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BANSALCLASSES

TARGET IITJEE 2007

ORGANIC CHEMISTRY
XII (ALL)

ALCOHOL & ETHER

CONTENTS
EXERCISE-1(A)
EXERCISE 1(B)
EXERCISE-II
EXERCISE-III
EXRECISE - IV(A)
EXRECISE - IV(B)
ANSWER KEY
EXER CISE-IfA)

Q. 1 Which of the following reaction is called as 'Bouveault-Blanc reduction'


(A) Reduction of acyl halide with HyPdBaSC^
(B) Reduction of ester with Na/C^OH
(C) Reduction of anhydride with Li A1H4
(D) Reduction of carbonyl compounds with Na/HgHCl

Q.2 Glycol on treatment with PI3 mainly gives-


(A) Ethylene (B) Ethylene iodide (C) Ethyl iodide (D) Ethane

Q.3 Acrolein is formed when glycerol is heated with-


(A) Acidified KMn04 (B) Br2 water (C) KHS04 (D) HN0 3

Q. 4 Glycerol on treatment with oxalic acid at 110C forms-


(A)Allyl alcohol (B) Formic acid (G) C0 2 and CO (D) Glyceric acid

Q. 5 If the starting material is 1-methyl-1,2-epoxy cyclopentane, of absolute configuration, decide which


one compound correctly represent the product ofits reaction with sodium methoxide in methanol.

Q. 6 When phenol is treated with PC15, the yield of chlorobenzene is generally poor because ofthe formation
of
(A) Benzoyl chloride (B) p-chorophenol (C) o-chlorophenol (D)Triphenyl phosphate

Q. 7 In the following reaction,finalproduct is


14
CICH2CH-CH.2 NaOC2H<

14 14
(A) CICH2CHCH2OC2H5 (B) ClCH2CHCH2ONa

OH
14 14
(C) CH2-CHCH2OC2H5 (D) CH2-CHCH2OC2H,

fe Bansal Classes Alcohols & Ethers [13]


Q. 8 Consider the reaction of HI with the following:

0 0
Which forms di-iodide on reaction with HI (excess)?
(A) I and II both (B) II only (C) I only (D)none
Q. 9 Ethanol on reaction with acetic anhydride gives
(A) Acetic ester (B) Formic ester
(C) Ethanoic acid (D) Acetic ester and Ethanoic acid both
Q. 10 Ethanol cannot be dried by anhydrous CaCl, due to formation of the following solvated product
(A) CaCI2-2C2H5OH (B) 2CaCl2-3C,H5OH (C) C a C l ^ C ^ O H (D) CaCl2-C2H5OH
Q.ll Rate of hydration of

will be in order:
(A) I < II < III (B) I < III < II (C) II < I < III (D) III < II < I
Q . 12 The reaction of CH3OC2H5 with HI gives
(A)CH3I ~ (B)C2H5OH (C) CH3I + C2H5OH (D)C2H5I + CH3OH
Q.13 The number of methoxy groups in a compound can be determined by treating it with
(A) HI and AgNO, (B) Sodium carbonate (C) Sodium hydroxide (D) Acetic acid
Q. 14 Most acidic alcohol out of following compounds is
(A) (CH3)3C-OH (B)CH3CH2OH (C)CH3OH (D)PhOH
Q.15 Action ofHN0 2 on CH3NH2 gives following as major product
(A) CH3OH "(B) CH 3 -0-CH 3 (C) CH 3 -0-N=0 (D)CH 3 -N0 2
Q . 16 A compound 'X' with molecular formula C3HgO can be oxidised to a compound' Y' with the molecular
formula C1H602, 'X' is most likely to be
(A) Primary alcohol (B) Secondary alcohol (C) Aldehyde (D) Ketone

Q.17 Diethyl ether and air gives ether hydroperoxide. The mechanism ofthe reaction is
(A) Nucleophilic substitution (B) Free radical addition
(C) Free radical substitution (D) None of the above

Q.18 Ether on carbonylation gives


(A) Alkanoic acid (B)Alkanone (C)Alkylalkanoate (D)Alkanal

Q. 19 I0R - O- R > RI + R'OH true about this mechanism


i
H
(A) SN1 in gas phase (B) SN2 in aqueous phase
(C) both of the above (D) none
Q 20 Phenol with Hinsberg's reagent gives
(A) Sulphone (B) Sulphanilic acid (C) Sulphonic ester (D)Sulphonal
fe Bansal Classes Alcohols & Ethers [13]
0 .21 Select the odd structure out
(A) CH 3 -CH(OH)-CH 2 -CH3 (B) CH r CH(OH)-CH 2 -CH,-CH 3
(C) CH3-CH(OH)-CH3 (D) CH 3 -CH 2 -CH(0H)-C 2 H 5

, KHSO, * LiAlH4
Q.22 Glycerol A
A and B are :
(B) Glyceryl sulphate, acrylic acid
(A) Acrolein, ally! alcohol
(D) Only acrolein (B is not formed)
(C) Ally] alcohol, acrolein
Q 23 An ether is heated with phosphorous penta sulphide to give
(A)Alkanthiol (B) Dialkyl sulphide (C) Hydrogen sulphide (D)Thioester

H+/H2
Q.24 Phenol A >B ^ C
(ii)C02/140C CH3COOH,A
In this reaction, the end product C is:
(A) salicylaldehyde (B) salicylic acid (C) phenyl acetate (D) aspirin

Q.25 In the Liebermann's nitroso reaction changes in the colour of phenol occurs as:
(A) Brown or red-greenish red-deep blue (B) red-deep blue-green
(C) red-green-white (D) white-red-green

Q.26 ^ A. 'A'is

CH2OH CH2OH

(C)
CH,

7 r>cH3 cold v
>A
CrO,
>B
Q.27 I^IJ alkaline K M N 0 4 " ACOH
A and Bare:
.CH, CH,
OH J ^ ^ O L L
(A)
OH'I J=0

CH3 CH3
(C) OH (D) no formation ofA and B
OH ' OH

fa Bansal Classes Alcohols & Ethers [36]


Q.28 B *
NaBH,
r v CH = CH - CHO H2/Pt
>A

A and Bare:

(A) ( V CH 2 CH 2 CH0, ( / - C H = CH-CHJOH

(B) ^ / - CH 2 CH 2 CH 2 OH, J - CH = CH - CH 2 OH

(C) ( JV- CH= <


CH-CH 2 OH in both cases

(D) CH 2 CH 2 CH 2 0H in both cases

CH,
CH,OH h
Q.29 B 4r CH.-C-CH, 2 18 >a
CH,ONa \J " H+
o
A and B are

CH,
l CH, CH, CH,
3 ~ 3

(A)CH,-C-CH, ,CH3-C-CH2 (B) C H 3 - C CH 2 , C H 3 - C - C H 2

18
OH OH OH OCH, OHlgOH OH OCH,

CH, CH, CH, CH,

(C) CH 3 - C - C H , , CH, - C C H , (D) C H , - C C H , , C H , - C CH,

IBOH OH
18 18
0OH OH 3OH OH OCH 3 OH

Q.30 Oxalic acid + A >

henceA ^ B , B i s :

0 = ^
(A) (B) (C)CH2-0-CH2 (D) None

OH OH

fa Bansal Classes Alcohols & Ethers [36]


' CH2CH3 rH=PH_
K
0H

Q.31
CH2CH2OH

Select schemes A, B, C out of


I acid catalysed hydration II HBO !IS oxymercuration-demercuration
(A) I in all cases (B) I, II, III (C) II, III, I (D) III, 1, II

Q 32 Dehydration of the alcohols

-OH
-OH
OH OH
(I) (II) (III) (TV)
will be in order
(A) IV > III > II > I (B) I > II > III > IV (C) IV > II > III > I (D) II > IV > I > III

Mg/ether
Q 33 CI-LMgBr ^ A R > r. H I F,
H,0+

E is

(A) (B) (Q (D)

