CN110498772A - A kind of Terminal Acetylenes multicomponent synthesis 1,4- replaces the method for 1,2,3- triazole - Google Patents
A kind of Terminal Acetylenes multicomponent synthesis 1,4- replaces the method for 1,2,3- triazole Download PDFInfo
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Abstract
The invention belongs to nitrogenous compound preparation technical fields, disclose a kind of Terminal Acetylenes multicomponent synthesis 1,4- replaces 1, the method of 2,3- triazoles, comprising: 1.2 equivalent of (quasi-) halide, 1.5 equivalent of nitrine reagent are added into reaction flask, 1.0 equivalent of Terminal Acetylenes, 0.1 equivalent of cuprous iodide and solvent polyethylene glycol 400, are then stirred to react；Contact plate is analysed by thin layer to determine after reaction, water, ethyl acetate extraction is added, and combined ethyl acetate after ethyl acetate layer is dried over anhydrous sodium sulfate, is concentrated under reduced pressure to give crude product；Column chromatographs up to corresponding Isosorbide-5-Nitrae-substitution 1,2,3- triazole, or directly carries out column chromatography for separation through petroleum ether and ethyl acetate after reaction for eluant, eluent and purify to obtain target product Isosorbide-5-Nitrae-substitution 1,2,3- 3-triazole compounds.Raw material sources of the present invention are abundant, cheap, environmentally friendly；Reaction condition is mild, and the reaction time is short, and reaction yield is higher.
Description
Technical field
The invention belongs to nitrogenous compound preparation technical fields more particularly to a kind of Terminal Acetylenes multicomponent to synthesize Isosorbide-5-Nitrae-substitution 1,
The method of 2,3- triazole.
Background technique
1,2,3- triazole is a kind of critically important nitrogenous compound, is industrially widely used in pigment, fiber
Brightener, the preservative of metal and alloy and the stabilizer of organic matter and polymer, agriculturally be used for herbicide, sterilization
Agent, in medicine in the drug of a variety of different function.Due to this kind of compound and there is no in nature, it all passes through
It is prepared by the method for chemistry.There are many seminars to report the synthetic method of 1,2,3- triazole in recent years.Most common system
Include: for 1,2,3- triazole method
First method: Terminal Acetylenes hydrocarbon and two component of organic nitrine synthesize 1,2,3- under the conditions of catalyst (common copper catalysis)
Triazole.Considerable report is about the click reaction under different condition.Such as Huisgen propose earliest using this method come
1,2,3- triazole compound is synthesized, however in most cases, what this method obtained is the mix products of regional isomerism,
And it is confined to strong electrophilic alkynes and participates in reaction.Later, Fokin and Sharpless reported the Azide of Cu (I) catalysis
The method that object and terminal alkynes conversion zone selectively synthesize bis- substitution -1,2,3- triazole compound of 1,4-
[Angew.Chem.Int.Ed.2002,41(14),2596-2599]；Casas-Solvas in 2004 is reported in toluene solvant and adds
The nitrogen azoles of bis- substitution -1,2,3- triazole of 1,4- under heat condition synthesizes [Org.Lett.2004,6 (21), 3687-3690]；
Chassaing in 2007 etc. is also reported in the nitrogen azoles synthesis of the bis- substitution -1,2,3- triazole of 1,4- in room temperature condition toluene solvant
[Org.Lett.2007,9(5),883-886]；The Terminal Acetylenes and organic nitrine that Wang in 2008 etc. reports copper bromide catalysis are in water
It mutually needs to be added under the conditions of ligand PhSMe and synthesizes nitrogen azoles [the Green Chem.2008,10 of bis- substitution -1,2,3- triazole of 1,4-
(4),452-456]；For another example, the Terminal Acetylenes and organic nitrine that Alonso in 2010 etc. reports Nanometer Copper CuNPs catalysis are in alkali Et3N
Under the conditions of synthesize bis- substitution -1,2,3- triazole of 1,4- [Eur.J.Org.Chem.2010,2010 (10), 1875-1884]；Deng
Deng.
