Unit 11 Aldehydes, Ketones and Carboxylic Acids: Points To Remember
Unit 11 Aldehydes, Ketones and Carboxylic Acids: Points To Remember
Unit 11 Aldehydes, Ketones and Carboxylic Acids: Points To Remember
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182 | Chemistry-XII
UNIT 11
Points to Remember
. (Collin’s reagent)
(ii) Dehydrogenation of 1º alcohols :
. RCH2OH
Cu/573 K
→ RCHO + H2
(iii) From Rosenmund reaction/reduction :
. RCOCl + H2
Pd/BaSO 4
→ RCHO + HCl
(iv) Hydration of alkynes :
. CH ≡ CH →
=[CH 2 CHOH]
→ CH3CHO
4 1% HgSO Tautomerism
40% H SO 2 4
. R – CH = CH – R (i) O3
(ii) Zn/H O
→ 2RCHO + H2O2
2
. R'MgX + R – C ≡ N →
. R – C = O + NH3 + Mg (OH) X
. |
. R'
(iv) From acid chlorides :
. O
. ||
RCOCl + R2Cd → 2R – C – R' + CdCl2
Physical Properties:
Reactivity :
(i) + I effect of alkyl groups decreases the +ve charge on carbonyl carbon.
1. ROSENMUND REDUCTION:
Acyl chlorides when hydrogenated over catalyst, palladium on barium sulphate
yield aldehydes
O
Pd-BaSO4
C – CI + 2[H] CHO
2. STEPHEN REACTION
3. ETARD REACTION
On treating toluene with chromyl chloride CrO2Cl2, the methyl group is oxidized
to a chromium complex, which on hydrolysis gives corresponding benzaldehyde.
OR
CH3 CH(OCrOHCI2)2 +
CHO
CS2 H3O
+ CrO2CI2
4. CLEMMENSEN REDUCTION
6. ALDOL CONDENSATION
Aldehydes and ketones having at least one a-hydrogen condense in the presence
of dilute alkali as catalyst to form p-hydroxy ehydes (aldol) or b-hydroxy ketones
(ketol).
,
CH3—CH—CH2—CHO
OH
When aldol condensation is carried out between two different aldehydes and / or
ketones, a mixture of self and cross-aldol products are obtained.
8. CANNIZZARO REACTION
Aldehydes which do not have an a-hydrogen atom, undergo self oxidation and
reduction (dispropotionation) reaction on treatment with concentrated alkali, to
yield carboxylic acid salt and an alcohol respectively.
H-CHO + H-CHO + Conc.KOH → CH3OH + HCOOK
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Aldehydes, Ketones and Carboxylic Acids | 187
CARBOXYLIC ACID
1. HELL-VOLHARD-ZELINSKY REACTION (HVZ)
Carboxylic acids having an a – hydrogen are halogenated at the a -position
on treatment with chlorine or bromine in the presence of small amount of red
phosphorus to give a -halocarboxylic acids.
(i) X2/ Red phosphorus
RCH2 – COOH R – CH – COOH
(ii) H2O
X
X = CI, Br
α – halocarboxylic acids
2. ESTERIFICATION
Carboxylic acids react with alcohols or phenols in the presence of a mineral acid
such as conc.H2SO4 as catalyst to form esters.
+
H
RCOOH + R'OH RCOOR' + H2O
2. CH3—CH2—C≡≡CH
40%H 2SO4
1%HgSO
→ A
isomerism
→ CH3—C—CH3
4
O
Structure of ‘A’ and type of isomerism in the above reaction are respectively
(a) Prop-1-en-2-ol, metamerism (b) prop-1-cn-ol, tautomerism
(c) prop-2-en-2-ol, geometrical (d) prop-1-en-2-ol, tautomerism
3. Compound A and C in the following reaction are ............
CH3—CH==CH—CH2—C—CH3 CH3—CH==CH—CH2—C—OH
(a) Tollen's reagent (b) Benzoyl peroxide
(c) I2 and NaOH solution (d) Sn and NaOH solution
5. Toluene
KMnO
→ A → B
4SOCl H lPd
→ the product ‘C’ is:
2 2
BaSO 4
Identify X, A, Y, Z.
