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Carboxylic Acids and Acid Derivatives Carbonyl PDF
Carboxylic Acids and Acid Derivatives Carbonyl PDF
LEARNING MODULE
CHEMISTRY
1. CARBONYL COMPOUNDS
2. CARBOXYLIC ACIDS & ACID
DERIVATIVES
Theory 03 - 30
EXERCISE-I
Subjective Questions 31 - 34
Objective Questions 35 - 42
EXERCISE-II
Subjective Questions 42 - 44
Objective Questions 45 - 53
EXERCISE-III
EXERCISE-IV
ANSWRE KEY 69 - 76
EXERCISE-I
EXERCISE-II
EXERCISE-III
EXERCISE-IV
CARBONYL COMPOUNDS
A-4. Arrange the following compounds in decreasing orders of rate of addition of HCN.
(a) (b)
A-5. Arrange the following compounds in decreasing orders of Keq for hydrate formation.
(b)
A-7. Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not. Explain why ?
A-8. Give the structure of the carbonyl compound and amine used to form the following imines.
(a) (b)
A-9. Show which alcohol and carbonyl compound react to give each of the following product.
(a) (b)
Ph H
CH3
C C=N H SO
(a) + NaHSO3 (b) 2
4
C2H5 OH
O
D2O
(c) CH3 C CH3
18
(d) + H
||
O16
OH /
(b) Ph–CH2–CHO
OH /
(c) Ph–CO–CH3
B-2. Indicate the starting aldehyde or ketone from which each of the following compounds are formed by an aldol
condensation reaction.
(a) 2–Ethyl – 3–hydroxy hexanal ; (b) 4–Hydroxy–4–methyl–2–pentanone
B-3. When acetone is treated with excess of benzaldehyde in the presence of base, the crossed condensation
add two equivalents of benzaldehyde and expels two equivalent of water and forms [X]. Identify the structure
of [X] when [X] reacts with NH2OH how many stereoisomers are formed.
B-4. Predict the products of following cross condensation reaction,
CH3
|
OH /
(a) CH3 — C — C H + CH3 – C – H
| || ||
CH3 O O
OH /
Ph – C H + CH3 – CH2 – C – H
(b)
|| ||
O O
Ph – C H + OH /
C – CH3
(c)
|| ||
O O
B-6. Show which esters would undergo claisen condensation to give the following –ketoester.
(a)
(b)
(c)
+ +
OH
CH3 C H + H C H
C-2. Product
|| ||
O O
excess
Section (D) : Redox reactions
D-1. Write the product of following reaction,
LiAlH
4
(a) (p) (q) + (r)
CHO CHO
(a) + Ag2O (b) + K2Cr 2O 7 / H2SO 4
HO HO
CHO CHO
(c) + - (d) + KMnO4
+ Ag(NH3)2 OH
|| (cold, dil.)
O
3 CH CH CH CH Li Ph C O
F-2. CH3I + Ph3P 2 2
2
2
benzene
F-3. Product.
F-4. Compound (X) with molecular formula C9H10O forms a semicarbazone and gives negative Tollen’s and Iodoform
tests. Upon reduction it gives n-propyl benzene. Deduce the structure of X.
(A) (B)
(C) (D)
(A) (B)
(C) (D)
NH NH
2
2
O16
|| D2O18
A-5. CH3 C H
The intermediate is :
A-6. Aromatic carbonyl compounds having molecular formula C8H8O react with NH2OH how many oximes can be
formed :
(A) 8 (B) 10 (C) 12 (D) 6
CH2–OH
CH3O H
A-7. H OH [ X]
H OCH3
CH2OH
A-8. The general order of reactivities of carbonyl compounds towards nucleophilic addition reactions
(A) H2C = O > (CH3)2 C = O > Ar2C = O > CH3CHO > ArCHO.
(B) H2C = O > CH3CHO > (CH3)2 C = O > ArCHO > Ar2C = O.
(C) ArCHO > Ar2C = O > CH3CHO > (CH3)2 C= O > H2C = O.
(D) Ar2C = O > (CH3)2C = O > ArCHO > CH3CHO > H2C = O.
A-9. The correct order of reactivity of PhMgBr with following compounds will be.
PhMgBr
(C6H5)2CO, CH3 – CH = O , (CH3)2 C = O
CH3
(A) (B)
(C) (D)
NaOH
C-2. In the reaction, (CH3)3CCHO + HCHO
A + B.
heat
KOH
C-3. + HCHO (A) + (B)
C-4. In the cannizzaro's reaction the intermediate that will be the best hydride donar ?
(A) (B)
(C) (D)
heat
+ conc. NaOH ?
(A) (B)
(C) (D)
O O
|| ||
( X)
D-1. (CH3)2C = CHCH2 CH2CCH3 (CH3 )2 CHCHCH2 CH2CCH3
|
OH
O O
|| ||
(Z)
(CH3 )2 CHCCH 2 CH2 CCH 3
x y z
(A) H2CrO4 B2H6, THF/H2O2,OH OH /
(B) B2H6, THF/H2O2,OH H2CrO4 / CrO3 OH /
(C) B2H6, THF/H2O2,OH OH H2CrO4 / CrO3
(D) H2CrO4 OH B2H6, THF/H2O2,OH
O
||
Ph – CHO
LiAlH 4
[X], Product (X) in this reaction is :
D-2.
OH /
(A) (B)
(C) (D)
D-7.
E-1. 2 Major Product is :
Br / H
(B) D O / OH
2
(C) D O / OH (D) D O / OH
2 2
(A) (B)
Product B is :
(1) 2 / OH
F-4.* EtO ( 2)H
(P) (Q) (R)
H
(a) + HO – NH2
(b) H
+ NH2 – NH2
2. When semicarbazide reacts with a ketone (or aldehyde) to form semicarbazone. Only one nitrogen atom of
semicarbazide acts as a nucleophile and attack the carbonyl carbon of the ketone. The product of the
reaction consequently is R2–C=N–NH–CONH2 rather than R2–C=NCONH–NH2. What factor account for the
fact that two nitrogen atom of semicarbazide are relatively non nucleophile ?
3. Cyclopropanone exists as the hydrate in water but 2-hydroxy ethanal does not exist as its hemiacetal
expalin why ? [Claiden]
4. Show how would you accomplish the following synthesis
(a)
O O
CH2 - Br CH2 - Ph
(c)
5. (a) Cis-1, 2-Cyclopentanediol reacts with acetone in the presence of dry HCl to yield compound K, C8H14O2,
which is resistant to boiling alkali, but which is readily converted into the starting material by aqueous acids.
What is structure of K ?
(b) Trans-1, 2-Cyclopentanediol does not form an analogous compound. Explain why ?
6. On the basis of following reaction answer the following questions.
H
|
*
Ph C H CH O + NH2 .NH C NH C* CH2 CH3
H
| || |
Me O Me
( d mixture) (pure optical isomer )
EtO
(a) +
EtO
(b) +
1. EtO
(c) +
2. H2O /
8. Write the components which on crossed claisen condensation could be used to prepare the following esters.
CH3COO Na
(a) OHC CHO + CH3 C O C CH3
|| ||
O O
excess
CN
(b) CH3CHO + CH2 Pyridine /
CN
OO O
|| || ||
(c) OH / KOH
(d) C 6H5 CCC 6H5 + C 6H5 CH2 CCH2C6H5
ethanol
EtO
11. + CH2 = CH – C – Ph Product (P) is :
||
O
Section (C) : Cannizzaro's reactions
12. Write the product of the following reaction,
CHO CDO
(a) + OH /
OMe OMe
CHO CHO
(b) + OH /
NO2
– –
OH OH H
13. PhCOCHBr2 A B
C
The compound 'C' is :
14. Glyoxal (CHOCHO) on being heated with concentrated NaOH forms.
( i) conc . NaOH,
15. + CHO
Product is :
| (ii ) H3O
COOH
Section (F) : Miscellanious reactions
16. The compound C4H8CI2 (A) on hydrolysis gives a compound C4H8O, (B). The compound (B) reacts with
hydroxylamine and gives a negative test with Tollen’s reagent. What are (A) and (B) Support your answer
with proper reasoning and give the equations of reactions.
17. A ketone (A) which undergoes haloform reaction, gives compound (B) on reduction with LiAlH4. (B) on
heating with conc. H2SO4 gives (C) which forms monoozonide (D). (D) on hydrolysis in presence of zinc dust
gives only acetaldehyde. Identify (A), (B and (C). Write reactions involved.
18. Compound ‘X’ (C5H10O) reacts with KCN in dilute H2SO4 followed by heating with dilute acid , results in
compound ‘Y’ which is achiral and gives effervescence with NaHCO3 . Reduction of ‘X’ forms ‘Z’ (achiral)
which gives positive Lucas test . X responds negatively to iodoform and Fehling’s tests . Identify ‘X’ , ‘Y’ and
‘Z’ .
1. Products
(C) CHD2 – CH2 – OH , CD2 = CH2 (D) CHD CH2 OH , CD2 = CH2
|
OH
(A) (B)
(C) (D)
(1) 3( 2) ( )
4.
CH2 OH
(A) (1) | H (2) Mg / (3) H C O H / H+
CH2 OH ||
O
CH2 OH
(B) (1) | H (2) Mg / (3) CH3 C O Et / H+
CH2 OH ||
O
CH2 OH
H (2) Mg / THF (3) CH3 C O Et / H
+
(C) (1) |
CH2 OH ||
O
CH2 OH
(D) (1) | H (2) Mg / THF (3) H C O H / H+
CH2 OH ||
O
(Y) is
(A) (B)
(C) (D)
6. Product is
(A) (B)
(C) (D)
(C) , and
(D) , and
(i) KCN / H SO
2 4
9. Product is
(ii) LiAlH 4
H SO
A
B.
