Alcohols, Ethers & Phenols 7.

Chapter 7 Alcohols, Ethers & Phenols

INTEXT EXERCISE: 1
1.

7. CH3CH2COCH2CH3 + CH3CH2MgBr

2.

8. Oxymercuration-reduction follows Markownikov’s

rule. Thus

3. LiAlH4 reduces ester, aldehyde and ketones to

alcohols.
4. In hydroboration alkenes are converted to alcohols
according to anti-Markovnikov’s rule.
5. Rate of SN1 reaction is
t-Bu X > iso - PrX > EtX > MeX
and order of ionisation energy
t-BuX < iso - PrX < EtX < MeX.

Thus option (a) is correct.

6. 9. 3-Chloro-1, 2-epoxypropane.
10. Esters react with Grignard reagents to form tertiary
alcohols.
7.2 Chemistry
INTEXT EXERCISE: 2

5.
1.

6. According to stability of carbocation, as dehydration

involves formation of carbocation.
7. Ring expansion, so q will migrate.

8.
2. H2CrO4 doesn’t oxidize 3o alcohol.
3. PCC converts 2o alcohol to ketone. 9. Polar arotic solvent favours SN2 mechanism.
4. Decolorize Br2 water means unsaturation reacts with 10. The correct answer is (c)
Na metal means acidic reacts with chromic acid
means alcohol not carbonyl.

Phenyl has better migrating tendency.

INTEXT EXERCISE: 3
1. EWG on Aryl halide increases rate of substitution. 6. I! is not a strong base so it do not gives E2 reaction.
2. (CH3)3CBr + NaOC2H5 can’t be applied for 7. Try Yours Self
synthesizing the ether because sod exthoxide, being
a strong base, will preferentially cause elimination
8.
reaction.
-OC 2 H5
(CH3)3CBr (CH3)2C = CH2 + HBr 9. The C6H5 group stabilizes the incipient carbocation
thereby favouring the attack at benzylic carbon to
In isobutene + ethanol, isobutene will form tert-
give 2-chloro-2-phenylethanol, i.e.,
butyl cation which reacts with ethanol, a nucleophile
to form ether. 2
+
H+
(CH3)2C = CH2 (CH3)2 CCH3 O
(i) CH 3 CH 2 OH
(ii) - H +
(CH3) 3 COCH 2 CH3

3.

Strong anionic nucleophile and 1o alkyl halide 10.

favours SN2 mechanism.

4.

Thus, option (a) is correct.

5.
 Alcohols, Ethers & Phenols 7.3
INTEXT EXERCISE: 4
1. When one of the alkyl groups is 3o and another is 1o, 8. Base catalysed epoxied opening is a typical SN2
nature of reagent determines the type of mechanism reaction in which attack of the nucleophile takes
(SN1 or SN2). A polar solvent or reagent capable of place at the less hindered epoxied.
forming ions (viz. conc. HI) will cause SN1 reaction,
while a non-polar solvent or a reagent not capable of 9.
forming ions (anhydrous HI) will cause SN2 reaction
HCl/ 3
2. CH3—CH2—CH2—O—CH2—CH3
CH3—CH2—CH2—OH + CH3—CH2—Cl

3.

So option (b) is correct.

4.
10. (1)

5. In this case nucleophile attacks on the carbon

of oxirane ring which is highly substituted and
reaction is SN1 reaction.

(2)

In this case nucleophile attach on less hindered

6. carbon of the oxirane ring and reaction is SN2
reaction
(3) NaBH4/CH3OH → this only affected in reduction
to 2o alcohol
7. In the acid-catalysed ring opening of an (4) In etherification reaction carboxylic acid and
unsymmetrical epoxied, the nucleophile attacks alcohol give -OH and H+ respectively.
primarily at the more substituted carbon atom
because such carbon of the protonated epoxide has a
considerable positive charge.
This resembles like a more stable 2o or 3o
carbocation and hence the reaction is SN1 like. These bonds are affected.
All 1, 2, 3 and 4 statements are correct.
So option (d) is correct.

