1. CHE 311 Organic Chemistry I
Dr. Jerome K. Williams, Ph.D.
Saint Leo University

2. Chapter 4. The Study of Chemical Reactions
Halogenation: A First Mechanism
Free Radical Stabilities
Reaction Profile Diagrams
Hammond Postulate
Reactive Intermediates

3. Chlorination of Methane
Requires heat or light for initiation.
The most effective wavelength is blue, which is absorbed by chlorine gas.
Many molecules of product are formed from absorption of only one photon of light (chain reaction).
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Chapter 4

4. The Free-Radical Chain Reaction
Initiation: Generates a radical intermediate.
Propagation: The intermediate reacts with a stable molecule to produce another reactive intermediate (and a product molecule).
Termination: Side reactions that destroy the reactive intermediate.
Chapter 4

5. Initiation Step: Formation of Chlorine Atom
A chlorine molecule splits homolytically into chlorine atoms (free radicals).
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Chapter 4

6. Lewis Structures of Free Radicals
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Free radicals are reactive species with odd numbers of electrons.
Halogens have seven valence electrons, so one of them will be unpaired (radical). We refer to the halides as atoms, not radicals.
Chapter 4

7. Propagation Step: Carbon Radical
The chlorine atom collides with a methane molecule and abstracts (removes) an H, forming another free radical and one of the products (HCl).
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Chapter 4

8. Propagation Step: Product Formation
The methyl free radical collides with another chlorine molecule, producing the organic product (methyl chloride) and regenerating the chlorine radical.
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9. Overall Reaction
Chapter 4

10. Termination Steps
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A reaction is classified as a termination step when any two free radicals join together, producing a nonradical compound.
Combination of a free radical with a contaminant or collision with wall are also termination steps.
Chapter 4

11. More Termination Steps
Chapter 4

12. Hint Initiation steps generally create new free radicals.
Propagation steps usually combine a free radical and a reactant to give a product and another free radical.
Termination steps generally decrease the number of free radicals.
Chapter 4

13. Primary, Secondary, and Tertiary Hydrogens
Chapter 4

14. Chlorination Mechanism
Chapter 4

15. Bond Dissociation Energies for the Formation of Free Radicals
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16. Stability of Free Radicals
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Highly substituted free radicals are more stable.
Chapter 4

17. Chlorination Energy Diagram
Lower Ea, faster rate, so more stable intermediate is formed faster.
Chapter 4

18. Solved Problem 3 Solution
Tertiary hydrogen atoms react with Cl• about 5.5 times as fast as primary ones. Predict the product ratios for chlorination of isobutane.
Solution
There are nine primary hydrogens and one tertiary hydrogen in isobutane.
Copyright © 2006 Pearson Prentice Hall, Inc.
(9 primary hydrogens) x (reactivity 1.0) = 9.0 relative amount of reaction
(1 tertiary hydrogen) x (reactivity 5.5) = 5.5 relative amount of reaction
Chapter 4

19. Solved Problem 3 (Continued)
Solution
Even though the primary hydrogens are less reactive, there are so many of them that the primary product is the major product. The product ratio will be 9.0:5.5, or about 1.6:1.
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Chapter 4

20. Rate of Substitution in the Bromination of Propane
Chapter 4

21. Energy Diagram for the Bromination of Propane
Figure: 04_10.jpg
Title:
Energy Diagram for the Bromination of Propane
Caption:
Reaction-energy diagram for the first propagation step in the bromination of propane. The energy difference in the transition states is nearly as large as the energy difference in the products.
Notes:
Chapter 4

22. Hammond Postulate
Related species that are similar in energy are also similar in structure.
The structure of the transition state resembles the structure of the closest stable species.
Endothermic reaction: Transition state resembles the product.
Exothermic reaction: Transition state resembles the reactant.
Chapter 4

23. Energy Diagrams: Chlorination Versus Bromination
Chapter 4

24. Endothermic and Exothermic Diagrams
Chapter 4

25. fluorination is nearly nonselective.
Hint
Free-radical bromination is highly selective, chlorination is moderately selective, and
fluorination is nearly nonselective.
Chapter 4

26. Radical Inhibitors
Often added to food to retard spoilage by radical chain reactions.
Without an inhibitor, each initiation step will cause a chain reaction so that many molecules will react.
An inhibitor combines with the free radical to form a stable molecule.
Vitamin E and vitamin C are thought to protect living cells from free radicals.
Chapter 4

27. Radical Inhibitors (Continued)
A radical chain reaction is fast and has many exothermic steps that create more reactive radicals.
When an inhibitor reacts with the radical, it creates a stable intermediate, and any further reactions will be endothermic and slow.
Chapter 4

