[AndersHoveland]

Here are two unusual reactions that could be used to prepare hydrazinium nitroformate, a rocket fuel oxidizer, from easily available precursors using surprisingly simple procedures. sensitivity to friction: not less than 20N, sensitivity to shock: not below 2 Joules

Trinitromethane
Ethylnitrolic acid (1-Nitro-1-oximinoethane, CH3C(NOH)NO2)
was prepared by mixing acetone with nitric acid (of 24% concentration) and a little fuming HNO3 and allowing the mixture to stand for eight days at room temperature. An extraction with ether gave, on evaporation, some acetylmethylnitrolic acid.
Right after the strong oxidation, a clear thick yellow oil with a pungent odor was left behind. This oil contained one-third to one half acetylmethylnitrolic acid CH3C(=O)C(=NOH)NO2 in addition to other byproducts, including pyruvic and oxalic acids. The crystals of acetylmethylnitrolic acid melted at 62degC, with significant decomposition.  Substituting methyethyl ketone in place of acetone in the procedure results in products of acetic acid, formic acid, in addition to considerable amounts of ethylnitrolic acid CH3C(=NOH)NO2 and 1,1-dinitroethane. Bubbling NO2 into ethylnitrolic acid can produce trinitromethane, with acetic acid byproduct.

WARNING: liquid trinitromethane can form sensitive explosive mixtures with organic solvents, either do not use an organic solvent, or ensure that the trinitromethane is highly diluted in chloroform at all times. Do not add concentrated bases to trinitromethane. Never prepare more than 3g at any one time. The compound is much more stable as the nitroformate salt.

Semicarbazide

Hydrazodicarbonamide
A 12.9% solution (0.3 moles) of Biuret NH2CONHCONH2 was placed in a 2L glass at 5C with 12 hypochlorite solution (0.3 moles), reaction temp kept at 5C.  This formed NH2CON(Cl)CONH(-) Na+ in 98% yield.
 
The whole product was added to a 2L glass, the temperature raised to 100C, adding liquid ammonia (8.8 moles), maintained at 100C for 30min. The unreacted ammonia was then removed, product filtered, forming hydrazodicarbonamide NH2CONHNHCONH2 in 95% yield.
 
Biuret can be prepared by heating urea above its melting point. Further heating, however, will only produce cyanuric acid.
 
2 CO(NH2)2 → H2N-CO-NH-CO-NH2 + NH3 (gas)

Hydrazodicarbonamide reacts with a 1:1 molar ratio of concentrated NaOH to produce
semicarbazide H2NC(=O)NHNH2 and carbamic acid. Excess NaOH will result in hydrazine.

[AndersHoveland]

There should be between 0.8 to 1 mole of hypochlorite for each mole of urea.
For the one mole ratio of NaOCl, the yields were 50% with respect to urea, and 50% with respect to NaOCl. For the 0.8 mole ratio, the yields were 48.5% with respect to urea, and 60% with respect to NaOCl. For best yields, the hypochlorite solution should contain at least 3 moles of sodium hydroxide for every 0.8 moles of sodium hypochlorite.
Solutions of sodium hypochlorite and urea were first both cooled to 4degC, then mixed.
A glue solution was added, 0.5g of glue for each mole of sodium hypochlorite. The mixture was heated to 90degC, then allowed to cool. This exact temperature is very important for good yields from the reaction. Sulfuric acid was added into the solution so that the concentration of acid in the solution reached 20%. Hydrazine sulfate precipitated and was filtered out, then washed with alcohol and dried at 100degC. Note that the reaction cannot be done in a steel pot, as this catalyzes the decomposition of hydrazine.

[AndersHoveland]

Question:

Would Hydrazodicarbonamide react with a litmited ammount of NaOH to form semicarbazide and carbamic acid?
I thought this was the case, but after failing to find any references about this I am less sure.

Neither can I find any references about semicarbazide NH2C(=O)NHNH2 hydrolyzing with 1:1 molar ratio of base to form carbamic acid NH2C(=O)OH and hydrazine N2H4. One would think there would exist more information about the reactions of semicarbazide. If this is the correct reaction then it would also answer my first question. Obviously semicarbazide is normally produced from urea and hydrazine, but I was curious as to if semicarbazide could be made directly from the NH2CONHNHCONH2, without having to first completely hydrolyzing to hydrazine.

Please help, or at least give me your opinions.