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Ƒ To identify the functional groups present in an organic compound and 
Ƒ To characterize unknown organic compound.

 ‘ 


 
   
   

ualitative organic chemistry has been in use since long before the advent of modern
spectroscopy. Modern spectroscopic techniques have assisted the chemist by providing
spectra that can be interpreted to give more detail of the interaction between atoms and
functional groups. Some of you have difficulty identifying the structures using
exclusively nuclear magnetic resonance (NMR) spectra, infrared (IR) spectra, and mass
spectra (MS). The information obtained through chemical tests allows you to narrow
down the possible functional groups.

 ‘ 

 


G‘ ^nly distilled water should be used throughout the qualitative analysis procedures.
Impurities in tap water could lead to ³•
 ´ results.
G‘ ºhen using a medicine dropper, you can assume 20 drops is approximately
equivalent to 1 ml.
G‘ The ignition test will give you an indication as to whether or not your unknown is
aromatic.
G‘ If a reaction occurs when a solvent is added to a compound, is evidenced by a color
change for instance, the compound is consider to soluble in that solvent.
G‘ If any amount of the compound appears to dissolve in a particular solvent, consider it
to be soluble in that solvent.

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 è ‘ J



 
 

ÿou will work in groups on this project. Each group will be given one unknown (solid or
liquid) compound that the group will identify using various chemical classification tests,
spectral data and melting points of prepared derivatives.

All necessary reagents are provided for you in the laboratory.

D

   
! The result of all the tests (especially negative results) should be
regarded as strongly suggestive but not absolutely reliable.

Ƒ ºhen you have identified to which functional group class of compounds your
unknown belongs, you will prepare one or two derivatives, as necessary, to
accurately determine the actual identify of your unknown. All unknown
compounds contain at least one derivatizable functional group.
Ƒ -

  
 
    

 





    

 




 
 

 
    
 
  
 
 

  



    
Ƒ ÿou will not be able to rely on your laboratory instructor for help every step of the
way. The laboratory technician assistant will not be able to answer questions such
as ³©    

   ´ and ³           

?´ both
because s/he could in advertently steer you in the wrong direction and because you
must learn to trust your own judgment and move your own decisions in a problem
solving process such as this.

^nce you predict the structure of your unknown based on the chemical analysis and the
derivative that you synthesized you are expected to report it.

After preparing the appropriate derivative for your unknown, you will be given 3J,
3
, and 
of the unknown.

À
The process of identifying unknowns is analogous to solving a puzzle. ÿou must be
systematic don¶t jump to conclusion.

Five basic of experimental inquiry are useful for identifying an unknown compound.
These five areas of inquiry are:-

1.‘ Dreliminary examination

2.‘ Dhysical constants
3.‘ Classification by solubility
4.‘ Classification test for functional groups
5.‘ Synthesis of solid derivatives
6.‘ Spectroscopic analysis
‘
‘
‘
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If it is carried out intelligently, the preliminary examination may provide more

information with less effort than any other part of the procedure. It includes M 

 
(solid or liquid),
 , r, and   


.

The ignition test involves a procedure in which a drop or two of a liquid or about 50 mg
of a solid is heated gently on a small spatula or crucible. A yellow, sooty flame is
indicative of aromatic or a highly unsaturated aliphatic compound; a yellow but non-
sooty flame is characteristics of aliphatic hydrocarbons. The oxygen content of a
substance makes its flame more colorless or blue; high oxygen content lowers or prevents
flammability.

è ‘D 

 

If the unknown is a solid, its

 M is measured by the capillary tube method. For
an unknown that is a liquid, the   M  is determined by the micro boiling-point
technique.

^ther physical constants may be of use for liquids are the 

 
 
 and the

 .

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Solubility classification groups compounds on the basis of their solubilities in © 
,


,  ,  ,  and

Jè. The results of the solubility
tests can help classify molecules in to categories of functional group.

The following flow chart and procedure will help you to determine the solubility of your
unknown compounds.

‘
ë
 ‘
‘

Figure 1: Solubility Flow Chart

D

 Dlace about 1 ml of the solvent in small test tube. Add one drop of your
unknown liquid or a few crystals of an unknown solid directly into the
solvent. Gently tap the test tube with your finger to ensure mixing, and then
observe whether any mixing lines appear in the solution. The disappearance
of solid or the appearance mixing line indicates solubility. If the compound is
soluble add another drop or a few more crystals to ensure solubility. ÿou
may heat the solution gently in a worm water both to assist in dissolution.

w
è è‘
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Solubility results should narrow down the types of functional groups present in your
molecule. To verify the presence of these functional groups, and learn more about
structural and substitution patterns in your unknown, a series of functional group tests
have been developed and provided.

