Organic Chemistry I-Edit PDF

Organic Chemistry I
SCES 1220
PROF. DR. KHALIJAH AWANG
Organic Molecules
Nomenclature,
Physical Properties,
and
Representation of
Structure
Learning Outcomes
At the end of the lesson, the students should be able to:
 Identify organic functional groups

 Name chemical structures according to IUPAC names
 Draw chemical structures from IUPAC names
Organic Functional Groups
• Most organic molecules contain a carbon backbone

consisting of C-C and C-H bonds to which functional groups
are attached.
• A functional group is an atom or a group of atoms with

characteristic chemical and physical properties.
• Structural features of a functional group include:

• Heteroatoms—atoms other than carbon or hydrogen.
•  Bonds most commonly occur in C-C and C-O double
bonds.
Importance of Functional Groups
A functional group determines ALL of the

following properties of a molecule:
• bonding and shape
• type and strength of intermolecular forces
• physical properties
• nomenclature
• chemical reactivity
Alkanes are hydrocarbons containing only single bonds
General formula: CnH2n+2
6
Ethane, a Molecule with No Functional
Group
• This molecule has only C-C and C-H bonds.
• It contains no polar bonds, lone pairs, or  bonds.
• Therefore, ethane has no reactive sites (functional

groups).
• Consequently, ethane and molecules like it (alkanes)

are very unreactive.
8
Functional groups with C-C multiple bonds
These includes:
Alkenes – contain a double bond;
Alkynes – contain triple bond
Arenes (aromatic compounds) – contain alternate double bond and
single bond in a six-membered ring of carbon atoms.
C
C C
C C
C C C C C
Alkene Alkyne Arene

(aromatic ring)
Functional groups with C-O bonds
(i) Carbon oxygen single bond :
Alcohol, ether
(ii) Carbon-oxygen double bond – Carbonyl groups
A large number of important organic compounds contain these functional
groups.
There are several families under this group; aldehydes, ketones, carboxylic
acids, esters, amides and acid chlorides
The carbonyl carbon carry the partial positive charge (d+) and oxygen atom
carry the partial negative charge (d-).
O O O
C C H C C C C C OH
Aldehyde Ketone Acid carboxylic

O O O
C C O C C C N C C Cl
Ester Amide Acid chloride

Molecules can Contain Several Functional
Groups
Questions
1. Identify functional groups in the following molecules:
O H O
N
a. b. OH
CH 2OH
c. d. OCH 3
O O
2. Identify all functional groups presence in the following plant derived drugs:
CH 3
N
a. O
b. COOCH 3
NCH 3
OH COOPh
Morphine Cocaine
OH OH
CH 3
HO O
c. NHCH 3 d. O
O
O
Ephedrine H3CO OCH 3

OCH 3
Podophyllotoxin
Constitutional isomers have the same molecular formula,
but their atoms are linked differently
14
Nomenclature of Alkyl Substituents
Removing a hydrogen from an alkane results in an alkyl

substituent
If a hydrogen is replaced by an OH, the compound
becomes an alcohol;
if it is replaced by an NH2, the compound becomes an amine;
16
if it is replaced by a halogen, the compound becomes an
alkyl halide;
and if it is replaced by an OR, the compound becomes an
ether
Some common names are derived from the alkyl groups
17
Different Kinds of Carbons and
Hydrogens
A compound can have more than one name, but a
name must specify only one compound
The prefix “tert” is used for tert-butyl and tert-pentyl compounds
19
The use of an “iso” prefix:
20
Nomenclature of Alkanes
1. Determine the number of carbons in the longest
continuous chain
2. Number the chain so that the substituent gets the lowest
number
Numbers are used only for systematic names but not
common names
3. Number the substituents to yield the lowest possible number
in the number
1 2
of
3
the
4 5
compound
6 7 8
substituents are listed in

