Enant Chiral - Presnt.

Lecture 3
CHB 242 / 289 ORGANIC

Organic chemistry of biologically
important functional groups
containing O, N and S.
Copyright Steven Bottle, Chemistry, QUT, 1995
Alkanes - Alkyl/Aryl Halides

General
Formula: R-X
= F, Cl, Br, I
R = alkyl or aryl group
Little
importance in normal
biological processes
CHCl3
CCl4
CF2Cl2
Early Anaesthetic
Dry Cleaning Fluid
Freon Gas in Fridges
(Text: Pgs. 37 - 44)
Alkanes - Alkyl/Aryl Halides

Here
is an example of a solvent
commonly used by University students.
QuickTime a nd a
Graphics decompresso r
are nee ded to see this picture
With
trichloroethane this a solvent in

liquid paper.
Alkanes, Alkyl/Aryl Halides

Many
halogenated compounds play a

role in biological systems as
insecticides.
Cl
Cl
Cl
Cl
Cl
CCl3
DDT
Cl
Chlordane
Cl
Cl
Nomenclature
Ordered
alphabetically
Numbered
to give the lowest number at

the first point of difference:
H3C
Br
CH2
Br Cl
CH3
2-chloro-2,3-dibromo-5-fluoro-3-iodo-4-
methylpentane
Nomenclature Alkyl Halides

Ordered
alphabetically
Numbered
to give the lowest number at

the first point of difference:
H3C
Br
CH2
Br Cl
CH3
NOT:
4-chloro-2,3-dibromo-5-fluoro-3-iodo-2methylpentane!
Synthesis - Alkyl Halides

Addition
Of
to alkenes:
Br2 for instance:

C C
+ Br2
C C
Br Br
Synthesis - Alkyl Halides

Addition
Or
to alkenes:
of HBr for instance:
C C
+ HBr
C C
H Br
Synthesis - Aryl Halides

Dont
forget we can make aryl halides

via a substitution reaction:
CH3
CH3
+ Br
Br
Br
catalyst
35%
CH3
Br
65%
Reactions
Mostly
involve displacement:
Halides
groups.
Br
R O
+ Br -
are generally good leaving
10
Alkyl halides - Chirality

Alkyl
halides are not very significant

biologically, but are useful to introduce
the concept of chirality.
Chiral - from Greek meaning hand.
Look at your left and right hands
Same
gross physical characteristics

Four fingers, one thumb, one palm etc.
(Text: Pgs. 250 - 258)
11
Chirality
The
left and right hands have the same

gross physical characteristics, but are
different!
You
cannot wear a left glove on your right

hand.
The left and right hands are mirror images of
each other.
Two molecules may also be mirror images of
each other.
12
Chirality
Chirality
arises in organic molecules as

each group bound to a carbon occupies
a specific place in space.
QuickTime and a
Graphics decompressor
are needed to see this picture
13
Chirality
These
two halomethanes are nonsuperimposable mirror images of each

other and are said to be Chiral.
mirror
I
Cl
I
Br
A
Br
Cl
B
14
Chirality
These
two halomethanes are nonsuperimposable mirror images of each

other and are said to be Chiral.
15
Chirality
Br
Cl
Cl
The compounds are different

because A can not be superimposed over B.
Br
16
Chirality
Two
atoms align.
But two dont!
17
Chirality
Superimposing
the Iodine and Fluorine

atoms means the Chlorine and Bromine
do not correspond (and vice versa).
Br
Cl
F
I
Cl
Br
Cl
Cl
I
F
Br
Br
18
Chirality
Not
all mirror images are chiral (ie are

non-superimposable).
mirror
I
I
H
H
B
19
Chirality
Not
all mirror images are chiral (ie are

non-superimposable).
20
Chirality
These
two compounds are superimposable mirror images.
21
Chirality
These
two compounds are superimposable mirror images.
22
Chirality
The
other two are chiral isomers.
F
I
ClCl
I
F
Br
Br
23
Chirality
Rule
For Chirality:
Four different groups attached to
carbon.
24
Chirality
Chiral
compounds are special types of

isomers.
They have the same molecular formulae
and the same functional groups
attached to them.
They differ only in the 3D arrangement
of those groups.
25
Chirality
Non-superimposable
mirror images are

special isomers called ENANTIOMERS.
H3C
HOOC
IBUPROFEN
26
Chirality
It
is important to realise that each

enantiomer has exactly the same gross
physical properties as its mirror image.
MB, BP, solubility, reactivity etc. are all
the same.
However they interact with polarised
light differently.
27
Chirality
Chiral
substances are called optically

active because they rotate the plane of
polarised light.
Each enantiomer rotates the plane of
polarised light in the opposite direction.
28
Chirality
(+)-2-iodobutane
rotates the plane of

light clockwise by 15.9.
Its enantiomer (-)-2-iodomethane
rotates the light anti-clockwise by 15.9.
29
Chirality
(+)-2-iodobutane
rotates the plane of

light clockwise by 15.9.
30
Chirality
Its
enantiomer (-)-2-iodomethane
rotates the light anti-clockwise by 15.9.
31
Chirality
These
compounds are enantiomers:

non-superimposable mirror images.
32
Chirality
Rotate
the molecule on
the right 180.
33
Chirality
Rotate
the molecule on
the right 180.
34
Chirality
Rotate
the molecule on
the right 180.
35
Chirality
Rotate
the molecule on
the right 180.
Iodine does
not align.
36
Chirality
Rotate
the molecule on
the right 180.
Iodine does
not align.
37
Chirality
If
a substance rotates the light clockwise