ÿou need not to do every test for a functional group, but you should read through the
different tests to determine if that test would give you additional insights.

D 
  
  
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^rganic compounds containing >C=C< and/or ²CÎC± bonds are called unsaturated
compounds. These compounds undergo addition reaction with bromine water or the
solution of bromine in carbon tetrachloride, chloroform or glacial acetic acid. Addition of
bromine to an alkene results in the formation of vicinal dibromide. The reddish orange
color of the solution of bromine in carbon tetrachloride disappears on reaction with an
alkene. The reaction is as follows :
 
 
 
    
 

  

colorless

Alkenes decolorize the neutral/alkaline KMn^4 solution and vicinal glycols are formed
( 

). Reaction takes place as follows:






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j ‘ 

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D


: Dissolve 0.1 g or 5 drops of organic compound in 2 ml of carbon
tetrachloride in a test tube and add 2% solution of bromine in carbon
tetrachloride or bromine water drop by drop with continuous shaking.
Decolorization of bromine solution indicates the presence of unsaturation
in organic compound.

 ‘  


D


: Dissolve 25-30 mg of organic compound in 2 ml of water or acetone (free of
alcohol) and add 1% potassium permanganate solution containing equal
volume of 1% sodium carbonate solution. The discharge of the color of more
than one drop of potassium permanganate indicates the presence of
unsaturation in the organic compound. Carrying out the reaction under
alkaline conditions removes the possibility of confusion due to substitution
in aromatic compounds.

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M

Alcoholic compounds on reaction with ceric ammonium nitrate give a red colouration
due to the formation of a complex.

(NH4)2 [Ce(N^3)6] + 3R^H [Ce(N^3)4(R^H)3] + 2NH4N^3

ceric ammonium nitrate Red complex

Distinction between primary, secondary and tertiary alcohols can be done on the basis of
iodoform test and Lucas test. Ethanol and secondary alcohols which contain
CH3²CH(^H)R group (iodoform reaction) gives positive iodoform test. To carry out

A
reaction, potassium iodide and sodium hypochlorite solution are added to the compound
in the presence of sodium hydroxide solution. Drobably sodium hypochlorite first oxides
potassium iodide into potassium hypoiodite, which oxidizes CH3²CH(^H)R group to
CH3C^R group and then iodinates it in the alkaline medium of the reaction mixture by
replacing the Į-hydrogen attached to the carbon atom adjacent to carbonyl group by
iodine. Iodoform is formed after cleavage of C²C bond.

potassium potassium Na^H

CH3CH2^H CH3CH^ CI3CH^ CHI3 + HC^^Na
hypoiodite hypoiodite

Lucas reagent contains zinc chloride and concentrated hydrochloric acid. This reagent
reacts with primary, secondary and tertiary alcohols at different rates. Tertiary alcohols
react almost instantaneously, secondary alcohols react in about 1-5 min and primary
alcohols react very slowly. The reaction may take 10 min to several days.

RCH2^H + HCl ZnCl2 No reaction/Slow reaction

R2CH^H + HCl ZnCl2 R2CHCl + H2^
R3C^H + HCl ZnCl2 R3CCl + H2 ^

Alcohols are soluble in Lucas reagent but the formed alkyl halides are not soluble.
Therefore, formation of two layers in the reaction medium indicates the occurrence of the
reaction.
D

   

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D


: Take 1 mL solution of organic compound dissolved in a suitable solvent.
Add a few drops of ceric ammonium nitrate solution. Appearance of red
color shows the presence of alcoholic ±^H group.

    
    •        
 •    


  ••  
  

   •

••  
  

  

 

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D


: Take 0.2 ml of the compound in a test tube; add 10 ml of 10% aqueous KI
solution and 10 ml of freshly prepared Na^Cl solution. ºarm gently;
yellow crystals of iodoform separate.

