Reactions and their Mechanisms

Substitution
-Cl on -CH3 has been substituted with an -OH Br2 has been added to C2H2

Additions

Eliminations

HBr has been eliminated or removed form C2H5Br

Rearrangements

The carbon skeletal system, C6H12, has been rearranged

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Homolysis and Heterolysis of Covalent Bonds
Heterolysis – Cleavage of sigma bond occurs so that one fragment take away both electrons Double headed arrow shows the movement of two electrons

Homolysis – Cleavage of sigma bond occurs so that fragment takes away one electron. Single headed arrow shows the movement of one electrons

each

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Arrows are your thought process to solving reactions (-ve goes to +ve)
Double headed arrow shows the movement of two electrons Heterolysis requires that the bond be polarized which is due to the different electronegativities between the atoms
Double headed arrow shows the movement of two electrons

Often heterolysis is assisted by a molecule with an unshared pair of electrons (a base) that can form a bond to on to the atoms. (-ve goes to +ve)

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Acid-Base Reactions
Bronsted-Lowry acid → substance that can donate a hydrogen ion (H+) Bronsted-Lowry base → substance that can accept a hydrogen ion (H+) CH3COOH acid + ¯OH CH3COO ¯ + conjugate acid H2O

baseconjugate base

Lewis acid → substance that can accept a pair of electrons Lewis base → substance that can donate a pair of electrons FeBr3 + Br2 Lewis acid Lewis base FeBr4 ¯ Lewis base + Br + Lewis acid

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pH = -log[H+]

Review
kw = [H+][¯OH] = 1 x 10-14 pH + pOH = 14

pOH = -log[OH]

Brønsted-Lowry acids and bases

neutral solution → [H+] = [ ¯OH] = 1 x 10-7 pH = 7 acidic solution → [H+] > 1 x 10-7 pH range 0 to 7 basic solution → [H+] < 1 x 10-7 pH range 7 to 14

General formula for an acid HA; for a base B HA ka = [H+][A¯] [HA] taking the log of both sides Henderson-Hasselbalch equations pH = pka + log[A¯] [HA] pOH = pkb + log[B+H] [B] H+ + A¯ B + H2O kb = [¯OH][B+H] [B] B+H + ¯OH

strong acid [H+] ↑ , ka ↑, pka ↓ weak acid [H+] ↓ , ka ↓, pka ↑

strong base [¯OH] ↑ , kb ↑, pkb ↓ weak base [¯OH] ↓ , kb ↓, pkb ↑
ka x kb = kw =1 x 10-14 pka + pkb = 14

relationship between conjugate acid base pairs

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Lewis Acids and Bases
Makes you think about the electrons and how bonds are formed arrow show bond breaking arrow show bond formation

gained two electrons and becomes negatively charged

new bond

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Opposite Charges Attract and React
BF3 has substantial positive charge on the boron
NH3 has substantial negative charge localized at the lone pair

-ve goes to +ve

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The base donates its electrons that occupy the HOMO to the LUMO of the acid to produce a new sigma bond

BF3 is sp2 hybridized The LUMO (Lowest Unoccupied Molecular Orbital) is shown to the right. Most of the volume of the LUMO corresponds to the empty p orbital

NH3 is sp3 hybridized. The HOMO (Highest Occupied Molecular Orbital) is shown to the left and is where the nonbonding lone pair resides.

The van der Waals surface electron density is indicated by the mesh

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Heterolysis of Bonds to Carbons: Carbanions and Carbocations
Reaction can occur to give a carbocation or carbanion depending on the nature of Z

Carbocations have only 6 valence electrons and a positive charge

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Carbanions have 8 valence electrons and a negative charge

Organic chemistry terms for Lewis acids and bases Electrophiles (“electron-loving” reagents ): seek electrons to obtain a stable valence shell of electrons. They are electron-deficient themselves e.g. carbocations. Acid – accepts electrons Nucleophiles (“nucleus-loving” reagents): seek a proton or some other positively charged center. They are electron-rich themselves e.g. carbanions Base – donates electrons

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A mechanisms shows the flow of electrons that may occur to form your product. The pathway is guided by arrows. An arrow starts at a site of higher electron density (a covalent bond or unshared electron pair) and points to a site of electron deficiency.

In a few weeks you will have to know and understand the mechanism given to the right. This is a SN1 reaction.

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The first step to organic reactions is understanding acids and bases
Why do acids have different acidities? What makes a strong acid a strong acid? An acid is strong if it’s conjugate base is stable. If the base is not stable it is reactive and will react with a proton and shift the equilibrium to the left in the following equilibrium.

