C hemistry 31

R a dica l R ea c t ions
U N IV E R S ITY OF TH E PH ILIPP IN E S M A N ILA
P adre Faura, E rmita, M anila
A.Y. 2009 – 2010, S econd S emester
Ms. Anjelyn del Rosario
 Introduction: Alkanes
A lk a nes
– s a tura ted hydroc a rbo ns

– fairly unreactive; (old family name, pa ra ffin , meant little

reactivity)
– have relatively strong, almost NO N-P O LAR , S ING LE covalent
bonds
– have only strong δ bonds , they have no real sites that will
encourage substances to attack them
– D ue to lack of reactivity, alkanes need a very reactive species
to persuade them to react

2
 Breaking of Covalent Bonds
There are 3 ways to split the shared electron pair in an
unsymmetrical covalent bond.

U N E QUA L S PLITTIN G
produces ION S
known as H E T E R O LY S I S

E QUA L S PLITTIN G
produces R A D IC A LS
known as H O M O LY S I S

• If several bonds are present the weakest bond is usually broken first
• E nergy to break bonds can come from a variety of energy sources -
heat / light
• In the reaction between methane and chlorine either can be used,
however... C HE M 31 adr 3
• In the laboratory a source of UV light (or sunlight) is favoured.
 Free Radicals : Definition
• A R a dic a l is a reactive intermediate with a single unpaired
electron, formed by homolysis of a covalent bond.
• A radical contains an atom that does not have an octet of
electrons .
• Half-headed arrows are used to show the movement of
electro ns in radical processes.

• A carbon radical is sp2 hybridized and trigonal planar

C HE M 31 adr 4
 Free Radicals: Stabilities
R ela tive S ta bilities o f A lk yl
R a dic a ls

S ta bilized by res o na nc e S ta bilized by hyperc o njug a tio n

- D elocalization of electrons by the
overlap of a δ bo nd orbital with an
empty p orbital

T he m ore s ta ble the ra dic a l, the les s energ y required to m a ke

5 it.
 Free Radicals: Stabilities
R ela tive S ta bilities o f A lk yl
R a dic a ls

H yperc o njug a tio n

- D elocalization of electrons by the overlap of a δ bo nd orbital with
an empty p orbital
- occurs only if the δ bond orbital and the empty p orbital have the
proper orienta tio n
M ovement of electrons from the δ
bond orbital toward the p orbital of
e-s the ethyl radical dec rea s es the
c ha rg e o n the s p 2 c a rbo n
The unpaired electron is no lo ng er
lo c a lized solely on one atom, but is
s prea d o ut over a g rea ter vo lum 6 e
o f s pa c e
 The sp2 carbons of an alkene are called
Free Radicals: Stabilities
vinylic c a rbo ns . An sp3 carbon that
is adjacent to a vinylic carbon is called
R ela tive S ta bilities o f A lkanyla llylic c a rbo n.
R a dic a ls
• An a llylic ra dic a l has an unpaired electron on an allylic
carbon
• The allyl radical is more stable than other radicals because
two resonance forms can be drawn for it.

C HE M 31 adr 7
 Free Radicals: Stabilities
R ela tive S ta bilities o f A lk yl
R a• dic a ls
A benzylic ra dic a l has an unpaired electron on a
benzylic carbon
• Five contributing resonance structures

• B ecause of their delocalized electrons, allyl and benzyl

radicals are both more stable than other primary radicals.

C HE M 31 adr 8
 Radical Reactions
G enera l Fea tures o f R a dic a l R ea c tio ns
• R adicals are formed from covalent bonds by adding energy in
the form of heat (∆ ) or light (hν ).
• S ome radical reactions are carried out in the presence of a
ra dic a l initia to r .
– R adical initiators contain a especially w ea k bo nd that
serves as a source of radicals.
– P eroxides , compounds having the general structure R O — O R ,
are the most commonly used radical initiators.
– Heating a peroxide readily causes homolysis of the weak O —
O bond, forming two R O • radicals.
• R adicals undergo two main types of reactions —they react
with σ bonds, and they add to π bonds .
C HE M 31 adr 9
 Radical Reactions
R ea c tio n o f a R a dic a l X • w ith a C -H B ond.
• A radical X • abstracts a hydrogen atom from a C — H σ bond to
from H— X and a carbon radical.