Second method: (common copper is urged in catalyst for halide or phenyl boric acid etc., nitrine reagent and three component of Terminal Acetylenes hydrocarbon
Change) under the conditions of synthesize 1,2,3- triazole.Such as the halogenated hydrocarbons or halobenzene, nitrine of the report cuprous iodide catalysis such as Zhao in 2006
Change three components of sodium and Terminal Acetylenes synthesize in ionic liquid under alkaline condition 1,2,3- triazole [Tetrahedron Lett.2006,
47(10),1545-1549].Alonso in 2010 etc. reports the Nanometer Copper load halide of carbon, sodium azide and three groups of Terminal Acetylenes hydrocarbon
1,2,3- triazole [Adv.Synth.Catal.2010,352 (18), 3208-3214] is synthesized under the conditions of point water phase.For another example 2013
Chanda etc. reports bromide, sodium azide and three component of Terminal Acetylenes hydrocarbon the nitrogen protection condition in ethanol of nano cupric oxide catalysis
Lower synthesis 1,2,3- triazole [Chem.Eur.J.2013,19 (47), 16036-16043].
Ligand is added in some need in these synthetic methods, and alkali, some need heating, when some reactions is added in some need
Between it is long, the production of some catalyst is complicated, and reaction cost is higher, and some is reacted using poisonous and hazardous organic solvent, has
The scope of application is not wide, and limitation is larger, and some yields are lower, and some reaction process are cumbersome, thus limiting its application property.
It also needs additionally first to prepare organic nitrine in first method.Therefore it finds a kind of new easy to operate, low in cost, efficiently fast
Fast, environmentally protective method synthesizes 1,2,3-triazoles class compound, is still the target of Many researchers research in international coverage.
In conclusion problem of the existing technology is: there are still need volume for existing 1,2,3- triazole preparation methods
Outer addition alkali or ligand, reaction need to heat, and the reaction time is long, and catalyst production is complicated, using poisonous and hazardous organic molten
Agent, reaction cost is higher, reaction process and post-processing operation complexity etc..
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of Terminal Acetylenes multicomponents to synthesize Isosorbide-5-Nitrae-substitution 1,2,3- tri-
The method of nitrogen azoles.
The invention is realized in this way a kind of Terminal Acetylenes multicomponent synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole is described
Terminal Acetylenes multicomponent synthesize 1,4- replace 1,2,3- triazole method the following steps are included:
1.2 equivalent of (quasi-) halide, 1.5 equivalent of nitrine reagent, 1.0 equivalent of Terminal Acetylenes, iodine are added into reaction flask for step 1
Change cuprous 0.1 equivalent and solvent polyethylene glycol 400, is then stirred to react；
Step 2 is analysed contact plate by thin layer and is determined after reaction, water is added, ethyl acetate extraction is then added, merges
Ethyl acetate after ethyl acetate layer is dried over anhydrous sodium sulfate, is concentrated under reduced pressure to give crude product；
Step 3, column chromatograph up to corresponding Isosorbide-5-Nitrae-substitution 1,2,3- triazole, or after reaction directly through petroleum
Ether and ethyl acetate are that eluant, eluent progress column chromatography for separation purifies to obtain target product 1,4- substitution 1,2,3- triazole chemical combination
Object.
Further, the Terminal Acetylenes multicomponent synthesizes Isosorbide-5-Nitrae-substitution 1,2, and the method synthetic route of 3- triazole is as follows:
Further, the formula R of described (quasi-) halide1-X；In formula, X Br, Cl or I, acetoxyl group, methylsulphur acidic group,
P-methyl benzenesulfonic acid base, p-nitrophenyl sulfonic group or trifluoromethanesulfonate and other sulfonic groups.
