Alcohol, Phenol & Ether - Chemistry

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SUBJECT CHEMISTRY TOPIC ALCOHOL, PHENOL AND ETHER COURSE CODE AISM-09/C/APE Trans Web Educational Services Pvt. Ltd
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Contents :- ALCOHOL, PHENOL AND ETHER

Introduction, Aliphatic hydroxyl compound3 Preparation of Alcohols..5 Physical properties, chemical properties .15 Periodate oxidation..28 Pinacol, pinacol- rearrangement 30 Ether ..34 Preparation of ethers..35 Properties of ether.39 Chemical reaction ..40 Phenol.47 Physical properties ...50 Chemical properties..52 Mercuration59 Answers to exercises.82 Miscelleneous exercises.90 Solved problems..98 IIT level questions..102 Objective problems..109 Fill in the blanks117 Assignment problems..122
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ALCOHOL, PHENOL, ETHER

INTRODUCTION Hydroxy compound can be classified in the following three categories. Aliphatic hydroxy compound Monohydric i.e.
H H C H H C H OH Contain only one - OH group
Dihydric
H HO C H
Polyhydric
H C H OH Contain tw o - OH group
H H C OH
H C OH
H C OH H

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Contain three and more than three hydroxyl group. Monohydric alcohols are of three types.
Monohydric Alcohols
Primary or 10 R CH 2OH
Secondary or 20 OH R C H R
Tertiary or 30 Alcohol OH R C R R
Illustration 1: Classify the following into primary, secondary and tertiary alcohols:
CH3 OH
OH H3C
HO
(a) Solution: (a) Tertiary, (b)
(b)
(c)
Secondary,
(c)
Tertiary

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PREPARATION OF ALCOHOLS 1. From Alkanes
Alkanes having tertiary carbon on oxidation with cold alkaline KMnO 4 give tertiary alcohol.
H R C R R KMnO 4/OH R OH C R R
2.
From Alkenes Alkenes can be converted into alcohol by the following reactions:

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OH HOH/H 2SO 4 R CH OH (i) Conc. H 2SO 4 (ii) HOH OH R CH CH2 (i) Hg(OCOCH (ii) NaBH
4 3)2/HOH
CH 3
CH
CH 3
CH
CH 3
(i) BH 3/THF (ii) H 2O 2/OH CO H2 Co(CO)

4
CH 2
CH 2OH
(anti markonikov's product) R CH 2 CH 2 H2/Pt R CH 2CH 2CH 2OH CHO
[Oxo process]
3.
From alkyl halides Alkyl halides give alcohol with KOH/NaOH or with moist Ag 2O.
HOH/NaOH R X moist Ag 2O R OH
OH
4.
Reduction of aldehydes and ketones Trans Web Educational Services Pvt. Ltd
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(a)
Reduction by reducing agents (i) Aldehyde gives primary alcohol

O R C H [H] Reducing agent R CH 2OH
(ii)
Ketone gives secondary alcohol
O R C R [H] Reducing agent R
OH CH R
Reducing agents (i) (ii) (iii) (iv) (v) (vi) LiAlH4 NaBH4 Na/C2H5OH Metal (Zn, Fe or Sn)/Acid (HCl, dil H2SO4 or CH3COOH) (a) Aluminium isopropoxide/isopropylalcohol, (b) H2O H2/Ni Trans Web Educational Services Pvt. Ltd
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NaBH4 and aluminium isopropoxide reduces only carbonyl group and has no effect on any other group.
CH3
CH
CH CHO
NaBH4
CH3
CH
CH CH2OH
Reduction
with
aluminium
isopropoxide
is
known
as
MeerweinPonndorf Verley (MPV) reduction. LiAlH4 has no effect on double and triple bonds but if compound is - aryl, , - unsaturated carbonyl compound then double bond also undergoes reduction.
O H2C CH C CH3 LiAlH 4 H3C CH 2 OH CH CH3
H5C6
CH
CH
CHO
LiAlH4
H5C6
CH2
CH2 CH2OH
(b)
Reduction by Grignard reagents
Addition followed by hydrolysis

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O H C H R O C H MgX H H2O/H R OH C H 10 alcohol O R Mg X R' C H R H Mg OH X
OMgX C R' H H2O/H R
OH C R' 20 alcohol H Mg
OH
O OMgX R' C R'' R C R' R'' H2O/H R OH C R'' 30 alcohol R' Mg OH X
Methanol cannot be prepared by this method. 5. Reduction of carboxylic acid, Acid chlorides and esters: (a) Reduction by LiAlH4
O R C G LiAlH 4 R CH 2OH H G
G = OH (acid)

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G = Cl (acid chloride) G = OR (ester) (b) Reduction by BH3
Carboxylic acids and esters are reduced in to primary alcohol by BH 3.
O R C
O R C O R'
i BH3 / THF ii H2O/H
OH
i BH3 / THF ii H2 O / H
RCH 2OH
CH 2OH R'OH
(c)
Bouveault Blanc reaction
O R C OR'
Na/C2H5OH
RCH 2OH R'OH
Illustration 2:
COOCH 3 (CH2)n COOH
LiAlH4
(i) BH3/THF (ii) H2O/H

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Solution:
CH 2OH A = (CH 2)n COOH
If compound has
COOH as well as ester group then reactivity of ester is
more than acid towards LiAlH4.

CH 2OH B = (CH 2)n COOCH
3
Acid is more reactive than ester towards BH 3.
Exercise 1: Find A and B.

CH3
Hg OAC
(i) (ii)
THF / H2 O
NaBH 4 OH
CH3CH2COOCH3
CuO CuCr2 O4
A B
6.
From aliphatic primary amines It react with nitrous acid to give alcohol.

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Nature of alcohol depends on the nature of carbon having group.
NH2
Reaction proceeds through carbocation hence rearranged alcohol is obtained.

H3C CH 2 CH 2 NH2 NaNO 2/HCl H3C CH 2 CH 2OH H3C CH OH CH3
7.
From Oxiranes
Oxiranes react with Grignard reagent to give mono hydric alcohol. Nature of G.R is basic hence it attack on less hindered carbon of oxirane ring.
CH 2
H2 C O
Mg
H2 C
CH 2 R
OMgX HOH/H HO CH 2 CH 2 R
Illustration 3: (a) Find A, B, C, D, E.

O PhBr
Mg dry ether
(b)
CH3COOC2 H5
i CH3 MgBr ii H2O / H
D E

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Solution: (a)
A = PhMgBr
(b)
H3C CH3 C CH3
B =Ph
C = Ph
OH
OH
C2H5OH
8.
Fermentation of carbohydrates
C12H22O11 Sucrose
H2O Invertase
C6H12O6 glucose
C6H12O6 fructose
Zymase
2C2H5OH
2CO 2
Illustration 4: (i)
(i) C2H5MgBr H3C
H3C C CH2 O A
(ii) HOH/H
(ii) H3C
CH H3C
CH3 C CH CH2 CH3

Oxymercuration Demercuration

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Solution: (i)
H3C
CH3 C OH CH 2 C2H5 ( 2 methyl 2 pentanol)
(ii)
H3C
CH3 CH3 CH C OH (3 alcohol)

0
CH 2 CH 2CH 3
Exercise 2: (i) Identify A, B & C

MgBr RCO2Et + (CH2)5 MgBr
H 3O +
-H2 O
H 2 /Ni
(ii)
H
O C CH2 CH2 OH RMgX ( 1 eq) RH H
O C CH2 CH2 OM gX
O H C CH2 CH2 OH RM gX ( 2 eq) R H C(OH) CH2 CH2 OH
Account the reason for the above reactions. Trans Web Educational Services Pvt. Ltd
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PHYSICAL PROPERTIES Solubility Alcohols are soluble in water due to formation of H bonding between water & them. As the molecular mass increases, the alkyl group become larger which resists the formation of H bonds with water molecules and hence the solubility goes an decreasing. Boiling Point Intermolecular H bonding is present between alcohol molecules. This makes high boiling point.
O R
O R
O R
Amongst the isomeric alcohols, the order of boiling point is 1 alcohol. CHEMICAL PROPERTIES
> 2 > 3
Chemical properties of alcohols can be discussed under following categories:

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(A) (B) (C) (D) (E) (A)
Reaction involving breaking of carbon oxygen bond. Reaction involving breaking of oxygen hydrogen bond. Oxidation of alcohols. Dehydrogenation of alcohols. Some miscellaneous reactions of monohydric alcohol.
Reaction involving breaking of carbon oxygen bond Order of reactivity of alcohol. 3 > 2 > 1 (i) SN reaction

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HCl/Anhy ZnCl 2
NaX/H2SO 4
Cl
X NaHSO 4 H2O
OH
PCl5 or PCl 3
Cl
P/Br2 or PBr3
SOCl2 /Py ridine or SOCl2 /Ether
Br
Cl
SO 2 HCl
(ii)
Dehydration of alcohol
Dehydration of alcohol to give alkene. (a) Dehydrating agents are Anhyd ZnCl2/ , BF3/ , P2O5/ . (b) Reactivity of alcohols. (Ease of dehydration) 3 >2 >1 (c) Product formation always takes place by saytzeff rule. Trans Web Educational Services Pvt. Ltd
Conc H2SO4/ , KHSO4/ , H3PO4/ , Anhyd Al 2O3/ , Anhyd PCl 5/ ,
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OH H3C CH 2 CH CH3
Conc. H2 SO 4
H3C H3C
CH CH (Major)
CH3
CH 2 CH CH2 (Minor product)
* Alcohols on acetylation gives acetyl derivative which on pyrolytic elimination always gives Hofmann product.
OH H3C CH 2 CH CH3
CH3 CO 2 O / Py
OCOCH H3C CH 2 CH
CH3
H3C
CH 2 CH (Major)
CH2 H3C
CH CH (Minor)
CH3
Mechanism in presence of acidic medium E1 mechanism: follow saytzeffs rule.

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CH3 H3C C CH3 CH 2 O H H

Conc.H2 SO4
CH3 H3C C CH3 CH 2 O H H
CH3 H3C C CH 2 CH3

1,2methyl shift
CH3 H3C C CH3 CH 2
CH3 H3C C CH CH3
Exercise 3: Write mechanism
CH3 OH CH CH3 H
CH3
CH3
(B)
Reactions
due
to
breaking
of
oxygen
hydrogen
bond.
(Reactions due to acidic character of alcohols) (a) Alcohols are acidic in nature because hydrogen is present on electro negative oxygen atom. Trans Web Educational Services Pvt. Ltd
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(b)
Alcohol is weaker acid R stability of acid anions. Acidity of 1 > 2 > 3
H R
acidity
Alcohols give following reactions due to breaking of oxygen hydrogen bond. (i) Reaction with metal
H M
O M 1/2 H2 Metal alkoxide
M = 1st group metal. M = Al, Mg, Zn
3R OH Al
RO
Al
3 H2 2
Aluminium alkoxide

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(ii)
Esterification (With carboxylic acid)
O H R' OH R C OH R
O C O R' H2O
It is reversible acid catalysed reaction. It follow SN1 mechanism.
O H H3C C O H H3C
O C OH
H H3C
OH C OH R O H
OH H3C C OR
H2O
OH H3C C O H H OR H3C
OH C OH O R
O H3C C OR
Increasing the size of alkyl group on alcohol part decreases the nucleophilic character because steric hindrance increases.
Reactivity
1 Steric hindrence in RCOOH/ ROH

