CN105153052A - Method for preparing 1, 2, 3-triazole type compounds in ion liquid - Google Patents
Method for preparing 1, 2, 3-triazole type compounds in ion liquid Download PDFInfo
- Publication number
- CN105153052A CN105153052A CN201510541950.XA CN201510541950A CN105153052A CN 105153052 A CN105153052 A CN 105153052A CN 201510541950 A CN201510541950 A CN 201510541950A CN 105153052 A CN105153052 A CN 105153052A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- compound
- triazole
- nanometer copper
- triazole compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 1, 2, 3-triazole type compounds in ion liquid. The method includes steps of firstly, dissolving CuSO4.5H2O in water under room temperature, adding Zn granules, dripping hydrochloric acid solution to dissolve excessive Zn, allowing for reaction until no bubbles are generated, filtering, and washing filter cake with hydrochloric acid to obtain nano-copper catalysts; secondly, adding the nano-copper catalysts into the ion liquid, adding end group alkyne compounds and trinitride, stirring under room temperature for reaction to separate out solids, adding appropriate amount of diethyl ether, filtering, washing filter cake to obtain nano-copper catalysts for recycling, and purifying filtrate to obtain the 1, 2, 3-triazole type compounds. The method has the advantages that the nano-copper catalysts are simple to prepare, low in use amount, efficient and recyclable, traditional organic solvents are replaced by the ion liquid, and the method is environmental friendly.
Description
Technical field
The invention belongs to the synthesis technical field of 1,2,3-triazole compound, be specifically related to a kind of method preparing 1,2,3-triazole compound in ionic liquid.
Background technology
Along with developing rapidly of heterocyclic chemistry, the study on the synthesis of triazole class compounds and derivative thereof is subject to the great attention of investigator in the numerous areas such as organic chemistry, pharmaceutical chemistry, materials chemistry and organometallic chemistry always.Wherein, 1,2,3-triazole is a kind of five member ring heterocyclic compound containing three adjacent nitrogen atoms, hydrogen on its nitrogen can dissociate distribution, thus there is unique physical properties, the 5-membered aromatic azepine structure of its uniqueness can make it that interaction of multiple non covalent bond occurs, as hydrogen bond, with metallic ion coordination and hydrophobic and electrostatic interaction etc., thus show various biological activity, as antibacterial, antiviral, anticancer and tuberculosis etc., it is always the study hotspot in drug development and structure of modification field.Successfully development becomes 1 of medicine, 2,3-triazole compound has beta-lactamase inhibitor Tazobactam Sodium (Tazobactam), Tazobactam Sodium is the derivative of a penicillin, be after clavulanic acid, Sulbactam the 3rd be applied to clinical beta-lactamase inhibitor, comparatively the above two have had and have significantly improved (JournalofMedicinalChemistry, 1987 its inhibit activities, 30,1469).ADZ6140 is also a kind of 1, 2, the medicine of 3-triazole derivatives, first reversible oral P2Y12 adenosine diphosphate receptor antagonists of mating type in the world, be by Astrazeneca AB of the U.S. research and develop a kind of novel, there is optionally small molecules anticoagulation medicine, the reversible purine ADZ6140 acceptor acted on smooth muscle cell of this medicine, to the platelet aggregation that adenosine diphosphate (ADP) causes, there is good restraining effect, oral rear rapid-action, significantly reduce the cardiovascular death of Acute Coronary Syndrome Patients and probability (the Zhejiang chemical industry of heart attack, 2015, 46 (1): 8-15), compared with clopidogrel, greatly reduce patient's heart stalk, palsy or cardiovascular death equivalent risk.Current ADZ6140 gets permission listing in more than 40 countries.
2002, Sharpless finds that cuprous salt can the cycloaddition reaction of catalysis triazo-compound and end-group alkyne effectively, obtain regioselectivity single-minded 1,4-bis-replaces-1,2,3-triazole product (AngewandteChemieInternationalEdition, 2002,41 (14): 2596-2599).With traditional thermocatalysis Husigen reacting phase ratio, reaction conditions is gentle, speed is fast, productive rate is high and regioselectivity is good.After this, various copper catalyst system become the study hotspot of nitrine and end-group alkyne cycloaddition reaction, comprising: Cu, Cu (I), Cu (II)/reduction system and Cu (II).But these catalyst system often exist copper amount greatly, part toxicity is large, uses the shortcomings such as toxic organic solvents.Particularly Cu, that is: copper wire, copper billet etc., catalytic activity is very low, reacts hardly.Relatively common copper wire, copper billet, Nanometer Copper is that size is little as the major advantage of catalyzer, and specific surface area is large, fully can contact, drastically increase speed of reaction with reaction substrate, the few and reusable edible of consumption.
