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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.
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, cycloalkanes
unsaturated
Contains at least one carboncarbon double bond (-C=C-) or triple bond (-C C-). Examples: alkenes, alkynes.
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.
C4H10 CH3CH2CH2CH3 (Condensed structure)
H2C H2C
H2 C CH2 C H2 CH2
O CH3CH
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 C C H H H H
C C H Cl
Expanded structure
b)(CH3)3CCH=CHCH2-OH
CH3 CH3 H H C C H H OH
C C CH3
Skeletal Structure Shows only the carbon skeleton. Hydrogen atoms are not written. Other atoms such as O, Cl, N etc. are shown. When a line ends with nothing, the group at the end of it is CH3..
CH3
CH
i) CH3CH(Cl)CH2CH3
= Cl
ii)
H2C H2C
CH2 CH2
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 atom secondary carbon(2o) bonded to 2 C atoms tertiary carbon(3o) bonded to 3 C atoms quarternary carbon(4o) bonded to 4 C atoms
H H C CH3
10 carbon 10 carbon
CH3 H C H
20 carbon
CH3
CH3 H C CH3
30 carbon
CH3
H H CH3 H C
1
CH3 C CH3
1
C CH2
CH3
H H H
H H CH3 H C C
2
CH3 C CH3
2
C CH2
CH3
H H H
H H CH3 H C C
3
CH3 C
4
C CH2
CH3
H H H
CH3
Question
Expanded Structure Condensed Structure Skeletal Structure
CH3CH2CCl(CH3)2
CH3 H C C CH H H CH3
H H
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.
Cl2
CH2Cl2
Cl Cl
i.
A basic by which organic compounds are divided into different classes. ii. A basic for naming organic compounds iii. 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. CH3CH2CH3 - propane CH3CH2CH2CH3 - butane
Homologs Features
1. Obey a general formula: Examples: Alkane: CnH2n+2 Alkene: CnH2n Alcohol : CnH2n+1OH
2. Differ from the successive homolog by a CH2 unit. 3. Show a gradual change in the physical properties. (eg. increasing boiling point) 4. Have same functional group. 5. Have similar chemical properties.
6. Can be prepared by similar general methods.
Classification of organic compound Class of Compound (homologous series) Alkane Functional Group Example Structure Name CH3-CH3 carbon-carbon double bond carbon-carbon triple bond
Alkene
-C=C-
CH3CH=CH2
Alkyne
-C C-
CH3C CCH3
Aromatic
Benzene ring
Haloalkane
Alcohol
-OH
Hydroxyl
Phenol
-OH
Hydroxyl
Ether
-C-O-C-
Alkoxide
CH3-O-CH3
Aldehyde
Carbonyl
Carbonyl
Carboxyl
Ester
Acyl chloride
Anhydride Amide
O O -C-O-C-C=O N-NH2 -C N
Amine Nitrile
b)(CH3)3CCH=CHCH2-OH
Hydroxyl carboncarbon-carbon double bond
c)
O C OH
O C
NH2 CH
CH2 O
Carboxyl
O C OH
O C
O O C O C CH3
Carboxyalkoxy
CH3
anhydride
Carboxamide
C C
CH
Hydroxyl
NH2
NH2 CH
CH2 O
carboncarbon-carbon double bond
Carboxyl
Carboxamide Amino
O Cl C
O C Cl
Acyl chloride
Benzene ring
Lecture 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.
Molecular formula C5H12
CH3CH2CH2CH2CH3
pentane
CH3CHCH2CH3 CH3
2- methylbutane
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
Constitutional isomerism Isomerism resulting from different order of attachment of atoms. a) b) c) Three types Chain/skeletal isomerism Positional isomerism Functional group isomerism
a) Chain/skeletal isomerism The isomers differ in the carbon skeleton or parent chain(different carbon chain). They possess the same functional group and belong to the same homologous series. Example:
b)Positional isomerism These isomers have a substituent group/ functional group in different positions. ( but same parent chain) Examples C3H7Cl
substituent group
CH3CHCH3 Cl
2-chloropropane
CH3CH2CH2Cl 1-chloropropane
C4H8
functional group
CH2=CHCH2CH3 1-butene
CH3CH=CHCH3 2-butene
CH3 CH3
C8H10
C H3
1,21,2-dimethylbenzene
CH3
C H3 1,41,4-dimethylbenzene
CH3
1,31,3-dimethylbenzene
C6H13N
NH2 CH3
H2N CH3
CH3
CH2NH2
NH2
c)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 CnH2n+2O ; n > 1 CnH2nO ; n CnH2nO2 ; n CnH2n ; n 3 3 2 Classes of compounds alcohol and ether aldehyde and ketone carboxylic acid and ester alkene and cycloalkane
Examples C2H6O
CH3CH2OH ethanol
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
CH3CH2CH2CH=CH2 A
CH3CH2CH=CHCH3 B
CH3CH2C=CH3 CH3 C
CH3CHCH=CH3 CH3 D
CH3CH=CCH3 CH3 E F
A&B
||
CH3CH2CH2CH2C-OH A O
||
B O
||
CH3CH2CHC-OH CH3 O C O CH3C(CH3)2C-OH
||
D
||
CH3CH2CH2C-OCH3 E O
||
CH3CH2C-OCH2CH3 F
||
CH3CHC-OCH3 CHCCH3 G
Chain isomerism Positional isomerism Chain isomerism Chain isomerism Functional group isomerism
Lecture 5 Isomerism
Learning Outcomes: At the end of the lesson the students should be able to : Define stereoisomerism. Describe cis-trans isomerism due to restricted rotation about C=C bond and CC bond in cyclic compounds Identify cis-trans isomerism of a given structural formula.
