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Radical Substitution: Halogenation of Alkanes and Alkyl Substituents01:27

Radical Substitution: Halogenation of Alkanes and Alkyl Substituents

9.7K
In the presence of heat or light, alkanes react with molecular halogens to form alkyl halides by a substitution reaction called radical halogenation. This reaction has three steps: initiation, propagation, and termination, as seen in the radical chlorination of methane to produce methyl chloride.
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
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Preparation of Alkynes: Dehydrohalogenation02:34

Preparation of Alkynes: Dehydrohalogenation

17.8K
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
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Radical Substitution: Allylic Bromination01:27

Radical Substitution: Allylic Bromination

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In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
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Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

2.2K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
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Halogenation of Alkenes02:46

Halogenation of Alkenes

18.3K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
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E1 Reaction: Kinetics and Mechanism02:46

E1 Reaction: Kinetics and Mechanism

17.4K
Here, in contrast to the E2 reaction mechanism, we delve into the aspects of the E1 reaction mechanism, which has two steps: rate-limiting loss of the leaving group and abstraction of the beta hydrogen by a weak base. Typically, the experimental proof for the E1 mechanism is via kinetic studies or isotope studies. While the former demonstrates the first-order kinetics—the dependence of the reaction solely on substrate concentration—the latter proves the abstraction of hydrogen only...
17.4K

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Updated: Jan 3, 2026

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

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Alkyl Halides via Visible Light Mediated Dehalogenation.

Manjula D Rathnayake1, Jimmie D Weaver1

  • 1Department of Chemistry , Oklahoma State University , 107, Physical Science , Stillwater , Oklahoma 74078 , United States.

Organic Letters
|November 15, 2019
PubMed
Summary

Selective C-H bond bromination and chlorination are achieved using a perhalogenation/dehalogenation method. Photochemical reductions occur without photocatalysts, relying on electron donor-acceptor complexes or autophotocatalysis.

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Area of Science:

  • Organic Chemistry
  • Photochemistry
  • Synthetic Methodology

Background:

  • Selective functionalization of C-H bonds is crucial in organic synthesis.
  • Photocatalysis is a growing area, but mechanistic understanding is key.
  • Amine-containing substrates can complicate photochemical reactions.

Purpose of the Study:

  • To develop a novel method for selective bromination and chlorination of activated C-H bonds.
  • To investigate photocatalyst-free photochemical reduction mechanisms.
  • To address challenges in photochemical reactions involving amines.

Main Methods:

  • A perhalogenation/dehalogenation sequence for selective halogenation.
  • Photochemical reduction utilizing electron donor-acceptor complex formation or autophotocatalysis.
  • Mechanistic studies to elucidate reaction pathways.

Main Results:

  • High yields of net selective bromination and chlorination were achieved.
  • Photochemical reductions proceeded efficiently without external photocatalysts.
  • Reactions occurred even without apparent photon absorption, highlighting complex mechanisms.

Conclusions:

  • The perhalogenation/dehalogenation sequence offers a facile route to selective C-H bond halogenation.
  • Photocatalyst-free reductions are viable through specific electronic interactions or self-catalysis.
  • Unexpected reaction outcomes in photochemistry necessitate careful mechanistic investigation.