Organic Chemistry

Chapter 1 Introduction to Organic Molecules and Functional Group

1.1 FUNCTIONAL GROUP

A functional group is an atom or a group of atoms with
characteristic chemical and physical properties. It is the reactive part of the molecule.

Most organic compounds have CC and CH bonds.

However, many organic molecules possess other structural features: Heteroatoms atoms other than carbon or hydrogen.

Bonds - the most common bonds occur in CC and CO double bonds. These structural features distinguish one organic molecule from another. They determine a molecules geometry, physical properties, and reactivity, and comprise what is called a functional group.

Heteroatoms and bonds confer reactivity on a

particular molecule. Heteroatoms have lone pairs and create electrondeficient sites on carbon. Bonds are easily broken in chemical reactions. A bond makes a molecule a base and a nucleophile.

CC and CH bonds are important. They form the carbon backbone or skeleton to which the functional group is attached.

Ethane: This molecule has only CC and CH bonds, so it

has no functional group. Ethane has no polar bonds, no lone pairs, and no bonds, so it has no reactive sites. Consequently, ethane and molecules like it are very unreactive.

Ethanol: This molecule has an OH group attached to its

backbone. This functional group is called a hydroxy group. Ethanol has lone pairs and polar bonds that make it reactive with a variety of reagents.

The hydroxy group makes the properties of ethanol very different from the properties of ethane.

1.2 AN OVERVIEW OF FUNCTIONAL GROUP

Most common functional group:

a) b) c)

Hydrocarbon Compounds containing C - Z bond Compounds containing C = O group

Functional Groups: Hydrocarbon

a) Hydrocarbon
Hydrocarbons are compounds made up of only the elements carbon and hydrogen. They may be aliphatic or aromatic.

Functional Groups: Hydrocarbon

Aromatic compounds are so named because many of

the earliest known aromatic compounds had strong characteristic odors. The simplest aromatic hydrocarbon is benzene. The sixmembered ring and three bonds of benzene comprise a single functional group. When a benzene ring is bonded to another group, it is called a phenyl group.

Functional Groups: C-Z Bonds

b) C-Z Bonds
Examples of Molecules Containing C-Z Bonds

C-Z Bonds

Functional Groups: Hydrocarbon

Functional Groups: C=O Group

c) C=O Group
Compounds Containing the C=O Group:
This group is called a carbonyl group. The polar CO bond makes the carbonyl carbon an
electrophile, while the lone pairs on O allow it to react as a nucleophile and base.

The carbonyl group also contains a bond that is more

easily broken than a CO bond.

Functional Groups: C=O Group

Molecules Containing the C=O Functional Group

Functional Groups: C=O Group

Functional Groups

Remember
It should be noted that the importance of a functional group cannot be overstated. A functional group determines all of the following properties of a molecule:
1. bonding and shape
2. type and strength of intermolecular forces 3. physical properties 4. nomenclature 5. chemical reactivity

1.3 Intermolecular Forces

Intermolecular forces: Interaction exist between
molecules

Ionic compounds contain

oppositely charged particles held together by extremely strong electrostatic interactions. These ionic interactions are much stronger than the intermolecular forces present between covalent molecules.

Intermolecular Forces

3 different types of interactions:

a) van der Waals forces b) dipole-dipole interactions
strength increased

c) hydrogen bonding

Intermolecular Forces-van der Waals Forces

a) van der Waals Forces

Also known as London forces. Weak interactions caused by momentary
changes in electron density in a molecule.

Only attractive forces present in nonpolar

compounds.

Intermolecular Forces-van der Waals Forces

eg:

CH4 has no net dipole Its electron density may not be completely
symmetrical- created temporary dipole.

Will induce a temporary dipole in another molecule. Weak interaction of these temporary dipoles
constituents van der Waals forces.

Intermolecular Forces-van der Waals Forces

All compounds exhibit van der Waals forces. The surface area of a molecule determines the strength
of the interactions between molecules.

