Misplaced Pages

#860139

57-455: A free radical is an atomic or molecular species with unpaired electrons on an otherwise open shell configuration. Free Radical may also refer to: Free radical A notable example of a radical is the hydroxyl radical (HO · ), a molecule that has one unpaired electron on the oxygen atom. Two other examples are triplet oxygen and triplet carbene ( ꞉ CH 2 ) which have two unpaired electrons. Radicals may be generated in

114-408: A functional group or substituent , and "radical" now implies "free". However, the old nomenclature may still appear in some books. The term radical was already in use when the now obsolete radical theory was developed. Louis-Bernard Guyton de Morveau introduced the phrase "radical" in 1785 and the phrase was employed by Antoine Lavoisier in 1789 in his Traité Élémentaire de Chimie . A radical

171-422: A two-center three-electron N–O bond. The stability is reminiscent of the stability of nitric oxide and nitrogen dioxide . Additional stability is attributed to the steric protection provided by the four methyl groups adjacent to the aminoxyl group . These methyl groups serve as inert substituents, whereas any CH center adjacent to the aminoxyl would be subject to abstraction by the aminoxyl. Regardless of

228-460: A group that is instead electron-withdrawing, the SOMO then interacts with the empty π* orbital. There are no electrons occupying the higher energy orbital formed, while a new SOMO forms that is lower in energy. This results in a lower energy and higher stability of the radical species. Both donating groups and withdrawing groups stabilize radicals. Another well-known albeit weaker form of delocalization

285-490: A key role in these defense mechanisms. These are often the three vitamins, vitamin A , vitamin C and vitamin E and polyphenol antioxidants . Furthermore, there is good evidence indicating that bilirubin and uric acid can act as antioxidants to help neutralize certain radicals. Bilirubin comes from the breakdown of red blood cells ' contents, while uric acid is a breakdown product of purines . Too much bilirubin, though, can lead to jaundice , which could eventually damage

342-492: A lifetime that is less than a few nanoseconds. To avoid confusion, particularly for carbon-centered radicals, Griller and Ingold introduced the following definitions: "Stabilized should be used to describe a carbon-centered radical, R · , when the R−H bond strength is weaker than the appropriate C−H bond of alkane." "Persistent should be used to describe a radical that has a lifetime that is significantly greater than methyl [radical] under

399-400: A mediator in controlled radical polymerization . TEMPO was discovered by Lebedev and Kazarnowskii in 1960. It is prepared by oxidation of 2,2,6,6-tetramethylpiperidine . The structure has been confirmed by X-ray crystallography . The reactive radical is well shielded by the four methyl groups. The stability of this radical can be attributed to the delocalization of the radical to form

456-413: A new lower-energy filled bonding-orbital and a singly-filled new SOMO, higher in energy than the original. While the energy of the unpaired electron has increased, the decrease in energy of the lone pair forming the new bonding orbital outweighs the increase in energy of the new SOMO, resulting in a net decrease of the energy of the molecule. Therefore, electron-donating groups help stabilize radicals. With

513-464: A normal organic compound. Organic radicals are inherently electron deficient thus the greater the electronegativity of the atom on which the unpaired electron resides the less stable the radical. Between carbon, nitrogen, and oxygen, for example, carbon is the most stable and oxygen the least stable. Electronegativity also factors into the stability of carbon atoms of different hybridizations. Greater s-character correlates to higher electronegativity of

570-528: A number of ways, but typical methods involve redox reactions , ionizing radiation , heat, electrical discharges, and electrolysis are known to produce radicals. Radicals are intermediates in many chemical reactions, more so than is apparent from the balanced equations. Radicals are important in combustion , atmospheric chemistry , polymerization , plasma chemistry, biochemistry , and many other chemical processes. A majority of natural products are generated by radical-generating enzymes. In living organisms,

