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Orm Iv
Orm Iv
CONTENTS
Particular Page No.
Theory 01 –06
Exercise - 1 07 – 11
Part - I : Subjective Questions
Part - II : Only One Option Correct Type
EX
Part - III : Match the Columns
Exercise - 2 12 – 17
Part - I : Only One Option Correct Type
Part - II : Single or Double Digit Integer Type Questions
Part - III : One or More Than One Options Correct Type
Part - IV : Comprehensions
Answers 18 – 19
JEE(Advanced) Syllabus
Alkyl Halide : Nucleophilic substitution reactions of alkyl halides; Rearrangement reactions of alkyl
carbocation, Preparation of alkenes and alkynes by elimination reactions.
O
Haloarenes : Nucleophilic aromatic substitution in haloarenes and substituted haloarenes (excluding
Benzyne mechanism and Cine substitution).
Alcohols: Esterification, dehydration, reaction with sodium, phosphorus halides, ZnCl2/concentrated HCl.
Ethers : Preparation by Williamson’s Synthesis.
JEE(Main) Syllabus
Organic Reaction Mechanisms : Organic Compounds with functional groups Containing Halogens (x).
C
Alkyl Halides : Nature of C–X bond in haloalkanes, physical and chemical properties, mechanism of
substitution reactions, elimination reactions and rearrangement reactions, reactivity of C–X bond in
haloalkanes.
Some commercially important compounds : Dichloro, trichloro and tetrachloromethanes; freons, BHC,
DDT, their uses and important reactions.
Organic compounds with functional groups containing oxygen
Alcohols & Ethers : Methods of preparation, physical and chemical properties;
Electronic structure, Structure of functional group, some commercially important compounds.
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Organic Reaction Mechanisms-IV
Elimination reactions:
In an elimination reaction two atoms or groups (YZ) are removed from the substrate and generally
resulting into formation of bond.
| |
Elimination
C C
YZ
| |
Y Z
EX
-elimination : When two groups are lost from the same carbon atom to give a carbene (or nitrene).
This is also called 1,1-elimination.
-elimination : When two groups are lost from adjacent atoms so that a new bond is formed. This is
also called 1,2-elimination.
D
–elimination : It is also called 1,3-elimination, In this a three membered ring is formed.
Step-1 :
Step-2 : + B –H
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Organic Reaction Mechanisms-IV
Characteristics of E1 reaction :
(i) It is unimolecular, two step process.
(ii) It is a first order reaction.
(iii) Reaction intermediate is carbocation, so rearrangment is possible
(iv) In the second step, a base abstracts a proton from the carbon atom adjacent to the carbocation,
and forms alkene.
Rate of E1 = 3º Alcohol > 2º Alcohol > 1º Alcohol.
Rate of reaction stability of carbocation
(v) Kinetics Rate [Alkyl halide]
Rate = k [Alkyl halide]
(vi) Energetics The free energy diagram for the E1 reaction is similar to that for the SN1 reaction.
EX
D
CH3
|
Ex-1. CH3 CH2 C CH3 +
|
Br
O
Ex-2.
Dehydration requires an acidic catalyst to protonate the hydroxyl group of the alcohol and convert it to a
good leaving group. Loss of water, followed by loss of proton, gives the alkene. An equilibrium is
established between reactants and products. For E1 mechanism reagents are :
(i) H3 PO4/
(ii) H2SO4 / 160º
| | | |
C C acid
C C + H2O (Rearrangement may occur)
| |
H OH
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Organic Reaction Mechanisms-IV
Mechanism :
Step-1 :
Step-2 : +
EX
Step-3 : +
Remarks :
In first step, an acid-base reaction a proton is rapidly transferred from the acid to one of the unshared
electon pairs of the alcohol.
In second step the carbon oxygen bond breaks. The leaving group is water molecule.
Finally, in third step the carbocation transfers a proton to a molecule of water. The result is the
formation of a hydronium ion and an alkene.
