U1

Organic Chemistry, 5th Edition L. G. Wade, Jr.
Definitions
Old: derived from living organisms New: chemistry of carbon compounds From inorganic to organic, Whler, 1828
O NH4 OCN
+ -
Chapter 1 Introduction and Review
heat
H2N C NH2 urea
=>
2
Jo Blackburn Richland College, Dallas, TX Dallas County Community College District 2003, Prentice Hall
Chapter 1
Atomic Structure
protons, neutrons, and electrons isotopes
12 6
Atomic Orbitals
14 6
C
=>
2s orbital (spherical) 2p orbital
Chapter 1
=>
4
Chapter 1
Electronic Configurations
Aufbau principle: Place electrons in lowest energy orbital first. Hunds rule: Equal energy orbitals are halffilled, then filled.
Chapter 1
Table 1-1
=>
5 Chapter 1 6
=>
Bond Formation
Ionic bonding: electrons are transferred. Covalent bonding: electron pair is shared.
Lewis Structures
Bonding electrons Nonbonding electrons or lone pairs
H H C O H
=>
Satisfy the octet rule!

7 Chapter 1 8
=>
Chapter 1
Multiple Bonding
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.
H H
=>
C C
H H
=>
Chapter 1 10
Chapter 1
Electronegativity and Bond Polarity

Greater EN means greater polarity
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
H O H C
=>
3-
O O
Chapter 1
C O
P O
O
=>
12
Chapter 1
11
Ionic Structures
H H H C N H H H + Cl
-
Resonance
Only electrons can be moved (usually lone pairs or pi electrons). Nuclei positions and bond angles remain the same. The number of unpaired electrons remains the same. Resonance causes a delocalization of electrical charge.
=>
13 Chapter 1
Na
O CH3
or Na
_
O CH3
Chapter 1
Example=>
14
Resonance Example
_ O N O O O _ O N O O O N O _
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.
Example=>
Chapter 1 16
The real structure is a resonance hybrid. All the bond lengths are the same. Each oxygen has a -1/3 electrical charge. =>
Chapter 1 15
Major Contributor?
H + H C N H H
major
Chemical Formulas
H O
Full structural formula (no lone pairs shown) Line-angle formula
OH
H C H
C O H
O
H + H C N H H
minor, carbon does not have octet. =>
Chapter 1 17
Condensed structural formula Molecular formula Empirical formula

Chapter 1
CH3COOH C2H4O2 CH2O =>

18
Calculating Empirical Formulas

Given % composition for each element, assume 100 grams. Convert the grams of each element to moles. Divide by the smallest moles to get ratio. Molecular formula may be a multiple of the empirical formula. =>
Chapter 1 19
Arrhenius Acids and Bases

Acids dissociate in water to give H3O+ ions. Bases dissociate in water to give OH- ions. Kw = [H3O+ ][OH- ] = 1.0 x 10-14 at 24 C pH = -log [H3O+ ] Strong acids and bases are 100% dissociated.
HCl 1M + H2O H3O+ 1M
Chapter 1
+ Cl
=>
20
Brnsted-Lowry Acids and Bases

Acids can donate a proton. Bases can accept a proton. Conjugate acid-base pairs.
O CH3 C OH + CH3 NH2 CH3 O C O
-
Acid and Base Strength

+ CH3 NH3
+
Acid dissociation constant, Ka Base dissociation constant, Kb For conjugate pairs, (Ka)(Kb) = Kw Spontaneous acid-base reactions proceed from stronger to weaker.
O CH3 C OH + CH3 NH2 CH3 O C O
-
acid
base
conjugate base
conjugate acid
CH3
NH3
pKa 4.74
pKb 3.36
Chapter 1
pKb 9.26
pKa 10.64
=>
Chapter 1 21
=>
22
Determining Relative Acidity

Electronegativity Size Resonance stabilization of conjugate base =>
Electronegativity
As the bond to H becomes more polarized, H becomes more positive and the bond is easier to break.
=>
Chapter 1 23 Chapter 1 24
Size
As size increases, the H is more loosely held and the bond is easier to break. A larger size also stabilizes the anion.
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.
O CH3CH2OH < CH3C OH < CH3 O S O
Chapter 1
OH
=>
Chapter 1 25
=>
26
Lewis Acids and Bases

Acids accept electron pairs = electrophile Bases donate electron pairs = nucleophile
CH2 CH2 nucleophile + BF3 electrophile
_
BF3
CH2
CH2
End of Chapter 1
=>
Wave Properties of Electrons

