Part I

GENERAL PROCEDURE FOR THE SYSTEMATIC QUALITATIVE

ANALYSIS OF ORGANIC COMPOUNDS
i. Preliminary investigations.
a. Physical State.
b. Color
c. Odour.
d. Ignition on china porcelain.
e. Action of 30% sodium hydroide solution.
f. Action of hot concentrated sulphuric acid.
g. !eaction "ith ferric chloride.etc.
ii. #etection of elements$ %ive details for the detection of nitrogen& sulphur and
halogens
iii. #etection of functional groups$ %ive the procedure for the detection of functional
groups especially for the group's( that is found to be present.
iv. #etermination of melting 'boiling( point$ )he Compound is found to melt 'boil(
at....C.
v. Probable Compound$ On the basis of the standard data of the melting 'boiling(
points of substances having particular functional groups's(& the given compound is
most probably.........
vi. Special tests of the compound$ %ive the special test's(& if any& for the particular
compound.
vii. #erivatives$ %ive the methods of the preparation of at least t"o important
derivatives and also mention their melting points observed by you.
*
Result:
+ence the given organic compound is$
*. Aromatic,Aliphatic
-. Saturated,.nsaturated
3. Special element present,/ot present
0. 1unctional group present
2. 3elting point
4. Probable compound based on melting point and derivatives prepared5
PRELIMINARY INVESTIGATIONS
1. Phys!"l st"te "#$ !%l%u&
In organic compounds the colour is generally associated "ith the presence of
certain functional groups i.e. particular group in the compound is responsible for a
particular shade. +o"ever& it should also be noted that several organic compounds are
colourless in the pure state but oidi6ed to coloured compound by atmospheric air&
e.g. amines. )he different important groups along "ith their most usual colours are
summari6ed belo" in the solid and li7uid states.
A. S%l$s
Colour Possible compounds
8ello" Iodoform& ben6oin& 9en6yl anthracene&
7uionones and nitro compounds.
Orange Ortho:nitro aniline.
Pin; /aphthols.
9ro"n
#iamines& aromatic higher amines and
aminophcnols.
-
'. L(u$s
Colourless to red bro"n Amines.
8ello" to Orange /itro compounds.
). O$%u&.
3ost of the organic compounds possess characteristic odo"gt;e: odour of
some compounds is so characteristic that it can be used even to distinguish the
particular class of compounds or sometimes even a single compounded from that of
others.
O$%u& P%ss*le !%+,%u#$s
Carbolic or Phenolic Phenols
/aphthalene li;e /aphthalene& p:dichloro or p:dibromo ben6ene.
3ice li;e Acetamide.
9itter almond li;e 9en6aldehyde. nitroben6ene
Pleasant Alcohols& ethers& esters
<ery pungent =o"er aliphatic acids and their halogen derivatives.
-. Test .%& Al,h"t! %& "&%+"t! #"tu&e:
/ I0#t%#
)he nature of organic compound '"hether aliphatic or aromatic( can be
established by the ignition test.
)he compound is placed on a nic;el spatula. )he latter is then heated first
slo"ly and then strongly in a burner flame. If the compound burns "ith an non:smo;y
flame& it is an aliphatic compound 'ecept chloroform& chloral hydrate and ethyl
acetate "hich burn "ith a smo;y flame(5 "hile if it burns "ith a sooty or smo;y flame
the compound is aromatic in nature. )he aliphatic and aromatic nature of compound
may further be ascertained by the follo"ing tests.
3
i. Nt&"t%# test. )a;e * gm. 'or lml.( of the compound in a test:tube. Add
-ml. Of conc. +/O3 and -ml. of conc +
-
SO
0
. +eat the contents for about
2 minutes&cool and pour the contents in cold "ater: formation of a yello"&
oily li7uid or solid indicates the presence of an aromatic compound 5
other"ise it is an aliphatic compound.
ii. Le R%se# test. )a;e 0.- gm. 'or 3:0 drops( of the organic compound&3:0
drops of formaldehyde solution and 2ml& Of con +-SO0.Sha;e the
contents "ell and then "arm:formation of red& orange& violet or green
colour or precipitate indicates the presence of an aromatic compound5
other"ise it is an aliphatic compound.
iii. I0#t%# %# !h#" ,%&!el"#: Place a small amount of the compound on a
porcelain dish and then heat it first gently and then strongly. /ote the
change in appearance& the odour produced and the residue left.
1ollo"ing are the notable observations and inferences of various important
compounds.
Observation Inference
9urns "ith luminous flame Aroma>tic or unsaturated
Smo;y flame... Aliphatic compounds
Smell of ammonia Amides
<iolet vapours Iodoform
Chars but does not melt .ric acid& sulphonic acid& starch
#ar;ens& s"ells& chars "ith
9urnt Suger Odour
Carbohydrates& lartaratcs& lactates ? 0 glucose
and some citrates.
0
1. S%lu*lty
2/ A!t%# %. )34 s%$u+ hy$&%5$e s%lut%#:
)reat a small amount of the compound "ith nearly 2ml of the al;ali solution
and note do"n the change in the cold state.
Observation Inference
#issolves in /aO+& reprecipates on adding Aromatic acids& Phenol
Con. +C=
3iture sets to a "hite solid @sters of diabasic acids
+ighly coloured solution /itrophenols& nitoracids& salicylaldehyde
Colour becomes deep on standing polyhydricphenols& some aminophenols
8ello" to bro"n resin Aliphatic aldehydes
/o" heat the solution and note the change
Compound dissolves some esters or acid anhydrides
Ammonia is evolved Amides& imides& urea& thio:urea&
8ello" or bro"n solution sulphonamide sugars 'ecept sucrose(& polynitro
compounds& halogennophenols& halogenonitro
hydrocarbons.
Chloroform li;e odour Chloral.
/ A!t%# %. h%t !%#!e#t&"te$ sul,hu&! "!$:
)reat a small amount of the given compound "ith concentrated sulphuric acid&
note the change and then "arm it.
Observation Inference
@volution of CO
-
"ithout charring urea.
@volution of CO
-
and CO.
And miture becomes yello"
"ithout charring.
Aliphatic hydroy acids
@volution of CO and ,or CO
-
And SO
-
"ith immediate blac;ening
Carbohydrates& aliphatic hydroy acids.
9lac;ening but no effervescences. Polyhydric phenols.
Pungent vapours "ithout charring Carboylic acids 'simple(
/ A!t%# %. N"HCO
-
:
0.l g of the substance treated "ith -ml of saturated /a+CO3 soln.
2
#issolves "ith bris; effervescence of CO
-
Acid or acidchloride.
6/ A!t%# %. Dl. HCl:
0.2g of the substance treated "ith -ml of dil. +CI and sha;e "ell.
#issolves in +C* and reappears on adding 9asic substance 'Amines(
*0% /aO+ solution.
7. Re"!t%# 8th Neut&"l .e&&! !hl%&$e:
)his regent is fre7uently used for identifying the presence of phenols and
aliphatic a:hydroy acids.& )a;e nearly t"o ml. of the compound solution either in
"ater or in alcohol and add to it one or t"o drops of neutral ferric chloride solution
and note the changes as belo".
Observation Inference
!ed colour but disappears =o"er fatty acids& maleic acid
by adding dil.+C=. or amino acid.
Intense transitory bluish:green o:phenylene diamine
Colour.
Intense red:bro"n colour ortho or meta:phenylene diamine.
Or ppt.
Purple colour salicylaldehyde& salicylic acids& salicylamide
acetylsalicylic acid& phenyl salicylate.
9lue or red colour Phenols& resorcinols& cresols& arninophenols.
%reenish colour or ppt. Catechol. Auinolnes of naphthol.
#eep yello" colour aliphatic a:hydroy acids
Pale bro"n ppt. dissolves in
div +C=
#icarboyiic acids soluble in "ater.
1erric chloride may also be used for identifying certain amines. In practice& the
compound is dissolved in dilute hydrochloric acid and t"o drops of ferric chloride
solution are added to the solution.
Observation Inference
%reen or blue green colour diphenylarnine& aniline
/:methylaniline
<iolet colour P:anisidine.
!ed colour P:phenetidine.
4
!ed ppt. O:phanylenediamine.
9lue ppt. O:naphthylamine& o:toluidine.
9. Re"!t%# 8th T%lle#:s &e"0e#t:
0.* g of the substance dissolved in suitable solvent and add -ml of )ollenBs
reagent. Carm on "ater bath.
9lac; ppt or bright silver mirror Presence of Aldehydes& carbohydrates&
polyhydric Phenols or other reducing agents
;. Test .%& s"tu&"t%# %& U#s"tu&"t%#
*. Action of potassium permanganate$ Potassium permanganate is a very
important oidi6ing agent in neutral& acid as "ell as in al;aline medium.
. I# #eut&"l +e$u+:
#issolve the substance in "ater and then add to it 0:2 #rops of neutral
potassium permanganate solution "ith constant sha;ing :violet colour discharged in
case of olefinic compounds.
. I# "!$! +e$u+:
Perform above test using potassium permanganate solution acidified "ith
dilute sulphuric acid and then "arm the contents:violet colour discharged in case of
olefinic compounds& or easily oidisable compounds 'aldehydes& ;etones& oalates
and formates.(
. I# "l<"l#e +e$u+:
Perform the test as in 'i( but using solution made al;aline "ith a fe" drops of
dilute sodium carbonate solution :violet colour discharged in case of aldehydes&
Phenolic acids& formates and cinnamates.
In case colour is discharged on "arming ?a hydroy acids& vi6& citric& lactic&
tartaric& etc. may be present.
-. 0.0 g of the substance D* ml of "ater 3:0 drops of 9romine "ater. Sha;e "ell.
8ello" colour decolori6ed. .nsaturated compound
8ello" color persist Saturated compound
8ello" color decolori6ed E ppt Saturated compound : amines& phenol.
F
is 1ormed
=. TESTS FOR SPECIAL ELEMENTS
1. L"ss"0#e:s test .%& #t&%0e#> sul,hu& "#$ h"l%0e#s:
Preparation of Lassaigne's extract of sodium fusion extract: Place a fe"
crystals or drops of an un;no"n compound in a fusion tube. 3old the test tube in an
inclined position and place a freshly cut out piece 'the si6e of a "heat grain( of
sodium metal slightly above the substance. 3old the test tube hori6ontally using tongs
or "ooden clamp. 1irst heat sodium until it melts. /o" set the test tube in the vertical
position so that the hot drops fall onto the test:substance. 3eat the miture to redness.
Plunge the red hot tube once in a china dish having nearly *0:*2 ml. of distilled "ater
"hen the fusion tube "ill be torn out& if not& do so yourself "ith the help of tongs.
9oil the resulting product. 1ilter the hot solution and "ash the residue "ith small
amount of distilled "ater. )he filtrate so obtained is ;no"n as =assaigeBs filtrate or
etract and used for testing nitrogen& sulphur and halogens. =assaigneBs etract should
be colourless. 8ello" or bro"n colour indicates incomplete decomposition of the
original substance. If so& repeat the eperiment using a ne" portion of the same
substance.
/a D CD/ /aC/
- /a D S /a
-
S
/a D C D SD/ /aSC/
/a D G /aG
H
i. Test .%& #t&%0e#: )a;e a small 7uantity of the etract in a test tube and ma;e
it al;aline 'if it is not so( by adding a fe" drops of sodium hydroide. Add 0.*
to 0.- gms& of solid ferrous sulphate 'a blac; precipitate "ill appear if sulphuc
is present(& boil the resulting solution and then acidity it "ith cone. +
-
SO0 or:
+C=. )he formation of Prussian blue precipitate or green colour indicates the
presence of nitrogen.
4/aC/ D 1eSO
0
/a
0
1e 'C/(
4
D/a
-
SO
0
Sodium ferrocyanide
o-
1eSO
0
1e
-
'SO
0
(
3
3/a
0
1e 'C/(
4
D 31e
-
'SO
0
(
3
1e
0
'1e'C/(
4
(
3
D 4/a
-
SO
0
ferric ferrocyanide
P&e!"ut%#s: 'i( Since the yello" colour of ferric chloride fades the Prussian blue
colour& it is better to avoid the addition of ferric chloride during the above test.
Similarly& on the same ground acidification "ith conc. +
-
SO
0
is preferred to
concentrated +C=.
'iii( Some compounds li;e urea and its derivatives although possess nitrogen& they do
not respond the above test5 the reason being the deficiency of carbon in these
compounds and hence in the above test "henever there is some doubt& the "hole of
the process must be repeated using miture of the compound "ith some amount of
cane sugar to provide sufficient amount of carbon.
