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Lesson 8 Reactions of Halogenoalkanes

Halogenoalkanes contain a halogen covalently bonded to an sp3 hybridized carbon. They can undergo nucleophilic substitution reactions. There are two limiting mechanisms for these reactions - SN2 and SN1. SN2 is a bimolecular reaction where bond breaking and forming occur simultaneously. SN1 is unimolecular, with bond breaking between the carbon and leaving group fully occurring before bond formation with the nucleophile. The rate of nucleophilic substitution depends on the strength of the carbon-halogen bond.

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168 views

Lesson 8 Reactions of Halogenoalkanes

Halogenoalkanes contain a halogen covalently bonded to an sp3 hybridized carbon. They can undergo nucleophilic substitution reactions. There are two limiting mechanisms for these reactions - SN2 and SN1. SN2 is a bimolecular reaction where bond breaking and forming occur simultaneously. SN1 is unimolecular, with bond breaking between the carbon and leaving group fully occurring before bond formation with the nucleophile. The rate of nucleophilic substitution depends on the strength of the carbon-halogen bond.

Uploaded by

dela2
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© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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10/10/2019

Reactions of
Halogenoalkanes

Lesson 8
10/10/2019

STRUCTURE OF HALOGENOALKANES

Halogenoalkane - a compound containing a halogen covalently bonded to


an sp3 hybridized carbon; symbol RX where R is an - alkyl group and X is a
halogen
(F, Cl, Br or I)

methyl PRIMARY 1° SECONDARY 2° TERTIARY 3°


10/10/2019

Nomenclature
1. number the parent chain to give the substituent encountered first the
lowest number, whether it is halogen or an alkyl group
2. indicate halogen substituents by the prefixes fluoro-, chloro-, bromo-, and
iodo-, and list them in alphabetical order with other substituents
3. locate each halogen on the parent chain by giving it a number preceding
the name of the halogen
4. in haloalkenes, number the parent chain to give carbon atoms of the
double bond the lower set of numbers

Names Based on original alkane with a prefix indicating halogens and position.
CH3CH2CH2Cl 1-chloropropane CH3CHClCH3 2-chloropropane
CH2ClCHClCH3 1,2-dichloropropane CH3CBr(CH3)CH3 2-bromo-2-methylpropane
10/10/2019

STRUCTURAL ISOMERISM IN HALOGENOALKANES


Different structures are possible due to...
Different positions for the halogen and branching of the carbon chain

1-chlorobutane 2-chlorobutane

2-chloro-2-methylpropane 1-chloro-2-methylpropane
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Nucleophilic Substitution
nucleoph ilic
subs titution Nu +
Nu:- + C Lv C Lv

Nu cleophile Leaving
grou p

 Nucleophilic substitution: any reaction in which one nucleophile


substitutes for another at a tetravalent carbon
 Nucleophile: a molecule or ion that donates a pair of electrons to
another molecule or ion to form a new covalent bond; a Lewis
base
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NUCLEOPHILIC SUBSTITUTION
Theory • halogens have a greater electronegativity than carbon
• electronegativity is the ability to attract the shared pair in a covalent bond
• a dipole is induced in the C-X bond and it becomes polar
• the carbon is thus open to attack by nucleophiles
• nucleophile means ‘liking positive’

the greater electronegativity of the halogen


attracts the shared pair of electrons so it
becomes slightly negative; the bond is now
polar.
NUCLEOPHILES
• ELECTRON PAIR DONORS
• possess at least one LONE PAIR of electrons
• don’t have to possess a negative charge
• are attracted to the slightly positive (electron deficient) carbon
• examples are OH¯, CN¯, NH3 and H2O (water is a poor nucleophile)

OH¯ CN¯ NH3 H2 O


10/10/2019

NUCLEOPHILIC SUBSTITUTION - MECHANISM


• the nucleophile uses its lone pair to provide the electrons for a new bond
• the halogen is displaced - carbon can only have 8 electrons in its outer shell
• the result is substitution following attack by a nucleophile
• the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION

Points the nucleophile has a lone pair of electrons


the carbon-halogen bond is polar
a ‘curly arrow’ is drawn from the lone pair to the slightly positive carbon atom
a ‘curly arrow’ is used to show the movement of a pair of electrons
carbon is restricted to 8 electrons in its outer shell - a bond must be broken
the polar carbon-halogen bond breaks heterolytically (unevenly)
the second ‘curly arrow’ shows the shared pair moving onto the halogen
the halogen now has its own electron back plus that from the carbon atom
it now becomes a negatively charged halide ion
a halide ion (the leaving group) is displaced
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NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION


Basics: An important reaction step is the breaking of the carbon-halogen (C-X) bond
The rate of reaction depends on the strength of the C-X bond
C-I 238 kJmol-1 weakest - easiest to break
C-Br 276 kJmol-1
C-Cl 338 kJmol-1
C-F 484 kJmol-1 strongest - hardest to break

Experiment Water is a poor nucleophile but it can slowly displace halide ions

C2H5Br(l) + H2O(l) ——> C2H5OH(l) + H+ (aq) + Br¯(aq)

If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible) the displaced
halide combines with a silver ion to form a precipitate of a silver halide. The weaker the C-X
bond the quicker the precipitate appears.

Ag+ (aq) + X¯(aq) ——> AgX(s)

AgCl white ppt AgBr cream ppt AgI yellow ppt


10/10/2019

Mechanisms
 Chemists propose two limiting mechanisms for nucleophilic
substitution
a) SN2
b) SN1

 a fundamental difference between them is the timing of bond-


breaking and bond-forming steps

 a) SN2 - two processes take place simultaneously;


• S = substitution
• N = nucleophilic
• 2 = bimolecular (two species are involved in the rate-determining step)
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Mechanism - SN2
Reagent Aqueous* sodium (or potassium) hydroxide
Conditions Reflux in aqueous solution (SOLVENT IS IMPORTANT)
Product Alcohol
Nucleophile hydroxide ion (OH¯)

Equation e.g. C2H5Br(l) + NaOH(aq) ——> C2H5OH(l) + NaBr(aq)

• both reactants are involved in the transition state of the rate-determining


step
H
H H
slow - - fast
+ Br : Br : + :Br :
-
HO: C HO C HO C
:

: :

: :
: :

: :

: :
RDS
H Bromide ion
:

H H
H H H - a halide ion
bromomethane
Tran sition state w ith simultan eou s methanol
bond b reak ing an d bond forming

WARNING It is important to quote the solvent when answering questions.


Elimination takes place when ethanol is the solvent
10/10/2019

Mechanism - SN1
b) SN1 - Bond breaking between carbon and the leaving group is
entirely completed before bond forming with the nucleophile begins

 This mechanism is designated SN1 where

• S = substitution
• N = nucleophilic
• 1 = unimolecular (only one species is involved in the rate-determining step)
10/10/2019

Mechanism - SN1
• Step 1: ionization of the C-X bond gives a carbocation intermediate

H3 C slow , rate CH3


determining
C Br C+ + Br
H3 C
H3 C H3 C CH3
t-butyl bromide A carbocation intermediate;
its sh ape is trigonal p lan ar
10/10/2019

Mechanism - SN1
Step 2: reaction of the carbocation (an electrophile) with hydroxide ion (a
nucleophile) gives an alcohol

nucleophile

t-butyl alcohol
electrophile

SN1 is favoured for tertiary haloalkanes where there is steric hindrance to the attack
and a more stable tertiary, 3°, carbocation intermediate is formed.
10/10/2019

Predicting the Mechanism


 SN2 and SN1 are favoured by aqueous conditions
 SN1 is favoured by relatively stable carbocations

SN1 is favoured

SN2 is favoured

 Primary and methyl carbocations favour SN2


 Secondary carbocations give a mixture of SN2 and SN1 products
 Tertiary carbocations favour SN1
10/10/2019

ELIMINATION v. SUBSTITUTION
The products of reactions between haloalkanes and OH¯ are influenced by the solvent
SOLVENT ROLE OF OH– MECHANISM PRODUCT

WATER NUCLEOPHILE SUBSTITUTION ALCOHOL

ALCOHOL BASE ELIMINATION ALKENE


Modes of attack
Aqueous soln OH¯ attacks the slightly positive carbon bonded to the halogen.
OH¯ acts as a nucleophile

Alcoholic soln OH¯ attacks one of the hydrogen atoms on a carbon atom adjacent
the carbon bonded to the halogen.

OH¯ acts as a base (A BASE IS A PROTON ACCEPTOR)

Both reactions take place at the same time but by varying


the solvent you can influence which mechanism dominates.

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