4-Hydroxy-TEMPO

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4-Hydroxy-TEMPO
4-Hydroxy-TEMPO.svg
4-Hydroxy-TEMPO radical ball.png
Names
Preferred IUPAC name
(4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl
Other names
tempol; tanol; TMPN; 4-Oxypiperidol; nitroxyl 2; HyTEMPO
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.017.056 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C9H18NO2/c1-8(2)5-7(11)6-9(3,4)10(8)12/h7,11H,5-6H2,1-4H3 Yes check.svgY
    Key: UZFMOKQJFYMBGY-UHFFFAOYSA-N Yes check.svgY
  • InChI=1S/C9H18NO2/c1-8(2)5-7(11)6-9(3,4)10(8)12/h7,11H,5-6H2,1-4H3
    Key: UZFMOKQJFYMBGY-UHFFFAOYSA-N
  • CC1(C)CC(O)CC(C)(C)N1[O]
Properties
C9H18NO2
Molar mass 172.248 g·mol−1
AppearanceOrange crystals
Melting point 71–73 °C (160–163 °F; 344–346 K) [1]
629.3 g/L (20 °C)
Hazards
GHS labelling:
GHS-pictogram-exclam.svg [2]
Warning [2]
H302, H315, H319, H335 [2]
P261, P305+P351+P338 [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

4-Hydroxy-TEMPO or TEMPOL, formally 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, is a heterocyclic compound. Like the related TEMPO, it is used as a catalyst and chemical oxidant by virtue of being a stable aminoxyl radical. Its major appeal over TEMPO is that it is less expensive, being produced from triacetone amine, which is itself made via the condensation of acetone and ammonia. This makes it economically viable on an industrial scale. [3]

Example synthesis of 4-Hydroxy-TEMPO from phorone, which is itself made from acetone and ammonia 4-Hydroxy-TEMPO synthesis01.svg
Example synthesis of 4-Hydroxy-TEMPO from phorone, which is itself made from acetone and ammonia

In biochemical research, 4-hydroxy-TEMPO has been investigated as an agent for limiting reactive oxygen species. It catalyzes the disproportionation of superoxide, facilitates hydrogen peroxide metabolism, and inhibits Fenton chemistry. [4] 4-Hydroxy-TEMPO, along with related nitroxides, are being studied for their potential antioxidant properties. [5]

On an industrial-scale 4-hydroxy-TEMPO is often present as a structural element in hindered amine light stabilizers, which are commonly used stabilizers in plastics, it is also used as a polymerisation inhibitor, particularly during the purification of styrene.

It is a promising model substance to inhibit SARS-CoV-2 RNA-dependent RNA polymerase. [6]

See also

Related Research Articles

<span class="mw-page-title-main">Reactive oxygen species</span> Highly reactive molecules formed from diatomic oxygen (O₂)

In chemistry and biology, reactive oxygen species (ROS) are highly reactive chemicals formed from diatomic oxygen (O2), water, and hydrogen peroxide. Some prominent ROS are hydroperoxide (O2H), superoxide (O2-), hydroxyl radical (OH.), and singlet oxygen. ROS are pervasive because they are readily produced from O2, which is abundant. ROS are important in many ways, both beneficial and otherwise. ROS function as signals, that turn on and off biological functions. They are intermediates in the redox behavior of O2, which is central to fuel cells. ROS are central to the photodegradation of organic pollutants in the atmosphere. Most often however, ROS are discussed in a biological context, ranging from their effects on aging and their role in causing dangerous genetic mutations.

<span class="mw-page-title-main">2,2,6,6-Tetramethylpiperidine</span> Chemical compound

2,2,6,6-Tetramethylpiperidine, abbreviated TMP, HTMP, or TMPH, is an organic compound of the amine class. In appearance, it is a colorless liquid and has a "fishy", amine-like odor. This amine is used in chemistry as a hindered base. Although TMP finds limited use per se, its derivatives are a mainstay of hindered amine light stabilizers.