2 4
Heat
+ H2NOH Heat
11. Compound (X) C9H10O gives yellow coloured ppt with 2,4 DNP but does not give red coloured ppt with
Fehling’s solution. (X) on treatment with NH2OH/H+ gives compound (Y) C9H11NO. (Y) when treated with PCl5
gives isomeric compound (Z). (Z) on hydrolysis gives propanoic acid and aniline. What will be the correct
structure of (X), (Y) and (Z) ?
(A) ; ;
(B) ; ;
(C) ; ;
(D) ; ;
12. + Product
(A) (B)
(C) (D)
(A) (B)
O CH3
|| | KOH, H2O
15. CH3 CCH2 CCHO Product (C H O) : (mRikn (C H O)
7 10 7 10
|
CH3
16.
(A) (B)
(C) (D)
CHO
O
OH /
19. + Product is
COOH OH
O
Ph – CH
(A) (B) Ph – CH (C) (D) +
OH
Conc. NaOH
( i) CH ( COOC H ) / Pyridine
22. 2 2 5 2
(P) is
( ii) H O,
2
( i) CH ( COOC H ) / fifjMhu
2 2 5 2
(P) gS
( ii) H O,
2
(A) (B)
(C) (D)
CN OH
– CH CHO
– –
(A) CH3CH – 3 KCN + HCl Me – – CH
OH ( very fast) CN
CH CH O
H2O/H+
(B) (hydrate) 3 hydrate
( fast )
Ph – CH2 – CH = O
KCN / H O NH ,
3
H O , KCN / NH Cl
4 H O ,
2
(A) 3
(B) 3
2Br / CH COOH
3 3 NH
3 CrO / H
(D)
26. In the given reaction which one of the following statement is correct –
28. A compound (A) C5H10O forms a phenyl hydrozone and gives negative tollen's and positive iodoform test
compound can be :
(A) (B)
(C) (D)
O O
|| || (1) H O / H
(C) CH 3 – C – CH2 – CH 2 – C – OC 2H 5 2
( 2) NaOH( cao)
(D)
30. W X Y Z
31. Which of the following reactions is / are correct to get cinnammic acid :
(i ) OH
(A) MeCO(CH2)4COMe
(p)
( ii) H /
OEt
(B) (CH2)4 (q)
(C) PhCHO + 3
CH COO –
(r) (Ph)2 C — COO –
|
OH
OH
(D) PhCOCOPh (s)
2. Column-I Column-II
Aldol product Reactant required
(A) (p)
3. Column-I Column-II
PART - II : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
Aldehydes and Ketones reacts with NH2OH to form Aldoximes and Ketoximes respectively. Configuration of
these can be determined by Beckmann rearrangement as that group migrates which is anti w.r.t –OH.
R R H2 O
..
..
H SO4 H O
4. [X] 2 2 Ph – NH2 +
NH2OH 2 4 (1) H SO
6. (A) (B).
( 2) hydrolysis
Comprehension # 2
Carbonyl compound which contains –H gives aldol condenation reaction in presence of alkaline medium.
The reaction between two molecules of acetaldehyde take place as follows in presence of base.
(A) C6H5–CHO (B) CX3 – CHO (C) O2N CHO (D) C6H5–CH2–CHO
8. + Product (mRikn)
(C) (D)
11. Aldehyde having -Hydrogen does not give cannizzaro reaction because
(A) Such aldehyde will form enolate ion
(B) Such aldehyde will not form conjugate base of hydrate of aldehyde
(C) Such aldehyde may undergo polymerisation
(D) All of these
12. In the given reaction final product is (nh xbZ vfHkfØ;k eas vfUre mRikn gaS )
Comprehension # 4
Perkin reaction is the condensation reaction between aromatic aldehyde and aliphatic acid anhydride in the
presence of sodium or potasium salt of the acid of the corresponding anhydride to yield , unsaturated
aromatic acid.
Mechanism
CH3–COONa CH3–COO + Na
CH3–COO + CH3–COOH +
H O/
13. 2 Product is
(A) (B)
(C) (D)
( i) H O /
14. 2
(ii) H
H O/
15. + (CH3–CH2CO)2O 2 Product is
(A) (B)
(C) (D)
Comprehension # 5
Ester having -hydrogen on treatment with a strong base eg. C2H5ONa undergoes self condensation to
produce -keto esters.This is called claisen condensation.
16. +
17. + product is
(A) (B)
18.
(A) (B)
Comprehension # 6
X X
H
- I–I | - |
| R–C–C–H R C C H (1) HO, (2) I2 RCC X
R C C H + HO - a || | b || | C || |
|| | O H O H O H
O H
X
- d
X - HO- | (1) HO
CHX3 R – C – O R C OH + -CX3
f
R C C X
||
e || | (2) I2
||
O O O X
O
C – CH3
(C) CH3 – C – CH2 – CH2 – C (D)
|| ||
O O
O O
(A) (B)
(C) (D)
(A) (B)
(C) (D)
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
25. Statement-1 : Aldehyde and ketone undergo nucleophilic addition reaction with carbon nucleophile and
underog nucleophilic addition-elimination reaction with nitrogen Nucleophile.
Statement-2 : Addition of nucleophile on aldehyde and ketone form tetrahedral intermediate, in case of
tetrahedral intermediate of nitrogen nucleophile non bonding electrons are present on nitrogen which cause
water molecule to eliminate while in case of carbon and hydrogen nucleophile non bonding electron are not
present.
26. Statement-1 : The rate of addition reaction of alcohol on aldehyde can be increased by adding small amount
of base.
Statement-2 : Addition of alcohols to an aldehyde form acetal.
27. Statement-1 :
Statement 2: This is due to the fact that cinnamaldehyde does not have acidic – H
OH
33. Conc. KOH changes Ph–C–C–Ph to Ph–C–COO
O O Ph
35. Fehling solution (A) consists of aquous solution of copper sulphate, while Fehling’s solution ‘B’ consists of
an alkaline solution ............
36. The structure of the intermediate product, formed by the oxidation of toluene with CrO3 and acetic anhydride,
whose hydrolysis gives benzaldehyde is ...........
37. Ethanol vapour is passed over heated copper and the product is treated with aqeuous NaOH. The final
product is ..........
38. The conversion of carbonyl compound into alkane by reduction is termed as ............
C N H 2NHCONH 2
D
N aOD / D 2O ( excess )
C E
2. An alkene A (C16H16) on ozonolysis gives only one product B (C8H8O). Compound B on reaction with NaOH/
I2 yields sodium benzoate. Compound B reacts with KOH/NH2NH2 yielding a hydrocarbon C. (C8H10). Write
the structure of compound B and C based on this information two isomeric structures can be proposed for
alkene A. Write their structures and identify the isomer which on catalytic hydrogenation (H2/Pd-C) gives a
racemic mixture. [JEE 2001, 5/100]
3. A mixture of benzaldehyde and formaldehyde on heating 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 [JEE 2001, 1/35]
4. 1-Propanol and 2-Propanol can be best distinguished by [JEE 2001, 1/35]
(A) oxidation with alkaline KMnO4 followed by reaction with Fehling solution
(B) oxidation with acidic dichromate followed by reaction with Fehling solution
(C) oxidation by heating with copper followed by reaction with Fehling solution
(D) oxidation with concentrated H2SO4 followed by reaction with Fehling solution
5. Write structures of the products A, B, C, D and E in the following scheme. [JEE 2002, 5/60]
2H / Pd / C
E D
6. Five isomeric para-disubstituted aromatic compounds A to E with molecular formula C8H8O2 were given for
identification. Based on the following observations, give structures of the compounds.
(i) Both A and B form a silver mirror with Tollen’s reagent; also, B gives a positive test with FeCl3 solution.
(ii) C gives positive iodoform test.
(iii) D is readily extracted in aqueous NaHCO3 solution.
(iv) E on acid hydrolysis gives 1, 4–dihydroxybenzene. [JEE 2002, 5/60]
7. A biologically compound Bombykol (C16H30O) is obtained from a natural source. The structure of the compound
is determined by the following reaction.
(a) On hydrogenation, bombykol gives a compound A (C16H34O). Which react with acetic anhydride to
give an ester.
(b) Bombykol also react with acetic anhydride to give another ester. Which on oxidative ozonolysis (O3/
H2O2) gives a mixture of butanoic acid, oxalic acid and 10 acetoxy decanoic acid.
Determine the number of double bond in Bombykol. Write the structure of compound (A) and Bombykol. How
many geometrical isomer are possible for Bombykol. [JEE 2002, 5/60]
8. Compound 'A’ (molecular formula C3H8O) is treated with acidified potassium dichromate to form a product 'B'
(mol. Formula C3H6O). 'B' forms a shining silver mirror on warming with ammonical AgNO3 . 'B' when treated
with an aqueous solution of H2NCONHNH2. HCl & sodium acetate gives a product 'C'. Identify the structure of
'C’. [JEE 2002, 3/90]
CH3
|
(A) CH3CH2CH = NNHCONH2 (B) CH3 C N CONHNH2
10. HCl
A (C6H12) [JEE 2003, 4/60]
BC
(C 6H13 Cl)
alc KOH
B
D (isomer of A)
ozonolysis
D E (it gives negative test with Fehling solution but responds to iodoform test).
ozonolysis
A F + G (both give positive Tollen’s test but do not give iodoform test.)
conc. NaOH
F + G
HCOONa + a primary alcohol.
Identify to A to G.
