Dimethylaniline structure, properties, synthesis, uses

5156
Charles McCarthy
Dimethylaniline structure, properties, synthesis, uses

The dimethylaniline or dimethylphenylamine is an organic compound that is formed by a benzene ring with an amino group substituted with two methyl groups. Its chemical formula is C8HelevenN.

It is also known as N, N-dimethylaniline, as it is a derivative of aniline in which the hydrogens of the amino group are replaced by two methyl groups. This makes it a tertiary amine.

Structure of N, N-dimethylaniline. No machine-readable author provided. Mysid assumed (based on copyright claims). [CC BY-SA 3.0 (http://creativecommons.org/licenses/by-sa/3.0/)]. Source: Wikipedia Commons.

N, N-Dimethylaniline is a pale yellow to brown oily liquid with the characteristic odor of amines. It is a basic compound and reacts with nitrous acid to form a nitroso compound. When exposed to air it turns brown.

It is used in the manufacture of colorants for paints. It is also used as an activator for polymerization catalysts and in mixtures used for image recording. In turn, it has been used in the synthesis of antibacterial or antibiotic compounds such as certain penicillin-derived cephalosporins. N, N-dimethylaniline is also a base to obtain other chemical compounds.

It is a combustible liquid and when heated to decomposition it emits toxic fumes. Acute human exposure to N, N-dimethylaniline can lead to negative effects such as headaches, dizziness, decreased oxygen in the blood and bluish discoloration of the skin, among other symptoms..

Article index

  • 1 Structure
  • 2 Nomenclature
  • 3 Properties
    • 3.1 Physical state
    • 3.2 Molecular weight
    • 3.3 Melting point
    • 3.4 Boiling point
    • 3.5 Flash point
    • 3.6 Vapor pressure
    • 3.7 Autoignition temperature
    • 3.8 Density
    • 3.9 Refractive index
    • 3.10 Solubility
    • 3.11 Basicity constant
    • 3.12 Chemical properties
    • 3.13 Risks
  • 4 Synthesis
  • 5 Uses
    • 5.1 In the dye industry
    • 5.2 In the manufacture of photocurable mixtures
    • 5.3 In fiberglass manufacturing
    • 5.4 In the synthesis of antibiotics
    • 5.5 In catalysis of chemical reactions
    • 5.6 In various applications
  • 6 References

Structure

The following figure shows the spatial structure of N, N-dimethylaniline:

Spatial structure of N, N-dimethylaniline. Aeschylus [Public domain]. Source: Wikipedia Commons.

Nomenclature

- N, N-dimethylaniline

- Dimethylaniline

- Dimethylphenylamine

- N, N-dimethylbenzenamine

N, N is placed in the name to indicate that the two methyl groups (-CH3) are attached to nitrogen (N) and not to the benzene ring.

Properties

Physical state

Pale yellow to brown liquid.

Molecular weight

121.18 g / mol.

Melting point

3 ºC.

Boiling point

194 ºC.

Flashpoint

63 ºC (closed cup method). It is the minimum temperature at which it gives off vapors that can ignite if a flame is passed over it..

Vapor pressure

0.70 mm Hg at 25 ºC.

Autoignition temperature

371 ° C. It is the minimum temperature at which it burns spontaneously at atmospheric pressure, without an external source of heat or flame..

Density

0.9537 g / cm3 at 20 ºC.

Refractive index

1.5582 at 20 ºC.

Solubility

In water it is very slightly soluble: 1,454 mg / L at 25 ºC.

Freely soluble in alcohol, chloroform and ether. Soluble in acetone, benzene, and oxygenated and chlorinated solvents.

Basicity constant

Kb 11.7, which indicates the ease with which this compound accepts a hydrogen ion from water.

Chemical properties

N, N-dimethylaniline is a basic compound. Reacts with acetic acid to give N, N-dimethylanilinium acetate.

The group -N (CH3)two of N, N-dimethylaniline is a powerful activator of aromatic substitution at the position in order to of the benzene ring.

Reacts with sodium nitrite (NaNOtwo) in the presence of hydrochloric acid (HCl) forming p-nitroso-N, N-dimethylaniline. Also with nitrous acid it generates the same nitrosated compound in position in order to.

When N, N-dimethylaniline reacts with benzenediazonium chloride, in a mildly acidic medium, an azo compound of the type Ar-N = N-Ar 'is produced, where Ar is an aromatic group. Molecules with azo groups are strongly colored compounds.

