INORGANIC & ORGANIC CHEMISTRY BSMT | 1A MT A.

Y 2021 - 2022

9|ALKYL HALIDES LEC | MT 633 | LABRADOR

● Chlorofluorocarbons (CFCs)
OUTLINE
● Among the most widely used:
I. Structure of Alkyl Halides
○ Trichlorofluoromethane (Freon-11) (CCl3F)
II. Uses of Alkyl Halides
○ Dichlorodifluoromethane (Freon-12)
III. Nomenclature
(CCl2F2)
IV. Reactions of Alkyl Halides
● Much lower ozone-depleting alternatives are the
4.1 Nucleophilic Substitution
hydrofluorocarbons (HFCs) and the
4.2 β-Elimination
hydrochlorofluorocarbons (HCFCs), including:
○ CH2FCF3 (HFC-134a)
I. STRUCTURE OF ALKYL HALIDES ○ CH3CCl2F (HCFC-141b)

ALKYL HALIDE / HALOALKANE III. NOMENCLATURE

● Organic compound containing a halogen atom NOMENCLATURE

covalently bonded to an sp3 hybridized carbon
● Can be bonded to any of the halides (F, Cl, Br, I) ● Hydrocarbon chain
● Given symbol = RX ● Steps:
1. Locate the parent alkane
■ Parent alkane is the
hydrocarbon chain with the
longest chain
■ Greatest number of carbon
II. USES OF ALKYL HALIDES atoms in a continuous chain
2. Number the parent chain to give the first
DIFFERENT USES substituent encountered the lower
number
3. Show halogen substituents by the
● Solvents
prefixes fluoro-, chloro-, bromo-, and
○ Degreasers
iodo- and list them in alphabetical order
○ Dry cleaning fluid
with other substituents
● Reagents
■ Halogens are the least
○ For synthesis of other compounds
prioritized group making them
● Anesthetic
the last
○ Halothane (CF3CHClBr) is a general
4. Locate each halogen on the parent chain
anesthetic
■ Don’t forget to put the number
○ CHCl3 was used originally; toxic and
of the locant (halogen)
carcinogenic
● Examples:
● Freons, chlorofluorocarbons (CFCs)
○ Freon 12, CF2Cl2, replaced with Freon 22,
CF2CHCl, because it is not harmful to the
ozone layer
■ For refrigerators
■ Important industrial uses
● Pesticides
○ DDT (Dichlorodiphenyltrichloroethane)
■ Banned in the US POLYHALOALKANES

● Common solvents
● Generally referred to by their common or trivial
FREONS names
● Examples:

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○ Dichloromethane (Methylene chloride)

(CH2Cl2)
4.1 NUCLEOPHILIC SUBSTITUTION
○ Trichloromethane (Chloroform) (CHCl3)
○ 1,1,1-Trichloroethane (Methyl chloroform)
(CH3CCl3) ● General nucleophilic substitution:
○ Trichloroethylene (Trichlor) (CCl2=CHCl)

IV. REACTIONS OF ALKYL HALIDES

● The halogen atom may leave with its bonding pair

of electrons to give a halide ion which is stable –
a halide is called a good leaving group
○ Halogen is capable of becoming a good
leaving group
○ Halogen is the reason why alkyl halides
undergo reactions
TYPES OF REACTIONS OF ALKYL HALIDES
● Two limiting mechanisms for nucleophilic
substitutions
○ SN2: bimolecular (two species are
involved in the rate-determining step)
○ SN1: unimolecular (only one species is
involved in the rate-determining step)

1. Nucleophilic Substitution
○ If an atom replaces the halide in the
overall reaction
○ A good nucleophile replaces the halide

2. β-elimination
○ If the halide loss is accompanied by the
loss of another atom
○ Involves the formation of a carbon-
carbon double bond

● Difference between the two is that, for

S Ｎ2
nucleophilic substitution, a good nucleophile
replaces the halide, while for beta elimination,
the halide will be gone, wherein hydrogen in
commonly lost
● The two reactions are capable for alkyl halides
due to them having halogen atoms
○ Halogen atoms capable of becoming a
good leaving group (first point)
● Both reactants are involved in the transition state
of the rate-determining step
● Rate = k[RX][Nu_]
● The nucleophile attacks the reactive center from
the backside of the electrophilic carbon of the
alkyl halide

● Examples:

○ Reactants are bromocyclohexane and

sodium hydroxide
○ Base is very nucleophilic
○ It undergoes elimination because of its
base
○ After elimination, bromine and hydrogen
will be removed, thus forming carbon-
carbon double bond

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STEP 1: Break a bond to form a stable ion or molecule.