(A) (B)
(C) (D)
CH COONa
3
, X can be :
heat
O O O O
|| || || ||
(A) CH2 C O H (B) H C C O H (C) CH3 C O H (D) (CH3CO)2 O
|
Br
13. In conversion of 2-butanone to propanoic acid which reagent is used. [JEE 2005, 3/84]
(A) NaOH, NaI / (B) Fehling solution (C) NaOH, I2 / (D) Tollen's reagent
14. Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E. Compound E
on further treatment with aqueous KOH yields compound F. Compound F is : [JEE 2007, 3/162]
CO2H
(A) CHO (B) CHO (C) COOH (D)
CO2H
15. Match the compounds/ions in Column I with their properties/reactions in Column II. [JEE 2007, 8/162]
Column I Column II
(A) C6H5CHO (p) gives precipitate with 2,4 dinitrophenylhydrazine.
(B) CH3C CH (q) gives precipitate with AgNO3 .
–
(C) CN (r) is a nucleophile.
–
(D) (s) is involved in cyanohydrin formation.
16. In the following reaction sequence, the correct structures of E, F and G are [JEE 2008, 3/163]
*
(C) E = F= G = CHI3 (D) E = F= G = CH3
Write Up
A tetriary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to compounds
J and K. Compound J upon reaction with KOH gives benzyl alcohol and compound L, whereas K on reaction
with KOH gives only M.
M=
19. The structure of compounds J, K and L respecitvely, are : [JEE 2008, 4/163]
(A) PhCOCH3, PhCH2COCH3 and PhCH2COO K (B) PhCHO, PhCH2CHO and PhCOO–K+
– +
(C) PhCOCH3, PhCH2CHO and CH3COO–K+ (D) PhCHO, PhCOCH3 and PhCOO–K+
Write Up
A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr followed by
dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoes
intramolecular aldol reaction to give predominantly S.
1. MeMgBr 3 1. O 1. OH
P Q R
S
2. H , H2O 2. Zn, H2O 2.
3 . H2SO 4,
20. The structure of the carbonyl compound P is : [JEE 2009, 4/160]
21. The structures of the products Q and R, respectively, are : [JEE 2009, 4/160]
(A) , (B) ,
(C) , (D) ,
23. Match each of the compounds given in Column I with the reaction(s), that they can undergo, given in
column II. [JEE-2009, 8/160]
Column I Column II
(t) Dehydrogenation
1. O 1. NaOH( aq )
3 Y
2. Zn, H2O 2. heat
Comprehension
Two aliphatic aldehydes P and Q react in the presence of aqueous K2CO3 to give compound R, which upon
treatment with HCN provides compound S. On acidification and heating, S gives the product shown below :
(A) (B)
(C) (D)
(A) (B)
(C) (D)
O
O O || CH3
|| ||
OH
(A) (B) (C) (D)
OH OH OH
3. Which one of the following is reduced with Zn, Hg and HCl acid to give the corresponding hydrocarbon?
[AIEEE-2004]
(A) Ethyl acetate (B) Butan-2-one (C) Acetamide (D) Acetic acid
4. Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the corresponding
alcohol and acid ? [AIEEE-2004]
(A) Phenol (B) Benzoic acid (C) Butanal (D) Benzaldehyde
5. The best reagent to convert pent-3-en-2-ol into pent-3-ene-2-one is [AIEEE-2005]
(A) Pyridinium chloro-chromate (B) Chromic anhydride in glacial acetic acid
(C) Acidic dichromate (D) Acidic permanganate
6. The reaction [AIEEE-2005]
O O
-
R – C + Nu- R–C + X
X Nu
is fastest when X is :
(A) OCOR (B) OC2H5 (C) NH2 (D) Cl
7. Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid forms a
compound if water during the reaction is continuously removed. The compound formed is generally known as
[AIEEE-2005]
(A) an amine (B) an imine (C) an enamine (D) a Schiff's base
8. The decreasing order of the ratio of HCN addition to compounds A to D is [AIEEE-2006]
(a) HCHO (b) CH3COCH3 (c) PhCOCH3 (d) PhCOPh
(A) d > b > c > a (B) d > c > b > a (C) c > d > b > a (D) a > b > c > d
P 2 Mg
HCHO H O
CH3CH2OH A Ether
B C 2 D. The compound ‘D’ is
(A) n-propyl alcohol (B) propanal (C) butanal (D) n-butyl alcohol
10. In the following sequence of reactions, the alkene affords the compound 'B' [AIEEE-2008, 3/105]
O3 H 2O
CH3CH CHCH3
A B .The compound B is
Zn
:O H ..
2Ph CHO PhCH2OH + PhCO2
EXERCISE - 1
PART - I
A-1. The reactivity of carbonyl group towards nucleophilic reagent depends upon the extent of positive charge
present on the carbon. In ketones two alkyl group attach to the carbon reduce the positive charge on the
carbonyl carbon due to their electron repelling nature while in aldehyde the positive charge on carbonyl
carbon is reduced to lesser extent because only one alkyl group is present.
Also, In ketones steric hinderance is more than aldehyde.
A-2. IV > III > II > I A-3. IV > III > I > II A-4. d>b>c>a
A-5. c>b>a>d
A-7. Cyanohydrin is formed by nucleophilic attack on carbonyl group (C=O), 2, 2, 6-trimethylcyclohexanone has
more steric crowding and three methyl groups in tri methyl cyclohexanone which nearly neutralise the
positive charge on carbon hence CN– nucleophile does not react with 2,2,6-trimethylcyclohexanone.
A-10. (a) Ph CH SO3Na ; (b) C 2H5 C NHCH3 ; (c) CH3 C CH3 ; (d)
| || ||
OH O O18
CH3 O
| ||
B-4. (a) CH3 C CH CH – C H ; (b) Ph CH C C H ; (c) Ph CH CH C
| || | ||
CH3 O CH3 O
B-5.
CH2 OH
|
C-2. HO CH2 C CH2 OH + HCOO–Na+
|
CH2 OH
O O
(b)
COOH
|
COOH
|
(c) ; (d)
| OH
OH
(C) (D)
O O
Ph || Br ||
C6H5 C6H5
E-1. + , (Diastereomer).
Br CH3 Ph CH3
PART - II
Section (A) : Nucleophilic addition reactions
A-1. (B) A-2. (C) A-3. (D) A-4. (A) A-5. (B)
A-6. (B) A-7. (B) A-8. (B) A-9. (B) A-10. (A)
A-11. (B)
Section (B) : Condensation reactions
B-1. (D) B-2. (A) B-3. (D) B-4. (B) B-5. (D)
B-6.* (A, B, D)
Section (C) : Cannizzaro's reactions
C-1. (D) C-2. (A) C-3. (A) C-4. (C) C-5. (C)
C-6. (B)
Section (D) : Redox reactions
D-1. (B) D-2. (A) D-3.* (A, B, C) D-4. (A) D-5. (C)
D-6. (A) D-7. (B)
Section (E) : -Halogenation, haloform, -deuteration reactions
E-1. (A) E-2. (C) E-3.* (A, B, C) E-4.* (A, B, C) E-5.* (A, C)
Section (F) : Miscellanious reactions
F-1. (C) F-2. (B) F-3. (A) F-4.* (A, C, D) F-5. (C)
F-6. (B) F-7.* (A, B, C)
EXERCISE - 2
PART - I
Section (A) : Nucleophilic addition reactions
1. (a) (b)
N – NH – Ph
||
(c) (d) Ph – C – Ph
2. Two nitrogen atoms of semicarbazide that are adjacent to the (C=O) group have their lone pair present in
conjugation so nucleophilicity decreases.
3. H O
2
In cyclopropanone angle strain decreases after addition of water, while cyclic hemiacetal structure of
2-hydroxy ethanal will develope angle strain.
H2O
HO–CH2–CHO
Hemiacetal
(Not form due to angle strain)
CH2 OH
| H (i) LiAlH
4
4. (a) CH2 OH
(ii) H
CH2 OH
| H O O
CH2 OH
(b) Br – CH2 – CH2 – C – CH3 Br – CH2 – CH2 – C – CH3
||
O
(i) HCCNa
HC C – CH2 – CH2 – C – CH3
(ii) H ||
O
O O
CH2 - Br CH2 OH O O CH2 - Ph
(i) PhMgBr
| H CH2–Br
(c) CH2 OH (ii) H2O
5. (a) (b) The – OH groups in the trans isomer are too far apart for the cyclic structure to form.
6. (a) 4 (b) 2
Section (B) : Condensation reactions
CN
(b) CH3–CH = C
CN
(c)
11.
