CN107827829A - Preparation method of 5 amide groups, 1,4,5 trisubstituted 1,2,3 triazole in aqueous phase and Biomedia - Google Patents
Preparation method of 5 amide groups, 1,4,5 trisubstituted 1,2,3 triazole in aqueous phase and Biomedia Download PDFInfo
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- CN107827829A CN107827829A CN201711085347.0A CN201711085347A CN107827829A CN 107827829 A CN107827829 A CN 107827829A CN 201711085347 A CN201711085347 A CN 201711085347A CN 107827829 A CN107827829 A CN 107827829A
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- trisubstituted
- amide groups
- 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
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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
Abstract
The invention belongs to technical field of organic synthesis, a kind of 5 amide groups Isosorbide-5-Nitraes, 5 trisubstituted 1, preparation method of 2,3 triazoles in aqueous phase and Biomedia, in a solvent, under 1,5 cyclo-octadiene iridium chloride dimer catalyst action, catalysis alkynes aminated compounds prepares 5 amide groups 1 with nitrine, 4,5 trisubstituted 1,2,3 triazoles.5 amide groups Isosorbide-5-Nitrae in the present invention, 5 trisubstituted 1, the preparation method reaction condition of 2,3 triazole products is gentle, and product yield is not less than 80%.The reaction condition of the preparation method is gentle, green, reaction efficiency height, has potential biologic applications to be worth, 5 amide groups Isosorbide-5-Nitraes being prepared, and 5 trisubstituted 1,2,3 triazole compounds have potential physiologically active.
Description
Technical field
The invention belongs to technical field of organic synthesis, is related to a kind of new 5- amide groups-Isosorbide-5-Nitrae, 5- trisubstituted 1,2,3-
Preparation method of the triazole in aqueous phase and Biomedia.
Background technology
Alkynes-nitrine cycloaddition reaction is to prepare one of most important method of 1,2,3- triazoles.In recent years, an existing system
Row document or the patent report preparation method of 1,2,3- triazole compounds.
Medal seminars in 2001 and Sharpless seminars report copper catalysis Terminal Acetylenes-nitrine cycloaddition reaction respectively
(J.Org.Chem., 2002,67,3057 and Angew.Chem.Int.Ed., 2002,41,2596).The subsequent reaction is by wide
General research and concern.But for ynamine transition metal-catalyzed in aqueous phase-nitrine cycloaddition reaction, report is there is no at present.Such as
It is the emphasis that we pay close attention to that ynamine-nitrine cycloaddition reaction is where realized in aqueous phase.If the cycloaddition can be realized in aqueous phase
Reaction obtains 5- amide groups-Isosorbide-5-Nitrae, and the triazole products of 5- trisubstituted 1,2,3-, we will further use various Biomedias
To study application value of the reaction potentially in biological field.The trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5-
Class compound has potential physiologically active, therefore research its preparation method has important meaning.
It is raw material present invention employs various ynamines, uses 2.5mol% [Ir (COD) Cl]2As catalyst, at 23 DEG C
Under temperate condition, 5- amide groups-Isosorbide-5-Nitrae, 5- trisubstituted 1,2,3- triazole compounds are obtained with 80%~87% yield.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind to synthesize 5- amide groups -1,4,5- in aqueous phase and Biomedia
The method of trisubstituted 1,2,3- triazole compounds.
Technical scheme：
A kind of preparation side of new trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- in aqueous phase and Biomedia
Method, step are as follows：
In a solvent, at 1,5- cyclo-octadiene iridium chlorides dimer ([Ir (COD) Cl]2) under catalyst action, it is catalyzed alkynes
Aminated compounds and nitrine preparation 5- amide groups-Isosorbide-5-Nitrae, 5- trisubstituted 1,2,3- triazoles, reaction equation are as follows：
Wherein, R1And R2For hydrogen atom, alkyl, alkoxy or aryl, R1And R2It is identical or different；
R3For alkyl, alkoxy or aryl；
R4For alkyl or aryl；
I is alkynes aminated compounds；
Reaction temperature is -15 DEG C~25 DEG C, and the reaction time is 8h~16h, and the 5- acyls that yield is not less than 70% are prepared
The trisubstituted 1,2,3- triazoles of amido -1,4,5-.
Described alkynes aminated compounds and the mol ratio of nitrine are 1:1, the concentration 0.01-0.1mmol/ of alkynes aminated compounds
ml。
Described [Ir (COD) Cl]2Dosage be alkynes aminated compounds 0.5~50mol%.
Described solvent is water, phosphate buffered saline solution (pH=1~14), DMEM cell culture fluids, the cracking of HeLa cells
Liquid, Normal Mouse Serum (concentration is 50%~100%), normal human serum (concentration is 50%~100%), preferred solvent is water
Or phosphate buffered saline solution (pH=5.7).
