Organic Chemistry Laboratory, University of Santo Tomas

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COMPARATIVE INVESTIGATION OF ORGANIC COMPOUNDS

1. Physical state, color and odor
- The physical appearance of an unknown will be your first datum in the search to
discover its identity.
- Solid (amorphous or crystalline) or liquid.


2. Solubility Properties and Reaction with Litmus paper
- Solubility of organic compounds in H
2
O

indicates the polarity of the sample and the
intermolecular forces of attraction that exists between the sample and H
2
O.
- Reaction with litmus paper indicates the acidity/basicity of the H
2
O-soluble
samples.
- Red Blue (Base) RBB
- Blue Red (Acid) BRA
- Litmus paper that retains its color indicates a neutral compound.
- Solubility of organic compounds in 5% HCl and/or 5%NaOH also reveals the acidity
and basicity of the sample.
- The table below summarizes the solubility of different organic compounds in various
solvents.








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- The solubility of the sample in different solvents indicates the possible class of
organic compounds to where it belongs as shown in the figure.

Try this: In one whole sheet of paper, make a summary table for the solubility of the
organic compounds used in the experiment.
Which compounds are acidic? basic? Write the chemical equations of the
compounds when reacted with H
2
O, HCl and NaOH.

REVIEW: Types of Intermolecular forces of attraction (IMFA)
*Arranged in decreasing order of IMFA strength

a. Ion-dipole exist between ions and polar molecules.
e.g. NaCl and H
2
O (Na
+
and Cl
-
in H
2
O)

b. H-bonding exist between two polar molecules; a special type of dipole-dipole
interaction.
- occurs when there is an OH, NH and F bond

c. Dipole-dipole exist between two polar molecules.

d. Dipole-induced dipole exist between polar and non- polar molecules.

e. Van der Waals force exist between two non- polar molecules.
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Try this: Identify the IMFA exist on the reactions/chemical equations involved you just
did in the earlier part.


3. Ignition Test indicates the presence of unsaturation or high carbon to hydrogen ratio.
- C/H ratio, luminosity, sooty
- Degree of luminosity can be assessed by the presence of yellow flame and soot.


4. Infrared (IR) Analysis it identifies the functional groups present in the sample.
- It depends upon the interaction of IR light with the vibrating dipole moments of
molecules.
- The molecular vibrations of the organic compound are promoted to higher energy
state (exhibited as bond stretching and/or bending modes) as it absorbs energy (IR
radiation).
- The IR energy is measured in wave numbers (cm
-1
).


THINGS TO CONSIDER:

1. The Coordinates
The x-axis indicates the wave numbers and examined most of the time. On the
other hand, the y-axis describes the intensity of a given peak.

2. Peaks
Examining the peaks in IR spectra is the most important task at hand. Most of the
significant peaks can be seen in the diagnostic region (from 4000 to 1500cm
-1
).
*The fingerprint region is from 1500 to around 400cm
-1
.

3. Peak Quality
Certain functional groups are easy to identify from its peak quality. These
include: 1) broad, 2)strong (intense but not wide), 3) weak (tiny), 4) sharp (slim)
and 5) multiplet (overlapping peaks).

4. Diagnostic Peaks
Examining diagnostic peaks coupled with their molecular formula is enough to
elucidate the gross structure of the molecule.












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CHARACTERISTICS INFRARED ABSORPTION FREQUENCIES
BOND COMPOUND TYPE FREQUENCY (cm
-1
)
C-H Alkanes 2960 - 2850 (s)
C-H Alkenes 3080 - 3020 (m)
Aromatic Rings 3100 - 3000 (m)
C-H
Phenyl Ring Substitution Bands 870 - 675 (s) bend
C-H Alkynes 3333 - 3267 (s)
C=C Alkenes 1680 - 1640 (m,w)
CC Alkynes 2260 - 2100 (w,sh)
C=C Aromatic Rings 1600, 1500 (w)
Alcohols, Ethers, Carboxylic acids,
C-O
Esters
1260 - 1000 (s)
Aldehydes, Ketones, Carboxylic
C=O
acids, Esters
1760 -1670 (s)
Monomeric -- Alcohols, Phenols 3640 - 3160 (s,br)
H-bonded -- Alcohols, Phenols 3600 -3200 (b) O-H
Carboxylic acids 3000 - 2500 (b)
N-H Amines 3500 - 3300 (m)
C-N Amines 1340 - 1020 (m)
CN Nitriles 2260 - 2220 (v)
1660 - 1500 (s)
NO
2
Nitro Compounds
1390 - 1260 (s)
* v variable, m - medium, s strong, b r - broad, w - weak


























