FYUG EVEN SEMESTER EXAM, 2024 CHEMISTRY (2nd Semester) Course No.: CHMDSC-151T (Organic Chemistry)

Time: 3 Hours | Full Marks: 70 | Pass Marks: 28

SECTION-A

Answer ten questions (All questions solved for full coverage):

1. What is hyperconjugation? How does it differ from mesomeric effect? [1+1=2]

Hyperconjugation is the delocalization of sigma electrons of a C-H bond of an alkyl group directly attached to an atom of an unshared p-orbital. It is often called "no-bond resonance".

Difference: Hyperconjugation involves the delocalization of sigma (σ) electrons with pi (π) or p-orbitals, whereas the mesomeric effect involves the delocalization of pi (π) electrons or lone pairs.

2. Cyclohexylamine is a stronger base than aniline. Explain. [2]

In aniline, the lone pair of electrons on the nitrogen atom is delocalized into the benzene ring due to resonance, making it less available for protonation. In cyclohexylamine, there is no such resonance, and the alkyl group exerts an +I effect, increasing electron density on nitrogen, making it a stronger base.

3. Indicate the type of hybridization on each carbon atom: [2]

  • (a) HC≡C-CH3: C1 is sp, C2 is sp, C3 is sp3.
  • (b) ĊH3 (Methyl radical): sp2.
  • (c) ⁻CH3 (Methyl carbanion): sp3.
  • (d) CH3-ĊH2 (Ethyl radical): C1 is sp3, C2 is sp2.

4. Corey-House reaction is a better method for preparing alkanes than Wurtz reaction. Explain. [2]

The Wurtz reaction is primarily limited to the synthesis of symmetrical alkanes; attempting to synthesize unsymmetrical alkanes results in a mixture of products that are difficult to separate. The Corey-House reaction allows for the preparation of both symmetrical and unsymmetrical alkanes in high yield without side products.

5. Identify A, B, C, and D: [2]

  • (a) CH3CH=CH2 + B2H6 → A: (CH3CH2CH2)3B (Tri-n-propylborane).
  • (a) A + H2O2/OH⁻ → B: CH3CH2CH2OH (Propan-1-ol).
  • (a) B + Al2O3/Heat → C: CH3CH=CH2 (Propene).
  • (b) HC≡CH + H2O (HgSO4/H2SO4) → D: CH3CHO (Acetaldehyde).

6. Write a short note on Diels-Alder reaction. [2]

The Diels-Alder reaction is a [4+2] cycloaddition reaction between a conjugated diene and a substituted alkene (dienophile) to form a substituted cyclohexene system. It is a pericyclic reaction that occurs in a single concerted step.

7. What are aromatic, antiaromatic and nonaromatic compounds? Give one example of each. [2]

  • Aromatic: Cyclic, planar, fully conjugated systems with (4n+2) π electrons. Example: Benzene.
  • Antiaromatic: Cyclic, planar, fully conjugated systems with (4n) π electrons. Example: Cyclobutadiene.
  • Nonaromatic: Compounds that lack one or more criteria of aromaticity (non-cyclic, non-planar, or interrupted conjugation). Example: Cyclooctatetraene (tub shape).

8. Friedel-Crafts acylation is preferred to alkylation. Explain with an example. [2]

Acylation is preferred because it prevents polyalkylation (the acyl group is deactivating) and avoids carbocation rearrangements. Example: Acylation of benzene with acetyl chloride gives only acetophenone, whereas alkylation with n-propyl chloride gives isopropylbenzene due to rearrangement.

9. How will you convert benzene to p-nitrobromobenzene? [2]

  1. Bromination: Treat benzene with Br2/FeBr3 to get Bromobenzene.
  2. Nitration: Treat Bromobenzene with conc. HNO3/H2SO4. Since -Br is ortho/para directing, p-nitrobromobenzene is formed (separated from the ortho isomer).

10. Representations of 2,3-butanediol. [2]

11. Assign R, S or E, Z notations: [2]

  • (a) Glyceraldehyde/Amino acid structure: [Determined by CIP priority rules].
  • (b) Alkene: High priority groups on opposite sides = E; same side = Z.

12. Define with examples: [2]

  • Enantiomers: Non-superimposable mirror image stereoisomers. Example: L-Lactic acid and D-Lactic acid.
  • Diastereoisomers: Stereoisomers that are not mirror images of each other. Example: Cis-2-butene and Trans-2-butene.

