Chapter 22 - Organic Chemistry

22.1 Alkanes: Saturated Hydrocarbons

22.2 Alkenes and Alkynes

22.3 Aromatic Hydrocarbons

22.4 Hydrocarbon Derivatives

22.5 Polymers

22.6 Natural Polymers

Carbon is Special
1. Carbon can form strong and short C-C bonds.

2. The C-C bond is short enough to allow sideways overlap of the

unused p orbitals, resulting in π bonding. C easily forms carbon-
carbon double bonds, and even forms carbon-carbon triple bonds.

3. Carbon has no problem bonding to other elements

(H, O, N, S, etc.). Given where C is in the periodic table, it typically
forms four bonds, with the notable exception of carbon monoxide.
 Carbon is Special -- Try Comparing C to Si

1. The C-C bond is much stronger than the Si-Si bond. (Atomic
size increases down the group: bonds between atoms become
longer and weaker.)

2. BE (C-C) ~ BE (C-O). For Si, BE (Si-O) >> BE (Si-Si).

With availability of oxygen in nature, Si will exist mostly with
Si-O bonds.

3. Carbon has no d-orbitals to worry about. CH3-CH3 is

stable, while SiH3-SiH3 is very susceptible to species with
lone pairs of electrons to donate into the vacant d orbitals.

Some people spend their whole lives learning about Carbon!

Hydrocarbons C + H
Compounds containing only carbon and hydrogen with only single
bonds and no multiple bonds
- Saturated hydrocarbons
- Alkanes CnH2n+2
Compounds containing only carbon and hydrogen with only single
bonds and no multiple bonds, but a ring structure
- Saturated hydrocarbons
- Cycloalkanes CnH2n
Compounds containing only carbon and hydrogen with double
bonds
- Unsaturated hydrocarbons
- Alkenes CnH2n
Compounds containing only carbon and hydrogen with triple
bonds
- Unsaturated hydrocarbons
- Alkynes CnH2n–2
 Naming Hydrocarbons

Based on the longest chain of carbon atoms

Prefix + root + suffix

Location and nature of Class of organic compound

substituents on chain -ane for alkanes
(Table 22.2) (-ene for alkenes
-yne for alkynes)

Indicator of the # of C’s in the

longest chain (Table 22.1)

Numerical Roots for Carbon Chains and Branches

Root Number of Carbon Atoms

meth- 1
eth- 2
prop- 3
but- 4
pent- 5
hex- 6
hepta- 7
oct- 8
non- 9
dec- 10
see Table 22.1
 Alkanes

• Methane CH4
• Ethane C2H6 CH3CH3
• Propane C3H8 CH3CH2CH3
• Butane C4H10 CH3CH2CH2CH3
• Pentane C5H12 CH3CH2CH2CH2CH3
• Hexane C6H14 CH3CH2CH2CH2CH2CH3
• Heptane C7H16 CH3-(CH2)5-CH3
• Octane C8H18 CH3-(CH2)6-CH3
• Nonane C9H20 CH3-(CH2)7-CH3
• Decane C10H22 CH3-(CH2)8-CH3

Example Problem: Drawing Alkanes

Problem: Draw all possible structures for hydrocarbons that have:
a) 7 C atoms, no multiple bonds, and no rings.
b) 5 C atoms, one double bond, and no rings.
c) 5 C atoms, no multiple bonds, and one ring.
Plan: In each case, we draw the longest carbon chain and then work
down to smaller chains with branches at different points along
them. The process typically involves trial and error. Then we add
H atoms to give each C atom a total of four bonds.
Solution: (only the carbon backbone will be shown here)
a) compounds with seven C atoms: (9) [C7H16] C
C-C-C-C-C-C-C C-C-C-C-C-C C-C-C-C-C-C C-C-C-C-C
C C C
C C-C-C-C-C C
C-C-C-C C C-C-C-C-C C-C-C-C-C C-C-C-C-C
C C C CC C C C
 Drawing Alkanes (cont)
b) compounds with 5 C atoms and 1 double bond: (5) [C5H10]

C=C-C-C-C C=C-C-C C=C-C-C C-C=C-C

C C C
C-C=C-C-C

c) compounds with 5 C atoms and 1 ring: (5) [C5H10]

C
C-C-C-C C-C-C-C C-C-C
C C C
C-C
C-C-C C C
C-C C

Rules for Naming Organic Compounds – I

1. Naming the longest chain (root)
(a) Find the longest continuous chain of carbon atoms.
(b) Select the root that corresponds to the number of carbon atoms
in this chain.

2. Naming the compound type (suffix)

(a) For alkanes, add the suffix -ane to the chain root. (Several suffixes
are listed in table 22.2)
(b) If the chain forms a ring, the name is preceded by cyclo-.