alphabetical order
24
4. Assign the lowest possible numbers to all
of the substituents
1 2 3 4 5 1 2 3 4 5 6 7 8
5. If the same substituent numbers are obtained in both directions,
the first group cited receives the lower number
4 3 2 1 1 2 3 4 5 6 7
6. If a compound has two or more chains of the same length, the
parent hydrocarbon is the chain with the greatest number of
substituents
7. Certain common nomenclatures are used in the IUPAC system
1 2 3 4 5 6 7 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8
’ ’ ’ ’
1
’
’
’ ’ ’’
Some substituents have only a systematic name
10 9 8 7 6 5 4 3 2 1 1 2 3 4 5 ’
’ ’ ’ ’ ’
’ 6 7 8 9 10
’ ’ ’
Systematic Naming of Substituents
Systematic Method 29
•Determine longest chain starting with the point of attachment.
•Name longest chain as “alkyl.”
•Number and name substituents and add to “alkyl” as prefix.
•Name the substituent as (#-alkylalkyl). The parentheses distinguish substituent
numbering from the numbering of the longest chain.
4 carbons
4 carbons
Nomenclature of Cycloalkanes
1. No number is needed for a single substituent on a ring
2. Name the two substituents in alphabetical order

methyl methyl
2
1 3 2 3
1
2 ethyl
1
propyl
3. If there are more than two substituents, they are cited in
31
alphabetical order and numbering goes to the one that gives
the smallest number in the sequence
2
3 2
1
4 1
ALKENE
Compounds having a double bond (C=C) with general formula CnH2n
Name ends with –ene.
a) Give name based on parent structure

b) Give numbering to C atom in the chain.
c) Make sure the double bond is given the smallest number
possible.
d) Start from the end nearest to C=C bond
e) If the distance of C=C are the same from both ends, start
numbering from the end nearest to the substituent.
ALKYNE
Unsaturated compound containing triple bond
General formula for this group is CnH2n-2
The name ends with –yne. Example:
Nomenclature of Alkyl Halides
In the IUPAC system, alkyl halides are named as substituted

alkanes 7 6 5 4 3 2 1
4 2
6
7 5 3 1
3 4
2 5 3
4
2
5 6
1
1
Nomenclature of Ethers
As substituents:
5 4 3 2 1
1 5
3
2 4
35
Nomenclature of Alcohols
• In an alcohol, the OH is a functional group
• A functional group is the center of reactivity in a
molecule
36
1. Determine the longest hydrocarbon containing the functional
group:
Alcohol has higher priority than ether
2. The functional group suffix should get the lowest number:

1 2 3 4 5 6
37
3. When there is both a functional group suffix and a substituent, the
functional group suffix gets the lowest number:
3-bromopropan-1-ol 4-chlorobutan-2-ol 4,4-dimethylpentan-2-ol
4. The chain is numbered in the direction that gives a substituent the

lowest number:
38
5. The functional group substituent on a ring gets the number 1, but
the functional group is not numbered in the name:
CH3 HO CH3 OH
CH3
CH3
OH
3-methylcyclohexanol 1-methylcyclohexanol 2, 2-dimethylcyclopentanol
not not not
3-methylcyclohexan-1-ol 1-methylcyclohexan-1-ol 2, 2-dimethylcyclopentan-1-ol
6. If there is more than one substituent, the substituents are cited in

alphabetical order:
2
3
2 3
4 1
7 6 5 4 3 2 1
1 4
5
6
39
Nomenclature of Amines
40
The substituents are listed in alphabetical order and a number or
an “N” is assigned to each one:
41
Naming Quaternary Ammonium Salts
10 8 6 4 2 2 4 6 8 10
9 7 5 3 1 1 3 5 7 9
A disinfectant and Antiseptic
42
ALDEHYDE and KETONE
Both contain carbonyl group.
Parent aldehyde contain –CHO and given the terminal carbon
with number 1.
The end of an alkane –ane is replace with –al.
6 5
H H H3CH2C H
4 3 2 1
R C O H3CH2CC O H3CHCH2CHCC O
H3C
Aldehyde Propanal 2,4-Dimethylhexanal
O
O
1
6 2
5 3
4
Br
3-bromocyclohexanecarbaldehyde cyclopent-1-enecarbaldehyde
Ketone
This is also a carbonyl compound.
Carbonyl group occur in the middle of the chain.
The smallest position number is given carbonyl group. The rests
are relative to this position.
The end is replaced by –one.
R' CH2CH3 O
R C O H3CH2CH2CC O H2C CHCH2CH2CCH3
Ketone 3-Hexanone 5-Hexen-2-one

