Atom transfer radical cyclisations of activated and unactivated N-allylhaloacetamides and N-homoallylhaloacetamides using chiral and non-chiral copper complexes
作者:Andrew J. Clark、Floryan De Campo、Robert J. Deeth、Robert P. Filik、Sylvain Gatard、Nicola A. Hunt、Dominique Lastécouères、Gerard H. Thomas、Jean-Baptiste Verlhac、Hathaichanuk Wongtap
DOI:10.1039/a909666c
日期:——
Activated N-tosyl-2,2,2-trichloroacetamide 6a, N-benzyl-2,2,2-trichloroacetamide 6d, 2,2-dichloroacetamides 6b–c and 6e–f and 2-monohaloacetamides 11a–g undergo efficient 5-exo atom transfer radical cyclisations at room temperature mediated by CuCl or CuBr in the presence of tris(N,N-dimethylaminoethylene)amine 3 (trien-Me6). The efficiency and stereoselectivity of these cyclisations was found to be greater than existing published atom transfer procedures based upon CuCl(bipyridine), RuCl2(PPh3)3 and CuCl(TMEDA)2. The product distribution for the cyclisation onto alkyne 11g was found to be solvent dependent. Attempts to make larger ring sizes by endo cyclisation of N-tosylacetamides 19a–c led to a competing 5-exoipso aromatic substitution into the N-tosyl group followed by re-aromatisation and loss of SO2 to furnish an amidyl radical. Cyclisation of N-homoallylacetamides 25a–d proceeded smoothly to give δ-lactams with a range of catalysts based upon ligands 2 and 26. The stereoselectivity of cyclisation to give γ lactams could be somewhat influenced by using chiral enantiopure copper complexes 28–30 suggesting that the reactions may involve metal-complexed radicals.
Fast shuttling motions in solution have been observed by cyclic voltammetry in a CuI/II-based [2] rotaxane. In the reported system, the different coordination preferences of both copper oxidation states are exploited to promote the electrochemically-triggered gliding of the ring from a tetra to a pentacoordinated site and vice versa. The thread of this rotaxane consists of a tridentate 2,2′:6′,2′′-terpyridine
通过循环伏安法在基于Cu I / II的[2]轮烷中观察到了溶液中的快速穿梭运动。在报道的系统中,利用了两种铜氧化态的不同配位偏好,以促进环的电化学触发滑行从四到五配位,反之亦然。该轮烷的线由三齿的2,2':6',2''-吡啶吡啶螯合单元组成,该螯合单元通过其5-位直接键合到双齿1,10-菲咯啉单元的3-位。这种分布将两个配位点之间的距离减至最小,并减轻了四面体周围环境的拥堵。已经证明这两个因素极大地增加了切换过程的动力学。另外,在不同溶剂混合物中进行的电化学实验证明了溶剂对穿梭机理的影响。
NANOPARTICLES COMPOSITIONS CONTAINING POLYMERS AND ANTHRANILIC ACID DIAMIDE INSECTICIDES FOR PROPAGULE COATING
申请人:E. I. Du Pont de Nemours and Company
公开号:EP2793581A1
公开(公告)日:2014-10-29
ACRYLATE/METHACRYLATE-BASED RANDOM COPOLYMER/ANTHRANILIC DIAMIDE COMPOSITIONS FOR PROPAGULE COATING
申请人:TAM WILSON
公开号:US20120149563A1
公开(公告)日:2012-06-14
Disclosed is an insecticidal composition comprising by weight based on the total weight of the composition:
(a) from about 9 to about 91% of one or more anthranilic diamide insecticides; and
(b) from about 9 to about 91% of an acrylate/methacrylate-based random copolymer component having a water solubility of at least about 5% by weight at 20° C., a hydrophilic-lipophilic balance value of at least about 3, and an average molecular weight ranging from about 1,500 to about 50,000 daltons;
wherein the ratio of component (b) to component (a) is about 1:10 to about 10:1 by weight.
Also disclosed is a geotropic propagule coated with the insecticidal composition.
Further disclosed is a liquid composition comprising the insecticidal composition, and a method for protecting a geotropic propagule and plant derived therefrom from a phytophagous insect pest.