Name reactions of aldehydes and ketones and acids

1. Iodoform reaction
a. acetaldehyde and NaOH and I2

CH3CHO + 3I2 + NaOH CHI3 + 3NaI + 3H2O + HCOONa

Acetaldehyde iodoform

b. acetone and NaOH and I2

CH 3 -CO-CH 3 + 3I 2 + 4NaOH CHI 3 + 3NaI+ 3H 2 O + CH 3 COONa

Acetone iodoform

c. ethyl alcohol and I2

C 2 H 5 OH + 4I 2 + 6NaOH CHI 3 + 5NaI + 5H 2 O + HCOONa

Ethanol iodoform

2. Aldol condenstation
a. Acetaldehye with dilute NaOH

b. Acetone with dilute NaOH

3. Cross aldol condensation

a. Formaldehyde with acetaldehyde in presence of dilute NaOH

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4. Benzoin condensation
a. Benzaldehyde with alcoholic KCN

5. Perkin’s reaction
Benzaldehyde with acetic anhydride in presence of sodium acetate

C 6 H 5 CHO + (CH 3 CO) 2 O CH 3 COONa C 6 H 5 -CH=CH-COOH + CH 3 COOH

benzaldehyde cinnamic acid

6. Cannizarro reaction

a. Formadelhyde with conc NaOH

2HCHO + NaOH HCOONa + CH 3 OH

meth anal (conc) sodium formate methanol

b. benzaldehyde with conc NaOH

2C 6 H 5 CHO + NaOH C 6 H 5 COONa + C 6 H 5 CH 2 OH

benzaldehyde (conc) sodium benzoate benzyl alcohol

7. clemmensens reduction
a. acetaldehyde with zinc amalgam and conc HCl

CH 3 CHO + 4[H] Zn-Hg, conc.HCl CH 3 CH 3 + H 2 O

ace taldehyde ethane

b. Acetone with zinc amalgam and conc HCl

CH 3 -CO-CH 3 + 4[H] Zn-Hg, conc.HCl CH 3 CH 2 CH 3 + H 2 O

ace tone propane

8. Wolff kishner reduction

a. Acetaldehyde with hydrazine and glycol and KOH

CH 3 CHO + H 2 NNH 2 KOH/glycol CH 3 CH 3 + H 2 O + N 2

ace taldehyde ∆ ethane

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b. Acetone with hydrazine and glycol and KOH

CH 3 -CO-CH 3 + H 2 NNH 2 KOH/glycol CH 3 CH 2 CH 3 + H 2 O + N 2

ace tone ∆ propane

9. Rosendmunds reduction

a. Acetyl chloride with H2 in presence of Pd and BaSO4

CH 3 COCl + H2 Pd/BaSO 4 , S CH 3 CHO + HCl

Acetyl chloride boiling xylene acetaldehyde

b. Benzoyl chloride with H2 in presence of Pd and BaSO4

C 6 H 5 COCl + H2 Pd/BaSO 4 , S C 6 H 5 CHO + HCl

Benzoyl chloride boiling xylene benzaldehyde

10. HVZ reaction

a. Acetic acid with Cl2 and red P

Red P
CH 3 COOH + 3Cl 2 Cl 3 -C-COOH + HCl
Acetic acid trichloro acetic acid

Or

Red P
CH 3 COOH + Cl 2 Cl-CH 2 -COOH + HCl
Acetic acid monochloro acetic acid

11. Etards reaction

Toluene with chromyl chloride

CH 3 CHO
| |
+ 2(O) CrO 2 Cl 2 + H2O

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 12. Kolbe’s electrolysis
Electrolysis of sodium acetate

electrolysis
2CH 3 COONa + 2H 2 O CH 3 CH 3 + 2CO 2 + 2NaOH + H 2

13. Stephen’s reduction

Methyl cyanide in presence of SnCl2 and HCl

CH3CN + 2[H] + HCl SnCl2 CH3CH=NH H 2O CH3CHO + NH4Cl

methyl cyanide dil.HCl H+ ethanol

Important balanced equations of ALDEHYDES AND KETONES

1. Ozonolysis of ethene

CH 2 =CH 2 + O3 Zn/H 2 O 2HCHO + ZnO

ethene formaldehyde

2. Ozonolysis of but-2-ene

CH 3 -CH=CH-CH 3 + O3 Zn/H 2 O 2CH 3 CHO + ZnO

But-2-ene acetaldehyde

3. Ozonolysis of 2,3 -dime thyl bu t-2-ene

a. Ozonolysis of symme trical branched alkene:

