Alkenes and Electrophilic Addition

28
28.1 28.2 28.3 28.4 28.5

1
Alkenes and Electrophilic Addition

Introduction Nomenclature of Alkenes Physical Properties of Alkenes Preparation of Alkenes Reactions of Alkenes
A-Level 3A A-Level Book 3A
28. 1 Introduction
28.1 Introduction (SB p.167)
Alkenes
Unsaturated hydrocarbons containing the C=C double bond General formula of alkenes: CnH2n The carbon atoms involved in the C=C double bond are sp2-hybridized
Alkenes
The C=C double bond is made up of a bond and a bond Trigonal planar geometry Bond angle = 120o
The C=C double bond in ethene

4 A-Level 3A A-Level Book 3A
Alkenes
bond can be broken down easily alkenes are reactive compounds undergo mainly addition reactions
Alkenes
Limited rotation of the C=C double bond alkenes show geometrical isomerism e.g.
28. 2Nomenclatur e of Alkenes

28.2 Nomenclature of Alkenes (SB p.167)
IUPAC Rules of Naming of Alkenes

1. Select the longest possible straight chain that contains the C=C double bond determine the stem name use the ending of -ene

2. Number the parent chain so as to include both carbon atoms of the double bond Begin numbering with the end of the chain nearer the C=C double bond

3. Designate the position of the C=C double bond by using the number of the first atom of the double bond 4. Designate the position of the substituents by using the numbers obtained
10

e.g .
11

5. If two identical groups are present on the same side of the C=C double bond the compound is designated as cis If they are on opposite sides the compound is designated as trans
12

e.g .
Example 28-2
Check Point 28-2
28. 3 Physical Properties of Alkenes

28.3 Physical Properties of Alkenes (SB p.169)
Physical Properties of Alkenes
Some physical properties of several alkenes Name Condensed Boiling Melting Density at structural point (oC) point (oC) 20oC formula (g cm-3) CH2=CH2 CH3CH=CH2 -104 -47.7 -6.3 30 -169 -185 -185 -165 -140 0.514 0.595 0.641 0.673
Ethene Propene
But-1-ene CH3CH2CH=C H2 Pent-1-ene CH3CH2CH2C H=CH2
15 A-Level 3A Hex-1-ene CH3CH2CH2C 62.9 A-Level Book 3A
Some physical properties of several alkenes Name Condensed Boiling Melting Density at structural point (oC) point (oC) 20oC formula (g cm-3) CH3CH=CHC H3 (cis) 4 1 31 -139 -106 -138 0.621 0.604 0.650
cis-But-2ene
trans-But-2- CH3CH=CHC ene H3 (trans) 2CH3CH2C(CH3 Methylbut- )=CH2 1-ene

16

Alkenes are non-polar Dissolve in non-polar solvents or in solvents of low polarity Only very slightly soluble in water
17

M.p. and b.p of alkenes are lower than their corresponding alkanes Densities of alkenes are less than that of water
18
28. 4 Preparation of Alkenes
19
28.4 Preparation of Alkenes (SB p.170)
Cracking
Prepared by the cracking of alkanes of high molecular masses Give alkenes of low molecular masses
20
Cracking
e.g. 2CH3CH3 CH2 = CH2 + 2CH4 2CH3CH2CH3 CH3CH = CH2 + CH2 = CH2 + CH4 + H2
600 oC 600 oC
21
Elimination Reactions
Involve removal of atoms or groups of atoms from adjacent carbon atoms in the reactant molecule Formation of a double bond between carbon atoms
22
1. Dehyhalogenation 1. Dehyhalogenation Elimination of a hydrogen halide molecule from a haloalkane By heating the haloalkane in an alcoholic solution of KOH
23
1. Dehyhalogenation 1. Dehyhalogenation e.g.
24
1. Dehyhalogenation 1. Dehyhalogenation The ease of dehydrohalogenation of haloalkanes decreases in the order:
> Tertiary haloalkane

