ORGANIC CHEMISTRY
CHM 207
CHAPTER 5:
ALKYL HALIDES
5.1 Nomenclature of alkyl halides.
5.2 Structures and physical properties of alkyl halides.
5.3 Reactions of alkyl halides:
Formation of alcohol,
Formation of ether (Williamson synthesis),
Formation of amino compounds,
Formation of cyano compounds,
Formation of alkanes (Wurtz reaction),
Elimination reaction -dehydrohalogenation of alkyl
halides to form alkenes,
Nucleophilic substitution reactions (Reactions of
alkyl halides with hydroxide and cyanide ions).
5.4 Uses of alkyl halides
ALKYL HALIDES
• General formula: CnH2n+1X where n = 1,2,… and
X (halogen)
• Functional group: halogen, -X (X = F, Cl, Br, I)
• Naming alkyl halides:
- same as nomenclature of alkanes
CH3 CH3 CH3
5 4 3 1 6 5 4 3 2 1
2 CH3 CH2 C CH2 CH CH3
CH3 CH2 CH CH CH3
CH3 I
CI Br
iodomethane 3-chloro-2-methylpentane 4-bromo-2,4-dimethylhexane
no. of alkyl groups: 2
H
Classification of alkyl halides R' C X
R
o
a) Primary (1 ) c) Tertiary (3o)
no. of alkyl groups: none or one no. of alkyl groups: 3
H H R''
H C X H C X R' C X
H R R
b) Secondary (2o)
no. of alkyl groups: 2
H
R' C X
R
c) tertiary (3o)
no. of alkyl groups: 3
PHYSICAL PROPERTIES
• BOILING POINTS
- molecules with higher molecular weight have higher
boiling points.
- reasons: the molecule is heavier, slower moving, have
greater surface area, have larger London attractions,
resulting higher boiling points.
- example:
CH3F CH3Cl CH3Br CH3I
RMM 34 50.5 95 142
bp (°C) -78 -24 4 42
- compounds with branched have more spherical
shapes, have smaller surface area, resulting lower
boiling points.
CH3
CH3 CH3 C Cl
CH3CH2CH2CH2Cl CH3CH2CHCl CH3
bp 78 oC bp 67 oC bp 52 oC
- alkyl halides with more carbon atoms have higher
boiling points.
CH3Cl CH3CH2Cl CH3CH2CH2Cl
bp -24oC bp 12oC bp 47oC
• DENSITIES
- alkyl fluoride and alkyl chlorides (with one Cl atom) are
less dense than water.
- alkyl chloride with two or more chlorine atoms are
denser than water.
- all alkyl bromides and alkyl iodides are denser than
water.
REACTIONS OF ALKYL HALIDES
1. Formation of alkanes (Wurtz reaction)
• Equation:
2R-X + 2Na → 2NaX + R-R
dry ether
• Example:
reflux
2CH3I + 2Na CH3-CH3 + 2NaI
• Most suitable for preparation of higher alkanes
containing an even number of carbon atoms.
• Alkanes containing an odd number of carbon
atoms can be prepared by using a mixture of
two different alkyl halides.
• This reaction produces only low yields due
to the formation of other alkanes as by-
products.
