CN105439969B - A kind of method for preparing the triazole of 3,5 dioxo 1,2,4 - Google Patents
A kind of method for preparing the triazole of 3,5 dioxo 1,2,4 Download PDFInfo
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- CN105439969B CN105439969B CN201510831064.0A CN201510831064A CN105439969B CN 105439969 B CN105439969 B CN 105439969B CN 201510831064 A CN201510831064 A CN 201510831064A CN 105439969 B CN105439969 B CN 105439969B
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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
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
Abstract
The present invention proposes the method that one kind prepares the triazole of 3,5 dioxo 1,2,4, is characterized in the WO of oxygen vacancies be present3‑xNanometer sheet adds appropriate additive as raw material in a solvent using tungstic acid hydrate sodium in acid condition, directly synthesized with solvent heat or the step of direct-fired method one, the tungsten oxide nanometer sheet that oxygen vacancies be present is made first, tungsten oxide nanometer sheet catalysis oxidation sulfilimine is prepared 3 again, 5 dioxos 1,2,4 triazoles.Reaction condition of the present invention is simple, and cost is low, pollution-free, not only with important industrial application value, and has important environment and social effect.
Description
Technical field
The present invention relates to organic chemistry, and in particular to one kind prepares 3,5- dioxos -1,2, the method for 4- triazoles, refers to
One kind utilizes WO3-xNanometer sheet catalysis oxidation urazole is the method for 3,5- dioxo -1,2,4- triazoles.
Background technology
3,5- dioxos -1,2,4- triazoles are a kind of organic compounds with important biomolecule activity, are had extensive
Bioactivity, some 3,5- dioxos -1,2, the derivative of 4- triazoles not only show antitumor, antiviral, antibacterial etc. live
Property, 3,5- dioxos -1,2,4- triazole derivatives can be also used for active amino acid, polypeptide, albumen, vaccine it is compound
(PCT Patent, WO2013009564), clinically with important application.Usual 3,5- dioxo -1,2,4- triazoles pass through oxygen
It is prepared by urazole corresponding to change.Currently used oxidant has the immobilized nitric acid of dinitrogen tetroxide, silica, tetrabutylammonium high
(the 1.Journal of such as iodate, sodium metaperiodate+TBAB, chlorine, lodine chloride, silver nitrate, persulfate
Organic Chemistry,2007,vol.72,6816.2.Synthetic Communications,2009,vol.39,
4264.3.Journal of the Chemical Society-Perkin Transactions1,1996,167.).These oxygen
Agent is volatile to have strong corrosivity such as dinitrogen tetroxide, chlorine, lodine chloride etc.；What is had is expensive such as silver nitrate, height
Point hydrochlorate etc..So cause above all of oxidant not meet the requirement of Atom economy, it is more to there is trivial operations, accessory substance
Unfavorable product purification and easily pollution environment, the shortcomings of cost is high.Therefore, urazole can be oxidized to 3,5- dioxo -1 by exploitation,
Pollution-free, the inexpensive green oxidation method of 2,4- triazoles not only has important industrial application value, and with weight
The environment and social effect wanted.
The content of the invention
The technical problems to be solved by the invention are to provide the WO of oxygen vacancies be present3-xNanometer sheet is that catalyst utilized
The method that oxidation hydroxide urazole prepares 3,5- dioxo -1,2,4- triazole compounds.
In order to solve the above technical problems, the technical solution used in the present invention is：One kind prepares 3,5- dioxos -1,2,4-
The method of triazole, the WO of oxygen vacancies be present3-xNanometer sheet adds in a solvent using tungstic acid hydrate sodium as raw material in acid condition
Enter appropriate additive, directly synthesized with solvent heat or the step of direct-fired method one, its preparation methods steps are：
(1) 1~3 mM of Disodium tungstate (Na2WO4) dihydrate is dissolved in 15~25 milliliters of water, stirs 5~20 minutes, be made into
With transparent solution；
(2) 6~13 milliliters of ethanol is added into above-mentioned solution, is stirred 5~20 minutes；
(3) 15~25 milliliters of sulfuric acid is added into above-mentioned solution, is stirred 5~20 minutes；
(4) 0.1~0.6 gram of PEG20000 is added into above-mentioned solution, is stirred 5~20 minutes；
(5) said mixture is transferred to closed in 100 milliliters of reactors for having polytetrafluoro liner, 120~200 DEG C of stirrings 3
~5 hours, it is cooled to room temperature；
(6) reactant mixture after above-mentioned cooling is poured into 500 milliliters of distilled water, collect sediment, spend successively from
Sub- water and absolute ethyl alcohol washing, vacuum drying obtain the tungsten oxide (WO that oxygen vacancies be present3-x) nanometer sheet；
WO3-xNanometer sheet catalysis oxidation urine azole compounds prepare 3,5- dioxos -1,2,4- triazoles, and reaction equation is：
Detailed process is：
(1) 1 mM of urine azole compounds are added in reactor, add 1~5 milliliter of solvent, add catalyst
(WO3-x) 0.005~0.05 mM, 1~3 mM of 30% hydrogen peroxide, 20~100 DEG C are stirred 10~120 minutes, instead
Ying Shiwei：
(2) 10 milliliters are diluted to by above-mentioned, ether extraction, concentration removes solvent, rapid column chromatography, is calculated with gained sterling
Yield.