1unction of conc. +
-
SO
0
or +C= )he function of the acid is to dissolve the
precipitate of ferrous or ferric hydroide 'formed by reaction "ith 1eSO
0
and /aO+(
as the ferrous or ferric sulphate or chloride.
1eSO
0
D -/aO+ /a
-
SO
0
D 1e'O+(
-

1e
-
'SO
0
(
3
D 4/aO+ 3/a
-
SO
0
D -1e'O+(
3

I
1e'O+(
-
1eSO
0
or 1eCI
-
D-+
-
O
-1e'O+(3 1e-'SO0(3or1eCl3D4+-0
)est for sulphur$ 1ollo"ing tests may be adopted for sulphur.
i. Acidify the =assaigneBs etract "ith dilute acetic acid and then add a fe"
drops of lead acetate& a blac; precipitate "ill be formed.
'C+
3
COO(
-
Pb D /a
-
S -C+
3
COO/a D PbS
9lac;
ii. Add fe" drops of freshly prepared dilute solution of sodium nitroprusside
'since in a7ueous solution& it is unstable( to the etract& the appearance of a
purple colour confirms the presence of sulpur.
/a
-
J1e'C/(
2
/OK D /a
-
S /a
0
J1e'C/(
2
/O
2
K
Sod.nitroprusside Sod. Sodiom Sulphorino pruside
'<iolet(
. Test .%& #t&%0e# "#$ sul,hu& 8he# ,&ese#t t%0ethe&:
#uring performing the test for nitrogen if a blood red colour is developed after
adding ferrous sulphate crystals& nitrogen and sulphur seem:to be present together.
4 /aSC/ D 1e 'SO
0
(
3
-1e 'SC/(
3
D 3/a
-
SO
0
ferric sulphocyanide 'red colour(
*0
Conc.+-SO0
Or Conc. +Cl
Conc. +
-
SO
0
Or Conc +Cl
?. DETECTION OF FUNCTIONAL GROUPS
)he tests of various important functional group are summari6ed belo".
1. CAR'O@YLIC ACIDS
3ost aliphatic carboylic acids are soluble in cold "ater& "hile aromatic acids
are sparingly soluble in cold "ater but readily soluble in hot or boiling "ater. )he
presence of carboylic group can easily be the follo"ing tests.
2/ Lt+us tests:
=i;e phenols& the carboylic acids turn blue litmus solution to red. 1or this
test& one drop of blue litmus solution is added to the a7ueous solution of the acid& the
appearance of red colour indicates the presence of a phenol or an acids.
P&e!"ut%#: As sometimes 'vi6. in case of very "ea; acids( it becomes
difficult to note the change in colour thus the test must be performed on a "hite tile.
2/ S%$u+ *!"&*%#"te:
Add some drops of concentrated sodium bicarbonate solution to the acid in
test tube or better on a "atch glass or a "hite tile. @volution of effervescences of
carbon dioide indicates the presence of a carboylic group.
!COO+ D /a+CO
3
!COO/a D +
-
O D CO
-
Precaution$ Some phenols li;e -&0&4 :trinitrophenol and -&0&4:tribromophenol
also behave li;e acids and hence evolve carbon dioide on treatment "ith sodium
bicarbonate.
2/ l%$"teA%$$e test:
%rind e7ual amounts of the carboylic acid& potassium iodide and potassium
iodatc& the appearance of bro"n colour o"ing to the formation of free iodine indicates
the presence of a carboylic group.
4!COO+D2LIDLIO
3
4!COOLD3+
-
OD3I
-
In case the compound is li7uid ta;e a little amount of it& 2:4 drops of -%
potassium iodide solution and 2:4 drops of 0% potassium iodate solution. Cor; the
**
test:tube and place in boiling "ater for *:- minutes. Cool and add about 2:*0 drops of
starch solution. 9lue colour indicates COO+ group.
26/ Este& test:
Carm nearly * ml. of the acid& -ml. of methyl or ethyl alcohol and a small
amount of concentrated sulphuric acid for *:- minutes on the "ater bath& in a test
tube. Cool and pour the solution to a china dish:having some sodium carbonate
solution& fruity smell of ester indicates the presence of acid
!COO+ D C-+2O+ !.C:OC-+2D+-O
26/ Fe&&! !hl%&$e test:
/eutrali6e 0.2 gm of the acid "ith ecess of ammonia in a boiling test tube.
9oil the solution to remove ecess of ammonia& cool and a fe" drops of neutral ferric
chloride solution. /ote the colour of the resulting solution and ta;e out inference
according to the follo"ing facts.
A reddish bro"n colour or ppt. is obtained in case of aliphatic mono:
carboylic acids.
A buff or bro"nish coloured precipitate is obtained in case of aromatic
acids and some aliphatic acids li;e succinic and adipic acids.
An intense yello" colour is obtained in case of alpha hydroy acids this
test may also be applied as follo"s. 1irst add a fe" drops of ferric chloride
to a dilute a7ueous solution of phenol and then add this resulting violet
coloured solution to a solution of a alpha hydroy acid in "ater the violet
colour is discharged and a deep yello" tinge appears.
A violet or bluish colour is obtained in case of o:substituted aromatic
hydroy acids.
*-
O
6. Dete!t%# %. u#s"tu&"t%# # "!$:
i. #issolve a small amount of the acid in chloroform or carbon tetrachloride and add
to -:3 drops of bromine solution in the same solvent 'i.e. either C+C=3 or CC=0(.
#isappearance of bromine colour "ithout evolution by hydrobormic acid suggests
the presence of unsaturation in the compound. On the other hand& if the bromine
colour is discharged "ith the evolution of hydrobromic acid& a phenol& aromatic
amino or enol is indicated. )he evolution of hydrobromic acid may be easily
detected by eposing the vapours to a solution of silver nitrate in nitric acid held
on the end of a glass rod.
!.C+ M C+.! D 9r !.C+9r.C+9r.!
2/ '"eye&:s test:
Add one or t"o drops of *:- % L3nO
0
solution to small amount of the acid
dissolved in "ater or acetone disappearance of purple colour indicates the presence of
unsaturation.
Precaution: Some easily oidisable compounds li;e aldehydes& alcohols&
formic acid some aliphatic hydroy acids phenolic acids also respond this test.
26/ Test .%& D!"&*%5yl! "!$s: 3i 0.* g of the substance "ith 0.2g of resorcinol
and 0drops of con. +-SO
0
in a hard glass test tube. +eat for 3:2 minutes pour it into
dil. /aO+. An intense greenish yello" fluorescence indicates a #icarboylic acid.
*3
O+ O+
9r
9r
D +9r
!.C+:C+.!
!.C+ M C+.! O+ O+
'O( D +
-
O
LmnO
0
!.C+O

!COO+
'O(
L3nO0
LmnO
0
). ACID ANHYDRIDES
i. #issolve the compound in ben6ene or chloroform and add some aniline to
the resulting solution. Carm the solution for nearly *:- minutes& and cool.
A "hite precipitate of anilide is formed.
iii Anhydrides produce fruity smelling esters "hen "armed "ith n:butyl
alcohol.
-. PHENOLS
i. Lt+us test: =i;e acids. phenols also turn blue litmus solution colour to
red
ii. S%$u+ *!"&*%#"te: @cept highly negatively substituted phenols
'eg.picric acid(& Phenols in general do not decompose sodium bicarbonate
solution 'difference from acids(
iii. Fe&&! !hl%&$e test: Add one or t"o drops of neutral ferric chloride to a
dilute a7ueous or alcoholic solution of the compound in a test tube& the
appearance of a characteristic colour 'violet& blue or green( indicates the
presence of phenolic group.
4C
4
+
2
O+ D1eCl
3
J'C
4
+
2
0(
4
1eK
:3
D3+C= D3+
D
iv. )a;e a small amount of the phenol in a test:tube& add to it al;ali and a
small 7uantity of a cold solution of dia6otised
*
p:nitroantiine solution 'p:
nitro aniline "ith dil +Cl follo"ed by cold:/a/O
-
solution( red color.
*0
Ac
-
ODC
4
+
2
/+
-
Ac/+C
4
+
2
CO/+C
4
+
2
COO+
Anilic acid
DC
4
+
2
/+
-
COO+
COO+
v. Phthalein test.
)a;e a little 'nearly 0.-gm.( of the phenol and an e7ual amount of phthalic
acnhydride in a dry test tube. Add nearly -:3 drops of concentrated sulphuric acid and
fuse the miture gently for about *2 minutes. Cool and pour the contents to dilute
sodium hydroide solution. Characteristic colours of dyes are obtained as belo".
C%+,%u#$ C%l%u& %. the $ye .%&+e$ C%+,%u#$ C%l%u& %. the $ye F%&+e$
Phenol !ed !esorcinol %reen
o:Croseol !ed +ydro7uinone #eep violet
m:Cresol 9luish:purple N:/aphthol %reen
Catechol 9lue O:/apthol <ery faint green
vi. Nt&%us "!$ test: )a;e a little of the compound in a test iube& add nearly
*ml of Conc. +
-
SO
0
and then add a little sodium nitrite. Sha;e the contents
and "arm gently& appearence of green,purple or blue colour indicates the
presence of phenolic O+ group. )ransfer the contents in little "ater "hen
the blue colour changes to red or blue:red. )he colour "ill again change to
blue or green on addition of a little -0% Sodium hydroide.
*2
vii. AB% $ye test: #issolve -:3 drops of aniline in one ml. of concentrated
hydrochloric acid and cool it in ice. )o this solution add a fe" drops of
cold sodium nitrite solution and then add this solution to a cold solution of
phenol in an ecess of /aO+ solution. Coloured solution or precipitate
indicates the presence of a phenolic group.
Tests .%& ,%lyhy$&! Phe#%ls: 'i( )a;e about - ml. of dilute ammonium hydroide or
/aO+ solution and add to it a crystal as large as rice :grain of the original compound.
Sha;e the content of the test tube :formation of yello" colour changing to red:bro"n
indicates polyhydric phenols.
'ii( )a;e about 3:0 ml. of )ollenBs reagent in a test :tube and add to it *ml of the
a7ueous solution of the original compound :a grey or bro"n precipitate is formed
immediately in case of catechol& 7uinol& pyrogallol& gallic acid and tannic acid5 "ithin
30 seconds in case of orcinal and phloroglucinol5 and "ithin - minutes in resorcinol.
1. ALCOHOLS
Alcoholic group can be detected by the follo"ing tests.
i. A!t%# %. s%$u+: )a;e nearly *ml. of the alcohol 'in case of solid& dissolve it in
the dry ben6ene or ether( in a test:tube and add to it a small piece of freshly cut
sodium:evolution of bric; effervescences of hydrogen suggests the presence of
alcoholic group.
-!O+D-/a -!O/aD+-
2/ Re"!t%# 8th "!etyl !hl%&$e.
)a;e about * ml. of acetyl chloride in a dry test tube and add to it about 0.2
ml. of the original compound :vigorous reaction occurs 'i.e bubbles are freely
evolved( "ith in - minutes "ith the evolution of +C= fumes. 9ring a glass rod dipped
in /+
0
O+ :"hite fumes of ammonium chloride are produced. Chen the reaction
'bubbles( stops& add one ml. of "ater to dissolve the remaining +C= gas5 separation
of an oily layer along "ith the ester li;e odour Confirms the presence of alcohol.
*4
!O+ D C+
3
COCl !OCOC+
3
D +CI
+CI D /+
0
O+ /+
0
C D+
-
O
Dst#!t%# *et8ee# ,&+"&y> se!%#$"&y "#$ te&t"&y "l!%h%ls:
i. )a;e *ml of pure acetone& one drop or *0 mg. of the alcohol and then one drop of
the chromic acid regent. stir the miture immediately:greenish blue coloured ppt.
is formed "ithin t"o seconds in case of primary and secondary alcohols. If no
precipitate or colour change occurs at once tertiary alcohol is indicated.
ii. )a;e * ml. of the compound in a test tube and add 2 ml. of lucas reagent "ith
sha;ing. /ote the follo"ing observations formation of insoluble chloride layer at
once tertiary alcohol. Appearance of cloudiness "ithin 2 minutes secondary
alcohol. Solution remains clear "ith some dar;ening primary alcohol.
iii. #issolve 0.- gm. of the compound in about *0 ml. of 0.0*% solution of bromine
in carbon tetrachloride. Add about 0.- gm. of /:bromosuccinimide and place the
test tube in a "ater bath at H0PC./ote the colour obtained.