Further, R in the halide formula1It is selected from: C1~C50Alkyl, benzyl and various substituted benzene methyl, naphthalene
Methyl and various substitution menaphthyls, glycosyl etc.；
The various substituent groups can be it is monosubstituted, two replace and it is polysubstituted；
Described two replace the combination with multi-substituent for following any group: C1~C10Alkyl, alkoxy, hydroxyl, amine
Acyl group, haloform base, quaternary amine base, amino, itrile group, halogen atom, nitro, trifluoromethyl etc..
Further, the nitrine reagent includes: sodium azide, Lithium Azide, Lithium Azide, tetrabutyl ammonium azide, three
Methylsilyl nitrine or diphenyl phosphate azide.
Further, R in the structural formula of the Terminal Acetylenes2It is selected from: C1~C50Alkyl, phenyl and various substituted-phenyls, miscellaneous
Aromatic radical and various substitution heteroaryl perfume bases, naphthalene and various substituted naphthyls, glycosyl, trimethyl silicon substrate, ester group, carboxyl, amine
Base, aldehyde radical, hydroxyl, alkoxy etc.；
The various substituent groups can be it is monosubstituted, two replace and it is polysubstituted；
Described two replace the combination with multi-substituent for following any group: C1~C10Alkyl, alkoxy, hydroxyl, amine
Acyl group, haloform base, quaternary amine base, amino, itrile group, halogen atom, nitro, trifluoromethyl；
Further, the Terminal Acetylenes multicomponent synthesizes Isosorbide-5-Nitrae-substitution 1,2, and solvent is polyethylene glycol in the method for 3- triazole.
Further, -20~200 DEG C of the reaction temperature.
Further, the ratio between described (quasi-) halide, nitrine reagent, Terminal Acetylenes, amount of substance of copper catalyst are as follows: 1.2: 1.5:
1.0:0.1.
Another object of the present invention is to provide a kind of Terminal Acetylenes multicomponent synthesis 1,4- to replace 1,2,3- triazole
Synthesis Isosorbide-5-Nitrae-substitution 1,2 of method preparation, 3- triazole, the multicomponent synthesize Isosorbide-5-Nitrae-substitution 1,2, and 3- triazole structure formula is such as
Under:
Advantages of the present invention and good effect are as follows: use nontoxic polyethylene glycol to be used as reaction dissolvent and copper and urge
Agent is carried out it is not necessary that additional ligand and alkali is added by (quasi-) halide (1), nitrine reagent (2) and (3) three component of Terminal Acetylenes
Azide/1,3- Dipolar Cycloaddition, " one kettle way " synthesize target product Isosorbide-5-Nitrae-substitution 1,2,3- triazole.With existing method
It compares, the present invention can fit that substrate spectrum is wide, not need that additional alkali and ligand is added, reaction condition does not need mildly to heat, instead
Short between seasonable, operating procedure is easy, and without the use of poisonous and hazardous organic solvent, and reaction efficiency is high, environmentally protective, is
A method of with significant application value, the features such as industrial-scale production can be widely used in.It also has no so far
It is disclosed about report.
The abundances such as common solvent, catalyst, reagent, cheap in reaction process of the invention, to environment friend
It is good.Preparation method has reaction condition mild, and the reaction time is short, and reaction yield is higher, and post-reaction treatment is simple, environmentally friendly
Deng advantage.
The solvent polyethylene glycol 400 that the present invention uses is cheap, and abundance is non-toxic and tasteless, biodegradable, to ring
Border is pollution-free；It is not necessary that additional ligand and alkali is added, reaction cost is reduced；The catalyst cuprous iodide of use, in this reaction
Middle catalytic activity is high, and dosage is few, only uses 0.10 equivalent relative to raw material Terminal Acetylenes；Reaction speed is fast, and overwhelming majority reaction is 0.5
Or so hour reaction terminates, and is for a long time slightly 1.0h or so, has saved time cost；Azide/1,3- dipole-ring adds in reaction
Target product Isosorbide-5-Nitrae-substitution 1,2 is synthesized at three steps " one kettle way ", 3- triazole is not necessarily to separation of intermediates, reduces in cumbersome
Between treatment process；Post-reaction treatment is simple, yield is higher, product purity is higher, and reaction condition is mild, environmentally protective, is suitable for big
Amount prepares Isosorbide-5-Nitrae-substitution -1,2,3-triazoles, there is higher use value and social benefit, can be applied to industrialize a large amount of lifes
It produces.
