Professional Documents
Culture Documents
Session - 2009-10
ORGANIC CHEMISTRY
TOPIC : GOC - I
CONTENTS :
Structure Identification
* Monochlorination
* Catalytic Hydrogenation
* Ozonolysis
* Elements detection
* Identification of Functional Group by Lab. Test
63
STRUCTURE INDENTIFICATION
Monochlorination:(a)
Cl / h
CH3Cl + HCl
(i) CH4 2
Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl
Cl
Cl / h
2
(iii)
+ HCl
C
C
Cl2 / h
C C C Cl + HCl
(iv) C C C
C
C
Cl
Cl / h
2
(v)
+ HCl
Remarks:- When an alkane or a cycloalkane is treated with halogen (Cl2, Br2, F2, I2), a photochemical reaction takes
place and a C H bond cleaves and a C Cl bond is formed. If one H-atom is substituted by one halogen
atom. This is known as monohalogenation reaction.
Application:- If a molecule has more than one type of H-atom, then on monochlorination, it forms a mixture of
monochloroisomers. All these isomers are position isomers.
Conclusion:- Hence, it can be concluded that the total no. of position isomers (structural) of monochloro compounds
is equal to the number of different types of H-atoms present in the reactant. The different type of H-atoms are
also known as non-identical Hydrogens or non-equivalent Hydrogens or chemically different Hydrogens.
Ex.
Monochlori nation
2 Products (structure isomers)
(b) C C C C
Monochlori nation
2 Products (structure isomers)
(c) C C C C C
Monochlori nation
3 Products (structure isomers)
(d) C C C C
Monochlori nation
4 Products (structure isomers)
(a) C C C
C
CH3
Monochlori nation
5 Products (structure isomers)
(e)
Q.
Cl / h
only one monochloro isomer..
X(C5H12) 2
Ans.
X = Neopentane
Q.
Cl / h
Two monochloro
P(C6H14) 2
Remark : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated, but H-atoms of Benzene
ring are stable.
CH3
Ex.
CH2Cl
Cl / h
2
64
Q.
Cl / h
Two mohochloro
X(C8H10) (Aromatic) 2
Cl / h
One monochloro
Y(C8H10) (Aromatic) 2
Ans.
(X)
(Y)
Catalytic Hydrogenation of C = C; C C
General reaction:Ni
R CH2 CH2 R
(a) R CH = CH R + H2
Ni / Pt / Pd
R CH2 CH2 R
(b) R C C R + 2H2
H2
H2
R CH CH R R CH2 CH2 R
(Not isolated)
2H2 / Ni
(d)
(e)
3H2 / Ni
CH = CH2
H2 / Ni
room temperature
CH CH3
2
H 2/Ni
(100 150C)
(f)
H / Ni,
2
CH CH3
2
Remarks:(a) Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room temperature.
(b) All C C bonds(C = C, C C) are hydrogenated. The reaction cant be stopped at any intermediate stage.
Exceptions:Aromatic bonds which are stable at room temperature but can be hydrogenated at high temperature.
It can be concluded that the hydrogenation product of an alkene or alkyne or any unsaturated compound is
always a saturated compound.
The no. of moles of H2 consumed by 1 mole of compounds is equal to the no. of bonds presents.
All positional isomers of alkenes or alkynes (due to multiple bond) always give same product on hydrogenation.
65
Ex:- C = C C = C + Cl2 X
Ex.
C CC
C Cl
2H2 / Ni
(1)
Cl
Y =
(X)
Cl / h
2
Y + Z
Z =
Cl
CH3
CH3
H / Ni
2
(2)
CH3
CH3
H / Ni
2
(3)
Q.
Cl / h
2
5 Monochloro product
5 Monochloro product
H / Ni
Cl / h
Z(only one monochloro product)
X(C4H6) 2 Y 2
Identify X, Y, Z
Ans.
DU = 2
X
Identify the lowest molecular weight alkane which gives four structural isomeric monochloro products ?
C C CC
Q.
Ans.
Cl
C5H12
= 72g
Ans.
