Organic Chemistry

Li Wei Associate Professor

JiNing Medical College

1
 Chapter 1 Introduction

1.1 Organic Chemistry : A Modern Definition

1.2 The Uniqueness of carbon
1.3 Structure Formula
1.4 Condensed Structural Formulas
1.5 Bond Energy and Bond Length
1.6 sp3 Hybridization : The Tetrahedral Carbon
1.7 Functional Groups
2
 Why do you have the subject ?

1. The subject of organic chemistry is unique in

that it deals with vast numbers of substances ,
that directly influence our welfare and standard
of living .
Organic chemistry is crucial to our economy as
the source of countless manufactured products
that are essential to our comfort and well-being .
3
 The following substances are examples of
organic compounds .

petroleum products rubber

4
 paint
plastics

5
insecticides
wood made of paper
6
cosmetics clothes
7
vitamins drugs ,
8
etc .
2. The chemical substances that make up the
organs of our bodies , the food we eat for
nourishment, and the chemical reactions that
take place inside our bodies are also organic in
nature .

9
The chemical substances that make up the organs10
of our bodies are also organic in nature .
 The food we eat for nourishment are also organic in
11
nature , which contain sugars , lipids and proteins .
 The chemical
reactions that
take place inside
our bodies are
also organic in
nature .
(biochemistry)

12
3. Organic chemistry is a subject that is
fundamental to other related disciplines , such as

The science of medicine 13

 Organic
material
The science of biology extracted from
14
Chinese herbs .
The science of nursing Medical
laboratory
technology , etc .

The science of
dental hygiene 15
 All the above are involved in the subject of
organic chemistry . We can easily conclude :

Every aspect of our daily lives is influenced

by organic chemistry .

A basic knowledge of chemistry is essential for

students of biology , physics , ecology , and many
other subjects .
16
 Chapter 1 Introduction

1.1 Organic Chemistry : A Modern Definition

1.2 The Uniqueness of carbon
1.3 Structure Formula
1.4 Condensed Structural Formulas
1.5 Bond Energy and Bond Length
1.6 sp3 Hybridization: The Tetrahedral Carbon
1.7 Functional Groups

17
1.1 Organic Chemistry : A Modern Definition
Organic chemistry according to its original
definition dealt only with those substances of natural
organic origin—that is , products in living cells of
plants and animals . The science of chemistry was
thus separated into inorganic and organic .

18
 In 1828 , however , the German
chemist Wohler made the organic
compound urea from non-living chemical
substance, NH4OCN , Ammonium
Cyanate .
O
heat
NH4OCN NH2CNH2
ammonium cyanate urea
(inorganic) (organic)

Organic Chemistry has undergone a

substantial change since then , lots of
organic compounds were prepared in
laboratory . There are well over a million
synthetic organic compounds . 19
 The designation organic is persisted , but it
is not suitable for its modern meanings .

In fact, most of organic compounds contain carbon

and hydrogen, a large number contain oxygen as well,
many contain nitrogen, and some contain halogen, sulfur,
phosphorus, and other elements .
Today organic chemistry is defined as the study of
carbon/hydrogen-containing compounds and their
derivatives.

20
Petroleum and coal are two vast natural reservoirs .

21
1.2 The Uniqueness of carbon

Carbon has the unique property of forming a very

large number of compounds (over 4 million). There are
three reasons for this:

(a)Each carbon atom can form four single covalent

bonds .
(b) A carbon atom can form strong single , double and
triple covalent bonds with other carbon atoms.
(c) Carbon can form strong bonds with other elements.
22
 Why ?
Let’s look at
carbon atom .

(a) With a covalence numbers of four , carbon atom

neither gain nor lose electrons to be ion easily, it
can only form covalent bonds with other atoms .
(b) Compared to the radius of the Silicon atom in the
same group in periodic table , smaller carbon atoms
(no 2d orbitals ) can easily joint together to form 23
carbon chains or rings.
 They joint together to form stable chains or rings
of different size. It may be straight or branched chain.

Fig.1.1 : C
H C H H
H H H H H H H
C C C C
H C H C C C C C C C
H H H
H H H H H H H C
(a)methane (b)carbons in a straight chain(c)carbons in a branched chains

C C C
C C C C C C C C C C
C
C C C C
C C OH OH H NO2 Cl Cl
C
(d) (e) (f) (g) (h)
24
(d,e)carbons in rings (f,g,h)carbons with elements other than hydrogen
 The physical and chemical properties of each organic
compound depend on the structure of the molecule. The
structure of a molecule, in turn, depends on how the
atoms are bonded to each other .
This relationship between properties and structure is
fundamental to a good understanding of organic
chemistry .