In case of CH3ONa, -OCH3, being a strong

nucleophile, opens the strained epoxide ring in
a direct SN2 reaction, i.e., by attacking at the least
hindered carbon atom.
7.4 Chemistry
INTEXT EXERCISE: 5
1. Fris rearrangement at ortho position.

2. a) 5.

b)

c)
6.

d)

3.
7.

4. a) 8.

b)

c)
9. All these compounds have glycolic
groups.

d) 10. Greater the steric hindrance, slower is the oxidation.

INTEXT EXERCISE: 6
2.

1.

- I or - M ∝ Acidic Nature
- I or - M ∝ Basic Nature
 Alcohols, Ethers & Phenols 7.5

3.
8.

4. → All acidic hydrogens will be replaced (Ka) = x > y (Carboxylate anion stabilized by
H-bonding)
→ hydrogens at ortho and para positions will be
(Sol.) = y > x (Intermolecular H-bonding in y)
replaced by D+ via EAS
(Vol.) = x > y (Intramolecular H-bonding in x)
5. (MP) = y > X (More symmetrical structure of y)
9. In H2O (polar solvent) dibromophenol derivative
and in CS2 (non-polar) solvent monobromo phenol
derivative is obtianed.
10. o- and p-Nitrophenols are stronger acids than
m-nitrophenol.As a result, phenols (a) and (c) are
stronger acids than (b) and (d). In (c), the No2 groups
is flanked by two CH3 groups which push the NO2
6. Picric acid reacts with NaHCO3.
group out of the plane of the benzene ring. As a result
7. Due to intramolecular hydrogen bonding. of this steric hindrance, the electron withdrawing
resonance effect of the nitro group will be reduced
and hence the acidic character of the phenol will
decrease. Therefore, phenol (a) is the strongest acid.

EXERCISE - 1

1. 5. SeO2 oxidizes allylic carbon 2o Allylic C-will have

—OH group bonded.
6. Ester converts to 3o alcohol with Grignard reagent.

2. H2/Pt reduces the doulbe bond also

NaBH4 clearly reduces carbonyl group, protecting
the double bond.

3. 7.

8.

4. Product is
9. A is and D is
Optically active 3o alcohol.
Hence all options are correct
7.6 Chemistry
10. KMnO4 / H2O —→ Syn addtion; 22. MnO2 oxidizes
O 23. Carbocation is formed
||
R - C - O - O - H $ Anti addition Carbocation stabilizes by CH3– shift.
11. KMnO4 (alkaline) and OsO4/CH2Cl2 are used for
hydroxylation of double bond while O3/Zn is used
for ozonolysis. Therefore, the right option is (c) i.e.,
3CH3 CH = CH 2
B 2 H6
]CH3 CH 2 CH 2g3
24. Alkyl groups exercise +I effect and reduces acidity.
H2 O2
B NaOH
3CH3 CH 2 CH 2 OH H2O is most acidic as H is bonded to electronegative
1 - Propnanol
oxygen. H2O > 1o > 2o > 3o > R—C≡≡CH
ZnO - Cr2 O 3
12. CO + 2H 2 CH3 OH
25. Formation of carbocation is the slowest step.
13. 1º Alcohols on catalytic dehydrogenation give
aldehydes.
14. Reactions I and II give 2-propanol, i.e.,
26. In the first step, is formed,
I. CH3 CH = CH 2 + H 2 O
H+
Mark.add.
CH3 CHOHCH3 which under goes Kolbe’s reaction.
(i) CH 3 MgI
II. CH3 CHO (ii) H + /H 2 O
CH3 - CHOH - CH3 27. In the given compounds, ethanol is least acidic
OR in Q change CH3 to C2H5. In contrast reaction
III gives Ethanol and IV gives 1, 2-propanediol. 28. ( 3o alcohol ) order of reactivity is 3o > 2o > 1o >
CH3OH
(i) CH3 MgI
III. CH 2 O CH3 CH 2 OH
(ii) H + /H 2 O
Neutral (A) is a tertiary alcohol
IV. CH 2 = CHCH3 KMnO 4
CH 2 CH - CH3
| |
OH OH
29. Benzyl carbocation is most stable. Flourine
(i) B 2 H6
15. RCH = CH 2 (ii) H 2 PO 2 /NaOH
RCH 2 CH 2 OH destabilizes carbocation.
HNO 2
16. CH3 - CH - CH3 CH3 - CH - CH3 30. CH3- shift, most stable alkene is formed through
| | stable carbocation.
NH 2 OH
A 31. Due to intramolecular H-bond and minimum
5O? (i) CH 2 MgI
CH3 - CO - CH3 (CH ) COH
3 3 repulsion between CH3.
(ii) H + /H 2 O
B 1, 1 - Dimethyl ethanol

