Über Verbindungen mit Urotropin‐Struktur, XXVII Über eine Fragmentierung in der Adamantan‐Reihe

Abstract

3-Brom-adamantan-carbonsaure-(l)wurde

Molecule-Induced Alkane Homolysis with Dioxiranes

“…D. Reaction of 3 with DMD. Following procedure A, from 105 mg (0.78 mmol) of 1,3-dehydroadamantane ( 3 ) in 10 mL of CH 2 Cl 2 and 12.5 mL of a 0.063 M acetone solution of DMD (0.79 mmol) were obtained 55 mg of 3-methylenebicyclo[3.3.1]nonan-7-one ( 11 ) (0.36 mmol, 46%) and 11 mg of 1,3-dihydroxyadamantane ( 10 ) (0.06 mmol, 8%), identical from MS and NMR data to standard samples. , The conversion of 3 was virtually complete as determined after quenching the reaction mixture with water (only trace amounts of 1-hydroxyadamantane as a result of the addition of water to 3 were found). In a series of control experiments, we also ran this reaction with only 10% DMD under argon.…”

Adamantane: Consequences of the Diamondoid Structure

“…3.1 ]nonane skeleton(129,130). Compound LXVII, when treated with base, fragments in the fashion shown in Eq.…”

Synthesis of 5,5'-bi-2-oxaadamantane

“…The extract was combined with the organic phase and dried over anhydrous MgS04. Evaporation of the solvent at reduced pressure gave 1.09 g of crude 4. Crystallization of 4 from CHClg/acetone gave 761 mg (87% yield) of 4 as an off-white solid: mp 270-271 °C; 18C NMR 61.9 (C-3, C-3', C-5, and C-5'), 58.5 (C-4 and C-4'), 46.5 (C-6, C-6', C-10, and C-100, 46.1 (C-l and C-l'), 45.8 (C-2, C-2', C-9, and C-9'), 34.3 (C-7 and C-7'), 32.3 (C-8 and C-8'); NMR 2.80 (AB multiplet, 4 H), 2.33 (m, 1H), 2.22 (m, 4 ), 2.14 (bs, 4 ), 1.59 (bd, J = 2.9 Hz, 2 H); HRMS caled for CgoHggBrg (M+ -Br) 502.9579, found 502.9547.…”

“…Treatment of 3 with bromine containing a catalytic amount of aluminum bromide for 3 h at room temperature gives 3,3',5,5'-tetrabromo-l,l'-biadamantane (4) in 87% yield (Scheme I). Consistent with the presence of a center of symmetry in 4, its 13C NMR spectrum consists of only seven resonances.…”

“…Heating a solution of 4 in dioxane with 1 N aqueous sodium hydroxide at 180-185 °C for 24 h proceeds with 95 % conversion of 4 to give a 50:50 mixture of dland meso-l,l'-bi (7-methylenebicyclo[3.3.1]nonan-3-one) (5 and 6, respectively) in 75% yield and l-(3',5'dibromo-l'-adamantyl)-7-methylenebicyclo[3.3.1]nonan-3-one (12) in 8% yield. Enone 12 was separated from the Br-2 Br' 12 .0 mixture of 5 and 6 by column chromatography on silica gel with dichloromethane/ethyl acetate as the eluent.…”