Reaction in Organic Chemistry

AB + CD A C + B -D

Bond Cleavage
Heterolytic Bond Cleavage (Polarized Bonds) Generate Ionic Species (Cation and Anion) Homolytic Bond Cleavage (Generate Radicals) Radicals: Species Containing Unpaired Electrons
A B A + B

Heterolysis of CZ Bonds
Heterolysis of CZ Bonds Generates Ionic Species

Carbocation: Postively Charged C Atom

Carbanion:
C Z

Negatively Charged C Atom

Nucleophiles and Electrophiles

Carbocations: Electrophiles Seek Electrons in Reaction to Fill/Stabilize Valence Carbanions: Nucleophiles Seek Proton or Some Other Positive Center Nucleo From Nucleus (Where Positive Charge Resides)

Acids & Bases in Organic Chemistry

Many of the organic reactions you will study involve acid-base reactions. Understanding these reactions will require you to:

recognize organic compounds that can serve as acids or bases

throw away the idea that anything with an OH is a base and anything with an H is an acid!!!

Acids & Bases in Organic Chemistry

Common definitions of acids and bases:

Arrhenius acids and bases Bronsted-Lowry acids and bases Lewis acids and bases

Bronsted-Lowry Acid

any substance that can donate a proton (H+ ion) any substance that can accept a proton

Bronsted-Lowry Base

Acids & Bases in Organic Chemistry

Acid-base reactions always produce a new acid and a new base:

conjugate acid: The new acid formed when the base gains a proton conjugate base: The new base formed by removing a proton+from Ca(OH) HCl an acid
always found on the product side
Conj. base
2

always found on the product side

CH3CO2H + NaOH NaH + CH3CH2OH

CH3CO2Na + H2O
Conj. acid

CH3CO2H + NaOH

Acids & Bases in Organic Chemistry

Ca(OH)2 + HCl

CH3is CO2H + NaOH The strength of an acid or base CH3C it CH + NaN determined by the extent to which NaH + CH3CH2OH ionizes:
HA + H2O Ca(OH)2 + HCl . + H2O B. H3O
+

NaH + CH3CH2OH

+ A

CH3C

Ka = [H3O ][A ]

CH
+

[HA]

+ NaN
-

BH

+ OH

CH3CO2H + NaOH

CH3CO2Na + H2O [B]

Kb = [BH ][OH ]

+ dissociation HCl Ca(OH) Ka = acid 2 CH CO H + NaOH

constant NaH + CH3CH2OH Kb = base dissociation constant

CH CO Na + H O

Acids & Bases in Organic Chemistry

The relative strength of an acid can be determined using:

the magnitude of Ka (or pKa)

structural trends

As Ka increases, the strength of the acid increases. As pKa decreases, the strength of the acid increases. The strength of an acid, HX, depends on the electronegativity of the atom containing the acidic hydrogen (i.e. the electronegativity of X) the stability of the conjugate base, X-

Acids & Bases in Organic Chemistry

Within the same period (row), acidity increases as the electronegativity of element X increases (i.e. left to right)

electronegative elements can bear a negative charge more easily H-C < H-N < H-O < H-F

Within a group, the strength of an acid increases moving down the group

negative charge is more stable when spread out over a larger region (i.e. larger ion) HCl is stronger than HF

. . .. . .. . in Organic O . .O . . Chemistry O .. .. .. CH C COH .. CH OH CH 3 C OH .. .. Acidity increases when the charge on the 33

. . .O . .O .O .. .. .. Acids & Bases CH C OH CH C OH OH 3 C CH 33

conjugate base can be delocalized over two or more atoms through resonance.
. . . .O . . .. .O . .. O .. .. .. CH C OH CH C.. OH CH OH 3 C .. .. 33 . . .. . .O . . . .O .. O .. .. .. . . . . CH C O .. CH C.. O CH O 3 C .. .. 33

.. --.. .. . . . .O . . .. .. .O . O .. .. .. CH C CO .. CH O CH O 3 C .. .. 33

Stronger acid pKa = 4.74

.. CH3CH2.. OH
Weaker acid pKa = 15.9

...CH3CH2O . ..

