Scopoline Scopolinic acid

Lobelanine dioxime, obtainable in poor yield, undergoes a Beekmann transformation into the dianilide of l-methylpiperidine-2 6-diaeetie aeid (lobelinie aeid (HI) ). On oxidation by ehromie aeid in sulphurie aeid lobelanine furnished l-methylpiperidine-2 6-dicarboxylic acid (scopolinic acid (IV)) and benzoic acid. 

Oxidation by Chromic Acid. Under mild conditions, e.g., in acetic acid at atmospheric temperature this converts the dihydric alcohol or keto-alcohol bases to diketo-bases, e.g., the lelobanidines, Ci3H2902N, to lelobanines, C13H25O2N. Under more vigorous action the keto-alcohol and the diketo-bases are oxidised to benzoic acid (side-chain, Ph. CO. ), acetic and i iropionic acids (side-chain, C2H5. CO. ) and either scopolinic acid l-methylpiperidine-2 6-dicarboxylic acid (IV)) or methylgranatic acid (l-methylpiperidine-2-carboxylic-6-acetic acid) or both, these being from the methylpiperidine nucleus with residues of the two side-chains. 

Careful oxidation of lobinine removes two hydrogen atoms with the resulting formation of an optically active diketone, lobinanine, CisHjsOaN (designated earlier as lobinone, perchlorate, m.p. 133°, hydrochloride, m.p. 94°, [aJo — 18.6°) whereas vigorous oxidation with chromic acid produces benzoic acid and an unidentified acid which is identical neither with scopolinic acid nor with methylgranatic acid. 

When warmed with barium hydroxide, dilute alkalis or acids, hyoscin is hydrolysed, yielding tropic acid and a new base, CgHjsOjN, oscine o scopoline. Depending on the conditions of experiment, the tropic aci obtained may be either the pure Z-form or the partially racemised acid but the oscine obtained is invariably inactive. 

Nutrient deficiencies may also influence the production of allelochemics. The compounds studied in great detail have been the phenolic compounds and scopolin-related chemicals. Deficiencies of boron, calcium, magnesium, nitrogen, phosphorus, potassium, and sulfur have all been reported to enhance the concentration of chlorogenic acids and scopolin in a variety of plants (4). In other species, chlorogenic acids have decreased in plants that are deficient in magnesium or potassium. 

Nerium indicum Mill. Jia Zhu Tao (Indian oleander) (leaf, stem, flower, root) Oleandrin (toxic), oleandrose, neriodorin, nerioderin, karabin, scopoletin, scopoline, neriodin, ursolic acid, adynerin 33>45° Treats psychosis, congestive heart failure, analgesic, emmenagogue. 

Einhellig, F. A., Rice, E. L., Risser, P. G., and Wender, S. FI. 1970. Effects of scopoletin on growth, CO2 exchange rates, and concentration of scopoletin, scopolin, and chlorogenic acids in tobacco, sunflower, and pigweed. Bull. Torrey Bot. Club 97, 22-33... 

Trimethylsilylation N,0-bi s(trimethyl silyl)acetamide scopolamine4 , tropic 0 O acid, scopoline... 

This lactone, related to ferulic acid, could be formed by degradation of its glucoside, scopolin, or by direct cyclization of ferulic acid (H.87). It was noted that esculetin, the lactone corresponding to caffeic acid (H.86) has not been reported (Clifford, 1975a). 

When Z-scopolamine (Z-hyoscine) is warmed with barium hydroxide (52, 56, 232), dilute alkalies (232), or acids (60, 212) it is hydrolyzed to tropic acid and a new base (CsHisOjN), scopoline (oscine). Depending on the conditions of the experiment, the tropic acid recovered may be either the pure Z-form or the partially racemized acid, or may even be dehydrated to atropic acid (52, 64, 232). The scopoline isolated from these experiments is invariably optically inactive (212). By analogy with Z-hyoscyamine, Z-scopolamine would appear to be a base (scopoline) in which the alcoholic... 

The bromine-free hydroscopoline (like dihydroxytropane) is readily oxidized by chromic acid to scopolic acid or l-methylpiperidine-2,6-dicarboxylic acid (65, 68) which has since been synthesized (65, 161, 163). The oxidation of the dihydroxy compound, hydroscopoline, to a hydroxyl-free piperidine derivative would suggest (1) that there is a piperidine nucleus (also that pyridine is formed by the zinc dust distillation of norscopoline (64)) in hydroscopoline (and hence in scopoline) and (2) that the hydroxyls of hydroscopoline are not attached to the piperidine nucleus of this base. The close relationship of scopoline to tropine was first established by the reduction (hydriodic acid and phosphonium iodide at 200°) of hydroscopoline to tropane (167). Dihydroscopoline must be a dihydroxytropane with the hydroxyls, of necessity, located in the pyrrolidine nucleus to account for its oxidation to scopolic acid (LXI —> LXII). 

Failure to isolate a halogenated scopolic acid from the oxidation of hydroscopoline chloride has prompted some workers to conclude that the chlorine of hydroscopoline chloride, and hence the ether bridge of scopoline, cannot be attached to C2, C3, or C4 (170). This, combined Avith exhaustive methylation studies, favored a Cs-C ether bridge (LXIIIB). 

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