Detailed description of the invention
Fig. 1 is the method flow that Terminal Acetylenes multicomponent synthesis 1,4- provided in an embodiment of the present invention replaces 1,2,3- triazole
Figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Application principle of the invention is explained in detail with reference to the accompanying drawing.
Multicomponent synthesis 1,4- provided in an embodiment of the present invention replaces 1,2,3- triazole structure formula as follows:
As shown in Figure 1, Terminal Acetylenes multicomponent provided in an embodiment of the present invention synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole
The following steps are included:
S101: halide, nitrine reagent and Terminal Acetylenes be raw material, be added copper catalyst, at a certain temperature with stirred in solvent
Reaction is mixed until TLC monitors raw material fully reacting, reaction solution ethyl acetate or methylene chloride extraction, organic phase is through saturated common salt
Water washing, after anhydrous sodium sulfate is dry, decompression boils off solvent, both obtains crude product；
S102: crude product is that eluant, eluent progress column chromatography for separation purifies to obtain target product 1 through petroleum ether and ethyl acetate,
4- replaces 1,2,3- triazole compounds, or directly carries out column through petroleum ether and ethyl acetate after reaction for eluant, eluent
Chromatography purifies to obtain target product 1,4- substitution 1,2,3- triazole compound.
Terminal Acetylenes multicomponent synthesis 1,4- provided in an embodiment of the present invention replaces the method specific steps of 1,2,3- triazole are as follows:
(quasi-) halide (1) (1.2 equivalent), nitrine reagent (2) (1.5 equivalent), Terminal Acetylenes (1.0 equivalent), iodate are added into reaction flask
Cuprous (0.1 equivalent) and solvent polyethylene glycol 400, are then stirred to react.Contact plate, which is analysed, by thin layer determines that reaction terminates
Afterwards, water is added, ethyl acetate is then added and extracts, combined ethyl acetate, after ethyl acetate layer is dried over anhydrous sodium sulfate,
It is concentrated under reduced pressure to give crude product.Column chromatographs up to corresponding Isosorbide-5-Nitrae-substitution 1,2,3- triazole, or directly passes through after reaction
Petroleum ether and ethyl acetate are that eluant, eluent progress column chromatography for separation purifies to obtain target product 1,2,3- triazole compound.
Terminal Acetylenes multicomponent synthesis 1,4- provided in an embodiment of the present invention replaces its synthetic route of the method for 1,2,3- triazole
It is as follows:
The formula R of (quasi-) halide (1)1-X.In formula, X be halogen, OAc (acetoxyl group), OMs (methylsulphur acidic group),
OTs (p-methyl benzenesulfonic acid base), OMs (p-nitrophenyl sulfonic group) or OTf (trifluoromethanesulfonate) and other sulfonic groups, into
One step, X are preferably Br, Cl or I.
R in (quasi-) halide (1) formula1It is selected from: C1~C50Alkyl, benzyl and various substituted benzene methyl, menaphthyl
And various substitution menaphthyls, glycosyl etc..The various substituent groups can be it is monosubstituted, two replace and it is polysubstituted.It is described
Two replace and multi-substituent be following any group combination: C1~C10Alkyl, alkoxy, hydroxyl, amine acyl group, haloform
Base, quaternary amine base, amino, itrile group, halogen atom, nitro, trifluoromethyl etc..These groups the neighbour of aromatic rings or miscellaneous aromatic rings,
Between, contraposition on replaced.
Nitrine reagent (2) includes: sodium azide (NaN3), Lithium Azide (LiN3), Lithium Azide (LiN3), the tetrabutyl is folded
Ammonium nitrides (Bu4NN3), trimethyl silicon substrate nitrine (TMSN3) or diphenyl phosphate azide (DPPA) etc..It is preferred that sodium azide.
