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(phenetole)
Ethoxy benzene
Methods of preparation
Willamson synthesis
when alkyl halide is treated with sodium alkoxide, we get ether
RX + R-O-Na > R-O-R + NaX
CH3Br + NaOC2H5 > CH3-O-C2H5 + NaBr sodium ethoxide methoxy ethan
Secondary or tertiary halides readily undergo elimination reaction in the presence of strong base to form alkenes.
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phenetole
anisole
Dehydration of alcohols
Alcohols are dehydrated to ethers in presence of concentrated H2SO4
at 413 K.
If ethyl alcohol is passed over heated catalyst like Al2O3 at 520K we get ether
Physical properties
In ether central oxygen atom is sp3 hybrid state.
The bond angle in C-O-C is not exactly 109o28'. The deviation in angle is caused by the repulsive force between
alkyl group. C-O-C angle in dimethyl ether is 110o.
Thus ethers have bent structure and have dipole moment greater than zero. There is no H-bonding in ether.
Ethers are soluble in water, solubility of ethers is due to the capability of their molecules to form H-bond with
water molecules.
Chemical properties
Cleavage by acids
Ether can be cleaved by the use of halogen acid, H2SO4
373 K
C2H5-O-C2H5 + HI > C2H5OH + C2H5I
again C2H5OH will react with HI and gives C2H5I
C2H5OH + HI > C2H5I + H2O
Overall reaction is as under 373 K
C2H5-O-C2H5 + 2HI > 2C2H5I + H2O
Mechanism is as under
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In the above reaction, we will always get phenol and methyl iodide. It is due to fact that phenyl oxygen bond has
partial double bond character due to resonance and thus its cleavage is difficult as compared to alkyl oxygen
bond. Order of reactivity of halogen acids is
HI > HBr > HCl
Reaction with PCl5
heat
C2H5-O-C2H5 + PCl5 > 2C2H5Cl + POCl3
phosphoryl chloride
Ring substitution in aromatic ethers
Aromatic ether undergo electrophilic substitution in the benzene ring at the ortho and para positions.
User of ethers
1. Diethyl ether is used as an industrial solvent for oils, gums, resins etc..
2. An anaesthetic in surgery.
Aldehydes and ketones
The group R1, R2, R may be aliphatic or aromatic. The general formula of aldehyde and ketones are RCHO and
R1R2CO respectively. Here carbon is sp2 hybridized and bond angle is 120o.
Nomenclature of aldehyde and ketone IUPAC name of aldehydes are alkenals and for ketones it is alkanones.
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benzaldehyde benzaldehyde
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Aldehydes undergo further oxidation to carboxylic acids very easily. So oxidaiton of alcohols to aldehyde is
carried out under controlled reactron conditions. When alcohol vapours are passed over heated metallic catalyst
such as Cu, Ag, we get aldehydes, ketones. Primary alcohols give aldehyde and secondary alcohols give
ketone.
From carboxylic acid chlorides Acid chlorides (RCOCl) are converted to aldehyde by catalytic hydrogenation
The above reaction is called Rosenmunds reduction. Ketones are obtained by treating acid chlorides with
dialkyl cadmium.
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Acetone is less reactive towards nucleophiles because in acetone, the carbonyl carbon is attached to two methyl
group which are electron releasing nature, These methyl groups push electrons towards carbonyl carbon and
thus, decrease the magnitude of positive charge on carbon and make it less susceptile to nucleophilic. Both
aldehydes and ketones react with hydrogen cyanide (HCN) to form cyanohydrins as addition products
Reaction with NaHSO Both aldehyde and ketons form addition product.
The hydrogen bisulphite addition compound can be converted back in to the original aldehyde or ketone by
treating it with dilute acid or alkali.
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Addition of ammonia derivatives Aldehydes and ketones react with ammonia derivatives. The addition
compounds and water molecule give a compound containing
are as under
Ketones are not easily oxidised. They can be oxidised under vigorous condition using powerful oxidising
agents such as HNO3 KMnO4/H+, K2Cr2O7/H+ etc. On oxidation of ketones, cleavage of carbon-carbon bond
takes place and a number of carboxylic acids having less number of carbon atoms than the parent ketone are
formed.
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Oxidation reaction can be used to distinguish between aldehyde and ketones by using the reagent like
Tollen s r eagent , Fehling s soluit on. Tollen s r eagent . It is a ammoniacal solution of AgNO3
AgNO3 + NH4OH AgOH + NH4NO3
AgOH + 2NH4OH [Ag(NH3)2]+OH- + 2H2O
On treating the Tollens reagent with aldehyde we
get silver mirror.
