Radical addition reactions of fluorinated species Part 6. Regioselectivity of the Addition of Nucleophilic Radicals to Halogenopropenes and Evidence for a Steric Effect of the Chlorine Substituent.

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F67985858%3A_____%2F97%3A27020278" target="_blank" >RIV/67985858:_____/97:27020278 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Radical addition reactions of fluorinated species Part 6. Regioselectivity of the Addition of Nucleophilic Radicals to Halogenopropenes and Evidence for a Steric Effect of the Chlorine Substituent.

Popis výsledku v původním jazyce

Nucleophilic radicals derived from alkanols and cyclic ethers (oxolane, 1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane) were employed to test the regioselectivity of addition to 3-chloro-1,1,2,3,3-pentafluoropropene (1), 1,3-dichloro-1,2,3,3-tetrafluoropropene (2), 1,1,3-trichloro-2,3,3-trifluoropropene (3) and 1,3-dichloro-2,3,3-trifluoropropene (4). The regioselectivity was strongly dependent on the number of chlorine atoms at the terminal position and on the character of the additive. Thus the two chlorine atoms in 3 completely reversed the regioselectivity to an anti-Kharasch mode. The relative reaction rates were dramatically decreased with increasing number of terminal chlorine atoms in olefins. 1-3. The allylic chlorine atom in 1 appeared to mimic alonger perfluoroalkyl chain. Experimental results were compared with the shapes of frontier orbitals and electron densities calculated using PM3 and ab initio (3-12G and 6-311 + G**) methods. The transformations of the adducts to chlorofl

Název v anglickém jazyce

Radical addition reactions of fluorinated species Part 6. Regioselectivity of the Addition of Nucleophilic Radicals to Halogenopropenes and Evidence for a Steric Effect of the Chlorine Substituent.

Popis výsledku anglicky

Nucleophilic radicals derived from alkanols and cyclic ethers (oxolane, 1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane) were employed to test the regioselectivity of addition to 3-chloro-1,1,2,3,3-pentafluoropropene (1), 1,3-dichloro-1,2,3,3-tetrafluoropropene (2), 1,1,3-trichloro-2,3,3-trifluoropropene (3) and 1,3-dichloro-2,3,3-trifluoropropene (4). The regioselectivity was strongly dependent on the number of chlorine atoms at the terminal position and on the character of the additive. Thus the two chlorine atoms in 3 completely reversed the regioselectivity to an anti-Kharasch mode. The relative reaction rates were dramatically decreased with increasing number of terminal chlorine atoms in olefins. 1-3. The allylic chlorine atom in 1 appeared to mimic alonger perfluoroalkyl chain. Experimental results were compared with the shapes of frontier orbitals and electron densities calculated using PM3 and ab initio (3-12G and 6-311 + G**) methods. The transformations of the adducts to chlorofl

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

1997

Kód důvěrnosti údajů

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

Název periodika

Journal of Fluorine Chemistry

ISSN

0022-1139

e-ISSN

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Svazek periodika

86

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

17

Strana od-do

155-171

Kód UT WoS článku

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EID výsledku v databázi Scopus

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