4-Nitroaniline

Last updated
4-Nitroaniline
P-Nitroanilin.svg
4-Nitroaniline-3D-balls.png
P-nitroanilin.jpg
Names
Preferred IUPAC name
4-Nitroaniline
Systematic IUPAC name
4-Nitrobenzenamine
Other names
p-Nitroaniline
1-Amino-4-nitrobenzene
p-Nitrophenylamine
Identifiers
3D model (JSmol)
508690
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.002.555 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 202-810-1
27331
KEGG
PubChem CID
RTECS number
  • BY7000000
UNII
UN number 1661
  • InChI=1S/C6H6N2O2/c7-5-1-3-6(4-2-5)8(9)10/h1-4H,7H2 X mark.svgN
    Key: TYMLOMAKGOJONV-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C6H6N2O2/c7-5-1-3-6(4-2-5)8(9)10/h1-4H,7H2
    Key: TYMLOMAKGOJONV-UHFFFAOYAW
  • c1cc(ccc1N)N(=O)=O
Properties
C6H6N2O2
Molar mass 138.12 g/mol
Appearanceyellow or brown powder
Odor faint, ammonia-like
Density 1.437 g/ml, solid
Melting point 146 to 149 °C (295 to 300 °F; 419 to 422 K) (lit.)
Boiling point 332 °C (630 °F; 605 K)
0.8 mg/ml at 18.5 °C (IPCS)
Vapor pressure 0.00002 mmHg (20°C) [1]
-66.43·10−6 cm3/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg
Warning
H301, H311, H331, H373, H412
P260, P261, P264, P270, P271, P273, P280, P301+P310, P302+P352, P304+P340, P311, P312, P314, P321, P322, P330, P361, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
1
0
Flash point 199 °C (390 °F; 472 K)
Lethal dose or concentration (LD, LC):
3249 mg/kg (rat, oral)
750 mg/kg (rat, oral)
450 mg/kg (guinea pig, oral)
810 mg/kg (mouse, oral) [2]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 6 mg/m3 (1 ppm) [skin] [1]
REL (Recommended)
TWA 3 mg/m3 [skin] [1]
IDLH (Immediate danger)
300 mg/m3 [1]
Safety data sheet (SDS) JT Baker
Related compounds
Related compounds
2-Nitroaniline, 3-Nitroaniline
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

4-Nitroaniline, p-nitroaniline or 1-amino-4-nitrobenzene is an organic compound with the formula C6H6N2O2. A yellow solid, it is one of three isomers of nitroaniline. It is an intermediate in the production of dyes, antioxidants, pharmaceuticals, gasoline, gum inhibitors, poultry medicines, and as a corrosion inhibitor. [3]

Contents

Synthesis

4-Nitroaniline is produced industrially via the amination of 4-nitrochlorobenzene: [3]

ClC6H4NO2 + 2 NH3 → H2NC6H4NO2 + NH4Cl

Below is a laboratory synthesis of 4-nitroaniline from aniline. The key step in this reaction sequence is an electrophilic aromatic substitution to install the nitro group para to the amino group. The amino group can be easily protonated and become a meta director. Therefore, a protection of the acetyl group is required. After this reaction, a separation must be performed to remove 2-nitroaniline, which is also formed in a small amount during the reaction. [4]
Synthesis of nitroaniline.svg

Applications

4-Nitroaniline is mainly consumed industrially as a precursor to p-phenylenediamine, an important dye component. The reduction is effected using iron metal and by catalytic hydrogenation. [3]

It is a starting material for the synthesis of Para Red, the first azo dye: [5]

Synthesis of Para Red Synthesis Para Red.svg
Synthesis of Para Red

It is also a precursor to 2,6-dichloro-4-nitroaniline, also used in dyes.

Laboratory use

Nitroaniline undergoes diazotization, which allows access to 1,4-dinitrobenzene [6] and nitrophenylarsonic acid. [7] With phosgene, it converts to 4-nitrophenylisocyanate. [8] [9]

Carbon snake demonstration

When heated with sulfuric acid, it dehydrates and polymerizes explosively into a rigid foam. [10]

In Carbon snake demo, paranitroaniline can be used instead of sugar, if the experiment is allowed to proceed under an obligatory fumehood. [11] With this method the reaction phase prior to the black snake's appearance is longer, but once complete, the black snake itself rises from the container very rapidly. [12] This reaction may cause an explosion if too much sulfuric acid is used. [13]

Toxicity

The compound is toxic by way of inhalation, ingestion, and absorption, and should be handled with care. Its LD50 in rats is 750.0 mg/kg when administered orally. 4-Nitroaniline is particularly harmful to all aquatic organisms, and can cause long-term damage to the environment if released as a pollutant. [14]

See also

Related Research Articles

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Dimethylaniline</span> Chemical compound

N,N-Dimethylaniline (DMA) is an organic chemical compound, a substituted derivative of aniline. It is a tertiary amine, featuring a dimethylamino group attached to a phenyl group. This oily liquid is colourless when pure, but commercial samples are often yellow. It is an important precursor to dyes such as crystal violet.

