Alcohols Ethers and Phenol-03 - Assignments (New)
Alcohols Ethers and Phenol-03 - Assignments (New)
Alcohols Ethers and Phenol-03 - Assignments (New)
ASSIGNMENTS
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. Explain why ortho-nitrophenol is more acidic than ortho-methoxyphenol?
2. Why (CH3)3COH is less acidic than (CH3)3SiOH although carbon is more electronegative than Si?
3. What is the order of dehydration of following compounds?
(i) pO2NC6H4CH(OH)CH3 (ii) pH2NC6H4CHOH CH3
(iii) C6H5 CHOH CH3
OCH3 O
5. H
CH 3OH
H2 O
6. Alcohols are weaker acids than phenols but are stronger nucleophiles - explain.
7. Phenol is not soluble in aquous NaHCO3 but acetic acid is soluble - Explain.
8. Write the mechanism and comment on the migratory aptitudes in the reaction of aliphatic hydroperoxides
with aqueous acids to give only aldehydes and ketones as the major products.
9. Convert
(a) acetylene into n-butyl alcohol and (b) propane into allyl alcohol
10. Identify all unknown structures
OH
LEVEL - II
1. Write the equation for the reaction of hydrogen iodide with
(i) 1–propoxypropane
(ii) methoxybenzene
(iii) benzyl ethyl ether
Chemistry : Alcohols, Ethers and Phenols
What are A to C?
4. Starting from CH3—CHO as the carbonyl compound suggest the grignard reagent which you should
use to prepare the following compounds.
(i) 2, methyl, 2, propanol
(ii) Acetophenone (Phenyle methyle ketone)
OH
CH3
5. Predict A, B and C in the following sequence of reaction and also explain their formula.
PBr3
A Mg
B
Dry ether
Grignard 's Re agent C
H 3O
3, 4 dim ethyl 3 hexanol
6. An organic compound A on treatment with acetic in the presence of sulphuric acid produces an ester
B. A on mild oxidation gives C which with 50% KOH followed by acidification with dilute HCl generates
A and D. D with PCl5 followed by reaction NH3 gives E. E on dehydration produces phenyl cyanide.
Identify A, B,C,D and E
OH
8. Compound (A) reacts with sodium to liberate H2, forming a compound (B). When (A) is treated with
HCl + ZnCl2, an immediate reaction takes place liberating (C). When (A) is heated with H2SO4, (D) is
formed. Ozonolysis of (D) gives a 3 carbon aldehyde and 3 carbon ketone. What are (A), (B), (C) and
(D).
Chemistry : Alcohols, Ethers and Phenols
9. Devise a synthesis of the following compound, starting from toluene and using any necessary reagents.
COOH
Ph
CH3
H3C H3C
CH3
CH3
10.
HCl ?
OH
LEVEL - III
1. Give equations of the following reactions :
(i) reaction of propene with mercuric acetate followed by hydrolysis
(ii) oxidation of propan–1–ol with alkaline KMnO4 solution
(iii) reduction of bromine in CS2 with phenol
(iv) action of dilute nitric acid with phenol
(v) treating phenol with chloroform in presence of aqueous NaOH at 343 K
2. An open chain compound (A) C5H8O is optically active. When (A) is hydrogenated in presence of Pd
as catalyst, it absorbs two moles of H2 per mole of (A) to produce compound (B) C5H12O which is
optically inactive. However when (A) is warmed with dilute H2SO4 in presence of HgSO4 it gives
compound C(C5H10O2) which is still optically active. C responds to iodoform test. What are the structures
of A to C?
3. An organic compound (A) C10H12O gives red colour when treated with cerric ammonium nitrate and
also decolourises Br2 in CCl4 to give B(C10H12OBr2). A can show both geometrical and optical isomerism.
A on treatment with I2 and NaOH gives iodoform and an acid (C) after acidification. Give the structures
of A to C and also the stereoisomers of A.