dry ether
CH3I + 2Na + CH3CH2I CH3CH2CH3 + 2NaI + CH3CH2-CH2CH3 + CH3CH3
by-products
Reactions of alkyl halides
• Two types of reactions:
i) substitution reactions
ii) elimination reactions
a) nucleophilic substitution
- -
C C Nuc X
C C
H X
H Nuc
b) elimination
- -
B C C B-H X
C C
H X
NUCLEOPHILIC SUBSTITUTION REACTIONS
1) Formation of alcohol
R-X OH R-OH X
nucleophile
example
CH3CH2 Br NaOH CH3CH2 OH NaBr
ethyl bromide ethyl alcohol
2) Williamson ether synthesis
R-X R'O R-O-R' X
nucleophile
example
CH3 I CH3CH2 O Na+ CH3 O CH2CH3 Na+ I-
methyl iodide sodium ethoxide ethyl methyl ether
CH3CH2 OH Na CH3CH2 O Na+
sodium ethoxide
3) Amine synthesis
R-X NH3 R-NH2 HX
nucleophile
example
CH3CH2 Br H-NH2 CH3CH2 NH2 HBr
ethyl bromide ethylamine (primary amine)
HBr(g) + NH3 (g) NH4Br (s)
amine are also act as nucleophile (more reactive than ammonia)
C2H5Br H N C2H5 (C2H5)2NH + HBr
H diethylamine
(secondary amine)
C2H5Br (C2H5)2NH (C2H5)3N + HBr
triethylamine
(tertiary amine)
C2H5Br (C2H5)3N (C2H5)4N+ Br-
tetraethylammonium bromide
(quaternary salt)
4) Nitrile synthesis
R-X CN R-CN X
cyanide nitrile
(nucleophile)
H2O/H+
R-COOH (hydrolysis)
R-CN H2/Ni
R-CH2NH2 (reduction)
180oC
example
(CH3)2CHCH2CH2-Cl NaCN (CH3)2CHCH2CH2-CN NaCl
1-chloro-3-methylbutane 4-methylpentanenitrile
H2O/H+
(CH3)2CHCH2CH2-COOH
(CH3)2CHCH2CH2-CN H2/Ni
180oC
(CH3)2CHCH2CH2-CH2NH2
Mechanism of nucleophilic substitution reactions
H Nu- H
δ+ δ-
R C X R C Nu X-
H H
EXAMPLE
H OH- H
δ+ δ-
CH3 C Br CH3 C OH Br-
H H
formation of alcohol
Type of nucleophilic substitution
reactions: SN1 and SN2 reactions
• S = substitution
• N = nucleophilic
• 1 = a first order (unimolecular) reaction
• 2 = a second order (bimolecular) reaction
SN1 (Substitution, Nucleophilic,
unimolecular) reactions
• Unimolecular : only one molecule involved in the transition state
of the rate-limiting step.
• Example: the reaction between aqueous NaOH and tertiary alkyl
halides.
(CH3)3C-Br + OH- slow
(CH3)3C-OH + Br-
MECHANISM OF SN1 REACTION
STEP 1: FORMATION OF CARBOCATION
slow
(CH3)3C Br (CH3)3C+ + Br
-
rate limiting step
very reactive
STEP 2: NUCLEOPHILIC ATTACK
+ fast
(CH3)3C + OH- (CH3)3C-OH
• The reaction is first order and the rate
depends only on the concentration of the
tertiary alkyl halides.
Rate = k[(CH3)3CBr]
• The concentration of OH- does not have any
effect on the rate of reaction.
• OH- does not involved in the rate-limiting
step.
Carbocation rearrangement in SN1 reactions
• Rearrangement of the carbon skeleton will take place if a
more stable carbocation can be formed in the process.
• For example, hydrolysis of the secondary alkyl bromide, 2-
bromo-3-methylbutane, yields the tertiary alcohol, 2-methyl-2-
butanol.
CH3 H CH3 H
SN1
CH3 C C CH3 -
CH3 C C CH3 Br
H2O
H Br H slow step
o
2-bromo-3-methylbutane (2 carbocation)
shift of H
CH3 H CH3 H
H-OH
CH3 C C CH3 fast
CH3 C C CH3
H OH H
(3o carbocation) 2-methyl-2-butanol
• Reactivity towards SN1 substitution
mechanisms follows the stability of
carbocations:
SN1 reactivity: 3o > 2o > 1o > CH3X
retention inversion
SN2 (Substitution, Nucleophilic,
bimolecular) reactions
• The processes of bond breaking and bond forming occur
simultaneously (one bond is forming, one bond is breaking).
• The mechanism involves only one step.
• For example, hydrolysis of iodomethane (primary alkyl halides)
H δ+ H
δ-
HO C I δ- δ+ δ- H
-
H HO C I HO C I
H H
H H H
iodomethane transition state methanol
or
HO CH3 I HO CH3 I HOCH3 I-
rate-limiting
iodomethane transition state methanol step
• A second order reaction
• Rate equation = k[CH3I][OH-]
• Both iodomethane and the OH- are involved in the
rate-limiting step.