Ionization of the C-X bond gives a carbocation.

● UNIMOLECULAR - involves only one molecule

STEP 2: Reaction of a nucleophile and an electrophile to

form a new covalent bond.
An energy diagram for an SN2 reaction. There is one transition
state and no reactive intermediate.

S Ｎ1

● Bond breaking between carbon and the leaving

group is entirely completed before bond forming
with the nucleophile begins ● Electrophile is the carbocation intermediate
● Rate = k[RX] ● Nucleophile and the carbocation from the
previous step will meet to form a new covalent
bond - forming the substitution product

S Ｎ 1 & CARBOCATION REARRANGEMENTS

● When an SN1 reaction occurs from a 2° haloalkane,

a 2° carbocation is formed, which is prone to
rearrange to a more stable 3° carbocation
● Influenced by electronic factors that depend on
the type of carbocation or haloalkane
● Typically, SN1 occurs from secondary haloalkane, a
secondary carbocation is formed
○ However, if a more stable carbocation
can be formed, it will be rearranged to a
more stable tertiary carbocation; just
like what is illustrated below
An energy diagram for an SN1 reaction. There are two transition
states and one intermediate.

● S Ｎ 1 is two steps because the bond breaking is

completed first so that it will stabilize the
incoming carbocation - involving the formation of
carbocation intermediate. Then, it will complete ● The carbocation should rearrange to a more
the reaction by forming the substitution product. stable carbocation intermediate
● Primary haloalkane will not react towards SN1
● NOTE: The formation of carbocation intermediate ● Therefore, SN1 reaction will only be possible on
is essential in S Ｎ 1 because its stability is secondary and tertiary haloalkane
affected by electronic factors, which refers to
whether the formed carbocation is highly stable POINTS OF COMPARISON BETWEEN SN1 AND SN2
or not. It rearranges to a more stable carbocation
intermediate.
● What will affect the rate of reaction?

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○ Nature of Nucleophile by secondary, primary, and the

○ Nature of Haloalkane methyl group
○ Nature of Leaving Group ● SN2 reactions
○ Nature of Solvent ○ Governed by steric factors, namely the
relative ease of approach of the
NATURE OF NUCLEOPHILE nucleophile to the site of reaction
■ Governed by steric factors = SN2
● Nucleophilicity: a kinetic property measured by reactions do not want crowding
the rate at which a Nu— attacks a reference at the electrophilic carbon to
compound under a standard set of experimental which the nucleophile will form
conditions its backside attack
● E.g. rate at which a set of nucleophiles displaces ■ This is why the backside is its
bromide ion from bromoethane in ethanol at 25°C reaction mechanism because
the carbon needs to be
accessible without steric
hindrance
○ Relative rates: methyl > 1° > 2° > 3°
● Nucleophilicity will increase as the nature of the
■ Opposite of SN1
nucleophile is identified to be good, moderate, or
■ Most reactive are the methyl
poor
halides followed by primary
○ GOOD NUCLEOPHILE = bears negative
halides, secondary halides, and
charge (anionic), HIGH NUCLEOPHILICITY
then tertiary halides

● Good Nucleophiles: iodide, bromide, sulfides,

● This illustration shows the relative rates of the
thiols, hydroxyls, alkoxides, and methoxide
different variance of haloalkanes toward SN2 and
● Moderate Nucleophiles: chloride, fluoride,
SN1 reactivities
carboxylate, ammonia, sulfide, thiol
○ In SN1, we have secondary and tertiary
● Poor Nucleophiles: water, alcohols, carboxylic acids
■ Never by primary and methyl
○ In SN2, we have methyl and primary
● It can be seen (down to up), it ranges from neutral
■ Never by tertiary
to negatively charged species