4. Write the products in the following reactions.
CH CH2
(i) Ph CH
Ph Mg Br
OH
(ii) OH CH 3MgBr
H3C
(iii) O NaBH 4
O
Ni / H 2
(iv) Ph CH CH C CH CH2
Chemistry : Alcohols, Ethers and Phenols
5. Explain the formation of products (X) and (Y) from respective reagents (A) and (B).
O OMgBr
Ph Mg Br
Ph CH3 Ph CH3 X
Ph
O
OMgBr
Ph Mg Br
Ph CMe3 Ph CH CH C Y
Ph CMe3
CH3
6. Show how would you synthesise C OH with starting reagents containing not more than
CH2
H3C
5C atoms.
7. p-nitrophenol reacts with ethyl bromide and aq NaOH to give a compound A (C8H9O3N). A on treatment
with Sn and HCl gives B (C8H11ON). B on treatment with NaNO2, HCl and then with phenol gives C
(C14 H14 O2N2). C on reation with ethyl sulfate and aqueous NaOH gives D (C 16 H18 O2 N2 ). D on
treatment with SnCl2 gives E (C8H11ON). E reacts with acetyl chloride to give phenacetin (C10H13O2N).
Identify structure from A to E.
8. An alkene (A) yields a tertiary alcohol (C) containing an asymmetric carbon on oxymercuration -
demercuration reaction. Another isomeric alkene (B) gives the same alcohol (C) as one of the products
under the same reaction condition. On vigorous oxidation with KMnO4, (A) gives a carbonyl compound
(D) containing five carbon atoms and an acid (E) containing four carbon atoms. The carbonyl compound
(D) on reduction with LiAlH4 gives an optically active alcohol (F), containing two identical alkyl groups
on the same carbon atom.On the other hand alkene (B) gives on vigorous KMnO4 oxidation two
carbonyl compounds (G) and (H). (H) contains six carbon atoms and no two identical groups are
attached to the same carbon atom. Give the structures of (A) to (H) showing the reactions clearly.
9. Predict the product(s) of each reaction below. Be sure to specify the stereochemistry where appropriate.
(Ph, phenyl; *, isotope label)
(a) Ph—O—CH2—Ph
excess HI
(b) (H3C)2CH—O—C(CH3)3
1 equiv. HBr
O
1. PhO
(c)
2. H
Ph
Chemistry : Alcohols, Ethers and Phenols
(d) H H2 O
H H CH2CH3 H (cat.)
(e) H
H H CH2CH3
1. OH
2. H
H
(f) O 1. PhLi
2. H
CH3
10. 0.037g of an alcohol, ROH, was added to CH3MgI and the gas evolved measured 11.2 cm3 at STP.
What is the molecular weight of ROH? On dehydration, ROH gives alkene which in ozonolysis gives
acetone as one of the products. ROH on oxidation easily gives an acid containing the same number of
carbon atoms. Give structure of ROH and the acid containing the same number of carbon atoms. Give
structure of ROH.
Chemistry : Alcohols, Ethers and Phenols
SECTION - II
SINGLE CHOICE QUESTIONS
CH3 CH3
HBr
1. H3C A (predominant)
CH3 OH
A is:
CH3 Br Br CH3
CH3
CH3 CH3
OH
4. The correct decreasing order of acidic strength is
(a) C6H5OH C6H5CH2OH C6H5COOH C6H5SO3H
(b) C6H5CH2OH C6H5OH C6H5SO3H C6H5COOH
(c) C6H5COOH C6H5CH2OH C6H5OH C6H5SO3H
(d) C6H5SO3H C6H5COOH C6H5OH C6H5CH2OH
5. In which of the following case configuration about chiral C* is retained:
Me Me
Na CH Br CH ONa
(a) Ph OH
3
(b) Ph OH
TsCl
3
Et Et
Me
PCl CH Br
(c) Ph OH
5
3
(d) None of these.
