CN101665467A - Application of 1-amino-1,2,3-triazole serving as amination reagent - Google Patents
Application of 1-amino-1,2,3-triazole serving as amination reagent Download PDFInfo
- Publication number
- CN101665467A CN101665467A CN200810119424A CN200810119424A CN101665467A CN 101665467 A CN101665467 A CN 101665467A CN 200810119424 A CN200810119424 A CN 200810119424A CN 200810119424 A CN200810119424 A CN 200810119424A CN 101665467 A CN101665467 A CN 101665467A
- Authority
- CN
- China
- Prior art keywords
- amino
- reaction
- amination
- triazole
- solvent
- 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.)
- Pending
Links
Images
Abstract
The invention relates to application of 1-amino-1,2,3-triazole serving as an amination reagent. A novel use of the 1-amino-1,2,3-triazole is to use the 1-amino-1,2,3-triazole as a cheap amination reagent which can be used to introduce amino radicals to nitryl aromatic hydrocarbon and aromatic heterocyclic compounds with nitryl. The application comprises the following specific steps: (1) mixing the1-amino-1,2,3-triazole and sodium methoxide with solvent to obtain a suspension, wherein the solvent is dimethyl sulfoxide, N,N-dimethylformamide, methanol or ethanol; (2) dissolving reaction materials in the solvent to obtain a solution, wherein the reaction materials are amino radicals to nitryl aromatic hydrocarbon or aromatic heterocyclic compounds with nitryl; and (3) mixing the prepared solutions (1) and (2) under the condition of stirring at a temperature between 10 and 70 DEG C and performing reaction for 1 to 7 hours to obtain amination products. The introduction of the amino radicals to the nitryl aromatic hydrocarbon and the aromatic heterocyclic compounds with nitryl has extensive need and great significance in the fields of pharmaceutical synthesis and organic chemical synthesis.
Description
Technical field
The present invention relates to 1-amino-1,2,3-triazoles technical field, specifically a kind of 1-amino-1,2,3-triazoles is as the application of amination reagent.
Background technology
Triazole is meant the aromatic heterocycle that contains three N atoms, has two kinds: 1,2,3-triazoles and 1,2, and the 4-triazole, the 1,2,3-triazoles isomer is formula as follows:
Triazole has aromaticity, and 1,2,3-triazoles can distill, but thermostability is not too high, blasts when the halo 1,2,3-triazoles is higher than 260 ℃.
The character of triazole sees Table one.
Table one
Triazole class compounds has a lot of important use.In agriculture production, triazole class compounds has the effect of broad-spectrum sterilization and plant growth regulating activity.As triazolone, triadimenol, alkene azoles alcohol etc. has good prevention effect to common fungal disease, and has volume increase, and resistant to lodging and plant growth regulation has become important sterilant.Many 1H-1,2, the 4-triazole class compounds also has very strong fungicidal activity, and existing more than 40 kind commercialization constantly has efficient new drug to come out in recent years.Pathak and Wang Zhennian etc. also point out 1,2, and 4-triazole-5-vitriolic thioether analog derivative has higher biological activity than its parent compound, and prove that they have restraining effect to subtilis etc.
Aspect medical, 1,2, the 4-triazole class compounds is widely used pharmaceutical intermediate, has multiple biological activity, for example, antibiotic, anticancer, anti-inflammatory, spasmolytic, prevention structure bacteria growing, schistosomicide, anti-hypoglycemia and anti-platelet aggregation etc.Kaar, Jesionowski and Berberich be at J.Am.Chem.Soc., and 2003,125 (14): 4125-4131, reported that the compound that contains the 1,2,3-triazoles structure has vasodilator, physiological activity such as special such as anticancer and antiviral and receiving much attention, and carried out a series of study on the synthesis.
Aspect war industry, triazole can be made castexplosive and propelling agent.For example, Kaplan and Drake etc. are at J.Heterocyclic Chem., and 2005,42 (1): 19-28 has reported United States Air Force development in laboratory 1-amino-3-methyl isophthalic acid, 2,3-triazole nitrate (AMTN) contains can ionic liquid, and its alternative TNT is used for castexplosive and propelling agent.
Table two is the TNT of calculating and the comparison of the total detonation energy of AMTN, shock velocity and C-J pressure, and the result of AMTN all is higher than TNT.
Table two
The physico-chemical property of AMTN and TNT relatively list in table three.The density of AMTN and fusing point and TNT are approaching, and decomposition temperature, thermostability and impact sensitivity are suitable.
