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Revision as of 14:57, 25 February 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,054 edits Script assisted update of identifiers from ChemSpider, CommonChemistry and FDA for the Chem/Drugbox validation project - Updated: ChEMBL.← Previous edit		Latest revision as of 22:10, 31 October 2024 edit undo152.23.89.105 (talk) Edited for clarity
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	{{DISPLAYTITLE:''o''-Phenylenediamine}}		{{DISPLAYTITLE:''o''-Phenylenediamine}}
			{{Use mdy dates|date=January 2023}}
	{{chembox
			{{Chembox
⚫	| verifiedrevid = 402510429
			| Verifiedfields = changed
			| Watchedfields = changed
		⚫	| verifiedrevid = 415872334
	| Name = ''o''-Phenylenediamine		| Name = ''o''-Phenylenediamine
	| ImageFile = o-phenylenediamine.png		| ImageFile = o-phenylenediamine.png
	| ImageSize = 120px		| ImageSize = 120px
			| ImageFileL1 = O-Phenylenediamine-from-xtal-Mercury-3D-bs.png
⚫	| IUPACName = Benzene-1,2-diamine
			| ImageSizeL1 = 125px
⚫	| OtherNames = ''o''-Phenylene diamine<br>1,2-Diaminobenzene<br>1,2-phenylenediamine
			| ImageFileR1 = O-Phenylenediamine-from-xtal-Mercury-3D-sf.png
⚫	| Reference = <ref name=dupont></ref>
			| ImageSizeR1 = 125px
⚫	| Section1 = {{Chembox Identifiers
			| ImageFile2 = 1,2-diaminobenzene sample.jpg
		⚫	| PIN = Benzene-1,2-diamine
		⚫	| OtherNames = ''o''-Phenylene diamine<br />1,2-Diaminobenzene<br />1,2-Phenylenediamine
		⚫	| Reference = <ref name=dupont>{{Cite web |url=http://www.dupont.com/specintermediates/opd.html |title=DuPont Specialty Intermediates: o-Phenylenediamine (OPD)<!-- Bot generated title --> |access-date=2006-04-25 |archive-url=https://web.archive.org/web/20080622070101/http://www.dupont.com/specintermediates/opd.html |archive-date=2008-06-22 |url-status=dead }}</ref>
		⚫	|Section1={{Chembox Identifiers
	| Abbreviations =		| Abbreviations =
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
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	| InChI = 1/C6H8N2/c7-5-3-1-2-4-6(5)8/h1-4H,7-8H2		| InChI = 1/C6H8N2/c7-5-3-1-2-4-6(5)8/h1-4H,7-8H2
	| InChIKey = GEYOCULIXLDCMW-UHFFFAOYAR		| InChIKey = GEYOCULIXLDCMW-UHFFFAOYAR
			| ChEMBL_Ref = {{ebicite|correct|EBI}}
	| ChEMBL = 70582		| ChEMBL = 70582
	| StdInChI_Ref = {{stdinchicite|correct|chemspider}}		| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
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	| CASNo_Ref = {{cascite|correct|CAS}}		| CASNo_Ref = {{cascite|correct|CAS}}
	| CASNo = 95-54-5		| CASNo = 95-54-5
	| EINECS =		| EINECS = 202-430-6
	| PubChem =		| PubChem = 7243
			| UNII_Ref = {{fdacite|changed|FDA}}
			| UNII = 8B713N8Q0F
	| SMILES = Nc1ccccc1N		| SMILES = Nc1ccccc1N
	| InChI =		| RTECS = SS7875000
	| RTECS =		| UNNumber = 1673
	| MeSHName =		| MeSHName =
			| ChEBI_Ref = {{ebicite|changed|EBI}}
	| ChEBI =		| ChEBI = 34043
	| KEGG_Ref = {{keggcite|correct|kegg}}		| KEGG_Ref = {{keggcite|correct|kegg}}
	| KEGG =		| KEGG =
			}}
	| ATCCode_prefix =
		⚫	|Section2={{Chembox Properties
	| ATCCode_suffix =
			| C=6|H=8|N=2
	| ATC_Supplemental =}}
		⚫	| MolarMass= 108.144 g·mol<sup>−1</sup>
⚫	| Section2 = {{Chembox Properties
		⚫	| Appearance = white solid
	| Formula = C<sub>6</sub>H<sub>8</sub>N<sub>2</sub>
⚫	| MolarMass = 108.1 g/mol
⚫	| Appearance =
	| Density = 1.031 g/cm<sup>3</sup>		| Density = 1.031 g/cm<sup>3</sup>
	| MeltingPtCL = 102		| MeltingPtC = 102 to 104
			| MeltingPt_notes =
	| MeltingPtCH = 104
	| Melting_notes =
	| BoilingPtC = 252		| BoilingPtC = 252
			| BoilingPt_notes = Other sources: {{convert|256|to|258|C|F K}}
	| Boiling_notes =
	| Solubility =		| Solubility = soluble in hot water
	| SolubleOther =		| SolubleOther =
	| Solvent =		| Solvent =
	| pKa =		| pKa = {{ubl
			| 0.80 (doubly protonated form; 20&nbsp;°C, H<sub>2</sub>O)
⚫	| pKb = }}
			| 4.57 (conjugate acid; 20&nbsp;°C, H<sub>2</sub>O)<ref name="CRC97">{{cite book | editor= Haynes, William M. | year = 2016 | title = CRC Handbook of Chemistry and Physics | edition = 97th | publisher = ] | isbn = 978-1498754286 | page=5–89 | title-link = CRC Handbook of Chemistry and Physics }}</ref>
⚫	| Section3 = {{Chembox Structure
			}}
		⚫	| pKb =
			| MagSus = -71.98·10<sup>−6</sup> cm<sup>3</sup>/mol
			}}
		⚫	|Section3={{Chembox Structure
	| CrystalStruct =		| CrystalStruct =
	| Coordination =		| Coordination =
	| MolShape = }}		| MolShape =
			}}
	| Section4 = {{Chembox Thermochemistry		|Section4={{Chembox Thermochemistry
	| DeltaHf =		| DeltaHf =
	| DeltaHc =		| DeltaHc =
	| Entropy =		| Entropy =
	| HeatCapacity = }}		| HeatCapacity =
			}}
	| Section5 = {{Chembox Pharmacology		|Section5={{Chembox Pharmacology
	| AdminRoutes =		| AdminRoutes =
	| Bioavail =		| Bioavail =
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	| Legal_AU =		| Legal_AU =
	| Legal_CA =		| Legal_CA =
	| PregCat =		| Pregnancy_category =
	| PregCat_AU =		| Pregnancy_AU =
	| PregCat_US = }}		| Pregnancy_US =
			}}
	| Section6 = {{Chembox Explosive		|Section6={{Chembox Explosive
	| ShockSens =		| ShockSens =
	| FrictionSens =		| FrictionSens =
	| ExplosiveV =		| DetonationV =
	| REFactor = }}		| REFactor =
			}}
	| Section7 = {{Chembox Hazards		|Section7={{Chembox Hazards
	| ExternalMSDS =		| ExternalSDS =
	| EUClass = Toxic (T); Dangerous for the environment (N)
	| EUIndex =
	| MainHazards =		| MainHazards =
			| NFPA_ref = <ref>{{cite web|url=https://pubchem.ncbi.nlm.nih.gov/source/hsdb/2893 |title= Hazardous Substances Data Bank (HSDB) : 2893 - PubChem| publisher=PubChem}}</ref>
	| NFPA-H = 2		| NFPA-H = 3
	| NFPA-F = 1		| NFPA-F = 1
	| NFPA-R = 0		| NFPA-R = 0
	| NFPA-O =		| NFPA-S =
			| GHSPictograms = {{GHS06}}{{GHS07}}{{GHS08}}{{GHS09}}
	| RPhrases =
	| SPhrases =		| GHSSignalWord = Danger
			| HPhrases = {{H-phrases|301|312|317|319|332|341|351|410}}
	| RSPhrases =
			| PPhrases = {{P-phrases|201|202|261|264|270|271|272|273|280|281|301+310|302+352|304+312|304+340|305+351+338|308+313|312|321|322|330|333+313|337+313|363|391|405|501}}
	| FlashPt =
	| Autoignition =		| FlashPtC = 156
			| AutoignitionPt =
	| ExploLimits =		| ExploLimits =
	| PEL = }}		| PEL =
			}}
	| Section8 = {{Chembox Related		|Section8={{Chembox Related
	| OtherAnions =		| OtherAnions =
	| OtherCations =		| OtherCations =
	| OtherFunctn =		| OtherFunction =
	| Function =		| OtherFunction_label =
	| OtherCpds = }}		| OtherCompounds =
			}}
	}}		}}
	'''''o''-Phenylenediamine''' is a ] with the formula C<sub>6</sub>H<sub>4</sub>(NH<sub>2</sub>)<sub>2</sub>. This ] ] is an important precursor to many ]s. It is ]ic with ] and ].		'''''o''-Phenylenediamine''' ('''OPD''') is an ] with the formula C<sub>6</sub>H<sub>4</sub>(NH<sub>2</sub>)<sub>2</sub>. This ] ] is an important precursor to many ]s. OPD is a white compound although samples appear darker owing to oxidation by air. It is ]ic with ] and ].
	==Preparation==		==Preparation==
	Most commonly 2-nitrochlorobenzene is treated with ammonia, and the resulting 2-aminonitrobenzene is then hydrogenated:<ref name=Ullmann>Robert A. Smiley “Phenylene- and Toluenediamines” in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. {{DOI|10.1002/14356007.a19_405}}</ref>		Commonly, ] is treated with ] to generate ], whose ] group is then ]:<ref name=Ullmann>{{Ullmann|doi=10.1002/14356007.a19_405|title=Phenylene- and Toluenediamines|year=2000|last1=Smiley|first1=Robert A.|isbn=3527306730}}</ref>
	:ClC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + 2 NH<sub>3</sub> → H<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + NH<sub>4</sub>Cl		:ClC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + 2 NH<sub>3</sub> → H<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + NH<sub>4</sub>Cl
⚫	:H<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + 3 H<sub>2</sub> → H<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>NH<sub>2</sub> + 2 H<sub>2</sub>O
		⚫	:H<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub> + 3 H<sub>2</sub> → H<sub>2</sub>NC<sub>6</sub>H<sub>4</sub>NH<sub>2</sub> + 2 H<sub>2</sub>O
	In the laboratory, the reduction of the nitroaniline is effected with ] powder in ethanol, followed by purification of the diamine as the hydrochloride.<ref>{{OrgSynth | author = E. L. Martin | title = ''o''-Phenylenediamine | collvol = 2 | collvolpages = 501 | prep = cv2p0501 | year = 1943}}</ref>
			In the laboratory, the reduction of the nitroaniline is effected with zinc powder in ethanol, followed by purification of the diamine as the ]. Darkened impure samples can be purified by treatment of its ] with ] and ].<ref>{{cite journal|title=''o''-Phenylenediamine |year=1939|volume=19|page=70|author=E. L. Martin|journal=Organic Syntheses|doi= 10.15227/orgsyn.019.0070}}</ref>
	==Reactions and uses==		==Reactions and uses==
			''o''-Phenylenediamine ] with ]s and ]s to give rise to various valuable products. Its reactions with ]s to produce ].<ref>{{cite journal |doi=10.15227/orgsyn.019.0012 |title=Benzimidazole |journal=Organic Syntheses |date=1939 |volume=19 |page=12|first1=E. C.|last1=Wagner |first2= W. H.|last2=Millett }}</ref> Other carboxylic acids give 2-substituted benzimidazoles. The herbicides ] and ] are made in this manner. ] is another ] produced from o-phenylenediamine.<ref name=Ullmann/> Condensation with ] gives ].<ref>{{cite journal |doi=10.15227/orgsyn.030.0056 |title=2-Mercaptobenzimidazole|journal=Organic Syntheses |date=1950 |volume=30 |page=56|first1=J. A. |last1=VanAllan|first2=B. D.|last2= Deacon }}</ref> With ], ''o''-phenylenediamine condenses to give ], a corrosion inhibitor.<ref>{{cite journal |doi=10.15227/orgsyn.020.0016 |title=1,2,3-Benzotriazole |journal=Organic Syntheses |date=1940 |volume=20 |page=16|first1=R. E.|last1=Damschroder|first2=W. D.|last2=Peterson }}</ref>
⚫	''o''-Phenylenediamine condenses with ]s and ]s to give rise to a variety of useful products. Reactions with esters affords ]s. The herbicide ] is prepared in this manner. Also, ]dione may be prepared by condensation of ''o''-phenylenediamine with ]. Condensation with xanthate esters affords mercaptoimidazoles, which are used as antioxidants in rubber products. Treatment with ] give ], a corrosion inhibitor. Condensation of subtituted ''o''-phenylenediamine with various ]s is used in the preparation of a variety of pharmaceuticals.<ref>See for example, {{cite journal | author = Renault, J. et al. | title = Heterocyclic quinones. Quinoxaline-5,6 and 5,8 diones, potential antitumoral agents | journal = Eur. J. Med. Chem. | year = 1981 | volume = 16 | pages = 545–550}}</ref>
		⚫	]dione may be prepared by condensation of ''o''-phenylenediamine with ]. Mercaptoimidazole are commonly used as ] in ] production, obtained by condensing ] ]. Condensation of substituted ''o''-phenylenediamine with ]s yields various ].<ref>See for example, {{cite journal | author = Renault, J.| title = Heterocyclic quinones. Quinoxaline-5,6 and 5,8 diones, potential antitumoral agents | journal = Eur. J. Med. Chem. | year = 1981 | volume = 16 | pages = 545–550|display-authors=etal}}</ref>
	In ], phenylenediamine is an important ligand precursor. Schiff base derivatives, such as those derived from ], are excellent chelating ligands. Oxidation of its metal-phenylenediamine complexes affords the ] derivatives, which are intensely coloured and often exist in multiple stable oxidation states.<ref>{{cite journal | author = Warren, L. F. | title = Synthesis of and Complexes Based on ''o''-Benzoquinone Diimine with Cobalt, Iron, and Ruthenium | journal = ] | year = 1977 | volume = 16 | pages = 2814–2819 | doi = 10.1021/ic50177a028}}</ref>
			OPD is a ] in ]. ] of metal-phenylenediamine complexes affords the ] derivatives.<ref>{{cite journal | doi = 10.1039/C5CS00161G| title = New Avenues for Ligand-Mediated Processes – Expanding Metal Reactivity by the Use of Redox-Active Catechol, o-Aminophenol and o-Phenylenediamine Ligands| date = 2015| last1 = Broere| first1 = Daniël L. J.| last2 = Plessius| first2 = Raoul| last3 = Van Der Vlugt| first3 = Jarl Ivar| journal = Chemical Society Reviews| volume = 44| issue = 19| pages = 6886–6915| pmid = 26148803}}</ref> OPD condenses with ] to give ].
	==Safety==		==Safety==
	With an {{LD50}} of 44 mg/L (aquatic), ''o''-phenylenediamine is about 1000 times less toxic than the ''para''-isomer. Anilines are typically handled as if they are ]. For many applications, OPD has been replaced by safer alternatives such as ].<ref>{{cite book|title=Enzyme Immunoassays: From Concept to Product Development|author=Deshpande SS|page=169|year=1996|isbn=978-0412056017|publisher=Chapman &amp; Hall|location=New York}}</ref>		With an ] of 44&nbsp;mg/L (in water), ''o''-phenylenediamine is about 1000 times less toxic than the ]. ] are typically handled as if they are ]. For many applications, OPD has been replaced by safer alternatives such as ].<ref>{{cite book|title=Enzyme Immunoassays: From Concept to Product Development|author=Deshpande SS|page=169|year=1996|isbn=978-0-412-05601-7|publisher=Chapman & Hall|location=New York}}</ref>
	==References==		==References==
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	{{DEFAULTSORT:Phenylenediamine, o-}}		{{DEFAULTSORT:Phenylenediamine, o-}}
	]		]
	]		]
	]		]
	]
	]
	]
	]
	]
	]