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Experiment 21:: Esters: Synthesis and Fragrance

1) The document describes an experiment to synthesize isoamyl acetate from acetic acid and isoamyl alcohol using Fischer esterification. 2) The objectives are to synthesize the ester product, purify it through extraction and distillation, and analyze its purity using GC, NMR, and IR spectroscopy. 3) Fischer esterification is described as an acid-catalyzed nucleophilic acyl substitution reaction that forms an ester from a carboxylic acid and alcohol.

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90 views20 pages

Experiment 21:: Esters: Synthesis and Fragrance

1) The document describes an experiment to synthesize isoamyl acetate from acetic acid and isoamyl alcohol using Fischer esterification. 2) The objectives are to synthesize the ester product, purify it through extraction and distillation, and analyze its purity using GC, NMR, and IR spectroscopy. 3) Fischer esterification is described as an acid-catalyzed nucleophilic acyl substitution reaction that forms an ester from a carboxylic acid and alcohol.

Uploaded by

allforuno
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Experiment 21:

ESTERS:
SYNTHESIS AND FRAGRANCE
O
RCOH

H
+

R'OH

O
RCOR'

H2O

Objectives:

To synthesize an ester from acetic acid


with isoamyl alcohol under reflux.

To purify your product through acid-base


extraction and simple distillation.

To identify and analyze the purity of your


compound using GC analysis.

To identify your product by analyzing the


NMR and IR spectra.

Before coming to lab

Review these techniques:

Reflux

Acid-Base Extraction

Simple distillation

Drying over MgSO4

GC Analysis

FISCHER ESTERIFICATION

Fischer esterification is an acid catalyzed nucleophilic


acyl substitution.
Net effect is the replacement of an OH of a
carboxylic acid with the OR of an alcohol to produce
an ester.
O

O
+

R'

R'

It is an equilibrium reaction with an unfavorable Keq,


thus we can improve product yield in several ways:
Use an excess of the alcohol reactant.
Use an excess of the carboxylic acid reactant.
Remove water as it forms.

FISCHER ESTERIFICATION
H

O
C
H3C

CH3

O
+

OH

OSO3H
C
H3C

OH

OH

C
CH3

Carboxylic acids are not reactive enough to undergo


nucleophilic addition directly.

By using sulfuric acid as a catalyst, the carbonyl


group oxygen is protonated to give the carboxylic
acid a positive charge. This makes it more
reactive.

MECHANISM
1. Protonation
of the
carbonyl
oxygen
activates the
carboxylic
acid

O
C
H3C

CH3

O
+

OSO3H

OH

H3C

OH

3. yielding
a tetrahedral
intermediate.

OH

CH3

H 3C

OH

2. toward
nucleophilic
attack by the
alcohol

H
C

H 3C
O
HO 4
5
H

4. Transfer
of a proton
from one
oxygen to
another yields
a second
tetrahedral
intermediate

CH3

6
H

H 3C

O
H
C

H 3C
H

6. Loss of a
proton and
expulsion of H2O
regenerates the
acid catalyst and
gives the ester
product.

H
C

O
H

5and
converts the
OH group into
a good leaving
group.

CH3

H3C

C
H 3C

H
C

CH3

H 2O

H2SO4

OVERVIEW

Synthesize product ester under reflux.

Neutralize acetic acid with 10% NaHCO3.

Extract in ether, then wash with 10%


NaHCO3.

Dry organic layer.


Perform simple distillation to remove ether
from product.
Obtain final product mass, calculate %
yield, prepare GC sample.

EXPERIMENTAL PROCEDURE
(SYNTHESIS)

Combine

acetic acid, isoamyl alcohol


and sulfuric acid in a 25 mL round
bottom flask.

CaSO4 tube

Clamp flask to ring stand and add 3


boiling chips.

water out

Place water cooled condenser on top


of flask, with a CaSO4 drying tube in
the top.

water in

Heat to reflux. Reflux 30 minutes.


Cool to room temp.
Add 10% NaHCO3 slowly to flask.

25mL
heating mantle

to voltage regulator
iron ring

EXPERIMENTAL PROCEDURE
(PURIFICATION)

Transfer

liquid to separatory funnel.

