Organic Chemistry Summary

Basics
Halogens generally act as an electrophile, unless of course, it is e.g. Cl- already.
Strongest base is least electronegative.
Strongest acid is most electronegative.
Good leaving group Weak base, conjugate base of a strong acid.
Good nucleophile Strong base, conjugate base of a weak acid.
Factors on Acid Strength:
1. More s character, the more positive a molecule is and thus it has a
greater acid strength (pKa).
2. The more electronegative the atom gaining the electron pair, the more
acidic.
3. More resonance for conjugate base, more acidic.
Factors on Base Strength:
1. More s character, the more positive and tightly bound the molecule is
and thus electrons are harder to share, less basic.
2. The more electronegative the atom losing the electron pair, the less basic.
3. More resonance for conjugate acid, more basic.
A nucleophile is simply a base attacking at carbon, rather than at a proton.
Nucleophilic Substitution
Alkyl halides are good substrates for nucleophilic substitution reactions.
Leaving group carries away the bonding electrons. Nucleophile attacks the
carbon of the substrate.
Rate of SN1 depends on stability of carbocation (more substituents, more stable).
Rate of SN2 depends on energy of transition state. Higher energy = slower.
Alkyl Halides:
1o SN2
2o SN1/SN2
3o SN1
SN1 reaction is favoured with a good leaving group.
SN2 reaction is favoured with a good nucleophile.
Polar solvent will favour a SN1 reaction by providing stabilisation to carbocation.
SN2 has Walden inversion if the molecule has a chiral centre and the leaving
group is attached to the chiral centre. Invert R/S configuration.
SN1 proceeds as normal however remember that it can be attacked from either
sides, results in racemic product 50:50.

Nucleophilic Elimination
Nucleophile attacks at -carbon instead of -carbon attached to leaving group.
Formation of a C=C double bond. Otherwise same as substitution.
Leaving group is displaced.
N.B. -carbon has to be a carbon directly attached to the -carbon which is itself
directly attached to the leaving group.
Zaitsefs Rule Base induced elimination reaction produces the most stable
alkene product. This is the alkene with the most substituents attached to C=C
bonds.
Can give more than one product if different -carbons are attacked.
Elimination vs. Substitution
1o Alkyl halides SN2 occurs for good nucleophiles, E2 elimination occurs only if
a strong sterically hindered base is used.
2o Alkyl halides Substitution occurs if a weakly basic nucleophile is used. E2
elimination predominates if a strong base is used.
3o Alkyl halides E2 elimination occurs if a strong base is used, but SN1
substitution and E1 elimination occurs if a weakly basic nucleophile is used.
Elimination is favoured with strong, sterically hindered bases.
Elimination is favoured with a 3o substrate with more steric hindrance at carbon, and with more hydrogens susceptible to attack.
Electrophilic Addition Reactions
Addition of (E+ Nu-) to the C=C double bond.
Step 1. Electrophilic reagents adds to the C=C double bond
Step 2. Capture of the electrophilic carbocation intermediate by a nucleophile.
Markovnikovs rule Addition of HX to an alkene, the major product arises from
the H attaching to the less substituted carbon of the C=C, and X attaching to the
more substituted end. (Also the more substituted carbocation intermediate).
N.B. However remember there is still a minor product.
Note for halogenation of alkenes, that halides (e.g. Br), instead of seeing a C+, we
have a Br+ instead because it is more stable.
Electrophilic (Aromatic) Substitution
Step 1. Electrophilic reagents adds to the C=C double bond
Step 2. Wheland intermediate deprotonated (lose H+) by the Nu- to give an
electrophilic substitution product because maintaining aromaticity is of higher
priority.
Reaction is slower than with alkenes.
Electrophiles are attached to pi-electrons.