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Order of reactivity of alcohols CH3OH > 1 alc > 2 alc > 3 alc (iii) Ester formation with proton acid having OH group: to give inorganic ester. (a) R (b)
R O H HO
HO
O S O
O
O
O H2O
(nitrous acid)
(Alkyl nitrite)
OH
RO
OH
O Alkyl hydrogen sulphate
(iv) Alkylation of Alcohol
R O H
CH3
SO4 / NaOH
or CH3I / K 2 CO3
R O CH3
Methylation is mainly used for determination of hydroxyl groups in an unknown compound.
No. of hydroxyl groups
Molecular weight of methylated ether prodcued molecular weight of reac tan t 14
Exercise 4: Arrange the following in increasing order of acidic strength. Trans Web Educational Services Pvt. Ltd
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(a)
H3C CHOH CH3 (i) (ii) (iii) H3C CH2OH H3C OH H3C
CH3 C CH3 (iv) OH
(b) Arrange the following in increasing order of esterification: MeCOOH (i) (C) Oxidation of alcohol Oxidation of alcohol is dehydrogenation reaction which is 1, EtCOOH (ii) (Et)2CHCOOH (iii)
2elimination reaction.
O R C H
H R' 1, 2 elimination R
O C R' H2
So oxidation of alcohol (a)
numbers of
- hydrogen atom.
With mild oxidising agents like: (i) (ii) (iii) (iv) X2 Fenton reagent [FeSO4/H2O2] Jones reagent / CH3COCH3 [CrO3/dil. BaSO4] K2Cr2O7/H+ cold

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CH2OH
OH
[O]
RCHO
O
CH
R'
[O]
R'
CH3 H3C C CH3 OH [O] no reaction
Note: PCC (Pyridinium chloro chromate) is a selective reagent which converts 1 alc to aldehyde. (b) With strong oxidising agent Oxidising agents are (i) (ii) (iii) (iv)
KMnO4 / OH /
KMnO4 /H /
K 2Cr2O7 / H /
Conc. HNO3 /
H R C OH
RCH2OH
n carbon
RCOOH
n carbon
O R [O] R C R

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(D)
Dehydrogenation with Cu/573K or Ag/573K (a) 1 alcohol

R CH2OH
Cu / 573K
aldehyde
RCHO
(b)
2 alcohol
R CHOH R
Cu / 573K
ketone
R CO R
(c)
3 alc
CH3 H3C C CH3
undergo dehydration to form alkene.

CH3 OH
Cu/ 573 K
H3C
C CH2
H2O
Reduction
HI/Red P
(E)
Miscellaneous reactions of mono hydric alcohol (i) Methylation with CH2N2 in presence of BF3.
R O H
CH2N2 BF3
R O CH3
N2
(ii)
Haloform reaction Ethyl alcohol and 2 methyl alcohol gives haloform reaction.
H H C H H C H OH
CaOCl2 H2 O
(HCOO) 2Ca
CHCl

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Exercise 5: (i) Out of these compound which gives iodoform test: (a) (c) (e) (ii) CH3 (b) (d) CH2 CHOHCH3 PhCH2CHOHCH3 CH3CH2OH COOC2H5
PhCHOHCH3 CH3COCH2
NaBH4 CH3OH LiAlH4
(A)
(B)
Distinguishing 1 , 2 , 3 alcohol 1 alc No reaction room temperatur e 2 alc 3 alc
Test (I) Lucas test [ZnCl2 + HCl]
at White turbidity White turbidity after 5instantan eously

R3C OH ZnCl 2
H2O
10 min.
RCH(OH)R HCl
HCl
ZnCl 2 R CH Cl R
R3C
Cl

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(II) Victor Meyer test Red colour (P/I2,AgNO2, HNO2, NaOH)

RCH 2OH P/I 2
Blue colour
Colourless
R CHOH R P/I 2 R
R 3C OH P/I 2 R 3C I
CHI
RCH 2I AgNO 2 RCH 2NO 2 HONO

R R
AgNO 2 R 3C NO 2
AgNO 2
CHNO
NO 2 R C NOH Nitrollic acid NaOH NO 2 R C NO Na Sodium nitrolate (red )
R R C
HNO 2 No reaction (colourless)
HNO 2
NO 2
R N O (Pseudo nitrole) NaOH Blue

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PERIODATE OXIDATION Compounds that have hydroxyl group on adjacent atoms undergo oxidation cleavage when they are treated with aq. Periodic acid (HIO 4). The reaction breaks carbon carbon bonds and produced carbonyl compounds (aldehyde, ketones or acids)
H H H H3C C C H OH OH HIO 4 HC O CH 3CHO HIO 3 H2O
It takes place through a cyclic intermediate.
CH3 H H3C C C CH3 OH OH IO 4 H H3C
CH3 C C CH3 O I O O O O H3C CH3 C O H CH3 C O IO 3
Other examples
O R C C O R' HIO 4 RCOOH R'COOH

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HO
OH 2HIO 4 RCHO HCOOH R'CHO
R'
OH
This oxidation is useful in determination of structure. Illustration 5: Write the products of the reaction of t-butyl alcohol with PBr3, conc. H2SO4, CH3COCl, Na, CH3MgBr, Na2Cr2O7/H2SO4. Solution:
CH3
CBr, CH3
CH2 ; CH3
COCOCH3 , CH3
CO Na ,CH4 , no reaction .
Illustration 6: Write products (a)

H
H C C H C H OH O OH IO4
(b)
H
H C CH2 H C H OH CH3 IO4

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Solution: (a) (b) 2HCHO + CO2 No reaction (as it is not a vicinal diol)
Exercise 6: (a) Arrange the following alcohols in order of ease of
dehydration.
C6 H5
(b)
CH2OCH3 (a) CHOH CH2R IO4
CCH2OH, C6 H5 CHOHCH3 , C6 H5
COHCH3
Find product
H (b)O OH
HO
OH
IO4
HO
OH
R (c) R'
CHOH CH NH2
PINACOL PINACOLONE REARRANGEMENT Action of H2SO4 on 1, 2 diols. Ditertiory 1, 2 diols convert in to ketones on treatment with H2SO4. Trans Web Educational Services Pvt. Ltd
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OH OH R C R C R R H R R C R O C R
Mechanism
OH O H3C C C
H CH3 H H3C
OH C C CH3 Methyl shift

OH CH3
OH H3C C
CH3 C CH3 CH3
CH3 CH3
CH3 CH3
H3C
CH3
CH 3
Transition state O H3C C CH3 C CH3 CH3 -H H3C O C H C CH3 CH3
CH3 CH3
Migratory preference of the group Migration depends on the stability of Transition state. In general migration of C6H5 > alkyl Illustration 7: List three methods with chemical equations for the preparation of alcohols from alkenes. Trans Web Educational Services Pvt. Ltd
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Solution: Hydration, hydroboration and oxymercuration demercuration of alkenes. Hydration:
CH3 H3C C CH3 CH CH2

H2 O H
CH3 H3C C CHCH 3
CH3 OH
Hydroboration

i BH3 ii H2 O2 , OH
CH3 H3C C CH3 CH 2CH 2OH
Oxymercuration demercuration

i Hg OAC 2 , THF, H2O ii NaBH4
CH3 H3C C CHCH

3
CH3 OH

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Illustration 8: Which of the following alcohols would react fastest with Lucas reagent?
CH3 CH3CH2CH2CH2OH , CH3CH2 CHCH3 , CH3 CH CH2OH , H3C OH OH C CH3 OH
Solution:
COH , it being a tertiary alcohol.
CH3
Exercise 7: Find out (i)

H3C
Ph
Ph H
(ii)
CH3 A
CH3 H3C
Ph
Ph
OH
OH
OH
OH

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Exercise 8: Give a possible structure for the substance C 5H10O2 behaving in the following manner.
C5H10O 2
C6 H5 NHNH2
I2 ,NaOH
Fehling Solution
ETHER * * R R O R Alkoxy alkane (Di alkyl ether)
R = R Symmetrical ether. R Unsymmetrical or mixed ether.
O is to be counted with least number of C atom. Example: CH3 CH3 O O C2H5 Methoxy ethane C6H5 Methoxy benzene
There are various types of cyclic ethers also.

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O O Oxirane (Epoxide)
O
Oxetane (Oxacyclo butane) Tetra hydro furan (Oxacyclo pentane)
PREPARATION OF ETHERS (i) From 1 alcohol (a) With H2SO4
R O H R O H
H 2SO4 1400 C or Al2O3 / 525K
R O R symmetrical ether
Order of dehydration 1 > 2 > 3 alcohol (b) With diazomethane

R O H
CH2N2 C2H5O 3 Al
R O CH3 N2
(c)
Alcohol having at least one hydrogen at fourth carbon gives five membered cyclic ether with Pb(OAC)4. The reaction is free radical reaction which is initiated by heat or light.
H3C CH 2 CH 2 CH 2 OH
Pb OAC 4 h / C6H6 800 C
Tetrahydro furan

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H2C H
(CH 2)3
CH 2OH
Pb OAC 4 h / C6H6 800 C
CH3 2 methyl tetra hydro furan
Williamsons synthesis
SN 2 reaction of a sodium alkoxide with alkyl halide, alkyl sulphonate or alkyl
sulphate is known as Williamson synthesis of ethers.
R ONa R'L
SN2
R O R' NaL
X, SO2R'' ,
O SO2
OR'
In this reaction alkoxide may be alkoxide of primary, secondary as well as tertiary alcohol. Alkyl halide must be primary. In case of tertiary alkyl halide, elimination occurs giving alkenes With a secondary alkyl halide, both elimination and substitution products are obtained.
Na . O
R'
Na X

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CH3 CH 3Br Na O C CH3 Sodium ter. butoxide CH3 H3C O
CH3 C CH3 ter. butyl methyl ether CH3
Illustration 9: Write the product (i)

H3C
CH3 C CH3 O Na CH 3Cl (A)
(ii)
H3C
CH3 C CH3 Br C2H5ONa B C
Solution: (i)
H3C
CH3 C CH3 O CH3
(ii)
H3C
CH3 C CH2 C2H5Br
Exercise 9: Find product

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(i)
CH 2OH Br
NaOH p Xylene
(ii)
X
OH
NaOH / H2 O 25 0 C
Cl
(3)
From Alkane (a)

R
H3C C H3C CH2
i Hg OAC
2
OR' CH CH2
i Hg OAC
2
/ R'OH
ii NaBH4 / OH
R
OCH 3
CH
CH3
/ CH3 OH
ii NaBH4 / OH
H3C
C CH3
CH3
(b)
H3C
CH3 C CH2 H OCH 3

H2SO4
CH3 H3C C CH3 O CH3
(4)
From Grignard reagent - halo ethers with suitable
Higher ethers can be prepared by treating reagents.
Cl H3C O CH 2Cl CH 3MgI

Dry ether
H3C
CH 2CH 3
Mg I

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(5)
From Alkyl halide
2RI Ag2O
dry
R O R 2AgI
PROPERTIES OF ETHERS Dipole nature of ether Ethers have a tetrahedral geometry i.e. oxygen is sp 3 hybridized. The COC bond angle in ether is 110 . Because of the greater electronegativity of oxygen than carbon, the C moment. O bonds are slightly polar and are inclined to each other at an angle of 110 C, resulting in a net dipole
R
1100C
R O R O
net
The bond angle is slightly greater than the tetrahedral angle due to repulsive interaction between the two bulky groups.

