114615-82-6

Basic information

• Product Name: TETRAPROPYLAMMONIUM PERRUTHENATE
• Synonyms: TETRAPROPYLAMMONIUM PERRUTHENATE;TETRA-N-PROPYLAMMONIUM PERRUTHENATE;TETRA-N-PROPYLAMMONIUM PERRUTHENATE (VII);TPAP;Tetrapropylammoniumperruthenate,min.97%TPAP;1-Propanaminium, N,N,N-tripropyl-, (T-4)-tetraoxoruthenate(1-);Tetrapropylammonium Perruthenate (TPAP);Tetra-n-propylammonium perruthenate(VII), 98+%
• CAS NO: 114615-82-6
• Molecular Formula: C₁₂H₂₈N*O₄Ru
• Molecular Weight: 351.43
• EINECS: -0
• Product Categories: Boron, Nitrile, Thio,& TM-Cpds;Ammonium Polyhalides, etc. (Quaternary);Catalysts for Organic Synthesis;Classes of Metal Compounds;Environmentally-friendly Oxidation;Homogeneous Catalysts;Metal Complexes;Oxidation;Quaternary Ammonium Compounds;Ru (Ruthenium) Compounds;Synthetic Organic Chemistry;Transition Metal Complexes (Environmentally-friendly Oxidation);Transition Metal Compounds;Alkylammonium salt;Ru
• Mol File: 114615-82-6.mol
• Article Data: 8

Chemical Properties

• Melting Point: ~160 °C (dec.)(lit.)
• Boiling Point: °Cat760mmHg
• Flash Point: °C
• Appearance: green/crystal
• Density: g/cm³
• Storage Temp.: 2-8°C
• Solubility: Methanol (Slightly)
• Water Solubility: Insoluble in water.
• Sensitive: Hygroscopic
• Stability: store cold
• CAS DataBase Reference: TETRAPROPYLAMMONIUM PERRUTHENATE(CAS DataBase Reference)
• NIST Chemistry Reference: TETRAPROPYLAMMONIUM PERRUTHENATE(114615-82-6)
• EPA Substance Registry System: TETRAPROPYLAMMONIUM PERRUTHENATE(114615-82-6)

Safety Data

• Hazard Codes: O,Xi
• Statements: 5-8-36/37/38
• Safety Statements: 17-26-36
• RIDADR: UN 1479 5.1/PG 2
• WGK Germany: 3
• F: 3-10
• HazardClass: 5.1
• PackingGroup: III
• Hazardous Substances Data: 114615-82-6(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 114615-82-6 differently. You can refer to the following data:
1. A mild oxidant for the selective transformation of primary alcohols to aldehydes and secondary alcohols to ketones.
2. Tetrapropylammonium Perruthenate is used in sustainable oxidation reactions and has potential for chemical recycling.

Definition

ChEBI: A quaternary ammonium salt having tetrapropylammonium as the cation and perruthenate as the anion.

General Description

Tetrapropylammonium perruthenate is a mild oxidizing agent used for the oxidation of alcohols to corresponding carbonyl compounds. It is a non-volatile, air-stable, and readily soluble reagent, which can be used either stoichiometrically or catalytically with a suitable co-oxidant.

Purification Methods

It is a strong oxidant and may explode on heating. It can be washed with aqueous n-propanol, then H2O and dried over KOH in a vacuum. It is stable at room temperature but best stored in a refrigerator. It is soluble in CH2Cl2 and MeCN. [Dengel et al. Transition Met Chem 10 98 1985, Griffith et al. J Chem Soc, Chem Commun 1625 1987.] § Polymer supported reagent is available commercially.