17. Does not give acetylene

(C)

32. O—H bond undergoes cleavage most readily

18. CH3CH2OH and CH3OCH3 because oxygen being more electronegative can
accommodate the negative charge more effectively
after the cleavage.

19. 33. Only alicylaldehyde forms intramolecular

H-bonding, i.e.,

20.

21. 2° alcohol oxidizes but 3° does not.

 Alcohols, Ethers & Phenols 7.7
34. Four primary alcohols with M.F C5H11OH are 41. CH3 CH 2 CH = CH 2
HBr/H 2 O 2
Anti - Mark addn.
possible. These are:
C 2 H5 ONa
CH3 CH 2 CH 2 Br
(i) CH3CH2CH2CH2CH2OH
CH3 CH 2 CH 2 CH 2 - O - C 2 H5
(ii) CH3 CH 2 - CH - CH 2 OH 42. Williamson’s synthesis, i.e., C2H5Cl + C2H5ONa
|
CH3 C2H5OC2H5 + NaCl
-NaCl

(iii) CH3 - CH - CH 2 CH 2 OH NaOH Na

| 43. C 2 H5 Br (aqueous)
C 2 H5 OH C 2 H5 ONa
CH3 CH 3 I
C 2 H5 - O - CH3 + NaI
CH3 (williamson's synthesis)
Ethyl methyl ether
|
(iv) CH3 - CH - CH 2 OH 44. Although C2H5O- will abstract a proton from phenol
| to form but C6H5O- is a weaker nucleophile than
CH3 C2H5O-. Therefore, the better nucleophile, i.e.,
35. Since at 298 K, CO2 is a gas, H2O is a liquid and SO2 C2H5O- will attack C2H5I to from diethyl ether.
is a gas, therefore, option (b) is correct, i.e., C6 H5 OH + C 2 H5 O - $ C6 H5 O - + C 2 H5 OH
Stronger Weaker
298 K nucleophile necleophile
RSH + O2 CO2(g) + H2O(1) + SO2(g)

36. 1o-alcohols produces turbidity on heating with lucas

reagent.

37. Reactivity increases as the nucleiphilicity of the

halide ion increases , i.e. I- > Br- > Cl-. Thus option 45.
(c) is correct.

38. Since one mole of compound X reacts with Na to

evolve 1 mole of H2 gas, therefore, alcohol X should
be dihydric, i.e. HOCH2CH2CH2CH2OH + 2Na
→ NaOCH2CH2CH2ONa + H2
39. The most important clue to solve this problem is the 46. Only the acidic ArOH is converted first to its
conversion of Y ——→ Z. Since addition of H2SO4 conjugate base then to Me ether.
followed by hydrolysis i.e., hydration of alkenes
follows Markovnikov’s rule, therefore, Z can be 47.
only 2-propanol and not 1-propanol.
It further doesn’t react wth HI
48. It’s oxidation of ether, ∝-carbon will have a peroxide
bond.
49.

40. Di-t-butyl ether cannot be made by Williamson’s

synthesis, since t-alkyl halides prefer to undergo
elimination rather than substitution, i.e., 50.