(as you look at the source) it is called
Dextrorotatory and the symbol (+) is
placed in front of its name.
Enantiomers that rotate the light in the
opposite direction are called
Levorotatory and have the symbol (-).
38
Chirality
Importance
of Chirality.
The
body (and indeed Nature) is filled

with chiral molecules, especially enzymes,
which will only react with molecules of the
same chirality.
Think
of shaking hands.
It
must be done left to right or it wont

work.
39
Chirality - Examples
CH3
CH3
O
C CH2
CH3
CH2
CH3
(-) Carvone
[]20
= -62.5
D
(+) Carvone
[]20
= +62.5
D
(Spearmint oil)
(Caraway oil)
40
Minus
sugar:
The enantiomer of sucrose tastes just as

sweet, but it cannot be broken down by the
body!
Unfortunately
it must be made by
chemists and not plants so it is
expensive!
41
Sucrose
and its mirror image.
CH2OH
CH2OH
OH
HO
HO
OH
HO O
HOCH2
O
HO
O OH
O
OH
CH2OH
OH
HOCH2
CH2OH
OH
42
Lindane
- a common insecticide.
Cl
3Cl2
light
Cl
Cl
Cl
One of the nine

isomers produced
Cl
Cl
This is the only active

compound!
43
Ibuprofen:
Sold as a mixture of the two

enantiomers.
H3C
H
H3C
H
HOOC
HOOC
Only
one is biologically active!
44
Look
at this compound. Can it be

chiral?
O
N
O
O
H
45
Remember
the rule for chirality is that a

carbon must be bound to four different
groups.
46
Remember

groups.
O
N
O
O
H
47
Remember

groups.
O
N
Four!
O
O
H
48
What
would these isomers look like?
49
What
O
N
O
50
What
O
N
O
O
H
N
O
51
Chirality
There
is no real need to draw the

reflection to ascertain the structure of
the two enantiomers.
Chiral
compounds exist because of the

differing positions of the four groups in
space.
Switching
two of the groups will

produce the enantiomer for simple
systems.
52
Chirality
Draw
one enantiomer.
O
N
H
53
Chirality
Then
change the orientation of the

groups.
O
N
O
Swap
H
54
Chirality
These
two molecules are now nonsuperimposable.

O
N
O
Swap
N
N
H
H
55
Chirality
This
only makes enantiomers for

compounds containing one chiral
carbon.
Remember enantiomers are nonsuperimposable mirror images.
Let us look at an example that
demonstrates this.
56
Chirality
Lets
look at Peppermint:
OH
This
molecule can be chiral as there is a

carbon which has four different groups
attached.
57
Chirality
*
Lets
look at Peppermint:
OH
This
molecule can be chiral as there is a

carbon which has four different groups
attached.
This is indicated by the presence of a
star (Asterisk).
58
Chirality
*
H
OH
H
OH
Here
the four groups are in differing

positions in space.
The molecules are not super imposable.
And they would bend polarised light.
But they are NOT enantiomers!
59
Chirality
*
OH
H
OH
Enantiomers
are mirror images.

These two molecules are not mirror
images!
60
Chirality
*
H
OH
H
OH
Draw
the mirror image of the molecule

on the left and compare it.
H
OH
61
Chirality
*
OH
H
OH
If
you flip the reflected molecule you

can attempt to superimpose the two.
H
OH
HO
62
Chirality
*
OH
OH
It
appears that the two molecules on the

right of this slide are the same .
H
OH
H
HO
H
OH
63
Chirality
*
OH
OH
They
are not the same because there is

another chiral carbon in the molecule.
H
OH
H
HO
H
OH
64
Chirality
H CH3
*
*
H CH3
H
*
*
OH
H
OH
The
top methyl group is bound to a

carbon that has four different groups.
Scrambling of the bonds to one of the
chiral carbons does not produce a
mirror image (ie an enantiomer).
65
Chirality
H CH3
*
*
H CH3
H
OH
*
*
H
OH
Take
the molecule on the left and make

its mirror image.
H CH3
*
H
OH
66
H CH3
Chirality
*
*
H CH3
H
OH
*
*
H
OH
Take
the molecule on the left and make

its mirror image.
H CH3
*
H CH3
H
OH
HO
67
H CH3
Chirality
*
*
H CH3
*
OH
H
OH
Flipping
the reflection does not give a

super-imposable compound!
H CH3
H CH3
*
H
OH
H
HO
*
*
H CH3
*
*
H
OH
68
Chirality
H CH3
*
*
H CH3
*
OH
H
OH
Flipping
the reflection does not give a

super-imposable compound!
H CH3
The
methyl groups
do not line up.
*
*
H
OH
69
Chirality
H CH3
*
*
H CH3
H
OH
*
*
H
OH
These
are examples of yet another type

of isomer!
They are optically active (ie chiral).
But they are not mirror images.
They are called diasteriomers.
70
Chirality
H CH3
*
*
H CH3
H
*
*
OH
H
OH
The
situation is actually a little more

complex as there is another chiral carbon
in the molecule.
Can
you find it?
For
n chiral carbons in a molecule

there are up to 2n optical isomers.
71
H CH3
Chirality
*
*
H CH3
H
OH
*
*
H
OH
72
Chirality - Racemates
What
happens when HBr is added to

the alkene 1-butene?
An addition reaction occurs.
The product is 2-bromobutane.
(The
Is
Markovnikov product)
the product optically active?
73
The
result is an addition which gives a

chiral carbon.
74
The
result is an addition which gives a

chiral carbon.
H
CH2 CH3
C C
HBr
H Br
H C C* CH2 CH3
H
H
75
But
in fact the addition can occur from

either side!
H
CH2 CH3
C C
HBr
Both
compounds
are optically active,
but the mixture is not.
H Br
H C C* CH2 CH3
H
H
H
CH2 CH3
*
H C C H
H Br
76
A
mixture that contains both

enantiomers is called racemic.
Most chemical reactions produce
racemic mixtures.
Most biochemical reactions produce
only one optical isomer and are not
racemic.
77
78
Chirality - Review
Compounds
can be chiral if there is a

carbon which has four different groups.
Chiral compounds are said to be
optically active as they can rotate the
plane of polarised light.
Enantiomers are non super-imposable
mirror images.
79
Chirality - Review
Diasteriomers
are optically active

compounds which are not mirror
images of each other.
Diasteriomers must have at least two
chiral carbons.
80

Enant Chiral - Presnt.

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Lecture 3

CHB 242 / 289 ORGANIC

Copyright Steven Bottle, Chemistry, QUT, 1995

Alkanes - Alkyl/Aryl Halides

Alkanes - Alkyl/Aryl Halides

trichloroethane this a solvent in

Copyright Steven Bottle, Chemistry, QUT, 1995

Alkanes, Alkyl/Aryl Halides

halogenated compounds play a

Copyright Steven Bottle, Chemistry, QUT, 1995

to give the lowest number at

Copyright Steven Bottle, Chemistry, QUT, 1995

Nomenclature Alkyl Halides

to give the lowest number at

Copyright Steven Bottle, Chemistry, QUT, 1995

Synthesis - Alkyl Halides

Br2 for instance:

Copyright Steven Bottle, Chemistry, QUT, 1995

Synthesis - Alkyl Halides

of HBr for instance:

Copyright Steven Bottle, Chemistry, QUT, 1995

Synthesis - Aryl Halides

forget we can make aryl halides

Copyright Steven Bottle, Chemistry, QUT, 1995

are generally good leaving

Copyright Steven Bottle, Chemistry, QUT, 1995

Alkyl halides - Chirality

halides are not very significant

gross physical characteristics

Copyright Steven Bottle, Chemistry, QUT, 1995

(Text: Pgs. 250 - 258)

left and right hands have the same

cannot wear a left glove on your right

arises in organic molecules as

Copyright Steven Bottle, Chemistry, QUT, 1995

two halomethanes are nonsuperimposable mirror images of each

two halomethanes are nonsuperimposable mirror images of each

Copyright Steven Bottle, Chemistry, QUT, 1995

The compounds are different

Copyright Steven Bottle, Chemistry, QUT, 1995

Copyright Steven Bottle, Chemistry, QUT, 1995

the Iodine and Fluorine

Copyright Steven Bottle, Chemistry, QUT, 1995

all mirror images are chiral (ie are

Copyright Steven Bottle, Chemistry, QUT, 1995

all mirror images are chiral (ie are

Copyright Steven Bottle, Chemistry, QUT, 1995

two compounds are superimposable mirror images.

Copyright Steven Bottle, Chemistry, QUT, 1995

two compounds are superimposable mirror images.

Copyright Steven Bottle, Chemistry, QUT, 1995

other two are chiral isomers.

Copyright Steven Bottle, Chemistry, QUT, 1995

Copyright Steven Bottle, Chemistry, QUT, 1995

compounds are special types of

mirror images are

Copyright Steven Bottle, Chemistry, QUT, 1995

is important to realise that each

substances are called optically

Copyright Steven Bottle, Chemistry, QUT, 1995

rotates the plane of

Copyright Steven Bottle, Chemistry, QUT, 1995

rotates the plane of