CH 3 CH 3 O
| | ||
CH 3 -C = C-CH 3 + O3 Zn/H 2 O 2 CH 3 –C–CH 3 + ZnO
2,3 but-2-ene acetone

4. Hydrolysis of acetylene

CH≡CH + HOH HgSO 4 CH 2 =CH-OH rearr angement CH 3 CHO

Acetylene dil.H 2 SO 4 vinyl alcohol ethanal

5. Hydrolysis of propyne
OH
|
CH 3 -C≡CH + HOH HgSO 4 CH 3 -C=CH 2 rearrangement CH 3 COCH 3
propyne dil.H 2 SO 4 acetone

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6. Heating calcium formate

(HCOO) 2 Ca dry dis tillation H –CHO + CaCO 3

 formaldehyde

7. Heating calcium acetate

(CH 3 COO) 2 Ca dry dis till ation CH 3 –CO–CH 3 + CaCO 3



8. HCN with acetaldehyde

ace taldehyde ace taldehyde cyanohydrin

9. Acetone + HCN

CH 3 CH 3
| |
CH 3 -C=O + HCN CH-C-OH
|
CN
ace tone ace tone cyano hydrin

10. Benzaldehyde + HCN

CN
|
H-C=O H-C-OH

+ HCN

Benzaldehyde Benzaldehyde cyanohydrin

11. Acetaldehyde + sodium bisulpite

H H
| |
CH 3 -C=O + H-SO 3 Na CH 3 -C-OH
|
SO 3 Na
ace taldehyde ace taldehyde
sodium bisulphite

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12. acetone + sodium bisulpite

CH 3 CH 3
| |
CH 3 -C=O + H-SO 3 Na CH 3 -C-OH
|
SO 3 Na
ace tone ace tone
sodium bisulphate

13. benzaldehyde + sodium bisulpite

H H
| |
C 6 H 5 -C=O + H-SO 3 Na C 6 H 5 -C-OH
|
SO 3 Na
benzaldehyde benzaldehyde sodium bisulphite

Note: all aldeh ydes and ke tones give white ppt. with sodium bisulphite solution.

14. Formaldehyde + methyl magnesium bromide + water

HCHO + CH 3 MgBr + HOH CH 3 CH 2 OH + Mg(OH)Br

methanal dil.HCl ethanol

15. acetaldehyde + methyl magnesium bromide + water

CH 3 CHO + CH 3 MgBr + HOH CH 3 -CH-CH 3 + Mg(OH)Br

ethanal dil HCl │
OH
Isopropyl alcohol

16. acetone + methyl magnesium bromide + water

CH 3
│
CH 3 COCH 3 + CH 3 MgBr + HOH CH 3 - C-CH 3 + Mg(OH)Br
acetone dil HCl │
OH
Tert-butyl alcohol

17. formaldehyde with ammonia

6HCHO + 4NH3 (CH2)6N4 + 6H2O

Methanol hexa methylene
tetra amine
(urotropine)

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 18. acetaldehyde + hydroxyl amine

CH3CHO + NH2OH CH3CH=N-OH + H2O

ethanal acetaldoxime

19. acetone + hydroxyl amine

CH3
|
CH3COCH3 + NH2OH CH3C=N-OH + H2O
acetone acetoxime

20. benzaldehyde + hydroxyl amine

C 6 H 5 –CHO + H 2 N–OH C 6 H 5 -CH=N-OH + H 2 O

Benzaldehyde hydroxyl amine benzaldoxime

21. acetaldehyde with hydrazine

CH3CHO + H2N-NH2 CH3CH=N-NH2 + H2O

ethanal acetaldehyde hydrazine

22. acetone with hydrazine

CH3
|
CH3COCH3 + H2N-NH2 CH3C=N-NH2 + H2O
acetone acetonehydrazone

23. benzaldehyde with hydrazine

C6H5CHO + H2N-NH2 C6H5CH=N-NH2 + H 2O

benzaldehyde benzaldehyde hydrazine

24. acetaldehyde with phenyl hydrazine

CH3CHO + C6H5N-NH2 CH3CH=N-NH- C6H5 + H2O

ethanal acetaldehyde phenyl hydrazone

25. acetone + phenyl hydrazine

CH3
|
CH3COCH3 + C6H5N-NH2 CH3C=N-NH-C6H5 + H2O
acetone acetone phenyl hydrazone

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 26. benzaldeyde + phenyl hydrazine

