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Hydrocarbons:

Nomenclature and Reactions

IUPAC nomenclature

systematic nomenclature

I nternational
U nion of
P ure and
A pplied
C hemistry

colloquially:
eye-you-pac

the alkanes
Hydrocarbons
Paraffins
Alkanes: formula CnH2n+2

The alkanes: table 3-2


CH4

CH3 CH2 CH2 CH2 CH2 CH3


Methane

(CH4)

CH3 CH3
Ethane

(C2H6)

(C3H8)

(C4H10)

CH3 CH2 CH2 CH2 CH3


Pentane

Heptane

(C7H16)

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3

CH3 CH2 CH2 CH3


Butane

(C6H14)

CH3 CH2 CH2 CH2 CH2 CH2 CH3

CH3 CH2 CH3


Propane

Hexane

(C5H12)

Octane

(C8H18)

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3


Nonane

(C9H20)

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
Decane

(C10H22)

IUPAC nomenclature of alkanes


Single substituent group

1. Find the longest continuous chain of


carbon atoms and name it (use linear na
2. Number the chain starting from the end
nearest a branch.

3. Give the substituent a name based on th


number of carbon atoms it has. replace
-ane ending with -yl
4. Give the substituent a number
determined
on its location
5. Assemble
the on the chain.
name.

Finding the longest continuous


chain
of carbon atoms is not always
all possibilites
simple
must be examined
C-C

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

it wont always be
the horizontal one
as shown here

try these also ..

C-C

C-C

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

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

Sect. 3.3: Common alkyl groups


(C1 through C4): table 3-3
CH3

CH3 CH2 CH2 CH2


Methyl

CH3 CH CH2

Butyl

CH3
Isobutyl

CH3 CH2

(2-Methylpropyl)

Ethyl
CH3 CH2 CH2
Propyl
CH3 CH
CH3
Isopropyl
(1-Methylethyl)

CH3
CH3 CH2 CH
CH3

CH3 C
CH3

sec-Butyl

tert-Butyl

(1-Methylpropyl)

(1,1-Dimethylethyl)

Name this alkane


4

CH3 CH2 CH CH3


CH3
2-methylbutane

Find the longest continuous


carbon chain
1

CH3 CH2 CH CH3


CH2 CH3
4

3-methylpentane

You must choose the longest


continuous carbon chain
4

CH3 CH2 CH CH2 CH2 CH3


CH2 CH2 CH3
5

4-ethylheptane

Two different substituents


number chain from end closest to a group,
regardless of alphabetical order
locate where groups are on chain with
numbers
place groups in alphabetical order, with the
appropriate number
assemble the complete name, using hyphens
to separate numbers from text

Number from the end nearest


the first substituent

CH2 CH3
CH3 CH2 CH2 CH CH CH2 CH3
7

CH3

4-ethyl-3-methylheptane

Number from the end nearest


the first substituent

CH3
CH3 CH2 CH2 CH CH2 CH CH2 CH3
8

3-ethyl-5-methyloctane

CH2 CH3

Two or more identical


substituent groups
for two identical groups, use prefix di with the
name of the group: dimethyl, diethyl, etc.
dimethyl alphabetized as methyl, not dimethyl
use numbers to locate groups on chain
use commas to separate numbers
prefixes: di = 2 tri = 3 tetra = 4 penta = 5

Use di- with two substituents

CH3
1

CH3 CH CH CH3

CH3

2,3-dimethylbutane

Every substituent must get a


number

CH3
1

CH3 CH2 C
2

CH2 CH2 CH3

CH3

3,3-dimethylhexane

You need numbers, even though


it appears on the same carbon!

CH3
5

CH3

CH3 CH CH2 C
2

2,2,4-trimethylpentane

CH3

CH3

Number from the end nearest


first substituent
CH3
CH3 CH2 CH CH CH2 CH2 CH2 CH2 CH CH3
10

CH3

2,7,8-trimethyldecane

CH3

Number from the end which has


the first difference
CH3
CH3 CH2 CH CH CH2 CH2 CH2 CH CH2 CH3
1

CH3

10

3,4,8-trimethyldecane

CH3

Number from the end nearest


the first difference
Dimethyl alphabetized as methyl, not dimethyl

CH3
1

CH3 CH2 CH CH CH2 CH CH2 CH3


2

CH3

6-ethyl-3,4-dimethyloctane

CH2 CH3

If you can name this,


you can name almost anything!
CH3
1

CH3

CH3 CH CH2 CH CH2 C


2

CH3

7
8

CH
CH2
4-isopropyl-2,6,6-trimethylnonane
3 CH

CH3

CH2 CH3

The isopropyl group can be named


as a complex substituent

CH3
CH3 CH
2

1-methylethyl

Now, rename the isopropyl group.