R ea c tio n o f a R a dic a l X • w ith a C =C B o nd.

• A radical X • also adds to the π bond of a carbon— carbon double
bond.

10
 Radical Reactions
Tw o R a dic a ls R ea c ting w ith E a c h O ther.
• A radical X •, once formed, ra pidly rea c ts w ith w ha tever is
a va ila ble , usually a stable σ or π bond.
• O ccasionally, two radicals react to form a s igma bond.

• The reaction of a radical with oxygen (a diradical in its ground s tate

electronic configuration) is another example of two radicals reacting
with each other.

• C ompounds that prevent radical reactions from occurring are called

ra dic a l inhibito rs or ra dic a l s c a veng ers . B es ides O 2, vitamin
E and other related compoundsC HEare
M 31 adr
radical scavengers. 11
 The Reaction of Alkanes with Halogens
a log ena tio n R ea c tions
• Alkanes undergo s ubs titutio n rea c tions with halogens
(fluorine, bromine and chlorine) initiated by heat or light

• R adical halogenation can yield a m ix ture of

ha lo g ena ted c o m po unds because all hydrogen atoms
in an alkane are capable of substitution.
– For example, all degrees of methane halogenation will be
seen

• M onosubstitution can be achieved

C HE M 31 adr by using a la rg e 12
 The Reaction of Alkanes with Halogens
H a lo g ena tion o f A lk a nes — R ea c tio n M ec ha nis m

• Three facts about halogenation suggest that the mechanism

involves radical, not ionic, intermediates:

ra dic a l inhibitor

U N L I K E c a rbo c a tio ns

C HE M 31 adr 13
 Chlorination of Methane
R ea g ents c hlo rine a nd m etha ne

C o nditio ns U V lig ht o r s unlig ht - hea t is a n a lterna tive energ y

s o urc e

E qua tio n(s ) C H 4 (g ) + C l 2 (g ) ——> H C l(g ) + C H 3 C l(g )

chloromethane
C H 3 C l(g ) + C l 2 (g ) — — > H C l(g ) + C H 2 C l 2 (l)
dichloromethane C H 2 C l 2 (l) + C l 2 (g ) ——> H C l(g ) +
C H C l 3 (l) trichloromethane C H C l 3 (l) + C l 2 (g ) — — >
H C l(g ) + C C l 4 (l) tetrachloromethane

M ix tures free ra dic a ls a re very rea c tive - they a re trying

to pa ir their elec tro n
w ith s uffic ient c hlo rine, every hydro g en w ill eventua lly
be repla c ed.
14
M ec ha nis m C hlo rina tio n o f m etha ne pro c eeds via FR E E R A D I C A L
 Radical Reactions - Mechanism

m ec ha nis m for the m o no c hlo rina tio n

o f m etha ne

C HE M 31 adr AD R 15
 Chlorination of Methane

Initiation C l2 ——> 2C l • R A D I C A L S C R E AT E D

T he s ing le dots repres ent U N PA I R E D E L E C T R O N S

D uring initia tio n, the W E A K E S T B O N D I S B R O K E N a s it

requires les s energ y.
T here a re three pos s ible bo nds in a m ix ture o f a lk a nes a nd
c hlo rine.

412 348 242

A vera g e bond entha lpy k J m o l -1
16
T he C l-C l bond is broken in preferenc e to the others a s it is
 Chlorination of Methane

Propagation C l• + C H 4 — — > C H 3• + HCl

R A D I C A L S U S E D and
C l2 + C H 3• — — > C H 3C l + C l• then R E -
G E N E R AT E D

Free ra dic a ls a re very rea c tive bec a us e they w a nt to pa ir up

their s ing le elec tron .
T hey do this by a bs tra c ting a hydrog en a tom from m etha ne;
a m ethyl ra dic a l is form ed.
T he m ethyl ra dic a l is a ls o very
C HE M 31 rea
adr c tive a nd a tta c k s a 17
 Chlorination of Methane

C l• + C l• ——> C l2 R ADIC A LS
Termination
R E M OV E D
C l• + C H 3• — — > C H 3C l
C H 3• + C H 3• — — > C 2H 6
R em oving the
rea c tive free
ra dic a ls bring s
a n end to the
rea c tio n.