D
CH2–OH
CH–OH
OMe
15. +
(i)
(ii)
(iii)
17. (A)
OH
|
18. , C 2H5 C C 2H5 , C 2H5 CH C 2H5
| |
COOH OH
( Y ) (achiral) ( Z ) (achiral)
OH
|
, C 2H5 C C 2H5 , C 2H5 CH C 2H5
| |
COOH OH
( Y ) ( vfdjSy) ( Z ) ( vfdjSy)
PART - II
Section (A) : Nucleophilic addition reactions
1. (A) 2. (C) 3. (B) 4. (C) 5. (B)
6. (B) 7. (D) 8. (B) 9. (A) 10. (D)
11. (B) 12. (A)
Section (B) : Condensation reactions
13. (B) 14. (B) 15. (C) 16. (A) 17. (C)
18. (C) 19. (B)
Section (C) : Cannizzaro's reactions
20. (D) 21. (C)
Section (F) : Miscellanious reactions
22. (A)
Section (A) : Nucleophilic addition reactions
23. (A, C) 24. (B, C, D) 25. (A, B, C) 26. (A, B, C, D)
27. (A, B, C, D) 28. (A, D) 29. (A, B, D)
30. (B, D) 31. (Aa, B, D) 32. (A, B, C)
EXERCISE - 3
1. (A) - q ; (B) - p ; (C) - s ; (D) - r
2. (A) - p,q ; (B) - p,r ; (C) - q,s ; (D) - r,s
3. (A) - p, q, s ; (B) - p, q, r, s ; (C) - p ; (D) - q, r, s
4. (A) 5. (B) 6. (A) 7. (D) 8. (D)
9. (D) 10. (B) 11. (D) 12. (C) 13. (A)
14. (A) 15. (A) 16. (A) 17. (D) 18. (A)
19. (A) 20. (C) 21. (B) 22. (C) 23. (C)
24. (D) 25. (A) 26. (D) 27. (A) 28. (B)
29. (A) 30. (A)
31. True 32. True 33. True 34. False
35. Sodium potassium tarterate
36. C6H5CH(OCOCH3)2
37. Aldol
38. Clemmensen’s reduction or Wolf kishner reduction
EXERCISE - 4
PART - I
(D) = (E) =
2. A= or ;k
O
||
CH2 – CH2– CH3
5. A = Cl B= C=
Cl 'A'
D= E=
8. (A)
9.
10. A= B= C=
D= E= F & G are
PART - II
CH3
| acid
+ HO CH2 C CH2 OH
|
CH3
( excess )
R
2. above reaction has reagents ‘R’
3. Which of the following compounds on reaction with conc. NaOH followed by gives following cyclic ester..
(A) (B)
(C) (D)
H
4. x
Conc . OH y
excess /
H O
5. 3 A + B
(A) Benzyl alcohol (B) Benzaldehyde (C) Benzoic acid (D) Phenol
11. Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is : [JEE 97]
(A) MeCOCl (B) MeCHO (C) MeCOOMe (D) MeCOOCOMe
12. An organic compound C3H6O does not give a precipitate with 2, 4-dinitrophenyl hydrazine reagent also does
not react with metallic sodium it could be :
(A) CH3–CH2–CHO (B) CH3–COCH3 (C) CH2=CH–CH2–OH (D) CH2=CH–OCH3
13. The product of the reaction
(X) will be :
(C) (D)
(A) (B)
(C) (D)
15. (B) +
A and B are :
(A) ,
(B)
(D) ,
[X] , [X] is :
17. Among the following compounds which one will react with acetone to give a product that contains carbon-
nitrogen double bond ?
(A) C H N HC H (B) (CH3)3 N (C) (D) C6H5 N H N H2 .
6 5 6 5
H
CH2
C2H5
| CH
+N H5C2–N N–C2H 5
..
N
.. HC CH
(A) (B) (C) (D)
CH3
CH3 H3C CH3
P will be :
21. A compound (X) on treatment with SOCl2 produces another compound (Y). The latter on hydrolysis yields a
mixture of benzoic acid and methylamine. The compound (X) is :
(A) (B)
(C) (D)
22.
(A) X Y (B) X Y
23. Compound ‘A’ given below can undergo intramolecular aldol condensation reaction.
product formed is :
X can be :
(A) (B)
(C) (D)
25. ‘B’
[X]
(A) (B)
(C) (D)
H2O
+
28. Which of the following reaction will give -keto aldehyde as the final product ?
(A) + (B) +
29. An organic compound X on treatment with acidified K2Cr2O7 gives compound Y which reacts with I2 and
sodium carbonate to form Triodomethane. The compound X can be :
O
(A) Phenyl hydrazine (B) Hydroxylamine (C) Fehling solution (D) Sodium bisulphite.
(A) (B)
Compound (B) is :
33. Arrange the following compound in decreasing order of Keq for hydrate formation.
(A) III > II > I > IV (B) I > II > III > IV (C) II > III > I > IV (D) III > IV > II > I
KCN,EtOH
34. Product is :
H O 2
(A) (B)
(C) (D)
35. G H
, (X) will be :
(A) (B)
(C) (D)
HO
2
O O
|| ||
+ H
H3 C C (CH2 )2 C CH3
40. +
HCN H O
41. 3 Product
(A) Zn – Hg / Con.HCl
(D) Zn – Hg / Con.HCl
(A) 1 - Phenyl ethanol (B) 2-pentanone (C) 2- pentanol (D) Isopropyl alcohol
OH
(B) PhCHO +
OH
(D)
47. During aldol condensation between excess of formaldehyde and acetaldehyde in basic medium we can get
(A) Trihydroxy methyl acetaldehyde (B) Sodium formate
(C) CH2= CH – CHO (D) Tetrahydroxymethylmethane
48. Which of the following is possible combination to prepare 1 -phenyl 1,3 butadiene from Wittig reaction ?
51. Which one of the following -dicarbonyl-compound will not show enolisation ?
52. , unsaturated acids can be prepared by which one of the following reaction ?
HCCH H / Ni
H
53. 2CH2=O P 2 Q R
R is an ether which a good solvent for grignard reagent. Which of the following are correct.
(A) P = HO–CH2–CC–CH2OH (B) Q = HO–CH2–CH2–CH2–CH2–OH
(C) R = (D) R =
O O
54.
O O
55. Which of the following will undergo aldol condensation : [JEE-98, 3M]
(A) Acetaldehyde (B) Propanaldehyde
(C) Benzaldehyde (D) Trideuteroacetaldehyde
56. Among the following compounds, which will react with acetone to give a product containing > C = N – :
[JEE-98, 3M]
(A) C6H5NH2 (B) (CH3)3N (C) C6H5NHC6H5 (D) C6H5NHNH2
57. The enol form of acetone, after treatment with D2O, gives : [JEE-99, 2M]
OD O OH OD
| || | |
(A) CH3 C CH2 (B) CD3 C CD3 (C) CH2 C CH2D (D) CD3 C CD3
Assertion-Reason
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
58. Statement-1 : CCl3CHO forms an isolable crystilline hydrate.
Statement-2 : Powerfully electron withdrawing chlorine atoms stabilise hydrate by intramolecular H-bonding.
59. Statement-1 : Carbonyl compound are more soluble in water than the corresponding alkanes
Statement-2 : H-bonding between carbonyl oxygen and water makes carbonyl compounds more water
soluble than hydrocarbon
60. Statement-1 : Acetophenone and benzophenone can be distinguished by Iodoform test.
Statement-2 : Acetophenone and benzophenone both are carbonyl compound.
61. Statement-1 : Isobutanal does not give iodoform test.
Statement-2 : It does not have –hydrogen.
62. Statement-1 : Acetylene on treatment with alkaline KMnO4 produce acetaldehyde.
Statement-2 : Alkaline KMnO4 is a oxidising agent.
–
OH
68. Statement-1 :
Heat
Statement-2 :Polyccarbonyl compound with -H give intramolecular aldol condensation in alkaline medium.
69. Statement-1 : The addition of ammonia derivative to a carbonyl compound is carried out in weakly acidic
medium.
Statement-2 : In weakly acidic medium attacking nucleophile is also protonated.
70. Statement-1 : HCHO is always oxidized in the crossed cannizzaro reaction.
Statement-2 : HCHO is the most reactive aldehyde, it exist in aquous OH solution as the conjugate base
of its hydrate , there is also a statistical factor because HCHO has two aldehydic hydrogen
available for transfer while in other aldehyde hydrate anion has only one such hydrogen atom.
71. Statement-1 : Cannizzaro reaction is given by aldehyde having no -hydrogen atom.
Statement-2 : Cannizzaro reaction is redox reaction.
COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
P is an alcohol which on heating with Al2O3 forms an alkene Q. Q on ozonolysis produces R and S. When the
mixture of R and S is heated with NaOH, a redox reaction takes place and a mixture of an acid salt and
alcohol is formed.
72. The alcohol (P) is obtained by :
(A) (B)
(C) (D)
Comprehension # 2
Aldehyde and ketone undergo nucleophilic addition reaction because of polarity betwen >C=O group. The
reactivity of carbonyl groups toward nucleophile depends upon the nature of inductive effect of group present
at carbonyl carbon.
75. Which among the following is most reactive towards nucleophilic addition reaction.
(A) FCH2CHO (B) ClCH2CHO (C) Br CH2CHO (D) I CH2CHO
76. Which of the following is least reactive for nucleophilic addition reaction
(I) (II)
(III) (IV)
(A) III > II > I > IV (B) II > IV > III > I (C) II > III > I > IV (D) III > I > II > IV
Comprehension # 4
In presence of excess base and excess halogen a methyl ketone is converted first into a trihalo substituted
ketone and then into a carboxylic acid. After the trihalo substituted ketone is formed hydroxide ion attacks
the carboxyl carbon because the trihalo methyl ion is the group more easily expelled from the tetrahedral
intermediate. The conversion of a methyl ketone to a carboxylic acid is called a haloform reaction because
one of the product is haloform (CHCI3) or CHI3 or CHBr3.
O H ( excess )
R – C – CH3 R – C – OH + CI3 R – C – O + CH I3
|| 2 ( excess )
||
O ||
O O
81. Which of the following compound show haloform reaction and racemisation in OD– / D2O.
O
Me Me
(A) CH3CH2OH (B) Ph
(C) (D)
Et
Et
|
(1) 2 / OH
82. Ph – C – C – C – CH3 product is
|| | || ( 2 ) H
( 3)
O Me O
Me
|
(A) Ph – C – C – COOH (B) Ph – C – CH – Me
|| | || |
O Et O Et
(C) Ph – C – O – CH – Et (D) Ph – C – CH – OEt
|| | || |
O Me O Me
O
Ph
O (1) Na O
83. product is
( 2 ) H ,
HOOC Ph
O
(A) O (B) (C) (D)
Comprehension # 5
Following is the mechanism of Benzoin condensation reaction. Answer the following based on it
- O
O O OH H CN
|| | | ||
- a b - Ph – C – H | |
Ph C H + CN Ph – C – H Ph – C Ph – C – C – Ph
| | c
| |
CN CN -
O OH
H H CN
| | |
Ph C C Ph e Ph – C – C – Ph
| || | | d
OH O -
OH O
CH3 C – CH3
O
CH3 CI CI
CH – CH2
CH3 CH3
Comprehension # 7
Observe the following reactions and its mechanistic steps and intermediate products.
