Organic Chemistry lecture

Week 1-4 SY 2013-14 FIRST SEM

HISTORY OF ORGANIC CHEMISTRY and THE UNIQUE CARBON

Hilda R. Hagad CEU-Manila 2013-2014

HISTORY
Organic chemistry may have its beginnings with the big bang when the components of ammonia, nitrogen, carbon dioxide and methane combined to form amino acids, an experiment that has been verified in the laboratory by (Miller, 1950) Aboriginal peoples have been isolating organic compounds from natural materials, such as birch bark. Organic chemicals were used in ancient times by Romans and Egyptians as dyes, medicines and poisons from natural sources, but the chemical composition of the substances was unknown. In the early days of chemistry, scientists classified chemical substances into 2 groups: a. Inorganic compounds: those that were composed of minerals, such as rocks and nonliving matter. b. Organic compounds: those that were produced by living organisms, hence the name organic.
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Vitalism theory
Scientists believed (Berzelius, 1807) that organic chemicals found in nature contained a special "vital force" that directed their natural synthesis, and therefore, it would be IMPOSSIBLE to produce or synthesize organic substances in the laboratory. Vitalists hold that living organisms are fundamentally different from non-living entities because they contain some non-physical element or are governed by different principles than are inanimate things.

In 1828, German chemist Friedrick Whler disproved this theory by producing urea, an organic compound found in urine, from inorganic compo 4 unds.

 Understanding about the structures of organic chemistry began with a theory of bonding called valence theory (Kekule, Couper, 1858). Kekule gave the benzene ring structure

Modern Definitions

Introduction to Organic Chemistry

Organic chemistry is the study of compounds that contain the element carbon. Organic chemicals affect virtually every facet of our lives.

Products such as clothes, foods, medicines, gasoline, refrigerants, and soaps are composed almost solely of organic compounds.
Some organic products can be obtained directly from natural sourcescotton, wool, and silk. Others can be synthetically producednylon and polyester.
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THE UNIQUE CARBON ATOM AND THE CHARACTERISTICS OF ORGANIC COMPOUNDS

Characteristics of Organic Compounds

Examples of Organic Compounds

Methane is the main component of natural gas.

Ethanol is the alcohol present in alcoholic beverages.

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Characteristics of Organic Compounds

Examples of Organic Compounds
Capsaicin is responsible for the spiciness of peppers, and is used for topical pain-relief medicines.

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Characteristics of Organic Compounds

Examples of Organic Compounds
Caffeine is the stimulant found in coffee, tea, cola beverages, and chocolate.

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Section 1.1

The Special Nature of the Carbon Atom

Important atomic properties of carbon: It is much more likely to share electrons than gain or lose electrons. Therefore, covalent bonding occurs. It has four valence electrons. Therefore, it can be bonded to as many as four different atoms.

Carbon can bond to four different atoms, producing a molecule with a tetrahedron shape.

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Why are there so many organic compounds?

1. Carbon forms stable, covalent bonds with other carbon atoms Consider three allotropic forms of elemental carbon
Graphite in planar layers Diamond is a three-dimensional network Buckminsterfullerene is 60 C in a roughly spherical shape

Isomers
Many carbon compounds exist in the form
of isomers Isomers are compounds with the same molecular formula but different structures

An isomer example: both are C4H10 but have different structures

Butane Methylpropane

UNIT 1

Chapter 1: Structure and Physical Properties of Organic Compounds

Section 1.1

Isomers

Most organic molecules consist of more than one carbon atom bonded together in a chain or ring structure. Molecules with the same molecular formula but atoms in different arrangements are known as isomers. Constitutional or structural isomers: molecules with the same molecular formula, but the atoms are bonded in a different sequence.

These molecules are constitutional isomers.

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UNIT 1

Chapter 1: Structure and Physical Properties of Organic Compounds

Section 1.1

Isomers

Stereoisomers: molecules with the same molecular formula and sequence of atoms, but they differ in the threedimensional orientation of their atoms diastereomer: stereoisomers based on the presence of a double bond enantiomer: stereoisomers that are mirror-images of each other.

These molecules are diastereomers.

