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Aldehydes and Ketones PDF
Aldehydes and Ketones PDF
Aldehydes and Ketones PDF
Organic Compounds having C O group are called carbonyl compounds and C O group is known
wn
as carbonyl or oxo group. It's general formula is C n H 2n O (n = 1, 2, 3......) Carbonyl compounds are
grouped into two categories.
O
(a) Aldehydes : Aldehyde group is C H (also known as formyl group). It is a monovalent group
(b) Ketones : The carbonyl group ( C O) is a Ketonic group when its both the valencies are satisfied
by alkyl group. It is a bivalent group.
CH3 CH3CH2
C O C O
CH3 CH3
(Acetone or Dimethyl ketone) (Ethyl methyl ketone)
2–Propanone 2–Butanone
O O O O
Special Point : .. .. .. ..
C OH, C X, C NH2, C OR,
In all the compounds given above, lone pair of electrons and double bond are conjugate.
O O
..
C Z so resonance occurs. These compounds have C group still they are not carbonyl compounds
because carbonyl group takes parts in resonance with the lone pair of electrons.
Str ucture :
In C O compounds C-atom is sp2 hybridised which forms two bonds with C and H-atom respectively
and one bond with oxygen atom. The unhybridised atomic orbital of C-atom and the parallel 2p orbital
of oxygen atom give the bond in C O group.
C sp 2
C O Hence aldehydes and Ketones posses dipole moment.
General Met ho ds of Preparat ion :
(a) By K 2 Cr 2 O 7 / H 2 SO 4 :
Oxidation of primary alcohols gives aldehyde and oxidation of secondary alcohols gives Ketones.
Here, (K 2 Cr 2 O 7 / H 2 SO 4 ) is a strong oxidising agent.
[O ]
RCH 2 OH
K 2 Cr2 O 7 / H 2 SO 4 ( dil.)
RCHO (Aldehyde)
[O]
R CH R
K 2 Cr2 O7 / H 2 SO 4
R C R (Ketone)
OH O
Aldehydes are quite susceptible to further oxidation to acids -
[O] [O]
R CH 2 O H R—CHO R—COOH
Thus oxidation of primary alcohols is made at the temperature much above the boiling point of
aldehyde and thus aldehydes are vapourised out and prevented from being oxidised.
Note : Aldehydes can be prepared from 1° alcohol,secondary alcohols can be oxidized to ketones, by oxidation
with pyridinium chlorchromate (PCC) in CH 2 Cl 2 solvent, pyridinium dichromate (PDC) and with
Jones reagent(CrO 3 +H 2 SO 4 ) in acetone.
[(CH 3 )3 CO ]3 Al
RCH 2 OH + O O
R—CHO + HO— —OH
O
Cu
CH3 CHCH3
300 C CH3 C CH3 (Acetone)
OH
CH3 CH2
Cu
CH3 C OH
300 C CH3 C + H2O (Isobutylene)
CH3 CH3
Cl OH
O
CH3 C CH3 KOH(aq )
CH3 C CH3
H 2 O
CH3 C CH3
Cl OH
Acetone
unstable
OH OH
R R O O
R C C R' + HIO4 R C R + R' C R + HIO3 + H2O
OH OH
O O
2 –H O
RCH CH2 + O3 RCH CH2
Zn
RCHO + HCHO
Ozone O
Ozonide
O O
–H2O
R C CH2 + O3 R C CH2 R C O + HCHO
Zn
R R O R
1 – a l k y n e g iv es a ld e h y d e
o th e r a l k y n e k et o n e
H2O2 Tautomerism
R C CH + R2BH R CH CHBR2
–
RCH CHOH R CH2 C H + R2BOH
OH
O
H 2 O2
CH 3 —C C—CH 3 + R 2 BH CH3 CH C CH3
OH –
BR2
R2BOH+CH3
CH C CH3 CH3 CH2 C CH3 +R2BOH
OH O
O O O
(Nitro form) (Aci form) (Aldehyde)
1° nitro alkane
R O R OH R O Na R
NaOH HO
CH N C N C N C 3
O + N2O + H2O + NaOH
R O R O R O R
X O
CH 3 2 S O
R CH R
R C R
2° halide Ketone
( 1 0 ) From Grignard reagent s :
(a) By Cyanides :
H O/H OH
RMgX + R C N R C 2
N MgX R C R + NH3 + Mg
X
R O
(Ketone)
(b) By Esters : HCHO can't be prepared by this method.