Rinse reaction flask with ether and


transfer to separatory funnel.
Wash the organic layer with 10% NaHCO3.

Transfer the organic layer to a clean


flask.

125
mL

Dry over MgSO4.

Transfer liquid to a preweighed 50 mL


round bottom flask.

50mL

Clamp flask to ring stand.


50mL

EXPERIMENTAL PROCEDURE
(PRODUCT ISOLATION)

Set

up a simple distillation
apparatus, using a 25 mL round
bottom as the receiving flask.
Collect all distillate that boils under
40oC.

water out
water in

Record distillation range, Ti-Tf.


Heating Mantle

Allow reaction flask to cool to room


temperature.

Reweigh 50 mL flask to determine


final product mass (actual yield) and
calculate % yield.
Prepare GC sample.

iron ring
to
voltage
regulator

50mL
PRODUCT!!!

25mL
WASTE
SOLVENT

Table 21.1
Theoretical yield (g)

Actual yield (g)

% yield

Calculated value based on


limiting reagent!
(50mL RB flask + product)
(Empty 50mL RB flask)

ACTUAL YIELD
THEORETICAL YIELD

X 100

PHYSICAL STATE, COLOR


Product Appearance

Table 21.2
Compound
methanol
isoamyl alcohol
isoamyl acetate

GC Retention Times (min)


Standard
Sample

Area Percent

Adjusted

Area Percent

SOLVENT
REACTANT
PRODUCT

EXPERIMENTAL PROCEDURE
(IR ANALYSIS)

CH3
5

CH3CHCH2CH2OH
4

CH3

CH3CHCH2CH2OCCH3
4

Table 21.3
Functional
Group

sp3 CH
stretch

Base Values

Acetic acid

Isoamyl
alcohol

Isoamyl
acetate

Frequency
(cm-1)

Frequency
(cm-1)

Frequency
(cm-1)

Frequency
(cm-1)

2850-3000

C-O stretch
1000-1300
OH stretch
2400-3600
C=O stretch
1640-1750

EXPERIMENTAL PROCEDURE
(NMR ANALYSIS)

CH3
5

CH3CHCH2CH2OH
4

CH3

CH3CHCH2CH2OCCH3
4

O
C
H3C
1

OH
3

SAFETY CONCERNS

CAUTION:
H2SO4
is a
STRONG ACID!

WASTE MANAGEMENT
All aqueous washes from the extraction

can be flushed down the drain with plenty


of water!
Ester product and distilled ether should be
placed in the bottle labeled, ORGANIC
WASTE (Esters).

CLEANING

Clean round bottom flasks and distillation


glassware with wash acetone only!
Separatory funnel and all other glassware
should be cleaned with soap, water, and a
brush if necessary, followed by a wash
acetone.
DO NOT return any glassware to lab
drawer dirty or wet!

LABORATORY NOTEBOOK
(Pre-lab)
OBJECTIVE

(Must clearly state)

What compounds will be made and how

How the compounds will be purified


How the purity of the product will be determined

CHEMICAL EQUATION
Include the chemical equation from the top of page 177.

TABLE OF PHYSICAL DATA

(Complete the following table using a


site listed on WWW Links ONLY. Wikipedia is unacceptable!)
Compound
Isoamyl alcohol
Isoamyl acetate
Acetic acid
Sulfuric acid
Diethyl ether
methanol

MW (g/mol)

bp(oC)

d (g/mL)

REFERENCE TO PROCEDURE
full title including edition and author names

HAZARDS

(Must include)

page numbers where actual procedure can be found

LABORATORY NOTEBOOK
(In-lab)
DATA/CALCULATIONS

Initial volumes of isoamyl alcohol and acetic acid used


Distillation range
Weight of 50 mL round bottom flask
Weight of 50 mL round bottom flask + product
Final product weight
Physical state and color of product
GC vial slot #
Theoretical yield calculation (not just value!)
% yield calculation (not just value!)
Example of an adjusted area % calculation (not just value!)

EXPERIMENTAL PROCEDURE

In paragraph form, BRIEFLY describe the procedure that you actually followed
during the lab.
Paragraph must be written in PAST TENSE, PASSIVE VOICE.
Include any volumes or weights of chemicals used during the experiment.
Include any mistakes, accidents or observations if applicable.

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