627-456: A photosensitizer. Typical chemical transformations with this singlet dioxygen species involve, among others, conversion of cellulosic biowaste into new poylmethine dyes. In chemical equations, radicals are frequently denoted by a dot placed immediately to the right of the atomic symbol or molecular formula as follows: Radical reaction mechanisms use single-headed arrows to depict the movement of single electrons: The homolytic cleavage of

SECTION 10

#1732793894861

684-430: A prevalent radical, O 2 reacts with many organic compounds to generate radicals together with the hydroperoxide radical. Drying oils and alkyd paints harden due to radical crosslinking initiated by oxygen from the atmosphere. The most common radical in the lower atmosphere is molecular dioxygen. Photodissociation of source molecules produces other radicals. In the lower atmosphere, important radical are produced by

741-824: A series of 13-hydroxyoctadecadienoic acid and 9-hydroxyoctadecadienoic acid products that serve as signaling molecules that may trigger responses that counter the tissue injury which caused their formation. ROS attacks other polyunsaturated fatty acids, e.g. arachidonic acid and docosahexaenoic acid , to produce a similar series of signaling products. Reactive oxygen species are also used in controlled reactions involving singlet dioxygen 1 O 2 {\displaystyle {}^{1}\mathrm {O} _{2}} known as type II photooxygenation reactions after Dexter energy transfer ( triplet-triplet annihilation ) from natural triplet dioxygen 3 O 2 {\displaystyle {}^{3}\mathrm {O} _{2}} and triplet excited state of

798-540: A spin-paired molecule by breaking a covalent bond, leaving each of the fragments with one of the electrons in the bond. Because breaking a chemical bond requires energy, homolysis occurs under the addition of heat or light. The bond dissociation energy associated with homolysis depends on the stability of a given compound, and some weak bonds are able to homolyze at relatively lower temperatures. Some homolysis reactions are particularly important because they serve as an initiator for other radical reactions. One such example

855-528: A stoichiometric amount of sodium chlorite . TEMPO oxidations also exhibit chemoselectivity , being inert towards secondary alcohols, but the reagent will convert aldehydes to carboxylic acids. The oxidation of TEMPO can be highly selective. It has been proven that secondary alcohols are more likely to be oxidized by TEMPO under an acidic environment. The reason is when in this condition, secondary alcohols are more easily able to provide an H ion. In cases where secondary oxidizing agents cause side reactions, it

912-444: Is hyperconjugation . In radical chemistry, radicals are stabilized by hyperconjugation with adjacent alkyl groups. The donation of sigma (σ) C−H bonds into the partially empty radical orbitals helps to differentiate the stabilities of radicals on tertiary, secondary, and primary carbons. Tertiary carbon radicals have three σ C-H bonds that donate, secondary radicals only two, and primary radicals only one. Therefore, tertiary radicals are

969-409: Is α-tocopherol ( vitamin E ). The tocopherol radical itself is insufficiently stable for isolation, but the parent molecule is a highly effective hydrogen-atom donor. The C−H bond is weakened in triphenylmethyl (trityl) derivatives. A large variety of inorganic radicals are stable and in fact isolable. Examples include most first-row transition metal complexes. With regard to main group radicals,

1026-407: Is a chemical compound with the formula (CH 2 ) 3 (CMe 2 ) 2 NO. 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

1083-456: Is an important example of a stable diradical. Singlet oxygen , the lowest-energy non-radical state of dioxygen, is less stable than the diradical due to Hund's rule of maximum multiplicity . The relative stability of the oxygen diradical is primarily due to the spin-forbidden nature of the triplet-singlet transition required for it to grab electrons, i.e., " oxidize ". The diradical state of oxygen also results in its paramagnetic character, which

1140-541: Is an important source of radicals (see eq. 1 below). These reactions give the chlorine radical, Cl , which catalyzes the conversion of ozone to O 2 , thus facilitating ozone depletion ( eq. 2.2 – eq. 2.4 below). Such reactions cause the depletion of the ozone layer , especially since the chlorine radical is free to engage in another reaction chain; consequently, the use of chlorofluorocarbons as refrigerants has been restricted. Radicals play important roles in biology. Many of these are necessary for life, such as

