Nitroguanidine: Difference between revisions
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→Manufacture: Fix error from 01:22, 16 December 2022 - the BMR process is not the same as the BMA process |
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{{Distinguish|Guanidine nitrate}} |
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{{chembox |
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| verifiedrevid = |
| verifiedrevid = 444027788 |
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| ImageFileL1 = Nitroguanidine.svg |
| ImageFileL1 = Nitroguanidine.svg |
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| ImageSizeL1 = 120px |
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| ImageFileR1 = Nitroguanidine structure.png |
| ImageFileR1 = Nitroguanidine structure.png |
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| ImageSizeR1 = 100px |
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| IUPACName = 1-Nitroguanidine |
| IUPACName = 1-Nitroguanidine |
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| OtherNames = Picrite<br />NGu<br />NQ<ref>{{cite journal | last=Gao | first=Han | last2=Wang | first2=Qinghua | last3=Ke | first3=Xiang | last4=Liu | first4=Jie | last5=Hao | first5=Gazi | last6=Xiao | first6=Lei | last7=Chen | first7=Teng | last8=Jiang | first8=Wei | last9=Liu | first9=Qiao'e | title=Preparation and characterization of an ultrafine HMX/NQ co-crystal by vacuum freeze drying method | journal=RSC Adv. | volume=7 | issue=73 | date=2017 | issn=2046-2069 | doi=10.1039/C7RA06646E | pages=46229–46235| doi-access=free }}</ref> |
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| OtherNames = Picrite |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 10701 |
| ChemSpiderID = 10701 |
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| InChI = 1/CH4N4O2/c2-1(3)4-5(6)7/h(H4,2,3,4) |
| InChI = 1/CH4N4O2/c2-1(3)4-5(6)7/h(H4,2,3,4) |
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| StdInChIKey = IDCPFAYURAQKDZ-UHFFFAOYSA-N |
| StdInChIKey = IDCPFAYURAQKDZ-UHFFFAOYSA-N |
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| CASNo = 556-88-7 |
| CASNo = 556-88-7 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII = NAY6KWL67F |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 39180 |
| ChEBI = 39180 |
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| SMILES = NC(N)=N[N+]([O-])=O |
| SMILES = NC(N)=N[N+]([O-])=O |
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|Section2={{Chembox Properties |
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| Formula = CH<sub>4</sub>N<sub>4</sub>O<sub>2</sub> |
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| MolarMass = 104.07 g/mol |
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| Appearance = Colorless crystalline solid |
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| Density = 1.77 g/cm<sup>3</sup> |
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| MeltingPtC = 257 |
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| BoilingPtC = |
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| BoilingPt = 250 °C (decomp.) |
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| BoilingPt_notes = |
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| Solubility = |
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| Solubility = 3.45 g/kg (in water at 25 °C) |
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|Section4={{Chembox Explosive |
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| ShockSens = > 50 J |
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| FrictionSens => 350 N |
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| DetonationV = |
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| REFactor = 1.00 |
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|Section7={{Chembox Hazards |
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| ExternalSDS = |
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| EUIndex = Not listed |
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| AutoignitionPt = |
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| Autoignition = |
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|Section8={{Chembox Related |
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| OtherFunction = |
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| OtherFunction_label = |
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| OtherCompounds = [[Guanidine]]<br>[[Guanidine nitrate]] |
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'''Nitroguanidine''' - sometimes abbreviated '''NGu''' - is a colorless, crystalline solid that melts at 257 °C and decomposes at 254 °C. Nitroguanidine is an extremely insensitive but powerful high explosive. Wetting it with > 20 wt.-% water effects desensitization from HD 1.1 down to HD 4.1 (flammable solid).<ref>United Nations, Transport of Nitroguanidine, wetted, (UN 1336) in flexible IBCs, ST/SC/AC.10/C.3/2006/52, Geneva, 13 April 2006. Accessed at https://www.unece.org/fileadmin/DAM/trans/doc/2006/ac10c3/ST-SG-AC10-C3-2006-52e.pdf</ref> |
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Nitroguanidine is used as an energetic material, i.e., propellant or high explosive, precursor for insecticides, and for other purposes. |
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'''Nitroguanidine''' is a chemical compound. It is a colorless, crystalline solid. It melts at 232 °C and decomposes at 250 °C. It is not flammable and is an extremely low sensitivity explosive; however, its [[detonation velocity]] is high. |
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==Manufacture== |
==Manufacture== |
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Nitroguanidine is produced worldwide on a large scale starting with the reaction of [[dicyandiamide]] (DCD) with [[ammonium nitrate]] to afford the salt [[guanidinium nitrate]], which is then nitrated by treatment with concentrated sulfuric acid at low temperature.<ref name="Koch2019">{{cite journal | last=Koch | first=Ernst‐Christian | title=Insensitive High Explosives: III. Nitroguanidine – Synthesis – Structure – Spectroscopy – Sensitiveness | journal=Propellants, Explosives, Pyrotechnics | volume=44 | issue=3 | date=2019 | issn=0721-3115 | doi=10.1002/prep.201800253 | pages=267–292}}</ref> |