25
> Secondary haloalkane

Primary haloalkane
1. Dehyhalogenation 1. Dehyhalogenation Different classes of haloalkanes or alcohols have different reactivities May undergo different types of reactions under the same reaction conditions
26
1. Dehyhalogenation 1. Dehyhalogenation Dehydrohalogenation of secondary or tertiary haloalkanes can take place in more than one way A mixture of alkenes is formed
27
1. Dehyhalogenation 1. Dehyhalogenation e.g. CH3CH2CHClCH3

2-Chlorobutane alc. KOH heat But-1-ene (20 %)
CH3CH=CHCH3 + CH3CH2CH=CH2
But-2-ene (80 %)
The more highly substituted alkene (i.e. but-2-ene) is the major product
28
1. Dehyhalogenation 1. Dehyhalogenation The more highly substituted alkene is the alkene with a larger number of alkyl groups bonded to the C = C group The greater the number of alkyl groups that an alkene contains the more stable the molecule
29
1. Dehyhalogenation 1. Dehyhalogenation The relative stabilities of alkenes decrease in the order:
30
2. Dehydration of Alcohols 2. Dehydration of Alcohols Removal of a water molecule from a reactant molecule By heating the alcohols in the presence of concentrated sulphuric acid Give alkenes and water as the products
31
2. Dehydration of Alcohols 2. Dehydration of Alcohols Experimental conditions (i.e. temperature and concentration of concentrated sulphuric acid) closely related to the structure of the individual alcohol
32
2. Dehydration of Alcohols 2. Dehydration of Alcohols Primary alcohols generally required concentrated sulphuric acid and a relatively high temperature
33
2. Dehydration of Alcohols 2. Dehydration of Alcohols Secondary alcohols are intermediate in reactivity Tertiary alcohols dehydrate under mild conditions (moderate temperature and dilute sulphuric acid)
34
2. Dehydration of Alcohols 2. Dehydration of Alcohols The relative ease of dehydration of alcohols generally decreases in the order:
> Tertiary alcohol

35
> Secondary alcohol

Primary alcohol
2. Dehydration of Alcohols 2. Dehydration of Alcohols Secondary and tertiary alcohols dehydrate to give a mixture of alkenes The more highly substituted alkene is formed as the major product Example 28-4
36
Check Point 28-4

Addition Reactions
Hydrogenation Hydrogenation Alkenes can be prepared by hydrogenation of alkynes Depend on the conditions and the catalyst employed
37
Hydrogenation Hydrogenation
Lindlars catalyst is metallic palladium deposited on calcium carbonate further hydrogenation of the alkenes formed can be prevented
38
28. 5 Reactions of Alkenes
39
28.5 Reactions of Alkenes (SB p.174)
Why do Alkenes Undergo Addition Reactions Readily?

Presence of C=C double bond C=C double bond is made up of a bond and a bond
40

In addition reactions, one bond and one bond are broken two bonds are formed

41
Heat evolved during bond formation > Heat required during bond breaking Addition reactions are usually exothermic
42

The electrons of the bond are diffuse in shape less firmly held by the bonding carbon nuclei
Susceptible to the attack by electrophiles


Electrophiles that attack the C=C double bond protons (H+) neutral species in which the molecule is polarized, e.g. bromine
44
Electrophilic Addition Reactions

