LABORATORY MANUAL

SCH 2413
ORGANIC CHEMISTRY II

DEPARTMENT OF CHEMISTRY
KULLIYYAH OF SCIENCE
IIUM
1
CONTENT PAGE
General guidelines for laboratory SafetyRules 3
Components of Experimental Report 4
EXPERIMENT 1: RATES OF CONVERSION OF ALCOHOLS TO ALKYL
BROMIDES 5
EXPERIMENT 2: OXIDATION OF (–)-BORNEOL TO (–)-CAMPOR WITH
HYPOCHLOROUS ACID; SPESIFIC ROTATION 9
EXPERIMENT 3: KINETIC AND THERMODYNAMIC REACTION
CONDITIONS 12
EXPERIMENT 4: ACETANILIDE TO p-NITROANILINE 15
EXPERIMENT 5: SELECTIVE REDUCTIONS OF m-
NITROACETOPHENONE WITH TIN AND SODIUM BOROHYDRIDE. 18

2
General Guidelines for Laboratory Safety Rules

Please follow the following guidelines for your safety in the laboratory:

1. Every time you enter the lab, do not forget to wear goggles Students are advised not
to wear contact lens in the lab as the solvents (particularly organic solvents) are
mostly volatile and flammable.

2. Dress properly during a laboratory activity. Shoes must completely cover the foot.
No sandals allowed in the laboratory.

3. Do not bring food and drink into the laboratory.

4. Be prepared for your work in the laboratory. Read all procedures thoroughly before
entering the laboratory. Never fool around in the laboratory. Horseplay, practical
jokes, and pranks are dangerous and prohibited.

5. Observe good housekeeping practices. Work areas should be kept clean and tidy at all
times

6. All chemicals in the laboratory are to be considered dangerous. Avoid handling

chemicals with fingers. Always use a tweezer.

3
Components of Experimental Report

For each experiment done, a student is required to write a report and submit to the respective
lecturer. In your report, please include the following components:

a) Title and date

- What is the title of the experiment given and date of experiment was conducted.

b) Introduction
- In the introduction, the student needs to write what is the aims/objectives of the
experiment, what are the instruments used and the balanced chemical equations
involved in the experiment.

c) Procedure of the experiment

- It is better to write in your own words (flow chart, mind map) as it will reveal
your understanding of the experiment carried out.

d) Data and Observations

- The observations are described as the progress in the experiment. It includes (but
not limited to) colour and temperature changes, appearance of precipitate, the
weight of reagent and products, etc.

e) Discussion of data and conclusion

- In this section, you are required to interpret the data obtained and supported by
appropriate references.

f) References
- The references should be taken from books, journals and website.

g) Questions
- Answer all the questions in the lab manual when applicable.

4
 EXPERIMENT 1: RATES OF CONVERSION OF ALCOHOLS
TO ALKYL BROMIDES

The treatment of alcohols with a mixture of concentrated hydrobromic and sulfuric acids has
sometimes been used as a synthetic method for preparing alkly bromides. Depending on the
structure of the starting alcohol, the reaction can occur by either of two paths. The first step
for either path is rapid reversible protonation of the alcohol as shown in Reaction (1).

Keq
ROH + HBr ROH2 + Br -
(1)
Oxonium ion

If the alkyl group is capable of forming a reasonably stable cation, the next step involves loss
of water followed by rapid reaction of the resulting solvated cation with bromide ion to give
the product, as shown in Reactions (2) and (3).

k2
ROH2 R + H2O
Slow
Cation (2)

k3 (3)
R+ + Br - RBr
rapid

These reactions constitute an example of unimolecular solvolysis designated as SN1. Because

the slow or rate-determining step is given by Reaction (2), the rate expression can be written
as

Rate = k2 [ROH2 ]

and is dependant only on the concentration of the oxonium ion ROH2+.

The equilibrium constant for Reaction (1) is given by

[ROH2 ] [Br -]
Keq =
[ROH] [ HBr]

If we solve this for [ROH2+] and substitute into the rate expression, the results is
Rate = k2 Keq [HBr] [ROH]
[Br -]

5
Because the reaction is run with a large excess of aqueous hydrobromic acid, the values of
[HBr] amd of [Br-] are essentially constant and the rate law simplifies to

Rate = k[ROH]

Which is now first order in [ROH].

