Davoll and Evans. 5041 Y'he Synthesis of 9-Glycitylpu~ines, 3-GZycityl-[ 1,2,3]-triaxolo[d]pyrimidines, 8-Glycitylpteridines, and lO-C7'lycitylbe.~~zo[g]pteridines,including Riboflavin and Riboflavin 2-lmine.By J. DAVOLL and D. D. EVANS.5-Aniino-4-glycitylaminopyi-imidines, prepared froin appropriate &nitroor 5-nitroso-derivatives, have been converted by ring closure into the compounds named in the title.THE structural similarity between purine nucleosides, pteridines, and riboflavin has been noted by several authors,l. who have also suggested that 8-glycosyl-or S-glycitylpteridines may be involved as biosyiithetic intermediates. Recent work has shown that adenine and guanine can serve as precursors of the pyrimidine portion of riboflavin, and that 8-D-ribitylpteridines are also involved in its biosynthesis. The aim of the present work was the preparation of compounds which might be intermediates in these biosynthetic reactions or might act as antimetabolites to the compounds actually involved.Since all the required compounds (1-111) contain the carbon-nitrogen skeleton of a 5-amino-4-glycitylaminopyrimidine as part of their structures, the preparation of this class of compound was investigated. Suitable precursors were readily obtained from appropriate chloropyrimidines and glycitylamines in boiling aqueous or aqueous-ethanolic solution ; thus, 6-amino-4-chloro-5-nitropyrimidine and D-ribitylamine (2 mols.) gave 6-amino-5-nitro-4-~-ribitylaminopyrimidiiie (83% yield), which on catalytic hydrogenation afforded the triamine (Ia) ; the sorbitylamino-compound (Ib) was similarly prepared by starting from u-glucitylamine. N HOf' )NHR a : K = u-ribityl. b : R = D-sorbityl.4-Alkylarnino-2,5-diamino-6-hydroxypyrimidines (I1 ; R = alkyl) have been prepared by heating 2-amino-4-chloro-6-lljrdroxypyrimidine with an excess of alkylamines at 120-140" and then introducing a 5-amino-group by nitrosation or by azo-coupling l1 followed by reduction. Alternatively, 2-amino-4-chloro-6-hydroxy-5-pheiiylazopyrimidine

The synthesis and antiinflammatory activity of 5-substituted 2-arylbenzoxazoles are described. Initial screening on carrageenin-induced rat paw edema showed that alpha-methylacetic substitution in the 5 position was preferable to substitutions with the equivalent esters, amides, alcohols, amines or tetrazoles. Halogen substitution in the aryl ring led to the most active compounds which were 2-(4-chlorophenyl)-alpha-methyl-5-benzoxazoleacetic acid (14) and 2-(4-fluorophenyl)-alpha-methyl-5-benzoxazoleacetic acid (29). These compounds were three to five times more active than phenylbutazone as assessed from ED30 values determined on rat paw edema 5 hr after single oral doses.

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Road, Pontypool, Monmouthshire N P4 8YH Attempts to devise a synthesis of lysergic acid from 3,4-dihydrobenz[c,d]indol-5(1H)-one (I) via methy\ Nacetonyl-N-(I ,3,4,5-tetrahydro-5-oxo-l -(p-tolylsulphonyl)benz[c,d]indol-4-yl)carbamate (23) failed owing to difficulties in cyclising the latter to the tetracyclic ketone (4).Several alternative routes were examined and, inter alia, 4,8,9,1 Oa-tetrahydro-9-(hydroxymethyl) -9-methyl-6Hindolo [3,4-gh] [I ,4] benzoxazinium chloride (30) and 4-acetyl-6.6a.7.8-tetrahydro-8-imino-4H-indolo [6,5,4-cd] indolium acetate (40) have been prepared.

Prepared by treatment with 5% nitric acid on a steam-bath for 1 hr., filtration, washing till free from NO,-, boiling with methanol, filtration, and reactivation at 250"/10 mm. for 1 hr.t The ethereal solution was washed with 2~-sodium carbonate, and with water, and evaporated; the product was crystallised several times from benzene, dried in a vacuum, and sealed in small ampoules.