TROPYLIUM FLUOBORATE

Absolute ethanol (400 ml.) is vigorously stirred in a 1-1. widenecked Erlenmeyer flask immersed in an ice bath (Note 4). The tropylium hexachlorophosphate-tropylium chloride double salt4 is separated from the reaction mixture by suction filtration, washed briefly with fresh carbon tetrachloride, and transferred as rapidly as possible into the cold, well-stirred ethanol (Note 5). The salt dissolves rapidly and exothermally to give a reddish solution. Fifty milliliters (0.39 mole) of 50% aqueous fluoboric acid is added rapidly to the cold stirred solution (Note 6). The dense white precipitate of tropylium fluoborate that forms is separated by suction filtration, washed with a little cold ethanol and with ether, and air-dried at room temperature (Note 7) weight 34-38 g. (80-89%) decomposition point about 200° A j, HC1 218 mja (log e 4.70), 274 m/i (log e 3.61). The product is 98-100% pure (Notes 8 and 9). 

In a variation of this procedure that gives a nearly quantitative yield of good material, the intermediate salt is dissolved in 250 ml. of glacial acetic acid in a 2-1. beaker, and 100 g. of 50% fluoboric acid is added with stirring. When the evolution of gas has stopped, 11. of ethyl acetate is added to precipitate tropylium fluoborate. The fluoborate is separated by filtration, washed successively with ethyl acetate and ether, and dried in an oven at 40°.4... 

Phosphorus pentachloride, for conversion of pentaacetylgluconic add to add chloride, 41, 80 for oxidation of cycloheptatriene to tropylium fluoborate, 43, 101 with cyanoacetic acid, 41, 5 Phosphorus tribromide, reaction with 1.5-hexadien-3-ol, 41, 50 Phthalic anhydride, reaction with L-phenylalanine to yield N-phthalyl-L-phenylalanine, 40, 82 Phthalic monoperacid, 42, 77 N-Phthalyl-i.-alanine, 40, 84 N-Phthalyl-/3-alanine, 40, 84 N-Phthalylglycine, 40, 84 N-Phthalyl-l-/5-phenylalanine, 40, 82... 

The chief value of several procedures lies in current research interest in the products. Tropylium fluoborate (p. 101) is a good example. 

Tropylium fluoborate appears to be stable indefinitely under normal conditions. It sits uncomplaining on the desktop, for all the world resembling table salt. This stuff is no ordinary carbocation ... 

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