Topic 1.

5 INTRODUCTION TO ORGANIC CHEMISTRY Introduction to Organic Chemistry Nomenclature Isomerism

INTRODUCTION TO ORGANIC CHEMISTRY 1. Carbon compounds

Organic chemistry is the chemistry of carbon compounds. Carbon forms a vast number of compounds because it can form strong covalent bonds with itself. This enables it to form long chains (up to 5000 in length) of carbon atoms, and hence an almost infinite variety of carbon compounds are nown. The tendency of identical atoms to form covalent bonds with each other and hence form chains is nown as catenation. !ll organic compounds contain carbon. "ost contain hydrogen. Carbon always forms four covalent bonds and hydrogen one. The ph s!ca" and chem!ca" proper#!es o$ or%an!c compounds depend on #&o $ac#ors' a( The number and arran%emen# o$ carbon a#oms !n #he mo"ecu"e. ! number of important physical properties are determined by the number of carbon atoms in the molecule. The greater the number of carbon atoms, the larger the #an der $aal%s forces and the higher the melting points, boiling points and viscosity. &n many cases, all the carbon atoms are arranged in a straight chain. Often, however, there are shorter chains of carbon atoms branching off a longer chain. These are nown as branched molecules.
H
H H C H H C H H C H H C H H C H H

H C H H

H C C H

H C H H H

C H

'traight chain molecule

(ranched molecule

Carbon atoms can also be arranged to form rings. These are nown as cyclic molecules. The most common number of carbon atoms in a ring is ).
H H H H H H H C C C H C H C C H H H

Cyclic molecule

b( The $unc#!ona" %roups !n #he mo"ecu"e A $unc#!ona" %roup !s a spec!$!c a#om or %roup o$ a#oms &h!ch con$er cer#a!n ph s!ca" and chem!ca" proper#!es on#o #he mo"ecu"e. Organic molecules are classified by the dominant functional group on the molecule. ). *unc#!ona" %roups

These are the some of the most important functional groups found on organic molecules* Type of compound !l ane +ature of functional group C,C and C,- single bonds only (ie no functional group)

C
!l ene C.C double bond C -aloal ane ,Chloroal ane ,(romoal ane ,&odoal ane C

Cl, (r or & atom attached to a carbon atom

+.

Dra&!n% and &r!#!n% or%an!c compounds

Organic compounds can be represented in a number of ways* a) 'tructural formula showing all covalent bonds This is also nown as the d!sp"a ed $ormu"a or %raph!ca" $ormu"a. !ll covalent and ionic bonds between all atoms are shown* H H C H H C H H H H C C H C H H H

b) 'tructural formula, not showing all covalent bonds /nough information is shown to ma e the structure clear, but most of the actual covalent bonds are omitted. Only important bonds are always shown. 'traight chain al anes are shown as follows*
H H C H H C H H C H H C H H

is represented as C-0C-1C-1C-0 or C-0(C-1)1C-0.

(ranched al anes are shown as follows*

H H C H H H H C C H C H H H

is represented as C-0C-(C-0)C-0.

H H H H C H H H C C C

H H C H H H

is represented as C-0C(C-0)1C-0.

!l enes are shown as follows*

H H C H C H C H H

is represented as C-1.C-C-0.
H

H H C H C H C H

C H

is represented as C-0C-.C-C-0.

c) "olecular formula The molecular formula shows the number of each atom in one molecule of the compound. &t does not show une2uivocally the structure of the molecule.
H H C H H C H H C H H C H H

is written C3-40

H H C H C H C H

H C H H

is written C3-5

!l anes have the general molecular formula Cn-1n61. !l enes have the general molecular formula Cn-1n. -aloal anes have the general molecular formula Cn-1n647. d) /mpirical formula The empirical formula is the simplest whole number ratio of the number of atoms of each element in a substance. ,. Homo"o%ous ser!es

Organic compounds with the same functional group, but a different number of carbon atoms, are said to belong to the same homo"o%ous ser!es. /very time a carbon atom is added to the chain, two hydrogen atoms are also added. A homo"o%ous ser!es !s a ser!es o$ or%an!c compounds &h!ch ha-e #he same $unc#!ona" %roup. bu# !n &h!ch #he $ormu"a o$ each success!-e member !ncreases b /CH)/. /g -omologous series of al anes* C-3, C-0C-0, C-0C-1C-0, C-0C-1C-1C-0, C-0(C-1)0C-0, C-0(C-1)3C-0 etc !s a homologous series is ascended, the si8e of the molecule increases. Therefore the #an der $aal%s forces between the molecules become stronger and the boiling point increases.