HA

A¯ + H+

Acidity increases with increasing anion stability

Hence the strength of an acid is inversely related to the strength of its conjugate base. What makes the base stable? You must look at the structure of the molecule. What is the hybridization of the atom? Is the charge on an electronegative atom? Is the electronegative atom large so that the charge is spread over a larger area? Can the charge be delocalized throughout the molecule? All of these must be considered

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1. What atom is the charge on?
Acidity increases with increasing anion stability

HA

A¯ + H+

The more electronegative an atom, the greater its ability to carry a negative charge. Remember, electronegativity is the measure of an elements affinity for an electron or its ability to accept an electron. (CH3)3C-H (CH3)2N-H CH3O-H H-F

increasing electronegativity of the underlined atom; increasing acid strength increasing stability of anion
B 2.0 Al 1.5 Ga 1.8 C 2.5 Si 1.8 Ge 2.0 N 3.0 P 2.1 As 2.2 O 3.5 S 2.5 Se 2.6 Te 2.1 F 4.0 Cl 3.0 Br 2.8 I 2.5

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1. What atom is the charge on?

HA

A¯ + H+

A larger anion can disperse the negative charge over a larger volume and thus increases the stability of the conjugate base which is more important than electronegativity when comparing elements down a column in the periodic table. H-F
conjugate base

H-Cl

H-Br

H-I

increasing size of halogen increasing acid strength increasing stability of anion decreasing electronegativity of halogen
B 2.0 Al 1.5 Ga 1.8 C 2.5 Si 1.8 Ge 2.0 N 3.0 P 2.1 As 2.2 O 3.5 S 2.5 Se 2.6 Te 2.1 F 4.0 Cl 3.0 Br 2.8 I 2.5

Thus use electronegativity when comparing atoms in the same row and size when comparing atoms in the same column
Sec. 7 - Acid-base Reactions Forsey 14

2. The proximity of an electronegative atom to an acidic atom can help stabilize the conjugate base. (Induction) HA A¯ + H+
Inductive effects: Electronegative atoms pull electron density through the sigma bond from adjacent carbons making the carbon more positive. If the carbon is close to the anion this carbon can then pull electron density from the region that has the negative charge to make it more stable. CH3CH2CH2COOH CH2ClCH2CH2COOH CH3CHClCH2COOH CH3CH2CHClCOOH pka 4.83 4.52 4.05 2.86 increasing acidity increasing anion stability

H3COH pka 15.5

ClCH2CH2OH 14.3 increasing acidity increasing anion stability

F3CCH2OH 12.4

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δ− Cl δ− Cl

O
δ+ δ+

δ- Cl δ- Cl

δ+

O

-1

δδ− The chlorines make the adjacent carbons electron poor. The carbon can then pull electron density from the region that has the negative charge, and this effect will stabilize the negative charge How about these hydrogens Do the electronegative atoms help stabilize the conjugate base O This is destabilizing. The lone pairs on the electronegative atom and the lone pair on the carbon repel each other.

Cl

O

Cl

δ− O

+ H+

These protons are not very acidic

H F

δ−

F

+ H+
16

H

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What effect do alkyl groups
Which compound is more acidic?
H3C C H3C C OH O H3C C H 3C C O O
+ H+

CH3
O

CH3
O

+ H+
O

more acidic

H3C

C

OH

H3C

C

more stable conjugate base

Alkyl and aryl groups are electron donating through hyperconjugation or inductive effects which makes the anion less stable.

hyperconjugation through C-H sigma bond. This is not resonance. We will talk more about this later.

H
sp3

O C C sp
2

sp2

H

H

O

sp2

only one C-H σ bond shown

Resonance
17

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3. Resonance Stabilization
Resonance helps stabilize the negative charge by delocalizing or sharing the negative charge with more than one atom. For example which is more acidic methanol or acetic acid? In methanol the charge on the conjugate base is localized on a single oxygen whereas the conjugate base of acetic acid has the charge shared or delocalized over two oxygens. The conjugate base of acetic acid is more stable thus the equilibrium is shifted more to the right as compared to methanol making acetic acid more acidic. But which is more acidic acetic acid or phenol pka = 15.5 CH3OH O pka = 4.74 H3C C OH H3C CH3O ¯ + H+ O C O ¯ + H+ No resonance two resonance structures helps stabilize the negative charge and shifts the equilibrium to the right compared to CH3OH

pka = 9.92

OH

O ¯ + H+

Less acidic than acetic acid? But doesn’t the phenoxide have more resonance structure and should be more stable than acetate ion
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Sec. 7 - Acid-base Reactions

CH3O ¯ + H+
O O O O

+ H+

O H3C C O H3C

O C O

+ H+

Phenol has more resonance structures than acetic acid but acetic acid is more acidic, why? Which atom is able to handle a negative charge better, carbon or oxygen?