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CLASSIFICATION TESTS FOR HYDROCARBONS

1. Physical state, color and odor
- The physical appearance of an unknown will be your first datum in the search to
discover its identity.
- Solid (amorphous or crystalline) or liquid
- Most hydrocarbons are colorless and odorless. However, many liquid compounds
oxidize when they are stored for a long time. Often the oxidation products are
intensely coloredyellow, green, red, brown, or black. (e.g. phenol becomes red
upon oxidation)


2. Solubility in concentrated H
2
SO
4

- Solubility of organic compounds in H
2
SO
4
indicates whether the sample is a very
weak base (can be protonated) or a neutral compound (cant be protonated).
- The dissolution of compounds in H
2
SO
4
may also produce large amounts of heat
and/or a change in the color of the solution, precipitation or any combination of
these. (The reaction can be either violent or slow.)

*H
2
SO
4
-soluble (very weak base)
Esters Ketones
Alkenes Aldehydes
Alcohols

*H
2
SO
4
-insoluble (neutral compound)
Alkanes Aryl halides
Alkyl halides most aromatic hydrocarbons


3. Ignition Test indicates the presence of unsaturation or high carbon to hydrogen ratio.
- C/H ratio, luminosity, sooty
- Degree of luminosity can be assessed by the presence of yellow flame and soot.
- Aromatic compounds burn with sooty flame due to the incomplete combustion which
causes the formation of an unburned carbon.
- In terms of degree of luminosity, aromatic compound > unsaturated hydrocarbon >
saturated hydrocarbon.

*Complete combustion is indicated by a blue flame (non-luminous) and there is more
heat than light; the carbon is completely oxidized.



*Incomplete combustion is indicated by a yellow flame (luminous) and there is much
light than heat; the carbon is not completely oxidized.





x y 2 2 2
C H + O CO + H O
x y 2 2 2
C H + O CO + CO + C (soot) + H O
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4. Test for Active Unsaturation

a. Baeyers Test test for double bonds
Reagents: 2% KMnO
4
(+) result: decolorization of a purple solution; formation of a brown ppt. (MnO
2
)
- involves redox reaction
- Mn
7+
is reduced to Mn
4+
; alkene is oxidized to a diol.
- Alkenes react with potassium permanganate (KMnO
4
) to give a diol and MnO
2
.
- Aromatic compounds do not react because of their stability.

Cyclohexene + KMnO
4
1,2-cyclohexanediol + MnO
2
(purple) (colorless) (brown)


Try this: Draw the structure of cyclohexene and 1,2-cyclohexanediol.




b. Bromine Test test for double bonds
Reagents: 0.5% Br
2
in CCl
4

(+) result: decolorization of an orange solution
- Involves electrophilic addition reaction
- Alkenes react with Br
2
to form a trans-dibromoalkane.
- Aromatic compounds do not react because of their stability.
- However, aromatic compounds will react slowly upon using FeBr
3
or through the
action of UV light.

Challenge: Write the reaction mechanism for the bromine test on cyclohexene.








5. Test for Aromaticity: Nitration test for aromatic compounds
Reagents: HNO
3
, H
2
SO
4
(+) result: yellow globule/yellow oily layer
- involves electrophilic substitution reaction
- H
2
SO
4
acts as a catalyst and facilitates the formation of nitronium ion (NO
2
+
), an
electrophile
- One hydrogen atom in the benzene ring is substituted by the nitronium ion.


