1. Chapter 7 Alkenes: Structure and Reactivity

2. Alkene - Hydrocarbon With Carbon-Carbon Double Bond
Also called an olefin but alkene is better
Hydrocarbon that contains a C-C double bond
Includes many naturally occurring materials
Flavors, fragrances, vitamins

3. Why this Chapter?
C=C double bonds are present in most organic and biological molecules
To examine consequences of alkene stereoisomerism
To focus on an important alkene reaction: electrophilic addition

4. 7.1 Industrial Preparation and Use of Alkenes
Ethylene and propylene are important organic chemicals produced

5. Thermal Cracking
Thermal cracking may take place w/o catalyst at very high temperatures

6. 7.2 Calculating Degree of Unsaturation
Relates molecular formula to possible structures
Degree of unsaturation: number of multiple bonds or rings
Formula for a saturated acyclic compound is CnH2n+2
Alkene has fewer hydrogens than an alkane with the same number of carbons —CnH2n because of double bond
Each ring or multiple bond replaces 2 H's

7. Example: C6H10 Saturated is C6H10 therefore 4 H's are not present
This has two degrees of unsaturation
Two double bonds?
or triple bond?
or two rings?
or ring and double bond?

8. Degree of Unsaturation With Other Elements
Organohalogens (X: F, Cl, Br, I)
Halogen replaces hydrogen
C4H6Br2 and C4H8 have one degree of unsaturation

9. Degree of Unsaturation (Continued)
Organoxygen compounds (C,H,O) – Oxygen forms 2 bonds
these don't affect the formula of equivalent hydrocarbons
May be ignored in calculating degrees of unsaturation

10. Organonitrogen Compounds
Nitrogen has three bonds
So if it connects where H was, it adds a connection point
Subtract one H for equivalent degree of unsaturation in hydrocarbon

11. Summary - Degree of Unsaturation
Count pairs of H's below CnH2n+2
Add number of halogens to number of H's (X equivalent to H)
Ignore oxygens (oxygen links H)
Subtract N's - they have two connections

12. Degree of Unsaturation - Video

13. 7.3 Naming Alkenes Name the parent hydrocarbon
Number the carbons in chain so that double bond carbons have lowest possible numbers

14. Naming Alkenes (Continued)
Write the full name- Number substituents according to: 1) Position in chain, 2)Alphabetically
Rings have “cyclo” prefix

15. Many Alkenes Are Known by Common Names

16. Naming Alkenes Examples - Video

17. 7.4 Cis-Trans Isomerism in Alkenes
Carbon atoms in a double bond are sp2-hybridized
Three equivalent orbitals at 120º separation in plane
Fourth orbital is atomic p orbital
Combination of electrons in two sp2 orbitals of two atoms forms  bond between them
Additive interaction of p orbitals creates a  bonding orbital
Subtractive interaction creates a  anti-bonding orbital
Occupied  orbital prevents rotation about -bond
Rotation prevented by  bond - high barrier, about 268 kJ/mole in ethylene

18. Cis-Trans Isomerism in Alkenes (Continued)
Rotation of  bond is prohibitive
This prevents rotation about a carbon-carbon double bond (unlike a carbon-carbon single bond).
Creates possible alternative structures

19. Cis-Trans Isomerism in Alkenes (Continued)
the presence of a carbon-carbon double bond can create two possible structures
cis isomer - two similar groups on same side of the double bond
trans isomer - similar groups on opposite sides
Each carbon must have two different groups for these isomers to occur

20. Cis-Trans Isomerism in Alkenes (Continued)
Cis-Trans Isomerization requires that end groups differ in pairs
Bottom pair cannot be superposed without breaking C=C

21. 7.5 Alkene Stereochemistry and the E,Z Designation
Cis-Trans naming system discussed thus far only works with disubstituted alkenes
Tri- and Tetra substituted double bonds require more general method
Method referred to as the E,Z system

22. Alkene Stereochemistry and the E,Z Designation (Continued): E,Z Stereochemical Nomenclature
Priority rules of Cahn, Ingold, and Prelog
Compare where higher priority groups are with respect to bond and designate as prefix
E -entgegen, opposite sides
Z - zusammen, together on the same side

23. Alkene Stereochemistry and the E,Z Designation (Continued): Cahn-Ingold-Prelog Rules
Must rank atoms that are connected at comparison point
Higher atomic number gets higher priority
Br > Cl > S > P > O > N > C > H

24. Alkene Stereochemistry and the E,Z Designation (Continued): Cahn-Ingold-Prelog Rules
If atomic numbers are the same, compare at next connection point at same distance
Compare until something has higher atomic number
Do not combine – always compare

25. Alkene Stereochemistry and the E,Z Designation (Continued): Cahn-Ingold-Prelog Rules
Multiple-bonded atoms are equivalent to the same number of single-bonded atoms
Substituent is drawn with connections shown and no double or triple bonds
Added atoms are valued with 0 ligands themselves

26. Entgegen-Zusammen Naming Scheme - Video
1) Entgegen-Zusammen Naming Scheme for Alkenes Examples

27. 7.6 Stability of Alkenes
Cis alkenes are less stable than trans alkenes
Compare heat given off on hydrogenation: Ho
Less stable isomer is higher in energy
And gives off more heat
tetrasubstituted > trisubstituted > disubstituted > monosusbtituted
hyperconjugation stabilizes

