Post on 28-Dec-2015
1
Chapter 12 Unsaturated Hydrocarbons
12.1
Alkenes and Alkynes
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
2
Unsaturated hydrocarbons Have fewer hydrogen
atoms attached to the carbon chain than alkanes.
Are alkenes with double bonds.
Are alkynes with triple bonds.
Unsaturated Hydrocarbons
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
Alkanes Alkanes Alkenes Alkenes AlkynesAlkynes
CCnnHH2n+22n+2 CCnnHH2n2n CCnnHH2n+22n+2
General Formulasfor open chain coumpds
3
Bond Angles in Alkenes and AlkynesAccording to VSEPR theory: Three groups in a double
bond are bonded at 120° angles.
Alkenes are flat, because the atoms in a double bond lie in the same plane.
The groups attached to a triple bond are at 180° angles. Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
4
Naming Alkenes
The names of alkenes Use the corresponding alkane name. Change the ending to ene.
Alkene IUPACCommon
H2C=CH2 ethene ethylene
H2C=CH─CH3 propene propylene
cyclohexene
5
Ethene (ethylene)
Ethene or ethylene Is an alkene C2H4.
Has two carbon atoms connected by a double bond.
Has two H atoms bonded to each C atom.
Is flat with all the C and H atoms in the same plane.
Is used to accelerate the ripening of fruits.
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
6
Naming Alkynes
The names of alkynes Use the corresponding alkane name. Change the ending to yne.
Alkyne IUPACCommon
HC≡CH ethyne acetylene
HC≡C─CH3 propyne
7
Guide to Naming Alkenes and Alkynes
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
8
Naming Alkenes
Write the IUPAC name for CH2=CH─CH2─CH3 and
CH3─CH=CH─CH3
STEP 1 Name the longest carbon chain
butene
STEP 2 Number the chain from the double bond
CH2=CH─CH2─CH3 1-butene
1 2 3 4
CH3─CH=CH─CH3 2-butene
9
Comparing Names of Alkanes, Alkenes, and Alkynes
TABLE 12.1
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
10
Naming Alkenes with Substituents
CH3
│
Write the IUPAC name for CH3─CH─CH=CH─CH3
STEP 1 Name the longest carbon chain pentene
STEP 2 Number the chain from the double bond
CH3
│
CH3─CH─CH=CH─CH3 2-pentene 5 4 3 2 1
STEP 3 Give the location of each substituent 4-methyl- 2-pentene
11
Naming Alkynes with Substituents
CH3
│
Write the IUPAC name for HC≡C─CH─CH3
1 2 3 4
STEP 1 Name the longest carbon chain butyne
STEP 2 Number the chain from the double bond
1-butyne
STEP 3 Give the location of each substituent
3-methyl-1-butyne
12
Learning Check
Write the IUPAC name for each of the following:
1. CH2=CH─CH2─CH3
2. CH3─CH=CH─CH3
CH3
|3. CH3─CH=C─CH3
4. CH3─CC─CH3
13
Solution
Write the IUPAC name for each of the following:
1. CH2=CH─CH2─CH3 1-butene
2. CH3─CH=CH─CH3 2-butene
CH3
|3. CH3─CH=C─CH3 2-methyl-2-butene
4. CH3─CC─CH3 2-butyne
14
Learning Check
Write the structural formula for each of the following:
A. 2-pentyne
B. 3-methyl-2-pentene
15
Solution
Write the structural formula for each of the following:
A. CH3─CH2─C≡C─CH3 2-pentyne
CH3
B. CH3─CH2─C=CH─CH3 3-methyl-2-pentene
16
Chapter 12 Unsaturated Hydrocarbons
12.2
Cis-Trans Isomers
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
17
Cis and Trans Isomers
In an alkene, cis and trans isomers are possible
because the double bond Is rigid.
Cannot rotate.
Has groups attached to the carbons of the double bond that are fixed relative to each other.
CH3 CH3 CH3
CH = CH CH = CH
cis trans CH3
18
Cis–trans isomerism occurs because the electronic structure of the carbon–carbon double bond makes rotation energetically unfavorable.
Why are Double Bonds Rigid
19
Cis-trans isomers
Can be modeled by making a “double bond” with your fingers with both thumbs on the same side or opposite from each other.
Cis-Trans Isomers
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
20
Cis-trans isomers occur when
different groups are attached to
the double bond.
In a cis isomer, groups are attached on the same side of the double bond.
In the trans isomer, the groups are attached on opposite sides.