Ionic liquid, is generally the organic cation of nitrogenous or phosphorus heterocycle and inorganic anion composition, be the salt of liquid, because zwitterion number is equal, thus show electric neutrality on the whole, also known as ionic liquid at room temperature or organic ion liquid etc. under room temperature.The major advantage of ionic liquid is non-volatile or " zero " vapour pressure, it can be used as reaction solvent, is greatly better than volatile, inflammable and explosive organic solvent, and this is the important evidence that ionic liquid is considered to green solvent.Thermodynamic stability is high, has good solvability to organic and mineral compound, can be used for the reaction under high vacuum condition, ionic liquid has good ionic conductivity and thermal conductivity in addition, do not burn, pollution-free, be the solvent of a kind of strong polarity, low coordination ability.Due to these advantages, ionic liquid causes the extensive concern of countries in the world scientist.
Therefore, mentality of designing of the present invention is catalyzer with Nanometer Copper, take ionic liquid as solvent, green high-efficient ground synthesis 1,2,3-triazole compound.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of method preparing 1,2,3-triazole compound in ionic liquid of environmental protection.
The present invention adopts following technical scheme for solving the problems of the technologies described above, and a kind of method preparing 1,2,3-triazole compound in ionic liquid, is characterized in that concrete steps are: the synthesis of (1) Nanometer Copper catalyzer, by CuSO under room temperature
45H
2o is soluble in water, adds Zn grain, and constantly stirring has the garnet copper powder precipitation of fines out, solution becomes colourless by blueness, and drip the excessive Zn of dissolve with hydrochloric acid solution subsequently, reaction is to no longer emitting bubble, filter, obtain Nanometer Copper catalyzer with drying after hydrochloric acid washing leaching cake; The synthesis of (2) 1,2,3-triazole compounds, join in ionic liquid by Nanometer Copper catalyzer, then add end-group alkyne compounds and triazo-compound, stirring at room temperature is reacted, reaction terminates rear solid and separates out, add ether, filter, the Nanometer Copper catalyzer recirculation obtained after filter cake cleaning uses, target product 1 is obtained after filtrate is purified, 2,3-triazole compound, described ionic liquid is 1-butyl-3-Methylimidazole hexafluorophosphate ([Bmim] PF
6) or chlorination 1-butyl-3-Methylimidazole ([Bmim] Cl).
Further preferably, described end-group alkyne compounds is phenylacetylene or to Methoxy-phenylacetylene.
Further preferably, described triazo-compound is aziminobenzene, p-methylphenyl nitrine, Chloro-O-Phenyl nitrine or benzyl azide.
Further preferably, CuSO in step (1)
45H
2the mol ratio of O and Zn is 1:1.3-2.
Further preferably, in step (2), the mol ratio of end group acetylene compound, triazo-compound and Nanometer Copper catalyzer is 1:1:0.03.
The present invention compared with prior art has the following advantages: (1) reaction conditions is gentle, and easy to operate, the scope of application is wider; (2) Nanometer Copper catalyst preparing is simple, and consumption is few, efficient and can be recycled repeatedly; (3) ionic liquid replaces traditional organic solvent, is a kind of method of preparation 1,2,3-triazole compound of environmental protection.
Embodiment
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
The synthesis of Nanometer Copper catalyzer
By CuSO under room temperature
45H
2o(1mmol) soluble in water, add Zn grain (1.3mmol), continuous stirring has the garnet copper powder precipitation of fines out, solution becomes colourless by blueness, instill the excessive Zn of dissolving with hydrochloric acid subsequently, reaction, to no longer emitting bubble, is filtered, is obtained Nanometer Copper catalyzer with drying after hydrochloric acid washing leaching cake.
Embodiment 2
The synthesis of Nanometer Copper catalyzer
By CuSO under room temperature
45H
2o(1mmol) soluble in water, add Zn grain (2mmol), continuous stirring has the garnet copper powder precipitation of fines out, solution becomes colourless by blueness, instill the excessive Zn of dissolving with hydrochloric acid subsequently, reaction, to no longer emitting bubble, is filtered, is obtained Nanometer Copper catalyzer with drying after hydrochloric acid washing leaching cake.