Reactivity of ROH : 3° > 2° > 1°
D
Ex-3.
O
CH2OH CH2
Conc.H2SO 4
Ex-4. +
(I)
Minor
C
Migration
H of bond H
Ex-5.
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Organic Reaction Mechanisms-IV
Conc. H2SO 4 /
Ex-6.
EX
Mechanism : + BH
Characteristics of E2 reaction
1. This is a single step, bimolecular reaction
2. It is a second order reaction
3. Kinetics Rate [R – X] [Base]
Rate = k [R – X] [ ]
D
4. Rearrangment is not possible
5. For the lower energy of activation, transition state must be stable
6. E2 follows a concerted mechanism
7. The orientation of proton & leaving group should be antiperiplanar.
8. Here –H is eliminated by base hence called elimination
9. Positional orientation of elimination In most E1 and E2 eliminations where there are two or more
possible elimination products, the product with the most highly substituted double bond will
O
predominate. This rule is called the saytzeff or zaitsev rule.
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Organic Reaction Mechanisms-IV
TS-2
TS-1
EX
Formation of the Hoffmann product
Bulky bases can also accomplish dehydrohalogenations that do not follow the Saytzeff rule. Due to
steric hindrance, a bulky base abstracts a less hindered proton, often the one that leads to formation of
the least highly substituted product, called the Hofmann product.
H CH3
| |
CH3 C C CH2
| | | +
H Br H
D
+
Hofmann product
Bulky base :
O
(CH3CH2)3N:
Triethylamine
C
Stereospecific E2 reactions
The E2 is stereospecific because it normally goes through an anti periplanar transition state. The
products are alkenes.
Ph Ph Base
H
Ph H CH3
Ph H
= = Ph Ph
H CH3 CH3 Ph
CH3 Ph H
Br H
Br
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Organic Reaction Mechanisms-IV
Ex-8. +
Ex-9. +
Ex-10.
EX
Ex-11. t BuO
+
Mechanism :
H
| |
CC X
Step-1 : (conjugate base)
| |
D
Step-2 : – C C –
| |
Remarks :
First step consists of the removal of a proton ( ) by a base generating a carbanion.
In second step carbanion looses a leaving group to form alkene.
Condition: For the E1cB, (i) substrate must be containing acidic hydrogens and (ii) poor leaving
O
groups.
Ex-12.
C
Ex-14. R2C = O +
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Organic Reaction Mechanisms-IV
EX
A-4. When 1-Bromo-1-methylcyclohexane is heated in ethanol for an extended period of time, three
products result: one ether and two alkenes. Predict the products of this reaction, and propose a
mechanism for their formation. Also, mention the major elimination product.
Section (B) : Bimolecular elimination reaction (E2)
B-1. A halide with formula C6H13I is found to give two isomeric alkenes 2-methyl-2-pentene and 4-methyl-2-
pentene on dehydrohalogenation with alcoholic KOH. Suggest its structure.
B-2.
D
Explain why more alkylated alkene is formed predominatly if base is , while less alkylated
alkene is obtained majorly when base is used.
B-3. Bromocyclodecane on heating with ethanolic KOH, produces two alkenes. Write the two products also
mention the major one.
B-4. Which alkyl chloride would yield following pure alkene on reaction with alcoholic KOH ?
O
CH3
|
(i) CH3 C CH2 (ii) CH3–CH2–CH2–CH=CH2 (iii) CH3 CH2 C CH2
|
CH3
B-5. Predict all the alkenes that would be formed by dehydrohalogenation of the following alkyl halides with
sodium ethoxide in ethanol and identify the major alkene :
C
(a) ? (b) ?
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Organic Reaction Mechanisms-IV
EX
CH3MgBr
(A) CH3–CHO CH3 CH CH3
H2O
|
OH
Conc. H2SO 4
(B) CH3 CH CH3 CH3–CH=CH2
|
OH
PBr3
(C) CH3–CH2–OH CH3–CH2–Br
NaNH2
(D) CH3–CH2–COOH CH3 –CH2–COONa + NH3
A-2. Correct statement for E1 Reaction is :
(A) It is a two step process. (B) Rearrangement is possible.