The solvent refers to polar solvent, including methanol, ethanol, acetonitrile, acetic acid, N, N-METHYLFORMAMIDE.
The present invention uses a kind of method for preparing 3,5- dioxo -1,2,4- triazoles designed by above-mentioned technical proposal,
This method reaction condition is simple, and cost is low, pollution-free, not only with important industrial application value, and has important ring
Border and social effect.
Embodiment
The present invention prepares 3,5- dioxos -1,2, the method for 4- triazoles, the WO of oxygen vacancies be present3-xNanometer sheet is in acid
Appropriate additive is added in certain solvent using tungstic acid hydrate sodium as raw material under the conditions of property, with solvent heat or is directly heated
The step of method one directly synthesize.
Embodiment 1
(1) 1 mM of Disodium tungstate (Na2WO4) dihydrate is dissolved in 15 milliliters of water, stirred 5 minutes, is made into transparent molten
Liquid；
(2) 6 milliliters of ethanol is added into above-mentioned solution, is stirred 5 minutes；
(3) 15 milliliters of sulfuric acid is added into above-mentioned solution, is stirred 5 minutes；
(4) 0.1 gram of PEG20000 is added into above-mentioned solution, is stirred 5 minutes；
(5) said mixture is transferred to it is closed in 100 milliliters of reactors for having polytetrafluoro liner, 120 DEG C stir 3 hours,
It is cooled to room temperature；
(6) reactant mixture after above-mentioned cooling is poured into 500 milliliters of distilled water, collect sediment, spend successively from
Sub- water and absolute ethyl alcohol washing, vacuum drying obtain the tungsten oxide (WO that oxygen vacancies be present3-x) nanometer sheet.
Embodiment 2
(1) 2 mMs of Disodium tungstate (Na2WO4) dihydrate is dissolved in 20 milliliters of water, stirs 10 minutes, be made into transparent
Solution；
(2) 10 milliliters of ethanol is added into above-mentioned solution, is stirred 10 minutes；
(3) 20 milliliters of sulfuric acid is added into above-mentioned solution, is stirred 10 minutes；
(4) 0.3 gram of PEG20000 is added into above-mentioned solution, is stirred 10 minutes；
(5) by said mixture be transferred in 100 milliliters of reactors for having polytetrafluoro liner it is closed in, 160 DEG C of stirrings are 8 small
When, it is cooled to room temperature；
(6) reactant mixture after above-mentioned cooling is poured into 500 milliliters of distilled water, collect sediment, spend successively from
Sub- water and absolute ethyl alcohol washing, vacuum drying obtain the WO of the presence oxygen vacancies of bluish violet3-xNanometer sheet.
Embodiment 3
(1) 3 mMs of Disodium tungstate (Na2WO4) dihydrate is dissolved in 25 milliliters of water, stirs 20 minutes, be made into transparent
Solution；
(2) 13 milliliters of ethanol is added into above-mentioned solution, is stirred 20 minutes；
(3) 25 milliliters of sulfuric acid is added into above-mentioned solution, is stirred 20 minutes；
(4) 0.6 gram of PEG20000 is added into above-mentioned solution, is stirred 20 minutes；
(5) said mixture is transferred to it is closed in 100 milliliters of reactors for having polytetrafluoro liner, 200 DEG C stir 5 hours,
It is cooled to room temperature；
(6) reactant mixture after above-mentioned cooling is poured into 500 milliliters of distilled water, collect sediment, spend successively from
Sub- water and absolute ethyl alcohol washing, vacuum drying obtain the tungsten oxide (WO that oxygen vacancies be present3-x) nanometer sheet；
Embodiment 4
WO of the present invention3-xNanometer sheet catalysis oxidation N- (4- alkynes -1- amyl groups) urazole prepares N- (4- alkynes -1- amyl groups) -3,5- two
Oxo -1,2,4- triazoles, reaction equation are：
Concretely comprise the following steps：
(1) 1 mM N- (4- alkynes -1- amyl groups) urazole is added in reactor, adds 2 milliliters of acetonitrile, addition is urged
Agent (WO3-x) 0.02 mM, 2 mMs of 30% hydrogen peroxide, 30 DEG C are stirred 1 hour；
(2) water is added to release to 10 milliliters above-mentioned weak solution, ether extraction, concentration removes solvent, rapid column chromatography, obtains N-
(4- alkynes -1- amyl groups) -3,5- dioxos -1,2,4- triazoles, red solid, yield 93%；1H NMR(400MHz；CDCl3,
δ):7.58-7.40(m,5H)。
Embodiment 5
WO of the present invention3-xNanometer sheet catalysis oxidation N- phenyl urazoles preparation N- phenyl -3,5- dioxos -1,2,4- triazoles,
Reaction equation is：
Concretely comprise the following steps：
(1) 1 mM of N- phenyl urazoles are added in reactor, add 1 milliliter of water, add catalyst (WO3-x)