Cis-Trans Isomers
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
21
Cis-Trans Isomerism
Cis-trans isomers do not occur if a carbon atom in the double bond is attached to identical groups.
Identical Identical
2-bromopropene 1,1-dibromoethene (not cis or trans) (not cis or trans)
C C
H Br
H CH3
C C
H Br
BrH
H
H
H Br
22
Naming Cis-Trans Isomers
The prefixes cis or trans are placed in front of the alkene name when there are cis-trans isomers.
cis trans
cis-1,2-dibromoethene trans-1,2-dibromoethene
C C
Br H
BrH
C C
Br Br
H H
23
Pheromones
A pheromone
Is a chemical messenger emitted by insects in tiny quantities.
Called bombykol emitted by the silkworm moth to attract other moths has one cis and one trans double bond.
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
24
Learning Check
Name each, using cis-trans prefixes when needed.
C C
CH3 H
CH3H
C C
Br Br
H H
A.
B.
C C
CH3 Cl
ClH
C.
25
Solution
cis-1,2-dibromoethene
trans-2-butene
1,1-dichloropropene
C C
CH3 H
CH3H
C C
Br Br
H H
A.
B.
C C
CH3 Cl
ClH
C.
Identical atoms on one C; no cis or trans
26
Chapter 12 Unsaturated Hydrocarbons
12.3
Addition Reactions
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
27
Addition Reactions
In addition reactions, Reactants add to the
carbon atoms in double or triple bonds.
A double or triple bond is easily broken, which makes them very reactive.
TABLE 12.2
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
28
In hydrogenation,
Hydrogen atoms add to the carbon atoms of a double bond or triple bond.
A catalyst such as Pt or Ni is used to speed up the reaction.
Hydrogenation
HC CH + 2H2Ni
HC CH
H H
H H
H2C CH2
H HPt
H2H2C CH2 +
29
Adding H2 to double
bonds in vegetableoils produces Compounds with
higher melting points. Solids at room
temperature such as margarine,
soft margarine,
and shortening.
Hydrogenation of Oils
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
30
Learning Check
Write an equation for the hydrogenation of 1-butene using a platinum catalyst.
31
Solution
Write an equation for the hydrogenation of 1-butene
using a platinum catalyst. Pt
CH2=CH─CH2─CH3 + H2 CH3─CH2─CH2─CH3
32
Trans Fats
In vegetable oils, the unsaturated fats usually contain
cis double bonds.
During hydrogenation, some cis double bonds are converted to trans double bonds (more stable) causing a change in the fatty acid structure
If a label states “partially” or “fully hydrogenated”, the fats contain trans fatty acids.
33
Learning Check
(T) True or (F) False
A. ____ There are more unsaturated fats in vegetable oils.
B. ____ Hydrogenation converts some cis-double bonds to
trans- double bonds.
C. ____ Animal fats have more unsaturated fats.
34
Solution
(1) True or (2) False
A. T There are more unsaturated fats in vegetable oils.
B. T Hydrogenation of oils converts some cis-double
bonds to trans- double bonds.
C. F Animal fats have more unsaturated fats.
35
Learning Check
Write the product of each the following reactions:
Pt
CH3─CH=CH─CH3 + H2
Pt
+ H2
36
Solution
Pt
CH3─CH=CH─CH3 + H2 CH3─CH2─CH2─CH3
+ H2 Pt
37
Halogenation
In halogenation, halogen atoms add to the carbon atoms of a double bond or triple bond.
+ CH3CHC 2Cl2CH3
ClCl
ClCl
CHC
BrBr
CH2H2C Br2CH2 +H2C
38
Write the product of the following addition reactions: 1. CH3─CH=CH─CH3 + Cl2
2. + Br2
Learning Check
39
Solution
Write the product of the following addition reactions:
Pt1. CH3─CH=CH─CH3 + Cl2
Cl Cl l l
CH3─CH─CH─CH3
2.
Br
Br + Br2
40
Testing for Unsaturation
When bromine (Br2) is added to an alkane, the red color of bromine persists.
When bromine (Br2) is added to an alkene or alkyne, the red color of bromine disappears immediately.
Br2
Br2
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
15
41
Hydrohalogenation
In hydrohalogenation, the atoms of a hydrogen halide add to the carbon atoms of a double bond or triple bond.
ClH
CH3 CHCHCH3+ HClCH3CHCHCH3
Br
H + HBr
42
Markovnikov’s Rule
When an unsymmetrical alkene undergoes hydrohalogenation, the H in HX adds to the carbon in the double bond that has the greater number of H atoms .