1197-476: Is available. For combustion to occur, the energy barrier between these must be overcome. This barrier can be overcome by heat, requiring high temperatures. The triplet-singlet transition is also " forbidden ". This presents an additional barrier to the reaction. It also means molecular oxygen is relatively unreactive at room temperature except in the presence of a catalytic heavy atom such as iron or copper. Combustion consists of various radical chain reactions that

SECTION 20

#1732793894861

1254-514: Is conferred to the radical anion when the charge can be delocalized . Examples include alkali metal naphthenides , anthracenides , and ketyls . Hydrogen abstraction generates radicals. To achieve this reaction, the C-H bond of the H-atom donor must be weak, which is rarely the case in organic compounds. Allylic and especiall doubly allylic C-H bonds are prone to abstraction by O 2 . This reaction

1311-400: Is demonstrated by its attraction to an external magnet. Diradicals can also occur in metal-oxo complexes , lending themselves for studies of spin forbidden reactions in transition metal chemistry. Carbenes in their triplet state can be viewed as diradicals centred on the same atom, while these are usually highly reactive persistent carbenes are known, with N-heterocyclic carbenes being

1368-474: Is possible to stoichiometrically convert TEMPO to the oxoammonium salt in a separate step. For example, in the oxidation of geraniol to geranial , 4-acetamido-TEMPO is first oxidized to the oxoammonium tetrafluoroborate. TEMPO can also be employed in nitroxide-mediated radical polymerization (NMP), a controlled free radical polymerization technique that allows better control over the final molecular weight distribution. The TEMPO free radical can be added to

1425-431: Is that there are many chemically unstable molecules that have zero spin, such as C 2 , C 3 , CH 2 and so on. This definition is more convenient for discussions of transient chemical processes and astrochemistry; therefore researchers in these fields prefer to use this loose definition. TEMPO (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl or (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl , commonly known as TEMPO ,

1482-429: Is the N -oxoammonium salt . In a catalytic cycle with sodium hypochlorite as the stoichiometric oxidant, hypochlorous acid generates the N -oxoammonium salt from TEMPO. One typical reaction example is the oxidation of ( S )-(−)-2-methyl-1-butanol to ( S )-(+)-2-methylbutanal: 4-Methoxyphenethyl alcohol is oxidized to the corresponding carboxylic acid in a system of catalytic TEMPO and sodium hypochlorite and

1539-442: Is the basis of drying oils , such as linoleic acid derivatives. In free-radical additions , a radical adds to a spin-paired substrate. When applied to organic compounds, the reaction usually entails addition to an alkene. This addition generates a new radical, which can add to yet another alkene, etc. This behavior underpins radical polymerization , technology that produces many plastics . Radical elimination can be viewed as

1596-537: Is the basis of the radical chain reaction . The art of polymerization entails the method by which the initiating radical is introduced. For example, methyl methacrylate (MMA) can be polymerized to produce Poly(methyl methacrylate) (PMMA – Plexiglas or Perspex) via a repeating series of radical addition steps: Newer radical polymerization methods are known as living radical polymerization . Variants include reversible addition-fragmentation chain transfer ( RAFT ) and atom transfer radical polymerization ( ATRP ). Being

1653-433: Is the homolysis of halogens, which occurs under light and serves as the driving force for radical halogenation reactions. Another notable reaction is the homolysis of dibenzoyl peroxide, which results in the formation of two benzoyloxy radicals and acts as an initiator for many radical reactions. Classically, radicals form by one-electron reductions . Typically one-electron reduced organic compounds are unstable. Stability

1710-427: The aging process itself. Similarly, the process of mito hormesis suggests that repeated exposure to radicals may extend life span. Because radicals are necessary for life, the body has a number of mechanisms to minimize radical-induced damage and to repair damage that occurs, such as the enzymes superoxide dismutase , catalase , glutathione peroxidase and glutathione reductase . In addition, antioxidants play