EXERCISE 1 : Which of the alcohols, 2-propanol, 2-methyl-2-butanol, or 1-hexanol,

would be most likely to follow the described SN1 mechanism? Explain.

The oxonium ion generated in Reaction (1) can also react directly with bromide ion in
a bimolecular displacement or SN2 reaction as shown in Reaction (4).

k4
ROH2 + Br - RBr + H2 O
slow (4)

In terms of the slow step, Reaction (4), the rate law can be written

Rate = k4 [ROH2 ][Br -]

or by substituting the value for [ROH2+] from the equilibrium expression for Reaction (1),

Rate = k4 Keq [HBr][ROH]

In the presence of a large excess of hydrobromic acid, k4Keq[HBr] is a constant, so that the
expression again simplifies to

Rate = k [ROH]

Although primary alcohols would be expected to follow the S N2 path, secondary

alcohols might undergo reaction by either the SN2 or SN1 mechanisms (see EXERCISE 1).

EXERCISE 2: From your knowledge of the characteristics of the S N2 reaction, what

should happen to the rate constant for bimolecular displacement in Reaction (4) as the
structure of R is changed from primary to secondary to tertiary?
For this experiment you will bee assigned one alcohol from each of the two groups of
compounds (primary and secondary) listed below.

6
 Group A Group B
1-butanol (butyl alcohol) 2-butanol (sec-butyl alcohol)
2-Methyl-1-propanol (isobutyl alcohol) 2-pentanol (sec-amyl alcohol)
1-pentanol (amyl alcohol) Cyclopentanol
3-methyl-1-butanol (isoamyl alcohol) Cyclohexanol

After the samples have been placed into a tall narrow tub, mixed with an excess of
hydrobromic and sulfuric acids and heated, the depth of the layer of alkyl bromide product
that floats to the top will be measured with a ruler as a function of time.

A. GENERAL PROCEDURE

Heat a 400 mL beaker filled with water to 98 ± 1 o (just below the boiling point). The alcohols
and other reagents will be contained in burets in the hoods. When the temperature of your
water bath has stabilised, measure exactly 1.0 mL of each of the alcohols assigned to you into
two small (clean and dry) flask or beakers. Cool the containers in ice, add 2.0 mL of 48%
hydrobromic acid to each one , and then slowly add 1.0 mL of concentrated sulfuric acid
with gentle swirling. Mix throughly, pour the respective reaction mixtures into two labeled
glass tubes (10 mm o.d. x 30 x 30 cm, sealed at one end), and clamp the tubes in a vertical
position in the water bath. Note the time, and as the insoluble layer of alkyl bromide
separates, measure the height of the layer with milimeter-graduated ruler as close as possible
to the nearest 0.5 mm. Take initial readings at 1-min intervals and later ones at 2-min intevals.
Discontinue the measurements when the level of alkyl halide no longer shows any increase
(about 15 min for the first three alcohols in Group B and 35-70 min for cyclohexanol and the
alcohols in Group A).

EXERCISE 3: Although the alkyl bromides prepared in this experiment all have densities
greater than 1.2 g/mL they appear as an upper layer in the reaction mixture. Explain.

B. CALCULATION OF RATE CONSTANTS

As has been shown in the introduction to the experiment, the rate expression for either of the
two possible mechanisms will have the general form

d [ROH]
= Rate = k [ROH]
dt

7
Integration of this expression from the initial concentration of alcohol, [ROH] 0, to its
concentration at time = t, [ROH], leads to

– ln[ROH] + ln [ROH]0 = kt

which can be simplified and solved for k to give

k = 1/t ln [ROH]0
[ROH]

We recognise that the stoichiometric relationship between starting alcohol and product alkyl
bromide is 1:1 so that the value of [ROH] is directly proportional to h∞, the height of the alkyl
bromide layer when the reaction is completed. Similar reasoning leads to the conclusion that
the [ROH] is proportional to h∞ - h, in which h is the height of the alkyl bromide layer at any
time during the reaction. Substitution of these values into the rate expression gives

k = 1/t ln h∞
h∞ - h

Determine the values of k (in min-1) for each alcohol at each of the three temperatures by
plotting

ln h∞
h∞ - h

(vertical axis) versus time in min (horizontal axis) and obtaining the slope of the resulting
“best-fitting” straight line.

