4096-88-2Relevant articles and documents
Metallacycle-catalyzed SNAr reaction in water: Supramolecular inhibition by means of host-guest complexation
Lopez-Vidal, Eva M.,Fernandez-Mato, Antonio,Garcia, Marcos D.,Perez-Lorenzo, Moises,Peinador, Carlos,Quintela, Jose M.
, p. 1265 - 1270 (2014)
The performance of a PtII diazapyrenium-based metallacycle as a reusable substoichiometric catalyst for the SNAr reaction between halodinitrobenzenes and sodium azide at rt in aqueous media is reported. The results suggest that the c
Synthesis of nitrophenyl and fluorophenyl azides and diazides by SNAr under phase-transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents
Leyva, Elisa,Aguilar, Johana,González-Balderas, Regina M.,Vega-Rodríguez, Sarai,Loredo-Carrillo, Silvia E.
, (2020/12/01)
Two fast and mild methodologies to prepare nitrophenyl and fluorophenyl azides are presented. These aryl azides are extensively used as crosslinking, photoaffinity labeling, and click chemistry reagents. Substituted aryl azides are prepared by performing a SNAr substitution on halogenated benzenes with a phase-transfer catalyst (PTC) such as tetraethylammonium tetrafluoroborate (TEATFB), the reaction proceeds in several hours under rather mild temperatures (25°C to 70°C). Furthermore, aryl azides are also prepared within minutes under microwave irradiation at slightly higher temperatures (50°C to 70°C). These procedures could be applied in the preparation of other aryl azides. In the case of substituted pentafluoro benzene (pF), the type of products obtained in each reaction depends on the amount of sodium azide and the strength and position of electron-withdrawing substituents (COH, COR, COOR, CN, NO2, or F). A discussion on the mechanisms and the products obtained in these SNAr reactions is presented.
Thiophenol-formaldehyde triazole causes apoptosis induction in ovary cancer cells and prevents tumor growth formation in mice model
Jia, Yan,Si, Lihui,Lin, Ruixin,Jin, Hongjuan,Jian, Wenwen,Yu, Qing,Yang, Shuli
, p. 62 - 70 (2019/04/04)
In the present study a library of thiophenol-formaldehyde-triazole (TFT) derivatives was synthesized and screened against CAOV3, CAOV4 and ES-2 ovary cancer cell lines. Initial screening revealed that five-compounds 5a, 5b, 5j, 5h and 5i inhibited the viability of tested cell lines. Analysis of apoptosis revealed that increase in compound 5a (most active) concentration from 0.25 to 2.0 μM enhanced apoptotic cell proportion. Transwell assay showed reduction in invasive potential of CAOV3 cells on treatment with compound 5a. In wound healing assay increasing the concentration of compound 5a from 0.5 to 2.0 μM caused a significant (P 0.05) decrease in the migration potential. Western blotting showed that compound 5a treatment markedly decreased the level of matrix metalloproteinase (MMP)-2 and ?9 in CAOV3 cells. Treatment of CAOV3 cells with compound 5a caused a marked decrease in Focal Adhesion Kinase (FAK) activation. Tumor growth was inhibited in the compound 5a treated mice markedly than those of untreated group. The tumor metastasis to liver, intestine, spleen and peritoneal cavity was markedly decreased in mice treated with 10 mg/kg dose of compound 5a. Examination of Von Willebrand factor (vWF) expression in liver, intestinal and pulmonary lesions showed a marked decrease in the compound 5a-treated mice. The infiltration of macrophages in the metastatic lesions showed a significant decrease in compound 5a-treated mice. In conclusion, the compound 5a inhibited ovary cancer cell viability and induced apoptosis through decrease in expression of vWF and metalloproteinase, suppression of FAK activation and decrease in infiltration of macrophages. The compound 5a therefore can be investigated further for the treatment of ovary cancer.
