2,4-Dinitroanisole

2,4-Dinitroanisol.svg 1-Methoxy-2,4-dinitrobenzene 2,4-Dinitroanisole DNAN 119-27-7 8385 8080 204-310-9 1L0OD70295 correct EBI 84559 COC1=C(C=C(C=C1)[N+](=O)[O-])[N+](=O)[O-] InChI=1S/C7H6N2O5/c1-14-7-3-2-5(8(10)11)4-6(7)9(12)13/h2-4H,1H3 CVYZVNVPQRKDLW-UHFFFAOYSA-N 7 6 5 2 pale yellow granular crystals or needles 1.336 g/cm3 very slightly soluble 94.5 °C 02 07 08 Warning 223 302 351 201 202 264 270 281 301+312 308+313 330 405 501 2,4-Dinitroanisole (DNAN) is a low sensitivity explosive organic compound. It has an anisole (methoxybenzene) core, with two nitro groups (–NO2) attached.http://www.ntis.gov/assets/pdf/st-on-cd/ADA458880.pdf Characterisation of 2,4-Dinitroanisole: An Ingredient for use in Low Sensitivity Melt Cast Formulations Davies Phil J. Arthur Provatas 2006 DSTO-TR-1904 DSTO 12 October 2013 https://web.archive.org/web/20160304041436/http://www.ntis.gov/assets/pdf/st-on-cd/ADA458880.pdf 4 March 2016 dead dmy-all It is not explosive itself unless it is mixed with other explosive chemicals in certain ratios. It has 90% of the explosive power of TNT, is less dense, and has a higher melting point. Properties 2,4-Dinitroanisole crystallises in the monoclinic form. The unit cell has these sizes and angles: a=8.772 Å b=12.645 Å c=15.429 Å 81.89°, cell volume is V=1694 Å3, There are eight molecules in each unit cell, with four positions symmetric. The two asymmetric positions have the molecule bent in different ways. The methyl group can be rotated either at 5° or 13° out of the plane of the benzene ring. The ortho nitro group is rotated at 3° or 35°. The para nitro group is close to parallel with the ring plane.Nyburg S. C. Faerman, C. H. Prasad, L. Palleros, D. Nudelman, N. Structures of 2,4-dinitroanisole and 2,6-dinitroanisole Acta Crystallographica Section C 15 April 1987 43 4 686–689 10.1107/S0108270187094514 1987AcCrC..43..686N The specific heat of solid 2,4-dinitroanisole is given by Cp (Jmol−1K−1) = 0.3153 + 0.00265T (T in K). At 298.15 K. it is 219.02 Jmol−1K−1 The melting enthalpy is 20.2 kJmol−1 and solidification heat is 19.7 kJmol−1. These can differ so much as the liquid can be supercooled 22.8 °C. The initial decomposition temperature is 295 °C, and the explosion temperature is 312 °C. On explosion the adiabatic temperature rise is 4923 °C.Xing Xiaoling Zhao, Fengqi Ma, Shunnian Xu, Kangzhen Xiao, Libai Gao, Hongxu An, Ting Hu, Rongzu Specific Heat Capacity, Thermal Behavior, and Thermal Hazard of 2,4-Dinitroanisole Propellants, Explosives, Pyrotechnics 1 April 2012 37 2 179–182 10.1002/prep.201000077 Ignition temperature is 347 °C. Reactions 2,4-Dinitroanisole reacts without heat with a potassium cyanide solution to form a red coloured product via the isopurpuric acid reaction. In this cyanide is added in the meta position, and the ortho nitro group is reduced to -NHOH.Schechter Milton S. Haller, H L. Colorimetric Determination of 2,4-Dinitroanisole Industrial & Engineering Chemistry Analytical Edition 1 May 1944 16 5 325–326 10.1021/i560129a017 In alkaline conditions DNAN can be attacked at the methoxy position with nucleophiles to form Meisenheimer complexes. In these the ring develops a negative charge and another group is attached at the methoxy attachment point. So for example, sodium methoxide can produce the 6,6-dimethoxy-1,3-dinitro-1,3-cyclohexadiene anion. When heated under pressure with water and ammonia DNAN is converted to 2,4-dinitroaniline.https://www.orgsyn.org/demo.aspx?prep=cv2p0221 10.15227/orgsyn.015.0022 free 2,4-DINITROANILINE Wells F. B. F. B. Wells C. F. H. Allen amp Organic Syntheses 15 22 13 October 2013 1935 subscription With iron and acetic acid DNAN nitro groups can be reduced to amines forming 2,4-diaminoanisole.2,4-Diaminoanisole and its Salts IARC Monographs International Agency for Research on Cancer 79 629 https://monographs.iarc.fr/ENG/Monographs/vol79/mono79-21.pdf 2001 Formation 2,4-Dinitroanisole can be formed from p-nitroanisole or o-nitroanisole nitration. Also it can be formed from 1-chloro-2,4-dinitrobenzene by treatment with sodium methoxide (sodium in methanol) or sodium hydroxide with methanol. Over a period of days, alkalies will hydrolyse the ether bond to form 2,4-dinitrophenol.Murto Juhani Eero Tommila 1962 The Influence of the Solvent on Reaction Velocity XXI The reaction of 2,4-dinitrophenyl Alkyl ethers with Hydroxyl Ion in Water and in Methanol-Water and Ethanol-Water Mixtures Acta Chemica Scandinavica 16 1 63–70 10.3891/acta.chem.scand.16-0063 free Use 2,4-Dinitroanisole is used as an explosive replacing TNT. It is used in explosive mixtures such as IMX-101, IMX-104, PAX-48, PAX-21 and PAX-41 in the spider grenade. It can be melted and cast more safely. It has also been used as a dye ingredient and insecticide. Environment When mixed with soil, 2,4-dinitroanisole is modified by bacteria through the path 2-nitroso-4-nitroanisole, 2-hydroxyamino-4-nitroanisole to 2-amino-4-nitroanisole. This takes place on a time scale of a few weeks. In the human body it is converted to 2,4-dinitrophenol.Perreault Nancy N. Manno, Dominic Halasz, Annamaria Thiboutot, Sonia Ampleman, Guy Hawari, Jalal Aerobic biotransformation of 2,4-dinitroanisole in soil and soil Bacillus sp Biodegradation 1 September 2011 23 2 287–295 10.1007/s10532-011-9508-7 21881912 14789935 https://nrc-publications.canada.ca/eng/view/accepted/?id=126ea666-6fd7-48d1-923a-4d8cea0cd9e8 It was reported in 2014 that a Nocardia sp. bacterium was able to mineralize 2, 4-dinitroanisole as a sole carbon source, via well-established 2,4-dinitrophenol pathway.Fida Tekle Tafese Shannu Palamuru Gunjan Pandey Jim C. Spain 2014 Aerobic biodegradation of 2,4-dinitroanisole (DNAN) by Nocardioides sp. JS1661 Applied and Environmental Microbiology 80 24 7725–31 0099-2240 10.1128/AEM.02752-14 25281383 4249229 See also Trinitroanisole References 2 Category:Explosive chemicals Category:Nitrobenzene derivatives Category:Phenol ethers