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Organic Chemistry - Chapter 13 - Free Radicals
Organic Chemistry - Chapter 13 - Free Radicals
Status
Unit/Module Chapter 13
Week 2
13 FREE RADICALS
Radicals
- reactive intermediate with single unpaired electron ← homolysis of a covalent bond
- uses half-headed reaction in radical reaction
- do not have an octet of electrons → unstable & reactive
Classification
stability of radical increases as number of alkyl groups bonded to radical carbon increases → more alkyl group are more
polarizable than H-atoms, which can easily donate electron density to electron deficient radical, thus increasing stability
peroxides (RO—OR)
- heating, readily causes homolysis of weak O—O bond → RO· radical
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Reaction of a radical X· with a C=C bond: reaction with 𝜋 nonds
- using an electron from double bond → new C—X bond & other unpaired electron remains on the other carbon where the original
double bond is
- electron-rich alkene reacts with electrophiles by ionic addition mechanisms & with radicals because reactive intermedieate are
also electron deficient
- result: C—X bond & new radical
Halogenation of Alkanes
alkanes + halogens -hv or 𝚫→ alkyl halides
Halogenation
- radical substitution reaction: halogen (X) atom replaces a hydrogen via mechanism involving radical intermediates
- useful only with Cl₂ and Br₂— reaction with F₂ is too violent & with I₂ is too slow
13 Free Radicals 2
Monohalogenation
- substitution of a single H by X— through experimentally adding halogen X₂ to an excess of alkane
Mechanism of Halogenation
- all halogenation reaction of alkanes—reagardless of the halogen & alkane used— process by the same mechanism
Facts Explanation
[1] light, heat or added peroxide is light or heat provides energy required for homolytic bond cleavage to from radicals
necessary
breaking weak O—O bond initiates radicals reactions
Initiation:
- homolysis of σ bond to form two radicals
Propagation:
- radical reacts with another reactant to form a new σ bond & another radical
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Termination:
- two radicals combine to for a stable bond
- removal of radicals from reaction mixture without forming any new radicals to completely stop the reaction
combination of two radicals to form a bond, stoping the chain reaction of propagation
chlorination is unselective that yields a mixture of products, bromination is often selective that yields a major product
in bromination, major product results from cleavage of weakest (most stable, more substituted) C—H bond
Hammond Postulate
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📌 transition states in endothermic reactions resemble products → faster formation of more stable product
📌 transition states in exothermi reactions resemble reactants → relative stability of the product does not greatly affect the
relative energy of the transition state, resulting a mixture of products
more stable 2º radical is formed faster, hence the major product of bromination
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Halogenation as a Tool in Organic Synthesis
- it is a useful tool because it adds fuctional group to a previously functionalized molecule → alkyl halide.
- alkyl halide can be converted to alkene by elimination, and to alcohols and ethers by nucleophilic substitution
Reactants Product
if: reaction is at stereoegenic center → know the mechanism to predict strereochemistry of product
2-chlrobutane: has a new stereogenic center = two enantiomers → racemic mixture: [(R)- and (S)-2-chlorobuatNe
Racemic Mixture
- formed because first propagation step generates a planar, sp² hybridized radical— halogens can attach from either from or back side
hence, the equal amount of two enantiomers (R & S)
13 Free Radicals 6
Chlorination: Chiral (R)-2-bromobutane at C2 & C3
Chlorination at C2
- occurs at the strereogenic center
- abstraction of hydrogen atom C2 → forming trigonal planar sp² hybridized radical → reacts with Cl₂ from either side → new
stereogenic center = two enantiomer → racemic mixture
Chlorination at C3
- occure not at the steogenic center, but forms new stereogenic center
- C2 stereogenic center is retains
- abstraction of a H-atom at C3 → forming trigonal planar sp² hybridized radical → reaction new stereogenic center → product has
twi stereogenic centers: same configuration @ C2 but different for C3 → diastereomers
Chlorofluorocarbons (CFCs)
- suggested to be responsible for destroying ozone in upper atmosphere
- simple halogen containing organic compounds
- inert ordorless, and nontoxic, and have been used as refrigerants, solvents & aerosol propelllants
- volatile and water insoluble → readily escapes into upper atmosphere, where they decomposed by high-energy UV light → forming
radicals destroying ozone through radical chain mechanism
propagation: reaction of Cl· with O₃ → chloringmonoxide (ClO·) → recats with O-atoms → O₂ and Cl
- overall result: ozone (O₃) is consumed and O₂ is formed, wherein small amount of CFC can destroy large amount of O₃ ☹
Radical Halogenation at an Allylic Carbon
Allylic Carbon
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- carbon adjacent to a double bond
- through the homolysis of its C—H bond, it generates the allylic radical—unpaired electron on carbon adjacent to the double bond
Allylic Radical
- weaker C—H bond (more substituted), more stable the radical
- more stable thant 3º rdaical, because of it has more electron density to donate to stabilize the radical → hybrids
Resonance
- true structure if allylic radical isa hybrid of two resonance structures— 𝜋 bond and unpaired electron are delocalized
- delocalizing electron density lowers the energy of the hybrid, thus stabilizing the radical
inititation: homolysis of N—Br with light energy → forms Br·, initiating radical halogentaion
propagation: bromine radical abstracts an allylic H to afford allylic radical; allylic radical reacts with Br₂ to form allylic halide, bromine
radical formed as weel and repeatedly accour withough additional initiation
→ second chain propagation: needs low concentration of Br₂, which NBS generates
13 Free Radicals 8
Allylic Carbon: Product Mixtures in Allylic Halogenation
Halogenation at Allylic Carbon
- results a mixture of product, because the reaction proceeds by way of resonance stabilized radical
- abstraction of allylic hydrogen from alkene with Br· (from NBS) forms ally;ic radical which two different lewis structure can be drawns
- when two different resonance structures can be drawn for an allylic radical, two different allylic halides are formed by radical
substitution
Application: Antioxidants
Antioxidants
- compound that stops oxidation from occuring (radical inhibitor)
butyl hydroxy toluene (BHT_, added to packaged & prepped food to preven oxidation & spoilage
(radical inhibitors hence, terminates radical chain mechanism by reacting with radicals using hydroxy group bonded to a benzez
ring— phenol)
- radicals (R·) abstracts hydrogen atom from OH group of antioxidants → new resonance stabilized radical → new radical do not
partcipate in chain propagation but terminates the chain & halts oxidation processS
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Radical Addition Reactions to Double Bond
Addition to Double Bonds
- second common radical reactions
- electron-deficient radical reacts to alkene, an electron-rich
- radicals react with alkenes via radical chain mechanism:
initiation: homolysis of weak O—O bond & abstraction of H from H—Br → Br·
propagation: addition to terminal carbon, abstraction of H from HBr → new C—H bond Br· (repeats)
radical addition: (HBr without added light, heat or peroxides) Br· to less substituted carbon forming more stable radical
ionic addition: (HBr with added light, heat or peroxides) Br· to more substituted carbon forming a more stable carbocation
Polymers
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Radical Polymerization
preparation of polymers are by polymerization of alkene monomers by adding a radical to 𝜋 bond— resembles radical addition of HBr
to alkene except that a carbon radical rather than bromine atom is added to the double bond
inititaion: homolysis of weak O—O bond and addition of RO· to alkene → carbon radical
propagation: chain propagation— carbon radical adds to another alkene → C—C bond and another carbon radical. Addition formes
a radical with unpaired electron on the atom with Z substituent
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