CH3 CH2I CH, CH,


CH2CH3
OH OH
Et
Q.34 H+ ^ ? Product is:

Me o Ox /Et

(A)

H CI Ale. KOH
Q 35 \ 0 / \ / \ / > Major product is
H
(A) \ 0 / V ^ / \ U
(B) H \ q A A
H
(C) \ 0 / \ / \ (D)
CJ
x r

fa B a n s a l Classes Alcohols & Ethers [36]


o
RMgX
Q.36 ? P r o d u c t Obtained is:
R' H2O

R"

R R' R R

(A)R'-C-CH2OH (B)RCH2-C-0H (C)R'GH2-C-OH (D)R"CH2-C-OH


R" R" R" R'

0 OH

R H I,/NAOH , . . .
Q.37 CH, 2 ^ H+ ^ A ) A, A IS

o o
0 0 II
II
C-OH Cs
~OCH,
(A) <B>pr (C) (D)

CH3
Q.38 (A) < H H 2 SO 4
" * ( B ) A & B are:

\H Of H OCH,
?PH3
yj(
\H CP 3 \H
(A) & (B) &

ch H 3 CO CH3 HO CH 3
H.CO OH OH 3

(C) & CD)" &


H OH MeO CH 3 H 3 CO OH H 3 CO OH

Q.39 OCOCH3 AICI3 > 7 M a j o r P r o d u c t is:

(B) H 3 C O C

()\Or\Oy~OH
COCH,

<!Bansal Classes Alcohols & Ethers m


O-CH2CH=CH2
A
Q.40 Y Q Y ^, ? Product is:

OH OH
/R R\/ /R
(A) (B)
CH2CH=CH2 CH 2 -CH-CH 7

OH
R V A / R
(c) (D) no reaction
iJSiCH2CHCH9
OH
(i)CHCS3+KOH
Q.41 [X] here 'X' is:
OH (ii)CH 2 I 2 +NaOH

OH
(A)
HOOC' ^
j c g f OH X O H C /
\ ^ N
O H

OCH3

(C) l O l / H : (D)
OHC OHC OCH3

/OH OH
Q.42 Inthisdiol
(A) OH at C2 is more basic than that of at C5 (B) OH at C2 is more acidic than at C5.
(C) both have same basicity (D) both have same acidic strength

0H
Q.43 (CH3)2C = C(CH3)2 A ~ >B
H,O

(A) (CH3)2C-C(CH3)2 (B) (CH 3 ) 2 C-C(CH 3 ) 2


I I
O OH CI

(C) (CH 3 ) 2 C-C(CH 3 ) 2 (D) None


I I
OH OH
OH CH 2 -NH,
NaNO,
Q.44 | | >A
HCl

A is
OH CH-,-OH OH CH2-C1 OH CH 2 -NO, Q

(A) (B) ( C ) f l ( D ) f S

i&Bansal Classes Alcohols & Ethers fSJ


Mn0
Q.45 CH 2 =CHCHCH 2 CH 2 OH - -- )A.Ais

OH

(A) CH 2 = CHCCH 2 CH 2 OH (B) CH 2 = CHCHCH 2 CHO

O OH

(C) CH. = CHCCHCHO (D) CH 2 = CHCCH 2 COH


I!
o o

+
^ . HCO,H . H,0 , PthalicAnhydride
Q4b Acetophenone 2
> A 2
>B + C ; > Indicator (D)
C & D are

X K /OH
(A)CH3OH&(^Xc><J (B)PhOH&[0
OPh
II
0

o
OH II
K
(C) PhOH & HO. (D) CH 3 OH & [ O C-CH3
o
C- C-CH3
II
o
V- lo
Q. 47 m-Aminophenol on treatment with NaOH and C 0 2 gives which of the following as major product?
COOH
H, OH f ^ Y H

(A) (B) L J (C) (D)


XOOH ^Y^COOH
COOH NH,
OH

Question No 48 to 50 (3 questions)
500C No reaction

LiAlH 4

NaBH,
COOH

Q.48 Compound 13'is?

(A)' (B) ^ J - C O O H (C) ^ e ^ - C H 2 - O H (D) ( ^ T n j h c i i j

fa Bansal Classes Alcohols & Ethers [36]


Q. 49 Organic compound A does not undergo de carboxylation reaction because?
(A) Intermediate does not follow Saytzeffn rule
(B) Intermediate does not follow Hofmanris rule
(C) Intermediate does not follow Bredict's rule
(D) Intermediate does not follow MarkwoniKoffs rule
Q. 50 Total No. of stereoisomers of B are?
(A) 2 (B)4 (C)3 (D)6

EXERCJSE-I(B)
Q. 1 Compound which gives alcohol on reduction is/are 0 0
II II
(A) Me - C - CI (B) M e - C - N H , (C) M e - C H - C H 2 (D) M e - C - O C - M e
II II "
O o
Q.2 Phenol and ethanol are distinguished by the reaction with
(A) Red litmus (B) NaHCO, (C) FeCl3 (D)NaOH

H2 d l
Q. 3 In the reaction sequence, CaC2 >A ' B C , true about the product C is

(A) give yellow ppt. with NaOI (B) itsfinaloxidation product is carbonyl compound
(C) itsfinaloxidation product is C0 2 and H 2 0 (D) itsfinaloxidation product is CH3COOH

Q.4 Which can be cleaved by HI0 4 ?


0 0 OHO
II II I H
(A) CH3CH2CCH2CCH3 (B) CH3CHCCH2CH3

0 0
(C)
, ,
y / , (
11
(D) CH3CCH2CHCH2CCH3
11

OH 'OH \qh

Q5 HBO, oxymercuration-demercuration and acid catalysed hydration will not give same product in

(B)
O (cO (dO
Q. 6 Diethyl ether reacts with PCP5 to form
(A) Ethyl chloride (B) Phosphorous oxy trichloride
(C) Ethenol (D)Ethene

fe Bansal Classes Alcohols & Ethers [13]


Q.7 Select the correct synthesis products

(D) ( C ^ B r + (CH3)3CONa > (CH3)3CO-^o)

Q.8 The molecules of ether dehydrates in the presence of-


(A)A1 2 0 3 (B)H 3 P0 4 (C)H2S 2 0 7 (D) liq. NH 3

Q.9 Anhydride of alcohol is


(A) Ether (B) Aldehyde
(C) Alkyl hydrogen sulphere (D) Alkene

Q. 10 Lucas test is used to make distinction between 1, 2 and 3 alcohols


R O H + HC1 anhydrous ZnCl 2 > R C j | + H 2 0
c0nc
- White turbidity

This shows that


(A) ROH behaves as a base
(B) greater the value of pKa (alcohol), greater the reactivity with conc. HC1 and thus sooner the formation
ofwhite turbidity.
(C) alcohol which reacts fastest with Na metal, will give turbidity at fastest rate
(D) alcohol which gives red colour during Victor Mayor test, will give turbidity at slower rate then those
giving blue or white colour during Victor Mayor test.

Q. 11 If ethanol dissolves in water, then which of the following would be done


(A) Absorption of heat (B) Emission of heat
(C) Increase in volume (D) Contraction in volume
Q. 12 Which method is useful for the synthesis of ether?

(D) (CH3)3CBr + CH 3 CH 2 ONa

Q.13 Which of the following can react with TsCl


(A) Glycerol (B) Oximinoacetone
(C) Oil ofwintergreen (D) dimethyl amine

(!Bansal Classes Alcohols & Ethers [U]


Q. 14 Which is/are correct statements?
CH3 CH 3
\ / CH3OH
(A) H2S 4
H
/Urn
0 T CH 3

nucleophile attacks here when epoxv linkage is cleaved

CH; CH;
rm
(DJ
\ , \ ~ ~ K/ CH, OH
H | O CH 3

nucleophile attacks here when epoxy linkage is cleaved

O /

(C) This is only affected in reduction to 2 alcohol

O
" H+
(D) R-C^OH + HtO-R

I
These bonds undergo cleavage in the reaction

Q.15 3 -methyl-3 -hexanol can be prepared by


(A) CH3MgI and 3-hexanone, followed by hydrolysis
(B) C2H5MgI and 2-pentanone, followed by hydrolysis
(C) C3H7MgI and 2-butananone, followed by hydrolysis
(D) C4H9MgI and propanone, followed by hydrolysis
Q 16 In which cases product formed are not according to reaction?

