CN103772301A - Method for catalytically synthesizing 1,2,3-triazole compound by using carboxylation nano-hydroxyapatite and cuprous oxide as catalytic systems - Google Patents
Method for catalytically synthesizing 1,2,3-triazole compound by using carboxylation nano-hydroxyapatite and cuprous oxide as catalytic systems Download PDFInfo
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- CN103772301A CN103772301A CN201410023269.1A CN201410023269A CN103772301A CN 103772301 A CN103772301 A CN 103772301A CN 201410023269 A CN201410023269 A CN 201410023269A CN 103772301 A CN103772301 A CN 103772301A
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- 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
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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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Abstract
The invention discloses a method for catalytically synthesizing a 1,2,3-triazole compound by using carboxylation nano-hydroxyapatite and cuprous oxide as catalytic systems. According to the technical scheme, the method for catalytically synthesizing the 1,2,3-triazole compound by using the carboxylation nano-hydroxyapatite and the cuprous oxide as the catalytic systems is characterized in that a terminal alkyne compound and organic azide which are used as raw materials are mixed and stirred and react by using the carboxylation nano-hydroxyapatite and the cuprous oxide as the catalytic systems and water as a solvent under a room temperature condition so as to prepare the 1,2,3-triazole compound. The method has the advantages that the catalytic systems are simple, convenient to operate and wide in application range and can be repeatedly used, the carboxylation nano-hydroxyapatite is non-toxic, harmless, green, environmentally friendly and easy to treat after reaction and can be recycled, and the method is carried out under conditions of normal pressure and temperature, is economic and environmentally friendly and is a high-efficiency green method for preparing the 1,2,3-triazole compound.
Description
Technical field
The invention belongs to and catalyze and synthesize 1,2,3-triazole compound technical field, be specifically related to a kind of carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system and catalyze and synthesize the method for 1,2,3-triazole compound.
Background technology
Calendar year 2001 Sharpless and Meldal seminar find 1 of cuprous ion catalysis organic nitrine and alkynes, and 3-Dipolar Cycloaddition, claims again Huisgen cycloaddition reaction, this reaction can be under gentle reaction conditions, synthetic 1,2, the 3-triazole compound of atom economy.Prepared by the method contains 1,2, the compound of 3-triazole structure has extremely important using value at aspects such as medicine, functional materialss, wherein contain 1,2, the compound of 3-triazole structure has biological activity widely, as antibacterial, immune, and the psychiatric disorder for the treatment of nervosa, sacroiliitis, richets and tumour etc.The preparation method of people to 1,2,3-triazole compound and the character of compound conduct extensive research subsequently.
Preparation method's copper catalyst used of 1,2,3-triazole compound, includes direct use cuprous salt, such as cuprous chloride, cuprous bromide or cuprous iodide etc.; In-situ reducing cupric is cuprous ion, mainly comprises classical copper sulfate/sodium ascorbate system, neutralized verdigris/sodium ascorbate system and neutralized verdigris/zinc powder system etc.; Also have disproportionation reaction system, mainly comprise copper sulfate/metallic copper system and neutralized verdigris/metallic copper system etc.In addition the oxide compound of copper, Red copper oxide, cupric oxide also can be used as catalyzer and use.Also the Huisgen cycloaddition reaction that has at present in addition the catalysis of report metallic copper, although the operation under this condition is easy, and the preparation of catalyzer is also simple, shortcoming is when long as catalyzer the reaction time with bulk metal copper.For Reaction time shorten, can use Nanometer Copper as catalyzer, shortcoming is that in its process of preparing, Nanometer Copper is easily reunited.Also have recently report to use copper sulfate, neutralized verdigris etc. directly use as catalyzer, and mechanism relates to alcohol, and end-group alkyne etc. are reduced to monovalence copper by cupric and participate in catalyzed reaction.