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Chemical Reaction Dialkyl ethers reacts with very few reagents other than acids. The only active site for other reagents are the C H bonds of the alkyls. Ethers has ability to solvate cations (electrophile) by donating an electron pair from their oxygen atom. These properties make ether as solvents for many reactions. On standing in contact with air, most aliphatic ethers are converted slowly into unstable peroxides. Ether gives following reactions: 1. Nucleophilic substitution reactions

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Conc. H SO 4 2 1 mole warm Conc. H SO 4 2 2 mole warm
H O H / / h ig h p re s s u re
R R 2R R R R
OH R O O I R I R
SO 3H O SO 3H
SO 3H R H OH I H O
H HI ( 1 mole) Cold 2HI Cold 3 mole HI/Red P
H R
R C
Cl
/Anhy ZnCl 2 O
Cl R O
R O
R'
R'
R'
R'
PCl5 /
Cl R
Cl POCl
Note: Type of ethers also make a difference in the mechanism followed during the cleavage of CO by HI/HBr. Combinations 1R + 2R Mechanism follows Less sterically hindered SN2

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2R + 3R
More sterically hindered Nature of mechanism
SN1 decoded by
nature of solvent. 1R + 3R
Aprotic or Non polar SN2 Protic polar SN1
Methylcation is stabler than phenylcations (B) Dehydration with H2SO4/ and Anhy Al2O3/ (i) When both alkyl groups has -hydrogen.
H3C CH 2 O
CH
CH3
CH 2 CH3
Conc. H2 SO 4 /
H2C
CH 2
H3C
CH
CH
CH3 H2O
(ii)
When only alkyl group has

CH3 H3C C CH3 O CH3
Conc. H2 SO4
- hydrogen.
CH3 H2C C CH3 CH 3OH

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Hot conc. H2SO4 react with secondary and tertiary ethers to give a mixture of alcohols and alkenes. (CH3)3COCH3
(CH3)3CO
Cyclohexyl tert butyl ether
Conc.H2SO4 hot
(CH3)2C=CH2 + CH3OH
(CH3)2C=CH2 + HO
isobutene cyclohexanol
conc.H2SO 4 hot
(C)
Miscellaneous reactions (1) Halogenation: Monohalogenation takes place at (a)

H3C CH 2 O CH 2 CH3 Excess
Cl2 / h
carbon (with small amount)

Cl H3C CH O CH 2 CH3
(b) H C CH 3 2
O CH 2 CH3 Small
Cl2 excess / h
Cl 5C2
C2Cl 5
(2)
Reaction with CO: give ester
R O R CO
125 1800 C 200 atm, BF3
RCOOR
Illustration 10: Explain why sometimes explosion occurs while distilling ethers. Trans Web Educational Services Pvt. Ltd
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Solution: It is due to formation of peroxide

OOH CH3CH2OCH2CH3 + O2
h
CH3CHOCH2CH3
Illustration 11: The basicity of the ethers towards BF 3 has the following order, explain.
> (CH3)2O > (C2H5)2O >[(CH3)2CH] 2O O
Solution: There are steric effects in the Lewis acid-Lewis base complex formation between BF3 and the respective ethers. Illustration 12: What are crown ethers? How can the following reaction be made to proceed?

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CH2Br
KF
CH2F KBr
Solution: Crown ethers are large ring polyethers and are basically cyclic oligomers of oxirane which may have annulated rings. They are designated according to ring size and the number of complexing oxygen atoms, thus 18-crown 6 denotes an 18-membered ring with 6-oxygens. The molecule is shaped like a doughnut, and has a hole in the middle.
O O O O O O
These are phase transfer catalysts. This is a unique example of host-guest relationship. The crown ether is the host, the cation is the guest. The cavity is well suited to fit a K + or Rb+ which is held as a complex. Interaction between host and guest in all these complexes are mainly through electrostatic forces and hydrogen bonds. The reaction can be made to process by using catalytic amount of crown ether, 18-crown-6.

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Illustration 13: Explain why
is much more soluble than furan in water.
Solution: THF is more soluble than furan. In THF, in contrast to furan the electron pairs are available for H-bonding with water which makes it more soluble in water. Exercise 10: What chemical methods can be used to distinguish between the following pairs of compounds? (a) (b) (c) Ethoxy ethanol and methyl isopropyl ether. Butyl iodide and butyl ethyl ether. Ethyl propyl ether and ethyl allyl ether.
Exercise 11: Ether A cleaves much faster than B with conc. HI. Explain.

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HBr
CH3OH Br C2 H5
H3CO (A)
C 2 H5
HBr
CH 3 Br
H3CO (B)
HO
PHENOL These are organic compounds a hydroxyl group attached directly to a benzene ring.
OH
OH
CH 3
Phenol or carbolic acid
(o , p , m) Cresol
Preparation Industrial Method (i) From chloro benzene (Dows process) Trans Web Educational Services Pvt. Ltd
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Chlorobenzene is heated with NaOH at 673 K and under pressure of 300 atm to produced sodium phenoxide which on acidification yields phenol.
Cl ONa OH
NaOH / 623K 300 atm p
(ii)
Cumene Process
Cumene obtained from propene & benzene cumene on air oxidation followed by acidification with H2SO4 gives phenol & acetone.
CH3 CH3 H3C CH CH2
250 0 C H3 P O 4
HC CH3 Cumene
O2 95 - 1350
C CH3
OH
Cumene hydroperoxide
H, H 2O 50-900C OH O H3C C CH3
(iii) From benzene sulphonic acid It is fused with NaOH gives sodium salt of phenol.

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C6H5 SO3H
NaOH Fusion
C6H5 SO3Na
C6H5 ONa
H2 O / H
C6H5OH
(iv) From benzene diazonium chloride This gives Ar SN1 reaction with H2O to form phenol.
OH N N Cl
H2O/H
N2
Illustration 14: Starting from 1-methyl cyclohexene, prepare the following: (a)
CH3 OH OH H
(b)
CH3 OH
Solution: (a)
CH3
i KMnO4 ii H2 O
CH3 OH OH H

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(b)
CH3
H2 O / H
CH3 OH
Exercise 12: Starting from 1-methyl cyclohexene, prepare the following: (a)
CH3 OH OH H
(b)
CH3 OH OH OH
PHYSICAL PROPERTIES Phenol is needle shaped solid, soon liquefies due to high hygroscopic nature. It is less soluble in water, but readily soluble in organic solvents. Phenol has high boiling point due to presence of hydrogen bonding. Acidity of phenol Phenol is weak acid. It reacts with aqueous NaOH to form sodium phenoxide, but does not react with sodium bicarbonate. The acidity of phenol is due to the stability of the phenoxide ion, which is resonance stabilized as shown below: Trans Web Educational Services Pvt. Ltd
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(I)
(II)
(III)
(IV)
(V)
In substituted phenols, the presence of electron withdrawing groups at ortho and para positions such as nitro group, stabilizes the phenoxide ion resulting in an increase in acid strength. It is due to this reason that ortho and para nitro phenols are more acidic than phenol. On the other hand, electron releasing groups such as alkyl group, do not favour the formation of phenoxide ion resulting in decrease in acid strength. For example: (cresol are less acidic then phenol) Exercise 13: Arrange each group of compounds in order of decreasing acidity:

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OH
OH
OH
OH
(a)
NO 2
OH
CH3
OH OH NO2 OH
(b)
, NO2 NO2
NO2
Cl
CHEMICAL REACTIONS (A) Reaction due to breaking of O H bond
Phenol is more reactive than alcohol for this reaction because phenoxide ion is more stable than the alkoxide ion.
R O
O H
H O

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Reactions of phenol due to breaking of below:

Alcoholic FeCl3
H bond are given
O 3 ONa
Fe blue or violet colour (test for phenolic group).
NaOH
H2O
CH3
CH2 N 2 dry ether
Anisole O CH3
(CH3 ) 2 SO 4 NaOH

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Acylation
O OH
O R C Cl
pyridine Phenyl ester

O
or
O R C O
/ Pyridine
Fries rearrangement Phenolic esters are converted in to o and phydroxy ketones in the presence of anhydrous AlCl 3. Generally low temperature favours the formation of pisomer and higher temperature favour the o-isomer.

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OH O O C CH3
1600C
COCH
OH
600C
COCH 3
(B)
Reactions due to breaking of carbon- Oxygen bond Nucleophilic substitution reaction Phenols are less reactive than aliphatic compound because: (i) (ii) (iii) OH group is present on sp2 hybridised carbon. This makes CO bond stronger. O is more electronegative than halogens. This also makes CO bond stronger than CX. There is some double bond character between carbon and oxygen due to the resonance. This also makes CO bond stronger. However it give SN under drastic condition.

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NH2
NH3/Anhy ZnCl 2 3000C
OH Cl O P
PCl5 /
3 SH
P S5 / 2
(C)
EAS in Phenol: It is strong activating group.

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OH OH
20 % HNO 3 250C
NO 2
o-nitro phenol OH
Conc. HNO3 H2 SO 4 /
NO 2 p-nitro phenol NO 2 2, 4, 6, tri nitro phenol (picric acid) OH
O 2N
NO 2
Br2 / H2 O
Br
OH
or Br2 / CH3 COOH
Br 2, 4, 6, tri bromo phenol
OH Br
Br2 / CS 2
or Br2 / CCl4
OH
Br p-bromo phenol
o-bromo phenol
OH Br
OH
H2 SO 4
SO 3H
o-hydroxy benzene sulphonic acid OH SO 3H (Major) p-hydroxy benzene sulphonic acid R
X Anhy AlCl3
o-alkyl phenol

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OH O
HNO2
NCl
NO
p nitroso phenol
OH
N
Coupling reaction OH mild
OH
p hydroxy azo benzene Azodye OH
OH
CHO
i CHCl3 / alc KOH ii H2 O / H ReimerTiemann reaction
OH
Major product
OH CHO
ii CCl4 / alc KOH
OH
ii H2 O / H ReimerTiemann reaction
COOH Major
Salicylic acid
OH
i CO2 / NaOH 1200 C, 7 atm ii H
Kolbe ' s reaction
COOH COOH
OH CH 2OH
CH2 O
OH
OH
CH 2OH
ROH / H 2 SO 4

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MERCURATION Mercuric acetate cation. [HgOAC]+ is a weak electrophile which substitutes in ortho and para position of phenol. Usually donating product is O acetoxy mercuriphenol. The mercuric compound can be converted to iodophenol.
OH
OH
OH HgOCOCH
OH
Hg OCOCH3 Re flux
HgCl I2/CHCl
3
Aq. NaCl
Miscellaneous reaction (i) Reaction with Zn dust

OH
Zn Dust
ZnO
(ii)
Oxidation

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O
h
OH
p - benzoquinone (brow n in colour)
O OH
K2S2O 8/OH Elbs oxidation
p - quinol
OH
(iii)
Condensation with phthalic anhydride

OH OH
OH
OH
H O
C C O C O O Penolphthalein (Acid base indicator)

Conc. H2SO4 H2O
O C

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Exercise 14: Discuss the product formed in the bromination of p-phenol sulfonic acid. Mechanism of some important reactions 1. Reimer Tieman reaction
OH
OH
i CHCl3 , OH ii H
CHO
The electrophile is the dichloro carbene: CCl2, formation of carbene is an example of -elimination. (i)
Cl OH H C Cl Cl -HCl CCl 2
(ii)
OH
O H
OH
CCl2 Ar SE
CHCl CCl 2
o (dichloro methyl) Phenoxide ion

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(iii)
O Cl HC Cl OH
O O C H H Cl
OH
O O CHO H C H
2.
Kolbes reaction
OH OH
NaOH CO 2
i 1200 C, 7 atm ii H
COOH
Mechanism

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OH O Na C O O H C O (More reactive for Ar SE) O Na
NaOH
OH OH O COOH H2O/H Salicylic acid C O Na
Illustration 15: How will you convert? (i) (iii) Solution: phenol to aspirin phenol to oil of winter green. (ii) (iv) phenol to salol. phenol to benzoic acid.
(i)
OH
OH
COCH 3
i NaOH/ CO2 , 1200 C 4 7 atm ii H
COOH
CH3 CO 2 O H
COOH
Aspirin

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(ii)
OH
OH
OH
OH
i NaOH / CO2 , 1200 C 7 atm P ii H
COOH H
CO
Salol
(iii)
OH
OH
OH
i NaOH / CO2 , 1200 C 7 atmP ii H
COOH
CH3 OH H
COOCH
Oil of w inter green
(iv)
OH
OH
i NaOH / CO2 , 1200 C 7 atm P ii H
COOH
Zn dust
COOH
Illustration 16: What product would you expect in the following reaction? Explain.
OH
CHCl3 , KOH
CH3