(C) Good leaving group favours (D) All of these
A-3. Intermediate formed during E1 reaction is –
D
(A) Carbocation (B) Carbanion (C) Free radical (D) Carbene
EtOH /
A-4. CH3–CH–CH–CH3 Major elimination product X.
CH3 Cl
X is %
CH3 CH3 C2H5 CH3CH3
O
(A) CH3–CH–CH=CH2 (B) CH3–C=CH–CH3 (C) CH3–C=CH2 (D) CH3–C C–CH3
Conc. H SO
A-5.
2 4
Major Product
Major product is :
Conc. H SO
A-6. In the given reaction : 2 4
[X] as major product
[X] will be :
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Organic Reaction Mechanisms-IV
EX
A-8. Which of the following does not representing the correct product
(A) (B)
(C) (D)
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Organic Reaction Mechanisms-IV
OH
(A) CH 3–C=CH–CH 3 (B) CH 3–CH–CH=CH 2 (C) CH 2=C–CH 2–CH 3 (D) CH3–CH–CH–CH3
CH 3 CH3 CH3 CH3
B-7.
EX
(A) and
(B) and
(C) Both
(D) Both
D
OH/
CH3—CH2—N—CH2—CH2—CH3
—
CH3
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Organic Reaction Mechanisms-IV
List I List II
EX
(Q) Alc. KOH (2) SN2
(R) H SO (3) E1
2 4
(S) (4) E2
H O
2
D
Codes :
P Q R S P Q R S
(A) 4 2 1 3 (B) 2 4 3 1
(C) 3 1 2 4 (D) 2 1 4 3
Ph–CH2–CH2– Br + Ph–CH=CH2
(A) (p) SN1
(t) E1cB
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Organic Reaction Mechanisms-IV
CH3
EX
|
C – Ph
|
OH
IV
(A) III > I > IV > II (B) III >IV > I > II (C) I > III > IV > II (D) IV > III > I > II
2. Which one of the following compound undergoes E1 reaction most readily ?
CH3
(A) CH3–C–CH2–CH3 (B) CH3–CH2–CH2–Br
Br
CH3
(C) CH3–CH2–CH2–I (D) CH3–C–CH2–CH3
D
I
CH3OH
3. In the given reaction, [X]
Cl
aq. Acetone Conc. H3PO4,
4. Product
Step-1 Step-2
Intermediates for both the steps are respectively ?
C
(A) II > I > III (B) II > III > I (C) I > III > II (D) I > II > III
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Organic Reaction Mechanisms-IV
6. Which of the following will undergo fastest elimination reaction with alcoholic KOH.
(A) (B)
(C) (D)
Identify the product of the following elimination reaction X and Y respectively with stereochemistry :
EX
Ph CH3 H 3C Ph Ph Ph H3C CH3
(A) C=C C=C (B) C=C C=C
H Ph H CH3 H CH3 H Ph
cis cis
Ph CH3 H3C CH3 Ph Ph H3C Ph
(C) C=C C=C (D) C=C C=C
H Ph H Ph H CH3 H CH3
trans cis cis trans
8. Which mechanism has different reactivity order of alkyl halides (1º, 2º, 3º) than others :
(A) SN1 (B) SN2 (C) E1 (D) E2
9. The correct order of SN2 / E2 ratio for the % yield of product of the following halide is :
(P) (Q)
D
(R) CH3 – CH2 – I (S)
(A) R > S > Q > P (B) R > Q > S > P (C) P > R > S > Q (D) Q > P > R > S
12. Predict the possible number of alkenes and the main alkene in the following reaction.
Product
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Organic Reaction Mechanisms-IV
2. If the starting material is labelled with deuterium as indicated, predict how many total deuterium atoms
will be present in the major elimination product ?
