Insertion of Ketene and Diphenylketene to the Pnictogen-Heteroatom Bonds
作者:Fumio Ando、Yoshihiko Kohmura、Jugo Koketsu
DOI:10.1246/bcsj.60.1564
日期:1987.4
Ketene and diphenylketene insert across the heteroatom-metal bond of amino-, alkoxy-, and alkylthiopnictogens, R3−nMXn, to give the corresponding α-metallated acetamides, esters, and thioesters, R3−nM(CH2COX)n and R3−nM(CPh2COX)n (M=As, Sb, Bi; X=NR2, OR, SR; n=1,3), respectively.
prepared from the corresponding metal amides Me2MNR1R2; they were characterized by elemental analyses, IR and NMR spectroscopy. The carbon atom in organometallicdiazoalkanes of antimony and bismith is more nucleophilic than that in organic diazoalkanes as proved by 13C NMR spectra.
二甲基金属重氮化合物Me 2 MC(N 2)R(R = CO 2 Et; Me 2 M),是由相应的金属酰胺Me 2 MNR 1 R 2制备的。通过元素分析,IR和NMR光谱对它们进行表征。通过13 C NMR光谱证实,锑和Bismith的有机金属重氮烷烃中的碳原子比有机重氮烷烃中的碳原子更具亲核性。
Reaction of the Group 15 Metalloid Amides with Diketene by 1,4-Addition Mode
作者:Fumio Ando、Ryosuke Mio、Jugo Koketsu
DOI:10.1246/bcsj.66.1998
日期:1993.7
(dialkylamino)dimethylstibines react with diketene to yield N,N-dialkyl-4-dimethylarsino-3-oxobutanamides, N,N-dimethyl-4-diphenylarsino-3-oxobutanamide, and N,N-dialkyl-4-dimethylstibino-3-oxobutanamides, respectively. These group 15 metalloid-substituted 3-oxobutanamides exist as keto-enol tautomers and the keto isomers are predominant in solution or in neat state. This reaction is the first example of 1,4-addition
Cyclopentadienyls (CH3)2Mσ-C5H5 of indium, antimony and bismuth
作者:Peter Krommes、Jörg Lorberth
DOI:10.1016/s0022-328x(00)89508-x
日期:1975.4
The reaction of Me3In with monomeric cyclopentadiene yields the stable Me2InCp (I): the same product may be obtained by the reaction of (Me2InNMe2)2 with C5H6 via a soluble adduct Me2InCp · HNMe2 (II) which is easily converted into Me2InCp, for which a polymeric structure is suggested.
Me 3 In与单体环戊二烯的反应生成稳定的Me 2 InCp(I):通过(Me 2 InNMe 2)2与C 5 H 6经由可溶性加合物Me 2 InCp·HNMe的反应可得到相同的产物2(II),其易于转化为Me 2 InCp,为此提出了一种聚合物结构。