O OMgX OH
–ROH H2O
RMgX + H C OR H C OR H C OR H C O
R R R
(Alkyl formate) (Hemiacetal) (Aldehyde)
O OMgX OH
HO
RMgX + R C OR R C OR R C OR R C O 2
R R R
(Alkyl Alkanoate) (Hemiacetal) (Ketone)
(c) By acid chlorides :
R' X
R' C
Cl + RMgX C O + Mg
R Cl
O
( 1 1 ) From -keto acids :
The decarboxylation reaction takes place via formation of six membered ring transition state.
(a) HCOCH 2 COOH
110 C
CH 3 CHO+CO 2
(b) CH3 C CH2 C OH CH3 C CH3
–CO2
O O O
(B) For Aldehydes only :
(1) Reduction of acyl halides, esters and nitriles :
(a) Acyl chlorides can be reduced to aldehydes by treating them with lithium-tri-tert-butoxyaluminium
hydride, LiAIH[OC(CH 3 ) 3 ], at – 78°C.
O O
R R
( i ) LAH ( t BuO )3 , 78 C
( ii ) H 2 O
Cl H
(b) Both esters and nitriles can be reduced to aldehydes by DIBAL-H. Reduction must be carried out
at low temperatures. Hydrolysis of the intermediates gives the aldehyde.
O O
R R
(i ) DIBAL H,hexane, 78 C
(ii ) H 2 O
OR' H
O
(i ) DIBAL H,hexane, 78 C
R
R—CN (ii ) H 2 O
H
(2) Rosenmund's reduct ion :
Quinoline or sulphur act as a poisoned catalyst, controls the further reduction of aldehyde to alcohols.
Pd / BaSO 4
RCOCl + H 2
Quinoline or sulphur
RCHO + HCl
Pd
RCOCl + H 2 R C H O R CH 2 O H
Formaldehyde can not be prepared by this method.
Pd / BaSO 4
Example : C2 H 5 COCl + H 2
Quinoline or sulphur
C 2 H 5 CHO + HCl
Propionyl Chloride Propanal
(3) Stephen's reduct ion :
Alkyl cyanides are reduced by SnCl 2 and HCl.
H3O
C 2H 5— C N SnCl2 / HCl C 2 H 5 CH NH C 2 H 5 CHO + NH 3
(4) Oxo react ion or hydroformylat ion :
In this reaction symmetrical alkene gives 1 0 aldehyde while unsymmetrical alkene gives isomeric aldehyde
(Chain isomers).
Co
CH 2 CH 2 + CO H C H 3C H 2C H O
2 150 C
Water gas
Co
CH 3 —CH CH 2 + CO + H 2
150 C
CH 3 CH 2 CH 2 CHO + CH3 CH CH3
CHO
(C) For Ketones only :
(1) From Grignard's reagent :
2H 2 O X
RMgX + R—C N R C NMgX R C O + NH3 + Mg
OH
R R
O OMgX OH O
HO
RMgX + R C Cl R C Cl R C Cl R C + HCl 2
R R R
O
R R R
(2) From dialkyl Cadmium :
RCdR' (dialkyl Cadmium) is a organometallic compound.
RCOCl + RCdR' RCOR' + RCdCl
This reaction is superior than Grignard Reaction because the ketones formed, further reacts with Grignard
reagent to form 3° alcohols.