HNO
3
+ H
2
SO
4
NO
2
+
+ 2HSO
4
-
+ H
3
O
+
Benzene + NO
2
+
nitrobenzene

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Challenge: Write the reaction mechanism for the nitration test on benzene and
toluene.










6. Basic Oxidation test for alkylated aromatics or arenes
Reagents: 2% KMnO
4
, 10% NaOH

(+) result: green solution (MnO
4
)/brown ppt (MnO
2
)
- involves redox reaction
- NaOH provides a basic environment.
- The alkyl group of the aromatic compound is oxidized to a carboxylic acid. (Reaction
occurs with 1
0
and 2
0
alkyl side chain, but not with 3
0
.)
- Mn
7+
is reduced to Mn
6+
or Mn
4+
depending on the extent of the reaction.





























4 4
methylbenzene + KMnO benzoic acid + MnO
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CLASSIFICATION TESTS FOR ORGANIC HALIDES

1. Belstein Test - a quick preliminary check for halogens
(+) result: blue-gree flame
- The simplest method for establishing presence of a halogen, but does not positively
differentiate between Cl, Br, I
- The blue-green color is due to the emission of light from excited states of copper
halide that has vaporized in the burner flame.
- Heating the copper wire before the test is carried out removes traces of sodium
chloride that may be present on the wire from handling it with the fingers.
- Reactions in Belstein test






- CuX
2
is volatile and imparts a blue-green flame.


2. Reaction with Alcoholic AgNO
3
- test for S
N
1 Reactivity
Reagents: 2% ethanolic AgNO
3
(+) result: white ppt
* S
N
1 - substitution, nucleophilic, unimolecular
- The kinetics of the reaction depends only on the alkyl halide.



Substrate Effect:
- The more stable the carbocation intermediate, the faster the S
N
1 reaction.
- 3
0
> 2
0
> 1
0
> -CH
3


Leaving Group:
- good leaving group is needed
- TosO
-
> I
-
> Br
-
> Cl
-
H
2
O
more reactive less reactive

Nucleophile:
- hardly affected
- The nucleophile does not enter into the reaction until after rate-limiting dissociation
has occurred; thus cannot affect the reaction rate.

Solvent:
- Polar, protic solvent
- Polar solvent stabilize the carbocation intermediate by solvation, thereby increasing
the reaction rate.
- H
2
O

> 80% EtOH

> 40% EtOH

> EtOH
more reactive less reactive
(EtOH = ethanol)
[ ] reaction rate = RX k
0
2
2 2 2
Cu + O CuO
loop black solid
RX + CuO CuX + CO + H O

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Stereochemistry:
- Includes inversion and retention

*The S
N
1 reaction occurs when the substrate spontaneously dissociates to a
carbocation in a slow rate-limiting step, followed by a rapid attack of nucleophile. As a
result,S
N
1 reactions show first-order kinetics and take place with RACEMIZATION of
configuration at the carbon atom. They are most favored for tertiary substrates.


3. Reaction with NaI in Acetone test for S
N
2 Reactivity
Reagents: 15% NaI in acetone

(+) result: white ppt (insol. In acetone)
* S
N
2 - substitution, nucleophilic, bimolecular
- The kinetics of the reaction depends only on the alkyl halide and nucleophile.



Substrate Effect:
- The more stable the carbocation intermediate, the faster the S
N
1 reaction.
- -CH
3
> 1
0
> 2
0
> 3
0
(due to steric effect)

Leaving Group:
- good leaving group is needed
- TosO
-
> I
-
> Br
-
> Cl
-
> F
-
> HO
-
, H
2
N
-
, RO
-

more reactive less reactive

Nucleophile:
- Strong nucleophile works best.
- Nucleophlicity parallels basicity.
- Nucleophilicity usually increases going down a column of the periodic table.
e.g. HS
-
is more nucleophilic than HO
-

