Good ).ields of N-substi ti1 ted 1ire:Li lverc o b t a i~~e d 11)i reacting alnines \\.it11X-nitrosc~-N-melhylul.ea ill aqlleuui s o l~~l i c~n . I t has becrl showr~ t11;il N -~~i t r o s o -N-metl~>.lurea deconlposetl illto nlcthylnirrosnuiiclc a r d isocyanic ncitl. Sirnilarl>., S-~lilroso-hT, S ' -d i~~~c t l~> . l~~r e ;~ ;111d 3[11i11es gave rise to goocl yicltls of N-s~~bstit~l ted-N'-~~lethyli~rcas. IntroductionDn\lis antl 13lanchard (4) have sho\\.n that nitrourea ( I ) dccomI~osed in aqueous solution into isocyanic acid (I I I j and ilitraxnide (I1 j which is transfor-nicd into nitrous oxide (I\') ant1 \\-atel-. The for~uation of isoc?-anic acid was inferred from the reaction of nitrourea in aqueous solution \\;it11 amiues to yield N-substituted ilrcas, quantitati\.ely i r i several instances.'The I-eactiorl of nitrosourcas with aminrs has not been studied. I-Iowever, it may be postulated that X-meth).I-K-~lit~-oso~~rea (Vj decon~poses in aqueous solution into N-methl.1-N-nitrosa~~~icle (\'I) ant1 isocyanic acid (111) according to the niechanisrn suggestctl bl. T. L,. Davis (Equations ( I j antl (2)). I n strongll. alkaline solution compo~irltl \' is I;~lo\\.n to yield diazo~nethanc.When N-n~ctli!:l-N-ni tl-osourca (1') \vas boilctl in ncllleous solution, the stoichio~netric amount of nitrogen \vas evolvetl and the solution nras found to contain isocyanic acid and rnct-hanol. MYth anlines, a s \\,as espcctcd, thc isocyanic acid PI-oduced yielded N-substit~xtcd irrcas (VII) accol-rling to the lolloning equation:- For personal use only.

When 1-amidino-3-nitrourea is reacted in aqueous solutions of amines, nitrous oxide and carbon dioxide are eliminated and guanylureas are formed, together with disubstituted ureas as by-products. The infrared absorption spectra of some disubstituted ureas and nitrates of guanylureas are discussed with tentative assignment of bands to some groups.

The Darapsky degradation, by which a carbethoxy group is replaced by an amino group, has been applied successfully to substituted cyanoacetic esters for the preparation of 10 amino acids. The esters were formed by condensation of ethyl cyanoacetate with alkyl or arylalkyl halides. The hydrazides were obtained by treatment of the esters with hydrazine hydrate and identified by their anisal derivatives. Diazotization of the hydrazides gave rise to azides. These were transformed into carbethoxyaminonitriles by refluxing with absolute ethanol. The urethanes, on acid hydrolysis, yielded the amino acids. The following amino acids were synthesized: DL-β-methylleucine, DL-α-amino-β-methylisoheptanoic acid, DL-α-amino-β-cyclohexylpropionic acid, DL-C-o-methylcyclohexylglycine, DL-C-m-methylcyclohexylglycine, DL-C-p-methylcyclohexylglycine, DL-C-o-xylylglycine, DL-C-m-xylylglycine, DL-C-p-xylylglycine, DL-p-ethylalanine.

Nine α-amino acids, namely, dl-α-aminoundecylic acid, dl-α-aminostearic acid, dl-α-amino-β-methylcaproic acid, dl-α-amino-β-ethylvaleric acid, dl-α-amino-β-methylenanthic acid, dl-α-amino-α-acetylacetic acid, dl-α-amino-γ-cyclohexylbutyric acid, dl-α-(1-indanyl)-α-aminoacetic acid, and dl-proline have been prepared from ethyl alkylcyanoacetates. When a mixture of formic and hydrochloric acids and water was used, instead of hydrochloric acid, as hydrolyzing agent, α-amino-β-ethylvaleric acid and α-(1-indanyl)-α-aminoacetic acid were obtained with better yields. The following compounds, as far as the authors are aware, have been prepared for the first time: ethyl α-cyanoundecylate, α-cyanoundecylic hydrazide, anisal α-cyanoundecylic hydrazide, α-cyanoundecylic azide, α-carbethoxyaminoundecylonitrile, dl-α-aminoundecylic acid, 5-(n-nonyl)-hydantoin, α-cyanostearic hydrazide, anisal α-cyanostearic hydrazide, α-cyanostearic azide, α-carbethoxyaminostearonitrile, α-cyano-β-methylcaproic hydrazide, anisal α-cyano-β-methylcaproic hydrazide, α-cyano-β-methylcaproic azide, α-carbethoxyamino-β-methylcaproonitrile, dl-α-amino-β-methylcaproic acid and its copper salt, α-cyano-β-ethylvaleric hydrazide, anisal α-cyano-β-ethylvaleric hydrazide, α-cyano-β-ethylvaleric azide, α-carbethoxyamino-β-ethylvaleronitrile, dl-α-amino-β-ethylvaleric acid, and its copper salt, ethyl α-cyano-β-methylenanthate, α-cyano-β-methylenanthic hydrazide, anisal α-cyano-β-methylenanthic hydrazide, α-cyano-β-methylenanthic azide, α-carbethoxyamino-β-methylenanthonitrile, dl-α-amino-β-methylenanthic acid, and its copper salt, α-cyano-α-acetylacetic hydrazone, anisal α-cyano-α-acetylacetic hydrazone, α-cyano-α-acetylacetic azide, α-carbethoxyamino-α-acetylacetonitrile, dl-α-amino-α-acetylacetic acid, ethyl-α-cyano-γ-cyclohexylbutyrate, α-cyano-γ-cyclohexylbutyric hydrazide, anisal α-cyano-γ-cyclohexylbutyric hydrazide, α-cyano-γ-cyclohexylbutyric azide, α-carbethoxyamino-γ-cyclohexylbutyronitrile, 5-(β-cyclohexylethyl)-hydantoin, 1-in-danyl bromide, ethyl α-(1-indanyl)-α-cyanoacetate, α-(1-indanyl)-α-cyanoacetic hydrazide, anisal α-(1-indanyl)-α-cyanoacetic hydrazide, α-(1-indanyl)-α-cyanoacetic azide, α-(1-indanyl)-α-carbethoxyaminoacetonitrile, dl-α-(1-indanyl)-α-aminoacetic acid, and its copper salt, ethyl δ-chloro-α-cyanovalerate, δ-chloro-α-cyanovaleric hydrazide, anisal δ-chloro-α-cyanovaleric hydrazide, δ-chloro-α-cyanovaleric azide, δ-chloro-α-carbethoxyaminovaleronitrile.

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