Fehling solution
Alkaline soluiton of CuSO4 containing sodium potassium tartrate (Rochellesalt) as the complexing agent.
Aldehyde on warming with this solution give a red precipitate of Cu 2O.
R-CHO + 2Cu(OH)2 + NaOH RCOONa + Cu2O + 3H2O red ppt
It may be noted that Tollens reagent and Fehling solution are very weak oxidising agent. They can oxidise
aliphatic aldehyde. Tollens reagent will oxidise aromatic aldehyde also but fehling solution is not capable to
oxidise aromatic aldehyde.
Both reagents will not oxidise ketones. Both reagents may be used to distinguish between aldehyde and ketone.
Reduction Aldehydes and ketones are reduced to primary and secondary alcohol respectively by mild reduction.
Aldehyde and ketones are converted to their corresponding hydrocarbon by the following methods :
Clemmensen reduction Aldehyde and ketone are reduced to the corresponding hydrocarbon by treatment with
amalgamated zinc and concentrated HCl.
Wolff-Kishmer reduction Aldehyde and ketones are reduced to the corresponding hydrocarbon by the reaction
with hydrazine followed by reaction with glycol and KOH
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Aldol condensation Aldehydes and ketones which have at least one a hydrogen atom when treated with dilute
NaOH, they undergo condensation to form b hydroxy aldehydes or ketones. This is known as aldol condensation.
Aldol formed above when heated undergo dehydration to form a - b unsaturated aldehyde.
Cannizygaro reaction Aldehydes which do not have a hydrogen atom, such as formaldehyde and benzaldehyde,
when heated with concentrated NaOH (50%) solution, gives a mixture of alcohol and the salt of a carboxylic
acid.
conc.NaOH
2HCHO CH3OH + HCOO-Na
sodium acetate
conc. NaOH
2C6H5CHO C6H5CH2OH + C6H5COONa+
Formaldehyde reacts with ammonia to form hexamethylene tetramine.
6HCHO + 4NH3 (CH2)6N4 + 6H2O
Hexamethylene
tetramine
Hexamethylene tetramine is known as urotropine is used as medicine to treat urimary inflection.
By the polymerisaiton of formaldehyde and acetaldehyde we get polymers in solid forms
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Carboxylic acid
Organic compounds containing carboxyl groups
Acid may be aliphatic or aromatic depending upon the group alkyl or aryl attached to carboxylic group.
Nomenclature
Formula Common name
IUPAC name
HCOOH Formaic acid Methanoic acid
CH3CH2-COOH Propionic acid Propanoic acid
2-bromobutanoic acid
bromobutyric acid
_____
benzoic acid
___
2-buteneoic acid
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Due to H bonding they have higher boiling points. Lower members are soluble in water due to formation of H
bonding.
Chemical properties
Carboxylic acids are acidic in nature. They ionise in water
Acidic strength of carboxylic acid is much less than mineral acid. The carboxylate ion is stablised by resonance.
Chloroacate acid is stronger than acetic acid because chlorine is electron withdrawing atom, it will decrease the
electron density over carbonyl carbon. It favours delocalisation of negative charge. Thus chloroacetic ion is
stablised relative to the acetate ion. Hence chloroacetic acid in stronger than acetic acid.
All carboxylic acids turn blue litmus red.
Reactions with metals
Like Na, K, Ca, Mg, Zn etc. is as follows :
2CH3COOH + 2Na > 2CH3COONa + H2
2CH3COOH + Zn > (CH3COO)2Zn + H2
zinc acetate
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3CH 3COCl
H 3PO 3
Decarboxylation
Carboxylic acid lose CO2 under the following condition.
Sodium or potashium salt of carboxylic acid on heating with sodalime
(CaO + NaOH) give alkanes
CaO, Heat
CH3COONa + NaOH CH4 +Na2 CO3
When two COOH groups are attached to same carbon atom decarboxylation takes place simply on heating
Alkali metal salts of carboxylic acid undergo decarboxylation on electrolysis (Kolbes eletrolysis)
Ring substitution in aromatic acids Carboxylic group in benzoic acids is an electron withdrawing group and
therefore it is m-directing. The electrophilic substitution takes place at meta position.i.
i. Bromination
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ii. Sulphonation
iii. Nitration
Derivatives of carboxylic acids If we replace hydroxyl group by other group, we get derivatives of carboxylic
acids.
Acyl halides
These are derivatives of carboxylic acids in which -OH group of carboxylic acid has been replaced by halogen
atoms.
Nomenclature
This ic of the acids is replaced by yl and name of halogen is added in the nomenclature. For example CH3COCl.
