Nitroguanidine development

Single base" smokeless powder, developed mainly in the United States, uses only nitrocellulose. "Double base" smokeless powder, developed in Europe, is a blend of nitrocellulose and nitroglycerine. "Cordite," a British development, consists of 65% NC, 30% NG, and 5% mineral jelly. The mineral jelly (a hydrocarbon material) functions as a coolant and produces substantial amounts of CO 2, CO, and H 2O gas to improve the propellant characteristics. "Triple base" smokeless powder, containing nitroguanidine as a third component with nitroglycerine and nitrocellulose is also manufactured. 

Combustible cartridge cases (CCCs) based on nitrocellulose (NC), cellulose, nitroguanidine etc. have been developed in India and are reported to be useful for 105 mm APDS and HESH tank gun ammunition, 120mm FSAPDS and HESH tank gun ammunition and 125 mm FSAPDS tank gun ammunition. India has also developed advanced CCCs based on resins likely to be useful for 155 mm howitzer (artillery gun) ammunition in addition to the above-mentioned ammunition. 

Jousselin [26] prepared nitroguanidine by the action of anhydrous nitric acid or sulphuric acid on guanidine nitrate. The preparation of this substance by the action of sulphuric acid has been developed as an industrial method for the production of nitroguanidine. The method described by Marqueyrol and Loriette [27] follows somewhat different principles. It consists in acting with anhydrous nitric acid on guanidine sulphate which, in turn, is obtained on treating dicyandiamide with sulphuric acid. 

Investigations showed that the salts of other alkali metals are not so efficient in suppressing secondary flame as potassium salts. Fairly numerous experiments were carried out to clear up whether or not known antiknock substances, such as tetraethyl lead or nickel carbonyl prevent the development of a secondary flame. They proved to have no effect on its development. In practice, two methods for removing gun-flash may be employed, i.e. either a special flashless powder is produced, containing nitroguanidine or DNT and a small admixture of potassium sulphate,... 

It has been observed that the majority of remedies for preventing the development of flash lead to an increase of smoke (e.g. potassium salts give white smoke, aromatic nitro compounds give black-grey smoke due to the presence of unburnt carbon). Nitroguanidine is the only additive that does not appreciably increase smokiness. The burning of blackpowder in the primer produces an insignificant amount of smoke. 

N 52.61%, rosettes or flat ndls(from ale), mp 170—1°. It was prepd by Henry Smith(Ref 3) from me thy I hydrazine and 1-methyl-l-nitroso 3-nitroguanidine using a method developed by McKay Wright (Ref 2)... 

P Csl/rnoIfK f 3)- W s obt ic d by H nry(Rff 2) on heating 1-formamido-3-nitroguanidine with anhyd NaaCOa in a small amt of water for 25 min according to the procedure developed by J.Thiele K.Heidenreich,Ber 26, 2599(1893) for the prepn of aiuinoinethyicrx-azole. The reaction may be represented as follows ... 

Helf (Ref 2) considers the compd a suitable substitute for Nitroguanidine in propints as a flash and smoke suppressant Refs 1) Beil, not found 2) S. Helf, Long Range Research Leading to the Development of Ideal Propellants. . . , PATR 1752 (1949)... 

Preparation of nitroguanidine was developed by Jousselin. The German Army replaced picric acid with TNT. 

In the late 1980s Agro Kanesho announced the development of their own ne-onicotinoid insecticide AKD-1022 (12 Fig. 29.2.3.1), a representative of the 2-nitroimino-l,3,5-triazinane subclass containing a 2-chloro-5-thiazolyl moiety as heterocyclic group [34]. However, this compound was never commercialized, possibly due the crowded patent situation (see Section 29.2.3.2) or the lack of hydrolytic stability (Section 29.2.3.5). AKD-1022 (12) has also been described [35] to possibly be a proinsecticide of the acyclic nitroguanidine clothianidin (19) (see also Chapter 29.2.1). 

Optimisation at the cationic centre led to open-chain nitroguanidines, among which the monomethylated derivatives revealed outstanding activity, while other substitution patterns of the nitroguanidine possessed a species-de-pendent insecticidal profile. Whereas the sensitivity of Nephotettix cincticeps towards analogues with an additional acetyl-, benzoyl- or methylcarbamate-substituent, was approximately the same in comparison to the parent compound, Laodelphax striatellus (the small brown planthopper) proved clearly less sensitive. Careful analysis of the data led eventually to the decision, which structure to select and develop further (Fig. 8.55 and Tab. 8.3). 

---