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PDF Bansal Classes Organic Chemistry Study Material For Iit Jee PDF
PDF Bansal Classes Organic Chemistry Study Material For Iit Jee PDF
XII (ALL)
QUESTION BANK ON
ACIDITY, BASICITY
H-BONDING
&
TA UTOMERISM
I
ACIDITY. BASICITY. H-BONDING & TAUTOMERISM
Q. 1 Write equations showing the Lewis acid-base reaction that takes place when
(a) Methyl alcohol reacts with BF3.
(b) Methyl chloride reacts with AICI3.
(c) Dimethyl ether reacts with BF3.
Which of the following are lewis acids & which are lewis bases?
CH3
CH3 CH3
^/C?. 3 Which would you expect to be the stronger acid? Explain your reasoning in each instance.
' CH2C1C02H or CHC^CO.H
,Jb) CC13C02H or CHC12C02H
Jt) CH2FC02H or CH2FCH2C02H
Q. 4 Write equations for the acid base reaction that would occur when each of the following compounds or
solution are mixed. In each case label the stronger acid & stronger base,& the weaker acid & weaker
base.
(a) NaH is added to CH3OH
(b) NaNH2is added to CH3CH2OH
(c) Gaseous NH3 is added to ethyl lithium in hexane
(d) NH4C1 is added to NaNH2 in liq. NH3
(e) (CH3)3CONa is added to H 2 0
(f) NaOH is added to (CH3)3 C-OH
(g) C2H5OH is added to a solution of HC = C~Na+ in liquid NHV
Choose the member of each of the following pairs of compunds that is likely to be the stronger base.
v (a) NH 2 or NH3 ( Jb) OH orH 2 0 J c ) O H or SH
o- O
©
4
Choose the member of each of the following pairs of compunds that is likely to be the weaker base.
2
H 2 0 or H30® v , (b) H2S, HS- S ~ (C) CI", SH
J d ^ F - , OH~ MTV, CH3 J e ) HF, H 2 0, NH3 , OH- SH", SeH
<j| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [2]
Q.8 Label the reactants in these acid - base reactions as Lewis acids (electrophiles) or Lewis bases
(nucleophiles). Use curved arrows to show the movement of electron pairs in the recations.
CH 3 H CH 3 H
O :o:
(c)
II
H - C - H + :NH 3 ->H-C=RH
2
IS M
NH 3
(d) CH 3 - N H 2 + CH 3 - CH 2 - C I : — - > CH 3 - N H 2 - CH 2 CH 3 + : C I :
R
© CH3 - c - CH3 + H2SO4 CH 3 - C - CH 3 + HSO4
f A
Q. 9 Predict the products of the following acidbase reactions.
H 2 S0 4 + CH3COO- ^
Q.ll Which reagent in each pair listed here would be the more reactive Nu in a protic solvent ?
xJ$) CH 3 NH- or CH3NH2 (b) H 2 0 or H,0®
y M CH 3 0- or CH 3 COO ^ (d) CH 3 SH or CH 3 OH
k) Ph 3 N or Ph 3 P CH 3 COO" or OH
H.S orHS" NH 3 or NH4®
Q.12 Each ofthese molecules is electrophile. Identify the electrophilic atom & draw a mechanism for reaction
with a generalised nucleophile Nu", giving the product in each case.
F° V Y X
(a) (b) Y (c) [ J (d) CI - CI (e) MeO ® OMe
<j| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [3]
19 Explain which compound is the weaker base.
NH2 NH2
rol^Ta
^bf. CH 2 = C H - C H = C H - C H 2 " or CH^CH-CIV
0 0 0 0
II II II II
Jtf 0--C-C-0H or HO-C-C-OH
OH OH
1
j * ( o r * - [or"
« [OJ [or LO
•NO,
1
0» for " L Q „„
CH3
(c> ©
(i) (ii) (iii)
Q. 21 Dimethyl furmamide (DMF) is an example of polar aprotic solvent, aprotic meaning it has no hydrogen
atoms attached to highly electronegative atoms.
(a) Draw what you predict to be its most important resonance forms.
(b) DMF when used as the reaction solvent, greatly enhances the reactivity of nucleophiles. e.g.
NaCN + CH 3 CH 2 Br > CH^CIi, C = N + NaBr
Suggest an explanation for this effects.
<|g Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [5]
Q.13 Each of these molecules is nucleophile. Identify the nucleophilic atom & draw a mechanism for reaction
with a generalised electrophile E+, giving the product in each case.
WR-C.C- w J X (ONH.-NH,
OMe
I NH
p IT
( d ) M e O / ^OMe (e) M ^ M e
Q.15 Neither of these methods of making pentan-1,4 diol will work. Explain why not-what will happen
instead?
MeM
(i) CH0-CH 2 -CH 2 -CH 2 -0H - ^ > CH3-CH-CH2 -CH2 -CH2
followed by H + | |
OH OH
C H 3 - C H - C H 2 - C H 2 -CH 2
I I
OH OH
Q 16 Suggest what species would be formed by each of the following combinations:
(a) PhO - + CH3COOH
( b ) H N ^ N H + CH 3 COO-
(c) Pyridinium ion+trifluoroacetate ion
Q.17 Say which pka belong to which functional group in case of following amino acids:
^COOH
(i) cysteine: HS J : 1.8,8.3 & 10.8
NH2
Q.18 Record the following sets of compounds according to increasing pKa ( = - log Ka)
OH OH
<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [5'5]
NH 2 NH-C 6 H 5 NH 2
^ LO
(i) (ii) (iii)
NH,
NH,
V^O fO o CI
(i) (ii) (iii)
ff
^NH
© NH
§
J*
Q.24 Arrange the following in increasing acid strength:
o
_ T-C-CH,
(a) =o O f o
OH
(i) (iii)
OH
OH
CH 3 - OH
O,
CN
O O O 0 O
CH3-C-OH H0-C-C-0H HO-C-CH2CH2 J- OH
©
(ii) (iii)
<j| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [6]
v yO .25 Set the following in increasing order of pka:
jffi Methane sulfonic acid, acetic acid & methanol.
{ CH 3 - CH2 - CH 3 , CH2 = CH - CH3 , CH3 - CHO , CHO - C H j - CHO , CH4 Ui) ^
^Jfy CH3N02,(N02)2-CH2,(N02)3-CH
nu 9H
OH 9H OH X.
N
^ ho2 °2 -
o o
. . CN CN
^ Q-Q-J&
H H H H H CN
^ fafff CHO-CHL-CHO, C H 3 - C
0II
- C H 2 - CII- C H 3 , E t - 0 - CII - C H 2 - CII-•O - E t ,
0 0 0
Et - O - C - CH2 - C - CH3
II II
0 0
Q. 26 Cyanic acid (HO-CsN) & isocyanic acid (H-N=C=0) differ in the positions of their electrons but their
structure do not represent resonance structures.
(a) Explain
(b) Loss of a proton from cyanic acid yields the same anion as that obtained by loss of a proton from
isocyanic acid. Explain.
i
Q.28 Arrange the increasing order of acidic strength ofthe following compounds.
v>r ^ rb Col™,
CH,
[7]
<j| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism
x-(¥29 Explain which is a stronger acid.
O O
^ a ) CH3CH3 BrCt^NO,, CH3 - C - CH3 & CH3 - C - CH2CN
OH .
^ C O ) or Jd)(0
CH3
O=C~CH3 ' O=C-CH3
SH OH
Mo) <* ( O )
^jaf.5 0 Which ofthe following would you predict to be the stronger acid ?
y~CH2-C-QH CH3-CH2-C-OH
Q. 3 3 Explain why the 2-methylpyrrolidine boils at a higher temperature than its isomers N- methylpyrrolidine.
U- UneO'l
Q. 3 4 Although nitration usually causes elevation of B .P. yet the nitration of resorcinol to 2-nitroresorcinol
decreases their B. P. then their parent compound.
5 o-nitrophenol is sparingly soluble in water & has lower B .P. but p-nitrophenol is completely soluble in
water & has high boiling point.
r
6 When 3 0 ml of ethanol and 5 ml of water are mixed the volume of the resulting solution is less than
35 ml. Explain.
<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [8'5]
^ Ammonium salts are much more soluble in water than are the corresponding sodium salts. Explain?
QS 8 HF has a dipole moment of 1.82 D, its boiling point is 19.34°C. Ethyl fluoride has an almost identical
diploe moment & has a larger molecular weight, yet its B.P. is -31.TC. Explain.
J&39 HC02H & CH3C02H exists as dimer. Explain.
Q. 40 Cyclohexanol is more soluble in water then 1 -hexanol.
Q. 41 Explain why CH3OH and CH3CI^OH are reasonably good solvents for many ionic compounds compare
the solvent properties of ethanol and pentanol towards ionic compound.
Q.42 1,5-Pentanediol is soluble & 1-Pentanol is slightly soluble in I^O.
\J#A3 Compare the relativ^i^ oiling points Water solubilities oftoluene & phenol.
Q.44 Which isomer (o,m or p) ofhydroxacetophenone steam distills.
J^45 Give structure for ethanolamine showing two different intramolecular H-bonds & discuss their relative
strength. f
(a) o
OK^ = M
v r v >o0 ..
(b) Q (c) A ( d ) ( \
W W
NC^H H HoXr
HOaH
Q. 47 Trans isomer ofindigotin is stable w.r.t cis isomer. Explain.
A
Q. 4 8 What is the attacking site of conjugate base oftriketo form ofphloroglucinol in protic & aprotic solvent.
\JQC49 In each ofthe^ollowing pairs which is more stable:
H (I) (11)
O O
0 H
C / C /OH
C 3
(I) (nf " (1) N"2 (J^NH
0
0 H
C /
u (11)
<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [9'5]
In each of the following pairs which is less stable:
o o
C /OH £ /OH
(I) U)
(11) (ID
O
£ / 0 H
(I) (II)
0II 0
I!
O
U
OH
Xc
c c c
(e) a / V3
N
CH3 - cuf V
3 3
^CH2
a) ao
caf
3
\ H 22 / XCH3 CH^ N
CH3
(I) (II)
H O O L,
O^ a-0 0C__^0 fj CH, £ %
j » 0 ©
O (ii)
« ^ vo w CHy
2
(1) (II)
CH,
g CH CH O7" ° " f
CH
OH ... O CH,
(IT) (1) (II)
O
U
O^ O OH
(0 (II) ^H (I) (II)
Ph Ph Ph Ph
N
\ ($fCH22 = CH - NH2 ^ CH3-CH= NH
^0 ^ OH (1) ^ (II)
(I) (II)
I
Q. 53 In each ofthe following pairs which will have higher enol content:
O ^COOEt ft
C
i Jti) CHXHO and / \ (b) C \ and
X
^ CH 3 CH 3 C O O Et CH 3 CH 3
^COOEt ft ft
(c) C \ and
COO Et CH 3 CH 2 OCH 3
. FL FF " FL ' FL
C c
v and / \ / \
^ CH 3 CH 2 CH 3 CH 3 CH 2 OCH 3
0 0 0 0
II II II II
(e) and
CH 3 CH 2 CH 3 Ph CH 2 Ph
Q. 54 In each ofthe following pairs which will have less enol content:
^ C ^ V V ( b ) C T ° a n d Q °
and
and Q ° ^ ( ^ f
CI
Q. 5 5 In each ofthe following pairs which will have higher enol content:
II O
11
c
CH 2 - C H O and CH 2 - C H O (b) (qY \ r and y\
I I 3 CH 3 CH 3
NO 2 CI
o o
0 0 c r
A A j / \ / \
v > 0 / \ / \ and CH 3 CH CH 3
CH 3 CH 2 CH 3 ^2H5
(a)
0 ^ 0 ® -"Sr
O ^ C P andCP J d ) h > = 0 and h > 0
0 0
r.TjJ^ 0
and ^ ^ o
H H
57 Which ofthe following compounds can exhibit tautoimerism:
(a) CHj = C = O (b)CH2 = C H - 0 H (c)HO-CH = CH-OH
C
(d) CH3CN (e) \
^NO2
8 Which ofthe following compounds can not exhibit tautoimerism:
0 O II
o
(d)(6r0^ (e)@r°H
Which ofdie following compounds can exhibit tautoimerism:
0
NH
Which ofthe following compounds can not exhibit tautoimerism:
f r
« y ^
OMe
11
->A I
JL N5" "OH
H
<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [12'5]
Q. 62 5,5 - dimethylcyclohexane -1,3 -dione (dimedone) shows tautomerism.Write down tautomeric structure.
Q. 63 Draw enol forms of these carbonyl compounds and comment on the stability of the enol forms.
a
o
(a) "
»>oo
o
Q. 64 The proportion of enol in a sample of the two ketones below are shown. Why are they so different ?
O O
4x % enol (b) ( ^ J ^
C H B O ^ ^ - X ^ M I - CH = CH 2
Q.65 (a) Jf J
and
CH = CH 2
a
<» CU
Shows tautomeric forms of (a) & (b).
e x "?N :
I
H
What is the tautomeric form ofisatin.
Q. 67 1 , 3 - dicarbonyl compounds such as (A) are usually mostly enolized. Why is this ? Draw the enols
available to compounds A & B comment on the different pattern of enolization.
Q. 6 8 In each of the following sets of compounds write the increasing order of % enol content
JSC 6 A
(0 <TI> (HI) (IV)
(gong; N 0
(I)
(I) (11) 2
O2N
, —i § n m
—(IIJ) NO 2
<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [13'5]
(C)
(grv ^ o
(LI)
(1) NO, (111)
o
NO 2
(II) (111)
NO,
CI
Ct
O I o
u^LQj o
© (11) (III)
Q. 69 In each of the following sets of compounds write the decreasing order of % enol content.
O
(SQ
(a) 0(I) C(II) O ail)
0» o 0
(i) (II) (IV)
(III)
o
j a)y cNr
(11) (III) (IV)
o o
(d) o ^ j y o N"
H
o.
H
(1) (ii) (HI)
(IV)
o
o O
(e)
a) (HI) (TV)
(II)
Q.71 ^ A ^ ^ A ^ has lower boiling point than even when former has - OH group.
O O
A A a A
N
Q-72 CH{ CH3 CD3/ X
CD3 CH 3 \ N 2
Y X
CH3
(i) y do (in)
Among these give ease of enolization.
@ @ + ©©
Q.74 J k ^ ?
(Minor) (Major)
Na0Hl[,H20
O
OH , OH
(Major) (Minor)
This tautomeric system exist almost exclusively in favour of phenol and it is insensitive to change in
solvent.
<f| Bansal Classes Q. Bank on Acidity, Basicity, H-Bonding & Tautomerism [1'5]
ANSWER KEY
Q.2 LA b,e LB acdf
Q.3 (a) 2; (b) 1; (c) 1
Q.5 CH3CH3 + C H 3 C s C M g B r
Q.6 (a) 1; (b) 1; (c) 1; (d) 1; (e) 2; (f) 1
Q.7 (a) 2; (b) 1; (c) 1; (d) 1; (e) 1; (f) 3
Q. 11 (a) 1; (b) 1; (c) 1; (d) 1; (e) 2; (f) 2; (g) 2; (h) 1
Q.14 (a) 2<1<3; (b) 1<2<3; (c) 3<1<2
Q.18 (a) 3<2<1; (b) 1<2<3; (c) 3<2<1; (d) 2<1<3; (e) 2<3<1
Q.19 (a) 2; (b) 1; (c) 2; (d) 2
Q.20 (a) 3<2<1<4; (b) 1<2<3<4; (c) 3<1<2
Q.22 (a) 1>2>3; (b) 1<2<3; (c) 3<1<2; (d) 2<1<3; (e) 1<2<3; (f) 1<2<3<4<5
Q.23 (i) 1>2; (ii) 4>3>1>2; (iii) 1<2; (iv) 1<2
Q.24 (a) 1<2<3; (b) 3>1>2; (c) 1<3<2
Q 25 (i) 1<2<3; (ii) 1>5>2>3>4; (iii) 1>2>3; (iv) 1>3>4>2; (v) 1>3>2; (vi) 2>1>3;
(vii) 3>4>2>1
Q.28 (a) 3>1>2; (b) 1>2>3; (c) 2>3>1
Q.29 (a) 2; (b) 2; (c) 1; (d) 1; (e) 1
Q.30 (a) 2; (b) 2; (c) 2
Q.31 (a) 1; (b) 2; (c) 2; (d) 1
Q.32 4.25,1.34><10_5
Q.49 (a) 2; (b) 2; (c) 1; (d) 1; (e) ^
Q.50 (a)2; (b) 2; (c) 2; (d) 2; (e) 1
Q.51 (a) 2; (b) 2; (c) 1; (d) 2; (e) 1
Q.52 (a) 2; (b) 1; (c) 1; (d) 1
Q.53 (a) 1; (b)l; (c) 2; (d)l; (e) 2
Q.54 (a) 1; (b) 1; (c) 2; (d) 1; (e) 2
Q.55 (a) 1; (b) 1; (c) 1; (d) 1
Q.56 (a) 2; (b) 2; (c) 2; (d) 1; (e) 2
Q.57 a, b, c, d, e
Q.58 a, c, d
Q.59 b
Q.60 b
Q.68 (a) 2>1>4>3; (b) 3>2>1; (c) 3>2>1; (d) 3>1>2; (e) 3>1>2
Q.69 (a) 3>1>2; (b) 4>2>1>3; (c) 4>3>1>2; (d) 1>3>4>2; (e) 3>2>4>1
Q.72 3>1>2
ORGANIC CHEMISTRY
XII (ALL)
CONTENTS
EXERCISE-1(A)
EXERCISE 1(B)
EXERCISE-II
EXERCISE-III
EXRECISE - IV(A)
EXRECISE - IV(B)
ANSWER KEY
EXER CISE-IfA)
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
14 14
(A) CICH2CHCH2OC2H5 (B) ClCH2CHCH2ONa
OH
14 14
(C) CH2-CHCH2OC2H5 (D) CH2-CHCH2OC2H,
• 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
„ „ , 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)C02/140°C 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
A and Bare:
(B) ^ / - CH 2 CH 2 CH 2 OH, J - CH = CH - CH 2 OH
CH,
CH,OH h
Q.29 B 4r CH.-C-CH, 2° 18 >a
CH,ONa \J " H+
o
A and B are
18
OH OH OH OCH, OHlgOH OH OCH,
IBOH OH
18 18
0OH OH 3OH OH OCH 3 OH
henceA ^ B , B i s :
0 = ^
(A) (B) (C)CH2-0-CH2 (D) None
OH OH
Q.31
CH2CH2OH
-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
•Me o Ox /Et
(A)
H CI Ale. KOH
Q 35 \ 0 / \ / \ / > Major product is
H U
(A) \ 0 / V ^ / \ „ (B) H \ q A A
H
(C) \ / \ / \ (D)
0
CJ
x r
R"
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)
\H Of H OCH,
\H CP 3 \H ?PH3
(A) & (B) yj( &
ch H 3 CO CH3 HO CH 3
H.CO OH OH 3
(B) H 3 C O C
(°)\Or\Oy~OH
COCH,
OH OH
/R R\/ /R
(A) (B)
CH2CH=CH2 CH 2 -CH-CH 7
OH
R V A / R
(c) (D) no reaction
iJSiCH2—CH—CH9
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 is
OH CH-,-OH OH CH2-C1 OH CH 2 -NO, Q
(A) (B) ( C ) f l ( D ) f S
OH
O OH
+
^ . HCO,H
2 . H,0
2 „ , „ PthalicAnhydride
Q4b Acetophenone —> A >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
o
C-CH3
C- C-CH3
II
V- lo o
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
Question No 48 to 50 (3 questions)
500°C •No reaction
LiAlH 4
NaBH,
COOH
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
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
CH; CH;
rm
(DJ
\ , \ ~ ~ K/ CH,OH
H | O CH 3
O /
O
" H+
(D) R-C^OH + HtO-R
I
These bonds undergo cleavage in the reaction
(A) ^ ^ - O H + HNO3 h
2s°4 >
•NO,
0 H
(B) ( ^ y ~ +HN0 3 h
2s°4 ? Q-ONO.
(C) CH2 = CH-CHO + LiAlH4 —-> CH3 CH,CH2OH
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
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
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,
LiAlH 4 /H 2 0 gives
CH3-CH-CH^CH3
(B) I I PdCl2, H 2 0, 0 2 / LAH
CH 3 OH
OH
CH 3
OH
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
/ v C H 0
-»
/CHO
(i) Br MeO'
© Acraldehyde Glyceraldehyde
(iii)
Br - CH, CHO Ph CHOH CH2 CHO
O
CI
Q. 4 Outline a mechanism to account for different isomer formed when Me 2 C CH 2 reacts with CH3 OH
N /
o
Q.6
Product
Explain product formation. How two OH groups behave differently.
(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.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 170°C.
(b) Sodium chloride solution in water is added to decrease the solubility of organic compounds in water.
Q. 16 Carry out conversion of methyl alcohol into ethyl alcohol and vice versa.
Q. 20 t-butyl alcohol reacts less rapidly with metallic sodium than the primary alcohol. Explain why?
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.
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.
OO
(iv) C6H5COCC6H5 in the presence of pyridine
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
SOC 2 NaB 4
(b) CH, = CHCH,CH,CHCH, ' > C,H,,C1 — ^ > r HXIO " >C«H,,(
1 pyridine 5 5 11
I (ii)Zn/H20 ^
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).
COoH
(1)
(b) Cl- —H ™4 > compound E (C3H7C10) K0H H
' 2° > compoundF (C 3 H 6 0)
CH, '
(iii)
(iv)
R' R
(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.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.
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)?
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).
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.
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).
[REE 1990]
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
o nI Y
CH 3 / V CH3
F Ph OH
0 H
OH (IV)
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
O Na+(excess)
Q.ll < O ^ O H + C2H5I — ^ [JEE 2003]
; OH(anhydrous)
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. 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
H CI CH 3
following products:
CH3H CH 3 CH3H CH 3
H OHCH 3 OH H CH 3
CH3H CH 3
CH 3 O- -N0 2 (M)
H CH 3 OH
|
I
i
1I
i
i
i
I ]
•! i
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. 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]
EXER CISE-II
O
Ii
Q2 (a) Et-CH=CH-CHO (b) Ph-CHO (c) Ph - C - CH 2 - CH 2 - CH
OCH3 OCH 3
OH O®
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
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 170°C 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
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
/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.
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.
Q.27 Ethanol being very weak Lewis base and thus reacts with stronger acid HI
OH
(c)
Q.29 (A)\^J ( B ) ^
CJ
(D) CH2 = CH-CH2(C1) - CH3 (E) CH3CH(C1)CH2CH2CH0
CH?OH
Br
NFL OMe
Q.30 (a)[Ol r 2 (b) (c)Ph-CH(Cl)-CH 2OH
CH2Ph
Me' t)H OH
(d) H 3 C-CH 2 -CH 2 -CH 2 -S-CH 2 -(CH 2 ) 16 -CH 3
0 «Q
(C)
CI—| H ( F ) Me-CH-CH 2
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
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
EXER CISE-III
OH
H H H O
! I I I!
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
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)
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.10 C 2 H 5 OC 2 H 5 ; C 2 H 5 I; C 2 H 5 OH
(X) (Y) (Z)
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 —C—CH 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)
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)
Br
(C) C H 3 - C H C H ( C H 3 ) 2 (D) CH 3 CO CH(CH 3 ) 2
I
OH
OH
CH 3
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 <-
i | + J
CH, - CH - C - CH,
Me Me
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
Br
^ y / M e Me
Br~
2°carbonium 3° carbonium
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
ORGANIC CHEMISTRY
xni(XYZ)
AROMATIC
COMPOUNDS
CONTENTS
EXERCISE-I
EXERCISE - II
EXRECISE-III
EXRECISE-IV(A)
EXRECISE-IV(B)
ANSWER KEY
EXERCISE-I
Q. 9 Which order is correct for the decreasing reactivity to ring monobromination ofthe following compounds:
(I)C6H5CH3 (II) C6H5COOH (III)C6H6 (IV) C6H5NO2
(A) I > II > III > IV (B) I > III > II > IV (C) II > III > IV > I (D) III > I > II > IV
Q.10 Benzene on treatment with a mixture of conc. HN0 3 and conc.H2S04 at 90°C gives:
(A) Nitrobenzene (B) m-Dinitrobenzene (C) p-Dinitrobenzene (D) o-Dinitrobenzene
Q.ll Which of the following structures correspond to the product expected, when excess of C6H6 reacts with
CH2C12 in presence of anhydrous A1C13:
(B)Q-CHC L 2
€1
Q.13 Benzene reacts with n-propyl chloride in the presence of anhydrous A1CL to give predominantly:
(A) n-Propylbenzene (B) Isopropylbenzene
(C) 3-Propyl-1 -chlorobenzene (D) No reaction
Q.14 In the sulphonation. acetylation andformylationofbenzene the group of effective electrophiles would be:
Q.18 Chlorinaton oftoluene in die presence oflight and heat followed by treatment with aqueous NaOI I gives:
(A) o-Cresol (B)p-Cresol
(C) 2,4-Dihydroxytoluene (D) Benzyl alcohol
( A r ) r1 ^ ° r S (C)V^ fr (D) ^
N 2
NO2
NO-, NO, " NO, OoN
Q.20 In the reaction of p-chlorotoluene with KNH2 in liquid NH,, the major product is:
(A) o-Toluidine (B)m-Toluidine (C) p-Toluidine (D) p-Chloroanilinc
AICI3.A
Q.23 Which chloroderivative of benzene among the following would undergo-hydrolysis most readily with
aq.NaOH to furnish the corresponding hydroxy derivative.
.N02
(A)02N-/oV-C1 (B)02N-<O)-C1
(
NO2
Q.24 . The order of relative reactivity of the given halides towards SN2 reaction is:
(A) PhCH2Cl > PhCHClCH3 > PhCCl(CH3)2
(B) PhCH2Cl < PhCHCl(CH3) < PhCCl(CH3)2
(C)PhCHCl(CH3)>PhCH2Cl>PhCCl(CH3)2 .
(D) PhCHCl(CH3)>PhCCl(CH3)2 > PhCH2Cl
Q.25 An aromatic compound A' C7H6C12, gives AgCl on bonding with alcoholic AgN03 solution, and yields
C?H70C1 on treatment with sodium hydroxide. 'A' on oxidation gives a mono chlorobenzoic acid which
affords only one mononitro derivative. The compound A is:
CH,C1
CH2CI CH 2 CI
Q.27 Which of the following substituted benzene derivatives would furnish three isomers in significant amount
when one more substituent is introduced:
CI Br
C1
300°C
300 L
(C)'
V H1- CI + ale. KOH > (D) 1'If Jj + NaOH 200 atm>
(A) ( o f (B) (O [ £ )
OCH3
NaNH 2
Q.31 O ~~> A, maj or product A and reaction R are:
Br
OCH,
2
(A) I O I , elimination addition (B) j , elimination addition
l
2
OCH, OCH,
uvlight
(C)C6H6 + Cl2 > C6H6C16 (D)C6H5OH + CO + HCl > K>)
AC3
Q.39 { ( J ) + CH2CH2CH2C1 ' ' > hydrocarbon (X) major product X is:
CH,
CH,
IC
(A) < 0 ^ CH 2 CH-CH 3 (B) < O y ~CH
|
CH
Q-51 F OJ + H2 Ni, high temp, > (A). Which ofthe following can be isolated as the product ofthis reaction.
^ ^ high pressure
( A ) Q ( B ) 0 ( C ) 0 (
Q. 5 2 Which of the following is/are produced when a mixture of benzene vapour and oxygen is passed over
V 2 0 5 catalyst at 775 K?
(A) Oxalic acid (B)Glyoxal (C) Fumaric acid (D) Maleic anhydride
Q. 5 3 Which of the following is the least reactive in the case of bromination:
(A) Phenol (B) Aniline (C) Nitrobenzene (D)Anisole
Ois:
Q. 54 No. of 7t electrons in
(A)
O (B) (C)
Q. 5 6 Benzene on reaction with A' forms j Q) which on reaction with 'B' forms I Q
(A) (B) (Q
(D)
(A) (B)| (C)
lJ
Q. 61 Which ofthe following is most reactive towards sulphonation?
(A) m-Xylene (B)o-Xylene (C) Toluene (D) p-Xylene
Q. 62 Which of the following undergoes sulphonation at fastest rate ?
(A)C6H5NO2 (B) C6H5CH2NO2
Q. 64 When sulphonilic acid (p-H2NC6H4S03H) is treated with excess of bromine, the product is:
(A) tribromo product (B) dibromo product
(C) monobromo product (D)tetrebromo product
Q. 6 5 Ring nitration ofdimethyl benzene results in the formation ofonly one nitro dimethyl benzene. The dimethyl
benzene is:
GH 3 CH,
Q. 72 Which of the following species is expected to have maximum enthalpy in an electrophilic aromatic
substitution reaction?
H®+ E
(A) Species (II) (B) Species (III) (C) Species (IV) (D) Species (V)
Q. 7 3 For the electrophilic substitution reaction involving nitration, which of the following sequence regarding
the rate of reaction is true?