T his is no t very
likely a t the
s ta rt of the
rea c tio n
bec a us e of
their low
C HE M 31 adr 18
c onc entra tion.
 Chlorination of Methane
OV E R V I E W
I nitia tio n C l2 — — > 2C l • radicals
c rea ted

P ropa g a tio n C l• + CH4 ——> C H 3• + HCl radicals

us ed and
C l2 + C H 3• ——> C H 3C l + C l • then re-
g enera ted

Term ina tio n C l• + C l• — — > C l2 radicals

Srem
um oved
m a ry
D ue to la c k o f rea c tivity,
C l • +a lk
CH a nes need — a— very
> Crea
H 3 Ccltive s pec ies to
3•
pers ua de them to rea c t.
C H 3• + C H 3• — — > C 2H 6
Free ra dic a ls need to be fo rm ed by ho m o lytic fis s io n o f c ova lent
bo nds .
T his is do ne by s hining U V lig ht o n the m ix ture (hea t c o uld be
us ed).
C hlo rine ra dic a ls a re produc edC HEbec
M 31 a us e the C l-C l bo nd is the
adr 19
 Radical Reactions - Mechanism

E lec tron Flow fo r the M o no c hlorina tio n o f

M etha ne

C HE M 31 adr AD R 20
 Further Chlorination of Methane
Further
pro pa g a tio n I f ex c es s c hlo rine is pres ent, further
s ubs titutio n ta kes pla c e
T he equa tio ns s how the pro pa g a tio n s teps fo r the
form a tio n o f...

dic hlo ro m etha ne C l• + C H 3C l ——> C H 2C l• +

HCl
C l2 + C H 2C l• ——> C H 2C l2 + C l•

tric hlo ro m etha ne C l• + C H 2C l2 ——> C H C l2• +

HCl
C l2 + C H C l2• ——> C H C l3 + C l•

tetra c hlo ro m etha ne C l• + C H C l3 ——> C C l3• +

C HE M 31 adr 21
HCl
Chlorination of Ethane

22
 Radical Reactions

Halogenation of E thane— R eaction M echanism

C HE M 31 adr 23
 Radical Reactions

Halogenation of E thane— E nergetics

C HE M 31 adr 24
 Halogenation of Higher Alkanes
• E xperimental: C hlorination of C H 3C H 2C H 3 yields a 1:1 mixture of
C H 3C H 2C H 2C l and (C H 3)2C HC l.

• S ince the observed ratio between C H 3C H 2C H 2C l and (C H 3)2C HC l

is 1:1, the 2° C — H bonds must be more reactive than the 1° C — 25H
 Halogenation of Higher Alkanes

• Thus, when alkanes react with C l2, a mixture of products results, with
more product formed by cleavage of the weaker C — H bond than you
would expect on statistical grounds.
rela tive s ta bilities of a lk yl ra dic a ls

26
 Factors that Determine Product Distribution
P ercent Yield of M onohalogenated P roducts

R ela tive R a tes of A lk yl R a dic a l Form a tio n by a C hlorine

R a dic a l

C HE M 31 adr 27
Percent Yield of Monohalogenated Products
R ela tive A m o unts o f P ro duc ts
•pro ba bility - the number of hydrogens that can be abstracted
that will lead to the formation of the particular product
•rea c tivity - the relative rate at which a particular hydrogen is
abs tracted
rela tive a m ount = number of hydrogens × reactivity
perc ent yield =________________________________
relative amount x 100
sum of the relative amounts of all
the alkyl halide products

R a dic a l m ono c hlo rina tion of buta ne

C HE M 31 adr 28
 Percent Yield of Monohalogenated Products
R a dic a l m o no c hlorina tio n o f 2,2,5-
trim ethylhex a ne

N OTE :
Because radical chlorination of an alkane can yield several different
monosubstitution products as well as products that contain more than one
chlorine atom, it is not the bes t m etho d for synthesizing an alkyl halide.
C HE M 31 adr 29
 Radical Reactions
C hlo rina tio n vers us B rom ina tion
• Although alkanes undergo radical substitutions with both C l2 and
Br2, chlorination and bromination exhibit two important
differences.
1. C hlorination is fa s ter than bromination.
2. C hlo rina tio n is uns elec tive , yielding a mixture of
products, but bro m ina tio n is o ften s elec tive , yielding
one major product.

