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CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

CARBONYL COMPOUNDS
O
||
The organic compounds which contain carbonyl functional group [ - C - ] in their molecules are called carbonyl
functional group compounds.
 In a carbonyl group, a carbon atom is bonded to oxygen with a double bond
 The homologous series of both aldehydes and ketones have the general formula, CnH2nO
 Aldehydes and Ketones are carbonyl compounds

Aldehydes

 In Aldehydes, the carbonyl group is bonded to at least one hydrogen atom, and so it occurs at the end of the chain.

O
||
 An Aldehyde can be represented by the general formula, R – C – H

Ketones

 In Ketones, the carbonyl group is bonded to two carbon atoms, and so it occurs within a chain.
A ketone may be represented by the general formula. O
||
R–C–R
NOMENCLATURE

Aldehyde

Trivial name IUPAC RULE


The common names of aldehydes are  Select longest carbon chain containing >c=o group
obtained from the common names of  C of aldehyde will get number 1 which is usually
carboxylic acids containing the same number not written
of carbon atoms. The ending –ic acid in the  Write down the position of substitute and name
common name of the acid is replaced by the alphabetically
world aldehyde.  Replace the “e” of alkane by “al”

Ketone

Trivial name IUPAC RULE


 The alkyl radical alphabetically prefix to  Select longest chain containing carbonyl group
the ketone.  Start numbering with least number to C of carbonyl
 If both radical are same then use di with group
alkyl radical and are symmetric ketones.  Write down position and name of substitutes
 If both alkyl groups are different called alphabetically
unsymmetric or mixed ketones.  The position of carbonyl group is prefixed to the
alkanone
 Replace the “e” of alkane with “one”

OCCURRENCE

Aldehydes and ketones are present in many naturally occurring compounds.


Examples
 Aldehydic group is present in most of the sugars.
 Aldehydes are principle, constituents of a number of essential Oils used as fragrances and flavours.
 The ketonic group is present in camphor and menthone
CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

PREPARATION OF ALDEHYDES

Formaldehyde
Industrial method Laboratory method
By passing methanol vapours and air over iron oxide- By passing methanol vapours and air over platinised
o o
molybdenum oxide or silver catalyst at 500 C asbestos or copper or silver catalyst at 300 C

 Laboratory Method

Pt-asbestos
2CH3OH + O2 2HCHO + 2H2O
300oC

 Industrial Method

500oC
2CH3OH + O2 2HCHO + 2H2O
FeO, MoO3

Acetaldehyde
Laboratory method Industrial method
 By oxidation of ethyl alcohol with acidified sodium By oxidation of ethylene using palladium chloride
dichromate catalyst with cupric chloride as promoter.
 By dry distillation of mixture of calcium salt of formic
acid and acetic aid

 Laboratory Method


2CH3CH2OH + [O] 2CH3CHO + 2H2O
Na2Cr2O7 + H2SO4

O O
|| ||
CH3  C  O HCO
Heat
O Ca + O Ca 2CH3CHO + 2CaCO3
|| ||
CH3  C  O HCO

 Industrial Method

PdCl2 + CuCl2
2CH2 = CH2 + O2 2CH3CHO
H2O

REACTIVITY OF CARBONYL GROUP


2
Both carbon and oxygen are sp hybridized
+ 
-
Reactivity of carbonyl group is due to the
+ 
-
Polarity of carbon and oxygen >C = O
>C = O 2.5 3.5
Nu
+
E
CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

REACTION OF CARBONYL COMPOUNDS


Detail of reaction Remarks
base catalysed reaction  This reaction will take place with strong nuclephilic reagent
mechanism  Base reacts with reagent and releases nucleophile

Acid catalysed The proton of acid combines with the aldehyde oxygen atom and increase
the electrophilic character of the carbonyl carbon.

