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.

8/16 page 1971

$Benzoyltropeine d-camphor sulphonate crystallises readily from a mixture of ethyl acetate and alcohol, forming small, flattened needles, which melt at 240°: 0*1131 gave 0’2600 C02 and 0'0773 H20. C = 62'7; H = 7-6. C15H19O2N,C10H16O4S requires C = 62’9; H = 7’3 per cent. 04012, made up to 20 c.c. with water, gave aD + 0° 26r in a 2-dcm. tube, whence [a]D+10'8° and MD + 51-5°. The salt was submitted to a very thorough fractionation, but no resolution could be effected. xp-Tr opine. i/'-Tropine was prepared according to the method described by Willstatter (Ber., 1896, 29, 936). The base was purified by dis¬ tillation, followed by crystallisation from a mixture of benzene and light petroleum. The mother liquors from the first crystallisation contained a quantity of oily material, amounting to about 35 per cent, of the total product. As this could not be crystallised, it was benzoylated by heating with benzoyl chloride, and the resulting hydrochloride of the benzoylated product crystallised from alcohol. The material thus obtained formed colourless needles, melting at 241°, and appeared to be quite homogeneous; it yielded a picrate melting at 216—217°. The product, however, was found to be a mixture of the hydrochlorides of benzoyltropeine and benzoyl- i/'-tropeine, apparently in equal proportions, since, by the addition of successive portions of picric acid solution, it first yielded benzoyltropeine picrate (m. p. 249—250°), and finally benzoyl- j/'-tropeine picrate (m. p. 238—239°). xp-Tropine d-camphorsulphonate.—This salt crystallised readily from a mixture of alcohol and ethyl acetate, forming flat prisms, which were anhydrous, and melted at 224—226°: 0-1101 gave 0*2337 C02 and 0*0842 H20. C = 57*8; H = 8*5. C8H15ON,C10H16O4S requires C = 75'9; H = 8*3 per cent. i/'-Tropine <7-camphorsulphonate is very readily soluble in water, ethyl, methyl, and amyl alcohols, and in chloroform, but only very sparingly soluble in ethyl acetate, acetone, benzene, or toluene. It was fractionally crystallised from both cold and boiling solvents, but no evidence of resolution could be obtained: 0*4682, made up to 25 c.c. with alcohol (98 per cent.), gave aD + 0° 59; in a 2-dcm. tube, whence [a]D+ 26*3°. 0*4119, made up to 25 c.c. with water, gave aD + 0° 277 in a 2-dcm. tube, whence [a]D+13*7° and MD +51*2°. xp-Tropine d-bromo camphor sulphonate.— The solubilities of this salt are similar to those of the corresponding c^-camphorsulphonate.$