CN105218524A - " one kettle way " synthesizes the method that 3,5-bis-replaces-1,2,4-triazole compound - Google Patents
" one kettle way " synthesizes the method that 3,5-bis-replaces-1,2,4-triazole compound Download PDFInfo
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- CN105218524A CN105218524A CN201510681600.3A CN201510681600A CN105218524A CN 105218524 A CN105218524 A CN 105218524A CN 201510681600 A CN201510681600 A CN 201510681600A CN 105218524 A CN105218524 A CN 105218524A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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Abstract
The invention provides one " one kettle way " 3,5-bis-methods that replace-1,2,4-triazole compound of preparation as shown in general formula (I), in general formula: X
1, X
2, X
3, X
4in have at least one to be selected from nitrogen-atoms, all the other are selected from-CH; X
5, X
6, X
7, X
8in have at least one to be selected from nitrogen-atoms, all the other are selected from-CH.The present invention adopts cascade reaction, and all intermediate products do not add separation and purification, is namely raw material with aryl nitrile, with direct synthesising target compound under solvent thermal condition after the addition of methoxyl group negative ion, synthesis step is simple, and aftertreatment is also very convenient, easily realizes scale operation.
Description
Technical field
The invention provides a kind of synthetic method of 1,2,4-3-triazole compounds, specifically relate to the method that " one kettle way " synthesizes 1,2,4-3-triazole compounds, belong to technical field of organic synthesis.
Background technology
It is the important organic ligand of a class that 3,5-bis-replaces-1,2,4-triazole, there is magnetic, fluorescence, the performances such as gas adsorption, such as 3 by the metal complexes of its synthesis, the univalent copper complex of 5-bis-(2-pyridyl)-1,3,4-triazoles just has good photoluminescence performance.Having been reported about the preparation method of 3,5-diazacyclo 1,2,4-triazole in current document, is specifically raw material with aryl nitrile, and obtain imido grpup methylhydrazide with carrying out being separated after the addition of methoxyl group negative ion, then in ethylene glycol, high temperature reflux obtains target product.Whole requirements of process two step operation, and ethylene glycol boiling point is high, viscosity is large, is unfavorable for that the finished product are separated.
Summary of the invention
The invention provides a kind of 1,2,4-3-triazole compounds " one kettle way " and synthetic method, complicated to solve synthesis technique in prior art, and due to ethylene glycol boiling point high, viscosity is large, the technical problem of the product separation difficulty caused.
For this reason, the invention provides one " one kettle way " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound, and described 3,5-bis-replace-1,2,4-triazole compound has structure as shown in general formula (I),
Wherein: X
1, X
2, X
3, X
5in have at least one to be selected from nitrogen-atoms, all the other are selected from-CH; X
5, X
6, X
7, X
8in have at least one to be selected from nitrogen-atoms, all the other are selected from-CH;
Described method comprises the steps:
Make the back flow reaction 3 ~ 4 hours under catalyzer alcohol sodium solution existent condition of the compound shown in general formula (II), add compound shown in general formula (III) again, continue back flow reaction 15-30 minute, transfer to while hot in hydrothermal reaction kettle in 160 DEG C of reaction 10-12 hour; Reaction system is cooled to room temperature, decompress filter, obtains general formula (I) described compound, and the mol ratio of general formula described in above-mentioned reaction (II) and the compound represented by general formula (III) is 1: 1;
General formula (II) and the middle X of general formula (III)
1-X
8definition and general formula (I) in definition identical.
Preferably, described X
5, X
6, X
7in have one to be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
5and X
8be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
6and X
8be selected from nitrogen-atoms, all the other are selected from-CH.
More preferably, described X
1, X
2, X
3, X
4in have one or two to be selected from nitrogen-atoms, all the other are selected from-CH; X
5, X
6, X
7, X
8in have one or two to be selected from nitrogen-atoms, all the other are selected from-CH.Described X
1, X
2, X
3in have one to be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
1and X
4be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
2and X
4be selected from nitrogen-atoms, all the other are selected from-CH;
More preferably, described 3,5-bis-replace-1,2,4-triazole compound and are selected from following structural formula:
More preferably, the compound shown in described general formula (II) is selected from
compound shown in described general formula (III) is selected from
Preferably, described alcohol sodium solution is obtained by sodium Metal 99.5 is dissolved in methyl alcohol, and its concentration is 1mol/L.
The present invention adopts cascade reaction, and all intermediate products do not add separation and purification, is namely raw material with aryl nitrile, with direct synthesising target compound under solvent thermal condition after the addition of methoxyl group negative ion, the synthesis step that the present invention adopts is simple, and aftertreatment is also very convenient, easily realizes large-scale mass production.
Embodiment
Understand technical scheme of the present invention better to make those skilled in the art can be implemented, below in conjunction with specific embodiment, the invention will be further described, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
The preparation of 3,5-bis-(2-pyridyl)-1,2,4-3-triazole compounds
30mmol sodium Metal 99.5 is dissolved in 30ml methyl alcohol prepares alcohol sodium solution, add 10mmol2-cyanopyridine, back flow reaction adds 10mmol2-pyridine hydrazides after 3 hours, continue back flow reaction 15-30 minute, transfers to while hot in 50ml hydrothermal reaction kettle in 160 DEG C of reactions 12 hours.Reaction system is cooled to room temperature, decompress filter, and gained white solid is product 3,5-bis-(2-pyridyl)-1,2,4-3-triazole compounds, productive rate 60%.