Table three
United States Patent (USP) 5,728,841 and Chinese patent CN1061978C the method for a kind of 1-of preparation amino-1,2,3-triazoles (ATB) is disclosed, be applicable to industrialization, and safety, easy handling.
1-amino-1,2,3-triazoles chemical structural formula is as follows:
1-amino-1,2,3-triazoles is to carry out ring-closure reaction by ethyl dihydrazone to make, and the chemical structural formula of ethyl dihydrazone is as follows:
This reaction needed is carried out in aqueous hydrogen peroxide solution, and will add the reaction of a certain amount of transition metal oxide and just can carry out, and the chemical formula of transition metal oxide can be by following formal representation:
MmOn
It is as follows to react total formula:
Concrete preparation 1-amino-1,2,3-triazoles method is: the ethyl dihydrazone and the 1ml ethanol that add 813mg at reactor at room temperature mix.Add 2.0g used for dry cell manganese oxide to mixture, then under same temperature, stirred 2 hours.Then, further add the used for dry cell manganese oxide of 1.0g again, subsequently restir 5 hours under this temperature.Reacting liquid filtering after reaction finishes is removed insoluble substance, and underpressure distillation removes to desolvate and obtains 710 milligrams of (earning rate 91%) 1-amino-1,2,3-triazoles.As seen, the raw material of ATB is cheap and easy to get, and the preparation method is simple, and its cost is lower.
VNS represents nucleophilic substitution hydrogen, is a kind of carbon nucleophile to be incorporated into better method on the close electric aromatic ring, and its reaction is will have the carbanion of leavings group (X) earlier to be added on the close electric aromatic ring, removes leavings group and realizes reforming/aromatization by eliminating HX then.This method is widely used in nitro-aromatic and has the heterogeneous ring compound reaction of nitro.The VNS reaction also can take place in similar amino nucleophile (X-NH2), and X eliminates as the auxiliary group of stablizing negative charge and with the HX form, finally causes the reforming/aromatization of intermediate adducts.VNS amination reaction principle as shown in the formula:
VNS amination reaction method has advantages such as selectivity is strong, technology is simple, cost is low, environmentally friendly, has a extensive future in the synthetic field of many nitros polyamino aromatic series explosive.VNS amination simultaneously also provides a kind of more economical and environment amenable method for retired military explosives such as D explosive, picric acid, TNT change into high value added product, meets the developing direction of 21st century Green Chemistry.Should pay attention to exploitation and select for use inexpensive, reactive behavior is strong, environment amenable novel material and VNS aminating agent, further advances the industrial application of VNS amination method in the synthetic field of explosive.
VNS reaction be the earliest the ortho para proton of the class that proposed by the scholar Makosza.M that Polonizes in 1978 aromatic hydrocarbons that contains nitro by the reaction that amino etc. is replaced, become more distinctive, the broad-spectrum reaction in organic synthesis field at present gradually.
In order to overcome the shortcoming of traditional TATB synthesis method, U.S. Lao Lunsi livermore national laboratory (LLNL) energetic material center adopted VNS amination method with 2 in recent years, 4,6-trinitroaniline (picryl amine) is converted into triamino trinitrobenzene (TATB), this is that the VNS amination reaction is at one of the most successful application in the synthetic field of explosive (United States Patent (USP) 5,633,406).LLNL adopt VNS amination method will be in the past can only open burning or the explosion method retired military D explosive, picric acid and the TNT that destroy be converted into high value added product TATB, not only turn waste into wealth, and avoided burning or explosion method to destroy the harm that environment is brought.With traditional method relatively, VNS amination method has mild condition, relative cost is low, technology is simple, to obvious advantages such as environmental hazard are little.LLNL has successively selected TMHI, azanol and 4-amino-1,2 for use, and three kinds of reagent of 4-triazole (ATA) are used VNS amination method picryl amine is converted into TATB.Along with the active raising of reagent react, its cost also increases thereupon, as shown in Figure 1.The present about 200 yuan/kg of the domestic price of industrial goods ATA.