C HE M 31 adr 30
 Radical Reactions
e R ea c tivity– S elec tivity P rinc iple
• T he m o re rea c tive a s pec ies is , the les s s elec tive it
w ill tive
rela be. ra tes of ra dic a l form a tion by a brom ine ra dic a l
a t 125 °C

• A bromine radical is les s rea c tive and m o re s elec tive than

a chlorine radical.

31
 The Reactivity- Selectivity Principle
Why are the relative rates of radical formation s o different when a
bromine radical rather than a chlorine radical is used as the
hydrogen-abstracting reagent?
c o m pa re the ∆H ° va lues ! (∆H°= bonds being broken - bonds being for

N O T E : Bromination is a much slower reaction than

chlorination. C HE M 31 adr 32
 Chlorination vs. Bromination

B ro m ina tio n
• The differences in chlorination and bromination can be explained
by considering the energetics of each type of reaction.
• C alculating the ∆ H 0 using bond dissociation energies reveals that
abstraction of a 1 ° or 2 ° hydrogen by B r• is endothermic, but it
takes less energy to form the more stable 2 ° radical.

C HE M 31 adr 33
 Bromination
T.S . will
R em em ber H a m m ond pos tula te have a partially unpaired
electron on carbon
The same factors that stabilize the
radical product stabilize the partially
unpaired transition state.

more stable the transition

state, the smaller the E a, the
faster the reaction

C onc lus io n: B ecause the rate-determining step is endothermic, the

m o re s ta ble ra dic a l is fo rm ed fa s ter, and often a single radical
halogenation product predominates.C HE M 31 adr 34
 Chlorination vs. Bromination
C hlo rina tion
• C alculating the ∆ H ° using bond dissociation energies for
chlorination reveals that abstraction of a 1 ° or 2 ° hydrogen by C l• is
exothermic.

• S ince chlorination has an exothermic rate-determining s tep, the

trans ition state to form both radicals resembles the same s tarting
material, C H 3C H 2C H 3. Thus, the relative stability of the two radicals
is much less important, and both radicals are formed.
C HE M 31 adr 35
 Chlorination

E nergy diagram for the exothermic reaction:

C H 3C H 2C H 3 + C I• → C H 3C H 2C H 2• or (C H 3)2C H • + HC I

the relative stability of the two radicals

is much less important

C onc lus io n: B ecause the rate-determining step in chlorination is

exothermic, the transition state resembles the s tarting material, both
radicals are formed, and a mixture of products results .
C HE M 31 adr 36
 The Reactivity- Selectivity Principle
E nerg y D ia g ra m
c hlo rine ra dic a l a bs tra c tio n bro m ine ra dic a l a bs tra c tio n

C HE M 31 adr 37
 Reaction of Methane with Other Halogens

 The order of reactivity of methane substitution with halogens

is:
fluo rine > c hlo rine > bro m ine >
iodine

 The order of reactivity is based on the values of E a for the

first step of chain propagation and ΔH o for the entire chain
propagation

 The energy values of the initiation step are unimportant since

they occur so rarely
– O n the basis of Δ H o values for X 2, the initiation step
C HE M 31 adr 38
iodination should be most rapid
 Chlorination vs. Bromination
C hlo rina tio n is also highly exothermic overall, but more controllable with
a higher value of E act and lower overall ΔH o values

B ro m ina tion. The bromine atom has a significant E act in the first step of
propagation so the reaction is much more controllable and selective .
S till exothermic overall

C HE M 31 adr 39
 Fluorination

o uld Fluorina tio n be s elec tive?

