the alternative phenylacetylene of 160.8mg (1.1mmol) 4-phenetole acetylene (II-5), other operate with embodiment 1, obtain target product (I-5) 252.3mg, and yield is 90.33%, white solid.
1HNMR(CDCl
3)：δ＝7.71-7.73(m，2H)，7.58(s，1H)，7.39-7.41(m，3H)，7.32-7.7.33(m，2H)，6.93-6.94(m，2H)，5.58(s，2H)，4.07(q，J＝7.0Hz，2H)，1.44(t，J＝7.0Hz，3H).
The preparation of embodiment 20:1-benzyl-4-pyridyl-1,2,3-triazoles
With the alternative phenylacetylene of 153.5mg (1.1mmol) 4-pyridine acetylene hydrochloride (II-6), other operate with embodiment 1, obtain target product (I-6) 92.1mg, and yield is 38.97%, yellow-green colour solid.
1HNMR(CDCl
3)：δ＝8.65(d，J＝5.8Hz，2H)，7.80(s，1H)，7.70-7.71(m，2H)，7.41-7.44(m，3H)，7.33-7.35(m，2H)，5.62(s，2H).
The preparation of embodiment 21:1-benzyl-4-phenyl-1,2,3-triazoles
With the alternative benzyl bromine of 126.6mg (1mmol) benzyl chlorine (III-2), other operate with embodiment 1, obtain target product (I-1) 221.2mg, and yield is 94.00%.
The preparation of embodiment 22:1-ethyl acetate base-4-phenyl-1,2,3-triazoles
With the alternative benzyl bromine of 166.0mg (1mmol) 1-ethyl bromoacetate (III-3), other operate with embodiment 1, obtain target product (I-7) 228.2mg, and yield is 98.80%, white solid.
1HNMR(CDCl
3)：δ＝7.93(s，1H)，7.86-7.87(m，2H)，7.43-7.46(m，2H)，7.35-7.38(m，1H)，5.22(s，2H)，4.31(q，J＝7.2Hz，2H)，1.33(t，J＝7.2Hz，3H).
The preparation of embodiment 23:1-ethyl-4-phenyl-1,2,3-triazoles
With the alternative benzyl bromine of 156.0mg (1mmol) iodoethane (III-4), other operate with embodiment 1, obtain target product (I-8) 137.9mg, and yield is 79.60%, white solid.
1HNMR(CDCl
3)：7.84-7.86(m，2H)，7.78(s，1H)，7.42-7.46(m，2H)，7.33-7.36(m，1H)，4.48(q，J＝7.4Hz，2H)，1.62(t，J＝7.4Hz，3H).
Embodiment 24:
1-benzyl-4-phthalimide methyl-1,2,3-triazoles
With the alternative phenylacetylene of 203.7mg (1.1mmol) phthalic imidine propine (II-7), other operate with embodiment 1, obtain target product (I-6) 33.1mg, and yield is 10.4%, white solid.
1H?NMR(CDCl
3)：δ＝7.84(s，1H)，7.72-7.81(m，4H)，7.14-7.27(m，5H)，5.81(s，2H)，4.81(s，2H).
Embodiment 25:
1-benzyl-4-rubigan-1,2,3-triazoles
With 150.2mg (1.1mmol), to the alternative phenylacetylene of chlorobenzene acetylene (II-8), other operate with embodiment 1, obtain target product (I-10) 243.6mg, and yield is 90.3%, white solid.
1H?NMR(CDCl
3)：δ＝7.74-7.76(m，2H)，7.66(s，1H)，7.33-7.42(m，7H)，5.60(s，2H).
Embodiment 26:
Fluorophenyl-1,2,3-triazoles between 1-benzyl-4-
With the alternative phenylacetylene of fluorobenzene acetylene (II-9) between 132.1mg (1.1mmol), other operate with embodiment 1, obtain target product (I-11) 221.9mg, and yield is 87.6%, white solid.
1H?NMR(CDCl
3)：δ＝7.68(s，1H)，7.53-7.58(m，2H)，7.32-7.44(m，6H)，7.00-7.04(m，1H)，5.60(s，2H).
Embodiment 27:
With the alternative benzyl bromine of 137.0mg (1mmol) 1-bromination of n-butane (III-5), other operate with embodiment 1, obtain target product (I-12) 58.2mg, and yield is 28.91%, white solid.
