Die Mischoligomerisation von Butadien und Alkinen mit funktionellen Gruppen an NickelLigand-Katalysatoren und partielle Hydrierung der gebildeten 4,5-disubstituierten cis&, trcms-l,4,7-Cyclodecatriene fiihrt in guten Ausbeuten zu 1,2-disubstituierten cis-Cyclodecenen. Durch Ozonolyse mit anschlieoender Hydrierung lassen sich bei geeigneter Wahl der Alkine 2,11-Diketo-a,a-mono-oder -dimethylather, 2,l I-Diketo-1-alkanole, 10-Ketocarbonsauren
Syntheses with cis,cis,tuuns-1,4,7-Cyclododecatrienes from Butadiene and Alkyne Ethers, Alkynols and Alkyne EstersThe co-oligomerization of butadiene with alkynes having functional groups using a nickelligand catalyst followed by partial hydrogenation of the resulting 4,5-disubstituted cis,cis, trans-l,4,7-cyclodecatrienes leads in good yield to I ,2-disubstituted cis-cyclodecenes. 2,11-Diketo-&,a-mono-or dimethyl ethers, 2,1 I-diketo-1 -alkanols, 10-ketocarboxylic acids or diketo-&,a-dicarboxylic acids can be synthesized from the corresponding alkynes by ozoiiolysis and consecutive hydrogenation. The same reaction sequence using m,a-bifunctional mono-and dialkynes leads to a chain elongation by 8 or 16 C-atoms. A total of 7 alkynes were investigated. -The co-oligomerization of butadiene with 2-butyne was compared to that with 1,4-dimetboxy-2-butyne or 1 -niethoxy-2-pentyne. The number of methylmethoxy groups on the triple-bond influences the ratio of ten-membered ring (butadiene:alkyne 2 2: 1) to the corresponding twelve-membered ring (2:2) and the benzene derivatives (0: 3). The yields of the cyclodecatriene derivatives are higher than 90 % if the functional groups are separated by two or more methylene groups from the triple-bond. *) Korrespondenz bitte an diesen Autor richten, Adresse: Max-Planck-Institut fur Kohlenforschung,_Mulheim.
