A. 2-(Trichloromethyl)bicyclo[3.3.0]octane. To a 5-l. three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer are added 325 g. (3.0 moles) of cis,cis-1,5-cyclooctadiene (Note 1), 3 l. of chloroform (Note 2), and 14.6 g. (0.06 mole) of benzoyl peroxide. The resulting solution is stirred and refluxed (63–65°) on the steam bath (Note 3) for a total of 5 days. Four 7.3 g.-(0.03 mole-)portions of benzoyl peroxide are added, one on each consecutive day of reaction (Note 4). After a total of 5 days at reflux, the reaction mixture is cooled and washed with three 250-ml. portions of aqueous sodium bicarbonate (Note 5) and with 250 ml. of water, all the washes being discarded. The chloroform solution is dried with 30 g. of magnesium sulfate and filtered. The filtrate is distilled at atmospheric pressure using a short (8-in.) Vigreux column to collect 2760–2790 ml. of chloroform, b.p. 55–64°, which is discarded. The pressure is reduced and distillation continued to obtain two fractions: (1) b.p. 31° (47 mm.) to 65° (0.2 mm.), 300 g.; (2) b.p. 65–153° (0.2 mm.), 169 g. (Note 6). Fraction 2 is refractionated with the same Vigreux column to obtain 106–117 g. (approximately 35% based on unrecovered cis,cis-1,5-cyclooctadiene) of 2-(trichloromethyl)bicyclo[3.3.0]octane, b.p. 116–125° (5 mm.), n²⁵D 1.5110–1.5115 (Note 7). The product is pure (by gas chromatography) (Note 8) and may be used in the next step.

B. exo-cis-Bicyclo[3.3.0]octane-2-carboxylic acid. A mixture of 100 g. (0.440 mole) of 2-(trichloromethyl)bicyclo[3.3.0]octane and 500 ml. of 85% phosphoric acid is put into a 1-l. three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer. The mixture is stirred and heated at 150° for 16 hours, during which time it evolves hydrogen chloride and darkens. The product is then allowed to cool and is poured into a separatory funnel. One liter of water is added and the resulting mixture is extracted with four 250-ml. portions of ether. The combined ether extract is then extracted with four 250-ml. portions of 2% aqueous sodium hydroxide (Note 9), and the resulting alkaline extract is washed with 100 ml. of ether to remove any neutral material (Note 10). The alkaline extract is acidified (to pH 2–3) with concentrated hydrochloric acid, and the oil which precipitates is extracted with three 250-ml. portions of ether. The resulting ether extract is dried with 15 g. of magnesium sulfate, filtered, and evaporated at 50° (30 mm.). The residue is then distilled at reduced pressure to obtain 29–32 g. (43–47%) of exo-cis-bicyclo[3.3.0]octane-2-carboxylic acid, b.p. 91–96° (0.15 mm.), n²⁵D 1.4839–1.4847 (Note 11).