Introduction and Review

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 1

Organic Chemistry, 5th Edition

L. G. Wade, Jr.

ORGANIC CHEMISTRY

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 2

STUDY OF CARBON-CONTAINING COMPOUNDS

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 3

Classification of Matter

FIRE AGE - BASED ON COMBUSTION

COMBUSTIBLES - FUELS FROM ANIMALS AND PLANTS

OIL, WOOD, FAT

NON-COMBUSTIBLES -DIDNÕT BURN; PUT OUT FIRES

SAND, WATER, ROCKS

CLASSIFICATION OF MATTER

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 4

BERZILIUS’ DEFINITIONS

ORGANIC COMPOUNDS

CHARACTERISTIC PRODUCTS OF LIVING ORGANISMS

SUBSTANCES LIKE SUGAR AND OLIVE OIL

INORGANIC COMPOUNDS

PRODUCTS FROM NON-LIVING ENVIRONMENT

SUBSTANCES LIKE WATER AND IRON

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 5

Vital Force Theory

INORGANIC MATERIALS COULD BE CONVERTED

TO ORGANIC MATERIALS IN THE PRESENCE OF A

VITAL FORCE FOUND ONLY IN LIVING BODIES.

Woehler’s urea synthesis

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 6

Ammonium isocyanate + heat ------> urea

NH4CNONH2CONH2

“I have been able to make urea without aid of kidney

of man or dog.

1828

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 7

Post 1828

•Over 18,000 million compounds have been synthesized

•Pharmaceuticals

•Biochemicals

•Plastics

•Agrichemicals

•Paints

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 8

Why so many organic?

H O N X P S Se

FORMS COVALENT BONDS WITH MANY METALS

Li Mg Al Cd Fe

FORMS COVALENT BONDS WITH NON-METALS

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 9

AND

WITH ITSELF

CC

CC

C

CHAINS

CCH

CCH

C

CHAINS WITH BRANCHES

CC

C

C

C

C

C

C

RINGS

No limit

Atomic Structure

protons, neutrons, and electrons

isotopes

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 10

C12

6 6C

14

=>

Atomic Orbitals

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 11

2s orbital (spherical)

2p orbital =>

Electronic Configurations

Aufbau principle:

Place electrons

in lowest energy

orbital first.

Hund’s rule:

Equal energy

orbitals are half-

filled, then

filled.lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 12

=>

Table 1-1

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 13 =>

Bond Formation

Ionic bonding: electrons are transferred.

Covalent bonding: electron pair is shared.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 14

=>

Lewis Structures

Bonding electrons

Nonbonding electrons or lone pairs

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 15

Satisfy the octet rule! =>

C

H

H

H

OH

The octet rule is a chemical rule of thumb that reflects

observation that atoms of main-group elements tend to

combine in such a way that each atom has eight electrons in

its valence shell, giving it the same electronic configuration as

a noble gas.

TIPS

Neutral atoms

Carbon 4 bonds (double bonds count as 2 triple bonds count as 3) and NO lone pairs.

Nitrogen 3 bonds and one lone pair

Oxygen 2 bonds and two lone pairs

BORON 3 bonds BUT no lone pairs

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 16

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 17

TIPS2

C H-H+

CH- -

C+

N H-H+

N+H+

N HH+

O

H-H+

O+H+

O

H+

H

Multiple Bonding

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 18

=>

EXAMPLES

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 19

CO2SO2 C2H3N

C3H6O isomer problem

Dipole Moment

Amount of electrical charge x bond length.

Charge separation shown by electrostatic potential map (EPM).

Red indicates a partially negative region and blue indicates a partially positive region.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 20

C CH

H H

H

=>

Electronegativity and Bond

Polarity

Greater EN means greater polarity

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 21=>

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 22

EXAMPLES OF BOND POLARITY

C------BrC-------Li

C-------NBr--------Cl

Calculating Formal Charge

For each atom in a valid Lewis structure:

Count the number of valence electrons

Subtract all its nonbonding electrons

Subtract half of its bonding electrons

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 23

C

H

H

H

C

O

O P

O

OO

O

3-

=>

Ionic Structures

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 24

C

H

H

H N

H

H

H

+

Cl-

Na O CH3 or O CH3Na+

_

X

=>

Consider writing Lewis structure for NO3-2

The real structure is a resonance hybrid. All the bond lengths are the same. Each oxygen has a -1/3 electrical charge.