1767-401: The lung . This process promotes the development of emphysema . Oxybenzone has been found to form radicals in sunlight, and therefore may be associated with cell damage as well. This only occurred when it was combined with other ingredients commonly found in sunscreens, like titanium oxide and octyl methoxycinnamate . ROS attack the polyunsaturated fatty acid , linoleic acid , to form

Free radical (disambiguation) - Misplaced Pages Continue

1824-399: The 20th century the word "radical" was used in chemistry to indicate any connected group of atoms, such as a methyl group or a carboxyl , whether it was part of a larger molecule or a molecule on its own. A radical is often known as an R group . The qualifier "free" was then needed to specify the unbound case. Following recent nomenclature revisions, a part of a larger molecule is now called

1881-512: The breaking bond is drawn with a "fish-hook" arrow to distinguish from the usual movement of two electrons depicted by a standard curly arrow. The second electron of the breaking bond also moves to pair up with the attacking radical electron. Radicals also take part in radical addition and radical substitution as reactive intermediates . Chain reactions involving radicals can usually be divided into three distinct processes. These are initiation , propagation , and termination . Until late in

1938-449: The carbon atom (due to the close proximity of s orbitals to the nucleus), and the greater the electronegativity the less stable a radical. sp-hybridized carbons (50% s-character) form the least stable radicals compared to sp -hybridized carbons (25% s-character) which form the most stable radicals. The delocalization of electrons across the structure of a radical, also known as its ability to form one or more resonance structures, allows for

1995-840: The central nervous system, while too much uric acid causes gout . Reactive oxygen species or ROS are species such as superoxide , hydrogen peroxide , and hydroxyl radical , commonly associated with cell damage. ROS form as a natural by-product of the normal metabolism of oxygen and have important roles in cell signaling. Two important oxygen-centered radicals are superoxide and hydroxyl radical . They derive from molecular oxygen under reducing conditions. However, because of their reactivity, these same radicals can participate in unwanted side reactions resulting in cell damage. Excessive amounts of these radicals can lead to cell injury and death , which may contribute to many diseases such as cancer , stroke , myocardial infarction , diabetes and major disorders. Many forms of cancer are thought to be

2052-425: The electron deficiency to be spread over several atoms, minimizing instability. Delocalization usually occurs in the presence of electron-donating groups, such as hydroxyl groups (−OH), ethers (−OR), adjacent alkenes, and amines (−NH 2 or −NR), or electron-withdrawing groups, such as C=O or C≡N. Delocalization effects can also be understood using molecular orbital theory as a lens, more specifically, by examining

2109-425: The end of a growing polymer chain, creating a "dormant" chain that stops polymerizing. However, the linkage between the polymer chain and TEMPO is weak, and can be broken upon heating, which then allows the polymerization to continue. Thus, the chemist can control the extent of polymerization and also synthesize narrowly distributed polymer chains. TEMPO is sufficiently inexpensive for use on a laboratory scale. There

2166-451: The four methyl groups to impede the way of a reacting molecule so the structure is unstable. The stability of many (or most) organic radicals is not indicated by their isolability but is manifested in their ability to function as donors of H . This property reflects a weakened bond to hydrogen, usually O−H but sometimes N−H or C−H. This behavior is important because these H donors serve as antioxidants in biology and in commerce. Illustrative

2223-661: The gasoline-air mixture, tetraethyl lead was once commonly added to gasoline. This prevents the combustion from initiating in an uncontrolled manner or in unburnt residues ( engine knocking ) or premature ignition ( preignition ). When a hydrocarbon is burned, a large number of different oxygen radicals are involved. Initially, hydroperoxyl radical (HOO ) are formed. These then react further to give organic hydroperoxides that break up into hydroxyl radicals (HO ). Many polymerization reactions are initiated by radicals. Polymerization involves an initial radical adding to non-radical (usually an alkene) to give new radicals. This process