HO CD3 HO CH3
D D
Conc. H SO Conc. H2SO4
(a)
2 4
(b) D H
EX
3. The total number of alkenes possible by dehydrobromination of 3-bromo-3-methylhexane using
alcoholic KOH is :
OH
conc.H SO
4. In the given reaction : CH3–CH–CH–CH3
2 4
Alkenes
Ph
Total number of alkenes (Including stereo isomers) formed will be
Alc. KOH
5. Alkenes
the total number of possible alkenes in this elimination reaction is.
6. The difference of molecular weights of the major products P and Q form at the followng reactions is
D
OH
KOH/
(i) + CH3I P (organic product)
CH3
I
KOH/
(ii) + CH3CH2OH Q (organic product)
CH3
Calculate molecular mass [W] of product I and report your answer as N , where N = W 3.
2 5 C H OH
2-Bromo-1,1-dimethylcycopentane
2. Which of the following order is/are correct for the rate of E2 reaction ?
(A) 5-Bromocycloheptene > 4-Bromocycloheptene
(B) 2-Bromo-1-phenylbutane > 3-Bromo-1-phenylbutane
(C) 3-Bromocyclohexene > Bromocyclohexane
(D) 3-Bromo-2-methylpentane > 2-Bromo-4-methylpentane
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Organic Reaction Mechanisms-IV
3. Which of the following statement (s) is/are true about the following eliminations ?
t BuO EtO
(I) (II)
DMSO
(A) Hoffmann product is major product in I. (B) Saytzeff product is major product in I
(C) Hoffmann product is major product in II. (D) Saytzeff product is major product in II
(C) (D)
EX
5. Which of the following compounds can give E1cB reaction ?
(A) CF3–CHCl2 (B) C6H5 – CH– CH2F
NO2
(C) CH3–CH2–CH2Br (D) C6H5 – CH–CH2–CHO
OH
8. Which observation/s will be correct about the major products X and Y of the following reaction.
C
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Organic Reaction Mechanisms-IV
80% EtOH
10.
EX
What is / are true about above reaction ?
(A) Major product is given by SN1 reaction.
(B) Through E1 mechanism 3 alkenes are formed.
(C) 3-Methylpentan-3-ol is also formed as one of the product.
(D) Fractional distillation of elimination products will give two fractions.
PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
Alcohols undergo acid catalysed elimination reactions to produce alkenes. Because water is lost in the
elimination, this reaction is called dehydration reaction. Secondary and tertiary alcohols always give E1
reaction in dehydration. Primary alcohols whose -carbon is branched also give E1 reaction. The
reactivity of alcohol for elimination reaction is tertiary alcohol > Secondary alcohol > Primary alcohol.
D
1. Which of the following dehydration product (major) is incorrect ?
conc.H SO
(A)
2 4
conc.H SO
(B)
2 4
O
conc.H SO
(C) CH3CH2CH2CH2OH
2 4
CH3–CH=CH–CH3
conc.H SO
(D)
2 4
Product
(A) (B)
(C) (D)
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Organic Reaction Mechanisms-IV
Comprehension # 2
EX
(B) Only one transition state is formed in this reaction
(C) Walden inversion has occured at reactant ‘X’
(D) The reaction has molecularity two
4. The product ‘E’ is %
(A) CH3–CH2–CH=CH2 (B) CH3–CH=CH–CH3 (C) CH2=CH2 (D) CH3–CH=CH2
5. The product ‘F’ is :
Comprehension # 3
Answer Q.6, Q.7 and Q.8 by appropriately matching the information given in the three columns
of the following table.
D
Observe the three columns in which column-1 represents reactants, column-2 represents reaction conditions
while column-3 represents products.
Column-1 Column-2 Column-3
OH
C
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Organic Reaction Mechanisms-IV
EXERCISE – 1
PART - I
A-1. In basic condition very poor leaving group –OH will eliminate but in acidic medium –OH will be
converted into – OH2 which is very good leaving group.