-6ll6> ^6nU6> ^r
l x
66 ( B
) k
C6H6 < k
C6D6 < k
C6T6
k k k k k k
( Q CfiHfi = CfiD, = C,Tfi (D) C f i H f i >' CfiDfi < C,Tfi
Q. 74 For the electrophilic substitution reaction involving sulphonation, which ofthe following sequence regarding
the rate of reaction is true?
K K K k < k < k
(A) CFIHFI > C,D, > C,T, (B) C6H6 C 6 D 6 C 6 T 6
k k k
(D) CfiHfi > CfiD < C,Tfi
Q. 7 5 The order of relative reactivity of the given halides towards SN1 reaction is
(A) benzylchloride > p-methoxybenzylchloride > p-nitrobenzylchloride
(B) p-methoxybenzylchloride > benzylchloride > p-nitrobenzylchloride
(C) p-methoxybenzylchloride > p-nitrobenzylchloride > benzylchloride
(D) benzylchloride > p-nitrobenzylchloride > p-methoxybenzylchloride
D
(A)[o] (B)[o] (Ofof < )(Oj
NaOH H2, 0
Q.5 [OJ 395QC ' Product is:
Q.7 Electrophile NO® attacks the following in which cases NO® will be at metaposition:
• ^(0) iQ(o)
Q.15 The good method for converting benzene into propyl benzene is:
(A) C 6 H 6 + CH3CH2CH2C1 + Anhyd. A1C13
(B) C 6 H 6 + CH 3 CH 2 COCI+Anhyd. A1C13 and then treatment with Zn/Hg/HCl
(C) C 6 H 6 + CH 3 CH 2 C0C1 + Anhyd. A1C13 and then treatment with H 2 Ni
(D)C6H6 + Anhyd. A1C13 + cyclopropane
Q.16 Which of the following will undergo nitration slow than benzene?
NH, CI NHCOCH,
(D)
Q.21 The structure of the compound that gives a tribromo derivative on treatment with bromine water is:
CH
' CH3 SO3H COOH
° ?
Q.24 Of the species PhSH, PhSR, PhSR and Ph - S - OR the meta-substituted product is obtained from
H A I
(A)PhSR • (B) PhSR (C) PhSR
y ?
(D) P h - S - O R
II H II
0 0 o
(A) FO I+ CR0
3 IN C H
3 C 0 0 H
• (P) Tropylium ion
7> v
(C) [ O I + n-Pr Br + ZndL >? (R) Two types of products
CH 3
(S) Cumene
H-N-ME
I
Q.27 Match the following:
Column I Column II
o o
n>\ 11 11
(A) Compounds which on reaction (P) Ph—C^TT ^C-
with neutral FeCl3 gives
violet / Blue colour are
TMoTS] _
(C) Compounds which do not give (R) Ph-CH2-C-CH2CH3
yellow ppt. On reaction with NaOI
of enol form
r
(y) ® \ / OCH3 (i)NBS,Benzoyl peroxide,CC14,heat ^ p
3
V (ii)NaSCH,
CH,
JLNO 2 CI
N 0 2
(vi) L j i +CH3CH2ONa >G (vii) f | T + C6H5CH2SNa >H
N0 2
NO2
1
« O n - ^ ^ heat
Q. 2 Write the most stable resonance structure for the cyclohexadienyl anion formed by reaction of methoxide
ion with o-fluoronitrobenzene.
Q.3 Reaction of 1,2,3-tribrom-5-nitrobenzene with sodium ethoxide in ethanol gave a single product,
C8H?Br2N03, in quantitative yield. Suggest a reasonable structure for this compound.
Q.4 Offer an explanation for the observation that 4-chloropyridine is more reaction toward nucleophiles than
3-chloropyridine.
Q.5 2-Bromo-1,3 -dimethylbenzene is inert to nucleophilic aromatic substitution on treatment with sodium
amide in liquid ammonia. It is recovered unchanged even after extended contact with the reagent. Suggest
an explanation for this lack of reactivity.
Q. 6 Two isomeric phenols are obtained in comparable amounts on hydrolysis of p-iodotoluene with 1 M
sodium hydroxide at 300°C. Suggest reasonable structures for these two products.
Q. 7 Given the structure ofthe cycloaddition product formed when benzyne is generated in the presence of furan.
N
°2 H X H
a CH 2 CH,CH,GH 2 COCH 2 CH 3
C1
(i)ExcessNaNH2,NH3
(ii)H20
>
^
^ T r
"
COOCH 2 CH 3
CH 3 CH 3
NCH 2 CH 2 NHCH 3 NaNH2 f ^ j ^
(c) L j J ether ^
CI CH 3
F F
F x J^OCH 2 CH 2 OH F
T i] w > T iT J
(d) heat
F F
Q.l The cWorination oftoluene in presence of ferric cUoride gives predominatly: [JEE 1986]
(A) Benzyl chloride (B) m-chlorotoluene (C) Benzal chloride (D)o-andp-chlorotoluene
Q. 2 Aiyl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due to
(A) The formation of less stable carbonium ion (B) Resonance stabilization
(C) Longer carbon-halogen bond (D) The inductive effect [JEE 1990]
Q.3 The most basic compound among the following is: [JEE 1990]
(A)Benzylamine (B) Aniline (C)Aeetaniline (D) p-nitro aniline
Q.4 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives:
(A)o-cresol (B)p-cresol
(C) 2,4-dihydroxytoluene (D) Benzoic acid [JEE 1990]
Q.5 When nitrobenzene is treated with Br2 in presence of FeBr3 the major product formed is
m-bromonitrobenzene. Statements which are related obtain the m-isomer are: [JEE 1992]
(A) The electron density on meta carbon is more than on ortho and para position.
+
(B) The intermediate carbonium ion formed after initial attack of Br attack the meta position is least
destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para positions and not at meta position
(D) Easier loss of H+ to region aromaticity form the meta position thanfromortho and para position.
Q.6 Choose the correct statementfromthe ones given below for two aniline in: [JEE 1993]
+
NH 3 NH 3
(I) (II)
(A) II is not an acceptable canonical structure because carbonium ions are less stable than ammonium
ions .
(B) II is not an acceptable canonical structure because it is non aromatic
(C) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons
(D) II is an acceptable canonical structure
Q.7 Most stable carbonium ion is: [JEE 1995]
(A)p-N02-C6H4-+CH2 (B)C6H5+CH2
(C) p - CI - C 6 H 4 - +CH2 (D)p-CH30-C6H4 -+CH2
Q. 8 Arrange in order of decreasing trend towards SE reactions: [JEE 1995]
(I) Chlorobenzene (II) Benzene (IH) Anilinium chloride (IV) Toluene
(A) II > I > III > IV (B) III > I > II > IV (C) IV > II > I > III . (D) I > II > III > IV
Q.9 Among the following statements on the nitration of aromatic compounds, the false one is: [JEE 1997]
(A) The rate ofbenzene is almost the same as that of hexadeuterobenzene
(B) The rate of nitration of toluene is greater than that of benzene.
(C) The rate of nitration of benzene is greater than that of hexadeuterobenzene
(D) Nitration is an electrophilic substitution reaction
Q.10 Nitrobenzene can be preparedfrombenzene by using a mixture of conc. HN0 3 and conc. H 2 S0 4 . In
the nitrating mixture HN0 3 acts as a: [JEE 1997]
(A) Base (B)Acid . (C) Reducing agent (D) Catalyst
Q.ll Benzyl chloride (C6H5CH2C1) can be preparedfromtoluene by chlorination with: [JEE 1998]
(A)S02Cl2hv (B)SOCl2 (C)Cl2hv (D)NaOCl
w V / 0 -
w ° \ 5 /
(A)
O" O O" o
Q.13 A solution of (+) -2-chloro-2-phenylethane in toluene racemises slowly n the presence of small amount
of SbCl5, due to the formation of: [JEE 1999]
(A) Carbanion (B)Carbene (C) Free-radical (D) Carbocation
Q.14 Toluene, when treated with Br2/Fe,. gives p-bromotoluene as the major product, because the CH3 group:
(A) is para directing (B) is meta directing [JEE 1999]
(C) activates the ring by hyperconjugation (D) deactivates the ring
Q.15 Amongst the following the strongest base is: [JEE 2000]
(A) C6H5NH2 (B) p-02NC6H4NH2 (C) m-02NC6H4NH2 (D) C6H5CH2NH2
Q. 16 Identify the correct order ofreactivity in electrophilic substitution reactions ofthe following compounds :
CH, CI NO,
(A) I > II > III > IV (B) IV > III > II > I (C) II > I > III > IV (D) II > III > I > IV
(CH3)2NH ) ^ (i)NaNQ 2 HCl 0°~5°C ^ ^
Q.17 F 2
[JEE 2003]
DMF (ii)H 2 Catalytic Reduction
H3CX
(A)02N-^0/-nh (B) N
H2CX H3C
(C) (D) 1
h2C/
NH,
Q.18
Br
EXERCISE - IV (B)
A1C1
Q.l [ O J + (CH3)2CH.CH2C1 3 >(A) [JEE 1992]
(i) Br,,Heat,Light
Q-2 C H C
6 5 2H5 (ii)NaCN
>
[JEE 1994]
Q.3 An organic compound (A). CgH6 on treatment with dilute sulphuric acid containing mercuric sulphate
gives a compound (B), which can also be obtained from a reaction of benzene with an acid chloride in
the presence of anhydrous aluminium chloride. The compound (B), when treated with iodine in aqueous
KOH, yields (C) and a yellow compound (D). Identify (A), (B), (C) and (D) with justification. Show
how (B) is formed from (A) ? [JEE 1994]
Q. 4 Toluene reacts with bromine in the presence of light to give benzyl bromine while in presence of FeBr3 it
gives p-bromotoluene. Give explanation for the above observations. [JEE 1996]
Q.5 Show the steps to carry out the following transformations: [JEE 1998]
(a) Ethylbenzene > benzene
j? (b) Ethylbenzene > 2-phenylpropionic acid
Q.7 C6H5CH - CH2 (A) ('> NaNH 2(3-0 EQUIV)^ ( B ) [JEE 1998]
(ii)CH 3 I
Q. 8 Normally, benzene gives electrophilic substitution reaction rather than thus electrophilic addition reaction
although it has double bonds. [JEE 2000]
Q.9 , How would you synthesis 4 methoxyphenol from bromobenzene in NOT more than five steps? State
clearly the reagents used in each step and show the structures of the intermediate compounds in your
synthetic scheme. [JEE 2001]
ch
3
(ii) B r - { j K __ C2HsOH(aq.) ) neutral
CH,
.0 -O
N
N 0
Conc.HNO
/^/ 2 r
(C) (i)
Conc"• H 2 S O 4 ^
NO2
EXERCISE- II
Q.l A,B,D Q.2 A,C Q.3 A,B Q.4 A,B,C,D
Q.5 A,B Q.6 A,B,C Q.7 A,B,C Q.8 C
Q.9 A,B,D Q.10 B Q.ll A,B Q.12 A,B
Q.13 A Q.14 C,D Q.15 B,D Q.16 C
Q.17 C Q.18 A. Q.19 A,B,C Q.20 A,B,C
Q.21 B,C,D Q.22 B Q.23 B,C,D Q.24 C,D
Q.25 (A) Q, (B) P, (C) R, S, (D) R Q.26 (A) Q, (B) P,R,S, (C) R,S, (D) P,Q,R,S
Q.27 (A) P,Q,R,S, (B) Q, (C) P,Q,R,S, (D) p Q.28 (A) R, (B) S, R, (C) P, (D) S
EXERCISE-III
C6H5CH?S H,NNH CI Br
NO,
Q.l (i) (ii) (iii)
0,N
NO 2 OCH,
OCH 2 CH 3 SCH 2 C 6 H 5
.NO 2 NO,
OCH 2 CH 3
F 0CH 3/ 0~ Br J \ .Br
Q.2 Q.3
NO,
Q.4 Nitrogen bears a portion of the negative charge in the anionic intermediate formed in the nucleophilic
addition step in 4-chloropyridine, but not in 3-chloropyridine.
Y ci
EXERCISE - IV(A)
Q.l D Q.2 B Q.3 A Q.4 D Q.5 A,B Q.6 C Q.7 D
Q.8 C Q.9 C Q.10 A Q.ll A,C Q.12 C Q.13 D Q.14 A,C
Q.15 D Q.16 C Q.17 B Q.18 D Q.19 C
EXERCISE - IV (B)
C(CH3)3
Q.l [ O
OH
CFIH, COOH
Sodalime
(b) (i) fol fO] > [O
CN COOH
CHOCH CHXCH CHCH3 CHCH3
KCN
(")fO hv fo] -^[o
K0H (ALC)
Q.6 C 6 H 5 CH 2 CH 2 CHC1C 6 H 5 A > C 6 H 5 CH= CHC 6 H 5
(Cis and trans forms)
CH=CH, •,CHBrCH2Br C=CNa
Br-, NaNH2 3 eq. [ Q
Q.7 [ O ->fO
CH,I
C=C-CH,
SO.H
OMe OMe
H,0
ONa OH
Alternative rout
Br Br Br OMe
Br
Na0H
conc.H-SO,,
->IQ JO Me2S04
»i O ]
^ ^
Na0H
)[o
A high Pressure
1 H,cr
OMe
OH
Q.10 (O) •
SO.H
* o
OH
0
C-CH 2 -CHO C=CH-CHO
Q.ll ^
(A) . . ( B ) .
Keto Enol
Enol form is more stable due to extended conjugation
O
n
C-OH
KMnO„
(A)
o CI
Q.12 On ionization 7-bromo-1,3,4-cycloheptatriene gives tropolium ion which is aromatic with 671 electrons.
Br
(©) + Br
5-bromo-1,3-cyclopentadiene can't ionise as it will in that case give highly unstable antiaromatic cation
with 4 71 electrons.
Br
-X- + Br
(b) (i)
jCT + F is liberated; (ii) Bimomecular mechanism is not possible in (ii) case
-
CH3
(c) (i) due to presence of lone pair of nitrogen atom NO group is electron denating and ortho, para
directing
(ii) N0 2 group is electron withdrawing and meta directing
(d) Due to reduction of central ring, three four membered antiaromatic rings become stable while on
recuction of terminal ring only one antiaromatic ring can be stabilized.
CH 3
ORGANIC CHEMISTRY
XII (ALL)
CARBONYL COMPOUND
CONTENTS
EXERCISE 1(A)
EXERCISE 1(B)
EXERCISE II
EXER CI SE III
EXERCISE IV (A)
EXER CISEIV (B)
ANSWER KEY
EXERC1SE-UA)
Q. 1 Gem dihalide on hydrolysis gives:
(A) Vic did (B) Gem diol
(C) Carbonyl compound (D) Carboxylic acid
Q. 4 Arrange these compounds in decreasing order of reactivity for the nucleophilic addition reaction:
(I) Acid chloride (II) Aldehyde (III) Ketone (IV) Ester
Select the correct answer from the codes given below:
(A) I > II > III > IV (B) IV > III > II > I (C)III>II>I>IV (D) I > IV > II > III
Q.5 Acetalorketalis:
(A) Vic dialkoxy compound (B ) a, o-dialkoxy compound
(C) a-alkoxy alcohol (D) Gem dialkoxy compound
CH 2 -OH
<C4H,-OH+ OH (D)HCN
Q.ll Which one of the following compounds will give dimethyl glyoxal with Se02:
(A) Acetone (B) Acetophenone (C) Ethyl methyl ketone (D) Propanaldehyde
" U
Q.13 Consider the given reaction:
O O
c h c o o o h
C H 3 - C - C H 3 6 5 > C H 3 - C - O - C H 3
(I) CH3 - C - CH2 - C - CH3 (II) CH3 - C - CH3 (III) CH=CH (IV) CH,-CHO
Select correct answer from the codes given below:
Codes:
(A) I > IV> III > II (B) I > IV >11 >111 (C) III > I > IV > II (D) II > IV > I > III
CH3
(X) and (Y) will respectively be:
(A) CH 3 -CH 2 -CHO and CH 3 -CH 2 -CHO (B) CH3-CHO and CH 3 -CH 2 -CHO
CH3
CH,
Q.17 Number of products in the given reaction:
OH
C6HsCHO + CH3-CHO > Product
will be
(A) One (B) Three (C)Two (D)Four
Q.18 In the reaction:
5h/a
/\ _~_ yy 0 + wr " w > [X]
[X] will be
OH O OH OH O
OH
O
(A)f i f i (B)[ n i (c)[ n i ( D ) ( ^
ISJ
(!§Bansal Classes Carbonyl Compound
Q 20 The product of the reaction:
[X]
will be:
c6H5
*no2
is known as:
(A) Perkin reaction (B) Knoevenagel reaction
(C) Reformatsky reaction (D) Claisen-Schmidt reaction
CH 2 OH
Q. 24 Acetaldehyde can be converted into HO CH 2 - C - CH 2 OH by which reagent?
CH 2 OH
Q.27 Which will give silver mirror test with Tollens reagent:
(A)C6H5CHO (B)CH 3 -CHO (C) HCOOH (D) All of these
Q.28 Which one of the combinations will give propanaldehyde on dry distillation?
(A) (C6H5COO)2Ca and (HCOO)2Ca (B) (CH3COO)2Ca and (CH3CH2-COO)2Ca
(C) (CH3-CH2-COO)2Ca and (HCOO)2Ca (D) (CH3COO)2Ca and (CH3COO)2Ca
is knows as:
(A) Kolbe reaction (B) Tischenko reaction (C) MPV reaction (D) Oppeneur oxidation
CO BH 3 0
t ii)H202/0H
(Y)
(X) and (Y) are :
ISJ
(!§Bansal Classes Carbonyl Compound
Q.3 3 Cyanohydrin of which compound on hydrolysis will give lactic acid?
(A)C6H5CHO (B)HCHO (C) CH3CHO (D) CH3-CH2-CHO
3
Q.37 Compound TT^TI formed by the reaction of furfural ( ' ( " ^ • n u r i ) w i t h e t h a n o l i s
O CHUrl O LHU
(A) an aldol (B) an acetal (C)aketal (D)ahemiacetal
[21]
fa Bansal Classes Carbonyl Compound
Q. 41 Questions given below consist oftwo statements each printed as Assertion (A) and Reason (R); while
answering these questions you are required to choose any one of the following four responses:
(A) if both (A) and (R) are true and (R) is the correct explanation of (A)
(B) if both (A) and (R) are true but (R) is not correct explanation of (A)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true
Assertion: Benzaldehyde with HCN gives two isomeric compounds
Reason: Both nitrile and isonitrile compounds are possible when HCN reacts with carbonyl group.
Q. 42 When D-glucose is treated with Br, water then the product is:
C02H C02H OH CO 2 H
OH —OH —OH
HO-
HO- —OH
HO— HO—
OH —OH
(A) —OH
(B) —OH (Q (D)
—OH — OH —OH — OH
—OH OH OH
CO?H
OH
Q.43 [(CH^CQ] 3 A1 A
A is:
OH
(A) (B)
(Q (D)
a CH=CH-CHO
LlA1H4
) p r o d u c t is (B) ||^j-CH=CHCH 2 OH
Compound 'C fCF, - C - C ( C H 3 ) 3 1 was prepared in a three step sequence from ethyl trifluoroacetate.
I ^
[ 0 J
The first step in a sequence involved treating ethyl trifluoroacetate with NH 3 to give a compound A. A on
treatment with reagent 'X' (alongwith gentle heating) produces a compound B (which on hydrolysis can
produce an acid). B on treatment with an orango metallic, 'Y', followed by hyydrolysis produces C.
Based on above passing attempt the following questions:
CF 3 ^ c ^OCH 2 CH 3
(C) C F ^ ^ O C H . C H , I!
NH, NH
Q 46 Structure of B would be
O
(A) CF, - C - N H 2 (B) CF 3 -C=N (C) C F 3 - C H 2 - C N (D) C F 3 - C H 2 - N H 2
O
rSH
-SH
Q.49 C— — » E : 'E' is
RaneyNi
CF3 H CF3 S
n
\ / \ /
C
(A) / \ (B) / X ,
S
(CH 3 ) 3 C OH (CH3)3C
CF 3 H O
\ /
c
I
(C) / \ (D)CF3-C-S-C(CH3)3
(CH3)3C H
?
(A) C H 3 - C - C H 3 (B)CH3-CH2-C-CH3
s
o O
II • II
(C) Ph - C - CH 3 (D) CH3 - C 6 H 4 - C - CH 2 Ph
(P)
CH 3 CH,
Q.4 Two isomeric ketones, 3 -pentanone and 2-pentanone can be distinguished by:
(A) I , / N a O H (B)NaS0 3 H (C) NaCN / HCl (D) 2,4-DNP
C g H 5 - C • - CH3
C2H5
This alcohol can be prepared from:
° 11
O
II C 2 H 5 andCH 3 MgBr O
(C) C 6 H 5 C- (D) C 6 H 5 - CII - C l and C 2 H 5 MgCl
0
(C) C6H5 - CH2 - C - NH2 (D) C6H5CH2CN
Q. 13 Which one of the following reagent(s) is/are used for the conversion ofketone into hydrocarbons?
(A)LAH (B)N2H4/H202
(C) Mg Hg F^O (D) NaHgHCl
(A)CH3CHO (B)Ql0I1
OCH3
(C) CH3CH2CH2CH2CH --OCH
OCH3 (D)CH
(D) CH33-CH
-CH
^OCH,
OH
O
II O
II
(C) CH 2 OH - C - (CHOH) 3 - CH 2 - OH (D) HO - CH 2 - ( C H 2 ) 4 - C - CH 3
(B) CH,Z = C H - C - H —
H 2 O/H®
Q.20 Mixture of Ph-CHO & HCHO is treated with NaOH then Cannizzaro reaction involves:
(A) Oxidation ofHCHO (B) Reduction ofHCHO
(C) Oxidation of Ph-CHO (D) Reduction of Ph-CHO
°7A
h 2 N^ ^ ^ N N H
CH,
(A) It has four functional groups
(B) It has three functional groups
(C) on hydrolysis it produces only one amino acid
(D) on hydrolysis it produces a mixture of amino acids
Q. 24 Match List-I with List-II and select the correct answer using the codes given below the lists.
List-I (Compound) List-II (Used as)
O
II
(A) 1,4 addition (P) P h - C H 2 - C - C H = CH2
(B) Tautomerism (Q) PCC
O
Q. 25 Match list-1 with list-11 and select the correct answer using the codes give below the lists:
List-I List-II
KaB 4
(A) CH 2 CH-CHO - " > (P) Acetal
ISJ
(!§Bansal Classes Carbonyl Compound
Q. 26 Match list-I with list-II and select the correct answer using the codes give below the lists:
List-I List-II
0H
(A) C 6 H 5 CHO + HCHO > C 6 H 5 CH 2 OH + HCO O (P) Cannizzaroreaction
ANHY ALC 3
(B) C 6 H 5 -H+CH 3 COCI - ' > C 6 H 5 -CO-CH 3 (Q) Friedel Crafts reaction
ANHY ZNC 2
(C) C 6 H 6 +CO+HCI ' > C 6 H55 -CHQ (R) Reimer-Tiemann reaction
Cu.,CL
OH OH
ISJ
(!§Bansal Classes Carbonyl Compound
Q. 3 (b) Equilibrium constants for the dissociation (Kdiss) of cyanohydrins according to the equation
OH O
RCR'
I Kdiss II
RCR' + HCN
I
CN
Cyanohydrin Aldehyde Hydrogen
or ketone cyanide
have been measured for a number of cyanohydrins. Which cyanohydrin in each of the following pairs has
the greater dissociation constant ?
OH OH
I I
(i) CH3CH2CHCN or (CH3)2CCN
H
, HCCHCN
C ,
M OH Cfi6H<CCN
5 ?
<
(ii) FI
CH,
Q. 4 Some Grignard reagents react with ethyl orthoformate, followed by acidic hydrolysis, to give aldehydes.
Propose mechanisms for the two steps in this synthesis.
O-CH 2 CH 3 O-CH 2 CH 3 0
O-CH 2 CH 3 H
(CH3)3Cx/Ox ||
.C CH, NaQCH3 (CH3)3CCCH2OCH3
Cr CH3OH (88%)
w
Q o " ^
o
(C) C - CH3 - COCb/NeOH/HDH )
\ / (ii) H
Q. 8 Show how you would accomplish the following syntheses efficiently and in good yield. You may use any
necessary reagents.
O 0 0
(b)
(a)\ ^
O CHCH2CH3
CHO CHO
(,! i r - r r r « c r f - + c r i ?
Q. 9 Outline resonable mechanisms for each of the following reactions:
0
O
CH2CH2CH2CH2Br KOC ( CH 3 ) 3
benzene
(76%)
Q. 10 IdentifyAtoD:
Me2CH - CH2 - CHO > (A) HNO 2 > (B) A > (G) H2O/H+/A > (D)
(ii) CH3COOH
(i) BH3/THF I
(ii) H2O2/OH® I
(D)
Q. 12 Give the structure of the substance for each of the following reaction:
O
11
yO
c- CH 3
(a) (X) NaOH/A > r 1 (b) (Y) NaOH/A > / \\
CH
ISJ
(!§Bansal Classes Carbonyl Compound
(C) (Z)
o
Q.13 Each of the following reactions has been reported in the chemical literature. Write the structure of the
product (s) formed in each case.
(a)
(b) CI
Q.14 IdentifyAtoE:
CH^x/^O
(C)
(ii) H 2 0 / H ®
CI W
BA0
I ^ S _ D M S O ^ ( A ) .(B) ^ . C ^ (C) '",,A ' ( D ) ^ F ^ ( E )
K O H / A
l ^ J (ii)HOH
Q.17 Syntheses of each of the following compounds have been reported in the chemical literature. Using the
indicated starting material and any necessary organic or inorganic reagents, describe short sequence of
reactions that would be appropriate for each transformation.
(a) 1,1,5-Trimethylcyclononane from 5,5-dimethylcyclononanone
(B) H X / A V J FROM C 6 H 5 C
CH3 CH2
(c) R ^ V CCH 2 CH 2 CH 2 CH=CH 2 from o-bromotoluene and 5-hexenal.
u
ISJ
(!§Bansal Classes Carbonyl Compound
EXERCISE-III
Q. 1 Compound (A) C9H, 0O is inert to Br2 / CC14 and on vigrous oxidation with hot alkaline KMn04 yields
benzoic acid. (A) gives red precipitate with 2,4 DNP / HC1 / A.
(a) Write all possible structures of [A] and
(b) How can these isomers be distinguished by chemical tests?
Q.2 Compound (A) C8HgO is water insoluble and gives yellow precipitate with I2/NaOH. It reacts with NH^OH
in the presence of NH4C1 /NH4OH to give two geometrical isomers (B) and (C) having MF CgHgON.
These two compounds do not undergo dehydration. What will be structures of (A), (B) and (C) ?
Q. 3 A dithiane synthesis can convert an aldehyde to a ketone. The aldehyde isfirstconverted to its dithiane
derivative, which is deprotonated and alkylated. A mercuric chloride - assisted hydrolysis gives the
ketone. Show how this techinque might be used to convert benzaldehyde to benzyl phenyl ketone
Q.4 Wolff-Kishner reduction (hydrazine, KOH, ethylene glycol, 130°C) of the compound shown gave
compound A. Treatment of compound A with m-chloroperoxybenzoic acid gave compound B, which
on reduction with lithium aluminium hydride gave compound C. Oxidation of compound C with chromic
acid gave compound D (C9HI40). Identify compounds A through Din this sequence.
CO-
Q. 5 Reaction ofbenzaldehyde with 1,2-octanediol in benzene containing a small amount of p-toulenesulfonic
acid yields almost equal quantities of two products in a combined yield of 94%. Both products have the
molecular formula CI5H22U, Suggest reasonable structure for these products.
Q.6 The sex attractant of the female winter moth has been identified as the tetraene
CH3(CH2)8CH=CHCH2CH=CHCH2CH=CHCH-CH2. Devise a synthesis of this material from
3,6-hexadecadien-l-ol and allyl alcohol.
Q. 7 Hydrolysis of a compound A in dilute aqueous hydrochloric acid gave (along with methonal) a compound
B, mp 164-165°C. Compound B had the molecular formula C )6 H I6 0 4 . Whatistheresonable structure
for compound B?
/^-CHCH(0CH3)2
OH
Compound A
Q. 8 When HO-CHJ-CHJ-CHJ-CHJ-CHO this compound is dissolved in water it exist in the equilibrium
ofisomeric forms. Both forms are ring-chain isomers. Write the structure ofisomeric cyclic form and
give mechanism for the formation of cyclic form. When (I) is treated with CH3OH in dry HC1 a new-
product (iii) is obtained. Give structure of this compound.