In acidic medium , more stable carbocation (3o) is

formed
In acidic medium nucleophile attacks that carbon
which is more sterically hindered.
\ (A)
7.8 Chemistry
51. PhMgBr + H3C—CH2—OH Due to crowding in protonated ether (I), nucleophilic
attack by Cl- ion does not occur. Instead it undergoes
+ H3C—CH2OMgBr cleavage to give 3º-butyl alcohol and stable 3º-butyl
carbocation which subsequently reacts with Cl- ion
52. to form 3º butyl carbocation. Thus, it is the stability
of 3º-carbocation which favours the cleavage of
ether even with HCl.
61. All statements are correct, i.e. option (d) is correct.
62. HCO3– is a weaker proton acceptor than phenolate
ion
53. with HI forms
63. Fires Rearrangement

Which doesn’t react further. (D)

3
54. Ethyl iodide, i.e., C2H5OC2H5 + 2 HI Fries Rearrangement
2 C2H5I + H2O 64. The reaction of phenol with acetyl chloride to form
55. Diethyl ether itself being a Lewis base is not attacked phenyl acetate is called acetylation.
by nucleophiles, i.e. OH- ions. All others, i.e. 65. C6 H5 ONa + C 2 H5 I
3
C6 H5 OC 2 H5 + NaI
Phenetole
Ni
66. C6 H5 OH + 3H 2 C6 H11 OH
Phenol Cyclohexanol
and
67. Electron-donating groups (—OCH3, —CH3 etc.)
d+ tend to decrease and electron-withdrawing groups
CH3 - C / Nd - contain an electrophilic carbon (—NO2, —CN etc.) tend to increase the acidic
and hence are readily attacked by nucleophiles. character of phenols. Since —OCH3 is a more
Thus, option (d) is correct. powerful electron-donating group than —CH3
group, therefore, p-methylphenol is slightly more
56. Due to H-bonding,the boiling point of ethanol is acidic that p-methoxyphenol while p-nitrophenol
much higher than that of the isomeric diethyl ether. is the strongest acid. Thus, option (d), i.e.
57. Due to greater electronegativity of sp2-hybridized p-methoxyphenol, p-methylphenol, p-nitrophenol
carbon atoms of the benzene rings, diaryl ethers is correct.
are not attacked by nucleophiles such as I- ions and 68. Secondary alcohols on oxidation give ketones.
hence diaryl ethers are not cleaved by HI even at
69. Since carbonic acid(H2CO3) is a stronger acid than
525K
phenol which, in turn, is a stronger acid than water
Dry ether H + /H 2 O
58. RMgX + S RSMgX RSH and which in turn is a stronger acid than C2H2,
Mercaptan
therefore, the overall increasing order of acidity is
Red P/HI
59. C 2 H5 OC 2 H5 Cleavage of ethers
2C 2 H5 I option (d) i.e. C2H2, H2O, phenol, H2CO3.
Red P/HI
Reduction
2C 2 H6
Ethane
H+ 70.
60. (CH3)3 C—O—C(CH3)3

71. Electron-donating groups decrease while electron-

withdrawing groups increase the acidic character of
phenols. Thus p- methylphenol is a weaker acid than
phenol. Further, due to resonance stabilization of
p-nitrophenoxide ion over m-nitrophenoxide ion,
p-nitrophenol is a stronger acid than m-nitrophenol.
Thus the overall order is (c).
 Alcohols, Ethers & Phenols 7.9
72. Na reacts both with phenol and ethyl alcohol to 73. C6H5N2Cl + H2O —→ C6H5OH + N2 + HCl.
evolve H2 gas and hence cannot be used to distinguish
phenol from ethyl alcohol, All the remaining
reagents react only with phenol but not with ethyl
alcohol and hence can be used for distinguishing 74.
phenol from ethyl alcohol.

75. Information based.

EXERCISE - 2

1. 8. Grignard reagent will abstract acidic hydrogen to

form CH4.
9. NaBH4 doesn’t reduce ester.
10. SN2 causes inversion at chiral C-atom.
11. NaBH4 doesn’t reduce ester it only reduces Ketone.
12.
2.

Gem diols are unstable.