=>

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 25

N

O

OO

_ _

N

O

OO

_

N

O

OO

Resonance - More than one

Lewis Diagram

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 26

Resonance Rules

Must be legitimate Lewis structures

N

CH3

H3C

CH3

CH2+

-

N

CH3

H3C

CH3

CH2

NO NO Pentavalent nitrogen atom!!

Resonance structures?

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 27

N

O

O

: N

O

O

:

OK

C

H

H

H

O

H

C

H

HOH

H

NO NO

Only electrons can be moved (usually lone pairs or pi electrons).

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 28

Nuclei positions and bond angles remain the same.

C=C-C+ +C-C=C

The number of unpaired electrons remains the same

H3C CH3

..H3C CH3

. .

NO NO

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 29

DELOCALIZATION OF CHARGE

USUALLY IS STABILIZING

Delocalization of charge results in fractional charges

at alternate atoms

Major Resonance Form

has as many octets as possible.

has as many bonds as possible.

has the negative charge on the most electronegative

atom.

has as little charge separation as possible.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 30

Example=>

Major Contributor?

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 31

C

H

H

N

H

H

+C

H

H

N

H

H

+

major minor,

carbon does

not have octet.

=>

Chemical Formulas

Full structural formula (no lone pairs shown)

Line-angle formula

Condensed structural formula

Molecular formula

Empirical formula

CH3COOH

C2H4O2

CH2O =>

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 32

C

H

H

H

C

O

O H

OH

O

BrØnsted-Lowry Acids

and Bases

Acids can donate a proton.

Bases can accept a proton.

Conjugate acid-base pairs.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 33

CH3 C

O

OH + CH3 NH2 CH3 C

O

O-

+ CH3 NH3+

=>

acid base conjugate

base

conjugate

acid

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 34

EXAMPLES

CH3CO2H+ :NH3 CH3CO2

- + NH4+

ACID

BASE

CONJ BASE

CONJ ACID

H3C

O:

OH

+ H2SO4H3C

OH

OH

++ -HSO4

Amphoterism - ability to behave as an acid or base

Acid and Base Strength

Acid dissociation constant, Ka

Base dissociation constant, Kb

For conjugate pairs, (Ka)(Kb) = Kw

Spontaneous acid-base reactions proceed from stronger to weaker.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 35

CH3 C

O

OH + CH3 NH2 CH3 C

O

O-

+ CH3 NH3+

pKa 4.74 pKb 3.36 pKb 9.26 pKa 10.64

=>

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 36

EXAMPLES

Will NaOH neutralize phenol (C6H5OH)?

NaOH +

C6H5OH

HOH+

C6H5ONa

pKa = 10 pKa = 15.7

_-OH

C6H5OH

HOH + C6H5O-+

YES!!

Weaker acidStronger acid

Determining Relative Acidity

Electronegativity

Size

Resonance stabilization of conjugate base

=>

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 37

Electronegativity

As the bond to H becomes more polarized, H becomes more positive and

the bond is easier to break.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 38

=>

Size

As size increases, the H is more loosely held and the bond is easier to break.

A larger size also stabilizes the anion.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 39

=>

Resonance

Delocalization of the negative charge on the conjugate base will stabilize the anion, so the substance is a stronger acid.

More resonance structures usually mean greater stabilization.

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 40

CH3CH2OH < CH3C

O

OH < CH3 S

O

O

OH

=>

Lewis Acids and Bases

Acids accept electron pairs = electrophile

Bases donate electron pairs = nucleophile

lectuer 1 ..Assist.Prof.Dr.Mohanad Mousa Kareem 41

CH2 CH2 + BF3 BF3 CH2 CH2+_

nucleophile electrophile

=>