Directing effects in nitration of 1-adamantyl bearing aromatic ketones

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F70883521%3A28110%2F09%3A63508148" target="_blank" >RIV/70883521:28110/09:63508148 - 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

Directing effects in nitration of 1-adamantyl bearing aromatic ketones

Popis výsledku v původním jazyce

Nitration of four 1-adamantyl bearing aromatic ketones with mixed acid, acetyl nitrate, silver nitrate and guanidine nitrate was studied under various conditions. The ketones with conjugated carbonyl group or with a benzyl group were examined and a considerably high amount of ortho isomer was observed in all cases. The proportion of ortho nitration showed the same trends for both examined groups of ketones. Unprecedently, the ortho isomer was formed quantitatively upon the reaction of 1-(1-adamantyl)-3-phenylpropan-2-one with acetyl nitrate in acetic anhydride. Influence of electronic, steric and complexation effect of carbonyl group on regioselectivity is discussed. An alternative reaction pathway including complexation of nitrating agent and a pre-equilibrium of protonated and nitronium coordinated carbonyl in particular is suggested to play crucial and general role in nitrations of aromatic carbonyl compounds.

Název v anglickém jazyce

Directing effects in nitration of 1-adamantyl bearing aromatic ketones

Popis výsledku anglicky

Nitration of four 1-adamantyl bearing aromatic ketones with mixed acid, acetyl nitrate, silver nitrate and guanidine nitrate was studied under various conditions. The ketones with conjugated carbonyl group or with a benzyl group were examined and a considerably high amount of ortho isomer was observed in all cases. The proportion of ortho nitration showed the same trends for both examined groups of ketones. Unprecedently, the ortho isomer was formed quantitatively upon the reaction of 1-(1-adamantyl)-3-phenylpropan-2-one with acetyl nitrate in acetic anhydride. Influence of electronic, steric and complexation effect of carbonyl group on regioselectivity is discussed. An alternative reaction pathway including complexation of nitrating agent and a pre-equilibrium of protonated and nitronium coordinated carbonyl in particular is suggested to play crucial and general role in nitrations of aromatic carbonyl compounds.

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

<a href="/cs/project/GP203%2F06%2FP362" target="_blank" >GP203/06/P362: Cílená modifikace struktury biologicky aktivních látek</a><br>

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2009

Kód důvěrnosti údajů

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

Název periodika

Arkivoc

ISSN

1424-6376

e-ISSN

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Svazek periodika

2009

Číslo periodika v rámci svazku

12

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

20

Strana od-do

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Kód UT WoS článku

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EID výsledku v databázi Scopus

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