A-2. 1º carbocation R – CH2 would rearrange and 2-alkene would result. Even if 1-alkene is also formed
but, it would tend to rearrange in acidic medium to 2-alkene.
EX
CH3
A-3. (a) CH3 C CHCH3 (b) CH3–CH2–CH=CH–CH3
CH3 CH3 CH3
(c) C C (d) CH3 C CHCH3
CH3 CH3
A-4. +
D
B-1.
B-3. +
O
|
CH3
B-5. (i)
>
(ii)
>
(iii)
>
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Organic Reaction Mechanisms-IV
C-1. The compound must have acidic -hydrogen and a relatively poor leaving group.
C-2. In E1cB mechanism carbanion is formed as intermediate and 1st step is reversible.
EX
A-6. (B) A-7. (B) A-8. (C) B-1. (C) B-2. (D)
B-3. (A) B-4. (C) B-5. (A) B-6. (B) B-7. (A)
B-8. (B) C-1. (B) C-2. (C) C-3. (B) C-4. (A)
PART - III
1. (B) 2. (A p,r) ; (B q,s) ; (C s) ; (D t)
EXERCISE – 2
PART - I
1. (D) 2. (D) 3. (C) 4. (D) 5. (A)
6. (A) 7. (C) 8. (B) 9. (A) 10. (C)
D
11. (C) 12. (C)
PART - II
1. 23 2. 6 3. 5 4. 5 5. 3
6. 32 [Molecular Weights (P – Q) = 114 – 82 = 32] 7. 78
PART – III
1. (ABCD) 2. (BCD) 3. (AD) 4. (ABCD) 5. (ABD)
O
6. (ABCD) 7. (ABCD) 8. (BD) 9. (CD) 10. (ABC)
PART - IV
1. (B) 2. (C) 3. (C) 4. (A) 5. (C)
6. (D) 7. (C) 8. (D)
C
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Organic Reaction Mechanisms-IV
EX
question. ¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No
deduction from the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any question
will be treated as wrong response and marks for wrong response will be deducted accordingly as per
instructions 4 above.
H3O H3PO4
1. + PhMgBr A B C
C is :
2. The correct increasing order of reactivity for following alkyl halides towards elimination reaction with
D
alcoholic KOH is :
(1) II > I > III (2) I > II > III (3) II > III > I (4) III > II > I
O
conc. H2SO4
3. In the given reaction: [X] as major product
[X] will be :
O OH
NaOH,
4. (Product)
The major product of the above reaction is obtained by mechanism
(1) SN2 (2) E2 (3) E1cB (4) SN1
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Organic Reaction Mechanisms-IV
Conc. H SO
6.
2 4
Major product is :
7. Which of the following conformations of meso 2,3-dibromobutane will give bromoalkene with alcoholic
KOH ?
(1) Gauche form (2) Anti form
(3) Partial eclipsed form (4) Fully eclipsed form
8. 2-Bromopentane is heated with potassium ethoxide in ethanol. The major product obtained is
EX
(1) 2-Ethoxypentane (2) pent-1-ene
(3) cis-pent-2-ene (4) trans-pent-2-ene
CrO / H H 1) CH MgBr
9. 3
P
3
Q
R
2) H3O (major)
OH
R is :
(1) But-1-ene (2) 2-methylbut-1-ene
(3) 2-methylbut-2-ene (4) 2-methyl propene
C H O– K
2 5
Trans
O
(1) (2) (3) (4)
12. P, Product P is :
C
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Organic Reaction Mechanisms-IV
EX
16. Which of the following compound will give three alkenes after dehydrohalogenation.
(1) CH3–CH2–CH2–CH2–Br (2)
(3) (4)
OH
19. Typical features of E2 involve :
(1) Two step reaction
(2) Second step is the rate determining step
C
20. An alkyl chloride produces a single alkene on reaction with sodium ethoxide and ethanol. The alkene
further undergoes hydrogenation to yield-2-methylbutane. Identify the alkyl chloride from amongst the
following :
(1) ClCH2C(CH3)2CH3 (2) ClCH2CH2CH2CH3
(3) ClCH2CH(CH3)CH2CH3 (4) CH3C(Cl)(CH3)CH2CH3
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Organic Reaction Mechanisms-IV
