4,4'-Methylenedianiline

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Contents

4,4′-Methylenedianiline
4-4'-methylenedianiline.svg
Names
Preferred IUPAC name
4,4′-Methylenedianiline
Other names
MDA

dadpm
4,4′-Diaminodiphenylmethane
4,4′-Methylenebisbenzenamine
para,para′-Diaminodiphenylmethane
Dianilinomethane
4,4′-Diphenylmethanediamine

Bis(4-aminophenyl)methane
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.002.705 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 202-974-4
KEGG
PubChem CID
RTECS number
  • BY5425000
UNII
UN number 2651
  • InChI=1S/C13H14N2/c14-12-5-1-10(2-6-12)9-11-3-7-13(15)8-4-11/h1-8H,9,14-15H2 X mark.svgN
    Key: YBRVSVVVWCFQMG-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C13H14N2/c14-12-5-1-10(2-6-12)9-11-3-7-13(15)8-4-11/h1-8H,9,14-15H2
    Key: YBRVSVVVWCFQMG-UHFFFAOYAE
  • c1cc(N)ccc1Cc2ccc(N)cc2
Properties
C13H14N2
Molar mass 198.269 g·mol−1
AppearanceColorless solid
Odor faint, amine-like [1]
Density 1.05 g/cm3 (100°C)
Melting point 89 °C (192 °F; 362 K)
Boiling point 398 to 399 °C (748 to 750 °F; 671 to 672 K)
0.125 g/100 ml (20 °C)
Vapor pressure 0.0000002 mmHg (20°C) [1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
potential carcinogen [1]
GHS labelling:
GHS-pictogram-silhouette.svg GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Danger
H317, H341, H350, H370, H373, H411 [2]
P201, P260, P273, P280, P308+P313 [2]
Flash point 190 °C; 374 °F; 463 K [1]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 0.010 ppm ST 0.100 ppm [1]
REL (Recommended)
Ca [1]
IDLH (Immediate danger)
Ca [N.D.] [1]
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 ?)

4,4′-Methylenedianiline (MDA) is an organic compound with the formula CH2(C6H4NH2)2. It is a colorless solid, although commercial samples can appear yellow or brown. It is produced on an industrial scale, mainly as a precursor to polyurethanes.

Synthesis and applications

In the industrial production, MDA is produced by reaction of formaldehyde and aniline in the presence of hydrochloric acid. [3]

MDA is a common monomer in the synthesis of polymer materials. These include polyamides, [4] polyimides and polyimines. [5] MDA is also used extensively as a precursor to Methylene diphenyl diisocyanate (MDI). Here, MDA is treated with phosgene to produce MDI. MDI, in turn, is a precursor to many polyurethane foams. [6] [7] Lower quantities are used as hardeners in epoxy resins and adhesives, as well as in the production of high-performance polymers. [3] Additionally, hydrogenation of MDA can be performed to produce 4,4,diaminodicyclohexylmethane, which is also used in polymer chemistry. [8]

MDA can also be applied as a bidentate (bridging) ligand in the formation of metal-coordination complexes. [9]

Safety

MDA is considered a potential occupational carcinogen by the US National Institute for Occupational Safety and Health. The Occupational Safety and Health Administration has set a permissible exposure limit at 0.01 ppm over an eight-hour time-weighted average, and a short-term exposure limit at 0.1 ppm. [10]

It is suspected carcinogen. [6] It is included in the "substances of very high concern" list of the European Chemicals Agency (ECHA). [7] The compound was blamed in a mass poisoning in the vicinity of Epping, Essex, United Kingdom during 1965 during which 84 individuals were poisoned through accidental contamination of flour used to make bread. [11]

Related Research Articles

<span class="mw-page-title-main">Isocyanate</span> Chemical group (–N=C=O)

In organic chemistry, isocyanate is the functional group with the formula R−N=C=O. Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyanates are manufactured for the production of polyurethanes, a class of polymers.

<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.

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

1,2-Dibromoethane, also known as ethylene dibromide (EDB), is an organobromine compound with the chemical formula C
2H
4Br
2. Although trace amounts occur naturally in the ocean, where it is probably formed by algae and kelp, substantial amounts are produced industrially. It is a dense colorless liquid with a faint, sweet odor, detectable at 10 ppm. It is a widely used and sometimes-controversial fumigant. The combustion of 1,2-dibromoethane produces hydrogen bromide gas that is significantly corrosive.