2280-518: The historical definition of radicals contends that the molecules have nonzero electron spin. However, in fields including spectroscopy and astrochemistry , the definition is slightly different. Gerhard Herzberg , who won the Nobel prize for his research into the electron structure and geometry of radicals, suggested a looser definition of free radicals: "any transient (chemically unstable) species (atom, molecule, or ion)". The main point of his suggestion

2337-425: The intracellular killing of bacteria by phagocytic cells such as granulocytes and macrophages . Radicals are involved in cell signalling processes, known as redox signaling . For example, radical attack of linoleic acid produces a series of 13-hydroxyoctadecadienoic acids and 9-hydroxyoctadecadienoic acids , which may act to regulate localized tissue inflammatory and/or healing responses, pain perception, and

Free radical (disambiguation) - Misplaced Pages Continue

2394-513: The intramolecular interaction of the unpaired electron with a donating group's pair of electrons or the empty π* orbital of an electron-withdrawing group in the form of a molecular orbital diagram. The HOMO of a radical is singly-occupied hence the orbital is aptly referred to as the SOMO, or the Singly-Occupied Molecular Orbital. For an electron-donating group, the SOMO interacts with the lower energy lone pair to form

2451-630: The modern chemical sense, as they are permanently bound to each other, and have no unpaired, reactive electrons; however, they can be observed as radicals in mass spectrometry when broken apart by irradiation with energetic electrons. In a modern context the first organic (carbon–containing) radical identified was the triphenylmethyl radical , (C 6 H 5 ) 3 C . This species was discovered by Moses Gomberg in 1900. In 1933 Morris S. Kharasch and Frank Mayo proposed that free radicals were responsible for anti-Markovnikov addition of hydrogen bromide to allyl bromide . In most fields of chemistry,

2508-539: The most abundant radical in the universe is also the most abundant chemical in the universe, H . Most main group radicals are not however isolable , despite their intrinsic stability. Hydrogen radicals for example combine eagerly to form H 2 . Nitric oxide (NO) is well known example of an isolable inorganic radical. Fremy's salt (Potassium nitrosodisulfonate, (KSO 3 ) 2 NO) is a related example. Many thiazyl radicals are known, despite limited extent of π resonance stabilization . Many radicals can be envisioned as

2565-499: The most common example. Triplet carbenes and nitrenes are diradicals. Their chemical properties are distinct from the properties of their singlet analogues. A familiar radical reaction is combustion . The oxygen molecule is a stable diradical , best represented by O–O . Because spins of the electrons are parallel, this molecule is stable. While the ground state of oxygen is this unreactive spin-unpaired ( triplet ) diradical, an extremely reactive spin-paired ( singlet ) state

2622-537: The most stable and primary radicals the least stable. Most simply, the greater the steric hindrance the more difficult it is for reactions to take place, and the radical form is favored by default. For example, compare the hydrogen-abstracted form of N -hydroxypiperidine to the molecule TEMPO . TEMPO, or (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, is too sterically hindered by the additional methyl groups to react making it stable enough to be sold commercially in its radical form. N -Hydroxypiperidine, however, does not have

2679-408: The persistency. This distinction is necessary because these two types of stability do not always correlate with each other. For example, benzylic radicals, which are known for their weak benzylic C−H bond strength, are thermodynamically stabilized due to resonance delocalization. However, these radicals are kinetically transient because they can undergo rapid, diffusion-limited dimerization, resulting in

2736-468: The photodissociation of nitrogen dioxide to an oxygen atom and nitric oxide (see eq. 1.1 below), which plays a key role in smog formation—and the photodissociation of ozone to give the excited oxygen atom O(1D) (see eq. 1.2 below). The net and return reactions are also shown ( eq. 1.3 and eq. 1.4 , respectively). In the upper atmosphere, the photodissociation of normally unreactive chlorofluorocarbons (CFCs) by solar ultraviolet radiation

