Preparation of heptafluoronaphthyllithiums and -magnesiums: An unexpected difference in the reactivity of isomers C10F7H and C10F7Br towards organolithium and organomagnesium compounds

Preparation of heptafluoronaphthyllithiums and -magnesiums: An unexpected difference in the reactivity of isomers C10F7H and C10F7Br towards organolithium and organomagnesium compounds Full article

Journal

Journal of Organometallic Chemistry
ISSN: 0022-328X

Output data

Year: 2019, Volume: 899, Article number : UNSP 120889, Pages count : DOI: 10.1016/j.jorganchem.2019.120889

Tags

Heptafluoronaphthalene; Bromoheptafluoronaphthalene; Metalation; Alkyllithium; Ethylmagnesium bromide; Trimethylsilylheptafluoronaphthalene

Authors

Shmakov Mikhail M. ^1,2 , Bardin Vadim V. ^2,3 , Prikhod'ko Sergey A. ^1,2 , Adonin Nicolay Yu ^1,2

Affiliations

1	(Данные Web of science) RAS, SB, Boreskov Inst Catalysis, Acad Lavrentiev Ave 5, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Pirogova Str 2, Novosibirsk 630090, Russia
3	(Данные Web of science) RAS, SB, Vorozhtsov Novosibirsk Inst Organ Chem, Acad Lavrentiev Ave 9, Novosibirsk 630090, Russia

Significant differences in the reactivity of isomeric heptafluoronaphthalenes and bromoheptafluoronaphthalenes towards organolithium and organomagnesium compounds were found. Metalation of polyfluorinated naphthalenes 2-C10F7X (X = H, Br) occurs easily under the action of bases (BuLi, t-BuLi, LDA) as well as EtMgBr (X = Br) in ether. This fact was proven by F-19 NMR spectroscopy and by trapping of 2-C10F7M (M = Li, MgBr, Mg(2-C10F7)) with electrophile ClSiMe3. The interaction of 1-C10F7Br with BuLi or EtMgBr proceeds in a similar way. In contrast to 2-C10F7H, isomeric 1-C10F7H is the less acidic substrate and undergoes only the nucleophilic alkyldefluorination when combined with BuLi or t-BuLi. (C) 2019 Elsevier B.V. All rights reserved.

Shmakov M.M. , Bardin V.V. , Prikhod'ko S.A. , Adonin N.Y.
Preparation of heptafluoronaphthyllithiums and -magnesiums: An unexpected difference in the reactivity of isomers C10F7H and C10F7Br towards organolithium and organomagnesium compounds
Journal of Organometallic Chemistry. 2019. V.899. UNSP 120889 . DOI: 10.1016/j.jorganchem.2019.120889 WOS Scopus РИНЦ

Published print:

Oct 1, 2019

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