Allophanyl hydrazide

Submitted by Paul G. Gordon and Ludwig F. Audrieth Checked by P. LENsif 

Allophanyl hydrazide has been prepared previously as the hydrochloride by the zinc-hydrochloric acid reduction of 1-nitrobiuret.1 The new procedure2,3 outlined here entails the hydrazinolysis of allophanic esters in alcoholic solution. Excellent yields (80 to 84%) of allophanyl hydrazide are obtainable with a minimum of difficulty using readily available starting materials. The methyl and ethyl allophanates are prepared from urea and the corresponding chlorocarbonic esters.4 

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Audrieth P.G. Gordon, "The Chemistry of Allophanyl Hydrazide and Urazole,"... 

P.G.Gordon, "The Chemistry of Allophanyl Hydrazide and Urazole," Final Rept March 15, 1954, Univ of Illinois, Urbana, 111, pp 14 59 4)J.P-Picard W.P. Morton, Letter to Prof F.Audrieth from PicArsn, dated May 1955 (Contract DA-11-0 22-0 Rl> 33) 5) -.F. 

Alkali metal azides, 1 79 2 139 Alkali metal cyanates, 2 86 Alkali metal pyrosulfites, 2 162 Alkali metal sulfites, 2 162 Alkaline earth azides, 1 79 Allanite, extraction of, 2 44 Allophanyl azide, formation of, from allophanyl hydrazide, 5 51 Allophanyl hydrazide (1-amino-biuret), 5 48 hydrazones of, 5 51 from methyl and ethyl alloph-anates, 5 50 salts of, 5 51... 

Amines, coordination compounds with boron halides, 6 26 1-Aminobiuret (allophanyl hydrazide), 5 48, 50, 51 Aminoguanidonium hydrogen carbonate, 3 45 analysis of, 3 46... 

Ethyl allophanate, preparation of, for synthesis of allophanyl hydrazide and urazole, 6 48,... 

Audrieth P.G.Gordon, The Chemistry of Allophanyl Hydrazide and Urazsle, ... 

P.G.Gordon, "The Chemistry of Allophanyl Hydrazide and Urazole," Final Rept March 15, 1954, Univ of Illinois, Urbana, 111, pp 14-59... 

From Ethyl Allophanate. One hundred thirty-two grams of ethyl allophanate (1.0 mol), 100 ml. of 95% hydrazine (3.0 mols), and 1.5 1. of methanol are placed in a 3-1. standard-taper round-bottomed flask equipped with a reflux condenser and heating mantle. A few charcoal chips are added to prevent bumping. The reaction mixture is refluxed for 8 to 10 hours, after which it is cooled overnight in a freezer ( — 14°). The crystalline product is removed, washed with ethanol and ethyl ether, and air-dried. The yield is 63.7 g. (54% of theory) of allophanyl hydrazide, melting at 165 to 166° with decomposition. 

Allophanyl hydrazide is a white, crystalline, nonhygro-scopic compound which melts at 166° with decomposition. It is soluble in water, methanol, and ethanol (at their boiling points) to the extents of 14, 3, and 1.4 g./lOO ml. of solvent, respectively. It is a weak base, KB = 10-n. Melting points and formulas of typical salts are tabulated below. The compound is thermally unstable when heated at 110° for an extended period of time. As a typical hydrazine derivative, allophanyl hydrazide forms allophanyl hydrazones with carbonyl compounds. Among these, the water-insoluble benzaldehyde derivative (m.p. 208 to 209°) is easily prepared. Allophanyl hydrazide can also be treated with nitrous acid to give the water-insoluble azide, NH2CONHCON3, melting with decomposition at 193°. 

Anhydrous lanthanon nitrates, synthesis 11 Cyanogen, synthesis 12 Allophanyl hydrazide, synthesis 13 Urazole, synthesis 14 Organosilazane compounds, synthesis 16 IV-Nitrosohydroxyla-mine-iV-sulfonates, synthesis 31 Hydroxylamine-O-sul-fonic acid, synthesis 32... 

NH2CONHCON2H3 Allophanyl hydrazide, 6 48, 50 hydra-zones, 5 51 salts, 5 51 NH2CONHCON3 Allophanyl azide, 5 51... 

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