Standing wave vibrates in fixed location. Wave function, , mathematical description of size, shape, orientation Amplitude may be positive or negative Node: amplitude is zero
_
+ Chapter 1
Chapter 2 Structure and Properties of Organic Molecules
=>
30
Wave Interactions
Linear combination of atomic orbitals
between different atoms is bond formation on the same atom is hybridization.
Sigma Bonding
Electron density lies between the nuclei. A bond may be formed by s-s, p-p, s-p, or hybridized orbital overlaps. The bonding MO is lower in energy than the original atomic orbitals. The antibonding MO is higher in energy than the atomic orbitals. =>
Chapter 1 32
Conservation of orbitals Waves that are in phase add together. Amplitude increases. Waves that are out of phase cancel out. =>
Chapter 1 31
H2: s-s overlap
Cl2: p-p overlap

Constructive overlap along the same axis forms a sigma bond.
=> =>
HCl: s-p overlap

Question: Draw the predicted shape for the bonding molecular orbital and the antibonding molecular orbital of the HCl molecule.
Answer: See bottom of page 42 in your text. =>
Pi Bonding
Pi bonds form after sigma bonds. Sideways overlap of parallel p orbitals.
=>
Multiple Bonds
A double bond (2 pairs of shared electrons) consists of a sigma bond and a pi bond. A triple bond (3 pairs of shared electrons) consists of a sigma bond and two pi bonds.
Molecular Shapes
Bond angles cannot be explained with simple s and p orbitals. Use VSEPR theory. Hybridized orbitals are lower in energy because electron pairs are farther apart. Hybridization is LCAO within one atom, just prior to bonding. =>
=>
sp Hybrid Orbitals
sp2 Hybrid Orbitals

3 VSEPR pairs Trigonal planar e- pair geometry 120 bond angle
2 VSEPR pairs Linear electron pair geometry 180 bond angle
=> =>
sp3 Hybrid Orbitals

4 VSEPR pairs Tetrahedral e- pair geometry 109.5 bond angle
Sample Problems
Predict the hybridization, geometry, and bond angle for each atom in the following molecules: Caution! You must start with a good Lewis structure! NH2NH2 CH3-CC-CHO
O
=>
CH3
_ CH2
=>
Chapter 1 42
Chapter 1
41
Rotation around Bonds

Single bonds freely rotate. Double bonds cannot rotate unless the bond is broken.
Isomerism
Molecules which have the same molecular formula, but differ in the arrangement of their atoms, are called isomers. Constitutional (or structural) isomers differ in their bonding sequence. Stereoisomers differ only in the arrangement of the atoms in space. =>
43 Chapter 1 44
=>
Chapter 1
Structural Isomers
CH3 O CH3
CH3 and CH3
Stereoisomers
OH
Br C H3C C CH3 Br and H3C Br C C Br CH3
and
CH3
CH2
Cis - same side
Trans - across
Cis-trans isomers are also called geometric isomers. There must be two different groups on the sp2 carbon.
H H C C H
=>
Chapter 1 45
H3C
No cis-trans isomers possible

Chapter 1
=>
46
Bond Dipole Moments

are due to differences in electronegativity. depend on the amount of charge and distance of separation. In debyes, = 4.8 x (electron charge) x d(angstroms)
Molecular Dipole Moments

Depend on bond polarity and bond angles. Vector sum of the bond dipole moments. Lone pairs of electrons contribute to the dipole moment.
=>
Chapter 1
=>
47
Chapter 1
48
Intermolecular Forces
Strength of attractions between molecules influence m.p., b.p., and solubility; esp. for solids and liquids. Classification depends on structure.
Dipole-dipole interactions London dispersions Hydrogen bonding =>
Chapter 1 49
Dipole-Dipole Forces
Between polar molecules Positive end of one molecule aligns with negative end of another molecule. Lower energy than repulsions, so net force is attractive. Larger dipoles cause higher boiling points and higher heats of vaporization. =>
Chapter 1 50
Dipole-Dipole

London Dispersions
Between nonpolar molecules Temporary dipole-dipole interactions Larger atoms are more polarizable. Branching lowers b.p. because of decreased surface contact between molecules. CH
CH3
3
CH3
CH2
CH2
CH2
CH3
n-pentane, b.p. = 36C
CH3 CH CH2 CH3 isopentane, b.p. = 28C
H3C
CH3
CH3 neopentane, b.p. = 10C
=>
Chapter 1 51 Chapter 1
52
=>
Dispersions
Hydrogen Bonding
Strong dipole-dipole attraction Organic molecule must have N-H or O-H. The hydrogen from one molecule is strongly attracted to a lone pair of electrons on the other molecule. O-H more polar than N-H, so stronger hydrogen bonding =>
Chapter 1 54
=>
Chapter 1 53
H Bonds
CH3
Boiling Points and Intermolecular Forces