Because the structure of phenyl ring is being concentrated the negatron cloud in planar both sides, ring carbon atom place, and carbon atom is had shielding effect, be unfavorable for the attack of nucleophilic reagent, and help the electrophilic reagent attack, electrophilic substitution reaction takes place.But when on the phenyl ring strong electron-withdrawing group (as nitro, azo-group etc.) being arranged, the cloud density on the phenyl ring is weakened, more helps the attack of nucleophilic reagent, and nucleophilic substitution reaction takes place.The metastable chelation structure that reactant interacts and obtains can obtain metastable configuration between reactant by optimizing.
The structure of the relevant complex compound of reaction of the ATA amination reagent that employing quantum chemistry B3LYP/6-31G* method is optimized as shown in Figure 2.TNB is that trinitrobenzene, TNA are that trinitroaniline, DATB are the diamino trinitrobenzene.
The comparison of complex compound and amination reagent, the N-N bond distance of amination reagent ATA negative ion is 0.1379nm, behind the formation complex compound, three kinds of complex compound σ-TNB, σ-TNA, the N of σ-DATB (1)-N (2) bond distance has increased than the N-N bond distance of original amination reagent.
The VNS reaction is under high density, highly basic condition, σ-complex compound that nucleophilic addition(Adn) forms generates stable quinoid structure through β-elimination fast, and in σ-complex compound the negative electricity group leave away irrelevantly with the concentration of alkali, so nucleophilic reaction is mainly carried out along the direction of VNS reaction.Can determine that the VNS reaction is to experience a reversible nucleophilic addition earlier, obtains final product through an alkali inductive β-elimination reaction again.
Unique empty frequently being respectively-288.5cm of three transition states of B3LYP/6-31G* method optimization
-1,-175.5cm
-1,-514.4cm
-1ATA as the structure of the relevant transition state of the reaction of amination reagent as shown in Figure 3.
To amination reagent ion and TNB, TNA, DATB be optimized with frequency computation part after, can obtain the total energy of reactant, continuation is optimized reacting phase related substance molecule and obtains its energy, deducts the energy sum of reactant again, can obtain an energy difference, list in table four.σ-R represents the reactant complex compound, and TS represents transition state, and σ-INT represents through transition state to the complex compound between product.The first step reaction is the amination reaction of TNB, and the reaction of second step is the amination reaction of TNA, and three-step reaction is the amination reaction of DATB.
Table four (kJ/mol of unit)
From the potential energy surface of the ATA amination reaction of accompanying drawing 4 as can be seen, the order of the energy difference of the related compound of three-step reaction is that DATB＞TNA＞TNB. respectively goes on foot the reaction energy difference and has identical variation tendency.This identical variation tendency, particularly for complex compound and transition state, for different amination reagents, can predict the relation of the energy difference of transition state and reactant with the relation of the energy difference of complex compound and reactant, thus the complexity of pre-measured reaction.
Seek novel, cheap amination reagent, be used for nitro-aromatic and have demand and significance widely with the aromatics heterogeneous ring compound introducing amino group that has nitro.1-amino-1,2,3-triazoles has special structure, and its raw material is easy to get, and preparation technology is simple, generally is used for medicine intermediate, develops the suitability for industrialized production that its new purposes will help this compound, increases its market requirement.
Summary of the invention
The new purposes that the purpose of this invention is to provide a kind of 1-amino-1,2,3-triazoles, 1-amino-1,2,3-triazoles are used for nitro-aromatic and introduce amino group with the aromatics heterogeneous ring compound that has nitro as amination reagent.
Is research model with 1-amino-1,2,3-triazoles (ATB) as the reaction of amination reagent and trinitrobenzene compounds, because the asymmetry of amination reagent ATB, complex compound has different isomer, analyzes with the structure that energy is minimum.Adopt quantum chemistry B3LYP/6-31G* method to optimize ATB as shown in Figure 5 as the structure of the relevant complex compound of reaction of amination reagent.
The comparison of complex compound and amination reagent, the N-N bond distance of amination reagent ATB negative ion is 0.1360nm, behind the formation complex compound, three kinds of complex compound σ-TNB, σ-TNA, the N of σ-DATB (1)-N (2) bond distance has increased than the N-N bond distance of original amination reagent.
Unique empty frequently being respectively-779.7cm of three transition states of B3LYP/6-31G* method optimization
-1,-543.7cm
-1,-301.7cm
-1ATB as the structure of the relevant transition state of the reaction of amination reagent as shown in Figure 6.