3. SN1 reactivity depends on stability of carbocation.
13.
Hence D < A < B < C
4.

14. POCl3 does E2 elimination in alcohols.

15. Pb(OAc)4 causes clevage of vicinal diol.
16. Pinacol-Pinacolone rearrangement.
5. Acid will be
Alcohol will be C2H5O18H

6.

7.
17. In esterification H+ goes from alcohol & OH goes
from acid.
7.10 Chemistry
18. Towards sodium metal the reactivity of alcohol is 1o
> 2o > 3o.
30.
19. Ethers as they don’t have acidic hydrogen.

20. Higher the electronegativity between C–X, higher

will be the dipole moment

21. Vander Waal forces are responsible for boiling point.

22. ROH + R1Mg → R’H + ROMg

(C) CH3 – OH + CH3MgX —→ CH4 +CH3O –MgX
31. Protonation of alcohol molecule, i.e,
23. Ethyl Alcohol gives Iodoform test
CH3CH2OH + H+ —→ CH3CH2—
NaOH/I 2
(C) C2H5OH Iodoform Teste
CHI3 (yellow ppt)
32. Ethanol (CH3CH2OH), ethanol (CH3CHO) and
NaOH/I 2
CH3OH No ppt. 2-propanol (CH3)2 CHOH, all contain the group
CH3CHOH- and hence give +ve iodoform test
24. C2H5OH + R - Mg - X —→ RH + C2H2OMgX
C3H7OH – R - Mg - X —→ RH + C3H7OMgX
33.
25.

26.
KHSO 4 / 3
CH 2 OHCHOHCH 2 OH CH 2 = CHCHO
Glycerol Acrolenin(X)

Zn - Hg/Conc. HCl, 3
CH 2 = CHCH3
Propene(Y)

NBS/CCl 4
CH 2 = CHCH 2 Br
3 - Bromopropene(Z)

27. I-Propanol and 2-propanol in presence of Cu/D

undergo dehydrohydrogenation to give acetal dehyde
34. Dehydration of IV is most facile since it gives an
and acetone respectively which can be distinguished
aromatic compound. Dehydration of III gives a
by Fehiling solution since acetaldehydereduce while
conjugated diene which is stabilized by resonance.
acetone does not reduce Fehling solution
In contrast with alk. KMnO4 or acidic K2Cr2O7,
I-propanol will first give propionic acid while
2-propanol will first give acetone and then on
further oxidation will give acetic acid. Both these
acids cannot be distinguished by Fehling solution.
Option (d) is incorrect since conc. H2SO4 does not
bring about oxidation of alcohols. Dehydration of II gives only cyclohexene which is
28. Alcoholic iodine with NaOH gives iodoform not stabilized by resonance

CH3CH2OH + 3 I2 + 4 NaOH
—→ CHI3 + CH3COONa + 3 NaI + 3 H2O
29. Try Your Self In contrast, phenol (I) does not undergo dehydration.
Thus the case of dehydration is increases in the
order: I < II < III < IV.
 Alcohols, Ethers & Phenols 7.11
35. A mixed ether is formed
48.

49.

36.
37. Markownikov addition
38. Expected to be Markownikov addition
without rearrangement. Hence oxymercuration
Demercuration.
39. Williamson’s synthesis. Preferably 1o Halide is used
50. In acidic medium SN1 clevage.
for substitution.
40. In presence of Ag+ SN1 reaction occurs.
41. 3o carbocation will form and then OH will attack.
42. A → epoxide
51. Riemer Tiemann reaction with CCl4 gives Salicylic
acid.
4
52. With CHCl3 attacking species is : CCl2
53. Riemer Tiemann reaction
43. PBr3 converts alcohol into halide. Mg will form 54. R COOH > H2CO3 > PhOH > ROH
grignard 55. p-nitrophenol due to -m effect of -NO2 group.
56. Neutral FeCl3.
57. Claisen rearrangement to ortho then para then
tautomerize.
44. Nucleophile doesn’t attack phenylic C.

45. HI > HBr > HCl

46.