O
O O O
H3CC CH2 CCH2CH3 H3C C CH3 CH3
hexane-2,4-dione propanone
(acetone) 3-methylcyclohexanone
CARBOXYLIC ACID
The compound contains a carboxyl group (-COOH) and situated
at the end of the chain.
The other groups are relative to this position.
The name consists of two words. The end of the first word is
replaced with –oic, and the second word is given as acid.
Example:
O O O
4 3 2 7 6 5 4 3 2
O H3CHCH2CH2CC OH HO CH2CHCH2CH2CHCH2CC OH
1 8 1
H3CH2CC OH H3C H3C H3CH2C
Propanoic acid 4-Methylpentanoic acid 3-Ethyl-6-methyloctadioic acid

CARBOXYLIC ACID- attached to a ring
If –COOH group is attached to a ring, the name ends with
carboxylic acid.
Example:
COOH
COOH
1
Br
3-Bromocyclohexanecarboxylic acid Cyclopent-1-enecarboxylic acid

CARBOXYLIC ACID DERIVATIVES
The –OH group of the carboxyl group (-COOH) is replaced with –
Cl, OOCR, -OR’, or –NH2 group
There are several carboxylic acid derivatives. The four main ones
are:
a) Acid chloride b) Acid anhydride
c) Ester d) Amide
O O O O O
R Cl R O R' R OR' R NH2
Acid chloride Acid anhydride Ester Amide

Acid chloride
Given name by identifying parent chain carrying the acyl group
followed by the word chloride. Carbonyl carbon given number
one (1). The name for acyl group is obtain from the name of
carboxylic acid by replacing the end –ic with –yl
O O
Acetylchloride (from acetic acid) Benzoyl chloride (from
H3C Cl Ph Cl benzoic acid)
IUPAC: Ethanoyl chloride (from
ethanoic acid)
Acid anhydride
Given name by replacing the word acid with anhydride.
O O O O
H3C O CH3 Ph O Ph
Acetic anhydride or Benzoic anhydride

Ethanoic anhydride
Amide
The end is replaced with amide and word acid is dropped
O O
5 3
6
1
H3C NH2 H3C 4 2
NH2
Ethanamide Hexanamide
Substituted Amide
O F O
5
H3C
6
3 1
CH3
N CH3 H3C 4 2
N
H
CH3
N-Methylpropanamide 3-Fluoro-N,N-dimethylhexanamide
Ester
Identify the alkyl group attached to the oxygen first. Then
identify the carboxylic acid and the end is replaced with -oate
The word acid is dropped. Carbonyl carbon given number one (1)
O O
Cl
O O Cl
Common Names of
Benzene Derivatives
OH CH3 NH2 OCH3
phenol toluene aniline anisole
H O O O
C CH2 C C C
CH3 H OH
styrene acetophenone benzaldehyde benzoic acid

Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are
commonly used for the 1,2-, 1,3-, and 1,4-
positions, respectively.
3 or More Substituents
Use the smallest possible numbers, but
the carbon with a functional group is #1.
List substituents alphabetically.
OH
O 2N NO2 NO2 O
O 2N NO 2
H
Br
NO2 NO2
2,4,6-trinitrophenol 4-Bromo-2-nitrobenzaldehyde
1,3,5-trinitrobenzene
•Alkyl substituted benzene, also called arenes, are named
depending on the size of alkyl group.
•If alkyl group is smaller than 6 carbons, the arene is named

as an alkyl substituted benzene.
•If the alkyl group is larger than 6 carbons, the compound is

named as phenyl-substituted alkane.
•The name phenyl, sometimes abbreviated as Ph or C6H5

when benzene is considered as a substituent.
CH 3
H2
C CHCH 2CH 2CH 2CH 2CH 3
A phenyl group A benzyl group 2-Phenylheptane

