Introduction to Organic Chemistry

Advancem

ent

SpeculativeScience

Plato440 BC4 elements

Wöhler1828

Schrödinger1926

Gibbs 1873

DigitalComputers

1960

EmpiricalScience

QuantitativeScience

ExactScience

Organic Chemistry

Structure

Stability

Reactions

Reactivity

Energetics

statics dynamics

StructureSkeleton

Functional groups

O

OHO

CH3

O

Aspirin

Reactions

Reaction types

HO

HC O

H O

H

NucleophilElectrophil

Opposit charges attack by electrostatic attraction

+ -

Reagent types

C X

+

Y C Y + X

C C

+

XY C CX Y

Substitution

AdditionElimination

Electronegativity and its consequences

Electronegativity values for selected elements of the Periodic Table.

Li Be B C N O F

1.0 1.5 2.0 2.5 3.0 3.5 4.0

Na Mg Al Si P S Cl

0.9 1.2 1.5 1.8 2.1 2.5 3.0

K Br

0.8 2.8

H

2.1

= 1 - e -1/4[(EN)]2

1.1

Li H

1.9

H F

0.7

H O H

EN = f(IP + EA)

2

11.8

f 12.2

>>

C

Alkyl C C

Alkenyl

(vinylic)

C C

Alkynyl

Phenyl

C OH

Alcohol

OC C

Ether

O

C

C

Ketone C O

H

C

Aldehyde

C O

HO

C

Carboxylic Acid

C O

O

C

C

Ester

N

Amine C O

N

C

Amide

N

O

Nitroso

N

O

O

Nitro

N OH

Hydroxylamino N N

Azo

C C

O

Enol

C C

N

Enamine

Si

Silyl Si O

Siloxy

P

Phosphine P O

O

OO

Phosphate

S

H

Mercaptan S

C

C

Sulfide

SO

Sulfoxide* S

O

O

Sulfone*

SO

OO

H

Sulfonic acid* S

N

OO

Sulfonamide*

F Fluoride Cl Chloride

Br Bromide I Iodide

CC CC CC OH

OC C

O

C

CC O

H

C

C O

HO

C

C O

O

C

C

N C O

N

C

N

O

N

O

ON OHN NC C

O

C C

NC LiC NaC KC CuC BC AlC MgC Mg XC ZnC HgC SnC Pb

C Li

Organo-lithium C Na

Organo-sodium

C K

Organo-potassium C Cu

Organo-copper

C B

Organo-borane C Al

Organo-aluminum

C Mg

Organo-magnesium C Mg X

Organo-magnesium halide

C Zn

Organo-zinc C Hg

Organo-mercury

C Sn

Organo-tin C Pb

Organo-lead

Skeletons

C OHO(-)

(ion-dipole)

C O

H

O

H (dipole-dipole)

H O

H

C O

(hydrogen bond)

Ne Ne

Van der Waals interaction

A + B A B

A(+) + B (-)

A (-) + B (+)

homolyticdissociation

heterolyticdissociation

Organic Reactions. Acids and Bases

C X + Y C Y + XS

C C + XY C CAd

EX Y

C Cl HO C Cl(-) HO CSN2 : Cl(-)OH(-)

C Cl OH(-)C Cl(-) HO C OHCOH(-) + Cl(-)+SN1 : ++

(+)

C O C

O

OH

C

OH

OH+OH(-)

(-)

AdN:

C C H Cl C CH Cl(-) C C ClH++AdE: (+)

C CCl(-)H2O C CH Cl H2O C CH H3O+Cl(-)+ + ++E1: (+) +

C CHO(-) C CH Cl C C H2O Cl(-)

HHO(-)

Cl+ +E2: +

HO (-) +C Cl+ C Cl(-)HOSN2:

H Cl+ C Cl(-)CC C +

H (+)AdE:

HO (-) C Cl C Cl(-)H2OCH + C+ +E2:

H3N: + Hᵟ+- Clᵟ- H4N+ + Cl-

Base1 Acid2 Acid1 Base2

The Brønsted-Lowry model:

A H is a proton donor acid

: B is a proton accepting base

: :A H B A H B A H B

H bondedAcid Base Base Acid

complex

Lewis model

:A B A B

Lewis complex

Forward lewis

Reverse lewis

H3N: + Hᵟ+- Clᵟ- H4N+ + Cl-

Base1 Acid2 Acid1 Base2

Serine

C

H

N

H

C

O

H3C C

NH

CH3

O

H2C O

H

+

-

C

H

N

H

C

O

H3C C

NH

CH3

O

H2C O

+

H

-

A hydrogen bonded or A Lewis complex

Brønsted-Lowry complex (charge transfer interaction)

R C

O

O

Et

+

-H O

H

HR C

O

OH

Et

OH

H

R C

O

OH

Et

OH

H

R C

O

O

Et

O H

H

H

R C

OH

OH OH

H

R C

OH

O+H3O

Lewis Base

Bronsted Acid Bronsted Base

Lewis Acid

Bronsted Acid

Bronsted Base

Bronsted Base

Bronsted Acid

LewisComplex

Bronsted Acid

Base

Base

Acid

Acid

Inverse

Lewis Acid/Base

O

C C O C is losing electron (partially)

H

C C H C is gaining electron (partially)

C C e C is losing electron (completely)

C e C C is gaining electron (completely)

OX RED

Oxygen gain lost

Hydrogen lost gain

Electron lost gain