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HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006 1
6.1 : Introduction
Haloalkanes or alkyl halides
compounds that contains halogen atom bonded to an sp3 hybridized carbon atom.
General formula :
Classification methyl halide - halogen is bonded to methyl group Primary (10) halide - halogen is bonded to 10 carbon atom Secondary (20) halide - halogen is bonded to 20 3 carbon atom
CH 2
CH
General Formula R R R
Classification Tertiary (30) halide - halogen is bonded to 30 carbon atom Aryl halide halogen is bonded aromatic ring
to
CH 2 X
Example :
Classify the following haloalkanes :
Classification 10 20 30
iv.
30
5
substituents.
Locate and number the parent chain from the
direction that gives the substituent encountered first the lower number.
Show halogen substituents by the prefixes flouro-,
chloro-, bromo- and iodo-, and list them in alphabetical order along with other substituents.
6
Example :
i.
C 3C C Br C 3
-bromobutane
ii.
B rC C
Cl C C C C 3 C 3
1-bromo-3-chloro-4-methylhexane
7
Example :
iii.
CH 2 CH 2 F C H 3 C H 2 C H 2 CH C H 2 C H 2 C H 3
4-(2-flouroethyl)heptane
iv.
H3C
CH3 Cl
2-chloro-1,1-dimethylcyclopentane
Example :
v. Br
4-bromocyclohexene
vi.
CH 2Cl
vii.
CH 3 Cl
(chloromethyl)benzene
2-chlorotoluene
9
10
undergo nucleophilic substitution reactions in which the halogen atom is replaced by a nucleophile.
partially positive charge (+) carbon atom bonded to the halogen (-).
_ _ X:
11
General reaction :
R_X
Nu:
R _Nu
R_ X + NaOH
Example :
H2O
R_ OH + NaX
_ _ R X + CN
alcoh ol reflu x
_ _ R CN + X
Example :
CH3CH2Cl + excess NH3 CH3CH2NH2 + NH4+Cl
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15.2.2 :
They
Nucleophilic
Substitution
Nucleophilic
Substitution
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(A) :
Nucleophilic
Substitution
stabilities of carbocations.
reaction :
concentration of nucleophile.
17
R R_ C _ X R
s lo
R R_ C + R
carbocation
3o alkyl halide
halide ion
R _ _ R C + + Nu: R
fa st
R R_ C _ Nu R
18
Example 1 :
SN1 mechanism :
+ Br
CH 3 CH 3 _ C + CH 3
+ H2
fa st
CH 3 H _ _ CH 3 C O + H CH 3
CH 3 H _ _ CH 3 C O + H CH 3
H2O
CH 3 CH 3 _ C _ O H + H 3 O + CH 3
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Example 2 :
C 3
2Br + NaOH(aq)
21
Rearrangement :
CH3 CH 3_ C _ CH2 + CH 3 CH 3 CH3 _ C _ CH 2 + CH 3
, 2 -meth l s h if t
+ OH
fa st
Exercise 1 : Write a reasonable structures of products formed when 1-iodobutane reacts with i. ii. iii. KCN NaOH/H2O excess NH3
23
Exercise 2 : The structure of compound A is as follows: CH3 CH3 C Br CH3 i. Give IUPAC name for A ii. Compound A react with OH- forming an alcohol. Write the mechanism for the formation of this alcohol and name the reaction.
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state of the rate limiting step involves the collision of two molecules.
(steric effect).
Steric effect
is an effect on relative rates caused by the space-filling properties of those parts of a molecule attached at or near to the reacting site.
25
reaction :
R-X 2o
< R-X 1o
< CH3-X
increasing reactivity
26
General Mechanism :
R Nu:H C X H slow R Nu C X H H fast Nu C H
H
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R + X-
transition state
back side of the electrophilic carbon, that is, from the side directly opposite bonded to the halogen.
attacking
nucleophile
and
the
from
the
original
turns the tetrahedron of the carbon atom inside out, like umbrella caught by the wind.