R in the structural formula of Terminal Acetylenes (3)2It is selected from: C1~C50Alkyl, phenyl and various substituted-phenyls, heteroaryl perfume base with
And various substitution heteroaryl perfume bases, naphthalene and various substituted naphthyls, glycosyl, trimethyl silicon substrate, ester group, carboxyl, amido, aldehyde radical,
Hydroxyl, alkoxy etc..The various substituent groups can be it is monosubstituted, two replace and it is polysubstituted.Described two replace and more
Substituent group is the combination of following any group: C1~C10Alkyl, alkoxy, hydroxyl, amine acyl group, haloform base, quaternary amine base, ammonia
Base, itrile group, halogen atom, nitro, trifluoromethyl etc..These groups carry out on aromatic rings or the o-, m- of miscellaneous aromatic rings, contraposition
Replace.
Solvent is various polyethylene glycol (molecular weight 100-1000).It is preferred that polyethylene glycol 400 (i.e. PEG400).
Reaction temperature -20~200 DEG C, preferably room temperature.
Various catalyst be various copper simple substances and copper compound single group at or a few components mix.It include: cuprous iodide,
Cuprous bromide, stannous chloride, copper bromide, copper chloride, copper sulphate, copper nitrate, copper acetate, copper trifluoromethanesulfcomposite, copper oxide, oxidation
Cuprous, copper powder or nanometer copper simple substance and nanometer copper compound.
Catalyst most preferably cuprous iodide, optimum amount are 0.05 equivalent of Terminal Acetylenes.
(quasi-) halide (1), nitrine reagent (2), Terminal Acetylenes (3), copper catalyst the amount of substance can arbitrarily compare, it is optimal it
Than are as follows: 1.2: 1.5: 1.0:0.1.
Reactive mode: stirring, microwave, ultrasound, ultraviolet etc. or combinations thereof.From operation is simple and is easy to industrialize angle
Degree, is preferably stirred.
It is post-processed after reaction are as follows: water is added, ethyl acetate extraction, combined ethyl acetate, acetic acid is then added
After methacrylate layer is dried over anhydrous sodium sulfate, it is concentrated under reduced pressure to give crude product.Column, which chromatographs, replaces 1,2,3- tri- up to corresponding 1,4-
Nitrogen azoles.
The embodiment of the present invention synthesize 1,4- replace the preservative of 1,2,3- triazole preparation, drug, material, in chemical reagent
Mesosome etc..
Application principle of the invention is further described combined with specific embodiments below.
Embodiment 1: by phenylacetylene 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide 0.1mmol
It is added in polyethylene glycol 400 2.0mL, reaction 30min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:VEthyl acetate=
1- benzyl -4- phenyl 1,2,3- triazole is obtained after 3:1 processing.Product is white solid, yield: 95%.
Embodiment 2: by phenylacetylene 1.0mmol, sodium azide 1.5mol, trifluoro-benzyl bromine 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 20min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (3- trifluoromethyl benzyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield:
96%.
Embodiment 3: by phenylacetylene 1.0mmol, sodium azide 1.5mol, 4- methoxybenzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 25min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (4- methoxy-benzyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 95%.
Embodiment 4: phenylacetylene 1.0mmol, sodium azide 1.5mol, 3,5- dimethylbenzyl bromide 1.2mmol, iodate is sub-
Copper 0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 30min is stirred at room temperature, product is chromatographed through column after reaction
VPetroleum ether:VEthyl acetate1- (3,5- dimethyl benzyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, is produced
Rate: 96%.
Embodiment 5: by phenylacetylene 1.0mmol, sodium azide 1.5mol, 4- cyano-benzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 25min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (4- cyanobenzyls) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 93%.
Embodiment 6: by phenylacetylene 1.0mmol, sodium azide 1.5mol, 4- nitrobenzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 20min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (4- nitrobenzyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 91%.