<i>N</i>-Oxoammonium salt Class of organic compounds

N-Oxoammonium salts are a class of organic compounds with the formula [R1R2+N=O]X. The cation [R1R2+N=O] is of interest for the dehydrogenation of alcohols. Oxoammonium salts are diamagnetic, whereas the nitroxide has a doublet ground state. A prominent N-oxoammonium salt is prepared by oxidation of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, commonly referred to as [TEMPO]+. A less expensive analogue is Bobbitt's salt.

<span class="mw-page-title-main">Myricetin</span> Chemical compound

Myricetin is a member of the flavonoid class of polyphenolic compounds, with antioxidant properties. Common dietary sources include vegetables, fruits, nuts, berries, tea, and red wine.

<span class="mw-page-title-main">Triacetonamine</span> Chemical compound

Triacetonamine is an organic compound with the formula OC(CH2CMe2)2NH (where Me = CH3). It is a colorless or white solid that melts near room temperature. The compound is an intermediate in the preparation of 2,2,6,6-tetramethylpiperidine, a sterically hindered base and precursor to the reagent called TEMPO. Triacetonamine is formed by the poly-aldol condensation of acetone in the presence of ammonia and calcium chloride:

<span class="mw-page-title-main">Hindered amine light stabilizers</span>

Hindered amine light stabilizers (HALS) are chemical compounds containing an amine functional group that are used as stabilizers in plastics and polymers. These compounds are typically derivatives of tetramethylpiperidine and are primarily used to protect the polymers from the effects of photo-oxidation; as opposed to other forms of polymer degradation such as ozonolysis. They are also increasingly being used as thermal stabilizers, particularly for low and moderate level of heat, however during the high temperature processing of polymers they remain less effective than traditional phenolic antioxidants.

Polymer stabilizers are chemical additives which may be added to polymeric materials to inhibit or retard their degradation. Mainly they protect plastic and rubber products against heat, oxidation, and UV light. The biggest quantity of stabilizers is used for polyvinyl chloride (PVC), as the production and processing of this type of plastic would not be possible without stabilizing chemicals. Common polymer degradation processes include oxidation, UV-damage, thermal degradation, ozonolysis, combinations thereof such as photo-oxidation, as well as reactions with catalyst residues, dyes, or impurities. All of these degrade the polymer at a chemical level, via chain scission, uncontrolled recombination and cross-linking, which adversely affects many key properties such as strength, malleability, appearance and colour.

<span class="mw-page-title-main">Radical (chemistry)</span> Atom, molecule, or ion that has an unpaired valence electron; typically highly reactive

In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes.

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Oxoammonium-catalyzed oxidation reactions involve the conversion of organic substrates to more highly oxidized materials through the action of an N-oxoammonium species. Nitroxides may also be used in catalytic amounts in the presence of a stoichiometric amount of a terminal oxidant. Nitroxide radical species used are either 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) or derivatives thereof.

<span class="mw-page-title-main">TEMPO</span> Chemical compound

(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl or (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl, commonly known as TEMPO, is a chemical compound with the formula (CH2)3(CMe2)2NO. This heterocyclic compound is a red-orange, sublimable solid. As a stable aminoxyl radical, it has applications in chemistry and biochemistry. TEMPO is used as a radical marker, as a structural probe for biological systems in conjunction with electron spin resonance spectroscopy, as a reagent in organic synthesis, and as a mediator in controlled radical polymerization.

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<span class="mw-page-title-main">Deepak T. Nair</span>

Deepak Thankappan Nair is an Indian Structural Biologist and a scientist at Regional Centre for Biotechnology. He is known for his studies on DNA and RNA polymerases. Deepak was a Ramanujan fellow of the Science and Engineering Research Board (2008–2013) and a recipient of the National BioScience Award for Career Development. The Council of Scientific and Industrial Research, the apex agency of the Government of India for scientific research, awarded him the Shanti Swarup Bhatnagar Prize for Science and Technology, one of the highest Indian science awards, for his contributions to biological sciences in 2017. He was inducted as a fellow of the Indian National Science Academy in December, 2022.

<span class="mw-page-title-main">Aminoxyl group</span>

Aminoxyl denotes a radical functional group with general structure R2N–O. It is commonly known as a nitroxyl radical or a nitroxide, however IUPAC discourages the use of these terms, as they erroneously suggest the presence of a nitro group. Aminoxyls are structurally related to hydroxylamines and N-oxoammonium salts, with which they can interconvert via a series of redox steps.