Q. 9 Compound (A) C5Hg, decolourises bromine water and on reduction with H2/Pt gives compound (B)
having MF C5H!2. A gives compound (C) with I V Lindlars catalyst and compound (D) with Na/NH3
(/). Compound (C) and (D) are isomers having MF C5HK). (A) on hydration gives two isomeric
compounds (E) and (F) having MF C5H10O. (E) gives yellow precipitate with 12 / NaOH but (F) does
not. What will be the structures of (A) to (F) ?
Q. 10 An organic compound (A) contains 40% carbon and 6.7% hydrogen. Its vapour density is 15. On
reacting with a concentrated solution of potassium hydroxide, it gives two compounds (B) and (C).
When (B) is oxidised, original compound (A) is obtained. When (C) is treated with concentrated HC1,
it gives a compound (D) which reduces Fehling and ammonical AgN0 3 solution and also gives
effervescences with sodium bicarbonate solution. Write structures of (A), (B), (C) and (D) and explain
reaction.
Q.3 m-chlorobenzaldehyde on reaction with conc. KOH at room temperature gives: [IIT 1991]
(A) Potassium m-chlorobenzoate and m-hydroxybenzaldehyde
(B) m-hydroxybenzaldehyde and m-chlorobenzyl alcohol
(C) m-chlorobenzyl and m-hydroxybenzyl alcohol
(D) Potassium m-chlorobenzoate and m-chlorobenzyl alcohol
Q.4 Hydrogenation ofbenzoyi chloride in the presence ofPd and BaS0 4 gives: [IIT 1992]
(A) Benzyl alcohol (B) Benzaldehyde (C) Benzoic acid (D) Phenol
Q.5 An organic compound C 3 H 6 0 does not give a precipitate with 2,4-Dinitrophenyl hydrazine reagent and
does not react with metallic sodium. It could be: [ITT 1993]
(A) CH 3 CH 2 CH0 (B) CH3COCH3
(C) CH2=CH-CH2OH (D)CH 2 =CH-0-CH 3
Q. 6 Under Wolif Kishner reduction conditions, the conversions which may be brought about is?
(A) Benzaldehyde into Benzyl alcohol (B) Cyclohexanol into Cyclohexane
(C) Cyclohexanone into Cyclohexanol (D) Benzophenone into Diphenylmethane
[IIT 1995]
Q.8 IntheCannizzaro reaction given below, 2Ph-CHO oh" ) Ph-CH 2 OH+ PhC0 2 the slowest step is:
(A) the attack of OH" at the carbonyl group
(B) the transfer of hydride to the carbonyl group
(C) the ab straction of proton from the carboxylic acid
(D) the deprotonation of Ph-CH,OH [IIT 1996]
Q. 9 Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is
(A) MeCOCl (B)MeCHO (C) MeCOOMe (D) MeCOOCOMe
[IIT 1997]
Q 10 In a Cannizzaro reaction the intermediate which is the best hydride donor is: [IIT 1997]
H
O"
||
O
(A) CH 3 CH 2 - C - CH 3 (B) CH 3 CH 2 CH,CHO
(C) CH 3 CH 2 CHO + HCHO (D) CH 3 CH 2 COOH + HCOOH [IIT 1998]
Q. 14 Which of the following will undergo aldol condensation: [IIT 1998]
(A)Acetaldehyde (B) Propanaldehyde (C) Benzaldehyde (D) Trideutero acetaldehyde
Q 15 Which ofthe following will react with water: [IIT 1998]
(A)CHC13 (B)Cl 3 CCHO (C)CC14 (D) CICH2CH2CI
Q 16 A new carbon-carbon bond formation is possible in [IIT 1998]
(A) Cannizzaro reaction (B) Friedel-Crafts alkylation
(C) Clemmensen reduction (D) Reimer-Tiemann reaction
Q 17 The enol form of acetone, after treatment with D 2 0 gives: [IIT 1999]
OD O OH OD
I II I I
(A) C H , - C = CH 2 (B) CD 3 - C - CD 3 (C) CH 2 = C - CH 2 D (D) CD 2 = C - CD 3
Q. 18 Which of the following has the most acidic hydrogen: [IIT 2000]
(A) 3-hexanone (B) 2,4-hexanedione (C) 2,5-hexanedione (D) 2,3-hexandione
C I L 2 C I 1 3
° /V
v
ch3 • J. J
H 0
HO"
(A)Zn(Hg), HC1 (B ) H H 2 NH 2 , OH (C)H 2 /Ni (D) NaBH4
Q.20 A mixture of benzaldehyde and formaldehyde onheating with aqueous NaOH solution gives:
(A) benzyl alcohol and sodium formate (B) sodium benzoate and methyl alcohol
(C) sodium benzoate and sodium formate (D) benzyl alcohol and methyl alcohol [ IIT 2001 ]
Q.21 Compound A (molecular formula C 3 H 8 0) is treated with acidified potassium dichromate to form a
product B (molecular formula C^H^O). B forms a shining silver mirror on warming with ammonical silver
nitrate. B when treated with an aqueous solution of H 2 NCONHNH 2 . HC1 and sodium acetate gives a
product C. Identify the structure of C.
(A) CH 3 CH 2 CH = NlN'HCONH2 (B) CH , - C = NNHCONH,
i
CH 3
CH,
ISJ
(!§Bansal Classes Carbonyl Compound
/CHO OHCN
' Q \ ( O \ (i)NaOH(excess)100°C
Q.22 (ii)H+/H20
[IIT 2003]
s
CHO OHC /
any one of the products formed is :
/COOH HOOCv
(A)
COOH HOOC
CH 2 OH COOH
(C) OX—
COOH CH 2 OH
OCOCH3
Q.23 Acidic > Products formed by P & Q can be differentiated by: [IIT 2003]
^OCOCH, Hydrolysis
Q. 24 The order of reactivity of phenyl Magnesium Bromide with the following compounds is [IIT 2004]
H
3 C
A C H
3 H,C
A H Ph
A Ph
(I) (IT) (Til)
(D) All react with the same rate
(A) II > III > I (B) I > III > II (C) II > I > III
-COOH
'CHO
CH COONa
Q.25 +X 3 > [IIT 2005]
MeO
MeO
What is X?
(A) CH3COOH (B) BrCH2, COOH (C) (CH 3 C0) 2 0 (D) CHO-COOH
Q.26 The smallest ketone and its next homologue are reacted withNt^OH to form oxime.
(A) Two different oximes are formed (B) Three different oximes are formed
(C) Two oximes are optically active (D) All oximes are optically active [JEE 2006]
CH 3 CH 9 .
Q2 =Q C)kcn/h2s°4 >D. [IIT 1996]
H (ii)LiAlH4
Q. 3 Acetophenone on reaction with hydroxylamine-hydrochloride can produce two isomeric oximes. Write
structures ofthe oximes. [IIT 1997]
Q.4 An aldehyde (A)<CuHgO), which does not undergo self aldol condensation, gives benzaldehyde and
two mole of (B) on ozonolysis. Compound (B), on oxidation with silver ion, gives oxalic acid. Identify
the compounds (A) and (B). [IIT 1998]
Q.5 (a) Write the intermediate steps for each ofthe following reaction. [IIT 1998]
(i) C6H5CH(OH)C=CH > C6H5CH=CHC:HO
(ii)
Cf CH3
(b) Show the steps to carry out the following transformations.
(i) Ethylbenzene benzene
(ii) Ethylbenzene -» 2-phenylpropionic acid
Q. 6 (CH3)2CHOCH3 HI(excess).heat ) (A) + (B) [IIT 1998]
\J
J^xhc6H5 ^)LiAlH
Q.7
a [IIT 1998]
(C)
(ii)H+,heat
Q. 8 What would be the major product in each of the following reaction? [IIT 2000]
^Ph
Q. 9 Identify (A), (B) and (C), and give their structures. [IIT 2000]
0
-> A + B
L f — C (C 7 H ] 2 0)
CH„=CHCH.,CrNa + H2/Pd/C
^D-
Q. 13 An organic compound (P), C 5 H u ,0 reacts with dil. H 2 S0 4 to give (Q) and (R). Both (Q) and (R) give
positive iodoform test. The reactivity of organic compound (P) is 1015 times more than ethylene with
respect to dil. H 2 S0 4 . [IIT 2004]
(i) Identify the compounds (P), (Q) and (R).
(ii) Give reason for the extraordinary reactivity of compound (P).
Identify X and Y.
Q. 15 Which of the following disaccharide will not reduce Tollen1 s reagent? [IIT 2005]
. HOH2C CH2OH
CH2OH CH2OH OHJ—O H H O—IOH
H
—9 /H H\ J oho •KHHCK Xonm
(a) ^ ^ (b) H — O — H
OH H H OH
OH H ^ OH H
(P)
EXERCISE-I(A)
EXERCISE-KB)
OH OH
(e) CH3 - CH 2 - CH - C = CH (f) CH 3 - CH 2 - CH - (CH) 4 - CH 3
OH
H
(i) CH 3 -CH 2 -CH-NH-PH (j) CH 3 - CH 2 - CH - N - CH ,
!
CH 3
(k) C-C-C=N-OH (1) CH 3 -CH 2 -CH=N-NH 2
(m) CH 3 -CH 2 -CH 2 (n) p-Nitro phenyl hydrazon
(o) semi carbazane (p) CH,- CH 2 -CH=CH-CH 3
OH
(q) CH 3 - C H 2 - C H - C N (r) CH 3 -CH 2 -C0 2 H
OH CHO
(c) C - C - C - C = N - O H (d) C - C - C - C - P h
OH
(e) Ph - CH = C - CH 2 - CH 3 (0 C - C - C - C H - C = CH
I
CHO
Et
OH OH
i
Q 3(b) (I) (CH 3 ) 2 CCN (ii) C 6 H 5 CCN
CH 3
Q.4 R-Mg-X
CH,
O
(c)CHCl3 + ^ ^ - C - O H
CH2-OH
CH2-OH CH2-OH
(d) (i) H 2 , (ii) Ni; (e) (i) H2s (ii) Pd-C ; (f) NaBH 4
NH. OH
Q. 10 (A) Me 2 CH - C H . - C - CN (B) Me 2 CH - CH 2 - CH - CN
OH OH
CN CO2H CO2H
U CH, a CHO
CH22 -C=CH
o
1(
o
3
__/S-CH2-OH Ph
CH - PH
(a) CH 3 -/ Y=c<PH <b) fO
cr
O
CO,H
F CH2 — CH2
(D) f >-C-C-C02H
CO2H
+ H-C-C-C-C =C
(0 o
L(0 M 8 i (iii) PCC
(u)H' (iv) Ph 3 P=CH 3
EXERCISE-HI
CHO
(C) P h - C - C H 2 - C H 2 (D) P h - C H 2 - C - C H 2
O
o
Q.7 Ph—CH—CH—OH
/ \
o o
\ /
CH-CH
OH Ph
Q.8 OH OCHoJ
I I
CH- CH—
I I
CH 2 CH2
CH 2 O
I o
I CHO
CH 2? I
I CH7-
CL IO -
( a &(3)
(E) C - C - C - C - C (F) C - C - C - C - C
il
0
Q.10 Empirical formula of (A) = 0 ^ 0 ;
Molecular formula of (A) = CFIjO
HCHO CH 3 OH HCOOK HCOOH
Methanal (A) (B) (C) (D)
EXERCISE-IV (A)
Q. 1 C6H5CH = CHCOOC2H5
(D)
CH3ch2x^ ^OH
Q 2 Cx
H /" CH2NH2
(a racemic mixture)
CH=CH-OC-CHO
C 0 0 H
X ) ^ COOH
(B) (Oxalic acid)
OH
+
'CH,
— A
C H C H
1\ uv e ess),
HI 3\
Q.6 _ > H O C H 33 ^ Af > _ p C H L + CHgl
CH,/' 'CH,
CHC 6 H 5
C f i HcCHO I 7
Q.7 >
ase
+Base
(C) (D)
o
CHO CHO CH ? OH Mott COOH 0-CH=CH 2
C—CH3
Q.10 (A) ( O ) or [ O ] ( B ) [ 0 ] ( C ) ^ O O f O l ^ l O
OCH3 CH 2 OH OH CH 3 OH
OH
NO, NO,
Bu Bu
(E)
O-Pr
CI CI
(A) (B) (C)
ale. K O H
CH 3
CH 3 CH,
CH, I
x+ H,0 + C2H5OH
H- ^ O R CH. H3C 0' CH 3 )H3C" "O
Highly stable c a r b o c t a i o n
P is stabilized by r e s o n a n c e
Q . 15 In structure (P) both the rings are present in acetyl form therefore it will not hydrolyse in solution that why
Fehling solution cannot react with this.
In structure (Q) one ring present in the form of hemiacetal. This will hydrolysed in solution it can reduce
Fehling solution.
ORGANIC CHEMISTRY
XII (ALL)
CONTENTS
EXERCISE-I
EXERCISE-II
EXERCISE-III
EXRECISE -IV(A)
EXRECISE-IV(B)
ANSWER KEY
EXERCISE -1(A)
CH3
CH3
(C) C H 3 - C - C O O H (D) All will give same yield
CH3
Q. 5 Benzoic acid on treatment with hydrazoic acid in the presence of concentrated sulphuric acid gives:
(A) Benzamide (B) Sodium benzoate (C) Aniline (D) C6H5CON3
C2H5 C2H5
I N,H/Conc.H,SO, r l T n MXJ
CH3-C-COOH— ^-^CH3-C-NH2
C3H7 C3H7
is called:
(A) Schmidt reaction (B) Cirtius reaction
(C)Hofinann rearrangement (D) Lossen rearrangement
<fIBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 2
Q.7 In the given reaction:
CH3-CH2-COOH ^)AgN°3 > [X]
(ii)Br 2 /A
[ X ] will b e :
(A) Ethyl bromide (B) Propyl bromide (C) Propyl propanoate (D) All of these
Q.8 In the reaction sequence:
CH3 - CH - COOH — [ Y ]
I
OH
[Y] will be:
Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #3
Q.13 In the given reaction:
0 O
c2H5QNa >
[X]
C 2 H 5 OH
Q.17 Which one of the following compounds gives carboxylic acid with HN0 2 ?
O
(C) C H 3 -0C - O - C
fl- C H 3 (D) CH3COOC2H5
fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page #4
Q .18 In the reaction sequence:
O
H2 /Hffi
CH, - C - H - ^ - K A ) ° > Product
A
OH
(A) C H 3 - C - C O O H
OH
(B) H O O C - C - C H 3
1
I
H
OH OH
(C) Mixture of CH3 - C - COOH and HOOC - C - CH3
H H
OH
(D) C H 3 - C H - C O N H 2
Q.20 Which of the following reactions will give a-hydroxy acid as a product:
(A) CH 3 -CHO —(i)NaCN/HCl
(i)NaCN/HCl
)
(ii)H20/H®/A
(i)Zn
(B) CH 3 -CHO + Br-CH 2 -COOC 2 H,
(ii ) N H 4 C l / H O H
(iii)HOH/H® / A
X
(C) CH 2 - CH 2 - COOH NaOH/HOH ^
< f I B a n s a l Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 5
Q.22 In the given reaction:
OH
•COOH
O ]
CH 3
CH 3
(A) 11 > 1 > III > IV (B) I > II > 111 > IV (C) III >IV > II > I (D) IV > 111 > II > I
Q.26 Arrange following compounds in decreasing order of reactivity for hydrolysis reaction:
O
(NI)CH3-/R)YCOCI (IV)OHC-\OVC-CI
(A) II > IV > I > III (B) II > IV > III > I (C) I > II > III > IV (D) IV > III > II > I
<fIBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 6
Q.27 In the given reaction sequence:
B
CH,-CH 2 -OH (^Mn0 4 /8 H /A VKOH
3 2
(ii)H® (ii)NH3/A
(C) will be:
(A) Methylamine (B) Eltylamine (C) Propylamine (D)Acetamide
Q.28 Which one of the following on heating gives unsaturated acid:
(A) a-Hydroxy acid (B) P-Hydroxy acid (C) y-Hyroxy acid (D) 5-Hydroxy acid
Q.29 Which will form lactone on treatment with NaOH?
(A) a-Bromo acid (B) p-Bromo acid (C) P-Hydroxy acid (D) 5-Bromo acid
Q. 3 0 Which one ofthe following will go decarboxylation on heating?
(A) Succinic acid (B) Phthalic acid (C) Malonic acid (D)Adipicacid
Q. 31 In the given reaction:
(L)BF2/P
CHJ-COOH
6 > [X]
(ii)NaCN
(iii)H20/H®/A
[X] will be:
/COOH
(A) CH,. (B) COOH CHL-CH,-COOH
^COOH
CH2-CO\^ /CO \
Q. 3 2 Which optically active compound on reduction with LiAlH4 will give optically inactive compound?
(A) CH3 - CH - COOH (B) CH3 - CH 2 - CH - COOH
I I
OCH 3 OH
(fe Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 7
Q. 3 4 Which one of the following reactions can be used for the preparation of (3-hydroxy acid:
(A) Perkin reaction (B) Reformatsky reaction
(C) Aldol condensation '(D) Claisen condensation
0 [X]
0
Br
(A) (C) (D)
0 «CJ
Q. 3 7 Reducing property of formic acid is due to the presence of:
O O
II II ' (D) All of these
(A) - OH (B) - C - H (C)-C-OH
Q.3 8 In the given reaction:
O
A o ,
+ [X]
•CH,
[X] will be:
OH
(A) HOOC-CH2-CH2-CH -CH 3 (B) CH3-CH2-CH2-CH2-COOH
Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #8
Q.3 9 In the given reaction:
O
LlAm
° * > [A]
NaBH 4
[B]
[A] and [B] respectively be:
(A) CH 2 OH - CH 2 - CH 2 - CH - CH 2 OH and I I
OH t)H
OH OH
o
A
(C) Both are I J
OH
OH
2
C H ^ " C°OC 2 H 5
p
+ I y"dne > [X]
cooc
CH2^NH2 A
[X] will be:
H
H N o
(A)[ 7 (B)kN>0
I H
H
/COOC2H5
"N=Cv-C00C2H5
N=c /COOC2H5 CH 2
^OOC 2 H5
(C)[ (D)CH 2
/COOC2H5
-NHO v M r
iN =
^-COOC^Hg
^B ansa I Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 9
Q.41 In the given reaction sequence:
CH,-COOH CH,-CH,NH,/A
I •(A)- •>(B)
CH2-COOH
(B) will be:
O O
I!
(A) CH 2 -C-NH-C 2 H 5
(B)CH2-C- N-COH
2 5
CH, - C ^
2
o II
o0
CH,-COOH
(C) (D) I
CH,-COOH CH,-COOH
(ii)H20/H /A
CH3
I
(C) CH3-CH3 (D) CH3-C-CI
CH,
Q. 44 Sodium benzoate on heating with sodalime gives:
(A) Benzene " (B) Benzophenone (C) Methane (D) Calcium benzoate
Q.46 When propanoic acid is treated with aqueous sodium bicarbonate, carbon dioxide is liberated. The
carbon of the C0 2 comes from:
(A) Methyl group (B) Carboxylic group (C) Methylene group (D) Bicarbonate
Q 48 Which one of the following esters cannot undergo self Claisen condensation?
(A) CH3-CH2-CH2-COOC2H5 (B) C6HsCOOC2H5
(C) C 6 H n -CH 2 -COOC 2 H 5 (D) C6H5-CH2COOC2H5
Q. 49 Amides may be converted into amines by a reaction named after:
(A) Kekule (B)Perkin (C)Hofmann (D) Claisen
Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #10
Q. 5 0 The treatment of an ester with LiAlH4 followed by acid hydrolysis produces :
(A) Two aldehyde (B) One carboxylic acid and one alcohol
(C) Two alcohols (D) Two acids
Q.54 Which gas will be evolved out when [CH^O-LNT^ + (CH3)2CHNH2] is treated with sodium nitrite and
HCl:
(A) Chlorine (B) Ammonia (C) Nitrogen (D)N0 2
Q.60 Which of the following diazonium salt is relatively stable of 0-5 °C:
(A) CH3-N=N}®C1- (B) CH3C(CH3)-N=N}®C1-
(C) C6H5-N=N}®CL (D) (CH3)3C-N=N}®C1-
Q. 61 Alkylamine dissolve in hydrochloric acid to form alkylammonium chloride. The nitrogen in the latter salt is:
(A) Quadricovaient only (B) Tricovalent only
(C) Unielectrovalent only (D) Quadricovaient, Unielectrovalent
« J (B)0 (C,0 . ( D , 0
CI COOH CI CI
C6H5-NHX
Q.70 g cone HC1 > A + fi
C6H5-NH^ Heat
The unknown compounds A and B in the above reaction are:
(A) Phenyl mercaptan and aniline (B) Thiophenol and aniline hydrochloride
(C)
Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #12
(i)N 3 A
Q.73
V
Y < ^ ^ - < f Q V c O O H ° ' > X, What are X and Y.
(")KOD,Br 2 A (ii)KOH,Br 2 A
(A) X is Yis ( O ^
(C)both < ( C ? ) - N D 2
OH
Q. 75 The bond angles in methane (I), ammonia (II) and trimethyl amine (III) increase in the order:
(A) I >111 >11 (B) I >11 >111 (C) II > I > III (D) III > II > 1
<fIBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 13
Q. 78 The artificial sweetener aspartame (A) is converted to on storage for extended periods of
time in aqueous solution: ^ Q
H3N-CH-C-NH-CH-C-OCH3
CH2 CH 2 Ph
(A)
O O
I! II
(A) H 2 N - C H - C - N H - C H - C - O C H 3
CH 2 CH 2 Ph
CO.
CO 2 H
O^nh^ci^COV
(C)
D
1
kru / ^ N H ^ - Q
PhCH 2
I + CH3OH
(A)L V (C)ULnhJ
Q. 8 0 The synthetic sweetener aspartame, known commercially as Nutra sweet, is carboxylic acid. In aqueous
solution on standing it changes to:
(AA >
(C) \\
\ /F
//
NH
<fIBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 14
EXERCISE - KB)
Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #15
Q.7 Which is/are correct reactions):
(A ) CI + N H 3 —>ONH 4 CI
( C ) ^ — CI + N H 3 — < ^ + N H 4 C I
(D) + HN0 2 ^
Q. 8 Which of the following compounds will give acetic acid with KMn04/H®/A:
(A) CH3-CHO (B)CH3-CH=CH-CH3
(C) CH3-C=C-CH3 (D)CH3CH20H
Q.10 Which one of the following acids will form acetyl chloride with PC15?
(A) MeCOOH (B) MeCOOMe
(C) MeCOOCOMe (D) Me-CONE^
H ff
CH3-C-OH+CH3-QH > CH,-C-O-CH3+HOH
True about the above reaction is:
(A) Product is having smell like fruits
(B) Nucleophilic addition followed by elimination reaction
(C) folio ws A ac , mechanism
(D) it is irriversible reaction
Q.13 Which one of the following compounds will give HVZ reaction?
COOH
-COOH
(C) / - C O O H
Q.14 Sodium salt of which one of the monobasic acids on electrolysis does not give hydrocarbon:
(A) C6H5COOH (B)HCOOH
(C) Me3C-COOH (D) COOH-CH=CH-COOH
<fIBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 16
Q.15 Which one of the following acids undergoes decarboxylation on strong heating:
(A) Pyruvic acid (B) 3-butenoic acid (C) Formic acid (D) Salicylic acid
Q.16 Which one of the following compounds is least reactive with water?
o o o o
(A) CH3 - C - CI (B)C6H5-C-NH2 (C)CH3-C-NH2 (D)C6H5-C-C1
Q.17 Acetic anhydride is used as:
(A) Solvent (B) Dehydrating agent (C)Acetylating agent (D)Anticeptic
Q. 23 Which of the following compound can be produced if 1 -propane amine is treated with NaNO, and HCl
(A) Propane-l-ol (B) Propane-2-ol (C) 2-Chloropropane (D) 2-Propaneamine
Q. 24 Which of the following amine does not react with Hinsberg reagent to give base soluble product
(A) Neopentvl amine (B) secpropyl amine (C) diethyl amine (D) Ethyl methyl amine
Bansal Classes Carboxylic A cids & It's Derivative Aliph atic amin es Page #17
Q.27 Select correct statement (s):
(A) Cyclohexanone is oxidised to caprolactone which is hydrolysed under the reaction conditions
(B) Baeyer-Villiger oxidation involves migration ofH/alkyl/aryl groups which is in order H > tert-alkyl >
sec-alkyl > phenyl > primary alkyl > methyl
(C) Pinacolone (CH 3 ) 3 CCCH 3 is oxidised to t-butyl acetate by C 6 H 5 C0 3 H
O
(D) All of the above are correct statements
Q.28 Following equilibrium is favoured in the forward side because of:
R
Y°^C(CH3)3 R
Y 0 H +(CH 3 ) 3 COH
o o
(A)(CH 3 ) 3 CO e (alkoxide) - a strong nucleophile is formed
(B) (CH3)3C® (carbocation) is formed
C 6 H 5 - c - CH 2 - c - O C 2 H 5 + C 2 H 5 O H
II II
0 0
(B) H 3 c - C - OH + Cl2 C1CH2-C-OH (Q) C 2 H 5 0,e
o o
CH3
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 18
Q 31 Column I Column II
(Reagents reacting with PhCH 2 COOH) (Product formed)
(A) CH 3 MgBr (P) PhCH 2 COCl
(B) PC15 (Q) PhCH 2 COOCH 3
(C) NH 3 , followed by heating (R) CH 4 '
(D) CH 3 OH in the presence of conc. H 2 S0 4 (S) PhCf^CONHj
Q 32 Column I (Reactions) Column II (Products)
0
o
II
(B) (CH 3 ) 2 NH + C 6 H 5 COCI (Q) (CH 3 ) 2 N S
• m
o
II
(C) (oV
CHO + ^ ( J ^ - N H a (R) (CH 3 ) 2 N-C
o
9 ©
(D) CH 3 CH 2 NH 2 S0 2 C1 (S) C 2 H 5 NH - c - CH 2 CH 2 - C - O
0
(B) CH 2 OH-(CH 2 ) 2 -CHOH-C 6 H 5 (Q) LiAlH4
CM,
(C) C 6 H 5 CH = C H - COOH ->C 6 H 5 - CH = CH 2 OH (R) HjPd BaS0 4
(D) CH3COCI CH 3 -CHO (S) None
Q 35 Column I Column II
(A) RCN REDUCTION > (P) 1° Amine
(L)CH MGBR
(B)RCN 3 -> (Q) Alcohol
(ii)H20
HYDF0LYSIS
( O RNC - ) (R) Ketone
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 19
EXERCISE - II
excess
aqKOH
Q.2 Ester (A) — » B +C > (CH 3 ) 2 CHCH 2 QH
H2/Pd BaS04
(D) LiA1H
4 ? (CH 3 ) 2 CHCH 2 OH
Mo stAg2
Q.4 A ' °
KCN T j H^O ?
soci. ^^
Q.5 Acid (A) - >C
E+NaCl
NaOH T g
/NHSO3H
c „ o = <
Q.8 CaCN 2 + H O H - i ^ ( A ) - ^ ^ ^ ( B )
(H 2 0 2 )
a COOH
COOH
COOH
A >A _A_>B
•COOH
s
NTOOH A A „
Q.10 •H — A +B
x
COOH
A
Q.ll p h / = ^ . C 0 0 H -»U( )
4 I B a n s a l Classes Carboxylic Acids & It's Derivative Aliphatic amines Page #20
Zn/Hg/HC1
Q.12 PhMe + (A) — p - M e C ^ - C Q - C H ^ a ^ C O O H >(B)
(i)Ag+(ii)Br
CH 3 (CH 2 ) 1 4 COOH 2 >(D) -
C H 2 C 0 0 H
Q.14 [ p T C 0 0 H (A) Hd ) (R) _ic L > f^n Y-^CH.COOH A + C02+H20
COOH
qi5 +
l i v ;
COOH
O
CI
OH" / a\ OH" . (i)H 2 0
Q.16 [ I >(A) >(B)
(II)H30
A
Q, 18 Phthalicacid + NHL >D >E
o H ^^^
LiA1H4
Q.20 CH3-C-N~( ) > (A)
0 LlA1H
Q.21 [ P l y " ) (B)
o
Br /4KOH
Q-22 R-C-NH2+ 2 " >R-NH 2
0
Q.23 R - C - OR' __NaOH_^RCOONa + R'OH
4IBansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page #21
? RON, A ^
ff
Q.25 R - C - O H + HN3 h
2s°4 >RNH2
o o
II A,CI II
O
Q.27 R - C - CI + CFLN2 — > R-CFL-COOH
(ii)H20
Q. 33 Primary and secondary amide exist as dimer in solid and pure liquid state.
How will you bring about the following transformation:
^Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 22
EXERCISE - III
Q. 1 Show by a series of equations how you could synthesize each of the following compounds from the
indicated starting material and any necessary organic or inorganic reagents.
