Glucosinistrin (I), a nonreducing polysaccharide, was isolated from alc. extracts of white squill (II) (Scilla maritima).Acid hydrolysis of I gave D-fructose (III) and D-glucose (IV) in the ratio approx. 4:1.Shredded II was dried in an air stream at 60-70%, ground, and sieved; 1 kg. was successively stirred with 8.7 and 5 l. 96% EtOH.The united extracts contained about 60 g. solids; hydrolysis with 2% H2SO4 (50 min. at 90°) showed about 30 g. reducing compounds (calculated as III).The extracts evaporated in vacuo to about 1 l. gave 15-20 g. pale yellow hygroscopic precipitate of crude I, which washed with absoluteEtOH and Et2O, dissolved in 150 cc. H2O, C added, the mixture filtered, the filtrate evaporated in vacuo with addition of EtOH to remove H2O, the residue kept in an ice box several days, filtered, the white flocculent powder stirred with dry Et2O, decanted, and dried over P2O5 gave about 12 g. purer I, [α]20D -9.6° (c 5, H2O), still faintly reducing to Fehling solutionIt was precipitated 4 to 5 times from concentrated aqueous solution with 5:95 dry Et2O-absolute EtOH and washed with dry Et2O to give 8-9 g. I, deliquescent, microcrystalline powder, nonreducing to Fehling solution no color with iodine, decomposed at 145-166° (foaming), [α]20D -18.6° (c 3, H2O).I (500 mg.) in 25 cc. 1% H2SO4 kept at 80° 30 min., the solution cooled, made to 100 cc. with H2O, and stirred 2 hrs. with 20 g.Duolite A; ascending chromatography on S. and S. 2043b with 40:50:10 butanol-H2O-HOAc with a developing spray of 0.5 g. benzidine in 20 cc. EtOH plus 80 cc. absolute EtOH, showed III and IV.A similar hydrolyzate (40 min.) was neutralized with dilute NaOH solution, made to 50 cc., and aliquots analyzed to give III-IV 3.82:1 (or 3.77:1) [α]20D -63.0 to -63.5° (c 4).A 1:4 mixture of aqueous solutions of IV ([α]20D 52.5°, 24 hrs.) and III ([α]20D -92.0°) had [α]20D -62.2° (c 4, 24 hrs.).Control experiments showed that in N H2SO4 (48-72 hrs. at 20-25°) and in 0.4N H2SO4 (50 min. at 90°), no appreciable epimerization of III to aldoses occurred.I (100 mg.) in 20 cc. N H2SO4 kept 48 hrs. at 20°, brought to pH 6.5 with N KOH and to 170 cc. with distilled H2O, and analyzed showed 72.0 mg. III and 18.0 mg. IV (4:1 ratio).IV was also determined with glucose oxidase: 17.68 mg. IV/100 mg. I. I (4 g.) in 100 cc. 1% H2SO4 kept 50 min. at 80°, the mixture neutralized with BaCO3, C added, the mixture filtered, evaporated in vacuo to a thin sirup, MeOH and HOAc added, the solution nucleated with III, and kept in an ice box several days gave 650 mg. crystalline III, m. 90-5°, [α]20D -89.0°, intense blue in diphenylamine test; p-nitrophenylhydrazone, yellow needles, m. 167-71°.I (11 g.) in 300 cc. 1% H2SO4 kept 50 min. at 80°, the mixture neutralized with BaCO3, evaporated in vacuo to 100 cc., cooled to 0°, 8 g. Ca(OH)2 added, the mixture shaken, kept 30 min., the Ca fructosate centrifuged, the solution freed from Ca with CO2, evaporated in vacuo at 30° to a thin sirup, 2 cc. HOAc added, the solution nucleated with IV, kept 10 days in an ice box, stirred with absolute EtOH, filtered, and the crystals washed with Me2CO and Et2O gave 1.2 g. mixture of IV (950 mg.) plus III (105 mg.), which dissolved in water, the solution evaporated to a sirup, this nucleated with IV, and kept several days gave 600 mg. mixture of IV (580 mg.) plus III (20 mg.), m. 140-2°, [α]20D 48.0° (c 2.5, H2O, 24 hrs.), diphenylamine reaction weakly pos.; diphenylformazan derivative, red needles from butanol, m. 175-6.5°.I (5.0 g.) in 200 cc. 1% H2SO4 kept 50 min. at 80°, the solution neutralized with BaCO3, evaporated to a sirup, this cooled to 0°, 2 cc. concentrated HCl and 2 cc. EtSH added, the mixture shaken 15 min., 5 cc. H2O added, the solution cooled to 0°, filtered, and recrystallized from H2O to give 0.5-0.7 g. needles of IV di-Et dithioacetal, m. 126-7°, [α]20D -8.8° (c 1, MeOH).I ([α]20D -18.6°, 5 g.) was precipitated 5 times from concentrated aqueous solution with absolute EtOH, washed with absolute Et2O, and dried in vacuo, [α]20D -22.6° (c 2.5, H2O); hydrolysis and sugar analysis gave the III-IV ratio as 4.89:1.