PEGylated, Water-Soluble, Stable Aminyl Radical

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Abstract

We report the synthesis and kinetic study of PEGylated, water-soluble aminyl radical 2. The radical possesses four mPEG-3 groups replacing four methyl groups in the tert-butyl groups at the 3- and 6-positions of 1,3,6,8-tetra-tert-butyl carbazyl (TTBC). This structure is designed to mitigate the rapid decomposition of the radical via intramolecular 1,5-hydrogen atom transfer (1,5-HAT) that was observed in its constitutional isomer 1-H with four mPEG-3 groups in the vicinity of the nitrogen-centered radical (1- and 8-positions of TTBC). In dry, degassed acetone at 295 K, the radical 2 has a half-life, τ 1/2 = 49 h (ΔH = 17.9 ± 0.8 kcal mol -1 ), which is 3 orders of magnitude longer than that for 1-H, which decays via 1,5-HAT (τ 1/2 = 48 s, ΔH = 10.0 ± 0.3 kcal mol -1 ). Aminyl radical 2 aggregates at ambient conditions in water and has a half-life, τ 1/2 = 2 h.

Original languageEnglish (US)
Pages (from-to)7512-7518
Number of pages7
JournalJournal of Organic Chemistry
Volume82
Issue number14
DOIs
StatePublished - Jul 21 2017

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Hydrogen
Atoms
Water
Acetone
Isomers
Nitrogen
Decomposition
Kinetics

ASJC Scopus subject areas

  • Organic Chemistry

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PEGylated, Water-Soluble, Stable Aminyl Radical. / Wang, Ying; Rajca, Suchada; Rajca, Andrzej.

In: Journal of Organic Chemistry, Vol. 82, No. 14, 21.07.2017, p. 7512-7518.

Research output: Contribution to journalArticle

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N2 - We report the synthesis and kinetic study of PEGylated, water-soluble aminyl radical 2. The radical possesses four mPEG-3 groups replacing four methyl groups in the tert-butyl groups at the 3- and 6-positions of 1,3,6,8-tetra-tert-butyl carbazyl (TTBC). This structure is designed to mitigate the rapid decomposition of the radical via intramolecular 1,5-hydrogen atom transfer (1,5-HAT) that was observed in its constitutional isomer 1-H with four mPEG-3 groups in the vicinity of the nitrogen-centered radical (1- and 8-positions of TTBC). In dry, degassed acetone at 295 K, the radical 2 has a half-life, τ 1/2 = 49 h (ΔH ‡ = 17.9 ± 0.8 kcal mol -1 ), which is 3 orders of magnitude longer than that for 1-H, which decays via 1,5-HAT (τ 1/2 = 48 s, ΔH ‡ = 10.0 ± 0.3 kcal mol -1 ). Aminyl radical 2 aggregates at ambient conditions in water and has a half-life, τ 1/2 = 2 h.

AB - We report the synthesis and kinetic study of PEGylated, water-soluble aminyl radical 2. The radical possesses four mPEG-3 groups replacing four methyl groups in the tert-butyl groups at the 3- and 6-positions of 1,3,6,8-tetra-tert-butyl carbazyl (TTBC). This structure is designed to mitigate the rapid decomposition of the radical via intramolecular 1,5-hydrogen atom transfer (1,5-HAT) that was observed in its constitutional isomer 1-H with four mPEG-3 groups in the vicinity of the nitrogen-centered radical (1- and 8-positions of TTBC). In dry, degassed acetone at 295 K, the radical 2 has a half-life, τ 1/2 = 49 h (ΔH ‡ = 17.9 ± 0.8 kcal mol -1 ), which is 3 orders of magnitude longer than that for 1-H, which decays via 1,5-HAT (τ 1/2 = 48 s, ΔH ‡ = 10.0 ± 0.3 kcal mol -1 ). Aminyl radical 2 aggregates at ambient conditions in water and has a half-life, τ 1/2 = 2 h.

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