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ORGANIC CHEMISTRY
Meaning of “Organic”?
Initially scientists believed there was a special “force” in living organisms -this was assumed the unique component of organic material
In 1828 Wöhler synthesized urea (a known component of organic material) from inorganic ammonium cyanate
Later Justus von Liebig, a noted 19th century chemist, declared the synthesis of urea “the very first beginning of the actual scientific organic chemistry”
In a subsequent paper Wöhler and Liebig wrote: “sugar, salicin, and morphium will be produced artificially. Of course, we do not
know the way yet by which the end result may be reached since the prerequisite links are unknown to us from which these materials will be develop -
however, we will get to know them.”
Organic chemistry is now considered the chemistry of carbon
**Not only carbon!
There are few forms of only pure carbon (no other elements present)
Some examples of compounds with only carbon present:
graphite diamond
C60 spherical ball carbon nanotube
Carbon can form strong bonds with not only carbon but with other elements (e.g. hydrogen, nitrogen, oxygen, halogens)
Depending upon the order of the bond connections (both constitution and configuration) millions of compounds, all with potentially different properties, can be prepared
Why is this so important?
Almost every component of living organisms involve organic chemistry (proteins, enzymes, lipids, fats, carbohydrates, nucleic acids, etc.)
And the metabolic and other interactions in the body involve organic reactions
Understanding Organic Chemistry is Learning about Bonding and the location of Electrons
O
H
H H
H
H H
Consider a molecule called acetone
Shorthand drawing All atoms indicated 3-dimensional drawing
OO
H
H H
H
H H
Electron density plot
wedge and dash lines have meaning
By understanding, and predicting, the properties and orientation of bonds Organic reactions can be predicted without memorization
Compare these compounds:
Organic Chemistry focuses on the second row of the periodic table
Carbon is in the exact middle of the second row
This position allows carbon to form various bonds **more specifically it allows carbon to share electrons easily to form bonds
Organic chemistry is fundamentally about what electrons do, and how they ‘behave’
In Organic Chemistry we study how compounds react
During a reaction old bonds are broken and new bonds form
Bonds form – two atoms share electrons Bonds break – two atoms no longer share electrons
Therefore, if we know more about the electrons we can understand organic chemistry
What do we want to know?
Where are the electrons?
How tightly are the electrons held in a “bond”?
We already know many of these basic concepts from general chemsitry
Background of an atom
An atom consists of three types of particles: Proton (positively charged)
Neutron (neutral) Electron (negatively charged)
The number of protons determines the element (also is the atomic number) Carbon therefore has 6 protons located in the nucleus
Usually the nucleus also contains an identical number of neutrons as protons If the number is different it is called an isotope
These two particles have similar mass (~1830 times greater than an electron)
Consider a Carbon Atom
Nucleus – means “kernel of a nut”
Nucleus size is ~2 fm (1 fm = 10-15 m), atom size is ~1 Å (1 Å = 10-10 m)
For an uncharged 12C atom, there are 6 protons, 6 neutrons and 6 electrons
Therefore the nucleus, which is responsible for ~3600/1 parts of the mass, only encompasses ~1 x 10-15 part of the volume (remember V = 4/3 πr3)
Electrons
Unlike the protons and neutrons which are in the nucleus (a relatively fixed point) we cannot say with certainty where an electron is located at a certain time
(Heisenberg uncertainty principle)
What we can say is that ‘on time average’ the electrons are located in orbitals (regions of space)
*much bigger region than the nucleus
As the number of electrons increase they reside in concentric shells where each shell contains subshells known as atomic orbitals of different properties and shapes
shell atomic orbital
1 s 2 s,p 3 s,p,d 4 s,p,d,f
The different types of atomic orbitals have a characteristic number of orbitals
s 1 p 3 d 5 f 7
Organic chemistry is primarily concerned with only the first two shells (therefore only the s and p atomic orbitals)
Also due to only two spin states for an electron Only two electrons can be placed in each orbital
(Pauli exclusion principle)
Orbitals are filled by electrons starting in the lowest energy orbital
Carbon can therefore only have a maximum of 8 electrons in its outer (2nd) shell 4 atomic orbitals (1s and 3p) with 2 electrons per orbital
Electronic Configuration for Carbon through Fluorine
When filling degenerate orbitals electrons will go into different orbitals before pairing in the same orbital (Hund’s rule)
Bonding
Octet rule – atom is most stable if its outer shell of electrons is filled
Therefore an atom will give up, accept, or share electrons in order to achieve a filled outer shell
Often the inner shell of electrons is ignored (not counted for the octet rule)
Outer shell of electrons is also referred to as ‘valence’ electrons
Called ‘octet rule’ since second row atoms (which comprise organic compounds) have 8 electrons in their outer shell