(a) 2-Methylpropanoic acidfromtert-butyl alcohol
(b) 3 -Methylbutanoic acidfromtert-butyl alcohol
(c) 3,3-Dimethylbutanoic acidfromtert-butyl alcohol
(d) H02C(CH2)5C02H from H02C(CH2)3C02H
(e) 3-Phenyl-1-butanol from CH3CHCH2CN
/Br
(f) I A from cyclopentyl bromide
CO2H
rr"
(S) L / LN from (E)-C1CH=CHC02H
C02H
Q.2 On standing in dilute aqueous acid, compound Ais smoothly converted to mevaionolactone.
Me
TR^O (I)H3Q+ „ O"
I >CH2COOH * I LCH3
Suggest a reasonable mechanism for this reaction. What other organic product is also formed?
Q.3 Suggest reaction conditions suitable for the preparation of compound Afrom 5-hydroxy-2-hexynoic
acid.
0
OH H,}"
5-Hydroxy-2-hexynoic acid Compound A
(a) C A + BrMgCH9CH7CH,CH,MgBr —
O O " (ii)H,0
HC xCH2CH2CH2OH
h
n a ya
Q. 5 Identify compounds A through C in the following equations:
O °
(a) C H 3 0 ^ ~ ^ ~ CC1 + CCH — P - ^ U compound A (C22H1804)
OH
fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 23
o o
(b) CH3CCH2CH2COCH2CH3 - CH3 Mgl (1 equiv) diethyl ether > c o m p ( ) u n d g ( a l a c t o n G ; C^O,)
o
COH
heat
(c) > compound C (C9H405) + H 2 0
HOC
0 0
Q.6 An organic compound C4H604 (A) when heated with acetic anhydride give another compound C4H403
(B) which in turn react with ammonia to give a third compound C4H502N (C). Both (B) and (C) may be
hydroiysed to A. With chlorine A give monochloro-compound (D) which reacts with caustic potash to
give either C4H405K2 (E) or C ^ O ^ (F) depending upon the condition of reaction. Identify the
compound A to F.
Q.7 An organic compound A (C4Hc,NO) on treatment with bromine and alkali form another compound B
(C3H9N) on treatment with sodium nitrite and dilute hydrochloric acid. B yield C (C3HgO). C can be
oxidized to D (C3H60). Which can also synthesisedfrommethyl acetylene. Identify the compound Ato D.
Q.8 With bromine and caustic potash the straight chain compound C4H9ON (A) give C3H9N (B), with
caustic soda C4H702Na (C) and with phosphorous pentoxide gives C4H7N (D). With hydrochloric
acid D give C4H802 (E) ofwhich C is the sodium salt. B may be converted to an alcohol (F) and then to
a halide the grignard reagent from which react with carbon dioxide to give E. On oxidation F give.
Identify the compound Ato H.
Q. 9 Compound (A) with an empirical formula, C7Hc,N on diazotization give a product which undergoes
reaction with Cu2Cl2 & HC1 to give a compound (B). B on oxidation give a compound (C). Compound
(A) on treatment with Br2/H20 form C7H6NBr3 (D). Give the structural formula ofA, B, C & D.
Q.10 An organic compound A (C3H5N) on boiling with alkali give ammonia and sodium slat of an acid B
(C3H602) A on reduction give a compound 0 (C3H9N) which with nitrous acid give D (C3HgO). Give
the structural formula ofA, B, C and D.
Q.ll An organic compound (A) C3H?ON on heating with POCl2 give a compound B which on hydrolysis
give a compound (C) C3H602 with the liberation of ammonia. Compound Aon treatment with LiAlH4
form compound C3H9N (D). Compound D treating with HN0 2 liberate N2 gas on refluxing with
chloroform and alcoholic KOH give compound E which have foul smell. Identify compound A,B, C, D
and E.
Q. 12 An organic compound A (C8HgO) an treatment with NH2OH. HC1 give B and C. Compound B and C
can be converted into D and E respectively by treatment ofH 2 S0 4 . Compound B, C, D and E are all
isomer of molecular formula CgF^NO. When D is boiled with KOH, and oil F (C6H7N) separate out.
F react rapidly with CH3COCl to give back (D). On other hand. E on boiling with alkali followed by
acidification give a white solid G (C7H602). Identify Ato G.
Q.13 An organic compound A, (CgH9NO) on heating with conc. H 2 S0 4 give another isomer of (A) i.e. (B)
C8H9NO. Compound B on hydrolysis with dil HC1 give an aliphatic acid C, C2H402 and (D) on
treatment with NaN02 HC1 at 0°C give a compound (E) which give a white ppt. of AgCl on addition of
AgN03. Compound (E) react with alkaline (3-naphthol to produce orange dye what are to E.
Q.14 An organic compound A of the molecular formula C4Hg03 give effervescence with sodium bicarbonate
solution and can be acetyl ated. It can be separated into dextro and laevoisomers on heating it forms an
acid B with formula C4H602. Compound B give positive Bayer's test. Identify A and B.
fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 24
Q.15 An aromatic compound A, CgH5N02 can be condensed with an acid derivative (B) C 7 H,,0 4 Br in
presence of alkali to form compound (C), C15H15N06. Compound (B) can be prepared by action of
sodium followed by bromine gas on diethyl malonate. Compound (C) condensed again with ethyl chloro
acetate in presence of sodium to give compound (D) C19H21N08. D on heating with a base can be
converted into E and a salt of acid F (CgH604). Compound A can be obtained by heating F with
ammonia. E on boiling with mineral acid produce amino acid G (C4H7N04). Identify Ato C.
Q.16 An organic acid A(C3H403) is catalytically reduced in presence of ammonia to give (B) C3H7N02. B
react with acetyl chloride hydrochloric acid and alcohol. It can also react with nitrous acid to give
another compound (C) C3H603 along with evolution of N2. What are (A), (B) and (C)?
Q.17 A dibasic acid (A), C4H606, on heating with KHS04 give a monobasic acid (B), C3H403, with the
elimination of C0 2 and H 2 0. Acid (B) on reduction give another monobasic acid (C), C3H603. Both
(B) and (C) on heating with I2 and NaOH solution give yellow precipitate of iodoform and sodium
oxalate. Acid (A) react with two moles of acetyl chloride, while (C) reacts with one mole of acetyl
chloride. Acid (A) reacts with four moles of HI to form succinic acid, while (C) react with two moles of
HI to give propionic acid. Identify A, B, C and give equation for reaction.
Q.18 An organic compound of the formula C3H60 (A) gave iodoform test but not Tollen's and Fehling tests.
Two molecules of (A) condenes in presence of dry HCl gas to yield (B) of formula C6H10O. Compound
(B) decolourised Br2/CCl4 and cold dilute neutral KMn04, but no ppt. with ammonical AgN03 or
CuCl solution. It gave iodoform test and potassium salt of a compound on heating with I2 and KOH. The
potassium salt on treatment with H 2 S0 4 gave compound (C) of formula C5H802. Compound (C) on
heating with sodalime gave (D) of formula C4Hg. Identify compound Ato D & write the chemical
equation.
Q.19 An organic compound (A) of formula C3H6Qfroma monoxime with hydroxylamine and form iodoform
on heating with I2 and NaOH and sodium acetate. Compound A on reaction with NaCN and dil. H2S04
gave product B. Which on hydrolysis produced (C). Compound (C) on heating gave (D), which on
decarboxylation gave (E) of formula C3H6. Compound (E) on ozonolysis gave one molecule of
acetaldehyde and one of methanal. What are Ato E?
Q.20 Two moles of an ester (A) are condensed in the presence of sodium ethoxide to give a P-keto ester (B)
and ethanol. On heating in an acidic solution (B) gives ethanol and J3-keto acid (C). On decarboxylation
(C) gives 3 -pentanone. Identify (A), (B) and (C) with proper reasoning. Name the reaction involved in
the conversion of (A) to (B).
Q.21 An acidic compound (A), C4Hg03 loses its optical activity on strong heating yielding (B), C4H602
which reacts readily with KMn04. (B) forms a derivatives (C) with SOCl2, which on reaction with
(CH3)2 NH gives (D). The compound (A) on oxidation with dilute chromic acid gives an unstable
compound (E) which decarboxylates readily to gi ve (F), C3H60. The compound (F) gives a hydrocarbon
(G) on treatment with amalgamated Zn and HCl. Give structures of (A) to (G) with proper reasoning.
Q. 22 An organic compound (A), C5H803 on heating with soda-lime gives (B),which reacts with HCN to give
(C). The compound (C) reacts with thionylchloride to produce (D), which on reaction with KCN gives
compound (E). Alkaline hydrolysis of (E) gives a salt (F), which on heating with soda-lime
produces -butane. Careful oxidation of (A) with dichromate gives acetic and malonic acid. Give structures
of (A) to (F) with proper reasoning.
Q.23 An acid (A), C g H ? 0 2 Br on bromination in the presence of FeBr gives two isomers, (B) and (C) of
formula CgH602Br2. Vigorous oxidation of (A), (B) and (C) gives acids (D), (E) and (F) respectively.
(D), C7H502Br is the strongest acid among all of its isomers, whereas (E) and (F) each has a molecular
formula of C7H402Br2, Give structures of (A) to (F) with justification.
fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 25
EXERCISE - IV (A)
O
Q.l The reaction of R-C-NH 2 with a mixture of Br2 and KOH gives R-NH2 as a product. The
intermediates involved in this reaction are: [BIT 1992]
?
(A) R-C-NHBr (B)R-N=C=0 (C)R-NHBr
II
(D)R-C-N<
Br
Q.2 Which ofthe following carboxylic acids undergo decarboxylation easily: [IIT 1995]
(A) C6H5CO-CH2COOH (B) C6H5COCOOH
(C) C6H5CH2-COOH (D) C6H5CH2 - COOH
I .1
OH NH2
Q. 3 The molecular weight of benzoic acid in benzene as determined by depression infreezingpoint method
corresponds to : [IIT 1996]
(A) Ionization of benzoic acid (B) Dimerisation of benzoic acid
(C) Trimerisation of benzoic acid (D) Solvation of benzoic acid
Q.4 When propionic acid is treated with aqueous NaHC03, C0 2 is liberated. The 'C' of C0 2 comes from
(A) Methyl group (B) Carboxylic acid group
(C) methylene group (D) bicarbonate [IIT1999]
Q. 6 Which of the following acids has the smallest dissociation constant? [Ill 2002]
(A) CHXHFCOOH (B) FCH2CH2COQH (C) BrCH2CH2COOH(D) CH3CHBrCOOH
^OCQCH3
v
P Acidic v
Q. 9 Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of
sodium acetate? [IIT 2005]
fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 26
Q.10 The correct IUPAC name of C6H5G0C1 is
(A) Benzoyl chloride (B) Benzene chloro ketone
(C) Benzene carbonyl chloride (D) Chloro phenyl ketone [IIT 2006]
Q.ll Which ofthe following reactants on reaction with conc. NaOH followed by acidification gives the following
lactone as the only product? [IIT 2006]
O
\>
/
CH 7
EXERCISE - IV (B)
Q.l Compound (A) (C6H1202) on reduction with LiAlH4 yielded two compounds (B) and (C). The compound
(B) on oxidation gave (D) which on treatment with aqueous alkali and subsequent heating furnished (E).
The latter on catalytic hydrogenation gave (C). The compound (D) was oxidised further to give (F)
which was found to be monobasic acid (molecular mass = 60.0). Deduce the structure of (A), (B), (C),
(D)and(E). [IIT 1990]
Q.2 In the following reactions, identify the compounds (A), (B), (C) and (D) [IIT 1994]
PC15 + S0 2 —->(A) + (B)
(A) + CH3COOH > (C) + S0 2 + HCl
2(C) +b (CHACd - 2(D) + CdCL
Q.3 Complete the following equations by writing the missing A and B [IIT 1995]
(i) CH,CH,COOH ;f2
> (A) (i)Alc.KOH(excess) ) (g)
(ii)H
fe Bansal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 27
Q.6 Write the structure of product A&B: [IIT 2000]
O
CH3-C-O18C2H5 H3 +
° >A+B
Q. 7 Identify X, Y and Z in the following synthetic scheme and write their structure. Explain the formation of
labelled formaldehyde (H 2 C*0) as one of the products when compound Z is treated with HBr and
BaC*0 3 +H 2 S0 4 >C (gas) [C* denotes C14] [IIT 2001]
( )Mg/ether
CH22 = CH - Br '
(II)X
(iii)H30+
Q. 8 Mention two esters pro duced when a racemic mixture of 2-phenyl prop anoic acid is treated with (+)
2-butanol. What is the stereochemical relationship between these esters? [IIT 2003]
Q.9 Give major products A, B, C and D in following reaction sequence. [IIT 2004]
CH2-C1
KCN V A (i)NaOEt/EtOH v H,0® „
f /—-N 1 >n
( ) DMF (ii)PhCHO/ A
socl2
n
(ii) CH 3 NH 2
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 28
ANSWER KEY
EXERCISE -1(A)
EXERCISE - KB)
Q.l A,B,C Q.2 B,C Q3 A,B,C,D Q.4 A,B
Q.5 A,B,C Q.6 A,C Q7 A,C,D Q.8 A,B,C,D
Q.9 A,B,C,D Q.10 A,B,C Q.ll A,B Q.12 A,B
Q.13 B,C Q.14 B,C Q.15 A,B,C,D Q.16 B
Q.17 A,B,C Q.18 A,B,D Q.19 A,B,C,D Q.20 A,B,C,D
Q.21 A,B,C Q.22 D Q.23 A,B,C Q.24 A,B
Q.25 A,B,C Q.26 B Q.27 D Q.28 B
Q.29 (A)S,(B)R,(C)P,(D)Q
Q.30 (A)Q, (B)R,(C)P,(D)S Q.31 (A) R, (B) P, (C) S, (D) Q
Q.32 (A)Q,(B) S, (C)P,(D)Q Q.33 (A) S, (B) Q, (C) P, (D) R
Q.34 (A)S,(B)Q,(C)S,(D)R Q.35 (A) P, (B) R, (C) P,S, (D) Q
EXERCISE - II
Q.l (A) CH3CH(OOCCH3)2; (B) CH3CHO; (C) (CH 3 C0) 2 0
Q.2 (A) (CH3)2CHCOOCH2CH(CH3)2 ; (B) (CH3)2CHC0C1; (C) (CH3)2CHCH2C1
Q.3 (A) RCOND2; (B) RNH2; (C) ROH
Q.4 (A) CHgCl; (B) CH3OH; (C) HCOOH; (D) Ca(OH)2; (G) HCHO; (H) CH3C1; (I) KCN; (J) CH3CN;
(X)CH 3 COOH
Q.5 (A) CH3COOH; (B) CH3COONa; (C) CH3COCl; (E) (CH 3 C0) 2 0
Q.6 (A) HOOCCH2CH2COOMe; (B) C10CCH 2 CH 2 C00Me; (C) MeNH0CCH 2 CH 2 C00Me
Q.7 (A) 2NH3; (B) CH3COCl; (C) H 2 S0 4 + S0 3
O
^NH-
CH-,
Q.8 (A) HjNCONH^; (B) O \ Q.9 (A)k 1 ;(B)[ T
NH" "C
ft
rooH
S
o Ph-
H II
Q. 10(A) M (B) Q 11 (A) .00
COOH [
-C"
II
o
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 29
Q.12 (A) ' o ; (B) p-MeCg^CKLjCHjCHjCOOH
Q14 (A CN :c=o
> tOXc„,oH; (B
> ^lcH2cr(C) ^ o t -(D) tOD 1
H
COOH
Q.l 5(A) 1 00H
;(B) H ;(C) COOH
L°° Q.16 (A) H
COOH COOH
S
ONH 4 Me
Q.18 (D)[0 Q.19 (F) H'
-ONH4 ;(E) O y N-H
CH 2 OH
Q.20 (A)CH 3 CH2NH- Q.21
CH 2 OH
EXERCISE - III
CH 2 COOH CH2CO\ CH7CO\ CH 2 CICOOH
Q.6 (A) (B) p (C) ! > H (D) I
CH 2 COOH CH2CO/ CH 2 COOH
CH2CO/
Succinic acid Succinimide
Succinic anhydride
CHCOOK
CH 2 (OH)COOK
(E) (F)
CH 2 COOK CHCOOK
Potassium maleate
Q.7 (A) (CH 3 ) 2 CHCONH 2 ; (B) (CH 3 ) 2 CHNH 2 ; (C) (CH 3 ) 2 CHOH; (D) CH 3 COCH 3
Q.8 (A) CH,CH 2 CH 3 C0NH 2 ; (B) CH 3 CH 2 CH 2 NH 2 ; (C) C ^ C ^ C H ^ C O O N a ; (D) CH 3 CH 2 CH 2 CN
(E) CH 3 CH 2 CH 2 COOH; (F) CH^CHjCI^OH ; (G) CH 3 CH 2 CHO; (H) CT^CH^COOH
NH 2 CI CI
Q.9 ( A
) f O L „ (B)fOl„„ .(C) [ O
CH, •CH, COOH
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 30
0 CH, CH3OH O
C-CH3 ; ( B ) r f ^ r C = N - O H c ) r ^ [ - C = N |f>rNH-C-CH
Q.12 (A) ;( ;(D)
0
C-NH-CH, II
(E) (G) C-OH
CH3 o
II
Q.13 (A)^Q C = N-OH ;(B) N H - C - C H 3 ; (C) CH3COOH;
N
2Cr
(E)FO
OH
Q.14 (A) CH3 - CH - CH2 - COOH; (B) CH3-CH=CH-COOH
\
Q 15 (A) N_H; (B) Br-CH(COOEt)2; (C) ^N-CH(COOEt) 2 ;
COOEt
COOEt
C-OH
-CCHXOOEt. (E) H 2 N-CCH 2 COOEt; (F) C-OH
COOEt <i00Et 0
CH(OH)COOH
Q.17 (A) ] ; (B) CH3-CO-COOH; (C) CH,-CH(OH)-COOH
CH(OH)COOH
Q.18 (A) CH3-CO-CH3; (B) (CH3)2C=CHCOCH3; (C) (CH3)2C=CHCOOH; (D) (CH3)2C=CH2
Q.19 (A)CH3-CO-CH3; (B) (CH3)2C(OH)CN; (C) (CH3)2C(OH)COOH; (D) CH2= C-(CH3)-COOH
(E) CH3-CH=CH2
Q.20 Claisen condensation, (A) C2H5COOC2H5; (B) C2H5COCH(CH3)COOC2H5;
(C) C2H5COCH(H3)COOH
Q.21 (A) CH3CH(OH)CH2COOH; (B) CH3CH=CHCOOH; (C) CH3CH=CHCOCl
(D) CH3-CH=CHCON(CH3)2; (E) C^COCH^COOH; (F) CH3COCH3; (G) CH3CH2CH3
Q.22 (A) CH3-CO-CH2CH2-COOH; (B) CHgCOCK^CT^; (C) CH3C(OH)(CN)CH2CH3
(D) CH3C(C1)(CN)CH2CH3; (E) CH3C(CN)2CH2CH3; (F) CH3C(COONa)2CFL,CH3
-COOH
(E) O -Br
(F) lOjBr
Br
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 31
EXERCISE - IV (A)
Q.l A,B Q.2 A Q.3 B Q.4 D Q.5 C Q.6 C Q.7 D
Q.8 A Q.9 C
EXERCISE - IV (B)
CH 2 =CH-C*OOH(Y) LiA1H
4 >
H+
CH 2 =CHC*H 2 OH(Z) >
CH 2 =H-C* H J < > C* H 2 CH=C*H 2
I Br iBr
CH 2 =CH-C*H 2 Br BrCH2 - C H ^ C * ^
I 0 3 ZNH 2 0 I O ^ n f ^ O Br-C*H 2 CHO + HCHO Br-CH 2 CHO + HC*HO
H
Ph H ' (+)CH3CH2-C-OH
I I I
CH,
Q.8 CH3-C-COOH + CH3-C-COOH
| ~ | conc.H2S04,A
H Ph
(racemic mixture)
Ph H H H
I I I I
CH3-C-C-0-C-CH2CH3 + CH3-C-C-O-C-CH2CH3
' ! I I ' I II I
H 0 CH 3 Ph O CH 3
during esterification reaction only -COOH and - O H partcipates. There is no effect on structure or
configuration of carbon adjacent to these groups. So when(±) acid reacts with pure (+) alcohol two
esters are produced which are diastereoisomers of each other.
CN COOH CONHCH3
9VCN CH=C^O) CH=C-(p) CH = C
Q.9 <A)(g) ( B ) ^ (Ofgs ^ ( D ) ^ ^ ,
ii Ban sal Classes Carboxylic Acids & It's Derivative Aliphatic amines Page # 32
ORGANIC CHEMISTRY
XII (ALL)
CONTENTS
EXERCISE-I
EXERCISE-II
EXERCISE-III
EXERCISE IV
ANSWER KEY
EXERCISE-I
(Choose the correct option. Only one is correct)
(A>
\/\/ m Q A ( C , < X > „ c d
„ <$2 Which carbocation is least likely to form as intermediate?
( C )
(A)(C6H5)5C ( B ) Q e Cf) (D)CH 2 =CH
sj^. 3 2-chloropentane on halogenation with chlorine gives 2,3, dichloropentane. What will be the structure of
free radical species form in the reaction?
(A) Planar (B) Trigonal planar (C) Square planar (D) Pyramidal
What will be maj or product, when 2-methyl butane undergoes bromination in presence of light?
(A) 1 -bromo-2-methyl butane (B) 2-bromo-2-methyl butane
(C) 2-bromo-3-methyl butane (D) 1 -bromo-3-methyl butane
The smallest compound, which on photochlorination produces diastereomers is
(A) 3-methyl, 3-chloro hexane (B) 2-chloro butane
(C) 1 -bromo propane (D) 1 -bromo-3-methyl butane
Q.6 Which ofthe following will give two isomeric monochloro derivatives?
(A)2,3-dimethylbutane(B)n-hexane (C) Isopentane (D) Butane
Q.7 How many isomers can be producedfromthe molecular formula C4H10O?
(A) 8 (B)7 (C)6 (D)5
Ph
J& L>CH3 >?
3
^ CT H3O+
Halogen Derivatives
^Bansal Classes [2]
* /^v-OH
^0710 I J P. The product Pis:
^ OH
(A) | (B) (C) (D)
a ) O O H ( i i ) P O (iv)
(A) I < I I < I I I < I V (B) II < III < IV < I (C) I < III < IV < II (D) I < II < III = IV
Q.12 Identify Z in the following series of reaction:
Q H conc.H 2 SQ 4 ) X Br, > y alc.KOH > z
170 a C CC1- A
CH,
H,C-
3
(A) ( B ) H 3 C - ^ ( C ) H 3 C — ^ ( D ) H 3 C - ^
HO OH CH CH2
product will be
OH
(A) C 6 H 5 - CH - CH2 - COOH (B) C6H5-COOH, COOH-COOH and CHBr3
O
II
(C) C 6 H 5 - C - CH 3 , C0 2 and CHBr3 (D) Only CHBr3
, C1F2CX / F
c=C leg. -QEt ) A (major product). A is
tt/ \
OEt
C1F2CX .OEt CIF2CV / F I C1F2CX / F
F
(A) /=C (B) J>C (C) p h > - 9 - (D) > <
Ph F PhX OEt Ph I OEt X
F
F
CHs H+
(l5 J |\:H 3 > major product is
(A) 0 H
k X „ ! w (C) (D) ^ A x C H 3
Halogen Derivatives
faBansal Classes [3]
Q/T6 HBr reacts fastest with
^ (A) 2-methyl butane-2-ol (B) 3 -methyl butane-2-ol
(C) Butane-1 -ol (D) 2-methyl butane-1 -ol
,COCH3
-ex
Q.17 [ NaOBr ) Product
The product is
« o <»oc « o c ~ » o £ .
CH,
nu
/OH /OH
J?.f9 Which one of the following alcohol will undergo acid catalysed dehydration with greatest ease by E,
mechanism?
T OH
OH
NaCN
0C2O (A) C 3 H 6 0 > cyanohydrin of (A). Ifthe cyanohydrin is optically active, then the possible
H 2 SO 4
structure of (A) is
X I LL ROH/H+ V
sj^.22 J) » P (major org. product)
(q (d)
- a QH3 0
OR
Halogen Derivatives
^Bansal Classes [4]
Q.23 C1 3 £-CH = CH2 H3C—CH=CH2
(I) (II)
In addition of HOBr to (I) and (II)
(A) Br is at C2 in both cases (B) Br is at C2 in II and at C, in I
(C) Br is at C, in II and C2 in I (D) Br is at C j in both cases
4 Greatest amount of hydration is in
How many number of optically active isomers are possible for 2,3-dibromo butane 1,4-dioic acid?
(A) 2 (B) 3 (C)4 (D)l
H3C .CH,
H3C CH3
( ^ H ^ C / ^ ^ ^ v / 0 1 1 3 (B).
H3CV H3CV ^ .CH,
(C)H3c^/CH 3 (D)
H3C H
H3C H3c OH
CH, CH,
(C) /K/0** 3
(D) OH
V
HO CH
Halogen Derivatives
faBansal Classes [5]
1 Which of the following alcohol shows fastest reaction with HI ?
OH
(A) ( B )
A A
'OH
H (D)
( O h , C ^ ° I
(a)
fo) <b) f o J C H 3 (c)
(o) (D)
[ o
CH3
3 In which ofthe following molecule all the effect namely inductive, mesomeric & hyperconjugation operate
C H
( A ) < ^ - C 1 ( B ) \ _ / " 3 ( C ) ( > C O C H 3 (D)<
CH3 CH,
(I) O * + C l e , AH°
(C) AH° > AHj > AH° > AH° (D) AH° > AH° > AH° > AH°
Jtr
Correct order of basicity of various nitrogen in LSD is
Halogen Derivatives
faBansal Classes [6]
Q.36 One of the configuration of n-butane is drawn in the given figure. Anticlockwise rotation of C2 around
C 7 -C, bond by 120° will lead to
CH3
M
(A) gauche (B) staggerred (C) partially eclipsed (D) fully eclipsed
Which of following is correctly matched.
OH
(A) CH3 - C - CH 3 , E, reaction (B) CH3-CH2-CH2OH, E,cb reaction
I
CH3
OH
I
(C) CH3 - C - CH 3 , thermal reaction (D) CH 3 -CH 2 -CH2~N-Cr , E t cb reaction
I \CH3
CH3 3
O
eff © ©
(I) o - S - C 6 H 4 - C H 3 (II) O - S - C 6 H 5 (III) N 3 (IV) Br
O O
(A) II, I, III, IV (B) II, I, IV, III (C) I, II, IV, III (D) I, II, III, IV
^J^/40 Arrange decreasing order of reactivity of these compounds for nucleophilic substitution reaction
O
II
(I) CH3 - CH2 - O - S - CF3 (II) CH 3 -CH 2 -0-TsCl
o
OH C6H5
(A) III, IV, I, II (B) III, IV, II, I (C) I, II, III, IV (D) I, II, IV, III
tBansal Classes GOC [7]
X^41 X 3 < H H 3 + O H
^ A
' A i S
Ph
CH3 alc.KOH
Q.42 A, A is
CI.
Ph
ch3^C6H5 CH3\ /C6H5
(A) • » (B) (C) (D) None is correct
H ^C6H5 C6H5- CfiH< ^C6H5
CI OEt
46 EtOH RateR
s /
3 EtOH Rate R2
EtOH
> ——R-OEt RateR3
vX5
v
Halogen Derivatives
faBansal Classes [8]
Q A ^ (I) which is not correct about (I)
(A) I is more soluble than bromocyclopropane
(B) I gives pale yellow ppt. on addition with AgN03
(C) I is having lower dipole moment than bromocyclo propane
/ -Br
OH SCH3
OH OH
Q.50
CI CI
(A) I > II > III (B) II > I > III (C> II > III > I (D) III > II > I
Halogen Derivatives
^Bansal Classes [9]
EXERCISE-II
(iChoose the correct option. One or more than one are correct)
/f
O.l \ = / which is/are incorrect statements?
v
P Q
(A) P is cis- and Q is trans- (B)PisZandQisE
(C) P is R and Q is S (D) P and Q are having same structural formula
Q.2 CH 3 CH 2 N0 2 will not show. isomerism:
(A) Chain (B) functional (C) tautomerism (D) geometrical
CHCOOH
Q.3 (maleic acid) can form:
CHCOOH
(A) stereoisomer (B) geometrical isomer (C) position isomer (D) functional isomer
Q.4 Which can show tautomerism ?
o
CH 3 CH 3 H
Q.5 A A
V \ /
CH 3 H H CH 3
I II
I and II are not
(A) achiral-identical mirror images (B) chiral-enantiomers
(C) geometrical isomers of each other (D) racemic mixture
Q.6 In which of following compound chiral center is not affected on heating.
OH CH 2 COOH
(A) ( 5 > 0 H and y^OH both give colour with neutral FeCl3 solution
(B) 2-pentanone and 3-pentanone are metamers
(C) product formed when benzaldehyde reacts with hydroxylamine shows optical isomerism
(D) 1,2-dibromocyclohexane shows geometrical and optical isomerism.
