Chapter 3 Hydrocarbons: Nomenclature and Reactions

Chapter 3 Problems
Review Section 3.9 Read Essays on petroleum (p 204-207) and gasoline (p 221-223) for interest. I recommend that you do all problems except Prob. 8, 14, 33, 34 and 41 Skip ethenyl, 2-propenyl etc on p. 200 Read Section 3.15 and 3-16, but dont take them too seriously.

Sect. 3.1: IUPAC nomenclature

systematic nomenclature

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

colloquially: eye-you-pac

Sect. 3.2: the alkanes

Hydrocarbons Paraffins Alkanes: formula CnH2n+2

The alkanes: table 3-2

CH4 Methane CH3 CH3 Ethane CH3 CH2 CH3 Propane (C3H8) (C2H6) (CH4) CH3 CH2 CH2 CH2 CH2 CH3 Hexane (C6H14) CH3 CH2 CH2 CH2 CH2 CH2 CH3 Heptane (C7H16)

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3 Octane (C8H18)

CH3 CH2 CH2 CH3 Butane (C4H10)

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 Nonane (C9H20)

CH3 CH2 CH2 CH2 CH3 Pentane (C5H12)

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 Decane (C10H22)

Sect. 3.4: IUPAC nomenclature of alkanes

Single substituent group 1. Find the longest continuous chain of carbon atoms and name it (use linear names). 2. Number the chain starting from the end nearest a branch. 3. Give the substituent a name based on the number of carbon atoms it has. replace the -ane ending with -yl 4. Give the substituent a number determined on its location on the chain. 5. Assemble the name.

Finding the longest continuous chain of carbon atoms is not always simple
C-C C-C-C-C-C-C-C-C-C C
all possibilites must be examined 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 Methyl CH3 CH2 Ethyl CH3 CH2 CH2 Propyl CH3 CH CH3 Isopropyl (1-Methylethyl) CH3 CH2 CH2 CH2 Butyl CH3 CH CH2 CH3 Isobutyl (2-Methylpropyl) CH3 CH3 CH2 CH CH3 sec-Butyl (1-Methylpropyl) CH3 C CH3 tert-Butyl (1,1-Dimethylethyl)

Name this alkane

CH3 CH2 CH CH3 CH3
2-methylbutane 4 3 2 1

Find the longest continuous carbon chain

1 2 3

CH3 CH2 CH CH3 CH2 CH3

4 5 3-methylpentane

You must choose the longest continuous carbon chain

4 3 2 1

CH3 CH2 CH CH2 CH2 CH3 CH2 CH2 CH3

5 6 7 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 6 5 4 3 2 1

CH3
4-ethyl-3-methylheptane

Number from the end nearest the first substituent

CH3 CH3 CH2 CH2 CH CH2 CH CH2 CH3

8 7 6 5 4 3 2 1

CH2 CH3
3-ethyl-5-methyloctane

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 CH3 CH CH CH3

1 2 3 4

CH3
2,3-dimethylbutane

Every substituent must get a number

CH3 CH3 CH2 C

1 2 3

CH2 CH2 CH3

4 5 6

CH3
3,3-dimethylhexane

You need numbers, even though it appears on the same carbon!

CH3
5 4 3

CH3
2

CH3 CH CH2 C CH3

CH3
1

2,2,4-trimethylpentane

Number from the end nearest first substituent

CH3 CH3 CH2 CH CH CH2 CH2 CH2 CH2 CH CH3
10 9 8 7 6 5 4 3 2 1

CH3

CH3

2,7,8-trimethyldecane

Number from the end which has the first difference

CH3 CH3 CH2 CH CH CH2 CH2 CH2 CH CH2 CH3
1 2 3 4 5 6 7 8 9 10

CH3

CH3

3,4,8-trimethyldecane

Number from the end nearest the first difference

Dimethyl alphabetized as methyl, not dimethyl

CH3 CH3 CH2 CH CH CH2 CH CH2 CH3

1 2 3 4 5 6 7 8

CH3

CH2 CH3

6-ethyl-3,4-dimethyloctane

If you can name this, you can name almost anything!

CH3
1 2 3 4 5

CH3
6

CH3 CH CH2 CH CH2 C CH3 CH CH3

7 8

CH3

CH2 CH2 CH3

9

4-isopropyl-2,6,6-trimethylnonane

The isopropyl group can be named as a complex substituent

CH3 CH3 CH
2 1

1-methylethyl

Now, rename the isopropyl group. Notice the alphabetical order!