(A) ^ ^ - O H + HNO3 h
2s4 >
NO,

0 H
(B) ( ^ y ~ +HN0 3 h
2s4 ? Q-ONO.
(C) CH2 = CH-CHO + LiAlH4 -> CH3 CH,CH2OH

(D) ~ -Cl + CH3ONa > -OCH

Q.17 Dehydration of alcohols take place more rapidly with POCl3 than with H,S0 4 . Select the correct
statement(s) about the following dehydration reaction.

Is. j ) pyridine

(A) It does not involve carbocation. *


(B) It involves R-OPOC1, with - OPOC1, as a better leaving group.
(C) It involves E2 mechanism as pyridine base abstracts proton from the adjacent carbon as the same
time at which - OPOCl2 is leaving.
(D) It is E1 reaction without formation of carbocation.
fa Bansal Classes Alcohols & Ethers [36]
Q.18 Which of the following will get oxidised by Br2 / KOH into carboxylic acid?

(A) CH3-CH2-OH (B) CH - CH3


OH

(C) ( ^ y - C H 2 O H (D) Q S <


CII,

Q. 19 In Kolbe-Schmidt reaction, o-hydroxy benzoic acid is predominantly formed. This is because


(A) salicylate anion is a stronger base than phenoxide ion
(B) salicylate anion is a weaker base than phenoxide ion
(C) p-hydroxy benzoate ion is a stronger base than phenoxide ion
(D) p-hydroxy benzoate ion is a stronger base than salicylate ion

Q. 20 Methanol can be distinguished from ethanol by


(A) Heating with I2 and alkali (B) Treating with schifFs reagent
(C) Treating with Cr03 solution in dil. HjSO,^ (D) Treating with Lucas reagent

Q.21 Products form by following reactions are


OH
A.

CH,

OH OH
OH

CHO
C A ) ^ ( B ) ^ c h o (C) ^ .(D)
CH3 CH3 CH3 CHO CH

Q .22 For the reactions shown below, identify the correct statements) with regard to the products formed:

ph
(i) *>\y0 p (h) ph
^\7
(A) P and Q are identical
(B) P is recemic and Q is optically active
(C) P and Q are positional isomers
(D)hoth are optically active
Tilden NH
Q.23 C,NSNH, > (i) ? > (ii) (iii). The product (iii) can be
reagent HC1

(A) Alcohol ' (B) Ether (C)Alkyl chloride (D) Alkyl nitrite

fe Bansal Classes Alcohols & Ethers [13]


Q 24 Products form during dehydration of following alcohols are

(A)f ] (B)( ) (C)| (D)

Q. 25 Consider the following compound A (below)


.OH
\ /

cy \>H
O
Select the correct statement(s)
(A) It is more acidic than CH3OH (B) It is more acidic than CH 3 COH
(C) It reacts very fast with Lucas reagent (D) It is a diacid base
Q. 2 6 Match the following:
Reaction Mechanism
OH
(A) (P) change in number of carbon in cycle
CH=CH ? "

CH 2 ~OH
(B) OH (Q) Pinacol rearrangement

CH3CH3
3 H
(C) OH > (R) Oxidative bond cleavage
heat

O-CH,

<P) (S) Ketone as product

Q. 27 Match the column:


Column I Column II
(A) Identification of 1, 28c 3 Alcohols (P) Oxymercuration demercuration
(B) Identification of 1, 2& 3 Nitro alkanes (Q) Cu/300 heat
(C) Formation of alcohol by anti Markovnikov's (R) Victor Mayer's test
addition o f H 2 0
(D) Formation of alcahol by Markovnikov's (S) Hydroboration oxidation
addition
(i) Lucas test

& Bansal Classes Alcohols & Ethers [14]


Q.28 Match the column:
Column I Column H
(A) Oxidation of 1 alcohol in aldehyde (P) KMn0 4 /A

(B) Cr0 3 L U .HC1 (Q) Collin's reagent


N'

(C) Cr0 3 .2 (R) Jone's reagent


N
(D) Oxidation of alkene into acid (S) P.C.C

Q.29 Match the products of following: .


Column I Column II

(A) < 0 > 0 - C , 2 ^ 0 > (?) (0>i


(B) Violet color is obtain by the (Q) { o > CH
2 - OH

reaction of neutral FeCl3 with

(C) Reaction ofbenzaldehyde with (R) OH

LiAlH 4 /H 2 0 gives

(D) f n l + K i > ? (S) <OVCH2-I

Q.30 CH, - CH - CH = CH 2 ReageatR^ Alcohol


I
CH 3
which is true about alcohol and R?
Alcohol Reagent
(A) CH , - CH - CH 2 - CH 2 OH B2H6,H202/Na0H
"I
CH,

CH3-CH-CH^CH3
(B) I I PdCl2, H 2 0, 0 2 / LAH
CH 3 OH
OH

(O CH3--C-CH2CH3 Hg(OAc) 2 H^O / NaBH 4

CH 3
OH

(D) CH3-C-CH2CH3 dil. H2S0 4

CH 3

fa Bansal Classes Alcohols & Ethers [36]


EXER CISE-II

Q. 1 What reagents could you use for the following conversions


(a) MeC0(CH 2 ) 0 C0 2 Et -> MeCH0H(CH 2 ) 2 C0 2 Et
(b) H02C(CH2)4"C0Cr-> H02C-(CH2)4CH20H
(c) 0 2 N(CH 2 ) 2 CN -> 0 2 N(CH2) 2 CH 2 NH 2
(d) 0 2 N(CH 2 ) 2 CH = CH2 -> H2N(CH2)2CH=CH2
(e) Me2CHCOCl -> Me 2 CHCHO
(f) 0 2 N(CH 2 ) 3 CH0 0 2 N(CH2) 3 CH 2 OH
(g) 0 2 N(CH 2 ),CH=CH 2 -> 0 2 N(CH 2 ) 3 CH 3

Q.2 Following compounds undergoes reaction with Mn0 2 . What are the products in each case?
(a) CH 3 CH 2 CH=CHCH20H (tyPhCI^OH (c) PhCH(OH)CH 2 CH 2 OH

(d)MeCH=CH(CH 2 ) 3 OH (e) [ ^ > - O H

Q. 3 Carry out the following conversion

/ v C H 0 /CHO
(i) Br
-
MeO'
Acraldehyde Glyceraldehyde
(iii)
Br - CH, CHO Ph CHOH CH2 CHO
O

(iv) CO,Et -CH 2 OH

(v) CH2 - CH2 CHO Glyceraldehyde

CI

Q. 4 Outline a mechanism to account for different isomer formed when Me 2 C CH 2 reacts with CH3 OH
N /
o

in acidic and in basic medium.

Q. 5 Find the structures ofA to F.


mild
D ^ ^ C I L C O J I
C6H120
(A)

Q.6
Product
Explain product formation. How two OH groups behave differently.

Q.7 R2C = O + Et3Al -> C 2 H 4 + R 2 CHO AlEt2


Suggest a mechanism for the reaction.

fa Bansal Classes Alcohols & Ethers [36]


OH

Q.8 TsCl What are A to E?