InChI: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

Synthetic route

rhodium(III) chloride hydrate + tetrapropylammonium hydroxide (4499-86-9) → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
Stage #1: rhodium(III) chloride hydrate With sodium bromate; sodium carbonate In water at 30 - 40℃; for 5h; Stage #2: tetrapropylammonium hydroxide at 30℃; for 5h; Temperature;	99.7%
Stage #1: rhodium(III) chloride hydrate With sodium bromate; sodium carbonate In water at 20℃; for 2h; Stage #2: tetrapropylammonium hydroxide In water at 20℃; for 0.05h;	67%

sodium bromate + ruthenium trichloride hydrate + tetrapropylammonium hydroxide → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
With sodium carbonate In water mixt. of RuCl3 and NaBrO3, Na2CO3 in water stirred until color changed to yellow green, addn. of n-Pr4NOH with stirring, deep green pptn.; extd. with alcohol free CH2Cl2, dried over anhydrous Na2CO3, concd. in vac., recrystd. from CCl4; elem. anal.;	99%

ruthenium tetroxide (20427-56-9) + tetrapropylammonium hydroxide → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
With K2CO3 stirred at 0°C for 3 h; washed with ice-cold H2O, dried in vac.; elem. anal.;	96%

sodium periodate (7790-28-5) + ruthenium trichloride hydrate + tetrapropylammonium hydroxide → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
In water stirring of hydrated RuCl3 and NaIO4 in H2O overnight; addn. to an aq. soln. of n-Pr4NOH containing NaOH at 0-5°C under an atmosphere of O2;; ppt. was removed every 20 min, washed with ice-cold water, and dried under vac.;;	87%

sodium periodate (7790-28-5) + ruthenium(III) chloride trihydrate + tetrapropylammonium hydroxide (4499-86-9) → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
Stage #1: tetrapropylammonium hydroxide With sodium hydroxide In water Stage #2: sodium periodate; ruthenium(III) chloride trihydrate In water at 20℃; for 16h;	33%

ruthenium(III) trichloride hydrate + tetrapropylammonium hydroxide (4499-86-9) → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
With sodium periodate; sodium hydroxide In water at 20℃; for 16h;	33%

sodium bromate + tetrapropylammonium hydroxide + ruthenium dioxide hydrate → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
With sodium carbonate In water mixt. of RuO2 and NaBrO3, Na2CO3 in water stirred until color changed to yellow green, addn. of n-Pr4NOH with stirring, deep green pptn.; extd. with alcohol free CH2Cl2, dried over anhydrous Na2CO3, concd. in vac., recrystd. from CCl4;

ruthenium(III) chloride trihydrate + tetrapropylammonium hydroxide (4499-86-9) → tetrapropylammonium perruthennate (114615-82-6)

Conditions	Yield
Stage #1: ruthenium(III) chloride trihydrate With sodium bromate; sodium carbonate In water at 20℃; for 2h; Stage #2: tetrapropylammonium hydroxide In water at 20℃; for 0.05h;

tetrapropylammonium perruthennate (114615-82-6) + 4-hydroxycyclohexyl carboxylic acid ethyl ester (3618-04-0, 75877-66-6, 17159-80-7) + 4-methylmorpholine N-oxide (7529-22-8) → ethyl 4-oxocyclohexane-1-carboxylate (17159-79-4)

Conditions	Yield
In ethyl acetate; acetonitrile	98%
In dichloromethane	13.46 g (85%)

tetrapropylammonium perruthennate (114615-82-6) + (2Z)-3-(4-hydroxy-2-buten-2-yl)-5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-(n-propyloxy)naphthalene (277334-43-7) → (2Z)-3-[5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-(n-propyloxy)naphthalen-3-yl]but-2-en-1-al (180861-54-5)

Conditions	Yield
With 4-methylmorpholine N-oxide In dichloromethane	98%

tert-butyl N-(4-hydroxycyclohexyl)carbamate (224309-64-2) + tetrapropylammonium perruthennate (114615-82-6) + 4-methylmorpholine N-oxide (7529-22-8) → N-(tert-butoxycarbonyl)-4-aminocyclohexanone (179321-49-4)

Conditions	Yield
molecular sieves In dichloromethane; ethyl acetate	96%

tetrapropylammonium perruthennate (114615-82-6) + 4-methylmorpholine N-oxide (7529-22-8) + (4S)-4-(2-methyl-3(RS)-hydroxybut-2-yl)-2,2-dimethyl[1,3]dioxane (220367-72-6) → (4S)-4-(2-methyl-3-oxobut-2-yl)-2,2-dimethyl[1,3]dioxane (220367-71-5)