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Solution:
CHCl3
aq. KOH
O
: CCl2
O O
CCl 2
H2 O
CH3
H3C
CCl 2 H C 3
CHCl
It is an abnormal product formed in the Reimer-Tiemann reaction when the dienone cannot tautomerize to regenerate a phenolic system. Illustration 17: How would you distinguish between the following pairs? (a) (b) Solution: (a) Phenol gives coloration with FeCl 3 solution (b) Ethyl alcohol responds to the iodoform test Phenol and cyclohexanol Ethyl alcohol and methyl alcohol

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Exercise 15: How would you distinguish between the following pairs? (a) (b) 2-Pentanol and 3-pentanol 1-Propanol and phenol
Exercise 16. Offer explanation for the following observations: (a) (b) Why is phenol unstable in the keto-form? The following dehydration is extremely facile:
CH3
H
CH3
OH
(c) (d) (e) (f) (g)
Why does thionyl chloride provide alkyl chlorides of high purity? 2-Methyl -2- pentanol dehydrates faster than 2 methyl 1 pentanol. Phenol is acidic but ethyl alcohol is neutral. Ethanol responds to Iodoform test but tert- butanol does not. A tertiary alcohol reacts faster than a primary alcohol in the Lucas test.
Exercise 17: Trans Web Educational Services Pvt. Ltd

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How will you effect the following conversion? (a)

OH O
(b)
C2H5OH
CH3CH2CH2OH
Exercise 18: How will you effect the following conversion? (a)
OH
(b)
CH
CH2
CH2CH2OH
(c)
OH
CH3
CH3
(d)
OH
OH

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Exercise 19: Write mechanism

CH2OH
Cyclohexene
Some Commercially Important Alcohols And Phenols (i) Methanol: Methanol is also called wood spirit since originally it was obtained by destructive distillation of wood. Now a days it is prepared by catalytic hydrogenation of water gas.
CO 2H2
CuO ZnO CrO3 573 673K, 200 300K
CH3 OH
Uses: It is largely used as: (a) (b) (c) a solvent for paints, varnishes and celluloids. for manufacturing of formaldehyde.
for denaturing ethyl alcohol, i.e. to make it unfit for drinking purpose. Denatured alcohols is called methylated spirit. (d) in manufacture of perfumes and drugs.
(ii)
Ethanol: Ethanol is mainly prepared by hydration of ethene formation of carbohydrates gives only 95% alcohol the rest being water. This is called rectified spirit. Trans Web Educational Services Pvt. Ltd
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Uses: It is largely used as an (a) (b) (c) antiseptic. for paints, lacquers, varnishes, dyes, cosmetics, solvent
perfumes, tinctures, cough syrups etc. As an important starting material for manufacture of ether, chloroform, Iodoform etc. (d) (e) As an important beverages. As power alcohol a mixture of 20% absolute alcohol and 80% petrol (gasoline) with benzene or tetralin as a co-solvent. (f) As an antifreeze in automobile radiators.
(iii) Absolute alcohol: Absolute alcohol is 100% ethanol prepared from rectified spirit 95.5% alcohol as follows: In laboratory absolute alcohol is prepared by keeping the rectified spirit in contact with calculated amount of quick lime for few hours and then refluxing and distilling it. Phenol or Carbolic Acid Uses (i) (ii) As an antiseptic and disinfectant in soaps and lotions. In manufacture of drugs like, aspirin, salol, salicylic acid, phenacetin. (iii) In the manufacture of bakelite.

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(iv) dyes. (v)
In the manufacture of picric acid, phenolphthalein, azo As a preservative for ink.
Ethylene Glycol: Ethane 1, 2 diol Preparation: Lab preparation by hydroxylation. (i)
CH2 3 CH2
4 Cold dilute alkaline
2KMnO
4H2O
CH 2OH 3 CH 2OH
2MnO2 2KOH
Manufacture
CH2
O2 / Ag 575K
H2C O H2C Ethylene epoxide or oxirane

H2 O / 473K hydrolysis
CH 2OH CH 2OH
CH2
Physical properties: It is highly viscous because of the presence of two OH bond it undergoes extensive intermolecular H-bonding. Same reason owes to high solubility in water and high boiling point. Chemical properties Trans Web Educational Services Pvt. Ltd
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Reaction with sodium (i)
CH 2OH CH 2OH
Na, 323K 1 H2 2
CH 2ONa
CH 2OH Monosodium glycolate

CH 2Cl
Na, 433K 1 H2 2
CH 2ONa CH 2ONa Disodium glycolate

2HCl
(ii) (iii)
CH 2OH CH 2OH
2PCl 5
2POCl3
CH 2Cl
CH 2OH CH 2OH
CH 2Cl
2SOCl 2
2SO2 2HCl CH 2Cl Ethylene dichloride
(iv)
CH 2OH CH 2OH
CH 2Cl
HCl, 433K H2 O
CH 2Cl
HCl, 473K H2 O
CH 2OH
CH 2Cl
Ethylene chlorohydrin Ethylene dichloride
(v)
CH 2OH CH 2OH
H2C
RCH O
p toulene sulphonic acid
CHR
H2 O
H2C Cyclic acid
(vi) Oxidation: (a) CH 2OH

CH 2OH
Ethyelene
glycol
upon
oxidation
gives
different
products with different oxidising agents. For example.

CHO
O O
COOH CH 2OH Glycollic acid
CH 2OH Glycolaldehyde
CHO
O
COOH
O
COOH COOH Oxalic acid
CHO Glyoxal
CHO Glyoxalic acid
(b) With periodic acid HIO4 or lead tetra acetate. Trans Web Educational Services Pvt. Ltd
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CH 2OH CH 2OH
HCHO
HIO4
HCHO
H2O HIO3 Iodic acid
Also called malapride reaction.

CH 2OH CH 2OH HCHO
2 CH3COO 4 Pb 2CH3COOH CH3COO 2 Pb
HCHO
Dehydration (a) CH 2OH

773K
H2 C H2 C
O H2O
CH 2OH
(b) CH 2OH
CH 2OH
CH 2
ZnCl 2 H2 O
Tautomerize
CH 3 CHO
CHOH Vinyl alcohol
(c)
2
CH 2OH CH 2OH
conc. H2 SO4 distill
CH 2 CH 2 O CH 2 CH 2
O 2H2 O
1, 4 dioxane
(d)
2
CH 2OH CH 2OH
conc. H3 PO4 distill
CH 2 CH 2OH O CH 2 CH 2OH
H2 O
Diethylene glycol
Uses (a) (b) (c) Exercise 20: Trans Web Educational Services Pvt. Ltd
As a solvent. Antifreeze in the radiators of cars and aeroplanes. In manufacture of terylene and other polyester.
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How would you convert cyclohexane to 1, 6 hexanediol? Glycerol (Propane 1, 2, 3 triol) One of the most important trihydric alcohol. Preparation: (i) By Saponification of oils and fats.
H2 C HC H2 C O COR 1
3NaOH
CH 2OH CHOH CH 2OH
R1COONa R1COONa R1COONa Sodium salt of fatty acid (soap)
OCOR 2 OCOR 3
(ii)
From Propylene
CH3 CH CH2
Cl2 , 773K HCl
Cl CH2
CH
CH2
Allyl chloride
aq.Na2 CO3 423K, 12 atm
HO CH2
aq. NaOH NaCl
CH
CH2
Allyl alcohol
HOCl Cl OH trans Cl2 H2O
HOCH2
CHOH CH2Cl
glycerol
CH2OH CHOH CH2OH

glycerol
monochlorohydrin
(iii) Synthesis from its elements
2C H2
Electric ore Berthelets synthesis
CH CH
CH
Na in liq. NH3 196 K
Na C CH
Pr opylene
CH CH2
CH3I NaI
H3C C
Pr opyne
H2 / Pd BaSO4 Lindlar ' s catalyst
CH3

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Physical Properties Highly viscous due to three OH group due to which it undergoes extensive intermolecular H-bonding. Chemical Properties (i) It undergoes reaction of both secondary and primary alcoholic group.
CH 2OH CHOH CH 2OH
Na, room temperature 1 H2 2
CH 2ONa CHOH CH 2OH

monosodium glycerolate
Na, room temperature
CH 2ONa CHOH CH 2ONa , 'disodium glycerolate
(ii)
CH 2OH Excess of HCl HCl gas CHOH 383K, H2O gas, 383 K, 2H2O CH 2OH
CH 2Cl CHOH CH 2OH

Glycerol monochlorohydrin
CH 2OH CHCl CH 2OH Glycerol monochlorohydrin
CH 2Cl CHCl CH 2OH Glycerol , dichlorohydrin
CH 2Cl CHOH CH 2Cl Glycerol , dichlorohydrin
Excess of dry HCl gas, 383 K H2 O

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To replace the third hydroxyl group in either of two dichlorohydrins, PCl 5 or PCl3 is fused. (iii)
CH 2OH CHOH CH 2OH

3HI
3H2 O
CH 2I CHI CH 2I Unstable
I2
CH 2 CH CH 2I
HI Markonikof 's addition
CH 3 CHI CH 2I 1, 2 diiodopropane
I2
CH 3 CH CH 2
HI
CH 3 CHI CH 3 Isopropyl iodide
3.
Reaction with concentrated nitric acid:
H2C HC H2C Glycerol
OH OH OH
HO HO HO
NO 2 NO 2 NO 2
Conc HNO3 Conc. H2 SO4 283 298K
H2C HC
O O
NO 2 NO 2 3H2O
H2C O NO 2 Glyceryl trinitrate Noble's oil

Nitroglycerine
A mixture of glyceryl trinitrate and glyceryl dinitrate absorbed on Kieselguhr is called dynamite.

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4.
Reaction with KHSO4 Dehydration.
H H HO H C C C H Glycerol OH H OH
KHSO4 , 473 503K 2H2 O
CH2 C
Tautomerises
CH2 CH CHO Acrolein or Prop- 2-en-1-al
CHOH (unstable)
5.
Oxidation.
CHO CHOH CH 2OH CH 2OH [O] CHOH CH 2OH Glycerol CH 2OH C O [O] Glyceraldehyde [O]
COOH CHOH [O]
COOH CHOH COOH Tartromic acid
CH 2OH Glyceric acid
COOH CO COOH Mesoxalic acid
CH 2OH Dihydroxyacetone

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(i)
With dil. HNO3, a mixture of glyceric acid and tartronic acid is produced.
(ii) (iii) (iv)
With conc. HNO3, mainly glyceric acid is obtained. With bismuth nitrate, only mesoxalic acid is formed. Mild oxidising agents like bromine water, sodium hypobromite (Br2/NaOH) and Fentons reagent (H 2O2 + FeSO4) give a mixture of glyceraldehyde and dihydroxyacetone. The mixture is called glycerose.
(v)
With periodic (HIO4) acid.
CH 2OH CHOH CH 2OH Glycerol

(vi)
HCHO Formaldehyde
2HIO4
HCOOH Formic acid HCHO Formaldehyde
2HIO3 H2O
Iodic acid
With acidified potassium permanganate.

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CH 2OH COOH CHOH CH 2OH Glycerol

6. Reaction with phosphorous halides.
Acidified KMnO4
CO2
3H2O
COOH Oxalic acid

3PCl 5
CH 2Cl CHCl
3HCl 3POCl 3
CH 2Cl 1, 2, 3 - trichloropropane (Glyceryl trichloride)

with monocarboxylic acids. Glycerol reacts with
7.
Reaction
monocarboxylic acids to form mono-, di- and tri- ester depending upon the amount of the acid used and the temperature of the reaction. An excess of the acid and high temperature favour the formation of tri-esters. For example, with acetic acid, glycerol monoacetate, diacetate and triacetate may be formed.