Amination reagent ion and TNB, TNA after DATB is optimized, can obtain the total energy of reactant, and continuation is optimized the reaction associated molecule and obtains its energy, deducts the energy sum of reactant again, can obtain energy difference, as shown in Table 5.σ-R represents the reactant complex compound, and TS represents transition state, and σ-INT represents through transition state to the complex compound between product.The first step reaction is the amination reaction of TNB, and the reaction of second step is the amination reaction of TNA, and three-step reaction is the amination reaction of DATB.
Table five (kJ/mol of unit)
Can see from the potential energy surface of the ATB amination reaction shown in the accompanying drawing 7, compare, the energy of reaction complex compound and transition state with the potential energy surface of ATA amination reaction, consistent with the rule of ATA amination reaction, the each point energy is very approaching, so ATB can be used as amination reagent, is used for the VNS amination reaction.
1-amino-1,2,3-triazoles of the present invention is as amination reagent, and being used for nitro-aromatic can be with reference to United States Patent (USP) 5,633,406 with the method for the aromatics heterogeneous ring compound introducing amino group that has nitro, and concrete steps are as follows:
(1) ATB and sodium methylate and solvent obtain suspension, and solvent is dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), methyl alcohol or ethanol;
(2) reaction mass is dissolved in solvent and obtains solution, and reaction mass is nitro-aromatic or the aromatics heterogeneous ring compound that has nitro, and solvent is DMSO, DMF, methyl alcohol or ethanol;
(3) under 10-70 ℃ and agitation condition, with the solution mixing of (1) and (2) for preparing, reacted 1-7 hour, obtain aminated product.
The mol ratio of ATB and sodium methylate is 1: 1-3, the usage quantity of solvent transports with convenient stirring and material and is advisable.
The mol ratio of reaction mass and ATB determines that according to the amino on required whenever go up an amino in the reaction mass molecule, the mol ratio of reaction mass and ATB is 1: 1.1-2, the usage quantity of solvent is being advisable by whole solubilizing reaction things.
The temperature of reaction is low, and the required reaction times is longer.The temperature of reaction height, the required reaction times is short.When temperature of reaction is 40-60 ℃, reaction times-as be 3-5 hour.
Of the present invention-kind of the new purposes of 1-amino-1,2,3-triazoles, as the amination reagent of cheapness, can be used for nitro-aromatic and introduce amino group with the aromatics heterogeneous ring compound that has nitro.Nitro-aromatic is introduced amino group with the aromatics heterogeneous ring compound that has nitro and is had demand and significance widely in the synthetic synthetic field of organic chemistry that reaches of medicine.1-amino-1,2,3-triazoles has special structure, develops the suitability for industrialized production that its new purposes will help this compound, increases its market requirement.
Purpose of the present invention, technical scheme and effect will be elaborated in conjunction with the embodiments.
Description of drawings
Accompanying drawing 1 is a 4-amino-1,2, the relation of 4-triazole (ATA), azanol and three kinds of reagent reacts activity of TMHI and cost.
Accompanying drawing 2 is the structures that adopt the relevant complex compound of ATA amination reagent reaction of quantum chemistry B3LYP/6-31G* method optimization.
Accompanying drawing 3 is the transition state structures that adopt three ATA amination reactions of quantum chemistry B3LYP/6-31G* method optimization.
Accompanying drawing 4 is potential energy surfaces of ATA amination reaction.
Accompanying drawing 5 is to adopt the structure of the 1-amino-1,2,3-triazoles (ATB) of quantum chemistry B3LYP/6-31G* method optimization as the complex compound of amination reagent reaction.
Accompanying drawing 6 is the transition state structures that adopt three ATB amination reactions of quantum chemistry B3LYP/6-31G* method optimization.
Accompanying drawing 7 is potential energy surfaces of ATB amination reaction.
Wherein: on behalf of trinitrobenzene, TNA, TNB represent trinitroaniline, DATB to represent the diamino trinitrobenzene.
Embodiment
Embodiment 1.
1-amino-1,2,3-triazoles amination oil of mirbane.
(1) sodium methylate and ATB and solvent obtain suspension, and solvent is DMSO;
(2) reaction mass oil of mirbane is dissolved in solvent DMSO and obtains solution;
(3) under 10 ℃ and agitation condition, with the solution mixing of (1) and (2) for preparing, reacted 7 hours, obtain an aminated product.
The mol ratio of ATB and sodium methylate is 1: 1, and the usage quantity of solvent is advisable conveniently to stir and to transport.
The mol ratio of reaction mass and ATB is 1: 1.1, and the amount of solvent is being advisable by whole solubilizing reaction things.
