Nitroxydes-LXVIII

Briere, R.; Rassat, A.

doi:10.1016/0040-4020(76)80142-1

Cited by 24 publications

(15 citation statements)

References 11 publications

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“…Both Briere and Rassat 193 and Ingold et al 163 observed the formation of various decomposition products resulting from radical addition to nitrone intermediates. In the TIPNO decomposition studies presented here, no nitrone trapping products were observed.…”

Section: Scheme 18mentioning

confidence: 99%

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nilsen

Braslau

2005

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:Nitroxides bearing an a-hydrogen decompose upon heating in a bimolecular reaction. A new mechanism is proposed for the decomposition of t-butylisopropylphenyl nitroxide (TIPNO) involving the formation of a head-to-tail dimer, single electron transfer to form an oxammonium salt, epimerization to the corresponding nitrone, and elimination to form a conjugated oxime. This mechanism may provide insights into designing new nitroxides for use in controlled polymerization.

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Section: Scheme 18mentioning

confidence: 99%

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nilsen

Braslau

2005

J. Polym. Sci. A Polym. Chem.

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“…In all previous studies regarding the pyrolysis of nitroxides, the process involves complex rearrangements [1,15], coupling to ortho-or para-C in aromatic nitroxides [16] or bimolecular hydrogen abstraction [17,18]. The simplicity of the molecule employed in the present work and its lack of labile hydrogens can account for these differences.…”

Section: (6)mentioning

confidence: 84%

Reaction of di‐tert‐butylnitroxide radicals

Lissi

Rubio

Araya

et al. 1980

Int J of Chemical Kinetics

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Di-tert-hutylnitroxide (DTBN) is the simplest of the stable nitroxide radicals and is only consumed a t temperatures higher than 9OoC or in the presence of very reactive substrates. The pyrolysis of DTBN in solution gives, at least at low conversion, 2-methyl-2-nitrosopropane and di-tert-hutylnitroxide-tert-hutyl ether. The reaction involves, as the rate-limiting step, the cleavage of the C-N bond. This reaction takes place with an activation energy of 33 kcal/mol. DTBN is stable in the presence of styrene, aldehydes, hydrogen peroxide, wmethyl-N-ethyl nitrone, phenol, and triphenylmethane. On the other hand, it reacts readily with diethylhydroxylamine, ascorbid acid, ethanethiol, and hexanethiol. For the two former compounds the reaction involves a hydrogen transfer as the rate-determining step, and the reaction proceeds, a low conversion, with simple second-order kinetics. The reaction with the thiols is complex and shows a clear induction time.

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“…TMPNO was prepared by the method of Rassat, Lemaire et al (62) and further purified by vacuum sublimation. Its authenticity and purity were ascertained by means of elemental analysis, e.s.r., IH n.m.r., i.r.…”

Section: Methodsmentioning

confidence: 99%

Yttrium(III) and lanthanide(III) perchlorate complexes with the 2,2,6,6- tetramethylpiperidine nitroxide free radical

Mikulski

GELFAND

Pytlewski

et al. 1978

Transition Met Chem

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Summary2,2,6,6-Tetramcthylpiperidine nitroxide free radical (TMPNO) complexes with ya* and Ln 3÷ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er or Yb) perchlorates were synthesized and characterized by means of i.r. and e.s.r, spectral, magnetic susceptibility and molar conductance studies. The new complexes are of the general type [M(TMPNO')2(OH2)s(OCIO3)](CIOa) 2 (M = Y or Ln), involving two TMPNO, three aqua and one unidentate perchlorato ligand in the complex cation, and two anionic ClO4 groups. The NO bond-order in coordinated TMPNO is apparently two, as suggested by the i.r. evidence. The magnetic susceptibility and e.s.r, data were interpreted in terms of partial spin-spin coupling interaction between the unpaired electrons of the two TMPNO ligands, as well as unpaired f electrons, in the case of paramagnetic lanthanide(lll) ions. Severe steric hindrance, introduced during coordination of the free radical ligand through the NO oxygen atom, does not seem to allow accommodation of more than two TMPNO molecules in the inner coordination sphere of the central y3* or Ln 3÷ ion.

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Nitroxydes-LXVIII

Cited by 24 publications

References 11 publications

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Reaction of di‐tert‐butylnitroxide radicals

Yttrium(III) and lanthanide(III) perchlorate complexes with the 2,2,6,6- tetramethylpiperidine nitroxide free radical

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