NATURE OF HALOALKANE: STERIC FACTORS

NATURE OF HALOALKANE

● Steric factors
● SN1 reactions
○ Compare access to the reaction center in
○ Governed by electronic factors, namely
bromoethane and 2-bromo-2-
the relative stabilities of carbocation
methylpropane (tert-butyl chloride)
intermediates
○ Just like the explanation of steric effect,
○ Relative rates: 3° > 2° > 1° > methyl
which correspond to the crowding of the
■ Highly substituted haloalkanes
substituents around the electrophilic
■ In terms of reactivity, tertiary
center
are the most reactive, followed

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to form carbocations in it because both the

carbocation and the negatively charged leaving
group can be solvated.
○ This is the principle involved why S N1
prefers protic solvents because these
protic solvents can solvate the
carbocation as well as the leaving group

● Less crowding = easier access to the backside ● Polar protic solvents: Hydrogen bond donor
attack of the haloalkane, that is why S N2
reactions are governed by steric factors
● More crowding = blocks access to the backside of
the haloalkane

NATURE OF LEAVING GROUP

● The best leaving groups in this series are the

halogens I–, Br–, and Cl–
● OH–, RO–, and NH2– are such poor leaving groups
that they are rarely, if ever, displaced in
nucleophilic substitution reactions

● This is an example of the solvation mechanism of

water with RX
○ Solvates = the water molecules surround
the ions; surrounds the carbocation and
the halogen ions or halides

NATURE OF SOLVENT: APROTIC SOLVENT

● Excellent leaving groups are halides, followed by

● Aprotic solvent is a solvent that does not contain
water (H2O), then carboxylates
an –OH group and is not a hydrogen bond donor
● Poor leaving groups are OH-, CH3O-, NH2-
● Aprotic solvents favor SN2 reactions. Although the
○ This group (OH-, CH3O-, NH2-) are poor
solvents at the top of the table are polar,
leaving groups in substitution reactions
formation of carbocations in them is more
because they are better in other
difficult than in protic solvents.
reactions

NATURE OF SOLVENT: PROTIC SOLVENT

● Protic solvent is a solvent that contains an –OH

group and is a hydrogen bond donor

● These are examples of protic solvents because

they have OH groups
● NOTE: These solvents favor SN1 reactions. The
greater the polarity of the solvent, the easier it is

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● As we can see in this diagram, the solvation is
not efficient because it cannot solvate the
halogen atom
SUMMARY OF SN1 AND SN2
● NOTE: For secondary, it is either S N1 or SN2. To
distinguish whether the secondary haloalkanes
will favor SN1 or SN2, you just need to check the
reactants and reagents used.
○ For secondary haloalkanes, SN2 is
favored in aprotic solvents and with
good nucleophiles
○ When secondary haloalkanes are reacted
with protic solvents and poor
nucleophiles, then SN1 is favored
● For tertiary haloalkanes
○ SN2 does not occur but SN1 is highly
favored
● Another difference is that there is substitution at
a stereocenter
○ For SN2, there is inversion of
configuration because of the backside
attack
○ For SN1, the substitution will lead to
racemization
■ In racemization,
carbocation intermediate is
planar, and attack by the
nucleophile occurs with equal
probability from either side
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■ Meaning it will from another
stereoisomer which have
equimolar ratios of opposite
stereoisomers
EXERCISES
1. For number 1
○ The type of haloalkane is secondary
○ One of the reactants is an alcohol, which
is a poor nucleophile
■ CH3OH
○ The solvent is also alcohol
■ CH3OH
■ Since it has OH, it is definitely
protic
○ Given the following information, the
mechanism is SN1
■ If the haloalkane is secondary,
there is equal preference for
both mechanisms
■ To distinguish the mechanism,
check the other reactant and
the reagent or solvent as well
■ SN1 is favored if a poor
nucleophile and a protic solvent
are present for secondary
haloalkane
○ If the nucleophile is an alcohol, it will
form an ether as a substitution product
2. For number 2
○ The type of haloalkane (Br) is primary
○ If it is a primary haloalkane, we know
that it automatically favors SN2
○ The other reactant is a sodium iodide
the
(NaI)
○ The solvent (DMSO) is aprotic
○ Given the following information, the
product will have iodide replace bromide
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○ Since CH2Br is primary, automatic this