Notice the alphabetical order!
CH3
1

CH3

CH3 CH CH2 CH CH2 C


2

CH3

7
8

CH
CH2
2,6,6-trimethyl-4-(1-methylethyl)nonane
3 CH

CH3

CH2 CH3

Deciding on alphabetical order


for complex groups
Complex groups are alphabetized
under the first letter of the name

(1,3-dimethylbutyl) = d
(1,1,2-trimethylpropyl) = t
(1-ethyl-1,2-dimethylbutyl) = e

Naming complex substituents -this one is aphabetized under d

C H3
CH3 C H
4

C H3
C H2 C H

1,3-dimethylbutyl

Naming complex substituents


CH3 CH2 CH3
CH3 C

CH CH2 CH3
2

2-ethyl-1,1-dimethylbutyl

Name this compound!


CH3
CH3 CH2 C
CH3 CH2 CH2 CH2
1

C
5

CH2 CH3
2

CH2 CH2 CH2 CH3


6

CH2 CH2 CH3

5-(1-ethyl-1-methylpropyl)-5-propylnonane

Name this two ways -- (the complex


group)
CH3

CH3 C
CH3

CH2

CH3

CH
CH2

CH2

CH2

CH2

CH3
CH2

CH2

CH3

CH3

7-(1,1-dimethylethyl)-3-ethyl-7-methyldecane
7-tert-butyl-3-ethyl-7-methyldecane

Sect. 3.5: Common names of


alkanes

butane
isobutane
pentane
isopentane
neopentane

Sect. 3.6: the cycloalkanes


The names of the cycloalkanes always
contain the prefix cyclo
Cycloalkanes have the general formula
CnH2n

H
C

CH2 CH2
Cyclopropane

CH2 CH2

CH2 CH2

Cyclobutane

CH2

Cyclic molecules
H

C
HH

HH

H
C

C
C
H

CH2

CH2 CH2

CH2

Cyclopentane

CH2

H
H
H

H
H

CH2
CH2

CH2

CH2

CH2
CH2

Cyclohexane

Nomenclature of the substituted


cycloalkanes
If there is only one substituent, do not use the 1.
If there is more than one substituent, you must use all
numbers, including 1!
Number around the ring in a direction to get from the
first substituent to the second substituent by the shorter
path.
For equivalent degrees of substitution, number in a
direction that follows the alphabetical sequence.
A carbon with greater substitution has precedence in
numbering.

CH3
CH3

1,1-dimethylcyclohexane

CH3
CH3
CH3 CH2

4-ethyl-1,1-dimethylcyclohexane

Some
cycloalkanes
1,3-dimethylcyclopentane
CH3

2
3

CH3

CH3

CH3

Drawn
differently
but same
name.

1
2
3

CH3

CH3

4
3

2
1

CH2CH3
1-ethyl-4-methylcyclohexane
E before M

CH3CH2

CH3

3-ethyl-1,1-dimethylcyclobutane
The more substituted carbon
takes precedence even
though E comes before M.

Two ways of naming this


CH3

CH
CH3
1-isopropyl-2-methylcyclohexane
1-methyl-2-(1-methylethyl)cyclohexane

CH3

Numbering starts at the most


highly-substituted carbon
Cl

CH3
CH3
2

1
7

4
5

CH3

2-chloro-1,1,6-trimethylcycloheptane

Sect. 3.7: cycloalkyl groups

cyclopropyl

cyclopentyl

cyclobutyl

cyclohexyl

CH3 CH2 C

CH2 CH3

CH3

3-cyclobutyl-3-methylpentane

Rings with one substitutent


H3C

CH

CH2CH3

(1-methylpropyl)cyclohexane or
2-cyclohexylbutane

No locant is needed.
With one substituent on a ring , it is automatically on carbon 1.
1-(1-methylpropyl)cyclohexane is overkill, but OK!

