Investigations in the cyclobutane series. XXVI (1).

Solvolytic rearrangement of 1,2,3-tri-tert-butyl-3-dichloromethylcyclopropene and cis-3,4-dichloro-1,2,3-tri-tert-butylcyclobutene

“…Solvent was removed from the solid in vacuo; the material was recrystallized from water (69 ml) and dried in vacuo at 58°over calcium sulfate to give 18.3 g of product (45.5%),mp 233-250°. l-(Z)-(l-Deuterioethylidene>2-methyl-ira«s-3,4,4-trideuteriocyclobutane (16). 11 The phosphonium bromide 24 (18.3 g, 0.0442 mol), tetrahydrofuran (150 ml), and /¡-butyllithium (15.14% in hexane, 27.8 ml, 0.0530 mol) were stirred at room temperature for 1 hr under (19) Cf. E. L. Eliel, J. Chem.…”

“…With broad band deuterium irradiation the nmr spectrum of the longer retention time Z product 16 showed a doublet, J = 7.0 Hz, 1. 19 (C(2) methyl); a doublet, J = 5.4 Hz, 1.41 (C(3) proton); a doublet, / = 1.5 Hz, 1.51 (vinylic methyl); and a quintet, J = 7.0 Hz, of quartets, / = 1.5 Hz, 3.01 (C(2)). A small amount (8.4%) of 19 with C(3) hydrogen trans to the methyl was present as indicated by the doublet, J = 8.9 Hz, 2.06.…”

Convenient means of generating alkyl-substituted isobenzofurans as reactive intermediates

“…Compound 6 in the presence of hydrogen and Pd/C was reduced to corresponding 6-amino-7-(2,3,5-tri-0-acetyl-j3-D-ribofuranosyl)imidazo[4,5-d]-utriazin-(3J7)4-one (7). Compounds 7 and 9 under the influence of hydrogen and Raney Ni were ring opened to give previously unreported 2,5-diamino-l-(2,3,5-tri-0-acetyl-d-D-ribofuranosyl)imidazole-4-carboxamide (8) and 5-amino-2-methoxy-l-d-D-ribofuranosylimidazole-4-carboxamide (10), respectively.…”