H3O
Ex : CH3 C CH C OC2H5 CH3 C CH C OH CH3 C CH2 CH3
–C2H5OH –CO2
O CH3 O O CH3 O O
(–keto acid) (Butanone)
O
R COO O C H
Ca + Ca
2RCHO + 2CaCO 3
R COO O C H
O
Calcium formate (Also R C R and HCHO formed)
O
H COO
Ca
HCHO + CaCO 3
HCO O
R COO R
Ca C O + CaCO3
RCO O R
Calcium-alkanoate Ketone
Calcium salts of acids other then formic acid on heating together gives ketone
O
O
R COO O C R'
Ca + Ca 2R C R' + 2CaCO3
R COO O C R'
Ketone
O
To prepare ethyl methyl ketone Calcium acetate and Calcium propionate are used :
O
CH3
CH3 OCO O C CH2CH3 2 C O + 2CaCO3
Ca + Ca C2H5
CH3 OCO O C CH2CH3
O
Calcium Acetate Calcium propionate Ethyl methyl ketone
CH3
2 CH 3 COOH MnO
C O + CO2 + H2O
300 C CH3
MnO
RCOOH + HCOOH
300 C RCHO + CO 2 + H 2 O
MnO
RCOOH + R'COOH
300 C RCOR' + CO 2 + H 2 O
O
RCH CH 2 + PdCl 2 + H 2 O CuCl2
R C CH3 + Pd + HCl
Physical Proper t ie s :
State :
Only formaldehyde is gas, all other carbonyl compounds upto C 11 are liquids and C 12 & onwards solid.
Odour :
Lower aldehydes give unpleasant smell, higher aldehydes and all ketones have pleasant smell.
Solubility :
C 1 to C 3 (formaldehyde, acetaldehyde and propionaldehyde) and acetone are freely soluble in water
due to polarity of C O bond and can form H—bond with water molecule. C 5 onwards are insoluble
i n water.
H
1
So lub ility
C O H O Molecular weight
H-bonding
Boiling point : Boiling point Molecular weight
Boiling point order is - Alcohol > Carbonyl compounds > Alkane
This is because in alcohols intermolecular H-bonding is present but in carbonyl compounds H-bonding
doesn't exist, instead dipole-dipole vander waal force of at traction is present. Alkanes are non polar.
C O C O
Densit y : Densit y of carbonyl compounds is lower than water.
Chemical Proper t ie s :
1
React iv it y of carbonyl group Magnitude of +ve charge – I group
+ I group
Ex : Why carbonyl compound gives nucleophilic addition reaction (NAR) ?
E
C OE No Reaction
Carbocation (Less stable due to incomplete octet)
C O C O
Sol. ..
Nu E
C O C OE
Nu Nu
Anion (More stable due to complete octet)
H CH3 CH3
(I) (i) C O (ii) C O (iii) C O
H H CH3
(II) (i) ClCH 2 CHO (ii) NO 2 CH 2 CHO (iii) CH 3 CHO (iv) CH 3 CH 2 CHO
(III) (i) CH 3 CHO (ii) ClCH 2 CHO (iii) HCCl 2 CHO (iv) CCl 3 CHO
Cl
(-I) CH3(+I)
Ex. In Cl C C O and
C O , which one is more reactive ?
Cl H H
Chloral
S o l . I is more reactive than II.
Chemical Reactions :
Carbonyl compounds in general under goes neucleophilic addition reaction :
(A) Nucleoph i lic addit ion react ions :
(1) Addition of HCN :
H2O
Partial hydrolysis
C OH
CONH2
-Hydroxy amide
H3O
C O + HCN C OH Complete
C OH
hydrolysis
CN COOH
(Cyanohydrin) -Hydroxy acid
Ni/H2
C OH
CH2NH2
-Amino alcohol
H2O H
Partial hydrolysis C OH
H
CONH2
Glyconamide
H H
C O + HCN C OH H3O H
H C OH
H Complete
H
CN hydrolysis
COOH
(Formaldehyde cyanohydrin)
Glycolic acid
Ni/H2 H
C OH
H
CH2NH2
2-Amino ethanol
CH3
H2O C OH
Partial hydrolysis H
CONH2
Lactamide (2-Hydroxy propanamide)
CH3 CH3
C O + HCN * OH
C H3O
CH3
H H C OH
Complete
CN hydrolysis H
Acetaldehyde Cyanohydrin COOH
*(Racemic mixture) Lactic acid (2- Hydroxy propanoic acid)
Ni/H2
CH3
C OH
H
CH2NH2
1-Amino – 2-Propanol
(2) Addition of NaHSO 3 :
This reaction is utilized for the separation of carbonyl compounds from non - carbonyl compounds.