Addition of hydrogen  Compound produced called cyanohydrins


cyanide  On reaction with aqueous acid, cyanohydrins changes into carboxylic
acid
 This reaction is used for the synthesis of -hydroxy acid

O OH
|| NaCN/HCl |
H  C  H + HCN HCH
|
CN
Formaldehyde cyanohydrins

O OH
|| NaCN/HCl |
H  C  CH3 + HCN H  C  CH3
|
CN
Acetaldehyde cyanohydrins

O OH
|| NaCN/HCl |
CH3  C  CH3 + HCN CH3  C  CH3
|
CN
Acetone cyanohydrin

Addition of sodium  White ppt. of sodium bisulphate product is produced


bisulphate  On heating, bisulphate product again regenerates into aldehyde or
ketone
 This reaction is used to separate carbonyl compound from non carbonyl
compounds such as alcohols
CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

O OH
|| |
H  C  H + NaHSO3 HCH
|
SO3Na
Bisulphate product

O OH
|| |
CH3  C  H + NaHSO3 CH3  C  H
|
SO3Na
Bisulphate product

O OH
|| |
CH3  C  CH3 + NaHSO3 CH3  C  CH3
|
SO3Na
Bisulphate product

Aldol condensation  The reaction in which, two aldehydes, two ketones and aldehyde and
reaction ketones react in presence of base to give -hydroxy aldehyde or ketone
is called adol condensation
 Mechanism involve carbanion
H
dil.NaOH |
CH3  CHO + CH3  CHO CH3  C  CH2  CHO + H2O
Ehtanal Ehtanal |
OH
Aldol (3-hydroy butanal )

H
dil.NaOH |
CH3  CHO + C2H5  CHO C2H5  C  CH  CHO + H2O
Ehtanal Propanal | |
OH CH3
Adduct (3-hydroxy 2-methyl pentanal)

CH3
dil.NaOH |
CH3  COCH3 + CH3  COCH3 CH3  C  CH2  COCH3 + H2O
Acetone Acetone |
OH
Aldol (4-hydroxy 4-methyl pentanone)

Cannizzaro’s reaction  It is a self oxidation reduction reaction


 Oxidized product is salt of an acid
 Reduced product is alcohol
 Reaction is carried at 50% NaOH ethanol at room temperature
CHO COOK CH2OH
+ conc.KOH +
2

Benzaldehyde Potassium Benzoate Benzyl alcohol

2HCHO + conc.NaOH CH3OH + HCOONa


CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

Haloform reaction  Acetaldehyde, ethanol, methyl ketones and isopropyl alcohol undergo
such reaction.
 This reaction is used to distinguish between methyl ketone from other
ketones
 Iodoform is yellow crystalline solid
 It also distinguishes methanol from ethanol
 It also distinguishes acetaldehyde from other aldehydes
CH3CHO + 3I2 + 4NaOH CHl3 + HCOONa + 3Nal + 3H2O
CH3OCH3 + 3I2 + 4NaOH CHl3 + CH3COONa + 3Nal + 3H2O
Addition of ammonia  This is also condensation or addition elimination reaction
derivative  Reaction of aldehydes or ketone with hydroxylamine gives ethanaloxime
or propanoneoxime
 On reaction with phenylhydrazine carbonyl compounds give phenyl-
hydrazone

H+ H
CH3CHO + H2N  OH HO  N = C + H2O
CH3
Ethanaloxime

O
|| H+ CH3
CH3  C  CH3 + H2N  OH HO  N = C + H2O
CH3
Propanone oxime

O
|| H+ CH3
CH3  C  CH3 + C6H5HNNH2 C6H5NH  N=C + H2O
CH3
Propanone phenylhydrazone

H+ H
CH3CHO + C6H5HNNH2 C6H5NH  N=C + H2O
CH3
Ethanal phenylhydrazone

H+ CH3
CH3COCH3 + H2HNNH2 H2N N=C + H2O
CH3
Acetone hydrazone

H+ CH3
CH3CHO + H2NNH2 H2N N=C + H2O
H
Acetaldehyde Hydrazone

Reduction  Hydrogenation of aldehyde gives primary alcohol and that of ketone


gives secondary alcohol.

-
Sodium tetrahydroborate is source of H
 Alkoxide formation occurs
 Catalytic reduction is carried out in the presence of Pd, Pt, Ni and
CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

products remained same.

