Organic Chemistry

1. Introduction:

Vital Force Theory – Only living materials can produce organic compounds
Friedrich Wohler – Synthesized urea (organic) from ammonium cyanate (inorganic)
Valence - Combining ability of organic compound based on the fixed number of bonds
Catenation - Ability of carbon to bond with other carbons
Ionic Bond – Gaining or Losing electron
Covalent Bond – Sharing of electrons
- -
Formal charge = Group number – ½ shared e - number of unshared e
-
Resonance – Molecules represented in different Lewis structure that differ in the positions of e
Bond length – Optimum distance between the nuclei of two bonded atoms
Bond energy – Energy required breaking the bonding between a pair of atoms
Bond angle – Angle between two adjacent bonds
Hybridization – Mixing of two or more atomic orbitals to give the same number of new orbitals
Constitutional Isomers – same molecular formula but different connectivity of atoms

Higher boiling point:

1. Look for dipole-dipole interaction (higher)
2. Look for hydrogen bonds (higher)
3. Look for higher molecular weight (higher)
4. Look for branching (lower)

Functional Group:

2. Acids and Bases:

Bronsted Lowry Acids - proton donor

Bronsted Lowry Base – proton acceptor

Weaker Acids are always favored in equilibrium reaction

Acidity Prediction: (ARIO)

Lewis Acid – electron acceptor
Lewis Base – electron donor

3. Stereoisomerism:

Stereoisomers – same connectivity but differ in spatial arrangement

Enantiomer – mirror images but not superimposable
Chiral center – four different bonded atoms
Cahn-Ingold-Prelog System – R (to the Right) and S (to the left) enantiomer
Optical activity – ability of the molecule to rotate the plane of a plane polarized light
Dextrorotatory – positive rotation
Levorotatory – negative rotation
Racemic mixture – equal amount of enantiomers in solution

( )

n
No. of stereoisomers = 2 , n= chirality centers
Mesocompound – has multiple chirality centers but still achiral due to symmetry

4. General Organic Reactions

Hammond Postulate – Transition state resemble reactant if exergonic(-ΔG) or product if endergonic (+ΔG)

Tertiary carbocation are more stable that secondary and primary because of hyperconjugation

Electrophiles are reagents which in their reactions seek the extra electrons that will give them stability
Nucleophiles are reagents that seek a proton or some other positive center

Substitution Reaction:

Concerted Process – nucleophilic attack and loss of leaving group occurs simultaneously
nd
SN2 is a concerted process and 2 order kinetics
st
SN1 is a stepwise process and 1 order kinetics

Polar protic solvent favors SN1

Polar aprotic solvent favors SN2
5. Alkanes and Cycloalkanes
- also called paraffins or unsaturated hydrocarbons, sp3 hybridized

At room temp:
C1-C4 – gases
C5-C17 – liquids
C18- Cn – solids

Chair conformation – most stable cyclohexane conformation

Others: half chair, boat, twist boat

Primary reactions: radical reactions – reaction with light and heat forming radicals

6. Alkenes
- also called olefins, sp2 hybridized

Bredt’s rule - eight-membered ring is the smallest size ring that can accommodate a trans double bond in a bridged bicyclic
compound
Trans is more stable than cis

Elimination Reactions:

E2 (Elimination Bimolecular)
-One step mechanism, similar to SN2, Zaitsev is favored

E1 (Elimination Unimolecular)
-Two-step mechanism, similar to SN1, Zaitsev is always favored

Zaitsev product – double bond on the more substituted side

Hoffmann product – double bond on the less substituted side

If the base is bulky , Hoffmann product is favored

Addition Reactions:
7. Alkynes
- has triple bonds, sp hybridized
- One sigma bond and two pi bonds

Addition Reactions:

8. Aromatic Compounds
- benzene derivatives
- planar
- cyclic
- follows Huckel’s Rule: 4n+2= pi electron, n is a whole number

Bond order of benzene is 1.5

Annulenes – compounds containing single ring that contains fully conjugated pi electrons

Benzene is also known as [6]Annulene

Ortho-Para Director: Strongly activating – N in Amine, O in OH

Moderately activating – N attached to carbonyl, O attached to R
Weakly Activating – R group,
Weakly Deactivating - Halogens

Meta Directors: Moderately Deactivating – Cyanate, sulfonate, carboxyl, carbonyl

+
Strongly Deactivating – Nitro, -NR3 , -CX3,
Aromatic Substitution Reactions:

Other Aromatic Reactions:

9. Alcohols, Thiols, Sulfides and Ethers

Alcohols – has hydroxyl (-OH) functional group

Ethers – has alkoxy (-OR) functional group
Thiols – has marcapto (-SH) group
Sulfides – has -S-S- group

Boiling Point: Alcohol > Ethers

Grignard Reagents- carbon nucleophiles (usually with Mg) that can attack electrophiles

Oxirane- three membered ringed ethers

Epoxide- substituted oxirane

Reactions:
Alcohols and Phenols:

Ethers, Thiols, and Sulfides

10. Aldehydes and Ketones
- contains carbonyl group
- soluble in water

Reactions:
11. Carboxylic Acids and Derivatives
- contains Carboxyl group (-COOH)

Gilman Reagent – lithium aluminum dialkyl cuprate

Fischer Esterification – carboxylic acids are converted to esters by reacting with alcohols with acid catalyst
Saponification – Hydrolysis of esters in basic condition to form carboxylic acids

Reactions:
12. Amines
- contains amino functional group (-NH2)
o o o
Basicity: 2 > 1 >3 > Amine

Reactions: