Octet

Octet / Reactions

Anti-Markovnikov HBr Addition (Radical)

Anti-Markovnikov HBr Addition (Radical) (Addition.) Converts CC=C to CCCBr using HBr, ROOR (peroxide). Conditions: Peroxide initiator (light or heat).

Addition

Reaction details

Name

Anti-Markovnikov HBr Addition (Radical)

Type

Addition

Starting Material

CC=C

Product

CCCBr

Reagents

  • HBr

  • ROOR (peroxide)

Conditions

Peroxide initiator (light or heat)

Mechanism
  1. Smiles

    CC=C

    Description

    Propene

  2. Smiles

    CC=C

    Description

    Br• adds to less substituted carbon (more stable radical)

  3. Smiles

    CCCBr

    Description

    1-Bromopropane (anti-Markovnikov product)

Regiochemistry

Anti-Markovnikov: Br on less substituted carbon

Tips

  1. ONLY works with HBr (not HCl or HI)

  2. Peroxide initiates radical chain

  3. Opposite regiochemistry from ionic addition

  4. Radical stability: 3° > 2° > 1° (same as carbocation)

Related Reactions

  • hydrohalogenation

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Reactions

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Substitution

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SN2 with Cyanide (SN2 Substitution.) Converts CCI to CC#N using NaCN, KCN. Conditions: Polar aprotic solvent in DMSO or DMF. Stereochemistry: Inversion of configuration.

Substitution

SN1 Solvolysis

SN1 Solvolysis (SN1 Substitution.) Converts CC(C)(C)Br to CC(C)(C)O using H₂O. Conditions: Polar protic solvent, heat in Water or aqueous ethanol. Stereochemistry: Loss of stereocontrol (planar carbocation attacked from either face → racemization if chiral ce...

Substitution

SN2 with Tosylate Leaving Group

SN2 with Tosylate Leaving Group (SN2 Substitution.) Converts CCOS(=O)(=O)c1ccc(C)cc1 to CCN=[N+]=[N-] using NaN₃. Conditions: Polar aprotic solvent.

Substitution

SN2 with Azide

SN2 with Azide (SN2 Substitution.) Converts CCBr to CCN=[N+]=[N-] using NaN₃. Conditions: Polar aprotic solvent.

Substitution

E2 Elimination

E2 Elimination (E2 Elimination.) Converts CC(Br)CC to CC=CC using KOtBu, NaOEt, NaOH (conc.). Conditions: Strong base, heat in t-BuOH or EtOH. Stereochemistry: Anti-periplanar geometry required. E/Z depends on which H is removed..

Elimination

Study guides

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