C6H5CHO + C6H5N-NH2 C6H5CH=N-NH- C6H5 + H2O

benzaldehyde benzaldehyde phenyl hydrazone

27. acetaldehyde with red p and HI

CH3CHO + 4HI Red P C2H6 + H2O + 2I2

Acetaldehyde

28. acetone + red P and HI

CH3COCH3 + 4HI Red P C3H8 + H2O +2 I2

acetone

29. benzaldehyde + PCl5

C 6 H 5 CHO + PCl 5 C 6 H 5 CHCl 2 + POCl 3

30. benzaldehyde with Cl2 and An.AlCl3

CHO CHO
| |

+ Cl 2 an. AlCl 3 + HCl

Cl
benzaldehyde m -chlorobenzaldhyde

31. Benzaldehyde + conc nitric acid and concentrated sulphuric acid

CHO CHO
| |

+ HNO 3 H 2 SO 4 + H2O
conc conc
NO 2
benzaldehyde m-nitro benzaldhyde

32. Benzaldehyde + conc nitric acid and concentrated sulphuric acid

CHO CHO
| |

+ H 2 SO 4 + H2O
conc
SO 3 H
benzaldehyde m -benzaldhydesulphonic acid
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important balanced equations of acids

1. Hydrolysis of methyl cyanide

Dil HCl
CH 3 -C  N + 2H 2 O CH 3 -COOH + NH 3
methyl cyanide acetic acid

2. Hydrolysis of ethyl cyanide

Dil HCl
C 2 H 5 -C  N + 2H 2 O C 2 H 5 -COOH + NH 3
Ethyl cyanide propionic acid

3. Dry ice + methyl magnesium bromide

O
||
CH 3 - Mg-Br + C = O + HOH dil HCl CH 3 COOH + Mg(Br)OH
dry ice acetic acid

4. Acetic acid + NaOH

CH 3 COOH + NaOH CH 3 COONa + H2O

Acetic acid Sodium acetate

5. Acetic acid + Na

2CH 3 COOH + Na 2CH 3 COONa + H2

Acetic acid Sodium acetate

6. Acetic acid + sodium carbonate

2CH 3 COOH + Na 2 CO 3 2CH 3 COONa + CO 2  + H 2 O

Acetic acid Sodium acetate

7. Acetic acid + ammonia followed by heating

 ∆
CH 3 COOH + NH 3 CH 3 COONH 4 CH 3 CONH 2
Acetic acid -H 2 O acetamide

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 8. Acetic acid + PCl5

∆
CH 3 COOH + PCl 5 CH 3 COCl + POCl 3 + HCl
Acetic acid acetyl chloride

9. Acetic acid + ethyl alcohol + conc sulphuric acid

Conc.H 2 SO 4
CH 3 COOH + HOC 2 H 5 CH 3 COOC 2 H 5 + H 2 O
Acetic acid ethyl alcohol ethyl acetate

10. Acetic acid +P2O5

O
||
CH 3 -CO OH P2O5 CH 3 - C
O + H2O
CH 3 -C
CH 3 -COO H ||
O
Acetic acid (Acetic anhydride)

2 CH 3 COO H P2O5 (CH 3 CO) 2 O + H 2 O

11. Sodium acetate + sodalime

∆
CH 3 COONa + NaOH C 2 H 6 + Na 2 CO 3
Acetic acid CaO ethane

Benzoic acid:

12. Benzoic acid + NaOH

COOH COONa
│ │

+ NaOH + H2O

benzoic acid sodium benzoate

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13, benzoic acid + sodium carbonate

COOH COONa
│ │

+ Na 2 CO 3 + CO 2 + H2O

benzoic acid sodium benzoate

13. Benzoic acid + PCl5

COOH COCl
│ │

+ PCl 5 + POCl 3 + HCl

benzoic acid benzoyl chloride

14. Benzoic acid + ammonia followed by heating

COOH COONH 4 CONH 2

│ │ │
NH 3 ∆

benzoic acid benzamide

15. benzoic acid + ethyl alcohol + conc sulphuric acid

COOH COOC 2 H 5
│ │

+ HOC 2 H 5 + H2O

benzoic acid ethyl benzoate

16. sodium benzoate + soda lime

COONa
│
CaO
+ NaOH + Na 2 CO 3
∆
benzoic acid benzene

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 17. benzoic acid + conc sulphuric acid