2793-549: The products of breaking of covalent bonds by homolysis . The homolytic bond dissociation energies , usually abbreviated as "Δ H  °" are a measure of bond strength. Splitting H 2 into 2 H , for example, requires a Δ H  ° of +435 kJ/mol , while splitting Cl 2 into two Cl requires a Δ H  ° of +243 kJ/mol. For weak bonds, homolysis can be induced thermally. Strong bonds require high energy photons or even flames to induce homolysis. Diradicals are molecules containing two radical centers. Dioxygen (O 2 )

2850-694: The proliferation of malignant cells. Radical attacks on arachidonic acid and docosahexaenoic acid produce a similar but broader array of signaling products. Radicals may also be involved in Parkinson's disease , senile and drug-induced deafness , schizophrenia , and Alzheimer's . The classic free-radical syndrome, the iron-storage disease hemochromatosis , is typically associated with a constellation of free-radical-related symptoms including movement disorder, psychosis, skin pigmentary melanin abnormalities, deafness, arthritis, and diabetes mellitus. The free-radical theory of aging proposes that radicals underlie

2907-752: The radicals superoxide and nitric oxide and their reaction products regulate many processes, such as control of vascular tone and thus blood pressure. They also play a key role in the intermediary metabolism of various biological compounds. Such radicals can even be messengers in a process dubbed redox signaling . A radical may be trapped within a solvent cage or be otherwise bound. Radicals are either (1) formed from spin-paired molecules or (2) from other radicals. Radicals are formed from spin-paired molecules through homolysis of weak bonds or electron transfer, also known as reduction. Radicals are formed from other radicals through substitution, addition , and elimination reactions. Homolysis makes two new radicals from

SECTION 50

#1732793894861

2964-490: The reasons for the stability of the radical, the O–H bond in the hydrogenated derivative (the hydroxylamine 1-hydroxy-2,2,6,6-tetramethylpiperidine ) TEMPO–H is weak. With an O–H bond dissociation energy of about 70 kcal/mol (290 kJ/mol), this bond is about 30% weaker than a typical O–H bond. TEMPO is employed in organic synthesis as a catalyst for the oxidation of primary alcohols to aldehydes . The actual oxidant

3021-516: The result of reactions between radicals and DNA , potentially resulting in mutations that can adversely affect the cell cycle and potentially lead to malignancy. Some of the symptoms of aging such as atherosclerosis are also attributed to radical induced oxidation of cholesterol to 7-ketocholesterol. In addition radicals contribute to alcohol -induced liver damage, perhaps more than alcohol itself. Radicals produced by cigarette smoke are implicated in inactivation of alpha 1-antitrypsin in

3078-448: The reverse of radical addition. In radical elimination, an unstable radical compound breaks down into a spin-paired molecule and a new radical compound. Shown below is an example of a radical elimination reaction, where a benzoyloxy radical breaks down into a phenyl radical and a carbon dioxide molecule. The generation and reactivity of organic radicals are dependent on both their thermodynamic stability and kinetic stability, also known as

3135-456: The same condition." While relationships between thermodynamic stability and kinetic persistency is highly case-dependent, organic radicals can be generally stabilized by any or all of these factors: the presence of electronegativity, delocalization, and steric hindrance. The compound 2,2,6,6-tetramethylpiperidinyloxyl illustrates the combination of all three factors. It is a commercially available solid that, aside from being magnetic, behaves like

3192-490: The singlet radical can initiate. The flammability of a given material strongly depends on the concentration of radicals that must be obtained before initiation and propagation reactions dominate leading to combustion of the material. Once the combustible material has been consumed, termination reactions again dominate and the flame dies out. As indicated, promotion of propagation or termination reactions alters flammability. For example, because lead itself deactivates radicals in

3249-470: Was then identified as the root base of certain acids (the Latin word "radix" meaning "root"). Historically, the term radical in radical theory was also used for bound parts of the molecule, especially when they remain unchanged in reactions. These are now called functional groups . For example, methyl alcohol was described as consisting of a methyl "radical" and a hydroxyl "radical". Neither are radicals in

#860139