Et
Chemistry : Alcohols, Ethers and Phenols
6. H
what would be (X)
OH
(a) (b)
O O
Me
OH
CH3
(c) (d) None of the above
H3C C6H5
H
8. The reaction CH2
H2O
; gives
CH3
(a) OH (b)
OH
OH
9. The alcohol, C4H9OH when treated with a mixture of anhydrous. ZnCl2 and conc.HCl gave an
immediate oily layer. It will be
CH3
H3C
(a) H3C OH (b)
OH
CH3 H3C
H3C
(c) OH
(d)
H3C H3C OH
Chemistry : Alcohols, Ethers and Phenols
H3C H3C
(a) (b)
CH3 CH3 CH3 OH
CH3 CH3
O
H3C CH3
(c) (d)
OH CH3 H3C CH2 CH3
OH Al2 O3
A i) HI
B
350 C ii) AgOH
11. Write the final product of the following reaction: H3C
Product (B) is:
OH
H3C O CH3
(a) (b) H C
3
CH3
H3C O H3C
(c) (d)
CH3 CH2
12. Which one of the following will most readily be dehydrated in acidic solution?
OH
O OH
CH3
(c) H3C CH3 (d) H3C
OH OH
13. Consider the following pairs of alcohols (1,2,3,4):
(a) OH
H3 C
CH3
HO CH3
H3C and
(b)
OH CH3 H3C CH3
Chemistry : Alcohols, Ethers and Phenols
CH3 OH
CH3 CH3
(c) and
OH CH3
H3C CH3
(d) and OH
OH
14. Which of the following decreasing order of rate of dehydration with H2SO4 is correct for the alcohols.
OH
OH OH
CH2 CH
H3C CH (CH3 )2 OH
H3C
OH
(D) (E)
(a) (b)
(c) (d)
CH3
CH3
CH3 Cl
Cl H3C Cl
Chemistry : Alcohols, Ethers and Phenols
H 1. B2 H 6 1. O3
17. C7 H14 O(X) C 7 H12 C 7 H14O(Z)
2. H O / OH – 2 2
2. Zn / H 2 O
(A3 alcohol) (Y) (An isomer of X)
O
CH3
CH3
(a) OH (b)
OH
CH3
CH3
CH3
(c) (d)
HO CH3
OH
18. Which of the following does not react with aqueous periodic acid:
H2 C OH
H2 C OH
C O
(a) (b)
H2 C OH
H2 C OH
H2 C OH H2 C OH
CH2 HC OH
(c) (d)
H2 C OH H2 C OH
CH 3 MgBr (execess)
19. (C 2 H5 O) 2 CO H 3 O
A
A can be:
CH3 CH3
(a) H5 C 2 C OH (b) H5 C2 C OH
C 2 H5 CH3
CH3
H
Chemistry : Alcohols, Ethers and Phenols
O
O
OH
(a) (b)
OH
O O
CH3
(c) (d)
OH OH
Chemistry : Alcohols, Ethers and Phenols
SECTION - III
MULTIPLE CHOICE QUESTIONS
1. Propan-l-ol can not be prepared from propene by
(a) H2O/H2 SO 4 (b) Hg(OAc)2/H2O followed by NaBH4
(c) B2H6 followed by H2O2 (d) CH3CO2 H/H2 SO 4
2. Alcohols may act as –
(a) Oxidising agent (b) Reducing agent
(c) Lewis base (d) Bronsted acid
3. The reagents used for the ring alkylation of phenol are –
(a) C2H5Cl and anhyd AlCl3 (b) CH3CH=CH2 and H2SO4
(c) (CH3 )2CHOH and H2SO4 (d) CH3CH=CH2 and HF
4. Which of the following is the most reactive with HCl in the presence of ZnCl2?
(a) (Me2 CH)3 COH (b) (Me2 CH)2 CHOH
(c) Me2CH – CH2OH (d) C6 H5 OH
5. Which of the following compounds yield 1-methyl cyclohexanol by normal hydration process?
CH2 CH3
(a) (b)