<span class="mw-page-title-main">4-Amino-2,2,6,6-tetramethylpiperidine</span> Chemical compound

4-Amino-2,2,6,6-tetramethyl-4-piperidine is an organic compound with the formula H2NCH(CH2CMe2)2NH (where Me = CH3). Classified as a diamine, it is a colorless oily liquid.

In polymer chemistry, polymerisation inhibitors are chemical compounds added to monomers to prevent their self-polymerisation. Unsaturated monomers such as acrylates, vinyl chloride, butadiene and styrene require inhibitors for both processing and safe transport and storage. Many monomers are purified industrially by distillation, which can lead to thermally-initiated polymerisation. Styrene, for example, is distilled at temperatures above 100 °C whereupon it undergoes thermal polymerisation at a rate of ~2% per hour. This polymerisation is undesirable, as it can foul the fractionating tower; it is also typically exothermic, which can lead to a runaway reaction and potential explosion if left unchecked. Once initiated, polymerisation is typically radical in mechanism and as such many polymerisation inhibitors act as radical scavengers.

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<span class="mw-page-title-main">1-Hydroxy-2,2,6,6-tetramethylpiperidine</span> Organic compound

1-Hydroxy-2,2,6,6-tetramethylpiperidine is the organic compound with the formula C5H6Me4NOH (Me = CH3). A white solid, it is classified as a hydroxylamine. The compound has attracted interest as the reduced derivative of the popular radical 2,2,6,6-tetramethylpiperidin-1-yl)oxyl ("TEMPO"). It is a mild base.

<span class="mw-page-title-main">4-Acetamido-TEMPO</span> Chemical compound

4-acetamido-TEMPO is a stable radical used for oxidation reactions in organic chemistry. It is a derivative of TEMPO, from which it differs by the additional acetamide group.

<span class="mw-page-title-main">Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate</span> Chemical compound

Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is a hindered amine light stabilizer used to protect plastics and coatings such as paint from oxidation caused by weathering. like most compounds of this class, it's active form is an aminoxyl radical.

References

  1. Zakrzewski, Jerzy; Krawczyk, Maria (1 January 2011). "Reactions of Nitroxides. Part XII [1]. – 2,2,6,6-Tetramethyl-1-oxyl- 4-piperidyl Chloroformate – A New Reactive Nitroxyl Radical. A One-pot Synthesis of 2,2,6,6-Tetramethyl-1-oxyl-4-piperidyl N,N-Dialkyl-carbamates". Zeitschrift für Naturforschung B. 66 (5): 493–498. doi: 10.1515/znb-2011-0509 . S2CID   51802316.
  2. 1 2 3 4 Sigma-Aldrich Co., 4-Hydroxy-TEMPO. Retrieved on 2015-08-24.
  3. Ciriminna, Rosaria; Pagliaro, Mario (15 January 2010). "Industrial Oxidations with Organocatalyst TEMPO and Its Derivatives". Organic Process Research & Development. 14 (1): 245–251. doi:10.1021/op900059x.
  4. Wilcox, C. S.; Pearlman, A. (2008). "Chemistry and Antihypertensive Effects of Tempol and Other Nitroxides". Pharmacological Reviews. 60 (4): 418–69. doi:10.1124/pr.108.000240. PMC   2739999 . PMID   19112152.
  5. Lewandowski, M; Gwozdzinski, K. (2017). "Nitroxides as Antioxidants and Anticancer Drugs". International Journal of Molecular Sciences. 18 (11): 2490. doi: 10.3390/ijms18112490 . PMC   5713456 . PMID   29165366.
  6. Maio, N.; Lafont, B.A.P.; Sil, D.; Li, Y.; Bollinger, M.; Krebs, C. (2021). "Fe-S cofactors in the SARS-CoV-2 RNA-dependent RNA polymerase are potential antiviral targets". Science. 373 (6551): 236–241. doi: 10.1126/science.abi5224 . PMC   8892629 . PMID   34083449.