D-Lupanine

L. laxus Rydb. Sparteine, d-lupanine, trilupine (p. 132) and fourth... 

Sparteine is the most important uterine stimulant of this group, which inclhdes also d-lupanine, lupinine, trilupine, and cytisine. Nicotine is discussed here also because of a very close similarity to cytisine in its pharmacological actions. 

Since lupin seeds are used in some areas in cattle feeding, it is of practical as well as theoretical interest to determine the stage at which the seeds will be rich in the alkaloidal material responsible for toxicity. It has also been important to devise methods for the removal of alkaloids from the seeds so that the detoxified or debittered material can still be used as feed (111). Extraction procedures which accent the recovery of non-alkaloidal material have less interest to the alkaloid chemist than those which provide for the isolation of the pure organic bases. Given below are typical examples of the extraction procedures employed for the isolation of the lupin alkaloids lupinine, cytisine, Z-sparteine, d-lupanine, and anagyrine. The methods selected are representative of those utilized for the isolation of the less abundant or well-known lupin alkaloids as well. These methods are also representative of the different quantities of materials which are handled. One of the methods was selected (for anagyrine) to indicate some of the complexities of separation when there are a number of alkaloids present in a plant, rather than only one main alkaloidal constituent. The techniques of fractional distillation of the bases, fractional crystallization of alkaloid salts, such as perchlorates and picrates, and extractions dependent upon differential solubility have been employed for the isolation of pure individual alkaloids from a mixture. 

A partial synthesis of d-oc-isolupanine has been accomplished by Marion and Leonard (320) by mercuric acetate dehydrogenation of d-lupanine followed by catalytic hydrogenation of the Ci5Hj2N20 intermediate. 

When trilupine was treated with methyl iodide in the cold, a compound was obtained, Ci6H24N202-CH3l, m.p. 127 , which contained one oxygen atom less than required for trilupine methiodide and which appeared to be the methiodide of d-lupanine iV-oxide. Ochiai, Ito, and Maruyama (292) prepared d-lupanine W-oxide by the action of 3 % hydrogen peroxide on d-lupanine and described its methiodide as decomposing at 137°. 

Phytochemistry Roots contain tannins, up to 1.5 % total alkaloids (leontidine, leontine, leontamine, pachycarpine, and d-lupanine) and up to 30 % starch. The plant contains saponins with a hemolytic index of 1 240 in the aboveground portion of the plant and 1 6,000 in the tubers. Taspine, methylcytidine, and isoleontine were isolated from aboveground portion of the plant (Yunusov 1981). 

X-Lupanine. After separation of d-lupanine from df-lupanine (see above), the bases are recovered from the mother liquors as lupanine hydriodide, from which clean base is regenerated. This, on combination with U camphorsulphonic acid in acetone, yields 1-lupanine I-camphorsulphonate. 

The oxidation of lupanine has been investigated by a number of workers. Beckel noted that d-lupanine formed a perbromide, which on treatment with alcohol yielded cthoxylupanine dihydrobromide, C13H23ON2. OC2H5.2HBr (colourless needles, m.p. 227-8°, [a]J, ° — 129-4°), from which a number of interesting substances were obtained in yields too small for characterisation. 

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