Another name of a group

or

or C6H5
Phenyl

CH3
CH3 CH2 CH

CH

CH3

3-methyl-2-phenylpentane

Sect. 3.8: Degree of Substitution


methyl

CH3 R
primary (1)

methylene

R CH2 R
secondary (2)

methine R

CH R

R
tertiary (3)

quaternary (4)

Example

A hydrocarbon containing carbon atoms w


differing degrees of substitution
PRIMARY
QUATERNARY

CH3

TERTIARY

CH3
C

CH CH2 CH3

CH3 CH3

SECONDARY

All of the methyl groups (CH3) are primary.

Sect. 3.9 -- review


We already did this in Chapter 1

Sect. 3.10 and 3.11:


nomenclature of halides and
nitro compounds
F

Cl
fluoro

NO2
nitro

Br
chloro

I
bromo

iodo

CH 3 CH 2 Br
bromoethane (IUPAC)
ethyl bromide (common)

Br

bromocyclopropane

CH3
C H3 C

Cl

CH 3

2-chloro-2-methylpropane (IUPAC)
tert-butyl chloride (common)

CH 3 CH
Br

CH

CH 2 CH 3

CH 3

2-bromo-3-methylpentane

iodocyclohexane (IUPAC)
cyclohexyl iodide (common)

Br

Cl

1-bromo-2-chlorocyclohexane

CH3 CH

CH3

NO2
2-nitropropane

Sect. 3.12: Block diagram for


nomenclature

LOCANT

PREFIX

STEM

SUFFIX

numbers

substituents

number

-ALK(AN)-

ending

Sect. 3.13: alkene


nomenclature
ending is ene
identify the longest chain with the C=C
number from the end closest to the C=C
and assign a number - - i.e. 2-pentene
C=C is more important than groups!
now number the attached groups and place
them in alphabetical order

CH2 CH2

CH3 CH CH2

ethene (IUPAC)
propene (IUPAC)
ethylene (common) propylene (common)
CH3 CH2 CH CH2

1-butene

CH3 CH CH CH3

2-butene

CH3
C

CH

CH3

CH3
2-methyl-2-butene

CH3
CH3 CH

CH 2 CH2 CH

CH

6-methyl-2-heptene

CH 3

CH 3
CH 3 CH 2 CH

CH 2 CH2
C

CH 3 CH 2 CH2

H
C
CH3

trans-6-methyl-3-propyl-2-octene
(Dont worry about trans until Chapter 4)

CH3 CH3

4,4-dimethylcyclohexene

CH3

2-methyl-1,3-cyclohexadiene

CH2 CH3

CH2
CH3

2,5-diethyl-1,3-cyclooctadiene

Very important!

benzene
It is never cyclohexatriene!!!

Sect. 3.14: nomenclature of


alkynes
similar system used as with alkenes
ending is yne
identify the longest chain with the triple
bond
everything else is the same as alkenes

ethyne
acetylene

CH3 CH 2 C

1-butyne

CH3 C

propyne

CH

CH3 C

2-butyne

CH 3

ALKYNES

( -YNE )

The functional group has precedence in numbering.

CH3

C C CH2CH2CH3
2-hexyne

CH3

functional
group

C C CH CH3
CH3
4-methyl-2-pentyne

The suffix has


precedence
over any
substituents

4-chloro-4-methyl-2-pentyne

CH3
CH3 C

CH3

Cl
CH3
CH3 CH

Br
C

CH

5-bromo-2-methyl-3-heptyne

CH2 CH3

ene vs. yne: which one wins?


Number from the end closest to either the double
bond
or the triple bond, whichever is closest to the end.
Compounds are named: en-yne.
8

CH3-CH2-C

C-CH2-CH=CH-CH3
2-octen-5-yne

optional, but recommended ..


COMPUTER PROGRAM

ORGANIC NOMENCLATURE
Available in Chemistry
Computer Lab - CB280
Go to ChemApps Folder :
Chem Apps

then choose first

and then
Organic

Organic
Nomenclature

Sect. 3.15: physical


properties of hydrocarbons
the longer the straight chain, the higher
the boiling point -- van der Waals forces
isomers that are branched have lower
boiling points
hydrogen bonding increases boiling
points
Dipole-dipole attractions increase b.p.

