Brucine

Listed in the Aldrich Catalog as f-butyl 6-oxo-2,3-diphenyl-4-morpholinecarboxylate and benzyl 6-oxo-2,3-diphenyl-4-morpholinecarboxylate, 

Peter J. Sinclair Merck Research Laboratories, Rahway, NJ, USA 

Physical Data colorless needles (acetone/water) mp 178 °C [a]o -79.3° (cl.3, EtOH). 

Solubility very sol methanol, ethanol, and chloroform mod sol ethyl acetate or benzene. 

Form Supplied in colorless needles or plates. The free base, which is available from multiple commercial sources, is usually hydrated. Dihydrated and tetrahydrated forms have been characterized. Anhydrous brucine can be obtained by heating at 100-120 °C in vacuo for 24 h. The hydrated forms can be used for most applications. 

EPA Designated Toxic Waste, RCRA Waste Number P018 DOT Label Poison B, UN 1570 

Strychnine is a highly toxic alkaloid. It causes hypersensitivity to sensory stimuli. It is a powerful convulsant. This results in respiratory and metabolic acidosis (Hodgson et al. 1988). Death occurs from asphyxia after a few seizures. Its convulsant actions are attributed to the antagonism of the inhibitory effects of glycine. It excites all portions of the central nervous system. It produces green-colored vision, which is an effect of sensory disorders. Toxic symptoms from continued medication with strychnine 

Synonyms 2,3-dimethoxystrychnine 10,11-dimethoxy strychnine 2,3- dimethoxystry-chnidin-lO-one 

Brucine occurs in the seeds of strychnos species (Strychnos nux vomica L. and other species). It is used for denaturing alcohols and oils for separating racemic mixtures and as an additive to lubricants. It is also used for colorimetric analysis of nitrate. Therapeutically, it is used as a stimulant. 

White crystalline solid very bitter in taste mp 178°C (352.4°F) hydrated crystals (tetra-and dihydrates lose water at 100°C (212°F) pH of satnrated aqneons soln. 9.5 slightly solnble in water (0.07 g/100 mL), dissolves readily in alcohols and chloroform. 

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This substance (dA, I A) contains a free carboxyl group and is treated in warm acetone solution with an equimolecular quantity of the optically active base brucine (IB) upon cooling, the brucine salt (dA, IB) separates out first in a moderately pure condition, whilst the brucine salt (lA, IB) remains in solution ... 

The latter upon decomposition with dilute hydrochloric acid yields laevo sec.-octyl hydrogen phthalate the crystalline brucine salt, when similarly treated, affords the dextro sec.-octyl hydrogen phthalate. These are reerystallised and separately hydrolysed with sodium hydroxide solution to yield pure I- and d-sec.-octyl alcohols ... 

Introduce 197 g. of anhydrous brucine or 215 g. of the air-dried dihydrate (4) into a warm solution of 139 g. of dZ-acc.-octyl hj drogen phthalate in 300 ml. of acetone and warm the mixture vmder reflux on a water bath until the solution is clear. Upon cooling, the brucine salt (dA, IB) separates as a crystalline solid. Filter this off on a sintered glass funnel, press it well to remove mother liquor, and wash it in the funnel with 125 ml. of acetone. Set the combined filtrate and washings (W) aside. Cover the crystals with acetone and add, slowly and with stirriug, a slight excess (to Congo red) of dilute hydrochloric acid (1 1 by volume about 60 ml.) if the solution becomes turbid before the introduction of... 

Commercial brucine is usually the tetrahydrate Cj,H2404Nj,4Hj0 upon air drying, this loses two molecules of water of crystallisation and passes into the dihydmte. 

The filtrates from the decomposition of the brucine salts with dilute hydrochloride acid should be carefully preserved. The brucine Is recovered by the addition of an excess of dilute ammonia solution (1 4) if the solution becomes turbid before all the ammonia solution is added, introduce a little alcohol until the solution becomes clear. After several hours in an open beaker, filter oft the brucine, wash it well with cold water and dry it in the air. 

The decomposition of an oxaziridine by brucine, originally assumed to be a deoxygenation, proved to be a base-catalyzed decomposition (79TL3353). 

The resolution of sec.-octyl alcohol was first described by Pickard and Kenyon. The method employed by these authors differed from the foregoing in the following respects. The brucine salt of sec.-octyl hydrogen phthalate was crystallized several times from acetone until it reached optical purity and was then decom-... 

Glandular products, drugs of vegetable origin, such as quinine, strychnine and brucine, emetine, and digitalis glycosides ... 

Strychnine, brucine Oxidation is performed with potassium dichromate solution This oxidizes brucine to the o-qumone which can then be separated chromatographically [17]... 

Brucine Apply a drop of cone, nitric acid to the spots of applied sample solution and allow to react for 15 min. Then activate the TLC plate at 120°C for 15 min and develop after cooling. [22]... 

Strychnine hR( 50—55) appeared as a red and brucine hR( 35) as a yellow chromatogram zone on a colorless background. The detection limit for both substances was 10 ng per chromatogram zone. 

Dehydrocorydaline eontains four methoxyl groups. On reduetion it furnishes two stereoisomerides of eorydaline, m.p. 135°, and m.p. 158-9° (163-4° vac.), Spath) the latter ( 2f.9oeorydaline) by erj stallisation of the d-eamphorsulphonate can be partially separated into d- and Z-forms, the d-form of which is not identical with natural corydaline.The second isomeridc, m.p. 135°, has not been resolved into optically active components, but from the sulphonic acid the Z-compoiient has been isolated by crystallisation of the brucine salt, and this is taken to indicate that the inactive corydaline, m.p. 135°, is dZ-corydaliiie. °... 

S. cinnamomifolia Thwaites (Ceylon, India). Strychnine and brucine (Short, Year-hook Pharm., 1924, 646). 

S. ligustrina Bl. (East Indies). See 0-6 to 1-5 per cent., nearly all brucine stem bark 2-2 per cent, of which 0 5 per cent, is strychnine. 

S, Tieute Lesch. (Java). Upas tree. Strychnine with traces of brucine (Pelletier and Caventou, Ann. Chim. Phys., 1824, [ii], 26, 44 van Boorsma, Bull. Inst. Bot. Buit., 1902, No. 14, 3, 7). 

Owing to its use as a vermin-killer and to its importance in toxicology, a great deal of attention has been given to methods for the isolation of strychnine from biological materials and the detection of minute quantities. For critical reviews of such methods see Ainsworth Mitchell, Steyn,ii Ward and Munch. A microchemical method for the differentiation of str3 chnine and brucine has been described by Martini. i... 

Brucine, C2aH2e04N2. Brucine was first obtained in 1819 by Pelletier and Caventou from Strychnos Nux-vomica bark, then supposed to be derived from Brucea ferruginea. Its composition was determined by Regnault.i ... 

Preparation. The mother liquors from strychnine manufacture are concentrated and the alkaloids precipitated as neutral oxalates. The precipitate is dried and extracted with dry alcohol in which the strychnine salt is the more soluble. The less soluble salt dissolved in water is decolorised with charcoal, the alkaloid regenerated with ammonia and purified by crystallisation as the sulphate. According to Saunders, pure brucine may be obtained by slow crystallisation from a solution of the pure hydrochloride in alcoholic ammonia. A method of separation depending on the greater solubility in water of strychnine hydriodide was employed by Shenstone, whilst others have made use of the sparing solubility of strychnine chromate for the removal of small quantities of this alkaloid from brucine. For a large scale process see Schwyzer. ... 

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