EVOLVE 2023

CARBOXYLIC ACID AND DERIVATIVES

Prep & Prop of CARBOXYLIC ACID 08D

Marking Scheme : Single Correct (+3,-1) M M: 99 Time : 1 hr

Comprehension
 Hydrolysis of ester takes place by many ways. One corresponds to alkyl oxygen cleavage and another
one coresponds to acyl oxygen cleavage.

 Alkyl oxygen cleavage (AAL 1 or AAL 2)

 Alkyl oxygen cleavage (AAC 1 or AAL 2)

[Here: 1 means unimolecular; 2 means biomolecular]

During acyl oxygen cleavage (during acid catalysed reaction) protonation takes place at oxygen of

and during alkyl oxygen cleavage carbocation is attached by the same oxygen of . In the following
question which cleavage you do expect to yield the product. Ester of 1°, 2° alcohol follows AAC2 mechanism
but ester of 3° alcohol follows AAL 1 mechanism.

1. (a) AAL 1 (b) AAL 2 (c) AAC 1 (d) AAC 2

2. (a) AAL 1 (b) AAL 2 (c) AAC 1 (d) AAC 2

3. (a) AAL 1 (b) AAL 2 (c) AAC 1 (d) AAC 2

 Any 1, 2-dicarboxylic acid yields anhydride upon produced they dehydrade. But —CO2H groups at one
carbon yield decarboxylated products. Similarly  etc. hydroxy carboxylic acids dehydrate upon
heating and produce lactide,  unsaturated carboxylic acid and  or  lactone respectively on the basis
of this passage answer the followings

4.

(a) (b) (c) (d) None of these

5. (a) -lactone (b) -lactone (c) -lactone (d) lactide

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 Favorski rearragement is an excellent process to produce carboxylic acid with ring contraction, -chloro
or bromoketone upon treatment with base like OH– and consequent treatment with acid yields carboxylic
acid with ring contraction. Carbanion forms due to stability by –I, –R effect of ketone group. Answer the
followings on the basis of the above passage
6. Which carbanion with form PhCH2COCH2Cl
    ..
(a) Ph—CHCOCH2Cl (b) PhCH2COCHCl (c) PhCH—COCHCl (d) Ph—CH2COCH

7. What will be the product of the following reaction : PhCH2COCH2Cl (i) OH (ii) H O ? 2

(a) PhCH2CH2COOH (b) (c) Ph—COCH2COOH (d) none of these

8. Which can be the substrate to yield

(a) (b) (c) (d)

 In a research lab, three scientists synthesised three carboxylic acids but each using two different methods.
Method I Method II
Mg/ether CO2 H3O KCN H3O
RX RX
Mr Perkin Mr Amit
CH3
CH2 CH 2
CH2 CHBr CH3 C Cl
Cl OH
Method II Method I Method II CH 3Method I

Read the above approach and answer the following questions.

9. Method I gives better result in case of :
(a) X, Y (b) Y, Z (c) X, Z (d) X, Y, Z
10. Select the product of X, Y, Z by method I :
X Y Z
(a) CH2==CHCOOH RH (CH3)3CCOOH
(b) CH2==CHCOOH RH (CH3)2C==CH2
CH 2COOH
(c) CH2==CHCOOH (CH3)3CCOOH
OH
(d) CH2==CHCOOH RH (CH3)3CH
11. Following are the drawbacks faced by X, Y, Z in their syntheses either by method I or method II
(I) : method II used by X cannot be used as Br is attached to vinylic carbon
(II) : method II used by Y cannot be used as CN– replace both Cl– and OH– group.
(III) : method I used by Y cannot be used as RMgX is decomposed by OH group
(IV) : method II used by Z cannot be used as CN– being a select correct drawbacks :
Select correct drawbacks :
(a) (I), (II), (III) (b) (I), (III), (IV) (c) (I), (II), (IV) (d) (I), (II), (III), (IV)

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12. Consider folllowing reaction :

Consider following statements about this reaction and select incorrect statement(s) :
A : It is SN2 at carbonyl carbon from where OH is a leaving group.
B : It is SN2 at sulphur from where Cl is the leaving group.

C : Intermiediate is resonance stabilished

D : Reaction is spontaneous as HCl and SO2 gases escape

(a) A, B (b) B, C (c) D (d) A
13. Consider the following reaction :

B is an ester of :
(a) A (salicylic acid) (b) acetic acid
(c) both of these (d) none of these
14. (Refer above question) If A is heated, there is formation of another ester called salol. Salol is an ester of :
(a) benzoic acid (b) salicylic acid (c) acetic acid (d) carboxylic acid
15. Consider following ester formation from acid and alcohol. Alcohol is isotopically labelled with 18O.