Permanent orange colour Primary alcohol.
)ransient orange colour Secondary alcohol.
/o colour )ertiary alcohol.
7. CAR'ONYL COMPOUNDS 2Al$ehy$es "#$ <et%#es/
i. Aldehydes and ;etones& in general& are detected by reaction "ith -& 0:
dinitrophenylhyra6ine it form crystalline -.0:dinitro:phenylhyra6ine.
Add - drops or *.* gm. of the substance in dilute +C= to 3ml. of the -&0:
dinitrophenylhyra6ine solution 'reagent( in dilute +C= and sha;e the miture:yello"&
orange or red coloured crystalline precipitate may be formed at once& or on allo"ing
the miture to stand for *2 minutes& or on gentle "arming on a "ater:bath.
*F
ii. S%$u+ *sul,hte test: 3ost of the aldehydes and ;etones react "ith a
concentrated a7ueous solution of sodium bisulphite to form a crystalline solid.
CMO D /a+SO
3
iii. Solutions of many aldehydes and ;etones develop red colour "hen treated "ith
sodium nitroprusside and al;ali. )o a solution& of the substance add *ml of 3%
sodium nitroprusside solution and 2 drops of *0% /aO+ '!ed or pin; color(.
iv. It is important to note that the above tests are not positive in all aldehydes and
;etones. In case of ;etones only those ;etones "hich have at least one methyl or
ethyl group attached to the carbonyl group respond these tests.
v. Add /essierBs solution to etremely dilute a7ueous solution of aldehydes or
;etones voluminous precipitates. )his test is given only by simpler aldehydes and
;etones.
vi. Fehl#0:s test: 3i -ml. of fehling solution A 'copper sulphate solution( and
1ehling solution 9 'al;aline tartarate solution(. )o the mied solution add 3 drops
'or 0.*2gm.( of the suspected compound and "arm the resulting solution. )he
appearance of a red precipitate of cuprous oide indicates the presence of an
aldehydic group.
!:C+O D -Cu'O+(
-
!:COO+DCu
-
O D-+
-
O
Note that some ketones like benzoin also reduce Fehling solution.
vii. S!h..:s test: Add t"o drops of the compound under test to -ml. of the reagent
'pararosaniline hydrochloride solution& the colour of "hich is >ust decolourised by
passing SO
-
(. Sha;e the contents& appearance of a violet or red colour "ithin t"o
minutes indicates the presence of an aldehyde.
*H
O+
C
SO
3
/a
*I
/+
SO
-
+
SO
-
/+
/+
-
D
-ArC+O
Sha;e
C
SO
3
+
+
-
/
/+
C
Ar
+SO
3
+
C / C
Ar
SO
3
+
+
viii. T%lle#:s Test: )a;e nearly 3:0 ml. of the freshly prepared )ollenBs reagent in a
clean and dry test : tube and add to this -:3 drops 'or 0.* gm. in case of solid( of
the substance. Sha;e the solution and if no reaction occurs in the cold& "arm 'not
9oil( the tube gently in a bea;er of "ater at 20$ )he formation of a blac;
precipitate of metallic silver or silver mirror indicates the presence of a reducing
substance li;e aldehydes.
P&e!"ut%#s: 'i( )he reagent must freshly prepared but it must be "ashed
a"ay after use. As it forms eplosive substance if stored.
C+O D Ag
-
O COO+ D -Ag
(iii) ome ketones like p!ru"ic acid reduce the #ollen's reagent.
i. 'e#e$!t:s test: Add 2ml of 9enedictBs solution to 0.0ml. of -% solution of the
compound. 9oil the solution for t"o minutes and then cool rapidly. 1ormation of
a red precipitate suggests the presence of a reducing sugar or an aliphatic
aldehyde.
!C+O D -Cu
DD
'as citrate comple( D 0O+
:

9. CAR'OHYDRATES
)he carbohydrates may be detected by the follo"ing tests.
i. M%ls!h:s test: #issolve nearly 0.002gm. of the carbohydrate in one ml. of
"ater& add t"o drops of the molischQs reagent '*0% N:napthol in alcohol(
and sha;e. /o" add carefully -ml. of concentrated sulphuric acid along
the side of the test:tube and allo" it to stand for - minutes. )he formation
of a reddish violet colour at the >unction of t"o li7uids indicates the
presence of carbohydrate. ,BSha;eB the contents of the test:tube in a stream
of cold "ater& a deep purple solution is obtained& "hich on dilution "ith
cold "ater yields a violet precipitate.
-0
)ollenBs Silver
!eagent mirror
!COO+ D Cu
-
O D -+
-
O
'red(
Polysaccharides 3onosaccharides Sulphuric Dhydroyfurfural
)riarylmethane compounds '<iolet(
'iv(. '"&.%e$:s test: )he test is used in differentiating the monosaccharides from
disaccharides. )a;e one ml. of the freshly prepared 9arfoedBs reagent '0.33 gm. of
neutral copper acetate dissolved in 2 ml. of cold *% acetic acid( and add one ml. of
the carbohydrate solution to it. +eat the solution in a boiling "ater:bath& formation of
a red precipitate in the blue solution& or on the sides of the tube >ust above the li7uid&
"ithin t"o minutes indicates the presence of a monosaccharide 'glucose& fructose or
galactose(.
;. ESTERS
i. @sters are usually identified by their hydrolysis reaction. )a;e -:3ml of ester
solution in a test tube& add some sodium hydroide solution and a drop of
phenolphthalein& the pin; colour "ill be developed. +eat the reaction miture
for some time& the disappearance of pin; colour indicates the presence of an
ester group.
!COA!B Dal;ali D Phenolphthalein !COO+ D !BO+
=. ALIPHATIC PRIMARY AMINES
Aliphatic primary amines in general can be detected by the follo"ing tests.
i. Carbylamine reaction$ Carm a small amount '0.02 : 0.* gm. or - drops( of
the amine "ith - drops of chloroform and one ml. of alcoholic potash in a
test tube& a nauseating 'foul( odour of isocyanide 'carbylamine( indicates
the presence of a primary aliphatic or aromatic amine.
!/+
-
DC+Cl
3
D 3LO+ !/CD3LClD 3+
-
O
/ote$ It is al"ays advisable to decompose the isocyanide formed by adding
concentrated hydrochloric acid before thro"ing it in the sin;.
-*
heat
Pin; color Pin; color discharged
ii. Re"!t%# 8th #t&%us "!$: #issolve nearly 0.- gm. of the amine in 2ml.
of cone hydrochloric acid& cool it in ice and then add nearly -ml. of ice:
cold sodium nitrite solution& bris; effervescences of nitrogen "ill be
evolved in case the compound is primary amine. Sometimes& "arming on
the "ater:bath is re7uired in order to evolve the nitrogen.
!/+
-
D +O/O !O+D/
-
D +
-
O
iii. R+#:s test: )a;e fiearly 3:drops of the amino solution in 2ml.of "ater&
add to it *ml. of acetone and a drop of sodium nitropursside solution&
appearance of a violet colour "ithin t"o minutes indicates the presence of
primary aliphatic amino group.
?. AROMATIC PRIMARY AMINES
i. C"&*yl"+#! &e"!t%#: Same as in aliphatic primary amines.
ii. Re"!t%# 8th #t&%us "!$: #issolve nearly 0.* gm. of the given amine in
3ml. of concentrated hydrochloric acid in a small bea;er or a large hard
glass test tube. Cool it in ice to nearly 0PC and to this add 2ml. of ice cold
sodium nitrite a7ueous solution "ith constant sha;ing till a slight ecess of
nitrous acid predominates in the solution. Chen the reaction ceases& add
ice cold solution of O:naphthol in al;ali5 the formation of a bright red&
orange red or reddish blue precipitate or colour indicates the presence of
primary aromatic amino group. )he solubility of the dye in /aO+
indicates the presence of a hydroyl group in the amine.
13. ALIPHATIC AND AROMATIC SECONDARY AMINES
i. Re"!t%# 8th #t&%us "!$: #issolve nearly * gm. Of the compound in 3:
2 ml. of dilute hydrochloric acid and cool it is ice cold "ater. )o the above
solution add 0:2ml. *0% sodium nitrite solution drop "ise and "ith
constant sha;ing. Allo" the solution to stand or 2 minutes "hen a yello"
or "hite oil precipitate is produced.
ii. S+%#:s test: )a;e a fe" drops of the compound and add to it dilute
solution of sodium nitroprusside follo"ed by a fe" drops of dilute
acetaldehyde solution:deep blue or violet colours "ill be produced "ithin
five minutes.
--
11. AMINOAACIDS
Al,h"t!: )he presence of one of these acids may detected by the follo"ings
tests&
i. Add fe" drops of 0.-% solution of ninhydrin reagent to the a7ueous solution of
the substance a blue colour is produced.
ii. Add a fe" drops of ferric chloride solution to a7ueous or alcoholic solution of
amino acids 'red colour is developed(&
iii. S%&e#se# test: )a;e near about 0.2gm. of the compound in a test tube and
dissolve it in "ater or alcohol. Add t"o drops of phenolphthalein and then very
dilute sodium hydroide solution till a pin; colour is obtained& In other test tube
ta;e the similar things in the similar order only "ith the difference that here the
amino acid is replaced by 00% formalin solution. Add the solution from the
second test tube to the first5 the disappearance of the pin; colour is indication of
the amino acid.
-3
O
C
C
O
C
O+
O+
+
-
/.C+!.COO+
O
C
C
O
C M /
O
C
C
O
CO
-
D !C+O D +
-
O
Amino acid
9lue Color
A&%+"t!:
a. Aromatic amino acids are more acidic than the aliphatic amino acids cause
a vigorous evolution of carbon dioide from sodium bicarbonate.
b. )hey usually give reddish colour "ith ferric chloride solution.
c. =i;e aromatic primary amines& these undergo dia6otisation "ith nitrous
acid "hich couple "ith al;aline -:naphthol solution to give coloured a6o
dyes.
1). ALIPHA TIC NITRO COMPOUNDS
i. #issolve a small amount of the compound in concentrated sodium hydroide
solution and then add an ecess of sodium nitrite solution. /o" add some amount
of "ater follo"ed by drop"ise addition of dilute sulphuric acid. )he appearance
of a red colour "hich disappears on adding ecess of acid and reappears on adding
al;ali indicates the presence of a primary aliphatic nitro group. Secondary nitro
group on similar treatment produces a permanent dar; blue or blue green colour
soluble in chloroform. )ertiary nitro compounds do not respond this test.
ii. !eduction in neutral medium$ #issolve nearly 0.2gm. of the substance in an
e7uirnolar miture of alcohol and "ater by "arming. Add to it some amount of
6inc dust and solid /+
0
C*. 3eat the miture to boil and allo" the reaction to
comlete. 1ilter the solution and add )ollenBs reagent to the filtrate& a blac;
precipitate or mirror "ill be developed.
-0
Rn:/+
0
Cl
!/O
-
!/+O+ D +
-
O
!/+O+ D Ag
-
O !/O D -Ag D +
-
O
1-. AROMATIC NITRO COMPOUNDS
'i( Aromatic nitro compounds give the
'ii( test above
11. AMIDES AND EVIIDES
i. !eaction "ith nitrous acid$ =i;e primary amines& amides and imides evolve
nitrogen on treatment "ith nitrous acid.
!CO/+- D +O/O !COO+ D /
-
D +
-
O
ii. Re"!t%# 8th "l<"l: #issolve 0.- gm of the amide in ecess of concentrated
sodium hydroide solution. +eat the solution to boil& smell of ammonia gas
indicates the presence of amide group.
!CO/+
-
D/aO+ !COO/a D /+
3
)he evolution of ammonia gas can also be detected by the follo"ing tests.
a. 9ring a red litmus paper over the mouth of the test tube& it changes to blue.
b. 9ring a glass red dipped "ith concentrated hydrochloric acid to the mouth
of the test tube:dense "hite fumes of ammonium chloride.
iii. O#ly .%& "&%+"t! "+$es: )o a little of the compound& add some hydroylamine
hydrochloride solution in ethyl alcohol. 9oil the contents for about five minutes&
cool and then add about 0:2 drops of dilute '2%( ferric chloride solution:bluish
red colour
C
4
+
2
CO/+
-
D /+
-
O++C* C
4
+
2
CO/+O+ D /+
0
CI
iv. O#ly .%& "&%+"t! "+$es: )o the a7ueous solution of the aromatic amide add
about F:H drops of 4% hydrogen peroide and heat the contents to boiling. Cool&
add *:- drops of dilute '2%( ferric chloride solution bluish red colour in cold
-2
"ithin a short time or a bro"n colour on "arming.
