SYNTHESIS OF DIACETYLENE MACROCYCLES DERIVED FROM 1,2-DIETHYNYLBENZENE DERIVATIVES - STRUCTURE AND REACTIVITY OF THE STRAINED CYCLIC DIMER

被引:251
作者
ZHOU, Q
CARROLL, PJ
SWAGER, TM
机构
[1] UNIV PENN,DEPT CHEM,PHILADELPHIA,PA 19104
[2] UNIV PENN,RES STRUCT MATTER LAB,PHILADELPHIA,PA 19104
关键词
D O I
10.1021/jo00085a016
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Diacetylene macrocycles 2-4 (n = 1-3) (R = H, C4H9, C6H13, C10H21, C12H25, OC10H21) have been prepared from the oxidative coupling of 1,2-diethynylbenzene derivatives. These compounds can be produced in useful quantities and are of interest as precursors to novel conjugated organic polymers. The reported results indicate that when the R groups are large the dimeric macrocycle (n = 1) can be prepared in as high as 74% yield from the corresponding 1,2-diethynylbenzene in a one-step procedure. An alternate multistep procedure was found to produce the tetrameric macrocycle (n = 3, R = C6H13) in 45 % yield. The highly strained dimeric macrocycle was characterized by an X-ray structure and was found to be very reactive. The dimers undergo a rapid very exothermic polymerization at 100-125-degrees-C, indicative of a chain reaction. Reaction of the dimeric macrocycles with iodine results in intramolecular cyclization and a new 20pi electron tetraiodide fused ring system. Reaction of the tetraiodide with oxygen produces a related compound in which two of the iodides have been converted to ketones.
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页码:1294 / 1301
页数:8
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