Give the IUPAC name of the following compounds:
O
a) O Cl b) c)
O
O
d) e) f)
Cl N
H
OH
O
OH
N
O
g) h) i)
HO COOH O
OH
O
Cl O
C(CH3)3
j) N OH l) O
k) O
Cl
O
O Cl c)
a) b)
5-chloro-2-methylpentanal
(2-methylbutyl)cyclohexane (Z)-4-ethyl-2-methylhex-4-en-3-one
O O
e)
d) f)
Cl
N
O H
OH
3-methylcyclohexanol 5-methyl-4-oxoheptanoyl chloride OH
2-ethyl-3-hydroxy-N-methylbutanamide
N
O i)
g) h) O
HO COOH
OH
4-hydroxybutanoic acid isopropoxycyclohexane
(cyclohexane isopropyl ether)
3-cyano-4-methylhexanoic acid
O
j) k) l)
C(CH3)3
Cl O O
N OH
3-(dimethylamino)propan-1-ol O
Cl tert-butyl cyclohexanecarboxylate
methyl 3,4-dichlorohexanoate
Give suitable structures for the following compounds:
a) 1-Methylcyclopentanol
b) 5,5,5-Trichloro-3-penten-2-one
c) 4,4-Dimethylcyclohexanamine
d) 5-Amino-2-hexanone
e) Phenyl 3,3-dimethylbutanoate
f) 3,5-Hexadien-2-one
g) 2,4-Pentadienoyl chloride
h) N-Isopropylcyclohexylamine
i) N-Ethyl-N-methylcyclopentylamine
HO NH2 H2N
O 4,4-Dimethylcyclohexanamine
1-Methylcyclopentanol 5-Amino-2-hexanone
O
Cl O
Cl O
Cl
5,5,5-Trichloro-3-penten-2-one Phenyl 3,3-dimethylbutanoate
O O
Cl
3,5-Hexadien-2-one 2,4-Pentadienoyl chloride
N
N
H
N-Isopropylcyclohexylamine N-Ethyl-N-methylcyclopentylamine
INFRARED (IR)
SPECTROSCOPY
INFRARED (IR) SPECTROSCOPY
INFRARED (IR) SPECTROSCOPY cont’d
Almost all organic compounds
absorbs various frequencies of
electromagnetic radiation in the
infrared region. This region lies at
wavelengths longer than those of
UV and visible - 2.5 m - 25 m.
since the wavelengths are longer,
therefore the energy is smaller.
That is why infrared can only

cause transitions in the vibrational
and rotational states associated
with the ground state (electronic
ground state of the molecule.
For infrared spectrum the energy
unit is expressed in wavenumber (ῡ),
rather than wavelength () m. 4
3
2
1
ῡ (cm-1) = 0
4
3
cm-1 = x 10,000 2
1
0
Transitions
caused by IR Electronic states
 x 10,000 = 4,000cm -1 radiation Vibrational energy
states
In IR spectrum, region of
 x 10,000 = 400cm-1 absorption; 400  4,000 cm-1
DIFFERENT TYPES OF VIBRATIONS
Absorption stretches from

400  4,000 cm-1
25←2.5 m
WHY IR IMPORTANT???
i. Act as finger print of each molecule. No two

molecules have the same (identical) IR
absorption profile, peak by peak  helps
identify compound.
ii. Gives valuable info on the presence different

types of bods: N-H, O-H, C=O, C-O, C-C, C=C,
C≡C, C-Cl etc.
Helps structural elucidation process.
C≡C C=C C-C

2150 cm-1 1650 cm-1 1200cm-1
Increasing K
C-H C-C C-O C-Cl C-Br C-I
3000 cm-1 1200 cm-1 1100 cm-1 750 cm-1 600 cm-1 500 cm-1
Increasing 
Weak
Broad
Sharp
Strong
Important to note:
C=C 1680-1620 cm-1 (Weak)
C=O 1850-1630 cm-1 (Strong) i. Frequency of absorption:(ῡ)
ii. Intensity of absorption:-

(Weak) strong or weak
(Strong) iii. Shape of absorption :-
sharp or broad
NH2 – 2 peaks
Broad and NH – 1 peak
strong
O-H 3650  3200 cm-1