Reaction -2
+ + ACO
2. Identify A, B, C, D and E in the following scheme and write their strucute. [5 marks]
HgSO
A 4
B
dil. H2SO 4
3. CH3Cl A B C D.
Give the structures from A to D. [2 marks]
4. Give structure for compound A to E.
Cyclohexanol
Ethanal Butanol
6. Compounds (A) and (B) on reaction in ether medium and subsequent acidififcation and oxidation give
2,5-dimethyl-3-hexanone. What are (A) and (B) ?
7. An organic compound C8H12 decolourised the bromine water and Baeyer’s reagent. On complete bromination,
it gave a tetrabromo derivative C8H12Br4 having three asymmetric carbon atoms. On ozonolysis, (A) gives
, and HCOOH. What is 'A'
8.
9. (A) on hydration gives (B) which gives positive iodoform test. Also (A) gives white precipitate with Tollen's
reagent. (B) is also obtained from acetyl chlori de on treating with benzene in the presence of anhydrous
AlCl3 .
10. An alkene C6H12 after ozonolysis yielded two products. One of these gave a positive iodoform reaction but a
negative Tollen's test. The other gave a positive Tollen's test but negative iodoform test. The structure of C6H12 is.
11. Compound (A) C5H10O forms phenyl hydrozone and gives negative Tollen’s and Iodoform tests. Compound
(A) on reduction gives n-pentane. Give structure of (A). Explain the reactions.
12. The calcium salt of an acid A (C6H10O4) on dry distillation produced B (C5H8O). When B is reacted with Bromine
solution in acetic acid, ‘C’ (C5H7OBr) is obtained. ‘C’ is reacted with anhydrous acidic glycol (HOCH2CH2OH)
solution and PhMgBr is added to this solution carefully and then its is subjected to dilute HCl solution then
compound ‘D’ (C11H12O) is formed. ‘D’ reacted with hydroxylamine hydrochloride to give ‘E’ and ‘F’ having
molecular formula (C11H13NO). ‘E’ on heating with small amount of H2SO4 produced G which on hydrolysis
produced ‘H’. F under the same treatment yields I and J compounds respectively. E, F, G and I all are
isomeric and have molecular formula (C11H13NO). H have two hydrogen atom while J have only one
hydrogen atom. Identify compounds A to J. ‘H’ on reaction with SOCl2 followed by treatment with anhydrous
AlCl3 gives the following compound ‘X’.
X=
13. A compound has two isomers (A) and (B) of formula C5H10O. Isomer (A) on treating with NaOH (aq.) gives 2,
2-dimethylpropan-1-ol and 2, 2-dimethylpropanic acid salt. The isomer (B) on treating with NaOH (aq.) gives
3-hydroxy, 2-propylheptanal. What are A and B ?
(1) B H
2 6 HCl, ZnCl2 2
Mg / Et O
(1) Ph CHO
14. A B C CH3CH2CH2MgCl
D
( 2) H2O2 / OH ¯ ( 2) H3O ,
15. An organic compound (A) C4H9Cl on reaction with aqueous KOH gives (B). (A) on reaction with alcoholic
KOH gives (C) which is also formed on passing the vapours of (B) over heated copper. The compound (C)
readily decolourise bromine water. Ozonolysis of (C) gives two compounds (D) and (E). Compound (D) reacts
with NH2OH to give (F) and compound (E) reacts with NaOH to give an alcohol (G) and sodium salt (H) of an
acid. (D) can also be prepared from propyne on treatment with water in presence of Hg+2 and H2SO4. Indentify
(A) to (H) with proper reasoning.
CH3
|
(i) CH3 CHMgBr (ii ) H O / H Conc.H2SO 4
19. CH3CHO 2 A B
H O18 / H
C 2 D
20.
H O H SO 1. BH / THF
21. OH
Me2C = O + HCN
2
B
A 3
4
C 3 D.
2. H2O2 , OH ¯
22. An organic compound (A) C9H10O reacts with NH2OH to give two isomers B & C with same moleculer formula
C9H10ON.The compound B and C isomerizes to D and E respectively on treating with small amount of H2SO4.
Compound (F) C8H8O2 is formed either by (A) on treating with I2/KOH followed by acidification or by acid
hydrolysis of (D). Hydrolysis of (E) gives ortho–methylaniline. identify the structure from (A) to (E).
23. Compound A to D do not gives tollens test however compound C does. Give the structure of A to D.
HO CH2 CH2 OH Mg / Et 2O
4-bromobutanal HA (C H O Br)
6 11
1 2
(C6H111MgO2Br)
A B
CH3 OH,HA
(C7H14O2) (C6H12O2) [Solomon]
D C
24. Acetophenone on reaction with hydroxylamine hydrochloride can produce two isomeric oximes. Write structure
of the oximes. [JEE-97, 2M]
25. Complete the following giving the structures of the principal organic products. [JEE-97, 8M]
26. How many asymmetric cabon atoms are created during the complete reduction of benzil (PhCOCOPh) with
LiAlH4 ? Also write the number of possible stereoisomer of the possible product. [JEE 97, 3M]
MeMgBr
27. [JEE 97, 2M]
29. An aldehyde (A) (C11H8O), 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 compound
(A) and (B). [JEE-98, 2M]
30. Write the intermediate steps for each of the following reactions [JEE-98, 2M]
3 H O
C6H5CH(OH)C CH C H CH = CHCHO
6 5
A (i) LiAlH
4
31. B [JEE 98, 2M]
(ii) H ,
32. The compound X does not show any stereoisomerism. On oxidative ozonolysis it produces Formic acid and
Y. With HIO4 oxidation, Y forms only acetic acid. X on reaction with 1 mole of Br2 (with moderate heating)
forms most stable major product ‘Z’. Report molecular weight of ‘X’ and report whether ‘Z’ will show
stereoisomerism or not.
32. Compound ‘A’ (C8H8O) on treatment with NH2OH . HCl gives ‘B’ and ‘C’ . ‘B’ and ‘C’ rearrange to give ‘D’ and
‘E’ respectively on treatment with acid . ‘B’ , ‘C’ , ‘D’ , and ‘E’ are all isomers of molecular formula C8H9NO
. When ‘D’ is boiled with alcoholic KOH , an oil ‘F’ (C6H7N) separates out . ‘F’ reacts rapidly with CH3COCl to
give back ‘D’ . ‘E’ on boiling with alkali , followed by acidification gives a white solid ‘G’ (C7H6O2) Identify ‘A’
to ‘G’. [JEE-99, 7M]
33. Carry out the following transformation in not more than three steps : [JEE 99, 2M]
O
||
CH3 – CH2 – C C – H CH3 – CH2 – CH2 – C – CH3
35. Two different Grignard reagents, (X) and (Y) produce C6H5CH2C(CH3)2OH on reaction with (P) and (Q)
respectively. Give structures of (X), (Y), (P) and (Q). [REE 2000, 2M]
H
36. A [JEE 2000, 2M]
38. Identify A, B & C and give their structures : [JEE 2000, 3M]
Br
2 H
A + B
C (C7H12O)
NaOH,
39. An organic compound (A), C8H4O3, in dry benzene in the presence of anhydrous AlCl3 gives compound (B).
The compound (B) on treatment with PCl5, followed by reaction with H2 / Pd(BaSO4) gives compound (C),
which on reaction with hydrazine gives a cyclised compound (D) (C14H10N2). Identify (A), (B), (C) and (D).
Explain the formation of (D) from (C). [JEE 2000, 5M]
40. An organic compound A, C6H10O, on reaction with CH3MgBr followed by acid treatment gives compound B.
The compound B on ozonolysis gives compound C, which in presence of a base gives 1-acetyl cyclopentene
D. The compound B on reaction with HBr gives compound E. Write the structures of A, B, C and E. Show
how D is formed from C. [JEE 2000, 5M]
Matching :
41. Match the compounds/ ions in column I with their properties/reactions in column II.
Column-I Column-II
(A) CH3 – CH = O (p) Redox-reaction
(B) (q) Precipitate with Tollen`s reagent
44.
(B) + OH (q) Carbanion intermediate
Na / alcohol
(C) CH3COCH3 (r) Free radical intermediate
(D) PhCOCH3 + O H (s) Aldol reaction
48. Column – I Column – II
(A) + C N (p) Nucleophilic addition
HCl
(B) + NH2 –NH2 (q) Nucleophilic addition elimination
KOH
(C) + NH2 –NH2 (r) Reduction
2 D O
(D) + O D (s) -substitution
Excess
1. (A) (B)
(D) (E)
(C) (D)
(D) (E)
6.
D = CH3 – C C – CH3 E= F=
G =
9. (A) C 6H5 – C C – H (B)
11. (1) (A) forms phenyl hydrazone and thus carbonyl compound, i.e., an aldehyde or ketone.
(2) (A) give s negative Tollen’s reagent test and thus (A) is ketone.
(3) (A) also does not respond Iodoform test and thus it is not methyl ketone.
(4) (A) on reduction gives n-pentane and thus, (A) is straight chain compound.