Embodiment 2.
As different from Example 1: under 40 ℃, reacted 5 hours in (3), the mol ratio of ATB and sodium methylate is 1: 2, and the mol ratio of reaction mass and ATB is 1: 1.5.
Embodiment 3.
1-amino-1,2,3-triazoles amination dinitrobenzene.
(1) sodium methylate and ATB and solvent obtain suspension, and solvent is DMSO;
(2) the reaction mass dinitrobenzene is dissolved in solvent DMSO and obtains solution;
(3) under 60 ℃ and agitation condition, with the solution mixing of (1) and (2) for preparing, reacted 3 hours, obtain two amination products.
The mol ratio of ATB and sodium methylate is 1: 3, and the usage quantity of solvent is advisable conveniently to stir and to transport.
The mol ratio of reaction mass and ATB is 1: 4, and the amount of solvent is being advisable by whole solubilizing reaction things.
Embodiment 4.
As different from Example 3: under 70 ℃, reacted 1 hour in (3), the mol ratio of ATB and sodium methylate is 1: 2.5, and the mol ratio of reaction mass and ATB is 1: 3.
Embodiment 5.
1-amino-1,2,3-triazoles amination 4-nitropyridine.
(1) sodium methylate and ATB and solvent obtain suspension, and solvent is DMSO;
(2) reaction mass 4-nitropyridine is dissolved in solvent DMSO and obtains solution;
(3) under 50 ℃ and agitation condition, with the solution mixing of (1) and (2) for preparing, reacted 4 hours, obtain an aminated product.
The mol ratio of ATB and sodium methylate is 1: 2, and the usage quantity of solvent is advisable conveniently to stir and to transport.
The mol ratio of reaction mass and ATB is 1: 1.5, and the amount of solvent is being advisable by whole solubilizing reaction things.
Embodiment 6.
1-amino-1,2,3-triazoles amination para-nitrotoluene.
(1) sodium methylate and ATB and solvent obtain suspension, and solvent is DMSO;
(2) the reaction mass para-nitrotoluene is dissolved in solvent DMSO and obtains solution;
(3) under 60 ℃ and agitation condition, with the solution mixing of (1) and (2) for preparing, reacted 3 hours, obtain two amination products.
The mol ratio of ATB and sodium methylate is 1: 3, and the usage quantity of solvent is advisable conveniently to stir and to transport.
The mol ratio of reaction mass and ATB is 1: 4, and the amount of solvent is being advisable by whole solubilizing reaction things.
Embodiment 7.
As different from Example 6: solvent is DMF.
Embodiment 8.
As different from Example 6: solvent is a methyl alcohol.
Embodiment 9.
As different from Example 6: solvent is an ethanol.
Claims (1)
1, a kind of 1-amino-1,2,3-triazoles is as the application of amination reagent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810119424A CN101665467A (en) | 2008-09-01 | 2008-09-01 | Application of 1-amino-1,2,3-triazole serving as amination reagent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810119424A CN101665467A (en) | 2008-09-01 | 2008-09-01 | Application of 1-amino-1,2,3-triazole serving as amination reagent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101665467A true CN101665467A (en) | 2010-03-10 |
Family
ID=41802271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810119424A Pending CN101665467A (en) | 2008-09-01 | 2008-09-01 | Application of 1-amino-1,2,3-triazole serving as amination reagent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101665467A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508966A (en) * | 2012-06-29 | 2014-01-15 | 南京理工大学 | Preparation method of 1-amino-3-methyl-1,2,3-triazole nitrate |
| CN108191780A (en) * | 2018-01-31 | 2018-06-22 | 西北工业大学 | It is a kind of that preparation method of the cobalt as the ionic liquid containing energy of anion is closed using four different sulphur cyanogen of transient metal complex |
| CN110997139A (en) * | 2017-08-16 | 2020-04-10 | 公益财团法人微生物化学研究会 | Catalyst, method for forming amide bond, and method for producing amide compound |
-
2008
- 2008-09-01 CN CN200810119424A patent/CN101665467A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508966A (en) * | 2012-06-29 | 2014-01-15 | 南京理工大学 | Preparation method of 1-amino-3-methyl-1,2,3-triazole nitrate |