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Nitroguanidine is manufactured from [[guanine]], a naturally-occurring substance typically found in the excrement of bats and birds ([[guano]]). Guanine is extracted from the droppings and is then oxidized to form [[guanidine]].<ref>{{cite journal| first=A| last=Strecker| title=Untersuchungen über die chemischen Beziehungen zwischen Guanin, Xanthin, Theobromin, Caffein und Kreatinin| journal=Annalen der Chemie und Pharmacie| volume=118| pages= 151–177| year=1861| doi=10.1002/jlac.18611180203}}</ref> Guanidine is then nitrated to form nitroguanidine. The detailed process used to perform industrial-scale synthesis is considered proprietary and is not available for public release. A laboratory synthesis involves the fusion of [[sulfamic acid]] with [[urea]], followed by nitration of the formed guanidine sulfate.<ref>{{cite web |
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| url=http://www.sciencemadness.org/talk/viewthread.php?tid=8911 |
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:{{chem2|[C(NH2)3]NO3 -> (NH2)2CNNO2 + H2O}} |
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| title=Nitroguanidine: from sulphamic acid and urea| author = Axt | work= Sciencemadness Discussion Board |
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| date=August 1, 2007}}</ref> |
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The guanidinium nitrate intermediate may also be produced via the Boatright–Mackay–Roberts (BMR) process, in which molten [[urea]] is reacted with molten ammonium nitrate in the presence of [[silica gel]].<ref name="Koch2019"/><ref name="Steele1973">{{cite tech report |last1=Steele |first1=N. W. |last2=Doyle |first2=J. A. |last3=Whippen |first3=M. G. |last4=Gorton |first4=J. A. |author5=Hercules Inc. |author-link5=Hercules Inc. |date=December 1973 |title=Process Engineering Design for Manufacture of Guanidine Nitrate |publisher=[[Picatinny Arsenal]] |number=AD-772074}}</ref> However, owing to problems of reliability and safety, this process has never been commercialized despite its attractive economic features. |
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:{{chem2|2 NH2CONH2 + NH4NO3 -> [C(NH2)3]NO3 + 2 NH3 + CO2}} |
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==Uses== |
==Uses== |
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===Explosives=== |
===Explosives=== |
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Nitroguanidine has been in use since the 1930s as an ingredient in ''triple-base'' [[smokeless powder|gun propellants]] in which it reduces flame temperature, muzzle flash, and erosion of the gun barrel but preserves chamber pressure due to high nitrogen content. Its extreme insensitivity combined with low cost has made it a popular ingredient in insensitive high explosive formulations (e.g AFX-453, AFX-760, [[IMX-101]], AL-IMX-101, IMX-103, etc.).<ref>E.-C. Koch, Insensitive High Explosives: IV. Nitroguanidine - Initiation & detonation, ''Def. Tech.'' '''2019''', ''15'', 467-487.[https://www.sciencedirect.com/science/article/pii/S2214914719302168]</ref> |
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Nitroguanidine is used as an explosive [[propellant]], notably in ''triple-base'' [[smokeless powder]]. The nitroguanidine reduces the propellant's flash and flame temperature without sacrificing chamber pressure. These are typically used in large bore guns where barrel erosion and flash are particularly important. |
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Nitroguanidine's explosive decomposition is given by the following equation: |
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H<sub>4</sub>N<sub>4</sub>CO<sub>2 ''(s)''</sub> → 2 H<sub>2</sub>O<sub> ''(g)''</sub> + 2 N<sub>2 ''(g)''</sub> + C<sub> ''(s)''</sub> |
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===Pesticides=== |
===Pesticides=== |
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Nitroguanidine |
Nitroguanidine derivatives are used as [[insecticide]]s, having a comparable effect to [[nicotine]]. Derivatives include [[clothianidin]], [[dinotefuran]], [[imidacloprid]], and [[thiamethoxam]]. |
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===Biochemistry=== |
===Biochemistry=== |
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The nitrosoylated derivative nitrosoguanidine is often used to mutagenize bacterial cells for biochemical studies. |
The nitrosoylated derivative, nitrosoguanidine, is often used to mutagenize bacterial cells for biochemical studies. |
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==Structure== |
==Structure== |
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Following several decades of debate, it could be confirmed by [[Nuclear magnetic resonance spectroscopy|NMR spectroscopy]], and both [[X-ray diffraction|x-ray]] and [[neutron diffraction]] that nitroguanidine exclusively exists as the [[nitroimine]] [[tautomer]] both in solid state and solution.<ref>{{cite journal | title = Structure of nitroguanidine: nitroamine or nitroimine? New NMR evidence from nitrogen-15 labeled sample and nitrogen-15 spin coupling constants |author1=Bulusu, S. |author2=Dudley, R. L. |author3=Autera, J. R. | journal = Magnetic Resonance in Chemistry | year = 1987 | volume = 25 | issue = 3 | pages = 234–238 | doi = 10.1002/mrc.1260250311|s2cid=97416890 |url=https://zenodo.org/record/1229291 }}</ref><ref>{{cite journal | title = Structures of nitroso- and nitroguanidine x - ray crystallography and computational analysis |author1=Murmann, R. K. |author2=Glaser, Rainer |author3=Barnes, Charles L. | journal = Journal of Chemical Crystallography | year = 2005 | volume = 35 | issue = 4 | pages = 317–325 | doi = 10.1007/s10870-005-3252-y|s2cid=96090647 }}</ref><ref>S. Choi, Refinement of 2-Nitroguanidine by Neutron Powder Diffraction, ''Acta Crystallogr. B'' '''1981''', ''37'', 1955-1957.[http://scripts.iucr.org/cgi-bin/paper?S0567740881007735]</ref> |
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:[[File:Nitroguanidine tautomers.svg|left|300px]]{{clear-left}} |
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== References == |
== References == |
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[[Category:Explosive chemicals]] |
[[Category:Explosive chemicals]] |
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[[Category:Nitroamines]] |
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[[Category:Propellants]] |
[[Category:Propellants]] |
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[[da:Nitroguanidin]] |
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[[de:Nitroguanidin]] |
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[[fr:Nitroguanidine]] |
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[[lt:Nitroguanidinas]] |
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[[ja:ニトログアニジン]] |
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[[pl:Nitroguanidyna]] |