Synthesis of 1-Phenylazo-2-naphthol (Sudan-I)

John Raymund B. Brusas | 2013-50015

Department of Mining, Metallurgical and Materials Engineering, College of Engineering
University of the Philippines, Diliman, Quezon City 1101 Philippines
Date Performed: February 14, 2014
Date Submitted: March 5, 2014

Abstract
In this experiment, the synthesis of 1-Phenylazo-2-naphthol, commonly known as Sudan-I, was investigated. First was
the production of the phenyldiazonium ion from 0.2 mL aniline and nitrous acid or the diazotization reaction. Next was
the coupling reaction of the phenyldiazonium ion ith 0. 5g β-naphthol in 4.5 mL of 5% NaOH(aq). The crude product,
Sudan-I, was recrystallized to eliminate impurities. At the end, 0.09g of recrystallized Sudan-I was acquired with a red-
orange color and a melting point range of 128-131°C. Also, the experiment had a percent yield of 16% while the purity of
the synthesized Sudan-I was high or closely pure for its melting point was near to that of a pure Sudan-I which is 131-
132°C.

I. Introduction

Amines are organic derivatives of ammonia in the same alkylamines because of their five resonance forms
way that alcohols and ethers are organic derivatives of [Figure 2] (McMurry, 2008).
water. Like ammonia, amines contain a nitrogen atom
with a lone pair of electrons [Figure 1], making amines :NH2
both basic and nucleophilic. In fact, most of the
chemistry of amines depends on the presence of this
lone pair of electrons. They react with acids to form
acid–base salts, and they react with electrophiles in +
many of the polar reactions (McMurry, 2008). NH2 :NH2

:-
Figure 2. Resonance
structures of an arylamine
making it more stable than
alkylamine.
+ +
NH2 NH2
Figure 1. General structure of an amine.

Alkylamines are prepared by SN2 reaction of ammonia -:

or an amine with an alkyl halide while arylamines are
prepared by nitration of an aromatic ring followed by
:
I

reduction. Generally, arylamines are less basic than

alkylamines because the nitrogen lone-pair electrons
are delocalized by intera tio ith the aro ati ri g π
electron system and are less available for bonding to H+.
In resonance terms, arylamines are stabilized relative to
Amines react with alkyl halides by SN2 reaction and with
acid chlorides by nucleophilic acyl substitution
reactions. Amines also undergo E2 elimination to yield
alkenes if they are first quaternized by treatment with

Page 1
iodomethane and then heated with silver oxide, a agents and as textile dyes (Organic Chemistry Lab
process called the Hofmann elimination (McMurry, Manual, 2008).
2008).
Dyes are colored because they absorb light in the visible
On the other hand, arylamines are converted by region. The functional group responsible for this are
diazotization with nitrous acid into phenyldiazonium alled hro ophores, hi h ea olor earers . I
salts, ArN2+ X- [Figure 3]. The diazonio group can then be azo dyes, -N=N- links two aromatic rings. This extended
replaced by many other substituents in the Sandmeyer conjugation causes light to be absorbed in the visible
reaction to give a wide variety of substituted aromatic region. In addition to chromophores, dyes have color
compounds. In addition to their reactivity toward augmenters or deepeners called auxochromes of the
substitution reactions, diazonium salts undergo type –NHR, -NR2, -OH, and –OR (Organic Chemistry Lab
coupling with phenols and arylamines [Figure 4] to give Manual, 2008).
brightly colored azo dyes (McMurry, 2008).
In the art of dyeing, one must know both the structure
of the dye and fiber to determine the method to be
N
NH2 +
N used. Some dyes are capable of direct dyeing with some
fabric via chemical interaction called salt linkages. On
NaNO2, HCl Cl- the other hand, simple azo dyes do not directly bond
H2O, 0°C well to cotton because of the absence of functional
groups in the fiber responsible for the so-called
chemical interaction. However, they are capable of
Figure 3. Diazotization reaction, phenyldiazonium salt is dyeing cotton as a developed or ingrain dye. In this
formed from primary aromatic amines and nitrous acid. method, the dye is synthesized inside the fabric.
Individually, the two components used to synthesize the
N dye will diffuse into the pores and spaces between the
+ fibers in the fabric. After the individual components
N Y:
react inside the fibers, the dye is trapped within the
+ fibers. The fully formed dye version of azo dyes will be
too large to do this and could only bond to the surface
of the fibers (Organic Chemistry Lab Manual, 2008).