22. Which of the following is the correct major product for given reaction ?
H SO
2 4
Product
(1) (2)
(3) (4)
EX
23. Which of the following is a -elimination reaction ?
NaOH /
(1) HO–CH2–CH2–Br
(2) CHCl3 + KOH CCl2
HO /
(3)
NaNH2
(4) CH2=CH–Cl HCCH
24. Correct order of E2/SN2 ratio is :
P= Q= R = CH3–Br S = CH3–CH2–Br
D
(1) P > Q > S > R (2) P > Q > R > S (3) R > S > Q > P (4) P > S > Q > R
25. The product C of the following reaction sequence is :
EtO– (1eq)
C
27. What is the correct sequence of reagent/s for the following conversion:
CH3 CH CH3 CH3–CH2–CH2–I
|
Br
alc. KOH
HI aq. KOH H2SO4 HI
(1) (2)
alc. KOH HBr / R2O2 KI alc. KOH KI
HCl
(3)
(4)
acetone acetone
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Organic Reaction Mechanisms-IV
28. In which of the following reaction the single product formed is not the saytzeff’s product
H SO H SO
(1)
2 4
(2)
2 4
29. In the following reaction the correct order of percentage of products X, Y and Z is
CH3 CH3 CH3 CH3 CH2 CH3 CH3 CH3
| | | | || | | |
alc. KOH
CH3 CH2 C CH CH3 CH3 CH C CH CH3 + C2H5 C – CH CH3 + C2H5 C C CH3
| (X) (Y) (Z)
Br
EX
(1) X > Y > Z (2) Z > Y > X (3) Z > X > Y (4) Y > Z > X
2. Which of the following most readily undergoes E2 elimination with a strong base ? [NSEC-2000]
C
3. An alkyl chloride produces a single alkene on reaction with sodium ethoxide and ethanol. The alkene
further undergoes hydrogenation to yield 2-methylbutane. Identify the alkyl chloride from amongst the
following : [NSEC-2001]
(A) CICH2CH(CH3)CH2CH3 (B) CICH2CH2CH2CH3
(C) CICHC(CH3)2CH3 (D) CH3C(CI)(CH3)CH2CH3
4. On heating glycerol with conc. H2SO4, a compound obtained which has an unpleasant odour. This
compound is : [NSEC-2001, 2004]
(A) ethylene glycol (B) allyl alcohol (C) acrolein (D) glycerol sulphate
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Organic Reaction Mechanisms-IV
EX
H SO
2 4
Major product
Heat
9. Arrange the following compounds in order of decreasing reactivity in the elimination (bimolecular)
reaction with C2H5ONa [NSEC-2007]
10. Compound X on treatment with HI gives Y. Y on treatment with ethanolic KOH gives Z (an isomer of X).
Ozonolysis of Z (with H2O2 workup) gives a two-carbon carboxylic acid and four carbon ketone. Hence,
X is :
(A) 2-methyl-2-pentene (B) 4-methyl-1-pentene [NSEC-2009]
(C) 2, 3-dimethyl-2-butene (D) 3-methyl-1-pentene
O
11. The major product of the following reaction is : [NSEC-2009]
3(i) H PO , 150ºC
4
(ii) C6H5COOOH
13. The compound that is most reactive with alcoholic KOH is [NSEC-2014]
(A) CH2=CH–Br (B) CH3CH2Br (C) (CH3)2CH–Br (D) CH3COCH2CH2Br
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Organic Reaction Mechanisms-IV
Br
(i) Mg, ether (ii) CH O (iii) H , H O
(III) 2 2
Br
(i) aq. KOH (ii) CH MgBr, ether (iii) H O
(IV) 3 3
Br
EX
The processes that do not produce 1-methylcyclohexanol are
(A) II, IV (B) I, II (C) III, IV (D) I, III
17. Spodoptol, a sex attractant, produced by a female fall armyworm moth, can be prepared as follows. The
structure of Spodoptol is (pKa : terminal alkynes ~ 25, alcohols ~ 17) [NSEC-2016]
i. NaNH2 (excess)
ii. n-C4 H9Br (1eq)
iii. H2 /Lindlar cat
C
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Organic Reaction Mechanisms-IV
Important Instructions
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 22 questions. The maximum marks are 66.