58. Fact.
59. All are characteristic test of Phenol.
60. Information based.

47. If 1-alkyl group is 3o then Clevage of ether occurs

by SN1 mechanism. (CH3)3C - I + CH3CH2OH.
7.12 Chemistry
EXERCISE - 3

1. CH3 CH CH3 Conc.

CH3 CH CH2 + H2O 8. Hypoiodite oxidation (NaIO) or iodoform test is
H2SO4
given by the organic compounds having
OH O OH
H3C C or H3C CH groups.

9. (A), (B) and (D)

Br Br 10. (A) Since p-phenolsulphonic acid has more thermal
stability than o-phenolsulphonic acid and hence
CH3 CH CH3 + 2Na + CH3 CH CH3 ortho can be converted into para by heating.
Dry ether
(B) Phenol is more acidic than benzyl alcohol
because phenoxide ion is more stable than
CH3 CH CH CH3 benzyl alkoxide ion.
CH3 CH3 9.2
11. Number of moles = 92 ×10 -3
(2, 3!dimethyl butane)
= 10-4 mol
Molecular weight of Z(C6H14) = 6 × 12 + 14 × 1 Corresponding volume of gas
= 86 amu = n × 10-4 x 22.4 × 103
⇒ n=3

2. 12. (i) Anisole

(ii) Benzyl alcohol (iii) 2 Methyl phenol
4. Anisole, benzyl alcohol, 2-methyl phenol, 3-methyl (iv) 3 Methyl phenol (v) 4 Methyl phenol
phenol and 4-methyl phenol.
13. There are three chiral centres havins no plane of
5. ROH + (CH3CO)2O → ROCOCH3 + CH3COOH syametry.
1 alcohol (OH) group gives two carbon in the Hence number of isomers 2n = 23 = 8
formula
14. Phenols, carboxylic acid and sulphonic acid will
4 OH will give 8 carbons so reactants possess 4 react with Na2 CO3 soluction. Acloholic -OH and
alcohol. alkyne cannot react with corbonte tion.
15. (i) Write the five C atoms straight chain and put (—
OH) group at diffferent positions.
6.

(ii) Write the four atoms in straight chain and put Me

and (—OH) at different positions.

O
MeCOCl
7. R OH R O C Me
MeCOCl
C8H18O4 Mwt 262 (iii) Write the three C atoms in straight chain and but
two Me and (—OH) at different positions.
DMW = 262 - 178 = 84 = 2 × (42)
O
As 2 x (MW of C CH3) ! A.W. of H
Hence 2 OH groups are present.
Hence, total isomers including stereoisomers of
C5H12O are 8.
 Alcohols, Ethers & Phenols 7.13

16.

Hence, total isomers including stereoisomers of C4H7OH are 7.

17. 2.68 gm of (A) gives 14.08 gm of AgI Ester consists of two stereocentres. Chiral center
14.08×134 during whole reaction are not effected, that’s why
134 gm of (A) gives 2.68 all esters are optical active.
= 704 gm of AgI
19.
704
= 235 = mol of AgI
= 3 (OMe) groups
18. (dl) 2-methyl butanoic acid and (dl) 2-butanol

20.

EXERCISE - 4

1.
4.

SN2 Th on

N - atom better Nu then O atom

2. 5. 2o alcohols easily oxidise in ketones

6. will produce 3o carbocation which is

most stable then others hence fastest reaction

7.
3.
7.14 Chemistry

16.
8.

(C) is not possible as it is not oxidized by CrO3/H+.

Remaining both are possible structure.
17. B must be 3o alcohol. So A must be ketone.
9.
18. HIO4 oxidises

19.

10.
This reagent converts 2o OH into ketone and 1o OH
into Aldehyde. 20. (CH2CO)3 ⇒ C6H6O3
11. SOBr2 as no rearrangement occurs and also by As 1H is removed and group is added on
products are gases.
3—OH groups.
12. This is semipinacolone rearrangement.

21.

