1. Chapter 6 Overview of Organic Reactions

2. 6.1 Kinds of Organic Reactions
In general, we look at what occurs and try to learn how it happens
Common patterns describe the changes
Addition reactions – two molecules combine
Elimination reactions – one molecule splits into two

3. Kinds of Organic Reactions (Continued)
Substitution – parts from two molecules exchange

4. Kinds of Organic Reactions (Continued)
Rearrangement reactions – a molecule undergoes changes in the way its atoms are connected

5. 6.2 How Organic Reactions Occur: Mechanisms
In a clock the hands move but the mechanism behind the face is what causes the movement
In an organic reaction, we see the transformation that has occurred. The mechanism describes the steps behind the changes that we can observe
Reactions occur in defined steps that lead from reactant to product

6. Steps in Mechanisms We classify the types of steps in a sequence
A step involves either the formation or breaking of a covalent bond
Steps can occur individually or in combination with other steps
When several steps occur at the same time, they are said to be concerted

7. Types of Steps in Reaction Mechanisms
Bond formation or breakage can be symmetrical or unsymmetrical
Symmetrical- homolytic
Unsymmetrical- heterolytic

8. Indicating Steps in Mechanisms
Curved arrows indicate breaking and forming of bonds
Arrowheads with a “half” head (“fish-hook”) indicate homolytic and homogenic steps (called ‘radical processes’)
Arrowheads with a complete head indicate heterolytic and heterogenic steps (called ‘polar processes’)

9. 6.3 Radical Reactions Not as common as polar reactions
Radicals react to complete electron octet of valence shell
A radical can break a bond in another molecule and abstract a partner with an electron, giving substitution in the original molecule
A radical can add to an alkene to give a new radical, causing an addition reaction

10. Steps in Radical Substitution
Three types of steps
Initiation – homolytic formation of two reactive species with unpaired electrons
Propagation – reaction with molecule to generate radical
Example - reaction of chlorine atom with methane to give HCl and CH3.

11. Steps in Radical Substitution
Termination – combination of two radicals to form a stable product: CH3. + CH3.  CH3CH3

12. 6.4 Polar Reactions
Molecules can contain local unsymmetrical electron distributions due to differences in electronegativities
This causes a partial negative charge on an atom and a compensating partial positive charge on an adjacent atom
The more electronegative atom has the greater electron density
Elements such as O, F, N, Cl are more electronegative than carbon

13. Polarity Patterns in Some Common Functional Groups

14. Polarizability
Polarization is a change in electron distribution as a response to change in electronic nature of the surroundings
Polarizability is the tendency to undergo polarization
Polar reactions occur between regions of high electron density and regions of low electron density

15. Generalized Polar Reactions
An electrophile, an electron-poor species, combines with a nucleophile, an electron-rich species
An electrophile is a Lewis acid
A nucleophile is a Lewis base
The combination is indicated with a curved arrow from nucleophile to electrophile

16. Some Nucleophiles and Electrophiles

17. 6.5 An Example of a Polar Reaction: Addition of HBr to Ethylene
HBr adds to the  part of a C-C double bond
The  bond is electron-rich, allowing it to function as a nucleophile
H-Br is electron deficient at the H since Br is much more electronegative, making HBr an electrophile

18. Mechanism of Addition of HBr to Ethylene
HBr electrophile is attacked by  electrons of ethylene (nucleophile) to form a carbocation intermediate and bromide ion
Bromide adds to the positive center of the carbocation, which is an electrophile, forming a C-Br  bond
The result is that ethylene and HBr combine to form bromoethane
All polar reactions occur by combination of an electron-rich site of a nucleophile and an electron-deficient site of an electrophile

19. 6.6 Using Curved Arrows in Polar Reaction Mechanisms
Curved arrows are a way to keep track of changes in bonding in a polar reaction
The arrows track “electron movement”
Electrons always move in pairs
Charges change during the reaction
One curved arrow corresponds to one step in a reaction mechanism

20. Rules for Using Curved Arrows
The arrow goes from the nucleophilic reaction site to the electrophilic reaction site
The nucleophilic site can be neutral or negatively charged

21. Rules for Using Curved Arrows (Continued)
The electrophilic site can be neutral or positively charged
The octet rule should be followed

22. 6.7 Describing a Reaction: Equilibria, Rates, and Energy Changes
Reactions may go either forward or backward to reach equilibrium
The multiplied concentrations of the products divided by the multiplied concentrations of the reactant is the equilibrium constant, Keq
Each concentration is raised to the power of its coefficient in the balanced equation.

