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WHAT IS ORGANIC CHEMISTRY? Organic chemistry is the chemistry of carbon compounds. Organic compounds contain H as well as C, while other common elements are O, N, the halogens, S and P. There are many varieties of organic compounds ( more than 10 millions!!!) They may exist as simple or complex molecules; as gases, liquids or solid and coloured or colourless.
Examples :CH4
OCOCH3 COOH
O CH2 C NH O N COOH S
Cl
CH CCl3
Cl
All organic compounds consist of carbon atom. Properties of carbon atom: -has 4 valence electrons. -can form 4 covalent bonds.
C C C C C C
Single bond
Double bond
Triple bond
Hydrocarbons
saturated
Contains only single bonds ( -C-C- ) Examples: alkanes,
unsaturated
Contains at least one carbon-carbon double bond (-C=C-) or triple bond (-C C-). Examples: alkenes, alkynes.
cycloalkanes
Engineering
Biotechnology Agriculture
Structural formula shows how the atoms in a molecule are bonded to each other. 3 types of structural formula:
condensed structure expanded structure skeletal structure
2- Dimensional formula
Condensed Structure Does not show single bonds between carbon and hydrogen atoms, but double and triple bonds are shown. All atoms that are attached to a carbon are written immediately after that carbon.
C4H9Cl CH3CHCH2CH3 (Condensed structure)
H2C H2C
H2 C CH2 C H2 CH2
Expanded Structure Expanded structures indicate how atoms are attached to each other but are not representations of the actual shapes of the molecules.
C4H9Cl
Molecular Formula H
H H H H
C C
H Cl
C C
H H
Expanded structure
Skeletal Structure Shows only the carbon skeleton. Hydrogen atoms are not written. Other atoms such as O, Cl, N etc. are shown. i) CH3CH(Cl)CH2CH3 = Cl
ii)
H2C H2C
CH 2 CH 2
Example : Bromoethane
Br H C H H
Br C H H H
or
C H H Br
or
C H Br H
Indication ::bonds that lie in the plane :bonds that lie behind the plane :bonds that project out of the plane
Classification of C atoms:
A carbon atom can be classified as primary carbon(1o) bonded to 1 C secondary carbon(2o) bonded to 2 C tertiary carbon(3o) bonded to 3 C quarternary carbon(4o) bonded to 4 C
C
CH3
10 carbon
10 carbon
CH3 H C CH3
30 carbon
CH3
H H CH3
1
CH3
1
H H CH3
2 2
CH3
H H CH3
3
CH3
4
Question
Expanded Structure Condensed Structure Skeletal Structure
CH3(CH2)CCl(CH3)2
O
H H H H
CH3 C C CH CH3
Functional group
is an atom or group of atoms in an organic molecule which characterised the molecule and enables it to react in specific ways which determines its chemical properties.
ii. iii.
A basic by which organic compounds are divided into different classes. A basic for naming organic compounds A particular functional group will always undergo similar types of chemical reactions.
Homologous Series
is series of compounds where each member differs from the next member by a constant CH2 unit Members of the same homologous series are called homologs.
Homologs Features
1.
Differ from the successive homolog by a CH2 unit Show a gradual change in the physical properties
4.
5. 6.
Have same functional group Have similar chemical properties Can be prepared by similar general methods
Alkene
-C=C-
Alkyne
-C C-
Aromatic
Benzene ring
-CH3
Haloalkane
CH3Cl
Alcohol
-OH
Hydroxyl
CH3-OH
Phenol
-OH
Hydroxyl
-OH
Ether
-C-O-C-
Alkoxide
CH3-O-CH3
Aldehyde
Carbonyl
Carbonyl
Carboxyl
Ester
Carboalkoxy
Acyl chloride
Anhydride Amide
O O -C-O-C-C=O N-NH2 -C N
Amine Nitrile
molecules
a)(CH3)3CCH2CH=CH2 b)(CH3)3CCH=CHCH2-OH
c)
O CH3
OH C O C
O C CH3
NH2
NH2 CH C CH2 O
12.4 Isomerism
Learning Outcomes: At the end of the lesson the students should be able to : Define isomerism. Explain constitutional isomerism. chain isomers positional isomers functional group isomer
Isomerism
Stereoisomerism
Chain Isomerism
Positional Isomerism
diastreomer enantiomer
cis-trans isomerism
other diastereomers
Isomerism is the existence of different compounds with the same molecular formula but different structural formulae.