(5) Keeping in view of above facts and the formula of (A), i.e., C5H10O, (A) is
NH OH / HCl
2 +
H SO HO
2
4
2 HOOC CH2 CH2 CH2 CH NH2
|
Ph
(E) (G) (H)
H SO HO
2
4
2 H2N CH2 CH2 CH2 CH COOH
|
Ph
(F) (I) (J)
13. (A) (CH3 )3 CCHO (B) CH3 CH2CH2 CH2CH CH2 CHO
2,2 dim ethylpropa nal || |
O CH2 CH2CH3
(Pen tan 1 al )
14. (A) CH3CH = CH2 (B) CH3CH2CH2OH (C) CH3CH2CH2Cl (D) PhCH = CHCH2CH3
(C) (D)
(E) CHI3
OH OH
| |
21. (A) CH3 C CN (B) CH3 C COOH (C) CH2 C COOH (D) HOCH2 CH COOH
| | | |
CH3 CH3 CH3 CH3
O CH3
(C) (D)
HCl
24.
H2O
It shows two isomers which are geometrical isomers to each other and represented as follow :
C6H5 C6H5 OH
(i) C=N (ii) C=N
CH3 OH CH3
Syn-methyl anti-Syn-phenyl Syn-phenyl anti Syn-methyl
Ketoxime Ketoxime
O
Presence of acid
||
or CH3 C NH C 6H5
PCl5
or Acid anhydride
N phenyl acetamide
O
Pr esence of acid ||
or PCl 5
C 6H5 NH C CH3
or
Acid anhydride
N phenyl acetamide
(c) (d)
* *
26. Ph CH CH Ph
| |
OH OH
two chiral C atoms ; total 3 isomers :
27. 28.
CHO CHO
Ozonolysis
29. A = + | |
COOH COOH
Two moles
CHO
| Ag O COOH
B = 2 | oxalic acid
COOH
(B) COOH
OH
| H3O
30. C 6H5 CH C CH
H2 O
OH
O
C6H5 – C H – C CH C6H5 – CH = C = C H
( C 6H5 CHO )
(A ) (i ) LiAlH
31. 4
Base
Rearrangement
O3 HIO 4
32. X HCOOH + Y CH3COOH
So Y = CH3 – C – C – CH3
O O
X = CH3 – C – C – CH3
CH2 CH2
Z = CH 3 – C C – CH 3 (1,4 Addition)
CH2Br CH2Br
A= B=
O
||
C= D = CH3 C NH C6H5
O O
|| ||
E = C 6H5 C NH CH3 F = C6H5 – NH2 G = C 6H5 C O H
O
||
Na CH3 X BH3 / THF
33.
CH3CH2C CH CH3CH2C CNa
CH3CH2C CCH3 CH3 CH2CH2 CCH3
H2O 2 , OH ¯
O
||
CH3 – CH2 – CH2 – CH = O CH3 CH2CH2 CCH3
34.
CH3
|
+ CH3 C CH2 C 6H5
|
OH
CH3
|
CH3 C CH2 C 6H5
|
OH
40. A= ,B=
O
||
(a) Cl C CH2 C Cl (b) (c) Ph CH2 C Cl (d) Ph C Cl
|| || ||
O O O
O
||
H O
CH3 – C – Cl 2
r2
O
||
CH3 – C – Br H O
2
r3
O
|| H O
CH3 – C – I 2
r4
Identify the order of the rate of reaction r1, r2, r3 and r4, give reason.
B-3. Predict the products of the following reactions
(i) +
O
||
(ii) Ph C Cl +
O
||
AlCl3
(iii) CH3 – CH2 – C – Cl + Ph — H
H / Pd / C
(iv) 2
Quinoline fDouksyhu
NaOH
(a) (b) heat
H2O
2 HO
(c) + H2SO4 (d) +
D-2. Write balanced equation, having all the organic product , for the reaction of phenylacetamide with
(a) hot HCl (aq) (b) hot NaOH (aq)
D-3. What products would you expect from acidic & basic hydrolysis of each of the following amides ?
(a) N,N - Diethylbenzamide
(b)
(c)
H
(a) +
(b) + CH3NH2
H
(c) + CH3–CH2–OH (d) + AlCl
3
H O, acetic acid
A-3. 2
Product is :
H2SO 4heat
A-4. X Y
(i) P / Br
2
A-6. X, X is :
(ii) H2O
A-7. A, A is : A gS :
I. II.
III. NO2–CH2–COOH IV. HOOC–CH2–COOH
(A) III > I > IV > II (B) I > III > IV > II (C) III > IV > I > II (D) I > IV > III > II
Section (B) : Acid Halide
B-1.* The correct order/s of decreasing reactivity of the given compound towards hydrolysis under identical condition
is/are :
(A) CH3COCl > CH3CONH2 (B) CH3COCl > (CH3CO)2O
(C) CH3COOCH3 > CH3COCl (D) (CH3CO)2O > CH3CONH2
3 NH
B-2. Phosgene (COCl2) + 1 mol C2H5OH X, X is
O
||
H O
B-3. (CH3 )3 C C Cl + LiAlH4 (excess) (vkf/kD;) 3 X, X is : (X gS :)
+ LiAlH4 X,
O CH3
|| |
(A) (CH3 )3 C C H (B) CH3 C CH2 OH
|
CH3
(C) CH3 CH CH2 CH2 OH (D) CH3 – CH2 – CH2 – CH2 – CH2 – OH
|
CH3
A is gSA
(A) CH2=CH–OCH3 (B) CH2=CHOH (C) (CH2=CH)2CuLi (D) (CH2=CH)2Cl
O
||
B-5. PhCH2 C Cl CH3 CH2 SH X, X is
O O
|| ||
(A) Ph C S CH CH3 (B) Ph CH2 C S C 2H5
|
CH3
O O
|| ||
(C) CH3 CH2 CH2 C S Ph (D) CH3 CH C S Ph
|
CH3
O
||
B-6. + Cl C Cl X, X is gSA
O
NH
C
(A) (B) (C) (D)
C O
||
O
Section (C) : Ester
C-1. List the following esters in order of decreasing reactivity in the second step of a nucleophilic acyl substitution
reaction .
(A) IV > I > III > II (B) IV > III > I > II (C) III > IV > I > II (D) II > I > III > IV
C-2. Which one of the following is least reactive for hydrolysis reaction?
(A) (B)
(C) (D)
C-3. Which one of the following esters is most reactive for saponification ?
C-4.* Which of the following is not the correct order of esterification of following acids with CH3OH :
HCOOH , CH3 COOH , CH3 – CH2 – COOH , , is
I II III IV
(A) I = II = III = IV (B) I > II > III > IV (C) I < II < III < IV(D) I > IV > III > II
ethanol, H2SO 4
C-5. X, X is :
ethanol, H2SO 4
X, X gS
%
(A) (B)
(C) (D)
, [X] is gSA
(A) (B)
3 ¯ OCH
C-7.
X, X is
CH3OH
O O
|| ||
(A) H3 CO C (CH2 )5 OH (B) H3 CO C CH CH2 CH2 CH2 OH
|
CH3
O O
|| ||
(C) H3 CO C CH2 CH CH2 CH2 OH (D) H3 CO C CH2 CH2 CH CH2 OH
| |
CH3 CH3
CH NH
3 2
C-9.
X, X is
heat
(A) (B)
(C) (D)
[P] will be
(A) (B)
(C) (D)
(1) LiAlH4
D-1. X, X is
( 2) H2O
I II
III IV
O O -
15 OH, Br 2, heat
D-3.* – C – NH2 + – CH2 – C – NH2 X+Y
15 15
NH2 CH2 – NH2 CH2 – NH2 CH2 – NH2
15 15
CH2 – NH2 NH2 NH2 NH2
(A) (B)
E-3. + X, X is
LiAlH
4 PCC
2 2 NH – NH
E-4. A B C, Product (C) is
5. (a) List three reagents for converting a carboxylic acid to its acyl chloride.
(b) Select the most convenient of the three reagents, give a reason for your choice and write a balanced
equation for its reaction with R—COOH.
(i) PCl (excess)
SOCl2 OH ¯H / Pd / BaSO
6. 3
CH3COOH (X)
(Y) 2
4
(Z) W + S
(ii) H2O
9. A + B, find A and B.
Section D : Amide
10. The respective boiling points and molecular weights (in/gmol) of the following amides are : MeCONH2, 221ºC
and 59; MeCONHMe, 204ºC and 73 ; MeCONMe2, 165ºC and 87. Explain.
11. An organic compound (A) C4H7N does not react with acetyl chloride or nitrous acid. (A) when boiled with
acetic acid gave another compound B (C6H11O2N) and on reduction with lithium aluminium hydride formed C
(C4H11N). Compound (C) liberates nitrogen with nitrous acid. Identify compound (A) , (B) and (C).
12. Both cis- and trans-1,2-cyclohexanedicarboxylic acids form anhydrides on heating, but the anhydride formed
from the cis-1,2-cyclopentanedicarboxylic acid only. explain.
Section E: Anhydride
13. Complete the folliowing reaction
(a) Toluene + phthalic anhydride + AlCl3 (b) Product from (a) + Conc. H2SO4 +
14. Give the product of each of the following reactions :
PCl3 MeNH 2
(a) succinic anhydride + MeOH A B
C,
300 ºC
(b) phthalic acid + NH3 D E ,
(c) MeCH(CH2COOH)2 (CH3CO2 )O
F..
15. An organic compound A, C4H4O3, in dry benzene in the presence of anhydrous AlCl3 gives compound B.
The compound B on treatment with PCl5, followed by reaction with H2/Pd(BaSO4) gives compound C, which
on reaction with hydrazine gives a cyclised compound D (C10H10N2). Identify A,B,C and D. Explain the forma-
tion of D from C.