HCl
CH2CHCH3
CH2CHCH3 + HCl
ClH
CH2CHCH3 Does not form
C with the most H
Product that forms
43
Hydration
In the addition reaction called hydration An acid H+ catalyst is required. Water (HOH) adds to a double bond. An H atom bonds to one C in the double bond. An OH bonds to the other C.
H OH
H+ │ │CH3─CH=CH─CH3 + H─OH CH3─CH─CH─CH3
44
Hydration (Follow Markovnikov’s Rule)
When hydration occurs with a double bond that has an
unequal number of H atoms, The H atom bonds to the C in the double bond with
the most H. The OH bonds to the C in the double bond with the
fewest H atoms.
OH H H+ │ │CH3─CH=CH2 + H─OH CH3─CH─CH2
(1H) (2H)
45
Learning Check
Write the product for the hydration of each of the
following:
H+
1. CH3─CH2─CH=CH─CH2─CH3 + HOH
CH3
│ H+
2. CH3─C=CH─CH2─CH3 + HOH
H+
3. + HOH
46
Solution
H OH │ │1. CH3─CH2─CH─CH─CH2─CH3
CH3
│ 2. CH3─C─CH─CH2─CH3
│ │ OH H
OH3. H
47
Learning Check
Write the products of each reaction.
C.
B.
A.
HOH +CH3CHCHCH3
Pt
+ Cl2 CH2CHCH3
+ H2
H+
48
Solution
OHH
CH3CHCHCH3
C.
B.
A.
HOH +CH3CHCHCH3
H+
Pt
ClCl
CH2CHCH3+ Cl2 CH2CHCH3
H
H + H2
49
Chapter 12 Unsaturated Hydrocarbons
12.4
Polymers of Alkenes
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
50
Polymers
Polymers are Large, long-chain molecules. Found in nature, including cellulose in plants,
starches in food, proteins and DNA in the body. Also synthetic such as polyethylene and
polystyrene, Teflon, and nylon. Made up of small repeating units called
monomers. Made by reaction of small alkenes.
51
Polymerization
In polymerization, small repeating units called monomers join to form a long chain polymer.
monomer unit repeats
n
52
Common Synthetic Polymers
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
53
Polymers from Addition Reactions
TABLE 12.3
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
54
More Monomers and Polymers
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
55
Learning Check
What is the starting monomer for polyethylene?
56
Solution
Ethene (ethylene)
CH2=CH2
57
Learning Check
Name the monomer used to make Teflon and write a
portion of a Teflon polymer using four monomers.
58
Solution
F F │ │
F─C=C─F tetrafluoroethene
F F F F F F F F │ │ │ │ │ │ │ │
─C─C─C─C─C─C─C─C─ portion of Teflon │ │ │ │ │ │ │ │
F F F F F F F F
59
Recycling Plastics
Recycling is simplified by using codes found
on plastic items.
1 PETE Polyethyleneterephtalate
2 HDPE High-density polyethylene
3 PV Polyvinyl chloride
4 LDPE Low-density polyethylene
5 PP Polypropylene
6 PS Polystyrene Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
60
Learning Check
What types of plastic are indicated by the following
codes?
A.
B.
C.
3PV
5PP
6PS
61
Solution
What types of plastic are indicated by the followingcodes?
A. Polyvinyl chloride
B. Polypropylene
C. Polystyrene
.
3PV
5PP
6PS
62
Chapter 12 Unsaturated Hydrocarbons
12.5
Aromatic Compounds
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
63
Benzene Has 6 electrons shared equally among the 6 C atoms.
Is also represented as a hexagon with a circle drawn inside.
Benzene Structure
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
64
Benzene’s relative lack of reactivity is a result of its electronic
structure which contains six sp2-hybridized orbitals.
Benzene has two resonance forms.
The actual electronic structure, The actual electronic structure, resonance hybridresonance hybrid, is an average of , is an average of the different possibilities. the different possibilities.
BenzeneBenzene
65
Aromatic Compounds in Nature and Health
Vanillin Aspirin
Ibuprofen Acetaminophen
COH
O
O
C O CH3
CH
O
OCH3
OH
CH
CH3
COH
O
CH2
CH3
CHH3COH
NH
O
C CH3
66
Naming Aromatic Compounds
Aromatic compounds are named
With benzene as the parent chain.
