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CARBONYL COMPOUNDS
O
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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.
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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
Ketone
OCCURRENCE
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 HCO
Heat
O Ca + O Ca 2CH3CHO + 2CaCO3
|| ||
CH3 C O HCO
Industrial Method
PdCl2 + CuCl2
2CH2 = CH2 + O2 2CH3CHO
H2O
Acid catalysed The proton of acid combines with the aldehyde oxygen atom and increase
the electrophilic character of the carbonyl carbon.
O OH
|| NaCN/HCl |
H C H + HCN HCH
|
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
O OH
|| |
H C H + NaHSO3 HCH
|
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)
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
O H
|| NaBH4 |
HCH 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
H
|
C
|
O H O
dil H2SO4
3HCHO
HCH HCH
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
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
(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
(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.