To 350 ml. of anhydrous methanol contained in a 1-l. three-necked round-bottomed flask, to which is attached a reflux condenser protected by a drying tube, is added 20 g. (0.87 gram atom) of sodium (Note 1) in large pieces. The reaction is kept under control by cooling the flask in a pan of ice water. To the resulting solution of sodium methoxide is added a solution (Note 2) of 61 g. of hydroxylamine hydrochloride (0.88 mole) in 20 ml. of water; during the addition the mixture is swirled in order to avoid spattering. After 20 minutes the mixture is cooled to 0° and filtered with suction. The sodium chloride is washed with 350 ml. of anhydrous methanol. The combined filtrate and washings are warmed to 65° in a 3-l. round-bottomed flask, and a solution of 100 g. of finely powdered commercial crystalline glucose monohydrate (0.50 mole) in 200 ml. of warm 25% aqueous methanol is added, with stirring. The resulting solution is held at 65° for 2 hours and then concentrated under reduced pressure until no further distillate is obtained; the residue weighs 155–160 g. The resulting syrup (Note 3) is diluted with 300 ml. of methanol and again distilled, and this process is repeated once (Note 4).

A mixture of 100 g. of powdered, anhydrous sodium acetate and 677 ml. of 90% acetic anhydride (Note 5) is heated on a steam bath in a 3-l. round-bottomed flask under an efficient reflux condenser. Without interrupting the heating a solution of the syrupy glucose oxime in 50 ml. of glacial acetic acid and 100 ml. of cold acetic anhydride is added through a dropping funnel to the hot mixture (Note 6); this requires about 1 hour (Note 7). Heating is continued for another hour, and the bulk (380–420 ml.) of the acetic acid and any unchanged acetic anhydride is distilled under reduced pressure from a water bath. The residue is immediately stirred into 2 l. of cold water, stirred occasionally during the first 3 hours, and allowed to stand overnight.

After the mixture has been chilled to 0°, the brown, crystalline mass is filtered with suction and washed with 500 ml. of water. The solid is dissolved in 300 ml. of hot 95% ethanol, and the solution is heated with 10–15 g. of Norit for 5 minutes and filtered with suction. The filtrate is gradually cooled to 0°; the crystals are filtered with suction and washed with 20 ml. of cold ethanol. The weight of the first crop is 90–93 g. A second crop is obtained by concentrating the mother liquor under reduced pressure to 25 ml., boiling the solution with Norit, filtering, and chilling the filtrate to 0°. The total yield of colorless pentaacetyl d-glucononitrile melting at 82.5–83.5° is 95–96 g. (50%).