Pyridine
NaBr
Mg
dry ether D-S2-B
1.CHJCHO
2. HjO

Q. 9 Identify A to E in the Mowing reactions.


H+
(i) Me 2 CO+A Me2C.
\
o-J
MeCHO + HOCH2 CH2 SH

(i)
1.HCO3H
(iv)
2.H20

Q. 10 What are the order of rates of oxidation with HI0 4 ofthe following diols. Explain with reasons.
(a)Me 2 C(0H)C(0H)Me 2 (b) Me2C(OH)CH (OH) Me
(c) CH2(OH) CH2 (OH) (d) Me CH(OH) CH (OH) Me
Q. 11 t- Butanol in presence of fenton's reagent forms 2,5 dimethyl hexane 2,5 diol as one of the product.
Explain with the mechanism.

Q. 12 How you distinguish the following compounds?


(a) t butyl alcohol & n butyl alcohol
(b) ethyl alcohol & n propyl alcohol
(c) allyl alcohol & n propyl alcohol
(d) benzyl methyl ether & benzyl alcohol

Q.13 Differentiate:
(a) 1 -Hexanol and 1 -chlorohexane (b) Diethyl ether and n-butanol
(c) Diethyl ether and n-pentane

Q.14 Explain:
(a) No est erifi cation takes place between ethyl alcohol and excess of sulphuric acid at 170C.
(b) Sodium chloride solution in water is added to decrease the solubility of organic compounds in water.

Q.15 Predict A, B & C.


CH3OH - P+L2
>A +C

Q. 16 Carry out conversion of methyl alcohol into ethyl alcohol and vice versa.

^Bansal Classes Alcohols & Ethers PV


Q.17 Arrange the compounds (i) Ethanol, propane and 1-pentanol, (ii) Butane 1,2,3-pentanetriol and butyl
alcohol, (iii) Pentane, 1 -pentanol and 1 -hexanol, on the basis of (a) in order of increasing boiling points
and (b) in order of increasing solubility in water.

Q.18 Complete the following equations & comment:

(iii) Me2C = CH2 ^ ^ o >?


pressure

Q. 19 Complete the following equations:


(i) n - C3H7 - C02H > n - C4H9OH
H+
(ii) Me2CO + EtMgl ? >?

(iii) EtC02Et + 2MeMgI >? >?


T T
(iv) ^( / /=CHC0 2 Et
/=CHCO,Et T
> ^\ = C^=CHCH T
2OH
Mn0?

Q. 20 t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol. Explain why?

Q. 21 Diethyl ether behaves as base. Why?

Q. 22 What is the significance of proof spirit?

Q. 23 Sodium metal can be used for drying diethyl ether but not for ethanol. Why?

Q.24 Sometimes explosion occurs during distillation of ether sample. Give the reason.

Q. 2 5 Ethyl alcohol is denatured with methyl alcohol. Why?

2 4
Q.26 C2H5I A - >B
Ag20

Q. 27 Ethyl alcohol reacts with HI but not with HCN. Explain why?

Q. 2 8 Write the structure ofthe principal organic product formed in the reaction of 1 -propanol with each of the
following reagents:
(i) Potassium dichromate (K2Cr207) in aqueous sulfuric acid, heat
0
II
(ii) Acetic acid CHXOH in the presence of dissolved hydrogen chloride.

(iii) CH3 y~S0 2 Cl in the presence of pyridine

OO
(iv) C6H5COCC6H5 in the presence of pyridine

fe Bansal Classes Alcohols & Ethers [13]


o

m
(v) Presence pyridine

Q. 29 Complete the following series of equations by writing structural formula for compounds A through I:

NaHC
(a) ^\\ J j// HCl
C C ?HCf J1
5 H 3 ) C H O ^ ^ > C5 H 6 O
\\ // > S 7 ^ 5 8 H2S04,H20

Compound A Compound B Compound C

SOC 2 NaB 4
(b) CH, = CHCH,CH,CHCH, ' > C,H,,C1 ^ > r HXIO " >CH,,(
1 pyridine 5 5 11
I (ii)Zn/H20 ^

OH (D) (E) (F)

(c) ^ ^ N ^ P H > Compound G Compound H > Compound I


* ' ' ' CH,C1,
e.
heat

Q. 3 0 Predict the principal organic product of each of the following reactions. Specify stereochemistry where
appropriate.
/Br
(a) - ^ ( A )
methanol

H;C

CH3 H
(b) I |> + CH 3 ONa >(B)

CH2C6H5

(c) ( VCH-CH2
W V
(d) CH 3 (CH 2 ) 16 CH 2 OTs + CH 3 CH 2 CH 2 CH 2 SNa > (D)

Q. 31 Deduce the identify ofthe missing compounds in the following reaction sequences. Show stereochemistry
in parts (b) through (d).

(a) CH2 = CHCH 2 Br compound A(C4HgO) > compound B(C 4 H g Br 2 0)


(iii)H,0+ g
DC

compound D < compound C (C 4 H 7 BrO)

COoH
(1)
(b) Cl- H 4 > compound E (C3H7C10) K0H H
' 2 > compoundF (C 3 H 6 0)

CH, '

^Bansal Classes Alcohols & Ethers [19]


Q. 3 2 Choose the reaction in each ofthe following pairs that proceeds at the faster rate. Explain your reasoning.
(a) Base-promoted hydrolysis of phenyl acetate or m-nitrophenyl acetate
(b) Base-promoted hydrolysis of m-nitrophenyl acetate or p-nitrophenyl acetate
(c) Reaction of ethyl bromide with phenol or with the sodium salt of phenol.
(d) Reaction of ethylene oxide with the sodium salt of phenol or with the sodium salt of p-nitrophenol
(e) Bromination of phenol or phenyl actetate.
Q. 3 3 Explain why ArOR ethers are cleaved to give RI and ArOH rather than Arl and ROH.
Q.34 Explain the mechanism of following:

(iii)

(iv)
R' R

0-CH 7 -CH=CHR OH CH 2 -CH=CHR


CH=CH-CH 3 CH=C-CH 3

(v)

Me
0 35 Outline a synthesis of each alcohol from the indicated starting materials:
(a) Isopropyl alcohol from a hydrocarbon (b) n-butyl alcohol from acetylene
(c) allyl alcoholfrompropane, and (d) t-butyl alcohol from t-butyl chloride

Q.36 What product is expectedfromthe reaction of (f O with (a) LiAlH4 and (b) H^/Pt

Q.37 Give the product of the reaction ofPhjCHC^OH with HBr and explain its formation.

Q.38 Give the product and write a mechanism for the acid dehydration of cyclobutylcarbinol.

PC 5 KCN
Q.39 C2H5OH ' > (A) - > (B) - ->(C) ->(D) (E)

Q.40 CH3CH2CH20H (A) ->(B) + (C)

fe Bansal Classes Alcohols & Ethers [13]


EXERCISE-III
Q. 1 Compound (A) gives Lucas test within 5 minutes. 6g (A) when reacts with Na, 1120 mL of H2 is
generated at STP. fA) having one oxygen per molecule. What is the structural formula of (A)? Compound
(A) when treated with PBr3 gives (B) which when treated with benzene in presence of anhydrous A1C13
gives (C). What are (B) and (C)?

Q.2 An open chain compound (A) C5HgO is optically active. When (A) is hydrogenated in presence of Pd
as catalyst, it absorbs two moles of F^ per mole of (A) to produce compound (B) C 5 H 12 0 which is
optically inactive. However when (A) is warmed with dilute E^SC^ in presence of HgS04 it gives
compound C(C5H10O2) which is still optically active. C responds to iodoform test. What are the structures
of A to C?

Q .3 An organic compound (A) C10H12O gives red colour when treated with cerric ammonium nitrate & also
decolourises Br2 in CC14 to give B (C10H12OBr2). A can show both geometrical & optical isomerism. A
on treatment with L, & NaOH gives iodoform & an acid (C) after acidification. Give the structures ofA
to C & also the stereoisomers ofA.