Halogen Derivatives
faBansal Classes [10]
Sodahme
Q.9 C5Hg04 (A) C 4 H 8 0 2 (B) > (C)
A
C is hydrocarbon occupying 0.509 litre per g approximately. Hence A and B are:
(A) methyl malonic acid, propanoic acid (B) succinic acid, succinic anhydride
(C) Dimethylmalonic acid, 2-Methylpropanoic acid (D) Ethyl Malonic acid, Butanoic acid
O
II
o—c
h
Q-io ch 3 -o^^CH-CH 3 3°+ >
O O .
CI CH3
I I
(B) CH,3 - C - CHXH,
2 3
and CI - C
|
-H are enantiomers
H CH2CH3
(C) Argol (sodium potassium tartarate) will show optical isomerism.
(D) CH3CHO on reaction with HCN gives racemic mixture.
(C) C H 3 -oC - C H 2 -O
C-0-Et ( O V
0
Q.14 Which of the following are not resonating structures of each other:
Halogen Derivatives
^Bansal Classes [11]
Q.15 The unshared electron on the oxygen atom of an ether (basic centre) account for all the following except:
F
C2H5N. |
(A) Combination > 6= »B- F
c,H 5
F
/ cr
(B) Formation of oxonium salt with acids such as
(C) Formation ofperoxides (explosive)
(D) Chemical inactivity of ether
Q.16 Which ofthe following compounds yield most stable carbanion after rupture of (CJ-C2) bond:
0 0 O
II II II
(A) CH3 - C - CC13 (B) CH3 - C - CBr3 (C) CH3 - CH2 - C - CI3 (D) none of these
1 2 1 2 1 2
Q.17
N
I
H
pyrrole (I) pyridine (II) aniline (III)
which is/are correct statements ?
(A) I is more basic than II (B) II is more basic than I and III
(C) ID is more basic than II (D) all are aromatic bases
Q.18 Which is/are untrue statements)?
(A) Protonation increases electrophilic nature of carbonyl group
(B) CF3S03 is better leaving group than CH3S03
(C) Benzyl carbonium ion is stabilised by resonance
/OH
(D)CC13CH<" is unstable.
^011
Q.19 Which reacts with AgN0 3 to give ppt. ?
(B) <^0)-CH=CH-CH 2 Br
Or-
(A)<0)-Br
(C)| (D)(£>- B r
Q.20 Identify the correct statment(s).
0 1 II III
Oiv
(A) I & III are antiaromatic (B) III & IV are non-aromatic
(C) II alone is aromatic (D) II & IV are non-aromatic
Q.21 Which have acidic hydrogen?
(A)CH3COOH (B)(0>-<OH
H(X YH
C = C
(D) / \
o
Q.28 Which ofthe following compounds cannot exhibit keto-enol tautomerism?
O
CH,
(A) (B)
X I u
H3CN H 3 C » CH3
(C) H 3 C/ C = 0 ( D ) H 3 C ^
Q.29 In tautomerism
(A) a proton is moved around the molecule (B) electrons are moved around the molecule
(C) no actual movement occurs (D) shift of double bond occurs
Q. 1 Arrange the following compounds in decreasing order ofKeq for hydrate formation.
O
C C H
C 6 H 5 COCH 3 CI^O)- - 3
(!) (2)
0
o
N02-<O>-^CH3 CH3^0>-C-CH3
(3) «>
^Q.2 Arrange the following compounds in order of:
Decreasing SN1 reaction rate:
Ph
s f < 1 ^ P h
I Q CI Q
§ aD (II[) av)
a) (P) an)
(b) Explain which of these reactions would have the faster rate?
CH3
CI
I ©
(c) CH3CH2CH2 + :c S N: in CH3CH20H or DMSO.
Q.7(i)Choose the member of the following pairs of unsaturated hydrocarbons that is more reactive towards
acid-catalysed hydration and predict the regiochemistry of the alcohols formedfromthi s compound.
(a) (b) ^ ^ ^ or
(I) (II)
© (n)
(c) I or
(I) (ID
(ii) Predict on the basis of cabocation stability, which member of each of the following pairs hydrolyses at
the faster rate.
Jr Br
Br
(a) or I (b) | or Br
(I) (H) a)
(o[Q
©
(ii)
Q. 8 Assuming that cation stability governs the barrier for protonation in H - X additions, predict which
compound in each ofthe pairs in parts (a) to (b) will be more rapidly hydrochlorinated in a polar solvent.
(I) (II)
(a) CH2 = CH2 or
® <o> (O
Q .9 Select the member of each pair that shows faster rate of SN2 reaction with KI in acetone.
CH3-CH2-CH2-CH2-C1 or CH3 - CH - CH2 - CI
I
CH3
(I) (II)
CH3 - CH2 - CH2 - CI or CH3 - CH2 - CH2 - CH2 - Br
(I) (II)
CH,
J0T CH3 - CH - CH2 - CH2 - CI or CH3 - C - CH2C1
CH3 CH3
(I) (II)
Br Br
I I
(d) CH3-CH2-CH2-CH-CH3 or CH3 - CH - C % CH - CH3
I
CH3
©
(P)
Halogen Derivatives
^Bansal Classes [15]
Q.10 Select the member of each pair that undergoes SN1 solvoysis in aqueous ethanol more rapidly.
CH3
|
^iaf CH 3 -CH 2 -CH 2 -CH 2 -C1 or CH 3 -C-C1
ch3
CH2 = CH-CH 2 -C1 or CH3 - CH2 - CH2 - CI
ch3 ch3
I I
^Jcf CH 3 -C-C1 or CH3 - C - Br
ch3 ch3
.Br r^YBT
(d) Q T or
Q.ll In each ofthe following indicate which reaction will occur faster. Explain your reasoning.
(a) CH3CH2CH2CH2Br or CH3CH2CH2CH2I with sodium cyanide in dimethyl sulfoxide.
(b) 1 -chloro-2-methylbutane or 1 -chloropentane with sodium iodide in acetone.
(c) Hexyl chloride or cyclohexyl chloride with sodium azide in DMF.
(d) Solvolysis of 1 -bromo-2,2-dimethylpropane or tert-butyl bromide in ethanol.
(e) Reaction of 1 -chlorobutane with sodium acetate in acetic acid or with sodium methoxide in methanol.
(1) Reaction of 1 -chlorobutane with sodiumagde or sodium p-toluenesulfonate in aqueous ethanol.
Q.12 Classify each of the following species as electrophile or nucleophile & explain your choice.
(a)CH3C02- (b)CH30- (c)BF3 (d) CI (e) CMe3 (f):CCl2
(g)SiF4 (h)Br (i) :P(CH3)3 G)Me2CH (k) CH2 = CH2 (1) HCl
0H Ca( H)2
^Q.13 Propene > H " > I > J ° )K ) L(glycerol)
<x^Q:l 4 Of the following statements, which are true for SN2 reaction.
(a) Tertiary alkyl halides reacts faster than secondary.
(b) The absolute configuration ofproduct is opposite to that ofthe reactant when an optically active substrate is used.
(c) The reaction showsfirstorder kinetics.
(d) The rate of the reaction depends markedly on the nucleophilicity of the attacking reagent.
,(e) The mechanism is one step.
(f) Carbocations are intermediate.
(g) Rate oc [Alkyl halides]
- (h) The rate of the reaction depends on the nature of the leaving group.
l^/Q-1 5 Of the following statements which are true for SN1 reaction.
(a) Tertiary alkyl halides react faster than secondary.
(b) The absolute configuration of the product is opposite to that of the reactant when an optical active
substrate is used.
(c) The reaction shows first order kinetics.
(d) The rate ofreaction depends markedly on the nucleophilicity ofthe nucleophile.
(e) The mechanism is two step.
(1) Carbocations are intermediate.
(g) Rate oc [Alkyl halides]
(h) The rate of the reaction depends on the nature of the leaving group.
Halogen Derivatives
^Bansal Classes [16]
Q.16 Explain why CI - CH 2 - O - CH 2 - CH3 is hydrolysedmore rapidly than CH 3 - O - CH 2 - CH 2 - CI
Q.17 Ifthe temperature is not kept below 25 °C during the reaction ofprimary alcohols with p-toluenesulfonyl
chloride in pyridine, it is sometimes observed that the isolated product is not the desired alkyl
p-toluenesulfonate but is instead the corresponding alkyl chloride. Suggest a mechanistic explanation for
this observation.
Q.18 Because the SN1 reaction goes though a flat carbocation, we might except an optically active starting
material to give a completely racemized. In most cases, however, SN1 reactions actually give more of the
inversion product. In general, as the stability of the carbocation increases, the excess inversion product
decreases. Extremely stable carbocations give completely racemic products. Explain these observation.
Q.19 cis-1 -Bromo-2-tert-butylcyclohexane and trans-1 -bromo-2-tert-butylcyclohexane both react with sodium
ethoxide in ethanol to give 1 -tert-butylcyclohexene. The cis isomer reacts much more rapidly than the
trans isomer. Explain.
Q.20 The reaction of an amine with an alkyl halide gives an ammonium salt.
R:>N: + R'-x —> R3N -R'X-
amine alkyl halide ammonium salt
The rate of this SN2 reaction is sensitive to the polarity of the solvent. Draw an energy diagram for this
reaction in a nonpolar solvent and another in a polar solvent. Consider the nature of the transition state,
and explain why this reaction should be sensitive to the polarity ofthe solvent. Predict whether it will be
faster or slower in a more polar solvent.
Q.21 There is an overall 29-fold difference in reactivity of 1 -chlorohexane, 2-chlorohexane towards potassium
iodide in acetone.
(a) Which one is the most reactive? Why?
(b) Two of the isomers differ by only a factor of 2 in reactivity. Which two are these? Whcih one is the more
reactive? Why?
Q.22 The compound KSCN is a source of thiocyanate ion.
Write the two most stable Lewis structures for thiocyanate ion and identify the atom in each that bears a
formal charge of-1.
Q.23 With the help of following data show HBr exhibits the peroxide effect.
AH, 0 AH 2 °
-OCX
O o
D1
0 ' ^ o
Q.31 CH2 = CH - CH2 CH2 - C ~ OH ( Cyclic ester)
*a 3
(lactone)
This type ofreaction is called "bromolactonistaion". Suggest a mechanism.
Q.32 Draw mechanisms for these reactions, explaining why these particular products are formed.
Q MeOH F T
Q.33 Write a reasonable and detailed mechanism for the following transformation.
f y H NaCN ) , r \ H
k / \ r ethanol-water
Cyclopentyl bromide Cyclopentyl cyanide
proceeds faster if a small amount of sodium iodide is added to the reaction mixture. Can you suggest a
reasonable mechanism to explain the catalytic function of sodium iodide?
Q.35 The reaction of 2,2-dimethyl-1 -propanol with HBr is veiy slow and gives 2-bromo-2-methyl-propane
as the major product.
CH, CH,
I I
CH3CCH2OH f*rc > CH3CCH2CH3
CH3 Br
Give a mechanistic explanation for these observations.
Q.36 1-Bromobicyclo [2.2.11 heptane (the structure ofwhich is shown) is exceedingly unreactive towards nucleophilic
substitution by either the SN, 1 or SN,2 mechanism.
Br
1 -Bromobicyclo [2.2.1 ] heptane
Halogen Derivatives
^Bansal Classes [18]
Q. 3 7 We saw that acid-catalyzed dehydration of2,2-dimethyl-cyclohexanol afforded 1,2-dimethylcyclohexene.
To explain this product we must write a mechanism for the reaction in which a methyl shift transforms a
secondary carbocation to atertiary one. Another product of the dehydration of 2,2-dimethyIcyclohexanol
is isopropylidencyclopentane. Write a mechanism to rationalize its formation.
Cte ^ CC3
CH3
+ O^to
2,2-Dimethylcyclohexanol 1,2-Dimethylcyclohexene Isopropylidenecyclopentane
Q.3 8 When 2-bromo-2,3-dimethylbutane reacts with a base under E2 conditions, two alkenes (2,3-dimethyl-
1-butene and2,3-dimethyl-2-butene) are formed.
(a) Which of the following bases would give the highest percentage of the 1 -alkene ?
(b) Which would give the highest percentage ofthe 2-alkene"
CH3 CH2CH3 CH3
CH3CO~ CH3CH2CO~ CH3CH20_ CH3CH2CO~
CH3 CH2CH3 CH3
^Q.39 Dr. Don T. Doit wanted to synthesize the anesthetic 2-ethoxy-2-methylpropane. He used ethoxide ion
and 2-chloro-2-methylpropane for his synthesis and ended up with very little ether. What was the
predominant product of his synthesis ? What reagent should he have used ?
Q .40 The following reaction takes place under second-order conditions (strong nucleophile), yet the structure
of the product shows rearrangement. Also, the rate of this reaction is several thousand times faster than
the rate of substitution of hydroxide ion on 2-chlorobutane under similar conditions. Propose a mechanism
to explain the enhanced rate and rearragement observed in this unusual reaction. ("Et" is the abbreviation
for ethyl.)
Et2N: :NEt2
I I
H2C-CH-CH2CH3 "OH ) H2C-CH -CH 2 CH 3 +cr
CI OH
*Q.41 When ethyl bromide is added to potassium t-butoxide, the product is ethyl t-butyl ether.
CH3CH2 - Br + (CH3)3C - 0~ +K > (CH3)3C - O - CH2CH3
ethyl bromide potassium t-butoxide ethyl t-butyl ether
(a) What happens to the reaction rate if the concentration of ethyl bromide is doubled ?
(b) What happens to the rate ifthe concentration ofpotassium t-butoxide id tripled and the concentration of
ethyl bromide is doubled ? *
(c) What happens to the rate if the temperature is raised ?
Q. 42 Give a mechanism to explain the two products formed in the following reaction.
Hx /CH 3 Br CH3
H\ X H\ X I ^ C " C H3
C = c XCH3 NBS,hv C-C
X
CH3 + Br—C-C
H /
% H/ \h I
H
X
H
3-methyl-l-butene not rearranged rearranged
Halogen Derivatives
^Bansal Classes [19]
Q.4 3 Give the structures of all possible products when 2-chloro-2-methylbutane reacts by the El mechanism.
Q .44 Solvolysis of 1,2-dimethylpropyl p-toluenesulfonate in acetic acid (75°C) yieldsfivedifferent products:
three are alkenes and two are substitution products. Suggest reasonable structures for thesefiveproducts.
Q.45 Solution A was prepared by dissolving potassium acetate in methanol Solution B was prepared by
adding potassium methoxide to acetic acid. Reaction of methyl iodide either with solution A or with
solution B gave the same major product. Why ? What was this product?
Q .46 Solvolysis of2-bromo-2-methylbutane in acetic acid containing potassium acetate gave three products.
Identify them.
Q.47
(a) Write the structures or build molecular models of all the isomeric alkyl bromides having the molecular
formula C5HnBr.
(b) Which one undergoes E1 elimination at the fastest rate ?
(c) Which one is incapable of reacting by the E2 mechanism ?
(d) Which one can yield only a single alkene on E2 elimination ?
(e) For which isomers does E2 elimination give two alkenes that are not constitutional isomers ?
(f) Which one yields the mobt complex mixture of alkenes on E2 elimination ?
Q.48 Evidence has been reported in the chemical literature that the reaction
(CH3CH2)2CHCH2Br + KNH2 > (CH,CH2)2C - CH2 + NH3 + KBr
proceeds by the E2 mechanism. Use curved arrow notation to represent the flow of electrons for this
process.
Q.49 The given compound give mixture of six products on treatment with CH3OH. Write structures of all five
products and give mechanism of the reaction.
Q.50 Comment on the selectivity, (that is, say what else might have happened & why it didn't) shown in this
grignard addition reaction used in the manufacture of an antihistamine drug, A.
CI
Q. 51 Outline an efficient synthesis of each of the following compoundsfromthe indicated starting material and
any necessary organic or inorganic reagents:
(a) Cyclopentyl cyanidefromcyclopentane.
(b) Cyclopentyl cyanidefromcyclopentene.
(c) Cyclopentyl cyanidefromcyclopentanol.
(d) Isobutyl iodidefromisobutyl chloride.
(e) Isobutyl iodidefromtert-butyl chloride.
(f) Isobutyl azidefromisopropyl alcohol
Q. 5 2 Select the combination of alkyl bromide and potassium alkoxide that would be the most effective in the
synthesis ofthe following ethers:
Halogen Derivatives
^Bansal Classes [20]
Q. 5 3 Indicate the major alkene produced by each of the following
Br
ch
(a) CH 3 -CH 2 -CH 2 -C-CH3 3'§k/a >
CH3
CH3
(b) CH3-CH2-CH2-C-N(CH3)3OH^->
CH3
CH3
(c) (CH3)3 N - C - CH2 - CH3 O H >
CH3 f
(d) CH 3 -CH 2 -CH 2 -CH-CH 3 (CH
3>3COK >
Q.54 Choose the compound of molecular formula C7H13Br that gives each alkene shown as the exclusive
product of E2 elimination.
CH, r A /CH(CH3)2
(d) (6) L ^ C H = CH2 (f)|Q
k/cH3
(g)J^C(CH3)3
Qx5 5 Select the alkyl halide and a nucleophile that will give each ofthe following products.
^ CH3 - CH2 - CH2 - NH2 t/(fT) CH3 - CH2 - O - CH2- CH3
(c)CH = C-CH 2 -CH 2 -CH 3 Jdf(CH3)2CHS(CH3)2
Je)C6H5-0-CH2-CH3
Q. 5 6 Identify the product in each of the following reactions:
(a) C1CH2CH2CHCH2CH3 - i ^ ! l - > C 5 H 1 0 C l I
CI
(b) BrCH,CH2Br + NaSCH2CH2SNa > C4HgS2
(c) C1CH2CH2CH2CH2C1 + Na2S » C4H8S
Q. 5 7 Write the structure of the principal organic product to be expected from the reaction of 1 -bromopropane
with each ofthe following:
(a) Sodium iodide in acetone.
O
v (b) Sodium acetate ( CH3CONa ) in acetic acid.
(c) Sodium ethoxide in ethanol.
\Jd) Sodium cyanide in dimethyl sulfoxide.
Sodium azide in aqueous ethanol
^(fjSodium hydrogen sulfide in ethanol
w (g) Sodium methanethiolate (NaSCH3) in ethanol.
Na0H
(e) HO - CH2 - CH2 - CH2 - CH2 - CI >
Q. 5 9 Draw each of the following reaction in a way that clearly show the stereoisomerism of the products.
H CH3
me 01
(a) CH3 - C - Br + CH3ONa ^ > (b) CH3 - CH2 - C - Br + CH3OH —
C H 2 - C H 3 C3H 7
NaSH
(c) SN1
RCH = CH2 ^ A
CC14 hv BrCCA
hv
C
Give a mechanism for each of the reactions.
Q. 61 Complete the following reactions. Give all possible products in each case. Give mechanism ofthe reactions.
C H 3 HOWA
(a) V Moist A g 2 Q ) (b) CH 2 -CI >
^CH2C1
o
c c h (i)Br2/ a H
(b) r v - 3 a ° >(Q+(D)
\ / (ii) H
(ii) H
Na0H/F
(d) CH3 - CH - CH2 - CH3 ^ >G +H
CI
faBansal Classes Halogen Derivatives [22]
Q.65 Complete the following reactions
Electrolysis
(a) C 6 H 5 - CH - CH 3 + NaCl + HOH > A sweet smelling liquid
Br
XI aq.NaOH
(b) C6H5-CH
-CI
Q.66(i)What are the products of the following reactions ?
\ / 3
(a) PhCH = CHCH 3 + HBr >A (b) /c = c
\N +HI >B
H3C H
CH,
Peroxide
(c) l ^ J + HBr >C (d) + HC1 >D
CH2CH3
CH3 Br Na0H
Br, VC =- nCH
u2 2 v> v>
(A\
(c) H-tO K ) H
H3C "2° 2°
O
II
ale.KOI 1 ^ A S02C12 ) q Mg/Et2Q c (i)CH3-C-CH3 ) p H2SQ4/A ) ^
Q.68 CH3CH2CH2C1
(ii)aq.NH4Cl
o
Q.69 CLC - <!! - OH + Na >A - — > B. Find out A & B.
CHt-CHO
MeOCHjCl CHBft
?
<
->9 ® N^CO.E. 7
' BuLi BuOK
Ph - CH = CH
^pd Reaction of R-CO-NH2 with a mixture of Br2 and KOH gives R-NH2 as the main product. The
intemediates involved in this reaction are: [JEE 1992]
(A) R-CO-NHBr (B)RNHBr
(C) R-N=C=0 (D) R.CO.NBr2
Which one of the following has the smallest heat of hydrogenation per mole? [JEE 1993]
(A) 1-Butene (B) trans-2-Butene
(C) cis-2-Butene (D) 1,3-Butadiene
In the following compounds: [JEE 1996]
OH OH
NO,
(I) (HI)
The order of acidity is:
(A) III > IV > I > II (B) I > IV > III > II (C) II > I > III > IV (D) IV > III > I > II
v^4 OHwi
OH with HBr gives: [JEE 1998]
(A) CHXHBrCH
•O (B)CH H CHBr
3 2
O OH
(D) CH CH CHBr -TV.
Q.5
(C) CHXHBrCH.
o 3 2 ^~Br
A solution of (+) 1 -chloro-1 -phenylethane in toluene racemizes slowly in the presence of small amount
of SbCl5 due to formation of: [JEE 1999]
(A) carbanion (B) carbene (C) free radical (D) carbocation
Q.7 The enol form of acetone, after Prolonged treatment with D 2 0, gives: [JEE 1999]
OD O OH OD
I I
(A) CH 3 -C = CH2 (B) C H 3 - C - C H 3 (C) CH2 = c - C H 2 D (D) CD2 = C-CD 3
Amongst the following, the most basic compound is: [JEE 2000]
(A) C6H5NH2 (B) p-N02-C6H4NH2 (C) m-N02-C6H4NH2(D) C6H5CH2NH2
Q.9 An SN2 reaction at an assymetrical carbon of a compound always gives: [JEE 2001]
(A) enantiomer of the substrate (B) a product with opposite optical rotation
(C) a mixture of diastereomeres (D) a single stero isomers
Halogen Derivatives
^Bansal Classes [24]
[JEE 2001]
Q^M) The correct order of basicities of the following compounds is:
Q.ll Identify the correct order of reactivity in electrophilic substitution reaction of the following compounds:
^12 Left to right sp2, sp2, sp, sp hybridization is present in: [JEE 2 0 0 3 1
(A) H2C = CH-C=N (B) H2C=C=CH-CH3 (C) H O C - O C H (D) HOC-CH=CH 2
COOH
Q.14
when X is made to react with 2 eq. of NaNH2 the product formed will be: [JEE 2003]
(A)
(C)
Hs
Q.16
YVV5™3 [JEE 2004]
COOH
X
Q.17 1 -Bromo-3-chloro cyclobutene on reaction with 2-equivalent of sodium in ether gives [JEE 2005]
.CI
(A) j
Cf <B
C (C) (D)
•
JSO
O ,3H
H
f o l CH 3 COONa(excess)
Q.18 \ J (absolution)
[JEE 2005]
SO2COOCH3
(A) (B)
Me
COONa
S0 3 Na
CH,
I [JEE 2005]
Q.20 Ph - MgBr + CH3 - C - OH »A
I
CH,
CH, OH CH,
3
I I
(A) (D) CH3 - C - Ph
(B)CH3-C-OPh (C)
CH, CH,
Halogen Derivatives
^Bansal Classes [26]
Q.21 For 1 -methoxy-1,3-butadiene, which of the following resonating structure is the least stable?
CH3 H CH3
H CI CH3
N0
(K) M e O ^ O ^ - -<p)- 2 (L)MeO-<g> - ^ Q } -NO,
H OH CH3 OH H CH3
CH3 H CH3
H CH 3 OH
Q.23 When benzene sulfonic acid and p-nitrophenol are treated with NaHC03, the gases released respectively
are [JEE 2006]
(A) S0 2 , N0 2 (B) S0 2 , NO (C) S0 2 , C0 2 (D) CO2, CO2
CH3NH2 + CHC13 + KOH -» Nitrogen containing compound + KC1 + H20. Nitrogen containing
compound is [JEE 2006]
In this reaction, RCONHBr is formedfromwhich this reaction has derived its name. Electron donating
group at phenyl activates the reaction. Hofinann degradation reaction is an intramolecular reaction.
How can the conversion of(i) to (ii) be brought about? [JEE 2006]
(A)KBr (B)KBr + CH3ONa (C) KBr + KOH (D) Br2 + KOH
^27 Which is the rate determining step in Hofmann bromamide degradation? [JEE 2006]
(A) Formation of (i) (B) Formation of (ii) (C) Formation of (iii) (D) Formation of (iv)
Q.28 What are the constituent amines formed when the mixture of (i) and (ii) undergoes Hofinann bromamide
degradation?
D
(i) (ii)
(B) Q
> =- N
/ H 2 )' Q
W- M H 2 (C) i
(C) \-NH 2 $ \-NH;
D
Halogen Derivatives
^Bansal Classes [28]
EXERCISE-IV (B)
Q. 4 Draw the stereochemical structure of the products in the following reaction: [JEE 1994]
CNH<
_H NaOH > ?
BR-
SM2
CH,
Q. 5 Complete the following, giving the structures of the principal organic products: [JEE 1997]
(a) + KNH 9 •
Q. 6 Write the intermediate steps for each of the following reaction. [JEE 1998]
H,0
® C 6 H 5 CH(OH) C=CH > C 6 H 5 CH = CH-CHO
• o c r ^ o a ,
Q.7 Each of the following reaction gives two products. Write the structure of the products. [JEE 1998]
AlcK0H A
(a) C6H5CH2CHC1C6H5 ' >
Br
(b) CH 3 CONHC 6 H 5 2.Fe )
Q.8 Out of anhydrous A1C13 and hydrous A1C13 which is more soluble in diethyl ether? Explain with reason.
[JEE 2003]
Q.9 Match K a values with suitable acid: [JEE 2003]
K Acid
IJH3
.6; .o.
Q.12 Predict whether the following molecules are iso structural or not. Justify your answer. [JEE 2005]
(i)NMe3 (ii)N(SiMe3)3
Q.13 Give reasons: [JEE 2005]
H,C
Br c2H5OH(aq.) ^ acidic solution
(a) (0
CH,
3
(ii) B r _ / " \ _ y C2H5OH(aq.) ) neutral
\ = / rCH,
Na H(aq)
(b) (i)0, N ^V ° >F (liberated)
CH,
NaOH(aq.) . p i s n o t liberated
(ii)
H,C
H2N02
Conc.HNOg
(c) (i)
Conc.H2S04
NO,
NO, NO,
Conc.HNO
(ii) I
Conc.H2S04
NO,
Halogen Derivatives
faBansal Classes [30]
Q.10 Give resonating structures of following compound. [JEE 2003]
Y V
OH
Q.ll Which ofthe following is more acidic and why? [JEE 2004]
NH, NH 3
OJ IC>
Q.12 Predict whether the following molecules are iso structural or not. Justify your answer. [JEE 2005]
(i)NMe3 (ii)N(SiMe3)3
Q.13 Give reasons: [JEE 2005]
H3C
Br c2H5OH(aq.) ^ acidic solution
(a) ©
CH3
CH
(ii)Br-7^W C2H5OH(aq.) > neutral
\=j rCH,
Na H(aq)
(b) (Oo.N^V ° > F (liberated)
CH,
NO,
NO, NO,
Conc.HNQ3
(ii) I
Conc.H2S04
NO,
Halogen Derivatives
faBansal Classes [30]
NaBr+Mn 2
Q.14 ° A— ConcHN0 3 ) C(intermediate)-^^ D(Explosiveproduct)
FindA,B,C and D. Also write equations Ato Band Ato C. [JEE 2005]
Halogen Derivatives
faBansal Classes [31]
ANSWER KEY
EXERCISE-I
Q.l D Q.2 C Q.3 B Q.4 B Q.5 B Q.6 A Q.7 A
Q.8 D Q.9 A Q.10 B Q.ll A ' Q.12 C Q.13 C Q.14 C
Q.15 C Q.16 A Q.17 B Q.18 B Q.19 C Q.20 A Q.21 D
Q.22 A Q.23 C Q.24 C Q.25 D Q.26 A Q.27 D Q.28 C
Q.29 A Q.30 C Q.31 B Q.32 B Q.33 C Q.34 B Q.35 B
Q.36 A Q.37 A Q.38 C Q.39 B Q.40 D Q.41 B Q.42 A
Q.43 A Q.44 A Q.45 A Q.46 C Q.47 C Q.48 C Q.49 A
Q.50 D Q.51 D Q.52 C Q.53 C
EXERCISE-II
Q.l C Q.2 A,D Q.3 A,B,C,D Q.4 A,B,C,D
Q.5 B,C,D Q.6 A,B,D Q.7 A,B,D Q.8 C
Q.9 C,D Q.10 A,B Q.ll A,B Q.12 A,D
Q.13 A,C,D Q.14 C,D Q.15 D Q.16 A
Q.17 B,D Q.18 D Q.19 B,D Q.20 A,C
Q.21 A,B,C Q.22 B,C Q.23 A,B Q.24 A,C
Q.25 C Q.26 A,C,D Q.27 A,B,C Q.28 D
Q.29 A,D Q.30 B Q.31 D
EXERCISE-III
Q.8 (a) II, (b) I Q.9 (a) I, (b) II, (c) I, (d) I Q.10 (a) II, (b) I, (c) II, (d) II
Q .11 (a) H; 03)11; (c) I ; (d) H; (e) n Q.14 b,d,e,g,h Q .15 a,c,e,f,g,h
y O s x
Q 2.1 I | Q.38 (a) Et3CO®; (b) EtO® Q.45 MeCOOMe
OAC
Q.46 C - C - C - C , C-C = C-C, C - C - C - C
C C c
c c
Q.47 (b) C - C - C - B r ; (c) B r - C - C - C ; (d) C-C-C-C-C-Br; (e) C - C - C - C - C
C C Br
(f) C-C-C-C-C
Halogen Derivatives
faBansal Classes [32]
Q.50
C C
C
Br CH,Br
(f)
B r ^ ' ^[^-CMes
CI
Q.58 (a) C 6 H 5 -CH 2 -CH 3 -CN, (b) <^>-SCH 3 , (c) CH 3 -<CH 2 ) 9 -I, (d) <ON®-ch 3 I 0 , (e)
H Me Me
SH
Q.64 (a) CHI 3 +(CH 2 ) 4 (COOH) 2 , (b) CHBr 3 +Q-COOH, (c) CHCl 3 +[>-COOH, (d) CHF 3 + EtCOONa
Halogen Derivatives
faBansal Classes [33]
/
Q.66 (i) (a) P h - C H - E t , (b) Me 2 C(I)-Et, (c) (d) \ ^
Et
Br
OH
Ph ph
I ^k/COOH
Q.67 (a) Ph - C = C - C - Ph; (b) f O j
Ph
Q.68 Me 2 C=CH-CH=CH 2
Q.69 A::CC1 2 B:
CI CI
0 M e
Q.70 (i) & Ql>- ; (ii) r h A , COOEt
EXERCISE-IV (A)
EXERCISE-IV (B)
C(CH3)3
CH,
Halogen Derivatives
faBansal Classes [34]
h
Q.6 C6H5-CH-CeeCH > C 6 H 5 - C H - C = C H — 5 ^ - > C 6 H 5 - C H - C = CH
OH ®OH
H2
C 6 H 5 - CH = C = CH ° > C6H5 - C H = C = C H
+
OH 2
C 6 H 5 - CH = C = CH tautomerism , C 6 H 5 ~CH=CH-CHO
I "
OH 2
-FT
o^ch 3 " - c r X:H 3
H
NHCOCH 3 NHCOCH 3
H H
Q.7 (a) (b)[ f +r j
(Major) l^JJ
Br
Q. 8 Anhydrous A1C13 is more stable then hydrous A1C13 because it is having vacant 3p orbital ofA1 which can
accept lone pair of electrons from oxygen of diethylether.