N-H 3500  3300 cm-1
The region of OH and N-H absorption overlaps. How to
know if it is OH or N-H absorption???
Usually free OH (unchelated/no hydrogen bonding)

absorbs at higher frequency. However when hydrogen
bonding is present the absorption of OH overlaps into the
lower frequency of N-H region.
The difference: the OH absorption is usually very broad.
*
*
*
Less than 3000 cm-1 More than 4 CH2 group
C-H bands
Acetylenic ≃3300 cm-1
Vinylic or aromatic >3,000 but not higher than ≃ 3150 cm-1
Aliphatic < 3000 cm-1
Aldehydic 2850 &2750 cm-1 (weak absorption)
Spectrum very similar to that of decane (Fig. 2.7)

Absence of
CH3 bend
All spectrums are fairly simple
Saturated compounds have all the C-H stretches less

than 3000 cm-1. Only cyclopropyl C-H stretch is ≃
3100 cm-1 due to ring strain.
Strong bands may give absorptions called overtones.

These bands are usually weak. Absorptions are
multiples of 2 or 3 of the original band. For example
absorption at ≃ 910 give an overtone at ≃ 1800 cm-1
(900 x 2)
Look at:
i) =C–H stretch > 3000 cm-1
ii) C=C stretch ≃ 1600 cm-1
iii) C=C stretch is very weak
in trans alkenes. Cis
gives a medium band.
Sp C-H stretch – very distinctive of terminal alkynes (Overlaps

with OH and NH region), however, peak is sharper.
No C≡C stretch for 4-octyne because the bond is symmetric.

 Observe that as bond length increase ↑ IR frequency ↓

WHY?
 More energy is needed to stretch and bend stronger
bonds. Weaker bonds will need less energy,
 IR frequency ↓↓↓.
Less
Similar to absorption of C=C

of cyclopentene
The IR frequencies of
C=C ↑ as more alkyl
substitution.
Ring size decrease ↓
IR absorption
frequencies except
for cyclopropene.
(Stretching)
Increase in frequencies ↑
Effects of conjugation
Conjugation can occur with the presence of more double
bonds (arranged alternately) or with a carbonyl group.
More conjugation
cause lower IR
frequency
absorptions i.e in
butadiene
absorption occurs
at 1600 cm-1
Look for the (out of plane) oop band (strong).

> 3,000
≃ 750 cm-1 (s)

m
s s
(≃ 700 →900 cm-1)
(s)
(≃ 850 cm-1)
s s (≃ 700 →800 cm-1)

600
Intermolecular hydrogen bonding ≃ 3,300  3,400 cm-1
Intramolecular hydrogen bonding

 shift to lower frequency.

Methyl salicylate
O-H absorption bond ≃ 3,200 cm-1
Hydrogen bonded OH – 3300 cm-1  3,400 cm-1

Free OH ≃ 3,600 cm-1
The more dilute a solution in a (nonpolar) solvent
CCl4 the degree of O-H bonding is lesser.
Observe the strong C=O stretch. Usually the

strongest band. Only C-H stretch can be as
strong or stronger.
R-O-R ≃ 1120 cm-1

Conjugation (aryl and vinyl ethers) shifts to
higher frequency  ~ 1220 cm-1
CARBONYL COMPOUNDS
Aldehydes, ketones, acids, esters, amides, acid chlorides and
anhydrides.
STRONG ABSORPTION AT ≃ 1850 TO 1650 CM-1
cm-1
1810 1800 1760 1735 1725 1715 1710 1690
Anhydride Acid Chloride Anhydride Ester Aldehyde Ketone Carboxylic Acid Amide
(Band 1) (Band 2)
Differences in all these carbonyl absorptions can be

explained with resonance effect, inductive effect or/and
hydrogen bonding.
CONJUGATION EFFECT: shift absorption to lower frequency.
More single bond character

 Lower the force constant value
(K).
 Absorption at lower frequency
(cm-1) ↓
α,β unsaturated ketone Aryl-substituted acid

1715 → 1690 cm-1 1710 → 1680 cm-1
INDUCTIVE EFFECT:
Inductive effect – flow of
electrons towards :O: due to
higher electronegative value of
O as compared to C.
Inductive effect through σ
bond.
C=O becomes stronger
(shorter),  frequency of
absorption ↑.
1700 cm-1
1700 cm-1
Remember conjugation moves absorption to lower frequencies