H3O
C O + NaHSO3 C OH Carbonyl compounds. *(Regain)
SO3Na
HSO 3
H SO 32
OH
C
SO
3
C O + SO
–2
Slow
O H+
Na+
3 C Fast
SO3
OH
C
SO3Na
C O + H2 N Z H C N Z + H2O
Z
.. IMPE
–H O
–H
C OH + NH2Z C OH C OH2
2
C NHZ C NZ
NH2Z NHZ
NO2 NO2
Z =
NH NO2 NH2 NH NO2
R R
C O + H2 NNHC6H5 C NNHC6H5 (Phenyl hydrazone)
H H
NO2 NO2
R R
C O + H2 NNH NO2 C NNH NO2
H H
2,4-DNP (Brady's reagent) (2, 4 - dinitro phenyl hydrazone)
R R
C O + H2 NNHCONH2 C NNHCONH2 (Semi Carbazone)
H H
H H OH H OR
C HCl ( g )
O + ROH C ROH
C
HCl ( g )
R R OR R OR
Hemi-acetal Acetal
R R OR
C O + 2ROH HCl ( g ) C + H2O
R R OR
Ketal
Tri ethoxy methane [HC(OC 2 H 5 ) 3 ] remove the water formed during the react ion and so the react ion
proceeds in forward direction.
R SR R SO2R
R HCl ( g ) C C
C O + 2RSH
H2O
[O]
H SR H SO2R
H
Thioalcohol Mercaptal
R SR R SO2R
R HCl ( g ) C C
C O + 2RSH
H2O
[O]
R SR R SO2R
R
Mercaptal (Thio Ketal) Sulphones Compound
All sulphones compounds are hypnotic compounds.
H O CH2 O CH2
C O+ HCl ( g )
C
H2O
H O CH2 O CH2
Acid
C O + HC CNa C ONa C OH
Sodium Alkynide
C CH C CH
Acetylinic alcohol
H H HO I
C O + CH3 Mgl C 2
OMgl CH3CH2OH + Mg
H H OH
CH3
OMgl OH
OH
HO
CH 3 CHO + CH 3 Mgl CH3 C H CH3 2
C H + Mg
I
CH3 CH3
OMgl OH
CH3 HO I
C O + CH3 + Mgl CH3 C CH3 CH3 2
C CH3 + Mg
CH3 OH
CH3 CH3
Weak acid
OH
C O + HO
2
H2 O
C
OH
Cl Cl HO
Cl C CH + H2O Cl C CH
Cl O Cl HO
Ph Ph Ph Ph Ph Ph
P + CH2 + P
Ph CH2 Ph O Ph Ph O
(1-phenylvinyl) benzene triphenylphosphine oxide
Ph Ph
Ph Ph Ph
C6H5 Li
P + H3C—Br Ph P CH3 Br Ph P CH2 Ph P CH2 + C6H6 + LiBr
Ph Ph Ph Ph
(I) (II)
Conc.
HCHO + HCHO HCOONa + CH 3 OH
NaOH
OH
OH
H C H H C H
O O
(b) Transfer of hydride ion H to second molecule of HCHO
OH O OH O
H C H +C H H C+ H C H
O H O O
Formic Methoxide
acid ion
Proton exchange
(c) Proton exchange
H C OH + CH3O HCOO + CH 3 OH
O
HCOO + Na HCOONa
In mixed or crossed cannizaro reaction more reactive aldehyde is oxidised and less reactive aldelyde
is reduced.
CH 3 COOH CH 3 CH 2 OH
Example : CH 3 CHO CH 3 CHO ( C 2 H 5 O )3 Al
Esterification
CH 3 —COOCH 2 CH 3 (Ethyl acetate)
(4) Reaction With Halogen :
(a) Replacement of -H atoms :
This reaction is not shown by formaldehyde (HCHO), since -H atoms are absent, as enolisation
does not takes place in HCHO.
