Dinitroaniline

Dinitroanilines are a class of organic compounds 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.

Uses

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 ]}

Preparation

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

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

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
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		[5]		[6]		[7]
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

Dinitroanilines can be explosive and flammable when exposed to heat or friction.

References

1. Gerald Booth (2007). "Nitro Compounds, Aromatic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_411. ISBN   978-3527306732.
2. WO 1991001292  Method for the Preparation of Nitroanilines
3. Harry P. Schultz (1951). "2,6-Dinitroaniline". Organic Syntheses. 31: 45. doi:10.15227/orgsyn.031.0045.
4. K. P. Griffin, W. D. Peterson (1941). "1,2-Diamino-4-Nitrobenzene". Organic Syntheses. 21: 20. doi:10.15227/orgsyn.021.0020.
5. Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
6. Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
7. "3,5-Dinitroaniline". Sigma-Aldrich.
8. 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.