Dinitroaniline
Dinitroanilines are a class of organic compounds based on dinitroaniline, with the chemical formula C6H3(NO2)2NH2. Six isomers exist depending on the relative positions of the amino (NH2) and nitro (NO2) groups: 2,3-dinitroaniline, 2,4-dinitroaniline, 2,5-dinitroaniline, 2,6-dinitroaniline, 3,4-dinitroaniline, and 3,5-dinitroaniline. An organic compound with a dinitroaniline group is also said to be a dinitroaniline.
Uses
[edit]Dinitroanilines are intermediates in the preparation of various industrial chemicals including dyes and pesticides.[1] During World War I, Germany used them as Ersatz high explosives.[citation needed]
There are many dinitroaniline herbicides, beginning with trifluralin in 1964. These are all 2,6-dinitroanilines, and work by inhibiting microtubule formation, have low to moderate human toxicity, high aquatic toxicity and are usually applied pre-emergently, often to control grasses and broad-leafed weeds. They include benfluralin, butralin, chlornidine, dinitramine, dipropalin, ethalfluralin, fluchloralin, isopropalin, methalpropalin, nitralin, nitrofor, oryzalin, pendimethalin, prodiamine, profluralin, and trifluralin. Trifluralin, pendimethalin are the most widely commercially used.
Preparation
[edit]2,4-Dinitroaniline can be prepared by reaction of 1-chloro-2,4-dinitrobenzene with ammonia or by acid hydrolysis of 2,4-dinitroacetanilide.[2][1]
2,6-Dinitroaniline can be prepared in a multistep process involving nitration and sulfonation of chlorobenzene.[3]
Reactions
[edit]A characteristic reaction of the dinitroanilines is their reduction, first to the diamine, then to the triamine, and finally to the triaminocyclohexanes. Selective conversion to the diamine can be achieved using sulfide as a reducing agent.[4] Hydrogenation over nickel or palladium catalysts gives triaminobenzenes. Still further hydrogenation (of the ring) affords the triaminocyclohexanes.
Examples
[edit]| Dinitroanilines | ||||||
| Chemical name | 2,3-Dinitroaniline | 2,4-Dinitroaniline | 2,5-Dinitroaniline | 2,6-Dinitroaniline | 3,4-Dinitroaniline | 3,5-Dinitroaniline |
| Alternate name | 2,3-Dinitro-1-aminobenzene 2,3-Dinitrophenylamine 2,3-Dinitraniline |
2,4-Dinitro-1-aminobenzene 2,4-Dinitrophenylamine 2,4-Dinitraniline |
2,5-Dinitro-1-aminobenzene 2,5-Dinitrophenylamine 2,5-Dinitraniline |
2,6-Dinitro-1-aminobenzene 2,6-Dinitrophenylamine 2,6-Dinitraniline |
3,4-Dinitro-1-aminobenzene 3,4-Dinitrophenylamine 3,4-Dinitraniline |
3,5-Dinitro-1-aminobenzene 3,5-Dinitrophenylamine 3,5-Dinitraniline |
| Chemical structure | 
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| CAS Number | 602-03-9 | 97-02-9 | 619-18-1 | 606-22-4 | 610-41-3 | 618-87-1 |
| 26471-56-7 (isomeric mixture) | ||||||
| PubChem | CID 136400 from PubChem | CID 7321 from PubChem | CID 123081 from PubChem | CID 69070 from PubChem | CID 136407 from PubChem | CID 12068 from PubChem |
| Chemical formula | C6H5N3O4 | |||||
| Molar mass | 183.12 g/mol | |||||
| Appearance | colorless to yellowish combustible powder | |||||
| Melting point | 187.8 °C[5] | 136 °C (decomp.)[6] | 154–158 °C | 160–162 °C[7] | ||
| Density | 1.646 g/cm (50 °C)[8] | 1.61 g/cm[5] | 1.736 g/cm | 1.601 g/cm (50 °C)[8] | ||
| Solubility | soluble in water (1–2 g/L at 20 °C) | |||||
| GHS hazard pictograms |
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| H- and P-phrases | H300, H310, H330, H373, H411 | H302, H311, H332, H373 | H301, H311, H331, H373 | H301, H311, H331, H373 | ||
| P260, P264, P273, P280, P284, P301+P310 | P260, P301+P310, P320, P361, P405, P501 | P261, P280, P301+P310, P311 | P261, P280, P301+P310, P311 | |||
Safety
[edit]Dinitroanilines can be explosive and flammable when exposed to heat or friction.
References
[edit]- ^ a b Gerald Booth (2007). "Nitro Compounds, Aromatic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_411. ISBN 978-3527306732.
- ^ WO 1991001292 Method for the Preparation of Nitroanilines
- ^ Harry P. Schultz (1951). "2,6-Dinitroaniline". Organic Syntheses. 31: 45. doi:10.15227/orgsyn.031.0045.
- ^ K. P. Griffin, W. D. Peterson (1941). "1,2-Diamino-4-Nitrobenzene". Organic Syntheses. 21: 20. doi:10.15227/orgsyn.021.0020.
- ^ a b c Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
- ^ a b Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
- ^ a b "3,5-Dinitroaniline". Sigma-Aldrich.
- ^ a b C. L. Yaws (2008). Thermophysical properties of chemicals and hydrocarbons (1st ed.). New York: William Andrew Inc. p. 221. ISBN 978-0-815-51596-8.