Red copper oxide, as catalyst Huisgen cycloaddition reaction, has the feature of self, first, Red copper oxide make catalyzer and need to have the participation of water (
green Chem.2011,13,562); The second, commercially available Red copper oxide does not almost have activity; Three, original position produce Red copper oxide or grade cuprous oxide can improve Red copper oxide catalytic activity (
adv. Synth. Catal.2010,352,1600;
arkivoc,2013,139;
helv. Chim. Acta.2013,96,688); Four, inorganic or organic acid can improve the activity of Red copper oxide.The people such as Hu yue fei report activity using phenylformic acid as additive activating Red copper oxide practical and effectively catalysis process (
tetrahedron Letter,2011,52,3782), Jiang Yu in 2014 admire and wait people with hydrazine hydrate/neutralized verdigris catalyst system, prepare nano cuprous oxide and acetic acid at water situ, successfully catalysis Huisgen cycloaddition reaction, find Red copper oxide can activate with acid (
rSC advance,2014,4,1010).
Above-mentioned phenylformic acid, Glacial acetic acid etc. can be in aqueous phase system active oxidation cuprous, improve the activity of the catalysis Huisgen cycloaddition reaction of Red copper oxide, although effect is all fine, the drawback that but existence can not recycle.Consider preparation technology's green, the present invention is incorporated into carboxyl in hydroxyapatite structure, prepare carboxymethylated hydroxyapatite, in water, active oxidation is cuprous, catalysis Huisgen cycloaddition reaction, this catalyst system has the advantages such as simple and reliable, high yield, highly selective, easily separated, reusable and environmental protection.
Summary of the invention
The present invention provides a kind of environmental protection and catalyst system can reusable carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system to catalyze and synthesize the method for 1,2,3-triazole compound for overcoming the deficiencies in the prior art.
Technical scheme of the present invention is: a kind of carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system catalyzes and synthesizes 1,2, the method of 3-triazole compound, it is characterized in that: respectively take end-group alkyne compounds and organic azide as raw material, take carboxylated nanometer hydroxyapatite and Red copper oxide as catalyst system, take water as solvent, under room temperature condition, mix and blend reaction makes 1,2,3-triazole compound.
Carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system of the present invention catalyzes and synthesizes 1, in the method for 2,3-triazole compound, the mol ratio of each material is n(end-group alkyne compounds): (organic azide): (carboxylated nanometer hydroxyapatite): n(Red copper oxide)=100:100:2-10:2-10.
End-group alkyne compounds of the present invention is
,
,
,
,
or
.
Organic azide of the present invention is N
3cH
2cOOEt,
,
,
,
,
or
.
Carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system of the present invention can be reused.
The synthesis step of carboxylated nanometer hydroxyapatite of the present invention is: (1), take nanometer hydroxyapatite as starting raw material, makes the nanometer hydroxyapatite that contains two keys in toluene solvant in the thermotonus of 100-110 ℃ with silane coupling agent vinyl Trimethoxy silane; (2), in toluene solvant, the nanometer hydroxyapatite that contains two keys that step (1) is made reacts and makes carboxylated nanometer hydroxyapatite in 60-80 ℃ with Thiovanic acid under the effect of initiator Diisopropyl azodicarboxylate.
The present invention compared with prior art has a little following: (1) catalyst system is simple, easy to operate, applied widely, can reuse; (2) cuprous easy being easy to get of catalyst oxidation, and cheap; (3) carboxylated nanometer hydroxyapatite is nontoxic, and recoverable is easily processed environmental protection after reaction; (4) the present invention carries out under normal temperature and pressure conditions, and economic environmental protection is the method that one is prepared the efficient green of 1,2,3-triazole compound.
Embodiment
By the following examples foregoing of the present invention is described in further details, but this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.All technology realizing based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
The preparation of carboxylated nanometer hydroxyapatite (n-HA)
1) preparation of double bond containing nanometer hydroxyapatite (n-HA)
In reaction flask, add 10 g n-HA, 30 ml toluene, ultrasonic 2 h, add g) vinyltrimethoxy silane of 5.2 ml(5, stir, control 100-110 ℃ of temperature and react, 6 h, centrifugal, sherwood oil is washed, and is placed on 40 ℃ of vacuum drying ovens dry;
2) (5 g, containing two keys 6.4 × 10 in reaction vessel, to add respectively the nanometer hydroxyapatite that contains two keys
-3mol), Thiovanic acid (4.4 ml), AIBN(0.53 g) and toluene (30 ml), lucifuge, drum N
22 h, control temperature and react at 60-80 ℃, 48 h, and centrifugal, toluene is washed, and is placed on that 40 ℃ of vacuum drying ovens are dry obtains carboxylated nanometer hydroxyapatite.
