Chemistry of acetylenic ethers. Part 90: Cyclotetramerization of ethynyl ethers to 1,3,5,7‐tetra‐alkoxycyclo‐octatetraenes. Syntheses of 3,5,7‐triethoxy‐2,4,6‐cyclo‐octatrienone and of 1,3,5,7‐tetra‐alkoxy‐2,6‐dioxa‐adamantanes

Abstract

Cyclotetramerization of ethynyl ethers to 1,3,5,7-tetra-alkoxyoctatrienone and of 1 ,3,5,7-tetra-al koxy-2,tj-dioxa-adamantanes BY cyclo-octatetraenes. Syntheses of 3,5,7-triethoxy-2,4,6-cyclo-Ethoxyethyne and propoxyethyne are slowly tetramerized to 1 ,3,5,7-tetraalkoxycyclo-octatctraenes iindcr the influence of alkali aniides in liquid ammonia. By partial hydrolysis 1 ,3,5,7-tctracthoxycyclo-octatetraene (I) is converted into 3,5,7-triethoxy-2,4,6-cyclo-octatrienone (111). Treatnicnt with acidified cthanol or methanol leads to 1,3,5,7-tetracthoxy-2,6-dioxa-adaniantanc (V) and I ,3,5,7-tetraniethoxy-2,6-dioxa-adaniantane (IV), respectively. 1 Nohiit, Htrgikrri.ci, Yuki Cozci Kngabu Kyokai Shi 19, 20 (1961); Chcni. Abstr. 55, 7267 (1961). V. 0. R(~iXlrsf>l'd, crud A'. L . Mukovct.tkii, Russ. Cheni. Rev. 35, 510-523 (1966). L. S . i2.leriw~thcr, E. c'. C'olthiip, G. W . Ketitxdy and R . N . Reiisch, J . Org. Chern. 26, 5155 (1961). K . L. i\.lukovrtskii, V. 0 . Reikhsfil'ci and L. L. Erokhitiu, Zh. Organ. Khim. 2, 753 (1966); Chem. Abstr. 65, 13577 (1966). r' K . L . Makowr.vkii, L. L. Dokhitru and V. 0. Reikhsfil'd, Zh. Organ. Khim. 2, 759 (1966): Cheni. Abstr. 65, 13577 (1966). V . 0. Rc>ik-h.yj>l'd, B. I . Leiii and K . L. i211rk-or.ctskii, Zh. Organ. Khini. 2, 961 (1966); Cheni. Abstr. 65, 15251 (1966). W . Schufer, Angcw. Chem. 78, 716 (1966). J . R . Lato and M. I;: L m , J. Am. Chcm. Soc. 83, 2944 (1961). I' G . N . Schraiixr, B. N . Bustiuti and G. A. Fossc,lirrs, ihicl. 88, 4890 (1 966).i O U' .