Type of Bonds
If atoms give up or accept electrons an ion is formed
Consider lithium (3 total electrons)
There is only one valence electron
Lithium will therefore easily lose an electron to create a lithium ion (which has a filled outer shell)
The energy required to remove an electron is referred to as the ionization energy
Since lithium readily loses an electron to leave an atom with a complete outer shell it is called electropositive
Halogens, on the other hand, readily gain an electron to complete the outer shell
Consider fluorine (9 electrons, 7 valence electrons)
The outer shell needs one electron to be filled
In a covalent bond, however, electrons are shared between two atoms (not lose or accept as in the formation of ions)
The sharing of electrons can allow both atoms to fill the outer shell
Consider F2 (fluorine gas)
Each fluorine atom needs one electron to fill the outer shell
One atom cannot donate an electron and have both atoms with a filled outer shell
An alternative is to share two electrons (one from each atom) between both atoms
Represent each electron with a dot (called Lewis dot structures)
(only show valence electrons for a Lewis dot structure)
Both atoms now have 8 electrons in the outer shell (therefore octet rule is obeyed)
Differences between Ionic and Covalent Bonding
Lithium Fluoride Forms ionic bond by lithium ‘donating’ an electron to fluorine
Each outer shell is filled, but no electron density between two atoms
Fluorine gas Forms covalent bond by sharing electrons
Representation of Organic Structures
Lewis Structures As already shown with F2 each valence electron
is represented by a dot
Two dots between two atoms represents a single bond (two shared electrons)
Consider methane (a molecule with CH4 molecular formula)
Different Ways to Draw Organic Compounds
Organic chemistry has a shorthand for drawing compounds (need a way to indicate what atoms are connected by these covalent bonds)
Lewis Structures
Other representations
All structures shown represent the same compound (propane)
Polar Bonds
All covalent bonds shown so far have been between identical atoms
What happens if a covalent bond is formed between two different elements?
*Both atoms do not need to share the electrons equally
Even though the electrons are shared, the electrons can be closer, on time average, to one nucleus than the other
How to predict where the electrons are located?
Electronegativity Tables
Linus Pauling established values to associate with each element
Elements toward the upper righthand of the periodic table are more electronegative
Also can predict the relative electronegativity of two atoms by their relative placement in the periodic table
H (2.2) Li (1.0) Be (1.6) B (1.8) C (2.5) N (3.0) O (3.4) F (4.0)
Cl (3.2)
Br (3.0)
I (2.7)
The numbers are a relative indication of how much the electrons are ‘attracted’ to a certain atom
As the number becomes larger, the electrons are attracted more by that atom
Formal Charges
A formal charge represents a full charge on the atom (assuming no polarity of the covalent bond)
To calculate:
Formal charge = (group number) – (nonbonded electrons) – ½(shared electrons)
Use group numbers, not atomic numbers!
Consider ammonium:
Formal Charge = 5 – 0 – 1/2 (8) = +1
Acid/Base Reactions
Important considerations for Organic chemistry:
What makes a compound acidic? How do we determine acid strengths?
Need to first consider what definition of acid/base reactions we are using
Arrhenius definition: Acids – something that dissociates in water to give hydronium ion (H3O+) Bases – something that dissociates in water to give hydroxide ion (HO-)
The Arrhenius definition is used to determine the strength of an acid The strength is determined by how easily the molecule dissociates
in water to give a hydronium ion
Kw = [H3O+][HO-] = 1 x 10-14
In neutral solution the concentration of [H3O+] and [HO-] are equal
Therefore [H3O+] = [HO-] = 1 x 10-7 M
Acidic solutions have an excess of [H3O+]
Therefore [H3O+] > 1 x 10-7 and [HO-] < 1 x 10-7
Due to the magnitude, the acid strength is expressed in a logarithmic scale
pH = -log10 [H3O+]
Therefore in neutral solutions pH = 7
Acidic solutions pH < 7
Basic solutions pH > 7
The Arrhenius definition is poor for organic compounds Since very few will dissociate into hydroxide ions
Brønsted-Lowry definition is better for organic compounds
Acid – any species that can donate a proton
Base – any species that can accept a proton
As can be seen from the reaction above, every Arrhenius acid and base are still considered acids and bases with the Brønsted-Lowry definition
Other compounds, however, would not be considered bases under Arrhenius which do qualify with Brønsted-Lowry
Conjugate Acid and Base
An important concept with the Brønsted-Lowry acid/base definition is the resultant conjugate acid and base
(every acid becomes a conjugate base after the reaction)
H Cl H2O H3O Cl
base
acid
conjugate acid
conjugate base
Lewis Definition of Acids and Bases
G.N. Lewis postulated that an acid/base reaction need not involve a transfer of a proton
An acid/base reaction can refer to any reaction that involves the formation of new bonds
Lewis acid: a species that accepts a lone pair of electrons to form a new bond
