Conjugate addition with organometallics and nitration of nitroxide (aminoxyl) free radicals. Synthesis of potentially useful cross-linking spin label reagents

K. Hideg, H. Olga Hankovszky, H. Anna Halász, P. Sohár

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Abstract

3-Methoxycarbonyl-2,2,5,5-tetramethyl-2,5-dihydropyrrol-1-oxyl (1) was converted with PhMgBr-Cul in a conjugate addition into 3-methoxycarbonyl-2,2,5, 5-tetramethyl-4-phenylpyrrolidin-1-oxyl (2). Compound (2) was nitrated with concentrated H2SO4/HNO3 to give the para-nitrophenyl derivative (5). Nitration of other phenyl substituted nitroxides was also investigated. The reaction in strong acids could be carried out in the presence of an acid-sensitive nitroxide free radical. An alkyl nitro compound has also been prepared: a conjugate addition of nitromethane to (1) gave 3-methoxycarbonyl-2,2,5,5-tetramethyl-4-nitromethylpyrrolidin-1-oxyl (20). Both (2) and (20) could be transformed by transfer hydrogenation to amino compounds and then in several steps to potentially useful cross-linking spin label reagents.

Original languageEnglish
Pages (from-to)2905-2911
Number of pages7
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number11
Publication statusPublished - 1988

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Nitration
Spin Labels
Organometallics
Free Radicals
Nitro Compounds
Acids
Hydrogenation
Derivatives
nitromethane
4-nitrophenyl

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Conjugate addition with organometallics and nitration of nitroxide (aminoxyl) free radicals. Synthesis of potentially useful cross-linking spin label reagents",
abstract = "3-Methoxycarbonyl-2,2,5,5-tetramethyl-2,5-dihydropyrrol-1-oxyl (1) was converted with PhMgBr-Cul in a conjugate addition into 3-methoxycarbonyl-2,2,5, 5-tetramethyl-4-phenylpyrrolidin-1-oxyl (2). Compound (2) was nitrated with concentrated H2SO4/HNO3 to give the para-nitrophenyl derivative (5). Nitration of other phenyl substituted nitroxides was also investigated. The reaction in strong acids could be carried out in the presence of an acid-sensitive nitroxide free radical. An alkyl nitro compound has also been prepared: a conjugate addition of nitromethane to (1) gave 3-methoxycarbonyl-2,2,5,5-tetramethyl-4-nitromethylpyrrolidin-1-oxyl (20). Both (2) and (20) could be transformed by transfer hydrogenation to amino compounds and then in several steps to potentially useful cross-linking spin label reagents.",
author = "K. Hideg and Hankovszky, {H. Olga} and Hal{\'a}sz, {H. Anna} and P. Soh{\'a}r",
year = "1988",
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journal = "Journal of the Chemical Society, Perkin Transactions 1",
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T1 - Conjugate addition with organometallics and nitration of nitroxide (aminoxyl) free radicals. Synthesis of potentially useful cross-linking spin label reagents

AU - Hideg, K.

AU - Hankovszky, H. Olga

AU - Halász, H. Anna

AU - Sohár, P.

PY - 1988

Y1 - 1988

N2 - 3-Methoxycarbonyl-2,2,5,5-tetramethyl-2,5-dihydropyrrol-1-oxyl (1) was converted with PhMgBr-Cul in a conjugate addition into 3-methoxycarbonyl-2,2,5, 5-tetramethyl-4-phenylpyrrolidin-1-oxyl (2). Compound (2) was nitrated with concentrated H2SO4/HNO3 to give the para-nitrophenyl derivative (5). Nitration of other phenyl substituted nitroxides was also investigated. The reaction in strong acids could be carried out in the presence of an acid-sensitive nitroxide free radical. An alkyl nitro compound has also been prepared: a conjugate addition of nitromethane to (1) gave 3-methoxycarbonyl-2,2,5,5-tetramethyl-4-nitromethylpyrrolidin-1-oxyl (20). Both (2) and (20) could be transformed by transfer hydrogenation to amino compounds and then in several steps to potentially useful cross-linking spin label reagents.

AB - 3-Methoxycarbonyl-2,2,5,5-tetramethyl-2,5-dihydropyrrol-1-oxyl (1) was converted with PhMgBr-Cul in a conjugate addition into 3-methoxycarbonyl-2,2,5, 5-tetramethyl-4-phenylpyrrolidin-1-oxyl (2). Compound (2) was nitrated with concentrated H2SO4/HNO3 to give the para-nitrophenyl derivative (5). Nitration of other phenyl substituted nitroxides was also investigated. The reaction in strong acids could be carried out in the presence of an acid-sensitive nitroxide free radical. An alkyl nitro compound has also been prepared: a conjugate addition of nitromethane to (1) gave 3-methoxycarbonyl-2,2,5,5-tetramethyl-4-nitromethylpyrrolidin-1-oxyl (20). Both (2) and (20) could be transformed by transfer hydrogenation to amino compounds and then in several steps to potentially useful cross-linking spin label reagents.

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