J



 
D


: Dissolve 0.1 g or 4 to 5 drops of compound in 2 ml of water. If it does not
dissolve, add dioxane drop by drop to get a homogeneous solution. Add 2
ml of 5% sodium hydroxide solution followed by potassium iodide-iodine
reagent [D 
    
 •
 
    •     
 • © ] dropwise with
continuous shaking till a definite dark color of iodine persists. Allow the
reactants to remain at room temperature for 2-3 minutes. If no iodoform
separates, warm the reaction mixture in a water bath at 60°C. Add more
drops of potassium iodide±iodine reagent. If color of iodine disappears
continue addition of reagent till the color of iodine persists even after two
minutes of heating at 60°C. Remove excess iodine by adding a few drops of
sodium hydroxide solution with shaking. Dilute the mixture with equal
volume of water and keep it at room temperature for 10-15 min. A yellow
precipitate of iodoform is obtained if test is positive.

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 ‘ 



D


: Take 1 ml of compound in a test tube. Add 10 ml of Lucas reagent. Shake
well and note the time for the separation of two distinct layers.
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The ±^H group attached directly to the ring carbon of an aromatic ring is called phenolic
±^H group. Dhenols are weakly acidic, therefore they are soluble in Na^H solution but at
the same time they are not sufficiently acidic to be soluble in sodium hydrogencarbonate
solution. Dhenols give colored complex with neutral ferric chloride solution. For
example, phenol gives a
complex of violet color as follows :

6C6H5^H + FeCl3 [Fe(C6H5^)6]3± + 3HCl + 3H+

Colored complex
Resorcinol, ±, ± and ±cresol give violet or blue coloration, catechol gives green color
which rapidly darkens. 1 and 2±Naphthol do not give characteristics colors. Dhenols
condense with phthalic anhydride in the presence of concentrated H2S^4, Dhenol
condenses to give phenolphthalein which gives a dark pink color with Na^H solution.
This is called phthalein dye test.

cc
j ‘ 


 



D


: Take 2 ml of aqueous or alcoholic solution of the organic compound in a test
tube, add neutral ferric chloride solution dropwise and note the color change.
Appearance of a blue, green, violet or red color indicates the presence of
phenolic ±^H group.

 D 




D


: Take 0.1 g of organic compound and 0.1 g of phthalic anhydride in a clean
dry test tube and add 1-2 drops of conc. H2S^4. Heat the test tube for about
1 min in an oil bath/water bath. Cool and pour the reaction mixture carefully

cÀ
 into a beaker containing 15 ml of dilute sodium hydroxide solution.
Appearance of pink, blue, green, red etc. colors indicates the presence of
phenolic ±^H group in the compound. However, the color disappears on
addition of large excess of sodium hydroxide solution.

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oth aldehydes and ketones contain carbonyl group (>C = ^) and are commonly known
as carbonyl compounds. Identification of aldehydes and ketones is done by two important
reactions of carbonyl group i.e.
(i) Addition reaction on double bond of >C = ^ group and
(ii) ^xidation of carbonyl group.
Addition reactions of derivatives of ammonia are important from the point of view of
identification of carbonyl compounds. Addition is generally followed by elimination
resulting in the formation of unsaturated compound.
^
^ 



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These reactions are catalysed by an acid or a base and do not occur under strongly acidic
or basic conditions. Each reaction requires an optimum pH for its occurrence. Therefore,
maintenance of pH is very important while carrying out these reactions.

As far as oxidation is concerned, aldehydes are easily oxidized to carboxylic acids while
ketones require relatively stronger oxidizing agents. Distinction can be made between
these two types of carbonyl compounds on the basis of difference in their reactivity.

c
Following tests are performed for the identification of aldehydic and ketonic groups: ^n
reaction with 2,4-dinitrophenylhydrazine (2,4-DND), they form the respective 2,4±
dinitrophenyl hydrazones.
^ ^



 
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^ ^
 
   
 
       

These two carbonyl compounds (aldehydes and ketones) are distinguished on the basis of
tests using mild oxidizing reagents, like 
 

 and 
 

 or



 

. Tollen¶s reagent is an alkaline solution of silver cation complexed
with ammonia, and Fehling¶s and enedict¶s reagents are alkaline solutions containing
cupric ions complexed with tartarate and citrate ions respectively. Fehling¶s reagent is
freshly prepared by mixing equal amounts of Fehling¶s solution A and Fehling¶s solution
. Fehlings reagent deteriorates on keeping while Fehling¶s solutions A and  are quite
stable. Fehling¶s solution A is an aqueous copper sulphate solution while Fehling¶s
solution  is an alkaline solution of sodium potassium tartarate (Rochelle¶s salt). The
reagent contains Cu2+ ion complexed with tartarate ions. The structure of the complex is
given below:

Copper tartarate complex

enedict modified the original Fehling¶s test by using a single solution which is more
convenient for the test. enedict¶s solution is more stable than Fehling¶s reagent and can
cè
be stored for a long time. It is an alkaline solution containing a mixture of copper
sulphate and sodium citrate (2Na3C6H5^.11H2^).

