High-pressure synthesis of cyclic phenylacetylene oligomer

New conjugated oligomers were prepared by reacting phenylacetylene under high pressure of 0.11 to 0.92 GPa at 100–200°C for 0–5 h. The number-average molecular weight M?_n, the weight-average molecular weight M?_w, and the oligomer yield increased with pressure, tem-perature, and time. The average molecular weight of the oligomer showed the maximum value (M?_n: 830, M?_w: 2400) under 0.92 GPa, the maximum pressure, where phenylacetylene was oligomerized at a constant temperature. The structure of the oligomer was investigated from ESR, infrared, UV–VIS, field desorption mass (FDMS) spectra, and ¹³C NMR spec-trum. Analysis of the FDMS spectrum revealed that the molecular weight of the oligomer was multiple of the monomer. ¹³C NMR spectrum of the oligomer showed the absence of sp-carbon (? C?). We found that the oligomer had a cyclic structure. The cyclic oligomers of pentamer or more were new compounds. © 1995 John Wiley & Sons, Inc.