14691-89-5

Basic information

• Product Name: 4-ACETAMIDO-TEMPO
• Synonyms: 4-(acetylamino)-2,2,6,6-tetramethyl-1-Piperidinyloxy;4-Acetamido-2,2,6,6-tetramethyl-1-piperidinyloxyl;4-Acetamido-2,2,6,6-tetramethylpiperidinyloxy;N-(1-Hydroxy-2,2,6,6-tetramethyl-4-piperidinyl)acetamide;2,2,6,6-TETRAMETHYL-4-ACETAMIDO-1-PIPERIDINYLOXY;2,2,6,6-TETRAMETHYL-4-ACETAMIDOPIPERIDINE-1-OXYL;4-ACETYLAMINO-2,2,6,6-TETRAMETHYLPIPERIDIN-1-OXYL;4-ACETYLAMINO-2,2,6,6-TETRAMETHYLPIPERIDINE-N-OXYL
• CAS NO: 14691-89-5
• Molecular Formula: C₁₁H₂₁N₂O₂
• Molecular Weight: 213.3
• EINECS: 423-840-3
• Product Categories: Piperidine;Analytical Chemistry;ESR Spectrometry;Oxidation;Spin Labels;Synthetic Organic Chemistry;Radical Chemistry;Stable Radicals;TEMPO Derivatives
• Mol File: 14691-89-5.mol

Chemical Properties

• Melting Point: 143-145 °C(lit.)
• Boiling Point: 353.29°C (rough estimate)
• Flash Point: 176.8 °C
• Appearance: Orange-red crystalline powder
• Density: 1.0451 (rough estimate)
• Vapor Pressure: 1.9E-06mmHg at 25°C
• Refractive Index: 1.4620 (estimate)
• Storage Temp.: 2-8°C
• Solubility: Soluble in ethanol, acetone, acetonitrile, methylene chloride. I
• BRN: 3546225
• CAS DataBase Reference: 4-ACETAMIDO-TEMPO(CAS DataBase Reference)
• NIST Chemistry Reference: 4-ACETAMIDO-TEMPO(14691-89-5)
• EPA Substance Registry System: 4-ACETAMIDO-TEMPO(14691-89-5)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 36/37/38-22-36/37
• Safety Statements: 26-36-24/25-22
• WGK Germany: 1
• F: 9
• TSCA: Yes
• Hazardous Substances Data: 14691-89-5(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
4-ACETAMIDO-TEMPO is used as a catalyst for the oxidation of alcohols to carbonyl compounds in the presence of TsOH. This application is particularly useful in the synthesis of various organic compounds, as it provides a selective and efficient method for converting alcohols to their corresponding carbonyl compounds.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 4-ACETAMIDO-TEMPO is used as a catalyst for the oxidation of alcohols to carbonyl compounds, which is a crucial step in the synthesis of various drugs and drug intermediates. Its ability to selectively oxidize alcohols without causing over-oxidation makes it a valuable tool in the development of new pharmaceuticals.
Used in Material Science:
4-ACETAMIDO-TEMPO can be employed in the field of material science for the synthesis of novel materials with unique properties. The selective oxidation of alcohols to carbonyl compounds can be utilized to create new polymers, coatings, and other materials with specific characteristics, such as improved stability or enhanced reactivity.
Used in Environmental Applications:
4-ACETAMIDO-TEMPO can be used in environmental applications for the oxidation of alcohols to carbonyl compounds, which can help in the degradation of pollutants and the treatment of wastewater. Its selective oxidation properties make it a promising candidate for the development of new environmental technologies and processes.
Used in Analytical Chemistry:
In analytical chemistry, 4-ACETAMIDO-TEMPO can be used as a reagent for the detection and quantification of alcohols. Its ability to selectively oxidize alcohols to carbonyl compounds can be exploited in the development of new analytical methods and techniques for the identification and measurement of alcohols in various samples, such as biological fluids, environmental samples, and industrial products.

Purification Methods

Dissolve the 1-oxyl in CH2Cl2, wash it with saturated K2CO3, then saturated aqueous NaCl, dry (Na2SO4), filter and evaporate. The red solid is recrystallised from aqueous MeOH, m 147.5o. [Ma & Bobbitt J Org Chem 56 6110 1991, Rozantsev & Kokhanov Bull Acad Sci USSR, Div Chem Sci 15 1422 1966, Beilstein 22/8 V 174.]