F
compound.
Q.12 Not. NMe 3 is trigonal pyramidal while N(SiMe 3 ) 3 is trigonal planar due to back bonding.
Halogen Derivatives
faBansal Classes [35]
CH.3
Q.13 (a) (i) H5C6 - C - OC2H5 + HBr(acid); (ii) no reaction due to partial double bond character
CH,l3
(b) (i) 02N + F~ is liberated; (ii) Bimomecular mechanism is not possible in (ii) case
CH3
(c) (i) due to presence of lone pair of nitrogen atom NO group is electron denating and ortho, para
directing
(ii) N0 2 group is electron withdrawing and meta directing
(d) Due to reduction of centralring,three four membered antiaromatic rings become stable while on
recuction of terminal ring only one antiaromatic ring can be stabilized.
CH3
O2N> -NO2
Q.14 (A)H2S04, (B)Br2, (C) NO®, (D)
NO2
D
\
-OH
Q-15 (a)^Gauch = 5.55D;(b)(i)H
•H
CH3 H
HALOGEN DERIVATIVES
CONTENTS
EXERCISE-I (A)
EXERCISE 1(B)
EXERCISE-II
EXRECISE-III
EXRECISE-IV(A)
EXERCISE IV(B)
ANSWER KEY
EXERCISE-I (A)
(Choose the correct option. Only one is correct)
Qlf Which one is liquid at room temperature:
^ (A)CH3C1 (B)C2H5C1 (C)CH3Br (D)C2H5Br
^L The correct order ofmelting and boiling points ofthe primary (1 °), secondary (2°) and tertiary (3°) alkyl
halidesis:
(A)P>S>T (B)T> S>P (C) S > T > P (D)T>P>S
Q?f Pick up the correct statement about alkyl halides:
(A) They show H-bonding (B) They are soluble in water
(C) They are soluble in organic solvent (D) They do not contain any polar bond
Q.4 What would be the product when neopentyl chloride reacts with sodium ethoxide:
(A) 2-Methyl-2-butanol (B) Neo pentyl alcohol
(C) Both 1st & 2nd (D) 2-Methyl-2-butene
5 Reduction of alkyl halide by LiAlH4 is the type of reaction:
(A) Nueleophilic substitution reaction (B) Electrophilic substitution reaction
(C)Electrophilic Addition reaction (D) None of these
Q. 6 2-methyl butanoic acid is formed by the reaction CHC13, NaOH and
(A) Propene (B)Ethene (C)l-Butene (D)2-Butene
Q.7 CC14 + KOH (excess) » end product of the reaction is:
(A) K2C03 (B)C0 2 (C) C (OH)4 (D)HCOOK
Q. 8 The yield of alkyl bromide obtained as a result of heating the dry silver salt of carboxyic acid with
bromine if CC14 is:
(A) 1°> 3° >2° bromides (B) 1°> 2° >3° bromides
(C) 3° > 2° > 1° bromides (D) 3° > 1°> 2° bromides
Which of the following statements is invalid:
(A) The more stable the carbocation the faster it is formed
(B) Propyl cation changes to more stable isopropyl carbocation by 1,2 shift of a hydrogen
(C) Isopropyl chloride reacts with sodium ethoxide to form 1-ethoxypropane
(D) Propyl halides reacts with sodium ethoxide to form 1-ethoxypropane
Q.10 Nitrochloroform is prepared by the action of chloroform and:
(A) Hot aqueous solution ofKN03 (B) Hot aqueous solution ofNaN02
(C) Hot concentrated nitric acid (D) Hot dilute HC1 + aq. NaN02 solution
, Odl Which of the following compounds is most rapidly hydrolysed by S^l mechanism.
(A)C6H5CI (B) C\-CU2-CU=CU2
(C)(C6H5)3CC1 (D)C6n5CU2C\
o
H
Q.12 CH3MgBr + CH2 = CH - C - H 2° > product (major), product is
OH
(A) CH2 = C H - C - H (B) CH 2 -CH = CH-CH3
i i
CH3 OH
(C) CH3-CH2-CH2-CHO (D) None is correct
CI
CH Br
(c)(^J > j^j in three steps only
C1
/"\^ C H 2 C 1
(d) ^ J j > [^J in three steps only
O
I!
(e) Ph - CH2 - C - CI » Ph - CH^ - CI
O
(QPh-CHj-Cl > Ph - CH2 - C - CI
I
EXERCISE-III
Q.l A primary alkyl halide (X) C4H4Br reacted with alcoholic KOH to give (Y). (Y) reacts with HBr to give
(Z) an isomer of (X). On reacting with alkali metal such as sodium/dry ether gives (S) CgHj8 which was
differentfromthe compound produced when n-butylbromide was treated with Na. What (X), (Y), (Z)
and (S).
Q.2 On electrolysis an aqueous ethanoilc solution of so dium chloride gives sweet smelling liquid (X). (X)
gives isocyanide test and condenses with acetone tofromhypnotic (Y). What are (X) and (Y)?
Q.3 The alkyl halide C4H9Br (A) reacts with alcoholic KOH and gives an alkene (B), which reacts with
bromide to give dibromide (C). (C) is transformed with KOH & sodamide to gas (D) which forms a
precipitate when passed through an ammonical silver nitrate solution. Give the structure formulae of the
compounds (A), (B), (C) and (D) and explain reactions involved.
Q.4 An unsaturated hydrocarbon (A) C6H10 readily gives (B) on treatment with NaNH2 in liquid NH3.
When (B) is allowed to react with 1 -chloropropane, a compound (C) is obtained. On partial hydrogenation
in the presence of Lindlar catalyst, (C) gives (D), C9H18. On ozonolysis (D) gives 2,2-dimethylpropanal
and 1 -butanal. Give structures of (A), (B), (C) and (D) with proper reasoning.
Q. 5 One mole of each bromoderivative (A) and NH3 react to give one mole of an organic compound (B).
(B) reacts with CH3I to give (C). Both (B) and (C) react with HN02 to give compounds (D) and (E),
respectively. (D) on oxidation and subsequent decarboxylation gives 2 -methoxy-2-methylpropane.
Give structures of (A) to (E) with proper reasoning.
Q.6 A chloro derivative (A) on treatment with zinc-copper couple gives a hydrcarbon withfivecarbon
atoms. When 'A' is dissolved in either and treated with sodium, 2,2,5,5-tetramethylhexane is obtained.
What is the original compound A?
Q.7 A primary alkyl halide (A) C4HjBr reacted with alcoholic KOH to give (B). (B) reacts with HBr to give
(C) an isomers of (A). (A) on reacting with sodium gives (D) CgHlg which was differentfromthe
compound produced when n-butylbromide was treated with Na. What are (A), (B), (C) and (D).
Q. 8 One mole of a hydro carbon (A) reacts with 1 mole of bromine giving a dibromo compound C5HJ0Br2.
(A) on treatment with cold dilute alkaline KMn04 solution forms a compound C5H1202. on ozonolysis
(A) gives edquimolar quantities of propanone and ethanal. Deduce structure of (A).
Q.9 A hydrocarbon (A) was found to contain 85.7% carbon and 14.3% H. This compound consumes 1
molar equivalent of hydrogen to give a saturated hydrocarbon. 1 g of (A) just decolourised 3 8.05 of 5 %
solution by weight of Br2 in CC14. Compound (A) on oxidation with conc. KMn04 gave a compound
(C), C4HgO and (B) acetic acid. Compound (C) can easily be prepared by the action of acidic aqueous
mercuric sulphate on 2-butyne. Deduce (A), (B) and (C).
Q. 10 When a hydrocarbon (A) is treated with excess of hydrogen chloride, a dihalogen derivative (B) is
obtained. The compound (B) is treated separately with aqueous and alcoholic KOH to give compounds
(C) and (A) respectively both having three carbon atoms. Compound (C) does not reduce Tollen's
reagent and compound (A) give white precipitate with ammonical silver nitrate. Assign structures to
compounds (A) to (C).
Q.12 A dihalogen derivative (A) of a hydrocarbon having two carbon atoms react with alcoholic potash and
forms another hydrocarbon which gives a red precipitate with ammonical cuprous chloride. Compound
(A) gives an aldehyde when treated with KOH (aq). What is (A)?
Q.13 A white precipitate was formed slowly when AgN03 was added to a compound (A) with molecular
formula C6H13C1. Compound (A) on treatment with hot alcoholic KOH gave a mixture of two isomeric
alkenes (B) and (C) having formula C6H,2. The mixture of (B) and (C) on ozonolysis furnished four
compounds (i) CH3CHO, (ii) C2H5CH0, (iii) CH3COCH3, (iv) (CH3)2CH. CHO
What are (A), (B) and(C).
Q.14 0.369 g of a bromo derivative of a hydrocarbon (A) when vaporized occupied 67.2 mL at NTP. (A) on
reaction with aqueous NaOH gives (B). (B) when passed over alumina at 250° C gives a neutral compound
(C) while at 3 50°C it gives a hydrocarbon (D). (D) when heated with HBr gives an isomer of (A). When
(D) is treated with dil. F^SO^j, (E) is obtained. Identify (A) to (E) and explain the reactions.
Q.15 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 AgN03 solution. The compound (X) may be represent 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).
Q.l Chlorination oftoluene in the presence of light and heat followed by treatment with aqueous NaOH gives
(A)o-cresol (B)p-cresol
(C) 2,4-dihydroxytoluene (D) Benzoic acid [IIT 1990]
Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides due to
(A) The formation ofless stable carbonium ion (B) Resonance stabilization
(C) The inductive effect (D) sp2 hybridised carbon attached to the halogen
[IIT 1990]
, Qrf 1-Chlorobutane on reaction with alcoholic potash gives:
^ (A) 1-butene (B) 1-butanol (C)2-butene (D)2-butanol [ITT 1991]
The products of reaction of alcoholic AgN02 with ethyl bromide are [ITT 1991]
(A) Ethane (B) Ethyl nitrite (C) Nitroethane (D) Ethyl alcohol
Q.5 When nitrobenzene is treated with Br2 in presence ofFeBr3 the major product formed is:
m-bromonitrobenzene. Statements which are related obtain the m-isomer are
(A) The electron density on meta carbon is more than on ortho and para position
(B) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para position and not at meta position
(D) Easier loss of H+ to regain aromaticityfromthe meta position thanfromotho and para positions.
[ITT 1992]
0.10 Toluene, when treated with Br2/ Fe, gives p-bromotoluene as the major product, because the CH3
group [IIT 1999]
(A) is para directing (B) is meta directing
(C) activates the ring by hyperconjugation (D) deactivates the ring
0Cfl The order ofreactivity ofthe following alkyl halides for a S ^ reaction is: [ITT 2000]
(A) RF > RC > R-Br > R-I (B) R-F > R-Br > R-Cl > R-I
(C) R-Cl > R-Br > RF > RI (D) R-I > RBr > R-Cl > R-F
Q.13 CH3MgBr + Ethyl ester -» which can be formed as product, [IIT 2003]
(excess)
CH2CH3 CH,
CH2CH3 CH2CH3
CHjCH^ CH3
CH, CH,
EXERCISE-IV (B)
Q.l Fill in the blanks:
(a) Butan nitrile can be prepared by heating _ with alcohalic KCN. [IIT 1992]
jvf Amongst three isomers of nitrophenol, the one that is least soluble in wateris_ [IIT 1992]
Q.2 Identify the major product in the following reactions: [IIT 1993]
CI
CgHj — CH2 — CH - CH3 ? -> ?
KOH A
Q.3 An alkyl halide X of formula CfiH]3Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H12). Both alkenes on hydrogenation give 2,3-dimethylbutane. Predict the structures
ofX, YandZ. [IIT 1996]
H-
MeO-
Ph
Q.5
I
- -— _AicohaiicKOH—^ BWrite structures of (A) and (B).
Heat
H1(excess)
(b) (CH3)2CHOCH3 > A+B Write structures ofAandB. [IIT 1998]
Heat
Q. 8 How would you synthesis 4 methoxyphenol from bromobenzene in NOT more thanfivesteps? State
clearly the reagents used in each step and show the structures of the intermediate compounds in your
synthetic scheme. [IIT 2001]
Q.9 An alkene A (C16H16) on ozonolysis give only one product B (C8HgO). Compound B onreaction with
NaOH/I2 yields sodium benzoate. Compound B reacts with KOH/NT^NF^ yielding a hydrocarbon C
(CgHj Q). Write the structure of compound B and C. Based on this information two isomeric structures
can be prepared for alkene A. Write their structures and identify the isomer which on catalytic
hydrogenation (t^/Pd-C) gives a racemic mixture. [IIT 2001]
Q.10 Give maj or products A, B, C and D in following reaction sequence. [IIT 2004]
CH2-C1
K C N
> / a\ (i)NaOEt/EtOH . r m H3Oe .
( A ) > ( B )
DMF (ii)PhCHO/A ' ^
c(i)SOCl2 I
V^v (ii)CH3NH2
EXERCISE-I (B)
Q.l D Q.2 A,C Q.3 B,C Q.4 A,B
Q5 A,C,D Q.6 A,B,C, P Q.7 B Q.8 A,B,D
Q9 B,C,D Q.10 B,D Q.ll A,D Q.12 A,C,D
Q.13 A,C,D Q.14 A,C,D Q.15 B,D Q.16 A,B,C,D
Q.17 A,B Q.18 A,B,C Q.19 A,B Q.20 A,B,C
Q.21 A,C Q.22 B,C Q.23 A,B,C,D Q.24 B,C,D
Q.25 A 3, B 2 ,C 1,D —> 2 Q.26 A -> 4, B 3,4, C - > 3, D -> 1,2
Q.27 A—>2, B—>•!, C—>4, D - » 3 Q.28 ( A ) - S ; ( B ) - -Q; ( C ) - R ; ( D ) - P
Q.29 ( A ) - Q ; ( B ) - S ; ( C ) - R; (D) - P Q.30 (A)-Q;(B)-- R ; ( C ) - P ; ( D ) - Q
EXERCISE-II
Q.4 (ii)
Q-5 (A)\TSJ
H
Me Me Me
I I I
(c) (A) Me - C = CH - Me, (B) Me-C-CH 2 -Me, (C) Me-C-CH 2 Me
OEt I
o
(e)
N
Q.7 (d) Q.8 N
H
CH3
I
Q.ll (a)AsEt-I (b) B = CH3 - CH - OH (c) Me2C=CH2
OH
I
(d) Me2C=CH2 (e) Me-CH-CH2 & Me - OH - CH2
OH
Q.12 The mechanism of
® C1CH2CH2CH2CN (ii) PhCHF2
(iii) FCH2CH = CHC02Me (iv) Efl
(v) no reaction
Q.13 (i) Chloroform responds carbylamine test while ethyl alcohol does not. Carbylamine test- The compound
is heated with aniline and alcoholic caustic potash-an obnoxious smell of phenyl isocyanide (C6H5NC)
is produced.
(ii) Chlorine atoms of chloroform can be easily replaced by - OH group s on treatment with NaOH. Hence
chlorine atoms come in the form of sodium chloride. The solution thus when treated with silver nitrate
solution gives white precipitate of silver chloride. Chlorine atom in vinyl chloride is not readily replaced
by NaOH, hence it does not give precipiatet with AgN03 solution.
(iii) The two compounds are hydrolysed with aqueous NaOH when 1,1 -dibromoethane form acetaldehyde
while 1,2-dibromoethane gives glycol.
(iv) Chlorine atom in chlorobenzene is very less reactive, while chlorine in cyclohexyl chloride is very reactive.
Hence the two can be differentiated as above in (ii)
(v) Apply test (ii) as above; when benzyl chloride gives white precipitate with AgN03 solution, while O
chlorotoluene does not give precipitate. Alternately, the compounds are oxidised when o chlorotoluene
give o-chlorobenzoic acid when benzyl chloride gives benzoic acid (having non chlorine.)
(vi) n - Hexane does not respond CI" ion test even after fusion with Na and treatment with acidic AgN03.
the remaining three compounds are distinguished by their reactivity with alcoholic AgN03 solution.
shydrogenated carbon.
Q.21 KCN is an ionic compound [K+(:C =N:)-] in which both C and N carry a 1
to give alkyl cyanide AgCN
N atom and R-N = Cis
faBansalClasse
Q.22 The strong -1. E offluorineatom in F3C - C < produces partial +ve charge on C atom of CF3 which
ultimately increases+ve charge on 2nd carbon atom to destabilize it
F
t +5
i
F
In F3C+, the unshared pair of electrons in the p orbitals of each of thefluorineatom are shifted to C+ via
p-p orbital overlapping and thus stablizing F3C+ ion
Q.23 Dry gaseous hydro halogen acids are better electrophile. Also in aqueous solution F^O acting as nucleophile
may produce alcohol.
Q.24 KI reacts with RC1 to form RI. This RI molecule now hydrolysed easily to give ROH because alkyl
iodide are more reactive than alkyl chloride.
H0H
RC1 + KI -» RI • > ROH (more fast)
Q.25 The more pronounced the nucleophilic activity ofthe attacking reagent, then the more the SN2mechasnism
will be favoured. Since in SN1 mechanism the raegent doesnot enter into the rate determining step of
ionisation How ever it can also be expected that as the nucleophilic activtiy is so slow that the mechanism
will changefromSN2 to SN1
Q.26 The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl
chloride is facilitated.
Q.27 On movingfrom3° to 1 ° alcohol rate of ^ 2 reaction decreases and reaches to minimum and mechanesm
changesfromSN2 to SN1, Then rate of SN1 rate of reaction increases.
Q.29 tert-Butyl chloride, sec butyl chloride and CC14 with ale. silver nitrate
Br
Q.30 (a)As Q C ^ j] D. Q f
CuLi
-10 2 Hs
Q
1=
o
faBansal Classes NOMENCLATURE OFORGANIC COMPOUND [28]
Me Me
(b) (A) EtO Pr, (B) Pr EtO
H H
e ©
Q.31 A = CjqHjj-C^CH B e C10H21-C^CLi C-C-C-C-C-C-Br
C
D = C 1Q H 21 - C = C - (CH 2 ) 4 - CH - CH 3 E e C1qH21 - C = C - ( C H 2 ) 4 - C H - C H .
CH H H CH
CH
F-C10H21-C-C-(CH2)4-CH-CH3
H 0 H
EXER CISE-III
Br
Q.L CH3-CH-CH2-CI CH 3 - C = CH 2 CH3-C-CH
CH. CH 3
(X) 2 - Bromo - 2 - methyl propane
(Z) (isomer of X)
Q.2 (Y)
Chloretone (Hypnotic)
Br Br
(A) (B) (C)
CH 3 - CH2- C = CH
<P)
OCH 3 OCH 3
I
CH 3 - C(CH 3 ) - CH 2 - CH 2 NH 2
Q.5 CH3-C(CH3)-CH2-CH2-Br
(B)
(A)
OCH 3
OCH 3
(C) (D)
OCH,
CH3-CH-CH2-CH2-N-N = O
CH,
(E)
Q.6 (CH 3 ) 3 C - C ^ C L
CH 3 CH, CH,
I
C H 3 - C = CH H 3 C — C — CH 3
Br
Q.7 CH3-CH-CH2Br
(B) (Q
CH,
(A)
CH,
CH 3 - CH - CH 2 CH 2 - CH - CH 3
(D)
CH, ^CH,
Q.8
C=C
CH, "H
(A)
CH3 CH 2
CH^ CH2
Q.9 C = CH - CH, CH 3 -COOH ;c = o
CH3X
CH,
(A) (B) (Q
Q.10 CH3- C = CH
CI
(A) (B) (C)
(A) (B)
Q.16 HC^C-CH^Cl
EXERCISE-IV (A)
EXERCISE-IV (B)
Q.l (a) propyl chloride, (b) ortho
Br
Q.2 (i) C 6 H 5 -CH = CH-CH3 ; C 6 H 5 -CH-CH 2 -CH 3
(ii) C6H5COOMgI + CH4
CI ch3 ch3
H- -Ph
Q.4 MeO- - H (NGP due to MeO, so retention of configuration)
Ph
CH 3
Q.5 (a) Cis and trans forms of stibene C6H5CH=CHC6H5; (b) Cri-j ^>CH1 + CH31
h
Br
C=CNa G=CCH3
,CH-CH 2 Br
NaNH,(liq.) CH-J
Q.6 (A)fQ *(B)
CH,
Q.7 CH 3 -C-CH 2 CH 3
oc2h5
Alternative rout
Br Br OMe OMe
Br Br
naoh n a o h
o j - ^ ^ i o j > [ q j ^ l o j - . . _ > [ o j - ^ l q .
ONa OMe ONa OH
SOiH
KOH
Q.9 (A) PhC(Me)=C(Me)Ph °r z "- H 3° > (B) 2PhC - Me KU
" > (C) PhCH2Me
NH3-NH3
Two isomers ofA are cis and trans
CONHCH,
!
CN COOH CH = C
Br
(A) Br
Br
(C) (D)
Br
Me Me Me
f5 HO—|—H — H—|—CI — -> H- -OH
11 1
Et Et Et
B A
Steps I and II are
(A) both SN1 (B) both SN2 (C) ISN1, II SN2 (D) I SN2, IIS N 1
Q.16 What are A & B in the following reaction?
CI
Mg/THF . (i)CH3CHO ^
J\. f Jj
.^-Br (ii)aq.NH4Cl
MgCl CHOHCH3 CI CI
(A)
Br
*{S V ^-Br
(B)
MgBr
&
CHOHCHi
MgCl MgCl
H,0 +
Q.17 Ester A (C 4 H 8 0 2 ) + CH3MgBr > C4H10O
(2 pair) (alcohol)
(B)
Alcohol B reacts fastest with Lucas reagent. Hence A and B are
O O
O o
II II
(C) C H 3 - C - 0 - C 2 H 5 , ( C H 3 ) 2 C H 0 H (D) H - C - O - C 3 H 7 , ( C H 3 ) 3 C O H
Qc CI ET,0
?
MgCi CI
(A) (B) MgBr (Q (D) None of these
B r C H 3
1 V~V OH-
V^
H A _ A H
Ais:
HOV / Y ,CH 3 H\/ \/ 3
(A)
h/LAH
(C) Both
(B)
oh/V_AH
(D) None
CHCI3 + OH- » HCOO"
Intermediates ofthis reaction are
(A) :cci: (B) :CCL (C) both (D) None
3 Racemic mixture is obtained due to halogenation of:
J&
(A)n-pentane (B) Isopentane (C) neopentane (D)BothA&B
For CH3Br + OH" > CH3OH + Br
the rate of reaction is given by the expression:
Q.24 (A) rate = k [CH3Br] (B) rate = k[OH"]
(C) rate = k [CH3Br][OH_] (D) rate = k[CH3Br]° [OH"]°
Which will give white ppt. with AgN03?
The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A) Alkyl chlorides are immscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCI2 are soluble in water
(D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite
[194]
<!§Bansal Classes Halogen Derivatives
Q.27 True about alkyl halides is/are:
(A) Tertiary alkyl halides undergo £^2 substitutions
(B) Alkyl iodides on exposure to sunlight gradually darken
(C) Alkyl chlorides do not give beilstein test
(D) A nucleophilic substitution is most difficult in alkyl iodides
Q.28 The product formed when glycerol reacts with PC15 is-
(A) 1,2,3-trichloropropane (B) Glycero monochlorohydrin
(C) Glycero dichlorohydrin (D) All of these
Q.29 On heating glycerol with excess amount to HI, the product formed is-
(A)Allyl iodide (B) Isopropyl iodide (C) Propylene (D) 1,2,3-tri-iodopropane
To prepare 3-ethyl-3-pentanol the reagents needed are:
(A) CHgCHjMgBr + CH,-C- CH2CH3
Ii
0
(B) CH3MgBr + CH3CH2 - C - CH2CH3
II
O
(C) CH3CH2MgBr + CH3CH2 - C - CH2 - CH3
II
0
(D) CHgCHjCT^MgBr + CH3 - C- CH2CH3
II
O
Non-occurence of the following reaction
Br + CH3OH > BrCH3 + OH , is due to
(A) Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases
\_J^32 When ethyl bromide is treated with moist AgjO, main product is:
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above
yJJ^f When ethyl bromide is treated with dry Ag^, main product is:
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above
CH,
H- D c H O-
Q.34 H_ Br — — > ? Major product is:
C2H5OH
CH
Q.36 BR——H
E2
il -
(A)]
(C)]
3
^r^Trrtiztir™
Q.40
Q.41 A
042
( A ) Q CB)|£) ( C ) ^ .(D) I
— —
Q. 43 The appropriate naming for the second step in the haloform reaction is:
(A) Halogenation (B) Dehydrohalogenation
(C) Reduction (D) Dehydrogenation
Q. 44 Which product is obtained when bleaching powder is distilled with acetone:
(A) CC14 (B) CHClg (C) CH2C12 (D) CH3C1
+4H
CHCI3-
Zn/HCJ (aq.)
+6H
Zn/H 2 0
0 /^Y™3
Q.48 is converted into I by:
(A) (i) CH3~ Mgl, H30+ (ii) H2S04, A, (lii) HBr, R202
(B) (i) CH3- Mgl, H30+ (ii) H2S04, A, (iii) HBr
(C) (i) CH3-MgI, H30+ (ii) HBr
(D) (i) HBr, R ^ (ii) CH3-MgI, H30+
Q. 49 To form Malonic acid, by shortest possible route, we have to start a reaction from:
(A) Ethyledine chloride (B) Methyl chloride (C) Methylene chloride (D) Chloro ethan
[197]
<!§Bansal Classes Halogen Derivatives
EXERCISE-I (B)
(Choose the correct option. One or more than one are correct)
[X]is:
H
H
Br
Q.3 A solution of (R)-2-iodobutane, [a] = -15.9° in acetone is treated with radioactive iodied, until 1.0% of
iodobutane contain radioactive iodine, the specific rotation of recovered iodobutane is found to be
15.58°, which statement is correct about above information.