-
13. Since OH attacks on C==O orientatin of OH & SH
doesn’t change on hydrolysis

14. 22. is LAH for reduction of aldehyde to alcohol.

is O5O4 for vicdiols.
(1) CH3MgBr, H+ (2) H+, D
is NaIO4 for oxidation
(3) KMnO4, cold (4) CrO3
NaBH4.
In the above order reagents must be used.
15. In x attack on least hindered
So, first LiAlH4 then H+
In y attack on most hindered
So, LiAlH4 / AlCl3
 Alcohols, Ethers & Phenols 7.15
23. A is

28.
B is

C is

29.

30. 1o alkyl halide is more reactive than 2o alkyl halide.

24. So transition state in II reaction is more stable than I
reaction.
31. Correct product for (b) option.

Option (d) is also not feasible because aromatic

halide do not given SN reaction in normal condition.
25. b)
32.

c)

33. CH3OH give SN1 & E1 reaction so all products are

possible.
d)

So options (b), (c) and (d) are correct. 34.

26.

27.
7.16 Chemistry
35. This reaction known as Reimer-Tiemann 40.
formylation.
Mechanism

Step-I:

Step-II:
41.

Step-III:
42. Conc. H2SO4 and KHSO4 both are dehydrating
agent.
43. HIO4 oxidizes vicinal diol, vicinal diketone, vicinal
diol and other functional vicinal combination like
a-amino alcohols.
36. Acidity of o-nitrophenol is less than H2CO3. Hence
44. alc KOH gives elimination Rest can be used.
it is insoluble.
37.
45.

38.

Similarly (b) can be formed from another resonating

structure.
46. a, b, c, are e- withdrawing groups. Hence increases
acidity.
39. 47. Refer mechanism of ester hydrolysis (acid catalyzed)

Second epoxidation is faster because of activation

by the epoxy oxygen.
 Alcohols, Ethers & Phenols 7.17
48. 56.

diastereomer of W

57.

49. Blue colouration in victor meyer test is given by 2o

Alcohols.
58.
50. Reaction occurs through Benzyne mechanism.
51. It is difficult to carry out F.C. reaction on phenol so
‘d’ wan’t give reaction at room temperature.

52. is more stable than

as well as .
53.

59.

60.

54.

55.

This reaction is base catalyzed ring opening: in this

reaction attack on less substituted carbon atom.
7.18 Chemistry
61.

65.

As both -OH groups are trans, so cyclic transition

intermediate state can’t be formed when both groups
are trans.
62. 76. According to theory learn the name.
77. a) HCHO is prepared by HIO4
b) HCOOH is also prepared by HIO4 clevage and
also by reaction with oxalic acid.
c) Allyl iodide with HI
d) Acrolein by KHSO4.
78. a) Markonikov’s addition without rearrangement.
b) Anti Markonikov’s addition
c) Markonikov’s addition with rearrangement
d) Symmetric alkene & addition without
This reaction is acid catalyzed ring opening reaction: rearrangement
In this reaction nucleophile attack at the more
79. a) HCHO form 1o Alcohol
substituted atom.
b) Acetone forms 3o Alcohol
63.
c) gives 3o Alcohol

d) Ester will first give ketone then 3o Alcohol.

80. Protonated ketone is most acidic followed by
protonated alcohol.
Acidic strength order.
64.

1
pK a values \ Acidic strength
 Alcohols, Ethers & Phenols 7.19

$
# !
Cl NNa

1. !""NaOH Dow process

Temperature = 623 K
Pressure = 300 atm
2. Ceric ammonium nitrate for alcohol and CHCl3/ KOH is carbyl amine test for primary amines

HBr HBr
!
HBr
3. O O OH Br
Br Br
H
4. In (A), extensive inter-molecular H-bonding is possible while in (B) there is no Inter-molecular H-bonding.
CH3
H3C CH CH3 H3C C O O H
O2
5.

Cumene Cumene hydroperoxide

+
H2O H

OH

+ CH3COCH3
Acetone
Phenol
O O
OH O C O CH3 O C O CH3

6. + Cl C O CH3 NaOH Br2

O (A)
Br
(B)
O HI I
7. Heat
O OH
7.20 Chemistry