Cl
–HCl Cl2 Cl2
CH2 C H + Cl2 CH2 C H
–HCl
CH C H
–HCl
CCl3 C H
H O Cl O Cl O O
Chloral
O O
Tri chloro acetone
–3HCl
Example : CH3 CH2 C CH3 + 3Cl2 CH3 CH2 C CCl3
O O
Cl
C O + PCl 5 C + POCl 3
Cl
Phosphorus penta chloride
Cl
C O+ SOCl 2 C + SO 2
Cl
Thionyl chloride
(c) Haloform react ions :
Chlorine or bromine replaces one or more -hydrogen atoms in aldehydes and ketones, e.g.,
acetone may be brominated in glacial acetic acid to give monobromoacetone :
O O
Br2
CH3COCH3+ OH
Slow
H2O + CH3—CCH2
CH3C=CH2 CH3COCH2Br + Br
fast
– –
OH+ H CH2 C H CH2 C H + H2O
O O
Base Acetaldehyde Carbanion
Carbanion thus formed is stable because of resonance -
–
CH2 C H CH2 C H
O O–
(b ) Combination of carbanion with other aldehyde molecule :
O H O–
–
CH3 C + CH2 C O CH3 C CH2 CHO
H H
H+ H2O
Aldehyde
(other molecule)
OH H O
CH3 C CH2 C O CH3 CH CH CH
H –Unsaturated aldehyde
Aldol
Id en t ica l ca r b o n y l co m p o u n d s S im p l e o r s e l f a l d o l co n d e n s a t io n .
D iffe r e n t ca r b o n y l co m p o u n d s M ix e d o r cr o s s e d a l d o l co n d en s a t io n .
O OH H Crotonaldehyde
CH3 O CH3
CH3 C CH3 + H CH2 C CH3 CH3 C CH2 C CH3 C CH COCH3 + H2O
O O OH CH3
diacetone alcohol Mesityl oxide or
4–Methyl– 3–pentene– 2–one
O O
CH3 CH3 HCl gas CH3 CH3
C CH C CH3 + O C C CH C CH C
–H2O
CH3 CH3 CH3 CH3
Phorone
Mixed or Crossed aldol Condensat ion :
OH
CH3 CH + CH2 COCH3 CH3 CH CH2 COCH3 CH3 CH CH COCH3
Week base –H2O
O H OH
(Aldol)
CH3 CH3 CH3
OH
CH3 C + CH2 CHO CH3 C CH2 CHO CH3 C CH CHO
Week base –H2O
O H OH
(Aldol)
OH
Ex : CH 3 CHO + CH 3 CH 2 CHO
( WB ) Total 4 product s. Write structure of products ?
OH
S o l . CH3 CH + CHCHO
2 (Aldol)
–H 2 O CH 3 —CH CH—CHO
O H
CH3 CH2 CH + CH2 OH
CHO (Aldol)
–H 2 O CH 3 —CH 2 —CH CH—CHO
O H
CH3 CH3
OH
CH3 CH + CH CHO (Aldol)
–H 2 O CH3 CH C CHO
O H
CH3 CH3
OH
CH3 CH2 (Aldol)
CH + CH CHO
–H 2 O CH3 CH2 CH C CHO
O H
OH
CH3 C CH2 CH2 C CH3 CH3 C CH2 CH2 C CH2
(–H2O)
O O O O
O H3C O H3C O
H3C H
–H2O HO O
OH
CH 3 CHO + C 6 H 5 CHO Total 2 product.
WB
CH3 OH
CH + CH2 CHO (Aldol)
–H 2 O
CH 3 —CH CH—CHO
O H
(Crotonaldehyde)
C6H5 OH
CH + CH2 CHO (Aldol)
–H 2 O C 6 H 5 —CH CH—CHO
O H
(Cinnamaldehyde)
(6) Claisen condensation :
When two molecules of ester undergo a condensation reaction, the reaction is called Claisen condensation.
The product of the claisen condensation is a -keto e ster.
CH3
CH3CH2ONa
O + H3C
OC2H5
2H3C H3C C2H5
OH
O O O
-keto ester
After nucleophilic attack, the aldol addition and the Claisen condensation differ. In the claisen condensation,
the negat ively charged oxygen reforms the carbon oxygen -bond and eliminates the OR group.