Different structural formula that have the same molecular formula are called isomers.
1) Constitutional isomers (Structural isomers) are isomers with the same molecular formula but differ in the order of attachment of atoms. 2) Stereoisomers are isomers with the same molecular formula but different arrangement of atoms in space
a) Chain/skeletal isomerism The isomers differ in the carbon skeleton (different carbon chain). They possess the same functional group and belong to the same homologous series. Example:
CH3CHCH2CH3
CH3
CH3CCH3 CH3
2)Positional isomerism These isomers have a substituent group/ functional group in different positions. Examples C3H7Cl
CH3CH2CH2Cl
1-chloropropane
CH3CHCH3 Cl
2-chloropropane
C4H8
CH2=CHCH2CH3
CH3CH=CHCH3 2-butene
1-butene
C8H10
CH3 CH3
CH3
CH3
CH3
1,2-dimethylbenzene
1,3-dimethylbenzene
CH3
1,4-dimethylbenzene
C6H13N
NH2 CH3
H2N CH3
CH3
CH2NH2
NH2
3)Functional group isomerism These isomers have different functional groups and belong to different homologous series with the same general formula. Different classes of compounds that exhibit functional group isomerism :General formula Classes of compounds CnH2n+2O ; n > 1 alcohol and ether
CnH2nO ; n 3
CnH2nO2 ; n 2
CnH2n ; n 3
CH3OCH3
dimethyl ether
C3H6O
CH3CCH3
propanone
CH3CH2CH
propanal
C3H6O2
CH3CH2COH O
propanoic acid
CH3COCH3 O
methyl ethanoate
Exercise: 1. State how many are isomers with the following molecular formulae, identify the type of isomerism and draw the structural formula of the isomers.
a) C5H10
b) C5H10O2 c) CH3CH=C(Cl)CH3 d) C4H6Cl2 e) CH3CH2CH(OH)CH(Br)CH2CH3
Isomerism that resulting from different spatial arrangement of atoms in molecules. Two subdivisions of stereoisomers: i) Enantiomers (mirror image) ii) Diastereomers (non-mirror image)
Diastereomer
Cis-Trans Isomerism The requirements for geometric isomerism : i) restricted rotation about a C=C,double bond in alkenes, or a C-C single bond in cyclic compounds. ii) each carbon atom of a site of restricted rotation has two different groups attached to it.
Examples
H C H3C C H CH3
H3C C H C
CH3 H
trans-2-butene
cis-2-butene
CH3 H H CH3
cis-1,2-dimethylcyclohexane trans-1,2-dimethylcyclohexane
CH3 CH3
If one of the doubly bonded carbons has 2 identical groups, geometric isomerism is not possible. Example
H3C C H3C C
CH3
At the end of the lesson the students should be able to : Identify cis-trans isomerism of a given structural formula. Define chirality centre and enantiomers. Identify chirality centre in a molecule. Explain optical activity of a compound. Draw a pair of enantiomers using 3-dimensional formula. Define racemate. State the applications of chiral compounds in daily life.
Enantiomer
Optical Isomerism Optically active compounds have the ability to rotate plane-polarized light to the right (dextrorotary) and to the left (levorotary) The angle of rotation can be measured with an instrument called polarimeter.
