Ammodendrine-type alkaloids

Figure 7.10 Structures of the quinolizidine alkaloids, lupinine (21), lupanine (22), cytisine (23) and multiflorine (24) and of a dipiperidine alkaloid of the ammodendrine type (25).

Ammodendrine, C jH oONj, HjO (No. 1, table, p. 116). The base has m.p. 73 °, becomes anhydrous at 70-80°, and then melts at 50-60°, Wd i 0°. The salts are amorphous and deliquescent except the hydriodide B. HI, which forms a crystalline precipitate, m.p. 218-20°, from alcohol, and the perchlorate, m.p. 199-200°. An amorphous A-benzoyl derivative was obtained. With methyl iodide ammodendrine behaves as a secondary base, yielding first A-methylammodendrine hydriodide (a crystalline precipitate, m.p. 183-5°, from a mixture of alcohol and acetone), and at the second stage iV-methylammodendrine methiodide, m.p. 163-5°. On hydrogenation ammodendrine furnishes a dihydro-base, which is hydrolysed into acetic acid and 2 3 -dipiperidyl, C oHjoNj, and must be dZ-A-acetyl-3-a-piperidylpiperidine. Ammodendrine should therefore be acetyltetrahydroanabasine and is of biological interest as the first recorded occurrence of this type of alkaloid in the Leguminoss. ... 

The new alkaloid hystrine, C10H16N2 (liquid dihydrochloride, mp 209° [a]jj + 0°) and ammodendrine, but none of quinolizidine type (96). The former (LXV) was prepared from the latter by first reacting with hypochlorite to generate the W-chloro compound LXVI, treatment of which with alkali eliminated the elements of hydrogen chloride and hydrolyzed the acetyl group. The crude product was conveniently purified by conversion to the iV -nitroso derivative followed by reduction of the latter with cuprous chloride (97). 

Matrine (7) (+)-Ammodendrine (8) (-)-Tsukushinamine-A (9) Fig. 1 Types of structure of lupin alkaloids in Leguminous plants... 

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