CH3
1 2 3 4 5

CH3
6

CH3 CH CH2 CH CH2 C CH3 CH CH3

7 8

CH3

CH2 CH2 CH3

9

2,6,6-trimethyl-4-(1-methylethyl)nonane

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 C H3 C H
4 3 2

CH3 C H2 C H
1

1,3-dimethylbutyl

Naming complex substituents

CH3 CH2 CH3 CH3 C
1

CH CH2 CH3
2 3 4

2-ethyl-1,1-dimethylbutyl

Name this compound!

CH3 CH3 CH2 C CH3 CH2 CH2 CH2
1 2 3 4 5 1

CH2 CH3
2 3

CH2 CH2 CH2 CH3

6 7 8 9

CH2 CH2 CH3

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

Name this two ways -- (the complex group)

CH3 CH3 C CH3 CH2 CH CH2 CH2 CH2 CH2 C CH3 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

Cyclic molecules
H C H C H H H H C C H H C C H H H CH2 CH2 CH2 CH2 Cyclobutane H H H C C C H H H H C H H CH2 H CH2 CH2 Cyclopropane H C H H C H H C C C H H H H H CH2 CH2 CH2 CH2 CH2 Cyclopentane

H C

H C C

H CH2 H H 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 CH3
4 3 2 1 1 2 3

CH3
1

CH3

=
CH3

2 3

Drawn differently but same name.

CH3
1

CH3

CH2CH3
1-ethyl-4-methylcyclohexane E before M

CH3CH2

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

Two ways of naming this

CH3 CH3

CH CH3

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

Numbering starts at the most highly-substituted carbon

Cl
2 3 4 6 5 1 7

CH3 CH3

CH3

2-chloro-1,1,6-trimethylcycloheptane

Sect. 3.7: cycloalkyl groups

cyclopropyl

cyclobutyl

cyclopentyl

cyclohexyl

CH3 CH2 C CH3

CH2 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 methylene

CH3 R primary (1)

R CH2 R secondary (2)

methine

R CH R R

R C R R

tertiary (3)

quaternary (4)

Example
A hydrocarbon containing carbon atoms with differing degrees of substitution
PRIMARY QUATERNARY

CH3 C CH3 CH3

TERTIARY

CH3

CH CH2 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 fluoro Cl chloro Br bromo I iodo

NO2 nitro

CH 3 CH 2 Br

bromoethane (IUPAC) ethyl bromide (common)

Br

bromocyclopropane

CH3 CH3 C CH3 Cl

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

CH 3 CH Br

CH CH 3

CH 2 CH 3

2-bromo-3-methylpentane

iodocyclohexane (IUPAC) cyclohexyl iodide (common)

Br

Cl

1-bromo-2-chlorocyclohexane

CH3 CH NO2

CH3

2-nitropropane

Sect. 3.12: Block diagram for nomenclature

LOCANT numbers

PREFIX

N number

STEM

SUFFIX ending

substituents

-ALK(AN)-

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 CH3 CH CH CH3

1-butene

2-butene

CH3 C CH3
2-methyl-2-butene

CH

CH3

CH 3 C H 3 CH CH 2 CH 2 CH CH CH 3

6-methyl-2-heptene

CH 3 CH 3 CH 2 CH CH 2 CH2 C CH 3 CH 2 CH2 C CH3 H

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

CH3 C

ethyne acetylene

propyne

CH3 CH 2 C

CH

CH3 C

CH 3

1-butyne

2-butyne

ALKYNES
CH3

( -YNE )

The functional group has precedence in numbering.

C C CH2CH2CH3
2-hexyne
functional group

CH3

C C CH CH3 CH3
4-methyl-2-pentyne
The suffix has precedence over any substituents

CH3 CH3 C Cl C

4-chloro-4-methyl-2-pentyne
C CH3

CH3 CH3 CH C C

Br CH CH2 CH3

5-bromo-2-methyl-3-heptyne

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 7 6 5 4 3 2 1

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

Organic

and then

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
light
free-radical substitution reaction

+ Cl

Cl

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 monochlorination (one chlorine added)

BUT the reaction can repeat itself
COMMON NAMES

CH4

+ Cl2

CH3Cl + HCl CH2Cl2 + HCl CHCl3 CCl4 + HCl + HCl

methyl chloride

CH3Cl + Cl2 CH2Cl2 + Cl2 CHCl3 + Cl2

methylene chloride

chloroform

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 .. ..