NOMENC0ATURE O* ORGANIC COM1OUNDS "ost organic compounds can be named systematically by the &9:!C method. &n order to describe completely an organic molecule, three features must be described* the longest straight carbon chain on the molecule. the length and position of any branches on the molecule. the nature and position of any functional groups on the molecule.

1. The "on%es# s#ra!%h# cha!n on #he mo"ecu"e The longest straight chain on the molecule is indicated by one of the following prefi;es* +umber of carbon atoms in the chain 4 1 0 3 5 ) :refi; "eth, /th, :rop, (ut, :ent, -e;,

). The na#ure and pos!#!on o$ an $unc#!ona" %roups on #he mo"ecu"e a) A"2anes

!l anes are named using the ending ,ane*

H H C H
H H C H
H H C H H C H

"ethane

H C H
H C H H

/thane

:ropane

H H C H

H C H

H C H

H C H H

(utane

b)

A"2enes

!l enes are named using the ending ,ene. &n molecules with a straight chain of 3 or more carbon atoms, the position of the C.C double bond must be specified. The carbon atoms on the straight chain must be numbered, starting with the end closest to the double bond. The lowest,numbered carbon atom participating in the double bond is indicated <ust before the ,ene* H C H
H C H H
H C H H
H H C H C H C H

H C
H C H C H

/thene

:ropene

H C

H C

H C H
H C H H

(ut,4,ene

(ut,1,ene

c)

Ha"oa"2anes

-aloal anes are named using the prefi; chloro,, bromo, or iodo,, with the ending ,ane. &n molecules with a straight chain of three or more carbon atoms, the position of the halogen atom must also be specified. The carbon atoms on the straight chain must be numbered, starting with the end closest to the halogen atom. The number of the carbon atom attached to the halogen is indicated before the prefi;*
H H C H
H H C H H C Br

Chloroethane
C H
H C H H

Cl

1,bromopropane

H I C H
H H C H

H C H
H C H

H C H
Cl C H

H C H
H C H

H C H
H C H H

4,iodopentane

0,chloropentane

The position of all halogens in dihaloal anes e;cept those with one carbon atom must be specified. &f there is more than one of the same type of halogen atom on the molecule, the di (two), tri (three) or tetra (four) prefi;es must also be used.
H Cl C Cl
H Cl C H
H Br C H H C Cl

4,4,dichloroethane
C H
H C Cl
H C H H

4,1,dichloroethane

4,bromo,1,chloropropane

+.

The "en%#h and pos!#!on o$ an branches on #he mo"ecu"e

"any carbon chains are not, in fact straight but are branched. The presence of a branch is indicated one of the following prefi;es* (ranch
H H C H
H H C H H C H

:refi; "ethyl

/thyl

The position of the branch must be specified according to the number of the carbon on the straight chain to which it is attached. The carbons are always numbered from the carbon at the end of the chain closest to the functional group. &f there is no functional group, the carbons are numbered from the carbon at the end of the chain closest to the branch. /g
H H H C C C H H H C H H H

H H C H

H C H H

H C C H

H C H H H
H

C H H

1,methylbutane
H H H H H C H H C H C C H H H C H H H C C H

1,1,dimethylpropane
H H H H H C H H C H H H H C C C C H C H H H C H H H C H H

C H H

1,methyl,0,ethylpentane

0,0,diethylpentane

Cl CH3 C CH3 1,methyl,1,chloropropane CH3

CH3

CH CH3

CH2

Cl

1,methyl,4,chloropropane

"any organic compounds which appear to be different are in fact the same. They appear to be different because different notations are used, or because some of the bonds are simply rotated. /g butane can be represented in a number of ways* 'uch as
H
H
H H C H H C H H C H H C H H