Sect. 3.16: Combustion of


alkanes
CnH2n+2 + m O2

n CO2 + (2n+2)/2 H2O


+ HEAT!!!

where n = number of carbons


Example:
2 C6H14 + 19 O2

12 CO2 + 14 H2O

Sect. 3.17: Halogenation of Alkanes


chlorination

Cl

Cl

light

free-radical
substitution
reaction

Cl

Cl

examples
CH4 + Cl2
CH3CH2CH3 + Cl2
takes place at a refinery
or a chemical plant - not
easy to do in the lab

CH3Cl + HCl
CH3CHCH3 + HCl
Cl
+ CH3CH2CH2-Cl

The previous examples given


assumed
(one chlorine added)
monochlorination
BUT the reaction can repeat itself

COMMON NAMES

CH4

+ Cl2

CH3Cl

+ HCl

methyl chloride

CH3Cl + Cl2

CH2Cl2 + HCl

methylene chloride

CH2Cl2 + Cl2

CHCl3

+ HCl

chloroform

CHCl3 + Cl2

CCl4

+ HCl

carbon tetrachloride

fully chlorinated product

What are the


IUPAC names ?

The reaction must be initiated


It does not occur in the dark.
Exposure to ultraviolet light (sunlight) will start
the reaction.
Heat will also start the reaction.
Once reaction starts, it is exothermic and continues
almost explosively.
The first step is the dissociation of
chlorine :
h
or

.. ..
:Cl
:
Cl
.. ..

diatomic molecule

..
:
2 . Cl
..

chlorine
atoms
(radicals)

Abstraction of hydrogen atom


BY A CHLORINE FREE RADICAL (ATOM)
unpaired electron
= free radical

C ..H

C.

..
. Cl :
..
..
:
H-Cl
..

HYDROGEN ABSTRACTION

Chlorine takes the


hydrogen and one
of its electrons

Mechanism of chlorination of methane


CHAIN REACTION

1. Initiation
..
: Cl
..

..
Cl :
..

light

..
: Cl .
..

a free radical

dissociation
R
E
P
E
A
T
I
N
G
S
T
E
P
S

2. Chain Propagation (first step)


CH3

..
: Cl .
..

..
Cl :
..

. CH3
methyl radical

hydrogen abstraction
3. Chain Propagation (second step)

. CH3

..
: Cl
..

..
Cl :
..

CH3

..
Cl :
..

..
: Cl .
..

feeds back into


step two

4. Termination Steps

..
2 : Cl .
..
CH3.
..
: Cl .
..

. CH
3

. CH
3

recombinations

..
: Cl
..

..
Cl :
..

CH3CH3
..
: Cl CH3
..
These steps stop
the chain reaction

Monochlorination of propane:
Does one isomer predominate?
CH3CH2CH3 + Cl2
limited
amount

CH3CHCH+
CH3CH2CH2-Cl
3
Cl
A

QUESTION
WHAT ARE THE RELATIVE AMOUNTS OF A AND B ?
IS IT STATISTICAL ( 2 : 6 ) = (1 : 3 ) ?
DOES SOMETHING ELSE CONTROL THE OUTCOME ?

Monochlorination of propane
STATISTICAL VERSUS EXPERIMENTAL RESULTS

CH3CHCH3
Cl

CH3CH2CH2-Cl

A
STATISTICAL PREDICTION

25 %

75 %

CH3-CH2-CH3 = 6 : 2 or 3:1
ACTUALLY FOUND

50 %
Equal
amounts

50 %
Equal
amounts

Experimental results
show:
Secondary hydrogens are energenically more
easily removed than primary hydrogens

CH3CHCH3
H

CH3CH2CH3
Primary H

Secondary H

more reactive hydrogen

H
H3C

Stability of free
radicals explains
results!
CH3

H3C

CH2

H
C

secondary radical

primary radical

More stable and


easier to form!

Less stable and harder


to form

Stability of radicals: TERTIARY > SECONDARY >


PRIMARY

CH3
H3C

H
CH3

H3C

H
CH3

H3C

CH2

tertiary radical

secondary radical

primary radical

Most stable and


easiest to form!

less stable than


tertiary but more
stable than primary

Least stable and


hardest to form