Review the topics of atomic structure and chemical

bonding in your free time . ( Page 1—65 )
25
 1.3 Structure Formula
A structural formula, shows how the atoms in a
particular molecule are connected or bonded together .
We could use expanded structural formulas , in
which all bonds are shown , to represent organic
molecules .
Open-chain (acyclic) compounds :
H H H H H H H

H C C H H C N HH C C O H H C Cl
H H H H H H
ethane methylamine ethanol chloromethane

Each element satisfies its covalence number by

sharing one electron pair—forming a single bond— 26

with another atom connected to it .

 Carbon always has four single bonds , hydrogen
and chlorine one each, oxygen two, and nitrogen
three. Remember the covalence numbers of the
component atoms .

Ring (cyclic) compounds :

H H H H H O H
H C C H H C C H C C
H H
H C C H N H C C H
H H H H H
cyclobutane cycloethylamine tetrahydrofuran(THF)
27
 A carbon atom may also share more than one
pair of electrons with another carbon atom or
with other elements , such as oxygen and
nitrogen, to form multiple bonds .
If two pairs of electrons are shared , a double
bond (=) is formed ; if three pairs, a triple bond
(≡) is formed .

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

H C C H H C C H 28
Organic molecules with one double bond:
H H H H H H
H C C H H C C C H H C O
H
with two double bonds:
H H H H H
H C H
H C C C C H
C C
H
C C
H H
Organic molecules with one triple bond:
H
H C C H H C N H C C N
29
H
To summarize ,
(1) Structural formula show how atoms are
connected to one another in a molecule .
(2) The structural formula of a compound is correct
only if each element satisfies its covalence number .
(3) The covalence number may be satisfied by
forming single or multiple bonds .

30
 1.4 Condensed Structural Formulas

Expanded structural formula is time-consuming and

requires much space.
One way to simplify it , is to include only the bonds of
multivalent atoms and leave out the bonds of monovalent
elements (hydrogen and halogens) . The resulting
structures are called partially condensed formulas .

If we omit all bonds except carbon-carbon multiple

bonds , we have fully condensed formulas .
31
 Table 1.1 Examples of condensed formulas
Expanded structural formula Partially condensed formula Fully condensed formula
H H
H C C O H CH3 CH2 OH CH3CH2OH
H H ethanol
H H H H
H C C C C H CH3 CH2 CH2 CH3 CH3CH2CH2CH3
H H H H butane
H
HH C HH CH3
H C C C H CH3 CH CH3 CH(CH3) 3
H H H isobutane
H H O O
H C C C H CH3 CH2 CH CH3CH2CHO
H H propanal
H O H O
H C C C H CH3 C CH3 CH3COCH3
H H acetone
H O O
32
H C C O H CH3 C OH CH3COOH
H
Acetic acid
 Table 1.2 Some Condensed Cyclic Formulas
Expanded formula Partially condensed formula Fully condensed formula
H H H2
H C C H C

Cyclic compounds H C H H2C CH2 cyclopropane

can also be H H H2C CH2
H C C H
represented by H C C H
H2C CH2
partially condensed HH HH cyclobutane
H2
and fully condensedHC C C H C
H H H2C CH2
structural formulas. H C C H
H2C CH2
H H
H H H2
cyclopentane
H C H C
C C H H2C CH2
H
H C C H H2C CH2
C H C
H
H H H2 cyclohexane
H H H2
C H C
H
C C H HC CH2
C C H HC CH2 33
H C
H H
H C
H2 cyclohexene
1.5 Bond Energy and Bond Length

A molecule is more stable than the isolated

constituent atoms.
Energy
H + H H H releasing
H H
One bonding 
Two 1s atomic orbitals Overlap molecular orbital
Figure 1.2 Overlap of atomic orbitals between two hydrogen atoms
to form a Sigma bond

1.5.1 Bond energy The amount of energy released when

a bond is formed is called the heat of formation or bond
energy . 34
1.5.2 Bond dissociation energy
Conversely , the same amount of energy would
have to be supplied to break the bond .
The amount of energy must be absorbed to break
a bond is called the bond dissociation energy .

energy
H H H + H

For a given pair of atoms, the greater the overlap

of the atomic orbitals, the stronger the bond and the
35
greater the amount of bond dissociation energy .
 Table 1.3 Bond Dissociation Energies of
Some simple Molecules
Molecule Bond dissociation energy (kcal/mole )
H H 104
Cl Cl 58
H OH 111
H CH3 101
H3C CH3 83
H2C CH2 146
CH CH 200
H3C OH 89
H 2C O 166 36
1.5.3 Bond length The distance between nuclei in
the molecular structure is called the bond length .
Table 1.4 Bond Length of Some Covalently Bonded Atoms
Bond ° )
Bond length ( A
H H 0.72
C H 1.09
O H 0.96
C C 1.54
C C 1.34
C C 1.20
C O 1.43
C O 1.22

For a given pair of atoms , the bond length depends

upon the extent of overlap of their atomic orbitals .
when atoms are held together by more than one 37

bond, the bond lengths become shorter .