Q. 4 A(C7H]4) decolorises Br2 in CC14 reacts with Hg(OAc)2. THF-NaBH4 to form B (resolvable compound)
A C < K M n Q ^ - 3 hexanol
2.Zn/H20
l.B 2 H 6 .THF v
> YMaD
D (isomer ofA) 2 H 0 /0H- E (chiral) ^ > F (chiral carboxylic acid)
1 3
D (isomer ofA) >G< KMn0 4 /alkaline 2 m e t h y l 3 pen tanol
2.Zn/H20
Find out A to G.

Q. 5 Suggest short, efficient reaction sequence suitable for preparing each of the following compounds from
the given starting materials and any necessary organic or inorganic reagents.

(0 CH2OCH3 from - COCH, (ii) frombromobenzene and cyclohexanol

(iii) C6H5CH2CHCH3 frombromobenzene and isopropyl alcohol


I
OH
(iv) CfiH5CH2CH2CH2OCH2CH3frombenzyl alcohol and ethanol.

(v) from 1,3-cyclohexadiene and ethanol

(vi) C6H5CHCH2SCH2CH3fromstyrene and ethanol


I
OH

Q.6 A compound (X) reacts with thionyl chloride to give a compound (Y). (Y) reacts with Mg to form a
Grignard reagent, which is treated with acetone and the product is hydrolysed to give 2-methyl-2-butanol.
What are structural formulae of (X) and (Y)?

fe Bansal Classes Alcohols & Ethers [13]


Q. 7 The compound (D) reacts with BH3- Tetrahydrofuran and then alkaline H 2 0 2 to give chiral (E). Oxidation
of (E) with KMn04 (acidified) gives a chiral carboxylic acid (F). Ozonolysis of 'D' gives after reduction
with Zn the same compound (G), which is obtained by oxidation of 2-methyl-3 -pentanol with acidified
KMn04. Identify (D), (E), (F) and (G).

Q. 8 An organic compound (A) contains 60.12% Carbon, 13.13% Hydrogen and has vapour density 3 0. On
oxidation it gives (B) C 3 H 6 0 which on further oxidation by NaOH +12 produces a salt of the acid (C)
C2H402. When (B) is treated with hydroxyl amine, a compound of molecular formula C3H7NO (D) is
formed. What are (A), (B),(C) and (D)?

Q. 9 Compound (A) C 4 H |0 O reacts rapidly with metallic sodium, but undergos almost no reaction with
Lucas reagent. When (A) is treated with hot concentrated sulphuric acid, a new compound (B) C4H8 is
formed. If C4Hg is hydrated with sulphuric acid a new compound (C) C4H9OH is formed, which is
almost inert to metallic sodium but reacts rapidly with Lucas reagent. What are (A), (B) and (C)?

Q. 10 A compound (X) containing C, H and 0 is unreactive towards sodium. It does not add bromine. It does
also not react with Schiffs reagent. On refluxing with an excess ofHI, (X) gives only (Y). (Y) on hydrolysis
gives (Z) which can be converted to (Y) by the action of P +12, Compound (Z) on oxidation gives an
acid of equivalent weight 60. What are (X), (Y) and (Z)?

Q. 11 A compound (A) C ; H lf) n^ yields on acetylation (B) of formula C12H1808. How many hydroxyl groups
are present in compound? A l s o write structures of (A) and (B).

Q. 12 An optically active alcohol (A) (C6H10G) 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 Cr0 3 and does
not show any optical activity. Deduce the structures of (A) and (B).

Q.13 An unsaturated hydrocarbon (A) on hydration gave alcohol (B). Oxidation of (B) gave a ketone (C).
When the hydrocarbon (A) was submitted to ozonolysis it gave formaldehyde and acetaldehyde. What
one formula would you assign to A, B and C? Give the reactions involved.

Q. 14 Compound (A) reacts with sodium to liberate H2 forming a compound (B). When (A) is treated with
HC1 + ZnCl2, an immediate reaction takes place liberating (C). When (A) is heated with H2S04, (D) is
formed. Ozonolysis of (D) gives a three carbon ketone and another isomeric compound. What are (A),
(B), (C) and (D) ?

Q.15 An organic compound (A) (C4H]0O) reacts with HI giving a compound (B) (C4Hgl) which on reduction
gives a normat hydrocarbon having four carbon atoms. On oxidation A gives compound (C) (C4HgO)
and then an acid (D) (C4H802). Deduce th structures of, B, C and D giving reasons.

Q. 16 An organic compound (A) gives hydrogen on reacting with sodium. It also gives iodoform test and forms
an aldehyde of molecular formula (B) (C2H40) on oxidation. Name the compound (A) and (B).

Q.17 An organic compound (X) on analysis gives 24.24% C, 4.04%H. Further sodium extract of 1.0 g of (X)
gives 2.90 g ofAgCl with acidified AgNO, solution. The compound (X) may be represented by two
isomeric structures (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy compound,
while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z).

fe Bansal Classes Alcohols & Ethers [13]


Q.18 Compound (X) (C5HgO) does not react appreciably with Lucas reagent at room temperature but gives
a precipitate with ammonical silver nitrate. With excess ofMeMgBr, 0.42 g of (X) gives 224 ml CH4 at
STP. Treatment of (X) with H2 in presence of Pt catalyst followed by boiling with excess HI gives
n-pentane. Suggest structure for (X) and write the equations involved.

Q. 19 An alcohol (A) when heated with concentrated H^SC^ gives an alkene (B). When (B) is bubbled through
bromine water and the product obtained is dehydrohalogenated with excess of sodamide, a new
compound (C) is obtained. The compound (C) give (D) when treated with dilute H^SC^ in presence of
HgS04. (D) can also be obtained either by oxidising (A) with KMn04 orfromacetic acid through its
calcium salt. Identify (A), (B), (C) and (D).

Q. 20 Compound (A) contains only carbon and hydrogen. It decolorizes bromine in CC14 solution and reacts
slowly with concentrated HjSO^ Compound (A) reacts withHBr to form (B). (B) reacts with NaOH
to form (C). (C) on oxidation gave hexanone-3. Write structures of (A), (B) and (C).

Q. 21 A hydrocarbon (A) (molecular formula C5HJ0) yield 2-methylbutane on catalytic hydrogenation. (A)
adds HBr in accordance with Markownikoff s rule to form a compound (B), which on reaction with
silver hydroxide forms an alcohol (C) C5H120. Alcohol (C) on oxidation gives a ketone (D). Deduce
(A) to (D) and give the reactions involved.

Q.22 (A) (Vb ) ._JiM_> ( c) (^-Wk^A)


' 250C > (ii)AgOH ' 150C V
' (ii)H202,0H- '

In the above reactions scheme (A) and (C) are isomers. (B) has a formula of C5H10. (C) Can also be
obtained from the product of the reactions of CH3CH2MgBr and (CH3)2CO. Give structures of (A),
(B)and(C).

fe Bansal Classes Alcohols & Ethers [13]


EXERCISE-IV (A)

Q.l l O j + C0 2 > x -J*"-* T c n n H ; The product X in the reaction is:

[REE 1990]

w(OJ <B)(OJ (O^J (D)glC00Ni

Q.2 The products of combustion of an aliphatic thiol (RSH) at 298 K are: [JEE 1992J
(A) C02(/), H 2 0 (g) and S02(g) (B) C02(g), H 2 0 (g) and S0 2 (g)
(C) CO2(l), H 2 0 (I) and S0 2 (g) (D) C02(g), H^O (I) and S02(/)

Q. 3 An organic compound C 3 H 6 0 does not give aprecipitate with 2,4-dinitrophenyl hydrazine reagent and
does not react with sodium metal. It could be: [JEE 1993]
(A) CH3-CH2-CHO (B) CH3-CO-CH3 (C) CH2=CH-CH2OH (D) CH2= CH-OCH3

Q .4 The reaction products of C6H5OCH3 + HI A > are: [JEE 1995]


(A) C6H5OH + CH3I (B) C6H5I + CH3OH (C) C6H5CH3 + HOI (D) C6H6 + CH3OI

Q5 The order of reactivity of the following alcohols: [JEE 1997]