Addition of electrophiles to the C=C double bond of alkenes
45
1. Addition of Hydrogen Bromide 1. Addition of Hydrogen Bromide A molecule of HBr adds to the C=C double bond of an alkene Give a bromoalkane
46
1. Addition of Hydrogen Bromide 1. Addition of Hydrogen Bromide e.g. the addition of HBr to ethene produces bromoethane
47
1. Addition of Hydrogen Bromide 1. Addition of Hydrogen Bromide When but-2-ene reacts with HBr 2-bromobutane is formed as the only product
48
1. Addition of Hydrogen Bromide 1. Addition of Hydrogen Bromide When propene reacts with HBr the major product is 2-bromopropane the minor product is 1-bromopropane
49
Reaction Mechanism: Electrophilic Addition Reactions of Hydrogen Bromide to Alkenes Step 1: The alkene abstracts a proton from hydrogen bromide form a carbocation and a bromide ion
50
Reaction Mechanism: Electrophilic Addition Reactions of Hydrogen Bromide to Alkenes Step 2: The bromide ion reacts with the carbocation by donating an electron pair a bromoalkane is formed
51
Regioselectivity of Hydrogen Halide Addition: Markovnikovs Rule CH3CH=CHCH3 is a symmetrical alkene. CH3CH=CH2 is an asymmetrical alkene.
52
Regioselectivity of Hydrogen Halide Addition: Markovnikovs Rule A hydrogen halide can add to an asymmetrical alkene in either of the two ways The reaction proceeds to give a major product preferentially the reaction is said to exhibit regioselectivity
53
Regioselectivity of Hydrogen Halide Addition: Markovnikovs Rule
54
Regioselectivity of Hydrogen Halide Addition: Markovnikovs Rule Markovnikovs rule states that in the addition of HX to an asymmetrical alkene, the hydrogen atom adds to the carbon atom of the carbon-carbon double bond that already has the greater number of hydrogen atoms
55
Regioselectivity of Hydrogen Halide Addition: Markovnikovs Rule The products formed according to this rule are known as Markovnikov products
56
Stability of Carbocation and Mechanistic Explanation of the Markovnikovs Rule

Carbocations are a chemical species that contains a positively charged carbon Very unstable Exist transiently during the reaction Classified as primary, secondary or tertiary according to the number of carbon chains that are directly attached to the positively charged carbon
57
Stability of Carbocation and Mechanistic Explanation of the Markovnikovs Rule Carbocations are a reactive intermediate formed during the reaction react to give the product, or convert back to the reactant The more stable the carbocation the faster its formation
Stability of Carbocation and Mechanistic Explanation of the Markovnikovs Rule The stability of the carbocations increases in the order:
59
Stability of Carbocation and Mechanistic Explanation of the Markovnikovs Rule Alkyl groups stabilize the positively charged carbocation by positive inductive effect A greater number of alkyl groups release more electrons to the positively charged carbon increase the stability of the carbocation
Check Point 28-5A
61
Stability of Carbocation and Mechanistic Explanation of the Markovnikovs Rule Consider the addition of HBr to propene:
62
Stability of Carbocation and Mechanistic Explanation of the Markovnikovs Rule The hydrobromination of propene involves two competing reactions:
63
2. Addition of Halogens 2. Addition of Halogens Halogens normally react with alkenes by electrophilic addition
where X2 can be F2, Cl2 or Br2

2. Addition of Halogens 2. Addition of Halogens Alkenes react rapidly with Cl2 (or Br2) in 1,1,1-trichloroethane at room temp and in the absence of light Form dichloroalkanes (or dibromoalkanes)
65
2. Addition of Halogens 2. Addition of Halogens
66
2. Addition of Halogens 2. Addition of Halogens e.g.
67
2. Addition of Halogens 2. Addition of Halogens The decolourization of bromine in 1,1,1trichloroethane is a useful test for unsaturation
The reddish brown colour of bromine is decolourized
A drop of bromine dissolved in 1,1,1trichloroethane is added to an alkene
68
3. Addition of Bromine Water (HOBr) 3. Addition of Bromine Water (HOBr) In an aqueous solution of bromine, the following equilibrium is established: Br2 + H2O HBr + HOBr
Bromic(I) acid
69
3. Addition of Bromine Water (HOBr) 3. Addition of Bromine Water (HOBr) Bromic(I) acid reacts readily with an alkene at room conditions to form a bromohydrin
70
3. Addition of Bromine Water (HOBr) 3. Addition of Bromine Water (HOBr) e.g.
The consequent decolourization of the reddish brown colour of bromine water is also a test for unsaturation
4. Acid-catalyzed Hydration 4. Acid-catalyzed Hydration Alkenes dissolve in cold and concentrated sulphuric acid
72
4. Acid-catalyzed Hydration 4. Acid-catalyzed Hydration e.g.
73
4. Acid-catalyzed Hydration 4. Acid-catalyzed Hydration The presence of the large bulky group ( OSO3H) of the alkyl hydrogensulphate makes it very unstable Two possible further reactions may take place
74
1. Regeneration of Alkenes On heating, alkyl hydrogensulphates form alkenes and sulphuric acid
75
2. Production of Alcohols Alkyl hydrogensulphates can be easily hydrolyzed to alcohols by heating with water
76
Catalytic Hydrogenation
Alkenes react with hydrogen in the presence of metal catalysts (e.g. Ni, Pd, Pt) to give alkanes
77
e.g.
78
Useful in analyzing unsaturated hydrocarbons
79
Fats and oils are organic compounds called triglycerides esters formed from glycerol and carboxylic acids of long carbon chains Fats and oils are either saturated or unsaturated
80
Saturated fats solids at room temp usually come from animal sources
81
Unsaturated fats liquids at room temp primarily derived from plants
82
Fats and oils are similar in structure Only difference is the presence of C=C double bonds in the acid components of oils lower their m.p. make them liquids at room temp
83
Fats are stable towards oxidation by air More convenient to handle and store
84
Can be employed to convert the C=C double bonds present in oils to saturated fats (i.e. margarine) The conversion is also known as hardening of oils Advantage: turning rancid much less readily than unsaturated oils
85
Check Point 28-5B
Hydrogenation of vegetable oils produces margarine

