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Volumn 75, Issue 13, 2010, Pages 4514-4520

The role of structural effects on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites. A time-resolved kinetic study

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION RATE; ALKOXYL RADICALS; ALKYL GROUPS; AROMATIC RINGS; PHENOXYL RADICAL; PHOSPHORANYL RADICALS; RADICAL SCAVENGING; RELATIVE STABILITIES; STERIC EFFECT; STRUCTURAL EFFECT; TIME-RESOLVED KINETIC STUDY;

EID: 77954135916     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100703b     Document Type: Article
Times cited : (21)

References (58)
  • 30
    • 77954101265 scopus 로고    scopus 로고
    • Tris(2,4-Di- tert -butylphenyl) phosphite is available under the commercial name Irgafos 168
    • Tris(2,4-Di- tert -butylphenyl) phosphite is available under the commercial name Irgafos 168.
  • 37
    • 77954124016 scopus 로고    scopus 로고
    • · undergoes a rapid 1,2-H-atom shift reaction in water and alcohols (see ref 25). Accordingly, in MeCN the decay of this radical can be accelerated by the presence of small amounts of water
    • · undergoes a rapid 1,2-H-atom shift reaction in water and alcohols (see ref 25). Accordingly, in MeCN the decay of this radical can be accelerated by the presence of small amounts of water.
  • 42
    • 77954090411 scopus 로고    scopus 로고
    • ·, and accordingly, polar effects may also play a role in the addition of an alkoxyl radical to the phosphorus center
    • ·, and accordingly, polar effects may also play a role in the addition of an alkoxyl radical to the phosphorus center.
  • 43
    • 77954098621 scopus 로고    scopus 로고
    • For a critical discussion on the stereochemistry of formation of phosphoranyl radicals, see, for example, ref 2
    • For a critical discussion on the stereochemistry of formation of phosphoranyl radicals, see, for example, ref 2.
  • 46
    • 77954093944 scopus 로고    scopus 로고
    • The data collected in Table 2 do not allow to draw any conclusion on the question of apical vs equatorial β-scission in the intermediate phosphoranyl radical. For a critical discussion, see refs 2, 9, and 10
    • The data collected in Table 2 do not allow to draw any conclusion on the question of apical vs equatorial β-scission in the intermediate phosphoranyl radical. For a critical discussion, see refs 2, 9, and 10.
  • 47
    • 77954101549 scopus 로고    scopus 로고
    • The observed differences in rate constant reasonably reflect the significantly different experimental conditions employed in these studies
    • The observed differences in rate constant reasonably reflect the significantly different experimental conditions employed in these studies.
  • 49
    • 77954097064 scopus 로고    scopus 로고
    • It is important to point out that even though it is generally assumed that the displacement of phenoxyl radicals from triaryl phosphites by alkoxyl radicals is a concerted process, ESR evidence in favor of the formation of an intermediate phosphoranyl radical has been provided in the reactions of alkoxyl radicals with triphenyl phosphite (see ref 3a)
    • It is important to point out that even though it is generally assumed that the displacement of phenoxyl radicals from triaryl phosphites by alkoxyl radicals is a concerted process, ESR evidence in favor of the formation of an intermediate phosphoranyl radical has been provided in the reactions of alkoxyl radicals with triphenyl phosphite (see ref 3a).
  • 51
    • 77954109238 scopus 로고    scopus 로고
    • It is important to mention that as compared to phenolic antioxidants, triaryl phosphites are able, at least in principle, to scavenge 3 equiv of alkoxyl radicals
    • It is important to mention that as compared to phenolic antioxidants, triaryl phosphites are able, at least in principle, to scavenge 3 equiv of alkoxyl radicals.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.