3. Naming the branches (prefix)

(a) Each branch name consists of a subroot (number of C atoms) and
the ending -yl to signify that it is not part of the main chain.
(b) Branch names precede the chain name. When two or more
branches are present, name them in alphabetical order.
 Rules for Naming an Organic Compound-II
3. continued:
(c) To specify where the branch occurs along the chain, number the
main-chain C atoms consecutively, starting at the end closer to
a branch, to achieve the lowest numbers for the branches. Precede
each branch name with the number of the chain C atom to which
that branch is attached.
(d) If the compound has no branches, the name consists of the root
and suffix. 6 carbons hex-
CH3 methyl hex- + -ane = hexane
1 2 3 4 5 6
CH3 CH CH CH2 CH3 CH3
ethylmethylhexane
CH2 CH3
ethyl
3-ethyl-2-methylhexane
 Alkenes
Alkenes–Carbon compounds that contain at least one C=C double bond.
Alkenes have the general formula: CnH2n
Alkenes are called unsaturated hydrocarbons
The names of alkenes differ from those of alkanes in two respects:
1) The root chain must contain both C atoms of the double bond,
even if it is not the longest chain. The chain is numbered from
the end closer to the C=C bond, and the position of the bond is
indicated by the number of the first C atom in it.
2) The suffix for alkenes is -ene.
Examples:
H2C=CH2 H2C=CH-CH3 H3C-CH2-CH=CH2
Ethylene Propylene = Propene 1-Butene

H2C=CH-CH2-CH3 H3C-CH=CH-CH3 H2C=C-CH3

1-Butene 2-Butene 2-Methyl propene
CH3

Alkenes
C2H4 Ethylene H2C=CH2

C3H6 Propylene H2C=CH–CH3

C4H8 Butene H2C=CH–CH2–CH3

C5H10 Pentene H2C=CH–CH2–CH2–CH3

C6H12 Hexene H2C=CH–CH2–CH2–CH2–CH3

C7H14 Heptene H2C=CH–( CH2)4–CH3

C8H16 Octene H2C=CH–( CH2)5–CH3
 Some Structural Isomers of Alkenes

Naming and Drawing Alkanes, Alkenes,

and Alkynes–I
Problem: Give the systematic name for each of the following.
(a) CH3 (b) CH2-CH3
CH3 - CH - CH-CH3 CH3-CH2-CH2-CH-CH-CH3
CH3 CH2
CH3
(c) H 2 CH3 CH3
H2 CH3 (d) CH3-CH2-CH-C-CH3
H2 H2 CH3 CH3
(e) CH3-CH2-CH=C-CH-CH3
CH2-CH3
CH3
Plan: For (a) to (c), we first name the longest chain (root + -ane). Then
we find the lowest branch numbers by counting C atoms from the end
closest to a branch. Finally, we name each branch (root- + -yl) and put
them alphabetically before the chain name.
 Naming and Drawing Alkanes, Alkenes, and
Alkynes–II
Plan: For (e), the longest chain that includes the multiple bond is
numbered from the end closer to it.

Solution:
CH2 - CH3
H
(a) CH3
(b) CH3 - CH2 - CH2 - C - C - CH3
7 6 5 4 3
CH3 - CH - CH - CH3 2 CH2
1 2 3 4

CH3 1 CH3
2,3-Dimethylbutane 4-Ethyl-3-Methylheptane

Naming and Drawing Alkanes, Alkenes, and Alkynes–III

(c) H2 (d)
CH3 CH3
H2 3 CH3
CH3 - CH2 - C - C - CH3
5 4 3 2 1
H2 2 H2
1 chiral center H CH3
CH2 - CH3
2,2,3-Trimethylpentane
1-Ethyl-3-methylcyclohexane

(e)
H CH3 CH3
CH3 - CH2 - C = C - CH - CH3 CH3 - CH2 - C = C - CH - CH3
CH3 H CH3
cis-2,3-Dimethyl-3-hexene trans-2,3-Dimethyl-3-hexene
 Organic Optical Isomers
Consider carbon bonded to A, B, C, and D.
There are two possible structures.

B and C do not superimpose

The two structures are mirror
AA images of each other. They
are optical isomers of each other.

BC
DD
CB

Each of the two forms is asymmetric - no plane of symmetry.

An organic molecule is always chiral if it has a carbon atom that is
bonded to four different groups.
 Organic Molecules React in
Predictable Ways

Functional Groups – atoms or groups of atoms

that determine the reactive, structural, or other
functional characteristics of a molecule.