Conditions	Yield
molecular sieve In dichloromethane	94.5%

tetrapropylammonium perruthennate (114615-82-6) + 4-(1,3-dioxoisoindolin-2-yl)-3-hydroxybutyl acetate (558442-58-3) + 4-methylmorpholine N-oxide (7529-22-8) → 4-(1,3-dioxoisoindolin-2-yl)-3-oxobutyl acetate (558443-82-6)

Conditions	Yield
SiO2 In dichloromethane	92%

tetrapropylammonium perruthennate (114615-82-6) + 1-(2-Hydroxy-3-methoxymethoxy-butyl)-2-oxo-6-m-tolyl-4-trifluoromethyl-1,2-dihydro-pyridine-3-carbonitrile (566924-79-6) → 1-(3-Methoxymethoxy-2-oxo-butyl)-2-oxo-6-m-tolyl-4-trifluoromethyl-1,2-dihydro-pyridine-3-carbonitrile (566926-43-0)

Conditions	Yield
With 4-methylmorpholine N-oxide; silica gel In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran	90%

silica-gel + tetrapropylammonium perruthennate (114615-82-6) + Å molecular sieves + 4-hydroxymethyl-4-(5-benzyloxy-3-fluorophenyl)-3,4,5,6-tetrahydro-2H-pyran (179420-68-9) → 4-›3-(Benzyloxy)-5-fluorophenyl›-4-formyl-3,4,5,6-tetrahydro-2H-pyran

Conditions	Yield
With 4-methylmorpholine N-oxide In hexane; ethyl acetate	86%

tetrapropylammonium perruthennate (114615-82-6) + di-tert-butyl dicarbonate (24424-99-5) + trans-4-hydroxycyclohexylamine (27489-62-9) + trans-4-aminocyclohexanol hydrochloride (50910-54-8) + 4-methylmorpholine N-oxide (7529-22-8) → N-(tert-butoxycarbonyl)-4-aminocyclohexanone (179321-49-4)

Conditions	Yield
molecular sieves In tetrahydrofuran; sodium hydroxide; dichloromethane	84%

tetrapropylammonium perruthennate (114615-82-6) + 2-t-butyldiphenylsilyloxymethyl-2-propene-1-ol → 2-t-butyldiphenylsilyloxymethyl-2-propenal

Conditions	Yield
silica gel In dichloromethane; 4-methylmorpholine N-oxide	83%

tetrapropylammonium perruthennate (114615-82-6) + 8-(hydroxymethyl)dibenzo[b,f][1,4]oxazepin-11(10H)-one (623906-43-4) → 11-oxo-10,11-dihydrodibenzo[b,f][1,4]oxazepine-8-carbaldehyde (623906-45-6)

Conditions	Yield
With hydrogenchloride; silica gel In ethyl acetate; acetonitrile	83%

tetrapropylammonium perruthennate (114615-82-6) + (6S)-N-benzyl-2-azabicyclo[2.2.2]octan-6-ol (1217527-96-2) + 4-methylmorpholine N-oxide (7529-22-8) → 2-benzyl-2-azabicyclo[2.2.2]octan-6-one (41959-26-6)

Conditions	Yield
In ethyl acetate; acetonitrile	81%

tetrapropylammonium perruthennate (114615-82-6) + 2-(2-Chloro-5-methoxy-phenyl)-1-(2-chloro-pyridin-4-yl)-propan-1-ol (1134916-40-7) + 4-methylmorpholine N-oxide (7529-22-8) → 2-(2-chloro-5-methoxy-phenyl)-1-(2-chloro-pyridin-4-yl)-propan-1-one (1134916-41-8)

Conditions	Yield
silica gel In dichloromethane	81%

(1H-indol-4-yl)methanol (1074-85-7) + tetrapropylammonium perruthennate (114615-82-6) → 4-formyl indole (1074-86-8)

Conditions	Yield
With 4-methylmorpholine N-oxide; silica gel In dichloromethane	80%

tetrapropylammonium perruthennate (114615-82-6) + 3,16α-Bis(dimethylthexylsilyl ether) + Estriol (50-27-1) → 16α-hydroxyestrone (566-76-7)

