Chapter 2: Alkanes and Cycloalkanes

2004-5-29

2.1 Hydrocarbons Hydrocarbons are compounds that only contain H and C atoms, but they can be subdivided according to the following tree diagram depending on the bond types that are present
Hydrocarbons

Alkanes

Alkenes

Alkynes

Arenes

2004-5-29

Generic formula CnH2n+2 CnH2n CnH2n-2

2.2 Structure of alkanes

Generic formula of CnH2n+2

C H H
2004-5-29 3

2.3 Nomenclature and Conformational Analysis of alkane Structure: Alkanes are the simplest organic compounds, comprised of only sp3 hybridized C and H atoms connected by s bonds

2004-5-29

 Isomeric Alkanes (Constitutional isomer) Generic formula of CnH2n+2 When N>3, constitution isomer isomers can have different chemical, physical properties and biological properties.

2004-5-29

International Union of Pure and Applied Chemistry Systematic name Common name

2004-5-29

 Nomenclature: Functional group suffix = -ane Functional group prefix = alkyl

2004-5-29

Rules Summary: First find the longest continuous carbon chain, the parent chain, and name it Determine the names of any side chains. If there are side chains, number the carbon chain using a numbering system that will result in the smallest numbers for the side chains If there are multiple side chains of the same length, use the appropriate prefix: di, tri, tetra, etc. Lastly, if there are multiple side chains to list, list them in alphabetical order. When listing in alphabetical order, ignore any prefixes you may have added. For example, "dipropyl" would be listed after "ethyl".
2004-5-29 8

2004-5-29

Punctuation Rules In general: Letters that are placed before the words (i.e. "n") are generally italicized. There are no spaces between most words. Hyphens "-" are put between numbers and words. Commas "," are put between numbers.

2004-5-29

10

 Special Branches
Some side chains have special names: n-, iso, sec-, tert- (common)

2004-5-29

11

1 1
O

CH3 CH3
3
O

CH3

CH C CH2 CH3
1
O

O 4 2

CH3

primary secondary

tertiary

2004-5-29

12

2004-5-29

13

5 7 8 6 4

3 2

1 2 1 3

4 5

2,2,6,6,7-Pentamethyloctane

2,3,3,7,7-Pentamethyloctane Incorrect! 2=2 2<3

Locants are not added together, but examined one by one!

2004-5-29

14

1 1 3 5 2 4

2 8 6 7 9

5-(2-methylpropyl)nonane

2004-5-29

15

Conformational analysis Conformations: The different spatial arrangements that a molecule can adopt due to rotation about sigma bonds are called conformations and hence Rotamers or conformers. conformational analysis: The study of the energy changes that occur during these rotations is called conformational analysis Concept: Staggered conformation: GAUCHE, ANTI Eclipsed conformation: SYN The simplest Example: Ethane
2004-5-29 16

 Different diagram for conformation analysis: Wedge-dash Wedgediagrams (perspective formulas); Sawhorse projection; projection Newman Projections

2004-5-29

17

2004-5-29

18

Diagram: The conformation analysis of ethane

2004-5-29 19

What about butane

2004-5-29

20

10

2004-5-29

21

Diagram: The conformation analysis of butane

2004-5-29

22

11

2.4 Nomenclature and Conformational Analysis of cycloalkane Simple cycloalkanes

2004-5-29

23

CH3 CH3

CH3CH2

CH3

CH3

1,3-Dimethylcyclohexane 4-Ethyl-1-methylcyclohexane

3-Methylcyclohexene

1,3-

1-4-

3-

2004-5-29

24

12

Nomenclature Polycyclic rings: spiro and bicyclo

2004-5-29

25

Ring strain of cycloalkanes

BaeyerA.

2004-5-29

26

13

2004-5-29

27

Type of Strain The reason: Electron pairs repel each other / as far apart from each : other as possible 1) Angle strain 2) Steric strain

3) Torsional strain (dihedral angle ) 4) Ring strain a cyclic structure related non-cyclic

2004-5-29

28

14

 The energy change in the ring-flip of cyclohexane (chairchair)

2004-5-29

29

Conformation analysis of cyclohexane

Lets see the ring-flip of cyclohexane (chair - chair) Pay attention to axial(vertical), equatorial-bond(parallel)!