An example of an azo dye is 1-Phenyl-2-naphthol or

OH

Y: Sudan-I. It is an orange-red dyestuff used in coloring

-

waxes, oils, petrols and polishes. From the definition of

an azo dye stated above, it is a product of a diazonium
salt with a phenol or arylamine. By looking at the
structure [Figure 5], its individual components are
phenyldiazonium ion a d β-naphthol. From here, we
can synthesize Sudan-I using a phenyldiazonium salt and
N N β-naphthol employing diazotization and coupling
reactions. Also, we will apply the method of ingrain
dyeing as one of the characteristics of azo dyes.

Figure 5. The
N=N
Figure 4. Coupling reaction, the positively charged
phenyldiazonium ion serves as the electrophile toward activated OH structure of
aromatic substrates, Y can be –OH (phenol) or –NR2 (arylamine). 1-Phenyl-2-naphthol
(Sudan-I) is composed
Many of the coupling products are used as acid-base of phenyldiazonium salt
indicators, food coloring compounds, biological staining and β -naphthol

Page 2
II. Methodology B. Preparatio of β-naphthol solution

O the other ha d, dissol e 0. 5 g β-naphthol in 4.5 mL

Synthesis of 1-Phenyl-2-naphthol
Just for your safety: Wear a mask, rubber gloves and
lab googles throughout the experiment. Sudan-I is
carcinogenic and might enter your system.
5% NaOH(aq) in a beaker. Immerse in an ice bath and
cool to 4°C. This will be solution B [Figure 6B] (Organic
Chemistry Lab Manual, 2008).
Ingrain Dyeing

Pla e a fa ri to e d ed i the old β-

Materials and Apparatus naphthol solution, still immersed in an ice bath. Allow
aniline ice bath the fabric to soak for 2-3 minutes. Remove the fabric
concentarted HCl thermometer from the bath using tweezers and pat it dry between
NaNO2 crystals rock salt filter papers. Immerse the fabric in the phenyldiazonium
β-naphthol crystals cotton cloth 2x2 cm chloride solution. After several minutes, remove from
5% aq. NaOH tweezers the solution and rinse well with running water. Note the
50 mL Erlenmeyer flask filter paper color (Organic Chemistry Lab Manual, 2008).
50 mL beaker pipette
C. Synthesis of Sudan-I

Now, add slowly while stirring the phenyldiazonium

A B
hloride solutio A i to the β-naphthol solution (B).
This will be solution C [Figure 6C]. Allow the reaction to
stand for 5 minutes at 4°C. Filter the product and wash
it thoroughly with small portions of cold water (Organic
Chemistry Lab Manual, 2008). Afterwards, proceed to
recrystallization to purify the crude Sudan-I (See
Recrystallization Process).

C
Recrystallization Process

Recrystallization is one of the most important methods

Figure 6. Schematic diagram for the synthesis of Sudan-I.
A. Preparation of phenyldiazonium chloride solution
In a 50 mL Erlenmeyer flask, combine 0.2 mL aniline,
0.35 mL water and 0.5 mL concentrated HCl. Immerse in
an ice bath and cool to below 5˚C ou a use a
thermometer to verify the temperature and add some
rock salts to ensure the temperature is maintained).
for the purification of solids. It involves the preparation
of a saturated solution of the organic compound in an
appropriate solvent at an elevated temperature and
filtering this solution while hot. Insoluble impurities are
removed during hot filtration. Upon cooling, the organic
compound separates in the crystalline form leaving
soluble impurities in solution (Organic Chemistry Lab
Manual, 2008).
The solvent plays a critical role in recrystallization. An
ideal solvent should have the following properties:


Then, add 1 mL ice-cold distilled water. Add 0.3 g NaNO2
r stal. Keep the te perature elo 5˚C. This will be
solution A [Figure 6A] (Organic Chemistry Lab Manual,
2008).
It should dissolve the solid readily at an
elevated temperature and only sparingly at
room temperature.