CH3
7. Which of the following compounds are easily oxidized by K2Cr2O7 and H2SO4?
(a) CH3 CH 2 OH (b) (CH3) 2CHOH
(c) CH3 CHO (d) (CH3 )3 COH
8. Which of the following reactions are used in the preparation of alcohols?
LiAlH 4
(a) C 2 H5 Br aq. KOH
(b) (CH 3 ) 2 C O
Na / EtOH H 2O
(c) CH3 COOCH 3 (d) (CH 3 ) 2 CHBr
9. Alcohols can be prepared from alkenes by
(a) Hydration (b) Hydroboration
(c) Oxymercuration (d) none of these
10. When glycerol is heated with an excess of HI, it produces
(a) allyl iodide (b) propene
(c) glycerol tri iodide (d) 2-iodopropane
Chemistry : Alcohols, Ethers and Phenols
MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS
Write up - I
In a polyhydric alcohol, the total numbers of hydroxyl groups are estimated by the following methods :
(i) A known mass of the acetyl derivative of polyhydric alcohol is taken. It is mixed with an excess
volume of a standard alkali solution. Both are refluxed. Alkali is used in the hydrolysis of acetyl
derivative. The unused alkali is measured by doing titration with a standard acid solution and total
number of hydroxyl groups (n) can thus be calculated stoichiometrically.
CH3COCl nKOH
A(OH) n A(OCOCH3 ) A(OH) n ) nCH3COOK
Polyhydric Acetyl derivative
alcohol
(ii) Total number of —OH groups in vicinal position can be calculated by periodic acid or lead tetra
acetate oxidation.
CH3 CH3
C OH C O
HIO4
or Pb(COCOCH 3 ) 4
C OH C O
1. 0.436 of acetyl derivative of a polyhydric alcohol (molecular mass = 92) require 0.336 g KOH for
hydrolysis. The total numbers of hydroxyl group(s) in the alcohol are
(a) 1 (b) 2
(c) 3 (d) 4
2. The ratio of the number of moles of lead tetra acetate required for the oxidation of 1 mole of
glucose to that of 1 mole of fructose is
(a) 1 : 1 (b) 2 : 1
(c) 5 : 4 (d) 4 : 5
3. When 1 mole of glucose is oxidized by periodic acid, the product(s) formed are
(a) 4 moles of formic acid and 1 mole of formaldehyde
(b) 5 moles of formic acid and 1 mole of formaldehyde
(c) 3 moles of formic acid and 2 moles of formaldehyde
(d) 2 moles of formic acid and 4 moles of formaldehyde
Chemistry : Alcohols, Ethers and Phenols
Write up - II
Both symmetrical and unsymmetrical ethers can by prepared by Williamson’s synthesis which involves
the reaction between an alkyl halide and an alkoxide ion. The reaction occurs by SN2 mechanism.
Therefore, for good yields of ethers, the alkyl halide must be primary while the alkoxide may be
derived from 1°, 2° or 3° alcohols. Since 2° and 3° alkyl halides prefer to undergo elimination rather
than substitution reactions, therefore, they are not suitable starting materials in Williamson’s synthesis.
Likewise, vinyl and aryl halides being unreactive do not undergo Williamson’s synthesis. The reverse
process involving the cleavage of ethers to give back the original alkyl halide and the alcohol can be
carried out by heating the ether with HI at 373 K. If one group is methyl and the other is a 1° or a
2° alkyl group, the reaction occurs by SN2 mechanism. Because of steric hindrance, the I– ion attacks
the smaller alkyl group leading to the formation of methyl iodide and the alcohol derived from the
bulkier alkyl group. If, however, one group is methyl and the other is a tert–alkyl group, the reaction
occurs by SN1 mechanism and the alkyl halide is derived from the more stable carbocation
4. Which of the following reagents when heated will give a good yield of an ether
(a) Isopropyl bromide and sodium isopropoxide (b) Isopropyl bromide and sodium ethoxide
