- SYNTHESIS OF DI-t-ALKYLAMINES
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Di-t-alkylamines can be synthesized efficiently by a three-step process: (1) oxidation of a t-alkylamine to a t-alkylnitroso compound with peracetic acid in ethyl acetate (2) conversion of the t-alkylnitroso compound to a tri-t-alkylhydroxylamine by successive trapping of two t-butyl radicals and (3) sodium naphthalide reduction to the di-t-alkylamine.
- Corey, E. J.,Gross, Andrew W.
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- Chemoselectivity of Nitroxylation of Cage Hydrocarbons
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Abstract: The composition of reaction mixtures obtained by nitroxylation of 13 cage hydrocarbons with 100% nitric acid and its mixtures with acetic acid, acetic anhydride, and methylene chloride has been studied. More reactive substrates react with lowest
- Ivleva, E. A.,Klimochkin, Yu. N.,Leonova, M. V.
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p. 1702 - 1710
(2020/12/01)
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- The synthesis and evaluation of new α-hydrogen nitroxides for 'living' free radical polymerization
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Three N-alkoxyamines were synthesized for use in nitroxide-mediated radical polymerization. Upon thermolysis, they generate new acyclic α-hydrogen nitroxides: one adamantyl substituted and two diol-containing nitroxides. The initiators were tested in polymerization reactions in direct comparison with the initiator derived from the nitroxide TIPNO. Georg Thieme Verlag Stuttgart.
- Braslau, Rebecca,O'Bryan, Greg,Nilsen, Aaron,Henise, Jeff,Thongpaisanwong, Thanchanok,Murphy, Erin,Mueller, Laura,Ruehl, Jean
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p. 1496 - 1506
(2007/10/03)
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- Azodioxide radical cations
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This report provides the first examples of solution-stable azodioxide radical cations and describes their direct spectroscopic observation and, in one case, their thermal chemistry. The formal oxidation potentials, Eo′, for N,N′-dioxo-2,3-diazabicyclo[2.2.2]oct-2-ene (3), N,N′-dioxo-2,3-diazabicyclo[2.2.1]hept-2-ene (4), and N,N′-dioxo-1,1′-azobis(norbornane) (5) are 1.65, 1.68, and 1.54 V vs SCE, respectively. ESR spectroscopy shows the intermediate cations to be π radicals. Radical cation 5?+ (red, λm 510 nm) has a five-line ESR spectrum of a(2N) 1.1 G, while 3?+ (bronze) has a nine-line ESR spectrum simulated as a(4H) 0.86 and a(2N) 1.22 G. Both 3?+ and 5?+ decay in seconds to minutes at room temperature. Thermal decomposition of 5?+ results in C,N and N,N bond cleavage, yielding 1-norbornyl cation (trapped by solvent) and NO+ (trapped in low yield by the oxidant under chemical oxidation conditions). Two viable mechanisms are presented for 5?+'s thermal decay, both of which invoke nitrosoalkane monomer 5m as an intermediate. In a related study, oxidation of nitrosoalkane 2m is found to mediate its facile denitrosation. This work affords the first examples of electron-transfer-mediated C,N bond cleavage of azodioxides and of nitrosoalkanes. Substantial bond weakening is shown to accompany electron loss from these substrates. For 5, π oxidation leads ultimately to σ C,N bond activation.
- Greer, Melinda L.,Sarker, Haripada,Mendicino, Maria E.,Blackstock, Silas C.
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p. 10460 - 10467
(2007/10/03)
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- Oxidation of Primary Aliphatic Amines to C-Nitroso Dimers
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A biphasic system of ethyl acetate or dichloromethane and water containing sodium percarbonate (Na2CO3*3/2H2O2), sodium hydrogen carbonate and N,N,N',N'-tetraacetylethylenediamine oxidizes primary aliphatic amines to aliphatic C-nitroso dimers in most cases in good to excellent yields.
- Zajac, Walter W.,Walters, Thomas R.,Woods, James M.
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p. 808 - 810
(2007/10/02)
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