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Experiment 9, Synthesis of Organic Compounds

Catalig Antonio, Romer Tumasis


Maam Tolentino
December 3, 2014
I.

Abstract

Organic synthesis is a special branch of chemical synthesis and is concerned with the production of organic
compounds via organic reactions. There are three organic compounds that were synthesized. These three are
Sudan-1 of 1-phenylazo-2-naphtol, Soap and Aspirin. 1-phenylazo-2-naphtol is an azo-compounds that have the
general formula of

Ar N N Ar . By reacting arenediazonium salts

Ar N N X

with

phenols and other amines through azotization and then coupling reactions with highly activated aromatic
compounds you could produce dye such as Sudan-1. Soap is produce by hydrolysis of triglyceride (fat or oil) via
saponification then is reacted with a strong base such as NaOH or KOH to produce fatty acid salt. Aspirin or
acetylsalicylic acid could be synthesized by esterification or reacting salicylic acid with acetic anhydride and
catalyzing using H3PO4. After synthesizing those three organic compounds, the compounds were then subjected
to testing to find out some properties of these organic compounds.
II. Keywords: azo-dyes, azotization-coupling reactions, arenediazonium salts, saponification, triglyceride, fatty
acids, acetylsalicylic acid, salicylic acid, esterification
III. Introduction
Many of our necessities are organic
materials. Some of our everyday materials were
made in the laboratory by organic synthesis. In this
experiment, we synthesized dye, soap and aspirin.
We then reacted some chemicals in lab in order to
produce these products. By using the different
methods found on previous experiments. We found
out some physical and chemical properties of these
compounds. By knowing the reaction mechanisms
and pathways of these syntheses, we then could
find how these compounds could be formed
theoretically.
IV. Experimental
A. Synthesis of a Dye (1-phenylazo-2-naphthol)
1.4ml of water, 0.9 ml of aniline, and 2.1ml
of concentrated HCl were mixed in a 50ml beaker.
The mixture was then cooled to 0-5 degrees
Celsius and added 1 g of ice. The solution was then
mixed constantly. NaNO3 (0.75g in 3 mL H2O) was
continuously dropped until the solution has excess
acid
At constant 5 degrees Celsius, A drop of
the solution was placed on starch iodide paper to
test reaction for excess nitrous acid, indicated by a
blue color.
1.4 g of -naphthol was added in 3 M warm
NaOH(aq). After mixing, the solution was then
cooled to 5 degrees Celsius. The solution was then
stirred whille adding phenyldiazonium chloride. The
solution was kept at constant 5 degrees Celsius for
15 minutes.
The product was collected through filtration
on fluted filter paper. Cold water was used to wash
several portions of it. It was recrystallized from
ethanol. It was then dried and weighed.

A part of the product was then dissolved in


5 mL distilled water. To test for properties of the
compound, 3 drops of the solution was then added
to 2 mL 0.1 M NaOH. This test was repeated using
0.1 M HCl, NH4OH and CH3COOH.
B. Synthesis of Soap
A water bath was made by heating to
boiling a beaker with 2/3 water in a stove. After
preparing a water bath. 2.5 g of NaOH, 5ml distilled
water and 10ml of 95% ethyl alcohol was mixed in a
150ml beaker It was then added to 5 g of
hydrogenated shortening in a 150mL beaker. The
beaker was covered with a watch glass and heated
on the water bath. The mixture was then stirred
constantly to prevent splashing and 50% alcohol
were added to keep the volume of the mixture
constant. The reaction was said to be complete if
the oil or melted fat dissolved and gives a clear
homogenous mixture.
The soap was diluted by adding 15mL of
water and pouring it to brine made by dissolving
30g of NaCl in 100mL of distilled water. The mixture
was stirred thoroughly and the precipitated soap
was collected through fluted filter paper. The soap
was then washed with 10mL portion of cold water
twice.
2g of the crude soap was dissolved in 10mL
portions of cold distilled water to be used as the test
solution. The remaining soap was placed in an
evaporating dish, heat on the water bath and stirred
in it just enough soap to form a thick solution. The
soap solution was allowed to cool, which will solidify
into a smooth commercial soap.
C. Synthesis of Aspirin

Mixture of 2g of salicylic acid and 5ml


acetic anhydride was placed in an erlenmeyer flask.
The flask was then heated with a boiling water bath
for 5 minutes. The flask was then removed from the
bath and was added with 2ml water in one portion.
After decomposition was completed, the solution
was then added with 40ml of water and was stirred
until crystals began forming. The mixture was then
cooled in an ice bath for the crystallization to be
completed. The solution was then recrystallized in a
35ml of hot water. After recrystallization, the product
was dried and weighed.
V. Results
A. Synthesis of a Dye
Physical test

Chemical test:
least intense
most intense
moderately intense
intense

B. Synthesis of Soap
Physical Test
Appearance: candle like
Color: white
Texture: smooth
Odor: Bathroom odor/shampoo
Melting Point: 49-60 C
Chemical Test
CaCl2
MgCl2
FeCl2
H2O
Mineral oil
Methylene chloride
Litmus paper
C. Synthesis of Aspirin

