4-Nitrochlorobenzene

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4-nitrochlorobenzene
4-chloronitrobenzene.png
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Names
Preferred IUPAC name
1-Chloro-4-nitrobenzene
Other names
4-Chloro-1-nitrobenzene
4-Chloronitrobenzene
p-Nitrochlorobenzene
PNCBO
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.002.554 OOjs UI icon edit-ltr-progressive.svg
KEGG
PubChem CID
UNII
  • InChI=1S/C6H4ClNO2/c7-5-1-3-6(4-2-5)8(9)10/h1-4H X mark.svgN
    Key: CZGCEKJOLUNIFY-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C6H4ClNO2/c7-5-1-3-6(4-2-5)8(9)10/h1-4H
    Key: CZGCEKJOLUNIFY-UHFFFAOYAO
  • C1=CC(=CC=C1[N+](=O)[O-])Cl
Properties
C6H4ClNO2
Molar mass 157.55 g·mol−1
AppearanceLight yellow solid
Odor sweet [1]
Density 1.52 g/cm3 (20 °C)
Melting point 83.6 °C (182.5 °F; 356.8 K)
Boiling point 242.0 °C (467.6 °F; 515.1 K)
Insoluble
Solubility in other solventsSoluble in toluene, ether, acetone, hot ethanol
Vapor pressure 0.2 mmHg (30°C) [1]
Hazards
Flash point 12 °C (54 °F; 285 K)
Lethal dose or concentration (LD, LC):
812 mg/kg (rat, oral)
1414 mg/kg (mouse, oral)
440 mg/kg (mouse, oral)
420 mg/kg (rat, oral) [1]
164 mg/m3 (cat, 7 hr) [1]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 mg/m3 [skin] [1]
REL (Recommended)
Ca [1]
IDLH (Immediate danger)
Ca [100 mg/m3] [1]
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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4-Nitrochlorobenzene is the organic compound with the formula ClC6H4NO2. It is a pale yellow solid. 4-Nitrochlorobenzene is a common intermediate in the production of a number of industrially useful compounds, including antioxidants commonly found in rubber. Other isomers with the formula ClC6H4NO2 include 2-nitrochlorobenzene and 3-nitrochlorobenzene.

Contents

Preparation and reactions

4-Nitrochlorobenzene is prepared industrially by nitration of chlorobenzene:

ClC6H5 + HNO3 → ClC6H4NO2 + H2O

This reaction affords both the 2- and the 4-nitro derivatives, in about a 1:2 ratio. These isomers are separated by a combination of crystallization and distillation. [2] 4-Nitrochlorobenzene was originally prepared by the nitration of 4-bromochlorobenzene by Holleman and coworkers. [3]

The chloride substituent in 4-nitrochlorobenzene is more labile than in chlorobenzene. For example, it is readily displaced by sulfide nucleophiles, leading the way to 4-nitrothiophenol. [4] In another example, 4-nitrochlorobenzene is a favored substrate for cross-coupling reactions. [5]

Applications

4-Nitrochlorobenzene is an intermediate in the preparation of a variety of derivatives. Nitration gives 2,4-dinitrochlorobenzene, and 3,4-dichloronitrobenzene. Reduction with iron metal gives 4-chloroaniline. The electron-withdrawing nature of the appended nitro-group makes the benzene ring especially susceptible to nucleophilic aromatic substitution, unlike related chlorobenzene. Thus, the strong nucleophiles hydroxide, methoxide, fluoride, and amide displace chloride to give respectively 4-nitrophenol, 4-nitroanisole, 4-fluoronitrobenzene, and 4-nitroaniline. [2] [6]

Another use of 4-nitrochlorobenzene is its condensation with aniline to produce 4-nitrodiphenylamine. Reductive alkylation of the nitro group affords secondary aryl amines, which are useful antioxidants for rubber.

4-Nitrochlorobenzene is the precursor to the anti-leprosy drug Dapsone (4-[(4-aminobenzene)sulfonyl]aniline). Dapsone.svg
4-Nitrochlorobenzene is the precursor to the anti-leprosy drug Dapsone (4-[(4-aminobenzene)sulfonyl]aniline).

Safety

The U.S. National Institute for Occupational Safety and Health considers 4-nitrochlorobenzene as a potential occupational carcinogen. [7] The Occupational Safety and Health Administration set a permissible exposure limit of 1 mg/m3 The American Conference of Governmental Industrial Hygienists recommends an airborne exposure limit of 0.64 mg/m3 over a time-weighted average of eight hours. [8] [9]

Related Research Articles

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

1,4-Dichlorobenzene (1,4-DCB, p-DCB, or para-dichlorobenzene, sometimes abbreviated as PDCB or para) is an aryl chloride and isomer of dichlorobenzene with the formula C6H4Cl2. This colorless solid has a strong odor. The molecule consists of a benzene ring with two chlorine atoms (replacing hydrogen atoms) on opposing sites of the ring.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. Haloarenes are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<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">Chlorobenzene</span> Aromatic organochlorine compound

Chlorobenzene (abbreviated PhCl) is an aryl chloride and the simplest of the chlorobenzenes, consisting of a benzene ring substituted with one chlorine atom. Its chemical formula is C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals.