Design, combinatorial synthesis and biological evaluations of novel 3-amino-1'-((1-aryl-1H-1,2,3-triazol-5-yl)methyl)-2'-oxospiro[benzo[a] pyrano[2,3-c]phenazine-1,3'-indoline]-2-carbonitrile antitumor hybrid molecules
Lu, Yuanyuan,Wang, Linlin,Wang, Xiaobing,Xi, Tao,Liao, Jianmin,Wang, Zhixiang,Jiang, Feng
, p. 125 - 141 (2017/04/26)
A combinatorial chemical library of fifty-nine novel 3-amino-1'-((1-aryl-1H-1,2,3-triazol-5-yl)methyl)-2'-oxospiro[benzo[a]pyrano[2,3-c]phenazine-1,3'-indoline]-2-carbonitrile, designed as hybrid molecules of phenazine, pyran, indole and 1,2,3-triazole pharmacophores, were constructed in this study. Cytotoxic evaluation indicated that some compounds exhibited moderate cytotoxicity against HCT116, MCF7, HepG2 and A549 cancer cell lines in vitro, in which compound 36 was found to have best antiproliferative activity against the A549 cancer cell line with IC50 value of 5.4 μM. All compounds had low or no effect against L02 and HUVEC non-cancer cell lines. Compound 36 was further confirmed to mainly locate mitochondria in A549 cancer cells via laser-scanning confocal microscopy. Moreover, compound 36 was proved to increase ROS production and induce cell cycle arrest in S phase. Western blot analysis illustrated Bax/Bcl-2 ratio was increased at dose-dependent manner, and both cleaved caspase-3 and cleaved caspase-9 was enhanced by treated with compound 36. All the above evidences in vitro indicated that compound 36 might induce the apoptosis of A549 cancer cells via a mitochondria-dependent pathway.
Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted-Benzenesulfonates and Y-Substituted-Phenyl 4-Nitrobenzenesulfonates with Azide Ion: Regioselectivity and Reaction Mechanism
Moon, Ji-Hyun,Kim, Min-Young,Han, So-Yeop,Um, Ik-Hwan
, p. 1360 - 1365 (2015/07/15)
The second-order rate constants for reactions of 2,4-dinitrophenyl X-substituted-benzenesulfonates (4a-4f) and Y-substituted-phenyl-4-nitrobenzenesulfonates (5a-5f) with N3- ion have been measured spectrophotometrically. The reactions of 4a-4f proceed through S-O and C-O bond fission pathways competitively. Fraction of the S-O bond fission decreases rapidly as the substituent X in the benzenesulfonyl moiety changes from an electron-withdrawing group to an electron-donating group. The Hammett plots for reactions of 4a-4f are linear with ρX=1.87 and 0.56 for the S-O and C-O bond fission, respectively. The fact that the substituent X is further away from the reaction site of the C-O bond fission than that of the S-O bond fission is one reason for the smaller ρX value. The nature of the reaction mechanism (i.e., a stepwise mechanism in which expulsion of the leaving group occurs after the rate-determining step) is also responsible for the smaller ρX value obtained from the C-O bond fission. The Bronsted-type plot for the reactions of 5a-5f is linear with βlg=-0.63, which is typical for reactions reported previously to proceed through a concerted mechanism. Effects of substituents X and Y on regioselectivity and reaction mechanism are discussed in detail.
The α-effect in the SNAr reaction of 1-(4-nitrophenoxy)-2,4-dinitrobenzene with anionic nucleophiles: Effects of solvation and polarizability on the α-effect
Um, Ik-Hwan,Kim, Min-Young,Cho, Hyo-Jin,Dust, Julian M.,Buncel, Erwin
, p. 1109 - 1114 (2015/10/06)
A kinetic study on SNAr reactions of 1-(4-nitrophenoxy)-2,4-dinitrobenzene (1a) with various anionic nucleophiles in 80 mol% water-20 mol% DMSO at 25.0 °C is reported. The Bronsted-type plot for the reaction of 1a with a series of substituted phenoxides and HOO- results in an excellent linear correlation with βnuc = 1.17. However, OH- exhibits dramatic negative deviation from the Bronsted-type plot, while N3-, C6H5S-, and butane-2,3-dione monoximate (Ox-) deviate positively from linearity. HOO- is 680-fold more reactive than OH- but does not exhibit the α-effect. In contrast, Ox- is 166-fold more reactive than isobasic 4-Cl-C6H4O- and exhibits the α-effect. Differential solvation effects have been suggested to be responsible for the α-effect in this study, i.e., Ox- exhibits the α-effect, since it is 5.7 kcal/mol less strongly solvated than 4-Cl-C6H4O- in the reaction medium, while HOO- does not show the α-effect due to a strong requirement for partial desolvation before nucleophilic attack. The highly enhanced reactivity of polarizable N3- and C6H5S- and extremely decreased reactivity of nonpolarizable OH- are in accord with the hard-soft acid and base principle.