Acids & Bases in Organic Chemistry

Hybridization: Acidity increases when more s

character in the orbital. More s character will make more stable anion.
Consider Alkanes, Alkenes, Alkynes HCCH 25 sp 50 H2CCH2 44 sp2 33 H3CCH3 50 sp3 25

Acid: pKa: Hybrid. % s:

Acids & Bases in Organic Chemistry

Inductive Effect: Polarized Bonds (Electronegative Atoms) Affect Neighboring Atoms -- Also Called Electron Withdrawing Effect Consider Acid: H3CCH3 H3CCH2F H3CCH2 CH2F

The Further Away the Atom F; The Lesser the Inductive Effect less acidity

Acids & Bases in Organic Chemistry

You must be able to predict the relative strength of various acids:

pKa values indicate the following relative acidities:

strong inorganic acids > carboxylic acids > phenols > alcohols ~ water > terminal alkynes > alkanes

Be able to use structural trends.

CH3CO2

Acids & Bases in OrganicNChemistry CH

3 + 3

(CH )N CH3CO K of a base The strength is3CH inversely related 2 3 to its conjugate acid. CH

CH2)3acids N (CH Strong 3

form very weak conjugate bases.

-

Cl HCl Cl N Weak acids form stronger conjugate bases.

HCl

N CH3CO2H

CH3CO2

CH3OH

CH3O

Substances with negligible acidity form very NH3 NH2 strong bases. HCl CHconjugate Cl 3

CHNH CO K 3 3

NH2

(CH3CH2CH )3N
-

CH3

CH3CH OH 3 CH4

CH - 3O CH3

Acids & Bases in Organic Chemistry

You should be able to:

use the relative strength of various acids to predict the relative strengths of their conjugate bases use the strength of acids and bases to predict whether an acid/base equilibrium favors reactants or products.

Equilibrium favors the weaker acid (or the weaker base.

HCl

NH3 NH -& Bases in Organic 2 Acids Chemistry Cl

-

CH4 reaction CHfavor Example: Does the following the 3 reactants or products? CH OH CH O
3 3

CH3CH2OH + CH3NH

CH3CH2O

+ CH3NH2

. .

Acids & Bases in Organic Chemistry

The following reaction does not look like a classic acid-base reaction...neither reactant gains or loses an H+.
. .O . . CH3C H ...+ CH3.. O.
Lewis base

.. . . . O.

Lewis acid

CH3C H . ... OCH3

It is, however, a Lewis acid-base reaction. The Lewis acid-base definition is the broadest definition of acids and bases.

. .

Acids & Bases in Organic Chemistry

Lewis acid:

an electron pair acceptor . an electrophile electron lover a substance that accepts a pair of electrons to form a new bond
. .O . . CH3C H ...+ CH3.. O. .. . . . O. CH3C H . ... OCH3

. .

Lewis acid

Acids & Bases in Organic Chemistry

Lewis Base:

an electron pair donor a nucleophile nuclei lover a substance with a pair of electrons that can be donated to another nucleus to form a new bond

B
Lewis Base

+ H A
Lewis Acid

B H + A

Acids & Bases in Organic Chemistry

Common acids (materials with acidic protons) used in organic chemistry:

Inorganic acids: HCl HBr Strong acids HI H2SO4 H3PO4 O Carboxylic acids R C O H

..

H H with acidic Common acids (materials H H H protons) used or found in organic H .. chemistry:
. . . H O. H Phenols -. . C C .. C H . . . . H H O O H O H H C C C H

.. . . . . H O . . H O H H . O. H . . . . . . . H . H - . in Organic H O Acids & Bases Chemistry H O R O H R C O H .C C C H H C C C H -.

.C C C H H C C C H

H ..

O C

H H Alcohols O H

H
.. R C

H O H O H H Terminal Alkynes . . . . O H H . O. H
C C H H C C C H

Water

Acids & Bases in Organic Chemistry H H

H - .. C C

H C H

H C

C ..