.. : 2 . Cl ..

chlorine atoms (radicals)

diatomic molecule

Abstraction of hydrogen atom

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

C..H

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

HYDROGEN ABSTRACTION

Chlorine takes the hydrogen and one of its electrons

C.

Mechanism of chlorination of methane

1. Initiation .. : Cl ..
R E P E A T I N G S T E P S

CHAIN REACTION
.. Cl : .. light .. : Cl . .. a free radical

dissociation
2. Chain Propagation (first step) CH3 H + .. : Cl . .. H .. Cl : .. +

. CH3
methyl radical

hydrogen abstraction
3. Chain Propagation (second step) .. Cl : ..

. CH3

.. : Cl ..

.. Cl : ..

CH3

.. : Cl . ..

feeds back into step two

4. Termination Steps

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

recombinations

.. : Cl ..

.. Cl : ..

. CH 3

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

. CH 3

Monochlorination of propane: Does one isomer predominate?

CH3CH2CH3 + Cl2
limited amount

CH3CHCH3 + CH3CH2CH2-Cl Cl
A B

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
A STATISTICAL PREDICTION CH3-CH2-CH3 = 6 : 2 or 3:1 ACTUALLY FOUND 50 % 25 %

CH3CH2CH2-Cl
B 75 %

50 % Equal amounts

Equal amounts

Experimental results show:

Secondary hydrogens are energenically more easily removed than primary hydrogens

CH3CHCH3 H
Secondary H

CH3CH2CH3
Primary H

more reactive hydrogen

Stability of free radicals explains results!

H H3C C CH3 H3C CH2 H C H

secondary radical More stable and easier to form!

primary radical Less stable and harder to form

Stability of radicals: TERTIARY > SECONDARY > PRIMARY

CH3 H3C C CH3 H3C

H C CH3 H3C CH2

H C H

tertiary radical Most stable and easiest to form!

secondary radical less stable than tertiary but more stable than primary

primary radical Least stable and hardest to form

Another example: isobutane Which product should form in the largest amount?
CH3 H3C C H CH2 H

There are 9 primary Hs and only 1 tertiary H Statistically you could predict a 9:1 ratio or a 90% yield of 1-chloro-2-methylpropane! Wrong!!

Cl2
CH3 H3C C H CH2 Cl

Isobutane gives only 62% of 2-chloro-2-methylpropane! Why? Look at the stability of the intermediate radical.

CH3 H3C C CH3

H-Cl

Cl
CH3 H3C C H CH2 H

tertiary radical - more stable

CH3

H C H

Cl

H3C

C H

H-Cl

primary radical - less stable

The statistical factor predicts a 9:1 ratio (90%) However, the energy factor predicts that the ratio will be less than 90% and turns out to be 62%.
CH3 H3C C CH3 CH3

Cl2

H3C

C Cl

CH3

Cl

tertiary radical

38%

CH3 H3C C H C

CH3

H C H Cl H Cl

Cl2
H

H3C

C H

primary radical

62%

Draw the structure of all of the monochlorinated products. There are 6 total products. The next slide shows the remaining 5 products. Only ONE product is shown here!

2 l C

Cl
t a e h r o t h g i l

s a e m a s

! ! ! lt ! y n he t l e a mv i du eq l e c r e i c r a os wp tu eo hr Tg

Cl

e n a x e h l y h t e m 2 o r o l h c 1

Here are 5 more isomeric products that are formed!

2 l C

2-chloro-5-methylhexane

1-chloro-5-methylhexane

t a e h r o t h g i l

Cl

2-chloro-2-methylhexane

Cl

3-chloro-2-methylhexane
Cl

Cl

Cl

4-chloro-2-methylhexane

Ethylcyclopentane: monochlorination products

CH2 CH3
MONOCHLORINATION PRODUCTS

CH2 CH2 Cl

CH2 CH3

CH CH3 Cl

Cl CH2 CH3

CH2 CH3 Cl

Cl

Hydrochlorofluorocarbons (HCFCs)
F H C F Cl Depletes the ozone in the upper atmosphere

Sect. 3.18: hydrogenation of alkenes

C C + H H catalyst C H C H

catalyst = Pt, Pd, Ni

Hydrogenation is covered in more detail in Chap 4 well cover it there. Hydrogenation is included in this chapter (briefly) because it is a method of making ALKANES.

H2

Pd

H3 C H

CH3

Pt H2 CH3CH2CH2CH3

+
H