CH2 OH
CH3 O CH3
ethanol, b.p. = 78C

H3C N CH3 CH3 trimethylamine, b.p. 3.5C
dimethyl ether, b.p. = -25C

N CH3 H CH3CH2CH2 N H
CH3CH2
H propylamine, b.p. 49C ethylmethylamine, b.p. 37C
CH3
=>
Chapter 1 55
CH2
OH
CH3
Chapter 1
CH2
NH2
ethanol, b.p. = 78C
ethyl amine, b.p. 17C
=>
56
Solubility
Like dissolves like Polar solutes dissolve in polar solvents. Nonpolar solutes dissolve in nonpolar solvents. Molecules with similar intermolecular forces will mix freely. =>
Chapter 1 57
Ionic Solute with Polar Solvent
Hydration releases energy. Entropy increases.

Chapter 1
=>
58
Ionic Solute with Nonpolar Solvent
Nonpolar Solute with Nonpolar Solvent
=>
=>
60
Nonpolar Solute with Polar Solvent
Classes of Compounds
Classification based on functional group Three broad classes
Hydrocarbons Compounds containing oxygen Compounds containing nitrogen =>
=>
Chapter 1
61
Chapter 1
62
Hydrocarbons
Alkane: single bonds, sp3 carbons Cycloalkane: carbons form a ring Alkene: double bond, sp2 carbons Cycloalkene: double bond in ring Alkyne: triple bond, sp carbons Aromatic: contains a benzene ring =>
Chapter 1 63
Compounds Containing Oxygen

Alcohol: R-OH Ether: R-O-R' Aldehyde: RCHO Ketone: RCOR'
O CH3CH2 C H
O CH3 C CH3
=>
Chapter 1 64
Carboxylic Acids and Their Derivatives

Carboxylic Acid: RCOOH Acid Chloride: RCOCl Ester: RCOOR' Amide: RCONH2
O C NH 2
Chapter 1
Compounds Containing Nitrogen

O C OH
O C Cl
Amines: RNH2, RNHR', or R3N Amides: RCONH2, RCONHR, RCONR2 Nitrile: RCN CH3 C N O
N CH3
O C O C H3
=>
65 Chapter 1
=>
66
End of Chapter 2
Chapter 3 Structure and Stereochemistry of Alkanes
Chapter 1
67
Alkane Formulas
All C-C single bonds Saturated with hydrogens Ratio: CnH2n+2 Alkane homologs: CH3(CH2)nCH3 Same ratio for branched alkanes
H
Common Names
Isobutane, isomer of butane Isopentane, isohexane, etc., methyl branch on next-to-last carbon in chain. Neopentane, most highly branched Five possible isomers of hexane, 18 isomers of octane and 75 for decane!
=>
=>
69 Chapter 1 70
H H H H H C C C C H H H H H Butane, C4H10
Chapter 1
H C
H H H C C C H H H H Isobutane, C4H10
Pentanes
H H H H H H C C C C C H H H H H H n-pentane, C5H12
IUPAC Names
H H C H
H H H H C C C C H H H H H isopentane, C5H12
CH3 H3C CH3
C CH3
=>
71
Find the longest continuous carbon chain. Number the carbons, starting closest to the first branch. Name the groups attached to the chain, using the carbon number as the locator. Alphabetize substituents. Use di-, tri-, etc., for multiples of same substituent. =>
Chapter 1 72
neopentane, C5H12
Chapter 1
Longest Chain
The number of carbons in the longest chain determines the base name: ethane, hexane. (Listed in Table 3.2, page 81.) If there are two possible chains with the same number of carbons, use the chain with the most substituents.
H3C CH3 H3C CH2 C CH3
Chapter 1
Number the Carbons

Start at the end closest to the first attached group. If two substituents are equidistant, look for the next closest group.
1
CH CH2 CH CH2
CH3 CH2 CH3