EXPERIMENT 2: OXIDATION OF (–)-BORNEOL TO (–)-

CAMPHOR WITH HYPOCHLOROUS ACID; SPECIFIC
ROTATION

The following experiment illustrates the oxidation of a secondary alcohol to a ketone and
provides an opportunity to use thin-layer chromatography, infrared spectroscopy, and optical
8
rotation measurements to derive information about the structure and purity of an isolated
product. Additional techniques used include extraction and sublimation.
The unbalanced equation for the oxidation process is shown below.

HOCl O
HOAc
OH

(_)-Borneol (-)- Camphor

EXERCISE 1: Write a balanced equation for the oxidation of (–)-borneol to (–)-camphor

with HOCl (hypochlorite in acid) going to HCl.

A. PREPARATION OF (–)-CAMPHOR

Dissolve 500 mg (3.25 mmol) of (–)-borneol in 1.5 mL of glacial (i.e. concentrated) acetic
acid in a 25-mL erlenmayer flask with swirling at room temperature. Add about 4.0 mL of
fresh household bleach solution (e.g., Clorox, which is ca. 5.25% NaOCl) in one batch with
swirling. The solution will become noticeably warm and product will precipitate. Swirl the
reaction mixture occasionaly over the next 15 min and test the sample after 10 min by placing
one drop on wet starch-iodine paper. A blue color indicate excess hypochlorite. If the test is
negative, add a small amount of additional hypochlorite solution , swirl, let stand 5 min, and
test it again.

I- oxidation I2 starch blue starch-iodine complex

Dilute the reaction mixture with about 15 mL of water and transfer it to a 60-mL
separatory funnel with 15-mL of diethyl ether. Add 0.5-1.0 mL of saturated sodium bisulfite
solution to reduce any residual hypochlorite (negative test with starch-iodine paper) and
shake the mixture for at least 20-25 sec before draining the lower layer. Wash the ether layer
with about 8-mL of saturated sodium bicarbonate solution (gas evolution). Drain off the
lower aqueous layer, and transfer the ether to a small Erlenmayer flask (use a little ether
rinse). Dry the ether with a small amout of anhydrous Na 2SO4 (allow at least 10 minutes),
decant the solution into a tared 25-mL erlenmayer flask and carefully evaporate the ether. Use
the heat lamp to warm the flask, but only to room temperature. Weight the flask and calculate
the crude yield of camphor; it should be very good.

HOCl + HSO3- Cl- + 2H+ + SO4-

9
 Save a portion (1-2 mg) of this product for a melting point and a second portion (ca.
10 mg) for determination of the IR spectrum. Weight and sublime the remaining portion of
the product in an apparatus such as that pictured in Figure 1,. The central test tube in the
apparatus must be kept cold with ice water, but condensation of moisture from the
atmosphera should be avoided. Heat the camphor from the bottom with a heat lamp
(vertically mounted with steamed-bath rings or aluminium foil to shield all but the bottom of
the sublimator from the heat). Determine the yield of the sublimed product. Take the mp of
the sublimed product in a sealed capillary. Pure, dry (–) or (+)-camphor completely melts at
177-178 oC.

put ice water

chemicals to be sublimed

heat lamp

Figure 1: Sublimation apparatus

EXERCISE 2: Borneol can also be oxidised to camphor with other oxidising agent, such as
sodium dichloromate in acid. Write a balanced equation for this oxidation (Cr 2O72- is reduced
to Cr3+). What the weight of Na2Cr2O7.2H2O should be needed (theoretically) to oxidise 0.50
g of borneol?

B. INFRARED SPECTRUM

10
Take the IR spectrum of the crude and purified products as solutions (ca. 10% w/v) in dry
methylene chloride in a cavity cell. Be certain to rinse the cell at least twice with fresh
methylene chloride before and after you used it.

EXERCISE 3: What portion of the spectrum will not be useful because methylene chloride
was used as the solvent?

EXERCISE 4: What conclusions can be drawn about the presence or absence of unreacted
starting material?

EXERCISE 5: Which compound, (–)-borneol or (–)-camphor, has the highest vapor

pressure? (Hint: What are the listed boiling points?)

