N-Hydroxyphthalimide (NHPI)/lead tetraacetate reactions with cyclic and acyclic alkenes

被引：32

作者：

Coseri, Sergiu ^{[1
]}

机构：

[1] Petru Poni Inst Macromol Chem, Iasi 700487, Romania

来源：

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 2009年 / 22卷 / 05期

关键词：

N-hydroxyphthalimide (NHPI); phthalimide N-oxyl (PINO) radical; lead tetraacetate; adducts formation; oxidation; MOLECULAR-OXYGEN; HYDROGEN ABSTRACTION; OXIDATION; NHPI; EFFICIENT; FUNCTIONALIZATION; ALKANES; BENZYL; ACID;

D O I：

10.1002/poc.1466

中图分类号：

O62 [有机化学];

学科分类号：

070303 [有机化学];

摘要：

The reactions between phthalimide N-oxyl (PINO) radical and cyclohexene, cyclooctene, and trans-3-hexene were carried out. The PINO radical has been in situ generated from its hydroxylimide parent, N-hydroxyphthalimide (NHPI), applying two approaches: using metallic salts, such as lead tetraacetate and cerium (IV) ammonium nitrate (CAN), and a "metal free" system in which the role of metallic species has been undertaken by antraquinone. In the former case, the strong influence of lead tetraacetate (or CAN) on the NHPI's reactivity, induce two different channels for the reaction pathway, radical and non-radical, a complex mixture of both saturated and unsaturated diadducts together with the corresponding monoadduct being formed. This behavior will not occur in the case of PINO generation in non-metallic systems, in this case the reaction pathway proceed exclusively via radical mechanism, with the formation of monoadducts as sole products. Copyright (C) 2008 John Wiley & Sons, Ltd.

引用

收藏

页码：397 / 402

页数：6

相关论文

共 19 条

[1]

Hydroxylamines as oxidation catalysts: Thermochemical and kinetic studies [J].

Amorati, R ;

Lucarini, M ;

Mugnaini, V ;

Pedulli, GF ;

Minisci, F ;

Recupero, F ;

Fontana, F ;

Astolfi, P ;

Greci, L .

JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (05) :1747-1754

[2]

ANDERSON CB, 1963, J ORG CHEM, V28, P605

[3]

Synthesis of naphthalenediols by aerobic oxidation of diisopropylnaphthalenes catalyzed by N-hydroxyphthalimide (NHPI)/α,α′-azobisisobutyronitrile (AIBN) [J].

Aoki, Y ;

Sakaguchi, S ;

Ishii, Y .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (2-3) :199-202

[4]

Kinetic study of the hydrogen abstraction reaction of the benzotriazole-N-oxyl radical (BTNO) with H-donor substrates [J].

Brandi, P ;

Galli, C ;

Gentili, P .

JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (23) :9521-9528

[5]

Mechanisms of reaction of aminoxyl (nitroxide), iminoxyl, and imidoxyl radicals with alkenes and evidence that in the presence of lead tetraacetate, N-hydroxyphthalimide reacts with alkenes by both radical and nonradical mechanisms [J].

Coseri, S ;

Mendenhall, GD ;

Ingold, KU .

JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (12) :4629-4636

[6]

Oxidation of organic substrates by molecular oxygen mediated by N-hydroxyphthalimide (NHPI) and acetaldehyde [J].

Einhorn, C ;

Einhorn, J ;

Marcadal, C ;

Pierre, JL .

CHEMICAL COMMUNICATIONS, 1997, (05) :447-448

[7]

Catalytic oxyalkylation of alkenes with alkanes and molecular oxygen via a radical process using N-hydroxyphthalimide [J].

Hara, T ;

Iwahama, T ;

Sakaguchi, S ;

Ishii, Y .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (19) :6425-6431

[8]

A novel catalysis of N-hydroxyphthalimide (NHPI) combined with Co(acac)(n)(n=2 or 3) in the oxidation of organic substrates with molecular oxygen [J].

Ishii, Y .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1997, 117 (1-3) :123-137

[9]

Alkane oxidation with molecular oxygen using a new efficient catalytic system: N-hydroxyphthalimide (NHPI) combined with Co(acac)(n) (n=2 or 3) [J].

Ishii, Y ;

Iwahama, T ;

Sakaguchi, S ;

Nakayama, K ;

Nishiyama, Y .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (14) :4520-4526

[10]

Kinetic study of the phthalimide N-oxyl radical in acetic acid.: Hydrogen abstraction from substituted toluenes, benzaldehydes, and benzyl alcohols [J].

Koshino, N ;

Saha, B ;

Espenson, JH .

JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (24) :9364-9370