Kinetic study on SNAr reactions of 1-(Y-substituted-phenoxy)-2,4-dinitrobenzenes with Azide ion: Effect of changing nucleophile from hydroxide to Azide ion on reaction mechanism and reactivity
Seo, Hyeon-Ok,Kim, Min-Young,Han, So-Yeop,Um, Ik-Hwan
, p. 1764 - 1768 (2015/07/15)
Second-order rate constants (kN3-) for SNAr reactions of 1-(Y-substituted-phenoxy)-2,4-dinitrobenzenes (2a-2h) with (Formula presented.) in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C have been measured spectrophotometrically. The Bronsted-type plot is linear with β1g=-0.38. The Hammett plots correlated with (Formula presented.) constants exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ρY = 1.02 and r = 0.51, indicating that a negative charge develops partially on the O atom of the leaving Y-substituted-phenoxy moiety in the transition state. Accordingly, the reactions have been concluded to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs in the rate-determining step. Comparison of kN3- with the kOH- values reported previously for the corresponding reactions with OH has revealed that (Formula presented.) is only 6- to 26-fold than OH toward substrates 2a-2h, although the former is over 11 pKa units less basic than the latter. Solvation and polarizability effects have been suggested to be responsible for the unusual reactivity shown by (Formula presented.) and OH. Effects of changing nucleophile from OH to (Formula presented) on reaction mechanism and reactivity are discussed in detail.
Nanoparticles and Method to Control Nanoparticle Spacing
-
, (2009/04/24)
Disclosed herein are novel nanoparticles, particularly metal nanoparticles, such as gold nanoparticles. According to one embodiment of a method disclosed herein nanoparticles are functionalized via ligand exchange reactions. Also disclosed is a method for controlling nanoparticle spacing to produce nanoparticle arrays having defined spacing. Such nanoparticles and arrays thereof are particularly useful in nanoelectronics, nanophotonics, catalysis, sensors, and biotaggents.
Nitropyrazoles 15.* Synthesis and some transformations of 1-(2,4-dinitrophenyl)-4-methyl-3,5-dinitropyrazole
Zaitsev,Vatsadze,Dalinger,Kachala,Nelyubina,Shevelev
, p. 2109 - 2117 (2011/01/11)
The method for preparation of 1-(2,4-dinitrophenyl)-4-methyl-3,5- dinitropyrazole has been developed. Due to the larger CH-acidity of 4-Me-group compared to 1,4-dimethyl-3,5-dinitropyrazole, 1-(2,4-dinitrophenyl)-4-methyl-3, 5-dinitropyrazole is capable of reacting with substituted benzaldehydes to afford 4-[(E)-2-arylvinyl]-1-(2,4-dinitrophenyl)-3,5-dinitropyrazoles. Under the action of nucleophiles, dinitrophenyl group is detached from the former compounds leading to previously unknown N-unsubstituted 4-[(E)-2-arylvinyl]-3,5- dinitropyrazoles.
Ph3P/Br2/n-Bu4NNO2 as an efficient system for the preparation of N-nitrosamines and azides
Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh
, p. 4242 - 4244 (2008/09/20)
The combination PPh3/Br2/n-Bu4NNO2 was developed as a new reagent system for the efficient preparation of N-nitrosamines and azides from the corresponding amines and hydrazine derivatives, respectively, at 0 °C to room temperature, in excellent yields.