I
-
> Br
-
> Cl
-

Solvent:
- Polar, aprotic solvent
- HMPA

> CH
3
CN

> DMF

> DMSO > H
2
O > CH
3
OH
more reactive less reactive


Stereochemistry:
- Involves Walden inversion of configuration

*The S
N
2 reaction occurs as the entering nucleophile attacks the halide 180
0
away from
the leaving group, resulting in an umbrella-like Walden inversion of configuration at the
carbon atom. The reaction shows second-order kinetics and is strongly inhibited by
increasing steric bulk of the reagents. Thus, S
N
2 reactions are favored for primary and
secondary substrates.


[ ]
-
reaction rate = RX Nu: k

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CLASSIFICATION TESTS FOR HYDROXYL- AND CARBONYL-CONTAINING
COMPOUNDS

1. Solubility of alcohols in water
a. Alcohols are insoluble in water except under C
6
.
b. Factors affecting solubility:
i. number of carbon atoms
c. the higher the number of carbon atom, the more insoluble or less soluble
d. e.g. ethanol (CH
3
CH
2
OH) is more soluble than butanol (CH
3
CH
2
CH
2
CH
2
OH)
b. branching of carbon chain
- the more branching present, the more soluble (with the same number of
carbons)
- e.g. tert-butanol > sec-butanol > n-butanol
c. presence of polar functional groups ( -OH, -NH
2
, -CO
2
H)
- compound with polar functional group is more soluble
e.g. butanol > butane; 1,3-butanediol > butanol


2. Lucas Test differentiates 1
0
, 2
0
, 3
0
alcohols
Reagents: anhydrous ZnCl
2
, HCl
(+) result: based on turbidity (alkyl chloride formation); the rate of the reaction was
observed (time is noted)
- based on S
N
1 reaction (3
0
> 2
0
> 1
0
alcohols); depends on the formation of a stable
carbocations
- 3
0
alcohols form the second layer in less than a minute.
- 2
0
alcohols require 5-10 minutes.
- 1
0
alcohols are usually unreactive.
- The presence of ZnCl
2
(a good LEWIS ACID)

makes the reaction mixture even more
acidic, thus enhances the formation of carbocations.










3. Chromic Acid Test/Dichromate Test/Jones Test test for oxidizables or any
compounds that possess reducing property (has an alpha acidic hydrogen); 1
0
, 2
0

alcohols and aldehydes give a (+) visible result.
Reagents: 10% K
2
Cr
2
O
7
, 6M H
2
SO
4

(+) result: green or blue-green solution
- involves redox reaction; 1
0
, 2
0
alcohols and aldehydes undergoes oxidation,
chromium undergoes reduction (from Cr
+6
to Cr
+3
).
- A 1
0
, 2
0
alcohols and aldehydes will reduce the orange-red chromic acid/sulfuric acid
reagent to an opaque green or blue suspension of Cr(III) salts in 2-5 s.
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- A 1
0
alcohol reacts with chromic acid to yield aldehydes, which further oxidized to
carboxylic acid.
- A 2
0
alcohol react with chromic acid to yield ketones, which do not oxidize further.
- A 3
0
alcohols are usually unreactive.
- Aldehydes are oxidized to carboxylic acid.










4. DNPH Test/2,4-DNP test for carbonyl groups; positive for aldehydes and ketones
Reagents: 2,4-dinitrophenylhydrazine, ethanol, H
2
SO
4

(+) result: red-orange ppt (conjugated carbonyl compounds) or yellow ppt
(nonconjugated carbonyl compounds)
- Some high molecular weight ketones may fail to react or may yield oils.
- Mechanism: condensation or addition/elimination
- Involves nucleophilic addition of NH
2
to C=O and elimination of H
2
O
- Most aromatic aldehydes and ketones produce red dinitrophenylhydrazone.
- Many nonaromatic aldehydes and ketones produce yellow products.
- The reaction of 2,4-DNPH with aldehydes and ketones in an acidic solution is a
dependable and sensitive test.