Complex formation decreases the cupric ion concentration below that necessary for
precipitation of cupric hydroxide. These two reagents oxidize aldehydes while ketones
remain unaffected. The chemistry of these tests is as follows:

RCH^ + 2[Ag (NH3)2]+ + 2^H± ĺ 2Ag + 3NH3 + H2^ + RC^^NH4

From Tollen¶s reagent

RCH^ + 2Cu2+ (complexed) + 5^H± ĺ RC^^± + Cu2^ + 3H2^

Fehling¶s solution
However, aromatic aldehydes do not give positive Fehling¶s test. In enedict test also,
Cu2+ ions are reduced to Cu+ ions in the same manner as in the case of Fehling¶s reagent.

Aldehydes also give pink color with Schiff¶s reagent (the reagent is prepared by
decolorizing aqueous solution of ±rosaniline hydrochloride dye by adding sodium
sulphite or by passing S^2 gas). Ketones do not respond to this test.

j 
 
  

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D


: Take 2-3 drops of the liquid compound in a test tube or in case of solid
compound, dissolve a few crystals of it in 2-3 ml alcohol. Add a few drops
of an alcoholic solution of 2,4-dinitrophenylhydrazine. Appearance of
yellow, orange or orange-red precipitate confirms the presence of carbonyl
group. If precipitate does not appear at room temperature, warm the mixture
in a water bath for a few minutes and cool.

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Following tests namely Schiff¶s test, Fehling¶s test and Tollen¶s test are given by
aldehydes only.

J



D


: Take 3-4 drops of the liquid compound or dissolve a few crystals of organic
compound in alcohol and add 2-3 drops of the Schiff¶s reagent. Appearance of pink
colour indicates the presence of an aldehyde.

m



D


: Take nearly 1 ml of Fehling¶s solution A and 1 ml of Fehling¶s solution  in
a clean dry test tube. To this add 2-3 drops of the liquid compound or about
2 ml of the solution of the solid compound in water or alcohol. Heat the
content of the test tube for about 2 minutes in a water bath. Formation of
brick red precipitate of copper (I) oxide indicates the presence of an
aldehyde. This test is not given by aromatic aldehydes.





D


: Add 5 drops of the liquid compound or the solution of the solid organic
compound in water or alcohol to 2 ml enedict¶s reagent. Dlace the test tube
in boiling water bath for 5 minutes. An orange-red precipitate indicates the
presence of an aldehyde.

 


D


: (i) Take 1 ml of freshly prepared (~ 2 %) silver nitrate solution in a test tube.
Add 1-2 drops of sodium hydroxide solution to it and shake, a dark
brown precipitate of silver oxide appears. Dissolve the precipitate by
adding ammonium hydroxide solution drop-wise.

cw
 (ii) To the above solution, add an aqueous or an alcoholic solution of the
organic compound.
(iii) Heat the reaction mixture of step (ii) in a water bath for about 5 min.
Formation of a layer of silver metal on the inner surface of the test tube
which shines like a mirror, indicates the presence of an aldehyde.

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!M

^rganic compounds containing carboxyl functional groups are called carboxylic acids.
The term carboxyl derives its name from the combination of words carbonyl and
hydroxyl because carboxylic functional group contains both of these groups. These acids
turn blue litmus red and react with sodium hydrogencarbonate solution to produce
effervescence due to the formation of carbon dioxide. This is a test that distinguishes
carboxylic acids from phenols.

RC^^H + NaHC^3 RC^^Na + H2^ + C^2

They also react with alcohols in the acidic medium to produce esters.

RC^^H + R'^H Conc.H2S^4 RC^^R' + H2^

j‘ 



D


: Dut a drop of the liquid compound or a drop of the solution of the compound
with the help of a glass rod on a moist blue litmus paper. If the blue color of
the litmus paper changes to red, the presence of either a carboxylic group or
a phenolic group is indicated.



cÚ
 ‘ J 
 

 



D


: Take 2 mL of saturated aqueous solution of sodium hydrogencarbonate in a
clean test tube. Add a few drops of the liquid compound or a few crystals of
solid compound to it. The evolution of brisk effervescence of C^2 indicates
the presence of carboxyl group.