Conditions	Yield
In dichloromethane	76%

tetrapropylammonium perruthennate (114615-82-6) + 3-tert-butyldimethylsilyloxy-1-propanol (73842-99-6) → 3-(tert-butyldimethylsilanyloxy)propionaldehyde (89922-82-7)

Conditions	Yield
With 4-methylmorpholine N-oxide; silica gel In dichloromethane; acetonitrile	66%
With 4-methylmorpholine N-oxide; silica gel In dichloromethane; acetonitrile	66%

tetrapropylammonium perruthennate (114615-82-6) + 4-methylmorpholine N-oxide (7529-22-8) + 2-(3,4-dihydro-1(2H)-benzopyran-4-yl)ethanol (121278-43-1, 121278-44-2, 121278-49-7) → 2-(3,4-dihydro-2H-1-benzopyran-4-yl)ethanal (150515-77-8)

Conditions	Yield
silica gel In dichloromethane; ethyl acetate	64%

tetrapropylammonium perruthennate (114615-82-6) + 1-{4-[1-(3-Fluoro-benzyl)-1H-indazol-5-ylamino]-pyrrolo[2,1 f][1,2,4]triazin-5-ylmethyl}-(3R)-pyrrolidin-3-ol (529508-87-0) → 1-{4[1-(3-Fluoro-benzyl)-1H-indazol-5-ylamino]-pyrrolo[2,1-f][1,2,4]triazin-5-ylmethyl}-pyrrolidin-3-one (529509-31-7)

Conditions	Yield
With 4-methylmorpholine N-oxide; silica gel In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; ethyl acetate	61%

tetrapropylammonium perruthennate (114615-82-6) + ethyl 1-(p-chlorophenyl)-β-hydroxy-cyclopropanepropionate + 4-methylmorpholine N-oxide (7529-22-8) → ethyl 1-(p-chlorophenyl)-β-oxo-cyclopropanepropionate

Conditions	Yield
In Å molecular sieves; diethyl ether; ethyl acetate; acetonitrile	55%
In diethyl ether; silica gel; ethyl acetate; acetonitrile	55%

tetrapropylammonium perruthennate (114615-82-6) + (3E,7E)-homofarnesol (459-89-2) + 4-methylmorpholine N-oxide (7529-22-8) → homofarnesaldehyde (29484-45-5)

Conditions	Yield
silica gel In acetonitrile	50%

tetrapropylammonium perruthennate (114615-82-6) + methyl 5-(3-hydroxypropyl)-4-methylthiophene-2-carboxylate (177587-14-3) + Å molecular sieves + 4-methylmorpholine N-oxide (7529-22-8) → methyl 4-methyl-5-(3-oxopropyl) thiophene-2-carboxylate (177587-15-4)

Conditions	Yield
In dichloromethane	49%

pyridine (110-86-1) + tetrapropylammonium perruthennate (114615-82-6) + cobalt(II) acetate monohydrate → C23H27Co3N3O13Ru

Conditions	Yield
In acetonitrile at 20℃; for 16h; Inert atmosphere;	45%

3-(hydroxymethy)piperidine (4606-65-9) + tetrapropylammonium perruthennate (114615-82-6) + di-tert-butyl dicarbonate (24424-99-5) + 4-methylmorpholine N-oxide (7529-22-8) → 3-formylpiperidine-1-carboxylic acid tert-butyl ester (118156-93-7)

Conditions	Yield
molecular sieves In tetrahydrofuran; dichloromethane	43%

tetrapropylammonium perruthennate (114615-82-6) + (3RS,4RS)-3-[N-((1-naphthyloxy)acetyl)valinyl]amino-5-fluoro-4-hydroxypentanoic acid, tert-butyl ester → (3RS)-3-[N-((1-Naphthyloxy)Acetyl)Valinyl]Amino-5-Fluoro-4-Oxopentanoic Acid

Conditions	Yield
With 4-methylmorpholine N-oxide; silica gel In dichloromethane	40%

4-methoxypyridine (620-08-6) + tetrapropylammonium perruthennate (114615-82-6) + cobalt(II) acetate monohydrate → C26H33Co3N3O16Ru