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TIPS TO DETERMINE ISOMERS:

First, determine if the two structures have the same molecular formula. Second, carefully look at how the atoms are bonded together. If they have the same molecular formula but the atoms are bonded together differently then they are constitutional isomers. Third, if the atoms are bonded together in the same arrangement and there is a multiple bond, determine if the groups attached to the carbon atoms involved in the double bond are different so 18 that cis and trans forms are possible.

UNIT 1

Chapter 1: Structure and Physical Properties of Organic Compounds

Section 1.1

LEARNING CHECK
Are the following molecules isomers? If so, what type of isomers are they?

Answer on the next slide

UNIT 1

Chapter 1: Structure and Physical Properties of Organic Compounds

Section 1.1

LEARNING CHECK
Yes they are isomers.
They are stereoisomers, not constitutional isomers.

Isomers
All have the same molecular formula: C4 H8 a) b) c) CH3-CH2-CH=CH2 CH3-CH=CH-CH3 CH2-CH2 | | CH2-CH2

Important Differences Between Organic and Inorganic Compounds

Bond type
Organics have covalent bonds
Electron sharing

Inorganics usually have ionic bonds

Electron transfer

Structure
Organics
Molecules Nonelectrolytes Three-dimensional crystal structures Often water-soluble, dissociating into ions electrolytes

Inorganics

Important Differences Between Organic and Inorganic Compounds

Melting Point & Boiling Point
Organics have covalent bonds
Intermolecular forces broken fairly easily

Inorganics usually have ionic bonds

Ionic bonds require more energy to break

Water Solubility
Organics

Nonpolar, water insoluble

Water-soluble, readily dissociate

Inorganics

Characteristics of Organic Compounds

Common Features
1. All organic compounds contain carbon atoms and most contain hydrogen atoms. Carbon always forms four covalent bonds. Hydrogen always forms one covalent bond.

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Characteristics of Organic Compounds

Common Features
3. Some compounds have chains of atoms and some compounds have rings.

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Characteristics of Organic Compounds

Common Features
4. Organic compounds may also contain elements other than carbon and hydrogen. Any atom that is not carbon or hydrogen is called a heteroatom.

Each heteroatom forms a characteristic number of bonds, determined by its location in the periodic table.
The common heteroatoms (N, O, F, Cl, Br, and I) also have nonbonding, lone pairs of e, so that each atom is surrounded by an octet of e. # of bonds + # of lone pairs = 4
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Characteristics of Organic Compounds

Common Features

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Characteristics of Organic Compounds

Common Features
The most common multiple bond between carbon and a heteroatom is a carbonoxygen double bond.

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Shapes of Organic Molecules

VSEPR theory: The most stable arrangement keeps the groups on a central atom as far away from each other as possible. An atom surrounded by two groups is linear and has a bond angle of 180o.

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Shapes of Organic Molecules

An atom surrounded by three groups is trigonal planar and has a bond angle of 120o.

An atom surrounded by four groups is tetrahedral and has bond angles of 109.5o.

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Shapes of Organic Molecules

To draw a 3-D tetrahedron in 2-D, we use: a solid line for bonds in the plane a wedge for a bond in front of the plane a dashed line for a bond behind the plane

Every carbon with four single bonds is tetrahedral.

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Shapes of Organic Molecules

Nitrogen is attached to 3 atoms and has 1 lone pair, making its shape a trigonal pyramid.

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Shapes of Organic Molecules

Oxygen is attached to 2 atoms and has 2 lone pairs, making its shape bent.

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BONDING CHARACTERISTICS AND HYBRIDIZATION

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1.2 Atomic Structure: Orbitals

Quantum mechanics: describes electron energies and locations by a wave equation
Wave function is a solution of the wave equation Each Wave Function describes an orbital,

A plot of

describes the probabililty of finding the electron

The electron cloud has no specific boundary so we show the most probable volume. The boundary is called a probablility surface
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Shapes of Atomic Orbitals for Electrons

For the existing elements, there are four different kinds of orbitals for electrons based on those derived for a hydrogen atom. Denoted s, p, d, and f s and p orbitals most important in organic chemistry (carbon atoms have no d or f orbitals)