O O
O O
(i) CH3O
(ii) H + CHOH
3
O O H3C
CH3
O
O
CH3
O (i) CH3O OCH3
+ H3C—OH
(ii) H
O O
OCH3
(CH3CO)2O, AcONa O
O O
O OH
3-(-furyl) acrylic acid
O
OH
(CH3CO)2O, AcONa
O O
O O
phthalic anhydride phthalyl acetic acid
O O
O H5C6 O H5C6 O
C6H5CHO + R Pyridine R (i) H2O
Piperidine (ii) , –CO2
O O OH
O R O R
Malonic Ester Cinnamic acid
( 1 1 ) Schmidt Reaction :
This is the reaction between a carbonyl compound and hydrazoic acid in the presence of a strong acid
concentrated sulphuric acid. Aldehyde s give a mixture of cyanide and formyl derivat ives of primar y
amines, whereas ketones give amides :
2 4H SO
RCHO + HN 3 RCN + RNHCHO + N 2
2 4H SO
RCOR + HN 3 RCONHR + N 2
Schiff's Base
( 1 2 ) Benzoin condensation :
The benzoin condensation is essentially a dimerisation of two aromatic aldehydes under the catalytic
influence of cyanide ions to give benzoin (I).
2 C6H5CHO
KCN H3C
OH
H5C6
(I)
The hydrogen atom attached to the carbonyl group of aldehyde is not active enough to be removed
easily but the addition of the cyanide ion to the carbonyl carbon places this hydrogen in the alpha
position of the nitrile thus rendering it relatively acidic. The carbanion, thus generated, attacks the
carbonyl carbon of the second aldehyde molecule in a rate-determining step forming an unstable cyanohydrin
of benzoin which immediately breaks down into benzoin and hydrogen cyanide.
OH OH
O O
proton exchange
H5C6 + CN H5C6 CN
H5C6 CN H5C6 C
H N
H
O
OH O OH O O OH
H3C
Slow
H5C6 + C6H5 H3C CH3 H3C CH3 OH + CN
CN H CN H CN H H5C6
X
X O
HO
O O
OH
OH
However, in a 1, 2-diketone the group X may migrate to the adjacent electron-deficient carbonyl carbon
formi ng -hydroxy acid.
Thus, benzi l on treatment with a strong base forms benzilic acid (salt), hence the name benzilic acid
rearrangement.
O OH
O O O
C6H5 NaOH H5C6 H5C6
H5C6
OH ONa
O H5C6 H5C6
benzil sodium salt of benzilic acid
( 1 4 ) T he Beckma nn rear ra ngenment :
The acid catalysed transformation of a ketoxime to an N-substituted amide is known as the Beckmann
rearrangement.
–H2O
C=O + H2N—OH C=N—OH
Oxime
H
R R
O—H
H –H2O R'—C H2O
N N R'
R' OH R' OH2 N—R
N—R
O—H O
–H R'
R'
N—R NH—R
(1° alcohol)
[O] [O]
CH3CH2CH2 CH CH3 CH3CH2CH2 C CH3 CH 3 CH 2 COOH+CH 3 COOH
OH O
(2° alcohol)
O O
Glyoxal
CH3 C CH3 + SeO2 CH3 C C H + Se + H2O
O O O
Methyl glyoxal (Pyruvaldehyde)
(c) Bae yer's Vi l liger oxidat ion :
Both aldehyde and ketones are oxidized by peroxy acids. This reaction, called the Baeyer-villiger
oxidation, is especially useful with Ketones, because it converts them to carboxylic esters. For
example, treating acetophenone with a peroxy acid converts it to the ester phenyl acetate.
O
O R O
H5C6—O
H5C6 OH
O
CH3 H3C
phenyl acetate
Mechanism :
H H O
:O
:
:O: H—A :O O O
+
H3C O R
H3C C6H5 H3C C6H5 R O
H
:OH C6H5 A
:H
OH :A
H O
:
OH O H :O H—A
:
O +
O :O
O O O
H3C R O
R H3C H3C R
C6H5 C6H5 C6H5
H3C OC6H5
The product of this reaction show that a phenyl group has a greater tendency to migrate then a methyl
group. Had this not been the case, the product would have been C 6H 5COOCH 3 and not CH 3COOC 6H 5 .
This tendency of a group to migrate is called is migratory aptitude. Studies of the Baeyer-villiger oxidation
and other reaction have shown that the migratory aptitude of groups H > phenyl > 3° alkyl > 2° alkyl
1° alkyl > methyl. In all cases, this order is for groups migrating with their electron pairs, that is, as anions.