(c) Bromobenzene and sodium phenoxide (d) Sodium tert-butoxide and ethyl bromide
5. Which of the following ethers can be prepared by Williamson's synthesis?
(a) Benzyl methyl ether (b) Methyl vinyl ether
(c) Divinyl ether (d) Diphenyl ether
6. Benzyl ethyl ether reacts with HI to form
(a) p-Iodotoluene and ethyl alcohol (b) Benzyl alcohol and ethyl iodide
(c) Benzyl iodide and ethyl alcohol (d) Iodobenzene and ethyl alcohol
(D) CH3 Cl CH 3 O 4. CH C CH 2 CH 3
SECTION - V
(PROBLEMS )
O Na O Na
CH2Cl CHCl2
(a) (b)
CH3 CH3
O Na O Na
CCl3 CH2OH
(c) (d)
CH3 CH3
(a) mixture of (K) and (L) (b) mixture of (K) and (M)
(c) only (M) (d) only (K)
Chemistry : Alcohols, Ethers and Phenols
3. When phenyl magnesium bromide reacts with t–butanol, the product would be :
(a) benzene (b) phenol
(c) t–butyl benzene (d) t–butyl phenyl ether
4. How many structures of F is possible?
CH3
H Br2 / CCl4
[F] C 4 H8 Br2
H2 O
H3C OH 5 such products
are possible
(a) 2 (b) 5
(c) 6 (d) 3
OH
5. C 2 H 5 I
OC H
2 5
Anhy. C H OH
2 5
NO2
CH3 NO2
I II III IV
(a) III > IV > I > II (b) I > IV > III > II
(c) II > I > III > IV (d) IV > III > I > II
12. The products of combustion of an aliphatic thiol (RSH) at 298 K are :
(a) CO2(g), H2O(g) and SO2(g) (b) CO2(g), H2O(l) and SO2(g)
(c) CO2(l), H2O(l) and SO2(g) (d) CO2(g), H2O(l) and SO2(l)
13. Assertion : p–nitrophenol is a stronger acid than o–nitrophenol.
Statement : Intramolecular hydrogen bonding make the o–isomer weaker than the p–isomer.
(a) both assertion and statement are true and statement is the correct explanation of assertion
(b) assertion is correct and statement is wrong, statement is not the correct explanation of assertion
(c) assertion is wrong and statement is correct, statement is not the correct explanation of assertion
(d) both assertion and statement are wrong and statement is not the correct explanation of assertion.
14. In CH3CH2OH, the bond that undergoes heterolytic cleavage most readily is :
(a) C–C (b) C–O
(c) C–H (d) O–H
15. Phenol reacts with bromine in carbon disulphide at low temperature to give :
(a) m–bromophenol (b) o–and p–bromophenol
(c) p–bromophenol (d) 2, 4, 6–tribromophenol
16. Statement (S):Solubility of n–alcohol in water decreases with increase in molecular weight.
Explanation (E) : The reactive proportion of the hydrocarbon part in alcohols increases with increasing
molecular weight which permits enhanced hydrogen bonding with water.
(a) both (S) and (E) are correct and (E) is the correct explanation of (S)
(b) both (S) and (E) are correct but (E) is not the correct explanation of (S)
(c) (S) is correct but (E) is wrong
(d) (S) is wrong but (E) is correct
17. Hydrogen bonding is maximum in :
(a) ethanol (b) diethyl ether
(c) ethyl chloride (d) triethyl amine
Chemistry : Alcohols, Ethers and Phenols
O OH
H CHCl2
-
O O
H CHCl2
(c) I (d) OH
Chemistry : Alcohols, Ethers and Phenols
SUBJECTIVE QUESTIONS
1. An optically active alcohol A (C6H10O) absorbs two moles of hydrogen per mole of A upon catalytic
hydrogenation and gives a product B. The compound B is resistant to oxidation by CrO3 and does not
show any optical activity. Deduce the structure of A and B.
6. Each of the following reactions gives two products. Write the structures of the products :
Alc. KOH, heat
(i) C6 H5 CH 2 CHClC 6 H5
HI (excess)
(ii) (CH 3 ) 2 CHOCH 3 heat
7. Complete the following reactions with appropriate structures of products/reagents :
O
O CHC6 H5
(i) LiAlH 4
[A]
(ii) H heat
[B]
8. Explain briefly the formation of the products giving the structures of the intermediates.
H2 C
CH CH2 CH CH2
HCl +
CH CH2 Cl etc
(a) CH CH2 OH CH2 CH2 Cl
2
H2 C
CH3 CH3
CH CH CH CH
HCl
only
CH2 CH2 OH CH2 CH2 Cl
NaNH 2
(b) OCH3
NH 3
OCH3
Br H2 N
Chemistry : Alcohols, Ethers and Phenols
CH3
| NaOCH 3
(i) C2 H5 OH
CH3 —C — CH 2 Br (ii)
|
CH3
NO2
10. Identify A, B and C and give their structures :
O
CH3
CH3
Br2
NaOH
A B
C(C 7 H12 O)
O
11. How would you synthesis 4–methoxyphenol from bromobenzene in NOT more than five steps? State
clearly the reagents used in each step and show the structures of the intermediate compounds in your
synthetic scheme.
