ROBERTS. BARROWS AND H. G. LINDWALL
3430
Bromination of dimesitoylmethylethylene gave a cis-monobromo derivative from which the transisomer was made by inversion. The use of sodium
Vol. 64
bicarbonate in preventing secondary reactions during bromination is described. CHARLOTTESVILLE, VA.
RECEIVED JULY 6, 1942
[CONTRIBUTIOK FROM XICHOLS LABORATORY, NEWYORKUXIVERSITY 1
Condensation Reactions of Isoquinaldaldehyde BY ROBERTS. BARROWS AND H. G. LINDWALL The successful use of lepidine as a source of densation of equimolecular quantities of isocinchoninaldehyde’ suggested that l-methyliso- quinaldaldehyde and acetophenone was carried quinoline might similarly be oxidized through the out in the presence of sodium hydroxide for a action of selenium dioxide to yield isoquinald- short period of time, IV was obtained, but if aldehyde (I). The method of SpathJ2with modi- longer time was allowed or if sodium ethylate was fication, was used for the preparation of l-methyl- used, compound V resulted. With an excess of isoquinoline. The modification involved the sub- acetophenone and either sodium hydroxide or stitution of Raney nickel for platinized asbestos sodium ethylate, VI was the principal product. in the dehydrogenation of l-methyl-3,4-dihydroHO-- CH--CH*NOL HO-CH-CH~CO-CBH,, 1 isoquinoline. The 1-methylisoquinoline thus obtained was characterized by the preparation of several known derivatives. The oxidation of 1-methylisoquinoline by 111 Iv selenium dioxide was carried out in dioxane soluCH=CHCOCeHb CH (CH2COCeH,): tion with vigorous stirring; an excess of selenium 1 dioxide was avoided. The product (I), which is volatile with steam, reacts with Tollens reagent, V\/ gives a sodium bisulfite addition product, and VI forms an oxime, a phenylhydrazone and a semiNo product could be obtained from isoquincarbazone. The aldehyde (I) formed no hydrate. aldaldehyde and phenylacetic acid under condiA similar oxidation of 1,3-dimethpl-6,7-methyltions of the Perkin condensation, but two derivaenedioxy-isoquinoline was carried out. The tives of phenylacetic acid were condensed under product, an aldehyde, formed a monoxime, and is other conditions. Phenylacetonitrile and comtentatively assigned the structure 3-methyl-6,;pound I yielded VI1 in the presence of diethylmethylenedioxy-isoquinaldaldehydc(I1i . amine or sodium ethylate; ethyl phenylacetate CHO CHO and I gave VI11 when sodium ethylate was used O-.-(f\/‘’‘N
H2 __jc
j/ metal NOH R-CH2-CHr-CHR
I
+ >NH
NH,
The oximes (111) and (IV) however, were reduced in fair yields to the 1,3-diamino compounds (V) and (VI) using sodium and alcohol according to the method of Kohn.' The benzamides (VII) and (VIII) of these diamines were also prepared. I n order to obtain possible ephedrine-like amino alcohols the @-amino ketones (I) and (11) were reduced with sodium amalgam according to the method of K ~ h n . These ~ amino ketone hydrochlorides were not stable to catalytic hydrogenation though various conditions were employed. (4) Koho. Jlorralsh., 29, 519 (10118) (.-I) Kuhii, r b z d 28, 123 (ltNl7)
