Nitration of Methyl Benzoate

A B C 50% Yield =25% Multistep Synthesis

Ortho Meta Para Ortho Meta Para

Number Ring

Nucleophilic Aliphatic Substitution Electrophilic Aromatic Substitution

E+E+ + H + The electrophile REPLACES H + ARENE SUBSTITUTION

E - Y Mechanism

E - Y + H + Mechanism

Charge o and p

Energy Diagram

Nitrobenzene Nitration of Benzene

Nitronium Ion HONO H 2 SO 4 NO H 3 O HSO 4 - Nitration Reagent

Nitration Mechanism

G Second Group. Where go? How fast? Multiple Substituents

HNO 3 63% 3% 34% Nitration of Toluene

ORTHO META PARA Compare o, m, p

Favor: ORTHO and PARA. Electron Donating Ortho Para Electron Donating Groups

HNO 3 H 2 SO 4 6% 91% 3% Nitration of trifluoromethylbenzene

+ charge here bad Electron Withdrawing Groups

Ortho Meta Para Compare o, m, p

Meta Directors and DEACTIVATING Electron Withdrawing Group Meta Product Electron Withdrawing Groups

-NH 2 -OH -NHR -OR -OCR -NHCR O O Very Activating Ortho-Para Directors

-R -Ar -Halogens Activating Deactivating Ortho-Para Directors

-CR O -COH O -CN -SO 3 H -NO 2 Meta Directors

Side Products meta Main Reaction

1. Dissolve methyl benzoate in H 2 SO 4 2. Mix HNO 3 and H 2 SO 4 at 0 o C 3. Add HNO 3 / H 2 SO 4 dropwise to methyl benzoate at 0 o C Procedure

4. Let stand at room temperature 10 minutes 5. Pour onto ice Procedure

Filter

Recrystallize from methanol Dry Weigh m.p. Wash