The larger the surface area, the larger the attractive

force between two molecules, and the stronger the intermolecular forces.

Intermolecular Forces-van der Waals Forces

van der Waals forces are also affected by

polarizability.

Polarizability is a measure of how the electron

cloud around an atom responds to changes in its electronic environment.

Larger atoms, like

iodine, which have more loosely held valence electrons, are more polarizable than smaller atoms like fluorine, which have more tightly held electrons. Thus, two F2 molecules have little attractive force between them since the electrons are tightly held and temporary dipoles are difficult to induce.

Intermolecular Forces-van der Waals Forces

Intermolecular Forces-dipole-dipole int.

b) Dipole-Dipole Interactions
Dipole-dipole interactions are the attractive forces
between the permanent dipoles of 2 polar molecules. Eg: Acetone (below). The dipoles in adjacent molecules align so that the partial +ve and partial -ve charges are in close proximity. These attractive forces caused by permanent dipoles are much stronger than weak van der Waals forces.

Intermolecular Forces-hydrogen bonding

c) Hydrogen Bonding
Hydrogen bonding typically occurs when a
hydrogen atom bonded to O, N, or F, is electrostatically attracted to a lone pair of electrons on an O, N, or F atom in another molecule.

The strongest of them all.

Intermolecular Forces

Summary of Intermolecular Forces

Note: as the polarity of an organic molecule increases, so does the strength of its intermolecular forces.

Intermolecular Forces

APPLICATION-Nylon
Nylon-

is a polymer, composed from small units-called monomers-to form large organic molecule Monomer are covalently bonded to each other in repeating pattern Its long chain held by hydrogen bonding

1.4 PHYSICAL PROPERTIES

Strength

of compounds intermolecular determine by: a) Boiling point b) Melting point c) Solubility

Physical Properties: Boiling Point

a) Boiling point
The boiling point of a compound: temperature at which liquid
molecules are converted into gas.

In boiling, energy is needed to overcome the attractive forces

in the more ordered liquid state.

The stronger the intermolecular forces, the higher the

boiling point.

For compounds with approximately the same molecular

weight:

Physical Properties: Boiling Point

Eg 1: Note that the relative strength of the intermolecular forces increases from pentane to butanal to 1-butanol. The boiling points of these compounds increase in the same order.

For two compounds with similar functional groups:

The larger the surface area, the higher the boiling point. The more polarizable the atoms, the higher the boiling
point.

Physical Properties: Boiling Point

Eg 2: Figure below illustrate the effect of size and polarizability on boiling points.

Physical Properties: Boiling Point

Liquids with different boiling points can be separated in the laboratory using a distillation apparatus, showed below

Physical Properties: Melting Point

b) Melting point
The melting point: temperature at which a solid is
converted to its liquid phase.

In melting, energy is needed to overcome the attractive

forces in the more ordered crystalline solid.

The stronger the intermolecular forces, the higher the

melting point.

Given the same functional group, the more symmetrical

the compound, the higher the melting point.

Physical Properties: Melting Point

Because ionic compounds are held together by

extremely strong interactions, they have very high melting points.

With covalent molecules, the melting point depends

upon the identity of the functional group. For compounds of approximately the same molecular weight:

Physical Properties: Melting Point

The trend in melting points of pentane, butanal, and 1butanol parallels the trend observed in their boiling points.

Physical Properties: Melting Point

Symmetry also plays a role in determining the melting

points of compounds having the same functional group and similar molecular weights, but very different shapes.

neopentane packs well into a crystalline lattice whereas

isopentane, which has a CH3 group dangling from a fourcarbon chain, does not. Thus, neopentane has a much higher melting point.

Physical Properties: solubility

c) Solubility

Solubility is the extent to which a compound

(solute), dissolves in a liquid (solvent).

In dissolving a compound, the energy

needed to break up the interactions between the molecules or ions of the solute comes from new interactions between the solute and the solvent.

