Nitro-Aminoguanidine

Abstract

Nitroguanidine, HN=C(NH2)NHN02, was first prepared by Jousselin1 by dissolving guanidine nitrate in concentrated sulfuric acid, when the compound separated upon dilution with water. More recently several articles2 have appeared concerning this compound. It is used principally as an explosive. Thiele23 prepared nitrosoguanidine as well as aminoguanidine, HN=C(NH2)NHNH2, by reduction of nitroguanidine. Hofmann and Stollé3 and also Pellizzari and co-workers4 prepared diaminoguanidine hydrochloride, HN=C(NHNH2)2-HC1, by the action of cyanogen chloride on hydrazine in ethereal or aqueous solutions. Pellizzari and Gaiter5 also prepared triaminoguanidine by treating guanidine or its monoor diamino derivative with the calculated amount of hydrazine. This work was verified and a good yield of triaminoguanidine obtained by heating an alcoholic solution of guanidine nitrate and hydrazine at 100°for five hours.Apparently nitro-aminoguanidine, HN=C(NHN02)NHNH2, has never been prepared, as no reference to it was found in the literature. In 1920, while working on guanidine compounds, it was found that an interesting substance formed when nitroguanidine was heated with a solution of hydrazine. This substance is the subject of the present investigation. Preparation of Nitro-aminoguanidineThe nitroguanidine used in this experiment was prepared by dissolving guanidine nitrate in coned, sulfuric acid, and pouring this solution into ice water. The crystals obtained were twice recrystallized from water.2c,eHydrazine sulfate, 32.53 g., was placed in a 2000-cc. Erlenmeyer flask with 200 cc. of distilled water and 500 cc. of N ammonia water. When the hydrazine sulfate had dissolved, 26 g. of nitroguanidine was added. The flask was then heated to 50-60°, during which time the nitroguanidine went into solution, nitrous oxide gas began to evolve and the reaction liquor turned to an orange-red color. In about one hour at the above temperature, gas ceased to form and the liquor was rapidly evaporated to about one-third its volume. On cooling, a white crystalline powder separated which was filtered off, washed with cold water and dried in the air; yield, 13.1 g. This was purified by dissolving in boiling water containing decolorizing carbon, and filtering. Upon chill-1 (a)

1-Amino-3-nitroguanidine (ANQ) in High-performance Ionic Energetic Materials

“…10 mmol of silver dinitramide acetonitrile adduct was prepared according to the literature [9]. 1-Amino-3-nitroguanidinium chloride (1.47 g, 9.4 mmol) is dissolved in 10 mL of boiling water.…”

Inorganic Amino-Nitro-Guanidinium Derivatives

“…The salts crystallize in common space group (2: P2 1 /n, 3: P2 1 /c, 4: P-1, 5: Fdd2).  The good solubility and availability of 2-5 allows the metathesis reaction with different silver and barium salts under precipitation of low-soluble AgCl, AgBr, AgI or BaSO 4 for the synthesis of a variety of amino-nitroguanidinium salts as exemplarily shown for 1-amino-3-nitroguanidinium dinitramide [4].…”

“…Nitroguanidine is used in airbags and many other double-and triple-based propellant applications [2]. Interestingly, only very little correspondence on aminonitroguanidine is found in the literature [3][4][5]. We recently investigated the use of ANQ in energetic materials in its neutral as well as OPEN ACCESS protonated form [6].…”

A Review on the Reactivity of 1-Amino-2-Nitroguanidine (ANQ)

“…1-Amino-2-nitroguanidine (ANQ, 1 ) was first synthesized by Phillips in 1928 [1] and has played an important role in the synthesis of valuable biologically active compounds, such as pesticides and medicines [2,3,4,5,6,7,8,9,10,11,12,13,14,15,16]. In recent years, Klapötke has done a lot of research on the application of ANQ in high-energy nitrogen-rich materials, which began to attract significant interest in the field of energetic materials [17,18].…”

“…The crystals of ANQ are transparent yellow and crystallize in the monoclinic crystal system with the space group P 2 1 / c [19]. ANQ can dissolve in water to the extent of 0.34 % (mass fraction) at 20 °C and 3.0% at 70 °C, and is easily soluble in sodium hydroxide solution, but cannot be readily dissolved in common organic solvents [1]. The decomposition behavior of ANQ presents two intense exothermal processes, and peak temperatures at a heating rate of 5 °C min −1 are 192.48 and 196.20 °C, respectively, as presented in Figure 1 [20].…”