Embodiment 2
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, nitrine ethyl acetate and propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1, 2, 3-triazole compound, step is as follows: take respectively nitrine ethyl acetate (1 mmol), propargyl phenyl ether (1 mmol), 2 mol%(mol% are equivalent to the molar percentage of this material and principal constituent (determining the substrate of product amount of substance), in this specification sheets, be equivalent to the molar content that this material accounts for principal constituent end-group alkyne compounds, on as follows) Red copper oxide, the carboxylated nanometer hydroxyapatite of 2 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve to steam and obtain product, yield is 97 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?7.74?(s,?1H),?7.30-6.94?(m,?5H),?5.21?(s,?2H),?5.13?(s,?2H),?4.23?(q,?
J?=?7.2?Hz,?2H),?1.27?(t,?
J?=?7.2?Hz,?3H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?166.3,?158.2,?144.6,?129.6,?124.3,?121.3,?114.8,?62.4,?61.8,?50.9,?14.0.
Embodiment 3
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, nitrine ethyl acetate and to methylbenzene acetylene, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively nitrine ethyl acetate (1 mmol), to methylbenzene acetylene (1 mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 5 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve and steam acquisition product, yield is 95 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?7.87?(s,?1H),?7.73?(d,?
J?=?8.0?Hz,?2H),?7.24?(t,?
J?=?8.0?Hz,?2H),?5.19?(s,?2H),?4.28?(q,?
J?=?8.0?Hz,?2H),?2.38?(s,?3H),?1.30?(t,?
J?=?7.2?Hz,?3H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?166.4,?148.3,?138.2,?129.5,?127.5,?125.7,?120.7,?62.5,?51.0,?21.3,?14.1.
Embodiment 4
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, nitrine ethyl acetate and to nitro propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively nitrine ethyl acetate (1 mmol), to nitro propargyl phenyl ether (1 mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 10 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve and steam acquisition product, yield is 96 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?8.20?(dd,?
J?=?7.6?Hz,?2.0?Hz,?2H),?7.84?(s,?1H),?7.08?(d,?
J?=?8.0?Hz,?2H),?5.34?(s,?2H),?5.20?(s,?2H),?4.28?(q,?
J?=?7.2?Hz,?2H),?1.31?(t,?
J?=?7.2?Hz,?3H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?166.1,?163.1,?143.2,?141.9,?125.9,?124.5,?114.9,?62.6,?62.4,?51.0,?14.1.
Embodiment 5
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, aziminobenzene compound and propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 4-benzyloxy-1-benzyl-1H-1,2,3-triazole, step is as follows: take respectively aziminobenzene compound (1 mmol), propargyl phenyl ether (1 mmol), 5 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 5 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve and steam acquisition product, yield is 99 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?8.06?(s,?1H),?7.74?(d,?
J?=?7.6?Hz,?2H),?7.55-7.43?(m,?3H),?7.32?(t,?
J?=?8.0?Hz,?2H),?7.04-6.98?(m,?3H),?5.31?(s,?2H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?158.2,?145.1,?137.0,?129.8,?129.6,?128.9,?121.4,?120.9,?120.6,?114.8,?62.0.
Embodiment 6
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, aziminobenzene compound and to methylbenzene acetylene, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively aziminobenzene compound (1 mmol), to methylbenzene acetylene (1 mmol), 8 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 8 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve to steam and obtain product, yield 97 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?8.16?(s,?1H),?7.80?(dd,?
J?=?6.0?Hz,?7.6?Hz,?4H),?7.57-7.26?(m,?5H),?2.40?(s,?3H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?148.5,?138.3,?137.1,?129.8,?129.6,?128.7,?127.4,?125.8,?120.5,?117.3,?21.3.