0.05 mM, 3 mMs of 30% hydrogen peroxide, 70 DEG C are stirred 3 hours；
(2) water is added to release to 10 milliliters above-mentioned weak solution, ether extraction, concentration removes solvent, rapid column chromatography, obtains N-
Phenyl -3,5- dioxo -1,2,4- triazoles, red solid, yield 84%；1H NMR(400MHz；CDCl3,δ):7.58-
7.40(m,5H)。
Embodiment 6
WO of the present invention3-xNanometer sheet catalysis oxidation N- phenyl urazoles prepare 4- (4- alkynes-amyl group) -3,5- dioxos -1,2,4-
Triazole, reaction equation are：
Concretely comprise the following steps：
(1) 1 mM N- (4- alkynes-amyl group) urazole is added in reactor, adds 1 milliliter of acetonitrile, add catalysis
Agent (WO3-x) 0.03 mM, 2 mMs of 30% hydrogen peroxide, 30 DEG C are stirred 1 hour；
(2) water is added to release to 10 milliliters above-mentioned weak solution, ether extraction, concentration removes solvent, rapid column chromatography, obtains 4-
(4- alkynes-amyl group) -3,5- dioxos -1,2,4- triazoles, red solid, yield 86%；1H NMR(400MHz；CDCl3,δ):
4.02 (t, J=7.6Hz, 2H), 2.50 (t, J=7.6Hz, 2H), 1.96 (s, 1H), 1.75 (m, 2H).
In the various embodiments described above, solvent is often referred to polar solvent, including methanol, ethanol, acetonitrile, acetic acid, N, N- methyl first
Acid amides etc..
Claims (2)
1. one kind prepares 3,5- dioxos -1,2, the method for 4- triazoles, it is characterized in that the WO of oxygen vacancies be present3-xNanometer sheet
Catalysis oxidation urine azole compounds prepare 3,5- dioxos -1,2,4- triazole compounds, wherein urine azole compounds are3,5- dioxo -1,2,4- triazole compounds areReaction equation is：
Wherein, R is phenyl or 3- (acetenyl) propyl group；
Detailed process is：
(1) 1 mM of urine azole compounds are added in reactor, add 1~5 milliliter of solvent, add catalyst
(WO3-x) 0.005~0.05 mM, 1~3 mM of 30% hydrogen peroxide, 20~100 DEG C are stirred 10~120 minutes；
(2) 10 milliliters are diluted to by above-mentioned, ether extraction, concentration removes solvent, rapid column chromatography, is calculated and received with gained sterling
Rate；
The WO that oxygen vacancies be present3-xNanometer sheet is in acid condition using tungstic acid hydrate sodium as raw material, is added in a solvent suitable
When additive, synthesized with solvent heat or direct-fired method, its preparation methods steps are：
(1) 1~3 mM of Disodium tungstate (Na2WO4) dihydrate is dissolved in 15~25 milliliters of water, stirred 5~20 minutes, is made into uniformly
Transparent solution；
(2) 6~13 milliliters of ethanol is added into above-mentioned solution, is stirred 5~20 minutes；
(3) 15~25 milliliters of sulfuric acid is added into above-mentioned solution, is stirred 5~20 minutes；
(4) 0.1~0.6 gram of PEG20000 is added into above-mentioned solution, is stirred 5~20 minutes；
(5) said mixture is transferred to closed in 100 milliliters of reactors for having polytetrafluoro liner, 120~200 DEG C of stirrings are 3~5 small
When, it is cooled to room temperature；
(6) reactant mixture after above-mentioned cooling is poured into 500 milliliters of distilled water, collects sediment, use deionized water successively
Washed with absolute ethyl alcohol, vacuum drying obtains the tungsten oxide (WO that oxygen vacancies be present3-x) nanometer sheet.
2. one kind according to claim 1 prepares 3,5- dioxos -1,2, the method for 4- triazoles, it is characterized in that described molten
Agent nail alcohol, ethanol, acetonitrile, acetic acid or N, N-METHYLFORMAMIDE.
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Cited By (1)
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| EP3712137A4 (en) * | 2018-06-12 | 2021-08-18 | Tokuyama Corporation | Method for producing solid triazolinedione compound, solid triazolinedione compound, and method for producing triazolinedione compound |
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| CN109651273B (en) * | 2019-01-30 | 2021-12-31 | 山东安舜制药有限公司 | Green and environment-friendly preparation method of 1-H-1,2, 3-triazole |
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| WO2015018928A1 (en) * | 2013-08-09 | 2015-02-12 | Universiteit Gent | Urazole compounds |
| CN104672157B (en) * | 2015-02-12 | 2017-06-27 | 山东潍坊润丰化工股份有限公司 | A kind of preparation method of aryltriazolinones |
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| EP3712137A4 (en) * | 2018-06-12 | 2021-08-18 | Tokuyama Corporation | Method for producing solid triazolinedione compound, solid triazolinedione compound, and method for producing triazolinedione compound |
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