In a previous paper,2 the authors described dimethyl 4-aminophthalate and certain of its acyl derivatives. The present article deals with the free acid, its salts, and various other derivatives or experiments not reported in the earlier paper.The literature on the subject of the free 4-amino-o-phthalic acid is meagre and confusing.Miller3 subjected 4-nitrophthalic acid to the action of tin and hydrochloric acid. The reduction proceeded smoothly, no carbon dioxide was evolved, and presumably the double salt of tin chloride and aminophthalate was formed. This double tin salt remained in solution and could not be separated by freezing (differing in this respect from the corresponding 3-aminophthalic compound). When the tin was precipitated from this solution by hydrogen sulphide and the filtrate from the tin sulphide concentrated, only the hydrochloride of w-aminobenzoic acid remained.Bodé4 reduced 4-nitrophthalic acid to the double zinc acetate and aminophthalate by the Bemthsen and Semper method5 but found the yield inferior to that obtained from the 3-nitro acid. These double zinc acetates and aminophthalates can be diazotized direct and thus used for the preparation of other substituted phthalic acids or for direct coupling. Apparently, he did not attempt the isolation of the free aminophthalic acid.

In continuation of our studies in this field (1, 2), we have investigated the serviceability of certain familiar reactions for the synthesis of a number of quinoline, isoquinoline, and phenanthroline derivatives in which we were interested. The results obtained with the Skraup and the Conrad-Limpach-Knorr procedures are described in the pages which follow. Some phenanthroline derivatives have been claimed (3,4,5) to possess analgesic properties, others (5) to exhibit bactericidal activity. Some have been prepared (6,7,34) for pharmacological testing in other directions. The 1,10-phenanthroline (XXXI) is best known from the work of Walden, Hammett, and Chapman (8), who called attention to its ferrous cation complex as a remarkably sensitive oxidation-reduction indicator.The 1,8-phenanthrolines (XXXIII) have been studied but little. The onlyinvestigation on record appears to be that of Borsche and Wagner-Roemmich (9), in which the Doebner pyruvic acid reaction was applied to 5-aminoisoquinoline.To determine the possible availability of some simple initial compounds, certain preliminary syntheses were carried out from guaiacol and vanillin as raw materials (See Flow Sheets la and lb).

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BOCERT AND GOTTHELF have already shownZ that ketodihydroquinazolines may be prepared by heating together in sealed tubes anthranilic acid, or its acyl derivatives, with a nitrile, and the reactions there suggested in explanation of this synthesis, taking the case where an acylanthranilic acid was the starting-point, were as follows: /NH. CO. CH, /NH. CO. CH,

The 4-quinazoloaes (4-hydroxpquinazolines) are not easily brominated by the action of bromine in aqueous potassium bromide solution, in glacial acetic acid or in acetic anhydride solution. By employing the Juvalta* process, however, the halogen may be introduced. I n this way, monobromo derivatives have been obtained of 4-quinazolone and of 2-methyl-4-quinazolone. Griess,3 in 1869, showed that benzoylene urea could be nitrated, but did not prove the position of the nitro group. In 1890, Dehoff4 nitrated a-methyl and a,3-dimethyl-4-quinazolone, and his products were subsequently shown to be the 6-nitro derivatives by the investigations of Thieme3 and of Bogert and Cook.B According to our experience, the satisfactory nitration of 4-quinazolones requires a high temperature and the use of a mixture of fuming nitric and concentrated sulfuric acids, and but one nitro group can thus be introduced on the 4-quinazolone nucleus. Position 6 seems to be the point where the nitro group enters most readily. Of course, aryl Nor are the quinazolones readily nitrated.

Continuing the investigations in this field which have already appeared from these laboratories,1•2 experiments have been conducted with veratrole derivatives, whose purpose was the synthesis of the true papaverine analog in the quinazoline series. Although this goal has not yet been reached, some interesting reactions and products have been discovered and are here recorded.

Aromatic Alcohols by the Crossed Cannizzaro Reaction 905 When the azide was taken up in ether, a sparingly soluble by-product separated crystalline from benzene, m. p. 220-222°. A second by-product (140-160°) is found in the crude oily urethan. (4) The urethan yields 96% of 2-[ -amino-M-propylJ-dibenzofuran hydrochloride, m. p. 228-231°, corr. (M. and K" 219-220°).One gram of 2-[7-amino-re-propyl ]-dibenzofuran hydrochloride, 1 g. of 99-100% formic acid, and 10 g. of 37% aqueous formaldehyde were heated in a sealed tube for fifteen hours at 130-160°. After treatment of the basic reaction products with benzene sulfonyl chloride, 0.45 g. of the hydrochloride of 2-[ 7-(dimethylamino)-re-propyl ]dibenzofuran, m. p. 190-193°was obtained, and purified by repeated crystallization. Summary 1. The synthesis of benzofuro-[3,2-g]-quinoline and benzofuro-[2,3-f ]-quinoline from 3-aminodibenzofuran is described.2. The tetrahydro and N-methyltetrahydro compounds of the benzofuroquinolines were prepared.3. The constitution of the benzofuro-quinolines has been proved through the Emde degradation products of the N-methyltetrahydrobenzofuro-quinolines. University, Virginia