23. Magnitudes of Equilibrium Constants
If the value of Keq is greater than 1, this indicates that at equilibrium most of the material is present as products
If Keq is 10, then the concentration of the product is ten times that of the reactant
A value of Keq less than one indicates that at equilibrium most of the material is present as the reactant
If Keq is 0.10, then the concentration of the reactant is ten times that of the product

24. Free Energy and Equilibrium
The ratio of products to reactants is controlled by their relative Gibbs free energy
This energy is released on the favored side of an equilibrium reaction
The change in Gibbs free energy between products and reacts is written as “DG”
If Keq > 1, energy is released to the surroundings (exergonic reaction)
If Keq < 1, energy is absorbed from the surroundings (endergonic reaction)

25. Numeric Relationship of Keq and Free Energy Change
The standard free energy change at 1 atm pressure and 298 K is DGº
The relationship between free energy change and an equilibrium constant is:
DGº = - RT ln Keq where
R = cal/(K x mol)
T = temperature in Kelvin
ln Keq = natural logarithm of Keq

26. Thermodynamic Quantities

27. 6.8 Describing a Reaction: Bond Dissociation Energies
Bond dissociation energy (D): amount of energy required to break a given bond to produce two radical fragments when the molecule is in the gas phase at 25˚ C
The energy is mostly determined by the type of bond, independent of the molecule
The C-H bond in methane requires a net energy input of 106 kcal/mol to be broken at 25 ºC.
Table 6.3 lists energies for many bond types
Changes in bonds can be used to calculate net changes in heat

28. 6.9 Describing a Reaction: Energy Diagrams and Transition States
The highest energy point in a reaction step is called the transition state
The energy needed to go from reactant to transition state is the activation energy (DG‡)

29. First Step in Addition The C–H bond begins to form
In the addition of HBr the (conceptual) transition-state structure for the first step
The  bond between carbons begins to break
The C–H bond begins to form
The H–Br bond begins to break

30. 6.10 Describing a Reaction: Intermediates
If a reaction occurs in more than one step, it must involve species that are neither the reactant nor the final product
These are called reaction intermediates or simply “intermediates”
Each step has its own free energy of activation
The complete diagram for the reaction shows the free energy changes associated with an intermediate

31. 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

32. 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

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

34. 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”

35. 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

36. 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

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

38. 10.8 Oxidation and Reduction in Organic Chemistry
In organic chemistry, we say that oxidation occurs when a carbon or hydrogen that is connected to a carbon atom in a structure is replaced by oxygen, nitrogen, or halogen
Not defined as loss of electrons by an atom as in inorganic chemistry
Oxidation is a reaction that results in loss of electron density at carbon (as more electronegative atoms replace hydrogen or carbon)
Oxidation: break C–H (or (C–C) and form C–O, C–N, C–X

39. Reduction Reactions
Organic reduction is the opposite of oxidation
Results in gain of electron density at carbon (replacement of electronegative atoms by hydrogen or carbon)
Reduction: form C–H (or C–C) and break C–O, C–N, C–X

40. Oxidation Levels Functional groups are associated with specific levels
Tables indicates least oxidized (i.e., most reduced) to most oxidized.
Any reaction that converts a compound from a lower level to a higher level is an oxidation.

41. 10.2 Structure of Alkyl Halides
C-X bond is longer as you go down periodic table
C-X bond is weaker as you go down periodic table
C-X bond is polarized with slight positive charge on carbon and slight negative charge on halogen

42. Preparing Alkyl Halides from Alkenes: Radical Halogenation
Alkyl halide from addition of HCl, HBr, HI to alkenes to give Markovnikov product (see Alkenes chapter)
Alkyl dihalide from anti addition of bromine or chlorine

43. Preparing Alkyl Halides from Alkenes: Radical Halogenation
Alkane + Cl2 or Br2, heat or light replaces C-H with C-X but gives mixtures
Hard to control
Via free radical mechanism
It is usually not a good idea to plan a synthesis that uses this method

44. Radical Halogenation of Alkanes
If there is more than one type of hydrogen in an alkane, reactions favor replacing the hydrogen at the most highly substituted carbons (not absolute)

45. Relative Reactivity
Based on quantitative analysis of reaction products, relative reactivity is estimated
Order parallels stability of radicals
Reaction distinction is more selective with bromine than chlorine