(A) (B)
(C) (D)
2. When picric acid is treated with aqueous sodium bicarbonate a gas is liberated with effervesence.
The gas evolved would be :
(A) H2 (B) CO2 (C) 14CO2 (D) NO2
3.
(A) (B)
(C) (D)
CH3 – COOH P
(A)
(B)
(C)
(D)
12. Q.
(A) (B)
(C) (D)
14. In the given reaction
(A) x is (B) y is
Conc .HI
16.
P the producet P is.
excess
is
(i) KCN
(A)
(ii)H3O
(B)
(C)
(D)
C6H5–CN A B C, (C) is
O
||
NaOH
21. H2N NH2 Ph C Cl (excess) X, X is
O O O O O
|| || || || ||
(A) H C NH Ph (B) Ph C NH OH (C) Ph C NH2 (D) Ph C NH NH C Ph
Pyridine
22. +
X, X is
(A) (B)
(C) (D)
140C
23. + CH3CH2CH2CH2NH2 X,
H/ H O
2
[P], [P] will be :
, [X] is
EtO ¯
27.
X
EtOH
(A) X is (B) X is
(C) X is (D) X is
(A) (B)
(C) (D)
29. x , x is
acetaldehyde + X.
32.
NaOH /
33. X, X is gSA
HO 2
NH 3 / KOBr HNO2
34. X B C
(CH3)3 C – OH, X is:
(A) (CH3)3C – COOH (B) (CH3)3C – CH2O (C) (CH3)3C – CONH2 (D) none is true
CH3 O
| || Br2, NaOH
35. PhCH2 CH CH2 C NH2 X, X is
CH3 CH3
| |
(A) CH3 CH CH2 NH Ph (B) Ph CH2 CH CH NH2
|
OH
37. X, X is :
COOH
CH3 COOH
| OH
(A) CH3 – CH2 – CH2 – CH2 – OH > CH3 C OH (B) <
|
CH3 OH
Cl
Cl
Cl H3C H H3C COOH
(C) < (D) C C > C C
H COOH H H
Cl
39. The correct reagent sequence for the following conversion
, is
(A) (B)
(C) (D)
40. The correct order/s for the given pair of isomers is / are
1. Column-I Column-II
PART - II : COMPREHENSION
+ ..
O OH OH O
H
OH O
CH3–C CH3–C + Pr H Step 3
Step 1. CH3–C CH3–C–OH CH3–C–O–CH 2–CH 2–CH 3
OH Step 2
–H
OH OH +O –H2O
Pr H
O CH3
CH3
Type. 2 CH3–C + CH3–C–OH
Conc. H2SO4
CH3–C–O–C–CH3
OH CH3
CH3 O
..
O–H
CH3 CH3 CH3 –C CH3
H O
Mechanism CH3–C–OH CH3–C + + H2O CH3–C–O–C–CH3
Step 1.
CH3 CH3 O
CH 3
18
3. Conc. H2SO4
CH3–COOH + C2H5OH (P)
18
Conc. H SO
CH3–COOH + (CH3)3C–OH 2
4
(Q)
In the above reaction (P) and (Q) are respectively :
O O CH3 O O CH3
18 18
(A) CH3–C–O–C2H5 , CH3–C–O–C–CH3 (B) CH3–C–O–C2H5 , CH3–C–O–C–CH3
CH3 CH3
O O CH3 O O CH3
18 18 18
(C) C2H5–C–O–CH3 , CH3–C–O–C–CH3 (D) CH3–C–O–C2H5 , CH –C–O–C–CH
3 3
CH3 CH3
H
D OH
4. CH3COOH + Conc. H2SO4
(X)
CH3
CH3
Ph–C–OH Conc. H2SO4
CH3–COOH + (Y)
C2H5
(A) (X) is optically active while (Y) is optically inactive (B) Both (X) and (Y) are optically active
(C) Both (X) and (Y) are optically inactive (D) (X) is optically inactive while (Y) is optically active.
5. (+) Octan-2-ol esterifies with Acetic acid to give optically inactive racemised product. It must have gone by
(A) Type I mechanism (B) Type II mechanism
(C) Mix type I and type II mechanism (D) More by type I and less by type II mechanism
Comprehension - 2
Observe the following sequence of reaction and answer the questions based on it
Phenylacetylene x y z w
6. Compound z is
(A) (B)
(C) (D)
7. Which of the following statement is not correct
(A) y decolourises Br2 /H2O solution (B) on heating z CO2 is liberated
(C) w on reaction with NaOI gives yellow ppt (D) x liberates H2 gas with Na metal
8. Which of the following compound give benzoic acid on KMnO4 oxidation
(A) w (B) y (C) z (D) all.
Comprehension - 3
Hoffmann rearrangement
In the Hofmann rearrangement an unsubstituted amide is treated with sodium hydroxide and bromine to give
a primary amine that has one carbon lesser than starting amide.
General reaction :
OH
CO2R– NH
R – NH2
If the migrating group is chiral then its cofiguration is retained. Electron releasing effects in the migrating
group increases reactivity of Hofmann rearrangement.
(A) (B)
(C) (D)
10. Arrange the following amides according to their relative reactivity when reacted with Br2 in excess of strong
base
(A) IV > I > II > III (B) II > I > III > IV (C) II > IV . III > I (D) II > I > IV > III
11. + Products
Comprehension - 4
14. +
(C) + (D) +
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
17. Statement-1 :
18. Statement-1 : Acyl chloride undergo nucleophilic attack more rapidly than an alkyl chloride.
Statement-2 : The transition state of the acid derivative leading to the tetrahedral intermediate is less
sterically hindered than transition state in SN2 reaction of alkyl halide.
19. Statement-1 : The reaction of CH3SO2Cl with optically active 2-butanol gives an active methanesulphonate
which is treated with aq.NaOH giving back 2-butanol but having opposite configuration.
2. Which of the following carboxylic acids undergoes decarboxylation easily. Explain briefly. [JEE 95, 2M]
(A) C6H5 – CO – CH2 – COOH (B) C6H5 – CO – COOH
3. The molecular weight of benzoic acid in benzene as determined by depression in freezing point method
corresponds to : [JEE 96]
(A) ionization of benzoic acid (B) dimerization of benzoic acid
(B) trimerization of the benzoic acid (D) solvation of benzoic acid
4. A compound D(C8H10O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The filtrate
on acidification gives a white solid E (C7H6O2). Write the structures of D.E and explain the formation of E.
[JEE 96]
5. Complete the following giving the structures of the principal organic products. [JEE 97]
6. An ester A (C4H8O2), on treatment with excess methylmagnesium chloride followed by acidification, gives an
alcohol as the sole organic product. Alcohol B, on oxidation with NaOCl followed by acidification, gives
acetic acid. Deduce the structures of A and B. Show the reaction involved. [JEE 98]
7. Following reactions gives two products. Write the structure of the products.
8. Explain briefly the formation of the products giving the structures of the intermediates.
O
||
i. OH ¯ /
ii. H
H3 C CH C OH [JEE 99,5/120]
|
CH2 C OH
||
O
9. When propionic acid is treated with aqueous sodium bicarbonate, CO2 is liberated. The ‘C’ of CO2 comes
from : [JEE 99, 2/80]
(A) methyl group (B) carboxylic group (C) methylene group (D) bicarbonate
10. An organic compound A, C8H4O3, in dry benzene in the presence of anhydrous AlCl3 gives compound B. The
compound B treatment with PCl5, following by reaction with H2 / Pd(BaSO4) gives compound C, which on the
hydrazine gives a cyclised compound D (C14H10N2). Identify A, B, C and D. Explain the formation of D from C.
[JEE 2000, 5/100]
11. Which of the following acids has the smallest dissociation constant ? [JEE 2002, 1/35]
(A) CH3CHFCOOH (B) FCH2CH2COOH (C) BrCH2CH2COOH (D) CH3CHBrCOOH
12. There is a solution of p-hydroxy benzoic acid and p-amino benzoic acid. Discuss one method by which we
can separate them and also write down the confirmatory test of the functional groups present.
13. Statement-1 : Acetate ion is more basic than the methoxide ion.
Statement-2 : The acetate ion is resonance stabilized. [JEE-2004, 3/84]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