Its name will be ethanoyl chloride.
ClCH3COOH CH3COCl + OHethanoic acid
ethanoyl chloride
Formula Common name
IUPAC name
CH3COCl Acetyl chloride
Ethanoyl chloride
CH3CH2CH2COCl n- butyryl chloride Butanoyl chloride
Benzoyl chloride Benzoyl chloride
Preparation
From carboxylic acid we will get acyl chloride
CH3COOH + PCl5 CH3COCl + POCl3 + HCl
3CH3COOH + PCl3 3CH3COCl + H3PO3
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
Properties
Physical properties
The lower acyl chlorides are colourless liquids while the higher members are colourless solid with low melting
point, They fume in air due to the formation of HCl by hydrolysis.
Acyl chloride have no hydrogen bond (intermolecular) so they are having low boiling points.
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Reaction with benzene In presence of anhydrous AlCl3, acyl halide react with benzene and form ketones, this
reaction in called Friedal Craft acylation reaction.
Reduction
Acyl halides are reduced to aldehyde by the action of hydrogen in the presence of Pd/BaSO 4
Pd/BaSO4
CH3COCl + H2 > CH3CHO + HCl
This reaction is called Rosenmund reduction.
Uses of acyl chlorides
They are used for the preparation of ketones
They are used in dyestuffs and
Acid anhydrides
Acid anhydrides are the acid derivatives which are derived from carboxylic acids by the removal of water from
molecules of the acid.
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Properties
Physical properties
1. Lower members are colourless liquids. Higher members as well as aromatic acid anhydrides are solid.
2. They have higher boiling points than the corresponding acid. It is due to greater molecular size.
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Reduction
Aanhydrides are reduced by 4AlH4 togive alcohols
Esters
Esters are the derivatives of carboxylic acids in which the -OH group of the carboxylic acid has been replaced
by -OR group (Where R may be alkyl or aryl group)
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Nomenclature
An esters is named on the basis of the corresponding acid by changing ic to ate and preceeding this with the
name of alkyl or aryl groups attached to the oxygen atom.
Preparation
From carboxylic acids
Esters are generally prepared by heating carboxylic acid with alcohols in the presence of few drops of conc.
H2SO4 or dry HCl gas.
Properties
Physical properties
Esters have pleasant fruity odours. Esters do not form hydrogen bonds and hence they have lower boiling point
than the corresponding acids. They are less soluble in water but readily soluble in organic solvents.
Chemical properties
They are hydrolysed by water. The reaction is accelerated by dilute mineral acids (HCl, H2SO4) or alkalies.
Hydrolysis of ester by using alkalies is known as saponification.
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Reduction
Esters are reduced to alcohols with LiAlH4 or refluxing with Na/C2H5OH.
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D
CH3COONH4 CH3CONH2 + H2O
acetamide
C6H5COCl + NH3 C6H5CONH2 + HCl
benzamide
CH3COCl + 2CH3NH2 CH3CONHCH3 +
CH3NH3+Cln-methyl acetamide
From ammonium salts of carboxylic acids
Amides can be prepared by heating ammonium salts of carboxylic acids.
D
CH3COONH4 CH3CONH2 + H2O
ammonium
acetate aetamide
From nitriles
Alkane nitriles on partial hydrolysis produce amides
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Lower members are soluble in water due to formation of H bonding with water.
Chemical properties of amides Amides undego hydrolysis when treated with aqueous acid or bases
dil. HCl
CH3CONH2 + HOH CH3COOH + NH4Cl
dil. NaOH
CH3CONH2 + H2O CH3COONa + NH
dil.NaOH
C6H5CONH2 + H2O C6H5 COONa
+ NH3
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NaNO2/HCl
CH 3CONH2 + HONO CH3COOH + N2 + H2O
NaNO2/HCl
C6H5CONH2 + HONO C6H5COOH + N2 + H2O
Hofman bromamide reaciton
When a primary amide is treated with bromine in the presence of an alkali, a primary amine containing one
carbon atom less than the starting material is formed.
heat
CH3CONH2 + Br2 + 4KOH CH3NH2 + K2CO3 + 2KBr +02H2O
heat
C6H5CONH2 + Br2 + 4KOH C6H5CONH2 + K2CO3+ 2KBr + 2H2O analine
Uses of amides
Primary amides are used for the preparation of primary amines.They are used as solvent.
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SOLVED PROBLEMS
Q.1
Ans.