| CN110997139A (en) * | 2017-08-16 | 2020-04-10 | 公益财团法人微生物化学研究会 | Catalyst, method for forming amide bond, and method for producing amide compound |
| CN110997139B (en) * | 2017-08-16 | 2023-03-28 | 公益财团法人微生物化学研究会 | Catalyst, method for forming amide bond, and method for producing amide compound |
| CN108191780A (en) * | 2018-01-31 | 2018-06-22 | 西北工业大学 | It is a kind of that preparation method of the cobalt as the ionic liquid containing energy of anion is closed using four different sulphur cyanogen of transient metal complex |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chavez et al. | Energetic Trinitro‐and Fluorodinitroethyl Ethers of 1, 2, 4, 5‐Tetrazines | |
| López-Rodríguez et al. | Pathways for N-nitroso compound formation: secondary amines and beyond | |
| Thottempudi et al. | Synthesis and promising properties of a new family of high-density energetic salts of 5-nitro-3-trinitromethyl-1 H-1, 2, 4-triazole and 5, 5′-bis (trinitromethyl)-3, 3′-azo-1 H-1, 2, 4-triazole | |
| Huynh et al. | Green primary explosives: 5-Nitrotetrazolato-N 2-ferrate hierarchies | |
| Zhang et al. | Recent advances in synthesis and properties of nitrated-pyrazoles based energetic compounds | |
| Kumar et al. | A facile and regioselective synthesis of 1, 4-disubstituted 1, 2, 3-triazoles using click chemistry | |
| Vo et al. | 1, 1-Diamino-2, 2-dintroethene (FOX-7) in copper and nickel diamine complexes and copper FOX-7 | |
| CN101665467A (en) | Application of 1-amino-1,2,3-triazole serving as amination reagent | |
| Thottempudi et al. | Synthesis of trinitromethyl-and dinitromethyl-substituted azoles using nitrate salts in sulfuric acid | |
| Myers et al. | Synthesis and Electrochemical Behavior of Electron‐Rich s‐Tetrazine and Triazolo‐tetrazine Nitrate Esters | |
| Elkanzi et al. | Efficient and recoverable bio-organic catalyst cysteine for synthesis, docking study, and antifungal activity of new bio-active 3, 4-dihydropyrimidin-2 (1 H)-ones/thiones under microwave irradiation | |
| Muir et al. | Development of a Safe Continuous Process to Sodium Nitrotetrazolate via Solid Phase “Catch and Release” | |
| Fei et al. | New role for an N, N′-alkylidene bridge: taming the hygroscopicity of acidic energetic materials with enhanced stability | |
| Bubyrev et al. | Synthetic Studies towards CH‐Diazomethane Sulfonamides: a Novel Type of Diazo Reagents | |
| Phukan et al. | Synthesis of medicinally relevant scaffolds-triazoles and pyrazoles in green solvent ionic liquids | |
| Marchal et al. | Alkoxy‐5‐nitrosopyrimidines: Useful Building Block for the Generation of Biologically Active Compounds | |
| Wang et al. | FSO2N3-Enabled Synthesis of Tetrazoles from Amidines and Guanidines | |
| Govindaraju et al. | Citric‐Acid‐Catalyzed Green and Sustainable Synthesis of Novel Functionalized Pyrano [2, 3‐e] pyrimidin‐and Pyrano [2, 3‐d] pyrazol‐amines in Water via One‐Pot Multicomponent Approaches | |
| Zheng et al. | Copper-catalyzed tandem reaction of terminal alkynes and sulfonyl azides for the assembly of substituted aminotriazoles | |
| Xie et al. | Imidazole‐Based Energetic Materials: A Promising Family of N‐Heterocyclic Framework | |
| Mondal et al. | 7-Azaindole N-Oxide (7-AINO) Mediated Cu-Catalyzed N-Arylation: Mechanistic Investigation into the Role of Fluoride Ions | |
| Miron et al. | Closing the Loop: Triazolylpyridine Coordination Drives the Self‐Assembly of Metallomacrocycles with Tunable Topologies for Small‐Molecule and Guanine‐Quadruplex Recognition | |
| Soni et al. | The Riveting Chemistry of Poly‐aza‐heterocycles Employing Microwave Technique: A Decade Review | |
| Schmidt et al. | Heteroaromatic tripoles. 2, 6-bis (hetarenio) pyrimidin-4-olates: Hybrids between hetarenium salts and cross-conjugated mesomeric betaines | |
| CN101333170B (en) | Method for synthesizing 1,3,5-triamino-2,4,6-trinitrobenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100310 |