scholarly journals Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene

2016 ◽  
Vol 12 ◽  
pp. 192-197 ◽  
Author(s):  
Javier Ajenjo ◽  
Martin Greenhall ◽  
Camillo Zarantonello ◽  
Petr Beier
Keyword(s):  
Nucleophilic Substitution ◽  
Title Compound ◽  
Fluorine Atom ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Vicarious Nucleophilic Substitution ◽  
Direct Fluorination ◽  
Nitrogen Nucleophiles

3-Fluoro-5-nitro-1-(pentafluorosulfanyl)benzene was prepared by three different ways: as a byproduct of direct fluorination of 1,2-bis(3-nitrophenyl)disulfane, by direct fluorination of 4-nitro-1-(pentafluorosulfanyl)benzene, and by fluorodenitration of 3,5-dinitro-1-(pentafluorosulfanyl)benzene. The title compound was subjected to a nucleophilic aromatic substitution of the fluorine atom with oxygen, sulfur and nitrogen nucleophiles affording novel (pentafluorosulfanyl)benzenes with 3,5-disubstitution pattern. Vicarious nucleophilic substitution of the title compound with carbon, oxygen, and nitrogen nucleophiles provided 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzenes substituted in position four.

Nucleophilic substitution of meso-nitrooctaethylporphyrins

1985 ◽  
Vol 63 (2) ◽  
pp. 406-411 ◽  
Author(s):  
Liang-Chu Gong ◽  
David Dolphin
Keyword(s):  
Nucleophilic Substitution ◽  
Nucleophilic Addition ◽  
Nucleophilic Aromatic Substitution ◽  
Redox Potentials ◽  
Aromatic Substitution ◽  
Halogen Atoms

Nitrooctaethylporphyrins readily undergo nucleophilic aromatic substitution in the presence of HCl or HBr. In the presence of methoxide, nucleophilic addition to give a porphodimethane occurs, followed by autoxidation to the methoxyporphyrin. Unlike the nitrated complexes, the chlorosubstituted porphyrins exhibit redox potentials similar to those of unsubstituted analogs. Meso-halogenated porphyrins do, however, show steric distortion due to the bulk of the halogen atoms.

How Does Nucleophilic Aromatic Substitution in Nitroarenes Really Proceed: General Mechanism

Synthesis ◽  
2017 ◽  
Vol 49 (15) ◽  
pp. 3247-3254 ◽  
Author(s):  
Mieczysław Mąkosza
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Experimental Studies ◽  
Secondary Reaction ◽  
Nucleophilic Aromatic Substitution ◽  
General Mechanism ◽  
Primary Process ◽  
Nucleophilic Substitution Of Hydrogen ◽  
Aromatic Substitution

On the basis of previously published experimental studies and ab initio calculations, a general corrected mechanism of nucleophilic aromatic substitution was formulated. It was shown that conventional nucleophilic substitution of halogens is a slow secondary reaction whereas nucleophilic substitution of hydrogen is the fast primary process. The general mechanism embraces both of these alternative and complementary reactions.

scholarly journals Discovery of a Potent and Highly Isoform-Selective Inhibitor of the Neglected Ribosomal Protein S6 Kinase Beta 2 (S6K2)

Cancers ◽  
2021 ◽  
Vol 13 (20) ◽  
pp. 5133
Author(s):  
Stefan Gerstenecker ◽  
Lisa Haarer ◽  
Martin Schröder ◽  
Mark Kudolo ◽  
Martin P. Schwalm ◽  
...  
Keyword(s):  
Ribosomal Protein ◽  
Title Compound ◽  
Growth Factor Receptor ◽  
Selective Inhibitor ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
S6 Kinase ◽  
Ribosomal Protein S6 ◽  
Beta 2 ◽  
Ribosomal Protein S6 Kinase

The ribosomal protein S6 kinase beta 2 (S6K2) is thought to play an important role in malignant cell proliferation, but is understudied compared to its closely related homolog S6 kinase beta 1 (S6K1). To better understand the biological function of S6K2, chemical probes are needed, but the high similarity between S6K2 and S6K1 makes it challenging to selectively address S6K2 with small molecules. We were able to design the first potent and highly isoform-specific S6K2 inhibitor from a known S6K1-selective inhibitor, which was merged with a covalent inhibitor engaging a cysteine located in the hinge region in the fibroblast growth factor receptor kinase (FGFR) 4 via a nucleophilic aromatic substitution (SNAr) reaction. The title compound shows a high selectivity over kinases with an equivalently positioned cysteine, as well as in a larger kinase panel. A good stability towards glutathione and Nα-acetyl lysine indicates a non-promiscuous reactivity pattern. Thus, the title compound represents an important step towards a high-quality chemical probe to study S6K2-specific signaling.

