4,4'-Methylenedianiline: Difference between revisions

{{cs1 config|name-list-style=vanc}}

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 456502017

| Name = 4,4′-Methylenedianiline

| PIN = 4,4′-Methylenedianiline

| OtherNames =

4,-Diaminodiphenylmethane

4,-Methylenebisbenzenamine

''para'',''para''′-Diaminodiphenylmethane <br>

Dianilinomethane <br>

4,4′-Diphenylmethanediamine <br>

Bis(4-aminophenyl)methane

| CASNo = 101-77-9

| CASNo_Ref = {{cascite}}

| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}

| EINECS = 202-974-4

| =

| =

| ChEBI_Ref = {{ebicite|changed|EBI}}

| ChEMBL_Ref = {{ebicite|changed|EBI}}

| ChEMBL = 85728

| KEGG_Ref = {{keggcite||kegg}}

| =

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = GG5LL7OBZC

| ChemSpiderID =

| 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

| InChIKey = YBRVSVVVWCFQMG-UHFFFAOYAE

| StdInChI_Ref = {{stdinchicite|changed|chemspider}}

| StdInChI = 1S/C13H14N2/c14-12-5-1-10(2-6-12)9-11-3-7-13(15)8-4-11/h1-8H,9,14-15H2

| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}

| StdInChIKey = YBRVSVVVWCFQMG-UHFFFAOYSA-N

| MeSHName =

| RTECS = BY5425000

| = 2651}}

| C=13|H=|N=2

| Appearance =

| Odor = faint, [[amine]]-like<ref name=PGCH/>

| = 398

| RefractIndex =

| VaporPressure = 0.0000002 mmHg (20°C)<ref name=PGCH/>

}}

| Section3 = {{Chembox Hazards

| GHSPictograms = {{GHS health hazard}} {{GHS exclamation mark}} {{GHS environment}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|373|317|341|350|370|411}}<ref name="GESTIS">{{GESTIS|ZVG=26450 |CAS=101-77-9 |Name=4,4'-Diaminodiphenylmethane |Date=12 February 2021}}</ref>

| PPhrases = {{P-phrases|201|260|273|280|308+313}}<ref name=GESTIS/>

| MainHazards = potential carcinogen<ref name=PGCH>{{PGCH|0415}}</ref>

| PEL = TWA 0.010 ppm ST 0.100 ppm<ref name=PGCH/>

| FlashPtF = 374

| FlashPt_ref = <ref name=PGCH/>

| REL = Ca<ref name=PGCH/>

| IDLH = Ca [N.D.]<ref name=PGCH/>

}}

'''4,4′-Methylenedianiline''' ('''MDA''') is an organic [[Chemical compound|compound]] with the formula {{chem2|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 [[polyurethane]]s.

== Synthesis ==

In the industrial production, MDA is by reaction of formaldehyde and aniline in the presence of hydrochloric acid<ref name=industr_prodn>Data on manufacture, import, export, uses and release of 4- diaminodiphenylmethane ... http://echa.europa.eu/doc/consultations/recommendations/tech_reports/tech_rep_mda.pdf</ref>

MDA is a common monomer in the synthesis of polymer materials. These include polyamides,<ref>{{cite journal |doi=10.1021/acsomega.1c06983 |title= Direct Synthesis of Thermally Stable Semiaromatic Polyamides by Bulk Polymerization Using Aromatic Diamines and Aliphatic Dicarboxylic Acids | first1 = Taiki |last1 = Endo | first2 = Tomoya | last2 = Higashihara |journal = ACS Omega |year = 2022 |volume = 7 |issue = 10 |pages = 8753–8758|doi-access = free |pmid= 35309482 |pmc = 8928493 }}</ref> polyimides and polyimines.<ref>{{cite journal |doi=10.1021/acs.macromol.2c01595 |title= Raman Spectroscopy Reveals Phase Separation in Imine-Based Covalent Adaptable Networks |first1= S.K. |last1=Schoustra | first2 = M.H.P. | last2= De Heer Kloots | first3 = J. | last3 = Posthuma | first4 = D. | last4 = Van Doorn | first5 = J.A. | last5 = Dijksman | first6= M.M.J. |last6= Smulders |journal= Macromolecules |year= 2022 |volume= 55 |issue= 23 |pages= 10341–10355 |doi-access= free |pmid= 36530523 |pmc= 9753755 |bibcode= 2022MaMol..5510341S }}</ref> 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.<ref name=atsdr/><ref name=ECHA/> Lower quantities are used as hardeners in epoxy resins and adhesives, as well as in the production of high-performance polymers.<ref name=industr_prodn /> Additionally, hydrogenation of MDA can be performed to produce [[4,4'-Diaminodicyclohexylmethane|4,4,diaminodicyclohexylmethane]], which is also used in polymer chemistry.<ref name=Ullmannamine>{{cite encyclopedia| vauthors = Roose P, Eller K, Henkes E, Rossbacher R, Höke H |title=Amines, Aliphatic|encyclopedia=Ullmann’s Encyclopedia of Industrial Chemistry|year=2005|publisher=Wiley-VCH|place=Weinheim|doi=10.1002/14356007.a02_001|isbn=3-527-30673-0}}</ref>

MDA can also be applied as a bidentate (bridging) ligand in the formation of metal-coordination complexes.<ref>{{cite journal | title=Six transition metal–organic materials with the ditopic 4,4′-diaminodiphenylmethane ligand: Synthesis, structure characterization and luminescent properties | last1=Chisca | first1=D. |last2=Croitor|first2=L.|last3=Melnic|first3=E.|last4=Petuhov|first4=O.|last5=Kulikova|first5=O.|last6=Fonari|first6=M. S.| journal=Polyhedron|year=2020|volume=192|pages=114844|doi=10.1016/j.poly.2020.114844 }}</ref>

====

MDA is considered a potential occupational carcinogen by the [[National Institute for Occupational Safety and Health|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.<ref name=pocket>{{cite web | title = 4,4'-Methylenedianiline | url = https://www.cdc.gov/niosh/npg/npgd0415.html | work = NIOSH Pocket Guide on Chemical Hazards }}</ref>

It is suspected [[carcinogen]].<ref name=atsdr>{{cite web | url = https://wwwn.cdc.gov/TSP/ToxFAQs/ToxFAQsLanding.aspx?id=1000&tid=210 | title = ToxFAQs for 4,4'-Methylenedianiline | publisher = Agency for Toxic Substances and Disease Registry }}</ref> It is included in the "[[SVHC|substances of very high concern]]" list of the European Chemicals Agency ([[ECHA]]).<ref name=ECHA>{{cite web | url = http://echa.europa.eu/documents/10162/13640/mda_en.pdf | title = Background document for 4,4'-Diaminodiphenylmethane (MDA) | publisher = European Chemicals Agency | access-date = 2015-02-24 | archive-date = 2017-08-22 | archive-url = https://web.archive.org/web/20170822174713/https://echa.europa.eu/documents/10162/13640/mda_en.pdf | url-status = dead }}</ref> The compound was blamed in a mass poisoning in the vicinity of [[Epping, Essex|Epping]], [[Essex]], United Kingdom during 1965 during which 84 individuals were poisoned through accidental contamination of flour used to make bread.<ref name=NCBI>{{cite journal | vauthors = Kopelman H, Robertson MH, Sanders PG, Ash I | title = The Epping jaundice | journal = British Medical Journal | volume = 1 | issue = 5486 | pages = 514–6 | date = February 1966 | pmid = 5902696 | pmc = 1843808 | doi = 10.1136/bmj.1.5486.514 }}</ref>

==Related compounds==

* [[4,4'-Thiodianiline]]

* [[4,4'-Oxydianiline]]

* [[Dapsone]]

==References==

{{reflist}}

== External links ==

* International http://www.inchem.org/documents/icsc/icsc/eics1111.htm icsc1111

* {{cite web | publisher = Centers for Disease Control and Prevention | url = https://www.cdc.gov/niosh/npg/npgd0415.html | title = NIOSH Pocket Guide to Chemical Hazards }}

* {{cite web | url = http://ecb.jrc.it/DOCUMENTS/Existing-Chemicals/RISK_ASSESSMENT/REPORT/mdareport008.pdf | title = European Union Risk Assessment Report | archive-url = https://web.archive.org/web/20070317063316/http://ecb.jrc.it/DOCUMENTS/Existing-Chemicals/RISK_ASSESSMENT/REPORT/mdareport008.pdf | archive-date = 2007-03-17 }}

* Petersen, , Pedersen Memorandum for the Danish Veterinary and Food Administration on http://www.dfvf.dk/Admin/Public/DWSDownload.aspx?File=Files%2FFiler%2FF%C3%B8devaresikkerhed%2FMaterialer+og+genstande%2FPAA_from_black_nylon_cooking_utentils_2004.pdf An acute case of primary aromatic amines migrating from cooking utensils Danish Institute for Food and Veterinary Research 12 October 2004

{{DEFAULTSORT:Methylenedianiline, 4,4'-}}

[[Category:4-Aminophenyl compounds]]

[[Category:IARC Group 2B carcinogens]]

[[Category:]]