5. Fehlings Test - test for aldehydes
Reagents: CuSO
4
, NaOH ( Cu
2+
in alkaline solution)
(+) result: brick-red ppt (Cu
2
O/cuprous oxide)
- Involves redox reaction.
- Aldehyde is oxidized to carboxylic acid; ketones do not undergo oxidation.
- Copper is reduced (from Cu
2+
to Cu
1+
)

RCOH + 2Cu
2+
+ 5
-
OH RCOO
-
+ Cu
2
O + 3H
2
O


6. Tollens Test/Silver Mirror Test test for aldehydes
Reagents: AgNO
3
, NH
3

(+) result: silver mirror
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- The preparation of Tollens reagent is based on the formation of a silver diamine
complex that is water soluble in basic solution.
- Involves redox reaction.
- Aldehyde is oxidized to carboxylic acid; ketones do not undergo oxidation except
alpha-hydroxyketone.
- Silver is reduced (Ag
1+
to Ag
0
).
- Formic acid and hydroxylamine will also give a (+) result.










7. Iodoform Test test for methyl carbinol (2
0
alcohol with adjacent methyl group) and
methyl carbonyl groups
Reagents: 10% KI, NaClO
(+) result: yellow crystals or ppt (CHI
3
m.pt. 119-121
0
C)
- An alkaline solution of sodium hypoiodite, formed from sodium hydroxide and iodine,
will convert acetaldehyde and aliphatic methyl ketones into iodoform (haloform
reaction).
- Since the reagent is also an oxidizing agent, alcohols which are readily oxidized to
acetaldehyde or methyl ketones also give a (+) reaction.
- The mechanism of iodoform synthesis occurs through a series of enolate anions,
which are iodinated; hydroxide diplaces the Cl
3
-
anion though an addition/elimination
pathway.




















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CLASSIFICATION TESTS FOR CARBOXYLIC ACIDS AND DERIVATIVES

1. Hydrolysis of Acid Derivatives
a. Acyl Halides
- Reagent: H
2
O
- Acyl halides react with water to yield carboxylic acids.
- This hydrolysis reaction is a typical nucleophilic acyl substitution process, initiated by
the attack of water on the acyl halide carbonyl group.
- The tetrahedral intermediate undergoes elimination of Cl
-
and loss of H
+
to give the
product carboxylic acid and HCl.
- Sample Compounds: acetyl chloride (+)

CH
3
COCl + H
2
O CH
3
COOH + HCl

- The above reaction is accompanied by a warming effect.*
- Other reactions performed on the resulting mixture of the above reaction:

1. Hydrolysis with Aqueous Silver Nitrate
- Reagent: 2% AgNO
3

- (+) result is indicated by the immediate formation of the ppt of silver halide
- Acid halides, halide salts and 2,4-dinitroaromatic halides give immediate ppt.

2. Solubilty in Bicarbonate
- Reagent: saturated NaHCO
3

- Effervescence due to the evolution of CO
2
(formation of bubbles) indicated the
presence of carboxylic acid.
- All water-soluble compounds will dissolve in the bicarbonate solution, but only acids
will give bubbles.


b. Acid Anhydrides
- The chemistry of acid anhydrides is similar to that of acyl halides.
- The kinds of the reactions the two groups undergo are the same, though acid
anhydrides react more slowly.
- Acid anhydrides also undergo hydrolysis to form a carboxylic acid.
-
CH
3
COOCOCH
3
+ H
2
O 2 CH
3
COOH

- For other reactions, just refer to the acyl halides.
- Sample compound: acetic anhydride (+)


c. Esters
- Reagents: 25% NaOH, 10% HCl
- Basic hydrolysis of an ester converts an ester into the carboxylate salt of the parent
acid and the alcohol from which the ester was formed.
- Acidification of the carboxylate solution with HCl leads to the recovery of the parent
acid.