Page 3
  It should dissolve the desired solute but not the  It should be sufficiently volatile to permit easy
contaminant; or the desired component should removal from the purified crystals (Organic
recrystallize selectively from the solvent on Chemistry Lab Manual, 2008).


cooling.

Table 1. Lists of solvents for recrsytallization with their

It should not react chemically with the solute.
melting points and which they are useful for.
Boiling Point
Solvent Useful for Common Co-Solvents
(°C)
Salts, amides, some carboxylic
Water 100 Acetone, methanol, ethanol
acids
Methanol 65 General use Water, diethyl ether, benzene
Ethanol 78 General use Water, diethyl ether, benzene
Acetone 56 General use Hexane
Ethyl acetate 77 General use Ethanol, hexane
General use, low melting
Dichloromethane 40 Ethanol, hexane
compounds
General use, low melting
Diethyl ether 35 Methanol, ethanol, benzene
compounds
Chloroform 62 General use Ethanol, hexane
Toluene 111 Aromatic compounds
Benzene 80 Aromatic compounds Ethanol, diethyl ether, ethyl acetate
All solvents in this list except water and
Hexane 69 Hydrocarbons
methanol
Source: Organic Chemistry Laboratory Manual, 2008

Materials and Apparatus crystals but note that if you add too much solvent
crude Sudan-I Filtration Setup: ou’ll get o r stals at the e d .
ethanol fluted filter paper (2) 2. Now that the pure crystals are dissolved, we can
hot plate stemless funnel filter out the insoluble materials or the impurities.
ice bath iron stand Filter the solution using a fluted filter paper [Figure
pipette iron ring 8] in a stemless funnel and a hot ethanol in a beaker
glass rod beaker (receiving flask) at the receiving end (better if placed on a hot plate).
Rinse the Erlenmeyer flask with a small amount of
hot ethanol and filter again.
Figure 7.
Filtration Setup.
Use a fluted
funnel paper to
maximize the area
for filtration and
stemless funnel.
cnx.org

1. In a dry 25 mL Erlenmeyer flask, dissolve the

collected impure Sudan-I in hot ethanol (ethanol is
generally a good solvent for most organic
quiz2.chem.arizona.edu

