Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F19%3A00507252" target="_blank" >RIV/61388963:_____/19:00507252 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/19:10397317

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201902651" target="_blank" >https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201902651</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201902651" target="_blank" >10.1002/chem.201902651</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

Popis výsledku v původním jazyce

Direct fluorination of ortho‐, meta‐ and para‐substituted aromatic thiols and disulfides using elemental fluorine afforded substituted (pentafluorosulfanyl)benzenes. This work thus represents the first study of the scope and limitation of direct fluorination for the synthesis of new SF5‐containing building blocks. Fluorinations in batch and flow modes were compared. A comprehensive computational study has been carried out employing density functional and wave functions methods to elucidate the reaction mechanism of the transformation of ArSF3 to ArSF5. Eliminating various non‐radical pathways, it has been shown that the reaction proceeds by a radical mechanism, initiated by the attack of the F· on the ArSF3 moiety, propagated via almost barrier‐less F2 + ArSF4· → ArSF5 + F· step and terminated by the ArSF4· + F· → ArSF5. Most of the calculated data are in a very good agreement with experimental observations concerning the ortho‐substituent effect on the reaction rates and yields.

Název v anglickém jazyce

Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

Popis výsledku anglicky

Direct fluorination of ortho‐, meta‐ and para‐substituted aromatic thiols and disulfides using elemental fluorine afforded substituted (pentafluorosulfanyl)benzenes. This work thus represents the first study of the scope and limitation of direct fluorination for the synthesis of new SF5‐containing building blocks. Fluorinations in batch and flow modes were compared. A comprehensive computational study has been carried out employing density functional and wave functions methods to elucidate the reaction mechanism of the transformation of ArSF3 to ArSF5. Eliminating various non‐radical pathways, it has been shown that the reaction proceeds by a radical mechanism, initiated by the attack of the F· on the ArSF3 moiety, propagated via almost barrier‐less F2 + ArSF4· → ArSF5 + F· step and terminated by the ArSF4· + F· → ArSF5. Most of the calculated data are in a very good agreement with experimental observations concerning the ortho‐substituent effect on the reaction rates and yields.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GC18-00215J" target="_blank" >GC18-00215J: Nové syntetické přístupy k organickým pentafluorsulfanylovým sloučeninám</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

25

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

8

Strana od-do

11375-11382

Kód UT WoS článku

000479224000001

EID výsledku v databázi Scopus

2-s2.0-85070676635