Tetrapropylammonium perruthenate: Difference between revisions

|Verifiedfields = changed

|Watchedfields = changed

|verifiedrevid =

| = Tetrapropylammonium perruthenate

|IUPACName = Tetrapropylammonium perruthenate

|Section1={{Chembox Identifiers

|Abbreviations = TPAP<br>TPAPR

|CASNo_Ref = {{cascite|correct|??}}

|CASNo = 114615-82-6

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

|UNII = Y4N78L8V1T

|PubChem =

|PubChem_Comment = incorrect structure

|SMILES = CCC[N+](CCC)(CCC)CCC.O=[Ru](=O)([O-])=O

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID = 21170134

|InChI = 1/C12H28N.4O.Ru/c1-5-9-13(10-6-2,11-7-3)12-8-4;;;;;/h5-12H2,1-4H3;;;;;/q+1;;;;-1;/rC12H28N.O4Ru/c1-5-9-13(10-6-2,11-7-3)12-8-4;1-5(2,3)4/h5-12H2,1-4H3;/q+1;-1

|InChIKey = NQSIKKSFBQCBSI-DQAXOFGLAB

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

|StdInChI = 1S/C12H28N.4O.Ru/c1-5-9-13(10-6-2,11-7-3)12-8-4;;;;;/h5-12H2,1-4H3;;;;;/q+1;;;;-1;

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

|StdInChIKey = NQSIKKSFBQCBSI-UHFFFAOYSA-N

}}

|Section2={{Chembox Properties

|Formula = C₁₂H₂₈₄

|MolarMass = 351.43 g/mol

|Appearance = Green solid

|MeltingPtC = 160

| = (decomposition)

}}

|Section3={{Chembox Hazards

|GHSPictograms = {{GHS03}}{{GHS07}}

|GHSSignalWord = Warning

|HPhrases = {{H-phrases|272|315|319|335}}

|PPhrases = {{P-phrases|210|220|221|261|264|271|280|302+352|304+340|305+351+338|312|321|332+313|337+313|362|370+378|403+233|405|501}}

}}

'''Tetrapropylammonium perruthenate''' ('''TPAP''' or '''TPAPR''') is the [[chemical compound]] described by the [[chemical formula|formula]] N(C₃H₇)₄RuO₄. Sometimes known as the [[Steven V. Ley|Ley]] reagent, this [[ruthenium]] compound is used as a [[reagent]] in [[organic synthesis]]. This [[salt (chemistry)|salt]] consists of the [[tetrapropylammonium]] cation and the [[perruthenate]] anion, -.

== Uses ==

[[Image:.||frame|Oxidation of [[alcohol]] to [[aldehyde]] with TPAP (0.06 eq.) and [[N-Methylmorpholine N-oxide|''N''-methylmorpholine ''N''-oxide]] (1.7 eq.) with molecular sieves in [[dichloromethane]].<ref>A - of the John A. Hadfield Alan T. McGown John Butler [[Molecules (journal)|Molecules]] 2000 5 http://www.mdpi.org/molecules/papers/50100082.pdf </ref>]]

[[Ruthenium tetroxide]] is a highly aggressive oxidant, but TPAP, which is its one-electron reduced derivative, is a mild [[oxidizing agent]] for the conversion of [[Primary alcohol|primary alcohols]] to [[aldehyde]]s (the '''Ley oxidation''').<ref>{{cite journal |first1= Steven V. |last1= Ley |author-link1= Steven V. Ley|first2= Joanne |last2= Norman |first3= William P. |last3= Griffith |first4= Stephen P. |last4= Marsden |title= Tetrapropylammonium perruthenate, Pr₄N⁺RuO₄^&minus;, TPAP: A catalytic oxidant for organic synthesis |journal= [[Synthesis (journal)|Synthesis]] |volume= 1994 |issue= 7 |year= 1994 |pages= 639–666 |doi= 10.1055/s-1994-25538|s2cid= 95136192 }} (review article)</ref> Secondary alcohols are similarly oxidized to [[ketone]]s.<ref name="e-EROS">{{Citation|last1=Ley|first1=Steven V.|title=Tetra-n-propylammonium Perruthenate|url=http://doi.wiley.com/10.1002/047084289X.rt074.pub2|encyclopedia=Encyclopedia of Reagents for Organic Synthesis|pages=rt074.pub2|year=2011|place=Chichester, UK|publisher=John Wiley & Sons, Ltd|language=en|doi=10.1002/047084289x.rt074.pub2|isbn=978-0-471-93623-7|access-date=2020-09-04|last2=Norman|first2=Joanne|last3=Wilson|first3=Anthony J.}}</ref> It can also be used to oxidize primary alcohols all the way to the [[carboxylic acid]] with a higher catalyst loading, larger amount of the cooxidant, and addition of two equivalents of water. In this situation, the aldehyde reacts with water to form the [[geminal diol]] [[hydrate]], which is then oxidized again.<ref>{{cite journal |title= Applications of Zr-catalyzed carbomagnesation and Mo-catalyzed macrocyclic ring closing metathesis in asymmetric synthesis. Enantioselective total synthesis of Sch 38516 (Fluvirucin B₁) |first1= Z. |last1= Xu |first2= C. W. |last2= Johannes |first3= A. F. |last3= Houri |first4= D. S. |last4= La |first5=D. A. |last5= Cogan |first6= G. E. |last6= Hofilena |first7= A. H. |last7= Hoveyda |journal= [[J. Am. Chem. Soc.]] | year= 1997 |volume= 119 |issue= 43 |pages= 10302–10316 |doi= 10.1021/ja972191k}}</ref>

The [[organic oxidation|oxidation]] generates water that can be removed by adding [[molecular sieve]]s. TPAP is expensive, but it can be used in [[catalyst|catalytic]] amounts. The [[catalytic cycle]] is maintained by adding a [[stoichiometric amount]] of a co-oxidant such as [[N-Methylmorpholine N-oxide|''N''-methylmorpholine ''N''-oxide]]<ref>{{cite journal |title= Preparation and use of tetra-''n''-butylammonium per-ruthenate (TBAP reagent) and tetra-''n''-propylammonium per-ruthenate (TPAP reagent) as new catalytic oxidants for alcohols |first1= William P. |last1 = Griffith |first2= Steven V. |last2= Ley |author-link2= Steven V. Ley |first3= Gwynne P. |last3= Whitcombe |first4= Andrew D. |last4= White |journal = [[J. Chem. Soc., Chem. Commun.]] |issue= 21 |year= 1987 |pages= 1625–1627 |doi= 10.1039/C39870001625}}</ref> or molecular oxygen.<ref>{{cite journal |title= Tetra-''n''-propylammonium perruthenate (TPAP)-catalysed oxidations of alcohols using molecular oxygen as a co-oxidant |first1= Roman |last1= Lenz |first2= Steven V. |last2= Ley |author-link2= Steven V. Ley |journal= [[J. Chem. Soc., Perkin Trans. 1]]|issue= 22 |year= 1997 |pages= 3291–3292 |doi= 10.1039/A707339I}}</ref>

TPAP is also used to [[Glycol cleavage|cleave vicinal diols]] to form aldehydes.<ref name="e-EROS"/>

{{-}}

[[Category:Oxidizing agents]]

[[Category:Deliquescent materials]]