Beneficial effects of the present invention：The trisubstituted 1,2,3- triazoles products of 5- amide groups -1,4,5- in the present invention
Preparation method reaction condition is gentle, and product yield is not less than 80%.The reaction condition of the preparation method is gentle, green, reaction effect
Rate is high, has potential biologic applications to be worth, the 5- amide groups-Isosorbide-5-Nitrae being prepared, the triazole chemical combination of 5- trisubstituted 1,2,3-
Thing has potential physiologically active.
Embodiment
Below in conjunction with technical scheme, embodiment of the invention is further illustrated.
Embodiment 1：The preparation of 1- benzyl -4- phenyl -5- (pyrazoline 2- ketone groups) -1H-1,2,3- triazoles
Under air, 3- phenylene-ethynylenes-pyrazoline 2- ketone (0.2mmol, 37.4mg) is added in water (2mL), then
Add benzyl azide (0.3mmol, 40.2mg) and [Ir (COD) Cl]2(0.005mmol, 3.3mg), reaction mixing is stirred at room temperature
Thing, 12h to be reacted, is extracted with ethyl acetate after having reacted, selects dry solvent, column chromatography for separation obtains yellow solid product 54.4mg,
Yield 85%.
Embodiment 2：The preparation of 1- benzyl -4- p-methoxyphenyls -5- (pyrazoline 2- ketone groups) -1H-1,2,3- triazoles
Under air, 3- p-methoxyphenyls acetenyl-pyrazoline 2- ketone (0.2mmol, 43.4mg) is added to water
In (2mL), benzyl azide (0.3mmol, 40.2mg) and [Ir (COD) Cl] are added2(0.005mmol, 3.3mg), room temperature is stirred
Reactant mixture is mixed, 12h is reacted, is extracted with ethyl acetate after having reacted, selects dry solvent, column chromatography for separation obtains yellow liquid production
Thing 60.9mg, yield 87%.
Embodiment 3：The preparation of 1- benzyl -4- rubigan -5- (pyrazoline 2- ketone groups) -1H-1,2,3- triazoles
Under air, 3- rubigan acetenyl-pyrazoline 2- ketone (0.2mmol, 44.2mg) is added to water (2mL)
In, add benzyl azide (0.3mmol, 40.2mg) and [Ir (COD) Cl]2(0.005mmol, 3.3mg), reaction is stirred at room temperature
Mixture, 12h is reacted, is extracted with ethyl acetate after having reacted, selects dry solvent, column chromatography for separation obtains white solid product
56.7mg, yield 80%.
Embodiment 4：The preparation of 1- p-chlorobenzyl -4- phenyl -5- (pyrazoline 2- ketone groups) -1H-1,2,3- triazoles
Under air, 3- phenylene-ethynylenes-pyrazoline 2- ketone (0.2mmol, 37.4mg) is added in water (2mL), then
Add p-chlorobenzyl nitrine (0.3mmol, 50.1mg) and [Ir (COD) Cl]2(0.005mmol, 3.3mg), reaction is stirred at room temperature
Mixture, 12h is reacted, is extracted with ethyl acetate after having reacted, selects dry solvent, column chromatography for separation obtains white solid product
60.1mg, yield 85%.
Embodiment 5：Preparations of the 1- to methyl-benzyl -4- phenyl -5- (pyrazoline 2- ketone groups) -1H-1,2,3- triazoles
Under air, 3- phenylene-ethynylenes-pyrazoline 2- ketone (0.2mmol, 37.4mg) is added in water (2mL), then
Add to methyl-benzyl nitrine (0.3mmol, 44.1mg) and [Ir (COD) Cl]2(0.005mmol, 3.3mg), it is stirred at room temperature anti-
Mixture is answered, 12h is reacted, is extracted with ethyl acetate after having reacted, selects dry solvent, column chromatography for separation obtains white liquid product
54.9mg, yield 82%.
Claims (8)
1. a kind of 5- amide groups-Isosorbide-5-Nitrae, 5- trisubstituted 1, preparation method of 2, the 3- triazoles in aqueous phase and Biomedia, its
It is characterised by, step is as follows：
In a solvent, under 1,5- cyclo-octadiene iridium chloride dimer catalyst actions, catalysis alkynes aminated compounds and nitrine system
Standby 5- amide groups-Isosorbide-5-Nitrae, 5- trisubstituted 1,2,3- triazoles, reaction equation are as follows：
Wherein, R1And R2For hydrogen atom, alkyl, alkoxy or aryl, R1And R2It is identical or different；
R3For alkyl, alkoxy or aryl；
R4For alkyl or aryl；
I is alkynes aminated compounds；
Reaction temperature be -15 DEG C~25 DEG C, the reaction time be 8h~16h, be prepared yield be not less than 70% 5- amide groups -
The trisubstituted 1,2,3- triazoles of 1,4,5-.
2. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 1 are in aqueous phase and Biomedia
In preparation method, it is characterised in that described alkynes aminated compounds and the mol ratio of nitrine are 1:1, alkynes aminated compounds
Concentration 0.01-0.1mmol/ml.
3. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 1 or 2 are situated between in aqueous phase and biology
Preparation method in matter, it is characterised in that described 1,5- cyclo-octadiene iridium chloride dimers catalyst amount is ynamine class
0.5~50mol% of compound.
4. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 1 or 2 are situated between in aqueous phase and biology
Preparation method in matter, it is characterised in that described solvent is water, phosphate buffered saline solution, DMEM cell culture fluids, HeLa thin
The mice serum or mass percent concentration that cellular lysate liquid, mass percent concentration are 50%~100% are 50%~100%
Human serum.
5. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 3 are in aqueous phase and Biomedia
In preparation method, it is characterised in that described solvent be water, phosphate buffered saline solution, DMEM cell culture fluids, HeLa cells
The people that the mice serum or mass percent concentration that lysate, mass percent concentration are 50%~100% are 50%~100%
Serum.
6. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 1,2 or 5 are in aqueous phase and biology
Preparation method in medium, it is characterised in that described solvent is water or phosphate buffered saline solution.
7. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 3 are in aqueous phase and Biomedia
In preparation method, it is characterised in that described solvent is water or phosphate buffered saline solution.
8. the trisubstituted 1,2,3- triazoles of 5- amide groups -1,4,5- according to claim 4 are in aqueous phase and Biomedia
In preparation method, it is characterised in that described solvent is water or phosphate buffered saline solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269189A (en) * | 2020-03-24 | 2020-06-12 | 大连理工大学 | Preparation method of 5-dithio-1, 4, 5-trisubstituted 1,2, 3-triazole |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768125A (en) * | 2010-01-19 | 2010-07-07 | 浙江大学 | Triazole compound and preparation method thereof |
| CN101941949A (en) * | 2010-09-10 | 2011-01-12 | 大连理工大学 | Triazole heterocyclic compound and synthesis method thereof |
| CN103204820A (en) * | 2012-01-11 | 2013-07-17 | 同济大学 | 3-triazolyl-substituted-1-propylene compound and synthetic method thereof |
| WO2013189865A1 (en) * | 2012-06-20 | 2013-12-27 | F. Hoffmann-La Roche Ag | N-aryltriazole compounds as lpar antagonists |
| CN106966994A (en) * | 2017-03-15 | 2017-07-21 | 大连理工大学 | A kind of triazole of N sulfonyls 1,2,3 of new 4 allyl acetic acid ester group substitution and preparation method thereof |
-
2017
- 2017-11-07 CN CN201711085347.0A patent/CN107827829A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768125A (en) * | 2010-01-19 | 2010-07-07 | 浙江大学 | Triazole compound and preparation method thereof |
| CN101941949A (en) * | 2010-09-10 | 2011-01-12 | 大连理工大学 | Triazole heterocyclic compound and synthesis method thereof |
| CN103204820A (en) * | 2012-01-11 | 2013-07-17 | 同济大学 | 3-triazolyl-substituted-1-propylene compound and synthetic method thereof |
| WO2013189865A1 (en) * | 2012-06-20 | 2013-12-27 | F. Hoffmann-La Roche Ag | N-aryltriazole compounds as lpar antagonists |
| CN104395299A (en) * | 2012-06-20 | 2015-03-04 | 霍夫曼-拉罗奇有限公司 | N-aryltriazole compounds as lpar antagonists |
| CN106966994A (en) * | 2017-03-15 | 2017-07-21 | 大连理工大学 | A kind of triazole of N sulfonyls 1,2,3 of new 4 allyl acetic acid ester group substitution and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| BRADY T. WORRELL,等: "Halogen Exchange (Halex) Reaction of 5-Iodo-1,2,3-triazoles: Synthesis and Applications of 5-Fluorotriazoles", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
| SHENGTAO DING,等: "Iridium-Catalyzed Intermolecular Azide–Alkyne Cycloaddition of Internal Thioalkynes under Mild Conditions", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
| SOPHIE OPPILLIART,等: "1-Protected 5-amido 1,2,3-triazoles via ruthenium-catalyzed [3+2] cycloaddition of azides and ynamides", 《TETRAHEDRON》 * |
| 吕和平,等: "离子液体中纳米铜催化Huisgen-Click反应", 《合成化学》 * |
| 李晓莲,等: "含三氮唑杂环液晶中间体的合成", 《液晶与显示》 * |
| 李海根,等: "三分子(叠氮化钠、炔烃、乙酸酯)反应合成1,4-二取代-1,2,3-三氮唑", 《云南大学学报(自然科学版)》 * |
| 江玉波,等: "1,2,3-三氮唑衍生物的合成", 《化学进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269189A (en) * | 2020-03-24 | 2020-06-12 | 大连理工大学 | Preparation method of 5-dithio-1, 4, 5-trisubstituted 1,2, 3-triazole |
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