<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, where the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring in phenol 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.

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

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 (empirical) or P4S10 (molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.

Chlorotoluenes are aryl chlorides based on toluene in which at least one aromatic hydrogen atom is replaced with a chlorine atom. They have the general formula C7H8–nCln, where n = 1–5 is the number of chlorine atoms.

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

Disulfur dichloride is the inorganic compound of sulfur and chlorine with the formula S2Cl2. It is an amber oily liquid.

<span class="mw-page-title-main">1,2-Dichlorobenzene</span> Chemical compound

1,2-Dichlorobenzene, or orthodichlorobenzene (ODCB), is an aryl chloride and isomer of dichlorobenzene with the formula C6H4Cl2. This colourless liquid is poorly soluble in water but miscible with most organic solvents. It is a derivative of benzene, consisting of two adjacent chlorine atoms.

1,2,4-Trichlorobenzene is an organochlorine compound, one of three isomers of trichlorobenzene. It is a derivative of benzene with three chloride substituents. It is a colorless liquid used as a solvent for a variety of compounds and materials.

<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">4-Nitroaniline</span> Chemical compound

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.

4-Chloroaniline is an organochlorine compound with the formula ClC6H4NH2. This pale yellow solid is one of the three isomers of chloroaniline.

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

o-Anisidine (2-anisidine) is an organic compound with the formula CH3OC6H4NH2. A colorless liquid, commercial samples can appear yellow owing to air oxidation. It is one of three isomers of the methoxy-containing aniline derivative.

4-Nitrotoluene or para-nitrotoluene is an organic compound with the formula CH3C6H4NO2. It is a pale yellow solid. It is one of three isomers of nitrotoluene.

3-Nitrotoluene or meta-nitrotoluene is an organic compound with the formula CH3C6H4NO2. It is one of three isomers of nitrotoluene. A yellow liquid, it is used in the manufacture of meta-toluidine, which is an intermediate in the production of various dyes.

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

2-Nitrochlorobenzene is an organic compound with the formula ClC6H4NO2. It is one of three isomeric nitrochlorobenzenes. It is a yellow crystalline solid that is important as a precursor to other compounds due to its two functional groups.

2-Nitrotoluene or ortho-nitrotoluene is an organic compound with the formula CH3C6H4NO2. It is pale yellow liquid that crystallizes in two forms, called α (−9.27 °C) and β (−3.17 °C). It is mainly a precursor to o-toluidine, which is an intermediate in the production of various dyes.

<span class="mw-page-title-main">3-Nitrochlorobenzene</span> Chemical compound

3-Nitrochlorobenzene is an organic compound with the formula C6H4ClNO2. It is a yellow crystalline solid that is important as a precursor to other compounds due to the two reactive sites present on the molecule.

<span class="mw-page-title-main">4-Nitrobiphenyl</span> Chemical compound

4-Nitrobiphenyl is an organic compound with the formula C6H5−C6H4NO2. It is one of three isomers of nitrobiphenyl and probably the most widely used. It is a precursor to the antioxidant 4-aminobiphenyl. 4-Nitrobiphenyl is readily prepared by nitration of biphenyl. It can also be prepared by cross-coupling reactions.

References

  1. 1 2 3 4 5 6 7 NIOSH Pocket Guide to Chemical Hazards. "#0452". National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 3 Gerald Booth (2007). "Nitro Compounds, Aromatic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_411. ISBN   978-3527306732.
  3. ↑ "The nitration of mixed dihalogen benzenes" Recueil des Travaux Chimiques des Pays-Bas et de la Belgique. Amsterdam, 1915; pp. 204-235.
  4. ↑ Price, Charles C.; Stacy, Gardner W. (1946). "P-Nitrophenyl Disulfide, p-Nitrophenyl Sulfide and p-Nitrothiophenol1". Journal of the American Chemical Society. 68 (3): 498–500. Bibcode:1946JAChS..68..498P. doi:10.1021/ja01207a042.
  5. ↑ Wolfe, John P.; Singer, Robert A.; Yang, Bryant H.; Buchwald, Stephen L. (1999). "Highly Active Palladium Catalysts for Suzuki Coupling Reactions". Journal of the American Chemical Society. 121 (41): 9550–9561. Bibcode:1999JAChS.121.9550W. doi:10.1021/ja992130h.
  6. ↑ Brewster, Ray Q.; Groening, Theodore (1934). "p-Nitrodiphenyl Ether". Organic Syntheses. 14: 66. doi:10.15227/orgsyn.014.0066.
  7. ↑ CDC - Immediately Dangerous to Life or Health Concentrations (IDLH): p-nitrochlorobenzene
  8. ↑ CDC - NIOSH Pocket Guide to Chemical Hazards
  9. ↑ New Jersey Department of Health and Senior Services - Hazardous Substance Fact Sheet
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