B. Question Paper Format :
3. Each part consists of five sections.
4. Section 1 contains 8 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE is correct.
5. Section 2 contains 6 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
EX
of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 4 questions. The answer to each of the questions is a single-digit integer, ranging from
0 to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer among
the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1, 2,
3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY ONE
is correct.
C. Marking Scheme
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus one
D
(–1) mark will be awarded.
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s)
corresponding to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks will
be answered for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble corresponding
to the correct answer and zero mark if no bubble is darkened. No negative marks will be awarded for
incorrect answer in this section.
O
SECTION-1 : (Only One option correct Type)
This section contains 8 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.
Base
Cl Base
H
(i) (ii)
E2 E2
Cl
(A) Same for both conformers (B) i > ii
(C) ii > i (D) Can’t say anything about rate of E-2 reaction
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Organic Reaction Mechanisms-IV
O
OH
(A) (B)
OH
(C) (D)
OH OH
EX
OH OH
4. When the all-cis isomer of C6H6Cl6 (1, 2, 3, 4, 5, 6-Hexachlorocyclohexane) is heated with alc. KOH,
the most probable product is :
CHD2MgI Conc.H2 SO 4
5. CH2O
X Y
H3 O
In the above reaction compound X & Y respectively will be
D
OH
|
(A) CHD CH2 OH , CHO–CHO (B) CHD2–CH2–OH , CHO–CHO
(C) CHD2–CH2–OH, CD2=CH2 (D) CHD CH2 OH , CD2=CH2
|
OH
Conc. H SO / 60ºC
7.
2 4
The product is –
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Organic Reaction Mechanisms-IV
8. Which one of the following hexachlorocyclohexane is least reactive and which one is most reactive for
E2 reactions with a strong base for dehydrohalogenation.
(A) I least & II most (B) II least & I most (C) III least & I most (D) III least & II most
EX
This section contains 6 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.
9. In which of the following reactions the correct major products are mentioned
CH3
EtO
(A)
Br
H3C CD3 H 3C CD3
EtO
(B)
D
NaOEt
(C) EtOH
H SO ,
(D)
2 4
O
10. When ethyl bromide is added to potassium t-butoxide, the product is ethyl t-butyl ether.
CH3 CH2 – Br + (CH3 )3 C – OK (CH3 )3 C – O – CH2 CH3
ethyl bromide potassium t butoxide ethyl t butyl ether
(B) when the concentration of potassium t-butoxide is tripled and the concentration of ethyl bromide is
doubled rate will increase six times.
(C) Elimination product dominates when temperature is raised.
(D) when the concentration of potassium t-butoxide is tripled and the concentration of ethyl bromide is
doubled rate will increase three times.
CH CH O – CH CH O –
(A)
3 2
(B)
3 2
DMSO DMF
H O
(C)
2
(D)
13. Which of the following statements is/are correct for alkyl halide ?
(A) In most unimolecular reactions of alkyl halide SN1 reaction is favoured over E1 reaction.
EX
(B) E1 mechanism is favoured as compared to SN1 mechanism by branching at carbon
(C) In unimolecular reaction, increasing the temperature favours E1 mechanism
(D) E1 reactions are favoured by the use of weak bases and by the use of polar solvents.
(D) The compound gives product (P) on treatment with conc. H2SO4 as well as with Al2O3/
O
Section-3 : (One Integer Value Correct Type.)