COOH COOH
│ │

+ HOSO 3 H + H2O
Conc.
benzoic acid SO 3 H
m-sulpho benzoic acid

8) benzoic acid + conc nitric acid + conc sulphuric acid

COOH COOH
│ │
Conc.H 2 SO 4
+ HONO 2 + H2O

benzoic acid NO 2
m-notro benzoic acid

Test for Aldehydes and Ketones

Aldehydes / Tollen’s test Fehlings reagent Iodoform test
ketones /HCOOH [NaOH +I2]
Formaldehyde Silver mirror Brick red ppt of cuprous No observation
oxide
Acetaldehyde Silver mirror Brick red ppt of cuprous Yellow ppt of characteristic
oxide odour
Formic acid Silver mirror Brick red ppt of cuprous No observation
oxide
Benzaldehyde Silver mirror No observation No observation
Acetone No observation No observation Yellow ppt of characteristic
odour
All acids (including formic acid) gives brisk effervescene of CO2 with sodium bishulphite. This CO2
turns lime water milky
Answer presentation for selected few popular examples
1. Formaldehyde and acetaldehyde
Acetaldehyde gives yellow ppt of characteristic odour when boiled with NaOH and I2.
Formaldehyde does not answer iodoform test

2. Formaldehyde and benzaldehyde

Formaldehyde gives brick red ppt of cuprous aoxid with fehlings reagent. Benzaldehyde
does not answer fehlings test

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 3. Formaldehyde and formic acid
Formic acid gives brisk effervescene of CO2 with sodium bishulphite. This CO2
turns lime water milky. Formaldehyde does not react with sodium bisulphate
solution
Aldehydes and ketones give reason based questions
Give reason based questions
i. Formaldehyde undergoes nucleophilic addition reaction faster than acedaldehyde
Acetaldehyde has +I effect (CH3-) which reduces the ease of nucleophilic addition reaction

ii. Arrange the following as per increasing order of reactivity for nucleophilic addition
reaction
Benzaldehyde , formaldehyde , acetone , acetaldehyde

Ans Benzaldehyde < acetone <acetaldehyde < formaldehyde (nucleophilic addition

reaction)
iii. Formaldehyde does not undergo aldol condensation reaction
A. Absence of α hydrogen atom

Test for Acids

Specific test for formic acid
Formic acid gives silver mirror with tollens reagent
Formic acid gives brick red ppt of cuprous oxide with fehlings reagent
Specific test for acetic acid
Acetic acid + neutral FeCl3 → wine red colouration
Specific test for benzoic acid
Benzoic acid + neutral FeCl3 → buff coloured ppt

All acids liberate CO2 gas on reacting with sodium bicarbonate solution.

Acids
Inductive effect
+ I groups are electron pushing groups. Alkyl groups are +I groups. Bigger the alkyl group,
more is +I effect :CH3CH2CH2- > CH3CH2- > CH3-
-I groups are electron withdrawing groups. Electronegative elements or groups are –I group.
More electronegative element, more is –I group. : -NO2 > -F > -Cl > -Br > -I > C6H5-
Rules +I effect decreases the acidic nature

⮚ -I effect increase the acidic nature

⮚ -I effect decreases the basic nature

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i. Formic acid is more acidic than acetic acid

In acetic acid, the CH3 group has + I effect. +I effect decreases the acidic nature.

CH3 C O H H C O H
O O
ii.Chloro acetic acid is more acidic than acetic acid
In chloro acetic acid, Cl has –I effect, -I effect increases the acidic nature
iii.Fluoro acetic acid is more acidic than chloro acetic acid
-I effect of F is more than –I effect of Cl
Order of acidic nature is FCH2COOH >ClCH2COOH >HCOOH>CH3COOH>C2H5COOH
iv.Benzoic acid does not undergo electrophilic reaction easily
COOH – in benzoic acid is electron withdrawing group and deactivating group due to –M
effect. (due to which there are electron deficient centre’s at ortho and para position which
deactivates the electrophilic substitution)
Note: CHO- (benzeldehyde) , NO2- (nitro benzene) , COOH – benzoic acid are –M effect effect
v.Boiling point of acetic acid is more than ethane
Acetic acid exhibits hydrogen bonding where as ethane does not exhibit hydrogen bonding
vi.Acetic acid is soluble in water
Both exhibits hydrogen bonding

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