<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">Cyclohexanol</span> Chemical compound

Cyclohexanol is the organic compound with the formula HOCH(CH2)5. The molecule is related to cyclohexane by replacement of one hydrogen atom by a hydroxyl group. This compound exists as a deliquescent colorless solid with a camphor-like odor, which, when very pure, melts near room temperature. Millions of tonnes are produced annually, mainly as a precursor to nylon.

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

Toluene diisocyanate (TDI) is an organic compound with the formula CH3C6H3(NCO)2. Two of the six possible isomers are commercially important: 2,4-TDI (CAS: 584-84-9) and 2,6-TDI (CAS: 91-08-7). 2,4-TDI is produced in the pure state, but TDI is often marketed as 80/20 and 65/35 mixtures of the 2,4 and 2,6 isomers respectively. It is produced on a large scale, accounting for 34.1% of the global isocyanate market in 2000, second only to MDI. Approximately 1.4 billion kilograms were produced in 2000. All isomers of TDI are colorless, although commercial samples can appear yellow.

<span class="mw-page-title-main">Methylene diphenyl diisocyanate</span> Aromatic diisocyanate

Methylene diphenyl diisocyanate (MDI) is an aromatic diisocyanate. Three isomers are common, varying by the positions of the isocyanate groups around the rings: 2,2′-MDI, 2,4′-MDI, and 4,4′-MDI. The 4,4′ isomer is most widely used, and is also known as 4,4′-diphenylmethane diisocyanate. This isomer is also known as Pure MDI. MDI reacts with polyols in the manufacture of polyurethane. It is the most produced diisocyanate, accounting for 61.3% of the global market in the year 2000.

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

Ethylenediamine (abbreviated as en when a ligand) is the organic compound with the formula C2H4(NH2)2. This colorless liquid with an ammonia-like odor is a basic amine. It is a widely used building block in chemical synthesis, with approximately 500,000 tonnes produced in 1998. Ethylenediamine is the first member of the so-called polyethylene amines.

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

Benzidine (trivial name), also called 1,1'-biphenyl-4,4'-diamine (systematic name), is an organic compound with the formula (C6H4NH2)2. It is an aromatic amine. It is a component of a test for cyanide. Related derivatives are used in the production of dyes. Benzidine has been linked to bladder and pancreatic cancer.

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

Hexamethylene diisocyanate (HDI) is the organic compound with the formula (CH2)6(NCO)2. It is classified as an diisocyanate. It is a colorless liquid. It has sometimes been called HMDI but this not usually done to avoid confusion with Hydrogenated MDI.

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

Crotonaldehyde is a chemical compound with the formula CH3CH=CHCHO. The compound is usually sold as a mixture of the E- and Z-isomers, which differ with respect to the relative position of the methyl and formyl groups. The E-isomer is more common (data given in Table is for the E-isomer). This lachrymatory liquid is moderately soluble in water and miscible in organic solvents. As an unsaturated aldehyde, crotonaldehyde is a versatile intermediate in organic synthesis. It occurs in a variety of foodstuffs, e.g. soybean oils.

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

Nitroethane is an organic compound having the chemical formula C2H5NO2. Similar in many regards to nitromethane, nitroethane is an oily liquid at standard temperature and pressure. Pure nitroethane is colorless and has a fruity odor.

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

Glycidol is an organic compound with the formula HOCH2CHOCH2. The molecule contains both epoxide and alcohol functional groups. Being simple to make and bifunctional, it has a variety of industrial uses. The compound is a colorless, slightly viscous liquid that is slightly unstable and is not often encountered in pure form.

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

Cyclohexylamine is an organic compound, belonging to the aliphatic amine class. It is a colorless liquid, although, like many amines, samples are often colored due to contaminants. It has a fishy odor and is miscible with water. Like other amines, it is a weak base, compared to strong bases such as NaOH, but it is a stronger base than its aromatic analog, aniline.

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

Ethyl acrylate is an organic compound with the formula CH2CHCO2CH2CH3. It is the ethyl ester of acrylic acid. It is a colourless liquid with a characteristic acrid odor. It is mainly produced for paints, textiles, and non-woven fibers. It is also a reagent in the synthesis of various pharmaceutical intermediates.