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- Often you will find that either the carboxylic acid or the alcohol formed from the
hydrolysis of an ester is extremely soluble in H
2
O.
- Sample compound: ethyl acetate (+)

CH
3
COOCH
2
CH
3
+ NaOH CH3COO
-
Na
+
+ CH
3
CH
2
OH
CH3COO
-
Na
+
+ HCl CH
3
COOH + NaCl

- Evidence for an ester is indicated by: 1) the disappearance of organic layer |(if any),
2) odor of the sample (during heating), and 3) appearance of a ppt or odor of a
carboxylic acid.


d. Amides
- Reagent: 10% NaOH
- A red litmus paper turned to blue accompanied by an ammonia or amine-like odor,
indicates an amide.
- Amides of higher amines that do not turn the litmus paper blue may nevertheless
give an amine-like odor.
- Some amides will yield a precipitate or a separated liquid phase (the carboxylic
acid).

RCONR
2
+ NaOH RCOO
-
Na
+
+ R
2
NH
RCOO
-
Na
+
+ H
+
RCOOH + Na
+

- Sample compound: benzamide (+)

Try this: Write the chemical equation for the hydrolysis of benzamide.




2. Alcoholysis: Schotten-Baumann Reaction
a. Carboxylic acid
-
Reagents: ethanol, concd H
2
SO
4
- Involves Fischer esterification reaction; this is a nucleophilic acyl substitution
reaction carried out under acidic conditions
- Strong mineral acid such as H
2
SO
4
or HCl make the carboxylic acid more reactive
enough to be attacked by alcohol.
- The net effect of Fischer esterification is substitution of an OH group by OR.
- All steps are reversible.
- Sample compound: acetic acid (+)

- Reaction:
2 4
3 2
H SO
3 3 2 3 3 CH CH OH
CH COOH CH COOCH CH + H O
+


- Evidence of reaction: heat, HCl gas, phase separation, ester-like odor




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b. Acyl halide/Acid anhydride
- Reagents: ethanol, H
2
O, 20% NaOH
- The esterificaion reaction of an alcohol with acid chloride is strongly affected by
steric hindrance.
- Bulky groups on either partner slow down the reaction (reactivity: 1
0
> 2
0
> 3
0
ROH)
- Alcoholysis reactions are usually carried out in the presence of NaOH or pyridine to
react with the HCl formed and prevent it from causing side reactions.
- On the other hand, only half of the acid anhydride molecule is used; the other half
acts as the leaving group during the nucleophilic acyl substitution reaction.
- Thus, acid chlorides are preferred for introducing acyl substituents.
- Sample compounds: acetyl chloride (+)
acetic anhydride (+)

- Reaction: CH
3
COCl + CH
3
CH
2
OH CH
3
COOCH
2
CH
3
+ HCl
CH
3
COOCOCH
3
+ CH
3
CH
2
OH CH
3
COOCH
2
CH
3
+ CH
3
COOH

- Evidence of reaction: heat, HCl gas, phase separation, ester-like odor


3. Aminolysis: Anilide Formation
- Reagents: aniline, H
2
O
- Acyl halides react rapidly with ammonia or amines to give amides in good yield
- Acid anhydride also react but it takes a longer time
- Both mono- and disubstiuted amines can be used but not trisubstituted amines.
- Since HCl is formed durng the reaction, 2 equivalents of the amine must be used (1
eq. reacts with the acid chlorides and another eq. reacts with the HCl by-product)
- Sample compounds:
a. Acetyl chloride (+)
b. Acetic anhydride (+)
- A (+) test is indicated by the formation of a ppt.

Challenge: Write the reaction mechanism for the aminolysis of acetyl chloride and
acetic anhydride.








4. Hydroxamic Acid/Ferric Hydroxamate Test test for esters
- Reagents: hydroxylamine hydrochloride (NH
2
OHHCl), 1M KOH, 5% FeCl
3

- Preliminary test is done to eliminate those phenols and enols that give colors with
ferric chloride in acidic solution and that would therefore give a false-positive result
in the ferric hydroxamate test.
- If a color other than yellow results, the ferric hydroxamate test cannot be used.
- A (+) test is indicated by the formation of a blue-red (burgundy or magenta) color.
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- Esters react with hydroxylamine in basic solution to form hydroxamic acids, which
in turn react with ferric chloride in acidic solution to form bluish-red ferric
hydroxamates.