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Shapes of Atomic Orbitals for Electrons

s orbitals: spherical, nucleus at center p orbitals: dumbbell-shaped, nucleus at middle

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Orbitals and Shells

Orbitals are grouped in shells of increasing size and energy As shells increase in size, they contain larger numbers and kinds of orbitals

Each orbital can be occupied by two electrons (Pauli Exclusion Principle)

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Orbitals and Shells

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p-Orbitals
In each shell there are three perpendicular p orbitals, px, py, and pz, of equal energy Lobes of a p orbital are separated by region of zero electron density, a node

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1.3 Atomic Structure: Electron Configurations

Ground-state electron configuration of an atom lists orbitals occupied by its electrons. 1. Lowest-energy orbitals fill first: 1s 2s 2p 3s 3p 4s 3d (Aufbau (build-up) principle) 2. Electron spin can have only two orientations, up and down . Only two electrons can occupy an orbital, and they must be of opposite spin (Pauli exclusion principle) to have unique wave equations 3. If two or more empty orbitals of equal energy are available, electrons occupy each with spins parallel until all orbitals have one electron (Hund's rule).
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1.4 Development of Chemical Bonding Theory

Kekul and Couper independently observed that carbon always has four bonds

Friedrich August Kekule

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1.4 Development of Chemical Bonding Theory

van't Hoff and Le Bel proposed that the four bonds of carbon have specific spatial directions
Atoms surround carbon as corners of a tetrahedron

Note that a dashed line indicates a bond is behind the Note that a wedge page indicates a bond is coming forward

J. H. vant

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Tetrahedral Carbon:

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1.5 The Nature of the Chemical Bond

Atoms form bonds because the compound that results is more stable than the separate atoms Ionic bonds in salts form as a result of electron transfers Organic compounds contain covalent bonds, from sharing electrons (G. N. Lewis, 1916)
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1.5 The Nature of the Chemical Bond

Lewis structures show valence electrons of an atom as dots Hydrogen has one dot, representing its 1s electron Carbon has four dots (2s2 2p2) A stable molecule results when the outermost (valence) shell is completed: octet (eight dots) for 2nd period maingroup atoms (two for hydrogen)
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Number of Covalent Bonds to an Atom

Atoms with one, two, or three valence electrons form one, two, or three bonds Atoms with four or more valence electrons form as many bonds as they need electrons to fill the s and p levels of their valence shells to reach a stable octet
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Some simple molecules:

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Number of Covalent Bonds to an Atom

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Valences of Oxygen
Oxygen has six valence electrons (2s2 2p4) but forms two bonds (H2O)

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Valences of Nitrogen
Nitrogen has five valence electrons (2s2 2p3) but forms only three bonds (NH3)

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Non-bonding electrons
Valence electrons not used in bonding are called nonbonding electrons, or lone-pair electrons

Nitrogen atom in ammonia (NH3) shares six

valence electrons in three covalent bonds; the remaining two valence electrons are a nonbonding lone pair

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1.5 Valence Bond Theory

A covalent bond forms when two atoms approach each other closely so that a singly occupied orbital on one atom overlaps a singly occupied orbital on the other atom

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1.5 Valence Bond Theory

Electrons are paired in the overlapping orbitals and are attracted to nuclei of both atoms
HH bond results from the overlap of two singly occupied hydrogen 1s orbitals H-H bond is cylindrically symmetrical, sigma (s) bond
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Bond Energy
Reaction 2 H H2 releases 436 kJ/mol Product has 436 kJ/mol less energy than two atoms: HH has bond strength of 436 kJ/mol. (1 kJ = 0.2390 kcal; 1 kcal = 4.184 kJ)

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Bond Length
Distance between nuclei that leads to maximum stability If too close, they repel because both are positively charged If too far apart, bonding is weak The energy diagram on the right is called a Morse Diagram
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The concept of hybridization theory involves the following points :

1. Hybridization is the mixing of pure orbitals to form new hybrid orbitals which are equivalent and have definite orientations in space. 2. Only orbitals which lie close together in energy can be used in the construction of hybrid orbitals. 3. The number of hybrid orbitals always equals the number of component atomic 57 orbitals.