Lewis base: a species that donates a lone pair of electrons to form a new bond
H ClH2O H3O Cl
base acid
This definition is far more general, but any acid or base in Brønsted/Lowry definition remains the same in the Lewis definition
Introduces new terms that are used in many organic reactions A Lewis base is called a nucleophile - “lover of nuclei”
A Lewis acid is called an electrophile - “lover of electrons”
Evolution of Acid-Base Theories
Lavoisier (1789)
Arrhenius (1887)
Brønsted/Lowry (1923)
Lewis (1923)
HOMO-LUMO (1960’s)
Theory Acid Base
oxidized substance
substance to be oxidized
H+ source HO- source
H+ donor H+ acceptor
e-pair acceptor “electrophile”
e-pair donor “nucleophile”
unusually low LUMO
unusually high HOMO
increasing generality
Acid-Base Reactions
HO- H+ HO-H
Curved arrows designate e-pair shifts (not atomic motion)
Start arrow at e-pair location in starting material End arrow at e-pair location in product
Acid-Base Reactions
HO- H+ HO-H
NH3: H+ NH3-H
HO- BH3 HO-BH3
NH3: BH3 NH3-BH3
Arrhenius
Brønsted/Lowry
Lewis
Lewis
All of these acid-base reactions follow a similar arrow pushing mechanism
+
-‐
+ -‐
Acid Strength
Organic acids are defined by the acid dissociation constant (Ka)
Similar to pH measurements, this quantity is expressed in the logarithmic form
pKa = -log Ka
The stronger the acid, the smaller the pKa
Don’t confuse pKa with pH
pKa is a constant for a given acid referring to the pH where half of the acid is ionized pH refers to the concentration of hydronium ions in solution
How to Predict the Relative Strength of Acids
- Common point is the ability to stabilize a negative charge (molecules that can handle more excess electron density after deprotonation are stronger acids)
1. Amongst atoms of similar size, the atom with a greater electronegativity will be a stronger acid
2. Bigger atoms will be stronger acids
Consider size of atom where charge is located
This trend usually is relevant when comparing atoms in the same column (as the atom becomes larger going down a column,
the excess negative charge is more stabilized)
3. Polar bonds near anion source can stabilize negative charge (inductive effect)
Consider acetic acid derivatives:
Electron withdrawing groups can pull electron density away from another region of molecule (this “through bond” effect is called inductive)
4. Resonance can lower electron density on a given atom
What is resonance? (also called ‘delocalization’)
Look at a nitro group
The negative charge on the oxygen could be placed on either oxygen using Lewis structures
Which structure is correct?
It turns out neither structure is correct, but the charge is delocalized onto both oxygens - This process of being able to delocalize the charge onto more than one atom is called
resonance
“Rules” of Resonance
1. All resonance structures must be valid Lewis structures (e.g. cannot have 10 electrons on one carbon in one structure)
2. Only electrons move (cannot move nuclei, only electrons
– usually double bonds or lone pairs connected through an extended p orbital system)
3. Number of unpaired electrons must be constant
How does resonance explain acidity?
Consider pKa of organic molecules
Both structures place a negative charge on oxygen after loss of proton, but the pKa difference is greater than 11
A carbonyl group is a common resonance source
The negative charge can therefore be delocalized over both oxygen atoms
Comparison of Electron Density for Ethoxide versus Acetate anion
The excess negative charge is more stable on the acetate anion that can resonate, thus the conjugate acid is more acidic
Important to Remember: Not all resonance structures need to contribute equally
If two resonance structures are not of equal energy, then they will not contribute equally to the actual structure
This leads to major and minor contributors
Factors to affect stability of resonance structures:
- Placement of charge
When the only difference is the location of formal charge, structure is more stable when anion is placed on more electronegative atom
- Amount of Charge
Also related to number of bonds in a structure
While structure with four formal charges shown is a “valid” resonance form, if structure is dramatically higher in energy then it is practically an irrelevant resonance form
- Octet rule is important
Having all atoms with a filled octet rule is more stable than a resonance form that only has 6 electrons in one outer shell
Even if this requires a positive formal charge to be placed on a more electronegative atom
Second row atoms are always more stable with a filled outer shell
Curved arrows represent movement of electrons
As already observed in acid/base reactions, a curved arrow indicates movement of electrons
Arrows always show where electrons are moving
Formal charges on atoms are a result of electrons moving
Drawing resonance structures properly is an aid to predict location of electrons
Remember actual structure is a hybrid of all relevant resonance forms
These resonance forms allow a chemist to predict where excess electron density is located in a molecule
Excess negative charge is located on three carbon atoms, not on all five equally
Empirical Evidence for Resonance
Chemical properties of molecule are not like one resonance form
Have already observed this with acidity difference between ethanol and acetic acid