2004-5-29

30

15

2004-5-29

31

Mono-substituted

Equatorial Substituent
2004-5-29 32

16

 Why methyl- group on a-bond position is less stable?

Di-substituted (relative position: 1,2-; 1,3-; 1,4) 1,3-disubstituted

2004-5-29

33

Equilibrium Constants

2004-5-29

34

17

 Pay attention to cis- and trans- concept (describing the relatively position of the substituted groups) You must remember :the plane relates ring projection
2004-5-29 35

Lets see trans-1,4-dimethylcyclohexane

What about stable conformation?

Less stable

2004-5-29

36

18

 Quiz: why trans-decalin()is more stable than cisdecalin?

Reason: 1) e,e-bond position 2) Less steric strain

2004-5-29

37

2.4 Physical Properties and Intermolecular Forces

Intermolecular Forces Van der Waals Forces :The forces that exist between neutral molecules are known as the van der Waals forces

2004-5-29

38

19

 In order of increasing strength these are: (ref. CD) induced dipole - induced dipole (London or dispersion forces) dipole - induced dipole dipole dipole(which includes hydrogen bonds) Dipole-Dipole Interactions

2004-5-29

39

Hydrogen Bonding

Intermolecular Forces influence the properties (physical, chemical and biological) of molecules such as melting point, boiling point, solubility and reactivity
2004-5-29 40

20

 Melting Points of Alkanes

Hydrocarbon Physical Properties: low melting and boiling points and very low solubility in polar solvents such as water (hydrophobic)
2004-5-29 41

2.5 Free Radical Reactions

Reaction: bond cleavage and forming, the reaction mechanisms is very important for us to predicted the products Reactive intermediate: short-lived species that reacts quickly as it is formed , include: free radical, cation (carbocation), anion Radical: species with an unpaired electron (usually just draw the unpaired electron) Here we first discuss free radical reaction:

2004-5-29

42

21

Reactive intermediate : The structure of alkyl radical, cation, anion Radical : sp2 hybridization, a electron in p-orbit, electron deficient

2004-5-29

43

Cation (carbocation sp2 hybridization carbocation)

2004-5-29

44

22

 Anion sp3 hybridization

2004-5-29

45

Background of knowledge
Reaction Mechanisms Reaction mechanism: describes how a reaction occurs, it includes which bonds are broken and which new ones are formed the order in which bond-breaking and bond-forming steps take place the role of the catalyst (if any is present) the energy of the entire system during the reaction First: How to describe the energy change in a reaction? Potential energy (PE) diagram: a graph showing the changes in energy that occur during a chemical reaction Reaction coordinate: a measure of the change in position of atoms during a reaction
2004-5-29 46

23

1.

Potential energy (PE) diagram (or Reaction coordinate digram)

Transition state: an energy maximum on a PE diagram represents an unstable species of maximum PE formed during the course of a reaction

2004-5-29

47

2004-5-29

48

24

Potential energy diagram for two-step reaction Reaction intermediate an unstable species that lies in a potential energy minimum between two transition states Rate-limiting stepthe step in a reaction sequence that crosses the highest potential energy barrier; the slow step in a multistep reaction

2004-5-29

49

3.

Activation Energy, Ea: The difference in potential energy between reactants and the transition state (Relate to Kinetics, describes Rate) determines the rate of reaction if Ea is large, only a few molecular collisions occur with sufficient energy to reach the transition state, and the reaction is slow if Ea is small, many collisions generate sufficient energy to reach the transition state, and the reaction is fast

2004-5-29

50

25

4.

Thermodynamic Control and Kinetic Control

If more than one product is formed in a reaction, what determines the ratio of products? It depends on the reaction!