Per acid
Ex. CH3 C C2H5 ?
O
S o l . CH3 C OC2H5
O
CH3
Per acid
Ex. CH3 C C CH3 ?
CH3 O
CH3
S o l . CH3 C O C CH3
CH3 O
(D) Reduction :
(a) T he wolf kishner reduct ion :
When a ketone or an aldehyde is heated in a basic solution of hydrazine, the carbonyl group
is converted to a methylene group this process is called Deoxygenation because an oxygen is
removed from the reactant. T he react ion is know n as the Wolf-kishner Reduct ion.
COCH3
(i) NH2–NH2
(ii) OH/HOCH2–CH2OH
CH3
COCH3
Zn–Hg, HCl
Reflux
CH3
The nature of product depends upon the reducing agent used. It can be summarized as.
Allowed to s tan d
(c) 3HCHO (CH 2 O ) 3
at room temp. CH2
Meta formaldehyde (Trioxane) O O
Cyclic polymer (Trioxy methylene)
H2C CH2
Cyclic polymer doesn't show reducing
O
character with Tollen's reagent etc.
Ca OH 2
(d) 6HCHO C 6 H 12 O 6
or Ba OH 2
Formose sugar
A linear polymer ( -acrose)
Acetaldehyde :
CH2
CH
O O
Conc. H 2 SO 4
(a) 3 C H 3C H O
(CH 3 CHO) 3 H3C HC CH CH3
Room temp.
O
Para acetaldehyde
Paraldehyde (cyclic polymer)
Pleasent smelling liquid
Hypnotic compound
CH3 CH3
O
conc. H 2 SO 4 O O
(b) 4 C H 3C H O
0 C (CH 3 CHO) 4
O
CH3 CH3
Meta aldehyde
White crystalline solid.
Cyclic polymer
Used as solid fuel or killing snails
Urotropine (Hexamine)
White crystalline solid
Used in preparation of explosive
Used in treatment of urine infection diseases
Addition Conc. H 2 SO 4
CH3 CH + NH2 CH3 CH NH2 CH3—CH NH
Re action H2O
O H OH Acetaldimine
Acetaldehyde used in preparation
ammonia of cyclic polymer
CH3
CH
HN NH
3 H 2O . 3H2O
3 C H 3— C H NH HC CH
Trimerisation
H3C N CH3
H
Trimethyl hexahydro Triazine trihydrate
CH3 CH3
CH3 CH3 Mg Hg
C O+ O C CH3 C C CH3
water
CH3 CH3
OH OH
Pi nacol
(2) React ion w it h chloroform :
OH
CH3 CH3 OH
C O + CHCl3 C aq.NaOH
CH3 *CH COOH
CH3 CCl3
CH3
(Chloretone) (Lactic acid)
2-Hydroxy propanoic acid
O O
–H2O
CH3 C CH3 + O N OH CH3 C CH N OH
Oximino acetone
(4) Oxidation reaction : According to popoff's rule C O group stays w ith smaller alkyl group.
