2,3 - Bipyridyl alkaloids

The biological activity of noranabasamine has not been assessed. Anabaseine and other bipyridyl alkaloids are toxic and have nicotine-like effects (166,167). 

The high-performance liquid chromatography (HPLC) determination of quinolizidine alkaloids in Radix Sophora flavescens was assisted by using tris(2,2 -bipyridyl)ruthenium(n) electrochemoluminescence <2004MI237>. Tandem HPLC-MS techniques have allowed the development of a sensitive and specific method for the determination of sophocarpine, matrine, and sophoridine in rabbit plasma <2005MI1595>. 

ILs have been used in the CE-electrochemiluminescence (ECL) method to determine bioactive constituents in Chinese traditional medicine [58]. CE/Tris(2,2-bipyridyl) ruthenium(II) (Ru(bpy)3 +) ECL, CE-ECL, with an IL detection system was established to determine bioactive constituents in Chinese traditional medicine opium poppy, which contains large amounts of coexistent substances. Running buffer containing 25 mM borax-8 mM [C2CiIm][BF4] (pH 9.18) was used, which resulted in significant changes in separation selectivity and obvious enhancement in ECL intensities for those alkaloids with similar structures. Quantitative analysis of four alkaloids was... 

One example is the optically active amino acid derivative (S)-20n which contains a bipyridyl substituent (Scheme 3.14). The alkylation reaction in the presence of the cinchona alkaloid catalyst 33 proceeds with 53% ee (83% yield of (S)-20n) and gave the desired enantiomerically pure a-amino acid ester (S)-20n in >99% ee after re-crystallization [43]. Subsequent hydrolysis of the optically pure (S)-20n furnished the desired unprotected a-amino acid 35. A different purification method, subsequent enzymatic resolution, reported by Bowler et al., furnished the a-amino acid product 35 with enantioselectivity of 95% ee [44],... 

In these experiments radioactive a,/3-bipyridyl (8) was isolated and it appears from degradation studies that both rings of the alkaloid arise from nicotinic acid, so (8) can arise from anatabine (6) but not from anabasine (7), in which only one ring originates from nicotinic acid. 

A number of nemertine worms, such as Amphiporus or Nereis, produce alkaloids such as 2,3-bipyridyl, anabaseine, nemertelline, or nereis-toxin, which are toxic to predators such as crayfish 4,17,28,230,226,). Arthropod-made alkaloids include glomerine and homoglomerine in Glom-erus 215), adaline in Adalia 227), coccinelline, euphococcinine, and derivatives in Coccinella, Epilachna, and other coccinellid beetles 28,226,227,235), and stenusine in Stenus 215), which are considered to be antipredatory compounds 4,17,28,494-496). 

Cotinine and 2,3 -bipyridyl and their derivatives represent the major oxidized alkaloids in tobacco. Cotinine is synthesized from nicotine via enzymatic oxidation or autooxidation (1157, 17B03). 2,3 -Bipyridyl is formed by oxidation of anat-abine. Frankenburg et al. (1221a, 1222-1224) were the first to identify 2,3 -bipyridyl as a fermentation product along with... 

Most of the synthetic work has dealt with modification of known alkaloid structures. Dehydrogenation of anabasine (45) with pyridine N-oxide ° and /V-aminopyridinium chloride yielded 2,3 -bipyridyl in varying amounts. The same conversion was also effected by a longer procedure. The bromination of anabasine has been studied and a series of AT-substituted derivatives of this alkaloid have been prepared. 

Orelline and orellanine are two toxic alkaloids occurring in the mushroom Cortinarius orellanus Fries. Chemical and particularly spectroscopic investigations have revealed that orelline is the tetrahydroxy-2,2 -bipyridyl (53), tautomeric with (54), and orellanine is the corresponding bis-7V-oxide. ... 

Although a large variety of compounds can reduce tris(2,2 -bipyridyl)ruthenium(III), only certain species (e.g., aliphatic amines, amino acids, NADH, some alkaloids, aminoglycoside or tetracycline antibiotics, and the oxalate ion) will produce the characteristic orange luminescence with this reagent. Subtle differences in chemical structure can have a dramatic effect on chemiluminescence intensity. This is exemplified by the determination of the papaver alkaloid codeine (11) compared to structurally similar morphine (12). At pH 6.8, codeine can be determined down to a concentration of 10 mol 1 whereas morphine produces a chemiluminescent response equivalent to that of the blank. In many applications this degree of selectivity is most desirable. 

Yin J, Guo W, Du Y, Wang E (2006) Facile separation and determination of Aconitine alkaloids in traditional Chinese medicines by CE with tris(2,2 -bipyridyl) ruthenium(II)-based electrochemi-luminescence detection. Electrophoresis 27(23) 4836-4841. 

Yin J, Xu Y, Li J, Wang E (2008) Analysis of quinolizidine alkaloids in Sophora flavescens Ait. by capillary electrophoresis with tris(2,2 -bipyridyl) ruthenium (ll)-based electrochemiluminescence detection. Talanta 75(l) 38-42. doi 10.1016/j.talanta.2007.10.003... 

A hybrid FIA/HPLC system incorporating monolithic column chromatography was developed for the determination of six opiate alkaloids (morphine, pseudomorphine, codeine, oripavine, ethylmorphine, and thebaine) and four biogenic amines (vanilman-delic acid, serotonin, 5-hydroxyindole-3-acetic acid, and homovanillic acid) in human urine, using tris(2,2 -bipyridyl)ruthenium(III) and acidic potassium permanganate CL detection (Adcock et al., 2007). This hybrid system approaches the automation and separation efficiency of HPLC while maintaining the positive attributes of FIA, such as manifold versatility, speed of analysis, and portability. 

Complanadine (155), a member of the family of lycopodium alkaloids, has more recently been identified as an inducer of neurotropic factor excretion. The synthesis of this almost symmetrical alkaloid, potentially interesting for the treatment of diseases of the central nervous system, was based on two late-stage crossed [2 + 2 + 2] pyridine formation reactions that delivered the central bipyridyl unit. 

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