compounds except for alcohols). Swirl/heat a bit Figure 8. How

until all the crystals are dissolve (you may add to make a
enough hot ethanol if there are still undissolved fluted filter
paper.
Page 4
3. Afterwards, proceed to cooling down. Cool the
solution slowly, from hot (boiling) to room
temperature to 0°C (immerse in an ice bath). This is
the re r stallizatio part. If the solutio does ’t
start recrystallizing, scratch the inner sides of the
beaker with a glass rod or (if you have) add a seed
crystal.
4. Filter the solution to collect the pure crystals. Use a
fluted filter paper and rinse the pure crystals with
s all a ou t of old sol e t do ’t redissol e the
crystals). Let the crystals dry thoroughly overnight.
Lastly, take its mass (Organic Chemistry Lab Manual,
2008).
5. To determine the purity of the recrystallized Sudan-
I, proceed to melting point determination (See
Melting Point Determination).
Melting Point Determination
Melting point is a physical property wherein an organic
compound may be identified. Once the melting point
was determined, one can examine its purity (Organic
Chemistry Lab Manual, 2008).
Material and Apparatus
recrystallized Sudan-I MP Determination Setup
crystals thermometer
spatula oil bath
watch glass iron clamp
capillary tubes (2) iron stand
rubber bands hot plate
rubber cork with hole
1. Pulverize the crystal using a spatula on a watch
glass. Mound the pulverized sample and press the
open end of the melting point capillary tube into
the sample against the surface of the watch glass.
Lightly tap the sealed end of the tube on the
tabletop. Introduce more samples into the tube
until the sample fills about 2-4 mm height.
2. Place 25 mL of oil in a dry 50 mL beaker. Insert a
thermometer through a rubber cork, placing the
rubber cork above the highest reading in the
thermometer. Attach the melting point capillary
tubes containing the sample to the thermometer by
means of a thin strip of rubber bands. Be sure that
the bulb of the thermometer as well as the capillary
tubes are close enough to each other so that they
Page 5
are both submerge in the oil bath and the rubber
bands far enough that it will not be immerse in the
oil otherwise it will melt with the hot oil. Clamp the
thermometer by the cork and submerge in the oil
bath.
chemistry.mcmaster.ca
Figure 9.
Melting Point
Determination
setup. 
3. Make a preliminary test by heating the bath
strongly and observing within 5°C the temperature
at which the sample melts. After determining, cool
down the oil.
4. Attach another capillary tube containing the same
sample to the thermometer. Carefully determine
the melting point by heating the bath slowly, about
3°C per minute, when the temperature approaches
the melting point determined. As soon as the
droplet of liquid forms in the tube (start of melting)
until the last trace of solid has liquefied (end of
melting), record the temperature reading. This will
now be the melting point range of your compound
(Organic Chemistry Lab Manual, 2008).
III. Results and Discussion
As what stated in the introduction part, azo dyes like
Sudan-I are synthesize through diazotization of an
arylamine to a phenyldiazonium ion and afterwards the
coupling reaction of the phenyldiazonium ion with an
activated aromatic substrate. In the experiment, for the
diazotization reaction part is the production of
phenyldiazonium salt from aniline and nitrous acid
(remember solution A). On the other hand, the coupling
reaction is the formation of Sudan-I from the
phenyldiazo iu io a d β-naphthol (that was solution
C).
Diazotization Reaction
Figure 10. Schematic diagram for the diazotization reaction.
Nitrous acid (HONO) is a weak, unstable acid that is why
it is always prepared in situ. So, the role of NaNO2 and
HCl is to produce the nitrous acid and nitrosyl cation
(+NO) and a number of other species formed. For
simplicity, organic chemists group all these species
together and speak of the chemistry of one of them,
nitrous acid, as a generalized precursor to nitrosyl
cation [Figure 11] (Solomon, 2004).
+ +
H3O H3O
-H2O

nitrosyl cation
Figure 11. Preparation of the nitrous acid using NaNO2 and
decomposing to nitrosyl cation.
After the formation of the nitrosyl cation, the
diazotization reaction starts. There are three steps in
this reaction:
The nitrosyl cation (nucleophile) then reacts with the
nitrogen of the aniline (having two lone pairs) to form
an unstable N-nitrosoammonium ion [Figure 12] as an
intermediate. N-nitrosoammonium ion then loses a
proton to form an N-nitrosoamine (Solomon, 2004).
+
H3O
N-nitrosoamine
Figure 12. N-nitrosoamine from N-nitrosoammonium
intermediate.
Page 6
N-nitrosoammonium ion then loses a proton to form an
N-nitrosoamine, which, in turn, tautomerizes to a
diazohydroxide in a reaction [Figure 13] that is similar to
keto-enol tautomerization (Solomon, 2004).
+HA
-HA
Figure 13. Tautomerization of N-nitrosoamine to
diazohydroxide .
Then, in the presence of an acid, the diazohydroxide
loses water to form the diazonium ion [Figure 14].
+
+
Figure 14. Phenydiazonium ion.
Coupling Reaction
Phenyldiazonium ions are weak electrohiles; they react
with highly reactive compounds – with phenols and
arylamines – to yield azo compounds (Solomon, 2004).
Couplings between phenyldiazonium cation and
phenols take place rapidly in slightly alkaline solution.
Under these conditions an appreciable amount of the
phenol is present as a phenoxide ion, ArO-, [Figure 15]
and phenoxide ions are even more reactive towards
electrophilic substitution than are phenols themselves
(Solomon, 2004).
OH

Figure 15. Phenols couples slowly compare to phenoxide .
With phenols and aniline derivatives, coupling takes OH
place almost exclusively at the para position if it is open.
If it’s ot, oupli g takes pla e at the ortho positio
(Solomon, 2004). H2O
+ N N
Cl

HCl

+ N N
+

Figure 18. Under temperature more than 5°C,

phenyldiazonium ion reacts with nucleophilic substrates and
producing aromatic compounds.