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4. Hybridization
With increasing s character the lone pair of electrons are closer to the nucleus thus stabilizing the conjugate base (CH3)3CH pka > 70 CH2=CH2 44 increasing acidity increasing anion stability Conjugate base (CH3)3C¯ sp3 CH2=CH ¯ sp2 HC≡C ¯ sp HC≡CH 26

C¯ sp3

C¯ sp2

C¯ sp
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Sec. 7 - Acid-base Reactions

List the following compounds in order of decreasing acidity
CH4,
¯

NH3,
¯

CH3OH,

HF

B 2.0 Al 1.5 Ga 1.8

C 2.5 Si 1.8 Ge 2.0

N 3.0 P 2.1 As 2.2

O 3.5 S 2.5 Se 2.6 Te 2.1

F 4.0 Cl 3.0 Br 2.8 I 2.5

CH3

NH2

CH3O¯ F¯ + H+ + H+

+ H+

+ H+

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List the following compounds in order of decreasing acidity
a) HCl HBr HF HI
B 2.0 Al 1.5 C 2.5 Si 1.8 Ge 2.0 N 3.0 P 2.1 As 2.2 O 3.5 S 2.5 Se 2.6 Te 2.1 F 4.0 Cl 3.0 Br 2.8 I 2.5

b) CH3CH3 Conjugate base: CH3CH2 ¯ sp3

H2C=CH2 H2C=CH ¯ sp2

HC≡CH HC≡C ¯ sp

Ga 1.8

c)

OH O

OH

OH

>

>

Two resonance structures with the negative charge on two electronegative atoms (oxygen) is more stabilizing than 3 resonance structures with the negative charge on carbons. Sec. 7 - Acid-base Reactions Forsey 22

O

O

Cl OH

O OH

d)

1)

OH

2)
Cl

3)

B 2.0 Al 1.5 Ga 1.8

C 2.5 Si 1.8 Ge 2.0

N 3.0 P 2.1 As 2.2

O 3.5 S 2.5 Se 2.6 Te 2.1

F 4.0 Cl 3.0 Br 2.8 I 2.5

e)

1)

Cl

OH

2)

OH

3) CH3SH

4) CH3OH

Cl

O

The electronegative chlorine is electron withdrawing and pulls electron density from the oxygen into the aromatic ring making the conjugate base more
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Bases
The concept of base strength can sometimes be confusing to students. When there is a negative charge on different atoms it is straightforward since we can look at the electronegativity or hybridization of the atom to explain basicity. For example place the following molecules in decreasing basicity. a) CH3O¯, CH3NH¯, CH3CH2¯, F¯ b) I¯ , F¯ , Cl¯ , Br¯ c) CH2=CH¯ , CH3CH2¯ , HCC¯ Where does CH3NH¯ fit into the trend found in part c)

The sp3 nitrogen is a weaker base than an sp2 carbon because it is more electronegative. It is also a weaker base than a sp2 carbon but not a sp hybridized carbon because the change in hybridization which gives the orbital more s character has a greater stabilizing effect than increasing electronegativity. Sec. 7 - Acid-base Reactions

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Reactions from text Book
pKa+ pKb = 14
pKb = -24 pKb = -1.7

pKb = -24

pKb = -11

pKb = -24

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Order the bases from strongest to weakest.
H N NH2 N
A) B) C) D) 1>2>3 1>3>2 3>2>1 2>3>1

1
N

2

H δ+ H N
δδ-

3

First put the electrons on the nitrogen atoms Then think about the electrons. What is their hybridization, are they resonating?

N

H

δ-

Which electrons are most basic or available?
The sp3 nitrogen because it has more p character. Therefore 1 is the strongest base.

Now which electrons are more available? The electrons in structure 2 or 3? What is the difference?
The electrons on the nitrogen in compound 3 are part of an aromatic system and are thus very stable, whereas the electrons in compound 2 are in a sp2 hybridized orbital sticking out from the aromatic system. The electrons in compound B are more basic, less stable, more reactive and more available than 3. Answer: A Sec. 7 - Acid-base Reactions Forsey

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We are always looking at an equilibrium and which way it is shifted in a specific environment

∆G  = −RT ln K eq
∆G° = -ve value the reaction favors the formation of products and if smaller than – 13 kJ mol-1 the is said to go to completion (>99% converted) ∆G° = +ve value the reaction favors the reactants and the formation of products is unfavorable. ∆G° = ∆H° - T∆S° Exothermic reaction ∆H ° is -ve Endothermic reaction ∆H ° is +ve

HA

A¯ + H+

∆S° is +ve - Change from a more ordered system to less a ordered system ∆S° is -ve - Change from a less ordered system to a more ordered system Sec. 7 - Acid-base Reactions Forsey

We will come back to this when we look at reactions 27

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