(both C=O and C=C)
1700 due to conjugation. No C-H of aldehydes

Enol oop
bending
Broad due to hydrogen bonding

 strenghtens the C=O bonds

Esters absorbs at higher cm-1 due to inductive
effect of :O:
C=O bond length decreases

strengthens bond,
 frequencies ↑↑↑
Ketone absorption ≃ 1715 cm-1

Broad
Hydrogen bonding lowers frequency because

the C=O bond becomes longer due to
hydrogen bonding effect  methylsalicylate
absorbs at ≃ 1680 cm-1.
 Resonance effect more prevalent

than inductive
 Absorption at lower frequencies

than ketone (1715 cm-1)
Inductive effect
by  cm-1↑↑↑
as compared to
that of ketone
Electron moves towards Cl
Absorps at higher frequency

than ketone (1715 cm-1)
*2 C=O stretch absorptions.
Different types of amines can be differentiated !!!
Usually less intense than OH tertiary amine  NO

NH absorption
N-H stretch shape can be determine whether the

compound is a primary or secondary amine.
INFRARED SPECTRUM
IMPORTANT POINTS:
HELPS:
i ) Determine presence of functional groups: especially carbonyls,

hydroxyls, amines.
ii) Fingerprint region < 1,000 cm-1
Thank You

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Organic Chemistry I

At the end of the lesson, the students should be able to:

 Identify organic functional groups

• Most organic molecules contain a carbon backbone

• A functional group is an atom or a group of atoms with

• Structural features of a functional group include:

A functional group determines ALL of the

• This molecule has only C-C and C-H bonds.

• It contains no polar bonds, lone pairs, or  bonds.

• Therefore, ethane has no reactive sites (functional

• Consequently, ethane and molecules like it (alkanes)

Alkene Alkyne Arene

(i) Carbon oxygen single bond :

Aldehyde Ketone Acid carboxylic

Ester Amide Acid chloride

Ephedrine H3CO OCH 3

Removing a hydrogen from an alkane results in an alkyl

Some common names are derived from the alkyl groups

The prefix “tert” is used for tert-butyl and tert-pentyl compounds

substituents are listed in

Some substituents have only a systematic name

2. Name the two substituents in alphabetical order

a) Give name based on parent structure

In the IUPAC system, alkyl halides are named as substituted

2. The functional group suffix should get the lowest number:

3-bromopropan-1-ol 4-chlorobutan-2-ol 4,4-dimethylpentan-2-ol

4. The chain is numbered in the direction that gives a substituent the

6. If there is more than one substituent, the substituents are cited in

A disinfectant and Antiseptic

R C O H3CH2CH2CC O H2C CHCH2CH2CCH3

Ketone 3-Hexanone 5-Hexen-2-one

Propanoic acid 4-Methylpentanoic acid 3-Ethyl-6-methyloctadioic acid

3-Bromocyclohexanecarboxylic acid Cyclopent-1-enecarboxylic acid

R Cl R O R' R OR' R NH2

Acid chloride Acid anhydride Ester Amide

Acetic anhydride or Benzoic anhydride

phenol toluene aniline anisole

styrene acetophenone benzaldehyde benzoic acid

List substituents alphabetically.

•If alkyl group is smaller than 6 carbons, the arene is named

•If the alkyl group is larger than 6 carbons, the compound is

•The name phenyl, sometimes abbreviated as Ph or C6H5

A phenyl group A benzyl group 2-Phenylheptane

That is why infrared can only

Absorption stretches from

i. Act as finger print of each molecule. No two

ii. Gives valuable info on the presence different

C≡C C=C C-C

ii. Intensity of absorption:-

O-H 3650  3200 cm-1

Usually free OH (unchelated/no hydrogen bonding)

Less than 3000 cm-1 More than 4 CH2 group

Spectrum very similar to that of decane (Fig. 2.7)

All spectrums are fairly simple

Saturated compounds have all the C-H stretches less

Strong bands may give absorptions called overtones.

Sp C-H stretch – very distinctive of terminal alkynes (Overlaps

No C≡C stretch for 4-octyne because the bond is symmetric.

 Observe that as bond length increase ↑ IR frequency ↓

Similar to absorption of C=C

Look for the (out of plane) oop band (strong).

≃ 750 cm-1 (s)