Mesitylene or 1,3,5-trimethylbenzene is a derivative of benzene with three methyl substituents positioned symmetrically around the ring. The other two isomeric trimethylbenzenes are 1,2,4-trimethylbenzene (pseudocumene) and 1,2,3-trimethylbenzene (hemimellitene). All three compounds have the formula C6H3(CH3)3, which is commonly abbreviated C6H3Me3. Mesitylene is a colorless liquid with sweet aromatic odor. It is a component of coal tar, which is its traditional source. It is a precursor to diverse fine chemicals. The mesityl group (Mes) is a substituent with the formula C6H2Me3 and is found in various other compounds.

<span class="mw-page-title-main">Nitrobenzene</span> Chemical compound

Nitrobenzene is an aromatic nitro compound and the simplest of the nitrobenzenes, with the chemical formula C6H5NO2. It is a water-insoluble pale yellow oil with an almond-like odor. It freezes to give greenish-yellow crystals. It is produced on a large scale from benzene as a precursor to aniline. In the laboratory, it is occasionally used as a solvent, especially for electrophilic reagents.

<span class="mw-page-title-main">Nitration</span> Chemical reaction which adds a nitro (–NO₂) group onto a molecule

In organic chemistry, nitration is a general class of chemical processes for the introduction of a nitro group into an organic compound. The term also is applied incorrectly to the different process of forming nitrate esters between alcohols and nitric acid. The difference between the resulting molecular structures of nitro compounds and nitrates is that the nitrogen atom in nitro compounds is directly bonded to a non-oxygen atom, whereas in nitrate esters, the nitrogen is bonded to an oxygen atom that in turn usually is bonded to a carbon atom.

<span class="mw-page-title-main">Nitro compound</span> Organic compound containing an −NO₂ group

In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups. The nitro group is one of the most common explosophores used globally. The nitro group is also strongly electron-withdrawing. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid.

Cyclohexene is a hydrocarbon with the formula (CH2)4C2H2. It is an example of a cycloalkene. At room temperature, cyclohexene is a colorless liquid with a sharp odor. It has few practical applications.

In organic chemistry, an azo coupling is an reaction between a diazonium compound and another aromatic compound that produces an azo compound. In this electrophilic aromatic substitution reaction, the aryldiazonium cation is the electrophile, and the activated carbon, serves as a nucleophile. Classical coupling agents are phenols and naphthols. Usually the diazonium reagent attacks at the para position of the coupling agent. When the para position is occupied, coupling occurs at a ortho position, albeit at a slower rate.

<span class="mw-page-title-main">Sodium sulfide</span> Chemical compound

Sodium sulfide is a chemical compound with the formula Na2S, or more commonly its hydrate Na2S·9H2O. Both the anhydrous and the hydrated salts in pure crystalline form are colorless solids, although technical grades of sodium sulfide are generally yellow to brick red owing to the presence of polysulfides and commonly supplied as a crystalline mass, in flake form, or as a fused solid. They are water-soluble, giving strongly alkaline solutions. When exposed to moisture, Na2S immediately hydrates to give sodium hydrosulfide.

<span class="mw-page-title-main">Cyanamide</span> Chemical compound featuring a nitrile group attached to an amino group

Cyanamide is an organic compound with the formula CN2H2. This white solid is widely used in agriculture and the production of pharmaceuticals and other organic compounds. It is also used as an alcohol-deterrent drug. The molecule features a nitrile group attached to an amino group. Derivatives of this compound are also referred to as cyanamides, the most common being calcium cyanamide (CaCN2).

<i>o</i>-Phenylenediamine Chemical compound

o-Phenylenediamine (OPD) is an organic compound with the formula C6H4(NH2)2. This aromatic diamine is an important precursor to many heterocyclic compounds. OPD is a white compound although samples appear darker owing to oxidation by air. It is isomeric with m-phenylenediamine and p-phenylenediamine.

<span class="mw-page-title-main">Malononitrile</span> Organic compound with formula CH2(CN)2

Malononitrile is an organic compound nitrile with the formula CH2(CN)2. It is a colorless or white solid, although aged samples appear yellow or even brown. It is a widely used building block in organic synthesis.

<span class="mw-page-title-main">1,4-Benzoquinone</span> Chemical compound

1,4-Benzoquinone, commonly known as para-quinone, is a chemical compound with the formula C6H4O2. In a pure state, it forms bright-yellow crystals with a characteristic irritating odor, resembling that of chlorine, bleach, and hot plastic or formaldehyde. This six-membered ring compound is the oxidized derivative of 1,4-hydroquinone. The molecule is multifunctional: it exhibits properties of a ketone, being able to form oximes; an oxidant, forming the dihydroxy derivative; and an alkene, undergoing addition reactions, especially those typical for α,β-unsaturated ketones. 1,4-Benzoquinone is sensitive toward both strong mineral acids and alkali, which cause condensation and decomposition of the compound.

