Chemistry 31

Structural Effects
UNIVERSITY OF THE PHILIPPINES MANILA
Padre Faura, Ermita, Manila SS, 2009 2010
Ms. Anjelyn del Rosario
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Structural Effects
Types of Structural Effects
A. Electronic Effects - affect electron distribution in a molecule
Electron release or Electron-donating designated by a plus (+) because it increases electron density in certain parts of the molecule Electron withdrawal or Electron-accepting - designated by negative (-) because it decreases electron density in certain parts of the molecule

B. Steric Effect - generally associated with the presence of bulky groups resulting to crowding or congestion in a molecule. chem31 adr

Electronic Effects
1. Pi electron delocalization or Resonance
a. Electron Release Through Resonance, +R
present whenever an atom with at least one lone pair is bonded directly to benzene ring.
Groups exhibiting +R:

.. .. .. .. .. .. - OH, -OR, -NH2, -NHR, -NR2, -X: (Br, Cl) .. .. ..

electron delocalization enriches the ortho, para positions of the benzene ring. The ortho and para positions are likely to be attacked by electron-loving reagents.
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Electronic Effects
1. Pi electron delocalization or Resonance
b. Electron Withdrawal through Resonance, -R
Present whenever the substituent has an atom that is multiply bonded to a more electronegative atom
Groups exhibiting R:

-NO2 , -C(=O)H, -C(=O)R, -CN, -SO3H, -C(=O)OH, -C(=O)OR, -C(=O)NH2

The effect of electron delocalization in this case is to deplete the electron density at ortho and para positions. Ortho and para positions are likely to be attacked by nucleus(+) loving reagents.
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Electronic Effects
2. Sigma electron delocalization or Hyperconjugation
Involves delocalization of sigma electrons from C-H bond of the sp3-s type, that has a neighboring atom with p orbitals
there is considerable overlap between sp3 orbital (75% p) and unhybridized p (100% p).

Does not take place as readily as electron delocalization The greater the number of contributing structures, the greater the influence on electron distribution.

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Stabilization of Carbocation

Stabilization of Carbocation

Electronic Effects
3. Inductive Effect
Result in distortion of electron cloud because of the presence of strong electronegative groups or atoms, electron-repelling groups that have highly polarizable outermost electrons.

a. Electron Attracting Inductive Effects (-I)

i. Groups with excess (+ ) charge R-N-R -S-R -NH3+ -NO2+ R R ii. Electronegative atoms/ groups -NH2 , -OH , -NO2 , -OCH3 , -F , -O , -N , -Cl , -Br iii. Orbital Electronegative groups -CCH , -CN , -NN , phenyl iv. Polarizable outermost electrons -I
8

Electronic Effects
3. Inductive Effect
Result in distortion of electron cloud because of the presence of strong electronegative groups or atoms, electron-repelling groups that have highly polarizable outermost electrons.

b. Electron- Repelling Inductive Effects (+I)

Exhibited by alkyl groups and those that possess excess negative charge

i. Alkyl Groups ii. Negative Groups .. .. - , -O: -COOH , -S: .. ..

Electronic Effects
4. Steric Effects
These are structural effects as a result of the presence of bulky groups Bulky groups result in congestion in the molecule Congestion is relieved by twisting of bonds groups will be forced out of plane. electron distribution is affected

Experimental Observations and Structural Effects

1. Physical Properties a. Dipole Moment b. Boiling Point c. Melting Point d. Solubity 2. Chemical Properties a. Acidity b. Basicity
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Introduction to Organic Molecules

Intermolecular Forces
Intermolecular forces are also referred to as noncovalent interactions or nonbonded interactions. There are several types of intermolecular interactions. Ionic compounds contain oppositely charged particles held together by extremely strong electrostatic inter-actions. These ionic inter-actions are much stronger than the intermolecular forces present between covalent molecules.

Introduction to Organic Molecules

Intermolecular Forces Covalent compounds are composed of discrete molecules.

The nature of the forces between molecules depends on the functional group present. There are three different types of interactions, shown below in order of increasing strength:
van der Waals forces dipole-dipole interactions hydrogen bonding

Intermolecular Forces
Intermolecular Forces van der waals
van der Waals forces are also known as London forces. They are weak interactions caused by momentary changes in electron density in a molecule. They are the only attractive forces present in nonpolar compounds.
Even though CH4 has no net dipole, at any one instant its electron density may not be completely symmetrical, resulting in a temporary dipole. This can induce a temporary dipole in another molecule. The weak interaction of these temporary dipoles constituents van der Waals forces.

Intermolecular Forces
Intermolecular Forces van der waals All compounds exhibit van der Waals forces. The surface area of a molecule determines the strength of the van der Waals interactions between molecules. The larger the surface area, the larger the attractive force between two molecules, and the stronger the intermolecular forces.