scholarly journals From porphyrin benzylphosphoramidate conjugates to the catalytic hydrogenation of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin

2014 ◽  
Vol 10 ◽  
pp. 628-633 ◽  
Author(s):  
Marcos C de Souza ◽  
Leandro F Pedrosa ◽  
Géssica S Cazagrande ◽  
Vitor F Ferreira ◽  
Maria G P M S Neves ◽  
...  
Keyword(s):  
Microwave Irradiation ◽  
Catalytic Hydrogenation ◽  
Fluorine Atom ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution

Three new porphyrin aminoalkyl dibenzylphosphoramidates were synthesized by nucleophilic aromatic substitution of onep-fluorine atom of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPPF20) by primary aminoalkyl dibenzylphosphoramidates. The nucleophilic aromatic substitution was promoted by microwave irradiation inN-methyl-2-pyrrolidinone. Attempts to remove the benzyl groups of the phosphoramidate moiety by hydrogenolysis with 10% Pd/C led to the cleavage of the P–N bond and the reduction of the macrocycle to hydroporphyrin-type derivatives. The extent of the effect of the catalytic hydrogenation toTPPF20with 10% Pd/C was then studied with a variety of solvents. The results showed that ethanol/DMF is the solvent of choice to produce chlorinTPCF20and an ethanol/DMF/NEt3mixture is more adequate to produce isobacteriochlorin (TPIF20).

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

1995 ◽  
Vol 73 (2) ◽  
pp. 289-295 ◽  
Author(s):  
Alaa S. Abd-El-Aziz ◽  
Christine R. de Denus ◽  
Harold M. Hutton
Keyword(s):  
Nucleophilic Substitution ◽  
Room Temperature ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Efficient Route ◽  
Cyclopentadienyliron Complexes ◽  
Formation Of Complexes

A unique route to the synthesis of 2-alkyl-2-arylphenylsulphonylacetonitriles via the nucleophilic aromatic substitution (SNAr) of chloroarene cyclopentadienyliron complexes with 2-alkyl phenylsulphonylacetonitriles has been investigated. Reactions of chloroarene complexes (1a–d) with 2-alkyl phenylsulphonylacetonitrile (2a,b) in the presence of K2CO3 in DMF at room temperature led to the formation of complexes 3a–d and 4a,c,d in good yields. The use of alkylated phenylsulphonylacetonitriles as nucleophiles in the reactions with the p-dichlorobenzene complex (1e) allowed the formation of the disubstituted complexes (5,6). Photolytic demetallation provided an efficient route to the liberation of the arylated phenylsulphonylacetonitriles 7a–d, 8a,c,d, 9, and 10. Keywords: chloroarene, phenylsulphonylacetonitrile, nucleophilic substitution.

scholarly journals Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

2013 ◽  
Vol 9 ◽  
pp. 791-799 ◽  
Author(s):  
Magnus Liljenberg ◽  
Tore Brinck ◽  
Tobias Rein ◽  
Mats Svensson
Keyword(s):  
Nucleophilic Substitution ◽  
Density Functional ◽  
Reaction Rates ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Functional Theory ◽  
Aromatic Substrates ◽  
Complex Approach ◽  
Mechanistic Analysis ◽  
Rate Limiting

A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the “σ-complex approach”, has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirements for predictive reactivity models for the pharmaceutical industry. We also present new results regarding the reaction rates and regioselectivities in nucleophilic substitution of fluorinated aromatics. They were rationalized by investigating linear correlations between experimental rate constants (k) from the literature with a theoretical quantity, which we call the sigma stability (SS). The SS is the energy change associated with formation of the intermediate σ-complex by attachment of the nucleophile to the aromatic ring. The correlations, which include both neutral (NH3) and anionic (MeO−) nucleophiles are quite satisfactory (r = 0.93 to r = 0.99), and SS is thus useful for quantifying both global (substrate) and local (positional) reactivity in SNAr reactions of fluorinated aromatic substrates. A mechanistic analysis shows that the geometric structure of the σ-complex resembles the rate-limiting transition state and that this provides a rationale for the observed correlations between the SS and the reaction rate.