Conditions	Yield
In acetonitrile at 20℃; for 16h; Inert atmosphere;	38%

tetrapropylammonium perruthennate (114615-82-6) + 2-cyclopropyl-6-hydroxymethyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline (345964-18-3) + molecular sieves powder + 4-methylmorpholine N-oxide (7529-22-8) → 2-cyclopropyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline-6-carbaldehyde (345964-19-4)

Conditions	Yield
In hexane; dichloromethane; acetonitrile	37%
In hexane; dichloromethane; acetonitrile	37%

tetrapropylammonium perruthennate (114615-82-6) + 4-trifluoromethylpyridine (3796-24-5) + cobalt(II) acetate monohydrate → C26H24Co3F9N3O13Ru

Conditions	Yield
In acetonitrile at 20℃; for 16h; Inert atmosphere;	36%

Upstream product

• 14898-67-0 ruthenium trichloride hydrate 
• 7790-28-5 sodium periodate 
• 20427-56-9 ruthenium tetroxide 
• 4499-86-9 tetrapropylammonium hydroxide 

Downstream Products

• 89922-82-7 3-(tert-butyldimethylsilanyloxy)propionaldehyde 
• 509094-03-5 4-cyclohexylamino-3-nitrobenzaldehyde 
• 529509-31-7 1-{4[1-(3-Fluoro-benzyl)-1H-indazol-5-ylamino]-pyrrolo[2,1-f][1,2,4]triazin-5-ylmethyl}-pyrrolidin-3-one 
• 566926-43-0 1-(3-Methoxymethoxy-2-oxo-butyl)-2-oxo-6-m-tolyl-4-trifluoromethyl-1,2-dihydro-pyridine-3-carbonitrile 
• 280774-04-1 1-Isopropylpiperidine-4-carboxaldehyde 
• 17159-79-4 ethyl 4-oxocyclohexane-1-carboxylate 
• 252017-94-0 (R)-N-[2-Chloro-4-(thien-2-ylmethylsulphonyl)phenyl]-2-hydroxy-2-methyl-3,3,3-trifluoropropanamide 
• 406212-38-2 1-{2-[(4-methoxybenzyl)oxy]-6-nitrophenyl}ethanone 
• 242459-55-8 4-(3-[1-(1H-benzo[d]imidazol-2-ylsulfonyl)-2-piperidyl]-1,2,4-oxadiazol-5-ylmethoxy)benzaldehyde 
• 330936-13-5 (2R,3S)-3,5,7,3',4'-pentakis(benzyloxy)flavan-4-one 
• 41959-26-6 2-benzyl-2-azabicyclo[2.2.2]octan-6-one 
• 127406-55-7 4-(pyridin-3-yl)benzaldehyde 
• 146351-67-9 4-[[3-Bromo-2-[2-(1H-tetrazol-5-yl)phenyl]-5-benzofuranyl]methyl]-3-butyl-1-(2,2,2-trifluoroethyl)-1H-pyrazole-5-carboxaldehyde 
• 141293-85-8 4-phenyl-3-furaldehyde 

Relevant articles and documents

Hydrogen-Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

The Ley–Griffith oxidation, which is catalyzed by tetra-n-propylammonium perruthenate (TPAP, nPr4N[RuO4]), is a popular method for not only controlled oxidation of primary alcohols to aldehydes, but also a host of other synthetically useful transformations. While the fundamental reaction mechanism has recently been elucidated, several key hydrogen-bonding interactions between the reagents were implicated but not investigated. Herein the prevalence of H-bonding between the co-oxidant N-methylmorpholine N-oxide (NMO), the alcohol substrate, water and the perruthenate catalyst is established. These observations help to rationalize the importance of drying the reagents and lead to several practical suggestions.

N -Oxides rescue Ru(v) in catalytic Griffith-Ley (TPAP) alcohol oxidations

The redox and ligand exchange reactions of oxido-ruthenium complexes are central to the function of the Sharpless and Griffith-Ley one-step alcohol oxidation protocols. However, their mechanisms have not been elucidated. Cyclic voltammetry and UV-vis spec

ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

The Ley–Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.