With one side group named in front of benzene.
methylbenzene chlorobenzene
ClCH3
67
The naming of substituted benzenes, in which one
hydrogen is replaced, is as follows:
CH2 Cl NO2
ethylbenzene chlorobenzene nitrobenzene
F
fluorobenzene
CH3
Br
bromobenzene
Naming Aromatic CompoundsNaming Aromatic Compounds
68
Some Common Names
Some substituted benzene rings
Have common names used for many years.
With a single substituent use a common name or are named as a benzene derivative.
toluene aniline phenol
(methylbenzene) (benzenamine) (hydroxybenzene)
NH2 OHCH3
69
Aromatic Compounds with Two Groups
Two naming systems are used when two groups are
attached to a benzene ring.
Number the ring to give the lowest numbers to the side groups.
Use prefixes to show the arrangement:
ortho(o-) for 1,2-
meta(m-) for 1,3-
para(p-) for 1,4-
70
A common designation of
the position of the
second substituent is the
use of the prefixes, ortho,
meta, and para.
DOrtho Ortho
MetaMeta
Para
2
1
3
4
5
6
Naming Aromatic CompoundsNaming Aromatic Compounds
71
Aromatic Compounds with Two Groups
3-chlorotoluene 1,4-dichlorobenzene 2-chlorophenol
m-chlorotoluene p-dichlorobenzene o-chlorophenol
OHCH3
Cl
Cl
Cl
Cl
72
Learning Check
Select the correct name for each compound:1) chlorocyclohexane2) chlorobenzene3) 1-chlorobenzene
1) 1,2-dimethylbenzene2) m-xylene3) 1,3-dimethylbenzene
CH3
CH3
Cl
73
Solution
2) chlorobenzene
2) m-xylene3) 1,3-dimethylbenzene
CH3
CH3
Cl
74
Learning Check
Write the structural formulas for each of the following:
A. 1,3-dichlorobenzene
B. o-chlorotoluene
75
Solution
A. 1,3-dichlorobenzene
B. o-chlorotoluene
Cl
Cl
CH3
Cl
76
Learning Check
Identify the organic family for each:
A. CH3─CH2─CH=CH2
B.
C. CH3─C≡CH
D.
77
Solution
Identify the organic family for each:
A. CH3─CH2─CH=CH2 alkene
B. cycloalkane (alkane)
C. CH3─C≡CH alkyne
D. aromatic
78
didiphenylphenylmethanemethane 4-4-phenylphenyl-2-pentene-2-pentene
Naming Aromatic CompoundsNaming Aromatic Compounds
CC66HH55—— is the phenyl group. is the phenyl group.
• It is used to name compounds that cannot It is used to name compounds that cannot be easily named as be easily named as benzene derivativesbenzene derivatives..
79
Chapter 12 Unsaturated Hydrocarbons
12.6 Properties of Aromatic
Compounds
Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
80
Properties of Aromatic Compounds
Aromatic compounds Have a stable aromatic bonding system. Are resistant to many reactions (no additions).
Because aromatic compounds are not normal alkenes. The p-electrons delocalize in the conjugated system to make the aromatic structures more stable than the alkene system.
Undergo substitution reactions, which retain the stability of the aromatic bonding system.
81
Substitution Reactions
In a substitution reaction, a hydrogen atom on a benzene ring is replaced by an atom or group of atoms.
Type of substitution H on benzene replaced
by
Halogenation chlorine or bromine
atom
Nitration nitro group (—NO2)
Sulfonation —SO3H group
82
Halogenation
In a halogenation An H atom of benzene is replaced by a chlorine or
bromine atom. A catalyst such as FeCl3 is needed in chlorination.
A catalyst such as FeBr3 is needed in bromination.
ChlorobenzeneBenzene
FeCl3 HCl+
Cl
Cl2+
H
83
Nitration
In the nitration of benzene An H atom of benzene is replaced by a nitro (-NO2)
group from HNO3.
An acid catalyst such as H2SO4 is needed.
NitrobenzeneBenzene
H2SO4 HOH+
NO2
HNO3+
H
84
Sulfonation
In a sulfonation An H atom on benzene is replaced by a —SO3H
group from SO3.
An acid catalyst such as H2SO4 is needed.
Benzenesulfonic acidBenzene
H2SO4
SO3H
SO3+
H
85
Learning Check
Write the equation for the bromination of benzene including catalyst.
86
Solution
Write the equation for the bromination of benzene including catalyst.
HBr+
FeBr3
Br
Br2+
H