O
CH3 CH2 C CH3 CH 3 COOH + CH 3 COOH
CH3 O CH3 O
–H2O
CH3 C O + CH3 C CH3 CH3 C CH C CH3
Mesityl oxide
Fe
3CH3 C CH
Addition Polymerisation
(6) Reaction with ammonia :
CH3 O CH3 O
–H2O
CH3 C O + HCH2C CH3 CH3 C CH2 C CH3
HNH2 NH2
Diacetone amine
(7) Pyrolysis :
CH2 C O CH2 C O + CH4 HCHO
CO H 2
pyrolysis
H CH3 Ketene
CH 3 CHO CH 4 CO
Acetone
S.No. Te s t HCHO C H 3C H O C H 3C O C H 3
Only methyl C O
OH
4. Orthonitro benzaldehyde – – Bl ue
5. Tollen's reagent - Silver mirror Silver mirror –
Fehling's reagent - Red ppt Red ppt –
Mercuric chloride - Black ppt Black ppt –
Schiff's reagent - Pink colour Pink colour –
6. DNP O r an g e O r an g e O r an g e
colour colour colour
BENZALDEHYDE (C 6 H 5 CHO)
Oil of bitter almonds
General Met ho d of Preparat ion :
Chemical proper t ie s :
(Similar) (different)
C6H5CH(OH)CN C6HCOCl
5
HCN 170°/Cl2
C6H5COOCH2C6H5 AlCl3
Cl O
O
t BuOK
+ O
t BuOH
A
H5C2
O O O
H3C
O
O OH
–
C2H5 C2H5
(A) (B) (C) O (D)
O
C2H5
Ex 2. is the final product obtained when one of the following is reacted with base :
CH3
O O O O
(A) H3C CH3 (B) H3C CH3
O O O O
(C) H3C (D) H3C CH3
CH3
O
O O
Alkali
Sol. H3C CH3
CH3
O
O
CH3 C – OH
Ex 3. C C H
(A)
CH3 H
The product (A) in the given reaction would be :
O O O OH
C C
CO
=
–
O
=
O OH C–H
=
H
–
C H CH3
CH3
CH3
H
O
O O O
CH3 C – OH +
H
CH3 –H
+ H3C OH
C C C C–C–O–H C=C
Sol. CH3 H CH3 –CO2 H3C H
H enol
unstable unstable
H
H3C O
C–C
H3C H
3 CH MgBr
4 2 4 CO / H O
Ag 2 O HgSO / H SO
CHCH 2 3
O O O O
(A) H3C (B) HO O (C) H3C (D) H O
OH
O O
OH OH
OHC–CH–COOH
2
Ag2O
HOOC–CH2–COOH
(B)
Ex 5. In which of the following substrates, rate of Benzoin condensation will be maximum ?
:O :O: :O–H
:
O
:
:
O O
– –
=
– =
:
:
:
Sol.
N C + CN
N C–H
N C:
: :
: :
:O :O
::
:O H CN CN
:
(I) (II) (III)
Benzoin condensation is due to stability of intermediate (III) when negative charge on C extensively delocalised
in benzene ring, nitro and CN group. In all other cases, such dispersal is not extensively possible. On
the other hand, NO2– is also creating a positive charge center on carbonyl carbon, making it more susceptible
to nucleophilic attack of CN –.
Ex 6. This intermediate is converted into product in the wittig reaction :
Ph3 P O
–
–
–
–R1 R2 R1 R2
CH3
O
H
O O
O
OH CH 3 CHO
Step I
Step II
H3C O
H3C O H3C O H2O Step III
CH3
O O H
CH—CH3 OH
Step IV
H3C O H3C O
Which of following statements are correct for above reaction sequence ?
(A) Step I is acid-base reaction (B) Step II is nucleophilic addition reaction
(C) Step III is acid base reaction (D) Step IV is elimination reaction
Sol. (A), (B), (C), (D)
Ex 8. Which of the following oxidation reaction can be carried out with chromic acid in aqueous acetone at
5–10°C.
O
=
OH
(B) CH 3 (CH 2 ) 3 CH=CH–CH 2 OH CH 3 (CH 2 ) 3 CH=CH–CHO
(C) C 6 H 5 CH 3 C 6 H 5 COOH
(D) CH 3 (CH 2 ) 3 CH 2 OH CH 3 (CH 2 ) 3 CHO
Sol. (A), (B), (C), (D)
O
SeO 2
Ex 9. CH3 – C – CH3 A ; A will :
CH2OH
HOH2C – C – CHO
CH2OH
CH3 CH3
(A) H3C – C – C – CH3 (B) CH3 – C – O – C – CH3
OH OH O O
CH3 CH3
Mg / Hg
Sol. (A) 2CH 3 – CO – CH 3
H3C – C – C – CH3
H2O
OH OH
(Pinacol)
Ex 12. Benzaldehyde on reaction with acetophenone in the presence of sodium hydroxide solution gives :
(A) C 6 H 5 CH = CHCOC 6 H 5 (B) C 6 H 5 COCH 2 C 6 H 5
(C) C 6 H 5 CH = CHC 6 H 5 (D) C 6 H 5 CH(OH)COC 6 H 5
O
NaOH
Sol. (A) C 6 H 5 CHO + CH 3 COC 6 H 5
C6H5 – CH = CH – C – C6H5
H2O
OH
Sol. (C) H – CHO + CH 3 MgI CH 3 – CH 2 – OH + Mg
I