C
C C C C,
C
Q.
Ans.
DU = 2
Q.
CCCCCC
2 monochloro product
Find the structural isomers of
product?
Q.
Q.
Ans.
Cl / h
2
A
C 8H17 Cl
(C8H18 )
(Only one type )
Identify A ?
66
Q.
Ans.
C C
C C CC
C C
Write all isomeric alkynes which produce an isomer of heptane which on further monochlorination gives
(a) three monochloro products.
CC
C
(ii) C C C C C
C
Ans.
(i) C C C C C
(b)
Ans.
two monochloro
Nil
Q.
Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogenation produce such an alkane which gives two monochloro products ?
Ans.
C = C = C or C C C
Q.
Determine the M.W. of maximum unsaturated hydrocarbon which on hydrogenation gives C6H12 which on
further chlorination gives two monochloro.
CH2
Ans.
CH2
CH2
C6H6 = 78g
Ozonolysis:
It tells about position of unsaturation.
Remarks:(1)
(2)
(3)
The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.
(4)
General Reaction:- R CH = CH R
Ex:-
(1) O 3
R CH = O + O = CH R + ZnO + H2O
(2) Zn/H2O
(1) O 3
CH2 = O + CH2 = O
(2) Zn/H2O
(1) O 3
CH3 CH2 CH = O + O = CH2
(2) Zn/H2O
O3 / Zn
O / Zn
3 + OHC CH2 CHO (Propandial)
(4)
Applications:
The process is used to determine the position of C = C in a molecule.
If the products are rejoined, the position of C = C can be determined in the reactant molecule. All C = C (except
aromatic ones) undergo oxidative cleavage under normal conditions.
At higher temperature, the aromatic double bonds can also undergo ozonolysis.
O3
O = C C C C C = O + O = CH2
(1)
Zn
O ()
3
(2)
(4)
Q.
CH = CH CH3
low temperatur e
CH = O
(3)
Zn
O3 / Zn
+ O = CH CH3
O3
C6H5 CH = O
CH = CH
Zn
H / Ni
Cl / h
2 CnH2n 2 2
CnH2n1Cl
(P)
CnH2n 2
(Q )
(m products)
Single Compound
m3
(no isomer )
CH3
HCOOH + CH3 C COOH
CH3
Identify P ?
Ans.
P=
Q.
Find the structure of the hydrocarbon and the no. of monochloro products formed followed by hydrogenation.
Ans.
5 monochloro product
68
X
(Unsat. hydrocarbon)
H / Ni
2
Q.
Cl2
m products
h
(m 3 )
O 3 (Zn/H2O)
O
identify structure of X ?
Ans.
Q.
X =
H / Ni
2
X
(Unsat. H.C.)
Cl / h
2
m products
(m 7 )
O 3 (Zn/H2O)
C
X
Ans.
C=CC
Q.
Identify structure of X ?
Ans.
X is
Q.
H2
CCCCCC
X
O3 (Zn)
X is C C = C C = C C
69
Q.
O3
Zn, H2O
CH3
CH
3
O3
Zn, H2O
CH3
CH3
CH3
C C
+2
CH
3
Sol.
O O
Q.
Ex.1
(A) (C 9H18 )
Single monochloro produc
( Saturated
Hydrocarbon )
t
Cl2 / h
(B) (C8H18)
Cl / h
(C) (C 7H14 ) 2
s
Two monochloro products
( Saturated
Hydrocarbon)
Sol.
A=
or
Ex.2
C C
| |
B = CCCC
| |
C C
C =
Sol.
-Terpinene
Ex.3
Identify A & B
Sol.
A = CH3 C CH CH CH2
|
CH3
Ex.4
Identify A & m
A = Ph C C Ph
|
|
CH3 CH3
Sol.
m=3
Ex.5
H 2 / Ni
A
Cl / h n-products
2
O3
Zn/H 2O
H C H +
H C C CH2 CH2 C C H
Sol.
