Über Verbindungen mit Urotropin‐Struktur, XXXIII. Über eine neue Möglichkeit des Ringschlusses zu 1.3‐disubstituierten Adamantanen

Abstract

3-Methylen-bicyclo[3.3.l]nonanon-(7)(

Rigid C3‐Symmetric Scaffolds Based on Adamantane

“…The resulting product was purified by column chromatography (silica gel, petroleum ether/ethyl acetate, 4:1). 292 mg (0.79 mmol; 35 %) of colorless crystals was isolated; R f = 0.45 (petroleum ether/ethyl acetate, 4:1), m. [29] A mixture of 1,3,5,7-tetrahydroxyadamantane (4.51 g, 22.5 mmol), p-toluenesulfonic acid monohydrate (2.14 g, 11.3 mmol) and anisole (100 mL) was heated for 40 h with a Dean-Stark apparatus. Then the solvent was evaporated in vacuo and the crude product was dissolved in CH 2 Cl 2 .…”

“…Mass spectra were obtained with a Varian MS MAT 311A in EI mode. The following starting materials were synthesized according to literature procedures: 1,3,5-triphenyladamantane (11), [25] tetraphenyladamantane (13), [25] tribromoadamantane (7), [29] tetrahydroxy-adamantane (15). [34] Adamantane-1,3,5-tricarboxylic Acid (12): [25] 1.00 g of 11 (2.74 mmol) and 26.26 g of H 5 IO 6 (115.2 mmol) were dissolved in 70 mL of CCl 4 /CH 3 CN/H 2 O (2:2:3) and the reaction mixture was cooled to 0°C.…”

“…An exchange of phenyl groups for more electron-rich anisyl groups brought better results in this series. The 1,3,5,7-tetraanisyladamantane (16) can be synthesized from 1,3,5,7-tetrahydroxyadamantane (15) according to a protocol of Stetter [29] and is a reasonable substrate for oxidative degradation with RuCl 3 as indicated in Scheme 1. An interesting scaffold for chemoselective conjugation of unprotected biomolecules via click-chemistry is 1,3,5-triethynyladamantane (19).…”

Competing Fragmentation, Substitution and Elimination in the Solvolysis of Alkylated 3‐Chloropropanols and their Ethers. Fragmentation reactions no. 28

“…Evaporation of the solvent and sublimation yielded 2.12 g (5oo/o) of 3b, m.p. Adamantane-l,3-diol ( l l a ) was prepared according to [32]. From CHC13 m.p.…”

Synthesis and Reactions of Strained Hydrocarbons Possessing Inverted Carbon Atoms. Tetracyclo[3.3.1.13.7.01.3]decanes

“…This compound was purified by sublimation at 70°/1 mm and characterized by its n.m.r. spectrum and by base-promoted ring opening to 3-methylene-bicyclo[3.3.l]nonanone-7 (12 acetone containing solid NaCN and stirred at -70" for 24 h. After warming to room temperature, chromatography on Woelm neutral alumina gave I-iodo-3-ethoxyadamantane, m.p. 35-37" (sealed tube).…”