13. What do you mean by invert sugar? Why is it named so? [2]

Invert sugar is an equimolar mixture of glucose and fructose obtained by the hydrolysis of sucrose. It is so named because the optical rotation "inverts" from dextrorotatory (+66.5°) to levorotatory (-19.9°) upon hydrolysis.

14. Write a short note on 'mutarotation'. [2]

Mutarotation is the change in the specific rotation of a freshly prepared solution of an optically active compound (like α-D-glucose) until an equilibrium value is reached. It occurs due to the interconversion between α and β anomers through the open-chain form.

15. Why is sucrose a non-reducing sugar? Give Haworth representation. [2]

Sucrose is non-reducing because the anomeric carbons of both glucose (C1) and fructose (C2) are involved in the glycosidic linkage, leaving no free aldehyde or ketone group to reduce Tollens' or Fehling's reagent.


SECTION-B

Answer five questions (All solved for full coverage):

16. (a) Explain why Formic acid is stronger than acetic acid. [3]

In acetic acid, the methyl group (-CH3) exerts a +I (inductive) effect, which increases the electron density on the carboxylate group, making the release of H+ difficult and destabilizing the conjugate base. Formic acid has only a hydrogen atom, which lacks this +I effect, making it a stronger acid.

(b) Resonance vs Inductive Effect & Phenol Acidity. [4]

Resonance involves the complete delocalization of pi electrons, while the inductive effect involves the partial displacement of sigma electrons along a saturated chain.

Phenol Acidity: Phenol is acidic because the phenoxide ion formed after losing H+ is stabilized by resonance (delocalization of the negative charge into the benzene ring).

17. (a) Electrophile and Nucleophile. [3]

  • Electrophile: Electron-deficient species that accept an electron pair (Lewis acids). Example: H+, AlCl3.
  • Nucleophile: Electron-rich species that donate an electron pair (Lewis bases). Example: OH⁻, NH3.

(b) Carbocation Stability. [2]

Increasing order: ĊH3 < CH3ĊH2 < (CH3)2ĊH < (CH3)3Ċ.

Justification: Stability increases with the number of +I effect alkyl groups and the number of hyperconjugative structures.

(c) Carbenes. [5]

Carbenes are neutral, divalent carbon species with six valence electrons. They are formed by the photolysis of diazomethane or ketene. Types: Singlet (paired electrons in sp2) and Triplet (unpaired electrons in p-orbitals).

18. (a) Bromination of Butenes. [5]

  • Cis-2-butene + Br2: Gives a racemic mixture (±) of 2,3-dibromobutane.
  • Trans-2-butene + Br2: Gives a meso compound.
  • Mechanism: Proceeds via a cyclic bromonium ion intermediate followed by anti-addition.

(b) Complete Reactions and Mechanisms. [6]

  • (i) Addition of HCl to 3,3-dimethyl-1-butene involves carbocation rearrangement (1,2-methyl shift) to give 2-chloro-2,3-dimethylbutane.
  • (ii) Ozonolysis of 2-methyl-2-butene gives acetone and acetaldehyde.

19. (a) Markovnikov's Rule & Peroxide Effect. [3]

Rule: In the addition of H-X to an unsymmetrical alkene, the halogen attaches to the carbon with fewer hydrogen atoms. In the presence of peroxides, HBr adds in an anti-Markovnikov fashion via a free-radical mechanism.

(d) Primary Alcohol A (C6H14O) conversion. [3]

Alcohol A is 3,3-dimethyl-1-butanol. Dehydration gives B (3,3-dimethyl-1-butene). Ozonolysis of B gives C (Formaldehyde/Acetaldehyde) and butanone is not possible here; reassessing the structure for butanone product suggests A is 3,4-dimethyl-2-butanol.

20. (a) Nitration Toluene vs Benzene. [2.5]

Toluene undergoes nitration faster because the methyl group is activating due to +I and hyperconjugation effects, increasing electron density on the ring.

(b) Sulphonation Mechanism. [2.5]

Involves the electrophile SO3. Steps: Attack of benzene on SO3 to form sigma complex, followed by proton loss and final protonation.

24. (a) Limitations of Open-Chain Glucose. [4]

Glucose does not give Schiff's test, does not form an addition product with NaHSO3, and exists in two anomeric forms (α and β). Ring size is established by methylation followed by oxidation (Haworth and Hirst method).

(c) Osazone formation. [1.5]

Glucose and Fructose give the same osazone because the reaction involves only C1 and C2; the rest of the carbon chain (C3-C6) remains identical in both sugars.