146
A. T.
BLOMQUIST
AND
of ammonia and ethyl alcohol. From the reaction mass were isolated carbanilide and the triazine, which was very insoluble in boiling alcohol but dissolved in cold sodium hydroxide (10%). cY-Methyl-a,r-dicarbethoxyguanidine (XXIV), HNC(N( CHB)COOC~I'I~)NHCOOC~H~, was obtained from the potassium sallc OF dicarbethoxyguanidine and dimethyl sulfate in dry acetone on five hours of refluxing. Its structure was proved by the fact that it is different from the isomeric inethylimino compound (IV). Hydrolysis of Dicarbcthoxyguanidine.-.4 boiling saturated alcoholic solution of potassium hydroxide was treated with an equivalent weight of dicarbethoxyguanidine and boiled for a few minutes. The solution was evaporated on the steam-bath, the residue made up to the original volume with water and evaporated twice, and finally dissolvcrl in an equal volume of water and cooled. An almost quantitative yield of monocarbethoxyguanidine hydra1 el5 was obtained. The hydrochloride melted a t 128-130 a and the picrate a t 227 ', Phenyl Isocyanate and Carbethoxyguanidine. Carbethoxydicarboxanilidoguanidine (XXV), ( CsH5NHCONH)&( NCOOCtHs) .-Carbethoxyguanidine was treated with an excess of phenyl isocyanate and the reaction completed on the steam-bath. A little carbanilide was formed but the main product was the above diurea.16 ( l a ) I'irick and Blair. THISJ O U R N A L , 49, 509 (1927); Basterfirld a n d Paynter, ihid.. 48, 2177 (1926); Nencki, Ber., 7, 1588 (1874); J . Drakl. C h e m . . 121 17, 237 (1878). (16) Johnson, .Am. L'hem. J., 29, 4R2; 30, 172 (1903); Ref. 5, p 2224.
[CONTRIBUTION FROM THE
H. B. STEVENSON Phenyl
Isothiocyanate
~'01.56 and
Carbethoxyguanidine.
Hexahydro-l-phenyl-2-thio-4-imino-6-oxy-s-triazine (XX1 2
3
1
VI), QH;NCSNHC(NH)hH80.- -The mustard oil and l_-_-
___I-
guanidine were warmed in aicohol solution for cight hours or, with better yield, hratcd without a solvent at 115" for two hours. The triazine was difficultly soluble cscept in acids and strong bases. I t gave a methyl thio ether (XXVII) with dimethyl sulfate in dry acetone solution.
Summary 1-Methyl and 1-ethyl biuret have been formed from allophanic ester and carbonyldiurcthan by the action of methyl and ethyl amines. Amines have been found to easily hydrolyze thioallophanic ester to thiourea. Thiocarbonyldiurethan and its methyl ether have been found to give with amines alkyl and aryl dicat bethoxyguanidines. With hydroxylamine, hydrazine] o-phenylenediamine, and anthranilic acid, heterocyclic compounds have been synthesized. From dicarbethoxyguanidine, monocarbethoxyguanidine and a-methyl-a,y-dicarhethosyguanidine, were obtained] while with aniline and with phenyl isocyanate triazines were formed. LAWRENCE, KANSAS
BAKERLABORATORY
RECEIVED AUGLW 7, 1933
O F CHEMISTRY A T CORNELL LTNIVERSITY]
The Preparation and Reactions of Some Fury1 Isocyanates BY A. T. BLOMQUIST' AND H. B. STEVENSON A survey of the literature of the furan series affords relatively meager information regarding amines and their derivatives in which the nitrogen atom is directly attached to the furan nucleus. Only in those instances in which the furan nucleus has been substituted with negative groups, such a s nitro, carboxyl and carbethoxyl, has i t been possible to isolate aminofurans. Typical exanipies of amines which have been obtained in the furan series are 5-amino-2-furoic acid,2 3,4diamino-5-nitro-2-furoic acid,3 ethyl 3-amino-4nitro-2-furoate4 and ethyl 4-amino-5-acetamino2-fur0ate.j A11 attempts to isolate a simple amino derivative of furan, or of one of its homologs, have been (1) Natioiial KesFarch Fellow in Chemistry. ('2) Marquis. :I ET^. c h i m , (81 4, 190 (1905). 1 3 ! 'TrdulJe and I,kl/Z+r, Ber , 46, 3438 (191c3). 1.4) Kinkrs, K e r I ~ O P ) . c h i n . , 61, 353 (1932) f 5 ) (:ilmaii aiid Wurlnrr, 'I'ri~s J O I J K N A L . 65, 2OU3 (1:330).
unsuccessful. Marquis2 attempted the preparation of a-aminofuran by decarboxylation of .5amino-2-furoic acid and by hydrolysis of aacetaminofuran. Freundler6 and Leimbach' were also unsuccessful in preparing a-aminofuran by hydrolysis of the urethan obtained when furoyl azide was heated with methyl alcohol. The more precise information now available concerning the behavior of furan compounds has made it seem possible that suitable conditions might be developed for the isolation of simple aminofurans. Indeed, several types of furan compounds ( e . g., a-furfuryl chlorideSand 2-iodofurang), which could not be obtained by earlier workers, have recently been isolated in t,he pure state. Iirorri a consideration of the behavior of ( 6 ) I'rrnn7), ( 7 ) I.eimhdch. J Druki Ch6m , [ 2 ] 65, 3 5 (1!4Il:?) ( 8 ) l