3. For number 3 will be SN2
○ The type of haloalkane is secondary d. Primary (methyl halide); aprotic solvent = SN2
○ Since it is a secondary haloalkane, we ○ Iodine (I) will be replaced by (CH3)3N
must first take note of the reactants and
solvent to know which mechanism it
favors
○ The mechanism is SN2
■ Because the solvent is aprotic
■ There is no OH in the reactant
■ There is a good nucleophile
(CH3S)
● Although it is
recommended to use
the solvent as a basis
because it has greater
impact in the reactivity
of haloalkanes
○ The reactant with sulfide will replace Br
a. A shows faster SN2 reaction (less crowded)
as the substitution product
b. A shows faster SN2 reaction (less crowded)
■ SCH as the replacement of Br
c. A shows faster SN2 reaction (less crowded)
4. For number 4
○ The type of haloalkane is secondary
○ The mechanism it favors is SN2 4.2 β-ELIMINATION
■ Acetone is an aprotic solvent
■ SH- (thiol) is a good to moderate
β-ELIMINATION
nucleophile
■ For the product, Br will be
replaced by SH ● Removal of atoms or groups of atoms from
adjacent carbons to form a carbon-carbon double
bond
● Dehydrohalogenation
○ Type of β-elimination (elimination of HX)
○ Once HX group is eliminated, the
formation of carbon-carbon double bond
can be observed
● Example:

ZAITSEV’S RULE

● The major product of a β-elimination is the more

stable (more highly substituted) alkene
a. Secondary; poor nucleophile; protic solvent = SN1 ● When cis-trans isomerism is possible, the trans
○ Resulting product = portion of isomer is favored
nucleophile will replace chloride (Cl) ● Examples:
b. Secondary; moderate nucleophile; aprotic solvent
= SN2
○ Resulting product = portion of
nucleophile will replace iodide (I)
c. Primary; aprotic solvent = SN2
○ Resulting product = portion of
nucleophile which is iodide (I) will
replace CH2Br

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SUBSTITUTION VS ELIMINATION
● There are two limiting mechanisms for β-
elimination reactions:
○ E1 mechanism: at one extreme, ● Because many nucleophiles are also strong bases
breaking of the C-X bond is complete (OH– and RO–), SN and E reactions often compete
before reaction with base breaks the C-H ● The ratio of SN / E products depends on the
bond relative rates of the two reactions
■ Only R-X is involved in the rate- ● If the haloalkane is capable of forming mixed
determining step
products
■ Resembles SN1
■ Unimolecular ○ Mixed products: the haloalkane is
■ 2-step reaction capable of both nucleophilic
○ E2 mechanism: at the other extreme, substitution and β-elimination
breaking of the C-X and C-H bonds is
concerted
■ Both R-X and base are involved
in the rate-determining step
■ Resembles SN2

E1 MECHANISM
SN1 vs E1
● Step 1: Break a bond to give a stable molecule or
ion. Rate Determining ionization of C-X gives a ● Reactions of 2° and 3° haloalkanes in polar protic
carbocation intermediate and halide ion. solvents give mixtures of substitution and
elimination products
● Product ratios are difficult to predict
○ Product ratios are determined
experimentally explaining why it is hard
to predict

● Step 2: Take a proton away. Proton transfer from

the carbocation to a base (in this case, the
solvent) gives the alkene.

E2 MECHANISM

● A one-step mechanism: all bond-breaking and SN2 vs E2

bond-forming steps are converted
● Simultaneously (1) take a proton away and (2) ● It is considerably easier to predict the ratio of S N2
break a bond to form a stable ion or molecule
to E2 products

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SUBSTITUTION VS. ELIMINATION GUIDELINES

● The strength of a nucleophile will dictate the

order of a reaction (strong nucleophiles will react
more quickly)
○ Strong nucleophiles are those that bear
negative charge
● Primary halides usually undergo SN2 with good
nucleophiles
○ Primary halides are not capable of SN1
and E1 reactions
● Tertiary halides usually do not undergo SN2
reactions
○ More likely to undergo E2 with a good
base, or E1 and SN1 (with a polar protic
solvent and poor nucleophile), otherwise
● Secondary halides can react in all ways (hard to
predict)
● High temperatures favor elimination
● The nucleophile will usually favor one or the other
type of reaction
○ Depending on the nature of the
nucleophile
○ Example: t-butoxide favors elimination
while Br— and I— favor substitution

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