scholarly journals Synthesis of Alkylthio Benzene Derivatives Via Simultaneous Diazotization and Nucleophilic Displacement

2021 ◽  
pp. 100227
Author(s):  
Abraham Alvarado ◽  
Juan d. Deleija ◽  
Jose J. Gutierrez
1991 ◽  
Vol 88 ◽  
pp. 509-514 ◽  
Author(s):  
MA Cuevas Diarte ◽  
T Calvet ◽  
M Labrador ◽  
E Estop ◽  
HAJ Oonk ◽  
...  

2018 ◽  
Author(s):  
Christopher J. Smedley ◽  
Bing Gao ◽  
Suhua Li ◽  
Qinheng Zheng ◽  
Andrew Molino ◽  
...  

Sulfur-Fluoride Exchange (SuFEx) is the new generation click chemistry transformation exploiting the unique properties of S-F bonds and their ability to undergo near-perfect reactions with nucleophiles. We report here the first SuFEx based protocol for the efficient synthesis of pharmaceutically important triflones and bis(trifluoromethyl)sulfur oxyimines from the corresponding sulfonyl fluorides and iminosulfur oxydifluorides, respectively. The new protocol involves the rapid exchange of the S-F bond with trifluoromethyltrimethylsilane (TMSCF<sub>3</sub>) upon activation with potassium bifluoride in anhydrous DMSO. The reaction tolerates a wide selection of substrates and proceeds under mild conditions without need for chromatographic purification. A tentative catalytic mechanism is proposed supported by DFT calculations, involving formation of the free trifluoromethyl anion followed by nucleophilic displacement of the S-F through a five-coordinate intermediate. The preparation of a benzothiazole derived bis(trifluoromethyl)sulfur oxyimine with cytotoxic selectivity for MCF7 breast cancer cells demonstrates the utility of this methodology for the late-stage functionalization of bioactive molecules.<br>


Author(s):  
Autumn Flynn ◽  
Kelly McDaniel ◽  
Meredith Hughes ◽  
David Vogt ◽  
Nathan Jui

A photocatalytic system for the dearomative hydroarylation of benzene derivatives has been developed. Using a combination of an organic photoredox catalyst and an amine reductant, this process operates through a reductive radical-polar crossover mechanism where aryl halide reduction triggers a regioselective cyclization event, giving rise to a range of complex spirocyclic cyclohexadienes. This light-driven protocol functions at room temperature in a green solvent system (aq. MeCN), without the need for precious metal-based catalysts or reagents, or the generation of stoichiometric metal byproducts.


1985 ◽  
Vol 20 (2) ◽  
pp. 36-43 ◽  
Author(s):  
Klaus L.E. Kaiser ◽  
Juan M. Ribo ◽  
Brian M. Zaruk

Abstract This paper gives the results of part of a systematic investigation into contaminant toxicity to Photobacterium phosphoreum in the Microtox™ test. Reported are the toxicity values for 39 para-chloro substituted benzene derivatives of the general formula l-Cl-C6h4-4-X=CH2CH(NH2)COOH, F, SO2NH2, OCH2COOH, CH2COOH, CONHNH2, NHCOCH3, CONH2, CH=CHCOOH, SeOOH, CH2NH2, CH2CH2NH2, NO2, H, CF3, CHO, CH2OH, OH, CH3, CCl3, COCH3, COOH, NH2, SO2C6H5, Cl, CH2COCH3, COCl, CN, OCH3, NCO, NHCH3, I, COC6H5, CH2Cl, SH, CH2SH, NCS, CH2CN and SO2C6H4Cl. Except for the last compound, whose solubility is below the required concentration, the toxicities increase in the presented order with a total range of more than three orders of magnitude. The data are discussed in terms of quantitative structure-toxicity correlations with compound-specific structural parameters. In combination with a previously developed submodel on chlorinated benzenes, phenols, nitrobenzenes and anilines, the observed relationships allow the prediction of the toxicity of some 780 possible chloro derivatives of the general formula C6H5-nClnX, where n=&lt;5 and X is a functional group as listed above.


2007 ◽  
Vol 72 (5-6) ◽  
pp. 599-608 ◽  
Author(s):  
Maria Teresa A. R. S. da Costa ◽  
Maria Fátima C. Guedes da Silva ◽  
João J. R. Fraústo Da Silva ◽  
Armando J. L. Pombeiro

The conversion of the bis(diazenido) complex [ReBr2(NNPh)2(PPh3)2]Br (1) to the mono(diazenido) complex [ReBr3(NNPh)(PPh3)2] (2) is promoted by alk-1-ynes, whereas the reaction with CO leads to the mixed dicarbonylmono(diazenido) Re(III) species [ReBr(CO)2- (NNPh)(PPh3)2]Br (3). Both reactions are suggested to occur via related pathways involving a nucleophilic displacement of one of the diazenide ligands by Br-. Reduction of the phenyldiazenide ligand in 2 occurs in the attempted reaction with HC≡CPh to give the nitrido complex [ReBr2(N)(PPh3)2] (4) and the bis(diazenido) species [ReBr2(NNPh)2(PPh3)2] (5) and [ReBr(NNPh)2(PPh3)2] (6).


1969 ◽  
Vol 24 (11) ◽  
pp. 1365-1370 ◽  
Author(s):  
H.-H. Perkampus ◽  
U. Krüger ◽  
W. Krüger

The proton chemical shifts of aromatic compounds are strongly concentration dependent. Moreever, for molecules with a dipole moment a temperature dependence of the proton chemical shifts is observed. For hemellitone, p-methylanisole, o-chlortoluene, p-chlortoluene, pyrrole and N-methyl-pyrrole the enthalpies of a dipole-dipole association between -0,7 and -1,8 Kcal could be estimated by NMR measurements combined with the temperature dependence in the whole range of the molefraction (0 → 1).


2021 ◽  
Vol 6 (3) ◽  
pp. 425-429
Author(s):  
Haleemathul Zahadiya ◽  
Ruwan P. Wijesundera ◽  
Champika V. Hettiarachchi ◽  
Ishanie R. Perera

1978 ◽  
Vol 9 (31) ◽  
Author(s):  
V. A. GRINBERG ◽  
V. R. POLISHCHUK ◽  
L. S. GERMAN ◽  
L. S. KANEVSKII ◽  
YU. B. VASIL'EV
Keyword(s):  

SynOpen ◽  
2021 ◽  
Author(s):  
Valerio Zullo ◽  
Antonella Petri ◽  
Anna Iuliano

The synthesis of 6-aminoisomannide is easily achieved starting from the renewable, inexpensive and commercially available isosorbide, in 66% overall yield. A biocatalysed highly regioselective acetylation of the 3-endo hydroxyl group of isosorbide was followed by the stereospecific interconversion of the 6-exo hydroxyl group into azido group, through reaction with trifluoromethanesulfonic anhydride followed by nucleophilic displacement of the triflate group by sodium azide. Finally, reduction of the azido group and deacetylation of the 3-hydroxy group were performed one pot by using LiAlH4.


Sign in / Sign up

Export Citation Format

Share Document