Embodiment 3
The synthesis of Isosorbide-5-Nitrae-phenylbenzene-1H-1,2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim] PF
6) in, add aziminobenzene (1mmol) and phenylacetylene (1mmol) under room temperature, magnetic agitation, have solid to separate out, add appropriate ether after reaction terminates, filter, purifying filtrate obtains Isosorbide-5-Nitrae-phenylbenzene-1H-1,2,3-triazole, yield 95%.
Embodiment 4
The synthesis of Isosorbide-5-Nitrae-phenylbenzene-1H-1,2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim] PF
6) in, aziminobenzene (1mmol) and phenylacetylene (1mmol) is added under room temperature, magnetic agitation, has solid to separate out after reaction terminates, adds appropriate ether, filter, the Nanometer Copper catalyzer recirculation obtained after filter cake cleaning uses, and obtains Isosorbide-5-Nitrae-phenylbenzene-1H-1 after filtrate purifying, 2,3-triazole.Repeat to reclaim Nanometer Copper catalyzer number of times to the impact of reaction yield in table 1.
Table 1 repeats to reclaim Nanometer Copper catalyzer number of times to the impact of reaction yield
| Group | Multiplicity | Reaction times (h) | Yield (%) |
| 1 | 0 | 5 | 95 |
| 2 | 1 | 5 | 93 |
| 3 | 2 | 5 | 94 |
| 4 | 3 | 5 | 93 |
| 5 | 4 | 5 | 93 |
| 6 | 5 | 5 | 93 |
Embodiment 5
4-phenyl-1-(p-methylphenyl)-1H-1, the synthesis of 2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim] PF
6) in, add p-methylphenyl nitrine (1mmol) and phenylacetylene (1mmol) under room temperature, magnetic agitation, there is solid to separate out after reaction terminates, add appropriate ether, filter, purifying filtrate obtains 4-phenyl-1-(p-methylphenyl)-1H-1,2,3-triazole.
Embodiment 6
1-(2-chloro-phenyl-)-4-phenyl-1H-1, the synthesis of 2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim] PF
6) in, add Chloro-O-Phenyl nitrine (1mmol) and phenylacetylene (1mmol) under room temperature, magnetic agitation, there is solid to separate out after reaction terminates, add appropriate ether, filter, purifying filtrate obtains 1-(2-chloro-phenyl-)-4-phenyl-1H-1,2,3-triazole.
Embodiment 7
4-(4-p-methoxy-phenyl)-1-phenyl-1H-1, the synthesis of 2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim] PF
6) in, add aziminobenzene (1mmol) under room temperature and to Methoxy-phenylacetylene (1mmol), magnetic agitation, there is solid to separate out after should terminating, add appropriate ether, filter, purifying filtrate obtains 4-(4-p-methoxy-phenyl)-1-phenyl-1H-1,2,3-triazole.
Embodiment 8
1-benzyl-4-phenyl-1H-1, the synthesis of 2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate ([Bmim] PF
6) in, add benzyl azide (1mmol) and phenylacetylene (1mmol) under room temperature, magnetic agitation, have solid to separate out, add appropriate ether after reaction terminates, filter, purifying filtrate obtains 1-benzyl-4-phenyl-1H-1,2,3-triazole.
Embodiment 9
The synthesis of Isosorbide-5-Nitrae-phenylbenzene-1H-1,2,3-triazole
Take Nanometer Copper catalyzer (0.03mmol) in 0.5mL ionic liquid chlorination 1-butyl-3-Methylimidazole ([Bmim] Cl), aziminobenzene (1mmol) and phenylacetylene (1mmol) is added under room temperature, magnetic agitation, there is solid to separate out after reaction terminates, add appropriate ether, filter, purifying filtrate obtains 1,4-phenylbenzene-1H-1,2,3-triazole.
