Alcohol , Phenol and Ether(By: Jitender sir)

Questions
Explain the following name reaction:
(a) Reimer Tiemann (b) Kolbe reaction
(c) Hydroboration (d) Williamson`s synthesis
1. In esterification if we have used acid chloride instead of acid anhydride then we add pyridine a base. Why?
2. What is the condition in which alcohols behave as nucleophile and electrophile?
3. Explain why is o-nitrophenol more acidic than o-methoxyphenol.
4. Write the structures of the major products expected from the following reactions:
(a) Mononitration of 3-Methylphenol (b) Dinitration of 3-Methylphenol
(c) Mononitration of phenyl Ethanoate.
5. The following is not an appropriate reaction for the preparation of t-butyl ethyl ether.
CH3 CH3

H3C C Cl + H3C CH2 O Na H3C C O CH2 CH3

CH3 CH3

2-chloro-2-methylpropane 2-Ethoxy-2-methylpropane
(i) What would be the major product of this reaction?
(ii) Write a suitable reaction for the preparation of t-butyl ethyl ether.
6. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method. Give
reason.
7. Convert the following:
(i) Ethanol to Ethoxy ethane (ii) Prop-1-ene to propan-1-ol (iii) Methanal to benzyl alcohol
(iv) Ethanol to Butan-2-ol (v) Methyl magnesium bromise to 2-Methylpropan-2-ol
8. An organic compound A (C2H6O) react with sodium to form a compound B with the evolution of H2 and gives a
yellow compound C when treated with iodine and NaOH. When (A) heated with conc. H2SO4 at 413K, it gives a
compound D ( C4H10O) which on treatment with conc. HI at 373K gives E and A. D is also obtained when B is
heated with E. Identify A, B,C, D and E and write equations for the reactions involved.
9. Why sec. and tert. Alkyl haides undergo elimination process in Williamson`s synthesis?
10. Explain the mechanism of the following :
(i) Hydration of alkene (ii) Dehydration of ethanol at 443K
11. A compound C3H8O ( A) on dehydrogenation by Cu/573K give a compound C3H6O(B) which on reaction with
suitable Grignard reagent (C) to give compound (D) which on treatment with Cu / 573K gives an alkene (E) with
a molecular formula C4H8. Find out A ,B,C, D and E.
12. Arrange the following compounds in increasing order of boiling point. Propan-l-ol, butan-2-ol, pentan-l-ol.
13. How can you distinguish between phenol and benzyl alcohol?
14. Explain why nucleophilic substitution reactions are not very common in phenols.
15. Out of benzene and phenol, which one is more easily nitrated and why?
17. What happens when phenol is treated with.
(i) Acetyl chloride/Anhyd. AlCl3
(ii) Conc. HNO3
(iii) Dil. HNO3
(iv) Na2Cr2O7/H2SO4
18. Why is the C – O – H bond angle in alcohols slightly less than the tetrahedral angle whereas the C – O – C
bond angle in ether is slightly greater?
19. Phenol is a very weak acid. What substitution in the molecule can make it a stronger acid and a weaker
acid & why?
20. Which are the suitable reagent for the following reaction:
 (i) Propa-2-ol to propene (ii) 3o Alcohol to alkene(two reagents) (iii) Ethanol to Ethoxyethane
21. Why is phenol more acidic than an alcohol?
22. Now a days which new method we are applying for formation of picric acid?
23. How can you convert phenol to p-Benzoquinone?
24. Why C-O bond length is shorter in phenol as compared to alcohol?
25. Out of o-Nitrophenol and p-Nitrophenol which is more steam volatile?
26. Explain why phenols do not undergo substitution of the --OH group like alcohols?
27. Vapours of an organic compound when passed over hot reduced Cu at 573K give acetone. Identify the
compound.
28. Starting from phenol, how will you get salicylic acid?
29. Explain why cleavage of phenyl alkyl ethers with HBr always produces phenol & alkyl bromides and not
bromobenzene & alkanols. Also write the equation involved.
30. What happens when:
(a) Phenol is treated with ice cold bromine in CS2.
(b) RCH2OH is subjected to oxidation with KMnO4/H+.
31. Give chemical test to distinguish the following pairs of compounds:
(a) Methanol & Ethanol (b) Isopropyl alcohol & n-propyl alcohol (c) Ethanol & Phenol
32. Account for the following:
(a) phenol has smaller dipole moment than methanol
(b) For iodination of alcohols, H3PO4 is used and not H2SO4 with KI.
(c) Boiling points of ether are much lower than corresponding alcohols.
33. An organic compound A (C4H10O) reacts with HI giving a compound B (C4H9I) which on reduction gives
n-butane. On oxidation, A gives a compound C (C4H8O) and then an acid D (C4H8O2). Deduce the structures of
A, B, C and D.
34. An alcohol A (C4H10O) on oxidation with acidified potassium dichromate gives carboxylic acid B (C4H8O2).
Compound A when dehydrated with Conc. H2SO4 at 443 K gives compound C. Treatment of C with aqueous
H2SO4 gives compound D (C4H10O), which is an isomer of A. Compound D is resistant to oxidation, but
compound A can be easily oxidised. Identify A, B, C, D and write their structures.
35. Which product you will get when Cu is treated with the following compound at 573K?
(a) Propan-2-ol (b) 2-Methyl propan-2-ol
36. Why does electrophile only attack on ortho and para position in phenol?
37. Out of o-Nitrophenol and p-Nitrophenol which has more boiling point and why?
38. Out of following reaction which undergo SN1 and SN2 mechanism?
(i) Alcohol to alkene (ii) Alcohol to ether
39. Why Tertiary alcohol most probably follow SN1 mechanism?
40. Dehydration of secondary and tertiary alcohols to give corresponding ethers is unsuccessful. Why?
41. Why is bimolecular dehydration not appropriate for the preparation of ethyl methyl ether?
Ans Bimolecular dehydration is best used for the synthesis of symmetrical dialkyl ethers from unhindered primary
alcohols.
If two different alcohols are used, there is no way to control which -OH gets protonated (as obviously we are
using primary alcohols and both primary alcohols would be almost equally basic towards protonation) and which
-OH acts as a nucleophile, so a mixture of two different symmetrical and the desired asymmetrical ether is
obtained.
42. In Williamson`s synthesis reaction primary alkyl halide when treated with sodium alkoxide then only
substitution takes place and only we will get ethers but when we use secondary and tertiary alkyl halides, they
undergo elimination and only gives alkenes. Why?
Ans Because with 10 alkyl halide alkoxide ion behave as nucleophile only but with 2o and 3o alkyl halide alkoxide ion
behave like a strong base.
43. Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol and
 3-methylpentan-2-ol.
44.