– Fluorine shows almost no discrimination becaus e it is so

reactive

– S o reactive that only per fluoro compounds (all H replaced by

C HE M 31 adr 40
F) are made via direct fluorination
 Fluorination and Iodination
Wo uld Fluo rina tion be s elec tive?

irec t iodina tion is not a us eful rea c tio n

1. High E a in first propagation step means very few successful collisions

2. O verall reaction is endothermicC HE M 31 adr 41
 Factors that Determine Product Distribution
E xerc is e:
1. P redict the major product:

C HE M 31 adr 42
 Factors that Determine Product Distribution
E xerc is e:
2. C alculate the percent yield of the products in the (a)
monochlorination (b) monobromination of the following alkanes :

c hlo rine C HE Mbro m ine

31 adr 43
ra dic a l ra dic a l
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n
• An a llylic c a rbo n is a carbon adjacent to a double bond.
• Homolysis of the allylic C — H bond in propene generates an a llylic
ra dic a l which has an unpaired electron on the carbon adjacent to the
double bond.

• The bond dissociation energy for this process is even less than that
for a 3 0 C — H bond (91 kcal/mol).
• This means that an a llyl ra dic a l is more s table than a 3 0 radical.

C HE M 31 adr 44
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n
• The allyl radical is more stable than other radicals because
two resonance forms can be drawn for it.

C HE M 31 adr 45
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n
• B ecause allylic C — H bonds are weaker than other s p3 hybridized C —
H bonds, the allylic carbon can be selectively halogenated us ing NBS
in the presence of light or peroxides.

• NB S contains a weak N— B r bond that is homolytically cleaved with

light to generate a bromine radical, initiating an allylic halogenation
reaction.
• P ropagation then cons ists ofC HE M the
31 adr usual two steps of radical
46
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n

C HE M 31 adr 47
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n
• NB S also generates a low concentration of B r2 needed in the second
chain propagation step (S tep [3] of the mechanism).
• The HBr formed in S tep [2] reacts with NB S to form Br2, which is then
used for halogenation in S tep [3] of the mechanism.

• Thus, an alkene with allylic C — H bonds undergoes two different reactions

depending on the reaction conditions.

C HE M 31 adr 48
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n
Q ues tio n:
Why does a low concentration of B r2 (from NB S ) favor allylic substitution
(over ionic addition to form the dibromide)?
A ns w er:
• The key to getting substitution is to have a low concentration of
bromine (B r2).
• The B r2 produced from NB S is present in very low concentrations .
• A low concentration of B r2 would firs t react with the double bond to
form a low concentration of the bridged bromonium ion.
• The bridged bromonium ion must then react with more bromine (in the
form of Br¯) in a second step to form the dibromide.
• If concentrations of both intermediates — the bromonium ion and Br¯
are low (as is the case here), the overall rate of addition is very slow,
and the products of the very C HE M 31 adr
fast 49
and facile radical chain reaction
 Radical Reactions
R a dic a l H a lo g ena tio n a t a n A llylic C a rbo n
• Halogenation at an allylic carbon often results in a mixture of products .
C onsider the following example:

• A mixture results becaus e the reaction proceeds by way of a

res o na nc e s ta bilized ra dic a l .

50
 Radical Reactions
T he O zo ne L a yer a nd C FC s
• O zone is vital to life, and acts as a shield, protecting the earth’s
s urface from harmful UV radiation.

• C urrent research suggests that c hlo ro fluo ro c a rbo ns (C FC s ) are

responsible for destroying ozone in the upper atmosphere.

C HE M 31 adr 51
 Radical Reactions
T he O zo ne L a yer a nd C FC s
• C FC s are inert, odorless , and nontoxic, and have been us ed as
refrigerants, solvents, and aerosol propellants.
• They are water insoluble and volatile, and readily escape into the
upper atmosphere, where they are decomposed by high-energy
s unlight to form radicals that destroy ozone by a radical chain
mechanism.

C HE M 31 adr 52
 Radical Reactions
T he O zo ne L a yer a nd C FC s
• The overall result is that O 3 is consumed as a reactant and O 2 is
formed.
• In this way, a small amount of C FC can destroy a large amount
of O3.
• New alternatives to C FC s are hydroc hlo rofluoroc a rbons
(H C FC s ) and hydrofluoroc a rbons (H FC s ) such as
C H 2FC F 3.
• These compounds are decomposed by HO • before they reach
the stratosphere and therefore they do not take part in the
radical reactions resulting in O 3 destruction.

C HE M 31 adr 53