Embodiment above describes 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; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; under the scope not departing from 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 (5)
1. in ionic liquid, prepare the method for 1,2,3-triazole compound for one kind, it is characterized in that concrete steps are: the synthesis of (1) Nanometer Copper catalyzer, by CuSO under room temperature
45H
2o is soluble in water, adds Zn grain, and constantly stirring has the garnet copper powder precipitation of fines out, solution becomes colourless by blueness, and drip the excessive Zn of dissolve with hydrochloric acid solution subsequently, reaction is to no longer emitting bubble, filter, obtain Nanometer Copper catalyzer with drying after hydrochloric acid washing leaching cake; (2) 1,2, the synthesis of 3-triazole compound, Nanometer Copper catalyzer is joined in ionic liquid, then end-group alkyne compounds and triazo-compound is added, stirring at room temperature is reacted, reaction terminates rear solid and separates out, add ether, filter, the Nanometer Copper catalyzer recirculation obtained after filter cake cleaning uses, target product 1 is obtained after filtrate is purified, 2,3-triazole compound, described ionic liquid is 1-butyl-3-Methylimidazole hexafluorophosphate or chlorination 1-butyl-3-Methylimidazole.
2. the method preparing 1,2,3-triazole compound in ionic liquid according to claim 1, is characterized in that: described end-group alkyne compounds is phenylacetylene or to Methoxy-phenylacetylene.
3. the method preparing 1,2,3-triazole compound in ionic liquid according to claim 1, is characterized in that: described triazo-compound is aziminobenzene, p-methylphenyl nitrine, Chloro-O-Phenyl nitrine or benzyl azide.
4. the method preparing 1,2,3-triazole compound in ionic liquid according to claim 1, is characterized in that: CuSO in step (1)
45H
2the mol ratio of O and Zn is 1:1.3-2.
5. the method preparing 1,2,3-triazole compound in ionic liquid according to claim 1, is characterized in that: in step (2), the mol ratio of end group acetylene compound, triazo-compound and Nanometer Copper catalyzer is 1:1:0.03.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541950.XA CN105153052B (en) | 2015-08-31 | 2015-08-31 | A kind of method that 1,2,3- triazole compounds are prepared in ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541950.XA CN105153052B (en) | 2015-08-31 | 2015-08-31 | A kind of method that 1,2,3- triazole compounds are prepared in ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105153052A true CN105153052A (en) | 2015-12-16 |
| CN105153052B CN105153052B (en) | 2018-06-22 |
Family
ID=54794149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510541950.XA Expired - Fee Related CN105153052B (en) | 2015-08-31 | 2015-08-31 | A kind of method that 1,2,3- triazole compounds are prepared in ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105153052B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949240A (en) * | 2016-05-13 | 2016-09-21 | 河南师范大学 | Method for synthesizing 4-phosphonic acid-1,5-substituted-1,2,3 triazole compounds through catalysis of ionic liquid |
| CN105949136A (en) * | 2016-05-13 | 2016-09-21 | 河南师范大学 | Synthetic method of 1,5-substituted-1,2,3-triazole compounds |
| CN109012750A (en) * | 2018-07-12 | 2018-12-18 | 河南师范大学 | A kind of cuprous oxide catalysis system and its preparation method and application suitable for water phase click reaction |
| CN109503568A (en) * | 2018-12-29 | 2019-03-22 | 山东罗欣药业集团股份有限公司 | A kind of preparation method of Dasatinib |
-
2015
- 2015-08-31 CN CN201510541950.XA patent/CN105153052B/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| DILIP RAUT，等: "Copper nanoparticles in ionic liquids: Recyclable and efficient catalytic system for 1,3-dipolar cycloaddition reaction", 《CATALYSIS COMMUNICATIONS》 * |
| FRANCISCO ALONSO，等: "Copper nanoparticles in click chemistry: an alternative catalytic system for the cycloaddition of terminal alkynes and azides", 《TETRAHEDRON LETTERS》 * |
| YUQIN JIANG,等: "An Efficient Synthesis of 1,4-Disubstituted Triazoles in Water via CuCl2/Zn-Catalyzed Huisgen Cycloaddition", 《ZEITSCHRIFT FUR NATURFORSCHUNG. B: A JOURNAL OF CHEMICAL SCIENCES》 * |
| 梁荣辉，等: "纳米铜催化剂在有机反应中的应用", 《化学通报》 * |
| 楚广，等: "纳米铜粉的制备及其应用", 《金属功能材料》 * |