1.6 Hybridization: sp3 Orbitals and the Structure of Methane

Carbon has 4 valence electrons (2s2 2p2 ) In CH4, all CH bonds are identical (tetrahedral) sp3 hybrid orbitals: s orbital and three p orbitals combine to form four equivalent, unsymmetrical, tetrahedral orbitals (sppp = sp3), Pauling (1931)

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3 sp

Hybridization

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Tetrahedral Structure of Methane

sp3 orbitals on C overlap with 1s orbitals on 4 H atom to form four identical C-H bonds Each CH bond has a strength of 438 kJ/mol and length of 110 pm Bond angle: each HCH is 109.5, the tetrahedral angle.

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1.7 Hybridization: sp3 Orbitals and the Structure of Ethane

Two Cs bond to each other by s overlap of an sp3 orbital from each Three sp3 orbitals on each C overlap with H 1s orbitals to form six CH bonds

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1.8 Hybridization: sp2 Orbitals and the Structure of Ethylene

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Bonds From sp2 Hybrid Orbitals

Two sp2-hybridized orbitals overlap to form a s bond p orbitals overlap side-to-side to formation a pi () bond sp2sp2 s bond and 2p2p bond result in sharing four electrons and formation of C-C double bond Electrons in the s bond are centered between nuclei Electrons in the bond occupy regions are on 63 either side of a line between nuclei

Structure of Ethylene
H atoms form s bonds with four sp2 orbitals HCH and HCC bond angles of about 120 CC double bond in ethylene shorter and stronger than single bond in ethane Ethylene C=C bond length 133 pm (CC 154 pm)

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1.9 Hybridization: sp Orbitals and the Structure of Acetylene

Carbon 2s orbital hybridizes with a single p orbital giving two sp hybrids (two p orbitals remain unchanged) sp orbitals are linear, 180 apart on x-axis Two p orbitals are perpendicular on the y-axis and the z-axis

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Orbitals of Acetylene
Two sp hybrid orbitals from each C form spsp s bond pz orbitals from each C form a pzpz bond by sideways overlap and py orbitals overlap similarly

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Comparison of C-H bonds:

Molecule Ethane Ethylene Acetylene Bond Energy (kcal) Length (pm)

Csp3-H Csp2-H

100 106

110 108

Csp-H

132

106
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Comparison of C-C bonds:

Molecule Ethane Ethylene Acetylene Bond Energy (kcal) Length (pm)

Csp3-Csp3 Csp2-Csp2

90 146

154 133

Csp-Csp

200

120
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Hybridization & Geometry

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1.10 Hybridization of Nitrogen, Oxygen,Phosphorus, and Sulfur

Ns orbitals (sppp) hybridize to form four sp3 orbitals

One sp3 orbital is occupied by two nonbonding electrons, and three sp3 orbitals

have one electron each, forming bonds to H

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Hybridization of Oxygen in Methanol

The oxygen atom is sp3-hybridized Oxygen has six valence-shell electrons but forms only two covalent bonds, leaving two lone pairs

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Drawing Chemical Structures

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Example: Interpreting structures

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Solution:

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Drawing Organic Molecules

Condensed Structures
In a condensed structure, all of the atoms are drawn in, but the two-electron bond lines and lone pairs on heteroatoms are generally omitted.

A carbon bonded to 3 Hs becomes CH3. A carbon bonded to 2 Hs becomes CH2.

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Drawing Organic Molecules

Condensed Structures
Some bond lines can be drawn in for effect or to show specific bonding.

A carbon bonded to 1 H becomes CH.

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Drawing Organic Molecules

Condensed Structures
Identical groups can be condensed further:

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Drawing Chemical Structures

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Drawing Organic Molecules

Skeletal Structures
When drawing a skeletal structure: assume there is a carbon atom at the junction of any two lines or at the end of any line

assume there are enough hydrogens around each carbon to give it four bonds
draw in all heteroatoms and the hydrogens directly bonded to them

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Drawing Organic Molecules

Skeletal Structures

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Drawing Organic Molecules

Skeletal Structures

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