C. THIN-LAYER CHROMATOGRAPHY

Using commercial or home made silica gel plates, run a TLC comparison of samples of
authentic borneol, authentic camphor, and your purified camphor with methylene chloride
(reagent grade) as the developing solvent. The samples should be prepared as concentrated
solutions in a small amounts (100 µL) of methylene chloride in three labeled vials.

NOTE: Careful observation of the TLC plate may reveal a small spot with slightly longer R f
value than that for camphor.

D. OPTICAL ROTATION

Weight (to the nearest mg) 125-150 mg of purified camphor into a tared 5-mL volumetric
flask and fill it to the mark with ethanol. Be certain to mix the solution by inverting the flask
with the stopper in place. Fill a 1-dm (center-fill) polarimeter tube and use a polarimeter to
obtain a measured rotation at the sodium-D line (589 nm). Calculate the specific rotation and
compare it to the literature value for optically pure (–)-camphor of -43.8 o in ethanol. Look up
the specific rotation of (–)-borneol in ethanol and comment on whether or not a small amount
of the unreacted starting material would effect your rotation measurement.

EXPERIMENT 3: KINETIC AND THERMODYNAMIC

REACTION CONDITIONS

Consider a reaction in which two products can arise by two different reaction paths having
different activation energies. The reaction is said to be kinetically controlled if conditions are

11
such that the product that is formed more rapidly (by the path of lower activation energy) is
the dominant product. It is important that this may or may not be the more stable product.

If the reaction is carried out under conditions where the two products can be in the
equilibrium with each other (thermodynamically or equilibrium control), the more stable
product will always dominate. Thermodynamic control is always favored by the higher
temperatures and longer reaction times.

EXERCISE 1 : In the energy diagram #1, R represents the reactants and P1 and P2 the
products. Which product would dominate under kinetic control? Under thermodynamic
control? Consider the same questions for energy diagram #2.

The concepts of kinetic and thermodynamic control can also be applied to the
competition of two related reactants with a single reagent to form two related products, as in
the following experiment. We will use the reaction of an aldehyde or ketone with
semicarbazide to form a semicarbazone.

RCOR' + H2NNHCONH2 RR'C=NNHCONH2 + HOH

Semicarbazide A semicarbazone

More specifically, we will allow furfural and cyclohexanone to compete for a limited amout
of semicarbazide under conditions that allow us to compare the relative rates of formation
and the stabilities of the two semicarbazones.

O
CHO
O

cyclohexanone Furfural

12
A. SEMICARBAZONE FORMATION

Slowly dissolve 1.7 g (15.2 mmol) of semicarbazide hydrochloride in a solution of 3.0 g of

sodium bicarbonate in 35 mL of water in an Erlenmayer flask and when effervescence ceases,
add 1.5 mL (15.3 mmol) of cyclohexanone. Shake or swirl the mixture for 8 min and isolate
the product by suction filtration (suitable sized Buchner or Hirsch funnel). Recrystallise it
from a minimum amout of hot water, allow it to dry, and obtain a melting point.

Carry out the same procedure with 1.3 mL (15.7 mmol) of distilled furfural and a
reaction time of 20-25 min on a steam bath. (During the 20 min reaction time, begin the next
experiment). Recrystallise the product from hot methanol (20 mL/g of product), allow it to
dry, and obtain a melting point.

B. COMPETITIVE REACTIONS

Using the method described in Part A, prepare the semicarbazone of a mixture of 0.8 mL of
furfural, 1 mL of cyclohexanone, and 1 g of semicarbazide hydrochloride dissolved in a
solution of 2.0 g of sodium bicarbonate in 25 mL of water. Isolate the product after 5 min,
recrystallise it from a minimum amount of hot methanol (ca. 10 mL/g of product), and
identify the product by melting point or by comparison of its IR spectrum with that of
authentic samples of semicarbazones of cyclohexanone and furfural.

Repeat the experiment but heat the reaction mixture on a steam bath for 1.5 h.

C. INTERCONVERSION ATTEMPTS

Boil a mixture of 0.5 g of cyclohexanone semicarbazone and 0.4 mL of furfural in 10 mL of

water for approximately 20 min, allow the solution to cool, and collect the precipitate
semicarbazone. Recrystallise it from a minimum amount of hot methanol (ca. 10 mL/g of
product) and identify it.