H C H H

H C C H H H

H H

C C H H

H H C C H H H

C H

/g 4,chloropropane can be represented in a number of ways* 'uch as

H H C C H H H

H H C Cl

H C H

H C H H
Cl

H C H

H C H

H C H H

Cl

C H H

ISOMERISM Isomers are mo"ecu"es &h!ch ha-e #he same mo"ecu"ar $ormu"a bu# d!$$eren# s#ruc#ures. There are a number of different types of isomerism in organic compounds, but the only type re2uired for !' Chemistry is s#ruc#ura" !somer!sm. S#ruc#ura" !somers are mo"ecu"es &h!ch ha-e #he same mo"ecu"ar $ormu"a bu# a d!$$eren# arran%emen# o$ co-a"en# bonds. The different arrangement of covalent bonds can result from* i) The functional group being in different positions (pos!#!ona" !somer!sm) ii) ! different arrangement of the carbon s eleton (cha!n !somer!sm) iii) ! different functional group ($unc#!ona" !somer!sm) i) 1os!#!ona" !somer!sm

1os!#!ona" !somers are mo"ecu"es &!#h #he same mo"ecu"ar $ormu"a bu# &h!ch ha-e #he $unc#!ona" %roup on d!$$eren# pos!#!ons !n #he mo"ecu"e. !l anes do not show functional isomerism as they have no functional group. !l enes with four or more carbon atoms show positional isomerism* /g but,4,ene and but,1,ene
H C H H H H C H C H C H

H H C H C H C H

H C H H

-aloal anes with three or more carbon atoms show positional isomerism /g 4,chloromethylpropane and 1,chloromethylpropane
Cl
CH3 CH CH3 CH2 Cl

CH3

C CH3

CH3

ii)

Cha!n !somer!sm

Cha!n !somers are mo"ecu"es &!#h #he same mo"ecu"ar $ormu"a bu# a d!$$eren# arran%emen# o$ carbon a#oms. The arrangement of carbon atoms in an organic molecule is nown as the carbon s eleton.

Carbon s eletons containing up to three carbon atoms can only be arranged in one way = i.e. a straight chain with no branching*
C C C

Carbon s eletons containing four carbon atoms can be arranged in two ways* C
C C C C

C C

Carbon s eletons containing five carbon atoms can be arranged in three ways* C C C C C C C C

C C C C C C C Carbon s eletons containing si; carbon atoms can be arranged in five ways*
C C C C C C

C C

C
C

C
C

C C

C C

!ll molecules containing four or more carbon atoms can thus show chain isomerism* /g butane and methylpropane
H
H H C H H C H H C H H C H H

H C C H

H C H H H

C H H

/g pent,4,ene and 1,methylbut,4,ene

H H
H C H H H H H C H C H C H C H

H C H

C C

H H C H

H C H H

/g 4,chloropentane and 4,chloro,1,1,dimethylpropane

H H H
C C

H H
C

H H
C

H
C

H
C

H
C

H
C

Cl

Cl

H H

C H H

iii)

*unc#!ona" !somer!sm

*unc#!ona" !somers are mo"ecu"es &!#h #he same mo"ecu"ar $ormu"a bu# d!$$eren# $unc#!ona" %roups. eg !l anes which have a ring rather than a straight chain arrangement are nown as cycloal anes. They have the general formula Cn-1n, which is the same as al enes. Cycloal anes and al enes can thus show functional isomerism. /g cyclohe;ane and he;,4,ene
H H H H H H H C C C H C H C C H H H
H C H H H H H H C H C H C H C H C H

/g cyclobutane and but,4,ene

H H H C C H H C C H H H

H C H

H C

H C H

H C H H

+.

D!s#!n%u!sh!n% be#&een !somers

&somers tend to differ slightly in their melting and boiling points. "olecules with no branching tend to have higher boiling points than isomers with more branching. This is because they have a higher surface area, so they pac together better and so the van der $aal%s forces are stronger. /g isomers of pentane, C5-41* &somer :entane
H

'tructure
H C H H C H H C H H C H H C H H

(oiling point>oC 0)

"ethylbutane
H

H C H

H C H H

H C C H

H C H H H

15

1,1,dimethylpropane

H H H H
C C C

H H
C

40

H H

C H

H H