Embodiment 7
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, p-methoxyphenyl triazo-compound and propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively p-methoxyphenyl triazo-compound (1 mmol), propargyl phenyl ether (1 mmol), 10 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 10 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve and steam acquisition product, yield is 98 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?7.97?(s,?1H),?7.64-7.60?(m,?2H),?7.33-7.29?(m,?2H),?7.03-6.99?(m,?5H),?5.28?(s,?2H),?3.85?(s,?3H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?159.9,?158.2,?144.8,?130.4,?129.6,?122.3,?121.3,?121.1,?114.8?(2),?62.0,?55.6.
Embodiment 8
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, benzyl azides and to methylbenzene acetylene, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively benzyl azides (1 mmol), to methylbenzene acetylene (1mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 5 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve to steam and obtain product, yield 94 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?7.69?(d,?
J?=?7.6?Hz,?2H),?7.63?(s,?1H),?7.38-7.29?(m,?5H),?7.20?(d,?
J?=?8.0?Hz,?2H),?5.55?(s,?2H),?2.36?(s,?3H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?148.3,?138.0,?134.8,?129.5,?129.2,?128.8,?128.1,?127.7,?125.6,?119.2,?54.2,?21.3.
Embodiment 9
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, benzyl azides and propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively benzyl azides (1 mmol), propargyl phenyl ether (1 mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 2 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve to steam and obtain product, yield 96 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?7.53?(s,?1H),?7.38-7.26?(m,?7H),?6.97?(d,?
J?=?8.0?Hz,?3H),?5.53?(s,?2H),?5.19?(s,?2H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?158.2,?144.7,?134.5,?129.5,?129.2,?128.8,?128.1,?122.6,?121.3,?114.8,?62.1,?54.3.
Embodiment 10
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, benzyl azides and to nitro propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1,2,3-triazole compound, step is as follows: take respectively benzyl azides (1 mmol), to nitro propargyl phenyl ether (1 mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 5 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve and steam acquisition product, yield is 97 %.
1H?NMR?(CDCl
3,?400?MHz)?
δ:?8.15?(dd,?
J?=?9.2?Hz,?1.2?Hz,?2H),?7.62?(s,?1H),?7.38-7.28?(m,?5H),?7.04?(d,?
J?=?9.2?Hz,?2H),?5.55?(s,?2H),?5.26?(s,?2H).?
13C?NMR?(CDCl
3,?100?MHz)?
δ:?163.2,?143.1,?141.8,?134.3,?129.2,?128.9,?128.2,?125.9,?123.2,?114.9,?62.4,?54.3.
Embodiment 11
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, to nitrobenzyl triazo-compound with to chlorine propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1, 2, 3-triazole compound, step is as follows: take respectively to nitrobenzyl triazo-compound (1 mmol), to chlorine propargyl phenyl ether (1 mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 5 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve to steam and obtain product, yield is 92%.
1H?NMR?(DMSO-d6,?400?MHz)?
δ:?8.37?(s,?1H),?8.25?(d,?
J?=?8.4?Hz,?2H),?7.53?(d,?
J?=?8.4?Hz,?2H),?7.34?(d,?
J?=?8.8?Hz,?2H),?7.07?(d,?
J?=?8.8?Hz,?2H),?5.81?(s,?2H),?5.16?(s,?2H).?
13C?NMR?(DMSO-d6,?100?MHz)?
δ:?157.2,?147.6,?143.8,?143.3,?129.7,?129.4,?125.6,?125.1,?124.3,?116.9,?61.8,?52.4.
Embodiment 12
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, between nitrobenzyl triazo-compound and to nitro propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1, 2, 3-triazole compound, step is as follows: take respectively 2-methyl-5-nitro benzyl azides (1 mmol), to nitro propargyl phenyl ether (1 mmol), 2 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 5 mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, dry, revolve to steam and obtain product, yield is 99 %.
1H?NMR?(DMSO-d6,?400?MHz)?
δ:?8.85?(s,?1H),?8.37?(d,?
J?=?6.8?Hz,?2H),?8.26?(d,?
J?=?8.8?Hz,?2H),?7.82?(d,?
J?=?9.2?Hz,?1H),?7.34?(d,?
J?=?9.2?Hz,?2H),?5.46?(s,?2H),?2.32?(s,?3H).?1.68-1.58?(m,?2H),?0.92?(t,?