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CH 2O.COCH CHOH
CH 2O.COCH CHOH
CH 2O.COCH CHO.COCH
3
CH 2OH Glycerol monoacetate
CH 2O.COCH 3 Glycerol diacetate
CH 2O.COCH 3 Glycerol triacetate
8.
Acetylation. When treated with acetyl chloride, glycerol forms glycerol triacetate.

3CH3COCl
CH 2OCOCH CHOCOCH
3
3HCl
CH 2OCOCH 3 Glycerol triacetate

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9. (i)
Reaction with oxalic acid
H2C
OH
OOC COOH Oxalic acid

383K H2 O
H 2C
OOC
COO H
Heat CO2
H2C
OOCH
CHOH CH 2OH Glycerol
CHOH
CHOH CH 2OH Glyceryl monoformate
CH 2OH Glyceryl monoxalate CH 2OH

HOH, hydrolysis From water of crystallization
CHOH
HCOOH Formic acid
CH 2OH Glycerol
(ii) CH 2O H
CHO H CH 2OH Glycerol
HO CO HO CO Oxalic acid
503K 2H2 O
H2C HC
OOC OOC
503K 2H2 O
CH 2 CH CH 2OH Allyl alcohol
CH 2OH Glyceryl dioxalate (Dioxalin)
Uses: Glycerol is used: 1. In the preparation of nitroglycerine used in making dynamite. Nitroglycerine is also used for treatment of angina pectoris. 2. 3. As an antifreeze in automobile radiators. In medicines like cough syrups lotions etc.

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4.
In the production of glyptal or alkyl resin (a cross linked polyester obtained by the condensation polymerization of glycerol and phthalic acid) which is used in the manufacture of paints and lacquers.
5. 6.
In making non-drying printing inks, stamp colours, shoes polishes etc. In the manufacture of high class toilet soaps and cosmetics since it does not allow them to dry due to its hydroscopic nature. 7. As a preservative for fruits and other eatables.
8. Exercise 21:
As a sweetening agent in beverages and confectionary.
How does glycerol react with a. HI, b. (COOH) 2 and c. conc HNO3?

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ANSWER TO EXERCISES Exercise 1: (i)
H3C
OH HgOAC
H3C
OH
A=
B=
(ii)
A = CH3CH2CH2OH B = CH3OH
Exercise 2: (i)
followed by
R OH RCO 2Et + MgBr MgBr

H3 O
-H2O R H2/Pd R
(ii)
The R (carbanion) pulls acidic hydrogen from OH group making it an acid-base reaction instead of usual nucleophilic addition reaction. On further hydrolysis it produces reactant. But in the

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second case you have two moles of RMgX that completes the reaction because there are two R for two different sites. Exercise 3:
CH3 OH CH CH3 H
CH3 CH CH3 CH3 H CH3 H CH3 CH3 ring Expansion
Exercise 4: (a) (b) (iii) > (ii) > (i) > (iv) (i) > (ii) > (iii)
Exercise 5: (i) (ii)

(A) =
Only (c) and (d) gives iodoform test.

O O (B) = OH OH
OH
OH
Exercise 6: (a) (b)

C6H5
3
CCH2OH
C6H5 CHOHCH3
C6H5
C(OH)CH3
(i)
No reaction Trans Web Educational Services Pvt. Ltd

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(ii) (iii) Exercise 7: (i)

A=
6HCOOH RCHO + R CHO + NH3
CH3 Ph C O C CH3 Ph
(ii)
A=
CH3 Ph C O C CH3 Ph
Here
phenyl place.
migration takes
Here methyl migration takes place.
Exercise 8: Considering the reactions of C5H10O2, it is likely that C6H5NHNH3, I2, NaOH will react only with a keto group while CH3COCl and oxidation are reactions of an alcohol. Therefore two isomeric structures are possible for the original compound.
O CH 3 CCH 2CH 2CH 2OH and
O CH 3 CCH 2CH 2OH CH3

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Exercise 9: ,
X=
halo
alcohols undergoes Williamson
intramolecular
O
O
ether. Synthesis in the presence of NaOH by SN 2 reaction.
Y=
Exercise 10: (a) (b) (c) Ethoxyethanol give the Iodoform test. Butyl iodide with AgNO3 yields AgI precipitate. Ethyl allyl ether decolorize bromine water.
Exercise 11: The cleavage reaction of an ether by HI is initiated by protonation of the ether oxygen.
Attack by either SN1 or SN 2
H O CH 3 (B)
In the second step the attack by Br has to take place by SN1 or SN2 process. Since the system B is rigid either attack is very slow. The ether A does not pose such a problem Trans Web Educational Services Pvt. Ltd
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Exercise 12:
CH3 CH3
i OsO4 ii NaHSO3
(a)
OH OH H
(b)
CH3
C6 H5CO2 OH
CH3 O
H2 O H
OH CH3 OH H
Exercise 13:
OH
OH
OH
OH
(a)
>
>
>
NO 2
OH NO 2 (b) > > OH
CH3
OH OH
> NO 2
NO 2
NO 2
Cl

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Exercise 14: A phenol is highly reactive towards electrophilic substitution.
Treatment of phenol with aqueous solution of bromine results in the replacement of every hydrogen ortho and para to the tribromophenol.
OH Br
3Br2
OH group, and
it even cause the displacement of the sulfonic group to yield
OH Br 3HBr H2SO4
SO 3H
Br
Exercise 15: (a) (b) 2-Pentanol responds to the Iodoform test Phenol gives coloration with FeCl 3 solution
Exercise 16: (a) (b) (c) (d) Phenol loses the aromatic stabilization in the keto form. The alkene formed is more stable due to resonance. Because the other products during the reaction of thionyl chloride with alcohols are gaseous. 2-Methyl-2-pentanol yield a stable alkene

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(e) (f)
The
phenoxide
ion
formed
from
phenol
is
stabilized
by
resonance.
H Ethanol contains the H C CH3 OH grouping
(g)
A tertiary alcohol form a stable tertiary carbonation.
Exercise 17: (a)
OH
OH
H2 , Na
Na2 Cr2 O7 H ,
(b) C2H5 OH
PCl5
C2H5 Cl
KCN
C2H 5 CN
C2H5 CH2NH2
HNO2
C2H5 CH2OH
Exercise 18: (a)

H2 SO4 1600
SO 3H
NaOH
SO 3 Na
OH
H
(b) C6H5 CH CH2
HBr Peroxide
C6H5 CH2CH2Br
aqueous OH
C6H5CH2CH2OH

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(c)
CH3
CH3
CH3
H2 / Ni
H , H2 O
OH
OH
OH
H
HOCl
(d)
OH
H , H2 O
aq. KOH
Cl
Cl
OH
Exercise 19:
CH 2OH
CH 2
H , H2 O
ring expansion
Exercise 20:
O3
NaBH4
HO CH2
OH
Exercise 21: See the text.

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MISCELLANEOUS EXERCISES Exercise 1: Exercise 2: Write a note on: (a) Oxo process (b) absolute alcohol What happens when? (a) (b) (c) Exercise 3: ethanol vapours are passed over alumina at 600 K, excess of ethanol is heated with conc.H2SO4 at 413K, phenol is treated with acetyl chloride?
How is glycerol prepared from fats and oils? Why it is highly viscous? Give its uses?
Exercise 4:
Discuss the following reactions: (a) (b) Reimer and Tiemann reaction Kolbes reaction
Exercise 5:
Complete the following by putting structures of A, B, C, D.

CH3CH2CH2OH
PBr3
KOH als.
HBr
NH3
Complete the following. Exercise 6: Compete the following by drawing correct structures.
SO 3H
fu min g H2 SO4
..................
i fuse with NaOH ii H2 O / H
..................
Exercise 7:
How the sugar is converted to ethanol? Trans Web Educational Services Pvt. Ltd
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Exercise 8:
Write the structure of organic compounds A to F in the following sequence of reactions:

OH
Zn
HNO3 H2 SO4
Br2
H2 / V Pt
HNO2 HCl
H3O
Exercise 9:
Predict the products of the following reactions: (a)

C2 H5O Na
Br
(b)
CH3 CH2
O C6 H5
HBr

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ANSWER TO MISCELLANEOUS EXERCISES Exercise 1: (a) Oxo process: It is used for the preparation of alcohols. When alkenes are treated with carbon monoxide and hydrogen in presence of octa-carbonyl dicobalt at high temperature and pressure, aldehyde are formed, which on reduction with H2/Ni give alcohols.
CH2
Ethene
CH2
CO H2
CO Co
4 2
High temp. and pressure
CH3
2 Pr opanal
CH
CHO
H2 / Ni
CH3
CH2
CH2
OH
1 propanol
(b)
Absolute alcohol: 100% ethanol is known as absolute alcohol. 95.6% alcohol and 4.4% water form azeotropic mixture and boil at same temperature. To prepare absolute alcohol, rectified spirit (95% alcohol) and benzene mixture is fractionally distilled. The first fraction obtained at 331.8 K contains the azeotropic mixture of total water (7.5%) some alcohol (18.5%) and maximum benzene (74%). The second fraction, which is an azeoptroopic mixture of remaining benzene (nearly 68%) and some alcohol (32%) is obtained at 341.2 K. The third and last fraction consists of absolute alcohol which is obtained at 351K.
Exercise 2: (a) Dehydration with take place and ethylene is formed. Trans Web Educational Services Pvt. Ltd
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CH3CH2OH
Ethanol
Al2 O3 600K
CH2
CH2 H2O
Ethene
(b)
Diethylether is formed.
2C2H5 OH
OH
Conc. H2SO4 413K
C2H5OC2H5 H2O
Ethoxy Ethane
COCH 3
HCl
CH3COCl
Acetyl chloride
Phenol
Phenyl acetate
(c)
Phenylethanoate is formed.
Exercise 3: Glycerol is prepared by the Saponification of oils and fats i.e., hydrolysis of oils and fats with NaOH. Fats and oils are the esters of glycerol and higher fatty acids i.e. glycerides of fatty acids. Glycerol is very viscous with extensive intermolecular hydrogen bonding. Glycerol molecule contains three OH groups which form extensive hydrogen bonding. Hence the intermolecular forces are very high and molecules are highly associated. Due to this reason it is very viscous and posses high boiling point (563K). Trans Web Educational Services Pvt. Ltd
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H2C HC H2C O O O COR COR' COR"
3NaOH
H2C HC H2C
OH OH OH
RCOONa RCOONa RCOONa Sodium salt of fatty acids (soaps)
(Oil and fats)
Glycerol
Uses: (i) (ii) (iii) Used in the preparation of nitroglycerine which is main constituent of dynamite. Used as antifreezing agent in automobile radiators. Used as a sweetening agent in confectionery and beverages.
Exercise 4: (a) Reimer and Tiemann reaction: When phenol is refluxed with chloroform and sodium hydroxide at 340 K followed by hydrolysis, gives o-hydroxy benzaldehyde (main product) and p-hydroxy benzaldehyde (minor product). This reaction is known as Reimer and Tiemann reaction.
OH
OH COONa
CCl 4 340K
H2 O / H
OH COOH
Phenol
2-Hydroxybenzaldehyde (Salicyldehyde)