Physical Properties: solubility

Like dissolve Like

Polar compounds dissolve in polar solvents. Nonpolar or weakly polar compounds dissolve in
nonpolar or weakly polar solvents.

Physical Properties: solubility-solvent

Water and organic solvents are two different

kinds of solvents.

Water is very polar since it is capable of

hydrogen bonding with a solute.

Many organic solvents are either nonpolar,

like carbon tetrachloride (CCl4) and hexane [CH3(CH2)4CH3], or weakly polar, like diethyl ether (CH3CH2OCH2CH3).

Physical Properties: solubility-ionic comp.

Most ionic compounds are soluble in water, but

insoluble in organic solvents. To dissolve an ionic compound, the strong ion-ion interactions must be replaced by many weaker iondipole interactions.

Physical Properties: solubility-organic comp.

Organic compound is soluble in organic solvent. An organic compound is water soluble only if it
contains one polar functional group (O @ N) capable of hydrogen bonding with the solvent for every 5 C atoms it contains.

Eg: Compare the Solubility of butane and acetone in

H2O and CCl4.

Physical Properties: solubility-organic comp.

Since butane and acetone are both organic compounds

Butane, which is nonpolar, is insoluble in H2O. Acetone is soluble in H2O because it contains 3 C atoms
and its O atom can hydrogen bond with an H atom of H2O.

having a CC and CH backbone, they are soluble in the organic solvent CCl4.

Physical Properties: solubility-organic comp.

The size of an organic molecule with a polar functional

group determines its water solubility. A low molecular weight alcohol like ethanol is water soluble (small carbon skeleton of 5 C atoms), compared to the size of its polar OH group. Cholesterol has 27 carbon atoms and only one OH group. Its carbon skeleton is too large for the OH group to solubilize by hydrogen bonding, so cholesterol is insoluble in water.

Physical Properties: solubility

The nonpolar part of a molecule that is not

The polar part of a molecule that can

hydrogen bond to H2O is said to be hydrophilic.

attracted to H2O is said to be hydrophobic.

In cholesterol, for example, the hydroxy

group is hydrophilic, whereas the carbon skeleton is hydrophobic.

Solubility summary

end

Application

Application 1- Vitamins
Vitamins are either lipid or water soluble.

Application

Application 2- Soap

Soap molecules have two distinct parts: a hydrophilic portion composed of ions called the polar head a hydrophobic carbon chain of nonpolar CC and CH bonds, called the nonpolar tail.

Application: cell membrane

Application 3 - The Cell Membrane

Application: cell membrane

Transport Across a Cell Membrane: Polar molecules and ions are transported across cell membranes encapsulated within molecules called ionophores. Ionophores are organic molecules that complex cations. They have a hydrophobic exterior that makes them soluble in the nonpolar interior of the cell membrane, and a central cavity with several oxygens whose lone pairs complex with a given ion.

Application: cell membrane

Transport Across a Cell Membrane:

Application: cell membrane

Several synthetic ionophores have also been prepared, including one group called crown ethers. Crown ethers are cyclic ethers containing several oxygen atoms that bind specific cations depending on the size of their cavity.

1.5 Functional Groups and Reactivity

Recall that:

Functional groups create reactive sites in molecules. Electron-rich sites react with electron poor sites. All functional groups contain a heteroatom, a bond or both, and these features create electron-deficient (or electrophilic) sites and electron-rich (or nucleophilic) sites in a molecule. Molecules react at these sites.

Influence of Functional Groups on Reactivity

Influence of Functional Groups on Reactivity

An electron deficient carbon reacts with a nucleophile, symbolized as :Nu in reactions. An electron-rich carbon reacts with an electrophile, symbolized as E+ in reactions. For example, alkenes contain a CC double bond, an electron-rich functional group with a nucleophilic bond. Thus, alkenes react with electrophiles E+, but not with other electron rich species like OH or Br.

Influence of Functional Groups on Reactivity

On the other hand, alkyl halides possess an electrophilic carbon atom, so they react with electronrich nucleophiles.