Hydrastal hydrastic acid

Hordenine (Anhaline), 154, 155, 161, 633 Hunnernanrtia fuTrumoefolia, 173 hunnemannine, 173, 302 Hydrangea umbeUata, 781 Hydrastal hydrastic acid, 164, 165 Hydrastine, 162, 209, 210, 328 constitution, 163 formula, 166-7... 

The intermediate products (I) and (II) lose water, forming hydrohydrastinine and oxyhydrastinine respectively. Alkaline permanganate converts oxyhydrastinine into hydrastinic acid (III), C HgOgN, needles, m.p. 164° this in turn is oxidised by dilute nitric acid to hydrastic acid methylimide (IV), CJ0H7O4N, m.p. 227-8°, which, when warmed with potassium hydroxide solution, furnishes methylamine and hydrastic acid (V). 

From the pioneering experiments of Spath and Kahovec (128a) which were reviewed in Volume II, the partial formula XXI was proposed for tazettine to accommodate the degradation of the alkaloid to hydrastic acid by permanganate oxidation and to phenanthridine by zinc dust distillation. Tazettine methine, the product of the Hofmann degradation, was formulated as XXII to explain the formation of benzoic acid on oxidation with permanganate. Hofmann degradation of tazettine methine methohydroxide afforded 6-phenylpiperonyl alcohol. 

Unsevine (LXXXVIII) (mp 173°-174° [aJi, -t-170° in CHCI3) formed hydrobromide (mp 180°-183°), oxalate (mp 192°-194°), and methiodide (mp 249°-250°) salts (99). Oxidation of unsevine with either silver oxide (98) or chromium trioxide (56) afforded nivaline. Additional degradations of nivaline and unsevine follow the classic patterns established in the homolycorine and hippeastrine structural elucidations. Unsevine is oxidized by potassium permanganate to hydrastic acid (97, 100, 101). Hofmann degradation of either nivaline or unsevine affords the methine base LXXXIX (97, 100). In the case of unsevine, this reaction must... 

There is considerable interest in a number of other reactions of hydrastinine which are characteristic of carbinolamines of this type. It reacts with methyl iodide in indifferent solvents to yield a mixture of hydrastinium iodide and methylhydrastine methiodide (56), which when warmed with alkali generates trimethylamine and hydrastal (XXXI), the oxidation of which yields hydrastic acid. In methanol, hydrastinine reacts with methyl... 

Von Bruchhausen and Bersch (21, 22) reinterpreted Gadamer s data in conjunction with the later findings of Kling (28) and of Schwarz (29), who subjected chelidonine to Emde and Hofmann degradations. When its methine is oxidized with permanganate there results a mixture of hydrastic acid (II) and a dimethylaminomethylmethylenedioxybenzoic acid. The latter was erroneously formulated by Schwarz, whose formula indicated... 

CgHeOe [(OH)g(COOH)a == 1 2 4 5], rhombic prisms, forming an anhydride and melting at 247-5°. These observations show that hydrastic acid is 4 5-methylenedioxyphthalic acid. Freund and Lachman formulated these degradation products of hydrastinine thus —... 

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