<span class="mw-page-title-main">Thiophenol</span> Chemical compound

Thiophenol is an organosulfur compound with the formula C6H5SH, sometimes abbreviated as PhSH. This foul-smelling colorless liquid is the simplest aromatic thiol. The chemical structures of thiophenol and its derivatives are analogous to phenols. An exception is the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring is replaced by a sulfur atom. The prefix thio- implies a sulfur-containing compound and when used before a root word name for a compound which would normally contain an oxygen atom, in the case of 'thiol' that the alcohol oxygen atom is replaced by a sulfur atom.

<i>tert</i>-Butyllithium Chemical compound

tert-Butyllithium is a chemical compound with the formula (CH3)3CLi. As an organolithium compound, it has applications in organic synthesis since it is a strong base, capable of deprotonating many carbon molecules, including benzene. tert-Butyllithium is available commercially as solutions in hydrocarbons (such as pentane); it is not usually prepared in the laboratory.

The reduction of nitro compounds are chemical reactions of wide interest in organic chemistry. The conversion can be effected by many reagents. The nitro group was one of the first functional groups to be reduced. Alkyl and aryl nitro compounds behave differently. Most useful is the reduction of aryl nitro compounds.

<span class="mw-page-title-main">2-Nitroaniline</span> Chemical compound

2-Nitroaniline is an organic compound with the formula H2NC6H4NO2. It is a derivative of aniline, carrying a nitro functional group in position 2. It is mainly used as a precursor to o-phenylenediamine.

<span class="mw-page-title-main">2,4-Dinitrochlorobenzene</span> Chemical compound

2,4-Dinitrochlorobenzene (DNCB) is an organic compound with the chemical formula (O2N)2C6H3Cl. It is a yellow solid that is soluble in organic solvents. It is an important intermediate for the industrial production of other compounds.

In organic chemistry, thiocarboxylic acids or carbothioic acids are organosulfur compounds related to carboxylic acids by replacement of one of the oxygen atoms with a sulfur atom. Two tautomers are possible: a thione form and a thiol form. These are sometimes also referred to as "carbothioic O-acid" and "carbothioic S-acid" respectively. Of these the thiol form is most common.

2,4-Dinitroaniline is a chemical compound with a formula of C6H5N3O4. It is used as an explosive and as a reagent to detect and characterize aldehydes and ketones.

References

  1. 1 2 3 4 NIOSH Pocket Guide to Chemical Hazards. "#0449". National Institute for Occupational Safety and Health (NIOSH).
  2. "p-Nitroaniline". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 3 Booth, Gerald (2003-03-11). "Nitro Compounds, Aromatic". In Wiley-VCH (ed.). Ullmann's Encyclopedia of Industrial Chemistry (1 ed.). Wiley. doi:10.1002/14356007.a17_411. ISBN   978-3-527-30385-4.]
  4. Mohrig, J.R.; Morrill, T.C.; Hammond, C.N.; Neckers, D.C. (1997). "Synthesis 5: Synthesis of the Dye Para Red from Aniline". Experimental Organic Chemistry. New York, NY: Freeman. pp. 456–467. Archived from the original on 2020-09-15. Retrieved 2007-07-18.
  5. Williamson, Kenneth L. (2002). Macroscale and Microscale Organic Experiments, Fourth Edition . Houghton-Mifflin. ISBN   0-618-19702-8.
  6. Starkey, E. B. (1939). "p-DINITROBENZENE". Organic Syntheses. 19: 40. doi:10.15227/orgsyn.019.0040.
  7. Ruddy, A. Wayne; Starkey, Edgar B. (1946). "p-Nitrophenylarsonic Acid". Organic Syntheses. 26: 60. doi:10.15227/orgsyn.026.0060.
  8. Shriner, R. L.; Horne, W. H.; Cox, R. F. B. (1934). "p-NITROPHENYL ISOCYANATE". Organic Syntheses. 14: 72. doi:10.15227/orgsyn.014.0072.
  9. Sandin, R. B.; Drake, W. V.; Leger, Frank (1932). "2,6-Diiodo-p-Nitroaniline". Organic Syntheses. 12: 28. doi:10.15227/orgsyn.012.0028.
  10. Poshkus, A. C.; Parker, J. A. (1970). "Studies on nitroaniline–sulfuric acid compositions: Aphrogenic pyrostats". Journal of Applied Polymer Science. 14 (8): 2049–2064. doi:10.1002/app.1970.070140813.
  11. Summerlin, Lee R.; Ealy, James L. (1988). "Experiment 100: Dehydration of p-Nitroaniline: Sanke and Puff". Chemical Demonstrations: A Sourcebook for Teachers Volume 1 (2nd ed.). American Chemical Society. p. 171. ISBN   978-0-841-21481-1.
  12. "Carbon Snake: demonstrating the dehydration power of concentrated sulfuric acid". communities.acs.org. 2013-06-06. Retrieved 2022-01-31.
  13. Making a carbon snake with P-Nitroaniline, 7 April 2014, retrieved 2022-01-31
  14. "4-Nitroaniline". St. Louis, Missouri: Sigma-Aldrich. December 18, 2020.