On the other hand, remember the coupling part, if the

pH of the solution is too alkaline (pH > 10), however,
the arenediazonium ion itself reacts with the hydroxide
Figure 16. Coupling of the phenyldiazonium ion and β-naphthol ion to form a relatively unreactive diazohydride or
resulting to 1-phenylazo-2-naphthol. diazotate ion [Figure 19] (Solomon, 2004).

OH O-
Side Reaction

Because the reaction is a bit unstable, it is not

impossible for the reaction to give other side reactions. - -
OH OH

Most arenediazonium salts are unstable at temperature HA HA

above 5-10°C, and many explode when dry. Once
happened, the phenyldiazonium ion loses the nitrogen
[Figure 17] as the leaving group and a carbocation is Figure 19. Formation of diazohydroxide (middle) and
left. diazotate ion (right) from a slightly basic medium.

Data and Results

+
+
At the end, 0.09 g of Sudan-I was collected from 0.2 mL
a ili e a d 0. g of β-naphthol. The melting point of the
+ N N collected compound was determined to be between
128-131°C. The table below shows a tabulated data of
the basic information from the reaction.

Figure 17. Decomposition of phenyldiazonium ion under Compound Volume Mass Millimole
temperature greater than 5°C, producing N2 gas and an aniline 0.20 mL 7.75 g 2.20 mmol
electrophilic ring. β-naphthol 0.24 cm3 0.30 g 2.42 mmol
Sudan-I
0.07 cm3 0.09 g 0.36 mmol
From here, H2O and HCl present in the reaction can (collected)
react with the carbocation and produce phenol and Sudan-I
0.43 cm3 0.55 g 2.20 mmol
chlorobenzene, [Figure 18] respectively. (theoretical)

Page 7
 percent yield : 16% V. References
[1] Mcmurry J., (2008). Organic Chemistry 7ed.
Table 2. Comparison of the volume, mass and no. of moles of the Thomson Learning Inc. 919-959.
actual and theoretical yield. [2] Univerisity of the Philippines, Diliman, Institute
of Chemistry (2008). Organic Chemistry
Laboratory Manual. 8-11, 86-89.
Sudan-I Sudan-I
Properties [3] Solomons T.W., Fryhle C., (2004). Organic
(collected) (theoretical)
Chemistry 8ed. John Wiley & Sons, Inc. 963-972.
Color red-orange orange-red
Melting point 128-131°C 131-132°C VI. Appendices
Table 3. Comparison of the physical properties of the actual and
Sample Calculations:
theoretical yield.
Collected Sudan-I
pre-weighed vial: 14.1 g
Possible causes of errors: vial with t-BuCl: 14.19 g
1. The mixture was prepared not in an ice bath.
Phenyldiazonium decomposes easily at Actual Yeild
temperature more than 5C. This yields other
product like phenol and chlorobenzene (See a. mass of Sudan-I
Side Reactions). = 14.19 g – 14.1 g
2. Too much addition of NaOH. If the solution is = 0.09 g
too basic, phenyldiazonium no longer reacts
ith β-naphthol instead with the hydroxide ion b. millimoles of Sudan-I
and forms a relatively unreactive =
diazohydroxide or diazotate ion (See Side = 0.36 mmol Sudan-I
Reactions).
3. Crude Sudan-I as ’t recrystallized. Impurities Theoretical Yield
will not be removed from the sample which
causes the melting point to be lower than the a. millimoles of aniline
actual one.
=
IV. Conclusion = 2.2 mmol aniline
In this report, the synthesis of 1-phenylazo-2-naphthol
b. ili oles of β-naphthol
was investigated. The use of aniline under nitrous acid
produces the phenyldiazonium salt employing the =
diazotization reaction. Afterwards, β-naphthol was = 2.42 mmol β-naphthol
reacted with the phenyldiazonium ion under slightly
basic condition employing the coupling reaction. At the c. millimoles of Sudan-I
end, 0.09 g of the product was collected after being
recrystallized. The melting point range was 128-131°C. =
The percent yield was 16%. = 2.2 mmol Sudan-I

In terms of purity, the synthesized 1-phenylazo-2- Percent Yield

naphthol was close to pure. In comparison with its
actual melting point (131-132°C), the determined
melting point is near.

= 16%

Page 8