 ‘ -



D


: Take about 0.1 g compound in a test tube, add 1 ml ethanol or methanol and
2-3 drops of concentrated sulphuric acid. Heat the reaction mixture for 10-
15 minutes in a hot water bath at about 50°C. Dour the reaction mixture in a
beaker containing aqueous sodium carbonate solution to neutralize excess
sulphuric acid and excess carboxylic acid. Sweet smell of the substance
formed indicates the presence of carboxyl function in the compound.

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^rganic compounds containing amino group are basic in nature. Thus they easily react
with acids to form salts, which are soluble in water. oth, aliphatic and aromatic amines
are classified into three classes namely±primary (±NH2), secondary (-NH-) and tertiary
(-N<), depending upon the number of hydrogen atoms attached to the nitrogen atom.
Drimary amine has two hydrogen atoms, secondary has one while tertiary amine has no
hydrogen atom attached to nitrogen.

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D


Take 1 ml of given organic compound in a test tube and add a few drops of
dilute HCl to it. Shake the contents of the test tube well. If the organic
compound dissolves, it shows the presence of an amine.

C6H5NH2 + HCl C6H5NH3+ Cl±

(Anilinium chloride soluble in water)

 ‘  




D


: Take 2-3 drops of the compound in a test tube and add 2-3 drops of
chloroform followed by addition of an equal volume of 0.5 M alcoholic
potassium hydroxide solution. Heat the contents gently. An
obnoxious/unpleasant smell of carbylamine confirms the presence of
primary amino group in the compound.
     
   
    
  
   
    
  •

    

X ‘ j#



D


: (i) Dissolve nearly 0.2 g of the compound in 2 ml of dilute hydrochloric acid
in a test tube. Cool the content of the test tube in ice.
(ii) To the ice cooled solution adds 2 ml of 2.5% cold aqueous sodium nitrite
solution.
(iii) In another test tube, dissolve 0.2 g of ȕ-naphthol in dilute sodium
hydroxide solution.

c'
 (iv) Add diazonium chloride solution prepared in step (ii) into the cold ȕ-
naphthol solution slowly with shaking. The formation of a scarlet red dye
confirms the presence of aromatic primary amine.

 ‘ J
  
   


The preliminary examination and group classification tests indicate the particular class
(functional group) to which an unknown organic compound may belong. Further
characterization and identification depends on the selection and preparation of a suitable
solid derivative and accurate determination of its melting point.
D 
  
  
 M


  
 
   
 
 

 


 
  

The last step in the identification of an unknown compound, the experiment any
remaining doubt, is the synthesis of a solid derivatives whose melting point can be
compared with the melting points of known compounds.

Derivatization procedures have somewhat diminished in importance with the advent of

spectroscopy. However, this procedure still provides both physical data and an in insight
into the chemistry of the unknown, especially when the possibilities for the identity of the
unknown have similar boiling and melting points and similar spectra.

Derivatization is the process of conversion of one common organic compound into

another. Many derivatives are really synthesis.

$
  X
   


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$‘ 3,5-Dinitrobenzoate
$‘ 1-Naphthylurethanes
$‘ Dhenylurethanes
$‘ 4-Nitrobenzoate

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$‘ 1-Naphthylurethanes
$‘ 3,5-Dinitrobenzates
$‘ Dhenylurethanes
$‘ 4-Nitrobenzoates
$‘ Acetates
G‘ j 

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$‘ 2-4-dinitrophenylhydrazones
$‘ Semicarbazones
$‘ 4-Nitrophenylhydrazones
$‘ Dhenylhydrazones
$‘ ^ximes
$‘ ^xidation to acid (for ardehyde)
G‘  


$‘ Amides
$‘ Anilides
$‘ 4-Toluidides
$‘ Neutralization equivalent
$‘ 4- Nitrobenzyl esters
G‘ j


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$‘ Acetamides
$‘ benzamides
$‘ 4-toluenesulfoamides
$‘ enzenesulfonamides
$‘ Dhenylthioureas
$‘ Amine hydrochlorides
G‘ j



$‘ Methyl 4±toluenesulfonate
$‘ Methiodides

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 $‘ Dicrate
$‘ Amine hydrochlorides

 c‘D
M   
   


  

The most general derivatives of alcohols are urethanes and benzoate esters; the former
are best for 1^ and 2^ alcohols, whereas the latter are useful for all types of alcohols.

Urethane derivatives are prepared when the alcohol is treated with either phenyl
isocyanate ar naphthyl isocyanate.


 ¦

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 ¦

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enzoate esters are easily prepared from the reaction of the alcohol with 4-nitrobenzoly
chloride or 3,5-dinitrobenzoyl chloride.