Give a mechanism for this reaction.

45.. Give the products:
CH3
HI
(i) H3C CH2 CH CH2 O CH2 CH3
heat
CH3
HI
(ii) H3C CH2 CH2 O C CH3
heat
CH3
46. Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4- nitrobenzene
and why?
Br

(i) + CH3ONa

NO2

ONa
(ii)
+ CH3Br

NO2

47. Fill in the blank and find out the A, B, C ,D and E ?

H+ /H O
Cu/573K Na metal CH MgBr3 2
CH CH −Br
(i) CH2 = CH − CH3 ⎯⎯⎯⎯⎯
2 → A ⎯⎯⎯⎯⎯ → B ⎯⎯⎯⎯⎯
+
3 → C ⎯⎯⎯⎯⎯ → D ⎯⎯⎯⎯⎯⎯→
williamson`s
E
H /H2O

CH −Mg−Br Conc.H SO Na Metal H+ /H O SOC

(ii) A ⎯⎯⎯⎯⎯⎯
3
+ ⎯
→ B ⎯⎯⎯⎯⎯⎯
2 4 → CH = CH ⎯⎯⎯⎯⎯
443K 2 2
2 → C ⎯⎯⎯⎯
2 → D ⎯⎯⎯⎯⎯
Dry ether
→E
H /H2O

CH=CH2 H+/H2O (A) How we will get same compound (A) with Ethanal(CH3CHO)
(iii) B2 H /
6 OH
(B) How we will get the same product (B) with methanal(HCHO)

CH3 B2H6 / H2O2

20% H3PO4 / 358K
(iv) CH3 - C -OH (B) (C)
OH- / H2O
CH3
48.
CH3-CH(OH)CH LiAlH4
2CH2CH3
CH -CH2OH3
(A) (E)
Pentain-2-ol

(J)

H+ / H2O
CH33-CH
CH -CH22-OH
-OH CH2=CH2
(B) (K) (L)
Ethanal
( 1oAlcohol)

CH3 85% H3PO4

CH3-Mg-X (M)
(C) CH3-CH-OH 440K
Propan-2-ol
(2oalcohol)

(P)
O
CH3-C-CH3 Cu/573K
(N)

(D)

H+/H2O

49.

50. Write the names of reagents and equations for the preparation of the following ethers by Williamson’s synthesis:
(i) 1-Propoxypropane (ii) Ethoxybenzene (iii) 2-Methoxy-2-methylpropane (iv) 1-Methoxyethane
51. Show how will you synthesise:
(i) 1-phenylethanol from a suitable alkene.
(ii) cyclohexylmethanol using an alkyl halide by an SN2 reaction.
(iii) pentan-1-ol using a suitable alkyl halide?