Embodiment 7: by phenylacetylene 1.0mmol, sodium azide 1.5mol, 2- benzyl chloride bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 25min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (2- chlorobenzyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 94%.
Embodiment 8: by phenylacetylene 1.0mmol, sodium azide 1.5mol, α-naphthalene benzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 30min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (α-naphthalene benzyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 93%.
Embodiment 9: by phenylacetylene 1.0mmol, sodium azide 1.5mol, α-bromoacetophenone 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 25min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- (phenylacetyl methyl) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 89%.
Embodiment 10: by phenylacetylene 1.0mmol, sodium azide 1.5mol, full acetylated glucose bromide 1.2mmol, iodine
Change cuprous 0.1mmol to be added in polyethylene glycol 400 2.0mL, reaction 40min is stirred at room temperature, product is through column layer after reaction
Analyse VPetroleum ether:VEthyl acetate1- (the full acetylated glucosyl group of β -) -4- phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is that white is solid
Body, yield: 90%.
Embodiment 11: will be to chlorobenzene acetylene 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 35min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- benzyl -4- (4- chlorine) phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 95%.
Embodiment 12: meta-methoxy phenylacetylene 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, iodate is sub-
Copper 0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 35min is stirred at room temperature, product is chromatographed through column after reaction
VPetroleum ether:VEthyl acetate1- benzyl -4- (3- methoxyl group) phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield:
92%.
Embodiment 13: by o-methyl-benzene acetylene 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 35min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- benzyl -4- (3- methoxyl group) phenyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 92%.
Embodiment 14: 2- furyl phenylacetylene 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, iodate is sub-
Copper 0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 30min is stirred at room temperature, product is chromatographed through column after reaction
VPetroleum ether:VEthyl acetate1- benzyl -4- (2- furyl) -1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield:
90%.
Embodiment 15: by 1- pentyne 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide 0.1mmol
It is added in polyethylene glycol 400 2.0mL, reaction 25min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:VEthyl acetate=
1- benzyl -4- propyl 1,2,3- triazole is obtained after 3:1 processing.Product is colourless liquid, yield: 85%.
Embodiment 16: by ethyl propiolate 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 25min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether∶
VEthyl acetate1- benzyl -4- group-4 ethyl formate 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 98%.
Embodiment 17: by phenyl propargyl ether 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide
0.1mmol is added in polyethylene glycol 400 2.0mL, reaction 35min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:
VEthyl acetate1- benzyl -4- Phenoxymethyl 1,2,3- triazole is obtained after=3:1 processing.Product is white solid, yield: 93%.
Embodiment 18: by propargyl alcohol 1.0mmol, sodium azide 1.5mol, benzyl bromide 1.2mmol, cuprous iodide 0.1mmol
It is added in polyethylene glycol 400 2.0mL, reaction 30min is stirred at room temperature, product chromatographs V through column after reactionPetroleum ether:VEthyl acetate=
1- benzyl -4- methylol 1,2,3- triazole is obtained after 3:1 processing.Product is white solid, yield: 88%.
Embodiment 19: by phenylacetylene 1.0mmol, sodium azide 1.5mol, benzyl chloride 1.2mmol, cuprous iodide 0.1mmol
It is added in polyethylene glycol 400 2.0mL, room temperature ultrasonic reaction 20min, product chromatographs V through column after reactionPetroleum ether:VEthyl acetate=
1- benzyl -4- phenyl 1,2,3- triazole is obtained after 3:1 processing.Product is white solid, yield: 95%.
