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Free-Radical Chain Reaction and Polymerization of Alkenes

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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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Radical Reactivity: Electrophilic Radicals01:02

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Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
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Roots, often written as radicals, identify the quantity that must be raised to a specific exponent to produce a given value. A radical expression consists of two main components: the radicand, which is the value placed inside the root symbol, and the index, which indicates the degree of the root being taken. The notation n√a indicates the principal nth root of a. If n equals 2, the operation is the square root, while n = 3 defines the cube root. When n is even, a negative radicand does...
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The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
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Radical equations are mathematical expressions in which the variable is found within a radical, most commonly a square root or cube root. These equations frequently arise in science, engineering, and real-world measurements involving nonlinear relationships. To solve a radical equation, the standard procedure is to isolate the radical expression and then eliminate the radical by raising each side to a power equal to the index of the radical. This process may lead to extraneous...
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Easy access to elusive radical reactions

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