Chapter 19

Introduction to
Organic Chemistry

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19.1 The beginnings of organic chemistry
large number of remarkably stable compounds
consist of C, H, O and N –organic compounds
no organic compounds had been synthesized from
inorganic substance before the early 19th century
the vital-force theory –organic substances could
originate only from living material
1828 Wöhler
HCNO + NH3 ╳ NH4+CNO-
NH2
O=C urea
NH2
the sources of organic compounds are carbon-
containing raw materials –petroleum and natural
gas, coal, carbohydrates, fats, and oils

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19.2 The carbon atom
C electron structure 1s22s22p4
two stable isotopes: C-12 and C-13
a carbon atom usually forms four covalent bonds
with tetrahedral geometry

ex. methane CH4 carbon tetrachloride CCl4

H Cl
.. ..
H:C:H Cl:C:Cl
.. ..
H Cl

one, two, or three pairs of electrons can be shared

between two C atoms, forming a single, double, or
triple bond . . . .
·C—C·
. . ·C=C· ·C≡C·
through this bonding ability, long chains of C
atoms form by liking one to another

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organic molecules are classified according to their
structural features
each class of compounds contain a characteristic
atom or group of atoms called a functional group

4
19.3 Hydrocarbons
hydrocarbons –compounds composed entirely of
C and H atoms
saturated hydrocarbons have only C—C single
bonds
unsaturated hydrocarbons contain a double or
triple bond between two C atoms, include
alkene, alkyne and aromatic compounds
general classification of hydrocarbons

5
19.4 Alkanes
alkanes paraffins saturated hydrocarbons
straight- or branched-chain hydrocarbons with
only single bonds between the C atoms
allowed energies
the first member –methane CH4

each member of a series differ in formula from the

next member by a CH2 group, the series is known
as homologous series
the general formula for open chain alkanes is
CnH2n+2
combustion reaction generates heat
ex. CH4 + 2 O2 CO2 + 2 H2O + 802.5 kJ

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19.5 Structural formulas and isomerism
alkane molecules only contain C—C and C—H
bonds
alkane molecules are essentially nonpolar, and have
little intermolecular attraction and therefore
relatively low boiling points
three-dimensional structures
methane CH4 ethane C2H6 propane C3H8

butane C4H10 normal butane 2-methylpropane

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 normal propane bp 0.5oC mp -138.3oC
2-methylpropane bp -11.7oC mp -159.5oC
isomerism –the phenomenon that two or more
compounds have the same molecular formula
the individual compounds are called isomers
butane 2 isomers pentane 3 isomers
hexane 5 isomers heptane 9 isomers
octane 18 isomers nonane 35 ismers
decane 75 isomers
isomers are compounds with the same molecular
formula but different structural formula
ex. 19.1 write the structural formulas for three
isomers of pentane
C—C—C—C—C CH3CH2CH2CH2CH3
C CH3
| |
C—C—C—C CH3CHCH2CH3
C CH3
| |
C—C—C CH3CCH3 or C(CH3)4
| |
C CH3

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19.6 Naming alkanes
IUPAC system is generally unambiguous and
internationally accepted
common alkyl groups CnH2n+1
-ane -yl

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IUPAC rules for naming alkanes

ex.

2-methylbutane 2-methylpentane10
 2,3-dimethylbutane 2,2-dimethylbutane

3-methylhexane

2,3,4,6-tetramethylheptane

3-chloro-4-ethyl-2,4-dimethyloctane
ex.19.2 write the formulas for
(a) 3-ethylpentane
1 2 3 4 5 1 2 3 4 5
C—C—C—C—C CH3CH2CH2CH2CH3
|
CH3
(b) 2,2,4-trimethylpentane CH3
1 2 3 4 5 1 2 3 4 5
C—C—C—C—C CH3CCH2CHCH3 11
| |
CH3 CH3
ex. 19.3 name these compounds
6 5 4 3 2 1
(a) CH3CH2CH2CH2CHCH3
|
CH3
hexane 2-methylhexane
8 7 6 5 4 3
(b) CH3CH2CH2CHCH2CHCH3
| |2 1
CH3CH2 CH2CH3
octane 5-ethyl-3-methyloctane