28. Stability of Alkenes (Continued): Comparing Stabilities of Alkenes
Evaluate heat given off when C=C is converted to C-C
More stable alkene gives off less heat
trans-Butene generates 5 kJ less heat than cis-butene

29. Stability of Alkenes (Continued): Hyperconjugation
Electrons in neighboring filled  orbital stabilize vacant antibonding  orbital – net positive interaction
Alkyl groups are better than H

30. Stability of Alkenes - Video

31. 7.7 Electrophilic Addition of Alkenes
General reaction mechanism of electrophilic addition
Attack on electrophile (such as HBr) by bond of alkene
Produces carbocation and bromide ion
Carbocation is an electrophile, reacting with nucleophilic bromide ion

32. Electrophilic Addition of Alkenes (Continued): Electrophilic Addition Energy Path
Two step process
First transition state is high energy point
First step is slower than second

33. Electrophilic Addition of Alkenes (Continued)
The reaction is successful with HCl and with HI as well as HBr
HI is generated from KI and phosphoric acid

34. Ethylene: Electrophilic Addition Reactions - Video

35. 7.8 Orientation of Electrophilic Additions: Markovnikov’s Rule
In an unsymmetrical alkene, HX reagents can add in two different ways, but one way may be preferred over the other
If one orientation predominates, the reaction is regioselective
Markovnikov observed in the 19th century that in the addition of HX to alkene, the H attaches to the carbon with more H’s and X attaches to the other end (to the one with more alkyl substituents)
This is Markovnikov’s rule

36. Example of Markovnikov’s Rule
Addition of HCl to 2-methylpropene
Regiospecific – one product forms where two are possible
If both ends have similar substitution, then not regiospecific

37. Markovnikov’s Rule (restated)
More highly substituted carbocation forms as intermediate rather than less highly substituted one
Tertiary cations and associated transition states are more stable than primary cations

38. Markovnikov’s Rule (restated)

39. Markovnikov's Rule and Carbocations - Video
1) Markovnikov's Rule and Carbocations: Markovnikov's Rule and Carbocations. Figuring out which addition reaction is more likely.

40. 7.9 Carbocation Structure and Stability
Carbocations are planar and the tricoordinate carbon is surrounded by only 6 electrons in sp2 orbitals
the fourth orbital on carbon is a vacant p-orbital
the stability of the carbocation (measured by energy needed to form it from R-X) is increased by the presence of alkyl substituents

41. Carbocation Structure and Stability (Continued)
A plot of DH dissociation shows that more highly substitued alkyl halides dissociate more easily than less highly substituted ones

42. Carbocation Structure and Stability (Continued)
A inductive stabilized cation species

43. Carbocation Stability - Video

44. 7.10 the Hammond Postulate
If a carbocation intermediate is more stable than another, why is the reaction through the more stable one faster?
the relative stability of the intermediate is related to an equilibrium constant (DGº)
the relative stability of the transition state (which describes the size of the rate constant) is the activation energy (DG‡)
the transition state is transient and cannot be examined
What does the Hammond Postulate state?
“the structure of a transition state resembles the structure of the nearest stable species. Transition states for endergonic steps structurally resemble products, and transition states for exergonic steps structurally resemble reactants”

45. The Hammond Postulate (Continued): Transition State Structures
A transition state is the highest energy species in a reaction step
By definition, its structure is not stable enough to exist for one vibration
But the structure controls the rate of reaction
So we need to be able to guess about its properties in an informed way
We classify them in general ways and look for trends in reactivity – the conclusions are in the Hammond Postulate

46. Examination of the Hammond Postulate
A transition state should be similar to an intermediate that is close in energy
Sequential states on a reaction path that are close in energy are likely to be close in structure - G. S. Hammond

47. Competing Reactions and the Hammond Postulate
Normal Expectation: Faster reaction gives more stable intermediate
Intermediate resembles transition state

48. The Hammond Postulate and Selectivity - Video
1) Yale – Hammond Postulate: START at 40:45
2) The Hammond Postulate and Selectivity

49. 7.11 Evidence for the Mechanism of Electrophilic Addition: Carbocation Rearrangments
Carbocations undergo structural rearrangements following set patterns
1,2-H and 1,2-alkyl shifts occur
Goes to give moststable carbocation
Can go through less stable ions as intermediates

50. Hydride shifts in biological molecules

51. Carbocation Rearrangement - Video

52. Let’s Work a Problem
Addition of HCl to 1-isopropylcyclohexene yields a rearranged product. Propose a mechanism, showing the structures of the intermediates and using curved arrows indicate electron flow in each step.
The hydrogen is approached by the nucleophilic double bond. A new C-H bond is formed, along with a 3˚ carbocation. At the same time, Cl takes on 1more electron, making it a Cl anion.
There is a “Methyl” shift, creating a new C-H bond with the 1st 3˚ carbocation to give an isomeric 3˚ carbocation that is less hindered.
The Cl-ion then approaches the new carbocation. A Cl-C bond is formed which gives charged neutral product.