Oct., 1937
COMMUNICATIONS TO THE EDITOR
20i9
naphthylamine. On the other hand, piperonylmethylamine condensed with o-nitrochlorobenzene. Treatment of the reduced and diazotized FRANK H. HURLEY, JR. compound with copper powder did not give as THERICEINSTITUTE HOUSTON, TEXAS much tar as previously but none of the desired RECEIVED JUNE4, 1937 phenanthridine has yet been isolated. We also have been attempting to apply the SYNTHETICAL EXPERIMENTS IN THE CHELIDO- phenylnaphthylenediamine synthesis of Atkinson NINESANGUINARINE GROUP OF ALKALOIDS and Thorpe to the synthesis of benzophenanthriSir: dines, our starting material for trial runs being In a recent article under the above title that benzyl cyanide. In view, however, of the inabilhas just come to our attention, Richardson, Rob- ity of Robinson and Liguori to bring about ring inson and Seijo [ J . Chem. Soc., 835 (1937)] re- closure in the piperonyl and veratryl series, we port a general scheme for the synthesis of bases shall probably discontinue our own efforts in this of the chelerythrine-sanguinarinetype. We have direction. been working in this field for the past two years Our first work in this field was an attempt to and certain of our experiments have paralleled apply a modification of the Bischler-Napieralski those reported by Robinson and his co-workers. synthesis of isoquinolines. The N-piperonylWhile our work has not progressed as far as that amides of 7-piperonylisocrotonic acid and y p i of Professor Robinson, we should like to continue peronylpropionic acid were prepared but all atour efforts in this field and to submit a brief out- tempts at ring closure were unsuccessful. Apline of what we have been doing. parently ring closure can be effected only when Attempts to apply the Pschorr phenanthrene the nitrogen atom becomes a part of the ring synthesis in the synthesis of phenanthridines which is formed. were no more successful than those of the above Work on a series of reactions almost identical authors. Instead of using 6-nitropiperonal in our with those successfully used by Robinson and cotrial experiments we used o-nitrobenzaldehyde workers has been barely started. It differs in which condensed readily with a-naphthylamine. that we have been attempting to synthesize The Schiff base was reduced with tin and hydro- a,y-dipiperonylbutyric acid through piperonylchloric acid to give two products, one of which malonic ester and piperonylmethyl bromide and formed a monohydrochloride and the other a we expect to continue with this phase of the syndihydrochloride. Both compounds gave diazon- thesis. ium salts as indicated by coupling with p-naphIt will be noted from the formulas of Bruchtho1 but treatment with copper powder under hausen and Bersch [Ber., 63, 2520 (1930)] that various conditions gave only tar. Since it is orthoveratraldehyde and orthopiperonal will be possible that a trans configuration of the Schiff needed for the syntheses of the alkaloids thembase prevents ring closure, the nitro compound selves. We should therefore like to report the was converted to the methochloride, reduced with successful methylenation, using methylene sultin and hydrochloric acid and diazotized, but fate, of 2,3 - dihydroxybenzaldehyde obtained again treatment with copper powder gave only from the commercially available orthovanillin, tar. a series of reactions that is much simpler than Thinking that ring closure in the &position of that reported by Perkin and Trikojus [ J . Chm. the naphthalene nucleus might be difficult, at- Soc., 2925 (192G)I. tempts were made to bring about closure from the DEPARTMENT OF CHEMISTRY C. R. NOLLER UNIVERSITY R. 0. DENYES naphthalene side. Benzaldehyde could not be STANFORD Uwrv., CALIF. J. W. GATES made to condense with o-nitroaniline so no at- STANFORD W. L. WASLEY tempt was made to condense it with 2-nitro-aRECEIVED SEPTEMBER 23, 1937
ent International value for the atomic weight of sodium is 0.003-0.004 unit too high. ARTHUR F.SCOTT DEPARTMENT OF CHEMISTRY