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19.7 Alkenes and alkynes
alkenes contain at least a C=C double bond
alkynes contain at least a C≡C triple bond
the simplest alkene C2H4 ethene (ethylene)
the simplest alkyne C2H2 ethyne (acetylene)

general formula for alkenes: CnH2n

general formula for alkynes: CnH2n-2

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19.8 Naming alkenes and alkynes
to name an alkene (or alkyne) by the IUPAC system

ex. 4 3 2 1 4 3 2 1
CH3CH2CH=CH2 CH3CH=CHCH3
1-butene 2-butene
4 3 2 1 6 5 4
CH3CH2C≡CH CH3CH2CH2
|3 2 1
1-butyne CHCH=CH2
|
CH3CH2CH2
CH3 3-propyl-1-hexene
1 2 3 4| 5 6
CH3C ≡C—CH—CH—CH3
|
CH3 4,5-dimethyl-2-hexyne
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ex. write the structural formulas for
(a) 7-methyl-2-octene
8 7 6 5 4 3 2 1
CH3—CH—CH2—CH2—CH2—CH=CH—CH3
|
CH3
(b) 3-hexyne
6 5 4 3 2 1
CH3—CH2—C≡C—CH2—CH3

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19.9 Reactions of alkenes
alkenes are much more reactive than alkanes
addition reaction –a reaction in which two
substances join to produce one product
hydrogen, halogens, hydrogen halides and water
can be added to C=C double bond
ex. Pt 25oC
CH2=CH2 + H2 CH3—CH3
1 atm
CH2=CH2 + Br—Br BrCH2—CH2Br
CH2=CH2 + HCl CH3—CH2Cl
H+
CH2=CH2 + HOH CH3CH2OH

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19.10 Aromatic hydrocarbons
benzene and all substances with structures and
chemical properties resembling benzene are
classified as aromatic compounds
benzene C6H6
the structure

although benzene looks as highly unsaturated, it

does not readily undergo addition reactions like
a typical alkene
its typical reaction is substitution reaction:
C6H6 + Cl2 Fe C6H5Cl + HCl
the modern molecular orbital structure of
benzene

chlorobenzene

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19.11 Naming aromatic compounds
monosubstituted benzenes

disubstituted benzenes
ortho-, meta-, para- (o-, m-, p-)

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trisubstituted benzenes

ex. 19.5 write formulas and names for all

possible isomers of
(a) chloronitrobenzene C6H4Cl(NO2)

(b) tribromobenzene C6H3Br3

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19.12 Hydrocarbon derivatives
hydrocarbon derivatives –compounds that can be
synthesized from a hydrocarbon
the derivatives contain not only C and H, but
additional elements such as O, N, or halogen

two groups:
•compounds do not contain a C=O group
•compounds contain a C=O carbonyl group20
19.13 Alkyl halides
alkanes react with a halogen in UV light to produce
an alkyl halide R—X
halogenation UV light
RH + X2 RX + HX (X = Cl, Br)
ex. UV light
CH3CH3 + Cl2 CH3CH2Cl + HCl
UV light
CH4 + Cl2 CH3Cl + HCl
chloromethane
•alkyl halides are primarily used as industrial
solvents ex. CCl4 dry-cleaning solvent
•CH3Cl was once a popular anesthetic
•CFCs (chlorinated fluorocarbons) used in
aerosol propellents and refrigerants
deplete ozone layer

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19.14 Alcohols
alcohol molecules contain a hydroxyl (-OH) group
general formula is ROH
alcohols are classified as
primary (1o) secondary (2o) tertiary (3o)
H R R
| | |
R—C—OH R—C—OH R—C—OH
| | |
H H R

alcohol molecule can contain two or more –OH

groups if each –OH is attached to a different 22C
atom
 polyhydroxy alcohol is a general term for an
alcohol that has more than one –OH group per
molecule
methanol CH3OH
•volatile (bp 65oC), highly
flammable liquid
•poisonous, causing
blindness or death
•over 8 billion pounds are
manufactured annually
ethanol CH3CH2OH
•prepared by fermentation by using sugar as the
raw material and with yeast enzyme –zymase
C6H12O6 zymase 2 CH3CH2OH + 2 CO2
•an intermediate in the manufacture of other
chemicals (acetylaldehyde, acetic acid, ethyl
acetate, diethyl ether)
•a solvent for many organic substances
•an ingredient in alcoholic beverages
2-propanol –principal ingredient in rubbing alcohol
formulation
ethylene glycol (ethanediol) –used in antifreezes,
in manufacture of synthetic fibers
glycerol (1,2,3-pentanetriol) or glycerin –used in
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manufacture of polymers and explosives
19.15 Naming alcohols
to name an alcohol by the IUPAC system

ex.

