Preparation of an isocyano-beta-diketone via its metal complexes, by use of metal ions as protecting groups.
Preparation of an isocyano-beta-diketone via its metal complexes, by use of metal ions as protecting groups.
复制标题
使用金属离子作为保护基团，通过其金属配合物制备异氰基-β-二酮。
作者：
Yixun Zhang;A. Maverick
摘要制备了一种含有异氰化物和β -二酮官能团的配体，3-（4-异氰苯基）-2,4-戊二酮（HacphNC）及其金属配合物。由于其β -二酮部分的反应性，游离异氰基- β -二酮不能通过类似的甲酰胺HacphNHCHO脱水制备。相反，金属配合物Al(acphNC)(3), Fe(acphNC)(3), Cu(acphNC)(2)和Zn(acphNC)(2)由甲酰胺- β -二酮酸配合物Al(acphNHCHO)(3), Fe(acphNHCHO)(3), Cu(acphNHCHO)(2)和Zn(acphNHCHO)(2)脱水合成。通过草酸盐(C(2)O（4)(2-)）和HC(2)O(4)（-）处理，可以将游离的异氰酸- β -二酮HacphNC从其Al和Fe配合物中分离出来。除了这些o键配合物外，还可以通过Al(acphNC)(3)或HacphNC与Au(I)的反应制备C(N)键配合物。本文还报道了HacphNC、Al(acphNC)(3)、（HacphNC）AuCl、Cu(acphNHCHO)(2)、反式zn (acphNHCHO)(2)(H(2)O)(2)和其他两种中间体的x射线分析。
A ligand containing isocyanide and beta-diketone functional groups, 3-(4-isocyanophenyl)-2,4-pentanedione (HacphNC), and several of its metal complexes have been prepared. The free isocyano-beta-diketone could not be prepared by dehydration of the analogous formamide, HacphNHCHO, because of the reactivity of its beta-diketone moiety. Instead, the metal complexes Al(acphNC)(3), Fe(acphNC)(3), Cu(acphNC)(2), and Zn(acphNC)(2) were synthesized by dehydration of the formamido-beta-diketonate complexes Al(acphNHCHO)(3), Fe(acphNHCHO)(3), Cu(acphNHCHO)(2), and Zn(acphNHCHO)(2). The free isocyano-beta-diketone, HacphNC, can be liberated from its Al and Fe complexes by treatment with oxalate (C(2)O(4)(2-)) and HC(2)O(4)(-). In addition to these O-bound complexes, C(N)-bound complexes can be prepared by the reaction of either Al(acphNC)(3) or HacphNC with Au(I). X-ray analyses of HacphNC, Al(acphNC)(3), (HacphNC)AuCl, Cu(acphNHCHO)(2), trans-Zn(acphNHCHO)(2)(H(2)O)(2), and two other intermediates are also reported.