CH 3 CH 3
CH 3 / V CH3

F o nI 0 H
Y
OH
Ph
(IV)
OH
U) (II) an)
towards conc. HClis:
(A) 1 > II > III > IV (B) I > III > II > IV (C) IV > III > II > 1 (D) IV > II > III > I

Q.6 .Among the following compounds, the strongest acid is: [JEE 1998]
(A) HC=CH (B)C6H6 (C) C2H6 (D) CH,OH

Q.7 Benzenediazonium cliloride on reaction with phenol in weakly basic medium gives: * [JEE 1998]
(A) Diphenyl ether (B) p-hydrooxyazobenzene
(C) Chlorobenzene (D) Benzene

Q. 8 Which one of the following will most readily be dehydrated in acidic condition: [JEE 2000]
O O
0 OH OH A
X
/
AA V \
cb) A / V \
YX
0 H 0 H

Q.9 1 -propanol & 2-propanol can be best distinguished by: [JEE2001]


(A) Oxidation with alkaline KMn04 followed by reaction with Fehling solution
(B) Oxidation with acedic dichromate followed by reaction with Fehling solution
(C) Oxidation by heating with copper followed by reaction with Fehling solution
(D) Oxidation with concentrated H 2 S0 4followedby reaction with Fehling

fe Bansal Classes Alcohols & Ethers [13]


Q. 10 Identify the correct order ofboiling point ofthe following compounds: [JEE 2002]
CH 3 CH 2 CH 2 CH 2 OH CH 3 CH 2 CH 2 CHO CH 3 CH 2 CH 2 COOH
1 2 3
(A) 1 > 2 > 3 (B) 3 > 1 > 2 (C) 1 > 3 > 2 (D)3>2>1

O Na+(excess)
Q.ll < O ^ O H + C2H5I ^ [JEE 2003]
; OH(anhydrous)

(A) < 0 } - O C 2 H 5 < B ) @ - I (C)C 6 H 5 OC 6 H 5 (D)C 2 H 5 OC 2 H 5

Q. 12 Reaction of entainomerically pure acid with 1 chiral carbon and racemic alcohol with 1 chiral carbon
gives an ester which is: [JEE 2003]
(A) Meso (B) Optically active mixture
(C) Racemic mixture (D) Enantionmerically pure

Q.13 On acid catalysed hydration, 2-phenyl propene gives: [JEE 2004]


(A) 3-phenyl-2-propanol (B) 2-phenyl-1 -propanol
(C) 1 -phenyl-3 -propanol (D) 2-phenyl-2-propanol

Q. 14 Phenyl magnesium bromide reacting with t-Butyl alcohol gives [JEE 2005]
CH, /CH3
(A) Ph - OH (B) P h - H (C) Ph-0-C~C:H 3 ( D ) PI1-C-CH3
CH \ CH,

Q.15 Which is the best reagent to convert cyclohexanol into cyclohexene. [JEE 2005]
(A) conc. HC1 (B)conc.HBr (C) conc. H 3 P0 4 (D)HCl + ZnCl2

CH3H CH 3

Q. 16 Compound (X) C H 3 0 - < ^ O y > is reacted with aqueous acetone it gives

H CI CH 3
following products:

CH3H CH 3 CH3H CH 3

CH3O-<O) -<Q>NO2(K) CH 3 O-^> -^(O)-N02(L)

H OHCH 3 OH H CH 3

CH3H CH 3

CH 3 O- -N0 2 (M)

H CH 3 OH

(A) K, L (B) K, M (C) L only (D) M only [JEE 2005]


^Bansal Classes Alcohols & Ethers [25]
Q 17 + CI - CH 2 CH 2 - CH 3 ^ ^ > Q + Phenol [JEE 2006]

The major products P and Q are

(A)j^andCH3CH2CHO (B) j ^ j and CH3COCH3

(C)fSandCH3COCH3 (D) f S and CH3CH2CHO

I
i
1I

i
i
i

I ]
! i

feBansal Classes Alcohols & Ethers

I
EXER CISE-IV (B)
OA When t-butanol and n-butanol are separately treated with a few drops of dilute KMn04 in one case
only, purple colour disappears and a brown precipitate is formed. Which of the two alcohols gives the
above reaction and what is the brown precipitate? [JEE 1994]
(XZ 3,3-Dimethylbutan-2-ol losses a molecule of water in the presence of a concentrated sulphuric acid to
^ give tetramethyl ethylene as a major product. Suggest a suitable mechanism. [JEE 1996]

Q.3 A compound D (CgH10O) upon treatment with alkaline solution ofiodine gives a yellow precipitate. The
filtrate on acidification gives a white solid (E) (C7H602). Write the structures of (D) and (E) and explain
the formation of (E). [JEE 1996]
Q. 4 Which of the following is the correct method for synthesising methyl-t-butyl ether and why?
(i) (CH3)3CBr + NaOMe > (ii) CH3Br + tert-BuONa > [JEE 1997]

O = C-OH HOCH2
Q.5 I + I [JEE 1997]
O = C-OH HOCH2

Qj / Discuss why o-hydroxy benzaldehyde is a liquid at room temperature while p-hydroxy benzaldehyde is
a high melting solid? [JEE 1999]

Q.7 White the structures of the product A&B [JEE 2000]


CH
n
3 - C - 0u1 8 C H
^ ^2 5 n
h
3
2
>. A+B
O
Q.8 Cyclobutyl bromide on treatment with magnesium in dry ether forms an organometallic A. The
organometallic reacts with ethanal to give an alcohol B after mild acidification. Prolonged treatment of
alcohol B with an equivalent amount ofHBr gives 1 -bromo-1 -methylcyclopentane (C). Write the structures
ofA, Band explain how C is obtained from B. [JEE 2001]

Q. 9 Identify X, Y and Z in the following synthetic scheme and write their structure. Explain the formation of
labelled formaldehyde (H2C*0) as one of the products when compound Z is treated with HBr and
subsequently ozonolysed. Mark the C* carbon in the entire scheme. [JEE 2001]
BaC*03 + H 2 S0 4 > X (gas) [C* denotes C14]
CH2 - CH - Br ^ M * /ether >y LlAm
-* >Z
(ii)X,(iii)H,0+

Q.10 Mention two esters produced when a racemic mixture of 2-phenyl propanoic acid is treated with (+)
2-butanol. What is the stereochemical relationship between these esters? [JEE 2003]
Q. 11 An organic compound P(C5H10O) Reacts 1015 times faster then ethylene with dil.H2S04 to give two
products Q and R. Both Q and R give positive iodoform test. Identify P, Q and R and also give reason
for very high reactivity of P. [JEE 2004]

Q. 12 (X) C5H!3N NaNo 2 ,HCi > (Y) (Tertiary alcohol + other products)
-N2
(Optically active)
Find X and Y. Is Y optically active? Write the intermediate steps. [JEE 2005]

fe Bansal Classes Alcohols & Ethers [13]


ANSWER KEY
EXER CISE-I(A)

Q.I- B Q.2 A Q3 C Q.4 B Q.5 B Q.6 D Q.7 D


Q.8 C Q.9 D Q.10 c Q.ll A Q. 12 C Q.13 A Q.14 C
Q.15 B Q. 16 A Q.17 B Q.18 C Q. 19 D Q.20 C Q.21 D
Q.22 A Q.23 B Q.24 D Q.25 A Q.26 B Q.27 A Q.28 B
Q.29 A Q.30 A Q.31 C Q.32 C Q.33 D Q.34 D Q.35 D
Q.36 B Q.37 A Q.38 B Q.39 A Q.40 A Q.41 C Q.42 A
Q.43 A Q.44 D Q.45 A Q.46 C Q.47 C Q.48 C Q.49 C
Q.50 A

EXER CISE-I (B)

