Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene

Nicolai Stuhr-Hansen, Thorstein Finn Götze, Lars Henriksen, Theis Ivan Sølling, Annette Langkilde, Henning Osholm Sørensen

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    Upon treatment of o- and p(phenylseleno,)nitrobenzenes with sodium methoxide quantitative exchange reactions took place, affording the corresponding methoxynitrobenzenes. Upon reaction between 2,4-bis(phenylseleno)nitrobenzene 2 and sodium methoxide, an unusual regiopure formation of 4-methoxy-2-(phenylseleno)nitrobenzene 3 was observed. This product remained unreactive toward an excess of sodium methoxide, thus preventing the for-mation of 2,4-dimethoxynitrobenzene 6. The nature of the reactants and of the intermediate Meisenheimer complexes was examined by synthetic investigations, x-ray crystallography, and DFT calculations. We found that the observed selectivity can be understood in terms of traditional resonance considerations. (C) 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:101-108, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20519
    Original languageEnglish
    JournalHeteroatom Chemistry
    Volume20
    Issue number2
    Pages (from-to)101-108
    ISSN1042-7163
    DOIs
    Publication statusPublished - 2009

    Keywords

    • Materials characterization and modelling
    • Materials research

    Cite this

    Stuhr-Hansen, Nicolai ; Götze, Thorstein Finn ; Henriksen, Lars ; Sølling, Theis Ivan ; Langkilde, Annette ; Sørensen, Henning Osholm. / Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene. In: Heteroatom Chemistry. 2009 ; Vol. 20, No. 2. pp. 101-108.
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    title = "Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene",
    abstract = "Upon treatment of o- and p(phenylseleno,)nitrobenzenes with sodium methoxide quantitative exchange reactions took place, affording the corresponding methoxynitrobenzenes. Upon reaction between 2,4-bis(phenylseleno)nitrobenzene 2 and sodium methoxide, an unusual regiopure formation of 4-methoxy-2-(phenylseleno)nitrobenzene 3 was observed. This product remained unreactive toward an excess of sodium methoxide, thus preventing the for-mation of 2,4-dimethoxynitrobenzene 6. The nature of the reactants and of the intermediate Meisenheimer complexes was examined by synthetic investigations, x-ray crystallography, and DFT calculations. We found that the observed selectivity can be understood in terms of traditional resonance considerations. (C) 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:101-108, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20519",
    keywords = "Materials characterization and modelling, Materials research, Materialeforskning, Materialekarakterisering og materialemodellering",
    author = "Nicolai Stuhr-Hansen and G{\"o}tze, {Thorstein Finn} and Lars Henriksen and S{\o}lling, {Theis Ivan} and Annette Langkilde and S{\o}rensen, {Henning Osholm}",
    year = "2009",
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    volume = "20",
    pages = "101--108",
    journal = "Heteroatom Chemistry",
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    number = "2",

    }

    Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene. / Stuhr-Hansen, Nicolai; Götze, Thorstein Finn; Henriksen, Lars; Sølling, Theis Ivan; Langkilde, Annette; Sørensen, Henning Osholm.

    In: Heteroatom Chemistry, Vol. 20, No. 2, 2009, p. 101-108.

    Research output: Contribution to journalJournal articleResearchpeer-review

    TY - JOUR

    T1 - Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene

    AU - Stuhr-Hansen, Nicolai

    AU - Götze, Thorstein Finn

    AU - Henriksen, Lars

    AU - Sølling, Theis Ivan

    AU - Langkilde, Annette

    AU - Sørensen, Henning Osholm

    PY - 2009

    Y1 - 2009

    N2 - Upon treatment of o- and p(phenylseleno,)nitrobenzenes with sodium methoxide quantitative exchange reactions took place, affording the corresponding methoxynitrobenzenes. Upon reaction between 2,4-bis(phenylseleno)nitrobenzene 2 and sodium methoxide, an unusual regiopure formation of 4-methoxy-2-(phenylseleno)nitrobenzene 3 was observed. This product remained unreactive toward an excess of sodium methoxide, thus preventing the for-mation of 2,4-dimethoxynitrobenzene 6. The nature of the reactants and of the intermediate Meisenheimer complexes was examined by synthetic investigations, x-ray crystallography, and DFT calculations. We found that the observed selectivity can be understood in terms of traditional resonance considerations. (C) 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:101-108, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20519

    AB - Upon treatment of o- and p(phenylseleno,)nitrobenzenes with sodium methoxide quantitative exchange reactions took place, affording the corresponding methoxynitrobenzenes. Upon reaction between 2,4-bis(phenylseleno)nitrobenzene 2 and sodium methoxide, an unusual regiopure formation of 4-methoxy-2-(phenylseleno)nitrobenzene 3 was observed. This product remained unreactive toward an excess of sodium methoxide, thus preventing the for-mation of 2,4-dimethoxynitrobenzene 6. The nature of the reactants and of the intermediate Meisenheimer complexes was examined by synthetic investigations, x-ray crystallography, and DFT calculations. We found that the observed selectivity can be understood in terms of traditional resonance considerations. (C) 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:101-108, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20519

    KW - Materials characterization and modelling

    KW - Materials research

    KW - Materialeforskning

    KW - Materialekarakterisering og materialemodellering

    U2 - 10.1002/hc.20519

    DO - 10.1002/hc.20519

    M3 - Journal article

    VL - 20

    SP - 101

    EP - 108

    JO - Heteroatom Chemistry

    JF - Heteroatom Chemistry

    SN - 1042-7163

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    ER -