Polarimeter
The requirements for optical isomerism :i) molecule contains a chiral carbon or chirality centre or stereogenic centre (a sp3-hybridized carbon atom with 4 different groups attached to it)
P Q C* S
PQRS *designates chiral centre
CH3CHCH2CH3 OH
CH2CH3 H3C C* H OH H
CH2CH3 C CH3 OH
enantiomers
COOH H CH3 OH
HO
COOH H CH3
enantiomers
12.4.9 Racemate
A racemic mixture or racemate is an equimolar mixture of enantiomers which is optically inactive because the two components rotate plane-polarized light equally (same degree of rotation) but in opposite directions. Hence it does not give a net rotation of planepolarized light.
e.g:
Learning Outcomes: At the end of the lesson the students should be able to : Explain covalent bond cleavage:
homolytic heterolytic
a)
Homolytic Cleavage
Example:
X : X
X + X
free radicals
X X
b) Heterolytic cleavage
Occurs in a polar bond involving unequal sharing of electron pair between two atoms of different electronegativities. A single bond breaks unsymmetrically. Both the bonding electrons are transferred to the more electronegative atom. Formed cation and anion.
A:B
Reaction Intermediates
a) Carbocation b) Carbanion c) Free Radical They are unstable and highly reactive.
a)
Carbocation
Also called carbonium ion. A very reactive species with a positive charge on a carbon atom. Carbocation is formed in heterolytic cleavage.
Example : (CH3)3C Cl
Chlorine is more electronegative than carbon and the CCl bond is polar. The CCl bond breaks heterolitically and both the bonding electrons are transferred to chlorine atom to form anion and carbocation.
b) Carbanion
is
an anion counterpart a species with a negative charge on a carbon atom. Carbanion is formed in heterolytic cleavage.
(CH3)3C- + carbanion
b)
Free Radical
A very reactive species with an unpaired electron. Formed in homolytic cleavage. Examples:
i)
free radicals
Cl
Cl
uv
Cl + Cl
ii)
C
iii)
H 3C
H3C + H
Carbocation, carbanion and free radical can be classified into: Primary Secondary Tertiary
Carbocation Stability
The alkyl groups (electron-releasing group) stabilise the positive charge on the carbocation.
The stability of carbocation increases with the number of alkyl groups present.
Carbocation Stability:
Increasing stability
Carbanion Stability
o
Carbanion Stability:
Increasing stability
Free-radical stability
The stability of free radical increases as more alkyl groups are attached to the carbon atom with unpaired electron.
R R <R C . R Tertiary 30
Secondary 20
Increasing stability
Examples of electrophiles : cations such as H+, H3O+, NO2+ etc. carbocations. Lewis acids such as AlCl3, FeCl3, BF3 etc. oxidizing agents such as Cl2, Br2 and etc.
electrophilic sites are molecules with low electron density around a polar bond Examples: ii) i) + + -C = O (carbonyl) ; -C X (haloalkanes) + -C OH (hydroxy compounds)
iii)
b) Nucleophile means nucleus loving An electron-rich species and electron-pair donor. A nucleophile can be either neutral or negatively charged.
Examples of nucleophiles :
anions
carbanions
I) Addition Reaction
A reaction in which atoms or groups add to adjacent atoms of a multiple bond. Two types of addition :a) b) Electrophilic Addition Nucleophilic Addition
a)Electrophilic Addition Initiated by an electrophile accepting electron from an attacking nucleophile. Typical reaction of unsaturated compounds such as alkenes and alkynes. Example :
CH3CH=CH2 + Br2
CCl4
Room temperature
CH3CHBrCH2Br
electrophile
b)
Nucleophilic Addition
O CH3
CN CH3 C OH CH3
C CH3 + HCN
a) Free-radical Substitution Substitution which involves free radicals as intermediate species. Example :
CH3CH3 + Cl2
uv light
CH3CH2Cl + HCl
b)
Electrophilic Substitution
+ Br2 electrophile
Br + HBr
c)
Nucleophilic Substitution
Typical reaction of saturated organic compounds bearing polar bond as functional group, such as haloalkane with alcohol.
Example :
CH3CH2OH + Br-(aq)
carbon atoms of a molecule to form a multiple bond (double or triple bond). Results in the formation of unsaturated molecules. Example :
CH3CH2OH
IV)
Rearrangement Reaction
A reaction in which atoms or groups in a molecule change position. Occurs when a single reactant reorganizes the bonds and atoms.
Example :
C
H
tautomerisme C R H C OH
C R
O
Exercises
1.
2. Write an equation for the brominebromine bond cleavage in the bromination of methane. State the type of bond cleavage.
3.