(A) It has optical purity 96% (B) % of R in solution is 99%
(C) Racemic mixture is 2% (D) Final solution is dextrorotatory
CH 3 . A „
moistAg,U
2
CH 2 CI —>
£
CH 2 OH CH 2 OH CH
CH, „ ^ ^ X
Xchoh <&< 1 (C)C > (D)
OH
Br Br
CH 3
&/ ©
oh
e
011
(C) CH 3 CH 2 -CH-N CH 3 > (D) CH CH C H - C H >
CH, CH, S
S(CH3V
CH
H
CH
Q.7
I
H
CH3 CH 3
Br
(D) CH 3 -0-C 6 H 4 -CH 2 Br will react more readily than N0 2 -C 6 H 4 -CH 2 Br for S.
I
Q.10 Consider the given reaction
H-C-OTS NaCN
CH3CH2CH-CN
Q.ll Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction because
0
(A) - C - group ofbenzoyl chloride is in conjugation with benzene ring. This makes benzoyl chloride
more stable than acylchloride.
(B) CH3- group of acetyl chloride make C-Cl bond stronger due to the +1 effect.
(C) C6H5- group ofbenzoyl chloride make C-Cl bond weaker due to +R effect.
(D) Carbonyl carbon in benzoyl chloride is less electron deficient than acetyl chloride
II
s CH3
N-^OH
CMe3
(A) (B)
CMe, CMe,
(C) <P)
Br
Q.18 3-Phenyl-3-pentanol can be prepared from grignard reagent & other component which can be
(A) 3 -pentanone (B) Ethylbenzoate (C) Ethyl phenyl ketone (D) Propanoyl chloride
(C)
0> "0
(A) (B)
a
Q.22 SN1 & SN2 product are same in (excluding stereoisomer)
CH 3 CI
Q.25 Match the List I (reaction) withList II (reaction intermediate) and select the correct answer using the
codes given below the Lists.
List I Listn
(A) CF3-CHC12 alc.KOH/A > CF2 = CC12 (1) Transition state
CH3
(B) CH3 - C - OH > CH, - ~C~= CH, (2) Carbocation
CH,
CH,
alcKOH
(C) CH3-CH2-Br > CH 2 -CH 2 (3) Carbanion
Br
CH, CH,
Q.27 Match List I with List II and select the correct answer from the codes given below:
ListI List II
Q.28 Match List-I with List-II for given S n 2 reaction & select the correct answer from the codes given below
H,O
(A) R-MgX + HCHO > Adduct
n-carbon (P) Ketone
H3
(C) R - M g X + C 0 2 • Adduct ° >
n-carbon (R) Acid (n + 1) carbon
h
(D) R-MgX + Ph-C=N- • Adduct 3° >
(S) 1 0 Alcohol (n + 2) carbon
/OCH 3
W-
-C>
CH,0 CH,CH 2 Q >
(P)E1
(A)
CH,0
CH3O
0
II
c
CH 3 CH 2 O
(Q)E2
CB)
W
CH33
CH22CH2Br
CH,CH,OD
(R)Elcb
(C)
o o
Br
Br
ale. KOH (S)Ec
CD)
Q.2 On reaction between an alkyl halide and KOH in a mixture of water and ethanol, compare the two
mechanisms SNj and SN2:
(a) relative rates of CH3X,C2H5X,iso-C3H7X&tert-C4H9X
(b) relative rates for RC1, RBr and RI
(c) effect on rate of a rise in temperature
(d) effect on rate of increasing water content of the solvent.
(e) effect on rate increasing alcohol content of the solvent.
Q.3 In the following reaction is carried out in the weakly ionizing solvent, acetone (CH3)2C=0. (Bsisbrosyl,
p-bromo benzene sulfonyl)
n-C4H9OBs + X - >n-C4H9X + BsO-
The order of reactivity of halide ions depends or the salt used on their source :
+
ifLi X~ isused,I—^r-^Cl-
if (n-C4H))4N+ X - is used C l - > B r - > I ~
How do you account for this contrast in behavior ?
Q.4 Which of the following is the correct method for synthesizing 4,4-dimethyl-pent-2-yne, using sodamide
in liquid NH3? Given reasons.
CH3 CH3
(i) CH3C=CH + CH3 - C - Br > (ii) CH3 - C - C = CH + CH3I — >
CH3 CH3
Q.5 Give the products andfindall unknowns.
(a) I^N CH2 CH; CH, C ^ Br A >
CH3 Nal
H H
(C) n TsCl v *
Pyridine
A NaBr
B
CH, OH
H3 +
(a) 'CH3 + CH3CH2MgBr(l eq) ° > A
MgCl
(b) B
Ph-€OCl +
o
(2 eq)
O
(d) QCMgI + D
(1 eq.)
CH2
HCl
(e) •> E
H3C Ph
C2H5
Q.7 To prepare <J>-C-C2H5 by RMgX which is the incorrect pair
OH H,0
(a) <J)MgBr + (C2H5)2CO
I
H
Ci
Zn .
I Zndust' A — n
Q9 CH3-CH-CH-C
CHH 2, -- C
C 1I -- convert?
B
CH3
Q.10 What is/are the limitation in the formation of Grignard reagent by RX+Mg —dryether >
(a) R should not contain any acidic group
(b) R should not contain any electronegative group
(c) Alkyl halide should not be vicinal dihalide
(d) Alkyl halide can't be Tertiary.
Q.ll Identify the unknowns
(a) CH^jCHjCl + 1 ~ - » A
(b) (CH3)2CH-Br + KOH (aq.) —» B
(c) (CH3)3C-Br + KCN (ale.) -> C
(d) (CH3)3C-Br + KOH (aq.) -> D
CI
Conc NaUH
® CH 3 -CH-CH 2 -OH ) E,
0) C l C ^ O ^ C H ^ r + KCN ™ >A
SF
(ii) PhCHO * >B
Q.16 Iodoform gives precipitate with AgN03 on heating while CHC13 does not.
Q.17 Hydrogen atom of chloroform is definately acidic, but that ofmethane is not.
Q. 19 Treatment of Me3CCH = CH2 and Me3CCHOHMe with concentrated hydrochloric acid gives the
same two isomeric alkyl chlorides what are these two products.
Q.20 Iodine reacts with alcohols to give alkyl iodine only in presence of phosphorous.
Q.21 KCN reacts with R - 1 to give alkyl cyanide, while AgCN results in isocyanide as major product.
Q. 24 RC1 is hydroly sed to ROH slowly but reaction fastens on addition of KI.
Q.25 The mechanism of decomposition of Me3 S+ OH" is SN2 whereas of Me3S+1- is SN1.
Q. 26 Alkaline hydrolysis ofbenzyl chloride in 50% aqueous acetone proceeds by both ^ 2 and S^l mechanism,
when water is used as solvent, mechanism was now mainly SN1.
Q. 27 Ethanol is less reactive than methanol as well as isopropyl alcohols when treated with dry HCl gas.
Q.29 Arrange following compounds according to their reactivity with ale silver nitrate.
t-Butyl chloride, sec butyl chloride and CCL.
Q.30
C
+B NBS
^ q)Li a ^ » r 1 C ale.KOH.
(ii) CuF
CH,
(b) CH3CH2CH2 OH
H
(i)TsCl Hi) K
kii)C2HsO"K+ kii)C2H5OTs
(A) (B)
[ORGANIC CHEMISTRY
XII (ALL)
HYDROCARBON
REACTION CHART FOR ALKANES
GMP GR
H2,Ni ) X , , hv or UV light or 400 °C
(1) R-OCH 200~300°C
(1) »RX
or
R-CHCH, Sabatier senderen^
(2) Nitration R-N
reaction
Z n - C u + HCl
Sulphonation H 2 S 2 0 7
(2) R-X RedP-Hi,LiAlH4 (3) -> Alkyl Sulphonic acid
+HOHorROH
(3) R-Mg-X orNH3 orRNH2 S 0 + G 1 Reed reaction—^ R S Q Q
2 2
hv
Na, dry ether
(4) RX Wurtz reaction
A1CL/HC1 • , , „
Zn > branched alkanes
Isomerisation
(5) RX Frankland's reaction|
R - C - C l or ROH Pyrolysis
(6)
RedP/Hi SOO-TOO^-Alkenes+ CH4 o r C2H6
0
or Cr or Mo or V oxide
(7) + A1 2 0 3 500°C
' Aromatic compound
R-C-R or RCHO
conc.H 2 S0 4 H, Ni
(1) R-CH-CH-OH (1) 200-300°C
>R-CH-CH 3
-H.,0
(2) R-CH-CH-X
ale. KOH (2) ^R-CHX-CH2X
-HX
R-CH=CH, (3) HX > R-CHX-CH3
Zn dust
or (4) HBr, Peroxide ) R - C H - C H Br
(3) R-CH-CH<* for higher alkene
-X, Cn H,2n
(5) HOCl ) R - C H ( O H ) - C H CI
R - C H - C H . Zndust dil.H 7 S0 4
(4) (6) + H 0
>
R-CH2(0H)-CH3
X X I/2Q 2 .R-CH-CH?
(7) Ag300°C
Ni,H, O
S
(5) R - C CH
200-300°C R-CH-CH9
(8) +ch
2N2
(6) ^ ^ COOK Kolbe's electrolytic synthesis CHO
RCH-COOK (9) _J5^(RCH CH ) B
2 2 3
RD
CO +H2
CO+H-, ) -CH-CH3 R - C H .2 - C H 2
(7) (C2H5)4N+OH
(10) HCO(CO)4> 'CHO +
Pyrolysis CHO
^ R-C-O-CH2-CH2-R o.
O
(11) A
>CO2 + H2O
R
(14) strong oxidant ) C OH + + jj q
A1 2 (SQ 4 ) 3
(19) Isomerisation
200-300°C
H,0 AsCl,
8) CaC2 (10) Ca det& Bunsen reaction CHClCHAsCL
electric arc, 1200°C
9) 2C + H2 Berthelot'sprocess >
CH?CHO
(11) HgS0 4
10) CH3-CSCH (i)Na (ii)R-X
CO+HOH
10) CH-CsCH (i)CH3Mg!(ii)R-X (12) Ni(CO) 4
' CH =CH-COOH
CO + EtOH
(13) Ni,160°C * CH=CH-COOEt
(14) NaNH, .Na-CsC-Na
AgNO, +N114OH
(15) „ „ , ,
(Tollen snRe agent)
* Ag-CsC-Ag
° b
(16) CU 2 CI 2+ NH 4 OH ) Cu-C=C-Cu
(17) Combustion O2_»C0
2 + H,0
CHO
(18) Bayer Re agent
•-> H C O O H
CHO
Trimerisation
(21) »CgH8or 1,3,5,7-cyclo octa tetraene
[Ni(CN) 2 ]
Dimerisation
(22) "^butenyne
[Cu(NH3 ) 2 ] +
CH-CH
(23) —» II II
CH-CH
S
CH,OH3 )
CH(OCH3)2
(24) (BF 3 -HgO) CH-,
methylal
Q. 1 The reaction of E-2-butene with CH212 and Zn-Cu Couple in either medium leads to formation of
CH CH, CH, CH,
H> H
(B) H/\ /\CH3 c n , y yci-i? CH3/
(A) (C) (D)
(A) (C)
CI
(A) x > z > y (B) y > x > z (C) y > z > x (D) x > y > z
Me
11 DU u gQ
2
Q. 6 The major product P formed in g i v eHO-f-H
n ] ,, —±-> P reaction is
Me
p h C H 3 p h H
V _ / w
(C) '/'C (D) reaction will not take place
V
H H,C
amount.
Br
H 2 H
Q.8 ^ ° - M ^ P ( M a j o r ) - ^ Q (Major)
The structure of Q is
Br
Br
Br Br
CH3 M IS
[f (i)CH,COOOH ^
Q9 x
hACH3-^^
The probable structure of'X' is
CH 3 CH, CH,
CH,
18 H" -OH -OH -OH
18 .
"OH (C) -OH
(A) -OH (B)HO- -H -OH
CH, CH, CH,
CH,
HYDROCARBON [6]
faBan sal Classes
Q. 12 O-xylene on ozonolysis will give
O CH3-C = O o
CHO
(A) | & CH3-C-CHO (B) C H 3 _I = 0 & CH 3 -O-CHO
CHO
CH3-C = O o
CH. - C = O CHO CHO
(Q & ( D )
CH3-C = 0 ' C H
3 " 0 _ C H 0 &
CH3-C = O CHO CHO
COOCH,
0 S 0 4 (leg)
Q.13 •» X.
-COOCH3 H 2 0/ Acetone
Identify'X'.
,COOCH 3 COOCH,
OH OH
(A) OH (B) OH
COOCH, COOCH,
COOCH3
HO OH
(C) (D) Reaction will not occur
HO OH
COOCH,
OC2H5 PdCL.HOH
Q.14 ^z.
CuCi,,0,
OC 2 H 5 OC2H5
OC 2 H 5
0 0
CH, CH,
I I ' 0s04(lequiv.)
Q.15 CH, - C = C - CH 0 - CH = C H , A; Identify A
(Acetone/water)
CH3CH3 OH OH CH 3 CH 3
CH, CH,
I I
(C) C H 3 - C H — C CH 2 - C H - CH 3 (D) Reaction will not occur
I I
OH OH
[215]
l & B a n s a l Classes HYDROCARBON
Q, 16 | J + CH 2 N 2 (1 equi.) Pb
(QAc)2 )B; identify B
CH3
compound A will have structure.
(A) CH3CH2 - C = C - CH 2 CH 3 (B) CH3 - CH - CH = C - CH 2 CH 2 CH 3
CH3 CH 3 CH3
CH 3
CH3 CH3
Br
( c ) ( d )
o c t ( b ) o f 0 - 0 -
Q.21 Number of required 0 2 mole for complete combustion of one mole of prop ane -
(A) 7 (B) 5 (C) 16 (D) 10
Q.23 When n-butane is heated in the presence of A!Ci3/HCl it will be converted into -
(A) Ethane (B) Propane (C) Butene (D) Isobutane
Q.24 The reacting species of ale. KOH is -
(A) OH (B) OR' (C) OK" (D) RO
Q.25 The product of reaction between one mole of acetylene and two mole ofHCHO in the presence of
Cu2Cl2 -
(A) HOCH, - C = C - CH2OH (B) H2C = CH - C s C - CH2OH
(C) HC = C - CH2OH (D) None ofthese
Q.30 Which alkene on heating with alkaline KMn04 solution gives acetone and a gas, which turns lime water
milky-
(A) 2-Methyl-2-butene (B) Isobutylene
(C) 1-Butene (D) 2-Butene
Q. 3 6 A compound (C5Hg) reacts with ammonical AgN0 3 to give a white precipitate and reacts with excess of
KMn0 4 solution to give (CH 3 ) 2 CH-COOH. The compound is -
(A) CH 2 =€H-CH=CH-CH 3 ' (B)(CH 3 ) 2 CH-CsCH
(C) CH 3 (CH 2 ) 2 C=CH (D) (CH 3 ) 2 C=C=CH 2
Q. 3 7 Which ofthe following reagents cannot be used to locate the position of triple bona in CH 3 -C=C"CH 3
3
Q.38 CH 3 -CH 2 -C=CH c ^ CH 3 C=C-CH 3
A and B are -
(A) alcoholic KOH and NaNH 2 (B) NaNH, and alcoholic KOH
(C) NaNH 2 and Lindlar
BH, / THF tr n + (D) Lindlar and NaNH 2
A and B are -
(A)Both<^)-CH2OH (B)Both^)x-CH3
BH3
Q.40 B < ™F CH3-CS;CH HgSo 4 /H 2 so 4 A
H2O2 OH"
A and B a r e -
O O
II II
(A) C H 3 C H 2 C H O , C H 3 - C - C H 3 (B) C H 3 - C - C H 3 C H 3 C H 2 C H O
0 41 CH3CH=CH2 product X
Xis-
(A) CH 3 - CH - CH 2 D (B) CH 3 - C H - C H 2 0 H
OH D
OD
cc
Q. 42 CH 2 =CH-CH=CH 2 V i r > product. The major product is -
Br
Q.43 Mixture of one mole each of ethene and propyne on reaction with Na will form H 2 gas at S.T.P. -
(A) 22.4 L (B) 11.2 L (C)33.6L (D) 44.8 L
Q.44 Dehydration of 2,2,3,4,4-pentamethyl-3-pentanol gave two alkenes Aand B. The ozonolysis products
of A and B a r e -
O
II
(A) A gives (CH 3 ) 3 C - C - C(CH 3 ) 3 and HCHO
O CH 3
Product is -
(A) Cu-C=C-Cu (B) CH 2 =CH-C^CH (C) CH=C-Cu (D) Cu-C^C-NH 4
CH 3 CH 3
CH 3
O O
il II
(A) C H 3 - C - C H , , (CH 3 ) 3 C-COOH (B) C H 3 - C - C H 3 , (CH 3 ) 3 C-CHO
O
/H
Q.47 Alkene A °3 2° ) C H 3 - C - CH 3 + CH 3 COOH + CH, - C - COOH
O
A can be -
C(CH 3 ) 2
CHCH,
,CH3 I!
( A ) CH 3 -C-CH=C:
^CH, (B) CH 3 - C - CH = HC - CH 3
(C) Both correct
(D) None is correct
HO OH HO OH
Rj and R j are -
(A) Cold alkaline KMn0 4 , 0 s 0 4 / H 2 0 2 (B) Cold alkaline KMn0 4 , HC0 3 H
(C) Cold alkaline K M n 0 4 , C H 3 - 0 - 0 - C H 3 (D) C 6 H 5 C0 3 H, HCO ,H
CH.
H-C
Q.49 II alkalineKMnQ4 ^ ^ which. is tme about this reaction?
H—C
CH 3
A, B and C are -
A B C
3 3
HO CH, F F
(A) °"HO
HO CH 3 CH, O
(B) IHCHO
(C) I I r i r g»
(D) OOH
Q S 1
V J ^ '
A can b e -
(A) Cone. H 2 S0 4 (B) alcoholic KOH (C)Et 3 N (D)t-BuOK
Q. 52 BrCH 2 -CH 2 -CH 2 Br reacts with Na in the presence of ether at 100 °C to produce -
C H 2 - CH2
(A) BrCH 2 -CH=CH 2 (B) CH2=C=CH2 (C) \ / (D) All of these
( A ) / = \ ( B ) y = y (C ( D ) ^ > =
\
CH,3 (l)Hg(0Ac)2/H20/THF ?
OH
CH, / rr-OH 4-CH, , rr-CH,
(A)/ 3—OH
n_r»o (B)C
(E) I 3\ (C) (D)
-CH.
(D) C H 3 - C S C - C H 3 and C H 2 | CH2 ; CH 2 = C H - C H = C H 2
^CH^
CH 3
(C) CH 3 -CsCH and CH3MgBr (D) CH2=CH2and dil. H 2 S0 4 solution
Q. 5 8 A mixture of CH4, C 2 H 4 and C 2 H 4 gaseous are passed through a Wolf bottle containing ammonical
cuprous chloride. The gas coming out is
(A) Methane (B) Acetylene
(C) Mixture of methane and ethylene (D) original mixture
Q. 5 9 In the presence of strong bases, triple bonds will migrate within carbon skeletons by the
(A) removal of protons (B) addition of protons
(C) removal and readdition of protons (D) addition and removal of protons.
CHCOOH
Q.60 CH 2 =CH-CH=CH 2 + -> product X by reaction R X and R are
a
CHCOOH
COOH COOH
Diels Alder Friedel-Crafts
« a COOH
COOH
COOH
y^yCOOR
( Q l O i . Diels Alder (D) Friedel-Crafts
COOH COOH
CH3-C-NH2
(C)X= < ^ ^ M g B r ; Y=
A HgS04/H2SQ4 ^
Q.l B
BH,/THF
H 2 O 2 /OH
B is identical when A is -
(A) H - h - H (B) — H (Q (D)
Q.2 An alkene on ozonolysis yields only ethanal. There is an isomer of this which on ozonoly sis yields:
(A) propanone (B) ethanal
(C)methanal - (D) only propanal
(A) A (C)
Q.4 Aqueous solution of potassium acetate is electrolysed. Possible organic products are:
(A) n-Butane (B) C 2 H 5 COOC,H 5 (C) CH 3 -CH 3 (D) CH 2 =CH 2
HO HO OH
R, and R 2 are:
(A) cold alkaline KMn0 4 , 0 s 0 4 / H 2 0 2 (B) 0 s 0 4 / N a H S 0 3 ; A g 0 2 , H 3 0®
(C) cold alkaline KMn0 4 , C 6 H 5 C 0 3 H / H 3 0® (D) C 6 H 5 C 0 3 H ; 0 s 0 4 / NaHS0 3
H2/Pt
Q.6 (A) C 4 H 6 > (B) C 4 H g -> CH 3 COOH
Hence A and B are
(A) CH 3 C = CCH 3 , CH 3 CH = CHCH 3 (B) CH 2 = CHCH 3 = CH 2 , CH 3 CH = CHCH 3
O
A could be:
(A) NH 2 NH 2 , glycol/OH (B) Sn(Hg)/conc. HCl
SH SH
(B)
a CH, is an exocyclic Saytzeff product
NBS
Q.10 CH, = CHCHXH = CH2 > A, A can be
(A) CH, = CH CH CH = CH, (B) CH2=CHCH=CH-CH2Br
Br
Br
Q.ll Which are correct statements?
(A) meso-1, 2-dibromo-butane on reaction with Nal / acetone gives trans-2-butene
(B) d-or /-1,2-dibromobutane on reaction with Nal/acetone gives cis-2-butene
(C) meso -1,2-dibromo-butane on reaction with Nal / acetone gives cis-2-butene
(D) d-or/-1,2-dibromobutane on reaction with Nal/acetone gives trans-2-butene
Product is:
H H
(A) Ph- -CH2CC13 (B) Ph- - CH?Br
Br CCI3
Br CCI3
(C) Ph- •CH2CC13 (D) Ph- •CH2Br
The above compound undergoes ready elimination on heating to yield which ofthe following products?
Q.15 Which of the following will give same product with HBr in presence or absence of peroxide.
(A) Cyclohexene (B) 1-methylcyclohexene
(C) 1,2-dimethylcyclohexene (D) 1-butene
Q.16 The ionic addition of HCl to which of the following compounds will produces a compound having CI on
carbon next to terminal.
(A)CF3.(CH2)3.CH=CH2 (B)CH3.CH=CH2
(C) CF 3 .CHCH 2 (D) CH3.CH2CH=CH,.CH3
Q.22 Indicate among the following the reaction not correctly formulated.
(A) CH2=CH-CH3 > O^Cl-CHCl-CHG
HC^X
(B) HCsCH+CH^ > II N
HC y
1-1
photo
(C) (CH3)3CH + Cl2 ~ > (CH3)3C-C1 as major product
haiogenation
CH3
CI
CH.
CI OH
(CH
(D) C H 3 - C H 9 - C H - C H , 3)3CONA ) (4) C H 3 - C - C H 3
I
CH.
Codes: A B C D
(a) 4 3 1 2
(b) 4 3 2 1
(c) 3 4 2 1
(d) 3 4 1 2
(i)AgNO,
(C)RCOOH •R-Cl (3) Oakwood degradration
(ii)CI2/A
o
II CH2-CH3
C —CH,
(B) (2) Stephen's reduction
HO
Q. 29 List I List n
(A) n-Hexane » Benzene (1) Wurtz reaction
(B) CH=CH » Benzene (2) Coupling of reactants is taking place
(OCH^CH^CHj > 2,2,3,3 tetramethyl butane(3) A1CL + HCl at 3 00°C
(D) CH3-CH2-X > n-Butane (4) Polymerisation
(5) Aromatic procducts is formed
(6) Zn + A used as reagent
(7)Al203 at high temperature
H 2 Pd. .
(Q =~ — >9 (3) Cis isomer formed
BaSO.
PhC 3H
(D) Alkene ° >? (4) Syn addition
followed
by H30®
> V / THF
(b)COOH.
H
> < .H
COOH
1.BD3.THF
D
2.D 2 0 2 ,D0
>
CH 3
LlA1H ?
Q-2 CH3-C-C1 * >
i
CH 3
C
2 H 5 \c = c
/C2H5 , RF RN IT
3 3
Q.4 / \ — > A+B.WhatareAandB?
H H 2. H,OZH+
Na H
Q.5 k M ° > A. Write the structure ofA.
ALC
D Y H -
Br
O O
II II
CH. .CH
Q. 6 ^c=c ^ 22 ,, A. Write the structure of A
NO 2 -CH 2 CH 2 -NO 2
CH
(i) H 2 S0 4
0s04 (i) 0 3
(ii) A
(ii) Me2S
F r 'H2° C(Ct0H15Br)
e t t o
bromobutane >D ' CH3(CH;)3-CH(K
2, H,0+
KOII, ILO RSO/.A
A
Na
fused KOH
followed bv NaNH,
D + = O + CH,CO,H
optically active
KMn04(hot)
vOH
CH,
(Mi) (iv)
Me Me H3C OH OH
OH
Me Me
->
(i) A A
\ COjMe
o
+
I
('") H
J Ph
A
o
l.NaNH2(3equiv.)NH3 ^ g
2. CH3I
Q 14 (i) Compare the reaction of CH2 = CH, & CF2 = CF2 with NaOEt in EtOH
(ii) CC1, = CC12 does not decolourise Br2 solution - explain.
Q.17 Conversion:
(i) C2H2 » racemic 2, 3 dibromobutane (ii) 2 butyne > 2 pentyne
(iii) Ethyne » Acetone (iv) Methane > n Butane (v) Ethene » Propionic Acid
Q.18 Conversion:
(i) C2H2 > ethylidene diacetate (ii) C ^ -—> Butyne diol
(iii) C,H, > m nitroaniline (iv) cis but 2 ene > Trans but 2 ene
Q.23 When citral is allowed to react in presence of dilute acid with olivetol, there is obtained a mixture of
products, one of which is drug marijuana. Reaction is as follows.
(marijuana)
Explain the mechanism.
Q.24 The following cyclisation has been observed in the oxymercuration & demercuration of this unsaturated
alcohol. Propose a mechanism for this reaction.
2. NaBH 4
Cu+
Q.26 (a) MeCH2-C=CBr + CH=CMe > A
CI
0H
(b) CH 2 -CHC1 2 >B
OH
(c) CH2 = C H - C H - C H = C H - C H , — l e O H > C
H2S04
(d) / \—C=CH
\ / H2SO4/H2O
EXERCISE-HI
Q. 1 0.37 gm of ROH was added to CH3MgI and the gas evolved measured 112 cc at STP. What is the
molecular wt. ofROH ? On dehydration ROH gives an alkene which on ozonolysis gives acetone as
one of the products ROH on oxidation easily gives an acid containing the same number of carbon
atoms. Gives the structures ofROH and the acid with proper reasoning.
Q.2 An alkane A (C 5 H, 2 ) on chlorination at 3 00° gives a mixture four different mono chlorinated derivatives
B, C, D and E. Two of these derivatives give the same stable alkene F on dehydrohalogenation, On
oxidation with hot alkaline KMn0 4 followed by acidification ofF gives two products G and H. Give
structures ofA to H with proper reasoning.
Q.3 There are six different alkene A, B, C, D, E and F. Each on addition of one mole ofhydrogen gives G
which has the lowest molecular wt hydrocarbon containing only one asymmetric carbon atom. None of
the above alkene give acetone as a product on ozonolysis. Give the structures of A to F. Identify the
alkenes that is likely to give a ketone containing more than five carbon atoms on treatment with a warm
conc, solution of alkaline KMn0 4 .
Q.4 3,3-dimethyl-1 -butene and HI react to give two products, C 6 H, 3 I. On reaction with ale, KOH one
isomer, (1) gives back 3,3-dimethyl-l-butene the other (J) gives an alkene that is reductively ozonized
to Me 2 C=0. Give the structures of (I) and (J) and explain the formation of the later.
Q. 5 Three isomeric alkenes A, B and C, C5HR) are hydrogenated to yield 2-methvlbutane A and B gave the
same 3° ROH on oxymercuration - demercuration. B and C give different 1° ROH's on hydroboration
-oxidation. Supply the structures of A, B & C.
Q.6 Two isomeric alkyl bromides A and B (C5H, ,Br) yield the following results in the laboratory. A on
treatment with alcoholic KOH gives C and D (C 5 H, 0 ). C on ozonolysis gives formaldehyde and
2 methyl propanal. B on treatment with alcoholic KOH gives only C (C 5 H ]0 ). Deduce the structures of
A, B, C andD. Ignore the possibility of geometrical and optical isomerism.
Q.7 Give the structure of A, B and C.
(a) A. (C4Hg) which adds on HBr in the presence and in the absence of peroxide to give the same product
C4H9Br.
(b) B (C4H8) which when treated with H 2 S0 4 / H 2 0 give (C4H10O) which cannot be resoslved into optical
isomers.
(c) C (CgH12), an optically active hydrocarbon on catalytic hydrogenation gives an optically inactive
compound CfiH,4.