On substituted benzene derivatives:

EWG Aromatic ring is deactivated towards electrophilic substitution compared
to benzene. Electrophile attacks at the meta- position.
Halogen-substituted benzene derivatives are ortho- / para- directing even
though they are EWG.
EDG Aromatic ring is activated towards electrophilic substitution compared to
benzene. Electrophile attacks at the ortho- / para- positions.
N.B. Generalisiation IF there are lone pairs, then it is an ortho-para directing
group.
Wheland Intermediate is a carbocation intermediate formed when electrophile
attacks, it is resonance stabilized. It is deprotonated by Nu- (hence substitution).
Nucleophilic Addition
Characteristic reaction of carbonyl compounds. Carbonyl carbon is electrophilic
and very susceptible to attack by nucleophiles.
Step 1. Nucleophilic attack at the carbonyl carbon, giving a tetrahedral
intermediate.
Step 2. Depends on class of carbonyl group and its R1 and R2 substituents, also on
the nature of nucleophile.
Aldehydes and ketones
Carbon-centred nucleophiles are commonly organometallic reagents (e.g.
Grignard reagent, or Li).
Grignard reagent with simplest aldehyde; methanal, gives a 1o alcohol.
Grignard reagent with all other aldehydes gives 2o alcohol.
Grignard reagent with ketones gives 3o alcohol.
Grignard reagent with CO2 forms carboxylic acids.
N.B. Grignard reagents can be formed by combining most alkyl halides with Mg
metal. Reacts as R- and MgX+ with substrate.
Nitrogen centered nucleophiles with either aldehyde or ketone will result in
Conversion of the carbonyl compound into an imine derivative with water
formation as a by-product.
First step is also nucleophilic attack like Grignard, however second step is
an addition-elimination reaction. Addition of amine group and
elimination of water (OH- group). [Almost looks like substitution doesnt
it?]
Can also react with cyclohexanone to give the cyclohexanone imine derivative.

Carboxylic acids and their derivatives (Nucleophilic acyl substitution)

R1 = H or C and R2 = O, N or halogen
CAD is a carbonyl compound which has a leaving group attached directly to the
carbonyl carbon.
Acid chlorides are the most reactive of carboxylic acid derivatives (CAD). They
contain the best leaving group (Cl-).
Step 1. Nucleophile attacks the carbonyl carbon. Tetrahedral intermediate
formed. Double bond is lost (like an addition reaction).
Step 2. Tetrahedral intermediate breaks down with the expulsion of the leaving
group, regenerate the carbonyl group (like elimination, and double bond
formed).
Nitrogen and oxygen-centered nucleophiles
Reaction of CAD with N and O centred nucleophiles results in the
interconversion of one CAD with another.
*Nucleophile has to displace a better leaving group, if not, the reaction will not
proceed.
Oxidation
Converts from a functional group to another at a higher oxidation state.
Loss of e-, loss of H+, and/or gain of O. E.g. dehydrogenation.
Oxidation of alcohols by chromium trioxide CrO3
1o alcohol Aldehyde Carboxylic Acid
2o alcohol Ketone
3o alcohol No further oxidation because C-C bond is difficult to break.
Oxidation of alkyl benzenes
Must be at least one hydrogen adjacent to the ring if not oxidation wont work.
Oxidised for example by KMnO4. Forms benzoic acid. Overall gain of oxygens and
loss of hydrogens.
Dehydrogenation of alkanes to alkenes
Its like an elimination reactionloss of hydrogen thus considered oxidation.
Some oxidizing agents: CrO3, Na2Cr2O7, KMnO4, O2, O3

Reduction
Converts a functional group to another at a lower oxidation state.
Gain of e-, gain of H+, and/or loss of O.
Reduction of alkenes to alkanes
Is an addition of H, double bonds are reduced/removed.

Reduction of nitrocompounds
H2 gas reducing agent with PdC or PtC catalyst. Non-activating meta- to a
activating para-.
Reduction of carbonyl compounds
Only hydride reducing agents (NaBH4, LiAlH4) work well here.
- Aldehydes
Reduce to 1o alcohols. Reactive enough to be reduced by NaBH4 and obviously
LiAlH4 which is a very reactive agent.
- Ketones
Ketones always reduce to 2o-alcohols. Can be reduced by NaBH4.
- Esters and carboxylic acids
Esters and acids reduce to 1o alcohols but become aldehydes first.
Cannot be reduced by NaBH4 because it is less reactive.
Some reducing agents: NaBH4, LiAlH4, H2 with catalyst like Ni, PdC or PtC, Sn/HCl
or Zn/HCl