C
4
+
2
CO/+
-
D+
-
O
-
C
4
+
4
CO/+O+ D +
-
O
Tests .%& U&e": .rea& being the typical member of simple amides& gives certain
characteristic special tests.
i. 'u&et test: 1use a small amount of the urea in a test tube until it >ust melts and
ammonia is evolved. After some time "hen it resolidifies dissolve it in * ml. of
dilute sodium hydroide solution and then add one to t"o drops of very dilute
copper sulphate solution& a pin; colour "ill be developed changing to violet and
lastly deep blue. )his test is also given by o amide and malonamide.
-/A
-
:C:/+
-
/+
-
CO/+CO/+
-
D /+
3
ii. @"#thy$&%l test: #issolve a small amount of the compound in 20% acetic acid
and add to it * ml. of 2% anthydrol solution in methanol& a precipitate "ill
immediately be formed. )he test is given by urea as "ell as its derivatives.
iii. )a;e small amount of urea in a7ueous solution and add to it sodium hypobromite
solution& bris; effervescences of nitrogen and carbon dioide "ill be evolved.
iv. U&e" #t&"te test: 0.*g of the substance D*ml of "ater D*ml of con. +/O
3
. Sha;e
"ell. Chite ppt formed sho"s a diamide li;e urea. .rea oalate test$ 0.*g of the
substance sha;en "ith 3ml of saturated solution of oalic acid. Chite ppt
-4
9en6amide +ydroamic acid
O
O
!/+CO/+
-
D +O.C+
!/+CO/+ .C+
O D +
-
O
indicates the presence of urea.
17. SULPHONIC ACIDS
A&%+"t! sul,h%#! "!$s:
i. )hese may be detected by fusion "ith al;ali as follo"s. 3i about 0.2gm.of the
substance& 3gm. of potassium hydroide and 2 drops of "ater in a nic;el crucible.
+eat the crucible carefully& "ith occasional stirring& so that the miture melts and
remains in the molten state for about *0 minutes. Cool the melt& add about 2 ml. of
"ater and stir the contents to dissolve the mass '"arm& if necessary(. Acidify the
solution : SO
-
gas is evolved "hich may be detected by means of a filter paper
strip impregnated "ith acidified potassium dichromate solution.
ii. )reat the compound "ith phosphorus pentachloride and then "ith phenol in
al;aline medium. A crystalline derivative is obtained.
Ar:SO3+ ArSO-Cl ArSO-:O:C4+2
)he above formed sulphonyl chloride also reacts "ith ammonia to form
crystalline sulphonamide.
ArSo
-
Cl D /+
-
ArSO
-
/+
-
D+CI
19. THIOUREAS
i. 3eat a small amount of the substance "ith - ml. of a7. /aO+ to boiling for about
30 seconds. Cool and add one drop of CO
-
=ead acetate:dar; bro"n or blac;
colour.
!/+.CS./!.! D 0LO+ -!/+
-
D L
-
CO
3
D L
-
S D +
-
O
L
-
S D 'C+
3
COO(- pb pbs blac; precipitate D -C+
-
COOL
ii. )a;e a small amount of the compound in a test tube& add to it an alcoholic solution
of yello" mercuric oide& and "arm : a blac; precipitate of mercuric sulphide "ill
or formed.
-F
PCl
C
4
+
2
:O+
:+Cl
Sulphonamide
!/+.CS./+ D +gO !/+.CO./+! D +gS
iii. 1use 'melt( a small amount of the compound in a test tube& cool and dissolve the
product in "ater. Add a7. ferric chloride solution : a blood red colour "ill be
developed.
1;. HYDROCAR'ONS
Although hydrocarbons have no general test& they can be detected by the
follo"ing tests.
i. I%$#e test: #issolve 0.- gm. Or -:3 drops of the substance in 2 ml. of ben6ene.
)o this add 2 ml. of very dilute solution of iodine in ben6ene and sha;e5 solution
remains violet.
ii. F&e$el A C&".t !%#$e#s"t%# test: 'Only for aromatic hydrocarbons(. )a;e
0.2gm. of anhydrous AICI
3
in a dry test tube. +eat the test:tube "hen. AICI
3
sublimes to deposit on the upper end of the tube. /o" add -:3 drops of a miture
of e7ual amounts of the substance and chloroform. Allo" this solution to come in
contact "ith aluminum chloride : appearance of red& orange& blue or green colour
due to the formation of triphenylmethane dyes indicates aromatic hydrocarbons.
F%&+"l# Test
Sample D CCl
0
D+C+OD+
-
SO
0
Observation red color "ith blac; ppt.
Este&s:
*. Substance D* drop of phenolpthalein D /aO+ dorp"ise "hile "arming the pin;
color disharges
-. +ydroylamine test
Substaance D methanolic soln of hydroylamine D +Cl
3
#!OPS( D 1@C
#!OPS of 3eth. Soln of LO+& boil& cool& add a drop +Cl
3
E acidity "ith CO/C.
+Cl
Purple , "ine color ester confirmed
-H
P"&t II
DERIVATIVES AND THEIR PREPARATIONS
T"*le %. $e&6"t6es %. the 6"&%us !l"sses %. !%+,%u#$s
S. N% Cl"ss %. !%+,%u#$s Sut"*le $e&6"t6es
*. Acids Amides& Anilides& esters&bromo derivatives
-. Phenols Acetates& 9en6oates& etc
3. Alcohols Acetates& 9en6oates&
0. Aldehydes and Letones -.0 #initrophenylhydra6ones& Phenyl
hydra6ones& Oimes etc
2. Carbohydrates Osa6ones& Acetates& etc.
4. Amines Acetyl& 9en6oyl& 9romo& etc.
F. /itro compounds Polynitro& Amino and its derivatives.
H. Amides& Imides and Anilides +ydrolysis to acids& /itro& picrates& etc.
I. Sulphonic acids Sulphonamides& Sulphanilides.
*0. +ydrocarbons /itro
DERIVATIVES OF CAR'O@YLIC ACIDS
i. A+$e: Sha;e the solution of 0.2 gm. of the acid "ith *.2 ml. of phosphorus
pentachloride or thionyl chloride till the vigorous reaction ceasesS. Carm the
solution gently and then cool it. /o" add cautiously nearly *0 ml of concentrated
ammonia solution& and "hen the vigorous reaction ceases& stir& cool and filter the
product 'acid amide(. Cash the acid amide "ith cold "ater& crystalli6e from "ater
and dry.
ii. A#l$e %& PAT%lu$$e: Sha;e the solution of 0.2 mg of the acid "ith *.2 ml. of
PCl
2
or SOCl
-
till the vigorous reaction ceases. Carm the solution gently and then
cool it. Add nearly one ml. of aniline or p:toluidine 'as the case may be( and sha;e
the reaction miture vigorously. If necessary& "arm and then cool. 1ilter off the
anilide or p:toluidide& "ash it "ith cold "ater and crystalli6e it "ith alcohol and
dry.
Anilities or p: toluidide$ may also be obtained directly from the acid itself.
One gram of the acid is rellued gently under a very lo" flame for half an hour "ith
nearly t"o grams of the aniline or p:toluidine in a completely dry test tube. Cool the
reaction miture& filter off the product and "ash the anilide or p:toluidide "ith acid.
-I
Crystalli6ation may be accomplished by means of alcohol.
. Este&: Re,e"t "s # "!$s
iv. F%& "&%+"t! "!$s: 3i about *g of the substance "ith 2ml of 9r
-
in glacial
acetic acid slo"ly& "ith constant stirring till yello" color develops. Sha;e "ell for
*0:*2 mts pour it into 20 ml of "ater "ith stiring. 1ilter the yello" crystals& "ash
"ith "ater and recrystallise from dil AcO+.
DERIVATIVES OF ANHYDRIDES
i. A+$e: )reat the compound "ith *0ml. of concentrated ammonia solution in a
glass stopper llas; until a solid is formed& filter off the derivative& "ash "ith "ater
and recrystallise from "ater or dilute alcohol.
ii. A#l$e: 'for monobasic acids($ 3eat a miture of * ml. of aniline and * gm. of
the anhydride almost to boiling. Cool& add 3 ml. of "ater and stir the contents "ith
a glass rod. !ecrystallise the product 'anilide( from "ater or a7ueous ethanol.
'!CO(
-
O D C
4
+
2
/+
-
!CO/+C
4
+
2
D !COO+
DERIVATIVES OF PHENOLIC HYDRO@Y GROUP
'e#B%"te: #issolve *.0 gm. of the phenol 'or suspend *.0 gm. of the amine( in 2 ml.
of acetone and add -.2 ml. of ben6oyl chloride Add *0 ml. of a7. /aO+ gradually
"ith cooling and sha;ing& then add further 00 ml. of /aO+ solution. Stopper the tube
or the flas; and sha;e vigorously 'if the flas; or tube becomes hot it must be cooled
under tap Cater( till the odour of ben6oyl chloride has disappeared '"hich nearly
ta;es -0 minutes(. )he final solution should be al;aline to litmus.
30
OD/+3
!CO/+
-
D
!COO+
!.CO
!.CO
Acetate derivative$ )a;e * g of the phenolic compound in a clean and dry test
tube5 add -.2ml of acetic anhydride and a drop of cone& sulphuric acid. Cor; the tube&
sha;e it vigorously for 0:2mts and then transfer the miture to *2ml of cold "ater&
Stir the contents "ith a glass rod till the oil solidifies. 1ilter& "ash "ith "ater and
recrystallise from hot "ater.
DERIVATIVES OF ALCOHOLS
i. A!et"te: )a;e one gm. of the alcohol& 0.2 g of fused sodium acetate and 2 ml. of
acetic anhydride in a conical flas;. Sha;e and heat the miture on a "ater bath for
*.0 hours. )ransfer the "arm solution into F2 ml. of ice cold "ater "ith vigorous
sha;ing. Leep the solution for some time and filter the product. Cash "ith "ater
and crystalli6e from alcohol.
!O+ D 'C+
3
CO(
-
O !OCOC+
3
D C+
3
COO+
ii. 'e#B%"te: )a;e I ml. of the alcohol& *0ml. of acetone& 2 ml of ben6oyl chloride
and 20ml. of a7ueous sodium hydroide solution in a small flas;. Cool& cor; and
sha;e the flas; vigorously till the odour of ben6oyl chloride disappears. 1ilter off
the solid compound. Cash "ell "ith "ater and crystalli6e from alcohol.
DERIVATIVES OF ALDEHYDES AND CETONES
O5+e
For aldehydes and aliphatic ketones: #issolve 0.2 gm. of hydroylamine
hydrochloride and 0.2 gm. of the carbonyl compound& heat the miture on the "ater
bath& add ethanol drop "ise "ith sha;ing until a clear solution is obtained. Continue
refluing until a sample of the reaction miture gives a clear solution on adding to a
little -/ /aO+ solution '* to - hours(. Cool the product "hen the derivative "ill
crystalli6e out& recrystallistion may be done "ith ethyl alcohol& a7ueous ethanol or
petrol
3*
C+
3
COO/O
O+D'C+
3
CO(-0 O C
O
C+
3
DC+
3
C
O
O+
CMO D /+
-
O+ C M /O+ D +
-
O
For aromatic and some c!clic ketones: #issolve *gm. of the ;etone and 0.4
gm. of hydroylamine hydrochloride in a miture of 3 ml of ethanol and * ml. of
"ater. !eflu and Cool the reaction miture& add about -0 ml. of "ater and sha;e&
filter the unchanged ;etone 'if any( and acidify the filtrate "ith dil. +Cl 'test "ith
blue litmus(. 1ilter off the oime.
Phe#ylhy$&"B%#e: It should be noted that phenylhydra6ones of only the
aromatic carbonyl compounds are crystalline in nature "hile those of aliphatic
carbonyls are either oils or possess lo" m.p 1or aromatic carbonyl compounds&
dissolve 0.2 gm. of phenylhydra6ine 0.H gm. hydrochloride and 0.H gm. of sodium
acetate in 2 ml of "ater. Add 0.- to 0.0 gm. of the compound dissolved in alcohol to
the resulting solution. Sha;e the miture and "arm the solution on "ater bath for *0
:*2 mins& cool and filter of the derivate. !ecrystallise the phenlhydra6one from dilute
ethanol& "ater or ben6ene&
C M O D +
-
/.+/C
4
+S C M /.+/C
4
+
2
DERIVATIVES OF CAR'OHYDRATES
i. Os"B%#e: )a;e 0.2 gm of the po"dered sample in a sugar clean test:tube. In
another test:tube dissolve 0.0 gm. of phenylhydra6ine hydrochloride and.0.4 gm.
of crystalline sodium acetate in 0 ml of cold "ater and add this solution to first
test tube. =oosely cor; the test tube& immerse it in a boiling "ater:bath "ith
periodical sha;ing& Cool the solution& filter the osa6one precipitate and
recrystallise it from 20% alcohol.
ii. A!et"te: #issolve 0.2 mg. of the carbohydrate& 0.2 gm of po"dered anhydrous
sodium acetate and 3 ml of acetic anhydride in 2 ml. of glacial acetic acid by
refluing on a "ater bath. 1urther heat the solution for a period of t"o hours. Pour
cautiously the hot reaction miture in -2ml,cold "ater and stir the solution
vigorously to decompose the ecess of acetic anhydride. 1ilter off the product&
"ash "ith cold "ater and recrystallise from alcohol.
3-
Oime
DERIVATIVES OF PRIMARY AND SECONDARY AMINES
2/ A!etyl $e&6"t6e.
For primary amines: Suspend 0.2 gm of the amine in 0.*2 ml. of "ater and
add 0.2 ml. of glacial acetic acid and 0.2 mol. of acetic anhydride drop "ise "ith
sa;ing If the miture does not "arm spontaneously& it is heated cautiously over a
small flame for *2 minutes. Cool the reaction miture& if the oil does not solidify& stir
"ith a glass rod and cool in an ice bath. If on derivative separates& the acid in
neutralised "ith saturated sodium carbonate solution. 1ilter off the acetyl derivative
and recrystallise from "ater or a7ueous ethyl alcohol.
For mononitroanilines: )a;e * mg. of the compound and 2 ml. of acetic
anhydride in a *00ml."ide mouthed flas; fitted "ith a reflu condenser. +eat the
content to boiling for some time '- minutes for m:and p:nitro and *0 minutes for a
nitroaniline(& after refluing& add -0ml. of boiling "ater. In case of para compound&
solid material separates out on the addition of "ater. #issolve it by gradually adding
acetic acid "ith stirring and boil the contents in order to dissolve the oily material.
Cool& filter off the product and recrystallise from dil. Acetic acid.
For secondary amines: Carm a miture of 0.2 gm. of the amine and 0.2 gm.
of acetic anhydride on the "ater:bath for 2:*0 mins. Cool& add 3 ml. of "ater and stir
the miture until the derivative is solidified.
It should be noted that sometimes the amine is resistant to acetylating& for
"hich sulphuric acid 'as catalyst( may prove advantageous. One drop of concentrated
sulphuric acid is dissolved in * ml. of acetic anhydride& and one drop of this solution
is added to the reaction miture before "arming on the "ater bath.
/ 'e#B%yl $e&6"t6e: Suspend about 0.2 gm. of the compound in *0ml. of 2%
sodium hydroide solution in a small conical flas;. Add drop"ise *ml. of ben6oyl
chloride& the flas; should be "ell stoppered and sha;en vigorously bet"een additions
of the reagent. )he reaction miture should be ;ept cool throughout the addition.
1inally& sha;e the reaction miture vigorously for 2:*0 minutes and filter off the
product. Cash the derivative "ith "ater and recrystallise from alcohol.
33
DERIVATIVES OF NITRO COMPOUNDS
Nt&% $e&6"t6e:
/itration "ith concentrated nitric acid$ Add nearly * gm. of the compound
portion "ise "ith sha;ing to 2 ml. of concentrated nitric acid density at room
temperature 'cool under tap in case the reaction miture tends to become "arm(. Stir
the miture for *0 minutes and add some crushed ice "hen the product "ill be
crystalli6ed out either on standing or on scratching the sides of the test:tube "ith a
glass rod. 1ilter off the product& "ash "ith "ater and recrystallise.
DERIVATIVES OF AMIDES> IMIDES AND ANILIDES
i. Hy$&%lyss: )a;e 0.2 gm. of the compound and ecess of -2% sodium hydroide
solution in a conical flas; fitted "ith reflu condenser. !eflu the contents until
all ammonia has been driven off 'it ta;es about half an hour( and then cool. Add
concentrated hydrochloric acid drop "ise till the reaction miture is strongly
acidic and the acid separates out as a derivative. 1ilter and recrystallise from
alcohol.
!CO/+
-
D +
-
O !COO+ D /+
3
!CO/+! D +
-
O !COO+ D ! /+
-
ii. @"#thyl"+$e: Add about 0.2 gm. of the substance to nearly F ml. of F% solution
of anthydrol in glacial acetic acid. Sha;e the contents "ell and then allo"
standing for *0 minutes. If solid derivative is not obtained& heat the contents on a
"ater bath for about half an hour and then cool "hen solid anthylamide is
obtained. 1ilter it off and recrystallise from acetic acid.
DERIVATIVES OF SULPHONIC ACIDS
i. Sul,h%#"+$e: )a;e * gm. of the dry sulphonic acid and mi it "ith - gm. of
phosphorous pentachloride. +eat the miture on an oil bath at *20PC for about 30
minutes. Chen the reaction seems to be completed& cool the contents and treat
"ith *2ml. of cold "ater. Stir and "ash the sulphonyl chloride t"ice "ith cold:
"ater by decantation. /o" add 2ml. of the concentrated ammonia solution& "ith
stirring. +eat the reaction miture on a "ater:bath for 2 to *0 minutes and then
30
cool. )he amide "ill start crystalli6ing out& if not& evaporate the solution to
dryness on the "ater:bath. !ecrystallise the derivative from "ater or a7ueous
alcohol.
ii. Sul,l"#l+$e: Prepare the sulphonyl chloride as above in 'i( method. #issolve it
in acetone and treat "ith 0.2 ml. of pure aniline dissolved in acetone together "ith
-2ml. of deliver /aO+ solution. Sha;e the miture for *0 minutes& etract "ith
ether to remove ecess of aniline. Acidy the product recrystlli6e from dil. Alcohol.
DERIVATIVES OF HYDROCAR'ONS
i. Nt&"t%# %. h"l%0e#% hy$&%!"&*%#s: )a;e * ml. or * gm. of the compound in a
dry test:tube& add to it *.2 ml. conc +/O
3
and *.2ml. Conc +
-
SO
0
. Place the test:
tube in gently boiling "ater for 2 minutes "ith occasional sha;ing. Cool& add
*0ml. of "ater and sha;e. Pi;er off the product& "ash "ith cold "ater and
crystalli6e from alcohol.
ii. P!&"te: #issolve 0.2g of the compound 'amine& phenol or aromatic hydrocarbon(
in minimum amount of ethanol. Add to it nearly 3ml of a saturated solution of
picric acid in ethanol. Carm the reaction miture for one minute and then cool it
slo"ly. 1ilter off the picrate. !ecrystallise the picrate of amines and phenols from
alcohol.
C
*0
+
H
D C
4
+
-
'/O
-
(
3
O+ C
*0
+
H
C
4
+
-
'/O
-
(
3
O+
32
SO
-
O+ SO
-
Cl SO
-
/+C
-
+
2
PCl
2
+
-
/C
4
+
2
9en6ene sulphonyl chloride Sulphanilamide
P"&t III
LIST OF ORGANIC COMPOUNDS AND THEIR DERIVATIVES
+.,t:?1D> EAN",th%
Colored crystalline solid. Slightly soluble in "ater. !eadily soluble in /aO+&
alcohol& ether etc
*. /o colour "ith neutral 1eCI
3
in +
-
O but gives "hite ppt.
-. Sha;e a small amounl of the compound "ith miture having e7ual volume
of I
-
and Ll and add ecess of /aO+:violet colour& rapidly dar;ening and
follo"ed by a precipitate.
3. )a;e a small amount of the compound in test tube and add to it -ml. of a7
/aO+ solution and one drop of chloroform. Carm a blue colour. )his test
is also given by O:naphthol.
0. )a;e a small amount of the compound in a test tube& add to it - ml. of
/aO+& a drop of carbon tetrachloride and a pinch of copper po"der.
Carm the contents: blue colour 'distinction from O:naphthol(.
De&6"t6es:
i. 9en6oate 3.P. 24P
ii. Picrate 3.P. *HIP
iii. Acetate 3.P. 24P
iv. #ibromo 3.P*02P
v. P:/itroben6yl ether 3.P. *00P
vi. #initroben6oate 3.P.-*FP.
34
vii. P:)osyl 3.P. HHP
M,.)> Res%&!#%l
Pin;ish "hite crystalline solid. Odourless Soluble in +
-
O& ether& alcohol and
chloroform.
*. Cith neutral a7. 1eCl
3
sol. It gives blue violet colour
-. +eat * c.c. of the a7ueous solution of the original compound "ith * ml of
/aO+ solution and a drop of chloroform till a definite red of violet red
colour is produced. /o" fill up the test:tube "ith "ater:a red solution
appearing violet:red on sha;ing& giving no fluorescence on dilution
indicates resorcinol& "hile a violet:red solution changing to deep red&
yielding a green fluorescence indicates orcinol.
3. +eat a miture of small amount 'rice:grain( of phthalic anhydride and
t"ice this bul; of the original compound "ith - drops of conc. +
-
SO
0
until
the miture appears red:bro"n in colour. Cool and add a fe" drops of
"ater follo"ed by /aO+ solution gradually and "ith sha;ing until the
miture is al;aline. ta;e out *ml. of this solution in a test:tube and fill up
the latter "ith "ater : a yello":green fluorescence indicates resorcinol.
0. /o ppt& "ith lead acetate solution
2. Apply general tests of polyhydric phenols.
De&6"t6es:
i. #iben6oate 3.P. **FP
ii. #iben6enesulphonate 3.P. 4IP
iii. #i:p:toluenesulphonale 3.P.H0
iv. 3&2:diitroben6oate 3.P.-0*
3F
v. P:)osyl 3.P.H0P
vi. #ibromo 3.P.I *-P
+.,t: 1))D>
F
N",thth%l
Pin;:bro"n coloured crystalline solid having 1aint odour. Soluble in /aO+&
ether& alcohol and ben6ene5 sparingly soluble in "ater.
*. /o colour "ith neutral 1eCl
3
-. Cith titanic acid in conc. +
-
SO
0
gives red colour.
3. Its solution in /aO+ "hen "armed "ith chloroform gives a blue color
'/ote that if C+Cl
3
is replaced by CCl
0
no colour is obtained(.
0. Phthalein test : faint green colour "ith some fluorescence.
2. Perform )est /o.0 mentioned in N:napthol '3.P I0P(.
De&6"t6es:
i. Acetate 3.P. F0P
ii. 9en6oae 3.P.*0F.
iii. Oucrate 3.P *24P
iv. P:)oluenesulphonate 3.P. *-2B
v. 3&2:#initroben6oate 3.P. -*-P
vi. P.)osyl 3.P *-2P
3H
CAR'O@YLIC ACIDS
1--D C##"+! "!$
Shining cream colored crystals sparingly soluble in "ater and chloroform
soluble in alcohol and ether.
*. )a;e - ml. of the neutral solution of the compound& add an e7ual volume of a7
L3nO
0
solution and sha;e:purple colour of permanganate is discharged "ith the
appearance of bro"n ppt. and bitter:almond li;e odour of ben6aldehyde.
-. )a;e - ml. of the neutral solution of acid and add - ml. of al;aline L3/O
0
solution. +eat and filter. Cool the filtrate "hile crystals of ben6oic acid are
obtained.
De&6"t6es:
i. amide 3.P.I0F0
ii. Anilide3.P. *23P
iii. p:)oluidie3.P.*4HP
iv. #ibromo 3.P. -03P
v. p:/itraoben6yl ester 3.P **FP
vi. S9)3.P. *F2P
131G O5"l! "!$ 2Hy$&"te$/> 2COOH/
)
)H
)
O
Soluble in "ater.