_
CN+H2O
_
C=O+ CN
CN
OH
Cyanohydrin
Tetrahedral
intermediate
(ii) gem-Dialkoxy compounds in which the two alkoxy groups are present on the terminal carbon atom
are called acetals. These are produced by the action of an aldehyde with two equivalents of a monohydric
alcohol in the presence of dry HCl gas.
CH3
H
H OCH2CH3 CH3
C= O+
Acetaldehyde
H OCH2CH3
OCH2CH3
OCH2CH3
+H2O
Acetaldehyde
diethyl acetal
Ethyl alcohol
(iii) Semicarbazones are derivatives of aldehydes and ketones and are produced by the action of
semicarbazide on them in weak acidic medium.
CH3
CH3
O
C=OH2NNHCNH 2
CH3
pH3.5
H2O
CH3
Semicarbazide
C=NNHCONH2+H2O
Acetone semicarbazone
Acetaldehyde
diethyl acetal
(iv) Aldehydes and ketones having at least one ahydrogen undergo a reaction in the presence of dilute
alkali as catalyst to form bhydroxy aldehydes (aldol) or bhydrogen ketones (ketol). respectively. This is
known as Aldol reaction.
2CH3CHO
dil.NaOH
Ethanal
CH3CHCH2 CHO
|
OH
3-Hydroxybutanal
(Aldol)
Q.2
Ans.
(i)
2CH3CHO
Ethanal
Dil.NaOH
Aldol condensation
Dil.NaOH
CH3CHOHCH2CHO
3-Hydroxybutanal
4
NaBH4
(Reduction)
Ethanal
(iii) 2CH3CHO
Ethanal
(i) dil.NaOH
[Ag(NH3)2] OH
+
CH3CH=CHCHO
But-2-enal
Butane-1,3-diol
H3O /Heat
(H2O)
CH3CH=CHCHO
But-2-enal
Tollen's reagent
CH3CHOHCH2 CH2OH
CH3CH=CHCO2H
But-2-enoic acid
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CHO
[Ag(NH3)2]+OH
Tollens' reagent
C2H5
COOH
[O]
C2H5
2-Ehtylbenzoate
COOH
1,2-Benzenedicarboxylic
acid
o-Ehtylbenzaldehyde
(M.F.C9H10O)
2,4-Dinitrophenylhydrazine
NO2
CH=NNH
NO2
+H2O
C2H5
2,4-DNP derivative
Q.4
Ans.
Give simple chemical tests to distinguish between the following pairs of compound :
(i) Propanal and Propanone
(ii) Phenol and Benoic acid
(iii) Benzoic acid and Ethyl Benzoate
(i) Propanal and Propanone :
Iodoform Test : This test is given by propanone and not by propanal. Propanone on reacting with hot NaOH/
I2 gives a yellow precipitate of CHI3 while propanal does not.
2NaOH + I2 NaI + NaOI + H2O
CH3CCH + 3NaOI
Sodium
hypo-lodite
CHI3 +
CH3COONa + 2NaOH
Yellow
ppt.
Sodium acetate
(ii) Phenol and Benzoic acid : Benzoic acid reacts with NaHCO3 giving CO2 gas with effervescence, whereas
phenol does not.
COOH
COONa
+ NaHCO3
Benzoic acid
+ H2O + CO2
Sodium benzoate
Phenol decolourises Br2 water giving white ppt, benzoic acid does not.
Cl
COOH
Br
Br
+ 3Br2(aq)
Benzoic acid
+ 3HBr
Br
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COOH
+ NaHCO3
Q.5
Ans.
+ H2O + CO2
Pyridine
CH3COOC2H5 + HCl
Ethyl acetate
(CH3CO)2 +
OH
Pyridine
CH3COOC6H5 + CH3COOH
Phenyl acetate
CH3COCl + C2H5NH2
CH3CONHC2H5 + HCl
N-Ethylacetamide
(ii) Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium salts
are heated with sodalime (NaOH and CaO in the ratoi of 3:1). The reaction is known as decarboxylation.
RCOONa
RH + Na2CO3
Alkali metal salts of carboxylic acids also undergo decarboxdylation on electrolysis of their aqueous solutions
and form hydrocarbon having twice the number of carbon atoms present in the alkyl group of the acid. The
reaction is known as Kolbe electrolysis.
Q.6
Ans.
2-Methylpentan-3-one.
Q.7
Ans.
CH3
O
|
||
CH3CHCH2CNHCH3
|
||
CH3 O
n-Methyl-3-bromo butanamide
Q.8
Ans.
CH3C=CHCCH3
||
|
O
CH3
4-Methylpent-3-en-2-one
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EXERCISE - I
UNSOLVED PROBLEMS
Q.1
What is PCC ? What is its use in synthetic organic chemistry ? Illustrate with a suitable example.