<i>n</i>-Butylamine Chemical compound

n-Butylamine is an organic compound (specifically, an amine) with the formula CH3(CH2)3NH2. This colourless liquid is one of the four isomeric amines of butane, the others being sec-butylamine, tert-butylamine, and isobutylamine. It is a liquid having the fishy, ammonia-like odor common to amines. The liquid acquires a yellow color upon storage in air. It is soluble in all organic solvents. Its vapours are heavier than air and it produces toxic oxides of nitrogen during combustion.

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

Isopropylamine is an organic compound, an amine. It is a hygroscopic colorless liquid with ammonia-like odor. It is miscible with water and flammable. It is a valuable intermediate in chemical industry.

4,4′-Methylenebis(2-chloroaniline) is a substance used as a curing agent in polyurethane production. MOCA is an aromatic amine which is structurally similar to benzidine, a known human bladder carcinogen. MOCA has been shown to cause hepatomas in mice and rats, lung and mammary carcinomas in rats and bladder cancer in dogs. It is a proven human carcinogen standing on the WHO List of IARC Group 1 carcinogens, with a current threshold limit value of 0.01 ppm in the industrial atmosphere. Animal studies have resulted in tumor growth in the liver, lung, and bladder.

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

2-Nitropropane (2-NP) is an organic compound with the formula (CH3)2CH(NO2). It is used as a solvent. It is a colorless liquid and is classified as a nitro compound.

4,4'-Diaminodicyclohexylmethane is the name for organic compounds with the formula CH2(C6H10NH2)2. It is classified as a diamine. In the epoxy industry it is often referred to as PACM, short for para-diamino­dicyclohexyl­methane. It is used as a curing agent for epoxy resins It finds particular use in epoxy flooring. Another use is to produce diisocyanates, which are precursors to polyurethanes. The mixture is a colorless solid, but typical samples are yellowish and oily. The compound is produced as a mixture of three isomers by the hydrogenation of methylenedianiline. These isomers are, in decreasing order of their yield from the hydrogenation, trans-trans, cis-trans, and a small amount of cis-cis.

References

  1. 1 2 3 4 5 6 7 NIOSH Pocket Guide to Chemical Hazards. "#0415". National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 Record of 4,4'-Diaminodiphenylmethane in the GESTIS Substance Database of the Institute for Occupational Safety and Health, accessed on 12 February 2021.
  3. 1 2 "Data on manufacture, import, export, uses and release of 4-4' diaminodiphenylmethane" (PDF). Archived from the original (PDF) on 2011-10-01.
  4. ↑ Endo T, Higashihara T (2022). "Direct Synthesis of Thermally Stable Semiaromatic Polyamides by Bulk Polymerization Using Aromatic Diamines and Aliphatic Dicarboxylic Acids". ACS Omega. 7 (10): 8753–8758. doi: 10.1021/acsomega.1c06983 . PMC   8928493 . PMID   35309482.
  5. ↑ Schoustra S, De Heer Kloots M, Posthuma J, Van Doorn D, Dijksman J, Smulders M (2022). "Raman Spectroscopy Reveals Phase Separation in Imine-Based Covalent Adaptable Networks". Macromolecules. 55 (23): 10341–10355. Bibcode:2022MaMol..5510341S. doi: 10.1021/acs.macromol.2c01595 . PMC   9753755 . PMID   36530523.
  6. 1 2 "ToxFAQs for 4,4'-Methylenedianiline". Agency for Toxic Substances and Disease Registry.
  7. 1 2 "Background document for 4,4'-Diaminodiphenylmethane (MDA)" (PDF). European Chemicals Agency. Archived from the original (PDF) on 2017-08-22. Retrieved 2015-02-24.
  8. ↑ Roose P, Eller K, Henkes E, Rossbacher R, Höke H (2005). "Amines, Aliphatic". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a02_001. ISBN   3-527-30673-0.
  9. ↑ Chisca D, Croitor L, Melnic E, Petuhov O, Kulikova O, Fonari MS (2020). "Six transition metal–organic materials with the ditopic 4,4′-diaminodiphenylmethane ligand: Synthesis, structure characterization and luminescent properties". Polyhedron. 192: 114844. doi:10.1016/j.poly.2020.114844.
  10. ↑ "4,4'-Methylenedianiline". NIOSH Pocket Guide on Chemical Hazards.
  11. ↑ Kopelman H, Robertson MH, Sanders PG, Ash I (February 1966). "The Epping jaundice". British Medical Journal. 1 (5486): 514–6. doi:10.1136/bmj.1.5486.514. PMC   1843808 . PMID   5902696.
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