Pukateine methyl ether

The dl-pukateine methyl ether obtained in small yield in the analogous synthesis was isolated as the hydriodide and resolved by the successive use of d- and 1-tartaric acids into the 1-base, m.p. 136°, [a]ff° — 252° (EtOH), identical with the methyl ether of pukateine, and the d-base, m.p. 136°, [a] " -f 256-4° (EtOH). 

In addition to the alkaloids previously isolated from this plant the following were obtained (— )-pukateine 0-methyl ether, (— )-roemerine, (— )-mecambroline, (-I- )-boldine, (- - )-isoboldine, (-f )-laurolitsine, and (4-)-stepharine. Laureline and laurepukine, previously reported from this plant, were not obtained. Fractional crystallization followed by chromatography were the procedures used to effect the separations (124). 

Hofmann degradation of pukateine 0-methyl ether via the methiodide (m.p. 240-241°) and a mixture of methines which was optically active generated a vinylphenanthrene which upon permanganate oxidation formed what, in view of later confirmation, must be 4-methoxy-5,6-methylene-dioxyphenanthrene-8-carboxylic acid (m.p. 216-217°) and which upon decarboxylation generated 4-methoxy-5,6-methylenedioxyphenanthrene, isolated as its picrate (m.p. 183-184°). 

Pukateine, CisHiyOaN (76) crystallizes easily and melts at 200° (94). It is readily soluble in chloroform, moderately in hydrolytic solvents, and virtually insoluble in ethers and hydrocarbons [ ] —220° (ethanol). The hydrochloride is crystalline but the salts are not characteristic. Pukateine is soluble in alkali and is recoverable from its alkaline solution by treatment with carbon dioxide. In addition to the phenolic hydroxyl there is present in the molecule an W-methyl and a methylenedioxy group. 

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