Repeat the experiment with 0.5 g of furfural semicarbazone and 0.4 mL of

cyclohxanone.

EXERCISE 2: Describe the results of all these experiments in terms of the concepts of
thermodynamic and kinetic control. Assume that the energies of cyclohexanone and furfural
are about the same and draw an energy profile for both reactions that would explain the
behaviour you observed.

13
 EXPERIMENT 4: ACETANILIDE TO p-NITROANILINE

Nitration of an aromatic ring is one of several synthetically useful electrophilic aromatic

substitution reactions. In this experiment, the preparation of p-nitroaniline is accomplished by
the nitration of acetanilide followed by hydrolysis of the amide function.

14
 2H2SO4 + HNO3 NO3+ + H3O+ + 2HSO4-

O
O
NO2+
O2N NHCCH3
NHCCH3

1. H3O+ + CH3CO2-
O2N NHCCH3 O2N NH2
2. NH4OH

Only if nitration is carried out above 5o does any significant amount of o-nitroacetanilide
form. After hydrolysis of the crude nitroacetanilide product, small amounts of o-nitroaniline
can be separated from the more abundant p-isomer by the final recrystallisation procedure.

EXERCISE 1 : Nitration of aniline with a mixture of concentrated nitric acid and

concentrated sulfuric acid produces mostly m-nitroaniline. Explain.

EXERCISE 2 : How does the basicity of the nitrogen atom of acetanilide compare with that
for aniline?.

EXERCISE 3 : Mononitration of aniline at the ortho- and para- positions with cold mixture
of nitric acid and acetic acid is possible, but at higher temperature the formation of 2,4,6-
trinitroaniline prevails. Contrast these results with those for the nitration of acetanilide.
Which group, amino or p-acetamido, activates the aromatic ring more toward electrophilic
attack?

A. NITRATION OF ACETANILIDE

Weight 200 mg (1.48 mmol) of acetanilide into a small pear-shaped flask (or reaction vial)
and add 500 µL of concentrated sulfuric acid. Break up any lumps with a microspatula, stir
the mixture, and cool it in ice in a small beaker. While it is cooling, place 110 µL each of
concentrated nitric acid (1.65 mmol) and concentrated sulfuric acid (in that order) in a small
vial, mix them throughly, cool the acid mixture in ice for several minutes, and with a pasteur
pipette, add about ¼ of the acid mixture at a time followed by a 3-min interval. Stir and crush
the acetanilide after each addition. After the last addition, stir the mixture occasionally and
keep it cold for 10 min. Remove the reaction vessel from the ice and allow it to stand at room

15
temperature for 5-8 min with occasionally stirring followed by the addition of ice water (ca. 2
mL of ice and 2 mL of water) with stirring. Cool the suspension of yellow product, and filter
it with suction on a Hirsch funnel. Rinse residual solid from the flask with two approximately
1-mL portions of ice water. Allow the solid to suck dry for at least 5 min. (The yield of
nitrated acetanilide normally will exceed 80%.) Proceed to Part B.

B. HYDROLYSIS OF p-NITROACETANILIDE TO p-NITROANILINE

Transfer the crude p-nitroacetanilide back into the pear-shaped flask, add 3 mL of water, 1
mL of concentrated hydrochloric acid, and a small boiling stone to the flask. Fit the flask with
a condenser, and heat it for 20 min at reflux with the heat lamp in a vertical orientation.
Allow the golden –yellow solution to cool, then cool it in an ice bath, and in a hood, add 1-
mL of concentrated ammonium hydroxide to precipitate the yellow p-nitroaniline. Check
with pH paper to see that the solution is basic.

Cool the suspension in ice, filter the yellow product with suction on a Hirsch funnel,
rinse the remaining solid from the flask with a minimum amount of ice water, and allow the
crude product to suck dry for at least 5 min. Transfer the product to tared watch glass with a
microspatula, carefully remove the boiling stone, and dry the product with gentle heating
(heat lamp). Determine the yield of crude product based on acetanilide (normally the yield
will exceed 60% for the two steps).