1.6 sp3 Hybridization : The Tetrahedral Carbon
1.6.1 The structure of methane
H

109.5° C
H
H
H
Figure 1.3 The tetrahedral structure of methane
This is a pyramidlike structure, carbon atom at the
center and each hydrogen atom at a corner. Each of
the four carbon-hydrogen bonds is identical: each has
the same strength, 101 kcal/mole, and the same length
38
1.09 Ǻ . All H--C--H bond angles equal to 109.5º.
 Based on the electronic configuration of the ground
—state carbon , we can expect carbon to form not four
but only two covalent bonds , with a bond angle of 90°.
These are inconsistent with the pyramidlike structure .

Energy 2p x 2py 2pz

2s

1s

(a)The electronic ground state. 39

 1.6.2 sp3 hybrid orbitals ( Pauling)

By providing the required amount of energy to the

ground-state carbon, it is possible to promote one electron
from the 2s orbital to the 2pz orbital. The resulting carbon
is said to be in an excited state.
2p x 2py 2pz
promotion 2s

1s

(b)The excited state .

40
The carbon atom has
four unpaired electrons .
 This should account for the formation of four
covalent bonds. However , the bonds would be all the
same. So, a further proposal followed .
Energy 2px 2p y 2pz
sp3
hybridization
2s

1s 1s

(b) (c)

(b) The excited state . (c) The sp3 hybridized state of carbon

The four excited-state orbitals mix together to create

four equivalent 2s2p3 (2sp3 for short ) hybrid orbitals .
The merging of an s orbital and three p orbitals to give
41
four sp orbitals is referred to as sp hybridization .
3 3
1.6.3 The overlap of sp3 orbital
Figure 1.5 H
¦Ò
(a) sp3
C C
(a) the formation of a σ bond from the overlap of one
sp3 orbital with the s orbital of one hydrogen atom .
sp3 H

sp3 H
(b) C
+ 4 H
sp3
sp3
H H
C + 4 H H C H
H
(b) the overlap of four sp3 orbitals with the s orbital of
four hydrogen atoms to form the tetrahedral 42

methane molecule .
 The overlap of four sp3 orbitals with the s orbital of
four hydrogen atoms to form the tetrahedral methane
molecule .
The tetrahedral shape allows for the most effective
overlap between the orbitals , thus forming strong
bonds . 43
1.6.4 The tetrahedral shape
Whenever carbon is singly bonded to other atoms , it
utilizes sp3 –hybridized orbitals and assumes a tetrahedral
shape .
Cl Cl H H H H H
H C Cl Cl C Cl H C C H H C C C H
Cl Cl H H H H H
Chloroform Carbon tetrachloride Ethane Propane

a single tetrahedron each two tetrahedra three tetrahedra

44
1.6.5 The other hybrid orbitals
In molecules where the carbon atom is doubly or
triply bonded , it utilizes sp2 or sp –hybridized orbitals . For
this reason, such molecules are no longer tetrahedral. Look
at the formation of ethene molecule .
Energy 2px 2py 2pz
sp2
2pz
hybridization
2s

1s 1s

(b) (c)

(b) The excited state . (c) The sp2 hybridized state of carbon

The three excited-state orbitals mix together to create

three equivalent 2s2p2 (2sp2 for short ) hybrid orbitals . 45
46
1.7 Functional Groups

A functional group is a reactive portion of an

organic molecule , an atom , or a group of atoms that
confers on the whole molecule its characteristic
properties .

All compounds with the same functional group

belong to one family. Members of a given organic
family react in a similar and predictable manner .

51
 For alcohols , the hydroxyl group , OH (the
functional group ), attached to a singly bonded carbon
atom in a carbon chain of any length .

OH
CH3 OH CH3CH2 OH CH3 CH CH3 R OH
Methyl alcohol Ethyl alcohol Isopropyl alcohol General formula
for alcohol
52
Table 1.6 Functional Groups and Classes of Organic Compounds
Class General formula Functional group Specific examples
Alkane RH C C CH 3 CH 3

Alkene ( H )R CH CH2 C C CH2 CH 2

Alkyne ( H )R C CH C C HC CH
Alkyl halide X CH 3Cl
RX ( X= F,Cl,Br,I )
Alcohol R OH OH CH 3OH
Ether R O R' C O C CH 3 O CH3
O O O O
Aldehyde ( H )R CH C H H C H , H 3C C H
O O O
Ketone R C R' C C C CH3 C CH 3
O O O O
Carboxylic
acid ( H )R C OH C OH H C OH , H 3C C OH
O O O O
Ester ( H )R C OR C OR H C OCH 3 , H 3C C OCH 3
53
Amine R NH2 C NH2 CH 3 NH 2
The Summarization of Chapter 1
1.1 Organic Chemistry : A Modern Definition
1.2 The Uniqueness of carbon
1.3 Structure Formula
1.4 Condensed Structural Formulas
1.5 Bond Energy and Bond Length
1.6 sp3 Hybridization : The Tetrahedral Carbon
1.7 Functional Groups
54
1.1 Organic Chemistry : A Modern Definition
Most of organic compounds contain carbon and
hydrogen , a large number contain oxygen as well , many
contain nitrogen , and some contain halogen , sulfur ,
phosphorus ,and other elements .
Today organic chemistry is defined as the study of
carbon/hydrogen-containing compounds and their derivatives.