Select correct statement(s) :

(a) Molar mass of C is 88 (b) Molar mass of D is 20
(c) Molar mass of C is 90 (d) none of these

 Alkyl halides undergo SN reactions as well as El, E2 and ECB reactions, depending on the nature of
substrate and nucleophile. Carboxylic acids can be converted into a-bromo carboxylic acids and thus it
can be used as an intermediate in the synthesis of so many other compounds.

Based on the above intermediate, answer the following questions:

16. A used to carry out this conversion is:
(a) PBr3 (b) PBr5 (c) P; Br2/H2O (d) Br2, D
17. One sub-intermediate is also formed in the above reaction:

(a) (b) (c) (d) No sub intermediate is formed

18. Conversion of -carboxylic acid into -halo carboxylic acid is called:

(a) Cannizzaro reaction (b) Reformatsky reaction (c) Perkin reaction (d) Hell-Volhard-Zelinsky reaction

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19. For the conversion reagent used is:

(a) alcoholic NaOH (b) NaOH, H (c) both of these (d) none of these
20. Product of Q. 19 can also be synthesised by:
 
(a) RCH2CHO HCN H O  3
(b) RCH2CH2Br Mg / ether CO  H O 2 3

 
(c) RCH2CHOH KCN H O  3
(d) RCH==CH2 HBrO KCN H O  3

|
Br
21. For the following conversion we can use :
(a) KCN (b) C2H5ONa/H
(c) both (d) None

22. 
excess of NH3
SN 2
 Product is :

(a) with same configuration (b) with same configuration

(c) with inverted configuration (d) with inverted configuration

23. -Bromination of carboxylic acid can be performed on :

(a) C6H5COOH (b) C6H5C(CH3)2COOH (c) C6H5CH==CHCOOH (d) C6H5CH2COOH

 The synthetic sweetener aspartame, known commercially as Nutra sweet, is carboxylic acid.

Following questions are based on aspartame

24. Number of stereocentres present in it are :
(a) 1 (b) 2 (c) 3 (d) 4
25. Other artificial (synthetic) sweeteners are :
(a) sorbitol (b) saccharin (c) cyclamate (d) xylitol
26. In aqueous solution on standing it changes to :

(a) (b)

O NH COOH
(c) (d) no hydrolysis is possible
NH O

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 AIDS is a twentieth-century disease that has become a major medical problem in the world. The number
of drugs that are effective in treating HIV infection and AIDS is small.
The drug most used to great AIDS patient is zidovudine, also known as azidothymine, or AZT. If flights
an AIDS infect but does not cure it

The following questions are based on AZT.

27. Which group is not present in AZT ?
(a) Carbonyl (kero/aldehyde) (b) Oxirane (c) Peptide (d) Azide
28. Select correct statement (s) :
(a) It can tautomerise (b) It can give white precipitate with Lucas reagent
(c) It shows acidic property due to H attached to N (d) N3– can be replaed by Cl–

 Two chemical engineers (CE) at MIT were working on the same keto ester (A)
O
O
A:
O
for the synthesis of carbonyl compounds using same Grignard reagent CH3CH2MgBr but changing some
experimental steps.
CE Steps Product

Mr Petersykes A 
(i) CH 3CH 2MgBr(one equivalent)
+ X
(ii)H 3O


Mr Wade A 
(i) H 3O

 Y
(ii) CH 3CH 2MgBr(one equivalent)

29. Identify the product X and Y

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 Match the Column
30. Column - I Column-II
(Compound) (Rate of hydrolysis)
(a) MeCO2Me (p) 761
(b) ClCH2CO2Me (q) 1
(c) CHCl2CO2Me (r) 16,000
(d) CCl3CO2Me (s) 20,000
31. Column - I Column-II
Substituent in benzoic acid pKa

(a) (p) 3.91

(b) (q) 3.27

(c) (r) 2.94

(d) (s) 4.98

32. Column - I Column-II

(a) R2CHOH (1) COCl 2 (2) Me 2SO (3) Et3N
 (p) Me2S
(b) (RCO2)2Ca distillation (q) R2CO
(c) RCH(OH)R (1) (Me CO) Al (2) CH COCH 
3 3 3 3
(r) RCHO
(d) RCOCl (1) Pd (2) BaSO 4 (3) H2
 (s) HCl
33. Column - I Column-II

(a) (p)

(b) (q)

(c) (r)

(d) (s)

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All students are advised to solve DPPs within allowed time only.
All discussions are scheduled in every 4th doubt discussion class
–MKA Sir (Guruji)

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