73
CH3
2
CH3 CH CH3
6 7 =>
74
H3C CH CH CH2 CH2CH3

Chapter 1
CH2
=>
Name Alkyl Groups

CH3-, methyl CH3CH2-, ethyl CH3CH2CH2-, n-propyl CH3CH2CH2CH2-, n-butyl
C H3
CH3 CH CH2 CH3
CH3 CH3 CH CH2 isobutyl
CH3 H3C C CH3 tert-butyl
Propyl Groups
H H H H C C C H H H
H H H
H
H C C C H H H
isopropyl
n-propyl A primary carbon
C H3 C H
A secondary carbon =>
isopropyl
sec-butyl
=>
Butyl Groups
H H H H H C C C C H H H H
n-butyl A primary carbon H H H H H H C H C C C H H H sec-butyl A secondary carbon =>
Chapter 1 77
Isobutyl Groups
H
C H H H H C C C
H
C H H H H C C C H H H H
tert-butyl A tertiary carbon =>
Chapter 1 78
H H H
isobutyl A primary carbon
Alphabetize
Alphabetize substituents by name. Ignore di-, tri-, etc. for alphabetizing.
CH3 H3C CH CH CH2 CH2CH3
3-ethyl-2,6-dimethylheptane =>
Chapter 1 79
Complex Substituents
If the branch has a branch, number the carbons from the point of attachment. Name the branch off the branch using a locator number. Parentheses are used around the complex branch name.
1 2 =>
CH3 CH2 CH CH3
3 1-methyl-3-(1,2-dimethylpropyl)cyclohexane
Chapter 1 80
Boiling Points of Alkanes Physical Properties

Solubility: hydrophobic Density: less than 1 g/mL Boiling points increase with increasing carbons (little less for branched chains). Melting points increase with increasing carbons (less for oddnumber of carbons).
Branched alkanes have less surface area contact, so weaker intermolecular forces.
=>
82
Melting Points of Alkanes

Branched alkanes pack more efficiently into a crystalline structure, so have higher m.p.
Branched Alkanes
Lower b.p. with increased branching Higher m.p. with increased branching Examples:
CH3
=>
CH3 CH3
CH CH2 CH2 CH3 bp 60C mp -154C
CH3 CH3
CH
CH
CH3 CH3
CH3 C CH2 CH3 CH3 bp 50C mp -98C

84
bp 58C mp -135C
Chapter 1
83
Chapter 1
=>
Major Uses of Alkanes

C1-C2: gases (natural gas) C3-C4: liquified petroleum (LPG) C5-C8: gasoline C9-C16: diesel, kerosene, jet fuel C17-up: lubricating oils, heating oil Origin: petroleum refining
=>
Chapter 1 85
Reactions of Alkanes
Combustion
2 CH3CH2CH2CH3 + 13 O2 heat 8 CO2 + 10 H2O
Cracking and hydrocracking (industrial)

long-chain alkanes catalyst shorter-chain alkanes
Halogenation
CH4 + Cl2 heat or light CH3Cl + CH2Cl2 + CHCl3 + CCl4
=>
Chapter 1 86
Conformers of Alkanes
Structures resulting from the free rotation of a C-C single bond May differ in energy. The lowest-energy conformer is most prevalent. Molecules constantly rotate through all the possible conformations.
=>
Ethane Conformers
Staggered conformer has lowest energy. Dihedral angle = 60 degrees
H H H H H H Newman projection
Chapter 1
=> sawhorse
88
model
Chapter 1 87
Ethane Conformers (2)

Eclipsed conformer has highest energy Dihedral angle = 0 degrees
Conformational Analysis
Torsional strain: resistance to rotation. For ethane, only 3.0 kcal/mol
=> =>
Propane Conformers
Note slight increase in torsional strain due to the more bulky methyl group.
Butane Conformers C2-C3

Highest energy has methyl groups eclipsed. Steric hindrance Dihedral angle = 0 degrees
=> totally eclipsed

=>
92
Butane Conformers (2)

Lowest energy has methyl groups anti. Dihedral angle = 180 degrees

Methyl groups eclipsed with hydrogens Higher energy than staggered conformer Dihedral angle = 120 degrees
anti =>
Chapter 1 93
eclipsed
Chapter 1 94
=>

Gauche, staggered conformer Methyls closer than in anti conformer Dihedral angle = 60 degrees
Conformational Analysis
gauche
Chapter 1
=>
95 Chapter 1 96
=>
Higher Alkanes
Anti conformation is lowest in energy. Straight chain actually is zigzag.
Cycloalkanes
Rings of carbon atoms (CH2 groups) Formula: CnH2n Nonpolar, insoluble in water Compact shape Melting and boiling points similar to branched alkanes with same number of carbons =>
Chapter 1 98
CH3CH2CH2CH2CH3
H H H H H C C C C C H H H H H H H
Chapter 1
=>
97
Naming Cycloalkanes
Cycloalkane usually base compound Number carbons in ring if >1 substituent. First in alphabet gets lowest number. May be cycloalkyl attachment to chain.
CH2CH3 CH2CH3 CH3
Cis-Trans Isomerism
=>
Chapter 1 99
Cis: like groups on same side of ring Trans: like groups on opposite sides of ring =>
Chapter 1 100
Cycloalkane Stability
5- and 6-membered rings most stable Bond angle closest to 109.5 Angle (Baeyer) strain Measured by heats of combustion per -CH2 =>
Heats of Combustion Alkane + O2 CO2 + H2O