*. )a;e about - ml. of the a7. soluion of oalic acid& add - ml of glacial
acetic acid and -:3 drops of a7. CaCl
-
solution :"hite ppt. insoluble in
acetic acid but soluble in dil. +CI
-. Add 2 drops of conc +
-
SO
0
to a small amount of the compound in a dry
test:tube and "arm the contents gently by rotating the end of the tube over
a small flame and turn the mouth of the tube periodically to the flame
'characteristic blue flame of carbon monoide.(
3I
3. +eat the a7. Solution of the compound "ith acidic L3nO
0
purple colour of
L3nO
0
is discharged.
De&6"t6es:
i. Amide 'di( 3.P0*IPd
ii. Anilide 'di( 3.P.-020
iii. P:)oluidide 3.P.-4F0
T
Chite shining cystals& sparingly soluble in cold "ater but fairly in soluble hot
"ater& alcohol ben6ene& acetone. C+CI
3
& and CCl
0
9uffppt. "ith neutral a7ueous
1eCI3 solution.
De&6"t6es:
'i( Amide 3.P. *-HP
'ii( P:)oluidide 3.P. *2HP
'iii( Anilide 3.P. *40P
1-7D A!etyl s"l!yl! "!$ 2As,&#/
)a;e 0.- gm. of acid and -ml. of dil. /aO+ in a test tube. 9oil the contents for
2 minutes. Cool& add dil. +Cl :"hite precipitate of salicylic acid "ill be obtained.
00
*-*P 9en6oic acid
O
ACH
-
De&6"t6es:
i. amide 3.P. *3HP
ii. anilide 3.P *34P
iii. salicylic acid 3.P. *22P
iv. P:/itroben6yl eser 3.P. *00P
1=7D su!!#! "!$> COOH CH
)
CH
)
COOH
Soluble in "ater& alcohol and acetone Sparingly soluble in ether.
*. 3i a rice:grain of the original compound "ith double.he amount of
resorcinol and - drops of cone. +
-
SO
0
. %ently heat the contents until the
miture attains a red bro"n colour& cool& ad a fe" drops of "ater follo"ed
by a7. /aO+ till the solution becomes al;aline. )a;e out * ml. of this
solution into another test tube and fill he later "ith "ater 'yello" green
fluorescence(.
-. #erivatives$ Amides 3.p:-40 P c 5 Anilides:3.P:--H Pc
1?7D!> Plth"l! "!$
*. soluble in hot "ater and C+CI
3
Sparingly soluble in ether.
-. 3i. A rice grain for the substance "ith double the amount of phenol in a
dry test:tube. Add - drops of cone. +
-
SO
0
and heat gently till the miture
attains red:bro"n colour. Cool& add fe" drops of "ater follo"ed by
gradual addition of a7. /aO+ solution "ith sha;ing till the solution
becomes al;aline:red colour due to phenolphthalein formation5 the colour
is discharged on adding as acid.
3. 3i a rice grain of the substance "ith double the amount of resorcinol
Add - drops of conc +
-
SO
0
and heat gently till the miture attains red
bro"n colour. Cool& add fe" drops of "ater and then s7. /aO+ till the
solution becomes al;aline. )a;e out * ml. of this al;aline solution in
another test:tube and fill up the later "ith "ater 'yello" green
fluorescence.(
0*
De&6"t6es:
i. Amide 'di( 3.P. --0P
ii. Anilide 'di( 3.P-20P
iii. P:)oluidide 'di( 3.P. -0*P
1-3D Phth"l! "#hy$&$e
*. Insoluble in cold "ater but dissolves readily in hot "ater "ith
decomposition. Soluble in ben6ane and alcohol
-. !esponds tests mentioned under phthalic acid.
3. %ives fluorescence test
De&6"t6es:
i. Cith 6inc dust and acetic acid gives phthalide 3.P. F3P
ii. Amide 3.P. *0IP
iii. Anil 3.P. -*0P
iv. 'Anilic acid 3.P. *F0P
0-
O
C
C
O
O
ALIPHATIC HYDRO@Y ACIDS
133D Ct&! A!$ HCOOH. CH
)
OH 2COOH/CH
)
COOH> Ht. ;3
*. Soluble in "ater and alcohol but less in ether
-. Carm a small amount of the acid "ith conc +
-
SO
0
evolution of CO and
CO
-
ta;es place and the miture turns into yello" solution "ithout
charring. +eat the above solution for one minute& cool dilute "ith "ater&
add sodium hydroide solution follo"ed by sodium nitroprusside solution
intense red colour changing to violet on adding C+
3
COO+.
3. Chite crystalline precipitate on boiling the neutral solution "ith calcium
chloride solution 'note that no ppt. is formed in cold(
0. 9lue colour "ith O:naphthol in concentrated sullphuric acid
2. Perform test '0( mentioned on p
g
*0I:**0.
4. And fe" drops of Ag/O
3
solution to the a7ueous solution of the
compound 'a "hite ppt( in /+
-
O+ and ;eep the test tube in boiling "ater
bath 'a silver mirror is deposited on the "alls of test:tube(.
De&6"t6es:
i. Acetyl 3.P**2P
ii. Amide'tri( 3.P -*0P
iii. Anilide 'tri( 3.P.*HIP
1;3 T"&t"&! "!$> HOOC.CH2OH/.CH2OH/.COOH> E(.8t.;7
*. Soluble in "ater and alcohol& =ess soluble in ether.
-. Charring along "ith effervescences of CO and CO
-
on heating "ith
concentrated sulphuric acid
3. !educes ammonical silver nitrate solution 'see test /o. '4( in citric acid(
0. )o acid solution in "ater& add one drop of 1eSO
0
solution& sha;e and add
one drop of +
-
O
-
solution and then - ml. of /aO+ solution 'intense violet
03
colour.(
2. )o acid solution and cobalt nitrate solution follo"ed by ecess of sodium
hydroide solution no colour in cold& blue colour on "arming& again
colourless on cooling.
4. %reen colour "ith O:napthol in conc. Sulphuric acid the colour changes to
orange on dilution.
F. )a;e 3 ml. of neutral solution of acid& add * ml. of a7. CaCl
-
solution and
sha;e vigorously heavy& "rite crystalline ppt. soluble on boiling "ith *ml.
of glacial C+
3
COO+.(
H. )o the a7ueous solution add 2% solution of ammotmum vanadate& acidify
it "ith dil. C+
3
COO+ 'orange color(.
I. +eat 0.- gm. of acid& 0.- gm. of resorcinol and - ml. of conc& +
-
SO
0
in a
test tube violet red colour appears.
De&6"t6es:
i. Amide 'di( 3P II2Pd.
ii. Anilide 'di( 3.P.-40Pd.
iii. Acetyl 3.P. *-4P
PHENOLIC ACIDS
00
+%l. 8t 1-=. COOH M.P 17=D S"l!y le "!$.
*. Colourless needle type crystals. Sparingly Soluble in "ater for dissolves in
hot "ater& alcohol& ether and ben6ene.
-. Sha;e a small amount of the compound "ith cold "ater and then add a
drop of neutral a7. ferric chloride solution : violet colour.
3. )a;e a small amount of the compound in a dry test tube& add about *0
drops of methyl alcohol and *0 drops of conc. +
-
SO
0
. +eat the contents
gently& cool and pour these contents into a dish having 2 ml. of "ater
'odour of oil of "intergreen 'methyl salicylate(.
0. Add * ml. of cone. +/O
3
to a small amount '0.-gm.( of the acid. Place the
test:tube in a boiling "ater:bath for 2 minutes5 remove it and dilute "ith
"ater. )a;e out -ml. of this yello" solution and dilute "ith "ater. )a;e
out -ml. of this yello" solution 'picric acid( ma;e al;aline "ith a7. /aO+
and add - drops of ammonium sulphide. Place the test tube again in a
boiling "ater:bath forth minute 'deep red colour o"ing to formation of
al;ali salt of picric acid(.
De&6"t6es:
i. Amide 3.P 3IP
ii. Anilide 3.P *30P
iii. P:)oluidide m.p *.*24P
iv. S9) m.p l04P
v. Acetyl.p. *32P
02
ALDEHYDES
=3 V"#ll#
Slightly soluble in "ater. Soluble in organic solvents li;e ether& chloroform
ben6ene& etc red to violet colour "ith 1ecl
3
De&6"t6es:
i. -&0 : #initrophenylhydra6one m.p. -F0P
ii. Phenylhydra6one m.p *30P
iii. -&0 #initrophenylhyda6one m.p -40P
iv. Oime m.p. HHP
CETONES
'e#Bl
Pale yello". Insoluble in "ater. Place a pellet of LO+ in a dry porcelain dish
laced on a heated Cater bath. /o" place - rice grains of the compound on the LO+
pellet and carefully pour * ml. of absolute alcohol from the side of the dish 'deep
violet colour( @vaporate the contents :to: drynesse:remove any undissolved LO+&
and * ml of conc +
-
SO
0
.
04
C+O
C+
3
O+
C
O
O
C
De&6"t6es
i. #iphenyihydra6one m.p --2P
ii. -&0 #introphenylthdra6one 'di( m.p *HIP
iii. Oime 'di m.p. -3FP(
iv. Semicarba6one 'di( m.p -03P
'e#B%#
8ello" although pure ben6oin is colourless insoluble in "ater. Sparingly
soluble in ether. Soluble in alcohol.
*. )a;e a small amount of the compound and add to it *.ml of 1ehlingBs solution
'e7ual volumes of /o.l and /o.-( and * ml. of "ater 9oil the contents for 30
seconds : red ppt. of Cu
-
O
-. )a;e about 0.2 gm. of the original compound in a dry test:tube& add to it *.-2 ml.
of conc +/O
3
'Avoid large amount of +/O
3
"hich may cause nitrating of
ben6oin(. Place the test:tube in boiling "ater bath for about *0 minutes. Cool add
*0ml& of "ater and sha;e till the red oil solidifies& 1ilter off pale yello" product
ben6il& "ash "ith cold "ater and crystalli6e from alcohol.
CAR'OHYDRATES
119. De5t&%se 2$A0lu!%se/> CH
)
OH.2CHOH/
1
.CHO
*. Soluble in "ater and hot alcohol Insoluble in ben6enes and ether.
-. !educes 1ehlings solution& )ollens reagent and 9arfoedBs reagent
3. %ives rapid furfural test& P.0-
0. Apply test /o '0( mentioned under maltose using t"ice the amount of lead
0F
+
O+ O
C
acetate 'a salmon:pin; or rose:pin; colour(
De&6"t6es
i. Osa6one m.p -02P formed on "anning for 0H minutes
ii. Penta:acetate m.p :**-P 9 :*30P
iii. Oime m.p *3FP
C.HYDROCAR'ONS
=3 N",hth"le#e
Chite shining crystalline solid "ith characteristic odour. Insoluble in "ater
but soluble in alcohol& ben6ene and ether. Sublimes readily.
De&6"t6es:
*. Characteristic odour.
-. compound D C+Cl
3
D dry AICI
3
%reen colour.
i. /aphthalene picrate& m.p. *0IP$ place a small amount of the
po"ered naphthalene in a test:tube and dissolve it in * ml. of cold
ben6ene. Add - ml. of saturated solution of picric acid in ben6ene
and sna;e& filter off the precipitate5 "ash "ith fe" drops of cold
ben6ene and dry.
ii. Oidation "ith conc. +
-
SO
0
in presence of +gSO
0
gives phthalic
acid&m.p.lI2P.
0H
SIMPLE AMIDES AND IMIDES
D. A!et"+$e>CH
-
CONH
)
Soluble in "ater and alcohol5 insoluble in either.
De&6"t6es:
i. Picratem.p. *0FP.
ii. Anilidem.p.**2P.
iii. Ganthylamide m.p.-02P.
E. 'e#B"+$e C
9
HACONH
)
Sparingly soluble in cold "ater& soluble in hot "ater& alcohol and ben6ene&
sparingly soluble in either.
i. 3i a small amount of the substance "ith three times its bul; of dry soda
lime. Place this miture into an ignition tube and heal:a better almond
odour of ben6onitrile.
ii. +ydrolysis is ben6oic acid m.p.*-*P$ ta;e 0.2 gm. of the compound
*0ml.of a7. /aO+ and some porcelain pieces in a *00 ml. flac; fitted "ith
a refle condenser. !oil 'he contents under refle condenser for *0mts.
Cool and acidity "ith cone. 3CI. Cool and filter off the product Cash
"ith cold and crystalli6e from "ater.
De&6"t6es:
'i( anilide m.p. *40P
'ii( Ganthylamide m.p. --3P
1-)D u&e"> H
)
.N.CO.NH
)
*. soluble in "ater& in ecess of alcohol5 insoluble in either.
