Spiroorthocarbonates Containing Epoxy Groups

Chappelow etal, US Patent 6,653,486 (November 25, 2003) Assignee Curators of the University of Missouri Utility Photopolymerization Agents 

Dimethyl malonate (200 mmol) was dissolved in 300 ml DMF, cooled to 0 °C, and lithium hydride (500 mmol) added in one portion. To the cooled mixture was slowly added cis-l,4-dichloro-2-butene (228 mmol) and the mixture stirred 72 hours. Thereafter, the mixture was diluted with 500 ml 20% diethyl ether/hexanes then poured into 350 ml cold water. After washing with 300 apiece water and brine, the product was isolated in 50% yield, mp = 63.4 °C. H-NMR and IR data supplied. 

Lithium aluminum hydride (175 mmol) was added to 235 ml THF, cooled to 0°C, the product from Step 1 dissolved in 58 ml THF added, and the reaction stirred 4 hours. The reaction was quenched with the sequential addition of 6 ml water, 6 ml 3 M aqueous NaOH, and 17.5 ml water. The resulting cake was washed with 250 ml refluxing THF. The product was isolated in 86.2% yield as white needles, mp = 81.2 °C. H-NMR and IR data supplied. 

To the product from Step 2 (115.5 mmol) dissolved in 370 ml toluene was added p-toluenesulfonic acid (0.2 g) and tetraethylorthocarbonate (57.8 mmol) and the mixture refluxed until 12.5 ml ethyl alcohol was collected in a Dean-Stark apparatus. The mixture refluxed two hours and stirred at 102 °C overnight. The mixture was neutralized with 1 ml TEA, the product purified by flash chromatography on silica with CH2Cl2/hexanes, 2 1, and the product isolated as white crystals in 62% yield, mp = 174.5°C. H-NMR and IR data supplied. 

24-Dioxatrispiro[bicycle][3.1.0]hexane-3,5 -l,3-dioxane-2 2 -l,3-dioxane-5 3 -bicyclo[3.1.0[hexane] 

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