Q.l A,C,D Q.2 C Q.3 A,C Q.4 B


Q.5 A, B,D Q.6 A,B Q.7 A,B,C Q.8 A,B,C
Q.9 A,D Q.10 A,B,D Q.ll A,C Q.12 A,B,C
Q.13 A,B,C,D Q.14 AB,C,D Q.15 A,B,C Q.16 A,C,D
Q.17 A,B,C Q.18 A,B Q.19 Q.20 A
Q.21 A,C Q.22 C,D Q.23 A,B,C,D Q.24 A,B,C,D
Q.25 A,B Q.26 (A) P, Q, S; (B) R,S; (C) P ; (D) S
Q.27 (A) Q,R,T, (B) R, (C) S, (D) P Q.28 (A) Q,R,S (B) S (C) Q (D) P
Q.29 (A) R, S; (B) R; (C) Q; (D) P Q.30 A,B,D

EXER CISE-II

O
Ii
Q2 (a) Et-CH=CH-CHO (b) Ph-CHO (c) Ph - C - CH 2 - CH 2 - CH

(d) No reaction (e)

OCH3 OCH 3

Q. 4 In acidic medium Me 2 - C - CH 2 and In basic medium Me 2 C - CH 2

OH O

Q.5 (A) CH3-C-O-C-C-C-C, (B) C H r C H 2 O H , (C) CH3-CH2-CH2-CH2-OH,

O OH O
II i II
(D) C H , - 0 - H , ( E ) CH3- CH - C H - C H O (F) CH - C H = C H - C - H

faBansal Classes Alcohols & Ethers [28]


Q.9 (A) = C H 2 - O H

I
CH 2 -OH
Q.10 a > b > d > c
Q. 12 (a) Lucas reagent (b) Iodoform (c) PBr3 & AgN03 (d)Na
Q. 13 (a) 1-hexanol reduces organ red Cr0 3 to greenCr3^ while 1-chlorohexane gives white ppt. ofAgCl on
warming with ethanolicAgN03. \
(b) n-Butanol gives a positive test with Cr0 3 in acid and evolves H2 with sodium: while dry ethyl etheris
negative to both tests
(c) Unlike n-pentane, diethyl ether is basic and dissolves in conc. f^SC^
(C2H5)20 + H ^ > (C2H5)2OH++ HSO"
Q.14 (a) Ethyl alcoholfirstreacts with sulphuric acid to form ethyl hydrogen sulphate which readily lo ses a
molecule of sulphuric acid when heated with concentrated sulphuric acid at 170C to form ethylene,
(b) When sodium chloride is dissolved in water it reduces the polarity ofwater the space between water
molecuules are occupied by sodium and chloride ions with the result the solubilty ofthe organic compound
is reduced.
Q.15 CH3I, CH 3 -0-CH 3 , CH3I
Q.16 CH 3 OH p+12
) CH,I KCN ? CH 3 CN reduction ) CH 3 CH 2 NH 2 HONO ?

Methanol

CH3CH2OH _JO)_> CH3CQOH


Ethylamine Ethano!

C1
CH3OH ( KOH(aq.) CHGCL ( 2 ' CH,
Q.17 (a) In order of increasing boiling points:
(I) Propane < Ethanol <Pentanol-l
(ii) Butane < Butyl alcohol <1,2,3-Pentanetriol
(iii) Pentane < 1 -Pentanol < 1 -Hexanol
The explanion is based on molecular weight and hydrogen bonding
(b) In order ofincreasing solubility in water:
(i) Propane < Pentanol-1 <Ethanol
(ii) Butane < butyl alcohol < 1,2,3-Pentanetriol
(iii) Pentane < 1 -Hexanol < 1 -Pentanol
The explanation is based on hydrogen bonding

fe Bansal Classes Alcohols & Ethers [13]


Q.18 (i) MeOEt + HI ^ lMe^O-Et > Mel + EtOH > EtI
The reaction is SN2 the smaller group forms the iodide (steric effect) & stops at thefirststage in the cold.
When heated, the reaction proceeds to the second stage.
(ii) Et 2 0 N o reaction as there is no active H in the compound.
H
h s h Me3C H
(iii)
W
Me, = CH, 2 4- 2 > M e 3C + > Me 3 C-0-CMe 3 "H+ >Me3 3C-0-CMe33
pressure Pressure +

Q. 19 (i) n - C3H7C02H > n - C4H9OH


orB2H6

/OMgl H+
(ii) Me2CO + EtMgl >M 2 C<^ E t > MeXCOH)Et

IMgOx / M e
(iii) EtC02Et + 2MeMgI > C "2 ) EtCMe2OH
EtX XMe
CHC0
(iv) 2Et LiA1H4
>^^CHC^OH Mn 2
> (^^CHCHO
Q. 20 The +I.E. of three methyl groups on central C-atom oftert-butyl alcohol makes is partially negative with
the result that it pushes the electron pair of -OH bond towards H-atom and thus H-atom is not replaced
easily.
CH3 h
^ - 5 + 0 I ' -6 +8
CH3"^ C H CH 3 -CH 2 -CH 2 -> C 0-- H
t I
CH3 H
(less partial +ve charge) (more partial +ve charge)
Q.21 Oxygen atom in diethyl ether molecule has two lone pair of electrons available for co-ordination. Therefore
ethers behave as Lewis base forming oxonium salts.

r ^ > 0 : + HC1 > f^OH+Cl- (dialkyl oxonium chloride)


Q.22 Proof spirit is a technical term representing 57.1 % by volume ethanol-water mixture for the purpose of
tax lavied on its production. The percentage represents the weakest possible percentage which allows
the gun powder to catch fire.
Q. 23 Sodium metal reacts with ethanol to form sodium ethoxide ion because of active H atom in ethanol. Ether
do not have such active H and thus can be dried by sodium
1
C2H5OH + Na > C2H5ONa + - H 2
Q.24 Due to the formation of explosive peroxide by oxidation.

Q.25 Addition of methyl alcohol or naphtha or pyridine is made into ethyl alcohol to make sure that it will not
be used for bevarage purposes. This process is known as denaturation of alcohol.

^Bansal Classes Alcohols & Ethers [30J


Q.26 C2H5OH, C 2 H 5 HS0 4 , C 2 H 5 - 0-C 2 H 5

Q.27 Ethanol being very weak Lewis base and thus reacts with stronger acid HI

Q.28 (i) CH3CH2COOH (ii) CH3COOCH2CH2CH3 (iii) MePhS020CH2CH2CH3


O
-CH 2 CH 2 CH 3
(iv) PhCOOH + PhCOOCH2CH2CH3 (v)

OH
Q.29 (A)\^J ( B ) ^ (c)
CJ
(D) CH2 = CH-CH2(C1) - CH3 (E) CH3CH(C1)CH2CH2CH0

(F) CH3-CH(C1) CH2CH2CH2OH

CH?OH

Br
NFL OMe
Q.30 (a)[Ol r 2 (b) (c)Ph-CH(Cl)-CH2OH
CH2Ph
Me' t)H OH
(d) H 3 C-CH 2 -CH 2 -CH 2 -S-CH 2 -(CH 2 ) 16 -CH 3

Q.31 (A) CH 2 =CH-CH 2 -CH 2 OH (B) Bi-CH2CH(Br)CH2CH2OH


Br CH 2 OH

Q
(C)
CI| H ( F ) Me-CH-CH 2
0 Me O

Q. 3 2 (a) m-nitrophenyl acetate (better leaving group)(b) p-nitrophenyl acetate (better leaving group)
(c) sodium salt of phenol (better nucleophile) (d) sodium salt ofphenol (better nucleophile)
(e) Phenol (more activated aromatic ring.)
Q.33 S n 2 attack on a carbon of a benzene ring does not occur nor does the high energy C6H5+ form by an
SN1 reaction. Hence ARL cannot be a product even in an excess of conc. HI

Q.36 (a) (b) 0 < H

Ph
I
Q 37 Ph - C - CH3
I
Br
fe Bansal Classes Alcohols & Ethers [13]
r
Q 38 V-Cli-,OH ^" / v
> - H 2 Q H

Q.39 (A) C2H5C1; (B) C2HSCN; (C) C2H5COOH; (D) C2H5COONH4


(E) C2H5CONH2
Q.40 (A)C3H7Br; (B) CH3CH=CH, (C) CH3CHBrCH3 (D) CH3CHNH2CH3

EXER CISE-III
OH

Q.l A: CH3 - CH - CPI3

H H H O
! I I I!

