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CI 13.

1 Halogenoalkanes
Are man-made compounds with one or more halogen atoms (F,
Cl, Br, I) attached to a carbon atom. The attached halogen changes
the chemical properties of alkane chains…they are very
unreactive, and so have been very useful to humans.

Naming halogenoalkanes (haloalkanes)


(similar rules to naming alcohols, just add the halogen as a prefix):
• halogens are in alphabetical order.
• lowest numbers possible are used.

CH3CH2CH2Cl is 1-chloropropane
CH3CHClCH2Cl is 1,2-dichloropropane
CH3CHBrCH2CH2Cl is 3-bromo, 1-chlorobutane.
CH3CHICHBrCH2Cl 2-bromo,1-chloro,3-iodobutane
2-bromo, 3-chloro, 1-iodopentane
CH2ICHBrCHClCH2CH3

Physical properties of halogenoalkanes


• immiscible with water
• The bigger the halogen atom /the larger the number of
halogen atoms the higher the boiling point.
• Larger halogen atoms (Br or Cl) cause greater environmental
damage than smaller halogen atoms (F); this is important
when designing replacements for CFCs.

Chemical reactions of halogenoalkanes


Carbon –halogen (C-Hal) bonds can break either homolytically or
heterolytically.
Homolytic Fission forms radicals eg when a halogenoalkane
absorbs radiation of the right frequency.
H H

H C Cl + hv  H C + Cl

H H
Chloromethane methyl radical chlorine radical

Shorthand is: CH3-Cl + hv  CH3 + Cl (occurs in stratosphere).

Heterolytic fission is more common in lab conditions using polar solvents


such as ethanol or ethanol and water. The polar C-Hal bond can break,
leaving a negative halide ion and positive carbocation.

CH3 CH3

CH3 C Cl + hv  CH3 C+ + Cl-

H H
2-chloro-2-methylpropane carbocation chloride ion
(negatively charged substances may react with the positive carbocation
causing a substitution reaction).

Importance of reaction conditions…for determining how bonds break

Eg. Bromoethane C-Br bonds break:

• Heterolytically, forming ions when dissolved in a polar solvent


(say a mixture of ethanol and water) BUT
• Homolytically, in the gas phase at high temp. or when dissolved in a
non-polar solvent, such as hexane.

Different halogens, different reactivity.
All reactions with halogenoalkanes involve breaking the C-Hal bond. The
C-F bond is the strongest (bond enthalpy 467 kJmol-1) and therefore the
hardest to break, whereas the C-I bond is relatively weaker (228 kJmol-1)
and therefore easier to break. C-Hal bonds get weaker, and so more
reactive, down group 7.
Chloro compounds are fairly unreactive and remain in the troposphere
long enough to reach the stratosphere, where they react with and destroy
the ozone layer.

Substitution reactions of halogenoalkanes

Halogenoalkanes can hydrolysed by hydroxide ions to form alcohols.

Eg. Bromobutane forms butanol:

CH3–CH2–CH2–CH2–Br + OH-  CH3–CH2–CH2–CH2–OH + Br-

The C-Br bond is polar The oxygen atom on OH- is –vely charged.
+ −
δ δ _
C–Br H–O

The partial positive charge on the carbon atom attracts the negatively
charges oxygen of the hydroxide ion. A lone pair of electrons on the O
atom forms a bond with the C atom as the C__Br bond breaks.

H H H H H H H H _
H C__C__C__C__Br
__
H C__C__C__C__O__H
__
+ Br
H H H H H H H H
_
Heterolytic fission results in IONS and not radicals.
O Curly arrows show the movement of electrons (full headed
H arrows for a pair of electrons…unlike radical reactions).

Halogenoalkanes can give substitution reactions with hydroxide ions


and other NUCLEOPHILES. Nucleophiles can donate a pair of electrons
to a positively charged carbon atom to create new covalent bonds.
Some common nucleophiles:

Name Formula Structure showing


lone pairs
Hydroxide ion OH- _

H__O

Ethanoate ion CH3COO- _


__ __
CH C O
3
O
Ethoxide ion C2H5O-
_
__
CH3CH2 O

Water molecule H2O


O
H H
Ammonia molecule NH3
N
H H
H
Cyanide ion CN- _
N C

The carbon atom attacked by the nucleophile may be part of a


carbocation and carry a full positive charge, or it may be part of a
neutral molecule (as in the above example with bromobutane) and carry a
partial positive charge as a result of bond polarisation.

If X- represents a nucleophile, the nucleophilic substitution process is:


+ −
δ δ

C–Hal  C__X + Hal-

X
Water as a nucleophile

Nucleophiles may be neutral or have negative charge, so long as it has a


lone pair of electrons which can form a bond to a carbon atom.
Eg. Water has 2 lone pairs of electrons on the O atom. First it attacks the
halogenoalkane (bromobutane in this case):

H H H H H H H H _
H C__C__C__C__Br
__
H C__C__C__C__O__H
__
+ Br
H H H H H H H H H

O
H H

The resulting ion loses H+ to form an alcohol:

H H H H + H H H H
____ __ __ __
H C C C C O H C__C__C__C__O__H
__
+ H+
H H H H H H H H H

The overall equation for the reaction of water with a genera;


halogenoalkane R__Hal is:

R__Hal + H2O  + R__OH + H+ + Hal-

Ammonia as a nucleophile

A lone pair of electrons on the N (similar to water) attacks the


halogenoalkane to produce an AMINE with an NH2 group:

R__Hal + NH3  R__NH3+ Hal- R__NH2 + H+ + Hal-


Using nucleophilic substitution to make halogenoalkanes

Halogenoalkane + OH- alcohol

Halogenoalkanes can be made via the reverse reaction of making alcohols;


the nucleophile is Hal-.

Eg. 1-bromobutane is made using a nucleophilic substitution reaction


between butan-1-ol and Br- ions, in the presence of a strong acid.
Ist step: H+ ions bond to O atom on the alcohol:

H H H H H H H H +
__ __ __ __ __ __ __ __ __ __ __
H C C C C O H C C C C O H
H H H H H H H H H
+
H
This gives the C atom to which the O is attached a greater partial positive
charge. It is now more readily attacked by Br- ions, forming bromobutane.

H H H H + H H H H
____ __ __ __
H C C C C O H C__C__C__C__Br
__
+ H2O
H H H H H H H H H
_
Br

The overall equation for the reaction is:

CH3CH2CH2CH2OH + H+ + Br-  CH3CH2CH2CH2Br + H2O

 Activity A4.2
 Problems for 13.1 pages 303- 304 questions 1- 9.