12. Convert,
OH
Aspirin
OH
Write resonance structure of the given compound.
Cl
KCN C2 H 5 ONa / C2 H5 OH H3O SOCl 2
14. (A) (B) (C) (D)
DMF C H CHO /
6 5 CH NH 3 2
Identify A to D.
O
OH
H / 1.O3 NaOH
15. X Y
2. Zn / CH COOH
3
Identify X and Y.
Chemistry : Alcohols, Ethers and Phenols
ANSWERS
EXERCISE - 1
(a) 2 phenyl-2-propanol (b) 5-bromo-2-heptanol
(c) 4-methyl cyclohex-3-ene-1-ol
EXERCISE - 2
O CH2 OH
H3O+
MgBr H2 C CH2
[O] O
(i) CH3MgBr
(ii) H3O+
O OH
CH3 CH3
EXERCISE - 3
Ni / H
(a) H3C COOH
2
H3C CH2 OH
O OH
O O
(c) H C C LiAlH 4
OCH3 HO CH2 CH2 OH
EXERCISE - 4
Cl
CH3
Chemistry : Alcohols, Ethers and Phenols
EXERCISE - 5
CH2
OH conc.
(i) H3C
H 2SO 4
n Hg(OAC) 2
H 2O
NaBH 4
CH3
conc.
CH3
H 2SO 4
H3C
H3C
OH
Br2
Br
CH3
NaNH 2
CH3 H3C
H3C
Br
(ii) H3 C
PCC nCH CH CH MgBr H O
OH H3C CHO
3 2 2 3
CH3
conc.
CH3 H3C
H 2SO4
H3C
OH
O O OH
CH3 MgBr (excess)
OH
(iii)
H 3O
EXERCISE - 6
HCHO 2HCOOH CO 2 CH 3 — CHO
Chemistry : Alcohols, Ethers and Phenols
EXERCISE - 7
Me Me
Me C OH + CH3I Me C I + CH3OH
Me Me
(A) (B)
EXERCISE – 8
O2 N Me O 2N Me
H
C C
Me2 N O OH Me2N O OH2
O 2N Me
C
H O O NMe2 O2 N
H2 O :
Me
C
H
O NMe2
CH3 O
O 2N C O NMe2 O 2N C Me
O H
HO NMe2
EXERCISE – 9
OH OH
OH
CHO MgBr
CHCl3
HO CH
NaOH
H 3O
Chemistry : Alcohols, Ethers and Phenols
EXERCISE – 10
HO CH3 HO CH3 HO CH3 OH OH
CH3 CH3
H
H
H3C H3C H3C H3C H3C
O OH OH OH OH
SECTION - I
(Subjective Questions)
SECTION - II
(Single Choice Questions)
1. (b) 2. (a)
3. (a) 4. (d)
5. (a) 6. (d)
7. (c) 8. (c)
9. (c) 10. (b)
11. (a) 12. (b)
13. (b) 14. (a)
15. (d) 16. (c)
17. (b) 18. (c)
19. (d) 20. (d)
SECTION - III
(Multiple Choice Questions)
1. (a, b, d) 2. (c, d)
3. (b, c, d) 4. (a)
5. (b) 6. (a, b, d)
7. (a, b, c) 8. (a, b, c, d)
9. (a, b, c) 10. (d)
Chemistry : Alcohols, Ethers and Phenols
SECTION - IV
(Comprehension Type Questions)
1. (c) 2. (a)
3. (b) 4. (a)
5. (a, b, c, d) 6. (b, c)
SECTION - V
SUBJECTIVE
Answers are given in the separate booklet.