(a) A-methoxymethane, X-ethanol, Y-ethanoic acid, Z-semicarbazide
(b) A-ethanol, X-ethano, Y-but-z-enal, Z-semicarbazone
(c) A-ethanol, X-Acetaldehyde, Y-Butanone, Z-Hydroazone
(d) A-Methoxymethane, X-ethanoicacid, Y-acetate ion and Z-Hydrazine
12. Which of the following reactions will not result in the formation of carbon
carbon bond?
(a) Cannizaro's reaction (b) Wurtz reaction
(c) Friedel craft reaction (d) Reimer Tiemann reaction
13. Priopionic acid with Br2/P yields a dibromo product It’s structure will be:
Br Br
(a)
CH3—CH2—CH—COOH (b)
CH3— C—CH2COOH
Br Br
(c)
CH3—CH2—COBr (d)
CH3—CH—COOH
Br Br Br
14. Reduction of aldehydes and ketones into hydrocarbons using zinc amalgam
and conc HCl is called:
(a) Dow process (b) Cope reduction
(c) Wolf-kishner reduction (d) Clemmenson’s Reduction
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15. Acetophenone when reacts with a base, yields a stable compound which has
the structure:
CH3 CH3
CH—CH2—C
(a) (b) CH—CH2—C
CH3 O
OH OH
CH—CH CH== CH—C
(c) (d)
OH OH CH3 OH O
(c)
CH3—C—CH3 (d)
CH3—C—CHO
CH3
O
NaOH
(B) + (ii) HVZ reaction
CHO O C—CH3
AlCl3
(C) + CH3—C—Cl (iii) Aldol condensation
(E) CH 3 CN
(i) SnCl2 /HCl
(ii) H O/OH +
→ CH 3CHO (v) Rosenmund's reduction
2
NaOH
(F) 2CH3CHO → CH3—CH==CHCHO (vi) Stephen's reaction
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ANSWERS
1. (b) 2. (d) 3. (b) 4. (c) 5. (b) 6. (b) 7. (b) 8. (d) 9. (a) 10. (d)
11. (b) 12. (a) 13. (a) 14. (d) 15. (d) 16. (b, d) 17. (b, c)
18. (b, d) 19. (a, c) 20. (a, b) 21. (a) 22. (d)
23. (a)—(iii), (b)—(iv), (c)—(i), (d)—(ii)
24. (a)—(v), (b)—(iv), (c)—(i), (d)—(ii), (e)—(vi), (f)—(iii) 25. 4
Ans. Methyl-2-methylbenzoate.
Q. 19. Why does benzoic acid not undergo Friedel-Craft reaction ?
Ans. – COOH group in C6H5COOH is an E. W. G. which deactivates the benzene ring.
Hence electrophilic substitution becomes difficult.
KMnO4
Ans. (i)
(i) (ii)
Q. 6. Which acid of each pair shown here would you expect to be stronger ?
(i) CH3CO2H or CH2FCO2H
(ii) CH2FCO2H or CH2ClCO2H
(iii) CH2FCH2CH2CO2H or CH3CHFCH2CO2H
(iv) or
Ans. (i) FCH2COOH (ii) CH2FCOOH
. F
. |
(iii) CH3 – CH – CH2COOH
(iv)
Q. 7. Carboxylic acids do not give reactions of aldehydes and ketones why ?
(i) (ii)
Q. 12. Benzaldehyde gives a positive test with Tollen’s reagent but not with Fehling’s
and Benedict solutions. Why ?
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Q. 15. .Aldehydes are easily oxidisable yet propanal can conveniently be prepared
by the oxidation of propanol by acidic K2Cr2O7.
Ans. Aldehydes having boiling points less than 373 K can be removed by distillation
therefore propanal can easily be prepared from propanol by distillation from the
alcohol acid dichromate solution.
