Trinitromethane

Structural formula
General
Surname	Trinitromethane
other names	Nitroform
Molecular formula	CHN 3 O 6
Brief description	colorless solid (below the melting point) pungent smelling oil (as a liquid)
External identifiers / databases
CAS number 517-25-9 EC number 208-236-8 ECHA InfoCard 100.007.489 PubChem 10602 Wikidata Q410296
properties
Molar mass	151.04 g mol −1
Physical state	firmly
density	1.806 g cm −3
Melting point	25.35 ° C
boiling point	48 ° C (17 torr)
solubility	easily soluble in water
Refractive index	1.4451 (24 ° C)
safety instructions
GHS hazard labeling no classification available
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Trinitromethane is an unstable nitro derivative of methane and thus a nitroalkane . The compound is the triple-substituted representative of the series of nitromethanes with nitromethane , dinitromethane , trinitromethane and tetranitromethane .

Extraction and presentation

Trinitromethane was first produced in 1857 in the form of its ammonium salt by Leon Nikolajewitsch Schischkow . In 1918, a synthesis was developed through the combined oxidation and nitration of ethyne with nitric acid , which allowed industrial production. The two reactants are reacted in a tubular reactor using the countercurrent principle. It can also be obtained in the laboratory by hydrolysis of tetranitromethane under mildly basic conditions. It can also be produced by reacting nitric acid with isopropyl alcohol . The ammonium salt is formed by the action of water or alcohol on trinitroacetonitrile .

properties

Trinitromethane is a strong acid. The colorless free acid is unstable, the intensely yellow anion (NO ₂ ) ₃ C ^- stable in aqueous solution. Two tautomeric structures can be formulated for trinitromethane . The equilibrium is almost entirely on the side of the CH-acidic structure. Quantum chemical calculations show a difference in free energy of 33.0 kJ · mol ⁻¹ to the N-OH-acidic structure. The ¹ H-NMR spectrum shows only a single signal at 7.52 ppm for the CH function. In the nitromethane series, this is the largest shift compared with methane with 0.33 ppm, nitromethane with 4.28 ppm and dintromethane with 6.10 ppm.

use

Trinitromethane itself cannot be used as an explosive substance. However, it serves as the starting substance for the manufacture of explosives and fuels. The reaction with formaldehyde gives trinitroethanol , from which the more explosive compounds di- (2,2,2-trinitroethyl) -urea and di- (2,2,2-trinitroethyl) -nitramine can be derived.

safety instructions

Trinitromethane explodes violently when heated rapidly. Solutions with a water content of less than 55% by mass can also decompose explosively.

Individual evidence

1. ↑ ^{a b} Trinitromethane (Chemyq)
2. ↑ ^{a b c d e} Josef Köhler, Rudolf Meyer, Axel Homburg: Explosivstoffe. 10th edition. Wiley-VCH, Weinheim 2008, ISBN 978-3-527-32009-7 .
3. ↑ ^{a b} Schoedel, H .; Dienelt, R .; Bock, H .: Trinitromethane . In: Acta Crystallographica C . 50, No. 11, 1994, pp. 1790-1792. doi : 10.1107 / S0108270194002131 .
4. ↑ David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Physical Constants of Organic Compounds, pp. 3-510.
5. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
6. ↑ KJP Orton: BP 125,000 (1918)
7. ↑ Orton, KJP; McKie, PV: XXXVI. — The action of nitric acid on unsaturated hydrocarbons. The action of nitric acid on acetylene . In: Journal of the Chemical Society . 117, 1920, pp. 283-297. doi : 10.1039 / CT9201700283 .
8. ↑ ^{a b c} Wetterholm, A .: Production of trinitromethane on an industrial scale . In: Tetrahedron . 19, Supplement 1, 1963, pp. 155-163. doi : 10.1016 / S0040-4020 (63) 80052-6 .
9. ↑ Gakh, AA; Bryan, JC; Burnett, MN; Bonnesen, PV: Synthesis and structural analysis of some trinitromethanide salts . In: Journal of Molecular Structure . 520, No. 1-3, 2000, pp. 221-228. doi : 10.1016 / S0022-2860 (99) 00333-6 .
10. ↑ ^{a b} Production of trinitromethane .
11. ↑ ^{a b} Richard Escales; Nitro explosives, p. 200, ISBN 978-3-8330-0114-7 .
12. ↑ Shechter, H .; Cates, HL Jr .: Addition Reactions of Trinitromethane and α, β-Unsaturated Ethers . In: Journal of Organic Chemistry . 26, No. 1, 1961, pp. 51-53. doi : 10.1021 / jo01060a010 .
13. ↑ Novikov, SS; Slovetskii, VI; Shevelev, SA; Fainzilberg, AA: Spectrophotometric Determination of the Dissociation Constants of Aliphatic Nitro Compounds . In: Russian Chemical Bulletin . 11, No. 4, 1962, pp. 552-559. doi : 10.1007 / BF00904751 .
14. ^ Brand, H .; Liebman, JF; Schulz, A .: Cyano-, Nitro- and Nitrosomethane Derivatives: Structures and Gas-Phase Acidities . In: European Journal of Organic Chemistry . 2008, No. 27, 2008, pp. 4665-4675. doi : 10.1002 / ejoc.200800583 .
15. ↑ ^{a b} Hofmann, W .; Stefaniak, L .; Urbanski, T .; Witanowski, M .: Proton Magnetic Resonance Study of Nitroalkanes . In: Journal of the American Chemical Society . 86, No. 4, 1964, pp. 554-558. doi : 10.1021 / ja01058a005 .
16. ↑ Gregory R. Fulmer, Alexander JM Miller, Nathaniel H. Sherden, Hugo E. Gottlieb, Abraham Nudelman, Brian M. Stoltz, John E. Bercaw, Karen I. Goldberg: NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics , and Gases in Deuterated Solvents Relevant to the Organometallic Chemist . In: Organometallics . tape 29 , 2010, p. 2176–2179 , doi : 10.1021 / om100106e (English).