1H?NMR(CDCl
3)：δ＝7.85-7.87(m，2H)，7.77(s，1H)，7.43-7.46(m，2H)，7.33-7.37(m，1H)，4.43(t，J＝7.2Hz，2H)，1.93-1.99(m，2H)，1.38-1.46(m，2H)，1.00(t，J＝7.5Hz，3H)。
Claims (7)
1. the 1H-1 shown in a formula I, 2, the preparation method of 3-triazole class compounds, described preparation method is: the halides shown in formula III is mixed with end-group alkyne compounds and sodiumazide shown in formula II, in reaction solvent under the katalysis of Porous Cu in 25～80 ℃ reaction 5～85h, reaction finish after, reaction solution aftertreatment makes the 1H-1 shown in formula I, 2,3-triazole class compounds; Described solvent is deionized water; The aperture of described Porous Cu is 5～20 μ m;
In formula I, formula II or formula III, X is halogen; R
1for C1 to C13 alkyl, benzyl, substituted benzyl or ethyl acetate base, the substituting group on described substituted benzyl phenyl ring is monosubstituted halogen or monosubstituted C1 to C5 alkyl; R
2for C6 to C13 alkyl, 5 yuan to 9 yuan cycloalkenyl groups, phenyl, substituted-phenyl or pyridyl, the substituting group of described substituted-phenyl is monosubstituted C1 to C5 alkoxyl group or monosubstituted halogen.
2. 1H-1 as claimed in claim 1, the preparation method of 2,3-triazole class compounds, is characterized in that: X is Br, Cl or I; R
1for benzyl, C1 to C4 alkyl or ethyl acetate base; R
2for phenyl, p-methoxyphenyl, to ethoxyl phenenyl, rubigan, a fluorophenyl, 4-pyridyl, 1-cyclohexenyl or C6 to C10 alkyl.
3. 1H-1 as claimed in claim 1, the preparation method of 2,3-triazole class compounds, is characterized in that: the aperture of described Porous Cu is 5 μ m.
4. 1H-1 as claimed in claim 1 or 2,2, the preparation method of 3-triazole class compounds, is characterized in that: described halides is 1:1.0～1.2:1.2～2:0.05～0.15 with the ratio of the amount of substance of end-group alkyne compounds, sodiumazide, Porous Cu.
5. 1H-1 as claimed in claim 3,2, the preparation method of 3-triazole class compounds, it is characterized in that: described halides is 1:1.1:2:0.05 with the ratio of the amount of substance of end-group alkyne compounds, sodiumazide, Porous Cu, and the volumetric usage of described reaction solvent is counted 4ml/mmol with the mole number of halides.
6. 1H-1 as claimed in claim 1 or 2, the preparation method of 2,3-triazole class compounds, is characterized in that: temperature of reaction is 55～60 ℃, the reaction times is 8～50h.
7. 1H-1 as claimed in claim 5, the preparation method of 2,3-triazole class compounds, is characterized in that: temperature of reaction is 55～60 ℃, the reaction times is 8～50h.
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| CN103012195B (en) * | 2012-12-03 | 2015-04-22 | 浙江工业大学 | Preparation method of aryl azide compound |
| CN104119285B (en) * | 2013-04-28 | 2016-06-29 | 中国科学院广州生物医药与健康研究院 | Compound and application thereof as estrogen-related receptor modulator |
| CN103275022B (en) * | 2013-06-08 | 2015-08-05 | 浙江工业大学 | 1-benzyl-1,2,3-triazole compound and its preparation method and application |
| CN103483279B (en) * | 2013-09-10 | 2015-04-01 | 浙江大学 | Preparation method of 1,4-disubstituted triazole compound |
| CN103880762B (en) * | 2014-04-08 | 2016-03-16 | 河南师范大学 | A kind of preparation method of 1,2,3-triazole compound |
| CN105130914B (en) * | 2015-09-06 | 2017-07-11 | 河南师范大学 | A kind of Cu2O‑Al2O3The method for catalyzing and synthesizing 1,2,3 triazole compounds |
| CN105130916B (en) * | 2015-09-30 | 2019-03-01 | 江西师范大学 | Method for efficiently preparing NH-1,2,3 triazole compound |
| CN106588788B (en) * | 2016-11-11 | 2019-07-16 | 河南师范大学 | The method of one pot of two-step method synthesis 1,2,3- triazole compound |
| CN108675988B (en) * | 2018-06-04 | 2020-05-19 | 西安交通大学 | Pyridine compound and application thereof |
| CN108912098B (en) * | 2018-06-04 | 2020-04-28 | 西安交通大学 | Pyrimidine compound and application thereof |
| CN115974847A (en) * | 2022-12-16 | 2023-04-18 | 中国药科大学 | 3- (1,2,3-triazole-4-yl) tetrahydroquinazoline-2,4-diketone derivative and preparation method and application thereof |
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