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Example 3 :
CH3CH2Br + NaOH(aq)
CH3CH2OH + NaBr
SN2 Mechanism :
CH3 :OHH C Br H slow CH3 OH C Br H H fast OH C H H
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CH3 + Br-
transition state
Comparison of SN1 and SN2 Reactions SN1 A two-step mechanism SN2 A one-step mechanism
A unimolecular rate- A bimolecular determining step rate-determining step Second order : First order : rate = k [RX] [Nu] rate = k [RX] Strong nucleophile Carbocation rearrangement Reactivity order : 3o > 2o > 1o Weak nucleophile No carbocation rearrangement Reactivity order : methyl > 1o > 2o
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haloalkane and hydrogen from an adjacent carbon to form a carbon-carbon double bond in the presence of a strong base.
General reaction :
H _C_C_ X
haloalkane
+ :B
_ C C
alkene
base
31
Example :
Br
i.
CH 3 CH 2O N a C H 3 C H 2OH
CH 3 C CH CH 3 CH 3
major
+ CH 3CHC CH 2
minor ii.
Br CH 3
C H 3 CH 2O N a C H 3 CH 2 OH
CH3
CH 3 +
CH2
major
minor
32
Example :
g eth er C H 3C H 2C H 2 gB r
eth er
g Cl
33
6.2.4.1 :
that make them useful as a starting materials in the synthesis of other organic compounds. (i). Synthesis of alkane The Grignard reagent is hydrolyzed to an alkane when warmed with H2O.
RMg X + H 2 O H+ R - H + M g( OH ) X
34
Example :
+ H i. C H 3 C H 2 Mg Br + H 2 O C H 3 CH 3 + Mg(OH) Br
ii.
C H 3 C H- Mg B r + H 2 O CH 3 H+ C H 3 C H 2 C H 3 + Mg(OH) B r
iii.
C H 2 Mg Cl
H 2 O/H +
CH3 + Mg(OH) Cl
35
(ii).
Synthesis of 1o alcohol Methanal reacts with the Grignard reagent, followed by the hydrolysis produces primary alcohol.
O R -Mg X + H- C -H H R - C -OMg X H H 2 O,H + H R - C -OH + Mg(OH) X H
36
Example :
i.
O C H 3 MgB r + H- C-H H3O+ H C H 3 - C-OH + Mg(OH) B r H
ii.
MgB r O + H- C-H H3O+ C H 2OH + Mg(OH) Br
37
(iii).
Synthesis of 2o alcohol Grignard reagent reacts with aldehydes to produce secondary alcohol.
O R-MgX + H -C-R' R' R-C- O MgX H H 2O,H + R' R-C- OH + Mg( OH )X H
38
Example :
i.
C H 3 C H 2 Mg B r + CH 3 CH 2 - C-H H 2 O /H + H CH 3 C H 2 - C- CH 2 C H 3 + Mg (OH) B r OH
ii.
MgCl O + C H 3 - C -H CH 3 H2O/H+ C -OH + Mg (OH) Cl H
39
(iv).
Synthesis of 3o alcohol Grignard reagent reacts with produce the tertiary alcohol.
O R - M g X + R '- C- R" R' R- C-O M gX R" H 2 O,H + R' R- C -OH + M g(OH) X R"
40
ketons
to
Example :
i.
ii.
Mg Cl O + C H 3 - C- C H 3 H3O+
CH 3 C -OH CH 3 + Mg (OH) Cl
41
(v).
Synthesis of carboxylic acid Grignard reagent reacts with carbon dioxide (CO2) followed by hydrolysis to form carboxylic acid.
O RMgX + O C O
O R-C- O-MgX + H 2 O O R-C- O H + Mg( O H)X
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R-C- O -MgX
H+
Example :
O C H 3 C H 2 MgI + C O 2 C H 3 C H 2 - C- O -MgI
O C H 3 C H 2 - C- O -MgI + H 2 O
H+
O C H 3 C H 2 C OH + Mg( OH )I
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(usually Na) to synthesise longer alkane. i. To prepare an even number of carbon atoms alkane 2RX + 2Na Example: 2CH3CH2Br + 2Na p CH3CH2CH2CH3 + 2NaBr
44
dry ether
RR + 2NaX
ii.
To prepare a odd number of carbon atoms alkane RX + RX + 6Na p RR + RR + RR + 6NaX
45
CHCl3 solvent for cleaning and degreasing work (chloroform) CF2Cl2 , Freon-12 propellants in aerosol sprays (dichlorodifluoromethane) CFC refrigerant gas (chloroflourocarbons) DDT 46 insecticide protects (DichloroDiphenylTrichloroethane)