Recrystallise about 60-70 mg of the crude p-nitroaniline on a microscale, and save the
remainder for Part C. For the recrystallisation use a 1:2 (by volume) mixture of toluene and
ethanol. Employ about 1.0 mL of solvent for each 10 mg of dry crude p-nitroaniline. After the
hot filtration step, add a short boiling stick and concentrate the solution to about 1/3 of the
original volume before allowing it to cool. The crystals can be washed with a very small
volume of the cold solvent mixture. Dry the final product, obtain a melting point (typically
147-148oC), and turn in the sample to your instructor.

C. THIN-LAYER CHROMATOGRAPHY

Examine and compare each of the following samples by TLC on silica gel with methylene
chloride for development: (1) crude p-nitroaniline, (2) recrystallised p-nitroaniline, (3)
authentic o-nitroaniline. Note that because of the color of these compounds, no method of
visualisation is needed. Turn in the remaining crude p-nitroaniline to our instructor.

D. INFRARED SPECTRUM

16
Take an infrared spectrum on the final product as a mull in mineral oil (e.g. Nujol). Although
the frequencies for the nitro are masked by the hydrocarbon absorption in this case, there are
well defined absorptions for the amino group in the N-H stretching and bending regions and a
a peak near 1592 cm-1 associated with aromatic ring that is clearly visible.

EXPERIMENT 5 : SELECTIVE REDUCTIONS OF m-

NITROACETOPHENONE WITH TIN AND SODIUM
BOROHYDRIDE.

The success or failure of many organic syntheses depends on the ability of the chemist to
choose appropriate reagents and conditions for the selective reaction of certain functional
groups while others remain untouched. As an example of such a selective process, only the
nitro group of m-nitroacetophenone is reduced by tin metal in acidic solution.
17
 O O

2 CCH3 + 3Sn + 14H + 2 CCH3 + 3Sn

4+
+ 4 H2O

O2N +
H3N
m-Nitroacetophenone

O O

CCH3 + OH - CCH3 + H2O

+
H3N H2N
m-Aminoacetophenone

In contrast, the use of sodium borohydride in ethanol reduces the carbonyl group
without affecting the nitro group. Although this reducing agent is comparatively expensive,
four mols of starting ketone are reduced for every mole of sodium borohydride consumed,
and the reaction can be conveniently done on a small scale.

O O

4 CCH3 + BH4 - + 4 EtOH 4 CCH3 + B(OEt)4-

O2N O2N
1-(m-Nitrophenyl)ethanol

EXERCISE 1 : Write a balanced equation for the reduction of nitrobenzene to aniline by

iron in aqueous acid.

EXERCISE 2 : From information in your lecture textbook, suggest a reducing agent capable
of reducing both the nitro and carbonyl groups of m-nitroacetophenone.

A. m-AMINOACETOPHENONE

Weight 100 mg (0.605 mg) of m-nitroacetophenone into a 10 mL pear-shaped flask. Weight

200 mg (1.69 mmol) of graduated tin (20 mesh) on an ordinary top loader (to the nearest 10
mg) and add it to the flask through a small funnel. Set up the flask for stirring and heating.
Prepare some dilute hydrochloric acid in a 10 mL graduated cylinder by adding about 0.5 mL
of concentrated HCl with a Pasteur pipette to 1.5 mL of water. Pour the dilute acid into the
18
flask through the condenser, and stir and heat the mixture until it begins to reflux (ca. 5 min)
and then long enough to dissolve all the tin (usually 30 min or less); a small amout of
undissolved tin will do no harm. (Use an aluminium foil reflector around the back of the flask
to concentrate the heat).

Add about 0.5 g of sodium hydroxide to 1.2 mL of water in a small test tube (12
mm x 100 mm) and set it aside to cool.

1. Weight the sodium hydroxide pellets quickly because of their extremely hygroscopic
nature.

2. If you are doing the reduction of m-nitroacetophenone to 1-(m-nitrophenyl)ethanol, now

is a good time to start the experiment.