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  ¦

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M6  
  M6  


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The reaction of alcohols with 3-nitrophthalic anhydride produces hydrogen 3-

nitrophthalate derivatives.

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j ‘ J
 
# 


D


: To 1 ml of benzoyl chloride in a test tube and 2 ml (1 g) of alcohol and 2
ml of strong Na^H solution. ºarm the tube gently and pour the contents in
25 ml water. Filter the solid formed, wash with water, dry and determine the
melting point.

À
 ‘ J
 

 


D


c: To 1 gm substance in a dry test tube adds 1 ml acetyl chloride. ºarm and
then pour in water after cooling. Filter the derivative formed; wash with
water: dry and determine the melting point.

D


 : Add 4 ml of acetic anhydride and 3 drops of conc. H2S^4 to a test tube
with 1gm of substance. ºarm in a water bath for 15 min. Cool and pour
in a beaker with 10 ml of water. Filter the derivative formed, wash with
water, crystallize from water, dry and determine the melting point.

 ‘ J
 M
 
 


D


: Dlace 1 ml of alcohol and 3 gm phenyl isocyanate in a dry test tube and keep
the tube in boiling water for 10 min. Cool and allow to stand until crystals of
phenyl urethane derivative appears. Filter, wash with water, crystallize from
alcohol, dry and determine the melting point.

X ‘ J
 
  
# 


D


: Dlace 0.5 g of 3,5-dinitrobenzoic acid and 1g of DCl5 in a dish. To this
semisolid add 1 ml of alcohol and stir. ºarm on a water both and allow
standing for about 2 min. Filter the solid formed, wash with cold water,
crystallize from alcohol on petroleum ether, dry and determine the melting
point.

Àè
 ‘D
M   
   
D
 

enzoate, acetates, and bromo compounds are useful derivatives of phenols.

j ‘ J
 
# 



D


: To the phenol (0.5 g) is added 5% sodium hydroxide (10 ml) in a well-
corked boiling tube or a small conical flask. enzoyl chloride (2 ml) is
added in small quantities at a time, and the mixture shaken vigorously with
occasional cooling under the tap or in ice-water. After 15 min the solid
benzoate separates out: the solution should be alkaline at the end of the
reaction; If not alkaline, or if the product is oily, add a solid pellet of sodium
hydroxide and shake again. Collect the benzoate, wash thoroughly with cold
water, and recrystallise from alcohol or light petroleum.

 ‘ J
 j

 


D


: Acetates of many simple phenols are liquids; however, this is a suitable
derivative for polyhydric and substituted phenols. The phenol (0.5 g) is
dissolved in 10% sodium hydroxide solution and an equal quantity of
crushed ice is added, followed by acetic anhydride (2 ml). The mixture is
vigorously shaken in a stoppered test tube until the acetate separates. The
product is filtered and recrystallised from alcohol.

 ‘ J
 

   


D


: The phenol (0.3 g) is suspended in dilute hydrochloric (10 ml) and bromine
water added drop wise until no more decolorization occurs. The bromo

Àë
 derivative which precipitates out is filtered off and recrystallised from
alcohol.

 ‘D
M   
   
 

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For low-molecular-weight, water-soluble aldehydes and ketones, it is often advantageous

to prepare the semicarbazones. This is usually synthesized from the reaction of the
aldehyde or ketone with semicarbazide hydrochloride.

¦ 


   

  
 
¦ ¦    
  ¦

    

   




The most useful derivatives of carbonyl compounds are hydrazones, 2,4-dinitrophenyl

hydrazones, Dhenylhydrazones, 4-nitrophenylhydrazones. These devivatives are prepared
from the reaction of the aldehyde or ketone with hydrazine, 2,4-dinitrophenyl hydrazine,
phenyl hydrazine a 4-nitrophenyl hydrazine respectively.

  
¦

  
¦ ¦ 
 ¦

 


       

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¦ ¦ ¦

      
 

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  ¦





  

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j ‘ J
 J


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D


: Dissolve 1 ml on 1 g of the aldehyde or ketone, 1 g of semicarbazide
hydrochloride and 1.5g of sodium acetate in 10 ml of water in a test tube.
Shake the mixture vigorously, and place the test tube in a beaker or boiling
water for 5 min. Remove the test tube from the beaker, allow it to cool, and
place it in a beaker of ice. Scratch the sides of the tube with a glass rod.
Isolate the crystals of the semicarbazone by filtration and recrystilize from
water or 25 to 50% ethanol.

