The resolution of benzoyloscine / by Frank Tutin.

  • Tutin, Frank.
Date:
1910
Catalogue details

Licence: Attribution 4.0 International (CC BY 4.0)

Credit: The resolution of benzoyloscine / by Frank Tutin. Source: Wellcome Collection.

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

    5/8 (page 1795)
    and in order, therefore, to confirm the identity of the product, it was converted into the aurichloride. This salt crystallised in small tufts of yellow needles and melted at 183—184°: 0'0864 gave 0'0284 Au. Au = 32’9. C15H1703N,HAuC14 requires Au = 33’0 per cent. Benzoyloscine nitrate, prepared from the above-described hydro- chloride, was very sparingly soluble in water, from which it crystallised in long, colourless needles. It melted and violently evolved gas at 195°. The corresponding picrate crystallised well in flattened needles, and melted at 185° without decomposing. Benzoyloscine (benzoylscopoline) has previously been prepared by the repeated evaporation of oscine benzoate with dilute hydro- chloric acid (D.R.-P. 79864), but the above-described method is far more expeditious, and gives much better yields. Benzoyloscine, d-Gamphorsulphonate. The benzoyloscine obtained from the above-described hydro- chloride was converted into its d-camphorsulphonate. This salt was dissolved in ethyl acetate containing a little alcohol, when, after some time, it separated in the form of a white powder. When examined under the microscope, this was seen to consist of minute, diamond-shaped crystals. Benzoyloscine d-camphorsulphonate melted at 167—168°, but, although it was submitted to a prolonged fractional crystallisation, no evidence of resolution could be obtained: 0-1476 gave 0'3312 C02 and 0 0918 H20. C = 6T2; H = 6 9. C15H17O3N,C10H16O4S requires C = 6T1; H = 6'7 per cent. 0'4226, made up to 20 c.c. with water, gave aD + 0°26/ in a 2-dcm. tube, whence [a]D +10-3°; [M]D +50'6°. Resolution of Benzoyloscine d-Bromocamphorsulphonate. The base was recovered from the previously-described cf-camphor- sulphonate, and neutralised with eZ-bromocamphorsulphonic acid. The salt so obtained crystallised fairly readily from water, but much more easily from a mixture of ethyl acetate and alcohol, forming colourless needles. After one- recrystallisation, it had somewhat the appearance of a mixture, and melted at 234—239°, previously softening at 211°. 0’4068, made up to 20 c.c. with -water, gave aD + 2°2/ in a 2-dcm. tube, whence [a]D + 60-0°; [M]D +285'0°. Since cZ-bromocamphorsulphonic acid has [M]D + 271°, it appeared that the benzoyloscine <Z-bromocamphorsulphonate was resolving.