Understanding Functional Groups is

the secret to learning organic chemistry!
As the periodic table is to inorganic chemistry, functional groups are
to organic chemistry.

Four Important Functional Groups

Alcohol group (Hydroxyl group) Ether group

.. ..
C
..O H
C
..O C

Carboxylic acid group Ester group

.. ..
O O
..
..
..

..
..

..
C
..O H C
..O C
 Alcohols
CH3OH Methyl alcohol (Methanol)

C2H5OH Ethyl alcohol (Ethanol) CH3CH2OH

C3H7OH Propyl alcohol (Propanol)

H3C CH2 CH2 OH H3C CH OH

n-Propyl alcohol
CH3
H3C CH2 CH2 CH2 OH 2-Propyl alcohol
n-Butyl alcohol

Ethers
Dimethyl ether H3C–O–CH3

Ethyl methyl ether H3C–O–CH2–CH3

Diethyl ether H3C–CH2–O–CH2–CH3

CH CH

CH C O C CH
Diphenyl ether

CH CH CH CH

CH CH
 Ketones
O
Dimethyl ketone
H3C C CH3
(Acetone)

O
Ethyl methyl ketone
H3C CH2 C CH3

Diethyl ketone
O

H3C CH2 C CH2 CH3

Aldehydes
O
Formaldehyde
(Methanal) H C H

O Acetaldehyde
(Ethanal)
H3C C H
O
CH
CH C C H
Benzaldehyde
CH CH
CH
 Carboxylic Acids
O
Formic acid
H C O H
O Acetic acid

H3C C O H
Propionic acid O
H3C CH2 C O H
O
Butanoic acid
H3C CH2 CH2 C O H

Esters: the Flavoring in Fruits

Benzyl acetate C9H10O2 –oil of jasmine O
CH3-C-O-CH2-
Isoamyl acetate C7H14O2–ripe apples
O CH3
CH3-C-O-CH2-CH2-CH-CH3
Ethyl 2-methylbutanoate C7H14O2–ripe apples
CH3 O
CH3-CH2-CH-C-O-CH2-CH3
Isoamyl acetate C7H14O2–bananas
O CH3
CH3-C-O-CH2-CH2-CH-CH3
Ethyl butyrate C6H12O2–pineapple O
CH3-CH2-CH2-C-O-CH2-CH3
Ethyl formate C3H6O2–rum O
H-C-O-CH2-CH3
 Esters–II
Amyl butyrate C9H18O2–apricot O
CH3-CH2-CH2-C-O-CH2-CH2-CH2-CH2-CH3

Ethyl formate C3H6O2–lemonade O

H-C-CH2-CH3
n-Octyl acetate C10H20O2–oranges
O
CH3-C-O-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3
Methyl salicylate C8H8O3–oil of wintergreen
O
C-O-CH3

OH

Amines
 Amines–I ..
N
NH3 Ammonia H H
H
CH3NH2 Methyl amine ..
N
(CH3)2NH Dimethyl amine H CH3
H
(CH3)3N Trimethyl amine
.. ..
N N
CH3 CH3 H CH3
CH3 CH3

Structure
of a
Cationic
Detergent
 Some Molecules with the Amide
Functional Group

Important Functional Groups in Organic Compounds

(see Table 22.4)
Functional Group Compound Type Suffix or Prefix of Example Systematic Name
name (Common Name)
H H
C C alkene -ene C C ethene
H H (ethelene)

C C
alkyne -yne H C C H ethyne
H (acetylene)
.. ..
alcohol -ol methanol
C ..O H H C
..O H
H H (methyl alcohol)
H
C O C ether ether H C O C H dimethyl ether
H
.. H H
C ..X haloalkane halo- chloromethane
..

H C Cl
H H (methyl chloride)
.. amine -amine
H .. ethylamine
C N H C C N H

H H H
 Important Functional Groups in Organic Compounds (cont)

Functional Group Compound Type Suffix or Prefix of Example Systematic Name

.. Name (Common Name)
..

..
..
O H O

C H aldehyde -al H C C H ethanal

..
..
H O H
(acetaldehyde)
..
..
O
H
C C C ketone -one H C C C H 2-propane
(acetone)
..
..

..
..
O H O
..O ..O
H H
C
.. H carboxylic acid -oic acid H C C
.. H ethanoic acid
(acedic acid)
..
..

O
H H O H
..

..
..
ester -oate ....O methyl ethanoate
..
C O C H C C C H
(methyl acetate
..
..

O
..

..
..
H H O H
C N
amide -amide
H C C
..N ethanamide
H (acetamide)
H
nitrile -nitrile H H ethanenitrile
..

C N
H C C N (acetonitrile,
H
.. methyl cyanide)