 ‘ J
 è
X  M
  #


D


: dissolve 100 mg or 3 drops of the unknown carbonyl compound in 2ml of
ethanol and add 3 ml of the 2,4±dinitrophenylhydrazine reagent. A large
quantity of crystals usually forms immediately; however, heating the
reaction mixture in water both at 50^C for 2 min may be necessary to
produce a derivative. Recrystallize the 2,4-dinitrophenylhydrazone from 30
ml of 95% ethanol by heating on a stream both. If the derivative dissolves
immediately, add water slowly until the cloud point is reached or until a
maximum of 5 ml water is used. If the derivative does not dissolve, add
ethyl acetate to the hot mixture until the derivative dissolves. Filter the hot
solution and allow stand at room temperature until crystallization is
complete. Isolate the crystals by suction filtration.

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 è
X D 

: In a small flask, add
0.4 g of 2,4-dinitrophenylhydrazine to 2 ml of conc. H2S^4. Add 3 ml of water drop wise,
with stirring, until the 2,4-DNDH is dissolves. Add 10 ml of 95% ethanol.

 ‘ J
 



D


: dissolve 0.5 g of the hydroxylamine hydrochloride in 3 ml of water. Add
2 ml of 10% Na^H and 0.2 g of the aldehyde or ketone. [If the carbonyl
compound is water insoluble, add a minimal amount of ethanol (Et^H) to
the mixture to give a clear solution]. ºarm the mixture on steam bath for
10 min and cool in an ice bath. Scratch the sides of the flask with a glass
rod to hasten crystallization.

 è‘D
M   
   
 




Three satisfactory derivatives of carboxylic acids are amides, anilides and -toluidides.
These derivatives are prepared by treating the corresponding acid chlorides with
ammonia, aniline on -toluidine.

The acid chlorides are most conveniently prepared from the acid and thionyl chloride
/Dhosphorous pentachloride.

R^Cl + 2NH3 RC^NH2 + NH4Cl

acid chloride amide
R^Cl + 2H2NC6H5 RC^NHC6H5 + C6H5NH3+ Cl-
acid chloride aniline anilide

R^Cl + 2H2NAr RC^NHAr + ArNH3+ Cl-

acid chloride -toluidine -toluidide

 M

ÀA
 RC^2H + S^Cl2 RC^Cl + S^2 + HCl

RC^2H + DCl2 RC^Cl + D^Cl3 + HCl

j ‘ J
 j



D


c: perform this reaction in the hood. Mix 1 g of the acid with 5 ml of S^Cl2.
Add one drop of N,N±dimethylformamide (DMF). Heat under reflux for
15-30 min. Dour the mixture cautiously in to 15 ml of ice-cold, conc.
aqueous ammonia. Extract the solution with three 10 ml portions of
methylene chloride. Isolate the methylene chloride (CH2Cl2) layer and
evaporate to dryness. Recrystallize the crude amide from ethanol.

D


: ^r mix 1 g of the acid with 1 g DCl5 in a dry dish and heat for a minute. To
half the crude acid chloride add 10 ml conc. NH4^H. Cool and filter, wash
the residue with water. Recrystallize the product from alcohol or water,
dry and determine the melting point.

 ‘ J
   
 è
   


D


: perform the experiment in the hood. Mix 1 g of the acid with 2 ml of S^Cl2.
Heat the mixture at reflux for 3 min. Cool the mixture, and add a solution of
1-2 g of aniline or 4-toluidine in 30 ml of benzene, and heat the mixture in a
hot-water bath for 2 min. Dour the benzene solution in to a separatory
funnel and wash successively with 2 ml of water, 5 ml of 5% HCl, 5 ml of
5% Na^H recover the benzene solution into a separation funnel and wash
successively with 2 ml of water, 5 ml of 5% HCl, 5 ml of 5% Na^H
solution and 2 ml of water. In the hood recover the benzene by distillation,
using a steam bath, and recrystallize the resulting amide from water or
ethanol.

À'
 ‘D
M   
   




Suitable derivatives of primary and secondary amines are acetamides, benzamides, and
benzenesulphonamides.

  


¦  ¦
¦
  ¦


 

 


  

 
¦   ¦

¦
  ¦




 



  


These transformations are satisfactory for derivatizing most primary and secondary
amines, but tertiary amines do not undergo such reactions. However, such amines form
salts that constitute solid derivatives. Thus a useful crystalline salt is formed upon
reaction with methyl iodide to afford a methiodide.