A=
n=7
71
1.1
1. Nitrogen
Test / Reaction
Remark
Lassaignes test
Na + C + N NaCN
2. Sulphur
Appearance
purple
2Na + S Na2S
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NO.S]
3. Halogens
of
presence of sulphur
Lassaignes test
X + Na NaX
4. Phosphorus
pyrophosphate indicates
phosphorus
H3PO4 + Magnesia mixture MgP2O7 + H2O
2MgNH4PO4 Mg2P2O7 + 2NH3 + H2O
5. Nitrogen
and
Sulphur
Lassaignes test
FeCl
Na + C + N + S NaSCN
3 Fe(SCN)3
72
73
Lucas Reagent
[Conc. HCl + anhyd. ZnCl2]
ROH
3
2
1
White ppt.
R OH + HCl
white ppt
+ H2 O
cloudiness
R C C Ag (white)
R C C Cu (red)
RCOOH + RCOOH
2HCHO
2ROH + Na 2RONa + H2
R C CH + Ag+
R C CH + CuCl
Red ppt.
Na
R C C R
Acid formed.
= O Compounds
O3(ozone)
O3
H2C = CH2 + O3
--------------
NR
NR
NR
NR
Pink colour
Disappears
Reaction
Observation
Br2 / H2O
[Bayers reagent]
alk. dil. cold KMNO4
conc. H2SO4
conc. NaOH
KMnO4
LiAlH4
Reagent
(R OH)
R C CH
CC
CC
C=C/
CC
CC
Functional
Groups
Lucas Test
I. ter.alcohol
II. sec. alcohol
III. pri.alcohol
Presence of active H
Ozonolysis
Ozonolysis
Bromination
Hydroxylation
Inert paraffins
Remarks
74
Amides
Ester
CH3CHO
or ArCOCH3
or
R COCH3
R CHO
Ar OH
Enols
Functional
Groups
Sodium bicarbonate
test
Effervescence evolve.
Pink colour
disappear on heating.
Smell of NH3
NaOH, phenophthalein.
Conc. NaOH,
RCOONa + NH3
Schiffs reagent : p-Rosiniline hydrochloride saturated with SO2 so it is colourless. The pink colour is resumed by RCHO.
RCONH2 + NaOH
(pink)
Litmus test.
Iodoform reaction
Tollens test
Fehlings test
DNP-test
Test of
enols / phenols
Remarks
H2O + CO2
+ H2
Reaction
Blue litmus
Schifts Reagent *
I2 / NaOH
Tollens reagent
Red ppt.
2, 4-Dinitrophenyl hydrazine
(2, 4-DNP) solution
Fehling solution
A&B
Coloured ppt.
(violet, blue, green buff)
Observation
FeCl3 (Neutral)
Reagent
75
Violet colour
Blue colour
Amino acids
Molischs reagent
(10% -naphthol in alcohol).
R2NH
Sec. Amines
red colouration
Liebermann test
Effervescence of N2
Nauseating odour
(Carbylamine)
black ppt
Observation
Carbohydrate
CHCl3, KOH
Mullikens test
Reagent
Ar. amines.
ArNH2
Amines (pri.)
RNH2
Nitro
Compounds
(RCH2NO2) or
ArNO2
Functional
Groups
ArNHOH
C=N C
(Blue colour)
CO
CO
C
OH
CO
+ H2N.CHR.COOH
(Amino acid)
OH
OH
(Ninhydrin)
CO
CO
Benzenediazonium
chloride
Naphthol
N=N-Cl +
OH
N=N
OH
orange-red dye
+ 2H2O
N2Cl
NH2.HCl
ROH + N2 + H2O
NaCl + HNO2
+ HNO2
Ag
Ag
NaNO2 + HCl
R NH2 + HONO
Reaction
Ninhydrin test
Dye test
Carbylamine
Reaction
Remarks
Examples
1.
: Structure Determination
Ex. 1
Ex. 2
Ex. 3
Ex. 4.
2.
Ex.5
Which of the following will not give (+ve) L.S. test for Nitrogen.
(A) CH3CH2NH2
(B)
(C)
76
H2C = CH CH2 OH
Benzyl C+ , 1
Other Examples
Ex.1
Ans.