2004-5-29

51

Radical Monochlorination of Methane

To answer these questions, we need to: 1. Understand the mechanism of the reaction (arrowpushing!). 2. Use thermodynamics and kinetics to analyze the reaction. 52 2004-5-29

26

A. Mechanism for the monochlorination of Methane Free-radical chain reactions have three distinct mechanistic steps: Initiation step, Propagation steps, and Termination step I. Initiation Step: generates reactive intermediate Cl2 absorbs energy and the bond is homolytically cleaved
(Remember to use fishhook arrows!)

2004-5-29

53

II.

Propagation Steps: The Meat of the Reaction

Reactive intermediates react with stable molecules to generate other reactive intermediates (allows chain to continue)

Reaction a) Chlorine radical abstracts a hydrogen from methane to form a methyl radical. b) Methyl radical abstracts a chlorine from Cl2 to form product and another chlorine radical
2004-5-29 54

27

III. Termination Steps: Unproductive Steps Consumption of reactive intermediates (radicals) without generation of new ones

Termination steps slow down and eventually stop the chain reaction

Termination reactions become most important at the end of a reaction, when there are very few reactant molecules left

2004-5-29

55

B.

Thermodynamics and Kinetics to Analyze Thermodynamics: energy changes that accompany chemical and physical transformations Thermodynamics are used to describe systems that are in their Equilibrium State

2004-5-29

56

28

Kinetics: Reaction Rates Reaction rate: how fast products appear and reactants disappear (measured experimentally) rate equation: relationship between concentration of reactants and observed reaction rate (determined experimentally and used to deduce reaction mechanisms)

2004-5-29

57

C.

Reaction-Energy Diagram for Radical Chorination of Methane

Bond dissociation energies:

2004-5-29

58

29

The Radical Product Formation for Butane (Mono-Substituted!)

1) Alkyl Radical Formation Rates

2004-5-29

59

2) Alkyl Radical Stabilities (lack of electron)

2004-5-29

60

30

3) Calculating the amounts of products

CH3CH2CH2CH3

2004-5-29

61

Quiz: what about the monochlorination of 2,2,5-Trimethylhexane? Pay attention: How many kinds of hydrogen in the molecule? Answer

2004-5-29

62

31

In conclusion: It is important that the initiation step involves cleavage of a fairly weak bond like ClCl. Other than that, the initiation step is not important in the overall thermodynamics and kinetics of the reaction. This is because one initiation step starts a chain that can go through thousands of propagation cycles. The termination steps are also unimportant in the overall energetic picture of the reaction, so let's focus on the propagation steps.

2004-5-29

63

Bromine Radical Formation (mono-substituted)

2004-5-29

64

32

 Rate-limiting step

2004-5-29

65

The difference between chlorination and bromination in potential energy diagram

2004-5-29

66

33

2004-5-29

67

The stabilities of some free radicals

Why? Electron Effect (inductive effect, resonance effect) Radical Stabilization

2004-5-29

68

34

2004-5-29

69

2004-5-29

70

35

2004-5-29

71

Hyperconjugation

2004-5-29

72

36

2004-5-29

73

2004-5-29

74

37

 Two important Substituted Product Benzylic substituted product and allylic substituted product

2004-5-29

75

Other important reagents for radical halogenations reaction: NBS and NCS Always used for the sythesis of benzylic substituted product and allylic substituted product

2004-5-29

76

38

2004-5-29

77

General Selectivity of Radical Halogenations Radical brominations are highly selective when one type of hydrogen is particularly reactive (resonance-stabilized).

2004-5-29

78

39

2.6 Anti-oxidation Reagents

In general, free raicals are unstable and active.

2004-5-29

79

Some nature products act as radical capture

2004-5-29

80

40

Summary Isomer (constitutional isomer) Nomenclature and Conformational Analysis (IUPAC nomenclature, diagrams--include Newman projection, Wedge-dash, Sawhorse diagrams; Alkanes and Cyclohexanes conformation, Ring strain) Physical Properties Free Radical Reactions (Reactive intermediate/ Transition state Reaction Mechanisms)
2004-5-29 81

41