Cool the reaction solution and the sodium hydroxide solution in ice for a few
minutes. Add all of the aqueous base to the reaction solution to precipitate the product and
convert Sn(IV) to soluble stannate. Stir the pale yellow slurry magnetically to ensure through
mixing and cool the pale yellow suspension in ice. Filter the pale yellow precipitate by
suction on the Hirsch funnel, rinse the last bit of solid from the flask with a small amount of
ice water, and wash the filtered solid with a few drops of ice water. Allow the crude product
to suck dry for about 10 min. Transfer it into a weighted vial and warm it in the vacuum oven
(Figure 5.9). The yield of uncrystallised solid should be greater than 80% with mp 94-97 oC.
Recrystallisation is optional.

If you crystallise the product, skip the vacuum drying step above and weight the
slightly moist material from the Hirsch funnel into a recrystallisation tube. Recrystallise the
sample from water near the boiling point (about 0.2 mL for each 10 mg of crude nearly dry
solid). Dry the fine pale yellow plate crystals throughly with a warm vacuum oven (Figure
5.9). This will require 1h. The final yield of product should be at least 65% with mp of 96-
98oC. (An infrared spectrum can be taken in carbon tetrachloride).

EXERCISE 3 (Optional, spectroscopic) : The IR spectrum of m-aminoacetophenone

exhibits a doublet at about 3500 cm-1 which is not present in the spectrum of m-
nitroacetophenone. Explain.

B. 1-(m-NITROPHENYL)ETHANOL

Dissolve 200 mg (1.21 mmol) of m-nitroacetophenone in 2.5 mL of warm absolute ethanol in

a 25 mL pear-shaped flask heated on a steam bath. Cool the solution in ice to produce a fine
suspension of solid. Add a magnetic stirring bar and stir the suspension (room temperature)
while you add 50 mg (1.32 mmol) of sodim borohydride; stir the suspension for 1- 2 min.
The solution will be yellow to light brown. Add 2 mL of water and heat the solution to
boiling (open flask) with a steam bath for 5 min to destroy excess borohydride. Allow the
solution to cool for a few minutes until hydrogen evolution has essentially stopped.
19
 When the solution is at room temperature, add 5 mL of water to force the product
from solution. Extract the cold suspension with three 2-mL portions of methylene chloride. A
magnetic stirring bar should be used to mix the layer vigorously followed by transfer of the
lower organic layer with a pasteur pipette to a small dry test tube (at least 14 mm x 125 mm),
which contains about 400-700 mg of anhydrous sodium sulfate. Stopper the tube with a cork
and allow the combined organic layers to dry for at least 10 min (occasional swirling). Decant
about half the solution into a small dry pear-shaped flask, and remove some of the solvent.
Add the remainder of the solution and remove ALL of the solvent. A small amount of
yellowish brown oil or solid will remain in the flask.

Cool it in the ice bath for a few minutes, add 200 µL of carbon tetrachloride with
an automatic pipet, and stir the mixture as you continue to cool it. A suspension of straw-
coloured solid product will result. (if no solid has formed, remove ALL of the carbon
tetrachloride by vacuum evaporation and repeat the procedure from the beginning of this
paragraph). Remove the liquid with a filter pipette, add about 200 µL more of carbon
tetrachloride, mix throughly, and remove that solution with a filter pipet. If it is a solid after
solvent removal, simply add 200 µL of carbon tetrachloride, mix it in the ice bath, and
remove the liquid with a filter pipet; repeat the wash once more.

Remove the solvent by evaporation.Transfer the solid to a weighted vial by

scraping the sides of the flask with a spatula and tapping the powder onto glazed paper first.
The yield of pale straw-colored product, mp 60-62oC should be a little above 60%. (An
infrared spectrum can be taken in chloroform).

EXERCISE 4 : Sodium borohydride reacts slowly with ethanol to evolve a gas. Write a
balanced equation for this reaction.

EXERCISE 5 (Optional, spectroscopic): Suggest at least one characteristic absorption each

in the IR spectra of m-nitroacetophenone and 1-(m-nitrophenyl)ethanol that could be used to
distinguish between these two compounds.

EXERCISE 6 (Optional, spectroscopic): What characteristic pattern of proton NMR

absorptions would be expected in the aliphatic region for 1-(m-nitrophenyl)ethanol?

EXERCISE 7 (Optional, spectroscopic): How could a NMR spectrum be used to

distinguish between the structures for m-nitroacetophenone and 1-(m-nitrophenyl)ethanol?

20