-. 'u&et test: +eat then cool the compound and then dissolve in "arm a7.
/aO+ sol. Add * to - drops of very very dil. Solution of CuSO
0
Pin; colour changing to violet and finally deep blue.
0I
3. @"#th A hy$&%l test: Compound D 22% C+
3
COO+ D *ml. of 2% solution
of anlh:hydrol in methyl alcohol the immediate formation
of ppt. indicates the presence of urea.
0. Cith sodium hypobromite solution 9ris; effervescences of /
-
and
CO
-
2. #issolve a small amount of urea in dil. +C= by heating. Cool& add about
3ml of /a/O
-
solution add sha;e. Pass the vapours of this test : tube to
another tube having 3 ml of baryta "ater. /o" close the mouth of the
baryta "ater tube "ith thumb and sha;e "ell :baryta "ater turns mil;y.
4. .rea nitrate m.p.*43P$ +eat a small amount of urea "ith "ater until a clear
solution is obtained. Cool add - ml. of conc. +/O
3
and again cool. 1ilter
off the product& "ash "ith cold "ater and dry.
De&6"t6es
i. Oalate m.p. *F*P
ii. Cith aniline hydrochloride it forms phenyl urea m.p. *0FP
iii. /&/B:#iacetyl m.p *2-P
iv. /./B:#iben6onyl m.p -*H:--0Pd.
AMINO ACIDS 2ALIPHATIC/
)-) $AGlye#e> H
)
N.CH
)
. COOH
*. Soluble in 0 parts of "ater& insoluble in alcohol and ether.
-. Add one or t"o drops of 1eCl
3
to the a7ueous solution of the compound:
'red colour(.
3. #issolve a small amount of the substance in "ater add to it - ml. of a7.
Copper sulphate solution : blue colour 'very much deeper than the a7.
CuSO
0
solution(.
0. )a;e - ml. of the a7ueous solution of the compound& add to it - drops of
phenolphthalein solution& - drops of a7. /aO+ and - :3 ml. of neutrali6ed
20
alcohol : disappearance of red colour.
De&6"t6es:
i. Preparation of ben6oyl derivative 'hippuric acid(& m.p. *HFP$ Place * gm.
of the compound& 3 gm. of solid /a+CO
3
and about -0 ml "ater in a *00
ml flas;. Sha;e the contents "ell and then add *.2 ml of ben6oyl chloride.
Sha;e the uncolored flas; vigorously till the odour of ben6oyl chloride
disappears. 1ilter off Cool& filter off the product& "ash "ell "ith cold
"ater and dry. Cash the solid product by stirring it "ith *0ml. of ben6ene
ta;en in a flas;. 1ilter off the product& "ash "ith bene6ene and crystallise
from "ater.
AMINO A PHENOLS
,A"+#% ,he#%l M.P 1=1 DC
*. Soluble in ecess "ater& sparingly soluble in ether.
-. Al;aline solution dar;ens rapidly in air.
3. Purple colour "ith 1eCl
3
or Ag/O
3
0. #issolve a rice grain of the substance in -0 ml. of "ater. )a;e out nearly 2
ml. of this solution and add to it * ml. of a7. /aO+ follo"ed by * ml. of
saturated a7. Phenol solution. Sha;e the contents:deep blue colour "ithin *
minute.
2. )a;e a small amount of the substance in test and add to it - ml. of
dichromate miture. +eat the contents to boiling 'pungent odour of
ben6o7uinone(
4. #issolve a small amount of the substance in 2 ml. of dil. +Cl cither on
2*
/+
-
O+
p:amino phenol 3.P *H0 PC
sha;ing or on "arming. Cool it& add 2 ml. canc. Sodium hypochlorite
solution '/aO+ D Cl
-
"ater( and sha;e yello" ppt. '7uinone chloromide&
m.p. H2P(.
De&6"t6es:
i. #iacetyl derivative& m.p. *20P. )o a small amount of the substance add 3
ml. of acetic anhydride and heat the contents to boiling for * minute "ith
occasional sha;ing. Cool& add 2 ml. of "ater and sha;e. 1ilter off the
derivative& "ash "ith cold "ater and dry.
ii. 3onoacetyl m.p *4HP
iii. 3onoben6oyl m.p -*4P
iv. #iben6oyl m.p. -30P.
THIOUREAS
M.P 1=3DC Th%u&e"> H
)
N.CS.NH
)
*. Soluble in cold "ater sparingly soluble in ether and alcohol.
-. 9oil a small amount of the substance "ith /aO+U/+
3
is evolved. )o the
solution add 2 ml. "ater and a drop of 1eCl
3
'a blood red colour due to
formation of ferric thiocyanate is formed.(
3. #issolve a small amount of the compound by heating "ith - ml. of dil.
Acetic acid. )o the hot solution add - ml. of potassium 1erro cyanide
solution green colour changing to blue.
0. +eat a small amount of the compound on a small flame until the solid
melts. Continue heating for 2 seconds. #issolve the residue by sha;ing
"ith - ml. of "ater and then add - ml. a7. 1eCl
3
. 1ill the test:tube "ith
"ater and sha;e 'deep red solution.(
2. Its solution in /aO+ gives blac; precipitate "ith lead acetate.
2-
De&6"t6es:
i. On heating "ith ben6yl chloride in alcohol it gives ben6yliso : thiourea
hydrochloride m.p *F0P.
ii. Ganthylm.p. *34P.
iii. )hiourea hydrochloride& m.p *34P.
AMINO SULPHONIC ACIDS
-HHP d Sulphanilic acid$
Chite Sparingly soluble in cold : "ater but soluble in hot "ater.
*. Add a pinch of substance to a solution of sodium bicarbonate :
effervescences of carbon& dioide are evolved.
-. On dia6otisation follo"ed by coupling "ith al;aline N:napthol& it forms an
orange:red dye.
3. #issolve a small amount of the substance in - ml of "ater by "arming. )o
the hot solution add bromine "ater "ith sha;ing until the solution gives
the yello" ppt.
0. +eat a small amount of the compound "ith -ml of potassium dichromate:
sulphuric acid miture to boiling 'pungent odour(
2. +eat the compound "ith soda :0ime :'characteristic odour(
De&6"t6es:
i. -&0&4:)ribromo m.p. **IP.
ii. p:/itroaniline 'obtained by treatment "ith cone. +/O
3
(. 3.P. *0HP.
23
iii. Sulphonamide& m.p. -00P.
iv. Sulphonanilide m.p.-00P. C+O
ALDEHYDES
M.P 1;?D 'e#B"$ehy$e>
Odour of bitter almond. Sparingly soluble in "ater.
De&6"t6es:
i. oime m.p. 32P.
ii. Phenylhydra6one m.p. *2HP
iii. -&0 : #initrophenylhydra6one m.p. -*0P
CETONES
M.P 79D A!et%#e> CH
-
COCH
-
.
3iscible "ith "ater.
'i( Cith I
-
D /aO+ in cold gives iodoform m.p **IP.
De&6"t6es:
i. Phenylhydra6one m.p. 0-P
ii. -&0 : #initrophenylhydra6one m.p *-HP.
iii. Semicarba6one m.p. *HFP.
3.P H0P 3ethyl ethyl ;etone. C+
3
COC
-
+
2
.
3iscible "ith "ater.
20
De&6"t6es:
*. -&0:#initrophenylhydra6one m.p. **2P
-. Semicarba6one m.p. *32P.
AROMATIC PRIMARY AMINES
M.P 1=-D A#l#e> C
9
H
7
NH
)
Soluble in *0 vol. of cold "ater but freely soluble in organic solvents.
*. Cith bleaching po"der it gives purple colour.
-. @vil odour of phenylisocyanate on "arming "ith ale. LO+ and C+Cl
3

De&6"t6es:
i. Acetyl 3.P. **3P.
ii. 9en6yol 3.P *40P
iii. )ribromo m.p **HP
iv. A6o : p: naphthol5 m.p. *3*P
QUESTIONS
*. Chat is the principle involved in the detection aromaticityV
-. Chich types of compounds "ill give positive reaction "ith neutral 1erric
chlorideV
3. Chat is carbylamine reactionV
0. Chat is dia6oti6ationV Chich compound "ill undergo dia6otisationV
2. A6o dye test:eplainV
4. Chat happens "hen monocarboyllic acids are treated "ith 1erric chlorideV
F. +o" "ill you confirm the presence of #icarboylic acidV
H. +o" can you detect the presence of unsaturationV
22
I. /ame some acidic organic compounds.
*0. /ame some basic organic compounds.
**. /ame some neutral organic compounds.
*-. /ame some aliphatic and aromatic primary amines.
*3. +o" can you distinguish aldehydes from ;etonesV
*0. Chat is 3olisch reagentV
*2. Chat is )ollenBs reagentV
*4. /ame some carbonyl reagents.
*F. /ame some easily oidi6able compounds.
*H. /ame some compounds "hich can reduce the carbonyl reagents.
*I. Chat happens "hen aldehydes are oidi6ed "ith L3+O
0
V
-0. Chy phenol& naphthol are acidic in natureV
-*. Chy ammonia is basic in natureV
--. Chat happens if an ester is hydrolysedV
-3. Chat is esterificationV
-0. Confirmatory test for urea
-2. Identification tests for amino acid.
24
P"&t IV
PREPARATIONS
@ercise /o.*. Preparation of Acetanilide from Aniline by acetyiation.
!e7uirements. Anline: -.2 ml
Acetylating Acetic anhydride :-&2 ml
3iture %lacial acetic acid:-.2 ml
PRINCIPLE:
Che+!"l &e"!t%#.
Amines can readily be acetylated to solid acetyl derivatives using acetylating
miture. 'Acetic acid is mied due to the high cost of acetic anhydride(. )his reaction
is an eg for /ucleophilic substitution reaction Aniline acts as nucleophile and the lone
pair elecrons on the nitrogen atom attac;s the carhonyl group of aceticanhydride and
the resuiting product is Acetanilide.
P&%!e$u&e: )a;e -.2 ml. of the aniline. -.2 ml. of acetic anhydride and -.2 ml.
of glacial acetic acid in a -20ml. conical flas;& Sha;e the reaction miture thoroughly
and then refle it gently for *2 minutes using air condenser. Pour the hot miture "ith
constant stirring to -00 ml. of ice cold "ater in a bea;er. 1ilter the product and "ash
"ith "ater. !ecrystalise the curde acetanilide either from boiling "ater or dilute
acetic acid -0 ml. of acid 00 ml. of "ater(.
Appearance $ Chite shining +a;es
8ield $ 0.2gms.
3.P. $ **2Pc
QUESTIONS
*. @plain the mechanism involved in acetylation.
-. Chich is the nucleophile in this reactionV
2F
3. +o" aniline is. /ucleophilicV
0. Indicate the anilide lin;age.
2. Chy is aniline aromaticV
E5e&!h!s!. ): T% ,&e,"&e As,&# 2"!etyl s"l!yl! "!$/ .&%+ S"l!yl! "!$ *y
"!e.yl"t%#.
Re(u&e+e#ts: Salicylic acid 2 gms.
Acetic anhydride F ml.
Conc. Sulphuric acid 3:2 drops.
Che+!"l &e"!t%#:
PRINCIPLE: Salicylic acid is a phenolic acid. )he phenolic group can easily
be acetylated using acetic anhydride. )his is an eg of /ucleophilic substitution
reaction. Phenolic hydroyl group of salicylic acid acts as nucleophile and the lone
pair of electrons on the oygen atom attac;s the carbonyl group of acetic anhydride to
form Aspirin.
P&%!e$u&e: )a;e all the three chemical compounds in the given proportions in
a -20 ml. flas;. Sha;e the miture thoroughly and "arm the reaction miture at 20 :
40Pc on a "ater : bath "ith continuous stirring. Allo" the reaction miture to cool
and add nearly *-2 ml. of:"ater& stir thoroughly and filter the product. !ecrystallise
the product from 20% alcohol or 20% acetic acid or hot "ater.
Appearance Colourless needles
8ield 2 gms.
3.P *34:*3FPC
2H
QUESTIONS
*. @plain the mechanismV
-. Chich is the nucleophileV
3. .se of Aspirin
0. Identification tests for aspirin
E5e&!se N%.-. T% ,&e,"&e )>1>9 A T&*&%+%"#l#e .&%+ A#l#e *y *&%+#"t%#.
Re(u&e+e#ts
Aniline -ml.
%lacial acetic acid *2 ml.