Relative Stability of Alkenes in Terms of Enthalpy Changes of Hydrogenation

Hydrogenation of alkenes is exothermic From enthalpy changes of hydrogenation predict the relative stabilities of alkenes
87
Enthalpy changes of hydrogenation of but-1-ene, cis-but-2-ene and trans-but-2-ene
88
Relative Stability of Alkenes in Terms of Enthalpy Changes of Hydrogenation

The pattern of the relative stabilities of alkenes determined from the enthalpy changes of hydrogenation:
89
Check Point 28-5C
90
The END
91
Give the IUPAC names for the following alkenes: (a)
Answer
(a) trans-3,4-Dichlorohept-3-ene
92
Back Give the IUPAC names for the following alkenes: (b)
Answer
(b) cis-3,4-Dimethyloct-3-ene
93
Back Draw the structural formula for each of the following alkenes: (a) cis-Hex-3-ene (b) trans-2,3-Dihydroxybut-2-ene (c) cis-1,2-Dichloroethene
(a) (c)
Answer
(b)
94
Classify the following alcohols as primary, secondary or tertiary alcohols. (a) CH3CHOHCH2CH3 (b) CH3CH2CH2OH (c) (CH3)2COHCH2CH2CH3
(a) It is a secondary alcohol. (b) It is a primary alcohol. (c) It is a tertiary alcohol.
Answer
Back
95
Back
Classify the following haloalkanes as primary, secondary or tertiary haloalkanes. (a) (c)
(b)
(a) A secondary haloalkane (b) A primary haloalkane (c) A tertiary haloalkane
Answer
Of the isomeric C5H11+ carbocations, which one is the most stable?

The more stable C5H11+ carbocation is the tertiary carbocation as shown below:
Answer
Back
97
Back
Both alkanes and alkenes undergo halogenation. The halogenation of alkanes is a free radical substitution reaction while the reaction of alkenes with halogens is an electrophilic addition reaction. Can you tell two differences between the products formed by the two different types of halogenation?
Alkenes give dihalogenated products while alkanes usually give polysubstituted products. Another difference is the position of the attachment of the halogen atom. For alkenes, the halogen atom is fixed to the carbon atom of the carbon=carbon double bond. In the substitution reaction of alkanes, the position of of the halogen atom 98 A-Level 3A varies. A-Level Book 3A
Answer
(a) What chemical tests would you use to distinguish between two unlabelled bottles containing hexane and hex-1-ene respectively? Answer
(a) We can perform either one of the following tests: Hex-1-ene can decolourize bromine water or chlorine water in the dark while hexane cannot. Hex-1-ene can decolourize acidified potassium manganate(VII) solution while hexane cannot.
99
(b) What is the major product of each of the following reactions? (i)
(ii)
Answer
(b)
(i)
(ii)
101
(c) Give the products for the following Ni reactions: conc. H2 (i) CH3CH = CH2 + H2 SO4 (ii) CH3CH = CHCH3 (iii) CH3CH = CHCH3 + Br2
Answer
102
Back
(c) (i) (ii) CH3CH2CH3
(iii)
103
(a) Arrange the following carbocations in increasing order of stability. Explain your answer briefly.
Answer
(a)
The increasing order of the stability of carbocations is:
Tertiary carbocations are the most stable because the three alkyl groups release electrons to the positive carbon atom and thereby disperse its charge. Primary carbocations are the least stable as there is only one alkyl group releasing electrons to the positive carbon atom.
(b) Based on your answer in (a), arrange the following molecules in the order of increasing rates of reaction with hydrogen chloride.
Answer
106
Back
(b)
The reaction of these compounds with hydrogen chloride involves the formation of carbocations. Therefore, the order of reaction rates follows the order of the ease of the formation of carbocations, i.e. the stability of carbocations:
Therefore, the rates of reactions of the three compounds with hydrogen chloride increase in the order:
107