Intermolecular Forces
Intermolecular Forces van der waals
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
Intermolecular Forces Dipole-dipole Interactions Dipoledipole interactions are the attractive forces between the permanent dipoles of two polar molecules. Consider acetone (below). The dipoles in adjacent molecules align so that the partial positive and partial negative charges are in close proximity. These attractive forces caused by permanent dipoles are much stronger than weak van der Waals forces.

Intermolecular Forces
Intermolecular Forces H-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.

Intermolecular Forces
Intermolecular Forces H-bonding
Note: as the polarity of an organic molecule increases, so does the strength of its intermolecular forces.

Dipole Moments
Compound
1. Ethyl chloride

Dipole Moment
2.05 D

Compound
7. Methanal

Dipole Moment
2.37 D

2. Vinyl chloride

1.44 D

8. Propanal
9. Methyl bromide

2.73 D
1.79 D 1.88 D

3. Benzene 4. Nitrobenzene

10. Ethyl Bromide

3.95 D

11. Isopropyl bromide 2.04 D

5. toluene
6. 2,3,5,6tetramethylnitro benzene

0.37 D
3.62 D

Physical Properties
Physical PropertiesBoiling Point
The boiling point of a compound is the 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
Physical PropertiesBoiling Point
Consider the example below. Note that the relative strength of the intermolecular forces increases from pentane to butanal to 1butanol. 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
Physical PropertiesBoiling Point
Consider the examples below which illustrate the effect of size and polarizability on boiling points.

Physical Properties
Physical PropertiesBoiling Point
Liquids having different boiling points can be separated in the laboratory using a distillation apparatus, shown in Figure 3.4.

Boiling Point and Melting Point

Physical Properties
Factors Affecting Boiling Point and Melting Point
1. Molecular Weight The higher the molecular weight, the higher the melting point and boiling point. a. The hydrocarbon chain gets longer, LDF gets stronger b. The molecules get denser and find it difficult to volatilize due to the effect of gravitational force
2. Branching The more branched a compound is, the lower the boiling point a. The surface area for interaction gets shorter b. The molecule cannot get close enough for stronger interaction

Boiling Point and Melting Point

Physical Properties
Factors Affecting Boiling Point and Melting Point
3. Polarity The more polar the compound, the stronger the dipole-dipole interactions, the higher the boiling point and melting point.
4. Molecular Symmetry Symmetrical molecules have lower boiling point than their asymmetrical counterparts The dipole moment in symmetrical molecules cancel out so that as a whole the molecules become nonpolar and therefore tend to form weaker interaction. 5. Intramolecular H-Bonding The presence of intramolecular H-Bonding decreses boiling point or meting point.

Boiling Point
Compound
1. Alkanes propane n-butane n-pentane isopentane neopentane -42.07C 0.50 36.07 27.85 9.50

Boiling Point

Compound
3. Alkynes

Boiling Point
-84 -23.22 8.07 40.18 71.33 80.09 182

Ethyne Propyne 1-butyne 1-pentyne 1-hexyne

2. Alkenes
ethene propene -103.71 -47.70

4.

Aromatics
Benzene Phenol

1-butene
1-pentene 1-hexene

-6.26
+29.97 +63.49

O-nitrophenol
P-nitrophenol toluene

214.5
279.0 110.6

aniline

184.4

Boiling Point
Compound
1. n-butyl amine 2. n-butyl alcohol 3. Diethyl ether 4. Butanal 5. Propanoic acid

MW Boiling Point
73 74 74 72 74 78C 118 35 76 141

6. Butanoic acid
7. n-pentyl alcohol

88
88

164
138

Physical Properties
Physical Properties Melting Point
The melting point is the 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
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
Physical Properties Melting Point
The trend in melting points of pentane, butanal, and 1-butanol parallels the trend observed in their boiling points.

Physical Properties
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. A compact symmetrical molecule like neopentane packs well into a crystalline lattice whereas isopentane, which has a CH3 group dangling from a four-carbon chain, does not. Thus, neopentane has a much higher melting point.

Melting Point
Compound
1. o-hydroxybenzaldehyde 2. p-hydroxybenzaldehyde

Melting Point (K)

266 388

3. o-methoxybenzaldehyde 4. p-methoxybenzaldehyde
5. o-aminobenzaldehyde 6. p-aminobenzaldehyde

309 273
312 344

Physical Properties
Physical Properties Solubility
Solubility is the extent to which a compound, called a solute, dissolves in a liquid, called a 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
Physical Properties Solubility
Compounds dissolve in solvents having similar kinds of intermolecular forces.
Like dissolves like. Polar compounds dissolve in polar solvents. Nonpolar or weakly polar compounds dissolve in nonpolar or weakly polar solvents. 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). Most ionic compounds are soluble in water, but insoluble in organic solvents.