• SN2 reactivity: CH3 X > 1o > 2o > neopentyl > 3o
• Factor that determines the order of reactivity in SN2
reactions is the steric effect.
• A steric effect is one in which the rate of chemical
reaction depends on the size or spatial arrangement
of the groups attached to, or near to, the reaction
site of the molecule.
Relative reactivities of primary,
secondary, and tertiary alkyl halides
• The reactivity of alkyl halides towards nucleophilic
substitution depend on the halogen.
• The rate of reaction decrease in the order
R-I > R-Br > R-Cl > R-F
(most reactive) (least reactive)
• Reason: C-X bond become stronger from I to F
Comparison SN1 and SN2 reactions
SN1 SN2
Rate of reaction First order Second order
Stereochemistry Racemic mixture Complete
(mixture of inversion inversion
and retention)
Reactivity Benzyl > allyl > ~ 3o CH3X > 1o > 2o > 3o
> 2o > 1o
Nucleophiles Weak nucleophiles Strong
nucleophiles
Elimination reactions-
dehydrohalogenation of alkyl halides
• Elimination: loss of two atoms or groups from the
substrate to form a pi bonds.
• Dehydrohalogenation (removal of hydrogen and a
halogen atom) of alkyl halide to form alkene.
C C C C HX
H X
alkyl halide alkene
HX = HCl or HBr or Hl
• The elimination reaction is occurred when the
reaction used strong base for examples,
t-butoxide ion ((CH3)3CO-) or OH- ion and heated
at high temperature.
• Dehydrohalogenation will yield an alkene that
has the larger number of alkyl groups as the
main product (Saytzeff’s rule).
• Elimination reactions can be divided into two:
i) E1 reaction
ii) E2 reaction
E1(Elimination, unimolecular) reaction
• The rate-limiting state involves a single molecular
than a collision between two molecules.
• A first order reaction.
• Rate equation: k[RX]
• E1 reactivity: Benzyl > allyl > 3o > 2o > 1o
MECHANISM OF E1 REACTION
STEP 1: FORMATION OF THE CARBOCATION (RATE LIMITING)
C C C C X
H X H
STEP 2: A BASE ABSTRACTS A PROTON (FAST)
B C C B-H C C
H
E2(Elimination, bimolecular) reaction
• A second order reaction.
• Rate equation: k[RX][Base]
• E2 reactivity: 3o > 2o > 1o
• Mechanism:
B
H
C C C C B-H X-
X
Comparison E1 and E2 reactions
E1 E2
Rate of reaction First order Second order
Reactivity 3o > 2o > 1o 3o > 2o > 1o
Base Do not need strong Strong base
base
Alkyl halides Reactions
Nu-
1O RCH2X RCH2Nu
SN2
Nu- strong R2CHNu +
SN2 + E2 alkene
2O
R2CHX
B- (strong)
alkene
E2
Nu- (weak) R3CNu +
3O SN1 + E1 alkene
R3CX
B- (strong)
alkene
E2
SOME COMMON NUCLEOPHILES
strong nucleophiles moderate nucleophiles weak nucleophiles
(CH3CH2)3P Br F
S-H NH3
H-O-H
I CH3-S-CH3
CH3 O H
(CH3CH2)2NH Cl
O
C N
CH3C O
(CH3CH2)2N
H-O
CH3-O
USES OF ALKYL HALIDES
• Solvents
- industrial and household solvents.
- carbon tetrachloride (CCl4) used for dry cleaning, spot
removing.
- methylene chloride (CH2Cl2) is used to dissolve the
caffeine from coffee beans to produce decaffeinated
coffee.
• Reagents
- as starting materials for making complex molecules.
- for example, the conversion of alkyl halides to
organometallic reagents (compounds containing carbon-
metal bonds) is important tool for organic synthesis.
• Anesthetics
- examples: chloroform (CHCl3) and ethyl
chloride.
• Freons: Refrigerants and foaming agents
- Freons (called chlorofluorocarbons, or CFCs)
is used as a refrigerant gas.
• Pesticides
- example: DDT (Dichloro Diphenyl-
Trichloroethane) is used as insecticides.