| 苏扬，等: "采用液相还原法从废铜料中制备纳米铜粉", 《广州化工》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949240A (en) * | 2016-05-13 | 2016-09-21 | 河南师范大学 | Method for synthesizing 4-phosphonic acid-1,5-substituted-1,2,3 triazole compounds through catalysis of ionic liquid |
| CN105949136A (en) * | 2016-05-13 | 2016-09-21 | 河南师范大学 | Synthetic method of 1,5-substituted-1,2,3-triazole compounds |
| CN105949240B (en) * | 2016-05-13 | 2017-10-31 | 河南师范大学 | 4 phosphonic acids 1,5 of ionic liquid-catalyzed synthesis replace the method for 1,2,3 triazole compounds |
| CN105949136B (en) * | 2016-05-13 | 2018-12-11 | 河南师范大学 | A kind of synthetic method of 1,5- substitution -1,2,3- triazole compound |
| CN109012750A (en) * | 2018-07-12 | 2018-12-18 | 河南师范大学 | A kind of cuprous oxide catalysis system and its preparation method and application suitable for water phase click reaction |
| CN109012750B (en) * | 2018-07-12 | 2020-12-25 | 河南师范大学 | Cuprous oxide catalytic system suitable for aqueous phase click reaction and preparation method and application thereof |
| CN109503568A (en) * | 2018-12-29 | 2019-03-22 | 山东罗欣药业集团股份有限公司 | A kind of preparation method of Dasatinib |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105153052B (en) | 2018-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105153052A (en) | Method for preparing 1, 2, 3-triazole type compounds in ion liquid | |
| Aizpurua et al. | Triazolium cations: from the “click” pool to multipurpose applications | |
| CN102741262B (en) | Pharmaceutical composition containing cyclometalated n-heterocyclic carbene complexes for cancer treatment | |
| Harikrishna et al. | A green, facile and recyclable Mn3O4/MWCNT nano-catalyst for the synthesis of quinolines via one-pot multicomponent reactions | |
| CN102603642B (en) | Nickel-containing sandwich polyoxometallate anti-cancer drug and synthesis method thereof | |
| CN102382013A (en) | Preparation method of carbasalate calcium | |
| Achar et al. | Synthesis, characterization, crystal structure and antibacterial properties of N–and O–functionalized (benz) imidazolium salts and their N–heterocyclic carbene silver (I) complexes | |
| CN105017110B (en) | A kind of preparation method of trifluoromethylthio copper (I) and trifluoromethylthio silver (I) | |
| CN104017001B (en) | A kind of method of chemosynthesis mosictin | |
| Arumugam et al. | Heterogenous copper (II) schiff-base complex immobilized mesoporous silica catalyst for multicomponent biginelli reaction | |
| Siddiqui et al. | Molecular self-assembly of cadmium-triazolate complexes via hydrogen bonding: Synthesis, structures and photoluminescent properties | |
| CN105198718A (en) | Preparation method for buparvaquone | |
| CN104478890A (en) | All-trans retinoic acid-camptothecin anticancer drug conjugate as well as preparation method and application thereof | |
| Yuan et al. | Supramolecular assembly of two two-folded helical structures based on 2-substituted 8-hydroxyquinoline complexes | |
| Soni et al. | A decade of synthesis of N-heterocyclic derivatives via magnetically retrievable Fe3O4@ SiO2@ Cu (II) nanocatalysts: A review (2013-present) | |
| CN102964387B (en) | Organic metal ruthenium ion pair compound and preparation method and application thereof | |
| Sultana et al. | Zn@ CS: An Efficient Cu-Free Catalyst System for Direct Azide-Alkyne Cycloadditions and Multicomponent Synthesis of 4-Aryl-NH-1, 2, 3-triazoles in H2O and DES | |
| CN103172637B (en) | Pyrimido [1, 2-a] benzimidazole compound and method for preparing same | |
| CN107417478A (en) | A kind of method of catalysis oxidation carbonyl compound into asymmetric 2-substituted carbamide | |
| Zolfigol et al. | Iodine‐Catalyzed Friedlander Quinoline Synthesis under Solvent‐Free Conditions | |
| CN109790191B (en) | Platinum complexes and methods of use thereof | |
| Mondal et al. | Fabrication of Ionic‐Liquid‐Embedded ZnO Nanoparticles: Application of a Synergistic Catalytic Effect to Thiol‐Induced 2‐Pyridone Synthesis | |
| Sudeep et al. | 1, 2, 3-Triazoles: A review on current trends in synthetic and biological applications | |
| CN104387384A (en) | Synthetic process of 5-bromo-7-azaindole | |
| CN104230778B (en) | The synthetic method of β-hydrocarbon oxygen acyl group-gamma-alkyl-N-alkyl-butyrolactam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180622 Termination date: 20200831 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |