Revision as of 17:22, 16 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 456500519 of page 2-Mercaptopyridine for the Chem/Drugbox validation project (updated: 'ChEMBL'). |
Latest revision as of 11:46, 29 December 2024 edit 80.134.170.207 (talk)No edit summary |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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{{chembox |
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| verifiedrevid = 456499589 |
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| verifiedrevid = 477213812 |
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| ImageFile = Thiol-Thione.png |
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| ImageFile = Thiol-Thione.png |
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| Name = 2-Mercaptopyridine |
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| ImageClass = skin-invert-image |
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| OtherNames = 2-thiopyridine; 2-thiopyridone; pyrid-2-thione; 2-pyridyl mercaptan; 2-pyridinethiol; 2-pyridinethione |
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| ImageSize = 240 |
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| Section1 = {{Chembox Identifiers |
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| ImageFileL1 = 2-Mercaptopyridine-(thiol)-3D-balls.png |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ImageAltL1 = 2-Mercaptopyridine molecule (thiol form) |
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| ImageFileR1 = 2-Mercaptopyridine-(thione)-3D-balls.png |
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| ImageAltR1 = 2-Mercaptopyridine molecule (thione form) |
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| Name = 2-Mercaptopyridine |
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| PIN = Pyridine-2-thiol |
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| OtherNames = 2-Thiopyridine<br />2-Thiopyridone<br />Pyrid-2-thione<br />2-Pyridyl mercaptan<br />2-Pyridinethiol<br />2-Pyridinethione |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 2005897 |
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| ChemSpiderID = 2005897 |
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| ChEMBL_Ref = {{ebicite|changed|EBI}} |
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| ChEMBL_Ref = {{ebicite|changed|EBI}} |
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| ChEMBL = <!-- blanked - oldvalue: 1235541 --> |
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| ChEMBL = 1235541 |
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| InChI = 1/C5H5NS/c7-5-3-1-2-4-6-5/h1-4H,(H,6,7) |
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| InChI = 1/C5H5NS/c7-5-3-1-2-4-6-5/h1-4H,(H,6,7) |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| DrugBank_Ref = {{drugbankcite|correct|drugbank}} |
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| DrugBank_Ref = {{drugbankcite|correct|drugbank}} |
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| DrugBank = DB03329 |
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| DrugBank = DB03329 |
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| EINECS = 220-131-9 |
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| PubChem = 2723698 |
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| Beilstein = 105787 |
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| SMILES = S=C1/C=C\C=C/N1 |
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| SMILES = S=C1/C=C\C=C/N1 |
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| InChIKey = WHMDPDGBKYUEMW-UHFFFAOYAE |
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| InChIKey = WHMDPDGBKYUEMW-UHFFFAOYAE |
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| StdInChIKey = WHMDPDGBKYUEMW-UHFFFAOYSA-N |
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| StdInChIKey = WHMDPDGBKYUEMW-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 2637-34-5 |
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| CASNo = 73018-10-7 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = EE982KT952 |
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| Section2 = {{Chembox Properties |
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| C=5|H=5|N=1|S=1 |
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| Appearance = yellow crystalline powder |
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| Solubility = 50 g/L |
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| MeltingPt = 128-130°C (400-403 K) |
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| Section7 = {{Chembox Hazards |
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|Section2={{Chembox Properties |
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| C=5 | H=5 | N=1 | S=1 |
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| Appearance = yellow crystalline powder |
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| Solubility = 50 g/L |
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| MeltingPtC = 128 to 130 |
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| MeltingPt_notes = }} |
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| GHSPictograms = {{GHS07}} |
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| GHSSignalWord = Warning |
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| HPhrases = {{H-phrases|315|319|335}} |
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| PPhrases = {{P-phrases|261|264|271|280|302+352|304+340|305+351+338|312|321|332+313|337+313|362|403+233|405|501}} |
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'''2-Mercaptopyridine''' is an ] with the formula HSC<sub>5</sub>H<sub>4</sub>N. This yellow crystalline solid is a derivative of ]. The compound and its derivatives serve primarily as acylating agents. A few of 2-mercaptopyridine's other uses include serving as a ] for ]s and ]s as well as forming a selective ]. 2-Mercaptopyridine oxidizes to ].<ref name=adams>{{cite book | doi = 10.1002/047084289X.rp286.pub3 | chapter = 2-Pyridinethiol | year = 2007 | last1 = Adams | first1 = Edward J. | title = Encyclopedia of Reagents for Organic Synthesis | last2 = Skrydstrup | first2 = Troels | last3 = Lindsay | first3 = Karl B. | last4 = Skrydstrup | first4 = Troels | last5 = Lindsay | first5 = Karl B.| isbn = 978-0471936237 }}</ref> |
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== Preparation == |
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2-Mercaptopyridine was originally synthesized in 1931 by heating 2-chloropyridine with ].<ref>{{cite journal | doi = 10.1002/jlac.19314870107 | title = Mercaptane und Sulfosäuren des Pyridins. XII. Mitteilung über Derivate des Pyridins | year = 1931 | last1 = Räth | first1 = C. | last2 = Binz | first2 = A. | last3 = Räth | first3 = C. | journal = Justus Liebig's Annalen der Chemie | volume = 487 | pages = 105–119}}</ref> |
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:ClC<sub>5</sub>H<sub>4</sub>N + Ca(SH)<sub>2</sub> → HSC<sub>5</sub>H<sub>4</sub>N + Ca(SH)Cl |
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A more convenient route to 2-mercaptopyridine is the reaction of ] and ] in ethanol and aqueous ].<ref>{{cite journal | doi = 10.1039/JR9580003610 | title = 721. Tautomeric pyridines. Part I. Pyrid-2- and -4-thione | year = 1958 | last1 = Jones | first1 = R. A. | last2 = Katritzky | first2 = A. R. | journal = Journal of the Chemical Society (Resumed) | pages = 3610}}</ref> |
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2-Mercaptopyridine derivatives can also be generated from precursors lacking preformed pyridine rings. It arises for example in the condensation of α,β-unsaturated ketones, ], and 4-methylbenzenethiol under ]. The reaction is conducted with a base catalyst.<ref>{{cite journal | doi = 10.1002/jhet.161 | title = An efficient and direct synthesis of 2-thiopyridinesviamicrowave-assisted three-component reaction | year = 2009 | last1 = Wang | first1 = Xing-Han | last2 = Cao | first2 = Xu-Dong | last3 = Tu | first3 = Shu-Jiang | last4 = Zhang | first4 = Xiao-Hong | last5 = Hao | first5 = Wen-Juan | last6 = Yan | first6 = Shu | last7 = Wu | first7 = Shan-Shan | last8 = Han | first8 = Zheng-Guo | last9 = Shi | first9 = Feng | journal = Journal of Heterocyclic Chemistry | volume = 46 | pages = 886 | issue = 5}}</ref> |
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== Structure and properties == |
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Similar in nature to 2-hydroxypyridine, 2-mercaptopyridine converts to the ] (or more accurately ]) ]. The preferred form is dependent on temperature, concentration, and solvent. The thiol is favored at lower temperatures, lower concentrations, and in less polar solvents.<ref>{{cite journal | doi = 10.1021/jo0263768 | title = 2-Pyridinethiol/2-Pyridinethione Tautomeric Equilibrium. A Comparative Experimental and Computational Study | pmid = 12467429 | year = 2002 | last1 = Moran | first1 = Damian | last2 = Sukcharoenphon | first2 = Kengkaj | last3 = Puchta | first3 = Ralph | last4 = Schaefer | first4 = Henry F. | last5 = Schleyer | first5 = Paul v. R. | last6 = Hoff | first6 = Carl D. | journal = The Journal of Organic Chemistry | volume = 67 | issue = 25 | pages = 9061–9}}</ref><ref name=beak>{{cite journal | doi = 10.1021/jo01296a002 | title = Displacement of protomeric equilibriums by self-association: hydroxypyridine-pyridone and mercaptopyridine-thiopyridone isomer pairs | year = 1980 | last1 = Beak | first1 = Peter | last2 = Covington | first2 = Johnny B. | last3 = Smith | first3 = Stanley G. | last4 = White | first4 = J. Matthew | last5 = Zeigler | first5 = John M. | journal = The Journal of Organic Chemistry | volume = 45 | pages = 1354 | issue = 8}}</ref> 2-Mercaptopyridine is favored in dilute solutions and in solvents capable of hydrogen bonding. These solvents will compete with other 2-mercaptopyridines to prevent self association.<ref name=beak/> |
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The ] for this reaction between mutual 2-mercaptopyridines is described below. The ratio is of monosulfide to disulfide in chloroform.<ref name=beak/> |
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:K<sub>association</sub> = (2.7±0.5)x10<sup>3</sup> |
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==Reactions== |
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2-Mercaptopyridine oxidizes to 2,2'-dipyridyl disulfide. As amines are good catalysts for the oxidation of thiols to disulfides, this process is autocatalytic. |
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2-Mercaptopyridine can also be prepared by hydride reduction of 2,2'-dipyridyl disulfide. |
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:C<sub>5</sub>H<sub>4</sub>NSSC<sub>5</sub>H<sub>4</sub>N + 2H → 2HSC<sub>5</sub>H<sub>4</sub>N |
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== Main reactions == |
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2-Mercaptopyridine and the disulfide are chelating ligands. 2-mercaptopyridine forms the indium(III) complex In(PyS)3 complexes in ].<ref>{{cite journal | doi = 10.1016/j.jhazmat.2007.10.052 | pmid = 18054158 | title = Effect of various chelating agents on supercritical carbon dioxide extraction of indium(III) ions from acidic aqueous solution | year = 2008 | last1 = Chou | first1 = Wei-Lung | last2 = Yang | first2 = Kai-Chiang | journal = Journal of Hazardous Materials | volume = 154 | issue = 1–3 | pages = 498–505}}</ref> 2-Mercaptopyridine may also be used to coat porous media in order to purify plasmid DNA of impurities such as RNA and proteins at relatively quick timescales to similar methods.<ref>{{cite journal | doi =10.1002/app.24417 | title =Biporous polymeric microspheres coupled with mercaptopyridine for rapid chromatographic purification of plasmid DNA | year =2007 | last1 =Li | first1 =Yuan | last2 =Dong | first2 =Xiao-Yan | last3 =Sun | first3 =Yan | journal =Journal of Applied Polymer Science | volume =104 | pages =2205 | issue =4}}</ref> 2-Mercaptopyridine is also used acylate phenols, amines, and carboxylic acids.<ref name=adams/> |
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Another application lies in metal-free catalysis: 2-mercaptopyridine can be used as a ] for ] C-H ] of ]. The particular pattern of ] and ] allows to cleave boron-carbons bonds and then form a new boron-carbon bond by ] mediated ].<ref>{{Cite journal |last=Rochette |first=Étienne |last2=Desrosiers |first2=Vincent |last3=Soltani |first3=Yashar |last4=Fontaine |first4=Frédéric-Georges |date=2019-08-07 |title=Isodesmic C–H Borylation: Perspectives and Proof of Concept of Transfer Borylation Catalysis |url=https://pubs.acs.org/doi/10.1021/jacs.9b04305 |journal=Journal of the American Chemical Society |language=en |volume=141 |issue=31 |pages=12305–12311 |doi=10.1021/jacs.9b04305 |issn=0002-7863 |pmid=31283206 |s2cid=195844973}}</ref> |
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== References == |
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{{reflist|30em}} |
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{{DEFAULTSORT:Mercaptopyridine, 2-}} |
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] |
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] |
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] |