55
1.2 The Uniqueness of carbon
(a)Each carbon atom can form four single covalent bonds .
(b) Carbon atom can form strong single , double and triple
covalent bonds with other carbon atoms.
(c)Carbon can form strong bonds with other elements.

Carbon atoms can joint together to form stable chains

or rings of different size . It may be straight or branched
chain .
56
1.3 Structure Formula

(1) Structural formula show how atoms are connected to

one another in a molecule .
Expanded structural formulas , in which all bonds
are shown , can be used to represent organic molecules .
(2) The structural formula of a compound is correct
only if each element satisfies its covalence number .
Carbon always has four single bonds , hydrogen and
chlorine one each , oxygen two, and nitrogen three.
(3)The covalence number may be satisfied by forming
single or multiple bonds . 57
 1.4 Condensed Structural Formulas
Left out the bonds of monovalent elements, the
structures including only the bonds of multivalent
atoms are called partially condensed formulas.
If we omit all bonds except carbon-carbon multiple
bonds, we have fully condensed formulas.

The properties of compounds depend on the structure

of the molecule. The structure, in turn, depends on how
the atoms are bonded to each other. This relationship is
fundamental to a good understanding of organic 58
chemistry .
1.5 Bond Energy and Bond Length
The amount of energy released when a bond is formed is
called bond energy .
The amount of energy must be absorbed to break a bond
is called the bond dissociation energy. The greater the
overlap of the atomic orbitals, the stronger the bond and the
greater the amount of bond dissociation energy .

The distance between nuclei in the molecular structure is

called the bond length. The bond length depends upon the
extent of overlap of their atomic orbitals. When atoms are
held together by more than one bond , the bond lengths
become shorter . 59
1.6 sp3 Hybridization : The Tetrahedral Carbon
Energy 2p x 2py 2pz 2p x 2py 2pz
2s promotion 2s

1s 1s

(a)The electronic ground state. (b)The excited state .

The carbon atom has

1. sp3 hybrid orbitals four unpaired electrons .
By providing the required amount of energy to the
ground-state carbon , it is possible to promote one electron
from the 2s orbital to the 2pz orbital . The resulting carbon is
said to be in an excited state . 60
 Energy 2px 2p y 2pz
sp3
hybridization
2s

1s 1s

(b) (c)

(b) The excited state . (c) The sp3 hybridized state of carbon

The four excited-state orbitals mix together to create

four equivalent sp3 hybrid orbitals . The merging of one s
orbital and three p orbitals to give four sp3 orbitals is
referred to as sp3 hybridization .
61
Four sp3 orbitals

The overlap of four sp3 orbitals with

the s orbital of four hydrogen atoms 62to
form the tetrahedral methane molecule .
 H

109.5° C
H
H
H
Figure 1.3 The tetrahedral structure of methane

Whenever carbon is singly bonded to other

atoms , it utilizes sp3 –hybridized orbitals and assumes
a tetrahedral shape .
63
2. sp2 hybrid orbitals

Energy 2px 2py 2pz

sp2
2pz
hybridization
2s

1s 1s

(b) (c)

(b) The excited state . (c) The sp2 hybridized state of carbon

The three excited-state orbitals mix together to create

three equivalent sp2 hybrid orbitals .
64
65
The formation of ethene molecule

H H
z z C C
H H

H H
sp2–hybridized orbitals C C
( the three pink orbitals ) H H
A planar structure
66
1.7 Functional Groups

A functional group is a reactive portion of an

organic molecule, an atom , or a group of atoms that
confers on the whole molecule its characteristic
properties .

All compounds with the same functional group

belong to one family . Members of a given organic
family react in a similar and predictable manner .

67
Ex. 1. Indicate the kind of hybridization you expect for
each carbon atom in the following molecules :
(1)Butane , CH3CH2CH2CH3 (2)1-Butene , CH3CH2CH=CH2

(3)1-Butene-3-yne ,CH2 CH C CH (4)Cyclobutene ,

Ex. 2. Rank the following of carbon-carbon bonds lettered

in the molecules in order of bond length:
b
(1) a (2) CH3 CH CH2
c d
(3) CH3 C CH (4) CH3 CH2 CH3

Answer : d > a > b > c 68