J?=?7.6?Hz,?3H).?
13C?NMR?(DMSO-d6,?100?MHz)?
δ:?163.6,?146.5,?142.7,?141.8,?141.5,?136.8,?133.3,?127.3,?126.3,?124.8,?121.5,?115.8,?62.2,?18.4.
Embodiment 13
Adopt the prepared carboxylated nanometer hydroxyapatite of embodiment 1, benzyl azides and to nitro propargyl phenyl ether, utilize cuprous oxide catalysis to prepare 1, 2, 3-triazole compound, step is as follows: take respectively benzyl azides (1 mmol), to nitro propargyl phenyl ether (1 mmol), 10 mol% Red copper oxide, the carboxylated nanometer hydroxyapatite of 10mol%, take water as solvent, be uniformly mixed at ambient temperature reaction, reacted solution extracts by ethyl acetate, shift out ethyl acetate layer, again to adding benzyl azides (1 mmol) in reaction system and to nitro propargyl phenyl ether (1 mmol), continue stirring reaction, after question response finishes, be extracted with ethyl acetate dry, revolve to steam and obtain product, 10 times so repeatedly.
The recycling of table 1 catalyst system
| Cycle index | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Yield (%) | 99 | 98 | 98 | 99 | 98 | 98 | 97 | 97 | 98 | 98 |
Circulate 10 times, the activity of carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system does not reduce substantially.
Above embodiment has described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; do not departing under the scope of the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (6)
1. carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system catalyzes and synthesizes 1,2, the method of 3-triazole compound, it is characterized in that: respectively take end-group alkyne compounds and organic azide as raw material, take carboxylated nanometer hydroxyapatite and Red copper oxide as catalyst system, take water as solvent, under room temperature condition, mix and blend reaction makes 1,2,3-triazole compound.
2. carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system according to claim 1 catalyzes and synthesizes 1,2, the method of 3-triazole compound, is characterized in that: in building-up process, the mol ratio of each material is n(end-group alkyne compounds): (organic azide): (carboxylated nanometer hydroxyapatite): n(Red copper oxide)=100:100:2-10:2-10.
3. carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system according to claim 1 catalyzes and synthesizes the method for 1,2,3-triazole compound, it is characterized in that: described end-group alkyne compounds is
,
,
,
,
or
.
4. carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system according to claim 1 catalyzes and synthesizes the method for 1,2,3-triazole compound, it is characterized in that: described organic azide is N
3cH
2cOOEt,
,
,
,
,
or
.
5. carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system according to claim 1 catalyzes and synthesizes 1,2, the method of 3-triazole compound, is characterized in that: described carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system can be reused.
6. carboxylated nanometer hydroxyapatite/cuprous oxide catalysis system according to claim 1 catalyzes and synthesizes 1,2, the method of 3-triazole compound, the synthesis step that it is characterized in that described carboxylated nanometer hydroxyapatite is: (1), take nanometer hydroxyapatite as starting raw material, makes the nanometer hydroxyapatite that contains two keys in toluene solvant in the thermotonus of 100-110 ℃ with silane coupling agent vinyl Trimethoxy silane; (2), in toluene solvant, the nanometer hydroxyapatite that contains two keys that step (1) is made reacts and makes carboxylated nanometer hydroxyapatite in 60-80 ℃ with Thiovanic acid under the effect of initiator Diisopropyl azodicarboxylate.
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| CN109503502A (en) * | 2018-12-29 | 2019-03-22 | 山东师范大学 | The preparation method of N- vinyl -1,2,3- triazole compound |
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| CN102086255A (en) * | 2010-12-09 | 2011-06-08 | 南昌大学 | Nano hydroxyapatite hybrid material and preparation method thereof |
| CN103484258A (en) * | 2013-09-22 | 2014-01-01 | 江苏大学 | Method for preparing biodiesel by using nano hydroxyapatite to catalyze triglyceride |
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| CN102086255A (en) * | 2010-12-09 | 2011-06-08 | 南昌大学 | Nano hydroxyapatite hybrid material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503502A (en) * | 2018-12-29 | 2019-03-22 | 山东师范大学 | The preparation method of N- vinyl -1,2,3- triazole compound |
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