Appearance - crystalline
Texture - fine
Color - white
Odor - sour-smell, vinegar-like
Melting point - 90-136 C
Chemical test
Reaction with methanol - from clear, it formed a
solution with two layers: purple at the bottom and
clear at the top
Reaction with salicylic acid - from clear to a fully
purple-colored solution
VI. Discussion
A. Synthesis of Dye

Appearance: powder
Color: red-orange
Texture: fine
Odor: paint-like smell
Melting Point: 131-133 C

0.1 M NaOH
1 M HCl
NH4OH
CH3COOH

Physical test

Soap dissolved, white,


foamy, bubbly, runny
More viscous
More bubbly/foamy but
less viscous, orange-ish
Bubbly, more watery
Bubbly, more viscous,
no
visible
separate
layers, looks dissolved
Residue/precipitate did
not dissolved
Blue/basic

Synthetic dyes, otherwise known as azo


dyes, are created by the reaction between a
diazonium salt with a phenol in the presence of
sodium hydroxide. In this experiment, 1-phenylazo2-naphthol, or more commonly known as Sudan-1,
was synthesized from aniline and -naphthol in
cotton.
Diazonium salts are prepared in a process
called diazotization. In diazotization, primary
amines are oxidized by nitrous acid (HNO2). It is
important to note that aliphatic diazonium salts
react immediately via SN1, E1 and/or SN2, since
molecular nitrogen is one of the best leaving
groups. However, aromatic diazonium salts can be
isolated and be used in other reactions, due to the
fact that benzene rings do not readily undergo SN 1
and SN2 reactions.
From the reaction of aniline to sodium
nitrate in hydrochloric, a diazonium salt,
phenyldiazonium chloride, was produced. From
here, the salt can either undergo coupling reaction
or nucleophilic aromatic substitution (NAS). NAS
does not occur in this experiment, because it was
made sure that the solution was cold. Low
temperature is required, because the diazonium salt
is very unstable and can decompose back into
aniline when it warms up.
The process, in which the components,
phenyldiazonium chloride and -naphthol, react, is
called coupling. The coupling reaction is an
electrophilic substitution, where the diazonium ion
reacts at the position with the greatest electron
availability. Since the diazonium ion is only weakly
electrophilic, the coupling component should have
strong, activating electron donating groups, such as
-OH2 or -NR2.
B. Synthesis of Soap

Alkali hydrolysis of fats and oil forms what we


call soaps. This process is also called
saponification. Vegetable oils and animal fats are
fatty esters in the form of triglycerides. The alkali, in
the form of a base, breaks the ester bond and
releases the fatty acid salt and glycerol. If
necessary, soaps may be precipitated by salting out
with saturated sodium chloride or table salt. NaOH
is used in the industry to produce solid soaps while
KOH is used to make liquid soaps.
C. Synthesis of Aspirin
Aspirin was prepared from the reaction of
salicylic acid and acetic anhydride. Phosphoric acid
was used as a catalyst. Upon addition of cold water,
acetic acid was formed and thus eliminated. Other
impurities like salicylic acid were removed upon the
process of recrystallization.
The melting point range of the purified and crude
samples were compared to the literature value and
it showed that the purified sample is logically near
to the literature value because of its narrow range.
The recrystallized product was differentiated from
commercial aspirin through iodine test and it
showed that the commercial aspirin contains starch.
VII. Answers to Questions
A. Synthesis of Dye
1. What are the reactions involved in the
synthesis of 1-phenylazo-2-naphthol?
The synthesis of 1-phenylazo-2-naphthol
was made through diazotization, followed
by a diazonium-coupling reaction.
2. Write the reaction pathway and mechanism
for the synthesis of 1-phenylazo-2naphthol.
Formation of the diazonium salt:

Mechanism of the formation of diazonium


salt:

3. Why should the temperature of the reaction


mixture be kept below 5 C?
It is needed in order to retain the equilibrium shift
towards the product side. Diazonium salts are very
much unstable so it might make a backward shift
forming once again aniline.
4. Explain the principle behind the use of
starch iodide paste in detecting excess
nitrous acid.
Nitrous acid oxidizes iodide ion to form iodine. The
iodide ion in starch reacts with nitrous acid to form a
blue complex. The blue coloration on the starch
iodine paste will indicate excess nitrous acid since
all iodide has been oxidized
5. Why is the rate of coupling of
phenyldiazonium ion with -naphthol
dependent upon the pH of the reaction
medium?
-naphthol was needed to be treated with a base,
because it would form diazotate ions when acidic,
slowing the coupling reactions down

Applications (Congo red)


Structure of congo red

Alkaline hydrolysis (reaction with water or dilute


alkali) of triglyceride (fat/oil) and Triglyceride is

reacted with lye or other strong bases


produce glycerol and fatty acid salts
2. Write the reaction pathway and mechanism
for the synthesis of soap.

