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Chapter 20

Radical Chemistry

Radicales: Estructura Electrónica y Geometría
Radicales: Estructura Electrónica y Geometría
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a ...
Espectroscopía de Resonancia Paramagnética Electrónica (EPR): Radicales Orgánicos
Espectroscopía de Resonancia Paramagnética Electrónica (EPR): Radicales Orgánicos
Ideally, an unpaired electron shows a single peak in the EPR spectrum due to the transition between the two spin energy states. However, coupling ...
Formación Radical: Visión General
Formación Radical: Visión General
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to ...
Formación de radicales: homólisis
Formación de radicales: homólisis
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up ...
Formación Radical: Abstracción
Formación Radical: Abstracción
The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For ...
Formación de radicales: Adición
Formación de radicales: Adición
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical ...
Formación de Radicales: Eliminación
Formación de Radicales: Eliminación
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. ...
Reactividad radical: Visión general
Reactividad radical: Visión general
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in ...
Reactividad radical: efectos estéricos
Reactividad radical: efectos estéricos
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the ...
Reactividad de radicales: efectos de concentración
Reactividad de radicales: efectos de concentración
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and ...
Reactividad de radicales: radicales electrofílicos
Reactividad de radicales: radicales electrofílicos
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For ...
Reactividad de radicales: radicales nucleofílicos
Reactividad de radicales: radicales nucleofílicos
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The ...
Reactividad de radicales: intramolecular vs intermolecular
Reactividad de radicales: intramolecular vs intermolecular
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an ...
Autoxidación radical
Autoxidación radical
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form ...
Oxidación radical de alcoholes alílicos y bencílicos
Oxidación radical de alcoholes alílicos y bencílicos
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are ...
Sustitución radical: halogenación de alcanos y sustituyentes de alquilo
Sustitución radical: halogenación de alcanos y sustituyentes de alquilo
In the presence of heat or light, alkanes react with molecular halogens to form alkyl halides by a substitution reaction called radical halogenation. This ...
Halogenación Radical: Termodinámica
Halogenación Radical: Termodinámica
The thermodynamic favorability of a reaction is determined by the change in Gibbs free energy (ΔG). ΔG has two components- enthalpy (ΔH) ...
Halogenación radical: estereoquímica
Halogenación radical: estereoquímica
Stereochemistry is the study of the different spatial arrangements of atoms in a given molecule. The stereochemistry of radical halogenations can be ...
Sustitución de radicales: cloración alílica
Sustitución de radicales: cloración alílica
Typically, when alkenes react with halogens at low temperatures, an addition reaction occurs. However, upon increasing the temperature or under reaction ...
Sustitución radical: bromación alílica
Sustitución radical: bromación alílica
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is ...
Sustitución de radicales: Hidrogenólisis de haluros de alquilo con hidruro de tributilo de estaño
Sustitución de radicales: Hidrogenólisis de haluros de alquilo con hidruro de tributilo de estaño
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the ...
Adición radical anti-Markovnikov a los alquenos: Resumen
Adición radical anti-Markovnikov a los alquenos: Resumen
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl ...
Adición radical anti-Markovnikov a los alquenos: mecanismo
Adición radical anti-Markovnikov a los alquenos: mecanismo
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain ...
Adición radical anti-Markovnikov a los alquenos: termodinámica
Adición radical anti-Markovnikov a los alquenos: termodinámica
The anti-Markovnikov addition of hydrogen halides to an alkene is thermodynamically feasible only with HBr. The radical addition reaction with other ...
Dioles vecinales mediante acoplamiento reductor de aldehídos o cetonas: Descripción general del acoplamiento de Pinacol
Dioles vecinales mediante acoplamiento reductor de aldehídos o cetonas: Descripción general del acoplamiento de Pinacol
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of ...
Alquenos mediante acoplamiento reductor de aldehídos o cetonas: reacción de McMurry
Alquenos mediante acoplamiento reductor de aldehídos o cetonas: reacción de McMurry
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used ...
α-hidroxicetonas mediante acoplamiento reductor de ésteres: descripción general de la condensación de aciloína
α-hidroxicetonas mediante acoplamiento reductor de ésteres: descripción general de la condensación de aciloína
The pinacol and McMurry reactions involve the reductive coupling of ketones or aldehydes. Similarly, the bimolecular reductive coupling of two ester ...
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