Common bases (or basic substances) used or found in organic chemistry: O H

O H

R ..
R

Hydroxide ion NaOH or KOH

H
H

O
O

R
R

Alkoxide ions Sodium methoxide

H + CH3O Na
+

Sodium ethoxide Potassium t-butoxide

CH3CH2O Na

CH3 CH3CO K CH3

+

H . O. H - .. C

C C in H Organic H C C C H Acids & Bases Chemistry

. H . O. H H

Common bases used (or basic substances) .. O H used or found in organic chemistry: CH

NH3 H H

Sodium hydride
NaH Sodium amide H H

+ O H CH CO K 3 N NaH

Amines or ammonia O

H NaNH 2

CH3

(CH3CH2)3N

NH3

Carbanions

CH3CH2O Na

..CH3 + R C CH2O Na + CH R' 3 R"

CH3

CH3CO Na

CH

Acids & Bases in Organic Chemistry

Example: Complete the following acid-base reactions.
Ca(OH) + HCl HCl Ca(OH) + 2 2 Ca(OH) + Ca(OH) + HCl HCl 22 CH CO H+ + NaOH NaOH CH CO H + NaOH 3 2 CH CO H 3 2 CH CO H + NaOH 33 22 NaH + + CH CH CH OH NaH + CH OH 3 2 NaH CH OH 3 2 NaH + CH CH CH OH 33 22 CH C CH CH + + NaNH NaNH CH C CH + NaNH CH C 3 3 22 CH C CH + NaNH 33 22

Lewis Acids and Bases

Other Lewis Acids: BF3 ZnCl2 FeBr3

Have Available Acceptor Orbital Other Lewis Bases: R-OH Br2

Have Lone Pair to Donate

Lewis Acid/Base Reactions Essentially Electrostatic

(Opposite Charges Attract)

Lewis Acids & Bases

Other good examples involve metal ions.
Co
2+

OH H BASE

Co

2+

OH H

ACID

Such bonds as the H2O ---> Co bond are often called COORDINATE COVALENT BONDS because both electrons are supplied by one of the atoms of the bond.

Lewis Acids & Bases

The combination of metal ions (Lewis acids) with Lewis bases such as H2O and NH3 ------>

COMPLEX IONS

All metal ions form complex ions with water and are of the type [M(H2O)x]n+ where x = 4 and 6.

[Cu(NH3)4]2+

Lewis Acids & Bases

Add NH3 to light blue [Cu(H2O)4]2+ -----> light blue Cu(OH)2 and then deep blue [Cu(NH3)4]2+

Acids & Bases in Organic Chemistry

Examples of Lewis Acid/Base Reactions
H O CH3C Lewis base H + H Cl O CH3C H + Cl

Lewis acid

O CH3C H
Lewis acid

O + CH3O
Lewis base

CH3C H OCH3

Type of Reaction in Organic Chemistry

Substitution:
Addition:

H3C

Cl

NaOH

H 3C

OH

NaCl

Br Br2 Br

Elimination: Rearrangement:

Br

-HBr

Fundamental Reaction Types based on mechanism

Elementary Mechanisms:
Decomposition (Cycloaddition) Pericyclic

Recombination

Rearrangement

Complex Mechanisms:
Insertion
Elimination

Addition
Substitution

Decomposition Reaction
A
ONO2 O2NO ONO2 CO2 + H 2 O + NO 2

B + C + D +...

Br

Br

Recombination Reaction
A+B
Cl +

C
Cl2

Cl

OH

OH

Pericyclic Reaction (Cycloaddition)

A-B + C-D A C B D

Rearrangement Reaction
A N C O
1 2 7 6 3 4 5 7 6 1 2

B C N O
3 4 5

Insertion Reaction
A-B=C + D D A :CH2 B C

Addition Reaction
A-B + C-D H Br A C B D H Br

Substitution Reaction
A + B-C A-B + C

Br

Br

Elimination Reaction
B +
base

B-H

+
alkene

X +

OH

Cl H2O

Cl