Alkenes and Electrophilic Addition

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Alkenes and Electrophilic Addition

Uploaded by

Copyright:

Available Formats

28

28.1 28.2 28.3 28.4 28.5

Alkenes and Electrophilic Addition

A-Level 3A A-Level Book 3A

A-Level 3A A-Level Book 3A

28.1 Introduction (SB p.167)

A-Level 3A A-Level Book 3A

28.1 Introduction (SB p.167)

The C=C double bond in ethene

28.1 Introduction (SB p.167)

A-Level 3A A-Level Book 3A

28.1 Introduction (SB p.167)

A-Level 3A A-Level Book 3A

28. 2Nomenclatur e of Alkenes

28.2 Nomenclature of Alkenes (SB p.167)

IUPAC Rules of Naming of Alkenes

A-Level 3A A-Level Book 3A

28.2 Nomenclature of Alkenes (SB p.167)

IUPAC Rules of Naming of Alkenes

A-Level 3A A-Level Book 3A

28.2 Nomenclature of Alkenes (SB p.168)

IUPAC Rules of Naming of Alkenes

A-Level 3A A-Level Book 3A

28.2 Nomenclature of Alkenes (SB p.168)

IUPAC Rules of Naming of Alkenes

A-Level 3A A-Level Book 3A

28.2 Nomenclature of Alkenes (SB p.168)

IUPAC Rules of Naming of Alkenes

A-Level 3A A-Level Book 3A

28.2 Nomenclature of Alkenes (SB p.168)

IUPAC Rules of Naming of Alkenes

Check Point 28-2

28. 3 Physical Properties of Alkenes

28.3 Physical Properties of Alkenes (SB p.169)

Physical Properties of Alkenes

But-1-ene CH3CH2CH=C H2 Pent-1-ene CH3CH2CH2C H=CH2

15 A-Level 3A Hex-1-ene CH3CH2CH2C 62.9 A-Level Book 3A

28.3 Physical Properties of Alkenes (SB p.169)

Physical Properties of Alkenes

trans-But-2- CH3CH=CHC ene H3 (trans) 2CH3CH2C(CH3 Methylbut- )=CH2 1-ene

A-Level 3A A-Level Book 3A

28.3 Physical Properties of Alkenes (SB p.169)

Physical Properties of Alkenes

A-Level 3A A-Level Book 3A

28.3 Physical Properties of Alkenes (SB p.169)

Physical Properties of Alkenes

A-Level 3A A-Level Book 3A

28. 4 Preparation of Alkenes

A-Level 3A A-Level Book 3A

28.4 Preparation of Alkenes (SB p.170)

A-Level 3A A-Level Book 3A

28.4 Preparation of Alkenes (SB p.170)

A-Level 3A A-Level Book 3A

28.4 Preparation of Alkenes (SB p.170)

A-Level 3A A-Level Book 3A

28.4 Preparation of Alkenes (SB p.170)

A-Level 3A A-Level Book 3A

28.4 Preparation of Alkenes (SB p.170)

1. Dehyhalogenation 1. Dehyhalogenation e.g.

A-Level 3A A-Level Book 3A

28.4 Preparation of Alkenes (SB p.171)

1. Dehyhalogenation 1. Dehyhalogenation The ease of dehydrohalogenation of haloalkanes decreases in the order:

> Tertiary haloalkane