28. Reactive Intermediates
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Reactive intermediates are short-lived species.
Never present in high concentrations because they
react as quickly as they are formed.
Chapter 4

29. Carbocation Structure
A carbocation (also called a carbonium ion or a carbenium ion) is a positively charged carbon.
Carbon is sp2 hybridized with vacant p orbital.
Chapter 4

30. Carbocation Stability
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More highly substituted carbocations
are more stable.
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31. Carbocation Stability (Continued)
Stabilized by alkyl substituents in two ways:
1. Inductive effect: Donation of electron density along the sigma bonds.
2. Hyperconjugation: Overlap of sigma bonding orbitals with empty p orbital.
Chapter 4

32. Unsaturated Carbocations
Unsaturated carbocations are also stabilized by resonance stabilization.
If a pi bond is adjacent to a carbocation, the filled p orbitals of the bond will overlap with the empty p orbital of the carbocation.
Chapter 4

33. Free Radicals
Carbon is sp2 hybridized with one electron in the p orbital.
Stabilized by alkyl substituents.
Order of stability: 3 > 2 > 1 > methyl
Chapter 4

34. Stability of Carbon Radicals
More highly substituted radicals
are more stable.
Chapter 4

35. Unsaturated Radicals
Like carbocations, radicals can be stabilized by resonance.
Overlap with the p orbitals of a p bond allows the odd electron to be delocalized over two carbon atoms.
Resonance delocalization is particularly effective in stabilizing a radical.
Chapter 4

36. Carbanions Eight electrons on carbon: six bonding plus one lone pair.
Carbon has a negative charge.
Carbanions are nucleophilic and basic.
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Chapter 4

37. Stability of Carbanions
Alkyl groups and other electron-donating groups slightly destabilize a carbanion.
The order of stability is usually the opposite of that for carbocations and free radicals.
Chapter 4

38. Basicity of Carbanions
A carbanion has a negative charge on its carbon atom, making it a more powerful base and a stronger nucleophile than an amine.
A carbanion is sufficiently basic to remove a proton from ammonia.
Figure: 04_16-02UN.jpg
Title:
Reactivity of a Carbanion
Caption:
Like amines, carbanions are nucleophilic and basic. A carbanion has a negative charge on its carbon atom, however, making it a more powerful base and a stronger nucleophile than an amine. For example, a carbanion is sufficiently basic to remove a proton from ammonia.
Notes:
Carbanions are a stronger base than amines, so they can deprotonate amines easily.
Chapter 4

39. Carbenes Carbon in carbenes is neutral.
It has a vacant p orbital so can react as an electrophile.
It has a lone pair of electrons in the sp2 orbital so can react as a nucleophile.
Chapter 4

40. Carbenes as Reaction Intermediates
A strong base can abstract a proton from tribromomethane (CHBr3) to give an inductively stabilized carbanion.
This carbanion expels bromide ion to give dibromocarbene. The carbon atom is sp2 hybridized with trigonal geometry.
A carbene has both a lone pair of electrons and an empty p orbital, so it can react as a nucleophile or as an electrophile.
Figure: 04_16-06UN.jpg
Title:
Carbenes as Reaction Intermediates
Caption:
Carbenes are uncharged reactive intermediates containing a divalent carbon atom. The simplest carbene has the formula CH2 and is called methylene, just as a –CH2- group in a molecule is called a methylene group. One way of generating carbenes is to form a carbanion that can expel a halide ion. For example, a strong base can abstract a proton from tribromomethane (CHBr3) to give an inductively stabilized carbanion. This carbanion expels bromide ion to give dibromocarbene. The carbon atom is sp2 hybridized, with trigonal geometry. An unshared pair of electrons occupies one of the sp2 hybrid orbitals, and there is an empty p orbital extending above and below the plane of the atoms. A carbene has both a lone pair of electrons and an empty p orbital, so it can react as a nucleophile or as an electrophile.
Notes:
The reactivity of carbenes lies in its orbitals. The carbon of carbenes have sp2 hybrid orbitals. Two of the hybrid orbitals are bonded to other atoms, one of the sp2 orbitals contains the lone pair of electrons so they can act as a nucleophile. Perpendicular to the plane of the sp2 orbitals is an unoccupied p orbital which allows them to act as an electrophile.
Chapter 4

41. Summary of Reactive Species
Chapter 4

42. Skill Building: Practice Problems
Problem 4-1 thru 4-4
Problem 4-18 thru 4-33