InChI:InChI=1/C11H22N2O2/c1-8(14)12-9-6-10(2,3)13(15)11(4,5)7-9/h9,15H,6-7H2,1-5H3,(H,12,14)

Upstream product

• 136708-42-4 4-(acetylamino)-2,2,6,6-tetramethyl-1-hydroxy-piperidinium p-toluenesulfonate 
• 136708-43-5 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinium acetate 
• 40908-37-0 N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide 
• 4168-79-0 4-hydroxyimino-2,2,6,6-tetramethylpiperidine 
• 36768-62-4 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE 
• 73322-05-1 4-acetamino-1H-perdeutero-2,2,6,6-tetramethylpiperidine 
• 826-36-8 2,2,6,6-Tetramethyl-4-piperidone 
• 1620751-78-1 N-[2,2,6,6-tetramethyl-1-(2-nitrobenzyloxy)piperidin-4-yl]acetamide 
• 110-89-4 piperidine 
• 201415-38-5 5-phenylbenzoxazole 
• 14691-88-4 4-amino-2,2,6,6-tetramethyl-1-piperidine-1-oxyl 
• 64-19-7 acetic acid 

Downstream Products

• 122586-91-8 N-(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)acetamide 
• 14691-88-4 4-amino-2,2,6,6-tetramethylpiperidinyloxy 
• 70588-04-4 4-amino-perdeutero-2,2,6,6-tetramethylpiperidine-N-oxyl 
• 630-19-3 pivalaldehyde 
• 14691-88-4 tempamine 
• 342630-78-8 5'-dimethoxytrityl-N₄-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)-2'-deoxycytidine 
• 159550-20-6 5'-dimethoxytrityl-N₄-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)-2'-deoxycytidine 
• 342630-68-6 3',5'-diisobutyryl-2-isobutyramido-N6-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)-2'-deoxyadenosine 
• 342630-70-0 5'-dimethoxytrityl-2-isobutyramido-N₆-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)-2'-deoxyadenosine 
• 342630-72-2 5'-dimethoxytrityl-2-isobutyramido-N₆-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)-2'-deoxyadenosine-3'-(2-cyanoethyl-N,Ndiisopropyl) phosphoramidite 
• 378245-34-2 acetic Acid 2-(4-acetylamino-2,2,6,6-tetramethyl-piperidin-1-yloxy)-2-phenylethyl Ester 
• 1350920-13-6 4-acetamido-2,2,6,6-tetramethylpiperidine-N-hydroxyammonium tetrafluoroborate 
• 36410-81-8 4-isothiocyanato-2,2,6,6-tetramethylpiperidine N-oxide 

Relevant articles and documents

Preparation of Some Homologous TEMPO Nitroxides and Oxoammonium Salts; Notes on the NMR Spectroscopy of Nitroxide Free Radicals; Observed Radical Nature of Oxoammonium Salt Solutions Containing Trace Amounts of Corresponding Nitroxides in an Equilibrium Relationship

Three new homologous TEMPO oxoammonium salts and three homologous nitroxide radicals have been prepared and characterized. The oxidation properties of the salts have been explored. The direct 13C NMR and EPR spectra of the nitroxide free radicals and the oxoammonium salts, along with TEMPO and its oxoammonium salt, have been successfully measured with little peak broadening of the NMR signals. In the spectra of all ten compounds (nitroxides and corresponding oxoammonium salts), the carbons in the 2,2,6,6-tetramethylpiperidine core do not appear, implying paramagnetic properties. This unpredicted overall paramagnetism in the oxoammonium salt solutions is explained by a redox equilibrium as shown between oxoammonium salts and trace amounts of corresponding nitroxide. This equilibrium is confirmed by electron interchange reactions between nitroxides with an N-acetyl substituent and oxoammonium salts with longer acyl side chains.

Synthesis and fluorescence properties of six fluorescein-nitroxide radical hybrid-compounds

Six fluorescein-nitroxide radical hybrid-compounds (2ab, 3ab, 4, and 5) were synthesized by the condensation of 5- or 6-carboxy-fluorescein and 4-amino-TEMPO (2ab), 5- or 6-aminofluorescein and 4-carboxy-TEMPO (3ab), and fluorescein and 4-carboxy-TEMPO (4), or by reaction of the 3-hydroxyl group of fluorescein with DPROXYL-3-ylmethyl methanesulfonate (5). Fluorescence intensities (around 520 nm) after reduction of the radical increased to 1.43-, 1.38-, and 1.61-folds for 2a, 2b and 3b respectively; 3a alone exhibited a decrease in intensity on reduction. Since 4 was readily solvolyzed in PBS or even methanol to afford fluorescein and 4-carboxy-TEMPO, its fluorescence change could not be measured. Hybrid compound 5 containing an ether-linkage between the fluorescein phenol and 3-hydroxymethyl-DPROXYL hydroxyl centers, was stable and on reduction, showed a maximum increase (3.21-fold) in relative fluorescence intensity in PBS (pH 5.0), despite its remarkably low absolute fluorescence intensity.

Selective Aromatic C-H Hydroxylation Enabled by η6-Coordination to Iridium(III)

We report an aromatic C-H hydroxylation protocol in which the arene is activated through η6-coordination to an iridium(III) complex. η6-Coordination of the arene increases its electrophilicity and allows for high positional selectivity of hydroxylation at the site of least electron density. Through investigation of intermediate η5-cyclohexadienyl adducts and arene exchange reactions, we evaluate incorporation of arene π-activation into a catalytic cycle for C-H functionalization.