9romine in glacial acetic acid 3 ml in *0 ml of
Ice glacial acetic acid
Che+!"l &e"!t%#:
PRINCIPLE: 9en6ene does not react appreciably "ith 9; but the presence of
activating groups li;e /+
-
on the ring can activate the substitution& can easily form
bromo drrivatives& "hen treated "ith a solution of 9r
-
in acetic acid. )his is an eg of
@lectrophilic substitution reaction. Since: /+
-
is an ortho& para director the incoming
bromonium ion 'clcehophele( is directed to form symmetrical tribromo aniline
Procedure. )a;e - ml. of aniline and *.2 ml. of glacial acetic acid in a conical flas;.
Place the 9as; in ice bath and add to it H.0 ml. of bromine "ater in *0 ml. of glacial
acetic acid drop"ise "ith constant stirring through a burette or separating funnel.
Pour the reaction miture to a bea;er having ecess '*00ml( of "ater. 1ilter the
product "ash "ith "ater and reerystallise from alcohol or rectified spirit.
2I
Appearance Colourless shining *ong needles
8ield 2 gm.
3. P. *-0PC
QUESTIONS
*. @plain the mechanism of reaction
-. Chich is the electrophileV
3. Chat type of group is:/+-V
0. @plain ho" ben6ene is more stalteV
E5e&!se N%.1 T% ,&e,"&e ,A'&%+%"eet"#l$e .&%+ Aeet"#l$e *y t&%+#"t%#.
Re(u&e+e#ts:
Aeetanilide - gm.
%lacial acetic acid *2 ml.
9romine in glacial acetic acid 3 ml. of bromine in *0 ml. of glacial
acetic acid.
Che+!"l Re"!t%#:
PRINCIPLE: )he anilide group present in aeetanilide. is a moderate
activating group "hich directs the incoming bromonium ion to ortho and para
positions. Practically only a little amount of ortho product is formed because of steric
hindrance of the bul;y functional group. )he formed ortho product is removed during
recrystallisation because it is completely soluble in alcohol or rectified spirit. )his
reaction is also an eg:for @lectrophilic substitution.
40
P&%!e$u&e: #issolve - gm. Of the aeetanilide in *2 ml. of glacial acetic acid
in -20ml. flas;. Add 3* ml. of bromine dissolved in *0 ml. glacial acetic acid from a
burette or a separating funnel to the aeetanilide solution drop by drop "ith continuous
stirring. Allo" the reaction miture to stand for half an hour. Pour the contents to a
bea;er having -20 ml. cold "ater. 1ilter the product& "ash "ith cold "ater& dry and
recrystallise from alcohol or rectified spirit.
Appearance Chite crystalline compound
8ield -.2 gm.
3.P. *4FPC
QUESTIONS
*. @plain the mechanism of reaction.
-. Chich is the electrophileV
E5e&!se N%.7 T% ,&e,"&e Phe#yl"B% A ,I A #",th%J.&%+ A#l#e *y $"B%tB"t%#
.%ll%8e$ *y !%u,l#0 &e"!t%#.
Re(u&e+e#ts:
Aniline -ml
Cone. +ydrochloric acid 0 ml
Sodium nitrite *g
O:/apthol *.I2 g
Sodium hydroide *0% **ml
Ice
PRINCIPLE: Aniline is an aromatic primary amine "hich can undergo dia6otisation
to form ben6ene dia6onium chloride in presence of sodium nitrite and con +Cl. )his
in turn undergoes coupling reaction "ith -:napthol phenyl a6o-:naphthol.
PROCEDURE: #issolve *.-ml of aniline in 0ml of con +Cl and Hml of "ater in a
conical flas; #ia6otise by addition of solution of *g of sodium nitrite in 2ml of "ater.
4*
Prepare the solution of *.I2g of -:naphthol in **ml of *0% /AO+ in a -20ml bea;er
cool the solution to 2PC immersion in ice bath or by direct addition of *0 :*2g of
crushed ice. Stir the naphthol solution vigorously and add the cooled #ia6onium
chloride solution very slo"ly. !ed colour develops and red crystals of phenyl a6o -:
naphthol separates out. Chen all the solution has been added allo" miture to stand
in ice bath for *0mts "ith stirring. 1ilter the solution "ash "ell "ith "ater and drain
thoroughly. !ecrystalli6e the product from glacialacetic acid.
Appearance #eep shining red crystals
8ield 3.2 g
3.P *3* c
QUESTIONS
*. @plain #ia6otisation.
-. +o" does nitrous acid is generatedV
3. Chy nitrous acid should be generated in situV
E5e&!se N%: 9 Dete&+#"t%# %. M5e$ Melt#0 P%#t
Aim$ )o determine the mied melting point of the follo"ing mitures and to report on
the purity of 'I( and to report "hether the product is formed in '-(
*. 9en6oic acid E -:/aphthol
-. Aspirin and Anilide of Aspirin
PRINCIPL@$ Presence of impurity generally decreases the melting point so if
t"o compounds having very close melting points are mied the melting point of the
miture "ill considerably be lo"er than that of either of the t"o compouns. So the
melting point determination helps to ascertain "hether the compound is pure or not.
In some cases the melting point of the compound is very close to its derivative
so it becomes very difficult to ascertain by means of melting point that "hether the
product is formed or not. In such cases& the derivative should be mied "ith the
original compound and the miture should be sub>ected to melting point
4-
determination. If the melting point of the miture is very lo" than that of either of the
components it is ascertained that the derivative is formed& because if the derivative
"ere not been formed the miture "ill have the same melting point as the original
compound.
PROCEDURE: Close one end of the capillary tube& by holding it in the edge
of a flame continuously rotating till it is sealed. Introduce nearly 0.2g of the
completely dried and finely po"dered compound by thrusting the open end of the
capillary tube into a small heap of the compound and tapping "ith the sealed end of
the tube on the bench. Place the capillary tube inside the electrically heated melting
point apparatus and note do"n the melting point. #etermine the melting point of pure
9en6oic acid E -:/aphlhol and miture of the t"o by placing the tubes beside each
other inside the apparatus. #etermine the melting point of Aspirin and the product
epected to be Anilide of aspirin and for the miture of the t"o compounds. !eport
3elting point of 9en6oic acid M
3elting point of -:/aphthol M
3elting point of 9en6oic acid E -:/aphthol M
+ence the given sample is P.!@,I3P.!@ M
3elting point of Aspirin M
3elting point of Anilide of Aspirin M
3elting point of miture M
E5e&!se N% ;: Ste&e% M%$els %. O&0"#! C%+,%u#$s
A+: )o construct the bail and stic; stereo models of 3ethane& @thane& ethylene
Acetylene& Acetone and 9en6ene and comment on the shape& structure& bond angle&
bond length etc.
PRINCIPLE: Carbon atom can eist in three hybridi6ed states depending on the
number of atoms attached to it.
43
C"&*%# "t%+ s SP
-
hy*&$Be$ . "tt"!he$ t% 1 "t%+s %& 0&%u,s.
C"&*%# "t%+ s SP
)
hy*&$Be$ . t s "tt"!he$ t% - "t%+s %& 0&%u,s.
C"&*%# "t%+ s SP hy*&$Be$ . t s "tt"!he$ t% ) "t%+s %& 0&%u,s.
SP
3
hybridi6ed carbon is tetrahedral in shape SP
-
hybridi6ed carbon is trigonal
in shape and SP hybridi6ed carbon is planar. So depending on the number of atoms
attached to the carbon atom the stereo model can be build for better understanding of
the molecular geometry.
PROCEDURE: Carbon atom is blac; colored and hydrogen atom is "hite
coloured. Chite stic;s are used to represent the bonds bet"een the atoms. )hree
different carbon atoms are available to provide tetrahedral& trigonal and planar
arrangement. Select the carbon atom according to the number of atoms attached to it.
9uild the model by inserting the stic;s into the holes provided in the corresponding
atom. 1inally report the shape& 3olecular orbital picture of the molecule& type of
hybridi6ation of carbon& /umber of sigma bonds and pi bonds& bond length and bond
angle.
QUESTIONS
*. 3olecular formula for 3ethane& @thane& ethylene and acetylene
-. State of hybridi6ation of carbon in 3ethane @thane and Acetylene.
3. Chat is the valency of carbon& oygen& nitrogen& hydrogenV
0. #efine valency.
2. #efine bond angle& bond length.
4. #efine orbital& molecular orbital.
F. Chy acetylene is more reactiveV
H. Chy bond length in al;enes& al;ynes is& less than al;anesV
I. #efine atomic "eight& molecular "eight. @7uivalent "eight and atomic
number.
*0. I.PAC name for Acetylene.
40
D*e#B"l "!et%#e *y Cl"se#:s A S!h+$t !%#$e#s"t%#
AIM
)o prepare diben6al acetone by claisenBs : Schmidt condensation
PRINCIPLE
Aromatic aldehydes condense "ith aliphatic ;etones or "ith mied al;yl: aryl
;etones in the presence of a7ueous al;ali to form a& O: unsaturated ;etones.
In the preparation of diben6alacetone - molecules of ben6aldehyde condenses
"ith * molecule of diben6al acetone. )his reaction is called claisenBs condensation.
PROCEDURE
*. In a *20ml conical flash place a cold solo of 2.0g of /aO+ pellets in 20ml
of +
-
O and 00ml of alcohol.
-. Chilst s"irling the contents of the flash& add a miture of 2.*ml of pure&
redistilled C
4
+
2
C+O and *.Iml of A.!. acetone. Sha;e fre7uently and
maintain the temperature at -0:-2c for *2min by immersion of the flas; in
a bath of cold +
-
O.
3. 1ilter off the precipitated diben6al acetone at the pump and "ash it in cold
"ater to eliminate the al;ali as completely as possible.
0. Crude precipitate is recrystalli6ed for ethyl acetate or !ectified spirit. Pure
diben6al acetone JA yello" crystal solidK
NOTE
Sufficient alcohol is employed to dissolve the ben6aldehyde and to retain the
initially formed ben6al acetone in solution until it has had time to react "ith the
second molecule of ben6aldehyde.
42
P&e,"&"t%# %. 'e#B"#l$e
A+
)o prepare and submit 9en6anilide
P&#!,le
Acylation of an Aromatic *,- amine may be readily achieved by using an acid
chloride.
In general& 9en6oyiation of aromatic&amines finds less application than
acetylation in preparative "or;& but the process is often employed for the
identification E characteri6ation of amines. In the schoyen : 9aumen 3ethod of
9en6oylation& the amine& or its salt is dissolved 'or( suspended in a slight ecess of H :
*2 % /aO+ E soln a small ecess of ben6oyl chloride is then added E the miture
vigorously sha;en in a stoppered vessel J9en6oylation proceeds smoothly E the
sparingly soluable ben6oyl derivative separates as a sold.
P&%!e$u&e
Suspend * g '*ml( the substance in -0 ml of 2% /aO+ soln in a Cell : cor;ed
boiling tube 'or( small concial flas;& E add - ml of 9en6oyl chloride 0.2 ml at a time
"ith constant sha;ing& and cooling in "ater if necessary sha;e vigorously for 2:*0
min until the odour of ben6oyl chloride has disappeared. 3a;e sure that the miture
has an Al;aline reaction. 1ilter off the solid ben6oyl derivative( "ash it "ith a little
cold "ater E !ecrystallise it from ethanol 'or( dil
44
SYNTHESIS OF 'ENKPPHENON O@IME
A+
)o prepare and submit 9en6ophenone Oime.
P&#!,le
9en6pphenone condenses "ith +ydroylamine in the presence of ecess of
/aO+ soln to yield the oime.
'C
4
+
2
(
-
CO D +
-
/O+
'C
4
+
2
(
-
CM/:O+ D +
-
O.
P&%!e$u&e
In a *00ml !9 1las; filed c a !eflu condenser place 2 gm of 9en6ophenone&
3 gm of +yproylamine +Cl& *0ml of ethanol E - ml of +
-
O& )o the resulting
miture no" add "ith sha;ing E.in portions 2.4 gm of solid /aO+ ta;ing care that
the rean does not become too vigorous Wn so cool the flas; under tap "ater. After the
addition of /aO+ is complete heat the flas; under !eflu:for *0 min. cool and pour
the contents of the flas; in a bea;er containing a soln of *2 ml of cone. +Cl in 20 ml
+
-
O. 1ilter the precipted Oime E "ash "ith cold "ater. !ecrystalli6erthe product
from methanol.
3.PMX*00 : *0-PC
8ield M 2 gms.
4F