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OH OH COONa
CCl 4 / NaOH 340K
H2 O / H
OH COOH small amount of 4-hydroxy benzoic acid is also formed 2-Hydroxy benzoic acid (Salicylic acid)
Phenol
If CCl4 is used in place of CHCl 3 the main product will be salicylic acid. (b) Kolbes Reaction: When sodium phenoxide is treated with carbon dioxide under pressure (4 to 7) and at 400 K, sodium salicylate is formed which on acidic hydrolysis gives salicylic acid. This reaction is known as Kolbes reaction.
OH OH COONa
CO2
4 7 atm 400K
H2 O / H
OH COOH
Phenol
(Major product)
Salicylic acid
Exercise 5:
CH3CH2CH2OH
1 Pr opanol
PBr3
CH3CH2CH2 Br
1 Bromopropane A
KOH alc.
CH3CH
Pr opene B
CH2
NH2 H3C CH CH3 2-Propanamine (D) NH 3 H3C CH CH3 HBr
Br 2-Bromopropane (C)

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Exercise 6:
SO 3H OH
SO 3H
fu min g H2 SO4
i fuse with NaOH ii H2 O / H
SO 3H
OH 1, 3 - Dihydroxy benzene
Exercise 7: Molasses, which is the main source of sugar is treated with yeast. The enzymes present in yeast ferment the sugar and ethanol is obtained. Sugar is converted to glucose and fructose by the invertase enzyme. Glucose is further converted to ethanol by the zymase enzyme.
C12H22O11 H2O
Sugar
Invertase
C6H12O6 C6H12O6
Glucose Frucot se
Zymase
2C2H5OH 2CO2
Ethanol
Exercise 8:
OH NO 2 NO 2 NH2
Zn
HNO3 H2 SO4
Br2
Sn / HCl
Phenol
Benzene [A]
Nitrobenzene [B] OH
Br m-Nitro (bromobenzene) [C] N2Cl
m-Bromo Aniline [D]
Br
H3 O
HNO2 HCl
Br m-Bromophenol [F]
Br m-Bromo Benzenediazonium [E]

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Exercise 9: (a)
O C2H5
(b)
CH3 CH2
CH2Br
C6H5 OH

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SOLVED PROBLEMS
Subjective:
Board Type Questions Problem 1: What happens when? (i) (ii) (iii) (iv) (v) Vapours of ethanol are passed over heated alumina at 523 K. Ethyl bromide is heated with dry silver oxide. Methyl magnesium bromide is treated with methoxy chloro methane. Ethyl alcohol is heated with diazomethane in presence of HBF 4. 2 methyl propene is heated with methanol in the presence of dil. H2SO4. Solution: (i) Diethyl ether is formed.
CH3 CH2 OH H O CH2CH3
Al2 O3 3500 C
CH3 CH2
O CH2
CH3
H2O
(ii)
C2H5 Br Ag2O C2H5 Br H5C2 O C2H5 2AgBr diethyl ether

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(iii) Ethyl methyl ether is formed.

Br H3C O CH 2Cl CH 3MgBr dry ether H3C O C2H5 Mg Cl
(iv) Ethyl methyl ether is formed

CH3 CH2OH
2 2 dim ago methane
CH N
HBF4
CH3 CH2
O CH3
N2
(v)
Tertiary butyl methyl ether

CH3 H3C C CH2 H O CH3 H2SO 4 H3C CH3 C CH3
O CH3 Methyl ter - butyl ether
Problem 2: Why phenol has smaller dipole moment than methanol? Solution: In case of phenol, the electron withdrawing inductive effect of oxygen is opposed by electron releasing resonance effect. Hence, phenol has smaller dipole moment. In case of methanol only electron withdrawing inductive effect is operative. Hence, it has higher dipole moment.

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Problem 3: Why di tert butyl ether can not be obtained by Williamsons method? Solution: In order to prepare the above ether the reagents to be used are tertbutyl bromide and tertbutoxide. Since the tertiary bromide prefers to under go elimination, therefore, major product of the reaction shall be iso butylene and not di tert butyl ether.
CH3 H3C C CH3 30 bromide Br Na O CH3 C CH3 tertbutoxide CH3 H3C CH3 C CH2 H3C CH3 C CH3 OH NaBr
Problem 4: Identify the product in the following reaction
OH
OH
ClCH2 COCl POCl3
CH3 NH2
i KMnO4 / OH ii H
Zn dust

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Solution:
OH
OH
OH A=
OH B=
COCH 2Cl
OH
COOH
COCH 2NHCH
OH C=
D=
COOH
Problem 5: Write the various product when ethanol reacts with sulphuric acid in suitable conditions. Solution:
C2H5OH
H2 SO 4 383K
C2H5HSO 4
H2SO 4/ 413 K H2SO 4/ 443 K
C2H5OC 2H5
H2C
CH2

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IIT Level Questions Problem 6: Give products expected when each of the following diols are reacted with periodic acid HIO4 (a) HO
CH2 CH OH
.
CH2 C6H5
(b)
OH
H C OH
Solution: (a)
H C H O H
O C CH 2 C6H5
(b)
O
Problem 7: Effect the following conversion (a)
CH2OH
CH2OH

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(b)
CH3OH
CH2CH2OH
Solution: (a)
CH 2OH H
CH 2 ring Expansion
H2O CH 2OH HBO CH2 Ph 3P CH2 O K2Cr 2O 7 OH
(b)
CH 3OH
PCl5
CH 3Cl
CH3 Anhy AlCl 3 NBS
CH 2Br
Mg dry ether
CH 2CH 2OH
HCHO H3 O
CH 2MgBr
Problem 8: Postulate a mechanism for the following reactions:

O CH3 HO H
Solution:

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OH H HO -H2O HO ring expansion O O H
-H
Problem 9: Conversion (a)

H OH H D
(b)
H2C CH2 O O
Solution: (a)
H H OH PBr 3 Pyridine H Br Mg/dry ether D2O H D MgBr

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(b)
H2C
CH2
MnO 4 KOH
HOH 2C
CH 2OH
H -H2O
OH
CH 2 CH 2 O CH 2CH 2OH
Intrmoleculadehydration H , , H O 2
Problem 10: Identify the products in the following reaction sequence.
OH
i CHCl 3 ii KOH , H
LiAlH4
CH3COOH H
H3C
Solution:
OH A= H3C CHO B= H3C
OH C= CH 2OH H3C
OH O CH 2 O C CH3
Problem 11: Distinguish between each pair of compounds by a simple test. Trans Web Educational Services Pvt. Ltd
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(a) (b) Solution: (a)
(CH3)2CHOH and (CH3)2CHSH
CH3CH2CH2OH and (CH3)2CHOH
The thiol gives a precipitate with heavy metal cations like
Hg 2 , Pb
and Cu
(b)
(CH3)2CHOH (2 alc) gives a yellow precipitate of CHI3 with I2/OH (iodoform test)
Problem 12: Write mechanism of the following reaction

OH
OH
H3 O
Solution:

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OH OH O H
O
H
Problem 13: Compound (A) C6H14O is insoluble in water and gives negative Lucas test. On treatment with conc. H2SO4 followed by hydrolysis it gives only one compound (B) (C3H8O). Compound (B) is soluble in water and gives red colour with ceric ammonium nitrate. (B) gives yellow precipitate (C) and compound (D) on treatment with I 2/Na2CO3 followed by acidification. Identify the compound A, B, C and D. Give the reasons. Sol.
H3C A= H3C O
HO
C CH3 CH3
CH3
B= CH3
C = CHI3 Problem 14:
D = CH3COOH

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Explain
the
low
boiling
point
and
decreased
water
solubility
by
onitro phenol and ohydroxy benzaldehyde as compared with this m and pisomers. Solution: Intramolecular H-bonding (chelation) in the o-isomers inhibits intermolecular attraction, lowering the boiling point and reduces H-bonding with H2O, decreasing water solubility. Intramolecular chelation cannot occurs in m and p isomers.
O H
O H
C H
O o - nitro phenol
o - hydroxy benzaldehyde

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Objective:
Problem 1: When ether is exposed to air for some time an explosive substance is produced (A) (C) Solution: (A) Peroxide peroxide oxide (B) (D) TNT super oxide
Problem 2: What is the major product obtained when phenol is treated with chloroform and aqueous alkali? (A)
OH
(B)
CHO
OH
CHO
(C)
HO CHO
(D)
OH
COOH
Sol. Trans Web Educational Services Pvt. Ltd

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(A)
Salicyldehyde
Problem 3:
CH3 H3C C CH 2 O
CH3 H3C C
18
H2 O18 H
A, A is
(A)
(B)
CH2 OH
H3C
CH3 C OH CH2 OH
18
OH
(C) Both Solution:
(D) none
Stability of carbocation is 3 > 2 > 1 (A)
Problem 4: Organic acid without a carboxylic acid group is .. (A) (C) ascorbic acid oxalic acid (D) (B) vinegar picric acid

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Solution: Picric acid is a phenol i.e. 2, 4, 6 tri nitro phenol (D) Problem 5: The product of the following reaction
H3C CH2
i BH3 / THF ii H2O2 ,OH
(A) (C) Solution:
1 pentanol pentane
(B) (D)
2 pentanol 1, 2 pentane diol
Anti Markowvnikov product. (A) Problem 6: Product in the reaction

C2 H5 Br
NaOH aq
NaOH
CH3 I
C will be
(A) (C)
propane butanol
(B) (D)
ethyl iodide methoxy ethane

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Solution:
C2H5Br
NaOH aq
C2H5OH
Na / CH3I William son's synthesis
C2H5OCH3
(D) Problem 7: Phenol can be distinguished from alcohol with (A) (C) Solution: Phenol gives violet colour with neutral FeCl 3. (C) Problem 8: Tert butyl methyl ether on heating with HI of one molar concentration gives (A) (C) CH3OH + (CH3)3C I CH3I + (CH3)3CI (D) (B) CH3I + (CH3)3COH none of these Tollens reagent (B) Neutral FeCl3 (D) Schiffs base HCl

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Solution:
CH3
C O CH3
HI
CH3 OH
CH3
C I
(A) Problem 9: Which of the following is the strongest acid? (A)

OH NO 2
(B)
HO Cl
(C)
HO NO 2
(D)
OH
NO 2
Solution: Due to greater electron withdrawing effect of NO2 group than Cl atom nitrophenols are stronger acids than pchloro phenol among nitro phenols P nitro phenol is the strongest acid. (C)

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Problem 10: Phenol is heated with phthalic anhydride in presence of conc. H 2SO4. The product is (A) (C) Solution: Phenolphthalein (A) Problem 11: An organic compound X of molecular formula C4H10O undergoes oxidation to give a compound Y of molecular formula C 4H8O2. X could be (A) (C) Solution: (A) & (C) CH3CH2CH2CH2OH (CH3)2CHCH2OH (B) (D) CH3CH2CH(OH)CH3 (CH3)3COH Phenolphthalein (B) salicylic acid (D) bakelite fluorescein

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Problem 12: Which of the following methods is/are not the industrial methods to prepare methanol? (A) (B) (C) (D) Solution: (B), (C) & (D) Problem 13: Which of the following reagent (s) or test (s), can be used to distinguish 2 methyl propanol and 2-methyl propanol2? (A) (C) Solution: (B), (C) & (D) I2/NaOH Victor-Meyer test (B) (D) HCl/anhyd. ZnCl 2 oxidation with Cu at 573 K catalytic reduction of carbon monoxide in presence of ZnOCr2O3. reacting methane with steam at 900 C with a Ni catalyst. reducing formaldehyde with lithium aluminium hydride. reacting formaldehyde with aqueous sodium hydroxide solution.