- Sample Compounds:
a. Ethyl acetate (+)
b. Acetamide (-)

Try this: Write the chemical equation for the hydroxamic acid test of ethyl acetate.




*IMPORTANT POINTS TO CONSIDER
- The chemistry of all acid derivatives is similar and dominated by a nucleophilic
acyl substitution reaction:

RCOY + :Nu
-
RCONu + :Y
-

- Nucleophilic acyl substitution reactions take place in two steps: 1) addition of the
nucleophile, and 2) elimination of a leaving group.
- Any factors that make the carbonyl group more easily attacked by nucleophile favor
the reaction.
- Steric and electronic factors affect the reactivity of the acid derivative towards
nucleophilic acyl substitution reactions.
- Steric factors: Unhindered, accessible carbonyl groups react with nucleophiles more
readily than do sterically hindered groups.
- e.g. CH
3
COCl > (CH
3
)
3
CCOCl
- Electronic factors: strongly polarized acid derivatives are attacked more readily than
less polar ones.
- Reactivity order: RCOCl (Acid halide) > RCO
2
COR (Acid anhydride) > RCOOR
(Ester) > RCONH
2
(Amide)

- RULE: A more reactive derivative will be transformed to a less reactive one.
- The same kind of reactions occur on acid derivatives:
1) Hydrolysis reaction with water to yield a carboxylic acid.
2) Alcoholysis reaction with alcohol to yield an ester.
3) Aminolysis reaction with ammonia or amine to yield an amide.
*Other reactions include reduction and Grignard reaction.




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CLASSIFICATION TEST FOR AMINES

1. Hinsbergs Test differentiates 1
0
, 2
0
, and 3
0
amines
- Reagents: 10% NaOH, benzene sulfonyl chloride, 6M HCl
- Formation of a white ppt (p-toluenesulfonamide) when the reaction mixture is
acidified indicates a 1
0
amine.
- *Most 1
0
amine yield a clear solution after the initial reaction, but some form sodium
salts or disulfonyl derivatives that precipitate during the reaction.

RNH
2
+ ArSO
2
Cl + 2NaOH ArSO
2
NR
-
Na
+
+ NaCl + 2H
2
O
ArSO
2
NR
-
Na
+
+ HCl ArSO
2
NHR + NaCl

- Most 2
0
amine yield a white solid that does not dissolve in H
2
O or 6M HCl.
- *A liquid residue that is more dense than H
2
O and insoluble in 6M HCl may be a 2
0

amines arenesulfonamide that has failed to crystallize.

R
2
NH + ArSO
2
Cl + NaOH ArSO
2
NR
2
+ NaCl

- 3
0
amines should not react.
- *Water-soluble 3
0
amines yield a clear solution that does not form a separate phase
on acidification.

R
3
N + ArSO
2
Cl no reaction
R
3
N + HCl R
3
NH
+
Cl
-


- Sample compounds: Aniline
N-methylaniline
N,N-dimethylaniline


2. Nitrous acid test differentiates 1
0
from 2
0
and 3
0
amines; also distinguish alkyl
amines from aromatic amines













*The chemistry of amines is dominated by the lone pair of electrons in nitrogen. The presence
of this lone pair makes amine both basic and nucleophilic.
- They react with acids to form acid-base salts. Also, they react with electrophiles in many of
the polar reactions.
Organic Chemistry Laboratory, University of Santo Tomas
18 msaesmalla2009
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References:

Mayo, D., Pike, R., and Trumper, P. (2000). Microscale Organic Laboratory with Multistep
Synthesis. John Wiley and Sons.

McMurry, J. (2000). Organic Chemistry. Brooks/Cole: NY

Garcia, C. (2005), Organic Chemistry Laboratory Manual