Novel nucleophilic aromatic substitution of the fluorine atom yielding a stable heptatrienide structure

2005 ◽  
Vol 54 (10) ◽  
pp. 2471-2472 ◽  
Author(s):  
Yu. G. Gololobov ◽  
O. A. Linchenko ◽  
Z. A. Starikova ◽  
I. A. Garbuzova ◽  
P. V. Petrovskii
Keyword(s):  
Fluorine Atom ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution

Synthesis of 2-amino-6,7,8,9-tetrahydro-6-phenethyl-3H-pyrimido[4,5-e][1,4]diazepin-4(5H)-one: a model for a potential pyrimido[4,5-e][1,4]diazepine-based folate anti-tumor agent

2015 ◽  
Vol 21 (6) ◽  
pp. 349-353 ◽  
Author(s):  
Austin W. Gann ◽  
Partha S. Ray
Keyword(s):  
Raney Nickel ◽  
Title Compound ◽  
Nucleophilic Aromatic Substitution ◽  
Reductive Cyclization ◽  
Aromatic Substitution ◽  
Tumor Agent

AbstractReductive cyclization of 2-{N-[(2-amino-4,6-dichloropyrimidin-5-yl)methyl]-N-phenethylamino}acetonitrile (5) with Raney nickel and hydrogen gave the chloropyrimido[4,5-e][1,4]diazepine 3 which could not be converted to 2 via an attempted nucleophilic aromatic substitution with hydroxide. The title compound (2) was prepared, however, by the reductive cyclization of 2-{N-[(2-amino-4-chloro-6-methoxypyrimidin-5-yl)methyl]-N-phenethylamino}acetonitrile (13) followed by treatment with trimethyliodosilane.

Methylsulfone as a leaving group for synthesis of hyperbranched poly(arylene pyrimidine ether)s by nucleophilic aromatic substitution

RSC Advances ◽  
2015 ◽  
Vol 5 (17) ◽  
pp. 12821-12823 ◽  
Author(s):  
Yue Guan ◽  
Chunbo Wang ◽  
Daming Wang ◽  
Guodong Dang ◽  
Chunhai Chen ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Hyperbranched Poly ◽  
Leaving Group

Using a novel leaving group, methylsulfone activated by pyrimidine, 4,6-dichloro-2-(methylsulfonyl)pyrimidine was used to synthesize two new hyperbranched poly(arylene pyrimidine ether)s with diphenol via a nucleophilic substitution polymerization.

scholarly journals N-(6-Chloro-3-nitropyridin-2-yl)-5-(1-methyl-1H-pyrazol-4-yl)isoquinolin-3-amine

Molbank ◽  
10.3390/m1181 ◽  
2021 ◽  
Vol 2021 (1) ◽  
pp. M1181
Author(s):  
Valentin Wydra ◽  
Stefan Gerstenecker ◽  
Dieter Schollmeyer ◽  
Stanislav Andreev ◽  
Teodor Dimitrov ◽  
...  
Keyword(s):  
Title Compound ◽  
High Resolution Mass Spectrometry ◽  
Nucleophilic Aromatic Substitution ◽  
Resonance Spectroscopy ◽  
Aromatic Substitution ◽  
X Ray Diffraction ◽  
Inhibitory Potency ◽  
X Ray ◽  
Step Procedure ◽  
Resolution Mass

Here we describe the synthesis of N-(6-chloro-3-nitropyridin-2-yl)5-(1-methyl-1H-pyrazol-4-yl)isoquinolin-3-amine via a three-step procedure including a Buchwald–Hartwig arylamination with benzophenone imine and a highly regioselective nucleophilic aromatic substitution. The title compound was analyzed by nuclear magnetic resonance spectroscopy (1H, 13C, HSQC, HMBC, COSY, DEPT90 and NOESY), high resolution mass spectrometry (ESI-TOF-HRMS) and infrared spectroscopy (ATR-IR) and its structure was confirmed by single crystal X-ray diffraction. The inhibitory potency of the title compound was evaluated for selected kinases harboring a rare cysteine in the hinge region (MPS1, MAPKAPK2 and p70S6Kβ/S6K2).

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