Adopt nuclear magnetic resonance analyser to carry out nuclear magnetic resonance spectroscopy to above-mentioned product, calculation result is as follows:
1hNMR (400MHz, d
6-DMSO), δ (ppm): 8.66-8.68 (2H), 8.14-8.16 (2H), 7.99-8.01 (2H), 7.52-7.55 (2H).
Embodiment 2
3-pyrazinyl-5-(2-pyridyl)-1,3,4-3-triazole compounds
30mmol sodium Metal 99.5 is dissolved in 30ml methyl alcohol prepares alcohol sodium solution, add 10mmol2-cyanopyrazine, back flow reaction adds 10mmol2-pyridine hydrazides after 3 hours, continue back flow reaction 15-30 minute, transfers to while hot in 50ml hydrothermal reaction kettle in 160 DEG C of reactions 12 hours.Reaction system is cooled to room temperature, decompress filter, and gained white solid is product 3-pyrazinyl-5-(2-pyridyl)-1,3,4-3-triazole compounds, productive rate 56%.
Embodiment 3
3-pyrazinyl-5-(2-pyridyl)-1,3,4-3-triazole compounds
30mmol sodium Metal 99.5 is dissolved in 30ml methyl alcohol prepares alcohol sodium solution, add 10mmol2-cyanopyridine, back flow reaction adds 10mmol2-pyrazine hydrazides after 3 hours, continue back flow reaction 15-30 minute, transfers to while hot in 50ml hydrothermal reaction kettle in 160 DEG C of reactions 12 hours.Reaction system is cooled to room temperature, decompress filter, and gained white solid is product 3-pyrazinyl-5-(2-pyridyl)-1,3,4-3-triazole compounds, productive rate 67%.
Adopt nuclear magnetic resonance analyser to carry out nuclear magnetic resonance spectroscopy to above-mentioned product 3-pyrazinyl-5-(2-pyridyl)-1,3,4-3-triazole compounds, result is as follows:
1hNMR (400MHz, d
6-DMSO), δ (ppm): 9.32-9.35 (1H), 8.73-8.77 (3H), 8.17-8.18 (1H), 7.99-8.01 (1H), 7.52-7.55 (1H).
The above embodiment is only that its protection domain is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention, protection scope of the present invention is as the criterion with claims.
Claims (7)
1. " one kettle way " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound, and described 3,5-bis-replace-1,2,4-triazole compound has structure as shown in general formula (I),
Wherein: X
1, X
2, X
3, X
4in have at least one to be selected from nitrogen-atoms, all the other are selected from-CH; X
5, X
6, X
7, X
8in have at least one to be selected from nitrogen-atoms, all the other are selected from-CH;
Described method comprises the steps:
Make the back flow reaction 3 ~ 4 hours under catalyzer alcohol sodium solution existent condition of the compound shown in general formula (II), add compound shown in general formula (III) again, continue back flow reaction 15-30 minute, transfer to while hot in hydrothermal reaction kettle in 160 DEG C of reaction 10-12 hour; Reaction system is cooled to room temperature, decompress filter, obtains general formula (I) described compound,
It is 2. according to claim 1 that " " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound to one kettle way, it is characterized in that, described X
1, X
2, X
3, X
4in have one or two to be selected from nitrogen-atoms, all the other are selected from-CH; X
5, X
6, X
7, X
8in have one or two to be selected from nitrogen-atoms, all the other are selected from-CH.
3. according to claim 2 " one kettle way " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound, it is characterized in that,
Described X
1, X
2, X
3in have one to be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
1and X
4be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
2and X
4be selected from nitrogen-atoms, all the other are selected from-CH;
Described X
5, X
6, X
7in have one to be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
5and X
8be selected from nitrogen-atoms, all the other are selected from-CH; Or, X
6and X
8be selected from nitrogen-atoms, all the other are selected from-CH.
4. according to claim 3 " one kettle way " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound, and it is characterized in that, described 3,5-bis-replace-1,2,4-triazole compound is selected from following structural formula:
5. according to claim 3 " one kettle way " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound, it is characterized in that,
Compound shown in described general formula (II) is selected from
compound shown in described general formula (III) is selected from
It is 6. according to claim 1 that " " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound to one kettle way, and it is characterized in that, described alcohol sodium solution is obtained by sodium Metal 99.5 is dissolved in methyl alcohol, and its concentration is 1mol/L.
It is 7. according to claim 1 that " " synthesis 3,5-bis-replaces the method for-1,2,4-triazole compound to one kettle way, and it is characterized in that, the mol ratio of described general formula (II) and the compound represented by general formula (III) is 1: 1.
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|---|---|---|---|---|
| CN104945383A (en) * | 2015-06-18 | 2015-09-30 | 山东金城医药化工股份有限公司 | Preparation method for topiroxostat |
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| CN104945383A (en) * | 2015-06-18 | 2015-09-30 | 山东金城医药化工股份有限公司 | Preparation method for topiroxostat |
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