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Problem 14: Phenol has higher pka value than (A) (C) Solution: (A) & (C) Problem 15: Which of the following reactions can be used to prepare methyl phenyl ether? (A) (B) (C) (D) Solution: (A) & (B) reacting sodium phenoxide with methyl chloride reacting phenol with diazomethane (CH 2N2) reacting sodium methoxide with chlorobenzene reacting C6H5OMgCl with chloromethane acetic acid p-nitrophenol (B) (D) p-methoxy phenol ethanol

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Fill in the Blanks Problem 16: Williamsons synthesis involves the reaction of an..with an. Solution: Alkyl halide, alkoxide Problem 17: An ether is more volatile than alcohol having the same formula due to absence of.. Solution: Intermolecular hydrogen bonding Problem 18: Anisole reacts with HI to form

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Solution: Methyl iodide and phenol Problem 19: Power alcohol is a mixture of absolute alcohol and.in the ratio. Solution: Petrol, 20 : 80 Problem 20: Glycerol on reaction with potassium hydrogen sulphite and heat yields a product whichto form acraldehyde. Solution: Tautomerise

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Problem 21: Phenol on exposure to air produces a..coloured product known as.. Solution: Red, phenoquione True and False Problem 22: t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol. Solution: True Problem 23: o-nitro phenol is more soluble in water than p-nitrophenol.

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Solution: False Problem 24: 2-methyl 2- propanol gives cloudiness with HCl and ZnCl 2 immediately at room temperature. Sol: True Problem 25: The hydroboration oxidation process gives product corresponding to Markonikovs addition of water to the carbon carbon double bond. Solution: False Problem 26: p-amino phenol has higher pka value than phenol. Trans Web Educational Services Pvt. Ltd
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Solution: True

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ASSIGNMENT PROBLEMS
Subjective:
LevelO 1. 2. Write all the canonical forms of phenol. Account for the following: (i) (ii) When HI react with methyl phenyl ether, phenol and methyl iodide are formed and not methyl alcohol and iodobenzene? An ether would posses a dipole moment even if the alkyl groups present in it are identical. 3. 4. O nitro phenol is less soluble in water than p nitro phenol. Why? 3, 3 dimethyl butane 2 ol loses a molecule of water in the presence of concentrated sulphuric acid to give tetra methyl ethylene as a major product. Suggest a suitable mechanism. 5. Complete the following sequences of reactions by supplying X, Y and Z: (a)
X
PBr3
Na Ether
CH3 CH3
Cl2 heat

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(b)
X
H2O/H
H3C
CH OH
CH3
Cu / 573K
(i) C2H5MgI (ii) H2O/H+
6. 7.
How will you convert phenol to salol? Name the reagents used in the following reactions: (i) (ii) (iii) (iv) Benzyl alcohol to benzoic acid. Phenol to 2, 4, 6 tribromo phenol. Ethanol to ethanol Ethene to ethane 1, 2 diol.
8.
Arrange the following set of compound in order of their increasing boiling points. (a) (b) Pentan1ol, butan1ol, butan2ol, ethanol, propan1ol, methanol. Pentan1ol, nbutane, pentanal, ethoxyethane.
9.
Arrange the following compounds in increasing order of their acid strength: Propan1ol, 2, 4, 6trinitrophenol, 3nitrophenol, 3, 5dinitrophenol, phenol, 4methyl phenol.
10.
(a)
Explain why a non symmetrical ether is usually prepared by heating a mixture of ROH and R OH in acid. Trans Web Educational Services Pvt. Ltd
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(b)
Would you get any di-tert-butyl ether from this reaction? Explain.
11.
How the following conversion carries out? (i) (ii) (iii) (iv) Propane benzyl chloride Propan2ol benzyl alcohol propanol1
Ethyl magnesium chloride Methanol to Ethanol
12.
Identify the major products in the following reactions. (i)

NO 2
(ii)
HNO3 H2 SO4
OH CH3
Br2 water
OCH 3
13.
Give one test to distinguish (a) (b) Ethanol and methanol Phenol & Benzyl alcohol
14.
Compound (A) C7H8O is insoluble in water and dilute NaHCO3 but dissolve in dilute NaOH solution. On treatment with Br 2 water it readily gives a precipitate of C7H5OBr3. Write down the structure of the compound.
15.
Give the mechanism of Reimer Tiemann reaction on phenol. Trans Web Educational Services Pvt. Ltd
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Level I 1. Write the product of the following reactions

i BH3 ii Oxidation
CH3
2.
Write the product A & B

H2/Pt CH CH CHO NaBH 4 A
3.
Write the product A & B

CH3
Cold alkaline KMnO4
Cr2 O 3 ACO H
4. 5.
Convert nitro benzene to m nitro phenol. An unknown compound A (C4H10O2) reacts with sodium metal to liberate hydrogen gas. A is inert towards periodic acid, it react with CrO3 to form B (C4H6O3). Identify A and B.
6.
Convert

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OH CH3 to OH
Write mechanism of above conversion. 7. Identify compounds A D in the following reaction.

CHC 6H5
i O3 ii Zn/H2O
dil. NaOH aq. ethanol
H2O
i O3 ii Zn/ H2O
D A
OH
H2 / Pt
OH
8.
Give mechanism of the following reaction

OH OH
i CCl4 NaOH/ ii H3 O
COOH
9.
Identify the product in the given reaction

1 equiv BH 3/THF A H2O2 OH B
CH3

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10.
Conc. H SO4 2
H2O
Identify X and Y.
11.
Identify A & B
CHCl N H OH
3
Pyrole 12. Give a simple test that distinguish between the compounds. (a) (b) 13. Allyl and n propyl alcohol. Benzyl methyl ether and benzyl alcohol.
How will you synthesize?

CH3 from phenol
14.
An organic compound (A) gives positive Libermann reaction and on treatment with CCl4/KOH followed by hydrogenation gives (B). B on reduction gives (C) C7H8O2. (B) react with (CH3CO)2O/CH3COOH give a pain reliever (D). Identify A to D.

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15.
Provide suitable mechanism

OH CH3 CH3
Level II 1. An ester A (C4H8O2) on treatment with excess of methyl magnesium bromide followed by acidification gives an alcohol (B) as the sole organic product. Alcohol (B) on oxidation with NaOCl followed by acidification gives acetic acid. Deduce the structure of A and B and show the reactions involved. 2. Propose a mechanism for the following reaction. (a)
Me Me Ph Me Ph O C Ph C Me OH OH Ph
(b)
OH
O
OH
3.
Give products

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CH3 H3C C CH3 O CH3 Conc. HI (2) C D
Anhydrous HI ether I
4.
CH(OH)Me H Me A [ C 9H16]
A on ozonolysis gives nonane 2, 8 dione. What is A and how is it formed? 5. An organic compounds (P) having molecular formula C 5H10O treated with dilute H2SO4 gives two compounds Q & R both gives positive iodoform test. The reaction of C5H10O with dilute H2SO4 gives reaction 1015 times faster than ethylene. Identify organic compound of Q & R. Give the reason for the extra stability of P. 6. Complete the following reaction.
OH
i OH ii Et Br
Zn / HCl
NaNO2 HCl, 500 C
C6H5OH NO 2 LiAlH 4 (E) (F) Soluble in NaOH D

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7.
(a) (b)
Diphenyl ether is not very easily prepared using Williamsons sysnthsis. Provide an useful synthetic route for the same. When phenol is treated with Br2 presence of H2O. 2, 4, 6 tri bromo phenol is obtained whereas on treatment with Br2 in presence of CCl 4. pbromo phenol is obtained. Explain.
8.
Write mechanistic step of the following reaction?
CH 2OH
9.
Compound (A) gives positive Lucas test in 5 minutes when 6.0 gm of (A) heated with Na metal, 1120 ml of H2 is evolved at STP. Assuming (A) to contain one of oxygen per molecule, write structural formula of (A). Compound (A) when heated with PBr3 gives (B) which when treated with benzene in presence of anhydrous AlCl 3 gives (C). What are (A), (B) and (C)?
10.
Carry out the following conversion.

OH
to

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11.
Treatment of compound (A) C8H10O with chromic acid & pyridine gives (B) C8H8O. Treatment of (B) with two equivalent Br2 yields (C) C8H6OBr2 which on treatment with caustic soda followed by acidifications gives a compound (D) C8H8O3. (D) liberates CO2 on treatment with NaHCO3 and is resolvable.
12.
Compound X, Y and Z are isomeric alcohol with formula C 5H12O. X and Y react with chromic acid solution, Y forming an acid A. The three isomers react with HBr with decreasing relative rates of Z > X >> Y, all giving the same C5H11Br (B) in varying yields. X alone can be oxidised by I2/OH to C. Write the structure of X, Y, Z with proper explanations.
13.
Predict the product (s) and write the mechanism of each of the following reactions (a)
1 mole HI
(b)
(A)
O CH3
Excess HI
(B)
CH3
14.
Find product (a)

H3C CH3 C CH2
OH
MeOH
H2SO 4
(A)
(b)
OH
(B)

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(c)
RCOOEt
MgBr (H2C) 5 MgBr H3O C H2/Ni D
(d)
CH 2OH C O 2IO 4 E F
CH 2OH
15.
(Z) C6H14O
alc. KOH
/ H2 SO 4
(A) C6H12
HCl
B C C6H13Cl
D (Isomer of A)
O 3/H 2O
(Given negative test with Fehling solution but responds to iodoform)
O3/H 2O
(both give positive Tollens test but do not give iodoform test)
Conc. NaOH
HCOONa
a primary alcohol
Identify A to G and Z.

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Objective:
LevelI 1. Which one of the following has the maximum acidic strength? (A) (C) 2. Phenol p-methyl phenol (B) (D) o-nitro phenol o, p-dinitro phenol
The boiling point to isomeric alcohols follows the order (A) (B) (C) (D) primary > secondary > tertiary tertiary > secondary > primary secondary > tertiary > primary all have same boiling point
3.
A mixture of benzoic acid and phenol may be separate by treatment with (A) (C) NaHCO3 NH3 solution (B) (D) NaOH KOH
4.
In the lucas test of alcohols, appearance of cloudiness is due to the formation of (A) (C) aldehyde acid chloride (B) (D) ketone alkyl chloride
5.
The dehydration of 1 butanol gives Trans Web Educational Services Pvt. Ltd
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(A) (B) (C) (D) 6.
1 butene as the main product 2 butene as the main product equal amounts of 1 butene and 2 butane 2 methyl propane
Ethyl alcohol is obtained when ethyl chloride is boiled with (A) (C) alc. KOH AlCl3 (B) (D) aq. KOH H2O2
7.
The number of methoxy groups in a compound can be determined by treating with (A) (C) Na2CO3 HI and AgNO3 (B) (D) NaOH CH3COOH
8.
Diethyl ether absorbs oxygen to form (A) (B) (C) (D) red coloured sweet smelling compound CH3COOH ether peroxide ether suboxide
9.
Which of the following compounds is oxidised to prepare methyl ethyl ketone? (A) (C) 2 propanol 2 butanol (B) (D) 1 butanol 2 methyl 2 propanol

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10.
Order of reactivity of HX towards ROH is (A) (C) HI > HBr > HCl HCl > HI > HBr (B) (D) HBr > HI > HCl HI > HCl > HBr
11.
Glycerol has (A) (B) (C) (D) one 1 and one 2 alcoholic groups one 1 and two 2 alcoholic groups two 1 and one 2 alcoholic groups two 2 alcoholic group
12.
Ethyl iodide reacts with moist silver oxide to produce (A) (C) ethane ethyl alcohol (B) (D) propane diethyl ether
13.
Reaction of tertiary butyl alcohol with hot Cu at 350 C produces (A) (C) butanol 2 butene (B) (D) butanal 2 methyl propene
14.
1 alcohol can be converted to aldehyde by using the reagent (A) (B) (C) (D) pyridinium chloro chromate potassium di chromate potassium permanganate all of above

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15.
Reaction of ethanol with H 2SO4 and suitable conditions can lead to the formation of (A) (C) C2H5HSO4 ethoxy ethane (B) (D) ethene all of them