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Q. 16. .Do the following conversions in not more than two steps
(i) Benzoic acid to Benzalolehyde (ii) Propanone to propene
Pol − BaSO 4
Ans. (i) C6 H5COOH →
SOCl2
C6 H5COCl → C6 H5CHO
H 2
H H KOH
Q. 18. Convert the following (i) Ethyl benzene to benzoic acid (ii) Ethanal to
but-2-enal
K Cr O / H +
Ans. (i) C6 H5C2 H5
2 2 7
→ C6 H5COOH
OH
|
H 3O + / ∆
(ii) 2CH3CHO → CH3CHCH 2 CHO → CH 2 CH = CHCHO
NaOH
dil.
CH3 CHO
(iii) (1) CrO2Cl2, CS2
+
(2) H2O
Toluence
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Q. 2. Predict the organic products of the following reactions :
(i)
(ii)
H NCONHNH
(iii) C6H5CHO
2 2→
(iv)
(v)
(vi)
COOH
(ii)
(iv) C6H5COCl/AlCl3
(v)
(vi)
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(ii) C6H5CH2OH
HBr
→ C6H5CH2Br
KCN
→ C6H5CH2CN
∆
. HO
→ C6H5CH2COOH 3
(iii)
MgBr
(iv)
(v)
Ans. (i)
(ii)
(iii)
(iv)
H2C CH2
O O
(v) CH3—CH2—C—CH3—CH2—CH2—CH3
(vi)
(ii)
(iii)
Electrophilic centre
(i)
Zn
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(ii) CH2
(iii)
Ans. (i)
(iii)
(ii)
C6H5 – C – H + HCN H OH HO H
C6H5 C6H5
d (+) l (–)
(iii) Due to formation of additional compound with NaHCO3 whereas impurities
. do not.
O OH
H2O/H
CH3 – C – H + NaHSO3 CH3 – CH – SO3Na
Ans. (i)
COCH3
AlCl3
HCl +
CH3COCl
(ii)
OH
–
(iii) 2CH3CHO OH D
CH3 – CH – CH2 – CHO CH3 – CH = CH – CHO
H+
LiAlH4
CH3CH2CH2CH2OH
2-Butanol
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Q. 11. Write the structures of organic compound A to F in the following sequence
of reactions :
D= E= F=
(iii)
(iii)
D+E
Ans. A = CH5COCH3
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B = C6H5CH2CH3
C = C6H5COOH
D = C6H5COONa
E = CHI3
CH 3COOH →
2 Cl /P
. (iii)
(b) Give simple tests to distinguish between the following pairs of compounds.
. (i) Benzaldehyde and Benzoic acid
. (ii) Propanal and propanone
– +
Ans. (a) (i) NOH (ii) CH2OH COO Na
. (ii) Cl–CH2COOH
(b) (i) Add NaHCO3, benzoic acid will give brisk ettervscence whereas
benzaldehyde will not give this test.
. (ii) Refer Q.7(e) of long answer type questions.
Q. 4. (i) How will you prepare (a) acetic anhydride and (b) acetyl chloride from
. CH3COOH ? Write the equation involved in each case.
(ii) Why is the boiling point of acid anhydride higher than the acid from
. which it is obtained ?
. (b)
(ii) Acid anhydride bigger size than corresponding acids and stronger van der
. Waal’s forces of attraction than their corresponding acids.
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(v) CH3COOH + C2H5OH
conc. H 2SO4
→ (vi) HCHO + NH3 →
(v) CH3COOC2H5 (vi) (CH2)6N4 (Urotropine)
Q. 6. (a) Write the chemical equation for the reaction involved in cannizzaro
reaction.
(b) Draw the structure of semicarbazone of ethanal
(c) Why pka of F-CH2COOH is lower than that of Cl–CH2COOH
(d) Write the product in the following reaction
(1) DIBAL - H
CH 3CH = CHCH 2CN
(2) H 2O
(e) How can you distinguish between propanal and propanone?
HCHO + HCHO
→ HCOONa + CH3OH
Conc. NaOH
Ans. (a)
(b) CH3CH = N–NHCONH2
(c) Stronger –I effect of fluorine makes F-CH2COOH to be stronger acid than
Cl–CH2COOH and less pka
(d) CH3CH = CHCH2CHO
(e) Silver mirror formed on adding ammonical silver nitrate to propanal and not
with propanone.
Source: EDUDEL