Risks

When heated to decomposition it emits highly toxic aniline vapors and nitrogen oxides NOx.

It is a combustible liquid.

It decomposes slowly in water exposed to sunlight. Does not biodegrade.

It volatilizes from wet soil and water surfaces. It does not evaporate from dry soil and moves through it. Does not accumulate in fish.

It can be absorbed through the skin. It is also rapidly absorbed by inhalation. Human exposure to N, N-dimethylaniline can decrease the oxygen content of the blood resulting in a bluish color of the skin..

Acute inhalation of this compound can lead to negative effects on the central nervous system and the circulatory system, with headaches, cyanosis and dizziness..

Synthesis

It can be produced in several ways:

- From aniline and methanol under pressure in the presence of acid catalysts, such as HtwoSW4. Sulfate is obtained which is converted to the base by adding sodium hydroxide.

Synthesis of N, N-dimethylaniline. Werderkli - Own work. Public Domain. Source: Wikipedia Commons.

- Passing an aniline vapor and dimethyl ether over activated aluminum oxide.

- Heating a mixture of aniline, anilinium chloride and methanol under pressure and then distilling.

Applications

In the dye industry

Due to the property of reacting with benzenediazonium chloride to form azo compounds, N, N-dimethylaniline is used as an intermediate in the manufacture of colorants..

It is a raw material in the synthesis of the dyes of the methyl violet family.

Methyl violet dye. No machine-readable author provided. Shaddack assumed (based on copyright claims). [Public domain]. Source: Wikipedia Commons

In the manufacture of photocurable mixtures

N, N-dimethylaniline is part of a photocurable mixture that undergoes the curing reaction as a result of high sensitivity to visible or near infrared light, so that it can be used for image recording or photoresist materials..

N, N-dimethylaniline is one of the components of the mixture that cause sensitization to wavelengths, in such a way that the composition is cured with light of low energy wavelengths.

It is estimated that the role of N, N-dimethylaniline is likely to suppress the radical polymerization termination reaction caused by oxygen..

In fiberglass manufacturing

N, N-dimethylaniline is used as a catalytic hardener in certain fiberglass resins.

In the synthesis of antibiotics

N, N-dimethylaniline participates in the synthesis of cephalosporins starting from penicillins.

Penicillin sulfoxides are converted to cepheme derivatives when heated in the presence of basic catalysts such as N, N-dimethylaniline.

These cephalosporins exhibit antibacterial activity against gram-positive and gram-negative organisms, as well as against penicillin-resistant staphylococci..

Antibiotics Alina Kuptsova. Source: Pixabay.

However, it should be noted that N, N-dimethylaniline remains in these antibiotics as an impurity..

In catalysis of chemical reactions

N, N-dimethylaniline is used in the activation of olefin polymerization catalysts.

It is used together with pentafluorophenol (C6F5OH) with which it forms the ionic compound [HNPhMetwo]+[H (OC6F5)two]-. This ionic compound has one or two active protons that activate the catalyst based on a transition metal.

Additionally, in the manufacture of resins, N, N-dimethylaniline has been used as a polymerization accelerator or promoter for the formation of polyester resins. Its action generates a rapid curing of the resin.

In various applications

It is used in the synthesis of other chemical compounds, for example, vanillin, and as an intermediate for pharmaceutical drugs.

It is also used as a solvent, as an alkylating agent, as a stabilizer, and to make paints and coatings..

References

  1. S. National Library of Medicine. (2019). N, N-Dimethylaniline. Recovered from: pubchem.ncbi.nlm.nih.gov
  2. Morrison, R.T. and Boyd, R.N. (2002). Organic Chemistry. 6th Edition. Prentice-Hall.
  3. (2000). N, N-Dimethylaniline. Summary. Recovered from epa.gov
  4. Zanaboni, P. (1966). Unsaturated polyester resinous composition having high stability and rapid curing at low temperatures using a mixture of dimethylaniline, triethanolamine and diphenylamine. U.S. Patent No. 3,236,915. February 22, 1966.
  5. Nudelman, A. and McCaully, R.J. (1977). Process for the rearrangement of penicillins to cephalosporins and intermediate compouns thereof. U.S. Patent No. 4,010,156. March 1, 1977.
  6. Kouji Inaishi (2001). Photocurable composition. U.S. Patent No. 6,171,759 B1. January 9, 2001.
  7. Luo, L. et al. (2012). Ionic bronsted acid. U.S. Patent No. 8,088,952 B2. January 3, 2012.

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