Q.2 (A) C - C - C - C = C (B) C - C - C - C - C (C) C - C - C - C - C

OH OH OH
OH Br OH O
Q3 (A) Ph - CH = CH - CH - CH 3 , (B) Ph - CH - CH - CH - CH 3 , (C) P h - C H = C H - C - O - H

Br

CH2 CH3 0
1! I II
Q4 (A) C - C - C - C - C - C , (B) C H 3 - C H 2 - C - C H 2 - C H 2 - C H 3 , ( C ) C-C-C-C-C-C

OH

CH2 CH3

(D) Et - CH - CH2 - CH = CH 2 , (E) Et - CH - CH2 - CH2 - OH, (F) Et - C H - C H 2 - C 0 2 H

CH 3

CH, CH, CO C
I II I .11 I
(D) CH3 - CH - CH - CH2 - CH 3 , (G) C - C - C - C - C , C - C - C - C - C -
OH
Q.6 C2H5OH C2H5C1
Ethyl alcohol Ethyl chloride
(X) (Y)

(!lBansal Classes Alcohols & Ethers [32]


H

Q.7 C H 3 - C H - C = CH 2 CH3-CH-C-CH2OH

CH 3 C 2 H 5 CH 3 C 2 H 5
(DJ (E)
H

CH3-CH-C-COOH CH, - CH - C = O

CH 3 C 2 HJ CH 3 C 2 H 5
(F) (G)
Q.8 (CH 3 ) 2 CHOH; CH 3 COCH 3 ; CH 3 COOH; CHGCCHG

NOH
(A) (B) (C) (D)

Q.9 (CH 3 ) 2 CHCH 2 0H; (CH^C-CH^ (CH 3 ) 3 COH


(A) (B) (C)

Q.10 C 2 H 5 OC 2 H 5 ; C 2 H 5 I; C 2 H 5 OH
(X) (Y) (Z)

Q.ll Four OH groups are present in compound A.


CH 2 OCOCH 3

CHOCOCH,
CH 2 CH CH CH 2
CHOCOCH,
OH OH OH OH
(A) CH 2 OCOCH 3
(B)
C2H5
Q. 12 C2H5
H X - C - C = CH
CH 3 CCH 2 CH 3
OH
(A) OH
n(B)

Q.13 CH 3 H CH 3 CH CH 3 CH 3 C CH 3
7
Vc OH o
H / \ H (B) (C)
(A)

fa Bansal Classes Alcohols & Ethers [36]


Q.14 CH 3 CH 2 CH 2 C(CH 3 ) 2 CH 3 CH 2 CH 2 C(CH 3 ) 2 CH 3 CH 2 CH 2 C(CH 3 ) 2
CI
OH ONa
(B) (C)
(A)
CH 3 CH 2 CH = C(CH 3 ) 2
(D)

Q.15 (A) CH 3 CH 2 CH 2 CH 2 0H (B) CH 3 CH 2 CH 2 CH 2 1


(C) CH 3 CH 2 CH 2 CHO (D) CH 3 CH 2 CH 2 COOH

Q. 16 (A) CH 3 CH 2 0H (B)CH 3 CHO

Q. 17 (X)C 2 H 4 C1 2 (Y)C1CH2CH2C1 (Z)CH 3 CHC1 2

Q.18 CH 2 CH 2 CH 2 C = CH
i
OH
(X)Pent 4-yn-l-ol

CH,
Q.19 (A) \CHOH (B) CH 3 -CH=CH 2 (C) C H . C . C H (D) CH 3 COCH 3
C H /
+1IBR
Q 20 CH 3 -CH 2 -CH=CH-CH 2 -CH 3 > CH 3 - CH 2 - CH 2 - CH - CH 2 - CH 3

Br

(A) (B)
CH 3 - CH 2 - CH 2 - CH - CH 2 - CH 3

OH
(C)

Q.21 (A) CH 2 =CH-CH(CH 3 ) 2 (B) C H 3 - C H - H C ( C H 3 ) 2

Br
(C) C H 3 - C H C H ( C H 3 ) 2 (D) CH 3 CO CH(CH 3 ) 2
I
OH

OH

Q.22 (A)HO-C-C-C-C (B) C = C ' - C - C (C)C-C-C-C

Alcohols & Ethers [36]


faBansal Classes
EXERCISE-IV (A)

Q.l D Q.2 B Q.3 D Q.4 A Q.5 C


Q.6 D Q.7 B Q.8 A Q.9 C Q.10 B
Q.ll D Q. 12 B Q.13 D Q.14 B Q.15 C
Q.16 A
EXERCISE-IV (B)
Q.l n-butanol is oxidised by KMn0 4 and not t-butanol as the latter does not contain H atom attached to
carbinol carbon atom.

CHjCHjCHjCHjOH + KMn0 4 -> CH,CH 2 CH 2 COOOK + Mn0 2 + KOH


n-Butanol Brown

CH 3

CH3-C-CH3 +KMn04 > No reaction

OH
t-Butanol

H Me H Me Me
j |
H+ H
-> C H 3 - C C - C H 3 - 2 > C H 3 - C H - C - C H 3
Q.2 CH3-C C-CH3-
1 1
Me
:OH Me HIOH Me
1,2-methyl shift

Me Me
-H+
C H 3 - C = C - C H 3 <- CH, - CH - C - CH,
i | + J
Me Me

Q.3 (D) Ph - CH - CH 3 (E) C fi H,COOH

OH

Q. 4 The ether formation involves nucleophilic substitution of alkoxide ion for halide ion.

R'0~+R-X a
R'0~+R
Slow
->R' 0 R X - ^ R ' - O - R + X-
3 alkyl halide can also involve elimination ofHX to give alkene in the presence of a base. So, it is better
to start with 3 alkoxide and 1 alkyl halide, i.e., equation (b)

Q.5
X Q.6 Due to intermolecular H-Bonding

Q.7 A = C H 3 - C - 0 H , B = C2H5018H

fa Bansal Classes Alcohols & Ethers [36]


Br Br Me
MgBr BrMgOCHMe HOCHMe
Q.8 Mg MeCHO . H,0

(A) (B) (C)


Mechanism
H-,0 CHMe CHMe
HOCHMe

Br
^ y / M e Me
Br~

2carbonium 3 carbonium

Q.9 X : C O , ; Y : C H , = C H - C O O H ; Z : CH,2 = C H C H -2O H ; C H , 0 RCT+RQC

Ph H (+)CH 3 CH 2 -C-OH

CH3
Q.10 CH 3 - C - COOH + CH 3 - C - COOH
conc. H,SO a , A
H Ph

(recemic mixture)

Ph H H H

CH, - C - C - O - C - CH 2 CH 3 + CH 3 - C - C - O - C - CH 2 CH 3

H O CH 3 Ph O CH,

during esterification reaction only - COOH and - OH participates. There is no effect on structure of
configuration of carbon adjacent of these groups. So when () acid reacts with pure (+) alcohol two
esters are produced whine are diastereoisomers of each other.

CH,

Q.ll P: C H 3 - C H 2 - 0 - C - C H 3
Q : CH 3 CH 2 OH
R: C H 3 - C - C H 3

when ethylene reacts with dil. H 2 S0 4 CH 3 CH 2 is produced during rate determining step, whereas P
gives resonance stabilized intermediate.

CH, CH,

CH3-CH2-O-C-CH3 C H 3 ~ C H 2 - O = C~CH3

due to extra stability of intermediate the rate of reaction is very fast

fa Bansal Classes Alcohols & Ethers [36]