Physical Properties
Physical Properties Solubility
An organic compound is water soluble only if it contains one polar functional group capable of hydrogen bonding with the solvent for every five C atoms it contains. For example, compare the solubility of butane and acetone in H2O and CCl4.

Physical Properties
Physical Properties Solubility
Since butane and acetone are both organic compounds having a CC and CH backbone, they are soluble in the organic solvent CCl4. Butane, which is nonpolar, is insoluble in H2O. Acetone is soluble in H2O because it contains only three C atoms and its O atom can hydrogen bond with an H atom of H2O.

Physical Properties
Physical Properties Solubility
To dissolve an ionic compound, the strong ion-ion interactions must be replaced by many weaker ion-dipole interactions.

Physical Properties
Physical Properties Solubility
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 since it has a small carbon skeleton of five 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
Physical Properties Solubility
The nonpolar part of a molecule that is not attracted to H2O is said to be hydrophobic.
The polar part of a molecule that can hydrogen bond to H2O is said to be hydrophilic. In cholesterol, for example, the hydroxy group is hydrophilic, whereas the carbon skeleton is hydrophobic.

Physical Properties
Physical Properties Solubility

Factors Affecting Solubility in Water

1. Nature of the Solute RCOOH, ROH, RNH2 > RCHO, RCOR > ROR > HC - with reciprocal H-bonding
2. Carbon- Chain length Within a functional group, solubility in water decrease as molecular weight increases a. As MW , the carbon chain gets longer b. That portion being hydrophobic, solubility in water decreases and the compound instead becomes soluble in nonpolar solvents.

Physical Properties
Physical Properties Solubility

Factors Affecting Solubility in Water

3. Branching As the molecule becomes more branched, the solubility in water increases. As the extent of branching increases, the hydorphobic portion gets shorter and that favors the formation of H-bond with water.
4. Tendency to form intramolecular H-bond This decreases the tendency of the compound to form H-bond with water thus decreases its solubility in the solvent.

Physical Properties
Physical Properties Solubility 1. Alcohol four-carbon dividing line 2. Amines 1 > 2 > 3 3. Alkyl halides 4. Ethers

Physical Properties
Application - Vitamins
Vitamins are either lipid or water soluble.

Physical Properties
Application - Soap
Soap:

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

Physical Properties
Application The cell membrane

Physical Properties
Application The 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.

Physical Properties
Application The cell membrane
Transport Across a Cell Membrane:

Physical Properties
Application The 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.

Physical Properties - Solubility

Exercise:
Rank the following groups of compounds in order of decreasing solubility in water:

Aromaticity
Criteria for Aromaticity Aromatic compounds are particularly stable.

Aromaticity
To be classified as aromatic, a compound must meet both of the following criteria:
1. It must have an uninterrupted cyclic cloud of electrons (often called a cloud) above and below the plane of the molecule. Lets look a little more closely at what this means:
For the cloud to be cyclic, the molecule must be cyclic. For the cloud to be uninterrupted, every atom in the ring must have a p orbital. For the cloud to form, each p orbital must overlap with the p orbitals on either side of it. Therefore, the molecule must be planar.

2. The cloud must contain an odd number of pairs of electrons.

Aromaticity
Hckels rule, or the 4n +2 rule
for a planar, cyclic compound to be aromatic, its uninterrupted cloud must contain (4n+2) electrons, where n is any whole number. For a compound to be aromatic, it must be cyclic and planar and have an uninterrupted pi cloud of electrons. The cloud must contain an odd number of pairs of pi electrons.
Example: a. What is the value of n in Hckels rule when a compound has nine pairs of electrons? b. Is such a compound aromatic?

Aromaticity
Annulenes Monocyclic hydrocarbons with alternating single and double bonds A prefix in brackets denotes the number of carbons in the ring.

Aromatic?

Aromaticity
Exercise:
Which of the following compounds are aromatic?

Aromaticity
Aromatic Heterocyclic Compounds
A heterocyclic compound is a cyclic compound in which one or more of the ring atoms is an atom other than carbon.

Aromaticity

Aromaticity
Antiaromaticity
Antiaromatic compounds are highly unstable. Aromaticity is characterized by stability, whereas antiaromaticity is characterized by instability.

Antiaromatic Compounds
it must be a planar, cyclic compound with an uninterrupted ring of p orbital-bearing atoms, and the cloud must contain an even number of pairs of electrons.

Aromaticity
Antiaromatic Compounds
it must be a planar, cyclic compound with an uninterrupted ring of p orbital-bearing atoms, and the cloud must contain an even number of pairs of electrons.

Aromaticity

Aromatic compounds are stable because they have filled bonding molecular orbitals.