Q.2
What is DIBAL-H ? What is its use in synthetic organic chemistry ? Illustrate with a suitable example.
Q.3
Q.4
Q.5
Q.6
Name the reagents you will use to bring about the following conversions :
(a) Ethane nitrile to ethanal
(b) Alkyl alcohoo to propenal
(c) But -2-ene to ethanal.
Q.7
Arrange the following compound in the increasing order of their boiling points :
CH3CH2CH2CHO, CH3CH2CH2CH2OH,
H5C2OC2H5, CH3CH2CH2CH2CH3.
Q.8
Q.9
Explain why
(i) Di-tert-butyl ketone does not give a precipitate with NaHSO3 whereas acetone does
(ii) Diakyl cadmium is considered superior to Grignard's reagent for the preparation of a ketone from an
acid chloride.
Q.10
An unknown aldehyde 'A' on reacting with alkali gives a b-hydroxyaldehyde, which loses water to form an
unsaturated aldehyde 2-butenal. Another aldehyde 'B' undergoes disproportionation on reaction in the presence
of conc. alkali to form products 'C' and 'D'. 'C' is an aryl alcohol with formula C 7H8O.
(i) Identify A and B
(ii) Write the sequence of the reactions involved
(iii) Name the product, when 'B' reacts with zinc amalgam and hydrochloric acid.
A compound X(C2H4O) on oxidation gives
Y (C2H4O2). X undergoes haloform reaction. On treatment with HCN 'X' forms product 'Z', which on
hydrolysis gives 2-hydroxy-propanoic acid.
(i) Write down structures of X and Y.
(ii) Name two products when X reacts with dil NaOH.
(iii) Write down the equations for the reaction involved.
Q.11
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(a) An organic compound 'A' with molecular formula C5H8O2, is reduced to n-pentane on treatment with
Zn-Hg/HCl. 'A' forms a dioxime with hydroxylamine and gives a positive Iodoform test and Tollen's test.
Identify compound 'A' and deduce its structure.
(b) Write the chemical equations for the following conversions (not more than 2 steps)
(i) Ethyl benzene to benzene
(ii) Acetaldehyde to butane-1, 3-diol
(iii) Acetone to propene.
Q.14
(a) Why carboxylic acids have higher boiling points than alcohols of comparable molecular masses.
(b) Write chemical reactions to affect the following transformations :
(i) Butan-1-ol to butanoic acid
(ii) Benzyl alcohol to phehylethanoic acid
(iii) 3-Nitrobromobenzene to
3-nitrobenzoic acid.
Q.15
(a) Two molecules of organic compound 'A' on treatment with a strong solution of NaOH gives two
compounds B and C. Compound 'B' on dehydrogenation with Cu gives 'A' while acidification of 'C' yields
carboxylic acid 'D' having molecular formula of CH2O2 Identify the compounds A, B, C and D.
(b) Explain why aldehydes are more reactive than ketones.
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EXERCISE - II
BOARD PROBLEMS
Q.1
Q.2
(ii) The boiling points of aldehydes and ketones are lower than of the corresponding acids.
(iii) The aldehydes and ketones undergoe a number of addition reactions.
(b) Give chemical tests to distinguish between
(i)
[CBSE 2008]
Propanone to propene
[CBSE 2008]
(a) Write chemical equations to illustrate the following name bearing reactions :
(i)
Cannizzaro's reaction
[CBSE 2009]
Ethanol to 3-hydroybutanal
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[CBSE 2009]
32
(a) Give chemical te4sts to distinguish between compounds in the following pairs of substances
(i)
[CBSE 2009]
[CBSE 2011]
Cannizzaro reaction
(ii) Decarboxylation
(b) Completel the following chemical equations
CH2CH3
(i)
KMnO4
KOH, heat
COOH
SOCl2
heat
(ii)
COOH
+
(iii) C6H5CONH
Q.9
H3O
heat
[CBSE 2011]
Rearrange the following compounds in the increasing order of their boiling points :
CH3 CHO, CH3 CH2 OH, CH3 CH2 CH3
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[CBSE 2013]
33
Propanone to Propan-2-ol
CH3CCH3
O
Zn-Hg
conc. HCl
(ii) CH3CCl + H2
Pd-BaSO4
COOH
Br2/FeBr3
(iii)
(b) Which acid of each pair shown here would you expect to be stronger ?
(i) Fe CH2 COOH or Cl CH2 COOH
OH
(ii)
Q.11
[CBSE 2013]
or CH3COOH
Cl
[CBSE 2013]
CH3
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