Stereoisomerism / optical isomerism : Isomerism that resulting from different spatial arrangement of atoms in molecules. Two subdivisions of stereoisomers: i) Enantiomers (stereoisomers that are mirror image and non-superimposable isomers ) ii) Diastereomers (stereoisomers that are not mirror images of each other)
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
transtrans-2-butene
CH3 C H
H3C C H
ciscis-2-butene
CH3 C H
CH3 CH3
cis-1,2cis-1,2-dimethylcyclohexane
CH3
CH3
trans-1,2trans-1,2-dimethylcyclohexane
If one of the doubly bonded carbons has 2 identical groups, geometric isomerism is not possible. Example
H3C C C H3C
CH3
Which of the following compounds can exist as a pair of cis-trans isomers? Draw each cis-trans pair and indicate the geometry of each isomer.
b. ClCH=CHBr Cl C=C H Br H
trans- isomer
H Br
Lecture 6 Isomerism
Learning Outcomes: 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
Clockwise rotation
Dextrorotatory isomer (d or +)
Anti-Clockwise rotation
Levorotatory isomer (l or -)
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
CH3CH2OH
CI
* CH3CCH2CH3
CI
OH
CH3CCH2CH3 CH3
CI OH C molecule contains a chiral carbon: B and D
* * CH3CCH2 CHCH3
OH
D
CH3CHCH2CH3 OH
CH2CH3 H3 C C* H OH
enantiomers
CH2CH3 C H CH3 OH
H3C
CH3
The optically active compounds -have chiral carbon -can rotate plane polarized light
COOH H CH3 OH
HO
COOH H CH3
enantiomers
ISOMERISM
Molecules with 2 or more chiral centre, diastereomer may exist diastereomer : stereoisomers that are not mirror images of each other
CH3
2 C*H
e.g. CH3
C*CH2CH3
OH OH
1C
C H H H
H O
O H
H O
CH3 H 2C H
5
H3C C H 2C H
(II)
O H
4C
(I)
C H H O
C H H H
O H
H3 C C H 2C H
OH
HO C H 2C H
(IV)
CH3
(III)
CH 3 HO H3 C H OH CH 2CH 3
(III)
CH 3 H HO OH CH3 CH 2CH 3
(IV)
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.
Lecture 7 12.5 Reactions of Organic Compounds Learning Outcomes: At the end of the lesson the students should be able to : Explain covalent bond cleavage:
homolytic heterolytic
Types of Covalent Bond Cleavage/Fission All chemical reactions involved bond breaking and bond making. Two types of covalent bond cleavage : Homolytic cleavage Heterolytic cleavage
a)
Homolytic Cleavage
Occurs in a non-polar bond involving two atoms of similar electronegativity. A single bond breaks symmetrically into two equal parts, leaving each atom with one unpaired electron. Formed free radicals.
Example:
X Xy
y
Xy + Xy
free radicals
X y yX
Br Br
y y
Bry + Bry
free radicals
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+ anion cation A:B A is more electronegative. A+ + B:cation anion B is more electronegative.
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 : H H (CH3)3C Cl
Chlorine is more electronegative than carbon and the C Cl bond is polar. The C Cl 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.
example: H- H+ (CH3)3C Li
b)
Free Radical
A very reactive species with an unpaired electron. Formed in homolytic cleavage. Examples:
i)
free radicals
yy
Cl Cl
uv
Cl + Cl
ii)
C
iii)
yy
H3C y y H
H3C
Carbocation, carbanion and free radical can be classified into: Primary Secondary Tertiary
Carbocation Stability The alkyl groups(electron-releasing/donating group) stabilise the positive charge on the carbocation. The stability of carbocation increases with the number of alkyl groups (R) present. R = - CH3 , -CH2CH3 , -CH2CH2CH3 etc
Carbocation Stability: H R R H H C H < H C R <H C R < R C R + + + + Methyl Primary Secondary Tertiary cation 10 20 30
Increasing stability
Carbanion Stability Alkyl group and other electron-donating groups destabilise carbanions. Electron withdrawing group (e.g: halogen) stabilise carbanions through the inductive withdrawal of electron density
Carbanion Stability: H R R H H C H > H C R >H C R > R C R Methyl anion Primary 10 Secondary 20 Tertiary 30
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. Molecules with incomlpete octet element. (Al, B, Be)
electrophilic sites are molecules with low electron density around a polar bond Examples: ii) i) H+ HH+ H-C = O (carbonyl) ; -C X (haloalkanes)
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 such as OH-, RO-, Cl-, CN- etc. carbanions ( species with a negative charge on carbon atoms ). double bond between two carbon atoms. molecule with lone pair electron ( NH3). Molecules with expanded octet elements. (S-12e , P-10e)
H+ H2O OHCNBr+
E N N N E
E N N N E
Br2
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
CH3CHBrCH2Br CHBrCH
electrophile
b)
Nucleophilic Addition
OH CH3 C CN CH3
a) Free-radical Substitution Substitution which involves free radicals as intermediate species. Example :
CH3CH3 + Cl2
uv light
CH3CH2Cl
+ HCl HCl
b)
Electrophilic Substitution
Typical reaction of aromatic compounds. The aromatic nucleus has high electron density, thus it is nucleophilic and is prone to electrophilic attack. Example: + Br2 electrophile
H H H = H H
Fe catalyst
Br + HBr
c)
Nucleophilic Substitution
Typical reaction of saturated organic compounds bearing polar bond as functional group, such as haloalkane with alcohol.
CH3CH2OH
+ Br-(aq) Br-
C H
tautomerisme C R H C OH
H C R O
Exercises 1. Explain how the free radicals are formed in homolytic cleavage. 2. Write an equation for the bromine-bromine bond cleavage in the bromination of methane. State the type of bond cleavage.
3.