The configuration of tropine and [psi]-tropine and the resolution of atropine / by Marmaduke Barrowcliff and Frank Tutin.

Barrowcliff, Marmaduke.

Date:: [1909?]

Credit: The configuration of tropine and [psi]-tropine and the resolution of atropine / by Marmaduke Barrowcliff and Frank Tutin. Source: Wellcome Collection.

9/16 page 1972

$It is deposited from cool, saturated solutions in large prisms, but separates from a boiling mixture of ethyl acetate and alcohol in fine needles. When anhydrous it melts at 180°, but it separates from moist solvents in needles, which contain one molecule of water of crystallisation, and melt at 112°: 0*9388 of hydrated salt, on heating at 100°, lost 0*0344 H20. HoO = 3*7. 0*1269 of anhydrous salt gave 0*2229 C02 and 0*0788 H20. C = 47*9 ; H = 6*9. C8H15ON,C10H15O4BrS,H2O requires H20 = 3*8 per cent. C8H15ON,C10H15O4BrS requires C = 47*8; H = 6*6 per cent. 0*4457 of anhydrous salt, made up to 25 c.c. with chloroform, gave aD + 2° 28' in a 2-dcm. tube, whence [a]D+69*l°. 0*5030 of anhydrous salt, made up to 25 c.c. wTith water, gave «aD+2° 26' in a 2-dcm. tube, whence [a]D+60*5° and MD-F 273*3°. Prolonged fractional crystallisation of this salt gave no evidence of resolution. Benzoyl-ip-tropeine d-camphor sidphonate. — Benzoyl-t/'-tropeine (tropacocaine) was prepared in a manner similar to that employed for the preparation of benzoyltropeine; the yield was practically quantitative. The hydrochloride of the base was found to melt at 283° (uncorr.), a temperature 12° higher than that recorded by Liebermann (loc. cit.) and by Willstatter (loc. cit.) for the melting point of benzoyl-t/'-tropeine (tropacocaine) hydrochloride. The aurichloride melted at 208°, and was analysed: 0*1391 gave 0*0468 Au. Au = 33*6. C15H]902N,HAuC14 requires Au = 33*7 per cent. Benzoyl-\p-tropeine d-camphorsulphonate crystallises very readily from a mixture of ethyl acetate and alcohol, forming large prisms, melting at 176—177°: 0*1236 gave 0*2846 C02 and 0*0823 H20. C = 62*8; H = 7*4. C15H19O2N,C10H1GO4S requires C = 62*9; H = 7*3 per cent. 0*5412, made up to 20 c.c. with water, gave aD + 0° 36' in a 2-dcm. tube, whence [a]D+ll*l° and MD + 51*8°. The salt was separated into a large number of fractions, but no evidence of resolution could be obtained. Benzoyl-xp-tropeine d-bromo camphor sulphonate.—This salt differs from the sulphonates above described, inasmuch as it forms a hydrate which is only sparingly soluble in cold water. This compound forms slender needles, which melt at 73°: 0*5420, on drying at 123°, lost 0*0464 H20. H20 = 8*6. C15H19O2N,C10H]5O4BrS,3H2O requires H20 = 8*8 per cent.$