O H
|| NaBH4 |
HCH H  C  OH
Water

O H
|| NaBH4 |
CH3  C  H CH3  CH  OH
Water

O CH3
|| NaBH4 |
CH3  C  CH3 CH3  CH  OH
Water

O CH3
|| Pd, Pt or Ni |
CH3  C  CH3 + H2 CH3  CH  OH

O H
|| Pd, Pt or Ni |
CH3  C  H + H2 CH3  CH  OH

O
|| Pd, Pt or Ni
H  C  H + H2 CH3  OH

Addition of alcohol  Acetal is produced on reaction of carbonyl with alcohol but ketones do
not react under these conditions.
 This reaction is also used in protention of aldehyde group.

OC2H5
Dry HCl |
CH3CHO + 2C2H5OH CH3  C  H + H2O
|
OC2H5
1, 1-diethoxyethane

ACID CATALYZED ADDITION REACTIONS

H
|
C
|
O H O
dil H2SO4
3HCHO

HCH HCH
Metaformaldehyde
O
CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

CH3
|
C
|
O H O
dil H2SO4
3HCHO

H  C  CH3 H  C  CH3

O Paraldehyde

OXIDATION

O O
|| K2Cr2O7 / H2SO4 ||
CH3  C  H + [O] CH3  C  OH

O O
|| K2Cr2O7 / H2SO4 ||
C2H5  C  H + [O] C2H5  C  OH

O O
|| K2Cr2O7 / H2SO4 ||
CH3  C  CH3 + 3 [O] CH3  C  OH + HCOOH

O O O
|| K2Cr2O7 / H2SO4 || ||
CH3  C  C2H5 + 3 [O] CH3  C  OH + CH3  C  OH

IDENTIFICATION OF CARBONYL COMPOUNDS

Aldehydes Ketones
Reduction gives primary alcohols Reduction gives secondary alcohols
Oxidation gives acid containing same number of carbon Oxidation gives acid containing smaller number of
atoms carbon atoms
They give silver mirror test with Tollen’s reagent Don’t give silver mirror test
They reduce Fehling’s solution and brick red ppt. of Don’t reduce Fehling’s solution
Cu2O is obtained
They reduce the Benedict’s solution and give brick red They don’t reduce the Benedict’s solution
precipitate of Cu2O
Aldehydes polymerize readily Ketones don’t polymerize
Aldehyde restore the pink colour of schiff’s reagent They don’t restore the colour of schiff’s reagent
These react with alcohol form acetals These do not react with alcohol
These do not react with sodium nitroprusside These react with sodium nitroprusside produces wine
red or orange red colour

(a) Uses of Fomaldehyde

(i) It is used in the manufacture of resins like urea-formaldehyde and plastics such as bakelite.
(ii) It is used in the manufacture of dyes such as indigo, para-rosaniline, etc.
(iii) Its 40% aqueous solution called formalin is used as an antiseptic, as an antiseptic , as disinfectant, a
germicide, a fungicide and for preserving animal specimens and sterlising surgical instruments.
(iv) It is used as a decolourising agent in vat dyeing.
CHEMISTRY Chapter 12: “Aldehydes and Ketones” 2nd – Year

(v) It is used in the silvering of mirrors.


(vi) It is used in making medicine urotropine used as a urinary antiseptic.
(vii) It is used in making formamint (formaldehyde + lactose) used a throat lozenges.
(viii) It is used in the processing of anit-poliovaccine.

(b) Uses of Fomaldehyde

(i) It is used in the production of acetic acid, acetic anhydride, n-butanol, ethanol, 2-ethyl-1-hexanol, vinyl
acetate, paraldehyde, ethylacetate, etc.
(ii) It is used to make acetaldehyde ammonia used as a rubber-accelerator.
(iii) It is used to make acetaldehyde ammonia used as a rubber-accelerator
(iv) It is used to make chloral hydrate, ethanol trimmer and tetramer. Chloral hydrate and ethanol trimmer are both
used as hypnotic drugs whereas ethanol tetramer is used as a slug poison.
(v) It is used as an antiseptic inhalant in nasal infections.
(vi) It is used in silvering of mirrors.
(vii) It is used to make phenolic resins and synthetic drugs.