Q.8 An alkylhalide, X, of formula C 6 H )3 Clon treatment with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H,2). Both alkenes on hydrogenation gives 2,3-dimethylbutane predict the stmctures
ofX, YandZ.
Q.9 Identify a chiral compound C, C, 0 H. 4 , that is oxidized with hot KMn0 4 to Ph COOH, and an achiral
compound D, C lt ,H ]4 , inert to oxidation under the same conditions.
compound (C) obtained by oxidation of 3-hexanol with KMn0 4 . Identity A, B and C compound D,
and isomers of A reacts with BHV THF and then F I ^ / O H to give chiral E. Oxidation of E with
KMn0 4 or acid dichromate affords a chiral carboxylic acid F. Reductive Ozonolysis of D, gives the
4
F and G. '
Q.ll
Q.13 A hydrocarbon A, ofthe formula CgH10, on ozonolysis gives compound B (C4H602) only. The compound
B can also be obtained from the alkylbromide (C3H5Br) upon treatment with magnesium in dry ether,
Q.14 An organic compound (A), C6H10 on reduction first gives (B), C6H12 and finally (C), C H [4 . (A)
S S V 6 S m C2l 4 f E ) C 2 0xidati
h "d fi d K M n O ^ ^ ^ ' ^ J °^ f f °no^B)
OF)'
Q.15 Compound A (C6H]2) is treated withBr2 to form compound B (C6H12Br2). On treating B with alcoi
KOH followed by NaNH, the compound C (C6H10) is formed. C on treatment with H2/Pt fo
2-methylpentane. The compound ' C does not react with ammonical Cu2Cl2 or AgN0 3 . When
treated with cold KMn0 4 solution, a diol D is formed which gives two acids EandF when heatec
KMn04 solution. Compound E is found to be ethanoic acid. Deduce the structures fromAto F.
(A) give snoj>pt. with Ag(NH 3 V andgfves optimally inactive (CX C 8 H, 4 ^ t h Hjnpreser
Q.17 A
HYDROCARBON [28]
Q.20 6g sample of a natural gas consisting of methane (CH4) and ethylene (C2H4) was burned with excess of
oxygen and 17.2g of carbon dioxide and some water was obtained as products. What percent by
weight of the sample was ethylene.
EXERCISE-IV (A)
Q. 1 Alcoholic solution ofKOH is a specific reagent for - [IIT4 90]
(A) Dehydration (B) Dehydrogenation
(C) Dehydro halogenation ' (D) Dehalogenation
Q.2 Of the following, unsaturated hydrocarbons are - [IIT'90]
(A) ethyne (B) cyclohexane (C) n-propane (D) ethene
Q. 3 1 -chlorobutane on reaction with alcoholic potash gives - [IIT 491]
(A) 1-butene (B) 1-butanol (C) 2-butene (D) 2-butanol
Q4 The hybridisation of carbon atoms in C-C single bond ofHCsC-CH=CH 2 is - [IIT '91]
(A) sp3-sp3 (B)sp 2 -sp 3 (C) sp-sp2 (D) sp2-sp2
Q.7 Which ofthe following compounds will show geometrical isomerism? [IIT '98]
(A) 2-butene (B)Propene (C) 1-phenylpropene (D) 2-methyl-2-butene
Q.8 In the compound CH2=CH-CH2-CH2-C=CH, the C 2 -C 3 bond is ofthe type - [IIT4 99]
(A) sp-sp2 (B) sp3-sp3 (C) sp-sp3 (D) sp2—sp3
Q. 9 Which one ofthe following alkenes will react fastest with H2 under catalytic hydrogenation condition -
[IIT '2000]
R R R H R R R R
y- \ / \ / \ /
(A) ; > = ( (B) > = < (C) > = < CD) / \
H H R H R H R R
Q. 11 In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti-Markovnikov
addition to alkene because - [T1TS42001]
(A) both are highly ionic
(B) one is oxidising and the other is reducing
(C) one of the step is endothermic in both the cases
(D) All the steps are exothermic in both cases
Q.14
Q.15 : MOW
D U
I> CH 3 J, u
(C) H 3 C - C - C H - C H 3 (D) H 3 C ~ C H - C H - C H 3
1, U
Q.16
Q 17 C 6 H 5 -C=C-CH 3 —
' in on
HYDROCARBON [30/
OH H+ x
2
Q.18 " _H 0 (mixture) > 5 compounds of molecular formula C4H8Br2
Q.19 2-hexvne can be converted into trans-2-hexene by the action of: [IIT' 2004]
(A) H 2 -Pd-BaS0 4 (B) Li in liq. NH3 (C)H 2 -Pt0 2 (D) NaBH 4
Q.20 When Phenyl Magnesium Bromide reacts with tert. butanol, which of the following is formed?
(A) Tert. butyl methyl ether (B) Benzene
(C) Tert. butyl benzene (D) Phenol [IIT '2005]
Q.21 1 -bromo-3 -chlorocyclobutane when treated with two equivalents ofNa, in the presence of ether which
ofthe following will be formed? [IIT'2005]
/Br /CI
(A) (B) ( C ) [ J (D)
NO
J
, C Hi33, —
- C H 2, ~~- CH
(C) , (D)
NO CI
CI
CH,
Q.24 H.C^I Ci 2'hv ) Nfisomeric products) r,H i ; Cl fractional distillation ) M(isomeric products)
CH
What are N and M?
(A) 6, 6 (B) 6, 4 (C) 4, 4 (D) 3, 3 [IIT 2006]
^ „ ale. KOH
Q.2 C6H5CH2CHCH3 ——>? HBr ^ [ I I T 19931
Br
Q. 3 an optically active hydrocarbon which on catalytic hydrogenation gives an optically inactive
C ( C 6 H j 2 ),
compound, C 6 H,. [IIT 1993]
Q. 4 Draw the stereochemical structure ofthe product in the following reactions. [IIT 1994]
Ho
R-CEEC-R
Lindlar catalyst
Q. 5 Write down the structures of the stereoisomers formed when cis-2-butene is reacted with bromine.
[ I I T 1995]
Q.6 An organic compound E(C 5 Hg) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis
gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E. [IIT 1995]
Q. 7 Give the structures of the major organic products from 3-ethyl-2-pentene under each of the following
reaction conditions. [IIT 1996]
(a) HBr in the presence of peroxide (b) B^/F^O
(c) Hg(0Ac) 2 /H 2 0;NaBH 4
Q.8 An alkyl halide, (X) offormula C6H13C1 on treatment with potassium tertiary butoxide gives two isomeric
alkenes (Y) and (Z) (C 6 H ]2 ). Both alkenes on hydrogenation give 2,3-dimethylbutane. Predict the
structures of (X), (Y) and (Z) [ITT 1996]
Q.9 3,3-Dimethyl-butan-2-ol loses a molecule of water in the presence of concentrated sulphuric acid to
give tetramethylethylene as a major product. Suggest a suitable mechanism. [IIT 1996]
Q. 10 One mole of the compound A (molecular formula C8H12), incapable of showing stereoisomerism, reacts
with only one mole of H 2 on hydrogenation over Pd. A undergoes ozonolysis to give a symmetrical
diketone B (C 8 H 12 0 2 ). What are the structure ofA and B? [IIT 1997]
Q. 11 Compound (A) C 6 H 12 gives a positive test with bromine in carbon tetrachloride. Reaction of (A) with
alkaline KMn0 4 yields only (B) which is the potassium salt of an acid. Write structure formulae and
IUPAC name of (A) and (B). [UT 1997]
Q.12 The central carbon-carbon bond in 1,3-butadiene is shorter than that of n-butane. Why?
[ I I T 1998]
Q.13 Write the intermediate steps for each of the following reaction [IIT 1998]
C6H5CH(OH)CEECH ->c6h5ch=chcho
Q 14 Write the intermediate steps for each of the following reaction. [IIT 1998]
H,C—C
/=c\
H D
3 A . > H 33C—C
/ \ / N
H3C CH,. CH 3 CH 3
Q.18 Explain briefly the formation on the products giving the structures of the intermediates. [IIT 1999]
C H
2 \
HCl „
(i) H,C OH > H,C r, + I /CH~CH 2 - C l + etc.
But
CH 3 CH,
! 3
CH H
HCl
(ii)
H,C OH H,C C CI
Ho
Q.19 Carry out the following transformation in not more than three steps. | HI' 1999]
O
Q.21 What would be the maj or product in each of the following reactions? [IIT 2000]
CH,
CH3-C-CH,Br C2H5OH ) H,
CH,
' ' I A (ii) Lindlar'sCatalyst
CH,
Q.22 On reaction with 4N alcoholic KOH at 175 °C 1-pentyne is slowly converted into equilibrium mixture
of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% 1,2-pentadiene (C). Give the suitable
mechanism of formation ofA, B and C with all intermediates. [IIT 2001]
Q.23 Identify X, Y and Z in the following synthetic scheme and write their structures. Is the compound Z
optically active? Justify your answer. [IIT 2002]
(i) NaNH2 ^ ^ H2/Pd-BaSQ4 ^ y alkaline KMnQ4 ^ j
CH3CH,C-=-C-H
(ii)CH3CH2Br
Q.25 If after complete ozonolysis of one mole of monomer of natural polymer gives two moles of CH2Q
andone mole of O = C - CH = 0 . Identify the monomer and draw the all-cis structure ofnatural polymer.
[IIT 2005]
EXERCISE-II
coo® coo w
-D D- -H
Q.l (a) (b) +
DO- -H H- -OD
H BH, H HO
COO® COO®
CFL
CH2-CH2-C-H
O = CH
Q.2 CHL-C = CH? Q.3 +
n_CH=i
CH=0 O = CH
C,HC C,H<
-OH OH- -H
Q.4 A + B are two enatiomers
OH- "H H- -OH
c2H5 C?H=
H D CH 7 NO 2
-CHO
Q.5 Q.6
-CHO
CH^NOt
CH 3
c c c
(v) ^
OH ONa
(E) C-C-C-C-C-C-C-C-C,(F)C-C-C-C=C-C-C-C-C,
OH
Br
(G) C - C - C - C - C - C - C - C - CV(H) C - C - C - C s C - C - C - C - C
Br
C C C C C
C-C
(D) H - C - C O O H
i
c
Phv /H Ph-CH-Et
c = c
Q.12 (A)PhC S CMgx, (B)Ph-C=C-CH 2 Ar,(C) H / \ c H _ A r ,(D) ^
Q.13 (i) 0
™ w ' r ' V N r " ' \ / ^ L > (iv)noreaction
C0 2 ME I I N
Br
W(A)p h _l H ^ C H 2 _ B r ,(B)Ph-C,C^H 3
O-CH3
C 1
Q.26 (A) M e C H 2 - C = C - O C M e , (B) CH2=C\/ I - CH,
, ( Q CH 2 = CH - CH == CH - CH
CI
Br OH
/
(D) <^JyC-CH3
\ Ii I I
, (E) CCI3 - C H - C H 3 (F) ^ J k c H 3 '
(G) A
0
/ \ / \ A0
EXERCISE-UI
H 13 C \
Q.l > CH-CH,OH
H3C/
H 3 C-C-CH 2 CH,
i
H
Q.6
CH3
(A) CH3-CH-CH (B) CH^r-CH^-CH-CI^ (Q CH2=CH-CH-CH3
CH
s
CH, CH3
(D) CH3CH=C~CH3
I
CH3
Q.7 CH=CH2
I
(A) CH3-CH=CH-CH3 (B) :c=c (Q CH^-C* -H
I
CK^CH^ ]
Q.10 OH
CH
2 CH3 O
(D) CH3 (E) CH3 (F) CHj
i I I
CH3-CH-C-CH2CH3 CH3CH-CH-CH2CH3 CHj-CH-CH-CHJ-C^
II
CH2 CH2OH CO,H
CH, CHj
CH, CH,
H
l
Q.16 CH3-C = C - C - C = C-CH3
I I I
H H CH3
Q.20 23.7
EXERCISE-IV (A)
Q.l C Q.2 A,D Q.3 A Q.4 C Q.5 A
Q.6 D Q.7 A,C Q.8 D Q.9 A Q.10 D
Q.ll C Q.12 B Q.13 B Q.14 A Q.15 B
Q.16 D Q.17 A Q.18 B Q.19 B Q.20 B
Q.21 D Q.22 A Q.23 A Q.24 B
EXERCISE-IV (B)
Br
CH=CH-CH, (L,H-CH9-CH3
CH 2 -CH-CH 3 ALC. KOH
Q.l CH, - C = C H - C H , Q.2 * F O
CH3
H
/R
Q.3 C H 3 - C H 2 - C - C H = CH2 Q.4 ,C = C
-H
I
CH3
(C6H12)
Br
CH 3 CH 3 CH 3 CH 3 CH 3 CH 3
Q.8 C H 3 - C - C H - C H 3 ; ( Y ) C H 2 = C - C - C H 3 ; (Z) C H 3 - C = C - C H 3
CI
Q.10 (A)
< B >o 0
Q.ll (A)CH3-CH2-CH=CH-CH2-CH3 (B) CH 3 CH 2 COOK
CH,
-CH, CH,
Q.21 (i) CH 3 - C - C H 2 - CH 3 (ii) I
O-C2H6
Et
Et Et -OH
Z
Q.23 (X) —»Et-CsC-Et (Y)->H>C=C<H ( )^ H Z is meso so optically inactive.
-OH
Et
Q.24 Bombykol :- H O - C - C - C - C - C - C - C - C - C - C = C - C = C - C - C - C
(A): - HO-tCH^ 5CH3 4 geometrical isomers are possible
CH 3
| H
Q.25 (a) CH 2 = C - CH = CH 2 (b) (CH2
Q.26 ( X ) I ^ J ,(Y) C H 3 - C - ( C H 2 ) 4 ~ C H = 0
CH,
CHEMISTRY
TARGET IIT JEE 2007
XI(PQRS)
NOMENCLATURE
OF
ORGANIC COMPOUNDS
CONTENTS
EXERCISE-I
EXERCISE - II
ANSWER KEY
IUPAC
(i) Word root: The word root represents the number of C atoms in parent chain.
No. of C atom W.R.
1 Meth Oct§fe>8
2 Eth Non3Jps>9
3 Prop. DecaSe 10
4 But UndetoSBsll
5 Pent Doded&L©12
6 Hex Tridecah©13
7 Hep
(ii) Primary suffix: Primary suffix is used to indicate saturation or unsaturation in carbon chain.
While writing name, primary suffix is added to word root.
Nature of C chain Primary suffix
(1) Saturated C chain ane
(2) Unsaturated C chain
C=C ene
C=C yne
2 C=C diyne
(iii) Secondary suffix: Secondary suffix is used to indicate functional group in organic comp. It is added
primary suffix by dropping its terminal "e".
Prefix: The part of the name C appears before the word root is called prefix. Different prefixes are
used for dif categories of group as:
(a) Alkyl groups:
CH3-CH2-CH2 > 1-propyl
CH3-CH-CH3 > 2-propyl
CHj-CH^CHj-CT^ > 1-Butyl
CH3-CH2-CH-CH3 > 2-Butyl
CH, *
2-Methyl-l-propyl
CH, - CH - CH,
(b) In IUPAC system,for nomenclature some groups are not considered as functional group but
treated as substituent. These functional group are always indicated by prefixes instead of
secondary suffixes.
-N02 Mtro
-OR Alkoxy
-CI Chloro
-Br Bromo
-I Iodo
-F Fluoro
-N=0 Nitroso
-N02 Nitro
=N Diazo
"[250]
tBansal Classes NOMENCLATURE OF ORGANIC COMPOUND ~
(c) In polyfunction^ compound, one ofthe functional group is treated as principal functional group
& indicated by secondary suffix while other functional groups are treated as substituents &
indicated by prefixes.
Rules:
For saturated compounds:
(i) Selection of longest chain :
(a) Longest continuous chain of carbon atoms is selected. This is called parent chain while all other
C atoms C are not included in parent chain is called side chain.
< ->6
C-C-C-C-C
(b) If more than one set oflongest chains are possible, the chain C max. no. of substituant acts as
parent chain.
c-c-c-c-c-c
c-c
c
C-C-C-C-C
CH,
(b) If two different alkyl groups or substituents are at same position from opposite ends, lowest no.
is given in alphabetical order.
* 2 & 4 & ^
c-C-C-C-C-C-C
-4 6 jS <-t 1
CH 3 C,H-
faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND JJ
(c) If two different substituents are at same position from opp. ends, lowest no. is assigned in order
of their alphabets.
1 2 3 4 4 3 2 1
c-c-c-c c-c-c-c
I I I I
CI I CI Br
itvs H j o v v J ^ If more than two substituents & side'chains are present, the sum oftheir numbers should be
C4OYV6L VW r. a c lowest at the first preference irrespective of the nature of substituent or side chain. This is K/a
"VDOUU lowest sum rule.
S u t e S * ^ 7 6 5 4 3 2 1 1 2 3 4 5
Jvaue, ^ ^ C-C-C-C-C — C-C C-C-C-C-C
H , C - C H - C H - C H 2 - CH 3
3 chloro, 2-methyl butane
CH3 CI
(b) If more than one similar alkyl group or substituents are present terms, tri like are used.
CH 3
I
H,C — C — CH-,
• | - 2,2-dimethyl propane 2;3-dimethyl
CH 3
(c) In case side chain is also branched, it is also numbered form carbon atom attached to main chain
& is generally written in brackets.
3 4 5 6 7
CH, - CH 2 — CH — CH 2 — CH 2 — CH 2 — CH 3
2 CH-CH3
1 CH 3
1 2 3 4 5 6 7 8
CH 3 - CH - CH2 - CH2 - CH - CH2 - CH2 - CH3
I I
CH3 1 CH-CH3
2 CH3
The use ofiso & related common prefixes for describing alkyl group as long as these are not further
substituted are also allowed by IUPAC nomenclature. While writing name in alphabetical order prefixes
iso & neo are considered to be part of fundamental name of alkyl group. However sec. & tert are not
considered to be part of fundamental name.
CH3-CH-CH2CH3
c-c-d-c-c-c-c-c-c-c
-CP(CH3)# _ - - - -
CH,
A
3
(Si) If double & triple bonds are at same position from either ends, lowest no is assigned to double bond
1 2 3 4
c=c-c-c=c
(iv) If both alkene & alkyne group are present, the org. compound is named as derivative of alkyne rather
than alkene.
CH 3 -€H=CH-C=CH
Pent-3-en-l-yne
In some cases all the double & triple bonds present in molecule can't be included in longest chain. In such
cases following prefixes.
CHJ = CH3-CH=
Methylene Ethylidene
CH=C- CH 2 =CH-
Ethynyl Ethenyl
C-C-C-C-C-OH
I I
OH C
I
c
(ii) The carbon atom of functional group is to be included in deciding the longest carbon chain.
C-C-CN 3 carbon chain
C-C-C-CHO 4 carbon chain
(lii) The lowest no is assigned to functional group even if prior rules are violated.
O
| 4 3 2
CH3
CH,
5 4| 3 2
CH 3 -C-CH 2 -CH-CH 3
I I
CI
1
(iv) The order ofnumbering a carbon chain, thus follows the order:
(a) Functional group
(b) Unsaturation
(c) Substituents & side chains
7 6 5 4 3 2 1
c=c-c-c-c-c-c
I
OH
1 2 3 4 5 6 7
c=c-c-c-c-c-c
I
OH
(v) If more than 1 functional group; then choice ofprincipal functional group is made on the basis following
order of preference:
0 0 0 o o
I! II II II II
Carboxylic acid > S0 3 H > - C - O - C - > - C - O R > - C - 0 C 1 >
> aldehyde > Ketone > alcohol > thiols > amines > ene > yne > halo > - O R
Q. 1 How many 10carbon atom will be present in a simplest hydrocarbon having two 3 ° and one 2° carbon
atom?
(A) 3 (B)4 (C)5 (D)6
5 1
^QA) The correct IUPAC name of the following compound is:
O=CH-CH2-CH~CHO
H~C =
(A) 1,1 -diformyl propanal (B) 3-formyl butanedial
(C) 2-formyl butanedial (D) 1,1,3-ethane tricarbaldehyde
Q.6 All the following IUPAC names are correct except: , (Wet
(A) 1 -chloro-1 -ethoxy propane (B) 1 -amino-1 -ethoxypropane ^ o V ^ ^ ^ ^ ^
(C) l-ethoxy-2-propanol (D) 1-ethoxy-1-propanamine v O1 " J 1
CH 3
Q.8 The IUPAC name of j3-ethox, ixy propionic acid (trivial name) is:
(A) 1,2-dihydroxy-l-oxo-3 - , pane (B) 1 -carboxy-2-ethoxy ethanol
(C) 3 -Ethoxy-2-hydroxy pro; (D) All above
HO - C = O CH 3
I I
Q.10 The IUPAC name of compound CH3 - C = C — C - H is:
I I
NH 2 CI
Q.14 How many carbons are in simplest alkyne having two side chains?
(A) 5 (B)6 (C)7 (D)8
CH,
I 3
(D) Iso-octane
I I
CH 3 CH3
faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND [8]
Q.16 Which of the following pairs have absence of carbocyclic ring in both compounds?
(A) Pyridine, Benzene (B) Benzene, Cyclohexane
(C) Cyclohexane, Furane (D) Furane, Pyridine
Q.19 How many secondary carbon atoms does methyl cyclopropane have?
(A) None (B)One (C)Two (D) Three
Q.21 As per IUPAC rules, which one of the following groups, will be regarded as the principal functional
group?
(A) -C=C- (B)-OH (C) - C - (D) - C - H
II II
o o
CI CH2CH3
Q.24 IUPAC name for the compound yC=C<^ is
h3C/ \
(A) E-3 -iodo-4-chloro-3 -pentene (B) E-2-chloro-3 -iodo-2-pentene
(C) Z-2-chloro-3 -iodo-2-pentene (D) Z-3-iodo-4-chloro-3 -pentene
Ph
Q.25 The IUPAC name ofthe compound is CH3 - CH - CH - NH2
I
CH3
(A) 1 -amino-1 -phenyl-2-methyl propane (B) 2-methyl-1 -phenyl propane-1 -amine
(C) 2-methyl-1 -amino-1 -phenyl propane (D) 1 -isopropyl-1 -phenyl methyl amine
CI
CH3
(C) CHXH2CH=CHCOCH3 ; Hex-3-en-2-one
(D) CH 3 -CHCH 2 CH 2 CHO ; 4-Methylpentanal
i
CH3
CH3
HO ^ CH,
(A) 1,1 -dimethyl-3-hydroxy cyclohexane (B) 3,3-dimethyl-1 -hydroxy cyclohexane
(C) 3,3 -dimethyl-1 -cyclohexanol (D) 1,1 -dimethyl-3 -cyclohexanol
CI
(A) 2-chloro-4-N-ethylpentanoic acid (B) 2-chloro-3-(N,N-diethyl amino )-propanoic acid
(C) 2-chloro-2-oxo diethylamine (D) 2-chloro-2-carboxy-N-ethyl ethane
Q.29 The IUPAC name ofthe compound Br(Cl) CH. CF3 is:
(A) haloethane (B) 1,1,1 -trifluoro-2-bromo-2-ch)oroethane
(C) 2-bromo-2-chloro-1,1,1 -trifluoroethane (D) 1 -bromo-1 -chloro-2,2,2-trifloro ethane
O 0H
and
R^YCH2CLI,OH
(b)l^J
True statement for the above compounds is:
(A) (a) is phenol while (b) is alcohol (B) Both (a) and (b) are primary alcohol
(C) (a) is primary and (b) is secondary alcohol (D) (a) is secondary and (b) is primary alcohol
Q.40 A substance containing an equal number of primary, secondary and tertiary carbon atoms is:
(A) Mesityl Oxide (B) Mesitylene (C) Maleic acid (D) Malonic acid
Q.45 The molecular formula of the first member of the family of alkenynes and its name is given by the set
(A) C3H2, alkene (B) C5H6, l-penten-3-yne
(C) C6Hg, l-hexen-5-yne 0 (D) C4H4, butenyne
CH 2 -C-OH
c < m
Q.46 The IUPAC name of compound | xCOOH
CH2-COOH
(A) 1,2,3 -tricarboxy-2,1 -propane (B) 3-Carbox-3-hydroxy-l,5-pentane dioic acid
(C) 3 -hydroxy-3 -Carboxy-1,5-pentane dioic acid (D) None
Q. 48 One among the following is the correct IUPAC name of the compound
H
I
N
(A) N-Formyl aminoethane (B) N-Ethyl formyl amine
(C) N-Ethyl methanamide (D) Ethylamino methanal
<
•OH
Q.50 The IUPAC name of 11 | is
S
CH3
NH
Q 56 The IUPAC name of 0,N - \0)~
_ CHOis:
s
OCH3
(A) 2-methoxy-4-nitro benzaldehyde (B) 4-nitro anisaldehyde
(C) 3-methoxy-4-formyl nitro benzene (D) 2-formyl-4-nitro anisole
0
Q. 57 The IUPAC name C - CH3 is:
(A) phenyl ethanone (B) methyl phenyl ketone
(C) acetophenone (D) phenyl emethyl ketone
Q. 5 9 The suffix of the principal group, the prefixes for the other groups and the name of the parent in the
structure
CH3 CI 0 0
(A) -oic acid, chloro, hydroxy, oxo, methyl, 4-heptene
(B) -oic acid, chloro, hydroxy, methyl, oxo, 4-heptene
(C) -one, carboxy, chloro. methyl, hydroxy, 4-heptene
(D) -one, carboxy, chloro, methyl, hydroxy, 4-heptene
faBansal Classes NOMENCLATURE OF ORGANIC COMPOUND JlOJ
Q. 60 The IUPAC name of compound
COOH-CH-COOH
I
COOH
(A) Tricarboxy methane (B) Propane trioie acid
(C) Tributanoic acid (D) 2-carboxy propanedioic acid
CH, -CHO
I 2
Q. 61 The IUPAC name of OHC - CH2 - CH2 - CH - CH2 - CHO is:
(A) 4,4-di(formylmethyl) butanal (B) 2-(formylmethyl) butane-1,4-dicarbaldehyde
(C) hexane-3-acetal-l, 6-dial (D) 3-(formyImethyl) hexane-1,6-diai
I] is:
^COCL
(A) 2-chlorocarbonyl ethylbenzoate (B) 2-carboxyethyl benzoyl chloride
(C) ethyl-2-(chlorocarbonyl) benzoate (D) ethyl-1 -(cblorocarbonyl) benzoate
(C) C H 3 - C - O - C H 2 - C H 2 (D)H-C-0-CH-CH3
II I II I
O CH3 O CH3
Q.ll
Q.l
O 0
Q.12
Q.2
COOH
Q.13
Q.4 Q.15
Q.16
q.5
CH2-CHCH3
Q.17 \Q/
6
Q / \ / \
q.7 Q.18
Q.19
Q.8
OH CH2CH2CH2CH3
Q.20
Q.9
CH3^^CH(CH3)2
Q.21
CH,
Q.10 Q.22 |^YC2h5
Q.34
Q.23
CH3 O
C-CH 3
^k.C-OCH
Q.24
a CH,
Q.35
3
CH3.CH.
Q.25 J
CH, Q.36
CH2CH2CH=CH2
Q.26
Q.37
Q.27
Q.38
0<1
C-CH2CH3
Q.28 Q.39
ff Q.40
C-OC2H5
Q.29
Q.41
Q.30
Br
Q.42
CHO
Q.31
OH
/CI
Q.43
A / C H O
Q 32
c xBr N
Q.44
-OH
OH 9H3
CHCH2CH3
O
Q.33 Q.45
COOC2H5
NH7
CH 3 CjHJ
Q.47
Q.56 Write IUPAC name of succinic acid
.-OH
Q.48 / \—CsCH
r>
O CI
II I
Q.49 CH- - C - CH- - CH - CH,
0 H
Q.50 O \
\ NH 2
Q.51 K Y V
OC 2 H 5
CH=CH-CH-CH=CH 2
Q.54
Me
Me
(a) Me = methyl group
Me
EXERCISE - II
Q.L CH, - CH - C - CH 2 - OH Q.8 CH =CH-C-CH2
! II I
CH2-CH3 O OH
2-ethyl-2-butene-1 -ol 1 -Hydroxy-3 -Butene-2-one
Q.2 CH3-CH2-CH-CH2-CH2-CH2 CH
3 CH3-CH-CH3
Q.9 CH 3 - CH 2 - CH - CH - CH,
4-Ethyl octane
CH 3
Q.3 CH = CH - CH,
3-Ethyl-2,4-dimethyl pentane
NO, OH
3 -nitro-2-propene-1 -ol
Q.10 CH 7 = C - CH, - CH - CH ,
OH O
I II 2-isopropyl-4-methyl-1 -pentene
Q.4 CH,2 = CH - CH - C - C = CH
6 5 4 3 2 1
Q.ll CH,-CH2 CH,
4-hydroxy-5-hexene- lyne-3-one I
C=C-CH
l-Hexene-3-yne
Q.12 CH,-C-CH2-C-CH3
iCN
II II
2-Formyl pentane nitrile o o