Kinetics and thermodynamics of reversible disproportionation-comproportionation in redox triad oxoammonium cations - Nitroxyl radicals - Hydroxylamines

Kinetics and equilibrium of the acid-catalyzed disproportionation of cyclic nitroxyl radicals R2NO· to oxoammonium cations R2NO+ and hydroxylamines R2NOH is defined by redox and acid-base properties of these compounds. In a recent work (J. Phys. Org. Chem. 2014, 27, 114-120), we showed that the kinetic stability of R2NO· in acidic media depends on the basicity of the nitroxyl group. Here, we examined the kinetics of the reverse comproportionation reaction of R2NO+ and R2NOH to R2NO· and found that increasing in -I-effects of substituents greatly reduces the overall equilibrium constant of the reaction K4. This occurs because of both the increase of acidity constants of hydroxyammonium cations K3H+ and the difference between the reduction potentials of oxoammonium cations ER2NO+/R2NO· and nitroxyl radicals ER2NO·/R2NOH. pH dependences of reduction potentials of nitroxyl radicals to hydroxylamines E1/3σ and bond dissociation energies D(O-H) for hydroxylamines R2NOH inwater were determined. For a wide variety of piperidine- and pyrrolidine-1-oxyls values of pK3H+ and ER2NO+/R2NO· correlate with each other, as well aswith the equilibriumconstants K4 and the inductive substituent constants ωI. The correlations obtained allowprediction of the acid-base and redox characteristics of redox triads R2NO·-R2NO+-R2NOH.

Photolabile protecting groups for nitroxide spin labels

Nitroxide spin labels can be protected against critical conditions of DNA/RNA or peptide synthesis by reduction and alkylation with light-sensitive groups such as nitrobenzyl- or aminocoumarins. High chemical stability qualifies tetraethylisoindoline 5 an

A revised preparation of (4-Acetamido-2,2,6,6-tetramethylpiperidin-1-yl) oxyl and 4-acetamido-2,2,6,6-tetramethyl-1-oxopiperidinium tetrafluoroborate: Reagents for stoichiometric oxidations of alcohols

Revised preparations of (4-acetamido-2,2,6,6-tetramethylpiperidin-1-yl)oxyl and the corresponding oxoammonium salt, 4-acetamido-2,2,6,6-tetramethyl-1- oxoammonium tetrafluoroborate are presented together with some of the important properties of these two oxidizing reagents. Georg Thieme Verlag Stuttgart New York.

Oxidation of α-trifluoromethyl alcohols using a recyclable oxoammonium salt

A simple, mild method for the oxidation of α-trifluoromethyl alcohols to trifluoromethyl ketones (TFMKs) using the oxoammonium salt 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (1) is described. Under basic conditions, oxidation proceeds rapidly and affords good to excellent yields of TFMKs, without concomitant formation of the hydrate. The byproduct of the oxidation, 4-acetylamino-2,2,6,6-tetramethyl-1- piperidinyloxy (1c), is easily recovered and can be conveniently reoxidized to regenerate the oxoammonium salt.

Oxidation of primary and secondary alcohols by 4-acetylamino-2,2,6,6- tetramethylpiperidine-1-oxoammonium tetrafluoroborate in aqueous media

water soluble oxidant 4-acetylamino-2,2,6,6-tetramethylpiperidine-1- oxoammonium tetrafluoroborate 1 oxidizes primary and secondary aliphatic, primary allylic, and primary and secondary benzylic alcohols to their corresponding aldehydes and ketones in aqueous media in good to excellent yields. ARKAT-USA, Inc.

Electron paramagnetic resonance (EPR) study of spin-labeled camptothecin derivatives: A different look of the ternary complex

Camptothecin (CPT) derivatives are clinically effective poisons of DNA topoisomerase I (Top1) able to form a ternary complex with the Top1-DNA complex. The aim of this investigation was to examine the dynamic aspects of the ternary complex formation by means of site-directed spin labeling electron paramagnetic resonance (SDSL-EPR). Two semisynthetic CPT derivatives bearing the paramagnetic moiety were synthesized, and their biological activity was tested. A 22-mer DNA oligonucleotide sequence with high affinity cleavage site for Top1 was also synthesized. EPR experiments were carried out on modified CPT in the presence of DNA, of Top1, or of both. In the last case, a slow motion component in the EPR signal appeared, indicating the formation of the ternary complex. Deconvolution of the EPR spectrum allowed to obtain the relative drug amounts in the complex. It was also possible to demonstrate that the residence time of CPT "trapped" in the ternary complex is longer than hundreds of microseconds.

Amination of benzoxazoles and 1,3,4-oxadiazoles using 2,2,6,6- tetramethylpiperidine-N-oxoammonium tetrafluoroborate as an organic oxidant

No transition metals are necessary to convert benzoxazoles and 1,3,4-oxadiazoles into the corresponding pharmacologically interesting 2-aminated heterocycles by formal direct C(2)-amination using tetramethylpiperidine-N-oxoammonium tetrafluoroborate (TEMPO+BF 4-) as an oxidant (see scheme; TEMP=2,2,6,6- tetramethylpiperidine; TfOH=trifluoromethanesulfonic acid).