166.6 164.0 157.4 158.7 158.6 157.4 158.3
Chapter 1
101
Long-chain
=>
Chapter 1 102
Cyclopropane
Large ring strain due to angle compression Very reactive, weak bonds
Cyclopropane (2)
Torsional strain because of eclipsed hydrogens
=>
=>
Cyclobutane
Angle strain due to compression Torsional strain partially relieved by ring-puckering
Cyclopentane
If planar, angles would be 108, but all hydrogens would be eclipsed. Puckered conformer reduces torsional strain.
=>
=>
106
Cyclohexane
Combustion data shows its unstrained. Angles would be 120, if planar. The chair conformer has 109.5 bond angles and all hydrogens are staggered. No angle strain and no torsional strain. =>
Chapter 1 107
Chair Conformer
=>
Chapter 1
108
Boat Conformer
Conformational Energy
=>
=>
Axial and Equatorial Positions
Monosubstituted Cyclohexanes
=>
=>
112
1,3-Diaxial Interactions
Disubstituted Cyclohexanes
=> =>
Cis-Trans Isomers
Bonds that are cis, alternate axialequatorial around the ring.
Bulky Groups
Groups like t-butyl cause a large energy difference between the axial and equatorial conformer. Most stable conformer puts t-butyl equatorial regardless of other substituents.
CH3 CH3
=>
Chapter 1
115
Chapter 1
116
=>
Bicyclic Alkanes
Fused rings share two adjacent carbons. Bridged rings share two nonadjacent Cs.
Cis- and Trans-Decalin

Fused cyclohexane chair conformers Bridgehead Hs cis, structure more flexible Bridgehead Hs trans, no ring flip possible.
H
bicyclo[3.1.0]hexane
bicyclo[2.2.1]heptane =>
=>
H
cis-decalin
trans-decalin
118
End of Chapter 3
Chapter 1
119

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Organic Chemistry, 5th Edition L. G. Wade, Jr.

Chapter 1 Introduction and Review

H2N C NH2 urea

Satisfy the octet rule!

Electronegativity and Bond Polarity

Calculating Formal Charge

Major Resonance Form

Condensed structural formula Molecular formula Empirical formula

CH3COOH C2H4O2 CH2O =>

Calculating Empirical Formulas

Arrhenius Acids and Bases

Brnsted-Lowry Acids and Bases

Acid and Base Strength

Determining Relative Acidity

Lewis Acids and Bases

Organic Chemistry, 5th Edition L. G. Wade, Jr.

Wave Properties of Electrons

Chapter 2 Structure and Properties of Organic Molecules

H2: s-s overlap

Cl2: p-p overlap

HCl: s-p overlap

sp2 Hybrid Orbitals

2 VSEPR pairs Linear electron pair geometry 180 bond angle

sp3 Hybrid Orbitals

Rotation around Bonds

Cis - same side

No cis-trans isomers possible

Bond Dipole Moments

Molecular Dipole Moments

n-pentane, b.p. = 36C

CH3 CH CH2 CH3 isopentane, b.p. = 28C

CH3 neopentane, b.p. = 10C

Boiling Points and Intermolecular Forces

ethanol, b.p. = 78C

dimethyl ether, b.p. = -25C

H propylamine, b.p. 49C ethylmethylamine, b.p. 37C

ethanol, b.p. = 78C

ethyl amine, b.p. 17C

Ionic Solute with Polar Solvent

Hydration releases energy. Entropy increases.

Ionic Solute with Nonpolar Solvent

Nonpolar Solute with Nonpolar Solvent

Nonpolar Solute with Polar Solvent

Compounds Containing Oxygen

Carboxylic Acids and Their Derivatives

Compounds Containing Nitrogen

Organic Chemistry, 5th Edition L. G. Wade, Jr.

Chapter 3 Structure and Stereochemistry of Alkanes

CH3 H3C CH3

Number the Carbons

CH3 CH2 CH3

H3C CH CH CH2 CH2CH3

Name Alkyl Groups

n-propyl A primary carbon

A secondary carbon =>

CH3 CH2 CH CH3

Boiling Points of Alkanes Physical Properties

Melting Points of Alkanes

CH CH2 CH2 CH3 bp 60C mp -154C

CH3 C CH2 CH3 CH3 bp 50C mp -98C

Major Uses of Alkanes

Cracking and hydrocracking (industrial)

Ethane Conformers (2)

Butane Conformers C2-C3