Organic Synthesis

starting with the aromatic ester methyl benzoate and finishing with the nitro aromatic acid 3-nitro benzoic acid:

O H H

C

OCH3
ester

O

H

C

OH acid

H H
in three separate stages

NO2
nitro
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Stage 1
O C

Nitration of the aromatic ring to form methyl 3-nitrobenzoate

OCH3 + HNO3

O

C

OCH3 + H2O NO2

Cool with concentrated H2SO4

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Identification of methyl 3-nitrobenzoate

O

C

OCH3

White crystalline solid at room temperature Melting point 77.5 oC

NO2

Impurities reduce melting point and discolour the solid

Compare with 3-nitrobenzoic acid
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mass spectrum of methyl 3-nitrobenzoate
O OCH3 m/z relative intensity C 75 14 76 24 104 27 NO2 150 100 181 23 C6H4(NO2)CO+ Mass of molecular ion:181

+

C6H4

+

C6H4CO+

C6H4(NO2)COOCH3+

Compare with 3-nitrobenzoic acid
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Infra red spectrum of methyl 3-nitrobenzoate
Compare with 3-nitrobenzoic acid

The “finger print” region < 1500 cm-1 unique pattern for each molecule C=O 1750 cm-1

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nmr spectrum of methyl 3-nitrobenzoate 1H NMR C8H7NO4 A 399.65 MHz
E Assign. A C D B D E Shift(ppm) 8.86 8.43 8.38 7.68 4.00

0.038 in 0.5 ml CDCl3 nucleargmagnetic resonance B
C

Compare with 3-nitrobenzoic acid
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Stage 2
O C OCH3

Hydrolysis of the ester group to form the 3-nitrobenzoate ion

O
-

C

O + CH3OH NO2

+ OH NO2

Reflux with concentrated NaOH alkaline hydrolysis
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Stage 3
O C O

Displacement of weak acid to form 3-nitrobenzoic acid

O + H+ NO2
Warm with HCl acid displacement

C

OH

NO2

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Identification of 3-nitrobenzoic acid
OH C

O

White crystalline solid at room temperature Melting point 141.0 oC Impurities reduce melting point and discolour the solid

NO2

Compare with methyl 3-nitrobenzoate
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mass spectrum of 3-nitrobenzoic acid
m/z relative intensity 65 100 121 44 167 53 Mass of molecular ion:167.0
O OH

+

C

NO2

C6H4(NO2)CO2H+ C6H4(NO2)+

Compare with methyl 3-nitrobenzoate
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Infra red spectrum of 3-nitrobenzoic acid
Compare with methyl 3-nitrobenzoate

The “finger print” region < 1500 cm-1 acid O-H unique pattern 2600 cm molecule for each -1 C=O 1700 cm-1

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nmr spectrum of 3-nitrobenzoic acid 1H NMR
D C7H4NO4 A 89.56 MHz B

0.025 g in 0.5 ml CDCl3
E C Assign. A B C D
Compare with methyl 3-nitrobenzoate

Shift(ppm) 11.67 8.96 8.49 8.47 7.74
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E

References Steve Lewis for the Royal Society of Chemistry Source of the spectral information http://www.aist.go.jp/RIODB/SDBS/menu-e.html

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