Acid, opianic

Constitution. Hydrastine contains two methoxyl groups and a methylenedioxy-group, and behaves as a tertiary base. The first insight into the inner structure of the base was obtained when Freund and Will showed that with dilute nitric acid it undergoes hydrolytic oxidation, yielding opianic acid and a new base hydrastinine, CiiHigOgN. This reaction is analogous with the similar hydrolytic oxidation of narcotine (p. 201) to opianic acid and cotarnine and hydrastinine is allied to cotarnine and can be prepared from it. 

When the alkaloid is heated with water at 150°, or boiled with dilute acids, it is hydrolysed into hydrocotarnine, and opianic acid. Similar decompositions are induced by acid oxidation or acid reduction, thus (1) dilute nitric acid furnishes opianic acid, CjoHioOj, and cotarnine, C12H15O4N (2) zinc and hydrochloric acid produce meconin, C10H10O4, and hydrocotarnine, C12H15O3N. 

Utilising the formulae assigned to the two products of hydrolysis of narcotine, viz., hydrocotarnine and opianic acid, Roser constructed a formula for the alkaloid which has been confirmed by Perkin and Robinson s synthesis of narcotine from meconin and cotarnine. ... 

Oxynarcotine, CjjHjaOgN. This alkaloid was separated by Mayer, and later by Beckett and Wright, from crude narceine. It crystallises from hot alcohol in small needles. Its close relationship to narcotine is shown by the formation of cotarnine, C12H15O4N (p. 201), and hemipinic acid when it is oxidised by ferric chloride narcotine under these circumstances furnishing cotarnine and opianic acid. Rabe and McMillan regard oxynarcotine and nomarceine as identical. 

Bicuculline, C2oHi,06N. (Items 1, 9, 10, 13, 14, 18, 20, 23-26, 34, 35, 38 list, p. 169). This alkaloid exists in two forms, m.p. 177° and m.p. 196°, and has [a], ° + 130- 5° (CHCI3). The hydrochloride has m.p. 259° (dec.) and from the methiodide, W-methylbicuculline, plates, m.p. 246°, has been prepared. Bicuculline contains no methoxyl groups it behaves as a lactone and is convertible by alkalis into bicucine, which is possibly the corresponding hydroxy-aeid (see below). It simulates hydrastine in its reactions and differs from that base by CH, indicating that a methylene-dioxy group replaces two methoxyl groups, and this view is supported by comparison of the products of oxidative hydrolysis of the two alkaloids. Both yield hydrastinine (p. 163) as the basic product, but while hydrastine provides as the second product, opianic acid,... 

A few other aldehydes have been used in the reaction, either under normal or pseudo-physiological conditions. Of these, glycolalde-hyde, 5-hydroxypentanal, phenylacetaldehyde, and benzalde-hyde condense readily, but hydroxy and methoxy derivatives of these aromatic aldehydes give the product in poor yield,presumably due to their instability, as evidenced by their tendency to undergo self-condensation in acid solution. Reaction with phthaldehydic acids, such as opianic acid, proceeded readily, whereas reaction with chloral did not occur,... 

The oxidative cleavage of narcotine to cotarme and opianic acid is an example of this reactivity. This reaction has been known since 1844, using manganese di-... 

Opianic acid (2-formyl-4,5-dimethylbenzoic acid) [519-05-1] M 210.2, m 150 . Crystd from water. 

Groups other than halogen or nitro in the two ortho positions also can influence the mode of reaction. For example, while opianic acid can be transformed in good yield into hemipinic add and meconine,79 pseudo-opianic add loses the formyl group under the influence of strong alkali.8 ... 

An improved method of preparation of cotarnine and opianic acid by the electrochemical oxidation of narcotine at a graphite anode in the presence of potassium dichromate has been described in a patent.3 In a study of the pharmacological effects of mescaline, the binding of the alkaloid with rat brain tissue has been examined, using 14C-labelled material.4 A technique for the separation, identification, and estimation of tyramine, methoxytyramine, and related phenethylamines by g.l.c. of their trimethylsilyl derivatives has been described in detail.5... 

The preparation of cotarnine and opianic acid by the electrolysis of narcotine in the presence of sodium hydrogen sulphate and calcium chloride has been described.3,111 The separation of narcotine, morphine, and codeine on t.l.c. plates112 and methods for the detection of metabolites of narcotine and gnoscopine in urine113 have been reported. 

The first anthranil ( azo-opianic acid ) was made by this method in 1881,113 but was not recognized as such. In 1882 Friedlander and Henriques109 prepared the parent compound, by reduction of o-nitrobenzaldehyde with tin and acetic acid. They thought it to be the anhydride of anthranilic acid, and hence arose the name anthranil. It has been shown, using O18, that the carbonyl oxygen is lost, and the cyclic oxygen atom is derived from the nitro group, in the reductive cyclization.141... 

Attempted salt formation No salts formed with HNOs, oxalic acid, opianic acid no precipitates with Hg(NOa)2, Pb(C2H30a)2, or Pb-(OH)OAc... 

The treatment of 3,4-dehydro-9-hydroxylaudanosine (18) with 2% acetic acid on the steam bath yields veratric aldehyde and hydroxylaudanosine, whereas the treatment of narco tine diol (19 R = OMe) and hydrastine diol (19 R = H) with acetic acid and tin(ii) chloride yields the reduced anhydro-compounds (20 R = OMe and H). The oxidation of narcotine with mercury(n) acetate and EDTA affords tarconine methyl ether (21), meconine, and opianic acid. ... 

Narcotine can be split into cotarnine and opianic acid by treatment with dilute sulfuric acid by oxidation with dilute nitric acid, chromic acid, potassium permanganate or with mercuric acetate (691). Hydrogenolysis (hydrochloric acid or sulfuric acid and zinc) affords hydrocotarnine and meconine. Treatment of hydrocotarnine with sodium in ethanol leads to cleavage of the methoxyl group with the formation of 8-hydroxy-1,2-dihydrohydrastinine. The phthalidetetrahydroisoquinoline alkaloids can be converted into rhoeadane see Section III,M and spirobenzylisoquinoline (see Section 111,0,1) precursors (692). 

Formyi-2,3-dimethoxybenzoic acid Opianic acid C10H10O5 619-06-1 210.183 nd (w) 160 s FtOH, eth... 

The importance of berberal (XIV) in determining the structure of berberine has already been pointed out. The condensation of opianic acid with noroxyhydrastine yields Isrberberal (XTX), and it was this compound... 

---