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Level II 1. 2 phenyl propene on acidic hydration gives (A) (C) 2. 2 phenyl 2 propanol 3 phenyl 1 propanol (B) (D) 2 phenyl 1 propanol 1 phenyl 2 propanol
The order of reactivity of phenyl magnesium bromide with the following compound is
O O O
Me (I)
Me
Me (II)
Ph (III)
Ph
(A) (C) 3.
II > III > I (B) II > I > III (D)
I > III > II all react with the same rate
Which one is the stronger base? (A) (C) CH3CH2O both of equal strength (B) (D) CF3CH2O can not say CH is in the
4.
The acidic character of 1 , 2 , 3 alcohols H2O and RC order (A) (B) (C) (D) H2O > 1 > 2 > 3 > RC RC 1 > 2 > 3 > H2O > RC 3 > 2 > 1 > H2O > RC CH CH CH CH > 3 > 2 > 1 > H2O

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5.
Choose the correct statement (s) for the reaction

OH OH
OCOCH
AlCl3 / CS2 heat
COCH
(a) COCH (b)

3
(A) (B) (C) (D) 6.
(b) is formed more rapidly at higher temperature (b) is more volatile than (a) (a) is more volatile than (b) (a) is formed higher yields at lower temperature
Predict the major product

Excess HI O
(A) (B) (C) (D) 7.
HO HO I
CH2 CH2 CH2
CH2 CH2 CH2
CH2 CH2 CH2
CH2 CH2 CH2 I
I OH
no reaction
Dipole moment of CH3CH2CH3, CH3CH2OH and CH3CH2F is in order (I) (A) (C) I < II < III (B) I < III < II (D) (II) I > II > III III < I < II (III)
8.
3 methyl 3- hexanol can be prepared by Trans Web Educational Services Pvt. Ltd
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(A) (B) (C) (D)
CH3MgI and 3 hexanone, followed by hydrolysis C2H5MgI and 2 pentanone, followed by hydrolysis C3H7MgI and 2 butanone, followed by hydrolysis any of the method above
9.
Ester (A)C4H8 O2
CH3MgBr
2 parts
H3 O
B C4H10 O
Alcohol B reacts fastest with Lucas reagent. Hence A and B are (A)
H3C O C O C2H5 , (CH 3)3COH
(B)
H
O C
O H C O C3H7 ,(CH 3)3COH
C3H7 ,(CH 3)2CHOH
(C)
H3C
O C O C2H5 ,(CH 3)2CHOH
(D)
10.
Vinyl carbinol is (A) (C) HO CH3 CH2 CH = CH2 (B) (D) CH3C(OH) = CH2
CH3 CH CH2OH
CH = CHOH
11.
The reaction of elemental sulphur with Grignard reagent followed by acidification leads to the formation of (A) (C) mercaptan thio ether (B) (D) sulphoxide sulphonic acid
12.
Conversion of chloro benzene into phenol by Dows process is an example of (A) (C) free radical substation (B) nucleophilic substitution electrophilic substitution (D) rearrangement Trans Web Educational Services Pvt. Ltd
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13.
For the preparation of tert-butyl methyl ether by Williamsons method the correct choice of reagents is (A) (B) (C) (D) methoxide and tert butyl bromide methanol and 2 bromobutane 2 butanol and methyl bromide tert-butoxide and methyl bromide
14.
Allyl alcohol is obtained when glycerol reacts with the following at 260 C (A) (C) formic acid both (B) (D) oxalic acid none
15.
The correct decreasing order of acidic strength is (A) (B) (C) (D) C6H5OH > C6H5CH2OH > C6H5COOH > C6H5SO3H C6H5CH2OH > C6H5OH > C6H5SO3H > C6H5OH C6H5COOH > C6H5CH2OH > C6H5OH > C6H5SO3H C6H5SO3H > C6H5COOH > C6H5OH > C6H5CH2OH

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ANSWERS TO ASSIGNMENT PROBLEMS
Subjective:
Level O 1. 2. Refer to text. (i) In methyl phenyl ether. The Ist step is protonation of ether to form phenyl methyl oxonium ion.
H O CH3 O CH3 OH
H step 1
I step 2
CH3I
Phenyl carbocation is highly unstable and bond between C 6H5O is stronger than OCH3 so I attacks on CH3 to form CH3I & phenol. (ii) Oxygen of ether is sp3 hybridised, therefore ethers have tetrahedral geometry. Due to more electronegativity of oxygen than carbon, CO bonds of ether are polar in nature.

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R
1100C
O R
Net dipole moment
The two dipoles do not cancel each other hence the molecule would posses dipole moment. 3. In O nitro phenol there is intramolecular hydrogen bonding. This inhibits its hydrogen bonding with water and reduces its solubility in water.
O H O N O
4.
H3C
CH3 C CH CH3 H H3C
CH3 C CH CH3
CH3 OH
CH3 OH 2 -H2O CH3 H3C C CH3 CH CH3 1, 2 methyl shift
CH3 CH3 H3C C C CH3 -H H3C
CH3 CH3 C CH CH3
tetra methyl ethylene

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5.
(a) (b)
X = CH3OH, Y = CH3Br, Z = CH3CH2Cl

C2 H5
X = CH3CH = CH2, Y = CH3COCH3, Z =
H3C
C CH3
OH
6.
OH
OH COOH
Kolbe ' s reaction i CO2 400K, OH ii H3 O
OH
OH
COO H Phenyl salicylate (salol)
7.
(i) (ii) (iii) (iv)
Alkaline KMnO4 Br2 water P.C.C 1% alkaline KMnO4 Methanol < ethanol < propan1ol < butan2ol < butan1ol < pentan1ol. nbutane < ethoxy ethane < pentanal < pentan1ol.
8.
(a) (b)
9.
Propan1ol < 4 methoxyphenol < phenol < 3 nitro phenol < 3, 5 dinitrophenol < 2, 4, 6trinitrophenol.
10.
(a) (b)
A mixture of three ethers, ROR, ROR obtained.
and R OR
is
Notbutanol does not solvate the 3 carbocation readily because of steric hindrance. Trans Web Educational Services Pvt. Ltd
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12. (i)
O 2N A=
NO 2
(ii)
Br A=
OCH 3
OH CH3
Br
13.
(a) (b)
Iodoform test given by ethanol. Neutral FeCl3 test given by phenol.
14.
m - Cresol
OH
CH3
OH 15. CHCl 3
OH
CCl 3
O
Cl
O
CCl 2
H OH CCl 2 CCl 2
O CHCl CHO 2 OH H2O

2

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Level I 1.
H H3C H
OH
2.
A= CH 2CH 2CH 2CHO B= CH CH CH 2OH
3.
A=
CH3 OH OH
CH3 B= OH O
4.
NO 2
NO 2
NH 2
funing HNO3 Conc. H2SO4 ,
NH4
NO 2
NO 2 NaNO 2/H 2SO 4
0 - 50C
OH N2 HSO
4
H2 O
NO 2
NO 2
5.
A= H3C
OH CH
O B= H3C C CH 2 COOH
CH 2 CH 2 OH

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6.
OH CH3
H
-H2O
ring exp ansion
(Hydride shift)
CH3
OH
CH3
OH
7.
O H C A= O B=
O H
O O C
C=
D=

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8.
OH
O Cl OH CCl 3
O H CCl 3
O CCl 3
OH O OH H3O COOH O OH CO 2 COOH
9.
A= H BH 2H CH3
B= H OH H CH3
10.
(X) =
(Y) =
HO
HO
O
OH
SO3H
11.
A= N H CHO B= N
Cl
12.
(a) (b)
Add Br2/CCl4 Allyl decolourises orange colour Add small piece of Na. H2 releases from alcohol.

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13.
OH
Cl
O CH3 Zn dust
O
AlCl 3
Zn(Hg)/HCl
CH3
14.
A=
OH
OH
COOH B=
Phenol
OH
Salicylic acid
OCOCH
CH 2OH
C=
COOH D=
C7H8O 2 2 hydroxy benzyl alcohol
Aspirin
15.
CH3
OH CH3
OH 2
H CH3 -H2O -H
CH3

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Level II 1
O H . C O
CH3 C H (A) CH3
H3C OH H3C (B) H
(a) .
H3C
Me
Ph H Ph Me
Me
Ph
Me
Ph
Ph
Ph
OH
OH
OH
OH
Me
Ph Me -H C Ph O Me
Ph
Ph H O
Me
H
Me
(b)
OH
H OH
-H2O
OH
OH
OH 2
-H

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3.
H3C
CH3 C CH3 O CH3
CH3
Anhydrous HI ether I
CH3I
H3C
C CH3
OH
CH3 Conc. HI (2) CH3OH H3C C CH3 I
4.
A
H2 C
Nonane 2, 8 dione (No loss of C)

CH 2 CH 2 C CH3 O3/H2O CH 2 CH 2 C CH3 H2 C CH 2 CH 2 C O CH 2 CH 2 C O
Me CH(OH)Me Me H CH Me Me 20 carbocation 1, 2 alkyl shift (ring expansion)
CH3
CH3
Me
Me
Me

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5.
H2C
CH3 H O (C5H10O) CH3 C2H5OH (R) H3C (Q) O H2O CH3 H3C
CH3 C
Stability by resonacne
H3C C H3C H3C O
O CH3 Highly stable carbocation
6 .
A=
OEt
OEt
OEt
B=
C=
NO 2
NH 3 Cl
N2Cl
D= OEt
OH
OH
OEt
F=
E=
NH2
NH2

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7.
(a)
OH NaOH O
Se/
(b)
H2O ionises phenol into the most reactive phenoxide anion and hence tri substitution occurs. Moreover H2O can stabilizing the arenium ion intermediate formed as well as the electrophile Br+. Hence the rate of reaction is fast and hence tri substitution results. Hence the rate of the reaction is slow and hence now substitution results.
8.
H H2 O
CH 2OH
CH 2
ring expansion
H H H

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9.
(A) is secondary alcohol. CnH2n+1OH = Molecular weight Molecular weight of (A) = CnH2n+1OH = 60 (n = 3) (A) C3H7OH
H3C CH OH
CH3 CH 3CH(OH)CH (A) PBr 3
3
6 11200 1120
60 gm A
CH3
HC CH 3CHBrCH (B)
3
Anhy AlCl 3 (C)
CH3
10.
OH
CH2
O CrO3
Ph3P CH3 Cl t BuLi
C H 2N 2 ,
11.
A=
CHCH OH
C B=
CH3
O C C= CHBr 2
D=
OH CH COOH

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12.
Hydride shift H3C
OH CHCH(CH3)2 (X) I 2/OH (CH3)2CHCOOH
CH3 Br C CH2 CH3 (B) CH3 Methyl shift (CH3)2CCH2OH (Y) Oxidation (CH3)3C.CH2OH (A)
SN' displacement
(CH3)2.C(OH)CH2CH3 (Z)
Oxid
No Reaction
13.
1 mole HI
O (a)
CH3
O H
CH3
OH I
CH3
I OH (A) CH3
(b) O
HI I CH3 OH CH3
H OH 2
SN 2 I I CH3 I (B)
H2 O I CH3
14. (a)
H3C
CH3 C CH3 OCH 3
(b)
CH3 C O CH3

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(c)
R
(d)
R
E = 2HCHO + F = CO2
15.
Z=
H2COH
D=
E = H3C
C O
CH3
A=
H3C
CH3
O H F=
B=
Cl CH3
CH3
Cl C=
G = HCHO

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Objective:
LEVEL - I 1. 4. 7. 10. 13. LEVEL - II 1. 4. 7. 10. 13. A A A A D 2. 5. 8. 11. 14. C C D A B 3. 6. 9. 12. 15. A C A B D D D C A D 2. 5. 8. 11. 14. A B C C A 3. 6. 9. 12. 15. A B C C D

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Alcohol, Phenol & Ether - Chemistry

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Alcohol, Phenol & Ether - Chemistry

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Contents :- ALCOHOL, PHENOL AND ETHER

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