通过使用芳基,用 2,2,6,6-四甲基哌啶-1-氧基 (TEMPO) 一步实现了非酸性脂肪族和苄基 C(sp3)-H 键的光驱动自由基氧基官能化酮作为唯一的催化剂。该转化是通过光激发芳基酮对起始物质中的 C(sp3)-H 键进行均裂而引发的。然后衍生的碳自由基立即被 TEMPO 捕获,导致 TEMPO 加合物的形成。衍生的 TEMPO 加合物作为醇等价物在合成上是通用的,因为它可以很容易地通过氧化转化为相应的酮,并通过还原转化为相应的醇。实现本催化反应的关键依赖于TEMPO独特的三重作用,它充当氧官能团的前体、再生芳基酮的氧化剂以及防止过度氧化的衍生TEMPO加合物的保护基团。
[EN] HYDROGEN PEROXIDE CATALYZED PROCESS FOR THE PREPARATION OF STERICALLY HINDERED N-HYDROCARBYLOXYAMINES<br/>[FR] PROCEDE DE CATALYSE DU PEROXYDE D'HYDROGENE POUR PREPARER DES N-HYDROCARBYLOXYAMINES STERIQUEMENT ENCOMBREES
申请人:CIBA SC HOLDING AG
公开号:WO2005005388A1
公开(公告)日:2005-01-20
Sterically hindered N-hydrocarbyloxyamines (I) are prepared from hindered amine N-oxyl compounds (II) by a process which uses peroxide or a hydrogen peroxide equivalent, a catalytic amount of a peroxide decomposing transition metal salt, metal oxide, or metal-ligand complex, a hydrocarbon solvent containing no activated hydrogen atoms, and an inert cosolvent, These compounds are useful as thermal and light stabilizers for a variety of organic substrates.
Hydrogen peroxide catalyzed process for the preparation of sterically hindered N-hydrocarbyloxyamines
申请人:Galbo P. James
公开号:US20050014948A1
公开(公告)日:2005-01-20
Sterically hindered N-hydrocarbyloxyamines are prepared from hindered amine N-oxyl compounds by a process which uses hydrogen peroxide or a hydrogen peroxide equivalent, a catalytic amount of a peroxide decomposing transition metal salt, metal oxide, or metal-ligand complex, a hydrocarbon solvent containing no activated hydrogen atoms, and a relatively inert cosolvent. These compounds are useful as thermal and light stabilizers for a variety of organic substrates.
A process a process of forming a non-halogenated flame retardant (FR) hindered amine light stabilizer (HALS) cross-linker is disclosed. The process includes forming a mixture that includes a first molecule having a hindered amine group. The first molecule corresponds to a functionalized 2,2,6,6-tetramethylpiperidine (TMP) molecule. The process also includes forming the non-halogenated FR HALS cross-linker via a chemical reaction of the first molecule a second molecule. The second molecule includes a phosphoryl group, a chloride group, and at least one cross-linkable (CL) moiety.
A broad variety of 2,2,6,6-tetramethylpiperidine-based N-alkoxyamines were prepared in a newly found reaction. By means of a copper-catalyzed fragmentation reaction of aldehyde peroxides in the presence of TEMPO or TEMPO derivatives, N-alkoxyamines were obtained in moderate to good yields.
HYDROGEN PEROXIDE CATALYZED PROCESS FOR THE PREPARATION OF STERICALLY HINDERED N-HYDROCARBYLOXYAMINES