Ex.2
Ans.
Ex.3
Ans.
Ex.4
Ans.
77
Ex.5
Ans.
Ex.6
C4H8
Ans.
CH3 CH = CH CH3
Ex.7
(A)
Ans.
A=
Ans.
Ans.
O
||
CH3 C O CH3
Ans.
A=
Ex.8
Ex.9
Na metal ve
Ex.10
A (C7H8O)
FeCl3 (neutral)
ve
Lucas
ve
Reagent
Ex.11
Ans.
78
1.
Reagents
(I)
(a) CH3 CH2 COOH
(b) CH3 C O CH3
NaHCO3 (+)
NaHCO3 ()
Acidic odour
Fruity/Sweet
odour
Na metal (+)
Na metal ()
O
(II)
(a) Ph CH2 C OH
Same
O
(b) Ph C O CH3
Same
Same
O
(III)
(a) Ph CH2 CH = CH2
Br2/H2 O (+)
(b) Ph
Br2/H2O ()
Dil KMnO4 ()
(IV)
(a) CH3 CH2 CH2 OH
Na metal (+)
Na metal ()
Ceric Ammonium
Nitrate (+)
,, ()
(V)
CH3
(a) CH3 C OH
CH3
Lucas Reagent
instant turbidity
Na metal (+)
In 5 min.
Na metal (+)
(+)
In 30 min.
Na metal (+)
(+)
(VI)
(a) CH3 CH2 CH2 CH2 NH2
NaNO2/HCl
(N2 gas )
Na metal (+)
N2 gas not
liberated
Na metal (+)
2.
Ans.
A
C
D
F
G
H
I
J
(B) NaHCO3
(C) 2, 4-DNP
(D) AgNO3 + NH4OH
OH
3.
Sol.
T =
79
POC - II
Separation of binary mixture of organic compounds
Theory of separation : Organic compounds have different solubilities in different solvents. So they can be
separated by use of appropriate solvents.
The organic compounds derived from natural sources or prepared in the laboratory are seldom pure. They are
usually contaminated with other substances.
Purification means the removal of undesirable impurities associated with a particular organic compound, i.e
to obtain the organic compound in pure state.
1.
2.
Chemical methods:Chemical methods of separation depend upon the nature of the functional group present in the component.
Hence these can be applied to solid as well as liquid compounds.
A chemical method can be applied only when one of the components of the mixture is soluble in a particular
solvent while the other is insoluble in the same solvent .
Separation is the first step during the actual analysis of organic mixture. It is the most important step in the
sense that if separation is incomplete the result will not be correct because the impure compound will give
tests of different functional group and its melting point will also be very much different from that of the pure
compound obtained from complete separation.
(i)
(ii)
(iii)
(iv)
(1)
Most of the aromatic compounds are water insoluble due to large hydrophobic group of six carbon atom
Aromatic acids are insoluble in water but soluble in aqueous NaHCO3 solution or NaOH solution, due to salt
formation.
Aromatic hydroxy compounds are water insoluble but are soluble in aqueous NaOH solution due to salt
formation.
Aromatic amine (Aniline 1, 2, 3) are organic base and water insoluble but are soluble in aqueous HCl
solution due to salt formation.
Aliphatic compoud with atleast two functional group ( which can form H-bonding) are water soluble.
Ex. Diacids, diols. diamines, hydroxy acids ( OH, COOH), Amino acids ( NH2 , COOH) .
oxalic acid , malonic acid, maleic acid, fumaric acid, glycol, glycerol, sucrose, glucose.
80
Ex.1
Compound A
Compound B
Appropriate Solvent
(1)
H2O
(2)
H2O
81
(3)
Fructose
H2O
(4)
aq. NaHCO3
(5)
aq. NaOH
(6)
aq. HCl
Ex.2
Sol.
Ex.3
Identify I & II
Sol.
Q,
Ex.4
P+Q+R
Identify P, Q, R
Sol.
PI
Q II
R III
82
(1)
(2)
(3)
III
83