Synthesis of Congo red


(diazotization and coupling step)

Reaction pathway producing glycerol and fatty acid


salt

Site of protonation largely responsible for the blue


color of Congo red: N=N
Two resonance structures for the second
protonated substance that shows the nature of the
chromophore responsible for the blue color:
Structures in (b) are when it is acidic (blue in color)
3. Why was the dilute soap solution poured in
a solution of sodium chloride in water?
Adding NaCl in the soap solution will precipitate the
soap, which is the process of salting out.
4. Explain the result obtained when the dilute
soap solution is treated with calcium
chloride, magnesium chloride and ferric
chloride solutions.

B. Synthesis of Soap
1. What is the reaction involved in the
synthesis of soap?

The salt solution was a Sodium salt which is polar.


Changing the sodium ions into Calcium,
Magnesium and Iron would make it non polar thus
being insoluble in water. Soap scum are formed
which is a white solution usually found in
bathrooms. If the soap became insoluble, it means
you synthesized a soap.
5. How does soap function as an emulsifying
agent for oil in water? Draw a picture of an

oil droplet and several soap molecules to


illustrate your answer.
The long hydrocarbon chain of the soap is nonpolar and hydrophobic while the "salt" end of the
soap molecule is ionic and hydrophilic.
Application
Suppose that you wanted to emulsify a
water insoluble compound in water. Would soap be
a reasonable choice for the emulsifying agent if the
water were slightly acidic? Why? If it would not be a
good choice, draw the structure of an organic
molecule that might be more suitable.
No, because the soap will not be able to form a
bridge between oil and water because of the H+
attached to the polar end of the soap instead of
water so an emulsion will not occur. Detergent is
used in place of soap because it can tolerate
slightly
acidic
water

C. Synthesis of Aspirin
1. What is the reaction involved in the
synthesis of Aspirin?
Esterification is the chemical reaction in which the
two reactants (typically an alcohol and an acid) form
an ester as the reaction product.
2. Write the reaction pathway and mechanism
for the synthesis of Aspirin

Ferric chloride reacts with phenol to give a purple


solution and since salicylic acid has a phenol group,
it is expected to give a positive result. When the
synthesized aspirin gives purple solution upon the
addition of ferric chloride then not all the salicylic
acid were consumed.
Application:
Salol is a white sparingly soluble crystalline
compound with a slight aromatic odour, used as a
preservative and to absorb light in sun-tan lotions,
plastics,
etc;
phenyl
salicylate.
Formula:
C6H4(OH)COOC6H5
Which is a stronger acid, aspirin or salol?
Aspirin is more acidic than salol because of the
stability of its conjugate base and its COOH
functional group. Aspirin will be hydrolyzed easily
because it is acidic.
VIII. Conclusion
Diazonium salts are wery useful in the
industry of chemistry because it could form many
common organic materials that are always used in
commercials and household. Sudan 1 or 1phenylazo-2-naphthol was made which is
responsible for a red orange color of our clothes.
Soaps are very important in our lives. It is
mainly use in cleaning both materials and our body.
By knowing how soaps are synthesize, it helps us
choose among those commercial soaps with are
better and more effective. The Vegetable oils and
animal fats you may throw could be synthesize into
soaps by further saponification.
Aspirin
or
acetylsalicylic
acid
are
synthesized by esterification of salicylic acid and
acetyl anhydride.
IX. References
http://www.freewebs.com/mpniistal/fr3_synthesis_of
_1_phenylazo_2_naphthol.pdf
http://www.chemistry.sc.chula.ac.th/bsac/Org
%20Chem%20Lab_2012/Exp.11[1].pdf

3. Explain why the recrystallization of Aspirin in the


water should not be heated above 80 deg Celsius.

http://devchandcollege.org/chemistry
%20notes/B.Sc.I%20Chemistry%20Diazonium
%20salts.pdf

Aspirin may decompose back into salicylic acid and


acetic anhydride when the temperature is too high.

http://www.sciencedirect.com/science/article/pii/S03
04389406013860

4. Explain the results obtained when Aspirin and


salicylic acid were treated with FeCl3.

http://swc2.hccs.edu/pahlavan/2425L9.pdf
http://www.orgsyn.org/

http://www.laney.edu/wp/chelifossum/files/2012/01/13-Saponification.pdf
Organic Chemistry 4th. Ed. Paula Yurkanis Bruice
pp. 700-702
http://theuplbcollegestudent.blogspot.com/2011/05/f
ull-report-synthesis-of-aspirin.html
http://www.pierce.ctc.edu/staff/dwoods/Chem131/Lab/Chem-131%20Lab-05%20094%20Synthesis%20of%20Aspirin%20%28std
%29.pdf
https://www.scribd.com/doc/129937670/Chem-31-1Experiment-9-Synthesis-of-Dye

http://www.thefreedictionary.com/salol
https://www.scribd.com/doc/171817662/Synthesisof-1-Phenylazo-2-Naphthol-or-Sudan-1#download
http://www.academia.edu/8542139/Synthesis_of_1Phenylazo-2-naphthol
I hereby certify that I have given substantial
contribution to this report.

Catalig, Antonio

Tumasis Romer