14. In conversion of 2-butanone to propanoic acid which reagent is used. [JEE-2005, 3/84]
(A) NaOH, NaI / (B) Fehling solution (C) NaOH, I2 / (D) Tollen's reagent
Passage
X
(A) + (B) +
(C) + (D) +
18. Statement-1 : p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid.
Statement-2 : o-Hydroxybenzoic acid has intramolecular hydrogen bonding.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True. [JEE 2007,3/162]
(A) (B)
(C) (D)
OCOCH3
COOH
(A) CH3 CHCOOH (B) CH2CH2 COOH (C) CH2 = CHCOOH (D) CH2CHCOOH
| | | |
OH OH Cl OH
6. p-cresol reacts with chloroform in alkaline medium to give the compound A which adds hydrogen cyanide to
form, the compound B. The latter on acidic hydrolysis gives chiral carboxylic acid. The structure of the
carboxylic acid is : [AIEEE-2005]
CH3 CH3
CH2COOH
(A) (B)
CH2COOH
OH OH
CH3 CH3
CH(OH)COOH
(C) CH(OH)COOH
(D)
OH OH
7. An organic compound having molecular mass 60 is found to to contain C = 20%, H = 6.67% and N = 46.67%
while rest is oxygen. On heating it gives NH3 alongwith a solid resdue. The solid residue give violet colour with
alkaline copper sulphate solution. The compound is : [AIEEE-2005]
(A) CH3CH2CONH2 (B) (NH2)2CO (C) CH3CONH2 (D) CH3NCO
8. A liquid was mixed with ethanol and a drop of concentrated H2SO4 was added. A compound with a fruity smell
was formed. The liquid was : [AIEEE-2009]
(A) HCHO (B) CH3COCH3 (C) CH3COOH (D) CH3OH
Exercise - 1
PART : I
O
||
E-2. (a) + CH3COOH (b) CH3 — NH — C — CH3 + CH3COOH
(c) (d)
PART - II
A-1. (C) A-2.* (B, C, D) A-3. (A) A-4. (B) A-5. (A)
A-6. (D) A-7. (A) A-8. (B) A-9. (D)
B-1.* (A, B, D) B-2. (D) B-3. (B) B-4. (C) B-5. (B)
B-6. (D)
C-1. (A) C-2. (B) C-3. (A) C-4.* (A, B, D) C-5. (C)
C-6. (C) C-7. (A) C-8. (B) C-9. (C) C-10. (B)
D-1. (A) D-2. (B) D-3.* (B, C, D) D-4. (B)
E-1.* (B, C, D) E-2. (C) E-3. (A)
LiAlH
4 PCC
2 2 NH – NH
E-4. A B C, Product (C) is
EXERCISE - 2
PART - I
O
|| 14
14 14 14 14 14
2. X CH3 – CN y CH3 – COOH z CH3 – C – C H3
(b) D = E= (c) F=
PART - II
1. (C) 2. (C) 3. (C) 4. (C) 5. (B)
6. (B) 7. (D) 8. (A) 9. (A) 10. (B)
11. (C) 12. (B) 13. (C) 14. (A) 15. (D)
16. (B) 17. (A) 18. (A) 19. (C) 20. (A)
21. (D) 22. (C) 23. (C) 24. (A) 25. (D)
26. (C) 27. (B) 28. (A) 29. (D) 30. (C)
31. (C) 32. (C) 33. (A) 34. (A) 35. (C)
36. (C) 37. (B) 38. (C, D) 39. (B, D) 40. (B, D)
EXERCISE - 3
1. (A) - (s) ; (B) - (q, s) ; (C) - (p, s) ; (D) - (p, r, s)
2. (A) - (p,s) ; (B) - (q,s) ; (C) - (p, s) ; (D) - (r)
3. (B) 4. (A) 5. (B) 6. (C) 7. (D)
8. (D) 9. (B) 10. (D) 11. (B) 12. (A)
13. (B) 14. (C) 15. (A) 16. (A) 17. (A)
18. (A) 19. (A) 20. (B) 21. (D)
22. (A) 23. (A) 24. (A)
25._ (T) 26._ (T) 27._ (F) 28._ (T) 29._ (T)
30._ Glacial 31._ Weaker de
EXERCISE - 4
PART - I
2. (A) 3. (B)
8. First, anion of Malonic ester is formed which attacks as a nucleophile on the other reagent.
9. When propionic acid is treated with aqueous sodium bicarbonate, CO2 is liberated. The ‘C’ of CO2 comes
from : [JEE 99, 2/80]
(A) methyl group (B) carboxylic group (C) methylene group (D) bicarbonate
11. (C)
12. +
Neutral FeCl3
Test : (1) Violet blue ppt.
13. (D) 14. (C) 15. (B) 16. (D) 17. (A)
18. (D) 19. (C)
PART - II
OC 2H5
dil. HCl
| (catalyst )
1. H3 C C OC 2H5 H2O X + Y (Alcohol)
|
OC 2H5
O O
|| ||
(A) X = CH3 C O C 2H5 (B) X = CH3 CH2 C O CH3
2. X,
O
||
H3 O
C 2H5 O C OC 2H5 + EtMgBr (large excess)
3. X, X is
KOH 2 PhCH Cl
6.
X, X is,
(A) (B)
(C) (D)
O
||
KOH (1 equiv.)
7. CH3 CH2 C OH X, X is, gS
(A) (B)
(C) (D)
1. LiAlD
4
8. X, X is gS
2. H2O
1. THF
9. + BrMgCH2CH2CH2CH2MgBr X,
2. H3O
(A) (B)
(C) (D)
CH2OH
10. R?
HO
H SO ( cat.)
11. 2
4
X,
O CH3 O
|| | ||
(A) Ph CH2 CH O C Ph (B) Ph C O C Ph
| |
CH3 CH3
Ph O Ph O
| || | ||
(C) Ph C O C CH3 (D) Ph CH CH2 O C CH3
|
CH3
O
|| (1) H3 O ,
LiAlH4
13. C 2H5 O C (CH2 )2 CN (excess
X,
) ( 2) ¯OH
1. PhMgBr
14. H2C = CHCH2CN
X,
2. H
Ph Ph
| |
(A) CH3 C CH CHO (B) CH2 CH CH CHO
( i ) CH MgBr (1 equiv )
3
P,,
( ii) H 2 O / H
(A) (B)
(C) (D)
P O MeMgBr
Ca ( OH)2 ,I2
16. 4 10
P
Q R, compound R is
H3O
18. H O
3
BH .THF
3 I2 / NaOH
20. H2O 2 .OH–
X,
H
24. A,
26. When RCOOH reacts with NaHCO3, CO2 is formed. CO2 contains carbon of
(A) RCOOH (B) NaHCO3 (C) Both (D) none
27. Consider following reactions
LiAlH4 LiAlH( t BuO)3
I H .Pd / BaSO
2
4 , II , III
(i) CH CH O
28. . + 3 2
A,
(ii) H
29.
Reactivity order of different nucleophiles (NH2– CH3COO–, OH) is in order :
(A) NH2– < CHC O O– < OH– (B) CH3COO– < OH– < NH2–
(C) NH2– < OH– < CH3COO– (D) CH3COO– < NH2 < OH–
CH OH
3
31. A, A is gSA
32. Give the structure of the expected product of the following reaction :
+ CH3NH2
product.
+ CH3OH H [X] is :
(excess )
C is gSA
(B) – – –CH2–CHO
(C) – – –CH2–
(D) –CH2–CHO
SOCl
2 (CH – CH ) Cd
A 3 22 B
Pyridine
B will be :
O Cl
H–O–N
LiAlH 4
O ?
O
O O
CH2OH
CH2OH NH2
CH2OH NH2
NH2 OH
O OH
(A) (B) (C) CH3CH2OH (D) H CH2 – OH
O O
HO OH CH2 – OH H
O
39. Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction because :
(A) group of benzoyl chloride is in conjugation with benzene ring. This makes benzoyl chloride more
stable than acyl chloride.
(B) CH3 group of acetyl chloride makes C–Cl bond stronger due to the + I effect.
(C) C6H5– group of benzoyl chloride makes C–Cl bond weaker due to + R effect.
(D) CH3–group makes C–Cl bond weaker due to + I effect and C6H5 group makes C–Cl bond stronger due to
– I effect.
PART - II SUBJECTIVE QUESTIONS
KOH (alc .) 2
Hg NH2OH
[C] [D] [E] [F]
Followed by NaNH2 dil. H2SO 4 H
Hydrolysis Heat
[B]
Dicarboxylic acid [C]
A
Acid 150 ºC
[A ] C H6 [C]
CH4 CH3Br 6 [B]
AlCl3 (anhyd .)
6. An organic compound ‘A’ on treatment with ethyl alcohol gives carboxylic acid ‘B’ and compound ‘C’. Hydrolysis
of ‘C’ under acidic conditions give ‘B’ and ‘D’. oxidation of ‘D’ with KMnO4 also gives B.B on heating with
Ca(OH)2 gives E with molecular formula C3H6O. E does not give Tollen’s test or reduce Fehling solution but
forms 2, 4-Dinitrophenyl hydrazone. Identify A, B, C, D, E.
7. When a gas A is passed through dry KOH at low temperature, a deep red coloured compound B and a gas
C are obtained. The gas A on reaction with but-2-ene followed by treatement with Zn/H2O yields acetaldehyde.
Identify A, B, C.
8. Complete the following sequence of reactions with appropriate structures.
P / Br2 ( i) KOH ( alc .)
CH3CH2COOH (A) (B).
( ii) H
9. An acidic compound (A), C4H6O3 looses its optical activity on strong heating yielding (B), C4H6O2 which
reacts readily with KMnO4 and decolourises it. (B) forms a derivative (C) with SOCl2 which on reaction with
(CH3)2 NH gives (D). The compound (A) also forms unstable compound (E) on treatment with dilute chromic
acid (E) decarboxylate readily to give (F) C3H6O which on treatment with amalgamated zinc and HCl gives
hydrocarbon (G). Give structures of (A) to (G).
PART - II
Br
|
1. (A) = CH3CH2CH2OH ; (B) = CH3CH = CH2 ; (C) = CH3CH — CH2Br ;
O
||
(D) = CH3C CH ; (E) = CH3 — C — CH3 ; (F) = CH3 — C — CH3
||
N – OH
O
||
3. A is CH3CH2CH2C — OC2H5 (Ethyl butanoate)
B is C2H5OH (Ethanol)
C is CH3CH2CH2CH2OH (1-Butanol)
D is CH3CHO (Ethanal)
O O O
|| || ||
6. (A) = CH3 — C — O — C — CH3 ; (B) = CH 3 C — OH
O O
|| ||
(C) = C 2H5 OC — CH3 ; (D) = CH3COOH + C2H5OH ; (E) = CH3 — C — CH3
1
(C) = O2
2
9. (A) = ; (B) =
(C) = ; (D) =