ex. 19.6 name the following alcohol

CH3CH2CHCH2CHCH3
6 5 4| 3 2| 1
CH3 OH
2-hexanol 4-methyl-2-hexanol

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ex. 19.7 write the structural formula of 3,3-
dimethyl-2-hexanol
1 2 3 4 5 6
C—C—C—C—C—C
CH3
|
CH3CH2CCH2CH2CH3
| |
OH CH3

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19.16 Ethers
ethers have the general formula ROR’

saturated ethers have little chemical reactivity, are

often used as solvent
alcohols (ROH) and ethers (ROR’ ) are isomeric
ex. ethanol CH3CH2OH bp 78.3oC
dimethyl ether CH3OCH3 bp -23.7oC
naming ethers
common name
CH3—O—CH3 dimethyl ether
CH3—O—CH2CH3 methyl ethyl ether 26
IUPAC system

CH3CH2—O—CH2CH3 ethoxyethane
CH3CH2CH2—O—CH2CH2CH2CH3
propoxybutane

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19.17 Aldehydes and ketones
aldehydes and ketones contain carbonyl group
C=O
aldehydes have at least one H atom bonded to the
carbonyl group, ketones have two alkyl (R) or
aromatic (Ar) groups bonded to the carbonyl group
aldehyes O O
|| ||
R—C—H Ar—C—H
ketones O O O
|| || ||
R—C—R R—C—Ar Ar—C—Ar
linear expression CH3CHO
CH3COCH3
formaldehyde poisonous, irritating gas
40% aqueous solution of formaldehyde is
called formalin
mainly used in the manufacture of polymers
acetone and methyl ethyl ketone (MEK) are
widely used as organic solvents

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19.18 Naming aldehydes and ketones
IUPAC name of aldehyde
-ane -anal
O
||
CH4 methane H—C—H methanal
O
||
CH3CH3 ethane CH3C—H ethanal
CH3 O
6 5 4| 3 2 1||
CH3CH2CHCH2CH2C—H 4-methylhexanal
IUPAC name of aldehyde
-ane -anone
O O
|| 5 4 3 2|| 1
CH3—C—CH3 CH3CH2CH2—C—CH3
propanone 2-pentanone
O CH3
1 2 3|| 4| 5 6
CH3CH2—CHCHCH2CH3
4-methyl-3-hexanone
non-IUPAC name
O O
|| ||
CH3—C—CH3 CH3CH2—C—CH 29 3
dimethylketone, acetone methyl ethyl ketone
ex. 19.8 write the formulas and the name for
the straight-chain five- and six-carbon
aldehydes
O
||
CH3CH2CH2CH2C—H pentanal
O
||
CH3CH2CH2CH2CH2C—H hexanal
ex. 19.9 give two names for the ketones:
(a) O CH3
|| |
CH3CH2CCH2CHCH3
5-methyl-3-hexanone
ethyl isobutyl ketone
(b) O
||
CH3CH2CH2C—Ph
1-phenyl-1-butanone
phenyl propyl ketone

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19.19 Carboxylic acids
organic acids known as carboxylic acids are
characterized by the functional group called a
carboxyl group
O
||
—C—OH —COOH —CO2H
IUPAC system to name carboxylic acid
-ane -anoic acid
CH4 methane HCOOH methanoic acid
CH3CH3 ethane CH3COOH ethanoic acid
CH3CH2CH3 propane
CH3CH2COOH propanoic acid
common names
HCOOH CH3COOH CH3CH2COOH
formic acid acetic acid propionic acid

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saturated fatty acids –carboxylic acids have even
numbers of carbon atoms ranging from 4 to 20
they exist in combined form in plant and animal
fats

aromatic acids

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19.20 Esters
carboxylic acids react with alcohols in an acid
medium to form ester RCOOR’
functional group of ester is –COOR’
O O
RC –C
OR’ OR’
esterification

naming the esters –the alcohol part is named first,

followed by the name of the acid modified to
end in -ate
ex. O
||
CH3C—OCH3
acid alcohol
methyl acetate

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19.21 Polymers
polymerization –the process of forming very
large, high-molar-mass molecules from
smaller units
polymer –the large molecule is called
monomer –the small repeating unit
polymer containing more than one kind of
monomer is called copolymer
macromolecule
plastics –capable of being molded or pliable
ex. polyethylene PE
n CH2=CH2 -CH2CH2[CH2CH2]nCH2CH2-
2500~25000 ethylene molecules joined in a
continuous structure
polyvinylchloride PVC
-(CH2CHCl)-n

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