Sparteines

Feeding experiments utilizing C-, N-, and H-labeled cadaverine (44) and lysine (24) in l upinus augustifolius a source of the lupine alkaloids (—)-sparteine (50, R = H,H) and (+)-lupanine (50, R = O), have been reported which lend dramatic credence to the entire biosynthetic sequence for these and the related compounds discussed above (41). That is, the derivation of these bases is in concert with the expected cyclization from the favored aH-trans stereoisomer of the trimer expected on self-condensation of the 1-dehydropiperidine (45). 

Solvent extraction techniques are useful in the quantitative analysis of niobium. The fluoro complexes are amenable to extraction by a wide variety of ketones. Some of the water-insoluble complexes with organic precipitants are extractable by organic solvents and colorimetry is performed on the extract. An example is the extraction of the niobium—oxine complex with chloroform (41). The extraction of the niobium—pyrocatechol violet complex with tridodecylethylammonium bromide and the extraction of niobium—pyrocatechol—sparteine complex with chloroform are examples of extractions of water-soluble complexes. Colorimetry is performed on the extract (42,43). Colorimetry may also be performed directly on the water-soluble complex, eg, using ascorbic acid and 5-nitrosahcyhc acid (44,45). 

The unstable CH TiCl [12747-38-8] from (CH3 )2 2n + TiCl forms stable complexes with such donors as (CH2)2NCH2CH2N(CH2)2, THF, and sparteine, which methylate carbonyl groups stereoselectively. They give 80% of the isomer shown and 20% of the diastereomer this is considerably more selective than the mote active CH MgBt (201). Such complexes or CH2Ti(OC2H2 methylate tertiary halides or ethers (202) as follows ... 

Although not of industrial importance, several asymmetric syntheses of (R)-pantolactone (9) have been developed. Stereoselective abstraction of the j Z-proton of the achiral 1,3-propanediol derivative (23) by j -butyUthium-(-)-sparteine, followed by carboxylation and hydrolysis, results in (R)-pantolactone in 80% yield and 95% ee (53). 

Billing 7 has provided a scheme for distinguishing between the hemlock bases and other alkaloids, such as sparteine, nicotine and lobeline. 

On hydrogenation at 80°, or on electrolytic reduction, aphyllidine is converted into d-sparteine (p. 133). On exhaustive methylation one nitrogen atom is eliminated in three stages, leaving a product, b.p. 235-255°/ll mm., as a viscous, yellow, alkaline oil of uncertain composition. Aphylline, on similar treatment, yields hemiaphylline, CjgH jON, b.p. 217-220°, as a viscous, yellow oil, not markedly basic. 

These observations suggest a similarity in structure to sparteine, and Orekhov has proposed for aphylline a formula identical with Clemo s formula for oxysparteine (p. 138 (VIII) with the change of CHj at position 10 into CO), aphyllidine having in addition an ethylenic linkage at C — C. ... 

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

Spartium junceum. Sparteine eytisine only in New Zealand... 

Owing to the use of lupin seeds for feeding animals, much attention has been given to the selection of species free from the more toxic alkaloids of the group, particularly sparteine, to methods of removing alkaloids from the seeds, a subjeet on which there is an extensive literature and to methods of estimating alkaloids in lupins on which a critical review has been published by Brahm and Andresen. ... 

In 1931 Winterfeld and Kneuer, as a result of their observation that jS-lupinane can be obtained from lupanine, and the formation of 2-methyl-pyrrolidine by the oxidation of sparteine, combined these two features in a partial formula (II) for lupanine, which could be developed in various ways depending on the mode of attachment of the methylpyrrolidine residue. In view, however, of Ing s demonstration of the relationship of anagyrine, CJ5H20ON2, to Z-lupanine, CJ5H24ON2, and d-sparteine, C15H28N2, it was elearly neeessary to consider formul for lupanine derivable from the two alternati-ves, which Ing had proposed for anagyrine and which are shown below as (III) and (IV) with the formul for lupanine derived from them (V) by Ing and (VI) by Clemo and Raper. Sparteine would be represented by (V) or (VI) with the change CO CH2. 

Constitution. Both nitrogen atoms in sparteine are basic and tertiary. 

The exhaustive methylation of sparteine was reinvestigated by Karrer,. Shibata, Wettstein and Jacubowitz. At each stage they reduced the unsaturated product formed and so ended up with a pentadecane, C15H32 (b.p. 242°/729 mm., D] 0-7740, 1-43351). The object of this work... 

The three hydrocarbons were synthesised, but their physical constants proved to be so similar and so like those of the pentadecane obtained from sparteine that no definite information as to the constitution of the alkaloid could be obtained from them. 

By oxidising sparteine sulphate with chromic acid, Willstatter and Marx obtained spartyrine, Ci5Hg4Ng (m.p. 153-1 , — 25-96 ), which... 

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