This section contains 4 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)
15. The order of following reaction is :
C
H SO /
2 4
17. CH3–C—CH–CH3
H3C Br
Report your answer as XY
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Organic Reaction Mechanisms-IV
18. The number of products (stereoisomers) formed in the following reaction is (consider only major
product)
EX
options (A), (B), (C) and (D)
C H O– (excess) /
19. 2 5
P (major)
D
Product P is
21. Which of the following substrate will undergo fastest reaction through E1cB route
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Organic Reaction Mechanisms-IV
22. Match List I (Reaction) with List II (Type of reaction) and select the correct answer using the code given
below the lists :
List I List II
(P) CH CH O – (1) E1
3 2
EX
CH CH O –
3 2
(Q) (2) E2
CH3CH2 OD
Ag O, moist
2
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
C
Que. 21 22
Ans.
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Organic Reaction Mechanisms-IV
PART - I
11. (3) 12. (2) 13. (4) 14. (3) 15. (3)
EX
16. (2) 17. (1) 18. (3) 19. (3) 20. (3)
21. (1) 22. (2) 23. (4) 24. (1) 25. (3)
26. (1) 27. (3) 28. (2) 29. (3) 30. (2)
PART - II
11. (A) 12. (A) 13. (D) 14. (D) 15. (B)
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Organic Reaction Mechanisms-IV
PART - I
CH3 CH3 CH3 CH3
OH
H2 SO 4
3.
–H2O
O OH O
NaOH,
4. (E1cB mechanism)
EX
Conc. H SO –H
6.
2 4
Alc. KOH
7.
OH
O
CrO / H 1) CH MgBr H
9. 3
3
OH O 2) H3O E1
R
CH3
Br
Conc. HBr NaNH / NH ( )
10. Ph
2 3
Ph Ph
OH
C
C H O– K
11. 2 5
12.
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Organic Reaction Mechanisms-IV
t BuOH
14. + t-BuO–K+
17. The reaction follows E1cb mechanism in which reactant undergoes D exchange alongwith an
elimination product.
+ CH3 CH3
CH2OH CH2 CH3
H Carbocation + elimination
18.
H2O rearrangement +
EX
19. It is a basic fact.
C H O –Na H / Ni
20. 2 5
2
E2
H SO
22.
2 4
(Pinacol–Pinacolone rearrangement).
23. -elimination is that elimination reaction in which substrate looses two atoms from 1 & 2 position.
CH CH + HCl
D
NaNH2 is strong base so give -elimination reaction.
–HBr
26. The T.S. involves
C
alc. KOH 2
HBr / R O2
27. CH3 CH CH3 CH3–CH=CH2 CH3 CH2 CH2
| |
Br Br
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Organic Reaction Mechanisms-IV
PART - III
1. The more stable conformation of chlorocyclohexane does not undergo an E-2 elimination easily while
the less stable conformer, with the chloro group in the axial position, readily undergoes an E-2 reaction.
2. [C] is incorrect because more than one isomer gives a single alkene on E2 elimination.
HIO4
2 0
3. [X] =
OH OH H2SO4
Pinacol-pinacolone
Rearrangement
O
EX
4.
5.
D
H
7.
H2 O* H
8.
O
No E2 reaction because -hydrogen and leaving group not present in anti
position.
C
H O
2
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Organic Reaction Mechanisms-IV
Conc. H SO O
14.
2 4
3
(Q)
Zn / H2 O
O
3
Zn / H2 O
15. E1
EX
(cis + Trans)
OH
conc. H2SO4
* + +
16.
(d + ) (E + Z)
CH3 CH3
SN1
CH3–C—CH–CH3 + CH3–C—CH–CH3
CH3
H3C OC2H5 H5C2O CH3
C2H2OH (d+ )
17. CH3–C—CH–CH3
D
CH3 CH3 CH3
H3C Br
E1
CH3–C=C–CH3 + CH3–C—CH=CH2 + CH2=C–CH–CH3
C H O– (excess) /
19. 2 5
20. CH2=CH2
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