PIIILIP S. B.IILEYAND ROBERT E. LLTTZ
-1 9s
\\,itc r, the I\ hitc precipitate w;i\ c o l l c c t ~ t ,weight 4 40 p., ,Lticaly4\: C, 28.81; H , 2 . G . .iritl
Summary There has been isolated from the nitration of melamine a product of the empirical formula, CaHa-&;O5. X convenient procedure for the preparation of triacetylmelamine has been developed, and bv nitration of this compound there
/ J O I S T COSTRl'I3L'TIOl'
1'01. (i!)
has been obtained a compound whose formula is CyHgN15012. By heating this compound in water, there has been obtained another compound, C9HgX9O9. Salts of these three new compounds have been obtained, and some of their properties have been determined, but their structures have not been elucidated. X possible structure for the compound, CyHgNgQy, has been suggested. RECEIVED OCTOBER3 , 1936
SASHVILLE, TEN.
FROM TIIE DEPARTMENT O F CHEMISTRY O F THEG S I V E R S I T Y OF LABORATORY O F T H E c S I V E R S I T Y O F \'IRGISIA]
TEXAS ASD
TIIE COI3R CFIEMICAI.
The Reaction of Alcohols with Dibenzoylethylene BY PHILIPS.BAILEYAND ROBERTE. LUTZ Ethanol, methanol and i-propanol have been found t o rea.ct with dibenzoylethylene (I) under slightly acidic conditions in the presence of secondary or tertiary amine salts. The product in each case was the corresponding %,5-diphenyl-3-alkoxyfuran (11). Although the yields were low (around 1S(l, ), it is of interest that such ti reaction occurs under the conditions emploved. , -
involved the presence of a n amine hydrochloride and enough hydrogen chloride to show a pH of 2-3 when indicator paper was dipped into the reaction mixture. When either the amine hydrochloride or the hydrogen chloride was omitted, the reaction could not be detected. An increase in hydrogen chloride concentration tended to eliminate the formation of the alkoxyfurans and increase the formation of by(a) CzH60H €1 C---OR products. Replacement of thc (h) CHaOH aniine hydrochloride with alco( c ) CsH70H (i) I1 11 c,;TI:,cocr~-d:I~ COC,;I13 > C6IIs /C-CsHj hol-soluble inorganic salts \o.' TIC1 + I~:,s~I+cI (lithium chloride or magnes1 I1 (3) R = CiHj iuiii chloride, all other condi(b) K = CHI K = call7 tions remaining the same) Zn + HOAc gave negative results. Segative resdts were also obtained when ammonium chloride was used, but this might have been OCyH, due to its low solubility in TI1 I \. alcohols. The high specificity The ethoxy and i-propoxyfurans (IIa and IIc) of these conditions is perhaps not surprising in are new compounds. The structure of the former view of the low yield a t best and of the many was proved by synthesis along another path; competing reactions which are possible. namely, reaction of dibenzoyldibromoethane (111) In these reactions there was obtained along with sodium ethoxide t o yield IV, followed by with the furans a mixture from which two colorreductive cyclization t o IIa. The methoxyfuran less, high-melting substances were isolated. These (lib) had previously been prepared in the same were obtained also in several experiments which way. Attempts t o prepare the i-propoxyfuran produced no furan. These new compounds. o f (IIc) by this method failed in the first step, composition close t o that of dihenzoylethyleiic namely, treatment of dibenzoyldibromoethane are under investigation. (111) with sodium i-propoxide, which led t o resin The addition of alcohols to a,b-unsaturated formation. 'There can be little doubt as t o the esters2 and ketones (dibenzoylacetylene) has structure of the compound, however, since it was been carried out in the presence of a sodium alobtained in a reaction identical with those which koxide catalyst. In the present work, however, yielded the corresponding inethoxy and ethoxy such a process led to resinification. Under somefurans. The new reaction constitutes the only what different conditions, fulvenes have been obway by which the i-propoxy. compound (IIc) tained by the treatment of dibenzoylethylene (and perhaps other higher ethers) can be prewith sodium ethoxide." pared a t the present time. (2) Purdie a n d M a r s h a l l , J . Chem. Soc., 69, 468 (1891); I
