cf. S. and Rauchalles, C. A. 20, 377.Candiolin (15.41% H2O, 17.05% Ca, 13.21% organic P) is treated with (CO2H)2, filtered from the Ca oxalate and then treated with brucine; crystallization of the precipitate from 7-8 parts boiling 70% EtOH (5 times) gives 75% of the brucine salt (I), [α]D -23.6°, practically free of aldose components.I (80 g.) in 1100 cc. 20% EtOH and 23.1 g. Ba(OAc)2.H2O, shaken 10 min., 2250 cc. EtOH added, the precipitate removed with a centrifuge and dissolved in 300 cc. 1% ice-cold H2O, EtOH and KOH added until the solution is neutral, gives 90-5% of the Ba fructosediphosphate.Shaking the Ba salt (50 g.) in 1 l. 1.688% MeOH-HCl at 25° gives a mixture of the 2 Me fructosides, which is separated into about equal weights of 2 fractions, [α]D 2.8-4.8° and -2 to -3°, by crystallization from a 1% aqueous solutionTransformation into the brucine salt and crystallization from 96% (α-form) or 50% (β-form) EtOH finally yielded Ba salts with [α]D 8.5° (H2O, c 1) and [α]D -8.75°, [α]5461 -10.4° (H2O, c 1); the P was removed by kidney phosphatase at a pH of 9, giving 80-90% of Me fructofuranoside (II), which was purified through the Ac derivative α-II has [α]D 56.9° (MeOH, c 1.4); β-II, [α]D -49.95°, [α]5461 -58.92° (H2O, c 1). β-II is split to the extent of 95.1% by invertin in 36 hrs.; that 100% is not reached is probably due to the presence of some tetra-Ac derivative; α-II, 21.65% in 24 hrs.N HCl gives 97.2% splitting of the β-II in 36 hrs.; half-period, 52.5 min.The diphosphoric acids are not attacked to a noticeable degree by invertin in 17 hrs.