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
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of Terminal Acetylenes multicomponent synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that the Terminal Acetylenes multicomponent
Synthesize 1,4- replace 1,2,3- triazole method the following steps are included:
1.2 equivalent of halide, 1.5 equivalent of nitrine reagent, 1.0 equivalent of Terminal Acetylenes, cuprous iodide are added into reaction flask for step 1
0.1 equivalent and solvent polyethylene glycol 400, are then stirred to react；
Step 2 is analysed contact plate by thin layer and is determined after reaction, water is added, ethyl acetate extraction is then added, merges acetic acid
Ethyl ester after ethyl acetate layer is dried over anhydrous sodium sulfate, is concentrated under reduced pressure to give crude product；
Step 3, column chromatograph up to corresponding Isosorbide-5-Nitrae-substitution 1,2,3- triazole, or after reaction directly through petroleum ether and
Ethyl acetate is that eluant, eluent progress column chromatography for separation purifies to obtain target product 1,2,3- triazole compound.
2. Terminal Acetylenes multicomponent as described in claim 1 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
Stating Terminal Acetylenes multicomponent synthesis 1,4- replaces the method synthetic route of 1,2,3- triazole as follows:
3. Terminal Acetylenes multicomponent as claimed in claim 2 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
State the formula R of (quasi-) halide1-X；It is X Br, Cl or I, acetoxyl group, methylsulphur acidic group, p-methyl benzenesulfonic acid base, right in formula
Nitrobenzene-sulfonic acid base or trifluoromethanesulfonate and other sulfonic groups.
4. Terminal Acetylenes multicomponent as claimed in claim 2 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
State R in halide formula1It is selected from: C1~C50Alkyl, benzyl and various substituted benzene methyl, menaphthyl and various substitution naphthalenes
Methyl, glycosyl；
The various substituent groups can be it is monosubstituted, two replace and it is polysubstituted；
Described two replace the combination with multi-substituent for following any group: C1~C10Alkyl, alkoxy, hydroxyl, amine acyl group,
Haloform base, quaternary amine base, amino, itrile group, halogen atom, nitro, trifluoromethyl.
5. Terminal Acetylenes multicomponent as claimed in claim 2 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
Stating nitrine reagent includes: sodium azide, Lithium Azide, Lithium Azide, tetrabutyl ammonium azide, trimethyl silicon substrate nitrine or folded
Nitrogen diphenyl phosphate.
6. Terminal Acetylenes multicomponent as claimed in claim 2 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
State R in the structural formula of Terminal Acetylenes2It is selected from: C1~C50Alkyl, phenyl and various substituted-phenyls, heteroaryl perfume base and various substitutions
Heteroaryl perfume base, naphthalene and various substituted naphthyls, glycosyl, trimethyl silicon substrate, ester group, carboxyl, amido, aldehyde radical, hydroxyl, alcoxyl
Base；
The various substituent groups can be it is monosubstituted, two replace and it is polysubstituted；
Described two replace the combination with multi-substituent for following any group: C1~C10Alkyl, alkoxy, hydroxyl, amine acyl group,
Haloform base, quaternary amine base, amino, itrile group, halogen atom, nitro, trifluoromethyl.
7. Terminal Acetylenes multicomponent as described in claim 1 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
Stating Terminal Acetylenes multicomponent synthesis 1,4- replaces solvent in the method for 1,2,3- triazole to be polyethylene glycol.
8. Terminal Acetylenes multicomponent as described in claim 1 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
State reaction temperature -20~200 DEG C.
9. Terminal Acetylenes multicomponent as described in claim 1 synthesizes Isosorbide-5-Nitrae-substitution 1,2, the method for 3- triazole, which is characterized in that institute
State the ratio between halide, nitrine reagent, Terminal Acetylenes, amount of substance of copper catalyst are as follows: 1.2: 1.5: 1.0:0.1.
10. the synthesis that a kind of Terminal Acetylenes multicomponent synthesis 1,4- as described in claim 1 replaces the method preparation of 1,2,3- triazole
Isosorbide-5-Nitrae-substitution 1,2,3- triazole, which is characterized in that the multicomponent synthesizes Isosorbide-5-Nitrae-substitution 1,2, and 3- triazole structure formula is as follows:
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| CN113307726B (en) * | 2021-04-27 | 2024-02-02 | 乐山师范学院 | Preparation method and application of propyne aryl ether compound |
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