¦
    ¦
 

  

Dicrate is also a useful derivative of tertiary amine. It is formed when picric acid is
reacted with tertiary amine.




 


¦
  ¦





      


j ‘ J
 j





D


: Reflux gently in a small dry flask under a dry condenser the amine (1 g) with
acetic anhydride (3 ml) for 15 min. Cool the reaction mixture and pour into
20 ml cold water. oil to decompose the excess acetic anhydride. Cool and
filter by suction the insoluble derivative. Recrystallise from ethanol.

 ‘ J
 
#



D


: Suspend 1 g of the amine in 20 ml of 5% aqueous sodium hydroxide in a
well-corked flask, and add 2 ml benzoyl chloride (fume hood!), about 0.5 ml
at a time, with constant shaking. Shake vigorously for 5 - 10 min until the
odor of the benzoyl chloride has disappeared. Ensure that the mixture
remains alkaline. Filter off the solid derivative, wash with a little cold water
and recrystallise from ethanol.

 ‘ J
 
#

 M 



D


: To 1 g of the amine in 20 ml of 5% sodium hydroxide solution in a well-
corked flask adds 1 ml benzenesulphonyl chloride (fume hood!). Shake the
mixture until the odor of the sulphonyl chloride disappears. Check that the
solution is alkaline. Acidify if necessary to obtain the precipitated
derivative. Concentrated hydrochloric acid added dropwise should be used.
Filter the product, wash with a little cold water and suck dry. Recrystallise
from ethanol.

c
X ‘ J
 3
  


D


: Mix 0.3 g of the amine with 0.3 ml methyl iodide in a test tube, warm the
mixture for several min. and then cool it in an ice bath-water bath. If
necessary scratch at the air-liquid interface with glass rod to induce
crystallization. Isolate the product by vacuum filtration and purity it by
recrystallization from absolute ethanol or methanol or from ethyl acetate.

- ‘ J
 D
 


D


: Add 0.3 ± 0.5 g of your unknown to 10 ml of 95% ethanol. If the sample
does not dissolve, shake the mixture until a saturated solution results and
then filter. Add the filtrate to 10 ml of a saturated solution of picric acid in
95% ethanol, and heat the solution to boiling. Allow the solution to cool
slowly, and remove the yellow crystals of picrate by filtration.

 ‘ JM


M
   

IR and NMR spectroscopy are crucial to organic structural determination. IR analysis is

an excellent functional group probe, which can be used in conjunction with the functional
group tests. Use of both IR and chemical tests may lead to structural diagnosis. NMR also
aids in the structural determination. NMR is essentially a method of determining the
relative positions and numbers of spin-active nuclei. oth 1H NMR and 13C NMR spectra
can yield useful information concerning the types of protons or carbon present, such as
aromatic or aliphatic; the number of adjacent protons (for 1H NMR); and the number of
protons attached to a particular carbon. ^nce some preliminary structures are chosen, MS
can be used to narrow down the choices by utilization of fragmentation patterns and
molecular weight.

À
X 
 &
 

(i) ºhat is ayer¶s reagent?

(ii) ºhy do alkenes and alkynes decolorize bromine water and alkaline KMn^4?
(iii) Explain why for the confirmation of unsaturation in a compound both the tests
namely test with bromine water and test with ayer¶s reagent should be performed.
(iv) ºhy does phenol decolorize bromine water?
(v) How will you distinguish between phenol and benzoic acid?
(vi) ºhy does benzene not decolorize bromine water although it is highly unsaturated?
(vii) ºhy does formic acid give a positive test with Tollen¶s reagent?
(viii) ^utline the principle of testing glucose in a sample of urine in a pathological
laboratory?
(ix) ºhy is enedict¶s reagent more stable than Fehling¶s reagent?
(x) How would you distinguish an aldehyde from a ketone by chemical tests?
(xi) How would you separate a mixture of phenol and benzoic acid in the laboratory by
using chemical method of separation?
(xii) ºrite the chemistry of diazotization and coupling reactions.
(xiii) How can you distinguish between hexylamine (C6H13NH2) and aniline (C6H5NH2)?
(xiv) How can you distinguish between ethylamine and diethylamine?
(xv) How can CH3^H and C2H5^H be distinguished chemically?
(xvi) ºhy is solution of iodine prepared in potassium iodide and not in water?
(xvii) ºhat is haloform reaction? ºhat types of compounds generally give this reaction?
(xviii) How can you distinguish the compounds 2-pentanone and 3-pentanone by simple
chemical test?